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Contents
USE OF GEOCHEMICAL FEATURES SUBALKALINE GRANITES OF THE SEVERNIY PLUTON (CHUKOTKA) FOR A PETROLOGICAL
AND METALLOGENICAL ESTIMATION

ALEKSEEV V.I. ................................................................................................................................................................. 10

COMPOSITIONAL CHARACTERISTICS OF CARBONATITE MAGMAS FROM THE BOLSHETAGNINSKII MASSIF, EASTERN SAYAN
ANDREEVA I.A., KOVALENKO V.I. ................................................................................................................................... 11
THE ROLE OF FLUIDS IN TRACE ELEMENTS MOBILITY: A CASE STUDY OF THE CONTACT ZONES OF THE KHIBINA AND
LOVOZERO ALKALINE MASSIFS, RUSSIA
ARZAMASTSEV A.A.*, ARZAMASTSEVA L.V.*, SHANINA S.N.**, ZARAISKY G.P.*** .................................................... 12
THE ALKALINE POLYPHASE PLUTONS IN THE NE FENNOSCANDIAN SHIELD, RUSSIA: DEEP STRUCTURE AND DURATION OF
MAGMATISM

ARZAMASTSEV A.A., ARZAMASTSEVA L.V., ZHIROVA A.M. ........................................................................................... 13

EVOLUTION OF THE MEIMECHITE MAGMAS BY THE DATA OF THE MICROPROBE RESEARCH MEIMECHITE TUFFOLAVAS
ASAVIN A.M., SENIN V.G. ............................................................................................................................................... 15
ABOUT THE COMPOSITION OF THE RARE SULFATE - PIKERENGITE FROM THE VEND-PALEOZOIC PALEOGUYOTS FROM WEST
TRANSBAYKAL REGION
ASAVIN A.M., SEDUCH I.A., ROMASHOVA T.V., FILIMONOV A.V. .................................................................................. 17
MINERALOGY AND GEOCHEMISTRY OF K-RICH BASALTS OF THE CENTRAL PART OF THE SREDINNYI RANGE, KAMCHATKA
BABANSKY A., SOLOVOVA I. ............................................................................................................................................ 19
COMPARATIVE MINERALOGY OF CARBONATITE COMPLEXES BELONGING TO DIFFERENT FORMATIONS
BAGDASAROV YU.A. ........................................................................................................................................................ 20
CORRELATION BETWEEN MODERN HETEROGENEOUS LITHOSPHERE AND PHANEROZOIC ALKALINE MAGMATISM
BALASHOV YU.A.............................................................................................................................................................. 21
PETROLOGY AND GEOCHEMISTRY OF RARE-METAL OF SYENITES IN THE UKRAINIAN SHIELD
BEZSMOLOVA N.V. .......................................................................................................................................................... 23
HIGH-PRESSURE MELTING RELATIONS OF DIAMOND-FORMING CARBONATITES: FORMATION OF SYNGENETIC PERIDOTITIC
AND ECLOGITIC MINERALS (EXPERIMENTS AT 7.0 AND 8.5 GPA)

BOBROV A.V.*, SPIVAK A.V.**, DIVAEV F.K.***, DYMSHITS A.M.*, LITVIN YU.A.** ................................................. 24
1-ATM EXPERIMENTS WITH ALKALINE MELTS: PROBLEMS, SOLUTIONS AND SOME RESULTS
BORISOV A.A. .................................................................................................................................................................. 26
USING THE COMPOSITION OF THE CARBONATE PHASE TO INVESTIGATE THE GEOCHEMICAL EVOLUTION OF SUBVOLCANIC
INTRUSIONS

BRADY, A.E., MOORE, K.R. ............................................................................................................................................. 27

OXYGEN AND ARGON ISOTOPE RELATIONSHIPS IN SAUDI ARABIAN MANTLE XENOLITHS
BUIKIN A.I.*, IGNATIEV A.V.** AND VELIVETSKAYA T.A.** ......................................................................................... 28
EXPERIMENTAL MELTING OF CARBONATED K-RICH GARNET HARZBURGITE AND ORIGIN OF KIMBERLITE MELTS
BULATOV V.K.*, GIRNIS A.V.**, BREY G.P.*** ............................................................................................................. 29
THE TYPOCHEMICAL FEATURES OF PYROXENES FROM PALEOZOIC PICRITE DIKES WITHIN SPITSBERGEN ARCHIPELAGO
BURNAEVA M.YU.*, ANTONOV A.V.**, SIROTKIN A.N. *** ........................................................................................... 30
STUDYING OF PHASE RELATIONS IN THE SYSTEM FORSTERITE-DIOPSIDE-JADEITE (EXPERIMENT AT 7.0 GPA)
BUTVINA V.G., LITVIN YU.A. .......................................................................................................................................... 32
EXPERIMENTAL STUDY ON MELTING PHASE RELATIONS AND DIAMOND FORMATION IN THE CARBONATE-RICH KIMBERLITE
FROM MAJUAGAA, SOUTHERN WEST GREENLAND
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BUTVINA V.G.*, NIELSEN T.F.D.**, SAFONOV O.G*., LITVIN YU.A.* ............................................................................ 35

MELILITITES IN THE ALKALINE VOLCANICS SERIES ON THE GORRINGE BANK (SW PORTUGAL)
CHERNYSHEVA E.A., KHARIN G.S. .................................................................................................................................. 36
MULTISTAGE FLUID HISTORY OF A COPPER PROVINCE WITH CARBONATITES, LAMPROPHYRES, AND ASSOCIATED ROCKS
COSTANZO A., MOORE K.R. ............................................................................................................................................. 37
MODULATED STRUCTURES IN ALUMINATE SODALITES
DEPMEIER W. ................................................................................................................................................................... 38
MINERALOGICAL PECULIARITIES OF CARBONATITES OF THE CHAGATAY COMPLEX (WESTERN UZBEKISTAN)
DIVAEV F.K., GOLOVKO A.V., GOLOVKO D.P. ................................................................................................................ 39
PETROCHEMICAL PECULIARITIES OF DEVONIAN MAGMATIC COMPLEX IN DNIEPER-DONETSK AVLAKOGENE
DONSKOY N. A. ................................................................................................................................................................ 42
ROLE OF STRUCTURAL FACTOR DURING FORMATION OF ALKALINE MASSIFS OF PROTEROZOIC SERIES OF NEPHELINE
SYENITES IN SOUTH-WESTERN PART OF THE RUSSIAN PLATFORM

DONSKOY A.N.................................................................................................................................................................. 43
IS OSHURKOVO GABBRO COMAGMATIC ROCK TO CARBONATITE?
DOROSHKEVICH A.G., RIPP G.S. ...................................................................................................................................... 44
GRAPHITE-BEARING DOLOMITE CARBONATITES IN NEWANIA, WESTERN INDIA
DOROSHKEVICH A.G.*, RIPP G.S.*, VILADKAR S.G.**. .................................................................................................. 46
GEOCHEMICAL PECULIARITIES OF APATITE IN ALKALINE ROCKS FROM THE UKRAINIAN SHIELD
DUBYNA A.V., KRYVDIK S.G., BONDARENKO S.N. ......................................................................................................... 48
EXPERIMENTAL STUDY OF FORMATION OF NA-RICH MAJORITIC GARNET IN THE CONTEXT OF DIAMOND DEEP-MANTLE
GENESIS

DYMSHITS A.M.*, BOBROV A.V.*, LITVIN YU.A.**........................................................................................................ 49

SPECIFICS OF GLOBAL EVENTS WITH WHICH ALKALINE MAGMATISM IS ASSOCIATED
ERLICH E.I. ....................................................................................................................................................................... 51
CARBONIFEROUS COMPOUNDS IN PEGMATITES OF DIFFERENT GENETIC TYPES: COMPARATIVE STUDY
ERMOLAEVA V.N.*, CHUKANOV N.V.**, PEKOV I.V.***................................................................................................ 52
CENOZOIC VOLCANISM OF THE NORTH-EASTERN ASIA
FEDOROV P.I.*, KOLOSKOV A.V.** ................................................................................................................................. 54
СORRELATIONS BETWEEN FLUORINE, IRON AND TITANIUM CONTENTS IN MAGNESIUM MEMBERS OF THE HUMITE GROUP
GERASIMOVA E.I *,**, PEKOV I.V *,**, KONONKOVA N.N. ** ........................................................................................ 55
INFLUENCE OF MELT COMPOSITION ON FE, MN, AND NI PARTITIONING BETWEEN CARBONATE-SILICATE MELTS AND
MANTLE MINERALS: EXPERIMENTS AND APPLICATIONS TO THE GENESIS OF KIMBERLITES AND INCLUSIONS IN DIAMONDS

GIRNIS A.V.*, BULATOV V.K.**, BREY G.P.*** ............................................................................................................. 58

EXPERIMENTAL INVESTIGATION OF THE INTERACTION OF BASALTIC MELTS WITH PERIDOTITE WITH IMPLICATION FOR
MANTLE-CRUST INTERACTION AND MAGMA ORIGIN

GORBACHEV N.S., KOSTYUK A.V., NEKRASOV A.N. ....................................................................................................... 60

ION-EXCHANGE PROPERTIES OF TERSKITE. II. EXPERIMENTAL STUDY IN MIXED SOLUTIONS
GRIGORIEVA A.A.*, PEKOV I.V.*,**, BRYZGALOV I.A.* ................................................................................................. 61
NEW ISOTOPE DATA OF CARBONATITES AND ALBITITE FROM GREMYAHA-VYRMES MASSIF
GROZNOVA M.V., ZAITSEV V.A., SOROKHTINA N.V., KOGARKO L.N. ............................................................................ 62
PETROLOGY AND GEOCHEMISTRY OF ALKALINE LAVAS HOLZUN ORE DISTRICT OF GORNY ALTAY
GUSEV A.I.*, GUSEV N.I.** ............................................................................................................................................. 64
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PETROGENESIS OF SOME ALKALINE AND SUB ALKALINE BASALTS FROM EGYPT

HUSSEIN AZIZ HEGAZY .................................................................................................................................................... 66
THE KOLA PENINSULA AS A UNIQUE ALKALINE MINERALOGICAL PROVINCE
KHOMYAKOV A.P............................................................................................................................................................. 66
DIAMOND POTENTIAL AND ORIGIN OF KIMBERLITES.
KOGARKO L.N. ................................................................................................................................................................. 67
ISOTOPE CARBON COMPOSITION OF GRAPHITE AND CALCITE IN CHAGOTAY CARBONATITES (UZBEKISTAN)
KOGARKO L.N.*, DIVAEV F.K.**,WALL F.***, SEVASTYANOV V.S.* ............................................................................ 69
LITHOSPHERIC MANTLE BENEATH EAST ANTARCTIC (OASIS JETTY)
KOGARKO L.N. ................................................................................................................................................................. 69
PECULIARITIES OF ULTRABASIC-ALKALINE MAGMA DIFFERENTIATION FROM GIGANTIC GULI INTRUSION (POLAR SIBERIA)
KOGARKO L.N., GERASIMOVA E.I.................................................................................................................................... 70
POTASSIC FLUIDS AS METASOMATIC AGENS OF K-RICH ROCKS ORIGIN
KOGARKO L.N. ................................................................................................................................................................. 72
POST-COLLISIONAL HERCYNIAN MAGMATISM IN THE TIEN SHAN: LITHOSPHERIC SHEARING VS. MANTLE PLUME ORIGIN
KONOPELKO D.*, SELTMANN R.**, BISKE G.*, MATUKOV D.***, SERGEEV S.*** ......................................................... 72
GEOCHEMISTRY OF FE-MN SEDIMENTS
KOROTKINA O.A.*, KOGARKO L.N.*, BAZILEVSKAYA E.S.**, KUBRAKOVA I.V.* ......................................................... 73
EXPERIMENTAL STUDYING OF ALCALIC-CARBONACEOUS METASOMATISM. GENESIS OF ALKALINE AND CARBONATITES
MAGMAS.

KOSTYUK A.V., GORBACHEV N.S. ................................................................................................................................... 76

EXPERIMENTAL STUDY OF FLUID INCLUSIONS IN HAKMANITE FROM KARNASURT MAUNTIN, LOVOSERSKY MASSIF
KOVALSKAYA T.N*, KOTELNIKOVA Z.A.**, KOTELNIKOV A.R.*, SUK N.I.*, KOVALSKY A.M.*, GOETTLICHER J.*** . 78
AMBIGUITY OF NEPHELINE SYENITE FAMILY ROCK NAMES AND HOW TO COPE WITH THIS PROBLEM
KRASNOVA N.I., KOROLEV N.M., PETROV T.G. ............................................................................................................... 80
GEOCHEMISTRY OF TI AND P IN ALKALINE AND BASIC ROCKS FROM THE UKRAINIAN SHIELD
KRYVDIK S.G., GURAVSKY T.V., DUBYNA A.V............................................................................................................... 82
POSTMAGMATIC GEOCHEMICAL PROCESSES IN KIMBERLITES
KUZNETSOVA L.G. ........................................................................................................................................................... 82
VOLCANOCLASTIC CARBONATITES FROM CHREBTOVY VOLCANO, KAMCHATKA
LANDA E.A., MARKOVSKY B.A. ...................................................................................................................................... 84
MODELS OF DIAMOND GENERATION IN DIFFERENT GEODYNAMIC ENVIRONMENTS
LAPIN A.V.*, BELOV S.V.** ............................................................................................................................................ 85
GEOCHEMICAL TYPES OF KIMBERLITES AND THEIR MANTLE SOURCES
LAPIN A.V.*, TOLSTOV A.V.**........................................................................................................................................ 86
ALKALINE PLUME-MAGMATISM OF CONTINENTS AND OCEANS AND ROOTS OF ALKALINE PLUMES
LAZARENKOV V.G. .......................................................................................................................................................... 88
PEROVSKITE FROM THE TIKSHEOZERO CARBONATITE: AGE AND GENESIS
LEPEKHINA E.N.*, ANTONOV A.V.*, SAVVA E.V.**, BELYATSKY B.V.***, SERGEEV S.A.* ......................................... 89
FORMATION OF DIAMOND AND SYNGENETIC MINERALS IN THE MANTLE MULTI-COMPONENT SILICATE-CARBONATE-
SULFIDE-CARBON SUBSTANCE: THE KEY ROLE OF CARBONATITES

LITVIN YU.A.*, KUZYURA (SHUSHKANOVA) A.V.*, BOBROV A.V.**, VASIL’YEV P.G.**, OKOYOMOVA V.YU.** ....... 91
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PHYSICOCHEMICAL FACTORS OF DIAMOND AND GRAPHITE FORMATION IN CARBONATITE MELTS ON EXPERIMENTAL

GROUNDS

LITVIN YU.A.*, SPIVAK A.V.*, SOLOPOVA N.A.**, LITVIN V.YU.*, BOBROV A.V.** .................................................... 93
ENDOGENOUS AND SEDIMENTARY CARBONATE ROCKS FROM THE BELOMORIAN PROVINCE: NEW GEOCHEMICAL, ISOTOPIC
AND GEOCHRONOLOGICAL DATA

LOKHOV K.I.*, SIBELEV О.S.**, SLABUNOV А.I.**, BOGOMOLOV E.S.*, PRILEPSKY E.B.* ........................................... 95
BAFERTISITE AND JINSHAJIANGITE FROM THE GREMYAKHA-VYRMES ALKALINE COMPLEX, KOLA PENINSULA
LYKOVA I.S.*, PEKOV I.V.*,*, KONONKOVA N.N.**, SHPACHENKO A.K.*** ................................................................. 97
ZIRCON FROM THE ECONOMIC ULTRAMAFIC-MAFIC KHARAELAKH INTRUSION (RUSSIA): FIRST U-PB AND HF-ISOTOPE
CONSTRAINTS ON TIMING AND SOURCE COMPOSITION

MALITCH K.N.*, GRIFFIN W.L.**, BADANINA I.YU.*, PETROV O.V.*, TUGANOVA E.V.*, BELOUSOVA E.A.**,
PEARSON N.J.**, KNAUF V.V.***, PRESNYAKOV S.L.* .................................................................................................. 98
NEW U-PB ISOTOPE CONSTRAINTS ON TIMING OF METASOMATISM IN A SUBCONTINENTAL MANTLE: EVIDENCE FROM
ZIRCON AT FINERO, ITALY

MALITCH K.N.*, KNAUF V.V.**, BADANINA I.YU.*, GARUTI G.***, PRESNYAKOV S.L.* ........................................... 100
PETROLOGY OF TESCHENITES AND ALKALINE PICRITES ASSOCIATED WITH THEM IN CARPATHIANS AND CAUCASIAN
REGIONS

MAMEDOV M.N., BABAYEVA G.J., KERİMOV V.M. ....................................................................................................... 102

THE GEOCHEMISTRY OF MAFIC-ULTRAMAFIC INCLUSIONS FROM POSTCOLLISION SHEAR ZONE (ILMENSKY-VISHNEVY
MOUNTAINS)

MEDVEDEVA E.V.*, RUSIN A.I.**, BANEVA N.N.** ..................................................................................................... 103

SOME MINERALOGO-GEOCHEMICAL ASPECTS OF OUTLOOKS OF COMPLEX USE OF ORES FROM DEPOSITS OF U-NA
FORMATIONS OF UKRAINE.

MELNICHENKO B.*, BONDARENKO S.**, SIOMKA V.**, GRINCHENKO O.***, IVANOV B.**** .................................... 104
LAMPROPHYRIC ROCKS OF THE DEVONIAN ALKALI IGNEOUS COMPLEX OF BELARUS
MIKHAILOV N.D., LAPTSEVICH A.G. ............................................................................................................................. 106
FINITE ELEMENT MODELLING OF THE GENERATION OF CARBONATITE MAGMAS: APPLICATION TO POST-OROGENIC
MANTLE PROCESSES

MOORE K.R., RYAN P.D.R. ............................................................................................................................................ 108

GEOCHEMISTRY AND PETROLOGY TORO ANKOLE KAMAFUGITE MAGMAS: ISOTOPIC CONSTRAINTS
MURAVYEVA N.S.*, BELYATSKY B.V.**, IVANOV A.V.***.......................................................................................... 109
MINERALOGY AND GEOCHEMISTRY OF REE MINERALS IN ESFORDI ALKALI-MAGMATIC PHOSPHATE MINE, BAFGH,
CENTRAL IRAN
NAZARY M.*, KHAJO M.** ............................................................................................................................................ 110
AGE, TYPES OF SOURCES AND GENESIS OF THE IL'MENO-VISHNEVOGORSKY COMPLEX IN LIGHT OF NEW ISOTOPE DATA
(URALS, RUSSIA)
NEDOSEKOVA I.L. .......................................................................................................................................................... 112
CHEMISTRY OF CANCRINITE-GROUP MINERALS OF DIFFERENT FORMATIONS
OLYSYCH L.V.*, PEKOV I.V.*,**, CHUKANOV N.V.*** ................................................................................................ 113
GENETIC CRYSTAL CHEMISTRY OF NATURAL FLUORITE-RELATED CA,REE FLUORIDES
PEKOV I.V.*,**, YAKUBOVICH O.V.* ............................................................................................................................ 115
MICACEOUS PICRITES OF THE SIKHOTE-ALIN RIDGE
PETUKHOVA L.L., PRIKHODKO V.S. ............................................................................................................................... 117
MAGMATIC ROCKS IN MOSCOW METRO DECORATION.
POGREBS N.A. ................................................................................................................................................................ 118
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ISOTOPE-GEOCHEMICAL PARADOX OF ACID ALKALINE ROCK COMPOSITIONS OF PALEOGENE CONTRASTING FORMATION OF

AMGUEMA - KANCHALAN VOLCANIC FIELD, CHUKOTKA
POLIN V.F.*, SAKHNO V.G.*, MAKSIMOV S.O.*, SANDIMIROV I.V.** .......................................................................... 119
MINERAL-MELT PARTITION COEFFICIENTS OF TRACE-ELEMENTS IN MELILITE-BEARING AND MELILITE-FREE ROCKS OF
CARBONATITE COMPLEXES

RASS I.T. ........................................................................................................................................................................ 120

MESOPROTEROZOIC NEPHELINE SYENITE COMPLEXES OF THE PRAKASAM ALKALINE PROVINCE, ANDHRA PRADESH,
INDIA
RATNAKAR J.*, ZAITSEV V.**, SRINIVAS M.*, KUMAR K. VIJAYA *** AND RATHNA K.*** ........................................ 122
MULTIPLE-STAGE DIAMOND FORMATION IN THE YUBILEINAYA PIPE OF THE YAKUTIAN KIMBERLITE PROVINCE
RUBANOVA E.V., GARANIN V.K. ................................................................................................................................... 124
REDOX REACTIONS IN CARBONATE-RICH MAGMAS
RYABCHIKOV I.D.*, KOGARKO L.N.** .......................................................................................................................... 126
CAMBRIAN BASALTIC MAGMATISM OF DIFFERENT GEODYNAMIC SETTINGS RECORDED IN THE KATUN ACCRETIONARY
COMPLEX - A TRANSITIONAL ZONE BETWEEN THE PALEO-ASIAN OCEAN AND SIBERIAN CONTINENT

SAFONOVA I.YU.*, SIMONOV V.I.*, KOMIYA T.**, KURGANSKAYA E.V.* .................................................................... 127
SOURCES OF CENOZOIC INTRA-PLATE MAGMATISM IN CENTRAL ASIA: IMPLICATION FROM GEOCHEMISTRY AND SR-ND-
PB ISOTOPE DATA
SAVATENKOV V.M.*, KUDRYASHOVA E.A.**, KOZLOVSKY A.M.**, YARMOLYUK V.V.**......................................... 129
CARBONATITIC ZIRCON – MYTH OR REALITY: MINERALOGICAL-GEOCHEMICAL ANALYSIS
SAVVA E.V.*, BELYATSKY B.V. **, ANTONOV A.V. *** .............................................................................................. 130
СOLLISION GRANITOIDES AND SIENITES OF THE URALS: CONDITIONS OF LOCATION, GEOCHEMICAL AND METALLOGENIC
SPECIALIZATION AND PRACTICAL SIGNIFICANCE

SAZONOV V.N*, OGORODNIKOV V.N**, POLENOV YU.A**.......................................................................................... 132

BA-TI-RICH OXYMICAS FROM OLIVINE MELANEPHELINITES OF THE UDOKAN LAVA FIELD, SIBERIA, RUSSIA: CHEMISTRY
AND SUBSTITUTIONS

SHARYGIN V.V. .............................................................................................................................................................. 134

FE-RICH DELHAYELITE FROM NEPHELINITE LAVAS, OLDOINYO LENGAI, TANZANIA
SHARYGIN V.V. .............................................................................................................................................................. 136
IMMISCIBLE MELT INCLUSIONS IN NEPHELINE PHENOCRYSTS FROM NEPHELINITE LAVAS, OLDOINYO LENGAI: HEATING
EXPERIMENTS AND COMPOSITIONAL CONSTRAINTS

SHARYGIN V.V.*, KAMENETSKY V.S.**, ZAITSEV A.N.***, KAMENETSKY M.B.** ..................................................... 138
FEATURES OF PROTEROZOIC ALKALINE AND SUBALKALINE MAGMATISM IN UKRAINIAN SHIELD: DEPENDENCE ON
GEODYNAMIC POSITION

SHEREMET E.M. ............................................................................................................................................................. 140

MODELING DISTRIBUTION OF POLYMERIZED ANIONS ON THE LIQUIDUS OF THE NA2O-SIO2 SYSTEM
SHILDT A.V.*, ARISKIN A.A.**, POLYAKOV V.B.*** ................................................................................................... 141
THE PECULIARITIES OF PLUME-TECTONIC PROCESSES IN THE EARLY PROTEROZOIC PECHENGA AREA FROM THE ISOTOPE
SM-ND AND RB-SR DATA.
SKUF’IN P.K. .................................................................................................................................................................. 142
THE LUMINESCENCE OF APATITE FROM PHLOGOPITE AND RARE METAL-APATITE-MAGNETITE ORES OF THE KOVDOR
MASSIF

SOKOLOV S.V. ([email protected]), RASSULOV V.A. ([email protected]) ...................................................... 144

FLUID AND MELT INCLUSIONS IN MINERALS OF WEST GREENLAND LAMPROPHYRES
SOLOVOVA I., GIRNIS A., KOPYLOVA M. ....................................................................................................................... 146
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TRACE ELEMENT PARTITIONING BETWEEN IMMISCIBLE SILICATE AND CARBONATE MELTS FROM PRIMARY MELT
INCLUSIONS

SOLOVOVA I.P., GIRNIS A.V. AND RYABCHIKOV I.D. .................................................................................................... 147

THE BEHAVIOR OF CL, F, AND H2O DURING THE LATE EVOLUTION OF ALKALINE MAGMAS ON THE ISLAND OF
PANTELLERIA
SOLOVOVA I.P., KOVALENKO V.I., GIRNIS A.V. ............................................................................................................ 148
ALBITITES OF THE KRYVYI RIG-KREMENCHUG ZONE
SYOMKA V.A, VELIKANOV JU.F, VELIKANOVA O.JU. .................................................................................................... 150
MINERALOGY OF ALKALINE ULTRABASIC ROCKS IN BOLYARKA INTRUSION (NORTH-WESTERN AREA OF THE UKRAINIAN
SHIELD)
TSYMBAL S.N.*, KRYVDIK S.G.*, TSYMBAL YR.S.*, GEIKO JU.V.**, BARAN A.N.** .................................................. 151
ALKALINE GRANITES OF THE SYADATOYAKHINSKY MASSIF (POLAR URALS)
UDORATINA O.V. ........................................................................................................................................................... 152
MULTI-SCALE NUMERICAL MODELING OF CARBONATITE-SILICATE MAGMA INTERACTION
VALENTINI L., MOORE K.R. ........................................................................................................................................... 154
MANTLE PLUMES AND LITHOSPHERE THICKNESS ARE FACTORS GOVERNING MAGMA FORMATION IN THE YAKUTIAN
DIAMONDIFEROUS PROVINCE
VASILENKO V.B. ............................................................................................................................................................ 155
CONDITIONS OF POLYLITHIONITE FORMATION BY EXPERIMENTAL DATA
VASIL'EV N.V.*, ZARAISKY G.P.**, SCHURIGA T.N.***. .............................................................................................. 156
THE ZR-TI MINERALIZATION IN CARBONATITES OF THE SAMCHAMPI ALKALINE CARBONATITE COMPLEX, ASSAM, INDIA
VILADKAR S.G.*, SOROKHTINA N.V.**, SENIN V.G.** ................................................................................................. 158
GEOCHEMISTRY OF ISOTOPES (SR-ND) AND TR OF LAMPROITES FROM THE ALDAN SHIELD
VLADYKIN N.V. ............................................................................................................................................................. 161
STUDY OF THE NATURE OF MAGMATIC COMPLEXES USING NRE RATIO VALUES
VOLODKOVA T.V. .......................................................................................................................................................... 162
FIRST DATA ON COMPOSITION OF VOLCANIC ROCKS FROM THE NORTHERN PART OF SREDINNY RANGE, KAMCHATKA
VOLYNETS A.O.*, PEVZNER M.M.** ............................................................................................................................. 164
OCCURRENCE AND COMPOSITIONAL VARIATION OF HIGH-NA-AL MELILITES AT OLDOINYO LENGAI, TANZANIA
WIEDENMANN D.*,**, KELLER J.***, ZAITSEV A.N.**** ............................................................................................. 166
GENESIS OF CARBONATITES: INFERENCES FROM A WORLD MAP AND DATABASE
WOOLLEY A.R. .............................................................................................................................................................. 167
MINERALOGICAL AND GEOCHEMICAL FEATURES OF HIGH-ALUMINA FENITES OF THE MONT SAINT-HILAIRE ALKALINE
COMPLEX, QUÉBEC, CANADA

YAKOVLEVA O.S.*, PEKOV I.V.*,**, BRYZGALOV I.A.*, HORVÁTH L.***, YAPASKURT V.O.*, GUSEVA E.V.* ........... 168
SHEET DIKE COMPLEX OF THE FOREARC OPHIOLITE
YURKOVA R.M., VORONIN B.I. ...................................................................................................................................... 169
MINERALOGICAL AND GEOCHEMICAL CHANGES OF NATROCARBONATITES DUE TO FUMAROLIC ACTIVITY AT OLDOINYO
LENGAI VOLCANO, TANZANIA
ZAITSEV A.N.*, KELLER J.**, JONES G.***, GRASSINEAU N.**** ................................................................................ 171
ZR GARNET FROM INTRUSIVE CARBONATITES OF KERIMASI VOLCANO, TANZANIA
ZAITSEV A.N.*, WILLIAMS C.T.**, KUZNETSOVA I.V.***, BRITVIN S.N.*, SPRATT J**., PETROV S.V.* ..................... 172
CHEMICAL DIFFERENTIATION OF PRODUCTS OF CRUSHING BY THE GRAIN-SIZE FRACTIONS: EXAMPLE OF KOVDOR
MAGNETITE ORE
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ZAITSEV V.A., ROSСHINA I.A. ....................................................................................................................................... 173

GRAPHITE-BEARING CARBONATITE OF GULI MASSIF
ZAITSEV V.A., SOROKHTINA N.V., KOGARKO L.N. ....................................................................................................... 175
SPINEL GROUP MINERALS IN DUNITES OF GULI MASSIF. I SPATIAL VARIATIONS.
ZAITSEV V.A. SENIN V.G. .............................................................................................................................................. 176
SPINEL GROUP MINERALS IN DUNITES OF GULI MASSIF. II NUMERICAL MODELING OF MAIMECHITE, PICTITE AND
KHATANGITE CRYSTALLIZATION.

ZAITSEV V.A. ERMOLAEVA V.N. ................................................................................................................................... 178

IS A MAGMA OF SUBALKALINE MONZO-GRANODIORITE SERIES PARENTAL TO LATE JURASSIC CALC-ALKALINE GRANITES
OF THE EASTERN TRANSBAYKALIYA AND ASSOCIATED RARE-METAL MINERALIZATION?

ZARAISKY G.P. ............................................................................................................................................................... 179

FAIRCHILDITE K2CA(CO3)2 IN CARBONATITES AT LOOLEKOP MINE, PHALABORWA IGNEOUS COMPLEX
ZHITOVA L.M.*, SHARYGIN V.V.*, NIGMATULINA E.N.*, ZHITOV E.YU.** ................................................................. 181
GEOCHEMICAL CONSTRAINTS ON THE GENETIC RELATIONSHIP BETWEEN A-TYPE PERALKALINE GRANITE AND
ANORTHOSITE FROM THE NEOARCHEAN KEIVY ALKALINE PROVINCE, NE BALTIC SHIELD

ZOZULYA D.R.*, EBY G.N.** ........................................................................................................................................ 183

LITHOSPHERIC ROOTS AND ASTHENOSPHERIC UPWARPS OF THE NE BALTIC SHIELD: SPATIAL CONTROLS FOR KIMBERLITIC
AND ALKALINE MAGMATISM

ZOZULYA D.R.*, PELTONEN P.**, O’BRIEN H.***, LEHTONEN M.*** .......................................................................... 185
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Use of geochemical features subalkaline granites of the Severniy pluton (Chukotka) for a petrological
and metallogenical estimation
Alekseev V.I.
Saint-Petersburg state mining institute named after G.V. Plekhanov (technical university), Saint-Petersburg,
Russia

In the report at the previous conference (Alekseev, 2008) it was stated that the cause of extremely wide spread
occurrence of rocks rich in rare elements in the Severny massif are the intrusion of subalkaline leucogranites of lithium-
fluoric geochemical type and associated volume metasomatic transformation of biotite granites of the main phase. The
problem of selection of intrusive bodies which are capable to be a petrogeochemical benchmark in regional petrological
and metallogenic investigations has arisen because of the convergence of chemical characteristics of the granites of
earlier and late complexes. Ongonite magmatism events can be used as such benchmark in folded areas (Kovalenko,
1977; Dergachev, 1991; Vladimirov e.a., 2007).
We studied granitoids of the chukchi complex which are notable for wide range of rock composition – from
granodiorites and adamellites to biotite granites and leucogranites. Vein phase and dykes consist of granite porphyry
and granodiorite porphyry, granite aplites, pegmatites and lamprophyre. For the first time in Chukchi Peninsula we
discovered ongonite dykes among coarsegrained biotite granites of Shelagski hogback (Chauncky district) (Alekseev,
2005). Twenty six thin dykes were described within the area where Ichuveemsky dyke belt crosses the central dome of
the Severny pluton. These dykes are thin and have submeridian strike and group in two vein series 3 and 1 km wide
which extend more than 5 km through the central dome in upper reaches of the Apapelhin and the Glubokaya.
The main petrochemical features of the chukchi ongonites are high alumina content (Shand ratio
А12О3/К2О+Nа2О+СаО = 1.11÷1.22) and superalkalinity (K2O+Na2O = 8,05÷9,47). Prevalence sodium over potassium
is typical, the latter is in its clarke concentration. Ongonites differ from granitoids of the region by their
leucocratic character and from lithium-fluoric granites they differ by their alkalinity and alumina content (fig.).

Fig. Chemical composition of the Severny pluton granitoids and granites of the Chauncky district.
1, 2 – rare metal granitoids of the Severny pluton: ongonites(1) and microcline-albite leucogranites (2); 3 –
biotite granites of the chukchi complex (numerals on the diagram: 1 – Peveksky, 2 – Yanranaisky, 3 – Inroginaisky, 4 –
Puirkanayansky, 5 – Paliansky, 6 – Puitliansky, 7 – Kukeneisky massifs); 4 – granite according R. Daly.

Geochemically ongonites are characterized by high concentration of F, Li, Rb, Sn, Nb and lower concentration
of Sr and Ba (table). According to rare metal content they refer to ultrararemetal granitoids (Kozlov, 1985). Elemental
formula:
Be12,3  Sn12.0  Li10.2  Cs9.5  F6.9  Rb5.3  B3.1  Nb1.7
.
Ba 0.02  Sr0.02  Zr0.16
Among regional peculiarities of rock composition we should note a high content of Be, Cs, B and abnormally
low Zr content. Thereby they resemble kalgutites – ultrararemetal ongonites which were described in Altai (Dergachev,
1991) but they differ from kalgutites by the absence of abnormal phosphorus content and not so intensive accumulation
of caesium. Stable boron accumulation in all granitoid varieties of the region is a significant factor. Probably that is
what caused the formation of tin-bearing tourmaline metasomatites in the hydrothermal phase. In addition the structures
of geochemical relations of rare elements in ongonites and tourmalinites differ sharply.
 11

In general chemical composition of Chukchi ongonites is analogous to similar rocks but it has special regional
features. Identified geochemical features of ongonites are proposed to use as indicators of rare metal magmatism. It is
especially significant for Kuiviveem-Puirkakaisky tin ore region which granitoids are characterized by high rare metal
content.

References:
Alekseev V.I. About an origin lithium-fluoric granites of the Severny massif (Chukotka) // Zapiski RMO, 2005.
№ 6. P. 19-30. (in Russia).
Alekseev V.I. The reasons petrochemical similarities subalkaline lithium-fluoric and normal granites of the
Severny pluton (Chukotka) // Materials of the All-Russian seminar "Geochemistry of magmatic rocks". The scientific
school «Alkaline magmatism of the Earth», Saint-Petersburg, 23-26 May 2008. M.: GEOKHI RAS, 2008. P. 3-4. (in
Russia).
Vladimirov A.G., Annikova I.Yu., Antipin V.S. Ongonit-elvanovyj magmatism of Southern Siberia // Litosfera,
2007. № 4. P. 21-40. (in Russia).
Dergachev V.B. Ongonites and elvanites // Izvestiya RAS. A series geological. 1991. № 10. P. 34-43. (in
Russia).
Kovalenko V.I. Petrology and geochemistry of rare metal granitoids. Moscow: Nauka, 1977. 206 p. (in Russia).
Kozlov V.D. Geochemistry of ore-bearing granitoids of rare metal provinces. Moscow: Nauka, 1985. 304 p. (in
Russia).

Таble. Comparison characteristic of chemical composition of the Severny pluton granitoids and standart
samples of lithium-fluoric granitoids
Lithium-fluoric granitoids of Mongolia and
Granitoids of the Severny pluton
Components Transbaikalia (Kovalenko, 1977)
1 2 3 4 5 6
SiO2, 75,30 73,63 71,42
74.84 76,41 76,38
масс.%
Al2O3 14.8 13.29 12,48 12,78 14,43 17,17
Na2O 5.1 4.18 3.53 4,60 4,77 4,13
K2O 3.43 4.31 4.55 4,46 3,70 4,42
F, г/т 4733 3700 3130 2900 6700 8200
B 53 35 38 10 – 72
Li 242 409 160 289 186 318
Rb 444 648 369 795 842 1870
Cs 31 43 35 18 6 148
Be 37 20 19 7 2 16
Sn 36 30 18 50 101 74
Nb 65 51 38 46 56 62
Zr 27 39 102 104 78 66
Sr 26 26 44 16 120 15
Ba 16 136 83 9 197 30
Note. Severny pluton: 1 – ongonites (6 tests), 2 – microcline-albite leucogranites (7 tests), 3 – biotite granites of
the main phase (10 tests); Standard samples: 4 – microcline-albite granite, Zhanchivlansky massif, Mongolia; 5, 6 –
ongonites, Baga-Gazruinsky dykes, Mongolia (5), Arui-Bulaksky massif, Transbaikalia (6). Dash – no information.

Compositional characteristics of carbonatite magmas from the Bolshetagninskii Massif, Eastern Sayan
Andreeva I.A., Kovalenko V.I.
Thе Organization of Russian Academy of Sciences InstituteoOf Geology of Ore Deposits, Petrography,
Mineralogy and Geochemistry Russian Academy of Sciences, Moscow, Russia.

The Bol'shaya Tagna мassif is situated in the eastern Sayan province of alkaline ultrabasic rocks and
carbonatites. This massif is a rounded and concentrically zonal-ring complex structure (4 km in diameter) that
demonstrates the consecutive formation of ijolite-melteigite, nepheline and subalkali syenite (microclinite), picritic
porphyritic rock, and carbonatite rocks. The abundance of syenites and microclinites and the intense development of
fluorite mineralization related to the formation of carbonatite rocks are distinguishing features of this massif. Three
types of fluorite carbonatites are recognized: (1) fine-grained calcite carbonatites with fine- and very fine-crystalline
fluorite, hematite, and apatite; (2) massive or banded ore consisting of fluorite, calcite, K-feldspar, and aegirine (fluorite
 12

crystals vary from fractions of millimeter to 1 cm in size); and (3) stringer-disseminated ore with fluorite crystals from
3-4 mm to 1 cm in size.
The studied sample is a coarse-grained fluorite carbonatite of the second type composed of carbonate (~ 60 vol
%), fluorite (~ 30%), K-feldspar (~ 5%), pyrite (2-3%), and barite (up to 1-2%). Carbonate is represented by calcite
with elevated contents of Mn and FeO. The two-phase exsolution structure is often observed, Mn-calcite and
kutnahorite (carbonate of dolomite group).
The primary melt inclusions and syngenetic crystalline inclusions were revealed in fluorite, K-feldspar, and
pyrite from fluorite carbonatite.
The crystalline inclusions represented by carbonates, fluorite, K-feldspar, aegirine, columbite, and pyrite.
Among crystalline inclusions of carbonates were determined calcite, Na-Ca-carbonate, and kutnahorite. Sporadic
columbite ingrowths in calcite have been identified. Columbite contains as much as 11 wt % MnO, 9.5 wt % FeO, and
4.6 wt % TiO. The crystalline inclusions of Na-Ca-carbonate in fluorite contains up to 44.6 wt % CaO, 18 wt % Na 2O,
4.5 wt % F, 3.7 wt % MnO, and 1 wt % FeO. The empirical formula of this mineral was calculated from the chemical
analysis as Na 6.05(Ca 8.27, Mn 0.55, Fe 0.14)8.96[CO3]7.00 (F 2.49OH 1.51)4.00. The calculated H2O and CO2 contents are 1.31
and 29.66 wt %, respectively, and the total is 101.09 wt %.
Primary melt inclusions in fluorite are completely crystallized and contain a residual gas phase and a number of
daughter minerals including carbonate, fluoride, and chloride. Carbonates are predominant and represented by calcite,
kutnahorite, Na-fluorcarbonate, nyerereite, and burbankite. Nyerereite (Na-Ca - carbonate) and burbankite (Ba-Sr-
carbonate) are rather rare minerals and have been identified as daughter phases in melt inclusions for the first time.
Fluoride minerals are represented by fluorite and villiaumite. Qualitative microprobe analyses have indicated the
presence of halite and sylvite among the daughter minerals. In general, the mineral assemblage of melt inclusions in
fluorite from carbonatites of the Bol'shaya Tagna carbonatite complex is consistent with mineral composition of
carbonatitic lavas of the Oldoinyo Lengai Volcano (Tanzania), where nyerereite, gregoryite, Ba-carbonate, fluorite, and
sylvite have been identified as phenocrysts and groundmass minerals in the lavas.
The thermometric experiments with melt inclusions were carried out on a Linkam TS 1500 microscopic heating
stage with visual control. The first indications of melting of crystalline phases were observed at 280 oC. The complete
homogenization of inclusions into salt melt was attained at 520-525oC. The similar magma temperature (544oC) was
measured during the eruption of the Oldoinyo Lengai Volcano in 1988.
During the subsequent cooling, the salt melt completely crystallized into a microgranular aggregate of quenched
crystals. A complete scanning of the chemical composition of homogenized melt inclusions in fluorite analyzed by
scanning over the whole area allowed us to estimate the composition of the salt melt that produced the fluorite
carbonatite. The melt is characterized by extremely high contents of Na 2O (up to 22 wt %) and CaO (up to 10 wt %), F
(up to 1.65), Ce2O3 (up to 1.3 wt %), Cl (up to 1.0 wt %) as well as by elevated contents of FeO (7 wt %), MnO (4-5 wt
%), K2O (3-8 wt %), SrO (0.6-0.8 wt %), and Ba (0.6 wt %), F, and Cl. This melt are chemically similar to the
compositions of the lavas from the Oldoinyo Lengai Volcano.
A compositional difference between the rock studied and melt inclusions, (particularly, in terms of CaO and
Na2O contents) may be accounted for by instability of sodium carbonates and chlorides and their removal with fluid
phase at the late stage of magma crystallization. The sodic phases could also have been leached by water from the rock,
but this process is less probable because leached cavities are absent in the rock.

The role of fluids in trace elements mobility: a case study of the contact zones of the Khibina and
Lovozero alkaline massifs, Russia
Arzamastsev A.A.*, Arzamastseva L.V.*, Shanina S.N.**, Zaraisky G.P.***
*Geological Institute of the Kola Science Centre RAS, Apatity, Russia
**Institute of Geology, Komi Science Centre RAS, Syktyvkar, Russia
***Institute of Experimental Mineralogy RAS, Chernogolovka, Moscow, Russia

The Paleozoic Khibina and Lovozero massifs are mostly composed of agpaitic syenites with minor foidolites,
ultrabasic alkaline rocks and carbonatites, which occupy the area of ca. 2000 km2. The host rocks exposed in the contact
zones are represented by the Late Archean tonalite-trondhjemite-granodiorite gneisses. Metabasalts and green schists of
the Early Proterozoic Pechenga-Imandra-Varzuga paleoriftogenic complex occur only in the southern contact of the
Khibina massif. Geological observations indicate that the thickness of the fenites varies from few meters up to 100
meters and even more. Common are alkaline syenite veins ("umptekite" in the Khibina) and albite-microcline
pegmatoids (the Lovozero) in fenitized gneisses.
The hallmark of the agpaitic syenites is their immense abundances of REE, Y, Sr, Zr, Hf, Nb, Ta, and Th. These
are either concentrated in apatite, titanite, perovskite, and other accessories or, given their concentrations in melts were
high enough, form their own discrete minerals, such as loparite, pyrochlore, and eudialyte, which economic deposits
provide the basis for the region’s mining industry.
In order to decipher the behavior of gases and trace elements in the fenitization process, two profiles across the
contacts of the Khibina and Lovozero massifs have been investigated. 78 samples from AR gneisses, fenites, alkaline
syenite veins, zircon and ilmenite bearing albite-microcline veins have been analysed for major and trace elements
 13

(ICP-MS for V, Cr, Co, Ni, Ga, Rb, Sr, Y, Zr, Nb, Ba, Hf, Ta, Pb, Th, U). The microprobe data have been used for the
mineralogical characteristics of the fenites. All samples have been analysed for gases (F, Cl, CO2, H2O, H2S).
The endocontact zones. The data obtained so far unequivocally give evidence for different agpaitic magma -
gneiss interaction in the Khibina and Lovozero endocontacts. In the Khibina, in the proximal vicinity of the contact the
alkaline rocks are represented by syenites, which are suggested to be formed as a result of contamination of agpaitic
syenites by gneisses. The endocontact extends up to 100 m. Within this zone the volatile content (H2O, F, Cl, CO2) in
the agpaitic syenites ("khibinites") is at least twice as higher when compared with the average for the rock complex,
therefore, pectolite, natrolite, and lamprophyllite are ubiquitous. The endocontact agpaitic syenites ("khibinites") are
significantly depleted in Zr, Hf, Nb, Ta, REE, whereas concentrations of Rb, Sr and Ba are close to average in the
whole complex. In the Lovozero massif the endocontact zone is only 5 - 15 m wide. In contrast to the Khibina, the
Lovozero contact rocks exhibit no evidence of volatile concentration. However, the endocontact lujavrite is
significantly enriched in Zr, Hf, Nb, Ta, REE, Y, which enter eudialite, loparite, apatite and other rare minerals.
The exocontact zones. Two types of fenite can be distinguished in the exocontacts of the Khibina and Lovozero
massifs.
The first type fenite (fenite I) form the narrow (< 5 m) zone in the immediate contact of the nepheline syenites.
Concentrations of Zr, Hf, Nb, Ta, REE, Y in the Khibina apogneiss fenite are notably higher when compared with
neighbouring nepheline syenite. The peak values of the above mentioned trace elements occur 3 m off the contact of the
massif. In the 10 m profile across the contact (Ce/Yb) N changes from 32.8 in agpaite syenite to 17.2 in apogneiss fenite,
whereas average (Ce/Yb)N in gneiss is 25±2. These data are in good agreement with those obtained previously in our
experiments (Zaraisky et al., 2008), which show preferable migration of HREE from agpaitic syenite into gneiss during
the metasomatic interaction process. Similarly, accumulation of Nb in apogneiss fenite in respect of the near-contact
syenite fits well with our experimental data.
The fenites II are closely related to the veins of alkaline rocks and pegmatoids that spread within the 500 m
range off the intrusions. Fenites II form 3-20 m wide halos, in which gneiss gradually transforms into a totally
recrystallized fenite. The newly formed alkaline phases, such as nepheline, and the protolith phases, e.g. quartz, are
common even in a single specimen. In the northern contact of the Lovozero massif fenites II form a 500 m wide zone
surrounding a net of albite-microcline veins with zircon and ilmenite. HFSE and REE concentrations in fenites II
positively correlate with intensity of metasomatic alteration. Furthermore, in the Lovozero and Khibina totally altered
fenites F content is higher than that in adjacent alkaline veins.
Since the volatiles and most of the trace elements exhibit distinct signs of mobility in the metasomatic process,
we have attempted to assess the role of the H2O, F, CO2 in the migration of LILE, REE and HFSE. Additionally, we
have performed a stepwise heating for extraction of H2, N2, CH4, C2H4, C2H6 within the range of 20-400, 400-500, 500-
600, 600-700 and 700-800oC in the set of the Khibina samples. From the correlation analysis between the above
volatiles and trace elements, the following conclusions can be drawn.
(1) The strong positive correlation with H2O appears to suggest that hydrothermal fluids, which followed
alkaline pegmatoid veins were responsible for the transport of the REE, Zr, Hf, Nb, Ta. Rb and Sr into the host gneisses.
(2) As the temperature of the fluid increases to >400 oC, the positive correlation between REE and CH4
decreases. For example, the KLa gradually changes from 0.74 to 0.56. By contrast, correlation between REE and C2H6
during heating increases. Zr, Hf, Nb, Ta, Rb show the same behavior during the step-wise heating.
In general, the now available information on the contact zone of the Khibina and Lovozero intrusions appears to
suggest that the alkaline magma-host rock interaction has occurred via porous media flow (in the immediate contact) or
by the discrete channels formed during marginal fracturing of the calderas. The obtained U-Pb age of single zircons
(359 ±5 Ma, SHRIMP II data) shows that formation of albite-microcline veins followed the main Lovozero and Khibina
intrusions, which occurred at ca 370 Ma (Kramm and Kogarko, 1994). Numerous concentric fissures were filled by
post-magmatic hydrothermal fluids, which are suggested to be the main agent of fenitization of Archean gneisses.
This study was financially supported by the RFBR grant 09-05-00224.

References:
Kramm U., Kogarko L.N. Nd and Sr isotope signatures of the Khibina and Lovozero agpaitic centres, Kola
Alkaline Province, Russia. Lithos. 1994. Vol.32. P.225-242.
Zaraisky G.P., Shamatrina, A.M., Arzamastsev, A.A. Experimental modelling of alkaline metasomatic reactions
in the contact zone of the Lovozero massif. // Geochemistry of igneous rocks. Proceedings of the XXV International
seminar. School: "Alkaline magmatism of the Earth". (St. Petersburg, 23-26.05.2008). St.Petersburg State University
Publ., 2008. P.59-60.

The alkaline polyphase plutons in the NE Fennoscandian Shield, Russia: deep structure and duration
of magmatism
Arzamastsev A.A., Arzamastseva L.V., Zhirova A.M.
Geological Institute of the Kola Science Centre RAS, Apatity, Russia

The Palaeozoic Kola Alkaline Province comprises giant nepheline syenite plutons, numerous carbonatite intru-
sions, and dyke swarms. It is a wide-spread opinion that the Khibina and the Lovozero massifs are made up mostly of
 14

agpaitic syenites with minor foidolites (Gerasimovsky et al., 1966; Zak et al., 1972), which were formed during a
relatively short time span (Kramm and Kogarko, 1994). Geological studies performed during the last two decades give
evidence for the presence of carbonatites, peridotites, pyroxenites, melilitic rocks, olivine melteigites, alkaline syenites
and zircon-bearing syenites in the Khibina and partly in the Lovozero. The geological position and the volume of these
rocks within the massif as well as their genetic relations are still under debate. Additionally, the wide spectrum of rock
types that comprise these giant polyphase massifs inspire us to decipher the sequence of the rock formation and to
revise the time span of intrusions. The performed studies included geological and geophysical investigations (1), Rb-Sr,
U-Pb, Sm-Nd, Ar-Ar isotope dating (2) and petrological modelling (3).
(1) The combined seismic and gravity data were used to create 3D velocity and density models of the Khibina
and Lovozero massifs deep structure down to the level of 12 km. The concentrically-zoned structure of the Khibina
complex extends throughout the depth range accessible to computation. The western and southern contacts dip inward
at angles of 65-70° to a depth of 4 km. The angles diminish to 30° within the depth range of 4 to 6 km but increase
again to 50-60° below a depth of 7 km. The eastern contact of the massif, which is close to the carbonatite stock, is
almost vertical to the depths of 3-4 km and tends to progressively slope more gently at the depths of 4-5 km. Within the
northern sector of the massif, the gravity anomaly indicates the presence of a large zone of alkaline ultramafic rocks.
Structural analysis of the central part of the massif indicates that there is a rounded plate-like positive gravity anomaly
beneath the foyaite core of the massif. This anomaly is suggested to be caused by remnants of a 2.5 km thick plate of
rocks, which characteristics are close to those of foidolites.
The southeastern, southern, and western contacts of the Lovozero massif are almost vertical to a depth of 4 km
within the nepheline syenite zone, but develop more gentle slopes at depths below 9-10 km. The northern and
northwestern contacts dip at smaller angles, that vary from 50-60° at the surface to 30-40° at depths of 4-5 km, but
become nearly vertical from this level to depths of 9-10 km. At depths below 2 km, the Lovozero complex consists of
two zones that significantly differ in density: a southeastern zone, which comprise rocks with a density of 2660-2750
kg/m3, and a northeastern zone, which rocks have a density greater than 2800 kg/m3. The northeastern zone probably
joins the Kurga alkaline-ultramafic massif at a depth of 7-8 km. The southwestern part of the Lovozero complex seems
to be composed of agpaitic syenite to a depth of at least 10 km. This is the most probable location of the magma conduit
of the nepheline syenite intrusion. In the central part of the massif, at Seidyavr Lake, we have detected a local negative
gravity anomaly which corresponds to a body of zircon-bearing syenite with a density of 2580-2630 kg/m3.
(2) In order to estimate the duration of magmatic activity in the Khibina-Lovozero area, in addition to already
published data (Kramm and Kogarko, 1994; ....), we have performed some geochronological studies of the earliest and
the youngest rocks.
The volcanogenic pile of the Lovozero massif. Five samples from xenoliths in nepheline syenites, composed of
alkaline picrite and alkaline basalt, show a poorly fitting regression line of 87Sr/86Sr vs 87Rb/86Sr that yielded 450+/-50
Ma. High dispersion (I Sr from 0.7021 to 0.7037) is suggested to be the result of an isotope resetting due to the influence
of a nepheline syenite magma.
The olivine melanephelinite dike which filled concentric faults 5 km south of the Khibina contact. 40Ar/39Ar age
determination give the age of 388±6 Ma.
The Rb-Sr isochron dating of the olivine melanephelinite from the pipe cutting the Khibina intrusion gives the
age estimation 358+/-31 Ma and the initial ratio of ISr=0.70385+/-17 with MSWD = 4.0 (N=7). The Sm-Nd isochron for
the same rock gives 362+/-91 Ma (N=6, Initial 143Nd/144Nd = 0.512256+/-0.00062. MSWD = 0.58).
The zircon from the albite-microcline veins in the outer contact of the Lovozero massif. The SHRIMP II U-Pb
single grains zircon dating gives the age estimation of 359+/-5 Ma (N-22, MSWD= 0.026).
The zircon from the zircon bearing alkaline syenite in the core of the Lovozero massif. The SHRIMP II U-Pb
single grains zircon dating gives the age estimation of 347+/-8 Ma (N-5, MSWD= 1.2).
(3) Taking into account the previous geochronological data (Kramm and Kogarko, 1994; Zaisev et al., 1997;
Arzamastsev et al., 1998; 1999; Bayanova, 2004) we suggest the following sequence of magmatic events in the central
Kola:
Premagmatic stage. 427±6 Ma. Mantle metasomatism, which preceded Paleozoic magmatism (Arzamastsev and
Belyatsky, 1999).
Early magmatic stage. 404±6 Ma. The collapsed Lovozero caldera originated in the Late Archean tonalite
trondhjemite-granodiorite complex; volcanic activity began in the northeastern part of the newly formed structure, the
formation of the subalkaline Kurga intrusion.
Main magmatic stage.
388 ± 6 Ma. The formation of concentric faults and the collapsed Khibina caldera originated at the contact
between the Late Archean tonalite-trondhjemite-granodiorite complex and the Early Proterozoic Pechenga-Imandra-
Varzuga paleoriftogenic complex.
388 - 371 Ma. Ultrabasic-alkaline magmas intruded mainly in the northern part of the Khibina caldera and in
the northeastern part of the Lovozero caldera. Formation of olivine pyroxenite, melilitic rocks, olivine melteigite
intrusions in the periphery of the calderas.
371 - 362 Ma. Main agpaite syenite series of the Khibina and Lovozero massifs originated. Further collapse of
the caldera and development of a layered ijolite-melteigite complex in the central portion of the Khibina caldera. The
ijolite-melteigite complex was cut by a series of conical faults, along which phosphate-bearing urtite-juvite-kalsilite
syenite intrusion was emplaced. In the central part of the ijolite-melteigite series a new series of conical faults formed
 15

and foyaite intrusion occupied the core of the Khibina massif.

367 - 366 Ma. The Khibina pulaskite and carbonatite stock formed.
Late magmatic stage.
363 - 359 Ma. Dike series of olivine melanephelinite, nephelinite, phonolite were formed.
359 ± 5 Ma. Formation of the microcline-albite pegmatoid veins with ilmenite and zircon.
347 ± 8 Ma. Late magmatic processes in the core zone of the Lovozero massif as indicated by the crystallization
of zircon bearing alkaline syenites.
This study was financially supported by the RFBR grant 09-05-00224.

Evolution of the meimechite magmas by the data of the microprobe research meimechite tuffolavas
Asavin A.M., Senin V.G.
Institute of Geochemistry and Analytical Chemistry, 117945, Moscow, Kosigina str.19 [email protected]

The origin of primary magmas which closely connected with the forming of large ultrabasic alkaline intrusions,
until now, remains the most interesting problem of geochemistry and petrology. In particular great interest is a question
of forming and evolution of the high-Mg meimechite and picrite effusive rocks from the Maymecha-Kotuyskoi
province (North of Siberia). To this problem is dedicated a number of geochemical works (Sheynmann 1968, Sobolyev
et al 1972; Vasil'yev, Zolotukhin 1975; Arndt et al, 1995; Basu et al. 1995; Kogarko of & Ryabchikov 2000, Kamo et
al, 2003 and other). In recent years appeared experimental studies (Elkin-Tanton et al 2007).
These works showed the high-temperature nature of meimechite melts (1550-1600C), and according to the data
of experimental works occurs at the depths more than 200 km at pressures 5.5 GPa. This model of the formation of
meimechite magma assumes extremely quick ascent to the surface of the large volume of melts, with the very weak heat
loss. Until now the majority of data was obtained for the dyke. The rate of cooling of subvolcanic bodies, apparently is
sufficiently significant, and liquid were crystallized during the sufficiently wide interval of time. The observed of the
hydrodynamic separation of the crystals of olivine into the dikes in particular testify about this. However, together with
the subvolcanic bodies in the region are widely exposed the effusive varieties of meimechite revealed in the escarps of
the rivers Maymecha and Delkan. In 1987 we have observe the thicknesses of tuff and lava flows of meimechite in the
estuary of the Delkan.
These are the fresh rocks of black color with a small quantity of phenocrysts of olivine and spinel. Petrographical
and geological signs indicate the surface explosive forming flows. There are forms in section of the sharp pieces
pyroclastic suspension, variations in the textures, fiemme pyroclastic breccia inferred to be a result of a fluidization.
We observe the presence of the tracks of lava flow and, more dense crusts on the rounded sections of tuff with the
concentric structure, as any volcanic bombs. A study of these products of explosive activity they will make it possible to
more correctly estimate the temperature conditions of the being raise magmatic column. Great interest presents
comparison with meimechite dykes and the search of the special features of geochemistry of mineralogy tuff-lavas
flows. There is a great interest of the estimation of the temperature conditions of their formation. Data by the
compositions of several tuff and lava flows are published in the table.
Table Concentration of main elements by the RFA methods.
Sample 9 -tuff 10 13 15 18 33 - lava
Ground Groundmass** Ground
rock mass tuff lava tuff tuff rock mass
SiO2 37.36 36.80 40.84 37.44 37.55 36.41 39.51 40.80 38.54
TiO2 1.59 2.24 5.52 1.26 1.79 1.24 1.05 2.57 2.43
Al2O3 1.90 2.40 1.23 1.31 1.95 1.38 1.51 2.20 2.08
FeO* 9.86 8.27 7.47 10.13 10.71 10.56 8.41 12.64 11.94
MnO 0.17 0.21 0.42 0.15 0.14 0.22 0.15 0.21 0.20
MgO 32.92 32.68 31.89 35.72 34.60 34.50 41.04 36.99 34.94
CaO 3.36 4.64 5.82 1.75 4.80 3.22 2.41 3.87 3.66
Na2O 0.91 0.91 0.02 0.09 0.07 0.10 0.00 0.07 0.07
K 2O 0.01 0.01 0.03 0.02 0.06 0.08 0.34 0.05 0.05
Cr2O3 0.28 0.39 0.33 0.51 0.24 0.57 0.18
P 2O 5 0.21 0.26 0.16 0.19 0.16 0.17 0.30 0.28
ppp 11.12 11.20 11.63 8.35 11.58 5.50 5.40
Total 99.69 100.00 93.57 100.17 100.46 100.02 100.26 99.70 99.59
Ca/Al 1.77 1.93 4.75 1.34 2.46 2.33 1.60 1.76 1.76

* total iron calculate as FeO.

** measure by the microprobe CAMEBAX 100 defocused beam 100m.
 16

In spite of the absence of a significant quantity of phenocrysts of olivine in the species effusion rocks remain
extremely magnesia. It is interesting to note that handmade sorting under binocular microscope groundmass without
olivine phenocrysts show the closely to total rock composition. There is the same result carry out the analysis of the
sections of bulk by the defocused wide ray by the microprobe. The difference did not descend the content of magnesium
in these analysis no more then several wt.% MgO. In the comparison with meimechite dykes the content of MgO in
them is considerably higher. The content of rare and rare-earth elements is compared with meimechite dykes.
Enrichment is noted by the light rare earth together with the high content of siderophilic trace elements. The contents
Sr, Th are very high (Fig). The composition of olivine about Fa 5-12 with high content Ni and Cr. In contrast to dyke
varieties in tuff meimechite is observed the wide interval of the compositions of both the changed glass and the olivine.
The presence of the large number of spinel phenocrysts is essential peculiarities also. Phenocrysts spinel large
frequently fused and crushed. There is the evidence about the forming tuff under the conditions for the active mixing of
liquids from different level sections of the magmatic camera.

A study of these species will make it possible to more fully present information about spectrum of the fusions
existing in the deep camera and cumulative process. There is the cumulus rocks type association can be attributed
phenocrysts of spinel.
The simulation of the crystallization of compositions according to the program MELTS (Ghiorso M. S et al
2002) showed that the equilibrium phase composition of phenocrysts and liquid, closely to the conditions of high
pressure and temperatures. However, the reaction of the congruent melting of olivine and spinel occurs on the surface
and are formed phenocrysts of clinopyroxene and olivine (Fa12-17) of the second generation more ferrous and more titan
spinel composition.
Our data confirm complex multistage nature of the meimechite’s magmas that is proves by composition and the
mineralogy of the effusive varieties. These proof speak that the deep magmatic cameras exist. In such camera ultrabasic
liquids with the crystals are contained. Macro compositions and the mineralogy of phenocrysts indicate the possibility
of the prolonged stages of the equilibrium crystallization of olivine and spinel in the regime of very high pressures and
temperatures.

References
1. Vasil'yev Yu. R., Zolotukhin V. V. Petrologiya ultrabasite of the north of Siberian platform and some problems
of their genesis. Novosibirsk: Science, 1975, 271 P. (in Cyrillic)
2. Sobolyev A. V., Panin l. I., Chepurov A.I. About temperatures of the crystallization of minerals in meymechite
according to the results of the homogenization of melted starts // Reports dissertation, 1972, Vol. 205, № 1. P.201-204.
(in Cyrillic)
3. Sheynmann] Yu. M. Ocherkya of deep geology (about the connection of tectonics with the appearance of
magmas). M.: Nedra, 1968, 231 P. (in Cyrillic)
4. Argdt N., Lehnert of the V. and Vasiliev Yu. R. Meimechites: highly of magnesian of litosphere-contaminated
of alkaline of magmas of from of deep of subcontinental of mantle // Lithos, 1995, the V. 34. P.41-59.
5. Kamo S., Czamanske G., Amelin Yu., Fedorenko of the V., Davis D., Trofimov of the V. Rapid of eruption of
Siberian of flood-volcanic of rocks and evidence of for of coincidence of with of the Permian-Triassic of boundary and
mass of extinction at 251 Ma // Earth and Planetary Science Letters, 2003, 214. P.75-91.
6. Kogarko L.N., Ryabchikov I.D. Geochemical of evidence of for of meimechite of magma of generation in of
the of subcontinental of lithosphere of Polar Siberia //Journal of Asian Of earth sciences 2000 V.18 195-203
7. Fedorenko V., Czamanske G., Zen' ko T., Budahn J., Siems D. Field and geochemical of studies of of the of
melilite-bearing arydzhangsky suite, and an overall of perspective on of the Siberian alkaline-ultramafic of flood-
volcanic of rocks// Int. Geol. Rev., 2000, 42. P.769-804.
8. Arndt, N., Lehnert, K., and Vasil'ev, YMeimechites: highly of magnesian of lithosphere-contaminated of
alkaline of magmas of from of deep of subcontinental of mantle//Lithos, 1995, v. 34, p. 41-59.
 17

9. Linda T. Elkins-Tanton, David S. Draper, Carl B. Agee, Jessica Jewell, Andrew Thorpe, P.C. Hess Of the of
last of lavas of erupted of during of the of main of phase of the Of Siberian of flood of volcanic of province: results of
from of experimental of petrology//Contrib of Mineral. Petrol. 2007 V.153: P.191 – 209
10. Ghiorso M. S., Hirschmann M. M., Reiners P. W., and Kress V. C. III The pMELTS: An revision of MELTS
aimed at improving calculation of phase relations and major element partitioning involved in partial melting of the
mantle at pressures up to 3 GPa. //Geochemistry, Geophysics, Geosystems 2002 3(5),
10.1029/2001GC000217(http://melts.ofm-research.org).

About the composition of the rare sulfate - pikerengite from the Vend-Paleozoic paleoguyots from
West Transbaykal region
Asavin A.M., Seduch I.A., Romashova T.V., Filimonov A.V.
Institute of Geochemistry and Analytical Chemistry, 117945, Moscow, Kosigina str.19 [email protected]

The existence of oceanic islands and seamounts is supposed to be the one of the main evidence of the plate
tectonic theory. But there is no such acient geological object which could be so similar to rock complex of oceanic
island. These structures must include the alkaline magmatism manifestation, sedimentary rocks close to recent riff
limestone on the oceanic islands and sequence of terrigenic rocks.
In the last years several possible applicants into place of paleoanalog of the oceanic hot spots were found. For
example in the North West Chine Perm age oceanic island structures were found. [LAI Shaocong, Zhang Guowei, Dong
Yunpeng, Pei Xianzhi & Chen Liang 2002, Wang Yongbiao 2005, Niu, ZhiJun 2008, ZhiJun Niu, Anwu Xu, JianXiong
Wang, Qi Fa Duan, XiaoMing Zhao and HuaZhou Yao 2008]. On South West of Japan Permian carbonatic-
volcanogenic complex in accretic prism was found which can be interpreted as part of the paleoguyot [Tetsuji Onoue
and Hiroyoshi Sano 2007]. Some Russian geologists found the interesting geological structure in Gornyi Altai and Tien
Shan [Dobrecov et al 2004, I. Safonova 2006-2008, Volkova N.I., Scliarov E.V. 2007]. They believed that there is the
Cambrian paleoguyots volcanic-sedimentary complex.
The one of the most interesting object on the Russian territory is the Vend-Paleozoic paleoguyots of the Djida
River region. It is a part of the several close geological complex which can be combined as full oceanic island sequence.
The full section includes the ultrabasic basement, pillow tholeitic flows (underwater structure of the lava flows),
subalkaline and alkaline basalts (with the trace element geochemistry signs of intraplate magmatism) and sedimentary
complex – limestone, dolomites, black chert.
One of very stunning features of the geological situation of area is existence of displays of huge rocks consisting
from the sedimentary rocks – dolomites, cherts, limestone. The landslide is interpreted as gravitas blocks from the upper
part of the island structure moving downslop to the basement. During our field research on this rocks we have found the
porosity of white, white-yellow species of the mineral which easy solutes in water. The data of the microprobe,
chemical and physical analysis show that this mineral is a pickeringite – sulfates of Fe and Mg (Fe,Mg)Al2(SO4)4·22
H2O.
For diagnostics of a mineral we used IR-spectrum methodic and X-Ray powder diffraction spectrum.
Geological data couldn’t give us the evidence of the paregenetic sulfate and sedimentary carbonatic rocks. The
presence of manifestations of dolomites and gypsum in the carbonate top of guyot permits us to relate discovered
mineralization with the primary special features of sedimentary complex of the paleoguyot.Our researches of the trace
elements composition pickeringite had shown the fitures which permitted us to make paleoreconstructions of
sedimentary conditions in oceanic island lagoon.

Figure 1. а – Porous pickeringite aggregates, б – fine-acicular pickeringite crystals forming sheaflike, or thinner
frequent, radial-columnar aggregates Figure is made by Raztek MRX-10D-ST microscope in reflected light.
 18

Table. Composition of pickeringite.

Sample 3751 3751 3750 3750 3751 3751 3750 3750
Wt.%
Na2O 0.01 d.l. d.l. d.l. d.l. 0.07 d.l. d.l.
K2O 0.09 0.09 d.l. 0.07 0.06 0.11 0.05 0.08
CaO 0.18 0.11 0.12 0.18 0.16 0.24 0.16 0.14
MgO 5.19 5.16 5.14 5.37 5.29 5.11 4.62 4.62
MnO 0.23 0.26 0.16 0.17 0.24 0.25 0.16 0.18
Cr2O3 d.l. d.l. 0.00 d.l. d.l. 0.02 0.02 0.04
FeO 1.59 1.58 2.64 2.70 1.69 1.82 2.82 2.74
Al2O3 9.14 9.44 9.89 9.63 8.90 9.07 8.14 8.33
TiO2 0.02 0.02 0.04 d.l. 0.02 0.03 0.04 0.04
P2O5 d.l. 0.04 d.l. 0.07 0.04 0.08 d.l. 0.08
H2O* 48.00 46.83 43.87 42.76 47.81 47.05 49.67 48.84
SO3 35.35 36.28 37.97 38.88 35.63 35.99 34.10 34.69
Co 0.02 0.03 0.01 0.02 0.02 0.02 0.02 0.03
Ni 0.06 0.06 0.07 0.06 0.07 0.06 0.07 0.07
Cu 0.06 0.05 0.10 0.09 0.06 0.07 0.11 0.11
Zn 0.02 0.02 d.l. d.l. d.l. 0.00 0.00 0.00
Ba 0.03 0.03 d.l. d.l. d.l. d.l. 0.03 0.04
Сумма** 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00
Formulae coefficients calculated for summa of 7 cations.
Na 0.00 0.00 0.00 0.00 0.00 0.02 0.00 0.00
K 0.02 0.02 0.00 0.01 0.01 0.02 0.01 0.01
Ca 0.03 0.02 0.02 0.02 0.03 0.04 0.02 0.02
Mg 1.12 1.09 1.02 1.05 1.14 1.08 1.02 1.01
Mn 0.03 0.03 0.02 0.02 0.03 0.03 0.02 0.02
Fe 0.39 0.38 0.59 0.59 0.41 0.43 0.70 0.67
Al 1.56 1.58 1.55 1.48 1.51 1.52 1.42 1.44
S 3.84 3.87 3.79 3.81 3.86 3.84 3.78 3.81
Ni 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Cu 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
* - H2O calculated by the 100% norm of cations.
d.l.. – Low the detected limit.

Conclusion.
The Paragenesis with. pickeringite (phase without natrium 0.1% wt and with noticeable potassium) proves
the poor salinity of the lagoon water. The complete absence of Cl and F says the same.
At sufficiently high contents of Ba (345 ppm) the contents of Sr is extremely low (10 ppm). Besides in all
the analysis abundance Fe is observed 0.7 a.f.
The low content of Ni, Co, Cu on the level .0.0n % is uncommon for this mineral. Usually these elements are
concentrated in sulfate, which are formed from mining waters in the zone of weathering. These data emphasize that
the source of substance for sulfate is syngenetic with carbonate sediment.

References:
1. Tsutomu Nakazawa, Tsukuba Carboniferous Reef Succession of the Panthalassan Open-Ocean Setting: Example
from Omi Limestone, Central Japan //FACIES 2001 I. 44 P. 25-31.
2. H. Sano · M. J. Orchard Necoslie breccia: mixed conodont fauna-bearing neptunian dyke in Carboniferous-
Permian seamount-capping oceanic buildup (Pope succession, Cache Creek Complex, central British Columbia)
//Facies (2004) 50:133–145.
3. Julia E. Hammer a,*, Michelle L. Coombs b, Patrick J. Shamberger a, Jun-Ichi Kimura Submarine sliver in North
Kona: A window into the early magmatic and growth history of Hualalai Volcano, Hawaii //Journal of
Volcanology and Geothermal Research 151 (2006) 157–188.
 19

Mineralogy and geochemistry of K-rich basalts of the central part of the Sredinnyi Range, Kamchatka
Babansky A., Solovova I.
Institute of Ore deposits, petrography, mineralogy and geochemistry RAS (IGEM), Moscow, Russia

The potassium-rich igneous suite of the Tigil anticlinorium in Western Kamchatka includes absarokites, mica
absarokites, trachybasalts and their holocrystalline analogues (shonkinites), and more silicic rocks (shoshonites and
latites). We studied absarokites, shonkinites and shoshonites from the region of the Anmanna River at the southeastern
base of Kekunaisky Volcano (collection of O.N. Volynets and A.B. Perepelov) and from the Uksichan caldera
(collection of A.D. Babansky and V.S. Rodin). The main focus is the compositions and crystallization conditions of
magmas trapped as melt inclusions in minerals at different stages of magmatic evolution. The phenocrysts of the rocks
are olivine, clinopyroxene (Table 1), phlogopite, Ca-rich plagioclase, and orthoclase. The least evolved absarokite
contains olivine and clinopyroxene (En40-44Wo47-51Fs9) with mg-numbers of 0.86–0.67 and 0.81–0.83, respectively.
Daughter clinopyroxene from melt inclusions (sample 7041) shows high TiO 2 contents of up to 2.5 wt %. The
groundmass contains Ti-magnetite and ilmenite.

Table 1. Chemical compositions of phenocrysts from the alkaline rocks, wt %

1 2 3 4 5 6 7
S 4 3 5 5 5 5 6
iO2 1.79 8.55 1.92 4.29 1.75 5.94 7.42
T 0 0 0 0 0
iO2 - - .64 .26 .46 .08 .00
A 3 0 1 2 1
l2O3 - - .59 .65 .49 7.03 9.74
F 2 2 5 1 8 0 0
eO 2.08 9.52 .80 6.34 .06 .81 .33
M 1 0 0 0
nO .19 .57 .04 .00
M 3 4 1 2 1 0 0
gO 9.38 4.95 4.80 6.85 5.67 .06 .00
C 0 0 2 1 2 9 0
aO .28 .08 2.62 .28 1.15 .69 .28
N 0 0 5 3
a 2O - - .32 - .45 .73 .65
K 0 1
2O - - - - - .51 1.02
S 0 0
rO - - - - - .21 .00
B 0 0
aO - - - - - .04 .33
m 0 0
g .76 .67 - - - - -
W 4 4
o - - 6.5 - 5.4 - -
E 4 7 4
n - - 4.3 5 6.8 - -
F 9 2 7
s - - .3 5 .7 - -
A 4
n - - - - - 7 1
A 5 3
b - - - - - 0 3
O 6
r - - - - - 3 6

Note. Anmanna River: (1) olivine from sample 7039, (2) olivine from sample 7042, (3) clinopyroxene from
sample 7039. Uksichan caldera: (4) orthopyroxene, (5) clinopyroxene xenocryst, (6) plagioclase, (7) K-feldspar.

Table 2. Chemical compositions of rocks (Anmanna River) and melt inclusions in olivine and clinopyroxene, wt %
1 2 3 4 5 6 7 8 9
Sample 7042 7039 7021 7039 7039 7039 7042 7039 7021
SiO2 51.17 52.76 55.26 50.18 54.07 55.07 48.1 45.5 48.9
 20

TiO2 1.73 1.15 1.44 2.3 0.85 0.83 0.68 0.95 0.64
Al2O3 15.2 17.31 19.21 15.36 14.29 14.28 15.98 13.28 12.86
FeO 11.4 9.62 5.1 6.29 6.32 6.08 7.256 8.723 6.77
MnO - - - - - - 0.16 0.19 0.17
MgO 5.31 4.87 3.27 5.76 5.32 5.17 8.59 12.33 12
CaO 6.66 6.36 4.91 11.06 8.8 8.77 8.02 7.22 5.41
Na2O 3.09 3.39 3.2 3 2.27 3.08 2.92 2.55 2.71
K2O 4.13 5.56 7.16 3.68 5.16 5.27 3.09 2.52 3.44
Total 98.69 101.0 99.55 97.63 97.08 98.55 94.79 93.26 92.90
K2O+Na2O 7.22 8.95 10.36 6.68 7.43 8.35 9.1 7.59 9.59
Т, °C 1160 1160 1115 1135 1165 1165 - - -

Note. (1–3) Inclusions in olivine, (4–6) inclusions in clinopyroxene, and (7–9) bulk rock compositions. T is the
homogenization temperature of melt inclusions.

The olivine-free alkaline basaltoids of the Uksichan caldera contain abundant phenocrysts of Mn-bearing
orthopyroxene (up to 2 wt % MnО, mg-number of 0.70–0.75) and feldspars, plagioclase (An47Ab50Or3) and alkali
feldspar (An1Ab33Or66) (Table 1). In addition, there are amphibole and Fe–Ti oxide phenocrysts.
The initial magma of the basaltoids is alkali-rich (up to 9 wt % Na2O + K2O at K/Na up to 1.6) and shows high
contents of volatile components (up to 0.2 wt % Cl and F), Р2O5 (up to 2 wt %), and Н2О. The bulk analyses of the
shonkinites contain up to 4 wt % H2O. The magmas of the Uksichan caldera were probably F-rich, which is indicated
by the F-rich composition of apatite (up to 6% wt % F). Also noteworthy are high contents of some incompatible trace
elements, especially Ba and Sr, which were detected in substantial amounts in feldspar compositions. Heating
experiments with the melt inclusions showed that the melt began crystallizing at relatively low temperatures, no higher
than 1180°C, which is in line with the high contents of alkalis and H 2O.

Comparative mineralogy of carbonatite complexes belonging to different formations

Bagdasarov Yu.A.
The Institute of Mineralogy, Geochemistry and Crystallochemistry of Rare Elements, Moscow, Russia

Carbonatites, like some other formations are very deficient in silica, silicate-magnetite-apatite, apatitolites,
calcitic magnetitolites, fluorite calcite, in individual case apatite iolite-urtites (Khibiny) are formed at final stages of
complex massifs with alkaline rocks of subcrustal, mantle origin.
I. Within well known formation of ultrabasic-alkaline rocks within carbonatites (UAC), the main rare metal ore
components are Nb, Zr, REE Ce, rarely Sr, Ba, U, Ta, Th, as well as phosphorus in apatite, in zones of hypergenesis –
minerals of crandallite group and others; fluorite, Fe in magnetite, rarely hematite and its hydroxides, sulfides of non-
ferrous metals – Cu, Zn and others. Under specific conditions of metasomatic formation of rare metal carbonatite facies
(stages) the peculiarities of acid-basic interaction of the mineral forming medium and substrate result in relative
separation of niobates, usually of pyrochlore group. In these cases they actively vary according to the value of Nb/Ta
ratio; zones of commercial areas of Ta-U mineralization (Nb/Ta ratio from 1.2 to 4-6), blocks of increased ratio (10-30)
and areas of totally pyrochlore mineralization (ratio of these elements 40-60 and more). In the first case (individual
massifs of this formation in Russia), absolute Ta2O5 content in rocks is more than 0.025-0.03 mass%, of uranium oxide
- 0.5-0.8 of this value.
The majority of these complexes is characterized by Na-type chemistry and their early silicate varieties are usually
represented by the rocks of jacupirangite-melteigite-iolite row, nepheline and alkaline syenites, melilites, picrites and
others. The rocks of K-types alkaline rocks with leucite and others are more rare and, as a whole, depleted of the above
mentioned rare elements.
2. Massifs of alkaline-gabbroid-carbonatite formational type in Russia are actually represented only by
individual units, mainly on the Kola Peninsula. Large carbonatites bodies with significant amounts of pyrochlore and
some silicate minerals of Nb, Ta, Ba and others, occur only within the complex Tikshiosero. Nb 2O5 content in ores
usually exceeds 0.07-0.1 mass%; in other complexes it is even less.
3. Formation of so called linear (linear-fractured) bodies of carbonatites and fenites, is more rarely than intrusive
silicate rocks of syenite composition. They are known as ”near fault zone carbonatite metasomatites” and others. This
formation was first identified by the author in 1979. Now they include the known carbonatites bearing complexes
Ilmen-Vishnevogorsk, Chernigovsky in Ukranian Priasov’e, Dubravinsky in the Belgorod region, Tatarka on the
Yenisei Ridge, Siilin’jarvi in Finland, perhaps, some occurrences of carbonatites on the Timansk Rildge, individual
units in Arctic Norway, India, Australia. Part of these occurrences has no silicate intrusive rocks that preceded
carbonatites; in contrast, Ilmen-Vishnevogorsk zone is characterized by predominant miaskite nepheline and alkaline
syenites, which many times exceed carbonatites mass. The latter, as a whole, are characterized by decreased Nb and Ta
content in all comparable temperature facies with similar amounts of Sr, Ba, and phosphorus and absence of high REE
concentrations, typical of some UAC carbonatite facies. Attention is drawn to drastic increase in amount of elements,
which are not typical of carbonatites elements – Cr, and Ni (10-20 times increase comparing to UAC formation).
 21

Distribution of Nb and Ta and associated U and Th in niobates is defined by the same factors, i.e. in the facies of
increased temperatures uraniferous tantaloniobates occur with Nb/Ta ratio in minerals equal from 3-5 to 10-20
(Chernigov and Vishnevogorsk); at low T-parameters, niobates with insignificant Ta and U amounts are typical
(Tatarka, Yenisei Ridge); in some cases niobates are absolutely absent (Dubravinsk zone). Carbonatites of this
formation were as a rule generated at great depth and under sharply reducing conditions, which is confirmed by
existence of weight graphite amounts (Chernigov zone), decreased contents of magnetite and Fe2O3 component in any
other minerals as a whole.
4. Several assemblages of carbonatite complexes are distinguished, which are associated with silicate rocks of
moderate alkalinity, sometimes with expressed K specific chemistry, in other combined Na-K chemistry, i.e. with
nepheline and leucite. Earlier (Ginsburg A.I. and Samoilov V.S., 1983), massifs of Mongolia and Mountain Pass in the
USA with rich REE deposits were assigned to them. These types are characterized by somewhat indefinite geologic-
petrochemical features; perhaps now, they can include nepheline-leucite complex Murun with abnormally high Sr and
Ba concentrations in the composition of some carbonatites; this massif is similar to massif Mushugai-Khuduk in
Mongolia with high REE contents in apatite and other.
The special place is taken by carbonatites, the association of which with low alkaline rocks (granosyenites) and
sometimes with typical granitoids is not clear. These assemblages are also characterized by increased concentrations of
cerium REE, Sr, Ba, fluorite and Fe minerals, siderite and oxides, sometimes in commercial concentrations. These are
carbonatites of Khalutinsk-Arshansk zone in Pribaikal’e, Karasug and many small occurrences of this type in Tuva.
Definite features of similarity are demonstrated by the largest in the world REE deposit Bojun-Obo in China, some
occurrences of carbonatites-like rocks in Vietnam and other. It is worth noting that in absence of nepheline or its
negligible amount in early alkaline rocks, later carbonatites are eliminated in niobates, within all above discussed
formational types of these rocks, including UAC (massif Palabora in South African Republic). As a whole, the bulk of
carbonatites associated with low alkaline rocks, except the above listed, contain low concentrations of Sr, Ba,
sometimes REE, negligible concentration of niobates and other.
5. In Muisk region (Vitim basin) small carbonatites bodies have recently became known, which yet didn’t reveal
genetic associations with any intrusive silicate rocks. They contain not high amounts of niobates and zirconates with
notable addition of strontium, rare earth carbonates. A drastic increase in chromium content, up to occurrence of
spinellides, close to chromite, and weight amounts of graphite can point to closeness of these occurrences to linear
carbonatites bodies formation (G.S. Ripp and oth., 2000s).
In future, this type of carbonatite occurrences, distinctly belonging to the “fund” of hardly discovered deposits,
will be very likely discovered.

Correlation between modern heterogeneous lithosphere and phanerozoic alkaline magmatism

Balashov Yu.A.
Geological Institute of the Kola Science Centre of Russian Akademy of Sciences, Apatity, Russia

Variations in the contents of rare earth elements, Sm/Nd and εNd(0) values in peridotite xenoliths have been used
to reveal the isotope-geochemical heterogeneity in the vertical section of the mantle continental lithosphere. The section
covers all the changes in the mineral composition of peridotites and their clinopyroxenes from the upper plagioclase
facies (Pl) to lower high temperature garnet peridotite (Gt2) facies in the range of ≈ 15-250 km.The uppermost (Pl-Sp)
and the lowermost high temperature garnet (Gt2) peridotite facies were established to be homogeneous in relation to the
middle part of the lithosphere section represented by spinel (Sp), spinel-garnet (Sp-Gt) and low temperature garnet (Gt1)
peridotite facies (Fig.1).
30
εNd(0)
Sp - Gt Gt 1
20
глубина, км

Pl - Sp 15-30
Sp 30-55
10 OM Sp - Gt 55-65

Sp Gt 1 65-140

0 Gt 2 140-240
Pl - Sp
PM Asth > 240-250

Asth
-10 Gt 2

Sm / Nd
-20
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
 22

Fig.1. The changes in the Sm/Nd ratio and εNd(0) values in peridotites from various depths correlate well
reflecting the successive transition from the «primary oceanic» (OM) value - Sm/Nd > 0.3247 (average for the primitive
mantle) and εNd(0) >> CHUR=0 to the values reflecting the effect of the mantle metasomatism and other secondary
factors which is registered by Sm/Nd << 0.3247 and appearance of εNd(0) < CHUR negative values.The comparison of
Sm/Nd and εNd(0) values of peridotites and alkaline magmas of various composition and age (Fig.2) showed a sheer
coincidence of these parameters for Phanerozoic alkaline rocks and carbonatites: (1)- (0.1-130 Ma) and (2-) (239-404
Ma) and a deviation of the εNd(0) values to distinctly negative values up to -30 and -45 for Precambrian alkaline series,
which reflects a dependence on the age of formation of these alkaline rocks in Precambrian: (3)- alkaline intrusions
(1160-1884Ma), (4)- carbonatites (1299-1872Ma), (5)- volcanites of greenstoun belts (4) (2575-2681Ma) and (6)-
carbonatites (2661-2677 Ma). [7- ocean mantle; 8- primitive mantle; HARZ и LHER –harzburgites and lherzolites].

15
εNd(0) LHER

0 HARZ 1
2

-15 PR 4
AR 5

-30 7

Sm / Nd
-45
0 0.1 0.2 0.3 0.4 0.5
Fig.2. The maximum range of variations in the REE distribution in the lithosphere peridotites in relation to the
influence intensity of the mantle metasomatism on them was revealed from variations of the light and heavy REE (with
La and Yb as an example –Fig. 3 and 4).

The optimal La enrichment in harzburgites and lherzolites exceeds the average mantle level by a factor of 15-
30.This is equal to La concentrations in pyroxenites – early mantle melts of lithosphere. If we compare this with the
oceanic mantle, the difference reaches two orders.. Thus, the role of the processes of the light lanthanoid secondary
supply into continental peridotite can be considered to be a real factor of formation of the anriched mantle zones of the
lithosphere that are sufficiently enriched in these elements for considering them to be potential sources for generation of
alkaline magmas with sharply increased concentrations of mobile rare elements, that is incompatible with Yb and other
heavy REE.

100
La, ppm
1 2 3 4 5

10

PM
1

OM
0.1

Sm/Nd
0.01
0.1 0.2 0.3 0.4 0.5
 23

10
Yb, ppm
1 2 3 4 5

0.1

Sm / Nd

0.01
0 0.15 0.3 0.45 0.6

Differentiation of La (Fig. 3) and Yb (Fig. 4) in mantle harzburgites (1) , lherzolites (2), primitive (3) and
oceanic (4) mantle and pyroxenite xenolites (5) of lithosphere.

References (1-83) may to see in the paper “Development of a Heterogeneity in the Lithosphere:
Geochemical Evidence” (Balashov Yu. A. Petrology, 2009, Vol. 17, No. 1, pp. 90–100).
This study was financially supported by RFBR grants 07-05-00572-a, 07-05-00759-a.

Petrology and geochemistry of rare-metal of syenites in the Ukrainian Shield

Bezsmolova N.V.
N.P. Semenenko Institute of geochemistry, mineralogy and ore formation NAS Ukraine, Kyiv, Ukraine

Nepheline-free rare-metal syenites, which are characterized by the high content of Zr, TR,Y, Nb, are typical of
the Ukrainian Shield. Two deposites and some occurances of the mentioned rare metals are connected with such type of
rocks syenites. These rocks are located in three regions of the Ukrainian Shield: Azov area (its Eastern part), south
margin of Korsun – Novomirgorod anortosite-rapakivi granite pluton. The common characteristic of nepheline-free
rare metal syenites of the Ukrainian Shield is given.
Nepheline-free rare-metal syenites, which are characterized by the high content of Zr, TR,Y, Nb, are typical of
the Ukrainian Shield. Two deposites and some occurances of the mentioned rare metals are connected with such type of
rocks syenites. Rare-metal syenites distinguish for high iron-contents of femic minerals (fayalite, hedenbergite, aegirine,
riebeckite, aegirine-hedenbergite, ferrohastingsite), and high background level of zirconium (0.1-0.3%) and rare earth
elements (0.05-0.2%). These syenites are genetically and spatially related to anorthosite-rapakivi granite plutons.
Nepheline-free rare-metal syenites are located in three regions of the Ukrainian Shield: Azov area (its Eastern
part), south margin of Korsun – Novomirgorod anortosite-rapakivi granite pluton and Korosten pluton. A wide
distribution of such syenites is observed in Azov area, where they compose half of the South-Kalchyk massif.
Azov deposit is located in the same massif. Different gabbroids – ferrogabbro, ultramafics, gabbro and gabbro-
norite, were also exposed by mapping drilling in the South-Eastern part of the South-Kalchyk massif. Isotopic age of
the rocks, which compose South-Kalchyk massif, is 1.8 Ma.
Syenites of South-Kalchyk massif belongs to subalkaline series and two-feldspat verieties. Dark-coloured
minerals are characterized by the high iron-contents (fayalite, hedenbergite, aegirine). The contents of dark-colour
minerals in syenites varies from 10 to 30-40%. Besides, FeO dominates over Fe2O3. Accessory minerals in syenites are
represented by apatite, ilmenite, orthite, and chevkinite. Leikocratic as well as melanocratic varieties of syenites occur.
Accoding to their structural features, all varieties - from fine-grained to coarse-grained and pegmatoide are observed.
Syenites of Azov deposit are characterized by increasing of alkalinity of rocks and minerals (absence of
oligoclase, high contents of alkalines in amphiboles and clinopyroxenes). Moreover, in these syenites britholite, orthite
and fluorite appears (in ore amount), by high content of zircon. Syenites of Azov deposit principally don’t different
from the syenites of South-Kalchyk massif by their structure signs and ratio of salic and mafic minerals.
Syenites of Velyka Vyska massif which spatially related to the South margine of Korsun-Novomirgorod pluton
is located among granites rapakivi, and some of them – among Novoukrainska granites. In this massif fayalite-
hedenbergite with ferrohastingsite sienites dominate, which contain about 10-15% of dark-coloured minerals. The
content of plagioclase in them usually is 5-10%. Sometimes melanocratic, enriched in zircon and ilmenite varieties of
syenites are observed. These syenites, on their chemical and mineralogical features, are similar to syenites of the Azov
deposit. These features include: mainly feldspar composition, increased content of acmite component (up to 9%) in
clinopyroxene, high content of zirconium (1,5% and more) and also often observed presence of accessory orthite and
chevkinite, sometimes fluorite. In syenites of Velyka Vygka massif are chacteristic higher contents of lanthanoids (up to
0.2%) and zirconium (up to 1%), compare to two-feldspar syenites of South-Kalchyk massif.
Yastrybetsky syenite massif is located 30 km to the North-West from Korosteny pluton within Sushchany-Perga
zone and lies among granites of Perga complex. Massif is represented by differentiated layered intrusion. Yastrybetsky
 24

massif consists of endocontact syenites, syenites of the main layered series, quarts syenites (central core), syenites of
the upper layered group. The thickness of syenites of the main layered series is more than 1000 m and the layer
(cumulative deposits) of the rich zirconium ores is related to them. Namely this kind of rocks is identical to syenites of
the Azov deposit.
Syenites of Yastrybetsky massif are represented by alkaline feldspar varieties. Oligoclase can be observed in
small quantity only in endcontact syenites. Dark-coloured minerals of syenites are strongly enriched in iron and are
represented by hedenbergite, aegirine-hedenbergite, aegirine, ferrohastingsite, ferroendenite, riebeckite. Fayalite had not
been found. Characteristic accessory minerals are zircon, fluorite, orthite, britholite, ilmenite, bastensite, parisite.
Apatite rarely occurs only in endcontact syenites. Structurally syenites of the Yastrybetsky massif are represented by
from medium – to coarse grained up to pegmatoid varieties.
Yastrybetskiy massif represents a layered intrusion. Rhythmic layering of the massif is displayed by interlaying
of leucocratic and mesocratic syenites. The cryptic layring is expressed by compositional trand of the rock-forming
minerals ( to the central core of the massif, from down to up in the main layered series, and from up to down in the
upper layered group) of the chemical composition of the rock forming minerals. Also the alkalinity of pyroxenes and
amphiboles increase in this direction, decrease the aluminaty of biotite and increase the content of orthoclase minal in
the alkaline feldspar. The age on zircon of syenites of the Yastrybetskiy massif, according to the last dating is 1,76 Ma.
The syenites of the Davydky massif also belongs to the rare-metal type and this massif is located on the North-
East margine of the Korosten pluton. Massif is composed by the layered series of gabbroids (gabbro, troctolites,
gabbrodiabases, andesine anorthosites). The central part is represented by syenites. In the Eastern cryptic part of the
massif some andesite anortozites are developed, but not in big quantity. Syenites of the Davydky massif are less
differentiated than syenites of Veilyka Vygkiy and Yastrybetsky massifs. Syenites of the Davydky massif have
increased content of titanium in pyroxene titanium hedenbergite or ferroaugite are, characterized by less zirconium
content (up to 0.1%) and lanthanoids. Besides zirconium minerals are represented by zircon as well as baddeleite.
As to other deposites of rare-metal syenites of the Ukrainian Shild, Khochyn and Karpylovka consist of biotite
and amfibolite syenites with the high content of zircon, orthite and apatite. In general they are similar to the biotite-
amfibole syenites of the Yastrybetsky massif.
So, nepheline-free rare-metal syenites, enriched in zirconium and lantanoids have quite a wide distribution
within the Ukrainian Shield. Deposites of the rich Zr, TR, Y ores are related to these syenites.

References:
Kryvdik S.G. Rare-metal of syenites in the Ukrainian Shield. Kiev: Geokhimia. 2002. №7. P. 707-717 (in
Russian).
Kryvdik S.G., Tkachuk V.I. Petrology of rare-metal of rocks in the Ukrainian Shield. Kiev: Nauk. dumka,
1990. 408p. (in Ukraine).

High-pressure melting relations of diamond-forming carbonatites: formation of syngenetic peridotitic

and eclogitic minerals (experiments at 7.0 and 8.5 GPa)
Bobrov A.V.*, Spivak A.V.**, Divaev F.K.***, Dymshits A.M.*, Litvin Yu.A.**
*Moscow State University, Moscow, Russia; **Institute of Experimental Mineralogy, Chernogolovka,
Russia; ***Institute of Mineral Resources, Tashkent, Uzbekistan

A substantial body of experimental results on diamond synthesis in carbonate media has been gained in recent
years. There are primary inclusions in diamond crystals containing fluid-carbonate material [1], which can be modeled
by the system K2O–Na2O–CaO–MgO–FeO–CO2 and was considered as a medium of diamond formation under high
pressure [2]. Diamond was successfully synthesized in multicomponent carbonate-silicate melts at 5–7 GPa and 1200–
1500°C [3]. The discovery of diamond in carbonate-silicate rocks of the Chagatai Complex [4] motivated our interest in
the experimental study of phase relations in these rocks [5]. Our experiments allowed us to simulate the initial (mantle)
silicate assemblage of the carbonate-silicate rocks of the Chagatai Complex. This assemblage was similar to that of
high-Ca eclogite and grospidite from kimberlite pipes, which provided an explanation for diamond discoveries in these
rocks. The association of carbonatite and kimberlite that was described in the Slave Craton (Canada) emphasized the
role of carbonatite as a possible new source of diamond [6]. Furthermore, diamonds were found in carbonatite matter of
Hawaiian magmas [7].
The discovery of diamondiferous carbonatites provides additional support to the theory of diamond genesis in
the Earth's mantle, according to which diamonds were formed in strongly compressed carbonatite melts [8]. The
carbonatite nature of the parental media in which spontaneous nucleation and growth of diamond occurred under PT-
conditions of its thermodynamic stability obtained convincing experimental support through the simulation of diamond
crystallization in melts chemically analogous to natural parent media both in simplified model systems and real
multicomponent compositions [8]. Under such conditions the matter of primary fluid-mineral inclusions transforms to
the state of carbonatite melts with an essential content of alkali silicate components.
The aim of this study was to study experimentally diamond nucleation and simulate the high-pressure mineral
assemblages in peridotite-carbonate and eclogite-carbonate systems with dissolved carbon. We simulated crystallization
of diamonds in melts with variable compositions of model peridotite [60 wt% olivine (Ol), 16 wt% orthopyroxene
 25

(Opx), 12 wt% clinopyroxene (Cpx), 12 wt% garnet (Grt)] and eclogite [50 wt% Grt, 50 wt% Cpx]. with carbonate of
dolomite composition (CaCO3·MgCO3), K2CO3, and multi-component K-Na-Ca-Mg-Fe-carbonatites. Carbonate-silicate
melts in all experiments performed at PT-conditions of diamond stability are completely soluble. Concentration barriers
of nucleation (CBN) [9, 10] were estimated at a pressure of 8.5 GPa for variable concentrations of silicate and carbonate
components in parental melts: 25, 30, and 30 wt.% of peridotite components and 35, 45, and 35 wt.% of eclogite
components, for CaCO3·MgCO3, K2CO3, and model carbonatite, respectively. At higher silicate concentrations in
carbonate-silicate melts, diamond grows only on seed being accompanied by thermodynamically unstable graphite
phase.
The appearance of peridotite minerals syngenetic to diamond in the studied diamond-forming melts was
established in special run series at P = 7.0 GPa and T = 1200–1800°С for the composition of peridotite30–carbonate70
(wt.%). Ol is a liquidus phase in the system with (CaCO3·MgCO3); at T < 1700°С, an association of Cpx + Ol +
carbonate-silicate melt (L) is stable; at 1600°С, Grt is added. The prevalence of Cpx over other silicates was established
for this system; none of the runs demonstrated the presence of Opx. It is assumed that in CaCO 3-rich systems Opx
enters into reaction like 2MgSiO3 + CaCO3 → CaMgSi2O6 + MgCO3 and practically is not presented as a proper phase.
In the system of peridotite–alkali carbonate (K2CO3) the following assemblages are established: Opx(Ol) + L (1800°C);
Opx + X phase [11] + L (1500°C); Opx + Ol + carbonate + L (1300°C), Opx + Ol + Si-wadeite + carbonate (1200°С).
Crystallization of melts with model multi-component (K-Na-Ca-Mg-Fe) carbonatite proceeds with the following change
of mineral parageneses as the temperature decreases: Ol + L → Ol + Cpx (Grt) + L → Ol + Cpx (Grt) + carbonate. In
principle, the appearance of Opx is possible in this system, but only if initial peridotite is enriched in this component,
and alkali carbonate (K2CO3) essentially prevails over CaCO3 among carbonate phases. In the eclogite-carbonate
system, for the composition of [Grt50Cpx50]35Carb65 (wt%), Grt and Cpx were obtained as liquidus phases depending on
the starting composition. Melt crystallization proceeds by the following scheme with a temperature decrease: L –
Cpx+L (Grt+L) – Grt+Cpx+L (Grt+Carb+L) – Grt+Cpx+Carb+L – Grt+CPx+Carb. It should be specially emphasized
that the compositions of the minerals synthesized in experiments were quite similar to the compositions of starting
phases. Some features which are typical for inclusions in diamonds, such as Na 2O admixture in garnet (up to 0.5 wt.%)
and K2O admixture in clinopyroxene (up to 1 wt.%) were established in run products. Incorporation of Na in Grt and K
in CPx provides evidence not only for high pressure, but also demonstrates and important role of alkaline components
in silicate-carbonante (carbonatite) melts during the diamond formation [12, 13].
The results obtained correspond to the carbonatite (carbonate-silicate) model of diamond genesis and point on
theoretical possibility of crystallization of peridotitic and eclogitic silicate minerals syngenetic to diamond in silicate-
carbonate melts under PT-conditions of diamond stability. The definite set of mineral inclusions in diamond is
determined by the chemistry of carbonate-silicate systems including carbonate composition.
This study is supported by the INTAS project 05-1000008-7938, RFBR grant 08-05-00110-a and the RF
President grant 4122007.5.

References:
1. Schrauder M., Navon O. Hydrous and carbonatitic mantle fluids in fibrous diamonds from Jwaneng, Botswana
// Geochim. Cosmochim. Acta. 1994. Vol. 58. No. 2. P. 761-771.
2. Litvin Yu.A., Zharikov V.A. Primary fluid-carbonatite inclusions in diamond: Experimental modeling in the
system K2O–Na2O– CaO–MgO–FeO–CO2 as a diamond formation medium // Doklady Earth Sciences. 1999. Vol.
367A. P. 801-805.
3. Litvin Yu.A., Zharikov V.A. Experimental modeling of diamond genesis: Diamond crystallization in
multicomponent carbonate-silicate melts at 5-7 GPa and 1200-1570°C // Doklady Earth Sciences. 2000. Vol. 373. P.
867-870.
4. Djuraev A.D., Divaev F.K. Melanocratic carbonatites – new type of diamond bearing rocks, Uzbekistan / In:
Mineral deposits: processes to processing (ed. S.J. Stanley). Rotterdam, Balkema. 1999. P. 639–642.
5. Bobrov A.V., Litvin Yu.A., Divaev F.K. Phase relations and diamond synthesis in the carbonate-silicate rocks
of the Chagatai complex, Western Uzbekistan: Results of experiments at P = 4-7 GPa and T = 1200-1700°C //
Geochem. Intern. 2004. Vol. 42. No. 1. P. 39-48.
6. Agashev A.M., Pokhilenko N.P., McDonald J.A. et al. A unique kimberlite-carbonatite primary association in
the Slap Lake dyke system, Slave Craton: evidence from geochemical and isotopic studies // The Slave-Kaapvaal
workshop, Merrickville, Ontario. 2001.
7. Frezzotti M.-L., Peccerillo A. Diamond-bearing COHS fluids in the mantle beneath Hawaii // Earth Planet.
Sci. Lett. 2007. Vol. 262. P. 273-283.
8. Litvin Yu.A. High-pressure mineralogy of diamond genesis. In Advances in High-Pressure Mineralogy (E.
Ohtani, ed.). Geological Society of America Special Paper 421. 2007. P. 83-103.
9. Litvin Yu.A., Litvin V.Yu., Kadik A.A. Experimental characterization of diamond crystallization in melts of
mantle silicate-carbonate-carbon systems at 7.0-8.5 GPa // Geochemistry International. 2008. Vol. 46. No. 6. P. 531-
553.
10. Litvin Yu.A., Bobrov A.V. Experimental study of diamond crystallization in carbonate-peridotite melts at 8.5
GPa // Doklady Earth Sciences. 2008. Vol. 422. No. 7. P. 1167-1171.
11. Bindi L., Bobrov A., Litvin Yu.A. Incorporation of Fe 3+ in phase-X, A2–xM2Si2O7Hx, a potential high-
pressure K-rich hydrous silicate in the mantle // Mineral. Mag. 2007. Vol. 71. No. 3. P. 265-272.
 26

12. Perchuk L.L., Safonov O.G., Yapaskurt V.O., Barton J.M.Jr. Crystal-melt equilibria involving potassium-
bearing clinopyroxene as indicators of mantle-derived ultrahigh-potassic liquids: an analytical review // Lithos. 2002. V.
60. P. 89-111.
13. Bobrov A.V., Litvin Yu.A., Bindi L., Dymshits A.M. Phase relations and formation of sodium-rich majoritic
garnet in the system Mg3Al2Si3O12–Na2MgSi5O12 at 7.0 and 8.5 GPa // Contrib. Mineral. Petrol. 2008. Vol. 156. P. 243-
257.

1-atm experiments with alkaline melts: problems, solutions and some results
Borisov A.A.
Institute of Geology of Ore Deposits, Petrography, Mineralogy and Geochemistry
Russian Academy of Sciences, Moscow, Russia; e-mail: [email protected]

A vertical tube furnace with controlled oxygen fugacities in combination with a loop technique is a standard
experimental design for one atm studies in geochemistry, cosmochemistry and petrology. However, the investigation of
alkalis-containing system, especially at low fO2 values, is very limited. The main reason is the loss of Na and K in open
systems where the oxygen fugacity is imposed by a gas mixture (CO/CO2, H2/CO2 etc). Therefore, a new experimental
device CSLT (crucible supported loop technique) was designed to prevent Na losses of experimental charges primarily
for experiments at low oxygen fugacities (Borisov et al., 2006). Later CSLT was modified to allow not only preventing
alkalis losses, but also saturating of initially alkalis-free melts with Na, K and Rb.
In brief, a single or a few sample loops place above alkali-rich melts in a quartz crucible. A lid loosely covers the
crucible, so that exchange with the surrounding gas is possible. Exchange with the furnace atmosphere is necessary for
controlling fO2 inside the crucible. The alkali-rich atmosphere inside the crucible allows maintenance of alkali
concentrations in the loop samples in the weight-percent level for hours or even days. In our practice we have used two
types of crucibles. Small crucibles (9.3 mm inner diameter, 20 mm height) were used for a single loop and larger
crucibles (15 mm inner diameter, 22 mm height) for a few loops.
CSLT has some limitations, however a few experimental studies in different areas of earth science were
conducted:
1.) We have experimentally studied the effect of Na2O on the solubility of Fe, Co, and Pd (Borisov et al., 2006).
All solubilities clearly decrease (correspondent activity coefficients increase) with increasing Na2O-contents. The
increase of FeO activity coefficients with increasing sodium found in this study may provide an explanation for
decreasing FeO with decreasing degrees of partial melting in experimentally produced mantle melts (Hirschmann et al.
1998), as melts at low melting degrees are sodium-rich.
2.) We have reported experimentally determined 1 atm olivine/melt DNa partitioning data for low fO2, a variety
of melt compositions and a temperature range of 1325-1522ºC (Borisov et al., 2008). We demonstrated that high-
current electron microprobe analyses (EPMA, I = 500 nA, 600 s on the peak) allow quantitative determination of Na 2O
in olivine down to about 10 ppm. The mean olivine/melt DNa from 12 experimental runs is 0.0031±0.0007 (1σ). This is
the recommended value for low pressures and a wide range of natural compositions.
3.) We have found relative activity coefficients of alkalis in multicomponent silicate melts (Borisov, 2008;
Borisov, submitted). Model melts (Di-An eutectic modified with variable amounts of silica and Ca2Si3O8 modified with
variable amounts of alumina) were experimentally saturated with Na, K and Rb at temperatures of 1300–1470° C.
Either binary Na2O-SiO2 and K2O-SiO2 or complex Na2O-K2O-SiO2 and Na2O-K2O-Rb2O-SiO2 melts were used as
alkalis sources. It was shown that alumina content in many cases has little influence on the degree of silicate melt
saturation with alkalis. In contrast, silica content strongly affects the solubility of alkalis in silicate melts. Model
calculations showed that the perfectly mobile behavior of alkalis leads to a potassium specifics in basalts contaminated
by crustal materials and, correspondingly, a sodic specifics in silicic melts from crustal xenoliths contaminated by the
enclosing basaltic melt.

References:
Borisov A.A. Experimental investigation of K and Na partitioning between miscible liquids. // Petrology. 2008.
Vol. 16. P. 552-564.
Borisov A.A. Dependence of alkalis activity coefficients on silica and alumina contents in silicate melts: an
experimental investigation. // Petrology. Submitted.
Borisov A., Lahaye Y. and Palme H. The effect of sodium on the solubilities of metals in silicate melts. //
American Mineralogist. 2006. Vol. 91. P. 762-771.
Borisov A., Pack A., Kropf A. and Palme H. Partitioning of Na between olivine and melt: An experimental study
with application to the formation of meteoritic Na2O-rich chondrule glass and refractory forsterite grains. // Geochimica
Cosmochimica Acta. 2008. Vol. 72. P. 5558-5573.
Hirschmann M.M., Baker M.B. and Stolper E.M. The effect of alkalis on the silica content of mantle-derived
melts. // Geochimica et Cosmochimica Acta. 1998. Vol. 62. P. 883-902.
 27

Using the composition of the carbonate phase to investigate the geochemical evolution of subvolcanic
intrusions
Brady, A.E., Moore, K.R.
Department of Earth and Ocean Sciences, National University of Ireland Galway, Galway, Ireland

Carbonatite is increasingly being associated with a broad spectrum of silicate magmas that vary widely in
composition and include such rocks types as wholly different as kimberlite and trachyte. To investigate the role of the
carbonate phase and its paragenesis in such rock associations, three diverse localities containing carbonated igneous
rocks ranging from bona fide carbonatites to carbohydrothermal residua are now examined in order to understand better
the carbonate component. They include a carbonated diatreme and subvolcanic dykes and sills from the Beara
peninsula along the south coast of Ireland, a carbonatite diatreme and related silicocarbonatite dykes from the Chagatai
region in Uzbekistan and a selection of ultramafic lamprophyres, carbonatite dykes and calcite kimberlites from
southern West Greenland.
The subvolcanic dykes, sills and diatreme on the southwest coast of the Beara Peninsula, Co. Cork contain a
significant carbonate component. The diatreme is interpreted as an alkaline ultramafic lamprophyre on the basis that its
assemblage of kaersutite megacrysts, Ti-phlogopite and Ti-magnetite supports an alkaline lamprophyric affinity, while
the absence of feldspars/feldspathoids and the presence of abundant Sr-rich groundmass calcite (2.00 wt % SrO) is
evidence of an ultramafic affinity. A small carbohydrothermal calcite carbonatite (0.80 wt % SrO) with fenite cross-cuts
the lamprophyre. Multiple populations of carbonate have been identified as minor or dominant minerals in the
assemblages of the mainly trachyte sills and lamprophyric tuffisite dykes, and include dolomite (FeOt 7.27 wt %),
ferroan dolomite (FeOt 14.58 wt %) and ankerite (FeOt 18.64 wt %). The carbonate textures (overgrowths) observed
in the trachyte indicates a secondary, metasomatic origin, consistent with the fact that the trachyte sills pre-date both the
diatreme and lamprophyric dykes. The abundance and intimate textural association of the carbonate with the mineral
assemblage in the lamprophyric dykes points towards a primary origin. This is reflected in the SrO concentration in the
carbonate minerals. The SrO content of the Fe-Mg carbonates in trachyte sills is less than 0.1 wt % in keeping with
secondary/late stage carbonate. Conversely, the SrO content of the Fe-Mg carbonates in tuffisite dykes ranges from
0.2-0.5 wt % which is appreciably high especially for Fe-rich carbonates strongly indicating a magmatic origin The Sr-
poor Fe-Mg carbonates represent metasomatism of the earlier trachyte sills by residual carbonates whereas the Sr-rich
Fe-Mg carbonates form part of the primary magmatic assemblage of the later cross-cutting lamprophyric dykes. New
stable isotope data indicates that all the carbonate phases on the Beara Peninsula have an ultimate mantle source. The
occurrence of such carbonatitic rocks with lamprophyres is not uncommon and is recognised as one of the seven main
carbonatite-silicate rock associations with 4% of carbonatites recorded globally occurring in association with (mostly
ultramafic) lamprophyres (Woolley & Kjarsgaard, 2008).
Contrasting with the lamprophyre composition of the Irish diatreme containing abundant mantle xenocrysts, the
Uzbekistan diatremes have silicocarbonatite composition and contain abundant lapilli and xenoliths of crustal rock. The
carbonate component of the diatreme host magmas has been identified as calcite and is more iron-rich than in the Irish
case (FeOt < 1.46 wt %) Interestingly, minor zoned dolomite rhombs have been found dispersed throughout the calcite
possibly indicating a more Fe-Mg rich carbonatite magma at depth. The related dykes under investigation are
composed of trachyte, with albite-chlorite- and albite-calcite-dominated assemblages comparable to the trachyte sills in
southwest Ireland. While the main carbonate component associated with the dykes is calcite, there are a number of
chemically distinct calcite compositions including Fe-rich calcite (up to 0.9 wt % FeO), Fe poor calcite (< 0.1 wt %
FeO), Sr-rich (up to 0.87 wt % SrO), and Sr poor calcite (< 0.1 wt % SrO). Unlike the Irish trachyte, the carbonate
appears to be part of the primary assemblage of these dykes. Carbonatite and trachytes occurrences are another of the
main silicate-carbonatite associations (Woolley & Kjarsgaard, 2008).
The calcite-rich kimberlites and carbonate-bearing lamprophyres (aillikites of the ultramafic lamprophyre branch
(UML)) from southern West Greenland contain mantle carbonate of deep origin. These kimberlite and ultramafic
magmas have been transported rapidly and directly from the mantle and thus the carbonate has not been subject to much
fractionation in contrast to the Irish and Uzbekistan samples. Carbonate is extremely abundant in the Greenland dykes
and constitutes virtually the entire groundmass. Two types of carbonate are identified within almost every sample
examined of kimberlite and UML: calcite (kimberlite: up to 56.27 wt % CaO, UML: up to 57.16 wt % CaO) and minor
dolomite (kimberlite up to 19.91 MgO wt %; UML up to 18.59 wt % MgO). There is no obvious difference between
these mantle calcite compositions and the calcite compositions of their subvolcanic equivalents at the Irish and
Uzbekistan localities and the compositions are not unique in any way. It is noticeable though that SrO content is in the
relatively low end of the range expected for carbonatites and is somewhat variable ranging from < 0.1 to 0.9 wt % SrO.
There are no marked distinctions observed between Sr-poor calcite and relatively Sr-rich calcite in the kimberlite and
UML dykes. It appears that Sr and other such trace elements are preferentially hosted in the co-existing silicate
minerals of the kimberlite and UML magmas, which are comparable to extrusive carbonatites that also have low
concentrations of trace elements. Current opinion is mixed on the carbonatite-kimberlite association with Mitchell
(2005) regarding calcite kimberlites as small volume late-forming differentiates unrelated to carbonatites or their
parental magmas, whereas Rock (1991) and Dalton and Presnall (1998) propose that ultramafic lamprophyres provide
the link between carbonatite and kimberlite magmatism.
 28

In summary, the carbonated locality magmatism represented by the rocks on the Beara Peninsula, Co. Cork,
Ireland can be compared to, and provides a crucial link between, the very compositionally different carbonated rocks of
south West Greenland and Chagatai, Uzbekistan. Furthermore, the idea that ultramafic lamprophyres provide the link
between kimberlite and carbonatite magmas can be explored further from the viewpoints of bona-fide primary
carbonatite from Greenland to late-stage carbohydrothermal carbonatite from Ireland.
This study was financially supported by INTAS project 05-100008-7983.

References:
Dalton, J. A. and Presnall, C. D. 1998. The Continuum of Primary Carbonatitic - Kimberlitic Melt
Compositions in Equilibrium with Lherzolite: Data from the system CaO-MgO-Al2O3-SiO2-CO2 at 6 GPa. Journal of
Petrology. 39, 1953-1964.
Mitchell, R. H. 2005. Carbonatites and carbonatites and carbonatites. Can. Min. 43, 2049-2068.
Rock, N. M. S. 1991. Lamprophyres. Blackie, London, 285 pp.
Woolley, A. R. and Kjarsgaard, B. A., 2008. Paragenetic types of carbonatite as indicated by the diversity and
relative abundances of associated silicate rocks: evidence from a global database. Can. Min. 46, 741-752.

Oxygen and argon isotope relationships in Saudi Arabian mantle xenoliths

Buikin A.I.*, Ignatiev A.V.** and Velivetskaya T.A.**
* Vernadsky Institute for Geochemistry and Analytical Chemistry RAS, Moscow, Russia ([email protected]);
** Far East Geological Institute RAS, Vladivostok, Russia

Mantle-derived xenoliths transported to the Earth’s surface by ascending magmas preserve textural, chemical
and isotopic informations about the physical and chemical evolution of their lithospheric source regions. In particular,
the chemical and isotopic signatures of xenolith phases (minerals, glass, fluid inclusions) may help to constrain the
nature and age of metasomatizing events. One of the most interesting and suitable objects in this respect is the
subcontinental mantle beneath the Saudi-Arabian rift shoulder, which was subjected to intense metasomatism affecting
mineral assemblages and also inducing cryptic metasomatic alterations that can be recognised in trace element patterns
(Brueckner et al., 1988; Henjes-Kunst et al., 1990; Kurat et al. 1993; Blusztajn et al., 1995; Baker et al., 1998, 2002),
including noble gases (Trieloff et al., 1997; Hopp et al., 2004, 2007).
Spinel-peridotite xenoliths of Cr-diopside group from Cenozoic volcanic fields of Arabian peninsula have
documented – in different degree – two stages of mantle metasomatism [Henjes-Kunst et al. 1987, 1990]. Early
metasomatism-1 led to the formation intra-granular Cr-Al-spinel, intra-granular Cr-pargasit (<2 vol. %), and inter-
granular Ba-phlogopite (sample SA84-63). The second metasomatic event (metasomatism-2) resulted in formation of
inter-granular amphibole and injection of inter-granular melt now consisting of patches of glass and phenocrysts of
olivine, clinopyroxene, amphibole and spinel (sample SA84-128/3). The study of argon isotope composition have
shown the presence mantle argon component in xenolith SA84-63 (metasomatism-1), while the xenolith SA84-128/3
(severely subjected to metasomatism-2) is characterized by close to atmospheric argon isotope composition, which
points to a strong atmospheric contamination. Argon, chlorine and potassium relationships indicate that the most
feasible contaminating agent was saline water introduced into the mantle source or intermediate magma chamber
(Buikin 2005; Buikin et al. submitted).
In order to check the assumption about subsurface saline water introducing into the source of metasomatism-2 as
well as to study the variations of δ18О values during mantle metasomatism we analyzed oxygen isotope composition in
differently metasomatized mantle xenoliths from Saudi Arabian volcanic fields. Mineral separates of olivine, clino- and
orthopyroxene and amphibole were picked up using a binocular. Oxygen was extracted by laser fluorination and isotope
composition was determined on MAT-252 MS in FEGI RAS.
 29

Fig. 1. δ18О - (40Ar/36Ar)max diagram for unequilibrated xenoliths from Saudi Arabia.

All the samples have δ18О characteristic of mantle minerals. One xenolith (SA84-38) has shown inter-mineral
oxygen isotope equilibrium yielding an enstatit-forsterit isotope geothermometer temperature of 1030 ºС. Three other
xenoliths have shown inter-mineral oxygen isotope disequilibrium. In these samples we observed a tendency to
decreasing of δ18О values in olivines from xenoliths unaffected by metasomatism-2 to the xenolith most severely
modified by this late metasomatic event. Similar tendency was observed in metasomatically overprinted xenoliths from
Caapvaal Craton (Zhang et al. 2000). Moreover, as shown in figure 1, there is a correlation between argon and oxygen
isotope composition in our unequilibrated samples: with decreasing ( 40Ar/36Ar)max ratios from less contaminated by
atmospheric argon xenolith (SA84-63) to the most contaminated sample (SA84-128/3), δ18О of olivines from these
xenoliths is also dropping down. If change of oxygen isotope composition (as well as argon) occurred during interaction
with agents of metasomatism-2, then decreasing of δ18О values should point to the lower δ18О of metasomatic fluid (or
melt) in comparison to the rock. In this case our data at least not contradict to the earlier assumption of introducing a
saline (i.e. sea or altered sea water) to the source of metasomatism-2. One should note that oxygen isotope composition
of pyroxenes from unequilibrated xenoliths almost not vary, although there is some decrease of δ18О in Cpx from
SA84-128/3.
One hornblende megacryst (SA84-42b) also suggests significant influence of a low 40Ar/36Ar component at the
late stage of magmatic evolution. Its K, Cl, Ar inventory and argon isotope composition also support the idea of the
presence of saline water as contaminating factor. We analyzed hydrogen isotope composition in this sample: δD = -
54‰. This value is higher than typical mantle one (~ -80‰), and could support our assumption about introducing of
subsurface water into the source of late metasomatism.
The study was supported by the Program of the Department of Earth Sciences RAS №8 and Grant of President
of Russian Federation for Young Scientists №МК-3013.2007.5.

Experimental melting of carbonated K-rich garnet harzburgite and origin of kimberlite melts
Bulatov V.K.*, Girnis A.V.**, Brey G.P.***
* Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences Russia
**
Institute of Geology of Ore Deposits, Petrography, Mineralogy and Geochemistry, Russian Academy of
Sciences, Russia
***Instutut für Geowissenschaften, J.-W. Goethe Universität, Frankfurt am Main, Germany

Experimental melting of carbonated K-rich garnet harzburgite was carried out at 6 and 10 GPa, 1100–1600oC in
a Walker-type multianvil apparatus. The main goal of the experiments was to determine the composition of melt near
the solidus of harzburgite with addition of potassium and magnesium carbonates as a proxy for metasomatized mantle
peridotite. The starting material was a mixture of natural olivine, orthopyroxene, and garnet with 5% MgCO 3 + K2CO3
(~1 wt % K2O). It was found that the near-solidus mineral assemblages of this material could not be reliably established
because of the small grains size and low amounts of K-bearing phases. Therefore, in order to clarify possible phase
relations near the solidus of K-bearing carbonated peridotite, an experimental series was performed with the SC1
lherzolite (Brey et al., 2008) blended with 10% MgCO 3 and 10% K2CO3.
 30

In the both systems, the beginning of melting was detected at ~1100°C at 6 GPa and ~1200°C at 10 GPa. Only
olivine, orthopyroxene, garnet and magnesite were found in the products of harzburgite-MgCO3-K2CO3 experiments.
The amount of K2O in the starting mixture (1.4 wt %) was too high to be accommodated in the silicates and carbonates.
Therefore, a K-bearing phase (or phases) must be present near the solidus of this mixture. Experiments with the K richer
starting material based on the SC1 peridotite showed that two K-bearing phases are stable near the solidus of the
lherzolite (SC1)–MgCO3–K2CO3 system. Phase X was found in the subsolidus experiments at 8 and 10 GPa, and K-Mg
carbonate, K2Mg(CO3)2, crystallized at 6–10 GPa. In the 10 GPa experiments it coexisted with magnesite over a wide
temperature range. The stability field of magnesite expands considerably with increasing pressure in the SC1–MgCO3–
K2CO3 system. In the harzburgite system, magnesite is stable up to about 1500°C both at 6 and 10 GPa. The melt from
the two experimental series are sharply different in K content. Those from the SC1–MgCO3–K2CO3 system are
dominated by K2CO3 and MgCO3 components with only minor CaO content. In contrast, the low-temperature melts
from the SC1–MgCO3–K2CO3 system are dominantly Ca–Mg-carbonate. The main temperature effect is an increase in
SiO2 content and a decrease in the Ca/Mg ratio. Similar to experiments in the lherzolite–CO2 system (Brey et al., 2008),
the melt composition changes from carbonatitic (<5 wt % SiO 2) near the solidus to carbonated silicate with up to 30 wt
% SiO2 at 6 GPa 1600°C and 10 GPa 1700°C. The contents of alkalis and Ca decrease with increasing temperature. The
potassium-rich melts from the harzburgite–MgCO3–K2CO3 experiments are significantly poorer in MgO compared with
those from the SC1–MgCO3–K2CO3 system. The content of Al2O3 depends primarily on pressure and is lower than 0.5
wt % in the 10 GPa experiments and up to almost 2 wt % in the 6 GPa experiments. FeO content is controlled by
temperature and increases from about 5 wt % at 1200°C to 20–25 wt % at 1700°C and 10 GPa. However, the very high
FeO content in the high-temperature experiments is in part due to the high oxygen fugacity in the experiments and
considerable amount of Fe3+ in the melt.
A comparison of the experimental carbonated silicate melt with the supposed primary kimberlite magmas
(Becker, Le Roex, 2006) has led us to the conclusion that the latter cannot be produced by single-stage melting of the
asthenospheric mantle. In order to explain the origin of “protokimberlite” carbonated silicate melts, we proposed a two-
stage scenario, including the formation of a liquid enriched in volatile and incompatible components in the
asthenospheric (lherzolitic) mantle and its interaction with depleted harzburgites (possibly, preliminarily
metasomatized) in the lower part of the continental lithosphere.

References
Becker, M., Le Roex, A.P. (2006). Geochemistry of South African on- and off-craton, group I and group II
kimberlites: Petrogenesis and source region evolution. Journal of Petrology 47, 673–703.
Brey, G.P., Bulatov, V.K., Girnis, A.V., Lahaye, Y. (2008). Experimental melting of carbonated peridotite at 6–
10 GPa. Journal of Petrology 49, 797–821.

The typochemical features of pyroxenes from Paleozoic picrite dikes within Spitsbergen Archipelago
Burnaeva M.Yu.*, Antonov A.V.**, Sirotkin A.N. ***
*FGUP VNIIOkeangeologiya, St.Petersburg, Russia;** FGUP VSEGEI, St.Petersburg,
Russia;***FGUNPP PMGRE, Lomonosov, Russia.

Picrite dikes are located within the West Spitsbergen Island, in the east and the south of an Andre Land in the
area of a Krjusspjunten Cape, a Peterman Cape (western coast of Vejde-Fiord), a Purpurdallen Valley, and also around
a glacier Rubinbreen - Haakon VII Land in the Devonian graben filled with redrocks. Geologists of FGUNPP PMGRE
discern two types of the dikes: those saturated with xenoliths (type 1) and with mica (type 2). The dikes have been
described earlier (Evdokimov, etc., 2006).
A pyroxene is one of the main rock-forming minerals for dikes of the both types. Discerned are three generations
of the mineral: phenocrysts, groundmass microlites and xenocrysts. The pyroxene makes 20 to 60 % in the total,
consisting mainly of microlites; phenocrysts and xenocrysts being under 1 %. Considered below is the composition of
precisely the pyroxenes from dikes without regard for those from xenoliths..
Phenocrysts represent short-prism grains 0.4 to 1.2 mm large, occasionally up to 3 mm long, often colored in
tints of brown, being rarely slightly greenish or achromatic. The grains are zonal with the largest showing up to 3 zones.
The groundmass pyroxene is present as long-prism grains colored brown, 0.05 to 1.0 mm long. The grains vary
in dike section from small (0.05 to 0.2 mm) at the rim up to elongated (0.2 to 1.0 mm) in the center. Twinned grains and
rosettes of needle-shaped units are discerned among microlites.
Microprobe analysis of the grains has been performed to reveal the features of composition of the pyroxenes
(analysts: A.V.Antonov (FGUP “VSEGEI”), Ju.L.Kretser (LLC “PC +”)). The results are shown in Table 1.
 31

Table 1. Average contents of major elements and calculated Fe3+, Fe2+ and Kok in pyroxenes of ultramafic
Paleozoic dikes within Spitsbergen Archipelago by generations
Cr2O
Type 1 SiO2 Al2O3 TiO2 FeOt MgO CaO Na2O 3 Fe2+ Fe3+ Кок
Microlites (n=11) 48,49 5,08 2,30 6,34 13,54 23,70 0,05 0,16 0,15 0,05 0,26
Phenocrysts (n=18) 50,59 5,16 1,23 6,33 14,61 20,99 0,69 0,11 0,15 0,07 0,32
Type 2
Microlites (n=9) 45,92 6,55 3,19 7,44 13,06 23,41 0,57 0,08 0,07 0,15 0,66
Phenocrysts (n=16) 49,74 5,57 1,40 7,43 14,11 20,54 1,15 0,03 0,11 0,12 0,52
n – quantity of analyses; Kok = Fe3+/(Fe3++Fe2+); FeOt – total ferrum defined as FeO; Fe2+ and Fe3+-
calculated with stoichiometry.
Started with phenocryst crystallization the process of mineragenesis had been completed by forming groundmass
microlites. Along the same direction, the composition of pyroxenes shows decrease in SiO 2, MgO, Na2O and increase in
TiO2, CaO, Cr2O3 in dikes of the both types; contents of Al2O3 being slightly lower in dikes of type 1 and much higher
in dikes of type 2. FeOt shows nearly no variations in quantity, but samples from dikes of type 1 contain for the most
part ferrous oxide. A share of ferric oxide increases in pyroxenes from picrites of type 2 (table 1). It should be noted
from the latter that oxidation of the environment for pyroxene generation in dikes of type 1 was of lower potential.
As a whole, the elements in pyroxenes of dikes of the both types demonstrate a similar nature. The difference is
observed but in the content of Al2O3 that may be a result of its high content in the melt and undersaturation of the melt
in SiO2 at final stages of its crystallization.
All the pyroxenes studied concern Ca-Mg-Fe-clinopyroxenes. Three mineral varieties (diopside, augite, fassaite)
are discerned by crystallochemical formulae (Mineraly, 1981). Among minals, dominating are diopside (20-77 %),
tschermakite (3-25 %), hedenbergite (0-43 %), enstatite (0-27 %). The highest average contents of the first two and the
latter two components have been revealed in microlites and in megacrysts of dikes of the both types, respectively.
Large phenocrysts of pyroxenes are characterized by zoning resulted from rapid change in crystallization
conditions when the mineral composition has not managed to come to equillibrium with the surrounding melt. To study
the zoning, 6 grains from 3 samples (table 2) were analyzed. Three zones are pronounced as a whole. Distribution of the
elements within the zones shows a similar pattern in all the samples. The content of SiO 2 and MgO is established to
increase toward the second zone then decreasing toward the rim. Al 2O3 and FeOt in most part of the grains decrease
toward the second zone then increasing toward the rim (exception is one grain from dike of type 1 showing subsequent
core-to-rim increase in aluminia). TiO2 and CaO increase from core to rim. The composition of the rim zone and in part
of the second zone of grains is similar to that of microlites that indicates their syngenetic pattern.

Table 2. Average composition of pyroxenes for the zones of dikes of the both types
Type of
SiO2 Al2O3 TiO2 FeOt MnO MgO CaO Na2O K2O Cr2O3
dike, zone
Type 1 (n=5)
core 50,74 6,14 0,87 6,39 0,00 14,28 20,15 1,23 0,00 0,00
Zone 2 51,23 3,26 0,77 5,64 0,00 15,32 22,80 0,12 0,00 0,18
rim 47,02 6,19 2,32 6,58 0,00 13,26 23,89 0,10 0,00 0,00
type 2 (n=1)
core 51,24 6,14 0,88 7,30 0,15 15,73 16,80 1,80 0,00 0,00
2 zone 52,82 2,76 0,68 5,45 0,00 17,47 20,62 0,00 0,00 0,00
rim 45,81 7,05 3,27 6,94 0,00 13,15 23,70 0,00 0,00 0,00
 32

Fig.1 The correlation between pyroxenes from

dikes of Spitsbergen and pyroxenes from
kimberlite groundmass for different areas within
coordinates MgO/FeOt-CaO.
Pyroxene fields from: 1 – picrite dikes of
Spitsbergen; 2 – kimberlites from the World
different occurrencies.

The factor analysis has been performed to compare the composition of pyroxenes from dikes of Spitsbergen with
that of pyroxenes of various formations (about 1100 ordinary analyses performed) (Dobretsov et al., 1971; Yefimov,
1983; Mal’kov, 1972, Nikishov, 1984). Pyroxenes from phenocrysts and groundmass of picrite dikes are as a whole
similar in content of basic elements to pyroxenes from basaltoids of various formation types. But the best similarity is
observed with compositions relevant to oceanic and continental alkaline-olivin-basaltic and alkaline-basaltoid
formations. The similarity is also observed with pyroxenes from kimberlete groundmass, however their most part much
differs in CaO, FeOt and MgO/FeOt. The exception is pyroxenes from kimberlite dikes of the Ontario region (Canada).
Considering the limit set up for the abstract volume, only a comparative diagram is presented for CaO-MgO/FeOt for
pyroxenes from dikes of Spitsbergen and for those from the kimberlite groundmass (fig. 1).

References:
Dobretsov N.L., Kochkin Yu.N., Krivenko A.P., Kutolin V.A. The rock-forming pyroxenes. Moscow: Nauka,
1971. 454 p. (in Russian).
Evdokimov A.N. et al. The first occurrence of accessory minerals of kimberlites in Paleozoic dikes of
Spitsbergen //Doklady RAN. V. 407, № 2, 2006. P. 275-279.
Mal’kov B.A. The petrology of dike series of alkaline gabbroids of North Timan. Leningrad: Nauka, 1972. 128
p. (in Russian).
Minerals: the Directory. Moscow: Nauka, 1981, V. 3, ed. 2. 613 p. (in Russian).
Nikishov K.N. The petrologic-mineralogical model of kimberlite process. Moscow: Nauka, 1984. 214 p.
Yefimov A.F.The typochemistry of rock-forming dark-color minerals of alkaline rocks. Moscow: Nauka, 1983.
256 p. (in Russian).

Studying of phase relations in the system forsterite-diopside-jadeite (experiment at 7.0 GPa)

Butvina V.G., Litvin Yu.A.
Institute of Experimental Mineralogy RAS, Chernogolovka, Moscow district, [email protected],
(496)5225876

Peridotites and eclogites, including diamond-bearing ones, are the basic ultra-basic and basic rocks of the upper
mantle (Ringwood, 1969, 1975; Sobolev, 1974; Marakushev, 1985; Taylor & Anand, 2004). These rocks are presented
in the assemblage of mantle xenolyths in kimberlites, but the basic minerals of peridotite paragenesis, olivine,
orthopyroxene, garnet and clinopyroxene as well as of an eclogite paragenesis, garnet and omphacite are wide-spread
synthetic inclusions in diamonds. The cases of finding minerals and peridotite and eclogite parageneses in diamond are
described. It implies that these parageneses can have a single mantle source. However, the formation of peridotite and
eclogite mineral parageneses at differentiation of the primary ultrabasite melt during physico-chemical single process is
possible only at overcoming the “eclogite” thermal barrier (O’Hara, 1968; Litvin, 1991).
Eclogite genesis is one of the most difficult and discussional problems of modern petrology. Among
investigators there is an opinion about eclogite heterogeneity not only on conditions of formation (crust, mantle), but
also by composition of the initial rocks (para-, orthoeclogites) as well as by the way of their formation (magmatic,
metamorphic, metasomatic). In literature diamond-bearing eclogite nodules of kimberlite pipes are often considered as
metamorphic, which are formed at subduction of the Archean or of the Proterozoic oceanic crust (MacGregor &
Manton, 1986; McCandless & Gurney, 1986, 1997 et al.). Only the presence of Na2O in garnet and K2O in
clinopyroxene is a criterion of their participation in mantle magmatic processes.
Together with the hypotheses considered on eclogite origin there exists a version suggested in papers (Kushiro,
1972; Kushiro & Yoder, 1974), according to which mantle eclogites could be formed due to peridotite substance in the
processes of fractional crystallization of ultrabasite magmas. The present paper is devoted to the experimental study of
this problem.
Physico-chemical transition from peridotite assemblage to the eclogite one can be only ensured by the processes
of fractional crystallization of mantle magmatic melts. The primary melting and magmatic evolution of mantle garnet
 33

lerzolite (or the Ringwood pyrolite) is controlled by a five-phase peritectics “p” Ol+Opx+Cpx+Grt+L and four cotectic
curves conjugated to it (Litvin, 1991). In melting and evolution of melts of both olivine eclogites and coesite and
corundum eclogites the corresponding five-phase eutectics are of a dominant importance. A general ridge for all
elementary tetrahedrons (simplexes) is a line of compositions diopside-pyrope (clinopyroxene-garnet) which bimineral
eclogite assemblages belong to. The internal section En-Di-Cor of the general tetrahendric diagram (symplex complex)
separates olivine-saturated and silica-saturated compositions. “Eclogite” thermal barrier is “thermal barrier” on
(O’Hara, 1968), on the cotectic line Opx+Cpx+Grt+L, connecting “peridotite” peritectic and “eclogite” eutectic points.
Meanwhile, at equilibrium (and fractional) crystallization of peridotite system in the peritectic point “p”
orthopyroxene vanishes as a result of the peritectic reaction “orthopyroxene + melt  clinopyroxene” (Davis, 1963;
Litvin, 1991). With further temperature decrease the composition of the remnant melt is controlled by the
nonorthopyroxene cotectics Ol+Cpx+Grt+L first, in the limits of the peridotite “simplex”, but then mechanism of
fractional crystallization is also realized in the limits of the olivine-eclogite “simplex” up to the corresponding
nonvariant eutectics.
The considered cotectics Ol+Cpx+Grt+L is of the greatest interest from the viewpoint of a possible change of
compositions of remnant melts from olivine-normative to silica-normative ones. One can assume that under the
conditions of fractional melt crystallization along the cotectic curve Ol+Cpx+Grt+L together with olivine jigging
accumulation of incorehent elements, including Na, Fe etc. takes place. It leads to a gradual increase of jadeite
component content in remnant melts what creates grounds for reactional interaction of jadeite and olivine components
with olivine vanishing and garnet formation in accordance with the reaction found in (Litvin et al., 2004). A gradual
decrease of olivine component content in remnant melts caused by that fact realizes a “turn” to the cotectic curve
Ol+Cpx+Grt+L in the direction of the boundary section En – Di – Cor and, probably its exit to the line Di–Prp
(clinopyroxene-garnet). Further under the conditions of fractional crystallization melt composition point can penetrate
into the volumes of coesite-eclogite, kyanite-eclogite and corundum-eclogite “symplexes”. Thus, an overcoming of
“eclogite” thermal barrier between olivine-normative peridotite-pyroxene and SiO2 – normative eclogite compositions
occurs. So, one can speak about the “destruction” of liquidus peridotite-eclogite thermal barrier in the limits of the
peridotite “simplex” as a result of realization of two reaction mechanisms: (1) vanishing of orthopyroxene as a result of
its peritectic reaction with the melt with clinopyroxene formation and (2) olivine vanishing as a result of its reactional
interaction of jadeite with garnet formation. If with respect to the first mechanism definite experimental evidence exists
(Litvin, 1991; Davis, 1963) then for the second mechanism it is absent.
Due to this fact the main purpose of this paper is an experimental study of phase relationships in the model
system forsterite-dioside-jadeite at pressure of 7 GPa and foundation of possible physico-chemical correct transitions
between peridotite and eclogite parageneses with overcoming liquidus “eclogite” thermal barrier. To construct a
diagram of a ternary system forsterite-diopside-jadeite it is necessary to study its boundary binary sections forsterite-
jadeite and fosterite-diopside as well as a number of internal polythermic sections. The section jadeite-diopside at 7 GPa
has been studied earlier (Bobrov, Litvin, Kojitani, Akaogi, 2006; 2008) and it is characterized by the unlimited
miscibility of jadeite and diopside components in solid and liquid states.
The first experimental results obtained at the initial stage of the investigation of this problem can be
characterized as follows.
Forsterite-jadeite section.
The experiments in this section have been done in the temperature range of 1100-18000C on which basis the
construction of fusibility diagram of the system forsterite-jadeite at 7 GPa has been started. The obtained experimental
data testify to the existence in the system of the liquidus fields Fo + L, Grt SS + L and CpxSS (on the basis of jadeite
phase) +L, as well as show indirectly a possible appearance of orthopyroxene as a liquidus phase. In subsolidus
experiments olivine-bearing assemblages on the basis of the paragenesis Ol+Grt+Opx+Cpx are found. Garnet there is
not a pure pyrope, but has the molecule Na2MgSi5O12 (Na-majorite) what manifests itself in the direct correlation of Na
and Si in the equations of this phase. OpxSS is not a pure enstatite, but forms a complicated solid solution En+Jd+Mg-
Ts. With jadeite content increase in the system olivine-bearing assemblages transfer into non-olivine ones, up to the
assemblage Cpx + Grt (jadeite-clinopyroxene has also enstatite component) being indirect evidence of a peritectic
character of solidus in this system) what has also been shown earlier in (Litvin et al., 2004). Due to this fact forsterite
vanishes in subsolidus in the region of compositions rather enriched by jadeite component. The performed experimental
investigations testify to complex topological relations of phases in this system at close solidus temperatures what needs
further studies. The experimental investigations done earlier and referring to this system (Litvin et al., 2004; Gasparik &
Litvin, 1997) testify to the appearance of a new phase of the composition Na 2Mg2Si2O7, which role in the formation of
subliquidus and subsolidus assemblages must be more studied.
Nevertheless, the obtained preliminary experimental data contain constructive data that make it possible to
consider the basic problem of this work and start experimental investigations of liquidus phase relations of the system
forsterite-diopside-jadeite.
The system forsterite-diopside.
The experiments in this section are given at pressure of 7 GPa in the range of temperatures 1600-17000C. The
system is pseudobinary due to the appearance of orthopyroxene component that forms an independent phase. According
to the preliminary data liquidus assemblages of this system at 7 GPa are Fo + L и DiSS + L, but the type of melting is
eutectic. It agrees with the above investigations at pressure of 3 GP (Davis, 1963) where some pseudobinarity of the
 34

system forsterite-diopside caused by the appearance of orthopyroxene minal in clinopyroxene solid solution can be also
seen.
The system forsterite-jadeite-diopside.
The experimental data and conclusions obtained for the boundary systems make it possible to start investigating
liquidus surface for fusibility diagram of the ternary system forsterite-jadeite-diopside at P 7 GPa. For the experimental
study polythermic sections of forsterite-(jadeite50diopside50) and forsterite-(jadeite25diopside75) have been chosen. The
obtained data testify to the fact that olivine vanishing and garnet formation are realized in both sections. The problem
of further investigations is to search minimum concentrations of jadeite in the composition of this system where a total
olivine vanishing takes place.
Thus, the performed experimental investigations of the model system forsterite-diospside-jadeite at pressure 7
GPa testify to the fact that forsterite (olivine) is a stable phase in the boundary system forsterite-diopside (olivine-
clinopyroxene). While introducing rather low contents of jadeite component into the composition of this system the
reaction of jadeite component with forsterite takes place in the melt. As a result, garnet appears as liquidus phase.
With the increase of the jadeite component concentration in the system the field of liquidus garnet expands, but a
physico-chemical control of crystallization differentiation of the remnant melts transforms from the monovariant
cotectics Fo + DiSS + L through the invariant peritectic point Fo + DiSS + Grt + L to the monovariant cotectics Grt +
Cpx + L, which is responsible for crystallization of bimineral garnet-omphazite eclogite parageneses. The obtained
experimental results testify unambiguously to the fact that in the system Fo-Di-Jd a physico-chemical mechanism of
overcoming liquidus peridotite-eclogite barrier at mantle magma differentiation is realized. Thus, a gradual transition
from olivine-bearing assemblages to those close by their characteristics to bimineral eclogites is provided.
Support RFBR: grants 07-05-00499, 08-05-00110, grant to the leading scientific school 5367.2008.5 (A.A.
Marakushev), President grant MK-194.2008.5.

References.
Bobrov A.V., Akaogi M., Kojitani H., Litvin Yu.A. Phase relations on the diopside-jadeite-hedenbergite join up
to 24 GPa and stability of Na-bearing majoritic garnet // Geochim. Cosmochim. Acta. 2008. V. 72. P. 2392-2408.
Bobrov A.V., Litvin Yu.A., Kojitani H., Akaogi M. CaMgSi2O6–CaFeSi2O6–NaAlSi2O6 join at 7—24 GPa and
1600—22500С: Modeling of mineral assemblages of the upper mantle and transition zone // Electronic Scientific
Information Journal “Herald of the Department of Earth Sciences RAS” № 1(24)′2006. URL:
http://www.scgis.ru/russian/cp1251/h_dgggms/1-2006/informbul-1_2006/term-2e.pdf.
Davis B.T.C. The system enstatite-diopside at 30 kilobars pressure // Carnegie Inst. Wash. Yb. 1963. V. 62. P.
103-107.
Gasparik T., Litvin Yu.A. Stability of Na2Mg2Si2O7 and melting relations on the forsterite-jadeite join at
pressures up to 22 GPa // Eur. J. Mineral. 1997. V. 9, pp. 311-326.
Kushiro I. Determination of liquidus relations in synthetic silicate systems with electron probe analysis: the
system forsterite-diopside-silica at 1 atmosphere // American Mineralogist. 1972. V. 57, pp. 1260-1271.
Kushiro I., Yoder M.S. Formation of eclogite from garnet lherherzolite: liquidus relations in a portion of then
system MgSiO3 – CaSiO3 – Al2O3 at high pressures // Carnegie Inst. Wash. Yb. 1974. V. 73. P. 266-269.
Litvin V.Yu., Gasparik T., Litvin Yu.A. The enstatite-nepheline system in experiment at 6.5 – 13.5 GPa:The role
of Na2Mg2Si2O7 for Ne-normative mantle solidus // Geochem. Internat. 2004. V. 38. # 1. P. 100-107.
Litvin Yu.A. Physico-chemical study of melting of deep-seated Earth's substance. Moscow: Nauka. 1991. 312 p.
(in Russian)
MacGregor I.D., Manton W.I. Roberts Victor eclogites: ancient oceanic crust // J. Geophys. Res. 1986. V. 91.
P.14063–14079.
Marakushev А.А. Mineral associations of diamond and the problem of formation of diamondiferous magmas //
Ocherki phys.-hem. petrology. Moscow. 1985. Iss. 13. P. 5-53. (in Russian)
McCandless T.E., Gurney J.J. Sodium in garnet and potassium in clinopyroxene: criteria for classifying mantle
eclogites // Geol. Soc. Austr. Spec. Publ. 1986. V. 14. P. 827–832.
McCandless, T.E., Gurney, J.J. Diamond eclogites: comparison with carbonaceous chondrites, carbonaceous
shales and microbial the lower mantle // Science. 1997. V. 278. P. 434–436.
O’Hara M.J. The bearing of phase equilibria studies on synthetic and natural systems on the origin and evolution
of basic and ultrabasic rocks // Earth Sci. Rev. 1968. # 4. P. 69-133.
Ringwood A.E. Composition and evolution of the upper mantle. In: “The Earth’s Crust and Upper Mantle”, Am.
Geophys. Union. Geophys. Monograph 13, 1969. P. 1-17.
Ringwood A.E. Composition and Petrology of the Earth’s Mantle. NY: McGraw-Hill, 1975.
Sobolev N.V. Deep-seated inclusions in kimberlites and the problem of upper mantle composition. Novosibirsk:
Science, 1974. 264p. (in Russian)
Taylor A., Anand M. Diamonds: time capsules from the Siberian Mantle // Chemie der Erde. 2004. V. 64. P. 1–
74.
 35

Experimental study on melting phase relations and diamond formation in the carbonate-rich
kimberlite from Majuagaa, Southern West Greenland
Butvina V.G.*, Nielsen T.F.D.**, Safonov O.G*., Litvin Yu.A.*
*Institute of Experimental Mineralogy, Chernogolovka, Russia; **Geological Survey of Denmark and
Greenland, Copenhahen, Denmark

Carbonate-rich hypabyssal kimberlites of the Majuagaa dyke, Maniitsoq, southern West Greenland could be
roughly characterized as a mixture of olivine and ilmenite (or Ti-magnetite) xenocrysts with the carbonate-rich (calcite
and dolomite) matrix [1]. The kimberlites are characterized by high CO2/H2O ratio, while low silicate content in the
groundmass is resulted from an active growth of melt-equilibrated olivine rims on olivine xenocrysts rather than
primary serpentine [1]. Subtraction of olivine and ilmenite results in a composition, which is close to carbonatite rather
than carbonate-silicate melt. Comparing this composition with the experimental data on melting of carbonated peridotite
[e.g. 2], it is suggested that the Majuagaa kimberlitic melt, probably, has resulted from low-degree partial melting
(about 0.6 %) of the pristine carbonated garnet lherzolite [1].
In order to further estimate a possible mantle source for the Majuagaa kimberlites, melting relations of the
texturally homogeneous sample are experimentally studied at pressure 8.5 GPa and temperatures 1200 – 1750oC using
the anvil-with-hole HP apparatus and a thermogradient cell. The studied interval of temperatures includes conditions of
subsolidus, subliquidus, and complete melting conditions for the kimberlite. Liquids forming both during partial and
complete melting of the sample are homogeneous carbonate-silicate melts (LCS). The quenched carbonate-silicate melt
only (i.e. complete melting) is observed at temperatures above 1730 OC. Compositional characteristics of this melt and
its MgO/CaO (~1.4) are very similar to the model Majuagaa kimberlite melt calculated from the rock bulk composition
after subtraction of olivine composition [1]. It means that this melt would coexist with olivine. However, olivine
Fo90Fa10 was firstly identified only at 1730oC. Garnet and Mg-bearing ilmenite (?) appear at about 1710oC forming
olivine + garnet + ilmenite + LCS cotectic assemblage. The melt at this temperature is more carbonatitic and shows
lower MgO/CaO ratio (~0.8). Such evolution of the melt is consistent with that identified for kimberlite-related systems
at high pressures [2-5]. Perovskite, apatite, and Ti-magnetite (?) subsequently join this assemblage at 1700-1680oC.
Appearance of carbonate phase, presumably, dolomite, at 1680OC manifests the solidus of the system. At lowest
temperature (down to 1200OC), the subsolidus includes the assemblage olivine + garnet + ilmenite (Ti-magnetite) +
Mg-aragonite(?) + Ca-Fe-magnesite + perovskite + apatite. No pyroxenes were observed in the solidus run products.
Their absence is, probably, related to low activity of CO 2 in the experiments, stabilizing olivine with calcic carbonate
(for example, 2olivine + 4CaCO3 + 2CO2 = 3dolomite + diopside).
Thus, the present experiments indicate that the Majuagaa carbonate-rich kimberlite has originated from the
carbonated garnet peridotite enriched in titanium. Experiments indicate very narrow temperature interval for formation
of the kimberlite melt, i.e. 50-70oC (~1760 - 1680oC). It is consistent with experiments by Dalton & Presnall [2] in the
model CMAS-CO2 system, but strongly disagrees with the results of experiments on natural peridotite-carbonate
systems [e.g. 3-5]. This narrow solidus-to-liquidus interval implies that the Majuagaa kimberlite, probably, is a near-
eutectic (olivine + garnet + ilmenite + dolomite + LCS) melt separated from the above carbonated garnet peridotite at
very low degree of partial melting. Addition of carbonate to the peridotite is, possibly, related to metasomatic processes
via CO2-rich fluids or complex carbonatite melts. The presence of the second agents is supported by recent observations
of chloride-bearing carbonatite inclusions in olivines from the Majuagaa kimberlites geochemically similar to the host
kimberlites [6].
High efficiency of the Majuagaa carbonate-silicate melts for diamond spontaneous nucleation and growth in the
case of oversaturation of this melt with dissolved carbon with respect to diamond is demonstrated with additional
experiments at 6.5 – 8.5 GPa and 1650 – 1780oC with the homogeneous mixture (3:2) of the kimberlite and spectral
graphite. Formation of diamond crystals of octahedral habit were observed within the 5 – 12 min period.
The study is supported by the INTAS project 05-1000008-793,8 RFBR grants 08-05-00110-a and 07-05-
00499-a, the RF President grants MK-194.2008.5 and MD-130.2008.5.

References:
[1] Nielsen T.F.D., Jensen S.M. The Majuagaa calcite-kimberlite dyke, Maniitsoq, Southern West Greenland //
Geological Survey of Denmark and Greenland, Report 2005/43. 2005.
[2] Dalton J.A., Presnall D.C. The continuum of primary carbonatitic-kimberlitic melt compositions in
equilibrium with lherzolite: data from the system CaO – MgO – Al2O3 – SiO2 – CO2 at 6 GPa // Journal of Petrology.
1998. V. 39. P. 1953-1964.
[3] Ryabchikov I. D., Brey G. P., Bulatov V. K. Carbonate melts coexisting with mantle peridotites at 50 kbar //
Petrology. 1993. V. 1. P. 189–194.
[4] Girnis A.V., Bulatov V.K., Brey, G.P. Transition from kimberlite to carbonatite melt under mantle
parameters: an experimental study // Petrology. 2005. V. 13. P. 1-15.
[5] Brey G.P., Bulatov V.K., Girnis A.V., Lahaye Y. Experimental melting of carbonated peridotite at 6 - 10
GPa. Journal of Petrology. 2008. V. 49. P. 797-821.
 36

[6] Kamenetsky V.S., Kamenetsky M.B., Weiss Y., Navon O., Nielsen T.F.D., Mernagh T.P. Alkali carbonates
and chlorine in kimberlites from Canada and Greenland: evidence from melt inclusions and serpentine. 9th International
Kimberlite Conference. 2008. Extended Abstracts. A-00028.

Melilitites in the alkaline volcanics series on the Gorringe Bank (SW Portugal)
Chernysheva E.A., Kharin G.S.
P.P. Shirshov Institute of Oceanology, RAS, Atlantic Branch, Kaliningrad, Russia.

Underwater rise Gorringe Bank (GB) is situated 220 km to south-west from the cape Saint Vincent at the south
of Portugal. It consists of two seamounts Gettysburg and Ormonde with a basement composed by uplifted and faulted
fragment of mantle and oceanic crust of Late Jurrassic age which is overlapped by the series of alkaline volcanics of
Paleocene age. Tectonic position of the GB is rather complicate. It is supposed that at the time of the Atlantic ocean
opening around 120-112 Ma, the Iberia plate was attached to the Africa plate. The plate boundery was located in the
Bay of Biscay and only after the Pyrenees formation it had jumped to the Azore-Gibraltar fracture zone, which had been
separating Africa and Eurasia plates up to now. It was in the late Eocene (near 37 Ma) that Iberia became the part of
Eurasia again. So, the history of Iberia and GB likely might be connected with the tectonic events in the north Africa
80-60 Ma ago. The main question is whether the alkaline magmatism of GB was of oceanic or continental origin.
The most detailed investigations of the alkaline rocks on the GB were carried out by G. Cornen (1982) and by
V.V. Matveenkov and A.I. Al’mukhamedov (1996). The main series of rocks have been divided (lamprophyres,
nephelinites, phonolites, trachytes). The whole rock analyses and some trace element contents were obtained. Using
these data, we have chosen some samples for more detailed research from the stone collections dragged in 12 cruis of
the scientific ship “Vityas’ ” and 16 cruis of “Academic Mstislav Keldysh”.
Three samples of the dark coloured “lamprophyres” have been taken. They are represented by pebbles (2-5 cm)
and poorly rounded boulders (10-20 cm), with biogenic limestone cover. All rocks have undergone strong alteration.
Petrographic observation have shown that these lavas have porphyric texture and flow structure with some vesicles and
small xenoliths of different rocks and minerals. Phenocrysts are represented by olivine (~ 10 %), fully replaced by
carbonate, altered melilite (~ 30 %), and fresh clinopyroxene (~ 50 %). The groundmass is composed of clinopyroxene
with few laths of melilite, difficult recognized interstitional analcime or nepheline, and great amount of tiny crystals of
magnetite. Melilite forms typical lath-shaped phenocrysts, 1-2 mm length. It is replaced by unrecognized white
finescaly substance, or by carbonate with brownish earthy material. Phenocrysts of clinopyroxene (augite), 1,5-2 mm
size, sometimes contain relics of the other pyroxene, more green in colour and anhedral. This phenomenon have been
described by Matveenkov and co-authors (1991) in the xenolith of pyroxenite from GB volcanics, and have been
marked also in melilitites of Nizhnesayansky carbonatite complex, which we researched some years ago (Chernysheva,
Belozerova, 2000). The “inner” pyroxenes possibly have been taken from the mantle rocks.
Thus, we classify this type of BG alkaline lavas as melilitites. Our conclusion is supported by chemical features
of these rocks. On the classification diagram by Le Bas (1989): (SiO2+Al2O3) – (CaO+Na2O+K2O), - our samples
take place in the field of melilitites. The rocks have high contents of MgO, CaO and TiO2, and low SiO2, and a
remarkable trace elements composition: at the rather high Cr and Ni they have very high Sr, Ba, Rb, Zr and some other
uncompatible elements – Nb, Ta, Th and LREE, - what represents “the family feature” of melilitites. On comparison
with the melilitites of the other localities (Wilson et al., 1995), easy to see the most similarity of GB rocks with the
Canary Island melilitites: (wt %) SiO2 - 38,94; 37,40; TiO2 - 2,94; 3,78; Al2O3 – 11,1; 9,35; Fe2O3 – 11,49; 12,40;
MnO – 0,22; 0,20; MgO – 9,65; 14,02; CaO – 14,41; 14,27; Na2O – 3,53; 2,97; K2O – 1,93; 1,41; P2O5 – 0,80; 1,38;
LOI - 5,62; 1,94; (ppm) V – 262; 296; Cr – 394; 373; Ni – 191; 337; Rb – 57,2; 32,7; Sr – 835; 1355; Ba – 866; 759; Y
– 27; 37; Zr – 510; 317; Nb – 197; 90; U – 3,65; 2,52; Th – 11,52; 10,13; Pb – 9,38; 4,58; La – 102; 101; Ce – 188; 216;
Nd – 77; 100; Sm – 12,1; 17,5; Eu – 3,37; 5,26; Yb – 1,95; 1,88; Lu – 0,27; 0,25.
It is known that the mafic alkaline volcanic rocks (melilitites, nephelinites, etc.), sometimes accompanied by
carbonatites, are widespread in the continental magmatic provinces of the Europe and Africa, related with extension
(“pre-rift”) and rifting of Late Tertiary-Recent age. In the central Spain (Iberia plate) there are many centres of alkaline
mafic-ultramafic volcanism with carbonatite-melilitite eruption of that age (Bailey et al., 2005). Some facts let us to
propose, that alkaline magmatism of the earlier Canary Islands, GB and North Africa could be connected with the
African mantle plume activity on the early Paleocene, long before the European rifting occured.
All researchers of GB described many kinds of xenoliths founded in the lavas. There are pyroxenite, amphibole
pyroxenite, melteigite, ijolite, syenite – the full range of intrusive rocks, usually occuring in carbonatite complexes.
There are also fragments and aggregates of minerals: perovskite with sphene, amphibole, mica, apatite. So, we came to
conclusion that the GB alkaline rocks belong to the typical continental carbonatite complex, destroyed and dislocated.
This study was financially supported by RFBR grant 06-05-64169-a.

References:
Cornen G. Petrology of the alkaline volcanism of Gorringe Bank (southwest Portugal) // Marine Geol. 1982.V.
47. N 1/2. P. 101-130.
Matveenkov V.V., Al’mukhamedov A.I. Alkaline volcanism of the Gorringe Bank, Atlantic ocean // Petrologiya.
1996. V. 4. N 1. P. 46-56 (in Russian).
 37

Matveenkov V.V., Al’mukhamedov A.I., Dashevskaya D.M. Xenoliths of the amphibole pyroxenites of the
Gorringe Bank (Northeastern Atlantic) // Doklady Acad. Nauk. USSR. 1991. V.316. N 3. P. 688-690 (in Russian).
Сhernysheva E.A., Belozerova O.Yu. Composition of the deep-origin xenoliths from melilitites and some
features of the primary alkaline melt evolution in the Nizhnesayansky carbonatite complex // Geokhimiya. 2000. N 7. P.
785-789 (in Russian).
Le Bas M.J. Nephelinitic and basanitic rocks // J. Petrol. 1989. V. 30. P. 1299-1312.
Wilson M., Rosenbaum J.M., Dunworth E.A. Melilitites: partial melts of the thermal boundary layer? // Contrib.
Mineral. Petrol. 1995. V. 119. P. 181-196.
Bailey K., Garson M., Kearns S., Velasco A.P. Carbonate volcanism in Calatrava, central Spain: a report on the
initial findings // Mineral. Mag. 2005. V. 69 (6). P. 907-915.

Multistage fluid history of a copper province with carbonatites, lamprophyres, and associated rocks
Costanzo A., Moore K.R.
Department of Earth and Ocean Sciences, School of Natural Sciences, National University of Ireland
Galway, Galway, Ireland

A sequence of Lower Palaeozoic sedimentary rocks in the southwest of Ireland is cut by copper-rich vein
mineralization (at Allihies) and also by hypabyssal intrusions of carbonated trachyte and lamprophyre (see Brady et al.,
this meeting). The presence of copper-bearing minerals in the intrusive rocks, and a spatial association between the
intrusions and copper-free quartz veining suggests that there may be a genetic relationship between igneous activity and
mineralization. This hypothesis is tested using fluid inclusions studies on mineral samples from three Allihies Mines,
and quartz veins and a calcite related to a carbonatite intrusion at Black Ball Head.
The mines at Allihies operated between 1812 and 1884, with total ore production of 297.000 (Williams, 1993).
Those sampled for this investigation were the Mountain Mine, Caminches Mine and Coom Mine. The mineralogy
consists primarily of copper, iron and molybdenum sulphides with their attendant secondary minerals in areas of
oxidation. Chalcopyrite is the main ore mineral and is often accompanied by pyrite, bornite, tetrahedrite, hematite (var.
specularite), molybdenite, and chalcocite. The molybdenite is often disseminated in the quartz giving it a grey colour.
The secondary mineral assemblage comprises copper, iron and molybdenum carbonates, oxides and some sulphides
such as malachite, covelline, goethite and limonite. Quartz is the main gangue mineral (Fig. 1).
A zoned diatreme at Black Ball Head has an outer zone rich in xenoliths of local sedimentary and igneous crustal
rocks and an inner zone of tuffisite hosting mantle xenoliths and xenocrysts. Coarse-grained calcite bodies, fibrous
calcite veins and small strings of medium-grained calcite have been observed in a discontinuous elliptical pattern,
dominantly in the inner zone of the diatreme, but also crossing the contact between the inner zone and the outer zone.
The variety of forms of calcite and their distribution indicate migration of extremely low viscosity carbonate magma or,
more likely, fluid percolating through the diatremic tuffisite. There are no other cases of carbonate veining in the region
and it is interpreted as a carbohydrothermal carbonatite on compositional and isotopic grounds (see Brady et al., this
meeting). Regional quartz veining has a spatial association with the margins of igneous intrusions and quartz has been
sampled from the contact of the outer zone of the diatreme with the sedimentary country rock. Many fluid inclusions
have been observed in both calcite from the largest of the carbonatite outcrops and the elliptically-arranged calcite
strings and in the quartz veining (Fig. 2) from the margin of the diatreme.
Fluid inclusion studies were carried out on primary inclusions as these represent the mineralizing fluids during
mineral deposition. Fluid investigations are here used to:
 classify and compare the different fluid inclusion types hosted in quartz and calcite;
 identify the composition of fluid species;
 resolve temperature and pressure of entrapment;
 investigate the relationship between fluids involved in Allihies mineralization and both regional and magmatic
fluids in the vicinity of the Black Ball Head intrusions.
 38

Fig. 1: Quartz crystals associated with a copper-rich Fig. 2: Primary fluid inclusions in quartz veining
vein from a sample collected for fluid inclusion studies from (Black Ball Head). Inset: a cluster of solid-rich fluid
the Mountain Mine Shaft. Scale bar 1 cm. inclusions showing negative crystal shapes. Scale bar 50
m.

In samples from Black Ball Head, primary fluid inclusions (FIs) are much more abundant in quartz than calcite
and occur as large two-phase fluid inclusions (up to 40 μm in length) distributed in trails or isolated within the crystals
parallel to crystal growth planes. Primary calcite-hosted monophase liquid inclusions are also very common and range
between 3 and 10 μm in length. Fluid inclusions in quartz crystals are generally distributed along planes in clusters
made of two-phase liquid-vapour inclusions and/or monophase liquid inclusions (Fig. 2). Numerous solid-rich fluid
inclusions are also observed. They generally have a negative crystal shape and contain between one and two solid
phases. (Secondary fluid inclusions were also observed and occur in both host minerals as trails of smaller FIs (3 to 25
μm in length) with linear and curvilinear distribution related to later phases of fracturing.)
In Cu-Fe-metal bearing quartz veins from the Allihies area, a large number of fluid inclusions are hosted within
quartz crystals, particularly those in proximity to sulphide minerals. Large (up to 50 μm in length) two-phase fluid
inclusions are the most abundant and are most commonly distributed along linear planes within the crystals or along
crystal rims. Solid-rich fluid inclusions generally contain only one solid phase and are also considered to be primary.
(Small secondary FIs (2 to 10 μm in length) are also very abundant and occur as either two-phase or monophase FIs that
are aligned along annealed fractures.)
Three fluid inclusion types have been identified and classified according to their phase ratios at room
temperature:
 TYPE 1: two-phase liquid-vapour inclusions (L+V) with 80 to 95 % liquid by volume are the dominant type.
 TYPE 2: single-phase liquid-only inclusions (L).
 TYPE 3: solid-rich fluid inclusions (L+V+S) generally contain one or two small solid phases in addition to liquid
or vapour. The most common solid present is a low birefringent mineral, anhedral or prismatic, and it is observed
in the largest FIs with size up to 40 μm across. However, most of the inclusions containing solids are too small to
show any distinctive optical characteristics. Type 3 inclusions normally show consistent liquid to solid phase ratios
indicating that the solids are true daughter minerals crystallised from the enclosed fluid after trapping.
Type 1 and Type 2 inclusions occur at both the Allihies and Black Ball Head localities and are hosted by both
quartz and calcite, whereas Type 3 inclusions are restricted to the host mineral quartz. Microthermometric results used
to derive estimates of the PVTX state of the fluids at the time of trapping will be presented to facilitate further
comparison between the fluids associated with magmatism and mineralization.
This presentation was financially supported by INTAS project 05-1000008-7938.

References:
Williams, R.A. The Berehaven Copper Mines, Allihies, Co. Cork S.W. Ireland. British Mining No.42. Kenmare:
A.B. O'Connor, 1993. 228pp.

Modulated structures in aluminate sodalites

Depmeier W.
Institute of Geosciences, University of Kiel, Kiel, Germany.

The general formula of aluminate sodalites can be written |M8(XO4)2|[Al12O24], where M and X are site symbols
and M represents bivalent cations like Ca2+ or Sr2+, and X = S6+, Cr6+, Mo6+, W6+. Our interest in aluminate sodalites
focuses on structural aspects of aluminate sodalites, their phase transitions, and related properties. Usually, phase
transitions in aluminate sodalites from a cubic high temperature phase to one or several non-cubic low temperature
 39

phases are of ferroic type: ferroelastic and ferroelectric phases have been identified. The main emphasis of the present
contribution will be on a special character of the non-cubic phases. It seems that the majority of these phases can be
conveniently described as modulated phases. Commensurately and incommensurately modulated phases have been
found, and the dimensions of superspace may vary between (3+1) and (3+3). The sensitivity of the modulations against
even small disturbances leads to quite complicated T – x phase diagrams. The reason for the occurrence of the
modulations lies in the fact, that the structure of sodalites in general can be broken down into three partial structures,
viz. i) the sodalite framework, ii) an interpenetrating net of cations, and iii) cage anions at the centres of the sodalite
cages. It is important to know that interactions i) – ii) and ii) – iii) are basically attractive, whereas i) – iii) is repulsive
in nature. In the particular case of aluminate sodalites of the given composition, the cage anions iii) are tetrahedral
oxyanions. Their orientation is not only incompatible with the latent cubic symmetry of the sodalite framework, but
leads to marked repulsion effects i) – iii), and deformation of the framework. It turns out that interactions i) – ii) on the
one side, and ii) – iii) on the other side are competitive, such that the system is frustrated and its free energy can be
lowered by a modulation. Cascades of phase transitions especially in the Ca-bearing members of the aluminate sodalite
family can be rationalized by the fact that the phase transitions from the cubic phase usually happen at an N-point of
the body-centred Brillouin zone meaning that the corresponding order parameter has six components. In real space the
cascades can be rationalized by an interplay of rotational and translational potentials becoming subsequently deeper or
shallower as a consequence of the above-mentioned interactions. Chaotic phases and phases due to sliding of
modulation waves are also anticipated.
The low symmetry phases are usually characterized by marked pseudo-symmetry with weak superstructure
reflections, sometimes very low degree of spontaneous deformation in the case of ferroelastics, and the strong
sensitivity against all kinds of defects and disturbances.
The long-standing studies studies were financially supported by DFG granst DE 412/*-*.

References:
Többens D. M., Depmeier W. The intermediate phase of strontium chromate aluminate sodalite. Z. Krist 2001
Vol. 216, P. 611-615.

Mineralogical peculiarities of carbonatites of the Chagatay complex (western Uzbekistan)

Divaev F.K., Golovko A.V., Golovko D.P.
GP “Centralnaya GGE” The State Geological Committee of Uzbekistan Republic,
Samarkand, Uzbekistan

The rocks of Chagatay trachyte-carbonatite complex form swarm of contiguous dikes and volcanic pipes, which
are distributed within basin of Chagatai Creek (the complex was called by creek’s name) on the northern slopes of
southern Nuratau Mts. Enclosing rocks are presented mainly by terrigenous formations of Djazbulak and Nakrut suites
of the Silurian age (sandstones, siltstones, sheets, tufaceous sandstones) with rare tectonic wedges of Ordovician
terrigenous Badamchala suite and Cambrian Kalsara suite of essential carbonate composition. Besides carbonatites and
trachytes within descripted territory among magmatic formations rare separated Silurian diabase dikes of Malgusar
complex and Triassic camptonites of southern Tien-Shan complex are developed.
In composition of Chagatay complex carbonatites are prevailed. They form dikes (thickness 0.5 – 5 m, extension
20 – 1000m, strike 20-30°, dip of high angles, rare 60-70°, total near 60 dikes and two volcanic diatremes (dimensions:
8x170m and 200x250m). Trachytes are of single dikes (total 3 dikes), their thickness 0.5-1.5m, and extension up to
100m. They are close associated with carbonatite dikes. Carbonatites are both rocks of considerably calcite
composition, so-called sevites, and rocks of transitional carbonate-silicate composition, so-called casenites, ringites and
melilitic carbonatites (alvikites). They differ between them both on features of mineralogical composition and on
structural-textural indications. Contacts between carbonatites varieties are both sharp and gradational. Judge by
available interrelations, the earliest formations are fine-grained vitreous eruptive breccias of carbonatites, which form
diatremes and dikes. They were dissected by fine- and medium-grained alvikite and sevite dikes. Interrelations between
them are reflected in geological outcrops. Interrelations of carbonatites and trachytes didn’t establish. Both dikes and
diatremes have clear intrusive contacts with enclosing rocks and contact alterations are manifested very weakly in
interval 0.1-0.5 m. Alterations are manifested by poor hornfels and finely squamosed biotite. Metasomatic alterations of
enclosing rocks are manifested poorly as well (weak albitization and limonitization in intervals 0.1-0.7 m.
The main rock-forming minerals of Chagatay complex’ carbonatites are the following: calcite, pyroxene, biotite,
garnet, melilite, apatite, magnetite and secondary minerals – amphibole, chlorite, albite, potash feldspar, hematite,
quartz, montmorillonite.
By texture and structure indications and features of mineral composition seven types of carbonatites are
distinguished: 1 - brecciated carbonatites with vitreous cement. They fill Taty pipe and some small pipes; 2 - biotite-
garnet-pyroxene ones, 3 - garnet-biotite; 4 - garnet-pyroxene-melilite; 5 – brecciated, rare massive dikes and small pipes
of apatite-magnetite carbonatites; 6 - sevites (carbonatites of considerably calcite composition); 7 - albitizated,
orthoclasizated, chloritizated carbonatites, which fill Chagatay diatremes and some dikes. These seven types of
carbonatites are distinguished very relative, because clear intrusive contacts were established only for vitreous
 40

brecciated carbonatites of Taty pipe and for considerably calcite carbonatites (sevites). Contacts between other types
didn’t establish. Some times dike’ composition changes gradually along the strike or from center to border.
According to classic description of Bregger and Eccerman the former five types of Chagatay carbonatites are
corresponded to so-named transitional silicate-carbonaceous rocks – casenites and ringites, the sixth – to sevites.
Visually carbonatites of the former five types are the massive, compact; fine- and medium-grained rocks of dark grey
and black color resembled diabases and pyroxenites. Only carbonatites of essential calcite composition are colored
light-grey and brownish-pinky.
1. Brecciated carbonatites with vitreous cement fill the largest volcanic pipe Taty (after denomination of
settlement, which is located near the pipe). Pipe’s body is made of eruptive breccia, which consists of rounded, oval and
sharply angular fragments of enclosing rocks (sandstones, siltstones, flints, carbon-bearing shales, limestones, and
marbles). It is characteristic, that small sharply angular fragments of white limestones retain their clear outlines and
don’t dissolve. Then we arrive to the conclusion that assimilation of limestones by carbonatites didn’t occur. This fact
can be explained by very quick carbonatites magma’s intrusion and cooling. Breccia was cemented by vitreous basic
mass with rare lath-like crystals of calcite. Composition of vitreous cemented mass was analyzed using electron
microprobe and it is corresponded to biotite-garnet-pyroxene carbonatites.
2.Biotite-garnet-pyroxene carbonatites consist of calcite (30-45%), pyroxene (20-30%), garnet (10-15%), biotite
(5-10%), magnetite (5-10%), apatite (0.5-2.5%), chlorite (1-5%), albite and orthoclase (1-5%).
Pyroxene is represented by columnar and keg-like crystals of greenish-grey diopside (Fig. 24) with mixture of
hedenbergite (7-20%) and enstatite (1-15%) molecules. Rarely it is found like prismatic-oblong crystals of ferruginous
aegirine-augite (acmite) with mixture of ferrosilite and johannsenite minals (up to 12.2 and 3.2% correspondingly).
Garnet forms xenomorphic, rarely hexagonal crystals of yellowish-brown color (andradite) with anomalous
interference colors. It has been substituted intensively for earthy isotropic hydrogarnet (hibschite).
Biotite forms fine xenomorphic flakes, with pleochroism from brownish-green up to grayish-yellowish color
within some dikes and from light-brown up to dark-brown within another ones.
Chlorite forms finely squamosed light-green aggregate as a pseudomorph of pyroxene, partly substitutes biotite
flakes.
Albite and orthoclase occur sporadically in rare thin section as xenomorphic transparent grains.
Calcite forms large tabular and prismatic grains often with rhombohedral ends. Dimensions of grains are up to 1-
3 mm on elongation with characteristic polysynthetic twinning and glomeroblastic intergrowths of small xenomorphic
tabular grains as well. Large tablets of calcite often content poikilitic inclusions of idiomorphic grains of pyroxene,
apatite and magnetite. Isotopic composition of carbon in calcite from the Chagatay carbonatites is varied from -4.3 up to
-5,2‰, what is characteristic for mantle depth of forming.
Texture of rock is typical poikilitic.
3.Garnet-biotitic carbonatites include: calcite (30-40%), garnet (5-40%), biotite (10-40%), magnetite (2-10%),
apatite (1-3%), chlorite (1-10%), albite (0-2%). Depending on correlation of calcite and femic minerals these rocks can
be divided into leucocratic and melanocratic varieties.
Garnet forms coarse porphyry idiomorphic grains of dimensions 0.5-2 mm. Mineral color is chiefly brown, rare
– yellowish-green. In coarse grains color can be zonal: in the central parts coloration is more intensive than in marginal
ones. Coarse grains of garnet substitute by pale-green chlorite.
Biotite is characteristic by idiomorphic flakes up to 1 mm long. They have greenish-brown and brown colors.
Partly biotite substitutes by chlorite. Contents of garnet and biotite are in inversely proportional dependence: the more
garnet, the less biotite and conversely: the more biotite, the less garnet, and some times in certain cases garnet
disappears completely.
4. Garnet-pyroxene-melilitic carbonatites form up to half a volume of mapping dikes.
In outward appearance the melilite carbonatites are fine-grained massive rocks, from light to dark grey-green
color. Chiefly they include: calcite, melilite, pyroxene, magnetite, garnet and apatite with insignificant admixture of
secondary albite, chlorite, calcite, hibschite and limonite.
Melilite contents in rock vary from 5 up to 40%. It forms oblong-prismatic crystals with square cross sections of
dimensions: from 0.1 x 0.5 mm up to 0.5 x 2.5 mm. Visually melilite crystals have honey-yellow color, in thin section
they are colorless, yellowish-brown and dark brown. Often crystals have subparallel orientation. Chemical composition
of melilite is corresponded to ferriferous ocermanite with subordinated quantity of gehlenite minal.
Pyroxene – diopside-hedenbergite – has a pale grey-greenish color. Its quantity in rock varies from 5 up to 30%.
Content of pyroxene is in inversely proportion dependence on melilite quantity. In chemical composition diopside minal
is prevailed. Contents of hedenbergite and tchermakite (oligoclase) minals are subordinated. Admixtures of enstatite
and aegirine are insignificant.
Calcite (20-40%) forms grains of two generations as well. The first one – magmatic generation include coarse
polysynthetic twinned tabular grains (0.5-1.5 mm), which contain abundant poikilitic inclusions of idiomorphic crystals
of melilite, pyroxene, garnet, apatite and magnetite.
The second generation is autometasomatic. It is represented by fine-grained aggregate, substituted by the veinlets
and spots of primary tabular calcite grains.
Rock texture is poikilitic, partly trachytoid, complicated by microgranoblastic texture.
5. Apatite-magnetite carbonatites are characterized by more small-granular texture (up to fine-grained
rocks). They often form eruptive brecciated dikes, rare small pipes (diameter 5-10 m), which are overfilled with
 41

xenoliths both enclosing sedimentary rocks and carbonatites of former injection phases. Carbonatites contain calcite
(40-50%), magnetite (15-25%), apatite (15-20%), pyroxene (5-10%), biotite (1-2%) and secondary chlorite and albite
(2-3%). In contrast to the third type of carbonatites in this type garnet forms fine (0.n mm) and finest (0.0n mm) grains
equally spaced in all over the rock. As a poikilitic inclusion garnet intercalates within more coarse (up to 0.5-1.0 mm)
plate grains in calcite. As a rule garnet was substituted completely by brown isotropic hydrogarnet (hibschite).
Pyroxene (pale greenish enstatite-hedenbergite-diopside) forms prismatic grains (up to 0.2-0.3 mm in
elongation).
6.Sevites (carbonatites of considerable calcite composition) are the least distributed rocks of the Chagatay
complex. As a rule they form compound dikes, rare small stock-like bodies. To all appearance sevites are the new
varieties of carbonatites. Indicative of this fact are their intrusive contacts with chilling zones in contacts with former
phases of carbonatites injections.
In samples were established the following accessory minerals: garnet, apatite, zircon, rutile, leucoxene, barite,
pyrite, magnetite and chromo-spinel. All these minerals have through wide-spread occurrence and were established
single finds of zircon, periclase, moissanite, corundum, iocite, arsenopyrite, galena, gold, graphite, diamond.
Garnet forms three varieties: 1 - in garnet-biotite carbonatites it forms coarse porphyric grains (up to 2.5 mm
across). Its composition is pyrope-spessartine-almandine; 2 - in biotite-pyroxene-garnet carbonatites garnet is
represented by abundant small grains of grossular-andradite composition equally spaced within rock’ mass; 3 - in
brecciated carbonatites garnet is of spessartine-grossular-almandine composition.
Apatite is represented by crystals of mainly hexagon-prismatic habit and their fragments. Often are found
crystals of flattened tabular habit, distorted crystals and columnar aggregates of grains. Crystals’ color is peculiar: red-
meat of various tints, rare grey-greenish, yellow and marshy-brown.
After results of microprobe analyses apatite composition varies from fluorine apatite to francolite.
Zircon is represented by rare colorless prismatic crystals (0.05 x 0.3 mm). In zircon there are admixtures: Hf, Nb,
Ta, La, Ce, Pr.
Pyrite. Main part of pyrite occurs in electro-magnetic fraction. It is represented by crystals of cubic habit and
their fragments. Pentagonal-dodecahedrons, compound combinations and their distorted crystals are met rare. It is
observed very tiny (<0.1 mm) grains of framboidal (spheroidal) pyrite. Often pyrite is oxidized and covered with film of
iron hydroxide. It is observed holopseudomorph of iron hydroxide on pyrite. Often pyrite forms inclusions in magnetite,
but some times contrary are observed magnetite inclusions in pyrite. Rare inclusions of pyrrhotite in pyrite are observed
as well.
Magnetite forms octahedron and hipidiomorphic grains, often appear inclusions within pyrite and hematite,
intensive substitute with hematite and non-metallic minerals, so that only outward rim was remained. Grains of
magnetite are of zonal structure: the central part is formed with titan magnetite (up to 17.7% TiO2) and marginal zones
– with titan-bearing magnetite (up to 2.1% TiO2). The central part is enriched with Al, Mn, Mg, Cr, V and Zn.
Ilmenite is presented as idiomorphic plates in inclusions within titan magnetite and forms exsolution phenomena.
As a rule it intensive substitutes by hematite.
Hematite. It is observed three varieties: 1. independent grains – fragments, 2. pseudomorphoses after magnetite,
3. diffused hematite in rocks’ fragments.
Galena forms growths with sphalerite and acantite. Often along the margins of galena grains are observed rims
of chalcopyrite, chalcocite and covellite.
Spinel composition is very unusual and is characteristic for all types of carbonatites of the Chagatay complex. It
is corresponded to magnochromite: high chromous (57-59% Cr2O3) and magnesium (6.6-9.5% MgO). Presence of
chromiumless noble spinel within brecciated carbonatites can be explained its xenogenous origin.
Corundum is met as small fragments (0.05-0.5mm) of white, blue, sky-blue, rare pink colors.
Rutile forms rounded and oval grains (0.2-0.4 mm across). Colors vary from bright orange transparent up to dark
cherry, opaque.
Muassanite is observed as fragments of irregular forms, some times with melted surface, light green or bluish
green colors. Dimensions: 0.1-0.3 mm.
Silver is presented practically in all samples, in shape of fine wires and rounded-flat grains. Its contents in rock
are ranged usually from 1.5 up to 3.5 g/t. In silver composition were established heightened contents of platinoides (Pt
up to 300g/t, Pd up to 200g/t and Ir up to 0.6 g/t).
Gold is observed as single grains in majority of samples. Often it forms intergrowths with hessite and fahlerz.
Dimensions of gold particles: from 0.05 up to 0.1mm. Their forms are pellets and interstitial; colour – yellow, dark
yellow.
Graphite forms separate flakes of black colour with greasy luster, up to 2 mm across. It is observed as cement in
interstitials of non-metallic minerals. Isotopic composition of carbon in graphite varies from -4.3 – 8.21‰. This fact
definitely points out mantle genesis of graphite.
Diamonds are represented mainly aggregates of octahedron crystals and intergrowths of grains with vague
manifested crystallographic and skeletal forms, dimension of which are 0.01-0.05mm (Fig. 33-34). Rare are met
octahedron monocrystals with plane crystal faces and sharp apexes and edges of crystals. Their dimensions 0/02-0/05
mm. Colour is mainly light grey with light greenish shade. Some times are met grains lighter and very rare – near black.
Rarely was it observed dark micro inclusions, which are located mainly within apex of crystals. Brilliant lustre.
 42

Hardness is more 9.5, which was determined on hardness standard. Determination of diamond was confirmed by
debaegram.
The presence of native elements within the Chagatay carbonatites indicated of low sulfur and oxygen potentials
and, correspondingly, of sharp reduction conditions within magmatic chamber.
The work was accomplished by financially supported by INTAS Fond №05-1000008-7938.

Petrochemical peculiarities of Devonian magmatic complex in Dnieper-Donetsk avlakogene

Donskoy N. A.
N.P. Semenenko Institute of Geochemistry, Mineralogy and Ore Formation of NAS, Kiev, Ukraine

In the region studied the Devonian magmatic rocks are widespread. They are separated into three subcomplexes.
The most old basic-ultrabasic is represented pyroxenites, dunites, gabbros and vein rocks. Their age is D 2-D3. The
basaltic subcomplex is most common. The recent subcomplex is alkaline nepheline-leicite one (upper D3).
Main magmatic stages are related with Hercynian orogenisis ones. In
http://www.multitran.ru/c/m.exe?t=3254584_2_1Breton orogenesis stage the renewing of old faults occurred. The
most intensive volcanic occurrences and mineral resources related have been discovered in zone of intersection of
sublatitudinal and http://www.multitran.ru/c/m.exe?a=110&t=1635707_2_1&sc=2submeridional faults.
In junction zone of Dnieper-Donetsk depression (DDD) with Azov block of Ukrainian Shield (Ush) the all of
three subcomplexes are represented to the best advantage. The Devonian magmatic occurrences have been discovered at
South part of the Dnieper-Donetsk http://www.multitran.ru/c/m.exe?a=110&t=2877024_2_1&sc=517avlakogene frame
in Khomuto-Rostov fault zone, intrusive stocks next to Zirka township (city of Mariupol), Kichiksu, Mariupolskiy and
Primorskiy massifs and other. There predominantly are 1 st intrusive subcomplex rocks at that area. The 3 d subcomplex
effusive rocks are predominantly located in central part of DDD (Belaya Tserkov’ bowing and other small occurrences)
and Pripyat depression.
Appointed petro- and geochemical characteristics are specific for Devonian volcanic complex: the 1 st
subcomplex rocks are enriched in TiO2, less in Fe2O3 and FeO, depleted in Al2O3 and SiO2.
The 2nd subcomplex rocks correspond average basaltoid, but they have more SiO 2, Al2O3, alkali, titanium and
less SiO2 and Na2O. The natrium prevails the sodium.
The 3rd subcomplex rocks are enriched in K2O, TiO2, Al2O3 and depleted in SiO2 и Na2O. K2O+Na2O/Al2O3
coefficient range is 0,88-1,65. The effusive rock compositions are close to intrusive rock ones, but they have more CaO
and alkali, depleted in MgO.
The main geochemical feature of Devonian magmatic complex is high titanium, copper (predominantly in
pyroxenites), fluorine, rare-earth elements of cerium group, relatively low SiO2. According this data the 3d subcomplex
rocks are attributed at ultrabasic and alkaline-basaltic magmatism.
Features of metasomatic processes. The Devonian magmatic occurrences are associated with metasomatic
processes. Alkalization is prevailed. Chloritization, serpentinization and ore serpentinite formation associate the 1st
subcomplex rocks. Scarnization and ore polymetallic sulfides formation processes associate the 2 nd subcomplex rocks.
Some alkaline metasomatic stages (fenitization) such as first, medium and final are distinguished. In the fist stage a
recrystallyzation of primary rocks and sodium, potassium, iron, magnesium input have occurred. The new aggregates
are represented biotite, http://www.multitran.ru/c/m.exe?a=110&t=139422_2_1&sc=27hornblende, albitite, potassium
feldspar, apatite and ore minerals. The medium stage is different for primary rocks. In syenite and granosyenite
hornblende and biotite have disappeared. Aegerine, sphene and nepheline have appeared. The final stage is specified by
uniform paragenesis: aegerine- augite, potassium feldspar, nepheline, sphene, ore mineral and apatite. The process of
potassium metasomatism, which related with beryllium, niobium and rare-earth mineralization, is actively displayed. In
comparison with average composition of rock of same type, increased amount of copper (0,3%), zinc (up to 1%), nickel
and molybdenum have been established. In appointed locations the explosive rocks have been transformed into mica
rocks.
Alongside with 1st magmatic subcomplex rocks prevalence, 2nd magmatic subcomplex rocks of latite- trachyte
type have been noticed. And the 3rd subcomplex rocks are represented small vein, jacupirangite, syenite- porphyry,
bostonite and nepheline syenite bodies. Study of Devonian magmatic rocks in Pripyat depression has shown that they
and magmatic rocks in junction zone of DDD with Azov block of Ush are the same type. General feature is
trachytization, silica depletion and high trace elements, such as zirconium, niobium and rare-earth elements. The
volcanogenic rocks are represented tuffs, more rarely lava flood. Abyssal igneous rocks are absent. Simultaneous
presence of nepheline and leicite is typical difference of nepheline rocks in Pripyat depression. They are strong altered
and contain a lot of sedimentary material.
In central part of DDD has also discovered a number of Devonian magmatite occurrences. Ancient dome, next to
city of Khorol, structural characteristics of tuffs and lava breccias indicate nearest crater presence. The volcanic rocks
compose effusive beds and tuff fields. Plutonic rocks have occurred into debris only. Three volcanogenic layers are
distinguished. They are probably to correspond volcanic stages. In the bottom layer, into debris the basic-ultrabasic
subcomplex rocks prevail over. Alkaline rocks dominate into debris of second layer and into thin beds of third one.
Nepheline rocks often occur than leicite ones. Meltegites, iolites and nepheline pyroxenites have been observed. In
another Devonian magmatism locations of studied region they are not noticed.
 43

The volcanogenic rocks in central part of DDD are enriched in rare-earth metals, predominantly in high
potassium and sodium rocks. High titanium, vanadium, zirconium, copper and lead are noted. On petrochemical and
geochemical criteria these rocks are similar to Devonian magmatites in Pripyat depression.
Devonian magmatic rocks specialization. The 1st subcomplex -titanium ores (ore pyroxenites, serpentinization
and chloritization products), the 2nd one – skarns with polymetalic sulfides, the 3rd one – complex nepheline ores,
carbonate metasomatites (enriched in copper, nickel and molybdenum, beryllium and niobium mineralization).

Role of structural factor during formation of alkaline massifs of Proterozoic series of nepheline
syenites in south-western part of the Russian Platform
Donskoy A.N.
N.P. Semenenko Institute of Geochemistry, Mineralogy and Ore Formation of NAS, Kiev, Ukraine

Proterozoic alkaline massifs of nepheline syenite series are predominantly concentrated in margin zones of
Ukrainian Crystalline Shield. They are located nearby huge tectonic structure. This structure is Dnieper-Donetsk
avlakogene, which divides Ukrainian Crystalline Shield (USh) from North and East. The formation of these alkaline
complexes is connected with a period of platform development in this region.
Most of alkaline massifs of this type such as Octyabrskiy, Malaya Tersa, Sherbakovka (next to border of Rostov
district in Russia) alkaline massifs and Chernigovka carbonatite one are located at Azov block (domain) in USh. Lately
massifs of same type were found at Western margin of USh. There were Proskurovka and Antonovka massifs and
Yastrebetskiy one (North-Western part of USh). Alkaline massif in Proterozoic shield was discovered at Lithuania,
Vareny zone. There is a prediction of finds of same massifs in Belarus. Alkaline syenites were discovered next to city of
Pinsk. These rocks use to frame alkaline massifs of nepheline series. As a rule the complexes of this type are located
into zone of deep fault intersection.
Tectonics of Azov block of USh has been the best studied (fig.). The alkaline massifs were forming in
Proterozoic era after the main structures of Azov block had been formed. Zones of deep faults frame the block. It is got
up regarding Northern and Eastern its borders. Joint zone is got up regarding the block.

Fig. Schematic tectonic map of Eastern part of Azov block. (Roman numerals in circle): I – Azov block; II –
Orekhovo-Pavlograd joint zone; IA – Western Azov block on 1st tectonic range, IБ - Central Azov interblock structure;
IВ - Eastern Azov block of 1st tectonic range.
The blocks of 2nd tectonic range (Arabic numeral): 1- Volchanka, 2 – Huliaipole, Andreevka.
Faults (Arabic numerals in circle): 1 – Azov-Pavlograd, 2 – Malaya Yanisol, 3 – South Donbass (Volnovaha), 4
– Berdyansk-Kalmiuss, 5 – Konka, 6 – Gruzskiy Elanchik, 7 – Krivoy Rog-Pavlovka.
Deep faults: 1 – 1st range, 2 – 2nd range, 3 – 3rd and upper range, 4 -faults, 5 - upthrow faults, 6 – slide apart
faults.
Massifs: granite (1 – Ekaterinovka, 2 – Starodubovka, 3 – Tokovka); 8 – undefined alkaline (1 – Octyabrskiy, 2
– Kalmius, 3 – South-Kal’chik, 4 – Elanchik); 9 – ultrabasic alkaline (1 – Chernigovka, Begim-Chokrak, 2 – Pokrovo-
Kireevo); 10 – plagiogranite-migmatite Saltychansk dome; 11 – anticlines; 12 – troughs; 13 – trough structures
(Kuibyshevsk-Sorokin, 2 – Fedorov); 14 – projections of basis strong metamorphised; 15 – dykes.
 44

Inasmuch as the alkaline massifs were forming under great influence of metasomatic processes which been
controlled by tectonic structures, we refer to appointed types of tectonic zones. The 1 st range tectonic zones frame
structures of 1st range. They use to be a great length and zonal. There are occurrences of igneous and metasomatic rocks
of different age on the territory of these zones.
The 2nd range tectonic zones are structures with deep faults, which divide blocks of 1 st and upper tectonic range.
There are dykes, occurrences of acid and basic magmatism, ultramafic and metasomatic rocks on territory of these
blocks. These zones have North-Western direction and a lot of feathering faults.
Deep fault zones, which associate with occurrences of alkaline metasomatic rocks, depend on the fault zones of
North-Western direction.
Over fault zones of North-Western direction ultrabasic and alkaline rocks, zones of fenitization, alkalization,
metasomatic rocks and carbonatites were developing. These structures were repeatedly renewed; dyke complex rocks
were developed there. They were of importance for forming a block structure of the massifs.
Peculiarities of a formation of Octyabrskiy massif and its frame are suggested to be in the following way.
Formation of large folded structures of North-Western direction was simultaneously occurring with slow block
elevation
Some tectonic stages have been established in North-Western part of Octyabrskiy massif (Mazurova Balka
deposit). These stages are related with faults' renewing along old fault zones. The two fault systems of North-Western
and North-Eastern direction are noted.
Some tectonic stages have been established in Northwestern part of Octyabrskiy massif (Mazurova Balka deposit).
These stages are related with renewing of fault displacements over old direction fault zones. Two fault displacement
directions have been noted to be Northwestern direction and North-Eastern one.
The appointed types of faults are distinguished:
1) which have been preceded formation of syenites of North-Western direction and 45-60º in contact zone of
base rock and syenites (pre-ore bearing stage);
2) controlled by albitite intrusion (ore-bearing stage);
3) related with albitite intrusions (ore-bearing stage);
4) fault zones formed until ore-bearing period, it occurred the renewing of displacement movement which slide
and crush ore bodies
5) small displacements, breccia post ore-bearing zones initiate steep displacements of North-Western direction in
nepheline rocks; they are related with lamprophyre dykes.
6) younger faults of slide type shift lamprophyre dykes
The nepheline complexes massifs of syenite series are related with ancient platforms such as USh, Belarus shield,
Lithuanian plate, Baltic Shield, Transvaal province, Canadian platform, which had been formed in Proterozoic era. The
nepheline series suite epochs of ectonic and igneous activity, which correspond periods of global reconstruction.

Is Oshurkovo gabbro comagmatic rock to carbonatite?

Doroshkevich A.G., Ripp G.S.
Geological institute SD RAS, Ulan-Ude, Russia.

There are some veins of carbonatites at northern part of Oshurkovo apatite-bearing basic massive. Veins are 0.6-
1 meters wide and over 100-200 meters long. Carbonatites are composed of calcite, magnetite, phlogopite, apatite and
barite-celestine. Monazite, allanite and zircon are accessory. The contacts of carbonatites with country rocks are sharp
and marked by titanite-phlogopite-magnetite-potash feldspar contact zones. Carbon and oxygen isotopic values for
calcite from carbonatites plot in the field of primary igneous carbonatites and oxygen isotopic values for silicate and
oxide minerals are similar to mantle-derived minerals (table). Isotopic thermometers were used to calculate the
temperature of carbonatite formation. Magnetite-phlogopite isotopic thermometer (Chacko et. al., 2001) gave
temperatures of 932-9460С. Calcite-magnetite formula of Chiba et al. 1989 yields temperatures of formation up to
6250С. U/Pb analysis (SRIMP II, zircon) of the carbonatite yielded age of 126.6 Ma and its age is similar to that of the
West Transbaikalia carbonatites (Khaluta, Yuzhnoe, Arshan).
Association of the carbonatites with silicate basic rocks of Oshurkovo massive has been favoured by many
authors (e.g. Nikiforov et al., 2002), but the hypothesis is not supported by reliable data. Dating by the Rb–Sr and К-Ar
methods have given early Cretaceous ages for the basic rocks of Oshurkovo massive (Kuznetzov, 1980; Litvinovsky et
al., 2002) and, thus, age determinations imply that the Oshurkovo basic rocks and carbonatites are broadly coeval. Our
U/Pb analysis (SRIMP II, zircon) of the basic rocks (gabbroes) yielded age of 280,62,7 Ma and showed the time
differences between formation of carbonatite and gabbro. In addition, Ca-bearing minerals (plagioclase, diopside-salite,
amphibole and apatite) that formed at early crystallization stage are the main minerals in basic rocks of Oshurkovo
massive. These facts are not consistent with hypothesis that Oshurkovo gabbroes and carbonatites are comagmatic
rocks.
In this connection, the most interesting as comagmatic rocks to carbonatites are pyroxene rocks that have been
discovered recently in Oshurkovo massive area. Pyroxene rocks form dykes with taxitic texture. They are characterized
by the presence of coarse grained schlieren. The rocks consist of diopside (60-80%) and potash feldspar. Calcite and
apatite are filling interstices. Amount of calcite is up to 10-15%. Titanite, allanite and magnetite are minor minerals.
 45

Diopside has 10-25% aegerine minal and contains the melt inclusions that were homogenized at 708-7200С. Potash
feldspar is characteristically enriched in barium (up to 7 wt. %) and contains 0,9- 1,9 wt. % of Na2O. Magnetite has up
to 8-10 wt. % of TiO2. Composition of apatite from pyroxene rocks is similar to that from carbonatites (fig. 1). They
both have higher REE, SO3 and SrO (at 2-3 time) than mineral from Oshurkovo gabbroes.

Table. Isotopic composition of  13

C ‰, 18O ‰ and initial 87
Sr/ 86
Sr ratios of minerals from Oshurkovo
carbonatites and pyroxene rocks.
Mineral  13C 18O ‰ 87
Sr/
‰ PDB SMOW 86
Sr
Carbonatite
Calcite -6,18 7,48 0,705
(20) 40 (6)
Phlogopite 4,8
(4)
Magnetite 0,75
(3)
Titanite (1) 3,6
Amphibole 5,2
(1)
Potash 6,7 0,705
feldspar (1) 34 (1)
Pyroxene rocks
Pyroxene 5,55 0,705
(2) 731 (2)
Titanite (1) 5,1
Potash 5,6
feldspar (1)
In brackets – number of analyses.

Fig. 1. Amount of SrO, REE and SO3 in apatites from gabbro (1), carbonatite (2) and pyroxene rock (3).
 46

Fig.2. Chondrite-normalized plot of the REE in the rocks of Oshurkovo massive. Chondrite values are from
McDonough & Sun (1995).

Pyroxene rocks contain 42-45 wt. % of SiO2, 1,2 wt. % of К2О and 2,2 wt. % of Na2О. They are rather different
in composition, with higher Ca and lower Al2O3 than Oshurkovo gabbroes. The REE patterns of pyroxene rocks are
similar to those for the carbonatites and different than basic rocks of Oshurkovo massive (fig. 2).
Thus, isotopic data can imply that the pyroxene rocks and carbonatites are probably coeval and have a common
magma source (see table). This study was financially supported by RFBR 08-05-98028.

References:
Chacko T, Cole DR, Horita J Equilibrium oxygen, hydrogen and carbon isotope fractionation factors applicable
to geological system, Stable isotope geochemistry // Reviews in mineralogy and geochemistry, 2001. Vol. 43: P. 1-62
Chiba H, Chacko T, Clayton RN, Goldsmidth JR Oxygen isotope fractionations involving diopside, forsterite
and calcite: applications to geothermometry // Geochim Cosmochim Acta, 1989. Vol. 53: P. 2985–2995
Nikiforov AV, Yarmolyuk VV, Kovalenko VI, Ivanov VG, Zhuravlev DZ Late Mesozoic carbonatites of
Western Transbaikalia: isotopic–geochemical characteristics and sources // Petrology, 2002 Vol.10 (2), P. 146–164
Kuznetzov A.N. Mineralogy and geochemistry of apatite-bearing diorites (South-West Transbaikalia), Nauka,
Novosibirsk, 1980, 102 p. (in Russian)
Litvinovsky B.A., Jahn B, Zanvilevich A.N., Shadaev M.G. Crystal fractionation in the petrogenesis of an alkali
monzodiorite-syenite series: the oshurkovo plutonic sheeted complex, Transbaikalia, Russia // Lithos, 2002, Vol. 64. P.
97-130
McDonough WF, Sun S. The composition of the Earth // Chemical Geology, 1995. Vol. 120: P. 223-253

Graphite-bearing dolomite carbonatites in Newania, Western India

Doroshkevich A.G.*, Ripp G.S.*, Viladkar S.G.**.
*
Geological Institute SB RAS, Ulan-Ude, Russia
**Carbonatite Research Centre, Amba Dongar Kadipani, India

The features of Newania carbonatites as primary mantle-derived melt have been described in (Viladkar, 1998).
There are high Mg#s of carbonatites (up to 19 wt. % of MgO), low initial Sr87/Sr86 rations (0.7021), mantle-like C and
O isotope rations (-5.1 and 8.1, repectively), absence of associated silicate rocks, and dolomite composition. Nd isotope
studies (Gruau et al., 1995), noble gases and N (Basu & Murty, 2006) in Newania carbonatites also indicate mantle
source. Newania certainly fits most of the criteria for a direct derived carbonatite magma; the key mineralogical features
of the Newania carbonatites as mantle-like carbonatites are presence of magnesite, graphite and Cr-rich magnetite.
Magnesite is an early crystallizing phase. Cr-rich magnetite and graphite are coexistent with carbonatite minerals and
precipitated from carbonate magma.
The Newania dolomitic carbonatites are fine- to medium-grained, massive and banded rocks containing crystals
and grains of amphibole and apatite. In the fine grained types the groundmass consists of dolomite. Dolomite is ferroan
dolomite with 5–12 wt. % FeO. Mineral has up to 1.4 wt. % SrO. Phlogopite, Fe-magnesite, columbite are minor
minerals. Monazite, ilmenite, aegerine, pyrrhotine, molibdenite, zircon, bismite, carbocernaite, pyrochlore, barite, rutile
are accessory. Amphibole and phlogopite form thin bands. In addition, amphibole contains rare relic of early pyroxene
(aegerine). Composition of amphibole varies from magnesio-arfvedsonite to magnesioriebekite. It is TiO2 and Al2O3
poor, but enriched in F (1.3-2 wt. %). Fe3+/Fe2+ varies from 0.5 to 1.0. Phlogopite is characterized by higher Fe/Fe+Mg
(2.7-3) and TiO2 (up to 1.1 wt. %). Fe3+/Fe2+ varies from 1.5 to 2.9. The F content ranges from 2.6 to 2.9 wt. %.
Magnesite forms rare, rounded to euhedral or subhedral grains (fig. 1, a,b), 0.5 -1.5 mm in size, in dolomite matrix.
Mineral was replaced by siderite along cracks, cleavage cracks and rim of magnesite grains. Siderite is associated
with secondary iron oxide (limonitic oxide), pyrite, Ba and Sr sulphates. Magnesite is ferroan magnesite, and siderite is
magnesium siderite. Both, magnesite and siderite contain a small amount of MnO and CaO. Apatite is coexisting
 47

mineral with phlogopite, amphibole and columbite (fig. 1, c); it forms single grains as well as the bands and lenses.
Mineral is fluorapatite with F content up to 4.9 wt. %. Mineral is highly strontium (SrO is up to 2.9 wt. %). Mineral
contains solid inclusions of columbite and graphite. Often secondary monazite forms thin shell around apatite grains
(fig. 1, d). Graphite forms flakes and their assemblages that dispersed in carbonatite. It also included as solid inclusions
in apatite, amphibole, magnetite, columbite and sometimes mineral forms thin shell around magnetite grains (fig. 2).
Magnetite occurs as crystals and rounded or anhedral grains with size up to 2-3 mm. Mineral contains irregular
and poikilitic inclusions of dolomite and apatite (fig. 1, e, f). The bulk of magnetite contains a larger proportion of
magnetite end-member with minor proportions of ulvospinel and magnesioferrite series. Mineral is enriched in
chromium (from 0.4 to 1.4 wt. %) and V2O3 ( up to 0.3 wt. %) contents. Magnetite grains usually contain external
composite ilmenite with trellis lamellae along {111} planes (fig. 1, g, h). Ilmenite is characteristically depleted in
chromium (0.16 wt. %) and enriched in vanadium (0.8 wt. %) relative to magnetite. Mineral is characterized by higher
Nb2O5 (1.9 wt. %) and MnO (1.2 wt. %).
Estimates of crystallization temperature for Newania dolomitic carbonatites were obtained from coexisting
apatite-phlogopite and ilmenite-magnetite pairs, using apatite-biotite thermometer of Ludington (1978) and Fe-Ti oxide
geothermometer of Andersen & Lindsley (1985). The apatite-biotite geothermometer yields temperature estimates in
the range 693-9780C. Estimates of the relative HF fugacity, log (fHF/fH2O), based on Andersen & Austrheim (1991),
using the apatite-phlogopite equilibrium temperature yield values between (-3.6) and (-4.9). Ilmenite-magnetite pairs
gave temperature for the Newania groundmass crystallization from 649 to 675 0C. The oxygen fugacity shows the
deviation from FMQ (3 to 3.5 log units relative to FMQ). The oxidation state of Newania source is embodied in
presence of Fe-columbite, and composition of phlogopite, amphibole and pyroxene that have higher amount of Fe 3+.

Fig. 1. Mode of occurrence of magnesite (mgnst), apatite (ap) and magnetite (mt) in carbonatites from Newania
(BSE images). a, b – replacement of magnesite (mgnst) by siderite (sid) with Fe oxides formation; c – apatite (ap) bands
in dolomite (dol) matrix; d - thin shell of monazite (mon) around apatite grains; e, f - crystals and anhedral grains of
magnetite; g - external composite ilmenite (ilm) in magnetite; h – lamellae of ilmenite in magnetite. dol – dolomite, c –
graphite.
 48

Fig. 2. Distribution of graphite (c) in Newania carbonatites (BSE images). ap – apatite, dol – dolomite, amf –
amphibole, clmb – columbite, mt – magnetite, ilm – ilmenite.

This study was financially supported by RFBR 08-05-98028 and INTAS grant 05-1000008-7938.

References:
Viladkar S.G. Carbonatite occurrences in Rajasthan, India // Petrology, 1998. Vol. 6 (3), P. 272-283
Gruau G., Petibon C., Viladkar S. Extreme isotopic signature in carbonatites from Newania, Rajasthan // Terra
Nova, Abstract Suppl, 1995. Vol. 1, P. 336
Basu S. & Murty S.V.S. Noble gases and N in carbonatites from Newania, India: Pristine N in subcontinental
lithosphere // Abstracts of Goldschmidt Conference, 2006, P. A40
Ludington S. The biotite-apatite geothermometer revisited // American Mineralogist, 1978, Vol. 63, P. 551-553
Andersen D.J. & Lindsley D.H. New (and final) models for the Ti-magnetite/ilmenite geothermometer and
oxygen barometer // Abstract AGU 1985 Spring Meeting Eos Transactions. American Geophysical Union, 1985. Vol.
66 (18), P. 416
Andersen T. & Austrheim H. Temperature-HF fugacity trends during crystallization of calcite carbonatite magma
in the Fen complex, Norway // Mineralogical Magazine, 1991, Vol. 55, 81-94

Geochemical peculiarities of apatite in alkaline rocks from the Ukrainian Shield

Dubyna A.V., Kryvdik S.G., Bondarenko S.N.
N.P. Semenenko Institute of geochemistry, mineralogy and ore formation NAS of Ukraine, Kyiv, Ukraine

Apatite is an ubiquitous mineral in alkaline and subalkaline rocks of the Ukrainian shield (USd), and its features
of composition reflects the chemistry of parental magmas and processes of their differentiation. Within USd we
distinguish two main complexes of alkaline and subalkaline rocks - alkaline-ultrabasic (carbonatitic) and gabbro-
syenitic. Their parental magmas may be melanephelinite and subalkaline basalts correspondly. These melts have
various trends of differentiation: the final derivates of alkaline-ultrabasic complexes are carbonatites and nepheline
syenite, and of gabbro-syenitic one - alkaline and nepheline syenites, including their agpaitic varieties.
In the rocks of these complexes significant differences in the composition of apatite are revealed. In the
carbonatites and associated rocks apatites are usually enriched in Sr (from 0.18 to 3.20% SrO) and REECe (from 0,85 to
8,55% REE2O3), while in agpaitic nepheline syenites and phonolites (Oktyabrsky massif) apatites is poor in Sr (0,12-
0,42% SrO) by very wide variation in the concentration of REE and Y. In addition, REE patterns of apatite from rocks
of gabbro-syenitic complexes are characterized by negative Eu-anomalies, while in the carbonatites these patterns are
more «flat» or with negligible anomalies. It is considered that the negative Eu-anomalies in apatites and rocks
containing them due to feldspar fractionation.
In carbonatite complexes of USd positive correlation between content of REE and Sr are observed. However, by
very high concentrations of REE2O3 (up to 11.0%) contents of Sr is no more than 2.4-4.5%. That is not so high, as
typical e.g. for apatites from Khibiny and Lovozero massifs. In ordinary ores of these massifs apatite contains 2.02-
8.44% SrO, but there is very enriched in strontium varieties (up to 62.86% SrO) (Chakhmouradian et at., 2002). It is
considered (Kogarko, 1977) parental magmas for these massifs have been of alkaline-ultrabasic composition
(melanephelinite type).
 49

The Ce/Y ratio in apatites from alkaline-ultrabasic rock complexes of USd varies from 9 to 53. At the same time,
with increase of REE content this ratio increases.
In apatite of agpaitic rocks in Oktyabrsky massif Ce/Y varies from 5 to 17 and as in carbonatites rise with
increasing REE amount. Whereas, apatites in South Kalchyk quartziferous rocks Ce/Y varies between 0.46 and 12. It is
not certain regularity of REE amount and this ratio sharply reduces in the yttrium-rich (up to 7.90% Y2O3) apatites. In
alkaline differentiates of acidic and basic composition and associated quartz-feldspar metasomatites, there are also
yttrium rich as well as Y-apatite (Marchenko, 1995).
REE, Sr, Y replace, as it is well known, calcium in the apatite, but there are two main schemes of heterovalent
isomorphism: britholitic (REE → Ca = Si → P) and belovitic (Na + REE → 2Ca).
Britholitic scheme of isomorphism was found in apatites from SiO 2 saturated and quartziferous melanocratic
carbonatites and ringites in Chernigovka complex (Azov area). These apatites have dissoluble SiO 2 (up to 3.70 wt.%),
and to 11.0% REE2O3. Exsolution inclusions of britholite and products of its alternation (orthite, quartz, calcite,
bastnasite, strontianite) (Kryvdik et al., 1990; Vorobiev, 2000) in these apatites are observed. These inclusions may
overfill apatites and they become brown (“sealing wax”).
Belovitic scheme of isomorphism is typical for apatites in SiO2 unsaturated rocks of USd: in agpaitic nepheline
syenites and phonolites (Oktyabrsky massif), as well as in olivine calcite-dolomite carbonatites (beforsite, Chernigovka
complex). In apatite from last carbonatites REE 2O3 content reaches to 7.34%, and Na2O – 1.41%. These apatites also
have high concentration SrO (up to 2.5, sometimes 4.3%), as it is typical for carbonatites in general. At the same time,
apatites with belovitic scheme of isomorphism in Oktyabrsky agpaitic phonolites are characterized by relatively low
contents of SrO (0.12-0.40%) by very high concentrations of Na2O (up to 2,7%) and REE2O3 (Ce2O3 - up to 7.19 %,
La2O3 – 2.55%, Nd2O3 – 3.96%) and moderate Y2O3 (0.05-0.67%). According to the chemical composition, these
apatites are very similar to Na-REE-apatite (belovitic) in agpaitic feldspar syenite of Ilimaussaq massif (Ronsbo, 1989)
and significantly differ from belovite apatite of Lovozero massif (Chakhmouradian et al., 2002; Bussen et al., 1972)
(above all by the strontium content). In previous publications (Kryvdik, Tkachuk, 1988) the similarity of agpaitic
phonolitic and feldspar syenites in Oktyabrsky and Illimaussak massifs had been noted.
Apatite from alkaline and other magmatic rocks of Ukraine are presented by F-variety, but the contents of
fluorine in these minerals differ among themselves. In a deep eroded massifs (abyssal facies) highly fluorine apatite (up
to 3.6-4.0% F) occur, and in hypabyssal ones – low fluorine (1.5% F and less) varieties and they often associate with
fluorite. The point is that in abyssal conditions fluorine does not form its own minerals (fluorite, REE-F-carbonate,
villiaumite) and belongs to apatite (up to full saturation), as well as in amphiboles and micas (up to 2.6% F). Whereas,
in hypabyssal massifs fluorite and low fluorine apatite as well as poor and fluorineless amphiboles and mica are
crystallized. However, this rule does not apply to agpaitic rocks where apatite is always high fluorine and can associate
with villiaumite (NaF) and/or fluorite.
Consequently, apatite is a very sensitive mineral-indicator of chemistry of mineral-forming environment.

References:
Bussen I.V., Sakharov A.S. Petrology of the Lovozero alkaline massif. Leningrad: Nauka, 1972. 296 p (in
Russian).
Chakhmouradian A.R., Reguir E.P., Mittchell R.H. Strontinum-apatite: new occurrences, and the extent of Sr-
FOR-Ca substitution in apatite-group minerals // The Canadian Mineralogist. 2002. Vol. 40. P. 121-136.
Kogarko L.N. Problem of genesis of agpaititc magmas. Moskow: Nauka. 1977. 294 p (in Russian).
Kryvdik S.G., Legkova G.V., Egorova L.N. Britholite as products of decay in rare earth apatite // Mineralogical
journal (Ukraine). 1990. Vol. 12. P. 92-99 (in Russian).
Kryvdik S.G., Tkachuk V.I. Eudialite-bearing agpaitic phonolites and dike nepheline syenites of Oktyabrsky
massif (Ukrainian Shield) // Geokhimia. 1988. №8. P. 1133-1139 (in Russian).
Marchenko E.Y., Pozharitskaya L.K., Nechelustov G.N. Strekozov S.N. Chemical composition of yttrium-
bearing and rare-earth phosphates in the Azov area (Ukrainian Shield) // Mineralogical journal (Ukraine). 1995. Vol.
17. P. 3-13 (in Russian).
Rønsbo J. Coupled substitutions involving REEs and Na and Si in apatites in alkaline rocks from the Ilimaussaq
intrusion, South Greenland, and the petrological implications // American Mineralogist. 1989. Vol.74. P. 896-901.
Vorobiev E.I. Polyphase type of decay in apatite // Geokhimia. 2000. №5. P. 661-664 (in Russian).

Experimental study of formation of Na-rich majoritic garnet in the context of diamond deep-mantle
genesis
Dymshits A.M.*, Bobrov A.V.*, Litvin Yu.A.**
* Moscow State University, Moscow, Russia, **Institute of Experimental Mineralogy, Chernogolovka,
Russia

The present work summarizes results of experimental study of silicate Prp (Mg3Al2Si3O12) – NaGrt
(Na2MgSi5O12) and Prp – Jd (NaAlSi2O6) as well as silicate-carbonate Prp – Carb (Na2CO3) systems responsible for
formation of sodium bearing garnet solid solution under PT conditions of diamond stability.
 50

The particular interest to Na-rich majoritic garnet arises from that it has been usually found as primary inclusion
into mantle-derived diamonds [1-6] and is known as mineral of rare ultra-deep xenoliths in kimberlites [7]. Of
paramount importance is that the only samples recognized so far as being from the asthenosphere and transition zone
are inclusions of majoritic garnets [8]. All this strongly suggests on possibility of the majoritic garnet formation in all
of the Earth’s mantle environments: upper mantle, transition zone and lower mantle that is reflected in a model
experiment-based PT-phase diagram for the Earth’s mantle material up to 25 GPa [9].
Our earlier experimental studies [10] have showed a good correlation between pressure, temperature and garnet
composition, especially for Si and Na concentrations. Finding of Na-rich majoritic garnets with specific for majoritic
garnet features of extreme high Si (up to 3.5 f.u.) and Na (up to 1.08 wt. %) content [1, 11] suggests for ultra-high
pressure genesis of diamonds which host the majoritic inclusions.
Experimental criterion of syngenesis of diamonds and their inclusions [12] gives plausible arguments for
physico-chemical nature of the mantle diamond-parent medium. It is also strongly applicable to the deep-mantle
formation of diamond with syngenetic majoritic garnet inclusions. Eventually, the experimental solution has to lead to
construction of “syngenesis” phase diagram for the majoritic garnet-bearing diamond-parent medium. The
experimental syngenesis criterion was successfully used on examples of diamond-forming melts of peridotite-
carbonate-carbon and eclogite-carbonate-carbon systems at 7.0 GPa [13-15]. Experimental results demonstrate
syngenetic formation of diamond with silicate peridotitic olivine (Ol), othopyroxene (Opx), clinopyroxene (Cpx), garnet
(Grt) and eclogitic Cpx and Grt minerals. Excess in Si and Na content for eclogitic garnets was identified. The
experimental data are in agreement with the carbonate-silicate (carbonatite) model of diamond genesis [12] and relevant
mineralogical data.
Hence experimental study of diamond-bearing systems potential for crystallization of sodium rich majoritic
garnets is of essential interest for the problem of ultra-high pressure diamond genesis. New experiments have been
carried out at 7.0 and 8,5 GPa for investigation of melting phase relations and compositional ranges of formation of Na-
bearing majoritic garnets in silicate pyrope - Na2MgSi5O12 and pyrope – jadeite joins as well as in silicate-carbonate
pyrope - Na2CO3 join under high pressure and temperature with the use of toroidal anvil-with-hole high-pressure
apparatus. Carbonate inclusions of CaCO3 and CaMg(CO3)2 composition in syngenetic relation with diamond host and
silicate minerals are first reported [16] as the deepest carbonate samples of the Earth’s mantle. This fact is not
contradicts to version of multi-component K-Na-Mg-Ca-Fe-carbonate-silicate parent melt for diamond and carbonate
minerals formation. The version is also supported by experimental conclusions [9]. If diamond-parent melt exists in
transition zone – lower mantle conditions it has to include Na-carbonate component that is undoubtedly indicated by
syngenetic formation of majoritic garnet and diamond.
In the pseudo-binary Mg3Al2Si3O12 – Na2MgSi5O12 system Na-bearing garnet is a liquidus phase up to 60 mol. %
NaGrt. At higher content of NaGrt in the system (>80 mol. %), enstatite (En) and coesite (Cs) are observed as liquidus
phases. Our experiments provided evidence for persistent sodium incorporation in Grt (0.3-0.6 wt. % Na2O) under
temperature and pressure control. The highest sodium contents were obtained in experiments at P = 8.5 GPa. Near the
liquidus (T = 1840˚C), the equilibrium concentration of Na-component in Grt is 5 mol. % Na2MgSi5O12. With the
temperature decrease, Na concentration in Grt increases, and the maximal Na 2MgSi5O12 content of 12 mol. % (1.52 wt.
% Na2O) is gained at solidus condition of the system (T = 1760˚C). Grossular-containing starting materials also
produces Na-garnet (up to 1 wt% Na2O) accompanied by pyroxene and Al-rich phases (kyanite, corundum, and spinel).
The Mg3Al2Si3O12 – NaAlSi2O6 system should be also considered as pseudo-binary, because Na is incorporated
in garnet as Na2MgSi5O12 [17] and pyroxene forms jadeite-enstatite (En) solid solution with Eskola (Esk) Mg0.5AlSi2O6
component. Main phases obtained in experiments were garnet, pyroxene, kyanite (sometimes corundum) and quenched
melt. Liquidus garnet appeared at a temperature < 1800˚C in a wide range of starting compositions and had a stable
Na2O admixture (up to 0.8 wt. % at 8.5 GPa and up to 0.6 wt. % at 7GPa) and elevated Si concentration (up to 3.128
f.u.). At near-eutectic temperatures (~1500˚C) garnet becomes progressively enriched in Na2MgSi5O12 and majorite
Mg4Si4O12. Garnets crystallizing from near-eutectic starting materials (Prp20Jd80) are the most sodium-rich. This fact
indicates the influence of melt alkalinity on the formation of Na-bearing majoritic garnets. It is of interest that the model
system is connected with pyroxene. Significant concentration of Esk molecule (up to 20 mol. %) and jadeite rich
pyroxene and its connection with kyanite may explain formation of natural kyanite eclogite [16] in the frames of
magmatic model. Kyanite crystallizes as accessory mineral of < 5% content in both pyroxene and garnet stability fields.
In pyrope–Na2CO3 system garnet as a solid solution of pyrope, NaGrt and majorite (Maj) was formed in the
range of 15−100 mol% Prp. The highest sodium concentration in garnet (0.8 wt% Na 2O) was registered at 1200˚C.
Starting compositions with <15 mol% Prp produce carbonate and pyroxene as liquidus phases.
The results obtained demonstrate that Na is incorporated in garnet as Na2MgSi5O12component independently on
the starting composition of the system. Thus, mechanism of the formation of Na-bearing majoritic garnets suggested on
mineralogical grounds earlier [18] and experimentally simulated [10] is confirmed. Crystallization of Na-bearing
garnets is mainly controlled by temperature, pressure and composition of the system. Increase of Na concentration in
garnet at constant PT-parameters may result only from the increase of melt alkalinity. Concentration of Na in carbonate-
silicate system is higher then in only silicate one that is indicative for the role of carbonate component in garnet
crystallization. Alkalinity also have positive impact on Na-rich majoritic garnet growth that is in good agreement with
existence of carbonatite inclusions enriched in H2O, CO2, K2O in diamonds under high internal pressure (4-7 GPa) [19,
20]. The increase of pressure causes the growth of melting temperature and regular increase of Na content in garnet.
 51

The study is supported by the INTAS grant 05-1000008-7936 “Diamond and graphite in carbonate magma”, the
RFBR grant 08-05-00110 and the RF President grant NSh-5367.2008.5.

References:
1. Moore R.O., Gurney J.J. Pyroxene solid solution in garnets included in diamonds // Nature. 1985. Vol. 318. P.
553-555.
2. Harte B., Harris J.W. Lower mantle association preserved in diamonds // Mineralogical Magazine. 1994. Vol.
58A. P. 384-385.
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diamonds from Sao Luiz, Brazil. In Fei Y et al. (eds) Mantle Petrology: Field Observations and High Pressure
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Superdeep diamonds from the Juina area, Mato Grosso State, Brazil // Contributions to Mineralogy and Petrology.
2001. Vol. 140. P. 734-753.
6. Stachel T. Diamonds from the asthenosphere and the transition zone. // European Journal of Mineralogy.
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15. Bobrov A.V., Litvin Yu.A. Peridotite-eclogite-carbonatite systems at 7.0-8.5 GPa: concentration barrier of
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Mineral. Petrol. 1971. V. 31. P. 1–12.
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Specifics of global events with which alkaline magmatism is associated

Erlich E.I.
Independent geological consultant,
2879 South Memphis St. Aurora, CO 80013, USA
 52

Summary of radiometric dates of alkaline magmatic rocks show that they are formed in the course of short
(several mln. years) global phases. Such phases are synchronous global wide. Areas of their distribution within certain
phase are not limited by lithosphere plates’ boundaries. It is suggested that the source of magmatic activity is located
below lower lithosphere probably at the boundary between core and lower mantle boundary.
High (0.8-0.95) correlation coefficients between radiometric dates of alkaline rocks on one hand and granitoids
and rejuvenated metamorphic rocks on the other clearly indicate that both types of magmatism are generated by the
same forces. Difference in chemical composition is associated with different tectonic nature of regions where
magmatism occurred. Well known association of kimberlite magmatism with stable cratons (Clifford rule) belongs not
to ancient platforms only but as well to median massifs with different timing of cratonization.

Carboniferous compounds in pegmatites of different genetic types: comparative study

Ermolaeva V.N.*, Chukanov N.V.**, Pekov I.V.***
*Vernadsky Institute of Geochemistry and Analytical Chemistry RAS, Moscow, Russia; e-mail: [email protected]
**Institute of Problems of Chemical Physics RAS, Chernogolovka, Russia;
***Lomonosov Moscow State University, Moscow, Russia
Organic compounds are known in pegmatites of different types. In peralkaline pegmatites, the content of organic
compounds is high as compared with parent magmatic rocks and strongly increases from early-pegmatitic to late,
hydrothermal stages [1, 2]. Similar behaviour is typical for a number of rare non-coherent elements (Th, U, REE, Zr,
Hf, Nb, Ta, W, Sn, Ti): both in alkaline and granitic formations, their contents increase to late-magmatic and
postmagmatic stages. In particular, «thucholite» (carboniferous substance containing U and/or Th) from granitic
pegmatites of Canada, where it was described for the first time, is associated with uraninite, zircon (cyrtolite), titanite,
allanite, samarskite [3, 4]. Carboniferous substance, containing oxides of U, Th, Y, Nb, Zr, was found in parageneses
with uraninite, titanite, allanite, cyrtolite, xenotime, monazite in granitic pegmatites of North Karelia and described as
«carburan» [5, 6]. Bituminous substances from agpaitic pegmatites studied by us earlier, are also associated with
minerals of rare elements including silicates and phosphates of REE, Th, U and show ability to selective accumulation
of all above-mentioned elements [7, 8]. Thus one can suppose the existence of a genetic connection between
carboniferous substances and a specific group of «bitumophilic» elements: U, Th, REE, Zr, Hf, Nb, Ta, W, Sn, Ti.
In this paper, we present the comparative study of carboniferous substances from different types of pegmatites.
In rare-metal pegmatites (Viitaniemi, Finland) [9], spherical inclusions of thucholite up to 1 cm in diameter occur in
sugar-like and lamellar albite in close association with zirkon, tantalite and pyrochlore. In amazonite pegmatites
related to alkaline granites (Ploskaya mountain, Western Keivy, Kola Peninsula) dispersed organic compounds was
discovered by IR-spectroscopy method in thorite from late-pegmatitic [10] albite aggregate. In mica-type granitic
pegmatite (Lopatova Guba, North Karelia), carboniferous substance forms pseudomorphs after cubic crystals of
uraninite and is accompanied by rare-element minerals (monazite-(Ce), xenotime-(Y), zircon). In hyperagpaitic
pegmatite (Koashva mountain, Khibiny massif, Kola Peninsula) large (up to 4 cm) spherical segregations of
bituminous substance occur in aegirine-natrolite aggregates in hydrothermally altered core and are associated with
titanosilicates (astrophyllite, lorenzenite, titanite, lemmleinite-K), zirconosilicate (catapleiite), and chlorbartonite.
Electron microprobe analyses and BSE images have been obtained using the digital scanning electron
microscope CamScan MV2300 (analysts A.N. Nekrasov, A.A. Muhanova, K.V. Van).
All studied samples are inhomogeneous being thin intergrowths of carboniferous substance with minerals of
specific rare elements. By morphological criteria [11], both known mechanisms (namely breakdown of metal-organic
complexes and substitution of uranium minerals by organic substances) can be realized during the formation of
carboniferous substances in pegmatites (Figs. 1, 2). As a result, microscopic crystals of mineral phases, that are
randomly distributed in an organic matrix, were formed. These crystals, in their turn, contain submicroscopic inclusions
of organic matter.
Figure 1. Left – disintegration growths
of thorium-calcium silicophosphate
(Th,Ca,Na)4(Mn,Ti,Nb)1-2(SiO4)4(PO4)·nH2O
in bituminous substance, Lovozero. Back-
scattered electron image. Right – rasvumite
(1) with Sr-containing fluorite rims (2) and
growths of thorium niobosilicate
(Ca,Na)2REETh4(Nb,Ti)1+xSi7-8(O,OH)y
·nH2O (3) in high-sulphur bituminous
substance (4), Khibiny. Back-scattered
electron image.
 53

Figure 2. Congestions of carbon substance (1) in

aggregate of hydroxide (carbonate?) of U and Pb (2) from
carburane, Lopatova Guba deposit. Back-scattered
electron image.

In thucholite from the zone of lamellar albite in the Viitaniemi pegmatite, electron microprobe analyses show
presence of very small (less than 1 m) equant particles of a phase containing only uranium as a detectable element
(presumably, uraninite). In thucholite from sugar-like albite zone in the Viitaniemi pegmatite, uranium is distributed
between carboniferous phase and spherical inclusions of autunite, or meta-autunite, aggregates
(Ca0.89Fe0.25Sr0.11Sb0.07Zr0.04Pb0.02)1.39[U2.08Ox][PO4]2 whereas thorium is present only in a mineral of the brockite-grayite
series with the empirical formula (Сa0.48Th0.39Al0.19Pb0.16Fe0.06U0.04Sr0.03Y0.03Ti0.01Zr0.01La0.01Ce0.01)1.42[PO4]S0.03. In
contrast to above-described samples carburan from Lopatova Guba deposit shows obvious features of the replacement
of a mineral phase (uraninite) by a carboniferous substance. Accumulations of the latter being depleted by mineral
inclusions are present in the polymineral aggregate forming pseudomorphs after cubic crystal of uraninite (Fig. 2).
Mineral phases of carburan are oxides and/or carbonates of U and Pb (U:Pb=3:1 in atomic proportions), uranium
phosphosilicate (U0.69Pb0.15Th0.14Dy0.03)1.01[Si0.61P0.35As0.05]1.01Ox·nH2O, and anglesite.
According to IR-spectroscopic data, all samples of carboniferous substances studied in the present work are
characterized by high contents of H2O and/or OH groups (3100-3600 sm-1). Bitumens from peralkaline pegmatites of
the Khibiny-Lovozero complex are characterized by high contents of both aliphatic hydro-carbone groups (С-Н-
stretching vibrations, the range 2800-3000 cm-1), and unsaturated organic compounds (a series of bands in the range
1200-1680 cm-1). IR spectrum of Viitaniemi thucholite shows lower contents of aliphatic hydrocarbon groups, but
higher contents of aromatic compounds. The phenomenon of entrapping of organic substances by growing crystals of
thorium minerals at low temperatures known in peralkaline pegmatites [7] was detected also in case of thorite from
amazonite pegmatite.
The above data demonstrates the general tendency to co-existence of carboniferous substances with minerals
concentrating specific uncoherent rare elements in pegmatites of different genetic types. Usual presence of minerals of
the above high-valence and high-force-strength transition elements in close association with organic substances in
objects under consideration can be explained by their well-known ability to catalyze many reactions of synthesis and
transformations of organic substances. Thus, we can ascertain in the existence of a group of «bitumophilic»
elements including U, Th, Y, Ln, Zr, Hf, Nb, Ta, Ti, W, Sn. It is remarkable, that this set of elements is very close to
the totality of elements concentrating in solid kaustobiolithes, as it was demonstrated on the basis of very large and
representative statistical material [12, 13]. In granitic pegmatites the temperature of the beginning of carburan formation
is approximately 700С that corresponds to the stage of crystallization of titanite, cyrtolite, xenotime-(Y), monazite-
(Се) and uraninite [5]. Unlike granitic pegmatites, in agpaitic pegmatites the parageneses of carboniferous
substances with rare-element minerals are formed under significantly lower temperatures, corresponding to the
hydrothermal stage.
This study was supported by RFBR grant No. 07-05-00130-а, grant of President of Russain Federation No.
863.2008.5 and grant of the Russian Science Support Foundation (I.V.P.).

References:
1. Florovskaya V.N., Zezin R.B., Ovchinnikova L.I., Pikovsky Yu.I., Teplitskaya T.A. Diagnostics of the Organic
Substances in the Rocks and Minerals of Magmatic and Hydrothermal Genesis. Moscow: Science, 1968. 250
pp. In Russian.
2. Petersilye I.A. Geology and Geochemistry of Nature Gases and Disperse Bitumen of some Geological
Formations of Kola Peninsula. Moscow-Leningrad: Science, 1964. 171 pp. In Russian.
3. Ellsworth R.V. Thucholite, a remarkable primary carbon mineral from the vinicity of Parry Sound, Ontario //
Am. Min. 1928. 13. 419-442.
4. Joubin F.R. Uranium deposits of the Algoma District, Ontario // Can. Inst. Min. Metall. Trans. 1954. 58. 431-
437.
5. Labuntsov A.N. Pegmatites of North Karelia and their minerals // In the book: Pegmatites of the USSR.
Moscow: Academy of Sciences of USSR, 1939. Vol. 2. 260 p. In Russian.
6. Zhirov К.К., Bandurkin G.А. Mineralogical-geochemical features of accessory carburanes from pegmatites of
North Karelia and Kola Peninsula // Materials on mineralogy of Kola Peninsula. Leningrad: Science, 1968. №
6. P. 210-220. In Russian.
 54

7. Chukanov N.V., Ermolaeva V.N., Pekov I.V., Sokolov S.V., Nekrasov A.N., Sokolova M.N. Rare-metal
mineralization connected with bituminous matters in late assambleges of pegmatites of the Khibiny and
Lovozero massifs // New Data on Minerals. 2005. Vol. 40. P. 80-95.
8. Chukanov N.V., Pekov I.V., Sokolov S.V., Nekrasov A.N., Ermolaeva V.N., Naumova I.S. On the problem of the
formation and geochemical role of bituminous matter in pegmatites of the Khibiny and Lovozero Alkaline
Massifs, Kola Peninsula, Russia // Geochemistry International. 2006. Vol. 44. No. 7. P. 715-728.
9. Lahti S. The granitoids and pegmatites of the Eräjärvi area. In: Geological Survey of Finland. 1989. Guide 26.
P. 26-36.
10. Voloshin А.V., Pakhomovskii Ya.А. The minerals and evolution of mineral-forming process in amazonitic
pegmatites of Kola Peninsula. Leningrad, 1986. 168 p. In Russian.
11. Eakin P.A., Gize A.P. Reflected-light microscopy of uranferous bitumens // Mineral. Mag. 1992. Vol. 56. P.
85-99.
12. Yudovich Ya.E., Ketris М.P. Admixtures of useful elements in coals. Ekaterinburg: Publishing House of
Uralian Branch of RAS, 2006. 538 p. In Russian.
13. Arbuzov S.I., Erschov V.V. Geology of Rare Elements in Coals of Siberia. Tomsk: D-Print, 2007. 468 p. In
Russian.

Cenozoic volcanism of the North-Eastern Asia

Fedorov P.I.*, Koloskov A.V.**
* Geological Institute of RAS, Moscow, Russia; ** Institute of Volcanology and Seismology of Far Eastern
Branch RAS, Petropavlovsk-Kamchatsky, Russia

1. At the northeast edge of Asia (Penzhina-Anadyr-Koryak and Eastern Chukotka regions) several stages of
Cenozoic magmatic activity are identifiable, linked to various geodynamic regimes.
The Maastrichtian-Mid-Eocene stage consists of high-Ti, low- and moderate-K tholeiites and alkaline olivine
basalts erupted in pull-apart systems and are connected with the most early rifting stage [Fedorov, Filatova, 1999,
Fedorov, Koloskov, 1999]. Basalts are laterally heterogeneous. The lateral zoning of rocks is expressed in the
replacement of K–Na compositions by potassic subalkaline and alkaline rocks going from southeast to northwest, i.e.,
toward the continent. The tholeiites have high Ti, Hf and low Ta and Nb concentrations. They are characterized by
fractionated REE distribution (Lan/Ybn=1,3-8,7). The isotope ratios of strontium, neodymium and lead are low
(87Sr/86Sr=0,702930-0,704215; εNd=3,8-5,7; 206
Pb/204Pb=18,167-18,340; 207
Pb/204Pb=15, 462-15,531;
208
Pb/ Pb=37,798-38,073; 8Pb=20-28). The alkaline olivine basalts are enriched in titanium (2,0-2,4% TiO2), and
204

are characterized by a strong LREE enrichment and a fractionated REE spectrum (Lan/Smn=1,9-3,9; Lan/Ybn=6,5-19,4).
The Eocene-Oligocene stage is linked to the formation of the Koryak sector of the West Kamchatka-Koryak
volcanic-plutonic belt. The belt is made up of rocks of a continuously differentiated andesite-basalt-rhyolite, moderately
potassic calcalkaline series and comagmatic intrusive granitoids. The rocks are characterized by a low titanium content
(TiO2=0,1-1,2%), high aluminum, and a strong Ta-Nb minimum. The 87Sr/86Sr and εNd ratios have strong lateral
variability (from 0,70447-0,70709 and 0,9-2,9 in rocks of the central Koryak highland to 0,70275-0,70375 and 8,9-11,2
in rocks of the northern portion of the Koryak highland and the Anadyr basin).
The Miocene areals of the Koryak highland are composed of lava flows of tholeiitic basalts, extrusives and
dacite dikes, typical of radiative continental margin rift formation. The basalts are high in titanium (TiO 2=1,3-1,9%),
with a highly fractionated distribution of REE (La n/Smn=1,9-3,9; Lan/Ybn=3,8-11,8) and a clear, negative Ta-Nb
anomaly. The isotope ratios of strontium, neodymium and lead are moderately depleted ( 87Sr/86Sr=0,703289-0,703669;
εNd=3,8-6,0; 206Pb/204Pb=18,20-18,42; 207Pb/204Pb=15,495-15, 524; 208Pb/204Pb=37,877-38,059; 8Pb=16-30).
The late Miocene-early Pliocene melanephelinites of the eastern Chukotka Peninsula are characterized by high
titanium and potassium contents (TiO2=2,6-5%; 2,3-4% K2O with Na2O/K2O=0,8-2,1), strongly fractionated REE
(Lan/Smn=6; Lan/Ybn=35), moderately low isotope ratios of strontium ( 87Sr/86Sr=0,7031080-0,7032970) and lead
(206Pb/204Pb=18,32-18,43; 207Pb/204Pb=15,474-15,509; 208Pb/204Pb= 38,03-38,19; 8Pb=23-29) with high neodymium
ratios (εNd=7,3-7,9) [Apt et al., 1998]. In the northern Priokhotsk area, mid- to late-Miocene melanephelinites are
distinguished by higher concentrations of Ta and Nb and a less fractionated REE distribution (La n/Smn=3,5;
Lan/Ybn=17,8) with more depleted isotope ratios of strontium, neodymium and lead (87Sr/86Sr=0,703036-0,703079;
143
Nd/144Nd=0,513052-0,513054; εNd=8,1; 206Pb/204Pb=17,907-17,925; 207Pb/204Pb=15,42-15,47; 208Pb/204Pb=37,505-
37,693; 8Pb=34-40) [Apt et al., 1998].
The Quaternary stage of volcanism consists of individual lava flows, small cinder cones, necks and dikes making
up the Cape Navarin areal, and also the central-type structures, cinder cones and lava flows of the Aluchin and Anuysky
volcanoes. The alkaline olivine basalts and basanites of Cape Navarin have high high field strength elements and large-
ion lithophilic elements and a strongly fractionated REE distribution (La n/Smn=2,9-4,0; Lan/Ybn=16-21). The isotope
ratios of strontium 87Sr/86Sr (0,703420-0,703918) and neodymium (εNd=4,5-6,7) are controlled by the mixing in of
PREMA and BSE components. The isotopic composition of Pb of these rocks is slightly enriched over chondritic
(206Pb/204Pb= 18,29-18,39; 207Pb/204Pb=15,487-15,543; 208Pb/204Pb=38,099-38,256 и 8Pb=30-40) [Fedorov et al.,
2005]. The subalkaline basalts of the Anuisky volcano and the Monni River lava flow are distinguished by high
concentrations of titanium (TiO2=1,5-1,6%), low aluminum (Al2O3=13,7-15,1%), high Nb and Ta, and a fractionated
 55

REE distribution (Lan/Smn=1,6-2,2; Lan/Ybn=6,7-9,6). However, the basalts of the Monni River lava flow have lower
87
Sr/86Sr ratios (0,702926) and higher 143Nd/144Nd (εNd=8,7), compared to the basalts of the cone of the Anuysky
volcano (0,703769-0,704485 and 3,7-5,4 respectively).
2. The data presented on the composition of the Cenozoic volcanic complexes of the Penzhin-Anadyr-Koryak
and Eastern Chukotka regions show the lateral heterogeneity of the volcanism and the change in the types of the
volcanic sources over the course of the Cenozoic. Most of these basalts are notable for their compositions which
simultaneously contain depleted, intraplate and subduction-zone characteristics [Fedorov, Filatova, 1999].
3. Study of mantle reservoirs for the late-Cenozoic volcanic rocks of the Bering Sea region using Sr-Nd-Pb
isotope systematics (Zou et al., 2000) and the ratios 87Sr/86Sr–206Pb/204Pb allows identificdation of three relatively
separate trends, linked at the baseline by comparable values of 87Sr/86Sr=0,70275-0,70295. This baseline may be
thought of as evidence for a common asthenospheric source. The lead isotope ratios define two sets of points, separated
by 206Pb/204Pb  18,5 and reflecting the influence of two compositionally heterogeneous lithospheric blocks of different
ages: the Asiatic and Alaskan [Koloskov, Fedorov, 2008]. Evidence for a primary role of decompression melting of the
Pacific asthenospheric mantle in this volcanism is given in a number of studies [Portnyagin et al., 2005, Flower et al.,
1998, Koloskov, 2008].

References:
Apt Yu. E., Akinin V. V., Wright J. E. Sr, Nd, and Pb Isotopes in Neogene Melanephelinites and Deep-Seated
Xenoliths from Northeast Russia // Geokhimiya. 1998. № 1. P. 28-37.
Fedorov P.I., Koloskov A.V. Cenozoic volcanism of southeastern Koryak Highland (Northeast Russia):
Petrogenesis of rocks and their formation // Tikhookeanskaya Geologiya. 1999. V. 18. № 5. P. 90-105.
Fedorov P.I., Filatova N.I. Geochemistry and Petrology of Late Cretaceous and Cenozoic Basalts from
Extensional Zones at the Continental Margin of Northeastern Asia //Geokhimiya. 1999. №. 2. P. 1-16.
Flower M.F.J., Tamaki K., Hoang N. Mantle extrusion: a model for dispersed volcanism and DUPAL-like
asthenosphere in East Asia and the Western Pacific / Eds. M.F.J. Flower, S.-L. Chung, C.-H. Lo, T.-Y. Lee. Mantle
dynamics and plate interactions in East Asia. Washington D.C.: AGU, 1998. P. 67-88.
Koloskov A.V. Sr-isotope anomaly on the Kurile islands: possible ways of an explanation // Sci. Conf. Devoted
to Volcanologist Day. 27-29 March 2008. Petropavlovsk-Kamchatsky: IVS RAS, 2008. P. 146-153.
Koloskov A.V., Fedorov P.I. Bering Sea region in the Last Cenizoic: Sr-Nd-Pb isotope systematics of volcanic
rocks // Geochemistry of magmatic rocks-2008. School «Geochemistry of Alkaline rocks». St.-Peterburg, 23-26 May,
2008. P. 76-77.
Portnyagin M., Hoernle K., Avdeiko G. et al. Transition from arc to oceanic magmatism at the Kamchatka-
Aleutian junction // Geology. 2005. Vol. 33. P. 25-28.

Сorrelations between fluorine, iron and titanium contents in magnesium members of the humite group
Gerasimova E.I *,**, Pekov I.V *,**, Kononkova N.N. **
*Lomonosov Moscow State University, Moscow, Russia
**Vernadsky Institute of Geochemistry and Analytical Chemistry of Russian Academy of Sciences
e-mail: [email protected]

Minerals of the humite group are monoclinic and orthorhombic orthosilicates with additional anions, the
members of a morphotropic series with general formula nA2SiO4·A(R)2 with A = Mg, Mn2+, Ca (+ subordinate Fe, Ti,
Zn, etc.) and R = F, OH (+ subordinate O). The group includes magnesium, manganese and calcium members. Five
mineral species form the magnesium subgroup, namely norbergite, Mg3[SiO4]F2, chondrodite, Mg5[SiO4]2F2, humite,
Mg7[SiO4]3F2, clinohumite, Mg9[SiO4]4F2, and hydroxylclinohumite, Mg9[SiO4]4(OH)2. The structures of humite-group
minerals consist of Mg(F,OH)2 layers and nMg2[SiO4] blocks which alternate along the a axis. The silicate blocks have
the same structure as olivine; their thickness increases with increase of n from norbergite to clinohumite.
Magnesium humite-group minerals are widespread in nature. They occur in skarn and skarn-greisen formations,
calciphyres, rhodingites, alkaline-ultrabasic complexes and some other types of rocks. They can be not only accessory
but also rock-forming minerals.
We have obtained 277 electron-microprobe analyses of magnesium members of the humite group: 23 for
norbergite, 167 for chondrodite, 46 for humite and 51for clinohumite and hydroxylclinohumite. The empirical formulae
were calculated on the basis of 4 cations (A+Si) for norberhite, 7 for chondrodite, 9 for humite, and 13 for clinohumites.
From these data, the average values and ranges of contents of fluorine (wt.% and apfu), iron [Fe/(Mg+Fe+Ti+Mn+Zn),
in atom proportions] and titanium [Ti/(Mg+Fe+Ti+Mn+Zn), in atom proportions] were calculated (Tables 1 and 2).

Table 1. Fluorine, iron and titanium contents (wt.%: average values and ranges) in the studied minerals
F TiO2 FeO
15.7 0.25 0.96
Norbergite 0.01- 0.07-
13.5-18.6
0.68 3.12
6.8 0.40 4.41
Chondrodite
0.0-10.9 0.00- 0.02-
 56
7.91 11.78
2.5 1.58 3.85
Humite 0.00- 0.12-
0.0-5.7
5.48 11.84
1.9 1.39 3.74
Clinohumite 0.00- 0.09-
0.0-4.4
5.34 12.49

Table 2. Contents of fluorine (apfu), iron (Fe/ΣMe) and titanium (Ti/ΣMe) and total value of Fe+Ti (Ti+Fe)/ΣMe:
atom proportions, average values and ranges
F Fe/ΣM Ti/ΣMe (Ti+Fe)/
e ΣMe
1.8 0.009 0.002 0.011
Norbergite 1.5- 0.000- 0.003-
0.000-0.004
2.4 0.030 0.034
1.3 0.043 0.004 0.047
Chondrodite 0.0- 0.000- 0.000-
0.000-0.070
2.2 0.118 0.121
0.6 0.039 0.015 0.054
Humite 0.0- 0.001- 0.008-
0.000-0.052
1.5 0.125 0.176
0.6 0.038 0.013 0.050
Clinohumite 0.0- 0.001- 0.004-
0.000-0.049
1.5 0.129 0.178
Note: ΣMe=(Mg+Fe+Ti+Mn+Zn)

Not only maximum F amount but also minimal values of Fe/ΣMe and Ti/ΣMe ratios are typical for norbergite.
Chondrodite is characterized by intermediate value for F, maximum for Fe and, like norbergite, very low amount of Ti.
Humite and clinohumite can be united as minerals with very close to each other, medium values of all discussed factors
(Table 2). Thus, we can distinguish three subgroups: 1) norbergite, 2) chondrodite, and 3) humite and clinohumite, with
individual features of Fe and Ti distribution.
Diagrams below show correlations between contents of Fe (Fig. 1a, c, d), Ti (Fig. 1b, d, f) and F in chondrodite,
humite and clinohumite (no reason to make such diagrams for norbergite with very low contents of Fe and Ti). Fe
content in humite and clinohumite increases with F increase while the content of Ti decrease. There are the anomalous
points (in the oval) for both minerals. In one case (arrow I) the content of F increases with decrease of Ti content in
clinohumite (Fig. 1d); in the other case (arrow II) increase of F does not correlate with the Ti/ΣМе ratio. Some values
for humite and clinohumite (in the oval) are not in common trends: the highest Fe content were found in F-poor
samples. Decrease of Ti in chondrodite also correlates with increase of F content. The graph of Fe:F correlation for
chondrodite is quite different from ones for other studied minerals. The Fe/ΣМе ratio increases with F content increase:
a field with the most concentration of points is in the range of 1.0 – 1.8 apfu F (Fig. 1i)
 57

Fig. 1. Correlations between Fe, Ti and F contents in humite, clinohumite and chondrodite

The conclusions from the above-discussed empirical data are as follows:

1) The negative correlation between Ti and F in the humite minerals is not caused by the F → OH substitution.
It is the most probably described by the following scheme: Mg2+ + 2F- → Ti4+ + 2O2-.
2) The Fe/ΣМе ratio in humite and clinohumite increases with increase of F content. Is could not be explained
basing on simple schemes of substitutions and requires a study of local situations in the structures of the
minerals. It could be caused by ordered distribution of Mg and Fe and differences in their anion
coordination.
3) In chondrodite, a “competition” of Fe and Ti takes place (Fig. 2a). The inverted situation (Fig. 2b, c) is, in
general, observed in humite and clinohumite: Ti and Fe correlate positively. Causes of these differences are
still not clear.

a b c
 58

Fig. 2. Correlations between Fe and Ti contents in humite, clinohumite and chondrodite

Thus, the statistic investigation of the correlations between fluorine, iron and titanium in magnesium members of
the humite group raised the more questions, than the answers were given. To clarify the nature of these empirically
found regularities, a structural study has been initiated.

Influence of melt composition on Fe, Mn, and Ni partitioning between carbonate-silicate melts and
mantle minerals: experiments and applications to the genesis of kimberlites and inclusions in
diamonds
Girnis A.V.*, Bulatov V.K.**, Brey G.P.***
* Institute of Geology of Ore Deposits, Petrography, Mineralogy and Geochemistry, Russian Academy of
Sciences, Staromonetny 35, Moscow, 119017 Russia
** Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, ul.
Kosygina 19, Moscow, 119991 Russia
*** Instutut für Geowissenschaften, J.-W. Goethe Universität, Altenhöferallee 1, D-60438 Frankfurt am
Main, Germany

It is commonly believed that the composition of kimberlites and xenoliths in them provide insight into the
composition of deep mantle zones. This suggestion is based on the concept of kimberlite formation by low-degree
melting of volatile-bearing peridotites in deep lithospheric or asthenospheric mantle zones. In this connection, the high
mg numbers of kimberlites and kimberlite-borne mantle xenoliths is regarded as evidence for the strongly depleted
character of kimberlite mantle sources (e.g. Becker, LeRoex, 2006; Bernstein et al., 2007). Quantitative interpretation of
these data requires the knowledge of element partitioning between primary kimberlite melts and peridotitic minerals.
The composition of primary melts formed in a carbonated peridotite under conditions of kimberlite magma genesis is
strongly dependent on temperature and ranges from carbonatitic (~5 wt % SiO 2) to carbonate-silicate kimberlite-like
compositions (30 wt % SiO2). It was shown that the partition coefficients of trace elements are variable within this
composition range (Girnis et al., 2006). We explored experimentally the behavior of some siderophile elements during
melting of carbonated peridotite at 6-10 GPa and 1200-1700°C. The experiments were carried out in a multianvil
apparatus using the method of pressure-induced melt segregation (Brey et al., 2008). The starting materials were
prepared from natural mantle minerals (SC-1 sample used by Brey et al., 2008) with addition of carbonate, carbonate +
water, and carbonate + calcium fluoride. In all cases, CO2 was the major volatile component. Experimental products
were analyzed using a JEOL Superprobe 8900 electron microprobe with five wavelength spectrometers. Fluorine was
analyzed with the electron microprobe, but water and CO 2 were only approximately estimated on the basis of analytical
totals and mass balance considerations.
The obtained results showed that the melt composition is strongly variable depending on temperature and the
bulk composition of starting peridotite. The lowest temperature melts are dominated by carbonates and contain about 5
wt % SiO2. With increasing temperature, the SiO2 content increases gradually to about 30 wt % at 1600-1700°C at 6-10
GPa. Simultaneously, the Ca/Mg ratio of the melt decreases appreciably and the melt approaches the field of kimberlite
compositions. The partition coefficients of Fe, Mn, and Ni between melts and minerals are also strongly variable, which
is illustrated in Figs. 1 and 2. It is known that the olivine-melt KdFe-Mg is close to 0.3 within a wide range of
thermodynamic conditions and melt composition. Our results show that Kd Fe-Mg is close to or even lower than 0.3 in
high-temperature kimberlite-like melts and increases to more than 0.5 in carbonate-dominated melts (Fig. 1). The
increase is especially significant in carbonate-fluoride melts containing more than 10 wt % F, where the mg-number of
olivine is very close to that of the coexisting melt (i.e. Kd Fe-Mg approaches 1). The similar effect is observed for Mn
partitioning (Fig. 2), i.e. Mn tends to partition into olivine as melt becomes poorer in SiO 2. The effect is especially
pronounced for F-bearing systems. The partition of Ni is known to be strongly temperature-dependent. Variations in
olivine-melt DNi are consistent with the temperature dependence obtained for volatile-free system. Within the analytical
errors, no significant effect of CO2 on Ni partitioning was established. Nonetheless, there is also a distinct increase in
DNi in F-bearing system. The same tendencies were observed for Fe and Mn partitioning between garnet and melt (Ni in
garnet was too low for reliable microprobe analysis).
 59

0.8 Partial melts

from carbonated

Melt
F-bearing peridotite

: (Fe/Mg)
0.6

Ol
(Fe/Mg)
0.4

0.2 Partial melts Partial melts

from carbonated from "dry"
peridotite peridotite
0
0 10 20 30 40 50 60
S iO 2 in melt, wt %

Fig. 1. Fe-Mg distribution coefficient between olivine and melt obtained in partial melting experiments with
natural CO2-free anhydrous peridotites (crosses, data from the literature), carbonate-bearing peridotites with an without
additional H2O (filled circles, our data), and carbonate-bearing peridotite with F (triangles, our data).

2
1.8
1.6

1.4
Melt

1.2
Mn : Mn

1
Ol

0.8

0.6

0.4
0.2
0
0 10 20 30 40 50 60
S iO 2 in melt, wt %

Fig. 2. Mn partitioning between olivine and partial melts from experiments with mantle peridotites. Symbols are
the same as in Fig. 1.

Thus, the obtained results show that the partitioning of Fe, Mn, and Ni between mantle melts and residual
minerals is strongly dependent on thermodynamic conditions and the bulk composition of peridotite. In particular, the
presence of volatile components significantly affects the behavior of these elements. A transition from CO 2-free
systems to carbonate-silicate compositions is associated with considerable changes in Kd Fe-Mg and DMn values. The
addition of F significantly increases this effect and makes Fe, Mn, and Ni more compatible in silicate minerals. This
dependence must be taken into account during modeling of mantle magmatism, especially at low degrees of melting.
The high olivine-melt KdFe-Mg values obtained for carbonate-rich melts suggest that kimberlite melts with high Mg/Fe
ratios could be derived from a less depleted source than it was supposed on the basis of Kd Fe-Mg values for CO2-free
silicate liquids. In particular, the presence of very highly magnesian olivines (mg > 0.95) as inclusions in diamond (e.g.
Creighton et al., 2008) does not necessarily implies the existence of an ultradepleted source (more depleted than the
residue after komatiite extraction), but can result from local effects related to redox reactions in volatile-rich melts. If a
carbonate-rich melt is formed in equilibrium with mantle peridotite containing olivine with mg = 0.90, its mg-number
will be high (~0.83) owing to the high Kd Fe-Mg values for carbonate-dominated melts. Then, carbonate components may
be lost owing to decarbonation and/or redox reactions (including diamond crystallization). In such a case, the mg value
of melt will remain unchanged, but much more magnesian olivine will crystallize from it owing to an increase in Kd Fe-
Mg
value (mg = 0.94 for KdFe-Mg = 0.3).
 60

References
Becker, M., Le Roex, A.P. (2006). Geochemistry of South African on- and off-craton, group I and group II
kimberlites: Petrogenesis and source region evolution. Journal of Petrology 47, 673–703.
Bernstein S., Kelemen P).B., Hanghoj K. (2007). Consistent olivine Mg# in cratonic mantle reflects Archean
mantle melting to the exhaustion of orthopyroxene. Geology 35, 459-462.
Brey, G.P., Bulatov, V.K., Girnis, A.V., Lahaye, Y. (2008). Experimental melting of carbonated peridotite at 6–
10 GPa. Journal of Petrology 49, 797–821.
Creighton S., Stachel T., McLean H. (2008) Diamondiferous peridotitic microxenoliths from the Diavik
Diamond Mine, NT. Contributions to Mineralogy and Petrology 155, 541-554.
Girnis A. V., Bulatov V. K., Lahaye, Y., Brey G. P. (2006). Partitioning of trace elements between carbonate-
silicate melts and mantle minerals: experiment and petrological consequences. Petrology 14, 492-514.

Experimental investigation of the interaction of basaltic melts with peridotite with implication for
mantle-crust interaction and magma origin
Gorbachev N.S., Kostyuk A.V., Nekrasov A.N.
Institute of Experimental Mineralogy RAS, Chernogolovka, Russia

The geophysical and geochemical data testify to a large-scale exchange of substance between a crust and a
mantle. The major mechanism of such interaction is subduction of oceanic slab. Consequence of this process can be
formation in a mantle of the chambers containing alongside with peridotite of protolithes ancient subducted of an
oceanic slab. For experimental modelling melting of such source the system peridotite-basalt-volatile (Н2О, Н2О+СО2)
in interval Т=1250-1400ºС, Р = 1.5-4.0 GPa, at content of volatiles in system 3-5 wt.% was investigated.
Experiments were carried out using of apparatus high pressure (piston cilinder and anvil with hole) by a
quenching technique. It was used two ampoules (platinum + peridotite) method (fig.1).

Fig.1. Back scattered electron images of the typical experimental sample. On the left –peridotite ampoule filled
of silicate glass, sulfide. Sharp grey zone – area of interaction between silicate melt and peridotite; on the right - reaction
zone between glass (melt) and peridotite with Opx substitute for Ol

At interaction with peridotite melts, formed at melting of initial tholeiite or olivine basalt, ("reactionary" melting,
the model of the closed system) were formed magnesian melts picritic-basalt type (tabl.1, № 1-2). At interaction of
andesite melts with peridotite (the model of the open system), were formed SiO2-rich magnesian melts lake boninites
(tabl. 1, № 3). The volume "reactionary" melts was defined by volume of initial basalt.
In parallel with "reactionary" melting, there was a partial, "film" melting peridotite which degree did not exceed
5 % . In result of partial melting of peridotite were formed intergranular melts andesite-dacite type (tabl. 1, № 4).
The composition of liquidus associations, equilibrium with magnesian "reactionary" melts answered garzburgites
Ol+Opx, and in the some cases - pyroxenites Cpx+Opx (fig. 2). Absence of Ol on the liquidus of magnesian basalts it is
possible to explain reactions (1-3) of Ol with formed basalt melts:

Mg2SiO4 (Ol) + SiO2 (m) = 2MgSiO3 (Opx);

Mg2SiO4 (Ol) + Al2O3 (m) = MgSiO3 (Opx) + MgAl2O4 (Sp);
Mg2SiO4 (Ol) + MgSiO3 (Opx) + Al2O3 (m) + SiO2 (m) = Mg3Al2 [SiO4]
 61

Tabl. 1. Major elements compositions (wt. % oxides) of the typical hydrous “reaction” (1-3) and intergranular
(4) mels. P = 2 GPa, T =1350ºC. The types of starting basalts: 1 – tholeiitic, 2 – olivine, 3 – andesitic. 4 - intergranular
melt.
№
SiO2 TiO2 Al2O3 FeO MgO CaO K2O Na2O Total
1 47.2 1.2 9.6 14.9 12.8 6,5 0.6 2.4 95, 2
2 46.0 1.0 11.2 14.3 13.5 7.0 0.7 2.2 95.0
3 61.2 0.6 12.7 6.9 10.4 5.0 1.4 1.2 99.5
4 62.8 0.7 14.9 2.7 0.3 5.7 1.8 1.1 90.0

Fig. 2. Back scattered electron images for experimental samples, which show of the "reactionary" and "film"
melting peridotite and character interaction between silicate melt and peridotite: Gl1 - the "reactionary" Gl2 –
intergranulary melts; on the left side – Ol peridotite-melt equilibrium, on the right side – Opx substitute for Ol .

Experiments have shown, that melting mantle with protolithes of an oceanic slab at "reactionary" melting for
produce magnesian melts so high temperatures not required as at direct partial melting peridotite. At identical Т and Р
volume generated melts, taking into account volume basitic components subduction oceanic slab, are much higher than
melts, formed at direct partial melting peridotite. Intraplate magmatism, including formation of huge magmatic
provinces can be connected to melting of the chambers, containing protolithes of an ancient oceanic slab.

Ion-exchange properties of terskite. II. Experimental study in mixed solutions

Grigorieva A.A.*, Pekov I.V.*,**, Bryzgalov I.A.*
*Lomonosov Moscow State University, Moscow, Russia;
**Institute of Geochemistry and Analytical Chemistry RAS, Moscow, Russia

Terskite, Na4ZrSi6O16·2H2O, is a zeolite-like zirconosilicate. The base of its crystal structure is a framework
consisting of branched chains of Si tetrahedra linked by isolated Zr-octahedra. Na atoms and H2O molecules are located
in the cavities of the framework (Pyatenko et al., 1999).
It was experimentally found that terskite has strong cation-exchange properties. Na can be easily exchanged to
K, Rb, Cs, Ca, Sr, Ba or Pb in solutions of their salts even under room conditions (Grigorieva et al., 2008).
Cation exchange properties of terskite can occur in nature. We can assume that cation composition of natural
solutions is heterogeneous. Basing of this assumption, we made a series of the ion-exchange experiments with mixed
(polycationic) solutions to study a character of selectivity of terskite. In the experiments, samples of terskite from the
Shkatulka pegmatite (Mt. Alluaiv, Lovozero alkaline massif, Kola Peninsula, Russia) were used. Several series of
experiments were performed: for twenty-four hours under room temperature and for three hours under 90 and 120°C.
Equivoluminous mixtures of 1M solutions of: (I) KCl and ВаCl2; (II) KCl, RbNO3, CsNO3, CaCl2, SrCl2 and BaCl2;
(III) KCl and CsNO3; (IV) CsNO3 and BaCl2 (last – only under 90°C and 120°C) were used.
Terskite demonstrates cation-exchange properties in all experiments. In the solution I (K+Ba), Na was the most
strongly replaced by Ba. As the temperature increases then the ability of the mineral to exchange Na to K decreases,
while for Ba, we observe significant increase of the exchange degree.
In the solution II (K+Rb+Cs+Ca+Sr+Ba) under the room temperature, monovalent cations enter to the mineral
the most strongly. Under 90ºC, Na replaced by both monovalent and bivalent cations. Under 120ºC, the degree of
exchange of Na by bivalent cations increases greatly. It is more strongly replaced by Ca (up to 3.2 wt. % CaO: recorded
in the samples tested under 120º while after the experiments under the room temperature, only up to 0.7% CaO was
found). At the same time, K content decreases: up to 0.5 % K 2O after the experiment under 120ºC while up to 1.3 % -
 62

under room conditions. Degree of exchange of Na to Cs decreases twice with the temperature increase: 4.1% Cs 2O was
recorded in the samples after experiments under 120ºC while up to 9.8 % - under the room temperature.
The series of experiments with the solution III (K+Cs) did not show considerable changes with temperature
increase. The replacement of Na by Cs is the strongest in all cases.
In the solution IV (Cs+Ba), increase of content of a monovalent cation (Cs), but not bivalent cation (Ba), is
observed with temperature increase: up to 8% BaO was recorded in the samples after experiments under the 90ºC and
up to 15 % BaO – under the 120ºC.
Thus, Na in terskite can be replaced by all cations used in the experiments. The strongest cation exchange was
recorded for Cs and Ba. The experiments showed that in the solutions with the most diversity of cations (solution II), a
role of reactions with bivalent cations rises with temperature increase. Under room conditions, the strong preference of
replacement of Na by other monovalent cations is observed. The only exception is the case of the solution IV (Cs+Ba):
temperature increase gives rising of degree of replacement of Na by Cs but not Ba.
This study was supported by grants of President of Russain Federation Nos. 863.2008.5 and 2192.2008.5 and
grant of Russian Science Support Foundation (I.V.P.).

References:
Grigorieva A.A., Pekov I.V., Bryzgalov I.A. Ion-exchange properties of natural zirconosilicate terskite //
Minerals as Advanced Materials I. Springer Verlag, Berlin – Heidelberg, 2008, 87-89.
Pyatenko Yu.A., Kurova T.A., Chernitsova N.M., Pudovkina Z.V., Blinov V.A., Maksimova N.V. Niobium,
Tantalum and Zirconium in the Minerals. M., IMGRE, 1999. 212 p.

New isotope data of carbonatites and albitite from Gremyaha-Vyrmes massif

Groznova M.V., Zaitsev V.A., Sorokhtina N.V., Kogarko L.N.
Institute of Geochemistry and Analytical Chemistry RAS, Moscow, Russia

Gremiakha-Vyrmes massif is located in north-east part of Kola Peninsula. Massif is extended in north-east
direction; it is 19 km long and 4-6 km width. It crosses mica- and oligoclase- granite gneisses of late-Achaean Kola –
Belomorean Sea complex.
Massif includes four spatial-connected rock complexes, which were formed one after another. They are: 1)
peridotites- pyroxenites- gabbro- anorthosites - and akerite-pulaskites; 2) alkaline syenites- alkaline granites 3)
nepheline syenites – juvites-ijolites-urtites (Kukharenko et al, 1971; Arzamastsev et al, 2006); 4) veins of alkaline
metasomatites and carbonatites with the thickness up to tens cm, crossing the rocks of basite-ultrabasite and foidolite
complexes (Osokin, 1987; Savatenkov et al, 1999). Alkali metasomatites and carbonatites are the latest phase in massif.
Earlier the similar rocks, located to secondary tectonic disturbances, were considered as the late hydrothermal veins,
connected with region-metamorphic processes (Polcanov et al, 1967).
Carbonatites belong to soevite type. Calcite-rich carbonatites are located in Aegirine Navolok section in the
central zone of massif and are surrounded by the foidolitic rocks. We analyzed two parageneses - rare graphite-bearing
calcite-rich carbonatites and graphite-free carbonatites. The first association, which is essentially alkaline, consists of
calcite, aegirine, biotite, substantial amount of albite and orthoclase, graphite, fluorapatite, titanite, zircon, some
unknown Ca and K silicates, rare ferriallanite-(Ce) and sulphides. The second association consists of ilmenite in place
of titanite, minor amount of albite and orthoclase, pyrochlore. Chemical composition of calcite from both parageneses is
identical and the mineral enriched in Sr up to 3 wt %. Graphite forms individual spherulites, sometime it contains single
inclusions of calcite.
Punlished data of the age of Gremiakha-Vyrmes rocks show their paleoproterozoic age. Variation of ages is from
1600-1675 Ma (K-Ar method (Polcanov et al, 1967)) to 2070±110 Ma (Sm-Nd method by foidolite complex rocks
(Kogarko, Karpenko, 1998)) and 2034±46 Ma (Sm-Nd method by calcite in carbonatites (Savatenkov et al., 1999)).
To establish more detailed age of carbonatites from this massif we studied Rb/Sr and Sm/Nd isotopic systems for
two samples of carbonatites and one sample of albitite from drill core on Aegirine Navolok.
Carbonaites was divided to silicate and carbonate parts by the chemical method. 30-50 g of crushed rock was put
in 2M HCl to dissolve carbonate fraction. Solution was decanted. Isotope study was carried out on mass-spectrometer
«Tims Triton» (GEOKHI RAS).
For graphite-bearing carbonatite Sm-Nd method shows age 1922±26 Ma and initial isotopic ratio
43
Nd/144Nd(T)=0.510261±18 , ENd =+2.2, MSWD=0.31 (fig. 1). Bulk-rock isotopic composition of graphite-free
carbonatite and albitite, recalculated to this age shows similar initial ratio 143Nd/144Nd(T=1922Ma)= 0.511591 ENd =+1.93
and 0.510266 ENd =+1.91 correspondingly.
Rb-Sr method shows for graphite-bearing carbonatite the age estimation 1713±16 Ma, and initial isotopic ratio
87
Sr/86Sri=0.702619±13, MSWD =1.11 (fig. 2), and for graphite-free carbonatite - 1730±16 Ma, initial isotopic ratio
87
Sr/86Sri=0.702719±12, MSWD =0.0023 (fig. 3). For albitite measured 87Sr/86Sr ratio is 0.707421±26 with 87Rb/86Sr
ratio of 0.50. After recalculation to the ages, estimated from carbonatites by Rb/Sr method, shows estimation
87
Sr/86Sri=0,6949, that is notably lower than we can see for carbonatites.
 63

Fig. 1. Isochrone for graphite-bearing carbonatite from Gremiakha-Vyrmes.

Fig. 2. Isochrones for graphite-free carbonatite (left) and for graphite-bearing carbonatite (right) from Gremiakha-
Vyrmes.

We suggest that Sm/Nd age estimation shows the true age of rock crystallization. Rb/Sr age estimations can be
explained by late metamorphic event (Pushkarev, 1990).
The study is supported by the INTAS grant 05-1000008-7936 “Diamond and graphite in carbonate magma” and
the RFBR grants
Referenses
Kukharenko, Bulakh A.G., Il’inskiy G.А. et al. Metalloorganic specifies of alkaline formations of East part of
Baltic shield // Trudy Lenengradskogo obschestva estestvoispytateley. Leningrad: Nedra, 1971. Vol. XXII. № 2. 280 p.
Arzamastsev A.A., Bea F., Arzamastseva L.V., Montero P. Protherozoic polyphase Gremiakha-Vyrmes massif,
Kola Peninsula: an example of mixing of basic and alkaline mantle melts // Petrology. 2006. Vol. 14. N 4. P. 384-414.
Osokin А.S. The placing and substance composition of apatite-titanomagnetite-ilmenite ores of Gremiakha-
Vyrmes massif. Apatity, Kola Branch RAS USSR. 1987. P. 90.
Savatenkov V.M., Pushkarev Y.D., Sergeev A.V., Sulimov R.B. Carbonatites of Gremiakha-Vyrmes massif as
indicator of new ore specialization of the massif (Russia) // Geology of ore deposit. 1999. Vol. 41. № 5. P. 449-454.
Polcanov А.А., Eliseev N.А., Eliseev N.E., Kavardin G.I. Gremiakha-Vyrmes massif, Kola Peninsula. Moskow:
Science, 1967. 236 p.
Karpenko S.F., Kogarko L.N. The source of protherozoic alkaline magmatism of Eastern part of Baltic shield //
Abstracts of XV Symposium by Geochemistry of isotopes by the name of academician А.P. Vinogradov. М. GEOKHI
RAS. 1998. P. 120.
Pushkarev Yu.D. Mega-cycles in the evolution earth crust-mantle system // Leningrad: Science, 1990. 216 p.
 64

Petrology and geochemistry of alkaline lavas Holzun ore district of Gorny Altay
Gusev A.I.*, Gusev N.I.**
*Biisky pedagogical state univercity, Biisk, Russia; Federal State Unitary Enterprise «A.P. Karpinsky
Russian geological research institute», Saint Petersburg, Russia
Holzun apatite-magnetite with REE deposit locate on the border of Republic Altay and Kaxahstan on the divide
of rivers Haidun and Talovy Turgusun. The ore country rocks of Holzun deposit exhibit by volcanogenic-sedimentary
Korgon suit (D1-2 krg). The two sequences derive in composite of Holzun ore horizon: low sedimentary-volcanogenic
with lavas and tuffs of trachytes, pantellerites, rhyolites, seldom trachyandesite and trachybasalt composites and upper
volcanogenic-sedimentary with lavas and tuffs of middle-alkaline rhyolite composite with seldom comendites.
The ore horizon extend in ore district more 9 km and it located to more deflect of Korgon trough that it is
elongate on N-N-W direction on 70 km. An all lavas on diagram TAS produce trend from phonotephrite to
trachyandesite, trachyte, tracydacite and rhyolite, felsite and attribute to high- K suite (fig. 1).

Figure 1. Diagram (Na2O+K2O) – SiO2 after (Peccerillo, Taylor, 1996) for lavas deposit Holzun
1- trachybasalt, 2- trachyandezibasalt, 3- trachyte, 4- tracydacite and trachyandesite, 5- felsite, 6- pantellerites, 7-
comendite.

In lavas of deposit Holzun observe maximum of Rb, K 2O, Be, Nb, Ta and F and minimum of B, Pb, H 2O and S,
that these characterize to mantle oceanic plumes. The model chondrit-normalized REE pattern show on figure 2.

Figure 2. Rare earth element patterns for rock types of Holzun areal Other legend on fig. 1.

The values of tetrad effect fractionation elements in all rocks for exclusion felsites (1, 12) are not reaching
considerably level. The tetrad effect fractionation in ribbon felsites classify to M-type. As is known, tetrad-effect M-
type detect in high evolutionary granitoid systems and volcanic series on late stages of differentiation (Masuda,
Ikeuchi, 1979). In consequence the mechanism of forming lavas Holzun deposit followed fractionation REE at the most
acid lavas differentiates – ribbon felsites.
High-K lavas of deposit Holzun form close trend to line regress of continental intraplate settings and mantle of
cjntinental plums on diagram of ratio tantalium to niobium. (fig. 3).
 65

Figure 3. Diagram ratio concentrations Ta – Nb for lavas deposit Holzun

Lines equations regression after (Kovalenko et al., 2007): I - for magmas MОR и DM (depleted mantle); II – for
oceanic island and mantle oceanic plums; III – continental intraplate settings and mantle continental plums. Other
legend on fig.1.
Close position of trend for lavas Holzun observe and on diagram of ratio uranium to niobium. The principal
distinct confine in appreciably more high concentrations of uranium in rocks of Holzun deposit and trend for rocks
types is perpendicular to line of regress intraplate settings and mantle continental plums.
High-K lavas of Holzun form common trend from trachyte and trachyriodacite to felsites and comendite on
diagram Th/Yb – Ta/Yb and confine in field intraplate mamgatism (fig. 4). There are confined wholly in field of basalt
association of archipelago Kergelen and partially in field of alkaline basalts and partially in field of alkaline basalts of
Baykal rift zone and gravitate to average composition alkaline basalts of oceanic islands (OIB).

Figure 4. Diagram Th/Yb – Ta/Yb for high-K lavas Holzun deposit.

Digital show fields of compositions: 1- tholeiites volcano Mauna Kea, Hawaii (Frey et al., 1991); 2- basalts
association archipelago Kergelen; 3- alkali basalts of Baykal rift zone; 4- traps of Deccan and Parana (Wilson, 1989).
The ratio of isotopes 87Sr/86Sr и 143Nd/144Nd for volcanogenic rocks of Holzun areal adjust influence mantle
source type PM in mantle array and evolution compositions to direction mantle source type EM 2, that it is typically
interpret how result of enriching mantle reservoir by subduction continental sediments. The evolution of basalt
magmatizm obey trends batch melting of mantle source type PM and influence subduction fluids with localization
composites volcanic rocks near boundary of plums and nonplums sources.

References
1. Frey F.A., Garcio M.O., Wise W.S. et al. The evolution of the Mauna Kea Volcano, Hawaii: Petrogenesis of
tholeitic and alkaline basalts // J. Geophis Res. 1991. V. 96. № B9. P.14347-14375.
2. Kovalenko V.I., Naumov V.B., Girnis A.V., Dorofeeva V.A., Jarmoluk V.V. Average contents magmas and
mantle Middle Oceanic Ridge and intraplate oceanic and continental settings on data study melt inclusions and chilled
glass of basalts // Petrology. 2007. V. 15. № 4. P. 361-396 (Russian).
3.Masuda A., Ikeuchi Y. Lanthanide tetrad effect observed in marine environment // Geochim J. 1979. V. 13. P.
19-22.
4. Peccerillo A., Taylor S. R. Geochemistry of Eocene calc-alkaline volcanic rocks from the Kastamonu area, Northern
Turkey// Contrib. to Mineral. and Petrol. 1996. 58. P. 63–81.
5. Wilson M. Igneous petrogenesis. London: Unwin Human. 1989. 466 p.
 66

Petrogenesis of some alkaline and sub alkaline basalts from Egypt

Hussein Aziz Hegazy
Geology Department, Assiut University,Assiut, Egypt
Email: [email protected]
Phone.002088 2321015

In an effort to understand the petrogenesis of mid-certiary basalts in Egypt, basalts samples from Sharm El-Qibli
and Sharm El-Bahari (Red Sea Coast), Mir (NW of Assiut) and Abu Roash (W. of Cairo) were studied mineralogically
and geochemically. Chemical analysis shows that they include oversaturated tholeiites and undersaturated, nepheline –
normative alkali basalt. Discrimination diagrams indicate that the basalts, erupted in anorogenic, within-plate
environment. The oceanic affinities apparent on the initial rifting stage of the Red Sea.
The content of P2O5 and K2O indicate that the tholeiitic basalt from Abu Roash and Sharm El-Bahari were
generated by 21-23% partial melting of pyrolite mantle at pressures less than 15 Kb, whereas the alkali basalt magma of
Sharm El-Qibli was formed at greater depth at 15-25 Kb. The crystallization temperature, deduced from the MgO
content was 1060ºC for the basalt from Mir, and between 1100ºC to 1200ºC for the basalts from the other localities.
Fe/Mg index, Mg/Mg+Fe and mafic/Felstic ratio indicate an increasing degree of fractionated prior to extrusion
in the following order: Sharm El-Bahari, Abu Roash and Mir. The close occurrence of alkali basalt at Sharm El-Qibli
and tholeiitic basalts at Sharm El-Bahari, might suggest the presence of deep fractures of varying extension tapping
magmas originating at different depths.

The Kola Peninsula as a unique alkaline mineralogical province

Khomyakov A.P.
Institute of mineralogy, geochemistry and crystal chemistry of rare elements, Moscow, Russia.

The second half of the 20th and the beginning of the 21st century have witnessed an unprecedented increase in
the rate of new mineral discoveries, as a result of which the overall mineral system has grown from 2000 to more than
4000 species in a relatively short time. By far the largest contribution to this achievement has come from the Kola
region, where the first 80 years of detailed research (1890 to 1970) yielded 45 mineral species new to science, whereas
the subsequent 35-year period (1970 to 2005) yielded about 200 new species. The 15-year period from 1991 to 2005
was particularly fruitful, producing 113 new IMA-approved minerals (Khomyakov, 2006). An unusually high rate of
these discoveries is indicated by figures relating to three equal-time intervals (1991–1995, 1996–2000, and 2001–
2005), during which 20, 33, and 60 new minerals, respectively, were discovered in this region. In all, over 250 new
minerals have been described to date from the Kola region, which is significantly higher than from any other
mineralogical province, including such unique provinces as Urals in Russia, Gardar in Greenland, or Monteregian in
Canada. Almost all of the new minerals from the Kola region were discovered in ore deposits related to three types of
alkaline rock associations: agpaitic nepheline syenite massifs, carbonatite-bearing complexes, and alkaline granites. On
the other hand, copper–nickel deposits associated with ultrabasic rocks in the same region have yielded only five new
minerals over the many decades of their comprehensive research.
A virtually inexhaustible source of new mineral discoveries on the Kola Peninsula, both in the recent period and
in previous years, are the world’s largest deposits of rare metals and phosphates, spatially and genetically associated
with the alkaline massifs of the Khibiny–Lovozero complex, which by far surpasses the other unique mineral localities
of our planet both in the total number of minerals (over 600) and in the number of newly described species (about 200),
representing all major classes of chemical compounds. As is well known, the first important discoveries of minerals
with unusual compositions and properties (lomonosovite–murmanite group, etc.) were made by Finnish researchers led
by W. Ramsay (1890s) and later by some Academy of Sciences institutions headed by A.E. Fersman, K.A. Vlasov, and
other prominent scientists. Thanks to their successful mineralogical studies, most notably discoveries of unique apatite,
loparite, and eudialyte deposits, the Khibiny and Lovozero alkaline massifs gained both worldwide renown and
national importance as a unique mineral treasure-trove. Their students and followers continued to make spectacular
achievements along these lines. This is evidenced by the following statistics: the first period of mineralogical
discoveries in these two massifs, from 1890 to 1970, yielded 33 mineral species unknown to science, whereas the
period from 1971 to 2005 yielded about 150 new minerals, the greater part of which (over 80 species) were discovered
with the author’s participation.
The author’s extensive research on the mineralogy of the Khibiny and Lovozero massifs (Khomyakov, 1995)
revealed that their deep unweathered horizons contain abundant pegmatoid rocks of an essentially new, hyperagpaitic
type, supersaturated with alkali, volatile, and rare elements. These rocks are characterized by the presence of a whole
series of highly unusual minerals, such as natrosilite Na 2Si2O5, natrite Na2CO3, and olympite Na5Li(PO4)2, which are,
respectively, the most alkaline water-soluble silicate, carbonate, and phosphate ever found in nature. The existence of
such salts as crystalline phases of rocks could not be predicted from traditional theories. Hence the discovery of their
abundant accumulations in Khibiny and Lovozero rocks actually signified the discovery of a previously unknown
phenomenon: the peralkaline state of natural substance. In this state, all electropositive elements that are less basic than
Na exhibit amphoteric properties, promoting their passage from the cationic part of the structure of agpaitic magma
into the considerably more capacious anionic part. As a result, agpaitic magma turns into a universal solvent, thus
 67

accumulating huge amounts of P, Nb, Та, Ti, Zr, Hf, REE, U, Th, Al, Ga, Sr, Ba, Be, Na, K, F, and other useful
components. This factor is responsible both for the supergiant sizes of mineral deposits associated with agpaitic
magmatism and for their pronounced multi-element character. It also explains why hyperagpaitic rocks are so rich in
minerals with unique compositions, structures, and properties.
The results of these studies, widely publicized in the scientific and popular literature and presentations in
various forums, inspired many Russian and foreign researchers to further investigate the mineralogy of these rocks. In
particular, very impressive progress in this area has been achieved by the research teams led by I.V. Pekov, N.V.
Chukanov, and V.N. Yakovenchuk (Pekov, 2005; Yakovenchuk et al., 2005), which have discovered many dozens of
new minerals. It should be emphasized that the bulk of these minerals have been identified, as in the author’s case,
within Khibiny and Lovozero, in hyperagpaitic pegmatite rocks. Following their discoveries on the Kola Peninsula,
many minerals characteristic of the region’s hyperagpaitic rocks were soon identified by foreign researchers in similar
rocks in the alkaline massifs of Greenland and Canada. At present, this line of research continues to grow both in
Russia and elsewhere, increasingly expanding our understanding of the structural and chemical diversity of the mineral
kingdom and confirming, with each new series of discoveries, the validity of our (Khomyakov, 1997, 2007) principle
of an unlimited number of mineral species in nature.
This study was supported by RFBR grant 07-05-00084-a.

References:
Khomyakov A.P. Mineralogy of hyperagpaitic alkaline rocks. Oxford, U.K.: Clarendon Press, 1995. 224 p.
(Translated from the Russian edition. Moscow: Nauka, 1990. 196 p.).
Khomyakov A.P. Recent mineral discoveries and the number of mineral species: a reconsideration // Structure
and evolution of the mineral world. Int’l mineral. seminar. Syktyvkar: Geoprint, 1997. P. 98-99 (in Russian).
Khomyakov A.P. The record contribution of the Kola region to the overall system of mineral species // Proc. III
Fersman scientific session, Kola Division, Russian Mineral. Soc. Apatity: K & M, 2006. P. 96-98 (in Russian).
Khomyakov A.P. Principle of an unlimited number of mineral species in structural and cultural aspects // III
Int’l symposium 'Mineral diversity. Research and preservation'. Working papers. Sofia: Zemyata i horata, 2007. P. 265-
271 (in Russian).
Pekov I.V. Genetic mineralogy and crystal chemistry of rare elements in highly alkaline postmagmatic systems.
Doctoral (geol.–mineral.) dissertation. Moscow State Univ., 2005. 652 p. (in Russian).
Yakovenchuk V.N., Ivanyuk G.Yu., Pakhomovskiy Ya. A., Men'shikov Yu. P. Khibiny. Apatity: Laplandia
Minerals, 2005. 468 p.

Diamond potential and origin of kimberlites.

Kogarko L.N.
Vernadsky Institute of Geochemistry and Analytical Chemistry, Moscow, Russia

Alkaline and carbonatitic magmatism appeared on Arhean-Proterozoic border- 2.5-2.7 b y The activity of
alkaline and carbonatitic magmatism increased continuously throughout the Earth's history (Fig. 1a). Moreover its
intensity increased throughout geologic time. Kimberlites appeared later (2000-1400 Ma) and also their activity
increased (Fig 1 b) At the same time the diamond potential of kimberlites continuously dropped.(fig 1 c). We develop
(Kogarko 2005) the conception of gradual oxidation of Earth mantle as result of subduction of oxidized oceanic crustal
material.
With the increasing of oxygen fugasity in mantle the stability field of diamond decrease and they are burned out
resulting in the decreasing of diamond potential of kimberlites.
At this moment the hypotesis of metasomatic origin of diamonds is widely accepted.
The question arises as to the genesis of high potassium melts-fluids in the mantle.When mantle diapir ascends
from a depth approximately 660km Ca-perovskite became unstable and react with Mg-perovskite, ferripericlase to
produce majorite, ringwoodite,and under further pressure decrease, wadsleite. This process is accompanied by partial
transition of K into majorite, since the K distribution coefficient in Ca-perovskite is 26 times higher as compared with
that in majorite (Corgne and Wood,2004). The remaining K likely remains beyond crystalline lattices of minerals in this
mantle zone. Taking into considerationvalues of the K distribution coefficient in Caperovskiteand majorite, it can be
confidently stated that the thermodynamic activity of K2O in the system increases by more than an order of magnitude
with thetransition of the Mg-perovskite–Ca-perovskite–ferripericlase association into the majorite–ringwoodite
paragenesis. This results in generation of conditionsfavorable for transition of K into the melt or fluid at thelower–upper
mantle boundary (approximately 660 km).The released fluids should migrate to the upper structural stages of the mantle
and carry out metasomatic alterations of host rocks. This should, in turn, lead to a decrease in the solidus temperature of
the mantle peridotite and formation of kimberlite melts. The occurrence of majorite garnets in kimberlites and
microinclusions in diamonds, which contain high-K alkaline liquids, supports our model of the genesis of potassic
mantle flows and kimberlites. Both these mechanismsare likely responsible for generation of kimberlites. The
subsequent development of the deepest potassic alkaline rocks in the Earth’s history is most likely explained, first, by
the formation of a rather cold thick mature lithosphere (a required condition for kimberlite generation) and, second, by
subduction of the continental crust at later stages of the Earth’s evolution.
 68

Fig. 1 Distribution of alkaline rocks, kimberlites, and diamond potential of kimberlites in the Earth’s geological
history. (a) Alkaline rocks;(b) kimberlites; (c) diamond potential (ratio of the numbers of diamond-free and diamond-
bearing pipes).

References
1. Коgarko L.N.(2005). Geology and Geophysic, 46,12, 1234-1245.
2. Corgne A. and Wood B.,(2004) Earth Planet. Inter.48, 143.
 69

Isotope carbon composition of graphite and calcite in Chagotay carbonatites (Uzbekistan)

Kogarko L.N.*, Divaev F.K.**,Wall F.***, Sevastyanov V.S.*
*Vernadsky Institute of Geochemistry and Analytical Chemistry, Moscow, Russia
**GP “Centralnaya GGE” The State Geological Committee of Uzbekistan Republic, Samarkand, Uzbekistan
*** Сamborne School of Mines, University of Exeter
The Chagatai carbonatite-trachyte complex is represented by dyke swarms and diatemes present in the basin of
Chagatai creek on the northern slopes of the South Nuratau mountains. The carbonatites are mainly calcite carbonatites
(sovites) but there are also carbonate-silicate rocks, so called kasenites, ringites and melilite carbonatites (alvikites).
Rare dykes of trachyte are also present. The rock-forming minerals in Chagatai carbonatites are predominantly calcite,
pyroxene, biotite, garnet, melilite, apatite, magnetite with secondary amphibole, chlorite, albite, K-feldspar, hematite,
quartz, and montmorillonite. A very interesting feature of the Chagatai carbonatites is the previous finding of diamonds.
The diamonds are very rare and are mainly represented by intergrowths of octahedral crystals and intergrowths of grains
with non-defined crystallographic forms and skeletal forms 0.01-0.05 mm across. Monocrystals of octahedral shape
with flat faces and acute vertices and edges are found occasionally; they are 0.02-0.05 mm diameter. Graphite is present
in some varieties of carbonatites, forming separate black flakes with a dull luster up to 2 mm across and also as cement
in interstices between gangue minerals. The carbon isotope composition of graphite and calcite was measured on a
DELTA plus mass-spectrometer. The 13C of graphite is -8.21, whereas 13C of calcite is -4.98. This yields an
equilibrium temperature of 775oC. Assuming a mantle source for Chagatai carbonatites and equilibrium between
calcite, graphite, CO2 and methane, we have calculated the composition of fluid phase. The estimated mole fraction of
CO2 is 0.7 and that of CH4 is 0.3.

Lithospheric Mantle beneath East Antarctic (Oasis Jetty)

Kogarko L.N.
- Vernadsky Institute of Geochemistry and Analytical Chemistry, Moscow, Russia
We report petrographic, major and trace (including rare earth) element data for 46 spinel and garnet peridotite
xenoliths from East Antarctic (Oasis Jetty) lithospheric mantle beneath Lambert-Amery Rift. The age of hosting
ultrabasic alkaline dykes is cretaceous (Layba et al.1987). Investigated spinel and garnet peridotite xenoliths represents
about 80 km thick cross of subcontinental litospheric mantle. High equilibration temperatures (820-1217о) of the
xenoliths suggests influence of the ascending plume.
Distinct correlations is observed between contents of MgO and other petrogenetic elements CaO, Al2O3, FeO,
Na2O, Co, Ni, V. Comparison of these correlations with estimated trends of batch and fractional melting of initially
fertile mantle peridotite (Niu, 1997) demonstrate, that Jetty peridotites plot at lower values for SiO2 and other
components.
Garnets are characterized by unusual high LIL element concentrations (Ba/La=4000) and clinopyroxenes from
the spinel peridotite suite are highly enriched in LREE [(La/Yb) N =14] and in HFSE.
The decoupling of major and REE elements and observed mineral assemblages( which include Sr- and LREE-
rich apatite,Ti- Ba-rich phlogopite, titanite, perovskite, henrymeierite) indicate that the upper mantle of East Antarctic
has been affected by very strong metasomatism. Henrymeierite was found in mantle material for the first time (Kogarko
et al, 2007).
Our isotopic data showed complete absence of isotope equilibrium among the rock forming minerals in the
xenoliths – Opx, Cpx and Grt. Garnets are characterised by the most radiogenic Sr isotope composition (0.709024-
0.714127), whereas Cpx exhibits the lowest 87Sr/86Sr ratios ( 0.702861-0.703711). On the one hand garnets are depleted
in terms of Sm-Nd system and on the other hand they are significantly enriched in radiogenic Sr. Such anomalous
signature in Antarctic mantle rocks confirm the influx of metasomatising fluid ( or melt) from the source with a time
integrated LIL-elements enrichment such as sources of kimberlites and lamproites (high radiogenic Sr and low
radiogenic Nd ) to the initially depleted mantle substrate.
It is probable, that that the interaction of primary dolomitic melts-fluids with mantle material according to
reactions :2Mg2Si2O6 + CaMg(CO3)2 = 2Mg2SiO4 + CaMgSi2O6 + 2CO2 (1)
3CaMg(CO3)2 + CaMgSi2O6 = 4CaCO3 +2Mg2SiO4+CO2 (2)
resulted in wehrlitization and carbonatization. The fluids responsible for this metasomatism were probably
derived from the plume that arrived beneath the region at this time.

References
1. Kogarko L.,Kurat G.,Ntaflos T. Henrynrymeyerite in metasomatised upper mantle of Eastern
Antarctica (2007) Can Min V45,part 3
2.Laiba, A.A., Andronnikov, A.V., Egorov, L.S. & Fedorov, L.V. (1987): Stock and dyke bodies of
alkaline ultrabasic composition in Jetty Peninsula (Prince Charles Mountains, East Antarctica). in Ivanov, V.L.
& Grikurov, G.E. (eds) Geological-geophysical investigations in Antarctica. Leningrad. 35-47.
3.Niu Y. (1997) Mantle Melting and Melt Extraction from Abyssal Peridotites: J.Petrology,V 38,8,
1047-1074.
 70

Peculiarities of ultrabasic-alkaline magma differentiation from gigantic Guli intrusion (Polar Siberia)
Kogarko L.N., Gerasimova E.I.
Vernadsky Institute of Geochemistry and Analytical Chemistry Russian Academy of Sciences, Moscow,
Russia

In the Polar Siberia there is the biggest in the world Gulinskiy ultramafic-alkaline complex. It was formed during
7 phases. According our data the age of the massif is 250 Ma, sinhronous with the formation of Siberian Trapps.
We investigated the chemical composition of Guli rocks and dyke series. The obtained data permit to distinguish
some petrological trends (Fig. 1). The sharp increase of SiO2 content is observed when the MgO reach about 10%.
Silica is practically constant during the long interval of Guli magma evolution. FeO shows maximum also in the same
region MgO concentrationcon. Al2O3, Na2O, K2O concentrations increase with decrease of MgO content, but when
MgO reach 10-15 %, more marked increase of alkalies and aluminium contents occure (fig. 2 c-h). Decrease of Al2O3,
Na2O, K2O concentrations occures in the latest evolution stages (MgO concentration is in interval from the first to tenth
percent) (fig. 2 c, e). The Cr2O3 concentration falls gradually and becomes extremely low from 10 % MgO (fig. 2 g).
CaO and TiO2 concentrations also pass through the maximum (on fig. 2 h showed diagram for TiO2) when MgO
approach close to 10 %.

a b

Fig. 1. Connection between MgO и SiO2 (mas.%) in а) Guli rocks; b) Guli dikes

Established regularities show the processes of crystallization differenciation of initial ultrabasic-alkaline magma,
the composition of which is close to meymechites and picrites (SiO2 content is nearly 40 %). Olivine and chromite
fractionate in the first evolution stages; SiO2 concentration stays practicaly constant (nearly 40 %) with a fast decrease
of MgO content. This process is quite long and received data witness about very wide field of olivine crystallization in
the process of ultrabasic-alkaline magma differentiation. The crystallization of spinel (chromite-titano-magnetite),
perovskite, apatite, melelite and to all appearance calcite is started in a melt when MgO content reaches nearly 10 %
and lower till first percent. This is confirmed by sharply decrease of CaO, TiO2, FeO contents and a growth of Al2O3,
Na2O and K2O concentrations. The fractionization of feldspars starts on the latest evolution stages, resulting in the
sharply decrease of Al2O3, Na2O, K2O contents (fig. 2 c, e).
Thereby, we can determine the order of crystallization and mineral fractionization in the way of the primary
magma evolution of Guli massif. This is olivine and chromspinelide, titano-magnetite, perovskite, apatite, melelite,
calcite and feldspars.
One should note, the strong resemblance of petrological trends of Guli massif rocks and dike series. The
evolution of dike rocks is showed on fig. 1 b, fig.2 b, d, f, h. The evolution of Guli massif rocks and dikes was a result
of crystallization differentiation processes and fractionation of olivine, chromit, titano-magnetite, perovskite, apatite,
melelite, calcite and feldspars. Such paragenesis of fractionated minerals showed the low pressure crystallization, which
had passed in shallow intermediate magma chamber under the similar physico-chemical parameters and besides
compositions of Guli massif primary magma and dikes series were the similar.
 71

a b
.

c d

e f

g h

Fig. 2. Connection FeO, Na2O, Al2O3, TiO2, Cr2O3 with MgO (mas.%) in a, c, e, g, I, j – Guli rocks and b, d, f, h –
Guli dikes
 72

Potassic fluids as metasomatic agens of K-rich rocks origin

Kogarko L.N.
GEOCHI RAS, Moscow, Russia

On the basis of data-base (about 6000 analyses of oceanic islands volcanics) we distinguished primary magmas
characterized by high MgO and Ni (about 2000 compositions). In this data-base we determined unique potassium-rich
melts with Na2O/K2O <1. This value is much lower than Na2O/K2O ratio in mantle rocks (average close to 12.5). The
majority of authors consider the high-potassium rocks as result of partial melting of metasomatised mantle material.
The question arises what was the mechanism of K-rich fluid in mantle environment.
At present, most geochemists accept the chondritemodel of the Earth’s composition, its upper and lower mantle
included. According to this model, the K content in the Earth’s primitive mantle is low (250 ppm) [1]. In the uppermost
blocks of the mantle, K is entirely concentrated in plagioclases. With increase in depth (and pressure), the plagioclase
disappears and potassium budget is determined mainly by clinopyroxene and, to a lesser extent, garnet with the K
distribution coefficient equal to approximately 0.04–0.12 for clinopyroxene and 0.038 for garnet [2]. Moreover, this
parameter in the pyroxene–melt equilibrium increases with depth (and pressure) [3]. Clinopyroxene with the Na
distribution coefficient equal to 0.8 represents the main Na-concentrating mineral. Under further increase in the
pressure, pyroxene and garnet react to form majorite with K and Na distribution coefficients equal to 0.015 and 0.39,
respectively [2]. In the depth interval of 410–660 km, majorite is associated with wadsleyite (410–500 km) and
ringwoodite (500–660 km),both practically lacking K and Na. At deeper levels of the mantle (below 660 km), the
majorite–ringwoodite association is replaced by the ferripericlase–Mg-perovskite–Ca-perovskite paragenesis. The
content of Ca perovskite in this mantle zone approximates 8%. The K distribution coefficient in Ca-perovskite is
relatively high (0.39), and that of Na is even higher (2.0) [4].Thus, practically all K and Na are concentrated in Ca-
perovskite from the upper zone of the lower mantle. When a mantle diapir ascends from a depth of approximately 660
km, Ca-perovskite turns into the unstablephase, which reacts with Mg-perovskite and ferripericlaseto produce majorite;
ringwoodite; and, under further pressure decrease, wadsleyite. This process is accompanied by partial transition of K
into majorite, since the K distribution coefficient in Ca-perovskite is 26 times higher as compared with that in majorite
[4].The remaining K likely remains beyond crystalline lattices The released fluids should migrate to the upper structural
stages of the mantle and carry out metasomatic alterations of host rocks

Reference:

1. Sun S., McDonough W. // Geol. Soc. Amer. Spec. Publ. 1989. V. 42. P. 313 – 342.
2. Corgne A., Wood B. J. // Earth and Planet. Inter. 2004. V. 48. P. 143 – 144.
3. Safonov O. G., Perchuk L. L., Litvin Yu. A. // Earth and Planet. Sci. Lett. 2006. V. 10. P. 1016 – 1031.
4. Corgne A., Libeske C., Wood B. J. et al, // Geochim. et cosmochim. acta. 2005. V. 69. № 2. P. 485 – 496.

Post-collisional Hercynian magmatism in the Tien Shan: lithospheric shearing vs. mantle plume origin
Konopelko D.*, Seltmann R.**, Biske G.*, Matukov D.***, Sergeev S.***
* St. Petersburg State University, Russia, [email protected]
** Centre for Russian and Central EurAsian Mineral Studies (CERCAMS), Department of Mineralogy,
Natural History Museum, London, UK
*** Center of Isotopic Research, A.P. Karpinsky All Russia Geological Research Institute (VSEGEI), St.
Petersburg, Russia

The Hercynian Tien Shan orogen formed during Late Palaeozoic collision between the Karakum-Tarim and the
Paleo-Kazakhstan continent. The western part of the Tien Shan is composed of three structural units or terranes: (1) the
Northern Tien Shan, the deformed margin of the Palaeo-Kazakhstan; (2) the Middle Tien Shan, a Late Paleozoic
volcano-plutonic arc; and (3) the Southern Tien Shan, an intensely deformed fold and thrust belt. The Middle and
Southern Tien Shan terranes are separated by the Southern Tien Shan Suture (STSS) formed after the closure of the
Paleo-Turkestan ocean.
The post-collisional intrusions are spread out in all the terranes of the Tien Shan regardless of the STSS, and
comprise diverse calc-alkaline, alkali-calcic granitoid and alkaline s.s. complexes closely associated in time and space.
Most of the intrusions are tectonically controlled and associate with major tectonic lineaments. Twenty intrusions in the
Northern, Middle and Southern Tien Shan along a ca. 2000 km – long profile from Aral Sea in Uzbekistan to the
Pobeda Peak in Kyrgyzstan were dated using U-Pb zircon method by SHRIMP-II facility in VSEGEI St. Petersburg. To
distinguish between subduction-related and post-collisional magmatism, 10 intrusions from the Middle Tien Shan
volcanic arc were included in the data set. The results show that all the post-collisional intrusions formed within a very
narrow time span from 295 Ma to 280 Ma. The intrusions of the Middle Tien Shan arc in Uzbekistan formed within a
320 – 305 Ma time span in subduction-related environment.
Two stages of gold mineralisation are associated with subduction-related and post-collisional granitoids, making
the Tien Shan the richest gold province in Eurasia. However, the two stages are represented by different genetic types of
Au mineralization: porphyry and hydrothermal systems in volcanic arc rocks and orogenic gold deposits in post-
 73

collisional rocks. The new data show that subduction-related calc-alkaline magmatism is restricted in space while the
post-collisional granitoids are spread out in all the terranes of the Tien Shan regardless of the STSS and comprise
compositionally diverse magmatic series.
Several authors suggested that diverse post-collisional magamatism originated from a mantle plume which
developed under Central Asia immediately after Hercynian collision. However based on tectonic analysis and timing of
post-collisional magmatic event we propose different model for a post-collisional evolution of the Tien Shan. From our
point of view the emplacement of the post-collisional intrusions and orogenic gold deposits was controlled by the trans-
crustal scale shear zones which formed as a result of the east-west strike-slip motions that affected the Tien Shan
subsequent to collisional events. Our data show that these motions took place in a relatively narrow time span from 295
Ma to 280 Ma. We believe that plate-scale shear zones provided suitable conduits for ascending asthenospheric material
and heat influx in the crust. The compositional diversity of post-collisional magmatism in various terranes of the Tien
Shan probably reflects different compositions of the crust.

Geochemistry of Fe-Mn sediments

Korotkina O.A.*, Kogarko L.N.*, Bazilevskaya E.S.**, Kubrakova I.V.*
* GEOCHI RAS, Moscow, Russia
** Институт океанологии им. П.П. Ширшова РАН 117997 Москва, Нахимовский проспект, 36
тел.(495) 124 63 55

The analysis of 17 Fe-Mn deposits from three regions of the Atlantic Ocean was performed. The samples were
collected near Elena Seamount, Strakhov Depression, and Cape Verde Seamount in 16th voyage of “Academician Ioffe”
ship and 23rd voyage of “Academician Nicolay Strakhov” scientific vessel in 2006. The analysis for major componenets
as well as for Ni, Co, Cu, P, S etc was performed by -ICP with the utilization of the spectrometers of the latest
generation. REE were measured by the same method after the ion-exchange separation of matrix components. BM was
separated from the matrix with the utilization of sorbents and analyzed by the ETAAS method.
The diagram Fe-Mn-(Ni+Co+Cu)*10 is commonly used for the geochemistry of Fe-Mn formations. The sum of
Ni+Co+Cu is called polymetallic index. Our data plotted onto this diagram fall into hydrogeneous field (fig. 1). The
prevailing mineral of hydrogeneous deposits is ferruginous vernadite. The rate of the growth of hydrogeneous deposits
varies from 1 to 15 mm per Ma. Their composition is characterized by Mn/Fe ratio close to 1, high concentrations of Co
and other microelements including REE.

Fig 1 Diagram Fe-Mn-(Ni+Co+Cu)*10

Rare earths
REE exhibit similar patterns in Fe-Mn deposites which is particularly obvious when normalized by the composition
of sheet (fig.2)
The following features of REE patterns may be noted:
The predominance of LREE over HREE.
Distinguishable positive Ce anomaly caused by the oxidation of Ce3+ to Ce4+. Tetravalent Ce is actively
accumulated during the precipitation of the Fe hydroxides. Ce content in the investigated crust is 3.5 times that of the
mean concentration in Atalantic seawater.
 74

Fig 2 REE contents in Fe-Mn crusts normalized by the composition of sheet.

Rare elements contents in Fe-Mn deposits

The investigations demonstrated that the distribution of rare elements in the Fe-Mn deposits of the studied
regions is variable. The elements like As, Mo, Ba,Co, Pb, Sc, Sr, V, Y, Zn are concentrated to a larger degree inh the
Fe-Mn deposits of Cape Verde Seamount (table 1).The maximum contents of Cu (2580 ppm), Ni (54 ppm) и Li (500
ppm) are in the vicinity of Elena Seamount (fig. 3).
The lowest Li (3,3 ppm) and Cu (220 ppm) contents were found at the Cape Verde Seamount ground. Near the
Elena Seamount As (158 ppm) and Y (78 ppm) show the lowest values. Other elements (Ba, Co, Ni, Mo, Pb, Sc, Sr, V,
Zn) attain minima in the neighbourhood of the Strakhov depression (table 1).

Table 1 Composition of Fe-Mn deposits

Place, ррm As Ba Co Cu Li Mo Ni Pb Sc Sr V Y Zn
Elena
Seamount 200 1640 3323 1425 38 367 3535 816 17,3 849 720,8 147 583
Strakhov
Depression 396 1168 2493 842 30 366 2150 596 16,8 700 720,0 181 460
Cape Verde
Seamount 521 1715 6955 382 16 541 2375 1388 17,6 1393 1169 200 668

Fig 3 Rare elements contents in Fe-Mn deposits

 75

Distribution of small elements in depth

Some regularity in distribution of a set of elements was observed in various depths from Strakhov Depression
(north, 5640 m) to Cape Verde Seamount (south, 1722 m). In small depths (Cape Verde Seamount) content of As, Pb,
Sr, Со, and Pt is 2 times larger in comparison with northern regions. Content of Fe, V, Y, Zn, Ba, and Mo is also larger
(fig. 4-5). Concentration of the other elements is less. For example, content of Cu and Li is 2 times less in comparison
with the Cu-Li content in the regions with small depth. Thus there is a regularity connected with As, Pb, Sr, Со, and Pt
accumulation in shallow regions, and accumulation of Cu and Li in deep-water regions.

1800

1600

1400

1200

1000
ррm

800

600

400

200
Mo Pb As Sr
0
1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000
depth, м

Figure 4. Dependence of small elements concentration on depth

1600

1400

1200

1000
ppm

800

600

400

200

0
0 1000 2000 3000 4000 5000 6000
Cu Li depth, м

Figure 5. Dependence of Cu and Li concentration on depth

 76

Noble metals
Concentration of Pt in the investigated samples is quite different. The largest concentrations of platinoids were
observed in Fe-Mn deposits of Cape Verde Seamount (0.2 ppm), the smallest concentrations of Pt were obtained in the
samples collected in the depth more than 5000 m near Strakhov Depression (0.04 ppm).
In the investigated samples of Fe-Mn deposits the Au concentration is almost constant. Maximum value of Au
concentration is 0.2 ppm near Strakhov Depression, minimum value is less than 0.1 ppm in the samples from Cape
Verde Seamount.
Platinoids accumulation occurs mainly in upper layers (mountains), while concentration of platinoids in
depression is minimal.
Distribution of gold and platinum depends on depth. The deeper, the larger accumulation of gold and less
platinum (figure 6). Platinum concentration reduction connected with oxygen absorption processes that more active in
the depths more than 2000 m.

0.25

0.2

0.15
ppm

0.1

0.05

0
0 1000 2000 3000 4000 5000 6000
Au depth Pt

Figure 6. Dependence Pt , Au on depth

Experimental studying of alcalic-carbonaceous metasomatism. Genesis of alkaline and carbonatites

magmas.
Kostyuk A.V., Gorbachev N.S.
Institute of Experimental Mineralogy RAS, Chernogolovka, Russia

Eclogites along with peridotites are widespread in nodules mantle xenolites from kimberlites and alkalic basalts.
They have their origin in eclogitization processes of basaltic rocks (basalt, gabbro) during the oceanic slab recycling.
Evidences of partial melting are widely spread in xenolites. A number of xenolites contains silicate glasses which are
enriched in alkalis (up to 16 wt.%), phlogopites, carbonates, sulphates, sanidine. Formation of such exotic structures is
resulted from partial melting of eclogites caused by the influence of deep alkaline fluids. We studied interactions of
eclogites with alcalic-carbonaceous at temperatures from 850 to 1450°C and at pressure 3.8-4 GPa experimentally.
Experiments were carried out in an anvil-with-hole apparatus by a quenching technique. The temperature is
measured by a Pt30Rh/Pt6/Rh thermocouple. At high temperature, pressure is calibrated using a curve of balance quartz
- coesite. Uncertainties are ± 5ºC for temperature and ± 0.1 GPa for pressure measurements. Duration of experiments
were from 6 to 8 hours. Products of experiments were studied by PC-controlled scanning electron microscope Tescan
VEGA TS 5130MM with detector of secondary and backscattered electron on the YAG-crystals and energy dispersive
X-ray microanalyzer with semi-conductor Si(Li) detector INCA Energy 350.
Association of graphite-garnet-clinopyroxene-phlogopite with accessory chromite were formed at near-solidus
(Т=850°С, Р=3.5GPa) alcalic-carbonaceous metasomatism of eclogite in C-saturated system. This association coexist
with intergranular alkali silicate melt (not more than 5%). Carbonate phase has not been found out. Clinopyroxenes
contain 11-13 wt.% of CaO and up to 3.0 wt.% K2O (tab.1).
 77

With increases of temperature up to 1300ºС at the same compositions degree of melting of eclogite increases (up
to 30 % and more)). The sample is presented by clinopyroxene, phlogopite, accessory chromite which cementing by
alkaline Na-K silicate melt. However, the carbonate phase is not found out too. (Fig. 1, tab. 2).
Composition of liquidus associations in high-temperature (up to 1450°С) experiments differs from phase
composition of near-solidus associations in low-temperature (850°С) experiments. At high-temperature experiments we
observed only Ca-clinopiroxene (with <0.1 % K2O), garnete and carbonate are not present. Possible explanation of
carbonate phases absence in these experiments it is low activity СО2. Balance С-СО-СО2 is displaced aside СО in the
presence of graphite at Т-Р parametres of experiment. Absence of a garnet on the liquidus of alkaline silicate melts we
also can explain as temperature effect.

Table 1. Representative phase composition of run products in C-saturated system. Т=850ºС, Р=3.5 GPa.
Ga Cpx Flog m Cht
SiO2 39.6 50.7 36.2 52.54 0.2
TiO2 0.4 0.1 0.3 0.75 0.4
Al2O3 19.1 7.0 18.0 13.44 31.3
Cr2O3 1.0 - 0.3 0.79 33.6
FeO 11.6 8.9 23.6 8.65 16.6
MgO 1.2 13.8 10.8 5.01 16.2
CaO 25.9 13.7 0.3 10.47 0.1
Na2O 0.6 2.1 0.6 7.6 0.3
K2O <0.1 3.0 9.5 0.64
Total 99.5 99.3 99.6 99.89 98.7

Table 2. Representative phase composition of run products in C-saturated system. Т=1300ºС, Р=3.9 GPa.

Cpx Flog m
SiO2 46.72 41.66 46.10
TiO2 3.60 1.55 0.37
Al2O3 14.44 14.61 19.87
Cr2O3 0.11 0.37 0.12
FeO 2.53 1.69 1.38
MnO 0.2 0.2 0.1
MgO 11.27 25.22 0.2
CaO 20.36 0.15 0.32
Na2O 2.08 0.56 8.60
K2O <0.1 9.01 3.61
Total 98.24 95.13 81.50

Fig. 1. Backscattered electron photograph of run

products. Melting of eclogite in C-saturated system at
T=1300ºС, Р=3.9GPa.
 78

Carbonatization of silicate melts were observed at alcalic-carbonaceous metasomatism and partial melting of
eclogite at Т=1200°С, Р=3.8GPa. Carbonatization of silicate melts occurred in C-unsaturated system with formation of
immiscibility alkaline silicate and carbonate liquids. Alkaline melts of phonolite composition coexist with carbonate
melts, Na-clinopyroxenes, phlogopites and chromites (tabl.3, fig.2).

Table 3. Composition of coexisting phase at alcalic-carbonaceous metasomatism and melting of eclogite.

Т=1200ºС Р=3.8 GPa.
Cpx Flog m Ка Cht
SiO2 52.1 40.1 49.0 2.4 0.65
TiO2 0.5 1.4 0.5 0.1 0.7
Al2O3 7.8 12.9 14.9 1.0 21.75
Cr2O3 0.8 0.2 0.2 0.1 37.93
FeO 8.4 18.0 5.0 12.0 28.79
MgO 10.0 7.9 1.2 1.2 7.05
CaO 14.3 1.7 2.4 20.6 0.26
Na2O 4.3 1.8 6.3 12.6 0.23
K2O 0.1 6.1 6.1 1.1 0.08
Total 98.4 92.2 83.6 52.0 97.44

Experimental samples are presented by large (tens micron) the tabular form silicate minerals, which are
cementing by silicate glass (quench silicate melt) with the oval form inclusions of carbonate phases (quench carbonate
melt). The size of carbonate phase is about 5-10 m. Carbonates are enriched (in recalculation on 100% oxide, without
СО2) by Ca (to 40 wt.% of CaO), Na (to 25 wt.% Na2O), contain SiO2 (to 5 wt.%), and characterized by high solubility
of sulphur (to 3 wt.% SO3) (fig. 2).

SiO2
0.00
1.00

m
0.25
0.75

0.50
0.50

0.75
0.25
Cpx

1.00 Flog Ka 0.00

MgO 0.00 0.25 0.50 0.75 1.00 CaO

Fig. 2. Melting of metasomatic eclogite, liquid silicate-carbonate immiscibility. At the left - structures of co-
existing phases: m – silicate melt, Ka – carbonate melt, Cpx – clinopyroxen, Flog – phlogopite. On the right –
backscattered electron photograph of run products.

During researches has been finding out that alcalic-carbonaceous metasomatism and melting of eclogite leads to
formation of alkaline and carbonate melts. Features of melt composition and associations of minerals coexisting with
them show us efficiency of alcaline-carbonate melts in metasomatic transformation of the upper mantle and the
important role of these processes in mantle magma-formation, including formation alkaline and carbonatite magmas.

Experimental study of fluid inclusions in Hakmanite from Karnasurt Mauntin, Lovosersky massif
Kovalskaya T.N*, Kotelnikova Z.A.**, Kotelnikov A.R.*, Suk N.I.*, Kovalsky A.M.*, Goettlicher
J.***
*IEM RAS, Chernogolovka, Moscow district, Russia, [email protected]
**IGEM RAS, Moscow. Russia
*** Insitute for Synchrotron Radiation, Karlsruhe, Germany

Lovozersky alkaline massif is located in the central part of Kola peninsula and includes gigantic deposits of rare
and radioactive elements. Data of alkalinity of post magmatic mineralgenetic solutions are necessary for understanding
the features of mineralogenesis process for alkaline complexes. Sodalite (hakmanite) is a typical mineral of pegmatites
of Lovozersky massif. Investigation of fluid inclusions in hakmanite (as it composition) supposes the conditions of it
formation.
The composition of hakmanite was determined by the microbeam method. which showed two types of
hakmanite in pegmatite №61 of Lovozersky massif – with Cl- and Cl- and SO42- anion groups. A slice of hackmanite
has been cut, and sulfur K-edge X-ray absorption spectra have been measured in the fluorescence mode at the bulk X-
ray absorption spectroscopy beamline (XAS) at ANKA using a five element Ge solid state detector (Canberra). A
 79

silicon 111 crystal pair was used as monochromator. Higher harmonics were eliminated by passing a mirror behind the
monochromator. To minimize absorption caused by the atmosphere and by the windows of the ionization chamber a
combined ionization-sample-chamber has been used at a nitrogen gas pressure of about 80 mbar. We have detected two
types of sulfur K-edge XANES spectra in a sodalite (hackmanite) sample from Lovosero massiv, Kola peninsula: One
indicates reduced sulfur species, the other one mainly sulfur as sulfate (fig. 1, 2). A suggestion how to attribute these
species to the sodalite pahses has been given, but has to be checked by performing micro-X-ray diffraction at the same
sample position where X-ray absorption spectra have been recorded.

Fig. 1. S K-edge XANES spectrum of an area at the slice of hakmanite where light pink colors dominate.

Fig. 2. S K-edge XANES spectrum of an area at the slice where blue colored parts have been observed.

Fig. 3. Fluid inclusion in hakmanite, Karnasurt, Lovozersky massif.

 80

We also investigated fluid inclusions in hakmanite (fig. 3). It is shown, that fluid inclusions in hakmanite contain
water, crystal of salt and gas bubble. The thermometry of 3-phase fluid inclusions showed that the temperature of
inclusion homogenization is about 200о. The temperature of ice-melt in inclusions is from -6.5 to -4.4 оС. On the basis
of these data we calculated the concentration of NaCleq in the fluid – 9.9 wt.%.
We carried out some experiments on synthesis of fluid inclusions in hakmanite. We used 1 M solution Na2SO4
and 2 M NaСl solution as a fluid component. The ratio shot/fluid was 1:6. High temperature gas pressure apparatus is
used to carry out the experiments. The charge of the starting material was placed inside gold capsule Synthesis was
carried out at Т=450°С and Р=1.5 kbar. The duration of the experiments was 31 days. The slices of hakmanite about
0,8*0,5 cm were used as starting materials. These slices were heated to 500°С and then were cooled in alcohol at room
temperature. Synthesized fluid inclusions were investigated by thermo-cryometric method with
Linkam-600. We measured concentrations of Na2SO4 and NaСl solutions after experiments by flameless atomic
absorption spectrometry method. We carried out the investigation of fluid inclusions in natrolite, which was found in
the same pegmatite.
This study was financially supported by RFBR grants № 06-05-64904, № 07-05-00217, 07-05-00389, Russian
Federation President grants МК-4797.2008.5 and Fund of native science support.

Ambiguity of nepheline syenite family rock names and how to cope with this problem
Krasnova N.I., Korolev N.M., Petrov T.G.
Saint-Petersburg State University, Saint Petersburg, Russia
[email protected], [email protected], [email protected]

There are no natural borders between chemical as well as mineral compositions of “different” rocks. Therefore,
the fluctuation limits both of rockforming oxides and mineral contents in one rock family are usually overlapping, and
the definition of their various types causes difficulties. Besides, unequivocal identification of rock types is interfered by
the fact that classifications published in reference books [1, 6] are based on different principles (mineral and/or
chemical composition, structure and texture, agpaite coefficient, etc.). The contradictions connected with determination
of a rock name, were always sharply shown among the alkaline series, and, in particular, among representatives of
nepheline (feldspathoid) syenite group.
Task of the work is: to illustrate the uncertainty of rock names in relation to their mineral composition, and also
to offer a way of describing mineral composition which will promote working out of a more precise nomenclature.
Deficiency of parallel chemical and mineral content analyses of alkaline rocks has compelled to use the data of
their normative composition, calculated by means of Norm-4 program applied by many geologists in the world. Here
we do not discuss the problem of conformity of the mineral composition received by CIPW method to real rock
composition since normative calculations in petrographic practice are standard. It is sufficient that the use of similar
chemical analyses leads to receiving of similar normative compositions, irrespective of the method by which the latter
were calculated.
Normative compositions for 418 chemical analyses of many alkaline rock varieties taken from 6 published and 2
own sources were calculated using Norm-4program. The results are presented in volume % (Vol. %), that corresponds
mostly to visual definition of a rock. RHA-Min comp_alkaline rocks.rar file on the web-site
http://geology.pu.ru/index.php?mod=mod1_6_2_4&nam=¦х=юф%20RHA&menu=6&smenu=46 displays the full
version of data.
Classifications of chemical and mineral composition were made using rank-entropy RHA-method [2]. Here R –
the rank formula – is a succession of components in the system ranged according to decrease of their contents in the
analysis. Two other parameters – H and A – are integral characteristics of ranged components distribution. The method
is described in more detail in [3, 5, 7]. As a result, we receive a set of rank formulas (in abbreviated form: R-Min) –
sequences of minerals e.g. of AbNeOrt… type that corresponds to a decrease of volume ratios (percents) of minerals in
rock Ab> Ne> Ort>….
Rank formula sets are ordered according to a certain “alphabet”. The sequence of these minerals received in their
chemical R-classification (R-Min-Catalogue-2007.rar file on the same web-site) serves as an “alphabet”.
Obtained data are shown as rank formulas of mineral volume % contents reduced to the 3 rd position. These data
illustrate a well-known domination of nepheline (Ne), orthoclase or microcline (Ort) and alkaline plagioclase (Ab)
complexes in composition of main nepheline syenite types. Similarity of many rank formulas for the whole syenite
family is crucially important for our work. So, formulas AbNeOrt and AbOrtNe are present in groups of foyaites,
khibinites, mariupolites, miaskites and lujavrites; formula OrtNeAb is common in groups of foyaites, khibinites,
rischorrites and juvites (data on the last two are available only in the full table on the web-site); OrtAbNe formula – in
groups of foyaites, khibinites, miaskites and lujavrites. Thus, the above-stated data evidently confirm the inconsistency
of classifications suggested in [6], and show that rigid criteria allowing unequivocal definition of a rock type are not
fixed to them in nepheline syenites family.
For resolving the next problem, the authors offer to use the following method BEFORE the establishment of
precise criteria of division on rock types during identification of varieties in nepheline syenite group. It is possible to
add to the term «nepheline syenite» the rank formula of mineral composition, reduced to three (or four) positions,
receiving the rock name e.g. «nepheline syenite OrtAbNe». Such names can be formed on the basis of quantitative
 81

calculations of their real mineral composition. First, it will allow considering really present minerals, instead of virtual
components, as K2SiO3, Na2CO3, corundum, etc. received sometimes during norms calculation. Secondly, it will
provide the account of minerals with volatile components, which include micas, amphibole, cancrinite, etc. occurring in
considered rocks. As is known, the presence of these minerals does not come to light by using Norm-4 program.
It will be possible to work out a rational nomenclature for various rock groups of this family after a critical
revision of such representative RHAmin collections from different regions. The values of complexity (H) and purity (A)
of composition, showing moniminerality degree of a rock can be used for specification of the description in the form of
rank formulas.
RHA-method allows creating a uniform, unequivocal classification of mineral compositions not only of
nepheline syenite group, but also for the whole rock variety. Such classification is open for addition of new types,
which were unknown before. The opportunity to create an unequivocal rock classification based on their mineral
composition using the mineral composition rank formulas was earlier realized on an example of phoscorites and
carbonatites [4, 7] – rocks which did not have a standard nomenclature. Besides, success of the offered method
application is shown on an example of well-studied rocks: granites (77 analyses), diorites (59), and gabbros (33
analyses). These results are accessible on separate pages of RHA-Min comp_alkaline rocks.rar file. Increase of
description detaility (rank formula length) will allow taking into consideration the peculiarities of rock mineral
composition significant for particular cases. Unambiguity of alphabetic ordering of RHA-descriptions of compositions
allows to store numerous data sets and to reveal groupings of similar rocks by their composition, to estimate
completeness of data for various groups, to reveal mistakes of different types. Presence of rather representative arrays of
rock types stipulates the opportunity of their identification by real modal composition.

Table. Reduced rank formulas of mineral composition (Rmin) for different representatives of nepheline syenite
family (N – quantity of analyses corresponding to given rank formula).

Abbreviations: Ab – albite; Aeg - aegirine; Crn - corundum; Di - diopside; Ne - nepheline; Ol - olivine; Ort -
orthoclase.

References:
1. A classification of igneous rocks and glossary of terms. Recommendations of the International Union of
Geological Sciences Subcommission on the Systematics of Igneous rocks. / Eds. R.W. Le Maitre, P. Bateman, A.
Dudek et. al. Int. Geol. Sci., published by Blackwell Sci. Publ., Oxford, London. 1989.
2. Petrov T.G. The justification of variant of general classification for geochemical systems. // Vestnik of
Leningrad State University. 1971. No 18. Pp. 30-38. (In Russian).
3. Petrov T.G. RHA-method as a problem solution of systemizing analytical data on material composition of
geological targets. // Otechestvennaya Geologiya. 2008. No 4. Pp. 98-105. (In Russian).
4. Petrov T.G., Krasnova N.I. Principle of creation of mineral rock classification using RHA-method (on an
example of phoscorites and carbonatites). // Geochemistry, petrology, mineralogy and genesis of alkaline rocks. Abstr.
of Allrussian Conf. 18-23 Sept. 2006. Miass. Pp. 191-196. (In Russian).
5. Petrov T.G., Farafonova O.I. Information-component analysis. RHA method. Textbook. St.-Petersburg. 2005.
168 p. (In Russian).
6. Petrographic code of Russia. Magmatic, metamorphic, metasomatic, impact rock-assemblages. Second
edition. St.-Petersburg. VSEGEI Press. 2008. 200 p. (In Russian).
7. Krasnova N.I., Petrov T.G., Balaganskaya E.G., Garcia D., Moutte J, Zaitsev A.N., Wall F. Introduction to
phoscorites: occurrence, composition, nomenclature and petrogenesis. In: Phoscorites and carbonatites from the mantle
 82

to mine: the key example of Kola alkaline province. (Eds. F. Wall, A.A. Zaitsev). Publ. Min. Soc. of GB et Irl. L.: 2004.
Pp. 45-74.

Geochemistry of Ti and P in alkaline and basic rocks from the Ukrainian Shield
Kryvdik S.G., Guravsky T.V., Dubyna A.V.
N.P. Semenenko Institute of geochemistry, mineralogy and ore formation NAS of Ukraine, Kyiv, Ukraine

Within the Ukrainian shield (USd) magmatic rocks from different areas of this region and from various rock
complexes are often of different geochemical characteristics. Alkaline and subalkaline ultrabasic and basic rocks are
usually enriched in Ti and P initially. In some dikes and volcanites of these rocks the contents of TiO 2 amounts to 9%
and P2O5 to 1-2%. But within USd, there are rocks with a high concentration of titanium and low of phosphorus and
vice versa.
High contents of TiO2 (to 5.4%) and P2O5 (to 2.3%) occur in kimberlites from Azov area and central part of US.
In different gabbroids Ti and P concentrate together during process of magmatic differentiation. It is typical or
anorthosite-rapakivi granite plutons which contain complex deposits of ilmenite, apatite and titanomagnetite. But
apatite-ilmenite (Stremygorod, Fedorivka, Davydky) and essential ilmenite (Nosachiv) deposits sometimes occur in
these plutons separately. It is established that increased contents of apatite is characteristic for subalkaline gabbroids
(olivine gabbro, gabbro-troctolite, troctolite) in which clinopyroxene is presented by titanian augite. Wheares essential
ilmenite gabbroids are of norite composition, i.e. they belong to rocks of normal alkalinity. It is considered that initial
contents of TiO2 was not higher than 4-6% and P2O5 about 0.7-1.2% in parental magmas (type of jotunites or enriched
in Ti and P alkaline basalts) of such ore gabbroids.
In alkaline-ultrabasic (carbonatic) complexes titanium and phosphorus are distinctly separated. Titanium
concentrates and can form deposits in early rocks – pyroxenites, jacupirangites, olivinites. The main titanian mineral of
these rocks is ilmenite (in Ukrainian complexes), and in another world’s region perovskite and titanomagnetite may be
form large deposits too. Whereas phosphorus concentrates in later carbonatitic and phoscoritic differentiates.
Titanium distribution between pyroxene and other minerals depends on two factors – alkalinity of rocks and
depth (pressure) of their crystallization. In ultrabasic and basic alkaline and subalkaline rocks from hypabyssal or
slightly eroded massifs a considerable part of titanium (2-6% TiO2) consist in clinopyroxenes (titanian augite,
titanaugite). Whereas in abyssal massifs of these rocks the titanium contents in clinopyroxene strongly decreased (to
0.1-1.0 TiO2) even in cases of high amount of TiO2 (to 10%) in containing rocks (e.g. alkaline magnetite-ilmenite
pyroxenites in Cherigovka carbonatite complex, Azov area).
In rocks of normal alkalinity clinopyroxenes are always characterized by low contents of titatium (0.1-0.3 TiO2)
independently on its amount in rocks (including their ore types, e.g. Nosachiv ilmenite deposit).
Within the USd some regional features of magmatic rocks in reference to concentration of Ti and P are
discovered. In the Eastern part of USd (Azov area) alkaline and subalkaline basic and ultrabasic rocks are rich in
titanium, while in the Western part of this region they are depleted by this element (even in cases of their significant
enrichment of phosphorus). This is explained by different geodynamic situation of melting of deep-seated magmas,
which formed the titanium and phosphorus deposits during the process of differentiation.

Postmagmatic Geochemical Processes in Kimberlites

Kuznetsova L.G.
Institute of Geology and Mineralogy, Siberian Branch of the Russian Academy of Sciences, Novosibirsk,
630090 Russia

Kimberlites are of special interest as derivatives of the deepest magmatic melts. They contain rock and mineral
fragments from the upper mantle and high-pressure accessories, of which diamond is the most important.
In addition to common studies of the xenogenous matter in kimberlites, much attention is given to the
petrochemistry of kimberlites themselves; particularly, to variations in contents of rock-forming oxides, rare earths, and
diamonds. These studies, though, are hampered by the fact that kimberlites, like other alkali and ultrabasic rocks,
undergo considerable postmagmatic alteration. Little is known about mass transfer accompanying these alterations, and
satisfactory criteria of alteration degree have not been developed.
We studied quantitative indices of mass transfer during postmagmatic kimberlite alteration and calculated the
equivalent insoluble constituent, quartz group minerals. The amount of this constituent, normative secondary quartz,
can be calculated by simple algorithms suitable for any silicate analysis of a kimberlite. It can be used as an index of
postmagmatic alteration intensity.
The main rock-forming kimberlite minerals are olivine, calcite, and phlogopite. Other minerals typically
constitute less than 1% of the rock volume. Olivine and phlogopite distributions determine the distributions of silica and
magnesium oxide, which show clear positive correlation. The correlation between mean contents of silica and
magnesium oxide in 90 kimberlite bodies of the Yakutian Diamondiferous Province is quite close: r= +82.
Both eucrystalline and cryptocrystalline secondary quartz varieties can be found in altered kimberlites. Their
direct quantitation is difficult; therefore, excess silica in altered kimberlites can be expressed as normative secondary
 83

quartz, Q. This index can be calculated on the base of mean contents of main rock-forming minerals of kimberlite and
mineral impurities: diopside and dolomite.
The following oxide ratios (wt%) in minerals were taken for calculating Q: in calcite СаО : СО2 = 1.27; in
diopside MgO : CaO = 0.86; in diopside SiO2 : CaO = 2.69; in phlogopite MgO : K2O = 3.72; in phlogopite SiO2:K2O =
5.81; in olivine SiO2: MgO = 0.81; and in dolomite MgO:CO2 = 0.45.
The algorithms listed below were used depending on initial data:
A. СаО > CO2 , not accounting dolomite. In this case, СаОclc = СО2 kmb × 1.27;
СаОdiops = СаОkmb – СаОclc; MgOdiops = СаОdiops × 0.86 ; SiO2diops = СаОdiops × 2.69;
MgOphl = K2Okmb × 3.72; SiO2 phl = K2Okmb × 5.81;
MgOol = MgOkmb – MgOdiops – MgOphl;
SiO2 ol = MgOol × 0.81; Q = SiO2 kmb – SiO2 ol – SiO2 diops – SiO2 phl.
According to algorithm (А): Q = SiO2 – 0.81 MgO – 2.0 CaO + 2.54 CO2 – 2.8 K2O.
B. At СО2>CaO and СО2 = CaО, not accounting diopside. In this case, СО2 clc= СаОkmb /1.27;
MgOdol=(СО2 kmb – СО2 clc) × 0.45; MgOphl = K2Okmb × 3.72;
MgOol = MgOkmb – MgOdol – MgOphl;
SiO2 phl = K2Okmb × 5.81; SiO2 ol = MgOol × 0.81; Q = SiO2 kmb – SiO2 ol – SiO2 phl.
According to algorithm (B): Q = SiO2 – 0.81 MgO – 0.28 CaO + 0.36 CO2 – 2.8 K2O.
C. Simplified algorithm not accounting diopside or dolomite: MgO phl =К2Оkmb × 3.72;
SiO2 phl=К2Оkmb × 5.81; MgOol = MgOkmb – MgOphl; SiO2 ol = MgOol × 0.81;
Q = SiO2 kmb – SiO2 phl – SiO2 ol
According to algorithm (C): Q = SiO2 – 0.81 MgO – 2.8 K2O.
Algorithms A and B are best used if CO2 data are available. Algorithm C is recommended for the most
common X-ray fluorescence analyses without determining volatile components.
By these algorithms, Q can be calculated for each analysis. The set of Q values for a particular kimberlite body
allows construction of a postmagmatic transfer model, where the distribution of Q value frequencies corresponds to
frequencies of contents of other elements. The class interval width for Q distributions is chosen arbitrarily to remain
constant for all kimberlite bodies. Six stages with rock alteration degrees increasing with Q are recognized. At stage
0, Q varies from –1.0% to large negative values. Rocks of this stage are considered kimberlites dolomitized during
secondary alteration. This is confirmed by their substantially dolomitic composition and presence of minerals of the
hypergenesis zone: gypsum, dioctahedral micas, and, probably, terrigenous quartz. Other stages include Q values
from –0.99% to 85.00%. Stage 1 includes Q values from –0.99 to 3.99%; stage 2, from 4.00 to 5.99%; stage 3, from
6.00 to 11.99%, stage 4, from 12.00 to 19.99%; and stage 5, ≥ 20.00%. The Aikhal pipe (Table 1) illustrates the
model of mass transfer during postmagmatic kimberlite alteration.

Table 1. Postmagmatic mass transfer in kimberlites of the Aikhal pipe (n*=331)

Alteration stages 0 1 2 3 4 5
nF ** 28.9 41.3 15.7 11.9 1.2 0.9
Mean contents
Q -4.33 1.62 4.85 8.03 14.46 25.83
SiO2 18.08 23.53 26.03 25.98 31.59 42.61
TiO2 0.42 0.43 0.44 0.42 0.34 0.29
Al2O3 2.32 2.28 2.24 3.22 4.26 4.81
Fe2O3 3.71 4.43 4.78 4.44 4.49 2.50
MnO 0.11 0.10 0.09 0.07 0.09 0.10
MgO 23.91 24.37 23.91 19.19 17.53 13.70
CaO 18.97 16.34 16.30 19.22 13.57 12.06
Na2O 0.12 0.17 0.18 0.26 0.37 0.21
K2O 1.09 0.78 0.65 0.86 1.05 2.03
P2O5 0.70 0.65 0.69 0.51 0.37 0.26
LOI 30.43 27.04 24.83 25.57 23.48 21.43
* n, number of analyses; ** nF proportion of analyses falling to the corresponding cluster.

The results of studies of qualitative mass transfer indices in Yakutian kimberlites experiencing postmagmatic
alteration based on Q can be summarized as follows:
Rock-forming oxides. The increase in Q is accompanied by decrease in MgO. Profound alteration is
accompanied by all other components except SiO2 and Al2O3.
Iron group elements (FeO, Fe2O3, Cr2O3, NiO, and CoO) can be accumulated in reaction zones or subtracted
from them. Generally, secondary rock alteration ends in increasing basicity (predominance of FeO over Fe 2O3).
Rare earths. The contents of rare earth elements (REEs) rapidly change at the postmagmatic stage. This can
be clearly traced with increasing Q. The main petrochemical factors of REE accumulation are contents of phosphorus
and titanium in kimberlites. 'The greatest REE subtraction is recorded in rocks rich in phosphorus and poor in
titanium.
 84

Isotope ratios. The 147Sm/144Nd, 143Nd/144Nd, and 87Rb/86Sr ratios decrease with accumulation of normative
secondary quartz (Table 2).
Table. 2. Mean isotope ratios in kimberlites with various secondary alteration degrees (the pipes
Internatsional'naya, Aikhal, Udachnaya-West, Udachnaya-East, Komsomol'skaya-magnitnaya, and Poiskovaya).
Q, % 0.02–3.92 4.40–5.90 16.00
Number of samples 14 6 2
147
Sm/144Nd 0.0848 0.0830 0.0788
143
Nd/144Nd 0.512572 0.512563 0.512527
87
Rb/86Sr 0.19037 0.1342 0.0397

Diamond presence. Change of the contents of diamonds in altered kimberlites was described most
comprehensively for the Botuobinskaya pipe. It has been shown on the base of a large body of facts that the increase
in Q is accompanied by a decrease in diamond grain size; as a result, the diamond potential of rocks decreases
dramatically. We observed a similar effect in the Nyurbinskaya pipe. Thus, postmagmatic metasomatism causes
depauperation of diamondiferous ores.
To conclude, we note that secondary kimberlite alteration is more notable in subsurface parts of pipes but also
involves deeper kimberlites.
As shown above, secondary alteration of kimberlites profoundly changes their geochemical indices. This fact
can be taken into account in petrological reconstructions. We consider kimberlites with –0.99<Q<3.99% to be
unaltered. Just these kimberlites should be used in geochemical correlations.

Volcanoclastic carbonatites from Chrebtovy volcano, Kamchatka

Landa E.A., Markovsky B.A.
VSEGEI, S.Peterburg, Russia
The problem of extrusive carbonatites is actual now [Wolley, Church, 2005]. Specific products of such extrusive
process are revealed in East Kamchatka among widely developed upper cretaceous ultramafic volcanites [Маrkоvsky,
Rotman, 1981]. In this area it was reconstructed Chrebtovy paleovolcano generated pillow lavas and volcanoclastic
rocks with picrite composition (average composition: SiO2 - 39,7, TiO2 - 0,25, Al2O3 - 4,3, Fe2O3-2,95, FeO - 7,9, MgO -
30,6, CaO - 5,4, Na2O - 0,2, K20 – 0,13, Sr – 134 ppm). Ultramafic volcanites are present in volcanoclastic layers as
fragments of various sizes. Many fragments are in full or in part «bleached», the size of the «bleached» fragments
usually from 1 to 10-15 cm, and first mm in the fine fragmentary tuffes. The total amount of such fragments in separate
layers rans up to 20-30 %. Bleaching is result of replacement of initial picrite mineralogy by aggregate with аndradite,
diopside, carbonates, and also apatite, strontianite, barite, sulfides. Thus some initial features of initial rocks, in
particular amygdaloidal structure are kept.
Pure carbonate component of such secondary product (calcite, sometimes magnesite) is presented only in very
thin veins, spots and in amygdaloidal infilling. Carbonate-silicate rocks saturated by carbonates with СаО content at a
level of 42 % and SiO2 - 11-12 % -are very rare. For the first time they were described [Rass, Frih-Har, 1987] as
carbonatites compared with such effusive rocks of some regions (Mongolia etc.). However in overwhelming majority
of samples SiO2 content in carbonate-bearing rocks is at a level of 25-40 % (average composition: of 16 samples, %:
SiO2 - 34,6, TiO2 - 0,53, Al2O3 - 2,73, Fe2 O3 - 7,6, FeO - 5,8, MgO-12,1, CaO - 21,1, Na2O - 0,14, К2О - 0,03, Р2О5 -
0,57).
But the main point is that in many volcanoclastic fragments one can see transitions without sharp contacts from
such carbonate-bearing rock to picrites and picrobasaltes kept both structural features and initial composition .So
carbonate-bearing rock is a product of the metasomatic process produced by carbonate rich fluid during formation of
volcanic units (in parallel with autometasomatic changes – serpentinization and chloritization). Earlier this process has
been named «rodingitization», and these rocks – «rodingites» [Маrkоvsky, Rotman, 1981; Seliverstov, Оsipenko,
1999]. However composition of garnets (аndradite, not grossular) and in a first time some mineralogical and
geochemical features, such as: presence Sr-apatite, Sr-carbonates (table 1) and very high Sr content (up to 60-80
thousands ppm) and Ва content (up to 4,5 thousand ppm) testify, that these rocks are not rodingites, but specific
metasomatic carbonatites. Probably, after E.M.Epstein such rocks must be called «carbonatitоides», in our case
аpоpicrobasaltic and apopicritic. Among typical extrusive carbonatites enrichment of silicates is known (Fort-Portal
etc)
Table 1. Composition of some minerals from carbonatitоides, %.
№№ BaO CaO SrO SO3 P2O5 La2O5 CeO2
1. - 38,24 7,77 - 53,55 0,12 0,27
2. 63,45 - 1,62 33,95 - - -
3. 0,78 7,80 59,71 - - - -
4. 0,98 9,66 57,20
1 Sr-apatite, 2- barite, 3,4 – Sr-carbonates (calciostroncianite?).
 85

According to our isotopic data (εNd = +8, 87Sr/86Sr=0,703743), carbonate-bearing fluid was formed as well as
ultramafic volcanites in depleted mantle from a source functioned simultaneously with a source of volcanites. The
specificity of this source which probably reflects to regional features of mantle processes under Kamchatka has defined
very low Nb content and rather moderate REE сontent in described carbonatitоides. Our data indicate that carbonatites
can be metasomatic in extrusive systems and can be generated without connection with foidites.

References:
Маrkоvsky B.A., Rotman V.K., Geology and petrology of ultramafic volcanism. Leningrad: Nedra, 1981.247p
(in Russia).
Rass I.T., Frih-Har D.N., About find of carbonatites in upper cretaceous ultramafic volcanites, Kamchatka ||
Dokl. AN SSSR,1987,Vol. 1987. 294, P. 182-186. (in Russia).
Seliverstov V.A., Оsipenko A.V/, Petrology of Kamchatka rodingites.Vladivostok: Dalnauka, 1999. 146 p (in
Russia).
Wooley A., Church A. Extrusive carbonatites: A brief review.|| Lithos,2005,Vol.85. P.1-14

Models of diamond generation in different geodynamic environments

Lapin A.V.*, Belov S.V.**
*Institute of Mineralogy, Geochemistry and Crystal Chemistry of Rare Elements, Moscow, Russia;
**Vernadsky Geological Museum of RAS, Moscow, Russia

In recent years wide development of non-kimberlitic diamondiferous rocks of orogenic foldbelts was identified in
zones of continental collision (Tjen Shan, Tibet, Gibraltar Arc, etc.) and accretion-collision zones of active continental
margins (Kamchatka Peninsula, Koriak Upland, Japanese Islands, etc.) as well as in ultrametamorphic rocks,
characterized by intensive deformation with abundance of blastomylonitic and blastocataclastitic textures (Northern
Kazakhstan, the Urals, Rudnye Mountains, Rodops, Gneiss Belt of Norway and oth.) (Kaminsky, 2007; Belov, Lapin et
al., 2008).
Diamondiferous kimberlitic rocks, predominant in the area of ancient cratons don’t play any significant part in
mobile zones and they are replaced by various non-kimberlitic sources of diamonds. In orogenic foldbelts in zones of
continental collision non-kimberlitic diamondiferous rocks are presented by dikes of alkaline lamprophyres like
minettes and kamptomonochiquites, pipes of alkaline basaltoids, dikes and pipes of lamproitelike rocks, dikes of
picrites, pipes and dikes of original carbonatitelike rocks of complex silicate- carbonate composition, ultrabasic rocks of
intrusions, belonging to ophiolitic and platinum bearing formations. In accretion-collision zones of active continental
margins, diamondiferous non-kimberlitic rocks are established in volcanic ultrabasic rocks of the comatiite type,
basalts and melabasalts, ultramafites in massifs of ophiolitic and platinum bearing formations, lamprophyric dikes. In
ultrametamorphite belts, typical of collision fold zones, diamonds are determined in gneisses, eclogites and their
metasomatised varieties.
Taking into account rather individual position of kimberlites, typical of stable ancient cratons, often attempts to
explain non-kimberlitic diamond mineralisation of igneous and metamorphic rocks with the help of model common
with kimberlites are not efficient. Thus, a problem arises about possible conditions for diamonds generation, that differ
from traditional kimberlitic diamond formation.
According to the modern data, the areas of kimberlitic diamondiferous rocks abundance are limited by ancient
Archean cratons, i. e. areas of early stabilization, which during the long period existed under conditions of quiet
amagmatic regimes. These conditions are in agreement with low value of thermal flow and weak penetrability of the
lithosphere for abyssal fluids and melts. Kimberlites, as a rule, don’t demonstrate apparent connection with large units
of break tectonics of the lithosphere (rifts, zones of abyssal fractures, etc.) and in respect of geologic-tectonical position
they behave as most abyssal formations that are initiated by processes generated in sublithosphere zones of the mantle,
perhaps, low parts of the upper mantle and the intermediate zone. Thus, the diamond in kimberlites, the stability of
which is determined by significant lithostatic pressure and low thermal gradients, is accompanied by abyssal mantle
paragenesis, including such typical accessory minerals as pyrope, picroilmenite, chrome diopside and others.
In contrast, occurrences of non-kimberlitic diamondiferous igneous and metamorphic rocks are, with rare
exception, confined to the most geodynamically active lithosphere blocks existing under conditions of stressed
deformation state. In this connection, the model of non-kimberlitic diamondiferous rocks generation should take into
account characteristic features of stressed-deformation state of the lithosphere, typical of orogenic foldbelts zones of the
continental collision and accretion-collision active continental margins.
According to М.V. Gzovsky (1975) the values of the highest tangential stresses can significantly increase
lithostatic load and come to 1,47 GPa at depth up to 20 km. Taking into account that relation of the highest tangential
stresses to main normal stresses, σ1 and σ3 is determined by the equation τ = (σ3-σ1):2, the value of the highest
compressing stresses will be σ3 = 2 τ +σ1;i.e. these stresses can be on the order of 3,5 GPa, which corresponds to
minimal pressure conditions required to diamond generation. These data conform with pressure parameters in collision
orogenic zones, received with the help of various calculation models. According to P.N. Kropotkin (1996) and V.T.
 86

Filatova and the coauthors (2002) Pressures in orogenic collision zones in the crust basement usually are from 3-6 kbar
to10-12 kbar and locally for short time reach 50 kbar.
Based on the data on physical-chemical geomechanics, the most favorable environment for diamond generation
and phase transition of graphite-diamond appears to be created in combination of compression and shift, when chemical
reactions are accelerated and intensified. Similar environment often occurs in abyssal tectonic zones confined to
ultrametamorphic belts (Kokchetav block, the Urals, etc.) and in orogenic zones of the continental collision (Tjen Shan,
Tibet and oth.), where stressed-deformation state of the lithosphere is often accompanied by magma formation, as well
as in accretion- collision zones of active continental margins, where non-kimberlitic rocks can be controlled by
seismofocal zones of focuses of paleoearthquake concentration.
With respect of different models of diamondiferous rocks formation in different geodynamic environments,
estimation-prospecting criteria and methods , directed to kimberlitic diamondiferous rocks, are rather rarely used for
diamond prospecting in mobile zones, collision folded systems, and active marginal zones of continents. Under these
conditions, both composition of non-kimberlitic diamond sources and paragenesis of its accessory minerals can
significantly vary depending on the composition of diamond producing substrate. Typical diamond minerals-
indicators(pyrope and oth.) occur only in lamproitelike rocks and ultrahigh pressure ultrabasic massifs. In different
types of rocks diamonds are always accompanied by moissanite and other carbides, native metals (Au, Ag, Pt, Pb, Cu
and oth.) and their alloys, graphite; coesitic pseudomorphs of quartz are often present.
Thus, one of the most important results of the new data on occurrences of non-kimberlitic diamondiferous rocks
is the variety of potential diamond sources and models of diamond formation as well as their dependence on
geodynamic regimes, peculiar to these or those lithosphere segments. Obviously, the above should be taken into account
in estimation and prospecting for diamonds in outer craton environment.

References:
Belov S.V., Lapin A.V. and oth. Metallogeny of Platform Magmatism (carbonatites, kimberlites, trappes).
Novosibirsk, Nauka, 2008. P. 580 (in Russian).
Kaminsky F.V. Non-Kimberlitic Diamondiferous Igneous Rocks: 25 Years on. // Journ. Geol. Soc. of India. V.
69. March 2007. P. 557-575.
Gzovsky M.V. The basics of Tectonophysics. M. Nauka. 1975. 535 p. (in Russan).
Kropotkin P. N. Tectonic Stresses in the Earth’s Crust // Geotectonics. №2.1996. p.3-15. (in Russian).
Filatova V.T. and oth. Tectonophysics of Intraplate Collision // Geology and Mineral Resources of the Kola
Peninsula. V.1. Apatites. 2002. p. 57-73. (in Russian).

Geochemical types of kimberlites and their mantle sources

Lapin A.V.*, Tolstov A.V.**
*The Institute of Mineralogy, Geochemistry and Crystal Chemistry of Rare Elements. Moscow, Russia.
**Botuoba Geoexploration Expedition ,ALROSA, Mirnyi , Yakutia, Russia.

Revealing of geochemical heterogeneity of kimberlites became, in recent years, one of the main achievements in
study of the abyssal mantle magmatism. It was firstly demonstrated in connection with discovery of Arkhangelsk
diamond bearing province (Arkhangelsk Diamondiferous Province, 2000).Geochemical parameters of kimberlites in
this province proved to be rather different from rock parameters of traditional diamond bearing districts of Yakutia, that
can be recognized as a formation standard of diamond bearing kimberlites. Later, after discovery of diamond bearing
kimberlites in Middle-Markha district (Nakynsk field), the geochemical heterogeneity of kimberlites was defined within
Yakutsk province itself (Lapin, Tolstov, 2007). Similar, geochemically unusual kimberlites were also recently revealed
in Slave Province, Canada (Pokhilenko et al., 2003; Lapin, Tolstov, 2005).
Relatively late discovery of a number of unusual manifestations of kimberlites is explained by abnormal
properties of these rocks, which are hardly detected by conventional exploration methods. They are characterized by
extremely low ilmenite contents and, consequently by low magnetization and low degree of contrast in the magnetic
field. Pyrope content in rocks (the main indicator element for kimberlites) is often not much higher than diamond
content, which makes it difficult to use mineralogical research methods. However, the most radical difference
between newly revealed occurrences of kimberlites and rocks of the formation petrotype concerns geochemical
properties of rocks. The received representative parameters of two kimberlite types show the high degree of their
geochemical contrast, which concerns, first of all, a group of high charge rare and radioactive elements and has deep
genetic reasons.
Taking into account the available data for kimberlites of the formation petrotype, which has moderately high
concentration of titanium and HFS elements, we can recommend the name “kimberlites of geochemical type N”; the
rocks with very low content of HFS elements and relatively poor in titanium (kimberlites of Zolotitskoe field in
Arkhangelsk Province and Nakynsk field, Yakutia) can be called “kimberlites of geochemical type D”. Ce/Y and Nb/Zr
ratios, alongside with Ce, Nb, Zr, U, and Th concentrations, that are higher in kimberlites of N type, are important
indicators for determination of a geochemical type of kimberlites. Correlation relations of elements (Nb – Ti, Ce – Y,
Ce – P and oth.) are individual in the rocks of two geochemical types (Fig. 1, 2).
 87

Fig. 1. Fig. 2.
Fig. 1. Correlations between the contents of (a) Zr and Nb,(b) Th and U in the kimberlites of the Nakyn and
Zolotitsa fields and traditional diamond-bearing regions of Yakutia. (1) Kimberlites from the traditional diamond-
bearing regions of Yakutia (Mir, International,Udachnaya, Aikhal, Yubileinaya, Komsomol’skaya, 23rd Party
Congress, Taezhnaya, and Dachnaya pipes); (2) kimberlites from the Nakyn field of Yakutia (Botuobiya and
Nyurbinskaya pipes); (3) V. Grib pipe in the Verkhotina field of the Arkhangelsk province; and (4) kimberlites of
the Zolotitsa field of the Arkhangelsk province (Lomonosovskaya, Pionerskaya, and Karpinskii pipes).
Fig. 2. Correlations between the contents of (a) Ce and Y and (b) Ce and P2O5 in the kimberlites of the
Middle Markha region and traditional diamond-bearing regions of Yakutia. Kimberlite pipes: (1) Yubileinaya, (2)
Komsomol’skaya, (3) Dachnaya, (4) Udachnaya, (5) Aikhal, (6) International, (7) Mir, (8) 23rd Party Congress,
(9) Taezhnaya, (10) Botuobiya, and (11) Nyurbinskaya.

Contrast differences in HFS elements distribution in petrochemically rather homogeneous types of rocks result
from the particular geochemical history of these elements in mantle rocks, which differs from geochemical history of
main components and coherent admixture elements (Cr, Ni, V and oth.). According to the analysis, the main factor,
determining distribution of non-coherent HFS elements in the mantle kimberlite source, is abyssal metasomatism,
caused by juvenile fluids flows, which is always accompanied by significant introduction of alkalies, titanium, high
charge rare and radioactive elements. Thus, there is a good reason to consider the lithosphere substrate, metasomatized
under the influence of juvenile abyssal fluids, as a mantle source of kimberlites, belonging to the geochemical type N. It
is also clear, that generation of kimberlites type D takes place under different conditions. Geochemical properties of this
type of kimberlites and their confinement to collision margins of ancient cratons and terrains allows to think, that rocks
with negative HFS elements and titanium anomaly are generated from the lithosphere substrate that was metasomatized
under the influence of volatiles introduced from the subducted oceanic crust.
The obtained data essentially change the idea of kimberlites as a geochemical object. The outlined concept has a
number of petrologic, mineralogical and exploration results. For petrology, it is important to get the reliable criteria for
participation of subduction processes in the mantle metasomatism and magmatism. For diamond minerageny it is
important, that the degree of kimberlite diamond content does not depend on their geochemical type and, hence, the
diamond rather falls into the category of protomineral of the mantle substrate, the subsequent metasomatism and fusion
of which, as well as transportation of the abyssal matter with kimberlite magma, can be accompanied by crushing,
growth and solution of diamond. In addition, the adequate geochemical image of kimberlites, which essentially changes
in the light of new data, is important for prediction of diamond bearing magmatites and diamond exploration
geochemistry.

References:
Arkhangelsk Diamondiferous Province: Geology, Petrography and Mineralogy, Ed.by O.A.Bogatikov,
Mosk.Gos. Univ., Moscow. 2000. 522 c, (in Russian).
Lapin A.V., Tolstov A.V., Vasilenko B.B. Petrogeochemical Characteristics of Kimberlites from Middle
Markha Region with Application to the Problem of the Geochemical Heterogeneity of Kimberlites Geochemistry
Jnternational. 2007. Vol. 45. pp.1197-1209 (in Russian).
Pokilenko N.P., McDonald J.A., Agashev A.M. et al. Kimberlites and Carbonatites of the Snap Lake/King
Lake Dike System: Structural Setting, Petrogeochemistry and Petrology of a Unique Type of Association. In Long
Abstracts of 8th Intern. Kimb. Conf., Victoria, Canada, 2003.
Lapin A.V., Tolstov A.V. Problems of the Geochemical Heterogeneity of Kimberlites. Prikl. Geochim. 2005.
2. P.77-93, (in Russian).
 88

Alkaline plume-magmatism of continents and oceans and roots of alkaline plumes

Lazarenkov V.G.
State Mining Institute named after G.V. Plekhanov, Saint Petersburg, Russia.

According to up-to-date concepts, the plume is a fluid-heat flow, which might be mainly hydrogenous and
generated in the D–layer of the liquid Earth’s core (Dobretsov et al., 2000, 2008; Letnikov, 2001; Brandon, 2005). Its
magmatic realization – the plume-magmatism – takes place in the asthenospheric Earth’s layer at depths down to 600-
700 km. The similar level of depth is suggested by seismic data for formation of potassic igneous rocks of Java Island
(Whitford, Nicholes, 1976). The plume moves in form of a fluid phase with properties of super conductivity, super
permeability and probably, with the super ascension rate from the depth of D-layer (about 2900 km) up to the boundary
of asthenosphere bottom.
Alkaline magmatism is first of all a continental phenomenon, and thus; it is developing under cratons: platforms
and shields, and in a lesser degree – in folded areas, mainly in hard median blocks (accretionary terranes). In margins of
continents the alkaline magmatism is observed in pericontinental areas of the passive ocean-continent transition zones
of Atlantic type (table 1).
In the oceans alkaline magmatism is developed weakly, as compared to continental crust, and the mere series
of oceanic alkaline formations seems to be clearly contracted, shortcut. There, the signs of plumes with high
alkalinity can be observed, in first turn, on islands located in continent-ocean transition zones near passive Atlantic
type margins. For instance, on Cape Verde Islands, on Canaries in the Atlantic Ocean or on Comoro Islands in the
Indian Ocean. Thus, the temporal series of the Canaries volcanic complexes have the following composition: tholeitic
(Cretaceous-Paleogene), alkali-rhyolite-trachyte-alkali-basaltic (13.7-13.0 Ma) phonolite-trachyte-alkali–basaltic
(4.4-3.4 Ma). The temporal series of Comoro Islands complexes is as following: alkaline-basalts (Miocene),
phonolite-trachyte-alkali-basalts (Miocene-Pleistocene), leucitite-phonolite-alkali–basalts (Emerick, Duncan, 1982).
Temporal series of insular alcaline margin complexes of perioceanic rifts (Canary Islands, Comoro Islands, Cape
Verde Islands, Islands of the Gulf of Guinea, etc.) correspond to the first members in the series of continental alkaline
volcanic complexes.

Table 1. Temporal series of volcanic formations in rift zones (Lazarenkov, 1988)

Continental Oceanic
Inter-platform rise Mid-oceanic
Intercontinental Pericontinental
blocks ridges
leucitic leucitic — —
alkali-rhyolitic alkali-rhyolitic — —
alkali-trachyte- alkali-trachyte-
— —
trachytic trachytic
phonolitic phonolitic — —
blue earth blue earth — —
phonolite- leucititic with phonolite- basanite-phonolite-
carbonatite leucititic with carbonatite leucititic
phonolite-trachyte- phonolite-trachyte- phonolite-trachyte-
alkali-basaltic alkali-basaltic alkali-basaltic
rhyolite (alkali- rhyolite (alkali- rhyolite (alkali- rhyolite (alkali-rhyolite)
rhyolite) – trachyte – rhyolite) – trachyte – rhyolite) – trachyte – alkali- – trachyte – alkali-
alkali-basaltic alkali-basaltic basaltic basaltic
alkali-basaltic alkali-basaltic alkali-basaltic alkali-basaltic
basaltic basaltic basaltic basaltic
Note. Series are given in order from the earlier to later ones (from bottom upward).

The signs of plumes with high alkalinity are observed on the lifted inter-plate blocks of oceanic islands located
on oceanic platforms (thalassocratons) - on Seychelles and Kerguelen Island in the Indian Ocean, on Hawaiian Islands
in the Pacific Ocean, etc. Thickness of crust in such platforms exceeds in 2-5 times the usual thickness of oceanic crust
– up to 20-40 km, and its cross-section is similar sometimes to the geologic section of continental crust, for instance,
beneath Seychelles (Ben-Abraham et al., 1984). The oceanic crust with increased thickness is a product of a long-lasted
geological history and alkaline rocks of such “mature” crust correspond to alkali-basalts and phonolite-trachyte-alkali-
basalts complexes, for example, of Hawaiian Islands.
Finally, some islands are located on the mid-ocean ridges; for instance, the large island of Iceland in the mid-
Atlantic ridge. Iceland, considered as a “hot spot”, has in the basement thin oceanic crust as thick as 10 km, and the
island is characterized by acid rhyolite-(alkali-rhyolite)-alkali-basalt volcanism. From formational point of view,
Iceland is not the unique place with rhyolite and alkali-rhyolite magmatism occurrence, because the South Atlantic
chain of islands strung along the mid-Atlantic ridge (Ascension, Tristan da Cunha, Gof, Buve islands) is also
characterized by occurrence of rhyolitic extrusive rocks (rhyolite-basaltic province of the Atlantic Ocean).
 89

Besides series of alkaline formations, there is one more important index of alkaline igneous activity in continents
and oceans – that is the rate of alkaline rock occurrence within those largest geotectonic structures. Its value is near
0,1% for continents, than in the oceans it makes maximum several parts per ten thousand, more probably some parts per
hundred thousand, or even some parts per million, i.e. it is extremely low (Lazarenkov, 1988). There are not known
petrographic provinces with more or less broad aureole of alkaline rocks occurrence in oceans.
Consequently, if continent areas were the place for active alkaline magmatism, the far more extensive oceanic
areas didn’t relate to such zones. From the concept of plumes this phenomenon may be regarded in the way that the
Earth’s continents did be areas of intensive and continual alkali gaseous drainage during the long-lasted period of time:
at least, from the end of Archaean - 2.7-2.5 Ga (Kogarko, 2004), but in vast areas of oceans the alkaline plumes
remained weakly developed and appeared, in this way, mainly in Cretaceous - Cenozoic time, i.e. within last 0.14 Ga.
What might be the reason for strong and continual alkaline plume-magmatism under continents and the weak,
short-live appearance of this phenomenon in oceans? According to the geochemistry studies of the largest oceanic
ultrabasic solid masses, for example, the world largest solid mass Dyu Syud in New Caledonia (4950 км2), and
investigations of mantle inclusions in oceanic alkali-basalts, in particular, at Hawaiian Islands, the ultrabasic oceanic
mantle is poor in alkalis and incoherent elements, at least down to the bottom of asthenosphere. Obviously, it didn’t
have much influence upon the plumes chemistry, in terms of variations in its alkalinity and contents of incoherent
elements. Thus, it is quite possible that oceanic mantle didn’t produce alkaline plumes for this reason. Judging from the
Earth’s geological development history, it may be assumed that envelop of the primary mantle had one and the same
genesis and more or less similar ultrabasic composition over the whole Earth – as under future oceans, so under future
continents. And if it was so, it may be supposed, with the unique initial composition of oceanic and continental mantle,
that continental mantle, like the oceanic one, was not the source of alkaline plumes and associated foidaphile elements.
Therefore, this source was probably connected with the liquid Earths’ core, first of all with its outer layer D.
Conclusion: Comparison between alkaline formations developed in continents and oceans leads to assumption
that the source of alkaline plumes was the liquid Earths’ core under the continents and, in far more seldom cases, under
oceans.

References:
Ben-Abraham Z., Nur A., Jones D., Koks A. Continental accretion: from the oceanic plateaus to the
allochthonous massifs // Modern problems of geodynamics. Moscow: Mir, 1984. P. 101-120.
Dobretsov N.L. About sources of mantle plumes. Reports of the Russian Academy of sciences, 2000. Vol. 373,
Num. 1. P. 84-86.
Dobretsov N.L. Geological consequences of thermochemical model of the plumes. // Geology and geophysics.
2008. Vol.49, Num. 7. P. 587-605.
Kogarko L.N. Alkaline magmatism in history of the Earth. // Tectonics and geodynamics. VSEGEI, St.
Petersburg, 2004. P. 76-81.
Lazarenkov V.G. Formational analysis alkaline rock continents and oceans. The formations analysis of alkaline
rocks of continents and oceans. Leningrad: Nedra, 1988. 236 p.
Letnikov F.A. Superdeep fluid systems of the Earth and problems of the ore genesis. // Mining geology. Geology
of ore deposits. 2001. V 43. Num. 4. P. 291-308.
Brandon A.D., Walker R.J. The Debate over core-mantle interaction. // EPSL. 2005. V. 232. P. 211-225.
Emerick C.M., Duncan R. Age progressive volcanism in the Comores Archipelago, western Indian Ocean and
implications for Somali plate tectonics. // EPSL. 1982. V. 60. P. 415-418.
Whitford D.F., Nicholls I.A. A Potassium variation in lavas across the Sunda arc Java and Bali. // Volcanism in
Australia, Amsterdam. 1976. P. 63-75.

Perovskite from the Tiksheozero carbonatite: age and genesis

Lepekhina E.N.*, Antonov A.V.*, Savva E.V.**, Belyatsky B.V.***, Sergeev S.A.*
*Centre of Isotopic Research, VSEGEI, St.-Petersburg, Russia
**Institute of Precambrian Geology and Geochronology RAS, St.-Petersburg, Russia
***VNIIOkeangeologia, St.-Petersburg, Russia

The ultramafic–alkaline–carbonatite complex Tiksheozero is located near the NE continental margin of the
Karelian Craton within Archaean tonalite–trondhjemite–granodiorite gneisses. The Tiksheozero carbonatite complex is
a typical ring complex where carbonatites are associated with intrusions of ultramafic and alkaline rocks. Klyunin and
Panichev (1987) postulated five separate intrusion phases: (1) olivinites; (2) pyroxenites; (3) theralites, jacupirangites
and ijolites; (4) nepheline syenites; and (5) carbonatites. Carbonatites occur as large bodies which are more than several
hundred meters wide and up to 3 km long. The main carbonatite associations are represented by calcite, apatite,
phlogopite (tetroferrriflogopite), magnetite, amphibole – high-temperature, and ankerite, dolomite, amphibole and
apatite – low-temperature carbonatite (Tichomirowa et al., 2006).
There were a lot of attempts to estimate of the real age of the massif by using various radiology methods. But the
results were not good enough and all of this concerns the carbonatites but not ultramafic counterparts. The first age
estimations of the Tiksheozero carbonatites were based on few K/Ar ages from biotites and amphiboles and
 90

corresponded to the range 2.0 – 1.8 Ga (Klyunin, Panichev, 1987). Lead-lead isochron for three apatite fractions was
published by Shchiptsov et al. (1991) and the age of carbonatites was ascribed to 1980 ± 170 Ma. Further detail
investigation of various isotope systems (Rb/Sr, Sm/Nd, U/Pb, C, O) for whole-rock samples and mineral separates
were undertaken by Tikhomirova with coauthors (2006). Obtained Rb/Sr isochrons varied from 1680 to 1910 Ma, Sm-
Nd – from 1700 to 1950 Ma, and Pb-Pb apatite–whole-rock isochron corresponded to 1850–1880 Ma. Thus, to
summarize these data the emplacement of the complex can be related to Palaeoproterozoic activity of the Neoarchaean
junction zone. But the exact time of massif intrusion has not been determined. Noteworthy there is not only large
disagreement in age estimations obtained by different isotope systems but big age-errors, bad isotope data correlations
and isochrons’ parameters are obvious as well. Such situation is quite typical for secondary metasomatic overprint on
primary magmatic systems and such conclusions were done by Tichomirowa et al. (2006) but the source and time of
this impact remained unknown.
We have made an attempt to estimate the time of carbonatite intrusion studying U-Pb system in zircons and
baddeleyite from drill core samples of carbonatites (Antonov et al., 2008; Belyatsky et al., 2008; Rodionov et al., 2008).
The obtained age estimation proved Proterozoic age of the carbonatites. But at the same time, the investigation of zircon
internal structures demonstrated a recrystallization of metamict parts under hydrothermal (metasomatic) environments.
This process probably took place much later during Caledonian orogenesis 450 – 410 Ma ago.
It is well known that perovskite is a rather ubiquitous mineral in alkaline-ultrabasic rocks and carbonatites. Also,
it is mineral geochronometer which in contrast to zircon could not be xenogenous and due to its crystallization from the
melt allows to estimate the time of intrusion emplacement properly. Therefore, we decided to support primary age
estimation of carbonatite intrusion by study of perovskite U-Pb isotope system.
Perovskites were found in the mineral separates of carbonatite sample from core hole 146/177-187. It should be
mentioned that perovskite was not observed in thin sections of the same sample under optical microscope revision and
scanning electron microscopy study as well. Anhedral single perovskite crystals are typically 100 to 500 mkm in size
(fig. 1). Chemical composition was analyzed by EDX technique (Link Pentafet Inka Energy with Si(Li) 10 mm 2
detector). Studied perovskite has composition close to CaTiO 3 and demonstrates only limited variations: Na – up to 1.2
wt.%, Fe – 0.6-1.7 wt.%, Sr – up to 0.9 wt.%, Ce – up to 3.7 wt.%, Nd – up to 1.6 wt.%. The most of perovskite grains
contains inclusions of rock-forming and accessory minerals: calcite, dolomite, mica, diopside, apatite, ilmenite,
pyrrhotite. A lot of holes after liquid inclusions were identified also.
SHRIMP analyses of perovskites were performed at Centre of Isotopic Research (VSEGEI, Sankt Petersburg,
Russia). The procedure for SIMS U-Pb perovskite analysis is similar to that described by (Ireland, 1990). Grains were
embedded in epoxy (probe mount) together with analytical standard, grinded and polished. As a standard we have used
perovskite from skarn of the Tazheran complex, Baikal Lake area. Tazheran perovskite U-Pb isotope composition was
previously analyzed by ID-TIMS method. Obtained U-Pb age corresponds to 458 ± 5 Ma that is in a good agreement
with other labs' data. Our SHRIMP-II dating of this perovskite grains gave 465 ± 15.
Sixteen perovskite grains from Tiksheozero carbonatites were analyzed. The measured U-Pb isotope data,
uncorrected for common Pb, were plotted on a Tera-Wasserburg diagram. The obtained spread in isotope composition
was really enough for construction best-fit regression line through all analysis data and a common Pb composition
(207Pb/206Pb=0.836). The age of studied perovskite corresponds to 381 ± 10 Ma (MSWD= 0.63) (fig.2).

Fig. 2. U-Pb SHRIMP perovskite data plotted on a

Fig. 1. Back-scattered electron image of perovskite Tera-Wasserburg concordia diagram.
from the Tiksheozero carbonatite. Analytical results are plotted as a total ratios,
Cc – calcite, Ilm – ilmenite, Apt - apatite uncorrected for common Pb. Solid line indicates mixing
trend between radiogenic lead and common lead of
present-day composition .
 91

Conclusions:
The obtained perovskite age is in contradiction with generally accepted Proterozoic age of the Tiksheozero
carbonatite and coincides with the age of the zircon recrystallization caused by overprinted hydrothermal (metasomatic)
process. So, it is possible to suppose that the studied perovskite is not primary magmatic mineral and its formation is
directly connected with the processes of recrystallization and metasomatic transformation of the carbonatite rocks.
Similar perovskite origin is described by Kukharenko et al. (1965) for Devonian alkaline-ultrabasic massifs with
carbonatites of the Kola Peninsula and northern Karelia. Moreover there are a lot of examples for metasomatic origin of
perovskite in skarns formed over carbonaceous rocks at the contact with alkaline and basic intrusions – typical localities
are Shishim Mountains, Ural, Tazheran complex, Siberia, etc (Mitchell, 2002). So, it is cannot be excluded that
metasomatic event which caused perovskite formation in Tiksheozero carbonatites is connected with the well known
alkaline magmatism, which was widespread in the Kola region 360-380 Ma ago (Kramm et al., 1993) and is the
plausible result of the upper mantle Paleozoic plume activity (Arzamastzev et al., 2002).

References:
Antonov A.V. et al., 2008. Mineralogical and geochemical peculiarity of accessory minerals from Tiksheozero
carbonatites complex. Geochemistry of magmatic rocks–2008. School «Geochemistry of Alkaline rocks». Absract
Volume, 4–5. (in Russian).
Arzamastsev, A.A et al., 2002. Palaeozoic processes of plume–lithosphere interaction in the Northeast Baltic
Shield: prolongation, volumes, conditions of magma generation. In: F.P. Mitrofanov, Editor, Geology and Raw
Materials of the Kola Peninsula, Apatity, KSC RAS, vol. 2, 104–145 (in Russian).
Belyatsky et al., 2008. Hydrothermal zircons from Proterozoic carbonatite Tiksheozero massif. 33 IGC. Abstract
CD-ROM. Oslo. MPI-07, 1257121.
Ireland, T.R., Compston, W., Williams, I.S. & Wendt, I., 1990. U-Th-Pb systematics of individual perovskite
grains from the Allende and Murchison carbonaceous chondrites. Earth and Planetary Sci. Lett., 101, 379–387.
Klyunin, S.F., Panichev, V.V., 1987. Geological building and mineral resources from the Panaryarvin zone and
its framework. North-West Geological Survey. Reprint, Monchegorsk. 56 p. (in Russian).
Kramm, U., Kogarko, L.N., Kononova, V.A. and Vartiainen, H., 1993. The Kola Alkaline Province of the CIS
and Finland: Precise Rb-Sr ages define 380-360 Ma age range for all magmatism. Lithos, 30, 33–44.
Kukharenko, A.A. et al., 1965. The Caledonian Complex of Ultrabasic, Alkaline Rocks and Carbonatites of the
Kola Peninsula and northern Karelia. Nedra, Moscow. 550 p. (in Russian).
Mitchell, R. H., 2002. Perovskites. Modern and ancient. Almaz Press. Canada. 320 p.
Rodionov, N. et al., 2008. Baddeleyite SHRIMP age: application for carbonatite massifs dating. 4 th International
SHRIMP Workshop. Abstract Volume. 103–105.
Shchiptsov, V.V. et al., 1991. The distribution of U–Th–Pb and rare earth elements in apatites of Karelia.
Mineral. Zh. 13 (4), 92–98 (in Russian).
Tichomirowa, M. et al., 2006. The mineral isotope composition of two Precambrian carbonatite complexes from
the Kola Alkaline Province – Alteration versus primary magmatic signatures. Lithos, 91, 229–249.

Formation of diamond and syngenetic minerals in the mantle multi-component silicate-carbonate-

sulfide-carbon substance: the key role of carbonatites
Litvin Yu.A.*, Kuzyura (Shushkanova) A.V.*, Bobrov A.V.**, Vasil’yev P.G.**, Okoyomova V.Yu.**
*Institute of Experimental Mineralogy, Chernogolovka, Russia; **Moscow State University, Moscow,
Russia.

In this work, melting phase relations of multi-component multi-phase system composed of eclogitic omphacite
(Omph-Cpx) + garnet (Grt) assemblage, K-Mg-Ca-carbonatite, sulfide pyrrhotite (Po) + pentlandite (Pn) +
chalcopyrite (Ccp) material and carbon (graphite, diamond) is first physico-chemically studied in high-pressure high-
temperature experiment in the context of diamond genesis. In general [1], experimental physico-chemical research of
diamond origin in the Earth’s mantle calls for compositions of starting materials that are chemically close to or
reproduce important constituent parts of the multi-component diamond-parent medium of essential chemical
variability.
At present, the criterion of syngenesis of diamonds and their primary inclusions [2] is crucial for physico-
chemical experimental untangling petrological and mineralogical details of diamond genesis. In connection with this,
«syngenesis» phase diagram is solely suited and most informative. The syngenesis diagram is taken its name from
the fact that it unravels the physico-chemical «secrets» of syngenetic relations between diamond and all the other
solid, liquid and volatile components and phases involved into diamond-forming processes under specific chemical
and PT physical conditions. The syngenesis diagram of the multi-component system under study at 7.0 GPa is
represented by its two-measure pseudo binary section «eclogite28carbonatite42sulfide30 – diamond» (wt. %) where
{eclogite = [(Grt: SiO2 40.00, TiO2 0.46, Al2O3 22.00, Cr2O3 0.04, FeO 20.90, MnO 0.52, MgO 9.02, CaO 8.18, Na 2O
0.17)40(Omph-Cpx: SiO2 54.80, TiO2 0.48, Al2O3 9.79, Cr2O3 0.05, FeO 6.40, MnO 0.07, MgO 8.97, CaO 13.10,
Na2O 6.70, K2O 0.30)60]}28{carbonatite = (K2CO3)50(MgCO3)25(CaCO3)25}42{sulfide = [Po: FeS]40[Pn: (Fe,
Ni)9S8]40[Ccp: CuFeS.2)20]}30; graphite is used as starting carbon material. Major constituent parts of the whole
 92

system under study are «eclogite40carbonatite60 – diamond» and «sulfide – diamond» systems which were taken
separately for experimental study. Two separate silicate40carbonate60 (carbonatite) – diamond and sulfide - diamond
syngenesis diagrams were constructed at 7.0 GPa. The curves of diamond solubility in carbonatite and sulfide melts
under partial and complete melting of the systems are determined and plotted as the key details of the proper
diagrams. The curves (together with solidus lines) are boundary for P-T-composition conditions of diamond-forming
phase fields and important for understanding the physico-chemical mechanism of diamond formation.
Earlier experimental study of the simplified silicate-carbonate-sulfide system [3, 4] demonstrates the complete
carbonate-silicate liquid miscibility as well as complete immiscibility of homogeneous carbonate-silicate and sulfide
melts which both are effective diamond-forming media. It was also found that syngenetic formation of diamond with
silicate and carbonate minerals in diamond-forming sulfide melt is impossible because solubility of silicate and
carbonate components in sulfide melts is critically low.
The effect of complete immiscibility of carbonatite and sulfide melts makes possible to superpose the both
sub-system diagrams experimentally studied here by projecting the image of one of them onto another one. As a
result the combined syngenesis diagram for the whole eclogite-carbonatite-sulfide-diamond system is constructed.
Special controlling experiments testify the validity of the combined syngenesis diagram. The pseudo binary diagram
demonstrates clearly the interrelation between syngenesis conditions of diamond and trapped phases in dependence of
PT parameters. In accordance with temperature and composition (pressure is constant in this case), conditions of
syngenetic formation of diamond with silicate-carbonate (carbonatite) and sulfide melts, garnet, sulfide solid solution,
clinopyroxene and carbonate minerals as well as their assemblages go evident. Hence the syngenesis diagram reveals
potential scenarios of capturing each of the coexisting phases by growing diamond and PT conditions for these
events.
Present experimental study is motivated by (1) a close natural association of diamond with silicate, carbonate
and sulfide minerals and melts which is identified by thorough mineralogical study of the growth inclusions in
diamond [5-9], (2) still disputable estimation of chemical composition of diamond-parent medium between
mineralogists that is contradictory favored as predominant silicate [10, 11], metal [12, 13], carbonatite [14, 15],
kimberlite [16, 17], sulfide [18, 19], C-O-H volatile [20, 21] one and (3) the first high-pressure experimental results
for melting phase relations of extremely simplified silicate (pyrope) – carbonate (aragonite) – sulfide (pyrrhotite)
system under PT conditions of diamond stability [3, 4].
The resulting data of this study as well as relevant experimental and mineralogical data support the view [2]
that multi-component carbonatite (carbonate-silicate) melt of variable composition is of decisive importance in origin
of the most mantle-derived diamonds and their syngenetic inclusions. The heart of the diamond-parent carbonatite
medium is argued as completely miscible carbonate-silicate melt over-saturated with dissolved elemental carbon. The
carbonatite melt hosts minor chemically variable components and phases as miscible and soluble (phosphate,
chloride, C-O-H volatile, etc) so immiscible and insoluble (sulfides, native metals, etc). Influence of the immiscible
components on PT conditions and kinetics of diamond nucleation and crystallization in parent carbonatite melts
seems not to be essential. Influence of the soluble components may be more perceptible but not critical because of
their comparatively lowered content in parent carbonatite melt (a steady-state of C-O-H volatile phases under mantle
conditions is of low probability).
Reliable approximation of the parent composition is multi-component system MgO – CaO - FeO (Fe, Fe2O3) –
MnO – Na2O – K2O – Al2O3 – Cr2O3 – TiO2 – ZrO2 - SiO2 – P2O5 – CuS (Cu2S) – FeS (FeS2) – NiS – KCl – NaCl –
SiC – CO2 (CO, CH4) – H2O – C. Congruent carbonate melting, complete carbonate-silicate liquid miscibility and
high elemental carbon solubility in carbonatite melts under conditions of diamond PT stability are key factors in
formation of diamond-parent carbonatite melt.
Process of formation of parent medium for diamonds relates to conditions of origin of carbonatite magma in
Earth’s mantle. The process may begin with metasomatic mantle peridotite carbonatization by chemically active
volatile C-O-H agents of plume origin. Ensuing formation and evolution of carbonate-silicate magma with hosting
miscible components (including carbon) and immiscible phases lead to multi-component diamond-forming
carbonatite.
Experimental study of physico-chemical role of the components highly soluble in multi-component diamond-
parent carbonatite melts (C-O-H volatile is among them) becomes urgent.
This study is supported by the INTAS project 05-1000008-793,RFBR grants 08-05-00110-a and 09-05-00751-
a.

References:
1. Litvin Yu.A., Butvina V.G. Diamond-forming media in the system eclogite-carbonatite-sulfide-carbon:
experiments at 6.0-8.5 GPa. Petrology. 2004. Vol. 12. P. 377-387.
2. Litvin Yu.A. High-pressure mineralogy of diamond genesis. In Advances in High-Pressure Mineralogy (E.
Ohtani, ed.). Geological Society of America Special Paper 421. 2007. P. 83-103.
3. Shushkanova A.V., Litvin Yu.A. Phase relations in diamond-forming carbonate-silicate-sulfide systems on
melting //Russian Geology and Geophysics. 2005. Special N.V. Sobolev vol. 46. No. 12. P. 1317-1326.
4. Shushkanova A.V., Litvin Yu.A. Experimental evidence for liquid immiscibility in the model system
CaCO3 –pyrope – pyrrhotite at 7.0 GPa: the role of carbonatite and sulfide melts in diamond genesis. The Canadian
Mineralogist. 2008. Special J. Gittins vol. 46. P. 991-1005.
 93

5. Stachel T., Harris J.W., Brey G.P. Rare and unusual mineral inclusions in diamonds from Mwadui,
Tanzania // Contributions to Mineralogy and Petrology. 1998. Vol. 132. P. 34-47.
6. Klein-BenDavid O., Logvinova A.M., Izraeli E.S., Sobolev N.V., Navon O. Sulphide melt inclusions in
Yubileinaya (Yakutia) diamonds// Victoria, Canada, VIII International Kimberlite Conference Long Abstract.
Mineralogical Society of America. CD-ROM FLA_0119.
7. Taylor L.A., Anand M. Diamonds: time capsules from the Siberian mantle // Chemie der Erde. 2004. Vol.
64. P. 1-74.
8. Titkov S.V., Gorshkov A.I., Zudin N.G., Ryabchikov I.D., Magazina L.O., Sivtsov A.V. Microinclusions in
dark-grey diamond crystals of octahedral habit from kimberlites of Yakutia // Geochemistry (Geokhimia). 2006. No
11. P. 1209-1217 (in Russian).
9. Logvinova A.M., Wirth R., Fedorova E.N., Sobolev N.V. Nanometre-sized mineral and fluid inclusions in
cloudy Siberian diamonds: new insights on diamond formation // European Journal of Mineralogy. 2008. Vol. 20. P.
317-331.
10. Williams A.F. The Genesis of Diamond (2 volumes). London: E. Benn Ltd. 1932. 636 p.
11. Marakushev A.A., Pertsev N.N., Zotov I.A., Paneyakh N.A., Cherenkova A.F. Some petrological aspects
of diamond genesis // Geology of Ore Deposits (Geologia Rudnykh Mestorojdeniy). 1995. Vol. 37. N2. P. 105-121
(in Russian).
12. Wentorf R.H., Bovenkerk H.P. On the origin of natural diamonds // Journal of Astrophysics. 1961. Vol.
134. P. 995-1005.
9. Chepurov A.I., Fedorov I.I., Sonin V.M. Experimental study of diamond formation under high PT-
parameters // Geology and Geophysics (Geologia i Geophysica). 1998. Vol. 39. No 2. P. 234-244 (in Russian).
13. Von Eckermann H.A. Comparison og Swedish, African and Russian kimberlites In P.J. Wyllie (ed.).
Ultramafic and Related Rocks. New York: John Wiley and Sons. 1967. P. 302-312.
14. Litvin Yu.A., Litvin V.Yu., Kadik A.A. Experimental characterization of diamond crystallization in melts
of mantle silicate-carbonate-carbon systems at 7.0 GPa // Geochemistry International. 2008. Vol. 46. P. 531-553.
15. Sobolev V.S. Conditions of diamond formation // Geology and Geophysics (Geologia i Geophysica). 1964.
No. 1. P. 3-20 (in Russian).
16. Arima M., Nakayama K., Akaishi M., Yamaoka S., Kanda H. // Crystallization of diamond from a silicate
melt of kimberlite composition in high-pressure and high-temperature experiments // Geology. Vol. 21. P. 968-970.
17. Marks P.S. Pyrrhotite and the origin of terrestrial diamonds // Mineralogical Magazine. 1972. Vol. 38. P.
636-638.
18. Bulanova G.P., Griffin W.L., Ryan C.G. Nucleation environment of diamonds from Yakutian kimberlites
// Mineralogical Magazine. 1998. Vol. 62. No. 3. P. 409-419.
19. Haggerty S.E. Diamond genesis in a multiply constrained model // Nature. 1986. Vol. 320. P. 34-38.
20. Sokol A.G., Pal’yanov Yu.N. Diamond crystallization in fluid and carbonate-fluid systems under mantle
PT parameters. Part. 2. Pecuilarities of diamond-forming processes (analytical review of experimental data) //
Geochemistry (Geokhimia). 2004. No. 11. P. 1157-1172 (in Russian).

Physicochemical factors of diamond and graphite formation in carbonatite melts on experimental

grounds
Litvin Yu.A.*, Spivak A.V.*, Solopova N.A.**, Litvin V.Yu.*, Bobrov A.V.**
*Institute of Experimental Mineralogy, Chernogolovka, Russia; **Moscow State University, Moscow,
Russia.
Here the purpose is experimental kinetic study of diamond and graphite nucleation and growth in multi-
component K-Na-Mg-Ca-carbonatite melt with dissolved carbon under conditions of diamond PT stability. Phenomenal
peculiarity of the carbonatite-carbon melt-solution, while oversaturated by elemental carbon in respect to diamond, is
nucleation and growth of thermodynamically unstable graphite phase jointly with diamond (similarly to other diamond-
forming «melt-carbon solution» systems including metallic [1], silicate [2], silicate-carbonate [3], etc.). Hence the
elucidation of the physico-chemical stimulation and mechanism of joint formation of the carbon polymorphs in mantle
carbonatite melts has to be understood not only for making better control over diamond crystal growth in carbonatite-
carbon growth medium but for revealing the reasons for co-existence of diamond and graphite under the Earth’s mantle
conditions as well as syngenetic formation of mantle-derived diamond with primarily included graphite therein.
Mechanism of graphite formation in carbonatite melts may be extended over the conditions of graphite PT stability as
well but for as long as pressure-induced congruent melting of carbonate solvent of carbon is attained and the couple of
solid carbon and carbonate-carbon melt-solution works as a strong self-buffering system [4].
Earlier experimental study of multi-component carbonatite-carbon systems [5] revealed that diamond formation
in their melts is very efficient under high pressure. The following investigations made it evident that carbonatite melts
are effective solvents for graphite and diamond [6], kinetic of diamond growth is sensitive to change of PT parameters
[7], and carbon dissolved in carbonatite melt is of elemental atomic and/or cluster form [8].
Present experimental investigation of diamond nucleation and growth is carried out with the use of starting
carbonatite compositions, wt. %: K2CO3 35.0, Na2CO3 10.0, MgCO3 25.0, CaCO3 30.0, which is a Fe-free version of
carbonatite composition studied earlier [7]: K2CO3 27.21, Na2CO3 2.89, MgCO3 17.36, CaCO3 26.91, FeCO3 25.63. To
 94

a large degree both the carbonatite compositions are chemical replicas of the carbonatite end member for multi-
component carbonate-silicate compositions of primary carbonatite inclusions in Botswanian diamonds [10]; graphite is
used as a starting carbon material. The experiments were carried out at fixed temperature of 1800 oC and variable
pressure within the 7.0 – 8.5 GPa range for time duration of 5 – 30 min. Quantity of spontaneously formed diamond
crystals in the volume unit of the sample after quenching and solidification of the growth melt was taken as the
conventional indicator of nucleation density for diamond phase («survived nucleation centers»). It was found that the
nucleation density is distinctly lowered from 1.8·103 nuclei·cm-3 to 1.1·103 nuclei·cm-3 for 30 min. duration while
pressure decreases from 8.5 to 7.25 GPa. At the same time the linear size of diamond crystals ranges from 40 µm to 160
µm; the maximal size is achievable at the lowest pressure. The normal growth rate for octahedral (111) face of diamond
crystal at 7.25 GPa is measured as changeable from 10 µm/min after 5 min to 6 µm/min after 10 min and to 2.3 µm/min
after 30 min of duration. The effect of lowering of normal rate of diamond growth arises from difference in density of
starting graphite and diamond. This is due to time-sensitive local pressure depression in the experimental samples while
the less dense starting graphite re-crystallizes into more dense diamond product (effect of «volume loss» in high-
pressure experiment). In case if diamond is used as a starting material the time-dependent diamond growth rate is close
to the linear one.
It is symptomatic that re-crystallized graphite crystals came into being at lowest pressures when the density of
diamond nucleation is minimal. This is a specific «signal» of some carbon over-saturation heterogeneity under
experimental conditions and pointed out that the field of diamond spontaneous nucleation and crystallization is close to
termination with further pressure decrease. The PT points of termination of diamond nucleation establish a boundary
line for the field of diamond nucleation inside of the PT-region of diamond stability. Effect of diamond nucleation
demonstrates that carbon solutions in carbonatite melts are highly over-saturated in respect to diamond phase (by
physico-chemical term, a «labile» over-saturated melt-solution). The resulting data of this study as well as relevant
experimental data [6] testify that degree of labile carbon over-saturation to diamond that is responsible for diamond
nucleation has regularly decreased with pressure lowering until the critical limit is attained in a boundary line.
The boundary line is a demarcation one between the higher pressure regions of «labile» and the lower pressure
region of «metastable» carbon over-saturation in respect to diamond. Metastable carbon over-saturation in respect to
diamond is responsible for seeded growth of diamond only (possibility of diamond nucleation is suppressed here). But,
it is also responsible for spontaneous nucleation and growth of single crystalline graphite (the process accompanies the
seeded growth of diamond from the growth medium of metastably over-saturated carbonatite melt-carbon solution). The
PT region of the metastably over-saturated solutions is limited by the graphite-diamond equilibrium line for which
diamond seed growth and unstable graphite crystallization are suppressed because carbonate melts reaches the state of
carbon saturation in respect to both carbon phases – diamond and graphite (solubility value for diamond and graphite
becomes equal as for thermodynamically stable phases). But, graphite can crystallize at lower pressures as
thermodynamically stable phase. Crystallization of unstable graphite phase under PT conditions of diamond stability
may be estimated as the example of realization of Ostwald’s rule [10]. The facts of nucleation and growth of unstable
single-crystalline graphite under mantle conditions are illustrated by syngenetic inclusions of graphite in diamond [11].
On this basis the assumption that graphite associated with diamond is indicator of «metastable» formation of diamond
may be estimated as mistaken.
Moreover, thermodynamically unstable graphite may be a primordial mineral of the Earth’s mantle. The
thermodynamics-based carbon phase diagram includes equilibrium graphite-diamond boundary [12] but it is not capable
to ascertain that both graphite and diamond phases are kinetically capable to exist firmly as thermodynamically unstable
phases far off the equilibrium boundary; these facts have been determined experimentally [13]. This means that the
direct transition of graphite to diamond and vice versa is not practically realizable in the one-component carbon system
at the most depths of the Earth’s mantle. But the equilibrium graphite-diamond line controls re-crystallization of
graphite to diamond and vice versa in the system «carbon solvent – carbon» [14]. For the re-crystallization, it is
important that solubility of thermodynamically unstable solid phase exceeds solubility of the stable one.
Hence formation of thermodynamically stable diamond and unstable graphite in carbonatite melt-carbon solution
is under control of the next physico-chemical factors: (1) pressure-induced high carbon solubility in congruent
carbonatite melts and formation of carbonatite-carbon melt-solution, (2) initiation of over-saturated carbon solution in
respect to diamond because of carbon solubility difference of unstable graphite and diamond if graphite is carbon source
or if temperature gradient exists over experimental sample in the case when diamond is a carbon source, (3) formation
of labile carbon over-saturation for diamond spontaneous nucleation, (4) formation of metastable carbon over-
saturation for seeded diamond growth and accompanying unstable graphite nucleation (following the Ostwald’s rule),
(5) carbon over-saturation degree is progressively dependent on pressure increase (at fixed temperature), (6) carbon
over-saturation degree is regressively dependent on temperature increase (at fixed pressure), (7) kinetics of diamond
and graphite nucleation and crystallization is progressively dependent on the degree of carbon over-saturation in
carbonatite melt.
This study is supported by the INTAS project 05-1000008-7938, RFBR grant 08-05-00110-a and the RF
President grant 4122007.5.

References:
1. Strong H.M., Hanneman R.E. Crystallization of diamond and graphite // Journal of Chemical Physics. 1967.
Vol. 46. No. 9. P. 3668-3676.
 95

2. Litvin Yu.A. Experiment in solution of the problem of diamond genesis // Transactions of the Russian
Mineralogical Society (Zapiski Rossiyskogo Mineralogicheskogo Obshchestva). 2007. Part 136. Issue 7. P. 138-158 (in
Russian).
3. Litvin Yu.A., Bobrov A.V. Experimental study of diamond crystallization in carbonate-peridotite melts at 8.5
GPa // Doklady Earth Sciences. 2008. Vol. 422. No. 7. P. 1167-1171.
4. Litvin Yu.A., Litvin V.Yu., Kadik A.A. Experimental characterization of diamond crystallization in melts of
mantle silicate-carbonate-carbon systems at 7.0-8.5 GPa // Geochemistry International. 2008. Vol. 46. No. 6. P. 531-
553.
5. Litvin Yu.A., Zharikov V.A. Primary fluid-carbonatite inclusions in diamond: Experimental modeling in the
system K2O – Na2O – CaO – MgO – FeO – CO2 as a diamond formation medium // Doklady Earth Sciences. 1999. Vol.
367A. P. 801-805.
6. Spivak A.V., Litvin Yu.A. Diamond syntheses in multi-component carbonate-carbon melts of natural
chemistry: elementary processes and properties // Diamond and Related Materials. 2004. No. 13. P. 482-487.
7. Solopova N.A., Spivak A.V., Litvin Yu.A., Urusov V.S. Kinetic peculiarities of diamond crystallization in
carbonate-carbon system at 8.5 GPa // Herald of the Division of Earth’s Sciences of the RAS. 2008. N0. 1(26). URL:
http://www.scgis.ru/russian/cp1251/h_dgggms/1-2008/informbul-1_2008/term-11e.pdf.
8. Spivak A.V., Litvin Yu.A., Shushkanova A.V., Litvin V.Yu., Shiryaev A.A. Diamond formation in carbonate-
silicate-sulfide-carbon melts: Raman- and IR-microspectroscopy // European Journal of Mineralogy. 2008. Vol. 20. P.
341-347.
9. Schrauder M., Navon O. Hydrous and carbonatitic mantle fluids in fibrous diamonds from Jwaneng, Botswana
// Geochimica et Cosmochimica Acta. 1994. Vol. 58. P. 761-771.
10. Ostwald W.Z. // Zeitschrift fur Physik und Chemie. 1897. Vol. 22. P. 289.
11. Glinneman J., Kusaka K., Harris J.W. Oriented graphite single-crystal inclusions in diamond // Zeitschrift fur
Kristallographie. 2003. Vol. 218. P. 733-739.
12. Leipunsky O.I. On artificial diamonds // Advances in Chemistry (Uspekhi Khimii). 1939. Vol. 8. No 10. P.
1519-1534 (in Russian).
13. Bundy F.P. Direct conversion of graphite to diamond in static pressure apparatus // Journal of chemical
Physics. 1963. Vol. 38. No. 3. P. 631-643.
14. Litvin Yu.A. High-pressure mineralogy of diamond genesis. In Advances in High-Pressure Mineralogy (E.
Ohtani, ed.). Geological Society of America Special Paper 421. 2007. P. 83-103.

Endogenous and sedimentary carbonate rocks from the Belomorian province: new geochemical,
isotopic and geochronological data
Lokhov K.I.*, Sibelev О.S.**, Slabunov А.I.**, Bogomolov E.S.*, Prilepsky E.B.*
* Isotopic Research Centre,VSEGEI, St.Petersburg, Russia; ** Institute of Geology, KarRC, RAS,
Petrozavodsk, Russia

In the Belomorian province of the Baltic Shield carbonate rocks (CR) are fairly scarce. One of the best-known
CR occurrences is located on Mramorny Island in the White Sea and was considered earlier [1, 4] an example of highly
metamorphosed sedimentary rocks. Together with this occurrence, we have studied veined, genetically obscure CRs
near the Town of Gridino and marbles discovered recently [5] in the River Pongoma - Lake Korzhino area and
interpreted as metasediments.
On Mramorny Island, CRs constitute a ca. 5-40 m thick and ca. 170 m long lens-shaped body thrown into
isoclinal folds. They are associated, interbedded and deformed jointly with amphibolites and are cut by granite-aplites
[4]. Kyanite-garnet-biotite gneisses, exposed in the central part of the islet, seem to be a fragment of host rocks. In the
Gridino area, CRs fill several closely-spaced, steeply dipping, branched veins that vary in thickness from 0.1 to 0.7 m
and are visible over a distance of ca. 10 m. Host rocks are represented by pyroxene-amphibole gneisses and
amphibolites. Skarnification processes are observed at vein contacts. The mineral composition and structural
characteristics of CRs from the above localities are similar. The rocks are medium-grained, coarse-grained and
xenomorphic-granular (heterogranoblastic, occasionally lepidogranoblastic). Their major minerals are dolomite (ca. 70-
90%), calcite (5-10%), biotite (up to 10%) and hornblende (up to 7%). Their minor minerals are clinopyroxene, chlorte,
apatite, plagioclase (up to 100% Аn) and quartz. Epidote, sphene, muscovite, rutile, zircon, ilmenite, pyrite and thorite
are present as accessories.
In the River Pongoma and River Sigma areas, CRs occur as abundant lenticular bodies, up to 5 х 2 m in size.
Together with alumina gneisses and amphibolites, they are a part of the clastic constituent of a tectonic melange
supported by migmatized garnet-amphibole gneisses (blastomylonites). CR bodies are spatiously restricted to the axial
part of the zone. Their mineral composition is dominated by dolomite (over 90%), calcite, quartz and chlorite being less
abundant. Amphibole and muscovite are encountered in the exocontact zones of lenses.
Isotopic data show that Gridino and Marble Island rocks are endogenous, possibly igneous carbonatites with a
considerable contribution of a mantle constituent (Fig. 1), and rocks from the mélange zone (Rivers Pongoma and
Sigma) are typical metasedimentary carbonate rocks commonly understood as marble.
 96

8
Mramorny isl. marbles and carbonate-silicate rocks
Gridino, marbles
6 Gridino, carbonated gneiss
Pon'goma riv., marbles
87
Sr/86Sr=0.70460
4 Sigma riv., marbles
TDM=3180 ma
87 eNd(2800)=-0.8
Sr/86Sr=0.70550 -0.70830
TDM=2870 ma
2 eNd(2420)=-1.3

0
Archean and Protherozoic
C PDB

metamorphised carbonaceos sediments

isotopic fractionation
in calcite - dolomite
13

-2


or calcite - CO2
systems
87
-4 Sr/86Sr=0.70297
TDM=2790 ma
eNd(2420)=+0.3

-6
mantle
carbonatites isotopic exchange by oxygen
-8 with water fluids and silicates

-10
5 7 9 11 13 15 17 19 21 23 25
 18O SMOW

Fig.1. Isotopic parameters of carbonate rocks from the White Sea region. Composition fields: metacarbonate
rocks [6], mantle carbonatites [7].

It is obvious from the isotopic composition of strontium and the εNd(T) value that Gridino carbonatites are less
heavily contaminated with crustal matter. However, the isotopic composition of their carbon is similar to that of mantle
carbonatites and their oxygen is slightly heavier presumably due to interaction with crustal matter, probably upon
metamorphic alteration in Svecofennian time, and Mramorny Island carbonatites contain carbonates (dolomite) with
significantly isotopically fractionated carbon and oxygen. Such an isotopic fractionation could have occurred either in a
calcite-carbon dioxide system or in a calcite-dolomite system [2, 3 et al.]. For igneous carbonatites the latter option
seems more preferable and implies the presence of complementary, largely calcitic rocks relatively light with respect to
carbon and oxygen isotopes. The strontium isotope ratio of metasedimentary carbonate rocks agrees with that of oceanic
water in Neoarchean time [6], and we estimate the age of sedimentation at ca. 2800 Ma.
We extracted zircons from Mramorny Island dolomitic carbonatites. They consist of two matter generations: 1)
cores that show a thin oscillatory zoning and Th/U >0.1 and 2) dark high-uranium homogeneous crusts with Th/U<0.1.
Matter from both zircon generations was analysed on SIMS SHRIMP-II. Both generations show concordant U-Pb age
values, the former marking a 2420±20 Ma magmatic stage and the latter being indicative of 1845±15 Ma metamorphic
alterations.
Thus, for the first time we have revealed endogenous carbonatites in the Belomorian complex the age of which
(ca. 2420-2450 Ma) agrees with the rifting epoch.

References:
1. Bibikova, Е.V., Slabunov, А.I., Bogdanova, S.V., Skjold, Т. Early Precambrian tectono-thermal evolution
of the Earth’s crust in the Karelian and Belomorian provinces of the Baltic Shield, as shown by U-Pb isotopic study of
sphenes // Geokhimia. 1999. No. 8. P. 842857. (in Russia).
2. Pandit, M.K., Sial, A.N., Sukumaran, G.B., Pimentel, M.M., Ramasamy, A.K., Ferreira, V.P. Depleted
and enriched mantle sources for Paleo- and Neoprotherozoic carbonatites of southern India: Sr, Nd, C-O isotopic and
geochemical constraints. // Chemical Geology, 2002, 189, p. 69-89.
3. Lokhov, K.I., Prasolov, E.М., Kapitonov, I.N., Kuzmin, V.K., Rodionov, N.V., Bogomolov, Е.S.,
Sergeyev, S.А. Isotopic geology of Early Precambrian calciphyres from the Okhotsk massif, Northeast Russia. Regional
geology and metallogeny, 2008, 35, p.56-71. (in Russia).
4. Stepanov, V.S., Slabunov, А.I. Amphibolites and carbonate rocks from the Pongoma Bay area, White Sea
// The Precambrian of North Karelia: petrology and tectonics. Petrozavodsk: KarRC, RAS. 1994. P. 630. (in Russia).
5. Sibelev, О.S., Kushkova, N.S., Anisimov, А.N. Tectonometamorphic rocks from the mélange zones of the
Belomorian Mobile Belt (Structural examples from the Lake Korzhino area) // Geology and useful minerals of Karelia.
Issue 9. Petrozavodsk, 2006. P. 23-36. (in Russia).
6. Veizer, J., Hoefs, J., Lowe, D.R., Thurston, P.C. Geochemistry of Precambrian carbonates: II. Archean
greenstone belts and Archean seawater. //Geochimica et Cosmochimica Acta, 1989 № 53. P.859-871.
7. Keller J., Hoefs J. Stable isotopic characteristics of recent natrocarbonatites from Oldoinyo Lengai / In:
Bell K., Keller J. (Eds) Carbonatite volcanism: Oldoinyo Lengai and petrogenesis of carbonatites. Springler, Berlin.
1995. P. 113-123.
 97

Bafertisite and jinshajiangite from the Gremyakha-Vyrmes alkaline complex, Kola Peninsula
Lykova I.S.*, Pekov I.V.*,*, Kononkova N.N.**, Shpachenko A.K.***
*Lomonosov Moscow State University, Moscow, Russia;
**Vernadsky Institute of Geochemistry and Analytical Chemistry RAS, Moscow, Russia;
***Geological Institute of Kola Science Centre RAS, Apatity, Russia

The layered titanosilicates bafertisite, Ba2Fe4Ti2O2(Si2O7)2(OH)4, and jinshajiangite,

NaBaFe4Ti2O(Si2O7)2(OH)3F, have been identified in 2007 by us in the Gremyakha-Vyrmes alkaline complex, NW part
of Kola Peninsula, Russia.
Minerals of the bafertisite group were not reported from Gremyakha-Vyrmes before. For jinshajiangite, it is first
find in Russia. The data on two finds of jinshajiangite were published. It was first described in an arfvedsonite dike in
alkali syenites near the Jinshajiang River, western Sichuan province, SW China (Hong Wenxing, Fu Pinqiu, 1982).
Second locality of jinshajiangite is Norra Karr alkaline massif, Sweden. The crystal structure of jinshajiangite was
studied by Rastsvetaeva et al. (2008) on Swedish sample. Bafertisite is more widely spread in nature than jinshajiangite.
One find of bafertisite in Russia, namely in the Burpala alkaline complex, Northern Baikal Region, was reported
(Ganzeev et al., 1971). Note that iron in the Burpala sample, analysed using wet chemical methods, was detected in
both bivalent and trivalent states. In its empirical formula, (Fe2++Fe3+) > Mn2+ but Mn2+ > Fe2+ as well as Mn2+ > Fe3+.
Thus, if its analysis is correct in part of the quantitative determination of the Fe 2+/Fe3+ ratio then, within the bounds of
modern mineralogical nomenclature, this mineral should be defined as hejtmanite, a Mn-dominant analogue of
bafertisite with the idealized formula for the end-member: Ba2Mn4Ti2(Si2O7)2O2(OH)4. In this case, our find of
bafertisite could be also considered as the first in Russia.
The described minerals were found in a pegmatite related to alkaline granites at northern coast of the Gremyakha
lake. Jinshajiangite occurs as needle-shaped crystals up to 2 mm long. The crystals typically form chaotic aggregates up
to 7 mm across. Jinshajiangite is golden-brown with red to yellowish-red tint. Bafertisite forms yellowish-red lamellar
crystals up to 1 x 3 x 4 mm. Associated minerals include albite, microcline, quartz, arfvedsonite, zircon, and apatite.
Bafertisite and jinshajiangite have been identified by chemical, X-ray diffraction and infrared spectroscopy data.
The X-ray powder patterns of bafertisite and jinshajiangite from Gremyakha-Vyrmes are similar to ones of these
minerals studied earlier (Kuan Ya-Hsien et al., 1963; Hong Wenxing, Fu Pinqiu, 1982). The main basal reflection (002)
of Kola jinshajiangite is characterized by the interplanar spacing 10.40 Å, the 001 reflex of Kola bafertisite is 10.95 Å.
The chemical composition of bafertisite and jinshajiangite was studied using the electron microprobe. Formulae
were calculated basing on 4(Si+Al). All iron was considered as bivalent, the O/OH ratio was calculated by charge
balance. The empirical formulae (cations have groupped according to structural data for the minerals) are:
bafertisite:
(Ba1.98Na0.04K0.03)Σ1.05(Fe3.43Mn0.37Mg0.03)Σ3.83(Ti2.02Nb0.03)Σ2.05(Si3.92Al0.08O14)(O1.84OH0.16)Σ2.00(OH2.39F1.61)Σ4.00;
jinshajiangite:
(Na0.57Ca0.44)Σ1.01(Ba0.57K0.44)Σ1.01(Fe3.53Mn0.30Mg0.04Zn0.01)Σ3.88(Ti1.97Nb0.06Zr0.01)Σ2.04(Si3.97Al0.03O14)O2.00
(OH2.25F0.73O0.02)Σ3.00.
The Kola jinshajiangite differs from the original Chinese sample in higher value of the Mn/Fe ratio and lower
value of the Nb/Ti ratio and lower F content. The Swedish mineral occupies intermediate position in its Mn/Fe ratio.
In its chemical composition, bafertisite from Gremyakha-Vyrmes is similar to bafertisite from its type locality,
the Bayan Obo alkaline complex, Inner Mongolia, China (Semenov, Chang Pei-Shan, 1959).
Chemically, bafertisite and jinshajiangite from Kola differ one from other not only in part of species-defining
sodium and barium cations but also in subordinate constituents. Bafertisite is characterized by higher content of fluorine
and lower content of niobium. Concentration of calcium in Kola bafertisite is below detection limit whereas in our
jinshajiangite, Ca, undoubtedly replacing Na, is significant admixture.
Barium minerals were not found in the Gremyakha-Vyrmes alkaline granites and their derivatives before
(Polkanov et al., 1967; Bulakh, 1997). Ba was accumulated probably because of its mobilization from potassium
feldspar as a result of albitization of granite interacted with feldspathoid rocks, namely nepheline syenites and ijolites.
This study was supported by grant of President of Russain Federation No. 863.2008.5 and grant of Russian
Science Support Foundation (I.V.P.).

References:
Bulakh A.G. On the mineralogy of alkaline granites of the Gremyakha Tundra, Kola Peninsula // Vestnik
SPbGU. 1997, ser. 7, issue. 3, p. 18-28 (in Russian).
Ganzeev A.A., Efimov A.F., Lyubomilova G.V. Manganese bafertisite from Burpala massif (Northern Baikal
Region) // Proc. of Fersman Mineralogical Museum of AN USSR. 1971, vol. 20, p. 195-197 (in Russian).
Hong Wenxing, Fu Pinqiu. Jinshajiangite – a new Ba-Mn-Fe-Ti-bearing silicate mineral // Geochemistry
(China). 1982, № 1, p. 485-464.
Kuan Ya-Hsien, Simonov V.I., Belov N.V. Crystal structure of bafertisite, BaFe 2TiO[Si2O7](OH)2 // Doklady
AN USSR. 1963, vol. 149, № 6, p. 1416-1419 (in Russian).
Polkanov A.A., Eliseev N.A., Eliseev E.N., Kavardin G.I. Gremyakha-Vyrmes Massif on Kola Peninsula. M.-
L.: Nauka, 1967, 236 pp. (in Russian).
 98

Rastsvetaeva R.K., Chukanov N.V., Rozenberg K.A. Crystal structure of jinshajiangite from Norra Karr massif
(Sweden) // Kristallografiya. 2008, vol. 53, № 4, p. 593-596 (in Russian).
Semenov E.I., Chang Pei-Shan. New mineral bafertisite // Science Record. 1959, vol. 3, № 12, p. 652-655 (in
Russian).

Zircon from the economic ultramafic-mafic Kharaelakh intrusion (Russia): first U-Pb and Hf-isotope
constraints on timing and source composition
Malitch K.N.*, Griffin W.L.**, Badanina I.Yu.*, Petrov O.V.*, Tuganova E.V.*, Belousova E.A.**,
Pearson N.J.**, Knauf V.V.***, Presnyakov S.L.*
* A.P. Karpinsky Russian Geological Research Institute (VSEGEI), St. Petersburg, Russia; ** GEMOC ARC
National Key Centre, Department of Earth and Planetary Sciences, Macquarie University, Sydney,
Australia; *** NATI Research JSC, St. Petersburg, Russia

Introduction. World-class PGE-Cu-Ni sulphide deposits occur in the Noril’sk-1, Talnakh and Kharaelakh areas
in the northwestern part of the Eastern Siberia, Russia. They are associated with sill-like ultramafic-mafic intrusions,
which are controlled by a long-lived intracontinental paleorift (Tuganova, 2000). These ‘Noril’sk-type’ intrusions range
in thickness up to 360 m and in length up to 25 km. In this study, we present new U-Pb and Hf-isotope data for 23
zircon grains from the Kharaelakh intrusion in order to: (1) provide age constraints on the magmatic evolution and (2)
specify the sources of materials involved in the generation of the host rocks.
Samples and analytical methods. A distinctive feature of the Kharaelakh intrusion is the presence of two
horizons of ultramafic rocks, distinguishing this intrusion from the Talnakh and Noril’sk-1 intrusive bodies. The rocks
investigated comprise (from top to bottom) olivine gabbro (samples 844-1, 844-6), plagiowehrlite (844-7) and
melanotroctolite (844-10,11). Forty grains of zircon were extracted using a ppm-mineralogy technique at NATI
Research JSC (Russia). Grains of zircons were hand picked from each concentrate, imaged by SEM and subsequently
mounted in epoxy blocks together with grains of the TEMORA and 91500 reference zircons. Transmitted and reflected
light photomicrographs and cathodeluminescence images were made in order to select grains and choose sites for
analyses, avoiding cracks and inclusions. The Sensitive High-Resolution Ion Microprobe (SHRIMP-II) at the VSEGEI
was used to perform 26 in-situ U-Pb analyses by applying a secondary electron multiplier in a peak-jumping mode
following the procedure described by Williams (1998). Age calculations use the routines of Ludwig (2003) and follow
the decay constant recommendations of Steiger and Jager (1977). In-situ Hf-isotope data were collected on the dated
spots within zircon grains. Twenty-six Hf-isotope analyses were carried out with a New Wave LUV213 laser-ablation
microprobe attached to a Nu plasma MC-ICP-MS at GEMOC, following the analytical procedures reported by Griffin et
al. (2002). The measured 176Lu/177Hf ratios and the 176Lu decay constant of 1.865x10-11 yr-1 reported by Scherer et al.
(2001) were used to calculate initial 176Hf/177Hf ratios. The present-day chondritic values of 176Lu/177Hf=0.0332 and
176
Hf/177Hf=0.282772 reported by Blichert-Toft and Albarede (1997) were used for the calculation of epsilon Hf values
(parts in 104 difference of initial Hf isotope ratios between the zircon sample and the chondritic uniform reservoir).
Morphology and internal structure. Zircon has been observed in thin sections as single grains or aggregates
enclosed in clinopyroxene, amphibole or mica, frequently intergrown with apatite. Separated zircon grains are
commonly idiomorphic to subidiomorphic prismatic, transparent to semi-transparent, light beige crystals that may
contain fissures; the elongation of zircon grains varies from one to three (sometimes up to 6-7). In the Pupin diagram
(Pupin, 1980), type D crystals predominate (76 %) among the investigated grains, indicative of alkaline-high
temperature conditions of formation. Observations under the petrographic microscope revealed distinct zircon
populations with different internal structure. However, zircons are characterized by similar fuzzy cathodeluminescence,
commonly with a total absence of the growth zoning typical of zircons from magmatic rocks.
U-Pb ages. Twenty-three zircon grains used for the U-Pb determinations yielded four groups of concordant U-
Pb ages. Colorless cores from complex grains 844-1_10 and 844-1_7, defined as population 1 (ZR 1), produced a
206
Pb/238U age of 347  16 Ma (mean square of weighted deviates (MSWD) = 1.2), which is significantly older than ages
found in the other types. Indeed, rims of zircons from these complex grains (population 2, ZR 2) gave a 206Pb/238U age of
265  11 Ma (MSWD=2.3), whereas dark cores from two other complex grains (i.e., 844-1_19 and 844-6_28) and the main
set of homogeneous grains (n=15) yielded slightly younger concordant 206Pb/238U age of 253.8  1.7 Ma, MSWD=0.064).
A younger concordant 206Pb/238U age of 235.7  6.1 Ma (MSWD=2.0) is typical of overgrowths over dark cores and a
minor group of homogeneous grains. For consistency, we refer to the groups of zircon with 206Pb/238U ages of 253.8 
1.7 and 235.7  6.1 as population 3 (ZR 3) and population 4 (ZR 4), respectively.
Hf-isotope data. The studied zircons show a wide range in Hf-isotope composition. Zircons of population 1,
represented by colorless cores in complex grains with 206Pb/238U ages between ca 338-355 Ma, yielded eHf (parts in 104
deviation of initial Hf isotope ratios between the zircon sample and the chondritic uniform reservoir) values from + 8.1
to + 8.7 (mean eHf + 8.4). Zircons of population 2 with 206Pb/238U ages between ca. 264.9-270 Ma (exemplified by rims
from the same complex grains) have Hf isotope compositions that are less radiogenic than the other zircon populations
(e.g. ZR1, ZR 3 and ZR 4). Population 3 zircons with 206Pb/238U ages between ca. 241.8-267.2 Ma and population 4
zircons with 206Pb/238U ages between ca. 229.4-239.6 Ma have similar mean eHf values (10.5 and 9.95, respectively),
which are only slightly higher than that of type 1. However, populations 3 and 4 zircons show a significant range in eHf
 99

(from +5.1 to +16.7 and + 4.9 to +13.1, respectively) with some points plotting close to the Depleted Mantle reference
line, while the least radiogenic points fall close to the values observed in ZR 2.
Genetic implications and concluding remarks. The U-Pb ages of the four zircon populations cover a
significant time span (347  16, 265  11, 253.8  1.7 and 235.7  6.1 Ma) suggesting a prolonged evolution of the
magmatic system. This magmatic activity is consistent with two recognised stages of active tectonism in the
development of the Siberian Craton (Malitch, 1975). The crystallisation of zircon population 1 corresponds to the final
stages of the Middle Paleozoic (D3-C1) tectonic cycle, whereas that of populations 2 to 4 matches the known duration of
the Early Mesozoic (P2-T2) tectonic event.
On the basis of results reported here we propose that mafic-ultramafic magmas were emplaced in the lithospheric
mantle or deep crust ca 90 Ma before the flood basalts, and that the magmas generated in Early Mesozoic (around 230-
260 Ma) picked up zircons from these earlier intrusions. We also suggest that this might represent a single long-lived
magma chamber. The age of zircon population 3 (253.8±1.7 Ma) slightly precedes that suggested for the basalts
(248.7±0.6 – 250.3.2±1.1 Ma, Reichow et al., 2009). Therefore, the timing of the magmatic episode exemplified by ZR
3 might be closely linked and possibly interpreted as coeval with flood-basalt volcanism. ZR 4 can be attributed to
thermal recrystallisation during or after the emplacement of the intrusion, clearly postdating the eruption of the basalts.
Hf isotope data show that majority of studied zircons have a clear juvenile component, and there is good
evidence of mixing with an older, possibly lithospheric component. The Hf-isotope data for zircons of population 3
suggest that the Kharaelakh magmas represent mixing between a juvenile source equivalent to the Depleted Mantle, and
a lithospheric source with Hf-isotope composition similar to the zircons of population 2. The smaller range of initial
176
Hf/177Hf values in population 4 might reflect progressive homogenization of these magmas during crystallisation, but
the present dataset is too small to say this with confidence.
The depleted mantle component was not previously recognised by whole-rock Nd- and Sr-isotope studies (Arndt
et al., 2003, among others). All rocks at Kharaelakh from which zircons were separated are characterised by eNd values
from + 0.8 to + 1.1. However, the existence of a highly depleted mantle source (eNd in the range of +3.7 and +5.1) has been
confirmed (Kogarko et al., 1988; Horan et al., 1995) in picritic lavas, both at Noril’sk (Gudchihinsky suite) and Maimecha-
Kotui (Maimechian suite) areas. Therefore, the slightly lower uniform Nd isotopic values typical of ore-bearing ‘Noril’sk-
type’ ultramafic-mafic intrusions were attributed to certain levels of crustal contamination, presumably in deep staging magma
chambers. Our data confirm that a lithospheric component is present. The Sm-Nd whole rock data reflect this (and the
homogenising effect of whole-rock analysis) more strongly, while the zircon data allow us to put better constraints on
the end-members of the mixing (DM vs an old lithospheric component with eHf ≈ 0 at 250 Ma).
In conclusion, our new findings suggest a prolonged period of mafic-ultramafic magmatic activity, from Middle
Paleozoic to Early Mesozoic, and interaction between juvenile magmas and an older lithospheric component, at least
during the ca 253 Ma magmatism. Consequently, these processes could lead to high degrees of separation and
concentration of ore elements and formation of specific ore magmas of unique scales and concentrations. We further
propose that ‘radiogenic’ Hf-isotope composition of zircon can be employed as an effective fingerprint for identifying
prospective intrusive host rocks and consequently is useful in exploration for sulphide-rich ores associated with
‘Noril’sk-type’ intrusions. Finally, our new data suggest that the Hf-isotope composition of defined zircon types can
provide a unique set of previously unknown constraints on petrologic history of the Kharaelakh intrusion.

References
Arndt N.T., Czamanske G.K., Walker R.J., Chauvel C., Fedorenko V.A. Geochemistry and origin of the
intrusive hosts of the Noril’sk-Talnakh Cu-Ni-PGE sulfide deposits // Economic Geology. 2003. Vol. 98, P. 495-515.
Blichert-Toft J., Albarede F. The Lu-Hf isotope geochemistry of chondrites and the evolution of the mantle-crust
system // Earth and Planetary Science Letters. 1997. Vol. 148. P. 243-258.
Griffin W.L., Wang X., Jackson S.E., Pearson N.J., O’Reilly S.Y., Xu X., Zhou X. Zircon chemistry and magma
genesis, SE China: in-situ analysis of Hf isotopes, Pingtan and Tonglu igneous complexes // Lithos. 2002. Vol. 61. P.
237-269.
Horan M.F., Walker R.J., Fedorenko V.A., Czamanske G.K. Osmium and neodymium isotopic constraints on the
temporal and spatial evolution of Siberian flood basalts sources // Geochimica et Cosmochimica Acta. 1995. Vol. 59. P. 5159-
5168.
Kogarko L.N., Karpenko S.F., Lyalikov A.V., Teptelev M.P. Isotope criteria of the meimechite genesis // Doklady
Academii Nauk SSSR. 1988. Vol. 301. P. 939-942 (in Russian).
Ludwig K.R. User’s Manual for ISOPLOT/Ex 3.00. A Geochronological Toolkit for Microsoft Excel. Berkeley
Geochronology Center Special Publication. 2003. No. 4. 70 pp.
Malitch N.S. Tectonic evolution of the cover of the Siberian Craton. Moscow: Nedra Press, 1975. 215 pp (in
Russian).
Pupin J.P. Zircon and granite petrology // Contributions to Mineralogy and Petrology. 1980. Vol. 73. P. 207-220.
Reichow M.K., Pringle M.S., Al’mukhamedov A.I., Allen M.B., Andreichev V.L., Buslov M.M., Davies C.E.,
Fedoseev G.S., Fitton J.G., Inger S., Medvedev A.Ya., Mitchell C., Puchkov V.N., Safonova I.Yu., Scott R.A.,
Saunders A.D. The timing and extent of the eruption of the Siberian Traps large igneous province: Implications for the
end-Permian environmental crisis // Earth and Planetary Science Letters. 2009. Vol. 277. P. 9-20.
Scherer E., Munker C., Mezger K. Calibration of the lutenium-hafnium clock // Science. 2001. Vol. 293. P. 683-
687.
 100

Stieger R.H., Jager E. Subcommission on geochronology: convention on the use of decay constants in geo- and
cosmochronology // Earth and Planetary Science Letters. 1977. Vol. 36. P. 359-362.
Tuganova E.V. Petrographic types, genesis and regularities of distribution of PGE-Cu-Ni sulfide deposits. St.
Petersburg: VSEGEI Press, 2002. 102 pp (in Russian).
Williams I.S. U-Th-Pb Geochronology by Ion Microprobe // In: McKibbe M.A., Shanks W.C., Ridley W.I.
(eds.) Applications of microanalytical techniques to understanding mineralizing processes, Reviews in Economic
Geology 1998. Vol. 7. P. 1-35.

New U-Pb isotope constraints on timing of metasomatism in a subcontinental mantle: evidence from
zircon at Finero, Italy
Malitch K.N.*, Knauf V.V.**, Badanina I.Yu.*, Garuti G.***, Presnyakov S.L.*
* A.P. Karpinsky Russian Geological Research Institute (VSEGEI), St. Petersburg, Russia; ** NATI
Research JSC, St. Petersburg, Russia; *** University of Modena and Reggio Emilia, Italy.

Introduction. The Finero phlogopite-peridotite represents a metasomatized residual mantle harzburgite,

exposed at the base of the lower-crust section in the Ivrea Zone, Western Alps (Hartmann and Wedepohl, 1993). It
forms the core of a concentrically zoned sequence of internal layered gabbro, amphibole-rich peridotite and external
gabbro (Fig. 1). The phlogopite peridotite contains small-size chromitite bodies, with a suite of accessory minerals such
as phlogopite, apatite, Ca-Mg carbonates, zirconolite, zircon, thorianite and uraninite, proposed to form during
alkaline-carbonatitic metasomatism process within the mantle (Zaccarini et al., 2004). Various aspects of the
metasomatism at Finero are currently debated including the provenance of contaminant fluids (mantle or crust), the
geodynamic environment (subcontinental mantle plume vs. subduction setting) and the extent of multiple metasomatic
events, which seemingly span about 85 Ma (293±13 Ma, Voshage et al., 1987 and 208±2 Ma, Grieco et al., 2001). In
this study, the combined application of a non-destructive technique to separate zircon from their host rocks and in-situ
analytical techniques for compositional and isotopic analysis has provided new, more detailed and more precise age
data on the formation of chromitite and related metasomatic events within a mantle tectonite at Finero.

Fig. 1. Simplified geological map of the Finero complex, showing location of the occurrences of chromitite
investigated (open triangles).

Samples and analytical methods. Chromitite samples were collected from the dump in the prospecting trenches
of Alpe Polunia and Rio Creves (Fig. 1). In thin sections, zircon at Rio Creves occurs as relatively large (up to 200 μm)
grains characterized by subhedral to euhedral shapes, whereas at Alpo Polunia zircon mostly show subhedral to
anhedral shapes. It has been commonly observed in contact with chromian spinel and olivine. About two hundred grains
of zircon were extracted using a ppm-mineralogy technique at NATI Research JSC (St. Petersburg, Russia), reaching
concentration factors between 40000 and 100000. Grains of zircon were hand picked from each concentrate, imaged by
SEM and subsequently mounted in epoxy blocks together with grains of the TEMORA (Middledale Gabbroic Diorite,
New South Wales, Australia) and 91500 (Geostandard zircon) reference zircons. Transmitted and reflected light
photomicrographs and CL images were made in order to select grains and choose sites for analyses, avoiding cracks and
inclusions. The Sensitive High-Resolution Ion Microprobe (SHRIMP-II) at the VSEGEI was used to perform 50 in-situ
U-Pb analyses by applying a secondary electron multiplier in a peak-jumping mode following the procedure described
by Williams (1998). Concordia age calculations were performed with ISOPLOT v. 3.00 (Ludwig, 2003) software.
Results. Separated zircon grains at Alpe Polunia are subhedral and colorless. They are characterized by
dominant smoky cathodeluminescense, with faint zoning or almost no internal pattern. Zircon grains at Rio Creves form
two distinct populations. Dominant zircon population is pale pink showing different shape features (subhedral,
 101

subrounded or elongated, frequently with slightly rounded edges). In cathodoluminescense, the main set of population is
represented by complex grains, which show development of core-rim relationship (most likely recrystallized rim on a
preserved core). Diffusive zoning patterns, which do not follow the grain outlines, has also been observed in
cathodoluminescense images. Subordinate zircon population show similar features revealed for zircons at Alpo Polunia.
Nine zircon grains from Alpo Polunia used for the U-Pb determinations yielded two groups of concordant U-Pb
ages (205.32.0 Ma, with mean square of weighted deviates (MSWD) = 0.018, probability (P) = 0.89, n=6 and 194.72.0
Ma, MSWD=0.3; P=0.58, n=6, respectively), being identical to age estimates as revealed in a relative probability plot
(Fig. 2A). At Rio Creves, three main age clusters has been recognized. The youngest age cluster, typical for
subordinate colorless zircon population and rims in complex grains of dominant pale pink population, show two
concordant 206Pb/238U ages (e.g., 208.64.0 Ma, MSWD=2.0; P=0.16, n=8 and 194.93.4 Ma, MSWD=0.45; P=0.50, n=3,
respectively). These ages are almost identical to those of zircon at Alpo Polunia. Two older age clusters are characterized
by the cores and core overgrowths from composite grains. They yielded concordant 206Pb/238U ages of 288.3  7.3 Ma
(MSWD=3.3, n=6) and 248.63.3 Ma (MSWD=0.13, P=0.72, n=8), respectively. These ages are reproduced within
uncertainty in a relative probability diagram (Fig. 2B). The significant time span represented by distinct zircon age groups
is interpreted as representing the timing of multiple events during zircon growth.

Fig. 2. Relative probability histogram for ion-probe U-Pb zircon ages at Alpe Polunia (A) and Rio Creves (B).

Discussion and concluding remarks. Since the pioneering work of Exley et al. (1982), the complex metasomatic
history at Finero has received much attention. New U-Pb results are consistent with the age range obtained for mantle
rocks, the phlogopite peridotite (293±13 Ma, Voshage et al., 1987) and chromitite (208±2 Ma, Grieco et al., 2001). The
former age estimate, based on a Rb-Sr whole-rock isochron for six phlogopite-bearing peridotites and one phlogopite
pyroxenite, has been interpreted as time of K metasomatic enrichment of the harzburgite. This event has been coeval
with the intrusion of alkaline ultramafic magmas into the deep crust of the Ivrea Zone during the late Carboniferous
(287±3 Ma, Garuti et al., 2001). The U-Pb age of 208±2 Ma for zircon at Alpe Polunia is corroborated by our ion-probe
U-Pb results for zircons of the same locality. It has been attributed (Grieco et al., 2001) to one of the major metasomatic
episodes. The U-Pb zircon ages identified at Rio Creves show notable differences. The U-Pb SHRIMP data do not
concur with the assumption of a single metasomatic event during chromitite formation. Therefore, we suggest a
prolonged formation and multistage evolution of zircon growth, as mirrored by multiple U-Pb ages. Firstly presented U-
Pb results for zircons from two chromitite localities (Alpe Polunia and Creves) place tight constraints on their distinctly
different temporal evolution, representing previously unknown stages of magmatic activity at Rio Creves. We thus
assume that different models suggested for the Ivrea Zone could be updated in light of new U-Pb constraints that
indicate the complex geological history of mantle rocks at Finero.
References:
Exley R.A., Sills J.D., Smith J.V. Geochemistry of micas from the Finero spinel-lherzolite, Italian Alps //
Contributions to Mineralogy and Petrology. 1982. Vol. 81, P. 59-63.
Garuti G., Bea F., Zaccarini F, Montero P. Age, geochemistry and petrogenesis of the ultramafic pipes in the
Ivrea Zone, NW Italy // Journal of Petrology. 2001. Vol. 42. P. 433-457.
Grieco G., Ferrario A., Von Quadt A., Koepprel V., Mathez E.A. The zircon-bearing chromitites of the
phlogopite peridotite of Finero (Ivrea Zone, Southern Alps): evidence and geochronology of a metasomatized mantle //
Journal of Petrology. 2001. Vol. 42. P. 89-101.
Hartmann G., Wedepohl K.H. The composition of peridotite tectonites from the Ivrea Complex, northern Italy:
resudues from melt extraction // Geochimica et Cosmochimica Acta. 1993. Vol. 57. P. 1761-1782.
 102

Ludwig K.R. User’s Manual for ISOPLOT/Ex 3.00. A Geochronological Toolkit for Microsoft Excel. Berkeley
Geochronology Center Special Publication. 2003. No. 4. 70 pp.
Voshage H., Hunziker J.C., Hofmann A.W., Zingg A. A Nd and Sr isotopic study of the Ivrea Zone, Southern
Alps. N-Italy // Contributions to Mineralogy and Petrology. 1987. Vol. 97. P. 31-42.
Williams I.S. U-Th-Pb Geochronology by Ion Microprobe. Applications of microanalytical techniques to
understanding mineralizing processes // Reviews in Economic Geology. 1998. Vol. 7, P. 1-35.
Zaccarini F., Stumpfl E., Garuti G. Zirconolite and Zr-Th-U minerals in chromitites of the Finero complex,
Western Alps, Italy: evidence for carbonatite-type metasomatism in a subcontinental mantle plume // Canadian
Mineralogist. 2004. Vol. 42. P. 1825-1845.

Petrology of Teschenites and alkaline picrites associated with them In Carpathians and Caucasian
regions
Mamedov M.N., Babayeva G.J., Kerimov V.M.
Geology Institute of ANAS, Baku, Azerbaijan.

Teschenites and genetically connected with them volcanogenic-alkaline picrites, tephrites, basanites, analcimites
and others are of restricted development among alkaline basic and ultrabasic rocks. According to data available
(Wilkinson, 1956; Grobovski et al., 2003; Jan Spicak et al., 2004; Skhirtladze N.I., 1943; Borsuk A.M., 1979 et al.) this
volcanoplutonic association is mainly Late Cretaceous, Eocene and sometimes is Oligocene.
Cretaceous teschenites and associated with them alkaline picrites, tephrites, basanites are mainly developed in
northwest and west provinces of Carpathian region (Spisak, Hovorka, 2004; Wladyka, Karwonski, 2006; Grabovski,
2003) and in north and south slopes of the Greater Caucasus (Borsuk, 1979; Skhirtladze, 1943; Dudauri, 1989, 2003)
and the Lesser Caucasus (Mamedov, 1999).
Above-mentioned association of rocks is localized among Jurassic and Cretaceous tuffogenic sedimentary and
volcanogenic formations. According to data of absolute geochronology they refer to the Late Cretaceous (Dudauri,
1989; Borsuk, 1979).
Teschenite intrusives form small bed-like, sil, laccolith-like outcrops among jurassic and Cretaceous geological
complexes.
Macroscopic rocks of intrusives of lying flank are dark-grey, sometimes – dark fully.
From lying flank to hanging one dark and dark grey colours become grey and light grey. Microscopic research
showed that these colours changes in rocks of studied intrusives are caused by quantitative variation of femic and salic
rockforming minerals. In this – from lying flank to hanging one – quantity of olivine elinopyroxene, titanomagnetite
and sometimes Kaersutite gradually reduces and quantity of plagioclase, potassium feldspars, analcime increases.
Chrysolite-hyalosiderite olivine, salite-fassaite clinopyroxene, labradorite-bytownite plagioclase, kaersulite-bar-
kevikite amphibole, ulvospinel titanomagnetite and analcime participate in melanocratic teschenites composition con-
fined to lying flank of intrusives. Small amount of apatite, granate, and biotite and other minerals is available as well.
Content of melanocratic minerals reduces from melanocratic teschenite to normal one. In this direction content of
plagioclase increases which is gradually enriched by albite molecule. In final differentiate of teschenite intrusives which
consists of teschenite – sienite and sienite, salite and fassaite clinopyxenes alternate by ferrosalite and hedenbergite and
the basic plagioclase – by oligoclase andesine. In some cases this paragenesis takes tabular, leistolike grains of
nepheline. In mesostasis of these rocks content of xenomorph analcime and potassium feldspar (50-60%) increases
noticeably.
Volcanic facies of teschenite intrusives is represented by volcanic breccia and lavobreccia, flows of tephrites,
basanites, melanocratic analcimites, alkaline picrites, analcime trachybasalts and trachydolerites.
Golden-brown megacrystal of phlogopite, size 3x5 sm, is found in lavobreccia of tephrites. Here the
crystallization process occurring in relatively deeper intermediate focus is connected also with formation of large
accumulative megacrystal of phlogopite. The next stage of crystallization of alkaline picritic melting probably occured
in less deep intermediate focus where porphyric paragenesis of minerals were forming. They consist of hyalosiderite
olivine, salite clinopyroxene and aluminous titanomagnetite. Final stage of crystallization of alkaline picritic melt is
represented by formation interstitial analcime with potassium feldspar. The latter is confined to analcime as the needles.
So, volcanoplutonic associations of rocks in Caucasus and Carpathians regions are comagmatic between each
other. Volcanic facies of teschenite melt formed at earlier stage of Late Cretaceous evolution stage of Caucasus-
Carpathians regions. Probably instrusive magmatism formed a bit later.
Evolution of teschenite melt was controlled by crystallized differentiation in intrusive chamber and intermediate
focuses. Availability of water (analcime) and hydroxyl (biotite, kaersutite, barkevikite) minerals in rocks composition of
teschenite melt prove the oxidizing conditions of crystallization. In these cases crystallization of aluminous
titanomagnetite exceeds crystallization salite clinopyroxene and frequently is confined to latter as inclusion.
Along with mentioned the other larger cations such as potassium, rubidium, barium of intrusive chamber and
intermediate focuses accumulate in residual melting anmd isomorphically include into content of potassium feldspar.
Due to duration of crystallization processes in intrusive chamber titanomagnetite is more enriched by ulvospinel
molecule. In this case alumina more concentrates in composition of bytownite plagioclase.
 103

Unlike intrusive chamber in intermediate focus mineral parageneses of intratelluric stage of alkaline picritic melt
crystallization were probably controlled by water fluids. Here impregnations of high aluminous titanomaagnetite were
crystallized before porphyric emissions of salite clinopyroxene and were enriched by proper spinel minal (MgAl2O4= 8-
12%).

Reference:
Borsuk A.M. Mesozoic and Cenozoic magmatic formations of the Greater Caucasus. Moscow: Nauka, 1979,
p.299 (in Russian).
Dudauri O.Z., Togonidze M.G., Bortnitsky Y.N. Potassium – argon age of teschenites in West Georgia //
Reports of AS of GSSR, 1989, 134, N1, p.137-140 (in Russian).
Dudauri O.Z. Petrology of Mesozoic intrusive complexes of Georgia. Dissertation for doing Doctor Degree
(geology and Mineralogy), Tbilisi, 2003, p.192-261.
Gugushvili V.I. Cretaceous volcanism of Georgian Block //Proceedings of Research Institute of as a GSSR,
1989, 134, №1, p.137-140 (in Russian)
Spisiak J., Hovorka D. Teschenite clan rocks and their possible analogues in the Western Carpathians //
Mineralogical society of Poland – Spesial papers. Volume 24, 2004, p.32-35 (in English).
Mamedov M.N. Petrology and geochemistry of Late Cretaceous and Eocene Formations of the Lesser Caucasus
and Talysh, 1999, p.400 (in Russian).
Rustamov M.I. South Caspian basin – geodynamic events and processes. Baku: Nafta-Press, 2005, 345 p. (in
Russian).
Skhirtladze N.I., Teschenite formation of West Georgia //Proceedings of AS of GSSR, series Mineralogy and
Petrography, v II, 1943,p.102 (in Russian)
Wilkinson J.F.C. Clinopyroxenes of alkali olivine-basalt magma //Amer. Miner., 41, 1956, p.p.724-743 (in
English).
Wlodyka R. Clinopyroxene and amphibole zoning patterns in teschenite rocks from the outer Western Polish
Carpatiean.
Grabowski I et al. Geochronology of teschenitic intrusion in the outer Western Carpatian of Poland constrains
from 40K40Ar ages and biostratigraphy // Geologica Carpathica, 54, 2003, p. 385-393 (in English).

The geochemistry of mafic-ultramafic inclusions from postcollision shear zone (Ilmensky-Vishnevy

mountains)
Medvedeva E.V.*, Rusin A.I.**, Baneva N.N.**
*Ilmensky State reserve of UB RAS Miass, Russia, ** Zavaritsky Institute of geology and geochemistry UB
RAS Ekateriburg, Russia

Information about alkali-ultramafic association of the Ilmeny-Vishnyevye Mountains was earlier restricted by
characteristic of metaultramafic rocks. The question about formational affinity of these rocks was always controversial
because geological situation of the region was regarded as strongly compressed and extensive anticlinorium with gneiss
core and schist frame. A new conception of its geological structure as a deep fragment of postcollisional regional shift
(Voroshchuk, Rusin, 2006) and petrochemical data let us to suggest that small blocks of mafic-ultramafic rocks are the
fragments of alkali-ultramafic central type intrusion (Rusin et al., 2006) separated more than 100 km long.
Granitoid blastomilonites, not Precambrian gneisses, contain the blocked bodies and are the principal rock types
of the axial zone (core of anticlinorium). Petrochemical data show that intrusion is characterized by three rock
associations: ultramafic-mafic, alkali-ultramafic (ijolite-jakupirangitic) and miascite-carbonatitic.
A lot of petrographic types of ultramafic (dunites, spinel olivinites, pyroxenites, websterites and others) and
mafic (garnetic, fassaitic, coisitic, anortitic, spinelic and others) rocks were established in last years (Korinevsky,
Korinevsky, 2007). Amphibolites are often characterized by very low SiO 2 (30-33 wt%) contents and increased Al2O3
(up to 28 wt%) and CaO (up to 16 wt%) contents. Obligatory presence of nepheline, olivine and vollastonite is
calculated during converting to normative composition. The similar situation with ultramafic rocks is at the central type
intrusion Lillebukt, North Norway (Arzamastsev et al., 2002), where deformation of the primary intrusion structure with
following metamorphism of amphibolite facies is observed. The rocks of this alkali-ultramafic type haven’t analogues
among other types of metamafic-ultramafic complexes of the Urals.
Results of ICP-MS analysis give us new information about geochemical specificity of the rock associations of
alkali-ultramafic intrusion. Total contents and REE distribution in ultramafic (0.97-358 ppm, La/Sm=4-82, and Се/Yb=
10-99) and mafic (16-517 ppm, La/Sm =2-38, and Се/Yb =7-50) rocks (fig. 1,a) are in agreement with their possible
affinity to two rock association noted above. REE contents in miascites (199-263 ppm) are lower than maximal REE
contents in alkali-ultramafic association. This fact, similar trends of differentiation and isotopic data (Kononova et al.,
1979) could be considered as an evidence of mantle genesis of miascites.
 104

Fig. 1. Variations of La/Sm and Ce/Yb ratios (a) and Ba and Sr contents (b) in the rocks of the Ilmeny-
Vishnyevye Mountains. 1 - host rocks, 2 - ultramafic rocks, 3 - mafic rocks, 4 - sienites, 5 - miaskites.

Such indicated for mantle magmatism elements as Sr and Ba (Kapustin, 1983), despite significant variations,
generally demonstrate the tendency to accumulation from ultramafites (Sr=90 ppm, Ва=274 ppm, Sr/Ва=0.94, n =12)
through “metamafites” (Sr=426 ppm, Ва=465 ppm, Sr/Ва=2.3, n = 21), to sienites (Sr=984 ppm, Ва=1985 ppm,
Sr/Ва=0.7, n = 8) and miascites (Sг=1164 ppm, Ва=1280 ppm, Sr/Ва=0.9, n =3) (fig. 1,b). Similar tendency is observed
in behavior of high-charging elements (ppm): ultramafites - Nb=5.0, Та=0.3, Zr=13, Hf=0.3, “metamafites” - Nb=7.8,
Та=0.8, Zr=73, Нf=1.9, sienites - Nb= 83, Та=18, Zr=65, Нf=2, miaskites - Nb=202, Та = 24, Zг=158, Нf=2.5.
Indicated Zr/Hf ratio in groups of rocks changes in close limits (45, 36, 30 and 56 respectively) but Nb/Ta ratio doesn’t
show clear regularities.
So, petrochemical peculiarities of these rocks show that alkali rocks of the Ilmeny-Vishnyevye Mountains are the
derivatives of the deep mafic-ultramafic magmatism and are not palingenic-metasomatic rocks formed during
transformation of continental crust under influence of hypothetical mantle fluids. We also have preliminary data about
Vendian-Cambrian age of the rocks of alkali-ultramafic association.
Possibility of affinity of "exotic" rocks from the Ilmeny Mountains such as sandyites, firsites and oth. to alkali-
ultramafic association will be regarded in the report
Researches were financially supported by RFBR (07-05-96020-Р_Ural_а), Department of Earth Sciences of RAS
№ 4 and № 10 and integration project between Urals and Siberian branches of RAS.

References:
Arzamastsev А.А., Arzamastsevа L.V., Kuzmin S. V. Mineral association of rocks of sienite-carbonatitic
intrusion Lillebukt (Northern Norway) as indicators of its forming conditions // Reports of Russian Mineralogical
Society. P.131 V.1 P. 47-63.
Voroshuk D. V., Rusin A. I. Basic geological section of the middle part of the Ilmeno-Vichnevogorsky
polymetamorfic zone // Guide-book of geological excursion. Ekaterinburg: UB RAS 2003 P. 64-95.
Kapustin U.L. Geochemistry of strontium and barium in rocks of carbonatitic complexes // Geochemistry. 1983.
№ 7. P. 931-944.
Kononova V.A., Donzova E.I., Kuznezova L.D. Izotopic composition of oxygen and strontium of the Ilmeno-
Vichnevogorsky alkaline complex and questions of genesis of miaskites // Geochemistry. 1979, № 12, P. 1784-1795.
Кorinevsky V.G., Кorinevsky E.V. Mafic and ultramafic rocks of the Ilmenigorsky complex // Lithosphere.
2007, № 2, P. 59-79.
Rusin A. I., Krasnobaev A.A., Rusin I. A. et al. Alkali-ultramafic association of the Ilmeny-Vishnyevye
Mountains // Geochemistry, petrology,mineralogy and genesis of alkaline rocks. Miass: UB PAS, 2006. P. 222-227.

Some mineralogo-geochemical aspects of outlooks of complex use of ores from deposits of U-Na
formations of Ukraine.
Melnichenko B.*, Bondarenko S.**, Siomka V.**, Grinchenko O.***, Ivanov B.****
* Institute of geochemistry of the environment, Kiev, Ukraine; ** Institute of geochemistry, mineralogy and
ore formation of M.P.Semenenko, Kiev, Ukraine; *** Kiev national Taras Shevchenko university, Kiev,
Ukraine; **** GE «Kirovgeology», SPE -46, Kiev, Ukraine.

Many uranium-ore formations of the world are often accompanied by rather considerable concentrations of
different useful element which can be additionally extracted in the course of ore processing. Practically each uranium-
ore formation is characterized by the presence of particular complex of colour, rare and noble metals which determine
typical geochemical features of this formation and in turn indicate peculiarities of its geological evolution. Proterozoic
deposits of uranium ore of Ukraine, that is genetically related to sodium-uranium (albitite) formation of hydrothermal-
metasomatic deposits, are not an exception. Most uranium ore deposits and manifestations of this type contain high
concentrations of scandium, rare-earth elements, vanadium and silver. Unlike geochemical and mineralogical features
of scandium and rare-earth elements that have been thoroughly studied on the Zheltorechenka uranium deposit
(Tarchanov 1991, Belevtsev, 1995) the behaviour of V and Ag are not widely discussed in geological literature.
 105

Deposits of U-Na formation are widely distributed in the central part of the Ukrainian Shield, mainly within
Ingul'sk geoblock. Here four uranium-ore regions are outlined known as Central (Vatutinka deposit), Novoukrainka
(Novokonstantinovka deposit), Kirovograd (Severinkovka, Michurinka deposits) and Krivorozhsk-Kremenchug
(Zheltorechena, Pervomaisk deposits) regions. All the uranium deposits are of the same age and were formed in the
course of paleo-proterozoic (1,8 - 1.7 billion years) activization of more ancient granito-gneissic substrate. But till now
there are no any widely accepted idea about the nature and conditions of their formation. Some spatial and age relations
established between the process of ore mineralization and certain rock complexes or structural blocks have rather
contradictory nature. That fact testifies to it, that the processes of ore-forming alkaline-sodic metasomatism developed
practically on all varieties of rocks from granitoids, migmatites, gneises to ferruginous quartzites and carbonate rocks.
Besides this the composition and geochemical features of the uranium ores are practically similar for all the deposits of
the central part of the Ukrainian Shield. Sodic metasomatites are represented by chlorite-epidote, riebeckite, riebeckite-
aegirine, aegirine, andradite-diopside, hydromica-phlogopite, carbonate-hematite albitites. Uranium mineralization is
represented by brannerite, uraninite and some minerals formed as a result of metasomatic alteration of primary
minerals. It is combination of the primary hypogenic and different hypergene mineralizations that caused complex
mineralogic and geochemical zonation typical of many uranium deposits. But at the same time V and Ag were found
present at different content in ores of practically all the urainium deposits.
Vanadium. There are no any vanadium deposits found in Ukraine.
The reliable evaluation of possible accompanying extraction of vanadium from ores of albitite type have not
been performed yet. But the probable needs for this element on the nearest period (till 2010) are estimated to be about
1000-1700 tons per year. Multiple geochemical data on uranium deposits of the Inlul's geoblock indicate constant
presence of the vanadium directly in ores ores or in near-ore altered rocks (Melnichnko, 1994). Some ore sites of
uranium deposits of Zheltorechenka group show high vanadium contents that reach up to 1 %, with ordinary values
varying from 0,05 to 0,3 %. Similar values were found on similar uranium deposits of the Kirovograd and
Novoukrainka groups.
Preliminary geochemical and mineralogical investigations carried out by us on the Vatutinka deposit have
shown, that vanadium is constantly present both in rich and poor ores with average contents of 0,02 to 0,07 %. It is also
found, that vanadium show high concentration only in some typomorphic minerals found in uranium ores. (see Table.
1).
Table. 1 Content of V2O3 in mineral and ores (%)
Content of Mineral Numbe
Mineral
V2O3 in mineral (%) in ores (%) r of analysis
Aegirine 0,10-0,49
5-20 12
(0,19)
Riebeckite 0.03 -0,32 1-10 8
Sphene 0,34-0,82
0,3 -3 12
(0,54)
Magnetite + 0,15-0,90
0,2- 3 10
hematite (0,40)
Brannerite 0,1-2,85
0,00-1 24
(1,03)
Davidite 0,25- 4,10
0,00-0,1 9
(1,60)
Lead titanates 0,40-2,75
0,00-0,1 7
(1,20)

Vanadium forms its own minerals, such as Сe-Wakefildite (CeVO4) with 18 % of V2O3, for which identification
additional detailed investigations are need to be carried out. Simple calculations allow to draw some conclusions. If in
the course of separation of uranium ores the fraction of vanadium bearing minerals averages 5-20 % it means, that total
contents of V2O3 under the optimistical scenario can reach 0,15-0,25 %. It is not excluded, that contents of vanadium
are considerably high on the other uranium deposits and therefore the importance of this problem is much higher.
Silver. This element was out of much attention for long period of time, though the facts of some silver
specialisation of sodic metasomatites were established on several deposits of the Krivorozhsk-Kremenchug belt where
some intervals with high silver content of more than 1 % have been found (Belevtsev J.N., 1995). Recently the ore body
with high silver concentrations were oulined within foot wall of the major uranium-ore zone of the Vatutinka deposit.
Spectral analysis data have shown high silver contents of 300 g\t on five-meter interval of silicified albitites in the
northern part and 70 g\t on 4,8 m interval of silicified granites in the central part of the Vatutinka deposit. Silver was
found as native phase and enter the compositon of matildite AgBiS2. Among associated minerals the galena, pyrite,
marcasite, chalcopyrite, sphalerite as well as minerals of uranium, titanium and barium were found as predominate
phases.
High concentrations of vanadium and silver in ores of U-Na formation are supplemented by geochemical
spectrum of already known useful elements (TRE, Sc, Zr) which concentration is genetically associated with processes
of formation of alkaline metasomatites. This fact testifies to unique feature of this formation and some peculiarities in
 106

behaviour of the specific elements (including vanadium and silver) in hydrothermal-metasomatic processes. Possible
evaluation of possible extraction of silver and vanadium during the processing of uranium ores might be interpreted as
urgent problem which resolved by specialists - technologist.

References:
Belevtsev Ya.N., Koval V.B, et. al. Genetic types and patterns of distribution of uranium deposits of Ukraine. -
Kiev, Naukova dumka. 1995
Tarhanov A.V., Kudlaev A.R., Petrin A.V., Kozyr'kov V.D. Zheltorechenska vanadium-scandium deposit //
Geology of ore deposits - 1991 - 33, № 6 - P. 50-56.

Lamprophyric rocks of the Devonian alkali igneous complex of Belarus

Mikhailov N.D., Laptsevich A.G.
Republican Unitary Enterprise «Belarusian Research Geological Exploration Institute», Minsk, Belarus,
[email protected]

Among petrographically various Devonian alkali igneous rocks found in the territory of Belarus lamprophyres
described by the presence of biotite and phlogopite in their mineral composition along with considerable amounts of ore
minerals are rare in occurrence. These rocks belong mainly to hypabissal formations and occur as small sills, dikes and
stocks in the Pripyat Trough and North-Pripyat igneous province (Korzun V.P., Makhnach A.S., 1977; Veretennikov
N.V. et al., 2007).
Within the Pripyat Trough lamprophyres are found among rocks of the Vasilievsk (Artukovskaya 3 borehole),
Vetkhino (Vetkhinskaya 1 borehole), Dnieper (Dnieprovskaya 1 borehole) palaeovolcanoes. In the North-Pripyat
igneous province lamprophyres are found in the southern part of the Luchin cluster of the Zhlobin diatreme field
(anomaly named «Shliakh Selianina»).
Lamprophyres of the Pripyat graben are feldspathic. In the Vetkhinskaya 1 borehole lamprophyres (vogesites
according to V.P. Korzun) were exposed in deposits of the Semiluki horizon (at a depth of 4.565-4.582m), where form a
small dike about 20 m in thickness. The rocks are fine-granular with porphyries of hornblende substituted by calcite and
chlorite (penninite). The bulk rock is composed of leistes of potassium-sodium feldspar sometimes showing trachytoid
texture. The whole rock mass is abundant in biotite scales confined to feldspar leistes or occurring as microporphyries.
There are numerous impregnations of ore minerals - titanomagnetite and magnetite, the first one being dominant.
Lamprophyres from the Artukovskaya 3 borehole at a depth of 4.514 to 4.518m adjacent on the north to the Vetkhino
palaeovolcano are in the similar geological position in a section, where these form a vein small in thickness (about 2 m)
in the Semiluki deposits and are similar to lamprophyres from the Vetkhino palaeovolcano, but the porphyries are larger
in size there. Lamprophyres have been also determined in the northwestern area of igneous rock occurrence within the
Pripyat graben (Dnieper palaeovolcano, Dnieprovskaya 1 borehole, depth of 3.564 m). They occur there as a dike about
5 m in thickness among quartzitic sandstones. The rock is a finely crystalline feldspar matrix, where coloured minerals
form the lamprophyric texture, and hornblende, biotite and ore minerals comprise about 60% of the bulk rock.
Pleochroic biotite from light yellow to dark-brown in colour together with porphyries and ore minerals form an
abundant spot impregnation. The porphyries of strongly altered olivine and pyroxene are often found in the rock.
Lamprophyres from the second region (North-Pripyat igneous province) occur in two boreholes of the «Shliakh
Selianina» anomaly: 761 (229-243m) and 763 (225-233m). In the borehole 761 lamprophyres were exposed in the
lower part of the section. Rocks are grey, dark-grey to black in colour, mainly massive in structure, microcrystalline,
often aphanitic in texture. Phlogopite (biotite), olivine, calcite, magnetite, monoclinal pyroxene are rock-forming
minerals. Calcite, serpentine-serpophite, hydrophlogopite, chlorite are determined among secondary minerals. Apatite
and spinel occur as accessories. The bulk rock is phlogopite which occurs as small scales or poikilocrystals with
magnetite impregnation, carbonate and a mix of secondary minerals: serpentine-serpophite, calcite, montmorillonite-
saponite with magnetite impregnation. Porphyric impregnations are represented by olivine pseudomorphs of two
generations, phlogopite (biotite), magnetite, pyroxene replaced by calcite and chlorite is rarely observed in the depth
range from 231 to 232m. The calcite abundance increases in the contact zones. Lamprophyres from the borehole 763
are overlain by melilite-lamprophyric breccias. The bulk rock is carbonate with melilite, hydromica and chlorite
pseudomorphs. Femic minerals are represented by phlogopite (biotite), magnetite. Lamprophyres in the bottom part
consist of olivine of two generations, sodalite; pyroxene porphyries occur sometimes. Carbonate makes a considerable
contribution to the bulk rock, which is typical of similar rocks (Williams X. et al., 1985).
Geochemical data obtained for the studied rocks suggest that lamprophyres from two regions show minor
geochemical distinctions. These are generally described by rather high titanium, iron and alkali contents. These rocks
are alkali varieties and in the TAS classification diagram occupy the bottom left part of all the ultrabasic rocks of the
Palaeozoic igneous province determined in Belarus. Lamprophyres are rich in potassium (Na/K=0.2-0.4), those from
the North-Pripyat’ province show an increase in the sodium content (Na/K=0.9). There is a difference in the coefficients
of alumina content. Rocks from the Pripyat graben are described by moderate alumina contents, and lamprophyres from
the North-Pripyat’ province are low in alumina, however, with such an insignificant distinction both rocks from two
regions are of miaskite nature (Ka<1), sometimes, insignificantly modified to the agpaitic one (Vetkhinskaya 1
borehole, Ka =0.7) (seeTable).
 107

Table Composition of lamprophyres (%)of the Pripyat graben and North-Pripyat region
оxides Feldspathic Lamprophyres of the North-Pripyat region
lamprophyres of the Pripyat
graben
SiO2 39.23 38.69 39.6 44.53 37.03 36.7 35.76 35.16 34.58 28.54 35.72 33.65
TiO2 2.09 3.55 2.77 3.11 2.06 2.19 1.84 2.1 2.14 2.36 2.23 2.39
Al2O3 8.17 9.83 11.16 9.85 4.4 4.4 3.9 4.6 4.3 4.53 4.31 4.37
Fe2O3 10.12 16.12 13.99 10.97 15.46 16.12 14.4 15.15 14.49 15.00 13.92 15.13
MnO 0.12 0.13 0.09 0.08 0.17 0.17 0.2 0.24 0.23 0.20 0.24 0.23
MgO 12.65 9.16 15.18 10.73 22.87 23.51 26.52 21.7 21.74 16.46 18.55 19.35
CaO 12.37 10.67 2.94 5.74 1.63 2.13 2.44 6.0 7.52 12.45 9.45 8.99
SrO 0.05 0.09 0.04 - 0.08 0.1 0.11 0.1 0.12 0.08 0.09 0.08
BaO 0.25 0.09 0.13 - 0.05 0.05 0.05 0.05 0.05 0.09 0.10 0.10
Na2O 0.36 1.08 0.59 1.89 0.5 0.55 0.23 0.39 0.3 0.58 0.35 0.36
K2O 2.76 3.00 3.46 6.67 2.19 1.99 1.99 2.63 2.58 2.31 2.20 2.37
P2O5 0.45 0.74 0.61 0.61 0.6 0.6 0.55 0.61 0.6 0.57 0.58 0.59
H2O 4.65 3.76 6.76 0.00 11.35 9.53 9.59 6.43 6.17 - - -
CO2 6.13 2.83 2.55 - 1.02 1.14 1.61 4.04 4.85 - - -
F 0.34 0.26 0.23 0.07 0.31 0.32 0.35 0.34 0.32 - - -
LOI 10.48 6.11 8.83 - 12.37 10.67 11.20 10.47 11.02 16.55 12.11 12.22
Total 99.7 100.04 100.11 94.25 99.76 99.50 99.50 99.60 100.02 99.75 99.85 99.86
Na2O+K2O 3.12 4.08 4.05 8.56 2.69 2.54 2.22 3.02 2.88 2.86 2.55 2.73
Na2O/K2O 0.13 0.36 0.17 0.28 0.23 0.28 0.12 0.15 0.12 0.25 0.16 0.15
al' 0.36 0.39 0.38 0.45 0.11 0.11 0.10 0.12 0.12 0.15 0.13 0.13
Ka 0.38 0.42 0.36 0.87 0.61 0.58 0.57 0.66 0.67 0.63 0.59 0.62

Figure Geochemical peculiarities of lamprophyres

Geochemical peculiarities of lamprophyres are presented in a diagram showing the distribution of trace elements
normalized to the primitive mantle (see Figure). With a rather similar pattern of the trace element distribution in
lamprophyres of both regions, those from the Pripyat graben show increased amounts of K, Nd, Sm, Zr, Hf, Eu, Sn, Sb,
Ti, Gd, Tb, Dy, Li, Y, Ho,Er, Tm, Yb, Lu and decreased amounts of U, Th, Pb as against their contents of rocks from
the North-Pripyat’ province. The maximum contents of Ba noted in lamprophyres of the North-Pripyat province,
 108

especially in their carbonatized varieties (where the Ba concentration in rock runs up to 1%), as well as of La and Pb
should be particularly emphasized.
The research was performed under the financial backing of the BRFFI, grant X08P-087.

References:
Korzun V.P., Makhnach A.S. Upper-Devonian alkali volcanogenic formation of the Pripyat Trough. Minsk,
Nauka i Tekhnika Publ. 1977. 164 p. (in Russian).
Sun S.S., McDonough W.F. Chemical and isotopic systematics of oceanic basalts: implications for mantle
composition and processes // Magmatism in the Ocean Basins. Geol. Soc. London Spec. Publ.1989.Vol. 42. P. 313-346.
Veretennikov N.V., Laptsevich A.G.,Vladykin N.V., Mikhailov N.D. Association of alkali lamprophyres and
carbonatites of the Luchin diatreme cluster as a positive magmatic criterion of forecast of and search for potentially
diamondiferous kimberlites // Innovations in Geological Science - a Way of Efficient and Multipurpose Utilization of
Mineral Resources. Minsk, 2007. P.55-58 (in Russian).
Williams H., Turner F., Gilbert Ch. Petrography. Vol.1. Moscow, 1985. 301 p. (in Russian).

Finite Element Modelling of the Generation of Carbonatite Magmas: Application to post-orogenic

mantle processes
Moore K.R., Ryan P.D.R.
Department of Earth and Ocean Sciences, School of Natural Sciences, National University of Ireland
Galway, Galway, Ireland.

Key carbonatite localities that have been investigated as part of INTAS project 05-1000008-7938 ‘Diamond and
Graphite in Carbonate Magmas’ are: (1) Western Greenland, where the distribution of kimberlites, lamproites and
carbonatites is correlated with depth to a fossil subducted slab (personal communication, Nielsen 2008); (2) the
Chagatai Complex of diamond-bearing silicocarbonatite dykes and pipes at the western end of the Southern Nuratau
Mountains (Tianshan Orogen), Uzbekistan; (3) Transbaikalia, Russia, where carbonatites are temporally correlated
both with break-up of the Siberian craton by rifting (Windley et al., 2007) and also potentially with delamination of the
lithosphere beneath Mongolia (Petit et al., 2002); and (4) The Kola Peninsula in Scandinavia, where the post-orogenic
Baltic Shield is rifted and has been heated at the base of the lithosphere by mantle upwelling (Bulakh et al, 2004).
These key localities can be tectonically summarised as suture zones that have later been subject to decompression or
heating and produced carbonate magmas as a consequence.
Published (Lapin et al., 2005) and new (personal communication, Savatenkov and Konopelko 2008) isotopic
data for sövite and silicocarbonatite dykes from Chagatai (Uzbekistan) are dominated by a mantle component, but have
a significant crustal component regardless of the abundance of xenoliths. Some mechanism is required for
contamination of the isotopic signature of carbonate magmas that, given the association of diamonds with
silicocarbonatite (whether as xenocrysts or phenocrysts) must ultimately have a deep source (Djuraev and Divaev,
1999; Moore et al, 2009). Carbonatites emplaced into the Central Asian Orogenic Belt have both subducted oceanic
lithosphere and subducted continental rocks (Windley et al., 2007) as potential source components. Release of CO 2- or
CO2-H2O-rich fluids of melts from a subducting slab has been linked to enhanced eclogitization, crustal isotopic
components in a mantle wedge, and diamond formation in a subduction environment (Ducea et al., 2005; Timm et al.,
2004). Furthermore, experimental petrology has shown that melts parental to carbonatite activity can be geochemically
related to fusion of eclogitic mantle (Treiman & Essene, 1983; Dasgupta et al., 2003).
An alternative mechanism to place eclogite in the lithosphere beneath intra-continental carbonatite activity is the
formation of deep crustal roots that are isostatically stable within the mantle if buoyancy is overcome by conversion to
eclogite facies assemblages. Such assemblages may be preserved long after the end of the orogenic process (Ryan
2001) and numerical modelling shows that such roots are subject to pressures > 3GPa and temperatures in excess of
700oC (Ryan & Dewey 1997), which is considerably lower than the solidus of carbonated eclogites and potentially
within the conditions of diamond stability. If a sufficiently dense eclogite layer forms, such that it becomes
gravitationally unstable, detaches and sinks, it is replaced by upwelling mantle, providing a heat source at the base of
the lithosphere.
Finite element modelling is used to investigate the production of carbonate magmas from carbonated eclogite in
tectonic configurations anologuous to the post-orogenic scenario in Central Asia, and other INTAS localities, where:
1. Subducted material remains at depth in the source region of carbonate magmas,
2. Delamination has caused the emplacement of a high-temperature peridotite, heating the base of a thermally
re-equilibrated lithosphere, and
3. Crustal stretching and thinning decompress post-orogenic lithosphere.
Initial findings are that maximum preservation of carbonated eclogites occurs in cold thick continental
lithosphere that has undergone minimal overstepping of the solidus, and that emplacement of hot mafic magmas at the
base of the lithosphere causes local, rapid, short-lived melting of carbonated eclogites without necessarily producing
associated silicate magmas.
This presentation was financially supported by INTAS project 05-1000008-7938.
 109

References:
Bulakh, A.G., Ivanikov, V.V., Orlova, M.P., 2004. Overviewof carbonatite-[hoscorite complexes of the Kola
Alkaline Province in the context of a Scandinavian North Atlantic Alkaline Province. Pp. 1-43 in: Phoscorites and
Carbonatites from Mantle to Mine: the Key Example of the Kola Alkaline Province Wall, F., Zaitsev, A.N. (editors).
Mineralogical Society Series 10.
Dasgupta, R., Withers, A.C., Hirschmann, M.M., 2003. Generation of carbonatitic melt through partial melting
of carbonated eclogite under mantle conditions. Eurocarb Abstract Volume, 16-18
Djuraev A.D., Divaev F.K., 1999. Melanocratic carbonatites – new type of diamond-bearing
rocks, Uzbekistan. In: Stanley, C.J. et al. (Eds.), Mineral Deposits: Processes to Processing.
Eds..Balkena, Rotterdam 1, 639-642.
Ducea, M.N., Saleeby, J., Morrison, J., Valencia, V.A., 2005. Subducted carbonates, metasomatism of mantle
wedges, and possible connections to diamond formation: An example from California. American Mineralogist 90, 864-
870.
Lapin, A.V., Divaev, F.K., Kostityn, Yu.A, 2005. Petrochemical Interpretation of Carbonatite-like Rocks from
the Chagatai Complex of the Tien Shan with Application to the Problem of Diamond Potential. Petrology 13 (5), 499-
511 (English), Translated from Petrologia 13 (5), 548-560 (Russian).
Moore, K.R., Wall, F., Divaev, F.K. and Savatenkov, V.M., 2009. Mingling of carbonate and silicate magmas
under turbulent flow conditions: Evidence from rock textures and mineral chemistry in sub-volcanic carbonatite dykes,
Chagatai, Uzbekistan. Lithos, in press, doi:10.1016/j.lithos.2008.11.013
Petit, C., Déverchère, J., Calais, E., Sankov, V., Fairhead, D., 2002. Deep structure and mechanical
behavior of the lithosphere in the Hangai-Hövsgöl region, Mongolia: new constraints from gravity
modeling. Earth and Plantary Science Letters 197, 133-149.
Ryan, P.D., 2001. The role of deep basement during continent-continent collision: a review. In: Miller, J.A.,
Holdsworth, R.E., Buick, I.S., Hand, M. (eds) Continental reactivation and reworking. Geological Society, London,
Special Publications 184, 39-55
Ryan, P.D., Dewey, J.F., 1997. Continental eclogites and the Wilson Cycle. Journal of the Geological Society,
London, 154, 437-442
Timm, J., Scherer, E.E., Haase, K., Schenk, V., 2004. Trace element fractionation during fluid-induced
eclogitization in a subducting slab: trace element and Lu-Hf-Sm-Nd isotope systematics. Earth and Planetary Science
Letters 227, 441-456
Treiman, A.H., Essene, E.J., 1983. Mantle eclogite and carbonate as sources of sodic carbonates and alkalic
magmas. Nature 302, 700-703
Windley, B.F., Alexeiev, D., Xiao, W., Kroner, A., Badarch, G., 2007. Tectonic models for accretion of the
Central Asian Orogenic Belt. Journal of the Geological Society, London 164, 31-47.

Geochemistry and petrology Toro Ankole kamafugite magmas: isotopic constraints

Muravyeva N.S.*, Belyatsky B.V.**, Ivanov A.V.***
*Vernadsky Institute of Geochemistry and Analytical Chemistry RAS, Moscow, Russia;
**VNIIOkeangeologia, Antarctic Geology Department, St.-Petersburg, Russia
***Institute of the Earth Crust SB RAS, Irkutsk, Russia

Kamafugites are silica-undersaturated high-potassium volcanic rocks originally named after three
petrographically-defined rock types – katungite, mafurite and ugandite from the Toro-Ankole province in the western
branch of the East African rift zone. They correspond to strongly potassic types of olivine melilitite to nephelinite in the
modern classifications. There are three volcanic fields: Fort Portal, Katwe-Kikorongo and Bunyaruguru in Toro-
Ankole, this study is focused on the Bunyaruguru volcanic field which stretches southwards from the south shore of
Lake George, partly over the floor of the western rift depression and partly over the adjacent plateau to the south and
east of the rift.
The simultaneously low SiO2 (<42 wt%), high MgO (up to 21.5 wt%), low Al2O3 (<10 wt%), and high CaO
contents (up to 16.45 wt%) of these volcanics express themselves in the presence of modal kalsilite, leucite, melilite and
perovskite. The common minerals of phenocrysts are olivine, leucite, clinopyroxene, Cr-spinelides and phlogopite.
There are perovskite and melilite phenocrysts in the katungites. Spinelides are frequently occurred as inclusions in the
olivines, which also contain fluid and, sometimes, carbonate, sulfate and sulfide inclusions. The absence of plagioclase
distinguishes them from the lava flows occurring in the rest of the western rift branch. These strongly silica-
undersaturated potassic rocks have been little studied by modern analytical methods, particularly radiogenic isotope
systems. The special features of the composition of investigated rocks are high Mg# (up to 79), high Ni content (up to
780 ppm) and Cr (up to 1170 ppm) in conjunction with the extreme incompatible trace elements enrichment: Nb up to
276 ppm; Ce/Y up to 26.38; Zr/Y up to 26.22; (La/Yb) n up to 142.69; (La/Sm)n up to 7.27. The composition of the
kamafugite phenocrysts confirms its “primitive” character: forsterite content up to Fo 92, NiO – up to 0.48 wt%, CaO
(min) – 0.07 wt%. Spinelides are the high-chromium varieties: Cr2O3 – up to 58.4 wt%, Al2O3 – up to 10.65 wt%, the
minimum of TiO2 – 2.36 wt%. The spinel composition trend for studied samples is quite similar to the kimberlite trend.
 110

Toro-Ankole kamafugitic lavas are characterized by minimal effect of fractional crystallization (except olivine
fractionation) in contrast to the lavas from volcanic fields of the western branch (Virunga, Kivu, Rungve). Some
geochemical characteristics of the rocks studied – Yb and Zr minima on spidergrams – testify to the participation of
garnet in residue in the process of their formation. To confirm this suggestion (the possibility of generation of
investigated rock in garnet peridotite layer) some calculations were carried out. The estimation has been done on major
elements, nickel and chromium kamafugite contents according to the method (Herzberg C., Asimow P. D., 2008). The
results show that the large part of the rocks studied may be formed during melting of garnet peridotites as a result of
removal or addition of some magnesian olivine. For two samples – katungite and mafurite, however, the model of
peridotite source does not suit and it is necessary, therefore, to attract another component to peridotite melting model –
pyroxenite or eclogitic.
Sr and Nd isotope signatures for kamafugites form a slightly enriched relatively to BSE cluster (87Sr/86Sr =
0.704629 – 0.705356; 143Nd/144Nd = 0.512488 – 0.512550). Some inverse correlation with major element contents is
observed: 87Sr/86Sr – CaO, 143Nd/144Nd – Mg#, 87Sr/86Sr – Mg#. Sr-Nd isotope data of Bunyaruguru kamafugites suggest
that its mantle source composition is nearly EM1 (Hofmann, A. W.,2003). But the range of Pb composition for
investigated is 206Pb/204Pb: 18.998 – 19.566; 207Pb/204Pb: 15.686 – 15.737; 208Pb/204Pb: 39.303 – 40.264. On these data
the mantle source composition for studied kamafugites is close to EM2 or Dupal characteristics. High “radiogenic” lead
ratios of kamafugites are in general agreement with high Th/U (4.16 – 5.01) in comparison with primitive mantle values
(3.9). Some indicator trace element ratios of kamafugites (Ce/Pb: 34.51 – 45.85 and Pb/Nd: 0.01 – 0.08) testify against
participation of continental crust material in their source.

References:
Herzberg C., Asimow P. D. Petrology of some oceanic island basalts: PRIMELT2.XLS software for primary
magma calculation // Geochemistry, Geophysics, Geosystems. 2008. Vol.9. N. 9
Hofmann, A. W. Sampling Mantle Heterogeneity through Oceanic Basalts: Isotopes and Trace Elements.// In:
Treatise on Geochemistry. Editor: R.W. Carlson . 2003. Executive Editors: H. D. Holland and K.K. Turekian. pp. 568.
Elsevier. Vol.2. P.61-101.

Mineralogy and geochemistry of REE minerals in Esfordi alkali-magmatic phosphate mine, Bafgh,
Central Iran
Nazary M.*, Khajo M.**
*Department of Geology, Islamic Azad University, Ashtiyan Branch, Ashtiyan, Iran; **Department of
Geology, Education district No.15, Ministry of Education, Tehran, Iran

The Bafgh district of Central Iran is the most important Fe metallogenic province in the region and a significant
district on a worldwide basis. Esfordi is a Kiruna-type Fe–P oxide deposit and one of the most P-rich of the Bafgh
 111

magnetite–apatite occurrences. It formed within a predominantly rhyolitic volcanic sequence that formed in a
continental margin tectonic regime and is of Cambrian age. The spatial association of the Esfordi ore body with alkaline
extrusive igneous rocks clearly indicates a genetic relationship between alkaline magmatism and iron-oxide ore
formation. It has been suggested that alkaline magma is the ultimate source of Fe-P-rich melts, which have been derived
from it by liquid immiscibility. The field relationships and the overall geological evidence at Esfordi indicate that the
rhyolitic host rocks, the products of intracratonic magmatism and a tensional geological setting (rifting), were roughly
synchronous and coeval with mineralization.
The Esfordi open-cut mine currently produces 103,000 tones of apatite concentrate a year, from a resource of 17
Mt with a grade of 13.5 wt % P2O5. Aside from the great resource and high grade of apatite ore, the economical
concentration of REE, make Esfordi the most important potential of REE in the Bafgh district too. The system is
enriched in REE (~ 0.2 – 1.5 %) with an associated array of accessory REE minerals. Routine, high quality REE assay
data were not available from the mine operation, but semi quantitative emission spectrographic data from isolated drill
holes, together with ICPMS data in the current investigation indicates that total REE contents broadly follows P levels.
The majority of the REEs are contained in apatite. However, some of the REE in apatite is probably contributed by
REE-bearing microscopic solid inclusions.
More than 25 samples from the different ore types, host rocks and igneous bodies were analyzed for REE by
ICPMS following microwave bomb HF/HClO4/HNO3 digestion and the major elements determined by X-ray
fluorescence (Philips PW1400 XRF sequential spectrometer). The REE composition of various mineral phases from 21
polished thin sections has been investigated by electron microprobe. Other than apatite, there are six different minerals
with significant REE contents at Esfordi which show systematic relationships in the paragenetic stages of Fe-oxide-P
mineralization and considered in three groups; phosphates, carbonates and silicates. Monazite, allanite, xenotime,
britholite, further more synchysis and bastnasite as minor phases, are minerals which have been identified by electron
microprobe analyses supported by optical methods and limited XRD:
,Allanite is the most abundant REE mineral in the Esfordi deposit. Allanites in this study are allanite-(Ce),
characterised by higher La/Nd and La/Y ratios and also (La/Sm) and (La/Y) ratios. Microscopic studies and BSE
images of Esfordi allanites show a zonation in some grains of allanite. Electron microprobe analyses show that the core
is more enriched in LREE than the rim in them. Britholite always occurs in brecciated apatite-rich zone associated with
allanite and monazite. Due to similarities between britholite and allanite, recognition of britholite by optical techniques
was cross-checked by electron microprobe point analyses.The britholites are enriched in HREE and Y. Monazite is one
of the most abundant REE mineral at Esfordi and has a close relationship with apatite. Xenotime occurs as a minor
phase, mainly in the brecciated apatite-rich ore as individual grains in the matrix. The Esfordi xenotime have traces of
SiO44- replacing PO43- , also minor substitution of U4+, Th4+ and Si4+ for Y3+ and Ca2+ for P3+ is indicated. The
fluorocarbonates synchysite and bastnaesite at Esfordi are mainly observed in the brecciated apatite-rich ore and apatite-
rich veins in altered host rocks. They are always observed in close relationship to the late pervasive carbonate alteration
and almost always occur in carbonate-rich matrix, replacements and veins. The Esfordi synchysites are synchysite-(Ce)
with high La and Nd and bastnaesites are bastnaesite-(Ce) which is the most common form of bastnaesite.
Esfordi apatites are generally dominant in the LREE similar to that of many Kiruna type magnetite apatite
systems. Based on field observations, petrographic and geothermometric studies, three different types of apatite were
identified. The first two generation of apatites have been affected (dissolved, leached and replaced) by subsequent
brecciation and late stage carbonate and quartz veining. Apatite 1 crystals has inclusions of monazite 1 within crystals
as 5 to 50 μm. A crude zonation may be observed in some apatite 1 grains with mineral (including monazite 1). Apatite
1 contains (La,Ce,Nd) up to 1.74 wt % with an average of 1.43 wt %. Rare earth mineral inclusions within apatite 2
are rare, however intergranular monazite 2, xenotime, and allanite 1 are common. Apatite 2 shows an average of 1.19
wt % (La, Ce, Nd). Apatite 2 is richer in Cl than apatite 1, averaging 0.43 wt %. Granular apatites contain (La, Ce,
Nd) up to 0.51 wt % with an average of 0.22 wt %. Apatites 3 crystals are without any solid inclusions and low
(La,Ce,Nd) content (averaging 0.11 wt %). Generally, Esfordi apatites are F-rich and relatively low in Cl (< 0.91 wt
%) and OH content.
The LREE content of apatites is strongly correlated with corresponding content of both Na and Si. The REE
abundances in minerals are largely controlled by substituting for Ca positions (McKay 1989). The selectivity of Ca-
bearing minerals for REE is largely depends on the size of the Ca positions in mineral structure relative to the REE. The
REE3+ and Y3+ ions substitute for Ca2+ with electrostatic balance provided by substitution of Si 4+ for P5+ or Na+ for
additional Ca2+ (Pan and Fleet 2002);
Na+ + (Y + REE3+) = 2Ca2+
Si + (Y + REE3+) = P5+ + Ca2+
4+

When the REE content of Esfordi deposit is compared with that of the Kiruna ores, it displays a stronger
LREE/HREE fractionation and a large Eu depletion, probably indicating a relationship to alkaline parent magma, in
turn suggestive of a rifting environment. Taylor and Fryer (1983) suggest that LREEs are preferentially mobilized in Cl-
rich fluids, whereas F and CO2-bearing fluids are rich in HREE. Esfordi apatites are F-rich and relatively low in Cl (<
0.91 wt %) and OH content. Thus, it is likely that HREE where selectively leached from Esfordi apatite by F and CO2-
rich late fluids, giving rise to the observed high LREE/HREE ratio.

References
 112

Daliran F. REE geochemistry of Bafq apatites, Iran; implication for the genesis of Kiruna-type iron ores. Mineral
Deposits; Processes to Processing. Balkema, Rotterdam .1999. P. 631-634.
Daliran F. The magnetite-apatite deposit of Mishdovan, East Central Iran. An alkali rhyolite hosted, "Kiruna
type" occurrence in the Infracambrian Bafq metallotect. Heidelberger Geowissenschaftliche Abhandlungen, Ph.D.
thesis, 1990. 37, 248.
Frietsch R. and Predhal J.A. Rare earth elements in apatite and magnetite in Kiruna-type iron ores and some
other iron ore types // Ore Geology Reviews 1995. Vol. 9, P. 489-510.
Jami M. Geology, Geochemistry and Evolution of the Esfordi Phosphate - Iron Deposit, Bafq Area, Central Iran.
NSW University, Ph.D. thesis, 2005. 328 P.
McKay GA. Partitioning of rare earth elements between major silicate minerals and basaltic melts. Reviews in
Mineralogy. Mineralogical Society Amer 1989. P 45-77.
Moore F., Modabberi S. Origin of Choghart Iron oxid deposite, Bafgh Mining district, Central Iran: New
isotopic and geochemical evidence // Journal of Sciences, Islamic Republic of Iran. 2003. Vol. 14(3), P . 259-269
University of Tehran, ISSN 1016-1104.
Pan Y., Fleet ME. Compositions of the apatite-group minerals: Substitution mechanisms and controlling factors.
In: Phosphates: Geochemical, geobiological, and material importance, MJ Kohn (Ed). Mineral Soc Amer. 2002. 13-49.
Taylor R.P. and Fryer B.J. Rare earth element geochemistry of granitoid mineral deposits // Canadian Inst Min
Metall Bull 1983, Vol. 76, P. 74-84.

Age, types of sources and genesis of the Il'meno-Vishnevogorsky complex in light of new isotope data
(Urals, Russia)
Nedosekova I.L.
Zavaritsky Institute of Geology and Geochemistry, Yekaterinburg, Russia

Il'meno-Vishnevogorsky miaskite-carbonatite complex – one of the world's largest alkaline complexes with
unique rare and rare-earth mineralization and deposits Nb, Zr and REE. Despite of a significant level of scrutiny of a
complex, a number of the important genetic questions remains till now debatable. First of all it is spatial and genetic
link between carbonatites, miaskites and fenites outside of series of the ultramafic-alkaline rocks (traditional for
carbonatites complexes of the ultramafic-alkaline formation) and, as consequence, a question of parent magmas for
Il'meno-Vishnevogorsky complex.
Recently, the carbonatites with Nb-REE mineralization have been opened in ultramafic massifs (Buldym,
Haldihin, Spirihin and other), which are located near to contacts with Vishnevogorsky and Il'menogorsky miaskite
intrusions [Levin et al., 1997; Nedosekova, 2007]. Now there is a question on genetic link between carbonatites and
ultramafic rocks of the Buldym massif and also miaskite-carbonatite complex.
The Sm-Nd and Rb-Sr isotopic compositions in carbonatites and ultramafic rocks of the Buldym massif and their
minerals were measured. U-Pb isotopic age determination on samples of monazite and zircon from late dolomitic
carbonatites of Buldym massif were performed. Thus, the first data about age and sources of substance ultramafic rocks
and carbonatites of the Buldym massif are received by us.
Sm-Nd isochron diagram for the rocks and minerals of the Buldym massif is constructed (fig. 1).

Fig. 1. Sm-Nd diagram for the samples of rocks and minerals from the Buldym ultramafic massif, Il'meno-
Vishnevogorsky complex, Urals. 505-27 – olivinite, 15-22 – olivinite with amphibole and phlogopite, 97-1 amphibole-
 113

olivinite rock, 3311 – early dolomite-calcite carbonatite I; 3311К, 915К – calcites from early dolomite-calcite
carbonatites I; 1-54, 10-21 – late dolomite carbonatites II.

Six samples of this rocks yielded isochron age of 602 + 24 Ma with an initial Nd ratio 0.511853 + 0.000016,
MSWD = 1.3. Isotopic compositions of ultramafic rocks (olivinites, olivinites with amphibole and phlogopite) and
early dolomite-calcite pirochlore-bearing carbonatites of the Buldym massif are presented on this isochron diagram.
Late dolomite monazite-bearing carbonatites of the Buldym massif have other isotopic compositions which are not
belonging these isochron (fig. 1; sample №1-54, №10-21). According to U-Pb datings of monazite the age of formation
dolomite carbonatites makes 254 + 30 Ma.
Thus, the first Sm-Nd isotopic data who testify about Pre-cambrian (V) age of ultramafic rocks and early
carbonatites of the Buldym massif are obtained. Based on U-Pb and Rb-Sr data, the introduction and crystallization of
miaskite-carbonatite complex has occured on the boundary Ordovician (O) and Silurian (S) times – 410–440 million
years ago [Kononova et al., 1979; Kramm et al., 1993]. The subsequent processes of metamorphism and metasomatism
of miaskite-carbonatite complex, related to the Hercynian orogeny (360–320 Ma) and postcollisional extension (260–
240 Ma), also are dated by U-Pb and Rb-Sr methods [Kononova et al., 1979; Kramm et al., 1983; Tchernyshev, etc.,
1987].
Initial ratio of isotopes Sr and Nd in ultramafic rocks and early dolomite-calcite carbonatites of Buldym massif
are characterized by uniform sizes ((87Sr/86Sr)602 = 0.7040–0.7048, (143Nd/144Nd)602 = 0.511842–0.511914, εNd = –
0.37… +1.03), that testifies about possible comagmatic genesis and uniform sources of their substance. Initial Sr and
Nd isotopic data for rocks of Buldym massif correspond to isotopic parameters enriched mantle EM1. Miaskite-
carbonatite complex has other isotopic parameters (87Sr/86Sr) 440 = 0.7034–0.7038, (143Nd/144Nd)440 = 0.512219–
0.512372, εNd = 2.9…+5.9, corresponding moderately depleted mantle and, possibly, other sources of substance.
Conclusion. The fragments of the ultrabasic rocks and carbonatites more ancient in comparison with miaskite-
carbonatite complex are established in Il'meno-Vishnevogorsky complex. Age of these rocks (~600 Ma) corresponds to
a stage continental riftogenes, previous disclosing of the Urals paleoocean. Isotopic composition of ultrabasic rocks and
carbonatites from Buldym massif is very close to enriched mantle EM1 and differes from those for rocks of miaskite-
carbonatite complex. Similar sources of substance have carbonatite complexes ultramafic-alkaline formations of East-
African rift, in particular carbonatite lavas, nephelinites, phonolites and xenolites of pyroxenites and ijolites from
carbonatite volcano Oldoinyo Lengai [Kramm and Sindern, 1998].

References:
Kononova V.A., Dontsova E.I., Кuznetsova L.D. The isotopic compositions O and Sr of Il'meno-
Vishnevogorsky alkaline complex and questions of genesis of miaskites // Geochemistry. 1979.12. P. 1784-1795 (in
Russia).
Kramm U., Blaxland A.B., Kononova V.A., Grauert B. Origin of the Ilmenogorsk-Vishnevogorsk nepheline
syenites, Urals, USSR, and their time of emplasement during the history of the Ural fold belt: a Rb-Sr study // J. Geol.
1983. V. 91. P. 427-435.
Kramm U. and Sindern S. Nd and Sr Isotope signatures of fenites from Oldoinyo Lengai, Tanzania, and the
genetic relationships between nephelinites, phonolites and carbonatites // Journal of petrology. 1998. V. 39. № 11-12. P.
1997-2004.
Kramm U., Chernyshev I.V., Grauert S. et al. Zircon typology and U-Pb systematics: a Case Study of zircons
from nefeline syenite of the Il’meny Mountains, Ural // Petrology. 1993. V. 1. № 5. P. 474-485.
Levin V.Y., Ronenson B.M., Samkov V.S. Самков В.С. et al. Alkaline-carbonatite complexes of Urals.
Yekaterinburg: Uralgeolcom, 1997. 274 p (in Russia).
Nedosekova I.L. New Data on Carbonatites of the Il'mensky-Vishnevogorsky Alkaline Complex, the Southern
Urals, Russia // Geol. Ore Deposites. 2007. V. 49. № 2. P. 146-164.
Tchernyshev I.V., Kononova V.A., Kramm U. et al. Isotope geochronology of alkaline rocks of Urals Mountains
in a view of data uranium-lead of a method on zircons // Geochemistry. 1987.3. P. 323-338 (in Russia).
This study was financially supported by the integration project (2008-2011)between branches of the Russian
Academy of Science «К-alkaline volcano-plutonic complexes of different structure of the Earth, processes of
differentiation passing in them and the division of magmas leading formation ore-bearing lamproites and carbonatites;
their deep sources».

Chemistry of cancrinite-group minerals of different formations

Olysych L.V.*, Pekov I.V.*,**, Chukanov N.V.***
*Moscow State University, Moscow, Russia;
**Vernadsky Institute of Geochemistry and Analytical Chemistry RAS, Moscow,Russia;
***Institute of Problems of Chemical Physics, Chernogolovka, Russia

The minerals of the cancrinite group (CGM) are hexagonal and trigonal tectoaluminosilicates with extra-
framework anions. Their general formula is: A7-8[Al6-ySi6+yO24]X1-4·nH2O, with extra-framework cations A = Na, K, Ca
(with subordinate Sr and Ba) and extra-framework anions X = (CO3)2-, (SO4)2-, Cl-, (OH)-, S2-, (C2O4)2- (with
 114

subordinate F- and (PO4)3-); y < 1.2, n = 0–5. Frameworks of CGM consist of coplanar interrupted layers of six-
membered rings of SiO4 and AlO4 tetrahedra. The stacking of these layers determines a framework with wide channels
and small undecahedral cages which host extra-framework cations and anions and H2O molecules.
There are 21 minerals of the cancrinite group up to date. Six of them, namely cancrinite
Na6Са[Si6Al6O24](CO3)·2H2O, cancrisilite Na7[Si7Al5O24](CO3)·3H2O, hydroxycancrinite Na8[Si6Al6O24](OH)2·2H2O,
vishnevite Na6K2[Si6Al6O24](SO4)·2H2O, kyanoxalite Na7(Al6-5Si6-7O24)(C2O4)0.5-1·5H2O and davyne
Na4K2Са2[Si6Al6O24]Cl(SO4,CO3)2·2H2O can be considered as a cancrinite ss subgroup minerals: all of them have a
small unit cell (a = 12.5–12.7, c = 5.1–5.4 Å).
We have discussed chemical data on 400 samples of all CGM from worldwide localities: 270 our samples and
130 earlier published analyses. All CGM can be subdivided into three main genetic types: 1) intrusive alkaline
complexes: magmatic rocks, pegmatites, metasomatic and hydrothermal bodies, 2) alkaline volcanic complexes and 3)
metamorphic and metasomatic formations not related to the alkaline magmatism. CGM of the first genetic type
(formation) are the most widespread. They are represented by cancrinite ss subgroup minerals with the only exception
of davyne uncommon for this type of rocks but typical for volcanic complexes and formations not related with alkaline
magmatism. Some CGM (cancrinite and vishnevite) are rock-forming minerals in intrusive alkaline complexes. CGM
of the second and third genetic types are mainly rare minerals with large unit cells. Davyne is the only representative of
the cancrinite ss subgroup in these two formation types.
The chemical diversity of CGM from intrusive alkaline complexes can be presented as:
1. A cancrinite–cancrisilite solid-solution series with general scheme of substitutions: Al3+ + Ca2+ + 0.5(CO3)2-
↔ Si +  + H2O. The minerals of this series reveal distinct positive correlation between Al/Si and Na/Ca ratios
4+

(Fig.1) while the extra-framework anion substitutions are subordinate.

2. A cancrinite–vishnevite isomorphous series with a break between members with (SO4)0.36 and (SO4)0.56. As the
SO4-group incorporates in cancrinite structure, the correlation between Al/Si and Na/Ca raties is violated and another
scheme is realized: 2(Na,K)+ + (SO4)2- ↔ Ca2+ + (CO3)2- (Figs.1-2). It seems crystallochemically important that in
some cases cancrinite is closely associated with vishnevite (Vishnevye Gory and Ilmeny, both Urals, Russia) and they
are significantly different chemically: cancrinite is Ca-enriched (4.3-6.8 wt.% СаО that corresponds to 0.8-1.2 Ca apfu)
and K-poor (0-0.4 wt.% К2О: 0-0.1 2 K apfu) while vishnevite, quite the contrary, is represented by K-rich variety (8.1-
8.7 wt.% К2О: 1.8-2.1 К apfu) and Ca-poor (0.5-0.9 wt.% СаО: 0.1-0.2 apfu). In these assemblages, cancrinite can
contain SO4 (up to 0.3 per formula: 2.4 wt.% SO3), as well as IR-spectra of vishnevite shows considerable amount of
CO3 groups.
3. A cancrinite–kyanoxalite solid solution series with the general scheme of substitutions: Al3+ + Ca2+ + (CO3)2-
↔ Si4+ + Na+ + (С2O4)2-. The Al/Si ratio in minerals of this series varies from 0.73 to 0.85.
4. A four-component solid solutions system (with breaks) of Ca-poor ([Ca+Sr]<0.2 apfu) minerals. The
components of this system are cancrisilite, hydroxycancrinite, vishnevite and kyanoxalite (Fig. 1). The most important
characteristics here are Al/Si ratio (varies from Al6.3Si5.7 to Al4.4Si7.6) and the type of extra-framework anion. This
system was found for peralkaline sodic complexes, first Lovozero (Kola Peninsula, Russia).

intrusive alkaline complexes_published data intrusive alkaline complexes_our data

volcanic alkaline complexes_published data volcanic alkaline complexes_our data
formations not related to the alkaline magmatism_published data formations not related to the alkaline magmatism_our data

1,30

1,20 hydroxycancrinite
e
vishnevite
1,10

1,00
Al/Si

0,90
cancrinite

0,80

0,70 kyanoxalite

cancrisilite
0,60

0,50
-0,03 0,47 0,97 1,47 1,97 2,47 2,97 3,47 3,97
∑2+, apfu

Figure 1. Correlation between the Al/Si ratio and content of bivalent extra-framework cations (mainly Ca) in
CGM of three genetic types: 1) intrusive alkaline complexes, 2) alkaline volcanic complexes and 3) formations not
related to the alkaline magmatism.
 115

4,00

3,50

3,00

2,50
Cl -, apfu

2,00

1,50

1,00

0,50 С - CGM vishnevite

0,00
0,00 0,25 0,50 0,75 1,00 1,25 1,50 1,75 2,00 2,25

S O 42- , apfu

Figure 2. Correlation between (SO4)2- and Cl- in CGM of three genetic types: 1) intrusive alkaline complexes, 2)
alkaline volcanic complexes and 3) formations not related to the alkaline magmatism; C-CGM are species with
prevailing C-bearing (carbonate or oxalate) extra-framework anions.

The majority of CGM from intrusive alkaline complexes are represented by Cl-poor to Cl-free CO3- and SO4-
dominant species (Fig.2).
Chemical composition of CGM from alkaline volcanic complexes is quite different (Fig. 1). Unlike CGM from
intrusive complexes (genetic type 1), these minerals are Ca-rich (1.7-3.6 apfu:10.2-16.7 wt.% СаО), with the Al/Si ratio
variations from 0.9 to 1.0 (Fig. 1). Their prevaling extra-framework anions are SO42- and Cl- showing distinct negative
correlation (Fig. 2). CO3-dominant CGM are almost absent in this formation.
Chemical composition of CGM from the formations not related to the alkaline magmatism (first from lazurite
deposits) is similar to that from alkaline volcanic rocks. These minerals are also Ca-rich and typically have SO42- and
Cl- as species-defining anions but their composition field is not so wide (2.4 ≤ ∑A2+ ≤ 2.8 apfu: Figs. 1 and 2).
This study was supported by grants of RFBR Nos. 07-05-00130-a, 08-05-00077-а and 09-05-91330-NNIO_а,
grant of President of Russain Federation No. 863.2008.5 and grant of Russian Science Support Foundation (I.V.P.).

Genetic crystal chemistry of natural fluorite-related Ca,REE fluorides

Pekov I.V.*,**, Yakubovich O.V.*
*Lomonosov Moscow State University, Moscow, Russia;
**Vernadsky Institute of Geochemistry and Analytical Chemistry RAS, Moscow, Russia

A remarkable crystal chemical feature of fluorite is its capacity for concentration of REE3+ (Y and lanthanides,
Ln) with formation of the interstitial solid solutions with general formula (Ca1-xREEx)F2+x. These crystals keep the space
group Fm3m, the fluorite unit cell and a unique cation site fully occupied jointly by Ca and REE, whereas additional one
or several partially occupied F sites appear. The upper limit of REE content possible for the fluorite structural type is
still unknown. The solid solution with 66 mol. % (REE)F3 in CaF2 was reported by Besse & Capestan (1967); among
structurally studied synthetic RE-bearing fluorites, the sample Ca0.607Ce0.393F2.393 (Aleksandrov & Garashina, 1969) is
the richest in REE. Yttrofluorite with (REE)F3 content up to 10, rarely to 20 mol. % is uncommon mineral known in the
derivatives of alkaline granites and in rare-earth granitic pegmatites. Tveitite-(Y), a cation-ordered rhombohedral
mineral structurally related to yttrofluorite with higher REE content is significantly rarer. Before our work it has been
described only in three pegmatites related to alkaline granites: two in Norway and one in Texas. The first crystal
structure determination of tveitite-(Y) (Bevan e.a., 1982) gave the approximative structural model (without details for
the atom distribution over structural positions) and an ambiguous mineral formula.
Recently, we found tveitite-(Y) in an amazonitic pegmatite related to alkaline-granite intrusion at Rovgora (W.
Keivy, Kola, Russia) and studied it in detail. Samples from Rovgora consist of two phases corresponding to varieties of
 116

tveitite-(Y) with different Ca:REE ratios. The REE-rich variety (it is the REE-richest known tveitite) forms regular 3D
system of lamellae in a matrix of the Ca-enriched variety. The structure of tveitite-(Y) was studied for the REE-rich
single-crystal from Rovgora and a refined formula was proposed. The mineral is trigonal, R-3, with a = 17.020, c =
9.679 Å (Yakubovich e.a., 2007). Tveitite-(Y) is considered to represent a fluorite-based interstitial solid solution. 11
independent F sites have been found in its crystal structure. Cation positions are practically the same as for Ca in
fluorite. Symmetry lowering is caused by subdivision of the single A site of fluorite in four independent sites in tveitite-
(Y): A1, A2, A3 and A4. Eight types of polyhedra AFn with potentially different cation occupancies may occur in
tveitite-(Y). The crystallochemical formula of tveitite-(Y) from Rovgora (Z=18) is:
(Y0.883Na0.106)A1(Ca0.841LREE0.159)A2(Ca0.716Na0.204HREE0.080)A3(Ca0.092Na0.074)A4F6.952. The idealized sitructural formula is:
(Y,Na)6(Ca,LREE)6(Ca,Na,HREE)6(Ca,Na)F42, or, in its simplified form can be presented as: (Ca,REE,Na)13(Y,Na)6F42.
In this mineral, LREE and HREE fractionate between two types of Ca-dominant sites different in both size and form of
polyhedra. We also solved the crystal structure of natural yttrofluorite, using a sample with (Ca 0.80Na0.02Y0.12Ln0.06)F2.20
composition from an alkaline-granite-related amazonitic pegmatite at Mt. Ploskaya (W. Keivy). This mineral represents
the fluorite ss structural type (Fm3m, a = 5.4926 Å) with an additional anion site F(2), which is typical for the synthetic
analogues of RE-fluorite.
The (REE)F3 content in natural yttrofluorite is not higher than 20 mol. % whereas it is not lower than 30 mol. %
in tveitite-(Y). Basing on the patterns of micro-heterogeneity of tveitite-(Y) samples from Høydalen, Norway (Bergstøl
e.a., 1977), and Rovgora, we may certainly conclude that this mineral is a product of the solid-state transformation of
cation-disordered REE-rich yttrofluorite. In Høydalen sample, differently oriented sub-individuals of polysynthetic
twins of tveitite-(Y) are chemically identical. It is probably caused by chemical identity (~30 at. % REE of sum of
cations) of the transformation product (rhombohedral tveitite) and the initial phase (cubic REE-fluorite). Rovgora
crystals could be formed as a result of a phase transition of the cubic proto-phase containing more REE (36-37 at. %)
with further breakdown to the system of isotypic but chemically different tveitite phases.
Many synthetic cation-disordered cubic (Fm3m) defect fluorite-type compounds occur in the compositional
(REE:Ca ratio) field corresponding to tveitite or its hypothetical proto-phases. Note that they were grown using the
Stockbarger method i.e. under high temperature with F-rich fluid, similar to the natural postmagmatic processes.
However, unlike quenched synthetic crystals, minerals were annealed for geologigal time favoring phase transitions and
breakdowns. Thus, yttrofluorite with (REE)F3 less than ~20 mol. % only could “successfully overcomes the time
examination” whereas its more REE-rich varieties are metastable and have been transformed.
A lot of synthetic compounds with structures different from the fluorite type are known in the CaF 2 – (REE)F3
system. Several of them lie in the same compositional field as yttrofluorite and tveitite. At the same time, (1) no
synthetic analogues of tveitite and (2) no other natural Ca,REE fluorides, except tveitite-(Y) and yttrofluorite. This fact
can be explained by a significantly simpler composition of synthesis systems using only Y or one of Ln together with
Ca and F, while a full series of REE is present in natural systems. The stabilization of tveitite-(Y) is probably possible if
threshold concentrations not only of Y, but also of both LREE and HREE would be overcome. From this point of view,
a transformation of one cationic site in fluorite structure in four different positions in tveitite looks reasonable.
An affinity of fluorite to Y and HREE compared to its affinity to LREE is significantly stronger. “Excessive”
increase of LREE in RE-fluorite results in its breakdown to yttrofluorite and fluocerite, (LREE)F3, a hexagonal phase
having different crystal structure. E.g., aggregates of yttrofluorite and fluocerite-(Ce) with a characteristic
“dactyloscopic” breakdown structure were reported in Katugin (Siberia, Russia) (Arkhangel’skaya, 1970). If CO 2 or P
present in the mineral-forming system then surplus of LREE released from fluorite to Y-poor bastnaesite-(Ce) or
monazite-(Ce) giving the “emulsion” impregnation in a fluoride matrix. A probability to find REE-rich fluorite with
LREE > Y in atomic proportions (“cerfluorite”) seems to be low, in spite of an existence of synthetic (Ca1-xLREEx)F2+x
with x > 0.3 which are metastable quenched phases.
The rare occurrence of yttrofluorite and, especially, tveitite-(Y) can be explained by specific chemical conditions
of their mineral-forming media. Thus, they could be considered as sensitive geochemical indicators. Except an
enrichment of the medium by Y, Ln and F, a deficiency of Ca, Na, CO2 and P looks necessary for their formation. An
increase of the Ca concentration, if the F activity is high, results in the increase of a fluorite amount and its depletion by
REE. An increase of the CO2, P or Na activities results in a re-distribution of REE into phases with different structures
i.e. the REE-depleted fluorite parageneses with rare-earth carbonates, or phosphates, or gagarinite-(Y), NaCaYF6,
should be expected. As a first step, yttrofluorite releases LREE (forming bastnaesite or monazite); the further increase of
CO2 or P activity initiates the depletion of yttrofluorite also by Y and HREE, with formation of the “usual” fluorite. The
decrease of F activity in the mineral-forming medium, when the REE, CO2 and Ca concentrations are high shift the
equilibrium < fluorite + bastnaesite/synchysite ↔ calcite + bastnaesite/synchysite > to the right, i.e. the parageneses
“fluoride + fluorocarbonate”, typical for the derivatives of alkaline granites, change to the parageneses “carbonate +
fluorocarbonate” that characterizes miascitic and, surely, carbonatitic systems.
This study was supported by grant of President of Russain Federation No. 863.2008.5 and grant of Russian
Science Support Foundation (I.V.P.).

References:
Aleksandrov V.B., Garashina L.S. New data on structures of CaF 2 – TRF3 solid solutions // Doklady AN SSSR.
1969. Vol. 189. No. 2. P. 307-310 (in Russian).
 117

Arkhangel’skaya V.V. On solid-solution breakdown structure in natural rare-earth fluorite // Doklady AN SSSR.
1970. Vol. 195. No. 6. P. 1411-1414 (in Russian).
Bergstøl S., Jensen B.B., Neumann H. Tveitite, a new calcium yttrium fluoride // Lithos. 1977. Vol. 10. P. 81-87.
Besse J.P., Capestan M. Solutions solides de CeF3 dans quelques fluorides divalents type fluorine // Bull. Soc.
Chim. de France. 1967. P. 1341-1344.
Bevan D.J.M., Strähle J., Greis O. The crystal structure of tveitite, an ordered yttrofluorite mineral // J. Solid
State Chem. 1982. Vol. 44. P. 75-81.
Yakubovich O.V., Massa W., Pekov I.V., Gavrilenko P.G. (2007): Crystal structure of tveitite-(Y): Fractionation
of rare-earth elements between positions and the variety of defects // Crystallography Reports. Vol. 52. P. 71-79.

Micaceous picrites of the Sikhote-Alin ridge

Petukhova L.L., Prikhodko V.S.
Institute of Tectonics and Geophysics n.a. Yu.A. Kosygin,
Far Eastern Branch of the Russian Academy of Sciences, Khabarovsk, Russia

Regarding the issue of diamond potential, the Sikhote-Alin ridge comprises rare and specific igneous formations
of high interest, such as micaceous picrites, which were discovered in the alluvial sediments of the Kedrovka river and
as part of dikes and volcanic pipes near the settlement of Ariadnoe (Primorsky Krai). Micaceous picrites were studied
by us along the left bank of the Malinovka river, in between the Pad Malaya, Pozhiga and Pad Bolshaya creeks, where
picrites comprise a thin subvertical dike of north-west strike and a small volcanic pipe within host terrigenous sediments
of Jurassic period.
Near the contact with host rocks the dike consists of brecciated variations of picrite, where rock debris are
represented mainly by sandstone, and the central part of the dike is structured by rocks with big-grained (sometimes –
large-grained) impregnations of amphibole, mica, and carbonaceous globules. Picrites are characterized by high
concentration of biotitite, quartz and carbonate rock. They are penetrated by thin veinlets of barite. The volcanic pipe is
formed by intensively altered and withered picrites, thus it is difficult to judge about its inner structure.
Micaceous picrites are grey-greenish rocks of porphyry structure and globular texture. They are impregnated by
kaersutite, phlogopite (amber mica, over 10%), clinopyroxene and rarely chromspinel. Their primary mass is comprised
of felted aggregate of kaersutite, phlogopite, ilmenite and igneous carbonate. Olivine has not been indicated in those
rocks.

Table 1. Representative assay results of micaceous picrites

Compo 5 7 13 16 Compo 5 7 14 16
nent nent
SiO2 38.46 38.47 39.42 38.04 Zr 423.00 438.65 447.12 265.00
TiO2 3.81 3.75 4.00 4.4 Nb 129.39 133.74 397.89 182.42
Al2O3 7.61 7.29 9.58 8.32 La 180.84 152.04 139.79 211.62
Fe2O3 8.38 0.65 1.97 4.88 Ce 406.13 363.38 301.86 467.16
FeO 8.36 8.21 14.69 13.03 Pr 45.87 42.70 34.89 52.28
Mno 0.28 0.29 0.41 0.37 Nb 173.76 167.35 140.32 207.05
MgO 18.09 17.74 15.02 13.74 Sm 30.52 30.29 29.92 40.49
CaO 10.90 10.08 12.39 14.06 Eu 8.75 8.49 9.06 11.32
Na2O 1.33 1.54 0.18 0.21 Gd 29.10 27.75 29.83 37.99
K2O 1.34 1.57 0.16 0.62 Tb 3.25 3.23 4.43 4.47
P2O5 1.44 1.42 2.19 1.43 Dy 13.38 13.21 23.33 19.48
Sc 32.29 34.09 35.10 26.72 Ho 2.2 2.23 4.25 3.40
Ti 24612.23 26873.50 28731.32 21135.82 Er 5.30 5.41 10.38 8.36
V 254.20 278.02 430.946 336.91 Tm 0.59 0.67 1.20 0.92
Cr 558.29 662.47 497.58 363.38 Yb 3.13 3.44 6.27 4.88
Ni 408.44 471.75 438.88 320.01 Lu 0.43 0.25 0.83 0.60
Co 68.86 77.98 72.74 52.65 Hf 9.74 9.70 9.89 5.97
Cu 45.34 64.46 84.06 70.84 Ta 8.07 9.39 12.22 12.25
Note: 5,7 – dike, 14,16 – volcanic pipe; oxides-mass. %, the rest-g/t. Assaying was done by the Central laboratory
“Dalgeology”, REE and rare elements were analyzed by Khabarovsk Innovation Analytical Center (Institute of Tectonics and
Geophysics) with ISP-MS.

According to the concentrations of silica, sum alkali and sum magnesium and calcium (see Table 1), the
rocks can be classified as alkaline picrites. Their original chemical composition has been probably distorted by strong
hydrothermal alternations, which enabled further active drift of many components. This assumption is indirectly proven
by high concentration of CO2 and high impurity level in the rocks.
Geochemical peculiarity of micaceous picrites lies in their enrichment with big ionic lithophilous elements
(Ti, Ta, Nb, Zr), light lanthanide elements and phosphorus, which may be indicative of specific composition of palliac
 118

source of micaceous picrites. Sum concentration of REE is very high and reaches 600 ppm. Besides they sharply
prevail over heavy elements; the ratio (La/Yb) is up to 60.
Judging by grades of iron group elements (Сr, Co, Ni, Ti, V) alkaline picrites are in the intermediate position
between ultrabasic and basic rocks. It has been indicated that processes of intensive alternation of rocks have not
resulted in substantial redistribution and migration of iron group elements. Nickel/copper ratio varies within 4.7 – 6.5;
chrome/vanadium proportion fluctuates from 2.4 to 1.0. Such ratio rates are characteristic of rocks of picrite family.

Table 2. Chemical composition of minerals of micaceous picrites

Component 1 2 3 4 5 6 7
SiO2 41,3 42,4 45,8 50,4 37,9 0,0 38,0
TiO2 4,7 3,1 2,9 1,2 3,6 5,15 4,9
Al2O3 12,1 11,1 8,4 3,5 15,6 10,5 15,5
FeO 9,7 14,5 10,0 6,4 7,3 40,3 10,3
Cr2O3 0,0 0,0 0,0 0,15 0,0 35,0 0,3
MgO 14,5 12,2 16,3 16,1 21,4 8,3 18,7
CaO 11,6 10,8 9,9 21,1 0,1 0,0 0,0
Na2O 3,0 3,0 4,6 1,0 0,8 0,0 0,7
K2O 1,7 1,9 0,9 0,0 9,0 0,0 9,1
MnO 0,0 0,1 0,2 0,0 0,0 1,0 0,0
Sum total 98,6 99,1 99,0 99,85 95,7 100,25 97,5
Note: 1 – 6 – dike of alkaline picrites; 7 – volcanic pipe; 1,2,3 – kaersutites; 4 – clinopyroxene; 6- chromspinel; 5,7 – mica.
Analyses were done with CAMEBAX-micro analyzer in the Institute of Volcanology and Seismology, Far Eastern Branch of the
Russian Academy of Sciences (Petropavlovsk-Kamchatsky).

Assays (see Table 2) of the main minerals of alkaline picrites illustrate peculiar features of their composition.
Low aluminiferous monocline pyroxene is related to diopside-sahlite with a small part of aegirine. Kaersutite and
phlogopite are characterized by high grades of titanium and aluminum. Analytical results of amphiboles of the rocks
indicate that kaersutite with high silica proportion and sum alkali contains minimal concentrations of titanium,
aluminum and calcium. Points of chromspinellid compositions bearing titanium coincide with a trend of chromspinellid
meimechites within the Sikhote-Alin ridge. Ilmenite of the major mass of picrites contains small amounts of
magnesium, manganese, aluminum and chrome. Ore minerals are represented by pyrite and chalcopyrite; accessory
minerals – by apatite, monazite, orthite and sphene. Comparative analysis of phlogopite’s composition in the dike rocks
and in the volcanic pipe (assays 5&7 Table 2) enables to conclude that picrite minerals of the volcanic pipe are more
ferrous.
Petro-geochemical data represented above show that micaceous picrites under study are intensively enriched
with K, Ti, Nb, Zr & REE. Thus they can be viewed as products of potassium-bearing ultramafic melts formed out of
metasomatically altered pallial source.

Magmatic rocks in Moscow Metro decoration.

Pogrebs N.A.
Russia state geological prospecting university (RSGPU), Moskow, Russia.

Stations of Moscow metro are unique in their architecture. The greatest architects made their project plans and
took part in construction during 1930th-1950th. Standard designs of the first stations were still used at the end of XX
and beginning of XXI centuries. Facing stones from different regions of Soviet Union and foreign countries were used
in the decoration of metro stations.
Magmatic rocks are the firmest and most proof against abrasion, so they are employed for floor and stair slabs.
Their utilization for lower parts of walls, pylons and pillars, pedestals and decoration of external metro pavilions is
quite seldom.
Floors of metro stations are made from 4-6 different kinds of rocks forming a geometric design. The chess-
board, rag-like and striped patterns and tile combinations are the most popular. Fine floral, meander- and wave-like
ornaments could be seen on some stations, now and then in combination with marble. Unmethodical pattern of rock
slabs was used extremely rare.
Ukraine was the main supplier untill 1970th. Granitoids of various color, structure and texture were quarried on
Ukrainian shield. They are: bright-red coarse-grained granitoids from Kapustinskoe, medium-grained – from
Emelianovskoe, red and brown medium-grained – from Tokovskoe, red gneiss-like – from Novodanilovskoe, fine-
grained red and light-rose – from Leznikovskoe. Grey medium-grained came from Yantsevskoe field, dark-gray ones –
from Zhezhelevskoe, and dark-gray with big rose phenocrists of feldspar – from Korninskoe.
Some addition of black labradorite from Golovinskoe, Turchinskoe and Siniy Kamen and gabbro-diorites from
Slipchitskoe was used also.
 119

Since 1970th a mine workings of Baltic shield’s (Karelian isthmus) facing stones: rose and gray trachytoid
rapakivi from Vozrozhdenie and gray coarse-grained granits from Kuznechnoe) began. Red medium grained gneiss-like
granits came from Siuskiunsaari and black gabbro-diabases came from Roprucheiskoe.
New sorts of granites: light-gray fine-grained ones from Bashkortostan (Mansurovskoe), rose and lilac medium-
grained ones from Kazakhstan (Zheltau and Kurtinskoe) appeared in metro decoration in 1980 th – 1990th. Various
granites from different foreign countries appeared also.

Isotope-geochemical paradox of acid alkaline rock compositions of Paleogene contrasting formation of

Amguema - Kanchalan volcanic field, Chukotka
Polin V.F.*, Sakhno V.G.*, Maksimov S.O.*, Sandimirov I.V.**
*Far East geological Institute, Vladivostok, Russia; **Vinogradov Institute of geochemistry, Irkutsk, Russia

Within the Amguema - Kanchalan volcanic field (AKVF) of the Okhotsk - Chukotka volcanogenic belt, the
Senonian-Paleogene contrasting series is distinguished including the Paleogene bimodal formation of the marginal-
continental-rifting type (Polin, 1990; Polin, Moll-Stalcup, 1999).
The bimodal formation is related with the belt areas emplaced on the crust with a thick granite-metamorphic
layer (Eskimos massif). It is dominated by trachybasalts, trachydacites, and trachydaciandesites. Trachyandesibasalts,
trachyandesites, trachyrhyolites as well as pantellerites, comendites, and alkaline granites are found in fewer amounts.
Manifestations of the sodic alkaline acid volcano-plutonism in the AKVF were controlled by sublatitudinal and
submeridional extension structures and were practically synchronous to the opening of the “pull-apart basins” type
structures with a voluminous basaltic volcanism. The sequence of magmatic events has been supported by isotopic
datings (Polin, Sakhno, et al., 2007).
Comendites and alkaline granites in the AKVF make up large volcanic and plutonic domes about the southern
periphery of the Belouvalensky volcanic graben and on the eastern flange of the Varenaisky volcano-tectonic trough.
Pantellerites, composing the subvolcanic domes and dikes, are found in the near-fault troughs and volcanic grabens
within the relics of basaltic volcanoes.
Geochemical comparison of alkaline acid rocks of the Paleogene contrasting formation with the rocks of the type
geodynamic regimes showed them to be almost analogous to acid members of the intraplate bimodal complexes (Polin,
Moll-Stolcap, 1999). In some characteristics they are similar to anorogenic granites.
Acid alkaline rocks of this formation were earlier considered as a result of the in-depth differentiation of
trachybasalts or as derivatives of the low degree partial melting of a mantle source common with trachybasalts. New
isotope-geochemical characteristics obtained made it necessary to revise this point of view and to correct the ideas of
the sources of alkaline-salic melts.
The model Sm-Nd age of the alkaline rock sources (Table) is consistent enough: T DM = 481-500 m.y., TDM2 =
516-580 m.y. The age for the one-stage model is close to the geological age of the Eskimos massif that is a complex of
the AKVF structure basement. As to isotopes, the alkaline rocks belong to ε Nd(+) type with the neodymium/neodymium
ratio values similar to those of the moderately depleted mantle. Calculation of the initial strontium-strontium ratios
(Table) showed unlikely low values of this parameter in them (in pantellerite and alkaline granite – close to BABI, and
in comendite and alkaline granite-porphyry – half as in BABI). So it is impossible to determine the interdistribution of
the neodymium and strontium isotopic ratios. When it is taken that the initial strontium ratios in the rocks of the alkaline
association are similar to those in the ancient granitic rocks (~ 0.700-0.702), then their figurative points will be close to
the field lower boundary of the (plume) HIMU component and will rather approximately correspond to the uppers of
the hyperbola of mixing for the rocks of the continental crust and continental tholeiitic basalts (For, 1989). So it is
difficult to explain the genesis of acid alkaline rocks of the AKVF as derivatives from the mixing of basaltic melts and
anatectic crustal meltings.

Table. Isotopic characteristics of alkaline rocks of Paleogene contrasting formation of АКVF

Sample 143Nd/144Nd ε60Nd Sr, ppm 87Sr/86Sr (87Sr/86Sr)i 206Pb/204Pb 207Pb/204Pb 208Pb/204Pb

PN-29-263 0,512832 4.44 17 0.717699 0.698936 18.146000 15.394000 37.928001

О-1408-3 0,512806 4.0 15 0.717857 0.689869 18.358000 15.478000 38.209999
PN-201-1515 0,512803 3.91 2 0.735698 0.475475 18.319000 15.418000 38.028000
PN-203-1530 0,512789 3.64 5 0.738847 0.649953 18.325001 15.367000 37.865002
Note. Samples: PN-29-263 – pantellerite, О-1408-3 – alkaline granite, PN-201-1515 – alkaline granite-porphyry,
PN-203-1530 – comendite. Calculations of epsilon neodymium were done for the depleted mantle using the method of
the IGGD, RAS, Saint-Petersburg, in accordance with data on absolute age of acid alkaline rocks: 59-61 m.y. (Polin,
Sakhno et al., 2007). The initial 87Sr/86Sr ratios were calculated for the obtained values of the absolute potassium-argon
datings.

The pattern of distribution of the neodymium and strontium isotopes could take place if the Sm/Nd and Rb/Sr
ratios in the source of these rocks were initially small and did not change markedly since the time when Nd and Sr
separated from the mantle reservoir. At the same time, Rb/Sr ratio in the alkaline acid melts must be initially high to
explain the determined high values of 87Sr/86Sr (Table). As the latter are defined only by the Sr anomalously low
content, especially in comendite and alkaline granite-porphyry, it is important to understand the cause of the remarkable
 120

“depletion” of the pantellerite-comendite series in the alkaline-earth cations including strontium. Such depletion is a
specific geochemical feature of pantellerites, comendites, and alkaline granites of the sodium profile.
Two mechanisms can be proposed to explain this phenomenon. Through the first mechanism the alkaline-earth
cations and, to a lesser degree, aluminum could be evacuated from the alkaline melts at the closing stages of their
evolution under the influence of a high-acid residual magmatic fluid (Polin, Moll-Stolcap, 1999). The second
mechanism implies the fluid-magmatic enrichment of the acid melt in silicates and/or chlorides of alkalis that broke
protocrystalline feldspar “motifs” (calcic, barium, and strontium feldspar clusters). This resulted in a mobile state and
evacuation of the divalent strong cations and produced an albite minal less capacious regarding aluminum and calcium.
The latter defines the increasing agpaite content of the system through its evolution that is characteristic of such series.
The acid alkaline melts could originate in the chambers of the subalkaline acid magma that had been preserved
from the preceding (Campanian-Maastrichtian) period of development of the trachydacite-trachyrhyolite-alaskite
formation that also belongs to the contrasting series (Polin, 1990; and others). Their enrichment in sodium is logically
explained by the processes of ascending diffusion through the parataxis and syntexis of acid and basitic magmas
(Dobretsov, Dobretsov, 1983; Borisov, 2008).
According to the lead, lead, and neodymium isotope ratio, the points of the acid alkaline rocks fall into the field
of volcanites of Iceland. No marked variability of compositions by the lead isotopes is observed, and there is an
essential departure of them from the field of the above-subduction rock compositions. As the lead isotopes are sensitive
indicators of the crust contamination, then the picture observed can seemingly testify that the Paleogene pantellerites,
comendites, and alkaline granites are neither the crust melts nor the derivatives of basalt contamination with a
significant amount of the crust material. However, taking into account the great volumes of acid alkaline rocks and
sharp bimodality of the formation in the structures of their occurrence (absence of the rocks of the intermediate between
trachybasalts and pantellerites-comendites composition), it is difficult to explain their melting from the mantle
substratum or origination through the basaltic melt differentiation. More real is the generation of the alkaline-salic melts
from remelting of the crust substratum juvenile by isotopic characteristics.
The isotope data obtained allow the conclusions as follows:
1) the source of the Paleogene alkaline acid magmas in the AKVF is a juvenile continental crust supplying the
subalkaline acid material transformed into the alkaline one through the interaction of basitic and acid magmas in the
peripheral chambers under the conditions of a probable local compression. Positive values of ε Nd(T) are explained by a
relatively short time interval since the moment of the formation of the crust source of alkaline rocks;
2) the paper has raised an important problem of disruption of the isotope systems at the late magmatic stage of
the existence of the acid alkaline melts of a sodic geochemical profile; this disruption is necessary to be considered in
the interpretation of isotope ratios both measured and initial.
This study was financially supported by the Projects of FEB, RAS, № 09-1-П14-02 and № 09-1-П16-02

References:
Borisov A.A. Experimental study of K and Na distribution between mixed liquids// Petrologiya (Petrology).
2008. V. 16. N 6. P. 593-605 (in Russia).
Dobretsov G.L., Dobretsov N.L. Problem of genesis of alkaline-salic rocks// Geologiya i Geophyzika (Geology
and Geophysics). 1983. N 1. (277). P. 69-73 (in Russia).
Polin V.F. Petrology of contrasting series of the Amguemo-Kanchalansky volcanic field, Chukotka.
Vladivostok: FEB of the USSR Acad. Sci. 1990. 228 p (in Russia).
Polin V.F., Moll-Stalcup E. J. Petrological-geochemical criteria of tectonic conditions of formation of Chukotka
member of the Okhotsk - Chukotka volcanic belt// Tikhookeanskaya Geologiya (Pacific Geology). 1999. V. 18. N 4. P.
29-47 (in Russia).
Polin V.F., Sakhno V.G., Ekimova N.I., Sandimirova G.P. Pantellerite – comendite - alkaline-granite association
of Paleogene bimodal formation of the Okhotsk - Chukotka volcano-plutonic belt // Doklady Akademii Nauk (Reports
of the Russian Acad. Sci.). 2006. V. 407. N 3. P. 388-393 (in Russia).
Epelbaum M.B. Silicate melts with volatile components. Moscow: Nauka. 1980. 254 p (in Russia).

Mineral-melt partition coefficients of trace-elements in melilite-bearing and melilite-free rocks of

carbonatite complexes
Rass I.T.
Institute of geology of ore deposits, petrography, mineralogy and geochemistry, Moscow, Russia

The differences in the concentrations and mineral/melt partition-coefficients of trace elements can be controlled
by differences in the concentrations of these elements in the parental melt, the conditions under which these melts were
derived in the mantle, by the crystallization sequence of minerals in the course of magma differentiation in the Earth’s
crust, and by the conditions of its crystallization [P, T, f(O2), P(CO2), a(SiO2)].
The problem of the composition of primitive mantle-derived magmas and specific features of their
differentiation in the Earth’s crust is of great importance to research in the genetic relationships between carbonatites
and associated silicate igneous rocks in alkaline-ultramafic-carbonatite complexes, as these rocks, along with
kimberlites and lamproites, are the products of the deepest mantle-derived magmas known at the Earth’s surface. More
 121

then 70% of known carbonatite massifs and kimberlite fields on the Siberian Platform are located along ridges in the
Moho discontinuity. Such ridges rise up to 15 km above the average depth of the discontinuity, as established by
Chernyshov, Bokaja (1984), and the largest massifs, Tomtor, Guli, Odikhincha (northwestern Siberia) occur at ridge
intersections (Kravchenko et al. 1997).
Melilite-bearing rocks are typical components of the alkaline-ultramafic complexes containing carbonatites.
They occur in 10 of 19 massifs of the Maimecha-Kotuy area (northwestern Siberian Platform), the largest alkaline
province in the world. Two coexisting series, strongly Ca-enriched melilite-bearing rocks and more common melilite-
free alkaline-ultramafic rocks compose the alkaline–ultramafic association (Kravchenko, Rass 1985; Peterson, 1989;
Nielsen, 1994). Compositions of rock-forming minerals demonstrate the essential distinctions dependent on their
affinity to rocks of the two series: olivine from the series with melilite is enriched in Ca, nepheline of the melilite-
bearing rocks has higher Ca and lower K contents, and clinopyroxene from melilite-bearing rocks is also enriched in
Ca, compared with clinopyroxene from melilite-free rocks, which is richer in Na content. The REE concentrations of
the clinopyroxene are higher in melilite-bearing than in the melilite-free rocks of the same massif. Carbonatites
associated with melilite-bearing rocks in alkaline–ultramafic complexes show low P coupled with high contents of Zr,
Nb and REE, whereas carbonatites in complexes without melilite-bearing rocks are enriched either in Nb (where
alkaline–ultramafic rocks have Na > K), or in REE (if K > Na) (Rass 1998). The trace-element composition of
carbonatites from complexes with and without melilite-bearing rocks inherits to some extent the contents of trace
elements from the parental alkaline–ultramafic magmas, which fractionate differently in the Earth’s crust.
The observed different major- and trace-element contents and the zoning patterns in coexisting minerals, trace-
element fractionation during differentiation of the parental magmas of these series in accordance with the Rayleigh
model with different partition-coefficients, as well as recent results on melt inclusions in olivine of melilite-bearing
rocks from the Guli and Kaiserstuhl carbonatite complexes (Rass, Plechov 2000; Solovova et al. 2005), provide strong
support for the existence of two different mantle-derived magmas parental for the above series (Kravchenko, Rass
1985). The separate primitive magma, essentially richer in Ca and poorer in Si, that is parental for melilite-bearing
series, was derived at ≤40 kbar (Kravchenko et al., 1992; Wilson et al.,1995; Gudfinnsson, Presnall, 2005) and was
originally enriched in CO2, Sr, REE, and Nb. This magma fractionated, during crystallization of melilite-bearing
differentiates, at shallower depths (<15kb), lower CO2 activity and higher oxygen fugacity, as compared with the
conditions of differentiation of the Ca-poor magma. In turn, the fractionation of the Ca-poor magma, parental to
melilite-free rocks, could begin at great depths (≥20 kbar), during its ascent toward the surface. The differences in
compositions of the initial magmas, generated at different depths from metasomatically and heterogeneously altered
sources in the mantle, defined different paths of magma evolution, which eventually led to the crystallization of
melilite-bearing or melilite-free rocks. According to the diagram for the system CaO–SiO2–MgO and phase equilibria
in the pseudoternary system titanite – nepheline – diopside (Veksler, Teptelev 1990), crystallization should proceed in a
different sequence, e.g., earlier crystallization of perovskite or magnetite, perovskite or pyroxene, and melilite or
pyroxene.
The compositions of the accessory minerals in melilite-bearing (i.e., Ca-rich) and melilite-free (i.e., Ca-poor)
series from the massifs Guli, Kugda, Odikhincha, Kara–Meni, and Turiy Cape, have been studied by electron-probe
micro-analysis (EPMA) techniques. Minerals from rocks in the above series display distinct compositions and zoning in
terms of both major and trace elements.
Magnetite in the melilite-bearing rocks is noticeably enriched in Al and Mg, and depleted in Mn compared to
that in melilite-free rocks. The higher Al content of magnetite from melilite-bearing rocks, and also the core-to-rim
increase of the grossular component in crystals of titaniferous andradite seem to result from higher contents of Al in the
initial magma. Magnetite from melilite-free rocks is richer in Ti, decreasing from the core of a crystal toward its
margin. Perovskite from melilite-bearing rocks has a higher Fe content than in melilite-free rocks. These features in the
melilite-free rocks may be caused by earlier crystallization of magnetite with respect to perovskite. Related differences
in Fe zoning in perovskite and in Ti distribution in magnetite of the melilite-bearing and melilite-free rocks are
controlled by the earlier crystallization of perovskite in the melilite-bearing rocks (Rass et al. 1996). The observed
difference in magnetite composition may be caused by different fugacity of oxygen in the two magma types, as the Ti
content of magnetite is very sensitive to the oxidation conditions. The compositional trends exhibited by perovskite in
the melilite-bearing and melilite-free rocks depend not only on the order of crystallization of perovskite and magnetite
(Chakhmouradian & Mitchell 1997), but also on higher f(O2), because Fe3+ in perovskite can be used as an oxygen
barometer (Canil & Bellis 2007). Therefore, the rocks with more Fe-rich perovskite might be more oxidized than the
ones with Fe-poor perovskite.
The concentrations of Sr in melilite-bearing rocks are an order of magnitude higher than in melilite-free ones.
The melilite/melt partition-coefficient for Sr is about 1 (Kuehner et al. 1989, Krigman et al. 1995). That is why the
occurrence of melilite as a rock-forming mineral in all differentiates controls the Sr contents and the pattern of zoning
in other minerals. In the melilite-free rocks, Sr is concentrated in apatite (apatite/melt partition coefficient > 1) and,
then, in perovskite. Both minerals in these rocks have higher Sr contents compared to those in melilite-bearing rocks.
Concentrations of Sr in apatite decrease from core to rim in melilite-free rocks, whereas there is no Sr zoning in
melilite-bearing rocks. The distribution of REE in apatite is also different in melilite-bearing and melilite-free rocks: Ce
increases from core to rim in melilite-bearing rocks, but its level of concentration in melilite-free rocks is below the
detection limit (or near it) (Rass, Laputina 1996). The SiO2 content of apatite in melilite-bearing rocks reaches ~1
 122

wt.%, caused by lower CO2 activity, and shows a core-to-rim decrease, whereas in melilite-free MF rocks, its
concentrations are noticeably lower.

References:
Canil D., Bellis A.J. Ferric iron in CaTiO3 perovskite as an oxygen barometer for kimberlite magmas. II. Applications
// J. Petrol. 2007. Vol. 48. P. 231-252.
Chakhmouradian A.R. , Mitchell R.H. Compositional variation of perovskite-group minerals from the carbonatite
complexes of the Kola alkaline province, Russia // Can. Mineral. 1997. Vol. 35. P. 1293-1310.
Chernyshov N.V., Bokaja, L.I. Element morphostructures of the Siberian Platform crust. // Structural Elements of the
Earth’s Crust and Their Evolution. Novosibirsk, Nauka, 1984. P. 144-150 (in Russ.).
Gudfi nnsson G.H., Presnall D.C. Continuous gradations among primary carbonatitic, kimberlitic, melilitic, basaltic,
picritic, and komatiitic melts in equilibrium with garnet lherzolite at 3–8 GPa // J. Petrol. 2005. Vol. 46. P. 1645-1659.
Kravchenko, S.M. , Rass , I.T. The alkalic ultramafic association, a “paragenesis” of two comagmatic series // Dokl.
Acad. Sci. USSR, Earth Sci. Sect. 1985. Vol. 283. No. 4. P. 111-116.
Kravchenko S.M., Rass I.T., Rya bchikov I.D., Dikov Yu.P. Ca-content increasing in mantle alkaline-ultramafic melts
by increasing of melting depths // 29th Int. Geol. Congress (Kyoto). Abstr. 1992. Vol. 2. P. 539.
Kravchenko S.M., Shakhot’ko L.I., Rass, I.T. Moho discontinuity relief and the distribution of kimberlites and
carbonatites in the northern Siberian Platform // Global Tect. Metall. 1997 Vol. 6. No. 2. P. 137-140.
Krigman L.D., Kogarko L.N., Veksler I.V. Melilite–magma equilibrium and the role of melilite in the evolution of
ultra-alkaline magmas // Geokhimiya. 1995. No. 1. P. 3-13 (in Russ.).
Kuehner S.M., Laughlin J.R., Grossman L., Johnson M.L., Burnett D.S. Determination of trace element mineral/liquid
partition coefficients in melilite and diopside by ion and electron microprobe techniques // Geochim. Cosmochim.
Acta. 1989. Vol. 53. P. 3115-3130.
Nielsen, T.F.D. Alkaline dike suites of the Gardiner complex and origin of alkaline-ultramafic association // Geochem.
Int. 1994. Vol. 31. No. 3. No. 37-56.
Peterson T.D. Peralkaline nephelinites. II. Low pressure fractionation and the hypersodic lavas of Oldoinyo Lengai //
Contrib. Mineral. Petrol. 1989. Vol. 102. P. 336-346.
Rass I.T. Rare-earth elements in the rock-forming minerals of melilitic rocks in alkaline-ultramafic complexes //
Geochim. Cosmochim. Acta. 1982. Vol. 46. P. 1477-1488.
Rass I.T. Geochemical features of carbonatite indicative of the composition, evolution, and differentiation of their
mantle magmas // Geochem. Int. 1998. Vol. 36. No. 2. P. 107-116.
Rass I.T., Girnis A.V., Laputina I.P. Kimberlite and turjaite crystallization under 7.2 kbar // Experiment in Geosciences.
1996. Vol. 5. P. 41-42.
Rass I.T., Laputina I.P. Composition and zonation of accessory minerals in alkali ultrabasites as indicators of the
composition and differentiation of the primary magmas // Geochem. Int. 1996. Vol. 33. No. 2. P. 62-77.
Rass I.T., Plechov P.Yu. Melt inclusions in olivines from olivine–melilite rock, the Guli massif, NW Siberian Platform
// Dokl. Earth Sci. 2000. Vol. 375A. P. 1399-1402.
Ryabchikov I.D. Generation of primary magmas in primitive and altered mantles // Proc. 27th Int. Geol. Congress
(Moscow). 1984. Vol. 9. P. 184-191.
Solovova, I.P., Girnis A.V., Rass I.T., Kononkova N.N., Keller J. Composition and evolution of fluidsaturated calcium-
rich melts: inclusions in the minerals of olivine melilitite from Mahlberg, Rhine graben // Geochem. Int. 2005. Vol. 43.
No. 9. P. 843-861.
Veksler I.V., Teptelev M.P. Conditions for crystallization and concentration of perovskite-type minerals in alkaline
magmas // Lithos. 1990. Vol. 26. P. 177-189.
Wilson M., Rosenbaum J.M., Dunworth E.A. Melilitites: partial melts of the thermal boundary layer? // Contrib.
Mineral. Petrol. 1995. Vol. 119. P. 181-196.

Mesoproterozoic Nepheline Syenite Complexes of the Prakasam Alkaline Province, Andhra Pradesh,
India
Ratnakar J.*, Zaitsev V.**, Srinivas M.*, Kumar K. Vijaya *** and Rathna K.***
*Department of Geology, Post-Graduate College of Science, Osmania University,
Saifabad, Hyderabad-500 004, Andhra Pradesh, India.
** Vernadsky Institute of Geochemistry and Analytical Chemistry, Moscow, Russia.
*** School of Earth Sciences, Swami Ramanand Teerth Marathwada University,
Nanded-431606, Maharashtra, India.

In the Indian subcontinent, the Archaean protocontinental core composed of the Dharwar, Bastar and Singhbhum
cratons, is skirted, on east and south, by the Precambrian charnockitic granulite terrain. The Prakasam alkaline province
(PAP) (Leelanandam, 1989; Ratnakar, 2006) in Andhra Pradesh is evolved in a sutured contact zone between these two
terrains of contrasting grades of metamorphism i.e. the core of amphibolite facies and the granulite terrain (Ratnakar
and Leelanandam, 1989).
 123

There are three main nepheline syenite complexes (NSCs) in the PAP, namely are Elchuru, Purimetla and
Uppalapadu intrusions. The alkaline rocks and carbonatites of the PAP are emplaced during the Mesoproterozoic rifting
during the period ~1.3-1.2 Ga (Ratnakar and Leelanandam, 1989; Ratnakar, 1995). They are subsequently deformed
during the Grenvillian and/or Pan-African. These events have been resulted also in overprint of mineral isochrons and
partly in zircon ages (Leelanandam et al., 2006; Upadhyay et al., 2006).
The Elchuru nepheline syenite complex, dated as 1321±17 Ma by U-Pb method on zircon, and 1242±33 Ma by
Rb-Sr whole-rock isochron method (Upadhyay et al., 2006, Subba Rao, et al., 1989) occupies an area of 16 sq km and is
roughly an oval- or skull-shaped intrusive, oriented in NE-SW. The complex is composed of predominant nepheline
syenite. Subordinate ijolite, malignite, shonkinite, nepheline diorite and melanocratic nepheline syenite occur as
elongate lenses up to several tens of meters in mesocratic and leucocatic nepheline syenite (Czygan and Goldenberg,
1989). At places the mafic rocks are intruded by apophyses and vines of nepheline syenite. Rare quartz-bearing syenite
forms the subvertical dyke in the nepheline syenite. The complex is traversed by lamprophyre dykes. Sovite
carbonatite was reported in the contact zone of the complex (Madhavan et al., 1989).
The 1369±28 Ma old Purimetla nepheline syenite complex covers an area of 7 sq km and is a distorted spindle-
shaped body oriented in NE-SW. The intrusive is chiefly composed of nepheline syenite. The hornblende syenite is
closely associated with amphibolite xenoliths in the pluton. Minor quartz syenite occurs in the massive nepheline
syenite and also outside the pluton (in amphibolite and in granite gneiss). Rare malignite occurs as a autholiths,
traversed by the bands and veins of nepheline syenite. Several ocellar lamprophyre dykes also occur (Ratnakar and
Leelanandam, 1986).
The 1348±41 Ma old Uppalapadu nepheline syenite complex spreads over 50 sq km and is roughly triangular in
plan view and oriented in NE-SW. The body is chiefly composed of nepheline syenite which contains inclusions of
granite gneiss, gabbro and horblende syenite; hornblende syenite carries inclusions of biotite schist, gabbro, quartz
syenite and ferrosyenite. Quartzite and migmatite masses occur along the contacts of nepheline syenite-hornblende
syenite, hornblende syenite-ferrosyenite and, ferrosyenite- hornblende syenite-gabbro. There are no mafic members but
a few dolerite dykes cut across the complex (Krishna Reddy et al., 1998; Vijaya Kumar et al., 2007). The field relations
suggest that oldest country rocks (amphibolite, granite gness, schist, quartzite and migmatite) are intruded firstly by
gabbro and ferrosyenite, followed by hornblende syenite and nepheline syenite in that order (Krishna Reddy et al.,
1998); the place of quartz syenite in this order is not clear.
The nepheline syenites of the province are typically miaskitic and the K2O/Na2O ratio varies between 2:1 and 1:2
(Ratnakar, 2007a). The NSCs are characterized by the association of nepheline syenite with comagmatic quartz syenite
that portrays liquidus relations of the petrogeny’s residua system (PRS) (Ne-Ks-Qz) (Hamilton and MacKenzie, 1965).
The cospatial quartz syenite in the NSCs is considered to originate as an off-shoot from the middle stage of the main
differentiation trend by fractionation of ferrohastingsite and biotite. In such a case the liquidus relations in PRS are soon
shifted to those of Ab-Or join (the ‘critical plane of Si-saturation’). For example, in the case of Purimetla alkaline
complex, Ratnakar and Leelanandam (1986) have proposed that Si-oversaturated rocks could form as an off-shoot
products by branching differentiation mechanism, from a part of the differentiating liquid, at the middle (syenitic) stage
of differentiation by fractional crystallization of ferrohastingsite and biotite that leads to accumulation of silica
oversaturated residues that eventually migrate to the oversaturated part of the residua system. In the case of Elchuru
alkaline complex, Ratnakar and Vijaya Kumar (1995) have advocated liquid immiscibility between the liquids of Si-
undersaturation and –oversaturation in the PRS. However, recent studies of trace element chemistry especially of REE
on the Purimetla complex (Ratnakar et al., 2006) proved ‘crustal contamination’ of middle stage liquids to increase the
levels of silica saturation whereby the residues crystallized as quartz syenite (Ratnakar, 2007b).
Isotopic studies on some of the NSCs also suggest signatures of crustal contamination. The initial 87Sr / 86Sr
ratios of the NSCs of southern India also suggest that parental basic magmas were derived primarily from mantle with
seemingly possible contamination with lower crust. It is now considered that the generation of quartz syenites in the
NSCs is due to assimilation fractional crystallization (AFC) rather than simple fractional crystallization (FC) as shown
earlier (Ratnakar and Leelanandam, 1986, Ratnakar, 2007).
The NSCs display strongly fractionated, LREE enriched and HREE depleted, patterns with flat, or positive, but
rarely negative Eu anomalies. The NSCs are enriched in large ion lithophile elements (LILE) reflecting differentiation
or enrichment of the mantle source before melting. It is considered that LILE enrichment in the sub-continental
lithospheric mantle (SCLM) is due to amphibole, phlogopite and apatite that exist due to influx of F, Cl and CO 2 by
mantle metasomatism. Small degree of partial melting of such a metasomatically enriched mantle has yielded alkaline
basic (lamprophyric) liquids that differentiated to form the Elchuru, Purimetla and Uppalapadu nepheline syenite
complexes in the PAP (Ratnakar et al., 2008a, 2008b).

References
Czygan W., Goldenberg G. Petrography and geochemistry of the Alkaline complexes of Sivanmalai, Elchuru
and Upallapadu, India. Geol.Soc.India Memoir 15, pp. 225-240.
Hamilton, D. L. and MacKenzie, W. S. (1965). Phase equilibrium studies in the system NaAlSiO 4(nepheline)-
KAlSiO4(kalsilite)-SiO4(quartz)-H2O. Min. Mag., v. 34, pp. 214-231.
Krishna Reddy, K. K., Ratnakar, J. and Leelanandam, C. (1998) A petrochemical study of the Proterozoic
alkaline complexof Uppalapdu, Prakasam alkaline province, Andhra Pradesh. Jour. Geol. Soc. India, v. 53, pp. 41-52.
 124

Leelanandam, C. (1989) The Prakasam alkaline province in Andhra Pradesh. Jour. Geol. Soc. India, v.53, pp.
41-52.
Leelanandam, C., Burke, K., Ashwal, L. D. and Webb, S. J. (2006) Proterozoic mountain building in Peninsular
India : an analysis based primarily on alkaline rock distribution. Geol. Mag., v.143, pp.195-212.
Madhavan V., Mallikhavrjuna R., Subrahmanyam K., Krishna S.G., Leelanandam, C. (1989) Bedrock geology
of Elchuru Alkaline Pluton, Prakasam Disreict, Andhra Pradesh. Geol.Soc.India Memoir 15, pp. 189-205.
Ratnakar, J. (2008) Nature of Precambrian alkaline magmatism in southern India : The nepheline syenite
complexes. Jour. Appl. Geochem., v. 10, pp. 60-75.
Ratnakar, J. (2007a) Lithosphere control of the of the Proterozoic alkaline magmatism : the miasktic nepheline
syenites of southern India. Gond. Res. (IAGR) Memoir No. 10, pp. 109-121.
Ratnakar, J. (2007b) What made the Proterozoic alkaline magmas in southern India to deliver nepheline syenites
at one time and quartz syenites at the other, in the Ne-Ks-Qz system ? International Seminar on Crustal Evolution,
Sedimentary Processes and Metallogeny, Dharwad, India. Abstracts, pp. 38-40.
Ratnakar, J. (2006) Precambrian alkaline complexes of southern India. International Seminar on Alkaline
Igneous Systems: Dissecting Magmatic to Hydrothermal Mineralizing Processes. Canada, Abstracts, p. 126.
Ratnakar, J. (1995) Structural loci of the Proterozoic alkaline plutons of southern Peninsular India. Jour. Indian
Acad.Geosci., v. 38, pp. 23-31.
Ratnakar, J. and Leelanandam, C. (1986) A petrochemical study of the Purimetla alkaline pluton, Prakasam
District, Andhra Pradesh, India. Neues Jahrbuch Mineral.Abh., v. 156, pp. 99-119.
Ratnakar, J. and Leelanandam, C. (1989) Petrology of the alkaline plutons from the eastern and southern
Peninsular India, Geol.Soc.India Memoir 15, pp. 145-176.
Ratnakar, J. and Vijaya Kumar, K. (1995) Petrogenesis of quartz-bearing syenite occurring within nepheline
syenite of the Elchuru alkaline complex, Prakasam province, Andhra Pradesh, India. Jour.Geol.Soc.India, v. 46, pp.
611-618.
Ratnakar, J., Vijaya Kumar, K. and Rathna, K. (2006) The Purimetla alkaline complex : a DARC from the
Precambrian suture zone, Prakasam alkaline province, Andhra Pradesh, south India. National Seminar on Active and
Fossil Suture Zones, Dehra Dun, India. Abstracts, p. 122.
Ratnakar, J. (2007) Lithosphere control of the of the Proterozoic alkaline magmatism : the miasktic nepheline
syenites of southern India. Gond. Res. (IAGR) Memoir No. 10, pp. 109-121.
Ratnakar, J., Vijaya Kumar, K. and Rathna, K. (2008a) Geochemical investigation of the alkaline mafic dykes in
the environs of the Prakasam alkaline province, Eastern Ghats belt, India. In : Indian dykes: Geochemistry,
Geophysics and Geochronology, Editors: Rajesh K. Srivastava, Ch. Sivaji and N. V. Chalapathi
Rao, Narosa Publ., New Delhi, India, pp. 291-308.
Ratnakar, J., Vijaya Kumar, K. and Rathna, K. (2008b) Meso-Proterozoic rifting and Grenville / Pan-African
collision in the Prakasam alkaline province, Andhra Pradesh, southern India : Evidence from nepheline syenite
compexes. International Conference on Tectonics of the Indian Subcontinent (TOIS), Intern. Assoc. Gond. Res. Conf.
Ser., No. 5, pp. 194-196.
Subba Rao T.V., Bhaskar Rao Y.J. Sivaraman T.V., Gopalan K. Rb-Sr age and petrology of the Elchuru alkaline
complex: Implication to the alkaline magmatism in the Eastern Ghat mobile belt.// Memeirs Geol. Sci. of India, No 15,
1989, pp. 207-223
Vijaya Kumar, K., Frost, C. D. Frost., R. B. Frost. and Chamberlin, R. (2007) The Chimakurthi, Errakonda and
Uppalapadu plutons, Eastern Ghats belt, India: an unusual association of tholeiitic and alkaline magmatism. Lithos,
v.97, pp. 30-57.
Upadhyay, D., Raith, M. M., Mezger, K. and Hammerschimdt, K. (2006) Mesoproterozoic rift-related alkaline
magmatism at Elchuru, Prakasam alkaline province, SE India. Lithos, v. 86, pp. 447-477.

Multiple-stage diamond formation in the Yubileinaya pipe of the Yakutian kimberlite province
Rubanova E.V., Garanin V.K.
Lomonosov Moscow State University

The Yubileinaya deposit is located 15 km northwest of the Aikhal village, in the Alakit-Markha field of the
Daldyn-Alakit region, Yakutian kimberlite province (Kharkiv et al., 1998).
Its diamonds are typically colourless and form octahedral and octahedral-dodecahedral (40%), laminar
dodecahedral (20-25%), and rounded (10%) crystals (Zinchuk and Koptil, 2003). Many diamonds of IV, VIII, IX, and,
more rarely, I groups contain graphite inclusions, which give them grey and black color. Yellow, yellow-green, grey-
green crystals of IV group account for 4 % of all diamonds and their percentage grows with increasing grain size
(Zinchuk and Koptil, 2003). The Yubileinaya pipe is also characterized by high concentration of twins and intergrowths
(30%) (Zinchuk and Koptil, 2003).
A large number of crystals (25%) from this deposit display resorption features (matting, cavities, etching).
Matting was caused by diamond oxidation during hydrothermal-pneumatolytic activity related to diatreme formation
and by the thermal effect of trap emplacement (Zinchuk and Koptil, 2003).
 125

The studied collection contains 12 large diamond crystals varying in weight from 4,98 to 10,75 ct. Due to large
size they have long history of diamond growth and their inner structure can provide full information about conditions
and stages of diamond formation in this pipe. The crystals are octahedral, cubic, and octahedral intergrowths in shape;
one sample is represented by two intergrown cubes. All samples are non- and semitransparent due to strong resorption,
graphitization, matting or a large amount of graphite inclusions. After detailed description of the diamond surface, all
crystals were cut through the center in order to study their inner structure and staged diamond formation.
Most crystals are zoned and contain nontransparent zones, which are supposedly saturated in graphite. These
zones differ in width, homogeneity and represent either single zone or several alternating zones.
Two intergrown coated octahedrons of different sizes were absolutely nontransparent, but after cutting zoning
was found in this sample. Four zones can be defined visually based on inner structure (figs. 1, 2).

Fig. 1. A plate of zoned crystal. The size is 12 mm. Fig. 2. Cathodoluminescence of zoned crystal.
Magn. 50 times

The central part of the largest crystal is transparent and doesn’t have any defects and inhomogeneities (first
zone). Only this zone has light blue photoluminescence. Very thin zoning identified in it using cathodoluminescence
(alternating zones of light and dark blue luminescence) points to quiet, stable and homogeneous diamond growth
conditions. This transparent crystal is surrounded by second zone, which is narrower and subtransparent due to high
concentration of inclusions in it. This zone cuts across growth zoning of the first zone and experienced partial
resorption, which results in the oval morphology of the crystal. Subsequent surface regeneration led to the capture of
numerous inclusions. The third zone consists of small (from tenth to 200 microns) intergrown microcrystals of different
sizes. This zone is nontransparent due to its structure. The undulating boundary between these zones also suggests
another dissolution stage. Third zone has weaker blue cathodoluminescence. Small crystals that build up this zone have
distinct outlines. The presence of these crystals results from oversaturation of material and formation of a lot of
crystallization centres. This moment can be defined as a new population formation. All except first (transparent) zone
are also observed in the smaller crystal of this intergrowth. These crystals are linked by third fine-grained zone.
Fourth zone is a coat consisting of parallel-columnar crystals. It has pistachio-yellow colour and grows on joined
crystals. Its growth is related to the formation of numerous diamond centres on the sample surface and oversaturation of
crystals’ environment during the growth. However, this oversatutation was lower as compared to that during the 3rd
zone formation. The coat has variable thickness, which can result from different oversaturation in the crystallization
material. The fact that this zone shows no cathodoluminescence also indicates the change in crystallization conditions.
IR-spectroscopy revealed heterogeneous distribution of the impurity defects, which supports the repeated
changes of crystallization conditions in the Yubileinaya pipe. The measurements were done by ,G.K. Khachatryan, the
senior scientist of Central Institute of Geological Exploration for Base and Precious Metals (TsNIGRI). The diamonds
are characterized by low concentration of nitrogen defects in 1 st zone (NA=160 ppm, NB=189), absence of hydrogen
defects, and high concenration of “platelets” (P) (12.6 cm-1). The second zone has the same concentrations of A, B, P
defects, but low concentration of hydrogen defects (H=0.3 cm-1). The outer zone (coat) lacks B and H defects, while A
and C defects account for, respectively, 525 ppm and 424 ppm. This zone contains water (3400cm -1) and carbonates
(1400 cm-1), which is a common feature of all columnar diamond coats.
The alternation of sharply different zones is the main evidence for significant changes in crystallization substrate
and multiple-stage diamond formation in the Yubileinaya pipe.
Inclusions from the 3rd zone were analyzed on electron microprobe at the Geological Department of MSU. Most
analyses were made only qualitatively due to their heterogeneity and destructions during cutting. There are only
epigenetic inclusions such as tetra-ferri-phlogopite, chlorite, biotite and ilmenite. Ilmenites contain low MgO
concentration (less than 3 wt.%). There are a lot of fractures, which provided easy penetration of epigenetic solutions to
primary inclusions during postcrystallization alteration (fig. 3).
 126

Fig. 3. Fractures propagated from the second inclusion- Fig. 4. Fluid inclusions. Magn. 200
bearing zone to the sample’s surface

Two transparent octahedrons are crowed with inclusions. Cathodoluminescence revealed no any heterogeneities
in growth. Many fluid inclusions (fig. 4) in these samples were formed during crystallization and post-crystallization
processes. The graphite was identified by Raman spectroscopy at the boundary of fluid inclusions and diamonds.
Graphitization was presumably caused by high-temperature post-crystallization processes and, therefore, occurs at the
contact between fluid inclusions and diamond, the most distorted part of the crystal (fig. 5). Moreover the graphite was
found in black and grey zones of non-transparent crystals. A peak at 1582-1586 cm-1 marks the presence of crystalline
graphite (fig. 6). Several samples display a weak peak of X-ray amorphous graphite at 1360 cm-1.

Fig. 5. Inclusions and graphitization in the diamond. Fig. 6. Raman spectrum of diamond with the graphite
Magn. 200.

References:
Zinchuk N.N., Koptil V.I. Diamond typomorphism os Siberia. Moscow, Nedra, 2003, p. 188-200 (in Russian).
Kharkiv A.D., Zinchuk N.N., Kruchkov A.I. Primary diamond deposits of the World. Moscow, Nedra, 1998 (in
Russian).

Redox reactions in carbonate-rich magmas

Ryabchikov I.D.*, Kogarko L.N.**
*Institute for Geology of Ore Deposits, Petrography, mineralogy and Geochemistry, Moscow, Russia
** Vernadsky Institute of geochemistry and analytical chemistry, Moscow, Russia

Compositions of co-existing minerals from graphite bearing carbonatites were obtained by the EPMA analysis
for beforsites from Chernigovsky complex (Ukraine)(KRIVDIK et al., 1997), Pogranichnoe dolomite-rich carbonatites
(DOROSHKEVICH et al., 2007), Chagaday carbonatites, Uzbekistan, Khibina alkaline igneous complex, which includes
carbonatites and graphite-bearing rocks (Kola Peninsula) (NIVIN et al., 2005), and carbonatites of Gremyakha-Vyrmes
magmatic complex (Kola Peninsula). In all cases graphite-bearing rocks contain magnetite. Sometimes late magnetite
and graphite form intimate intergrowths. Thermodynamic analysis of equilibria between magnetite, silicate minerals,
 127

carbonates and graphite permitted to estimate temperatures and oxygen fugacities prevailing during the formation of the
investigated rocks.
Chagaday graphite-bearing carbonatites, in which several grains of diamond were also reported, contain calcite,
apatite, magnetite, clinopyroxene, albite and K-feldspar.
Temperatures of equilibrium for mineral clinopyroxene+calcite+ titanomagnetite+titanite+graphite + albite +
nepheline depending on titanomagnetite compositions were calculated using equilibrium constants of the following
reaction:
4 CaFeSi2O6+3CaCO3+7 Fe2TiO4+0.5NaAlSiO4=7 CaTiSiO5+6 Fe3O4+3C+0.5NaAlSi3O8
These calculations demonstrated that for a given magnetite composition decrease in temperature causes
formation of graphite together with magnetite. Therefore, appearance of graphite in carbonatites may be caused by
cooling, and graphite may crystallize from melt, it may form by solid-state reactions, or precipitate from cooling
aqueous fluid.
fO2 values were estimated from the equilibrium constant of the reaction
6CaFeSi2O6+6CaCO3+12Fe2TiO4=12CaTiSiO5+10Fe3O4+6C+O2
Calculated fO2 values are 0.5 to 1 log units below QMF buffer. Similar values of oxygen fugacities were
estimated for other investigated graphite-bearing carbonatites.
Diamond forms in subcontinental lithosphere also due to the reductions of near-solidus carbonate-rich melts
arriving from asthenosphere or from rising plume. This reduction is caused by interaction of these melts with the rocks
of lower lithosphere, which are characterized by very low fO2 values.
This study was financially supported by RFBR grant 08-05-00356-а.

References:
Doroshkevich A. G., Wall F., and Ripp G. S. (2007) Magmatic graphite in dolomite carbonatite at Pogranichnoe,
North Transbaikalia, Russia. Contributions to Mineralogy and Petrology 153(3), 339-353.
Krivdik S. G., Zagnitko V. N., and Lugovaya I. P. (1997) Isotope composition of minerals in carbonatites of the
Chernigovsky massif (Azov Territory) as indication of crystallisation conditions (in Russian). Mineral Zhurn 19(6).
Nivin V. A., Treloar P. J., Konopleva N. G., and Ikorsky S. V. (2005) A review of the occurrence, form and
origin of C-bearing species in the Khibiny Alkaline Igneous Complex, Kola Peninsula, NW Russia. Lithos 85, 93-112.

Cambrian basaltic magmatism of different geodynamic settings recorded in the Katun accretionary
complex - a transitional zone between the Paleo-Asian Ocean and Siberian continent
Safonova I.Yu.*, Simonov V.I.*, Komiya T.**, Kurganskaya E.V.*
* - Institute of Geology and Mineralogy SB RAS, Novosibirsk, Russia; ** - Department of Earth and
Planetary Sciences, Tokyo Institute of Technology, Tokyo, Japan

The Paleo-Asian Ocean (PAO) was located between Siberia and East Gondwana from 750 Ma until the
Carboniferous (e.g. Zonenshain et al., 1990). Its western part included a chain of seamounts (Safonova, 2008) and
Kuznetsk-Altai island arc (Buslov et al., 2001), which existed in the transitional zone between the ocean and the
Siberian continent. The Cambrian oceanic subduction resulted in accretion of the seamounts to the island arc, and later
those units together were accreted to the SE margin of the Siberian continent during the closure of the PAO. The
accretion formed an accretionary complex (AC), which is presently hosted by the Katun zone of Gorny Altai in SW
Siberia. The Katun zone comprises two groups of basalts of different ages: 1) Early Cambrian oceanic basalts of the
Manzherok and Eskonga Fms. incorporated in the Katun AC, and 2) Middle Cambrian basalts of the Ust’-Syoma Fm.,
which dikes and lavas cut and discordantly overlap the accretionary units. The Early Cambrian basalts are associated
with oceanic plate stratigraphy (OPS) sediments: reefal limestone and slope facies sediments (Manzherok Fm.) and
siliceous shale and chert (Eskonga Fm.; Dobretsov et al., 2004; Safonova, 2008). Evidence for their Early Cambrian age
comes from the occurrence of abundant remnants of microphytoliths and calcareous algae in carbonates and sponge
spicules in siliceous shale (Terleev, 1991). The AC units are unconformly overlapped by Middle Cambrian rocks,
including the Ust-Syoma volcanogenic sedimentary formation. The basaltic dikes up to 10 m thick cut the AC over a
distance of 100 km suggesting an extension tectonic regime.
The Early Cambrian basalts of the Katun AC plot in the fields of subalkaline and alkaline basalts in the Nb/Y vs
SiO2 diagram and in the field of high-Fe tholeiites in the Al2O3-TiO2+FeO*-MgO classification triangle. According to
the concentrations of TiO2, LREE and Nb the samples can be divided into two groups: depleted and enriched (Figs.
1,3,4). In the depleted group SiO2=45.1-52.6; Fe2O3=11.2-12.1; TiO2=0.72-1.52; Al2O3=13.8-16.8; P2O5=0.14-0.66
wt.%; Mg#=33-64 (Figs. 1,2); Ba/Rb=3-300; Zr/Nb=19-32. Low LaNav (12.6), La/YbN (0.5-2.4) and Th (0.2-0.6 ppm),
and Nb depletions (Nb/Lapm=0.16-0.96; Nb/Thpm=0.24-0.69) make the depleted varieties similar to N-MORB (Fig. 3,4).
For the enriched varieties SiO2 spans 45.4-48.9 wt.%; Fe2O3=11.6-15.1; TiO2=2.0-4.2; P2O5=0.18-1,56; Al2O3=13.4-
18.1 wt.%; Mg#=35.4-53.3 (Fig. 1); Ba/Rb=4-170; Zr/Nb=3-15. High LREE (LaNav=52.8; La/SmN=1.3-3.65;
Gd/YbN=1.4-3.4) and Nb (Nb/Lapm=1.23-2.87; Nb/Thpm=1.85-4.75) suggest their mantle plume origin (OIB-type). The
observed variations in incompatible elements can be explained by the variable degrees of melting: high degrees within
the stability field of spinel for the MORB-type depleted basalts (Gd/Ybn=0.8-1.4; Mg#av=53) and low degrees within
the garnet stability field (Gd/Ybn>2; Mg#av=41) for OIB-type enriched basalts (Figs. 1,2).
 128

The Middle Cambrian samples are subalkaline and transitional basalts having variable MgO (5.75 and 14.77)
and Al2O3 (7.51 and 20.61), respectively; SiO2=45.0-54.2; Fe2O3=8.5-12.3; TiO2=0.58-0.89; P2O5=0.1-0.28 wt.% (Figs.
1,2). The samples are characterized by zero to weakly enriched LREE (La/Sm N=0.85-1.7) and depleted Nb (Figs. 3,4;
Nb/Lapm=0.3-0.8; Nb/Thpm=0.2-0.99). Similarly to subrasubduction basalts a part of samples have Th/Nb pm>La/Nbpm.
The others are closer to N-MORB, however possessing lower HFSE (Ti, Nb, Zr, Y) and higher Al 2O3 and MgO (Figs.
1,2). Generally, the major and trace element composition of the Ust-Syoma basalts is close to island-arc tholeiites (IAT-
type), but have lower REE. The Ust-Syoma basalts have characteristic porphyric texture with diopside and plagioclase
phenocrysts up to 5 mm size that makes them similar to lamprophyres. All the samples are characterized by wide
variation of alkalis and LILE (Na2O=0.8-3.8; K2O=0.2-3.34; Rb=1.1-69; Sr=3.5-817) possibly due to their mobility
during post-magmatic alteration.
The chemical composition of clinopyroxene phenocrysts from the Manzherok (OIB-type) and Ust-Syoma (IAT-
type) samples corresponds to diopside-augite and diopside-salite, respectively. Clinopyroxene monomineral
thermometry shows that the Manzherok basalts were formed at higher temperatures compared to the Ust-Syoma
samples (averages from several thermometers): 1130-1220оС and 1075-1120 оС, respectively.
According to Tatsumi (1991) high-Mg island-arc tholeiites can be melted near the volcanic front at mantle
depths close to the mantle-crust boundary. Therefore we suggest that the high-Mg Ust-Syoma basalts (Gd/Ybn<1.4;
Mg#=61.5-63; Figs. 1,2) possibly formed in mantle wedge, i.e. suprasubduction, conditions, as a result of the melting of
the subducting oceanic slab in the presence of fluid phases. Moreover, the signatures of extension regime (dikes),
similar to MORB low-Ti and high-Mg composition and occurrence of adakite-like rocks and granites of Cambrian age
in the frontal area of subduction (Shokalsky et al., 2000) allows us to suggest oceanic ridge subduction, which resulted
in formation of a slab window.

40
5

4 Al-IATs
30
TiO 2, мас.%

АТ
3
Al 2O 3/TiO 2

20
Т
2 EPR-MORBs

10 Hawaii OIBs
1

island-arc trends
0 0
0 1 2 3 4 5 0 1 2 3 4 5
FeO*/MgO Gd/Ybn

Fig. 1. Bivariant TiO2 vs FeO*/MgO plot. Fields Fig. 2. Al2O3/TiO2 – Gd/Ybn variation diagram
and trends of abyssal tholeiite (AT) and tholeiite (T) are indicating low to high degrees of partial melting. Symbols
after Miyashiro (1973). Symbols see Fig. 4. see Fig. 4.
1000
100.0

OIB
rock/primitive mantle

100 10.0
rock/chondrite

OIB
MORB

IAT

10 1.0

MORB

1 0.1
La Ce Pr Nd (Pm) Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Th Nb La Ce Nd Zr Hf Sm Eu Ti Gd Tb Dy Y Ho Er Tm Yb Lu

Eskonga Fm. Manzherok Fm. Ust-Syoma Fm.

Fig. 3. Chondrite-normalized rare-earth element
patterns. OIB, MORB and normalizing values are from Fig. 4. Primitive mantle-normalized trace element
Sun and McDonough (1989). IATs, Aleutian tholeiites, diagrams. OIB, MORB and normalization values are from
are from GEOROC database. Symbols see Fig. 4. Sun and McDonough (1989).

Conclusively, the available geological, mineralogical and geochemical data show that the Early Cambrian
depleted basalts formed in an oceanic spreading setting. Evidence for this comes from their association with siliceous
sediments, low to medium TiO2, and flat REE patterns (Figs. 1,3). The enriched basalts formed in an oceanic island
setting; they are associated with siliceous-carbonate slope facies sediments and characterized by high TiO 2, LREE and
Nb/Lapm (>1) suggesting an enriched mantle source. The OIB-type basalts were formed at depths of the spinel
(Gd/Ybn<1.5) and garnet (Gd/Ybn>2) facies (Fig. 2).
 129

The Ust-Syoma basalts (Middle Cambrian) are compositionally close to MORB and IAT. However, low TiO 2
and Nb, flat REE patterns at medium to high #Mg suggest their formation during ridge subduction. The typical IAT
chemical features (low Ti, La/Nbpm<Th/Nbpm, La/Smn=1.3; Figs. 3,4) are thought to be inherited from the mantle
wedge, which the basaltic melts were ascending through. Such a hypothesis requires more support by performing more
detailed geological, geochemical isotope and petrological studies.
The study was financially supported by RFBR-JSPS grant no. 07-05-91211.

References:
Buslov M.M., Saphonova I.Yu, Watanabe T. et al. Evolution of the Paleo-Asian Ocean (Altai-Sayan Region,
Central Asia) and collision of possible Gondwana-derived terranes with the southern marginal part of the Siberian
continent // Geoscience Journal. 2001. Vol. 5. P. 203-224.
Dobretsov N.L., Buslov M.M., Safonova I.Yu., Kokh D.A. Fragments of oceanic islands in the Kurai and Katun
accretionary wedges of Gorny Altai // Russian Geology and Geophysics. 2004. Vol. 45. P. 1381-1403.
Miyashiro A. The Troodos ophiolitic complex was probably formed in an island arc // EPSL. 1973, Vol. 19. P.
218-224.
Safonova I.Yu. Geochemical evolution of the Paleo-Asian Ocean intra-plate magmatism from the Late Neoproterozoic
to the Early Cambrian // Petrology. 2008. Vol. 16. P. 492-511.
Shokalsliy S.P., Babin G.A., Vladimirov A.G. et al. Correlation of magmatic and metamorphic complexes in
western Altai-Sayan // “GEO” SB RAS Publ., Novosibirsk. 2000. 187 p.
Tatsumi Y. Origin of subduction zone magmas based on experimental petrology // Physical Chemistry of
Magma. Springer-Verlag. 1991. Vol. 9. P. 268-301.
Terleev A.A.. Stratigraphy of Vendian-Cambrian sediments of the Katun anticline (Gorny Altai) //
Khomentovskiy V.V. (Ed.) Late Precambrian and Early Paleozoic of Siberia. 1991. Novosibirsk: UIGGM Publ. P. 82-
106 (in Russian).
Zonenshain L.P., Kuzmin M.I., Natapov L.M. Geology of the USSR: A Plate tectonic synthesis. Geodynamic
Monograph. 1990. Washington: American Geophysical Union. 242 P.

Sources of Cenozoic intra-plate magmatism in Central Asia: implication from geochemistry and Sr-
Nd-Pb isotope data
Savatenkov V.M.*, Kudryashova E.A.**, Kozlovsky A.M.**, Yarmolyuk V.V.**
* Institute of Precambrian Geology and Geochronology RAS, St.-Petersburg; ** Institute of the Geology of
Ore Deposits, Petrography, Mineralogy, and Geochemistry RAS, Moscow, Russia.

During Later Cenozoic within Central Asia the series of independently evolving volcanic areas (so-called
Central Asian Volcanic Province (CAVP)) has formed [1]. They are Udokan (UVA), Vitim (VVA), Southern Baycalian
(SBVA) and Khangai (KVA) volcanic areas. They are situated far from lithospheric plate margins and are characterized
by predominance of sub-alkaline and alkaline basalts. So, they relate to intra-plate processes. Geophysical studies of
CAVP [2] revealed presence of large-scale ledge of an asthenospheric mantle (or hot field of mantle) with roof elevated
on 100 km to surface. Moreover, directly beneath some volcanic areas the local elevation attending the 50 km to surface
was discovered. These elevations were interpreted as mantle diapires produced by thermal field of the mantle. Because
the feeding area was common the structurally separated volcanic areas were developed simultaneously [1]. This fact
also indicates the relation of CAVP with mantle plumes. Volcanic areas are characterized by the duration of
development exceeding a few 10 Ma, as well as by relations to grabens systems, the stable character of magmatism, the
regular migration corresponding to lithosphere displacements over hot spot, and by the link to dome-like elevation at
modern relief.
The geochemical characteristics of the basalts from the different areas of CAVP demonstrate no significant
differences. The basalts show smooth normalized REE spectrum with relative LREE enrichment. The trace element
enrichment implies that the basalts of CAVP correspond to OIB. However, CAPV basalts show enrichment in Ba and K
and depletion in U, Th, Zr, Hf and heavy REE compared with OIB. Because geochemical characteristics of basalts from
different CAVP area are similar the source of investigated basalts is common and melting environment is similar.
In spite of these similarities, some differences between the basalts from different areas as well as basalts from
single volcanic area occur. For example, the basalts from SBVA and KVA contain lower MgO compared with the
basalts from UVA and VVA; that mean higher fractionating degree. In addition, within KVA the basalts vary from
high-Mg to low-Mg types. These variations of chemical composition occur from centre to edge of KVA and they
apparently indicate different levels of magma generation. These levels appear to link with mantle dome structure.
In εNd versus εSr space, the basalts from CAVP form superposition confined by two trends from PREMA-like
mantle (FOZO [3]), one of which extend to EMI source and other extend to EMII source. In according to the ε Nd versus
εSr diagram, the basalts from SBVA and KVA derived from the source contained mixture of EMI and EMII
components. The basalts from VVA form trend from FOZO to EMII [4]. End-member of the basalts from UVA accords
with a weak depleted mantle isotope signatures.
In 206Pb/204Pb versus 207Pb/204Pb space, basalts from KVA and UVA also form some trend from FOZO. First
group of the samples forms array shifted to the field of ancient (Archean) recycled material. The latter was primarily
 130

enriched in U and then partly loosed it during Proterozoic period. Other group of the samples forms trend toward the
field of low-U/Pb ancient recycled material. This conclusion is in agreement with low Th and U concentrations in the
studied basalts. End-member component of the basalts from UVA is a weak depleted mantle. This suggests shorter
history of enriched source evolution compared with source of the basalts from KVA.
Thus geochemical and isotopic data demonstrate that source of the studied basalts appear to be involved material
of recycled lithosphere. The basalts from KVA and SBVA generally exhibit low ε Nd value (up to -12), reflecting
recycled lithosphere was ancient. In addition, their Pb isotope signature results from the long-term evolution of enriched
source. In contrast, isotope data on the basalts from UVA and VVA indicate the shorter history of enriched source
evolution. Sr-Nd-Pb isotope differences between end-member sources of the basalts from southern (KVA, SBVA) and
northern (UVA, VVA) reflect sublithospheric mantle heterogeneity. So, sublithospheric mantle apparently contain
buried lithosphere fragments of different age. Based on Sr–Nd–Pb isotopic results, we suggest that common component
for all of the studied basalts was asthenospheric mantle with εSr ~ 15, εNd ~ +5, 206Pb/204Pb ~ 18.5, at least in Central
Asia.
This work is supported by the Russian Academy Foundation (grants 07-05-00876, 05-05-64000, 07-05-90100).

References:
[1] Yarmolyuk V.V., Kovalenko V.I., Ivanov V.G. Intraplate Late Mesozoic-Cenozoic volcanic province of
Central Asia – projection of hot field of mantle. // Geotectonic, 1995, № 5, P. 41-67 (in Russia)
[2] Zorin Y.A., Balk E.V., Novosjolova M.P., Turutanov E.H. Thickness of lithosphere under Mongolo-Siberian
mountain country and contiguous regions. // Phisic of Earth, 1988, № 7, P. 32-42 (in Russia)
[3] Stracke A., Hofmann A.W. FOZO, HIMU, and the rest of the mantle zoo. // Geochem. Geophys. Geosyst.,
2005, V. 6, № 5, pp. 2-20.
[4] Jhonson J.S., Gibson S.A., Thomson R.N., Nowell G.M. Volcanism in Vitim volcanic field, Siberia:
geochemical evidence for a mantle plume beneath the Baikal rift zone. // J. Petrology. 2006. V. 46. P. 1309-1344.

Carbonatitic zircon – myth or reality: mineralogical-geochemical analysis

Savva E.V.*, Belyatsky B.V. **, Antonov A.V. ***
*Institute of Precambrian Geology and Geochronology RAS, St.-Petersburg, Russia
**VNIIOkeangeologia, St.-Petersburg, Russia
***Centre of Isotopic Research, VSEGEI, St.-Petersburg, Russia

Zircon crystallization in a wide range of temperature and physico-chemical conditions determines its wide
distribution as an accessory mineral in magmatic and metamorphic rocks of different composition and origin and allows
to use it as a reliable geochronometer for dating magmatic processes (Zircon, 2003). It is of common knowledge that in
magmatic systems undersaturated in silica, such as alkali-ultramafic and carbonatite melts, with sufficient amount of
zirconium, there takes place preferential crystallization of baddeleyite and other zirconium minerals (zirconolite,
zirkelite, etc.), zircon being unstable under such conditions should be dissolved (Barker, 2001). Nevertheless, for many
carbonatite–alkali-ultramafic massifs zircon is the prevailing accessory mineral occurring both in silicate and
carbonatite rocks very often in the form of large, up to first centimeters, crystals of pseudo-octahedral habit
(Kukharenko et al. 1965). Recent works on investigation of rare and trace elements distribution in zircon have
demonstrated that geochemistry of zircon could be reliable criteria for determination of their host rocks origin (Hoskin,
Ireland, 2000; Belousova et al., 2002). Moreover, zircon composition is widely used to define the provenance in
sedimentary analysis of sands and sandstones on the base of polycomponent classification and regression analysis
(CART), which allows to make wide palaeotectonic reconstructions (Veevers et al., 2006). One of the such
reconstruction methods (Burke et al., 2003) is based on mapping of post-collisional zones of crustal extension marked
by development of rocks belonging to alkaline complexes and carbonatites (ARC), which for their turn could be
distinguished by composition of detrital zircons at area sampling (Veevers, 2007). Successfulness of this method
appliance depends entirely on substantiation of classification characteristics – for typical representatives of carbonatite
massifs in initial database were taken Mud Tank carbonatite complex (723 Ma) in Central Australia and Kovdor
complex (380 Ma), Kola Peninsula. The following characteristics have been assumed as typical for “carbonatite”
zircons: average REE content 600-700 ppm at comparatively flat distribution, (Yb/Sm)n: 3÷30, Th/U up to 100 and
more, 2.3<Lu<20.7 ppm, Ta>0.5 ppm, Hf>0.62 %. We have decided to test plausibility of these characteristics on
zircons from carbonatite massifs of different age – from Archean Siilinjärvi massif, Proterozoic Tiksheozero and
Elet’ozero massifs, Paleozoic Lovozero and Khibiny massifs and Mesozoic carbonatitic dykes from Antarctica and
India.
We have analyzed more than 100 zircon grains for content of 20 rare and trace elements. Zircon in the studied
carbonatites is represented, as a rule, by well faceted large crystals and their particles. The crystals are cracked; the
surface very often is rough. The shape of grains is pseudo-octahedral – dipyramidal with prevailing development of
steep dipyramid (111) and subordinated development of prism (110), sometimes the zircons are short prismatic. Very
often the facets are asymmetric. The color of zircon varies from colorless, pinkish-grey to strongly colored yellowish-
brown shades. The crystals are semitransparent due to heterogeneity of its inner structure – abundance of cracks filled
with carbonate material, gas-liquid inclusions and cavities, there numerous inclusions of rock-forming minerals such as
 131

mica, amphibole, carbonates, apatite, magnetite. The size of the studied zircon grains varies from 1-2 mm to 1x2 cm. In
some cases we have marked corroded rim with fine dust-like baddeleyite which develops along the cracks (fig.1).
Character of CL images varies even for zircons from the same complex – from absolute absence of any luminescence to
bright colors over the whole grain without any regular inner structures. At the same time the back scatted electron
images show the traces of zoning. So, morphology of the studied zircons repeats the known features of zircons from the
other carbonatite massifs (Kramm et al., 1993; Сlaesson et al., 2000; Frantz et al., 2001; Amelin, Zaitsev, 2002;
Chakhmouradian, Williams, 2004; Zozulya et al., 2007).
REE patterns of the studied zircons is characterized by extreme variability – from weakly fractionated flat
chondrite-normalised REE distribution with general lower rare elements content to normal fractionated patterns with
prominent enrichment in heavy REE and well pronounced negative Eu and positive Ce anomalies, but there are
distributions with distinctly increased REE content with positive Eu and weak Ce anomalies (fig.2): (Sm/La)n: 2÷738,
(Lu/Gd)n: 1÷58, Ce/Ce*: 1.2÷194.1, Eu/Eu*: 0.7÷1.78, (La/Gd)n: 0.0005÷0.5, (Pr/Gd)n: 0.01÷1.0, (Gd/Yb)n: 0.03÷0.9.
It is necessary to point out that according characteristic ratios and element contents suggested by (Belousova et al.,
2002) for typically carbonatitic zircons in our case there are observed wide variations in (Yb/Sm)n: 0.9÷180, Th/U:
0.2÷512; [Hf]: 1020÷8700 ppm; [Lu]: 1÷94 ppm, [Nb]: 3÷ 2675 ppm; [Ta]: 4.7÷68 ppm and only lesser part (about
45%) of the studied zircons could be convincingly classified as carbonatitic. At the same time, variations in zircon
composition within the single complex could be compared with general variations and even in some grains there have
been observed fluctuations in content of some elements more than one order of magnitude (for example, [Th] – from 4.7
to 270, [Lu] from 1 to 11, [Y] – from 15 to 430 ppm). Zircons from carbonatitic dykes (Antarctica, India) showed the
least variations. Crystallization temperatures of the studied zircons by titanium-in geothermometer correspond to a
rather narrow interval of 570°–850°C. It is noteworthy, that elements which are greatly accumulated in carbonatites
(Chakhmouradian, 2006) – REE, HFSE, P, Y, Sr, Ca, in the studied zircons vary widely and do not demonstrate
essential enrichment in comparison with zircons from the other rock types.

Fig. 1. Back-scattered electron image of zircons from Fig. 2. Chondrite-normalised REE patterns for studied zircons.
the Tiksheozero carbonatite. 1 – averaged “carbonatite zircon” (Belousova et al., 2002); 2 –
light lamellas – baddeleyite inclusions Phalaborwa and 3 - Mud Tank carbonatites (Hoskin, Ireland,
2000).

Thus, independently from the origin of the certain carbonatite-alkali-ultramafic massive – from the primary
common melt due to immiscibility of carbonate and silicate melts, in the result of consistent intrusion of independent
melts from one developing mantle source or spatially close but essentially different in composition and time of
formation sources, mineral composition of carbonatites and first of all mineralogical-geochemical peculiarities of such
accessory minerals as zircon, baddeleyite, pyrochlore, perovskite etc. (Chakhmouradian, Williams, 2004), are
determined by interaction of carbonate fluid enriched in lithophile elements with carbonate and silicate minerals of the
matrix. Evolution of such fluid composition causes considerable changes in mineral geochemistry in the process of their
growth, changing of mineral forms and partial replacement of some minerals by the others (for example, the
relationship between zircon and baddeleyite), partial dissolving and further recrystallization. Especially well such
processes are revealed in old complexes where the later rather low-temperature processes are overprinted on the earlier
formed mineral assemblages in the course of tectonic activity in the region. In such cases there could be observed poly-
stage mineral systems (for example, zircon) formation of which could take place with considerable time intervals (till
dozens and hundreds of years) but its geochemistry will reflect the main evolution stages of massif transformation. In
any case, distinguishing the single geochemical type of “carbonatitic zircon” in reflection to genetic link with the host
carbonatites seems rather ill-founded, first of all due to the limited data on such unique fluctuation in composition of
these zircons.

References:
Amelin Yu., Zaitsev A.N. Precise geochronology of phoscorites and carbonatites: the critical role of U-series
disequilibrium in age interpretations. Geochim.Cosmochim.Acta, 2002, 66, 2399-2419.
Barker D.S. Calculated silica activities in carbonatite liquids. Contrib.Mineral.Petrol., 2001, 141, 704-709.
 132

Belousova E.A., Griffin W.L., O’Reilly S.Y., Fisher N.I. Igneous zircon: trace element composition asan
indicator of source rock type. Contrib.Mineral.Petrol., 2002, 143, 602-622.
Burke K., Ashwal L.D., Webb S.J. New way to map old sutures using deformed ARCs. Geology, 2003, 31, 391-
394.
Chakhmouradian A.R. High-field-strength elements in carbonatitic rocks: geochemistry, crystal chemistry and
significance for constraining the sources of carbonatites. Chemical Geology, 2006, 235, 138-160.
Chakhmouradian A.R., Williams T.C. Mineralogy of high-field-strength elements (Ti, Nb, Zr, Ta, Hf) in
phoscoritic and carbonatitic rocks of the Kola Peninsula, Russia. In: Wall F., Zaitsev A.N. (eds) Phoscorites and
carbonatites from mantle to mine: the key example of the Kola Alkaline Province. Min. Soc. London, 2004, 293-340.
Frants N.А., Savva E.V., Putintseva E.V. Rare-metal minerals (zircon, pirochlore, baddeleyite) from carbonatites
of Tiksheozero massif (N. Karelia). Vestnik SPGU, 2001, 4 (31), 76–83.
Hoskin P.W.O., Ireland T.R. Rare earth element chemistry of zircon and its use as a provenance indicator.
Geology, 2000, 28, 627-630.
Kramm U., Chernyshev I.V., Grauert B., Kononova V.A., Breker B. Typology and U-Pb zircon systematics from
nepheline seyenite from Ilmeny, Ural. Petrology, 1993, 1, 536–549.
Kukharenko, A.A. et al., 1965. The Caledonian Complex of Ultrabasic, Alkaline Rocks and Carbonatites of the
Kola Peninsula and northern Karelia. Nedra, Moscow. 550 p. (in Russian).
Veevers J.J. Pan-Gondwanaland post-collisional extension marked by 650-500 Ma alkaline rocks and
carbonatites and related detrital zircons: a review. Earth-Science Reviews, 2007, 83, 1-47.
Veevers J.J., Belousova E.A., Saeed A., Sircombe K., Cooper A.F., Read .E. Pan-Gondwanaland detrital zircons
from Australia analysed for Hf-isotopes and trace elements reflect an ice-covered Antarctic provenance of 700-500 Ma
age, Tdm of 2.0-1.0 Ga, and alkaline affinity. Earth-Science Reviews, 2006, 76, 135-174.

Сollision granitoides and sienites of the Urals: Conditions of location, geochemical and metallogenic
specialization and practical significance
Sazonov V.N*, Ogorodnikov V.N**, Polenov Yu.A**
* Institute of geology geochemistry, Urals branch of RAS, Ekaterinburg, Russia
** Urals State Mining University, Ekaterinburg, Russia

A collision process in the Urals took place in two time interval: 375 – 320 and 320 – 240 Ma.
In early stage quartz diorite, granodiorites, adamellites and granites (Berezovsk, Kochkar, Aidirla, Verkh-Isetsk
and others ore fields), specialized on Au, W, As at least measure Mo and fluid phase – on CO2, F-Cl, S, were formed. In
late stage were formed biotite (normal) granites, leucogranites (Murzinka-Aduy, Djabic, Adamov plutons and s.o.),
specialized on rare metals and big spectrum of non metallic mineralizations (asbestos, talc, mica, quartz etc.) and fluid
phase – on F; gabbro-granite-sienite complexes (Magnitogorsk ore region), specialized on Fe, at least measure Mo, Pb
and fluid phase – on Cl – F; alkaline granites and sienites of the Gumbeysky,
Stepnoy complexes and sienites of the Berzovsk gold field (Fershtater, 1987; Sazonov et al., 20071,2; Kholodnov,
2007).
In the Magnitogorsk gabbro-alkaline granite pluton there zones in vertical section are recognized: 1) upper
alkaline granitic and sienitic, 2) transitional gabbro-granitic and 3) lower gabbroic. In the pluton’s origin the main role
the main role took place intrachamber fractionation. We can see in a low pluton’s level skarns with magnetite
mineralization, but in a upper level – a week Mo and Pb mineralization (Kholodnov, 2007). The chemical compositions
of Magnitogorsk plutonites, a trend of distribution REE, Fe, Ti and Nb, Zr, P and some other elements in them are
typical for continental rifts. According to (Sazonov et al., 20071), a substan’s source for formation rocks of the
Magnitogorsk rifts was a boundary between mantle reservoirs EM1 and EM2. Position like this we can find in
[Kholodnov, 2006] who consider that the rocks of the Magnitogorsk pluton are the result of inter action of mantle
substance with slab’s pattern. In this situation it is stand clearly why gabbro of Magnitogorsk pluton specialized on Fe
and Cl but alkaline granites and sienites on Mo, Pb and F-Cl.
The Gumbeisk alkaline complex. This complex include some massifs-stocks subalkaline group (boundary
between C and P) which consist of sienite-diorite, sienite, quartz sienite, granosienite which controlled by diagonal fault
– element of suture zone of a duplex character. The massif’s host rocks are volcanites and sedimentary formations (D 2).
In the stocks there are two deposits and some manifestation of W (stockworc and skarn nature). A mineralization
besides W include Mo and Au (rare). Complex was formed with participation of mantle substance (Sazonov et al.,
20071).
Granitiid massifs of tonalite-granodiorite formation (I-type). They submitted batholiths or batholith like bodies
and consist of tonalities and granodiorites (prevail), rare gabbro and gabbrodiorites (may be absence), adamellites and
granites. Massifs are controlled by fault’s zones (they are duplexes often). In an endocontact of massifs there many
henoliths including gabbroic. In big massifs we can find granitoid’s, diorites’ and lamprophiry’s dykes and products of
hydrothermal activity. The last conclude quartz veins mainly. They fixed big (up to 1,5 km) shearing and breaking
fractures. These veins are not productive. The productive ones are more younger, in them native gold and sulfides
especially pyrite spread. I-type granitoids were formed thanks to earth crust and mantle substances.
 133

Granite massifs of granite formation (S-type). These granites’ nature is crust. They were formed because silic
substrat (gneissic block , R) was partly melting. F-type hydrothermal fluid was formed with such granites. Pegmatites
and quartz veins were formed in connection with them. The main value of both formations are rare metals and granulate
quartz. And may be mention emeralds and crystals.
Sienite of the Stepnoy complex. Monzodiorites are the main rocks of this complex. Many dykes (granites,
granosienites, sienites, sienodiorites) fixed in them. Construction? Composition and metallogeny specialization of these
massifs and massifs of Gumbeyka complex (see above) are analogous.
Alkaline rocks of the Berezovsk ore field. These rocks distinguished by M.B.Borodaevskaya (1951year) in the
contact of collision granitoid-porphiry dykes with antigorite serpentinite. There following zonation was picket out:
granite-porphiry – albite quartz-bearing sienite – albite sienite (without quartz) albitite – serpentinite. In formation of
metasomatites a mantle fluid (T > 400 OC, P>2 kbar, specialization on Na, CI – F) and components of granitoids and
serpentinites took place.
Today metallogenic and geochemistry (including such volatile elements as F, Cl, CO 2, S) specialization of
complexes rocks of different geodynamic environments are known. So this caused a possibility to pick out in
boundaries of structure-formation spots perspective on ore and non ore deposits. Besides a fluid specialization jf
collision patterns is important criteria of magmatic specialization and potential ore-bearing. It pre-determine by: spot of
melt’s generation (mantle, crust), nature of substrate and geodynamic regime. A fluid specialization (F, Cl an example)
is characteristic for all parts of ore-magmatic system – magmatites, ore bodies and associate metasomatites. Thas fluid
specialization is a base for formation analyses of magmatites, associated metasomatites and metallogeny.
The spots of localization granitoids’ both groups are: a) suture zones, b) zones crossing and conjugated of suture
zones with the faults of NW (diagonal) orientation, c) the Main granite axis of the Urals (there are some massifs located
in the W from the Main suture zones). In the Urals granitoid batholites are located in such domains where a deep to the
basalt strata consist of 21,5 km and thickness of the last is 30,6 km.
There are mach dykes (from acidic to basic composition) in the Uralian granitoid batholits. Dykes’ composition
pre-determined by poly step anatexis on the basite (gabbro) base and crystallization differentiation (Gold…, 2001;
Fershtater et al., 2007; Kholodnov, 2007). More late granitoids accompanied more acidic dyke complexes. This was a
reason for the next relations which everyone can see in the Shartash granite batholite (Central Urals): pegmatites cross
lamprophyres, from the one hand and lamprophires cross pegmatiotes from the other hand. Polystages granite massifs
and associated mineralization was forming in time from 60 to 100 Ma (Gold…, 2001; Fershtater et al., 2007).
Early granitoides are specialized on Au and W (see Korobeynikov, Mironov, 1992; Gold…, 2001; Fershtater et
al., 2007). As a rule, there is more gold in more basic granitoides. The dykes complexes more auric then hosted
granitoides. Dykes complexes are considerate as a fluid leader (Korobeynikov, Mironov, 1992; Gold…, 2001). In
apogranitoid fluid relatives F: Cl: S (perhaps and CO2) is such which quite enough for extraction of Au, but of
extraction chalkhophile elements and Fe in these conditions is not going on (Kholodnov, 2007). Late collision granites
specialized on F (instead of Cl) and rare metals, they are nonauriferous.
Most gold deposits of quartz-veined type conjugated with a bererzite-listvenite formation. Its metasomatites are
forming at high active of CO2, low concentration Cl and relatively nigh F in the fluid. During process of berezitization-
listvenitization F concentrated in muscovite, so content of F in the fluid increase. Cl take part in a transport Au,
evidence – appear of this element and its in the nuggets of gold.
Hydroxide minerals of late collision granites poor of Cl (0,0-0,05 Wt.%). But they rich of F: in apatites 4,0, in
biotites 1,5 Wt.% and more (Koroteev, Sazonov, 2005). Contents of F and K, Be, Ta, Nb, Li, Rb, Cs in late collision
granites are correlated. Active of F in an apogranite fluid essential pre-determine of composition of rare metal (Be, Ta,
Nb, Li, Rb, Cs) and W and W-Mo mineralization.
The collision process played a dual role in the Urals. On the one hand, it caused transformation in the previous
ore associations (chromites, Fe-quartzites, sulfide ores of massive sulfide deposits and other), on the other hand, in was
the reason of formation of different types of mineralizations in suture zones (antigorite serpentnites, talc and talc-
carbonate metasovatites, berezites, listvenites with quartz veins with native gold, and goldbearing sulfides).
Thus fluid specialization of collision granitoides is important criteria of magmatic specialization and potential
ore-bearing. It pre-determine by: spot of melt’s generation (mantle, crust), nature of substrate and geodynamic regime.
A fluid specialization (F and Cl an example) is characteristic for all parts of ore-magmatic system - magmatites, ore
bodies and associate metasomatites. Thus, fluid specialization is a base for formation analyses of magmatites,
associated metasomatites and metallogeny (Korobeynikov, Mironov 1992; Koroteev, Sazonov, 2005; Gold…, 2001;
Kholodnov, 2007).

References:
Gold deposits of the Urals / Sazonov V.N., Ogorodnikov V.N., Koroteev V.A., Polenov Ju.A. Ekaterinburg,
2001. 622 p (in Russian).
Fershtater G.B. Petrology of the main intrusive associations. Moscow: Nauka, 1987. 276 p (in Russian).
Fershtater G.B., Krasnobaev A.A., Bea F. et al. Stages of Paleozoic intrusive magmatism of the Urals orogen and
their geodynamic interpretation // Geodynamics, magmatism, metamorphism and ore-forming. Ekaterinburg, 2007. P.
89-120 (in Russian).
Kholodnov V.V. Halogens (F, Cl) – indicators of specialization of granitoids tonalite-granodiorite formation on
the gold-sulfide-quartz mineralization // The same. P. 857-884 (in Russian).
 134

Korobeinikov A.F., Mironov A.G. Gold’s geochemistry in endogenic process and gold deposits’ conditions of
formation. Novosibirsk: Nauka, 1992. 217 p.
Koroteev V.A., Sazonov V.N. Geodinamics, ore-formation, prognosis. Ekterinburg, 2005. 258 p (in Russian).
Sazonov V.N., Nedosekova I.L., Ogorodnikov V.N., Polenov Ju.A. Sienite and sienite-miaskite complexes of the
Urals // Geodynamics, magmatism, metamorphism and ore-forming. Ekaterinburg, 20071. P. 216-243 (in Rassian).
Sazonov V.N., Ogorodnikov V.N., Velikanov A.Ya. Formation and industrial-genetic types of gold deposits of
the Urals // The same, 20072. P. 715-728 (in Russian).

Ba-Ti-rich oxymicas from olivine melanephelinites of the Udokan lava field, Siberia, Russia: chemistry
and substitutions
Sharygin V.V.
V.S.Sobolev Institute of Geology and Mineralogy SB RAS, Novosibirsk, Russia

The first data about the presence and chemistry of Ba-Ti mica in olivine melanephelinites from oldest (14 Ma)
volcanoes of the Udokan lava field (Ingamakit, Munduzhyak, Peremychka, Lurbun) were documented by Stupak (1987)
and Litasov (1992). These rocks contain phenocrysts of olivine (Fo75-85), augite (Mg# - 0.95-0.85) and groundmass
consisting of olivine (Fo70-75), Ti-rich augite (Mg# - 0.85-0.80), Ti-magnetite (TiO2 - 12-24 wt.%), oxyfluorapatite (F -
2-3.5 wt.%), Ba-Ti-phlogopite, nepheline, leucite, ilmenite and rare K-feldspar, glass and post/late magmatic calcite. It
should be noted that Ba-Ti-rich micas were previously described in olivine nephelinites and related rocks around the
world (Mansker et al., 1979; Edgar, 1992; Zhang et al., 1993; Seifert, Kampf, 1994; Henderson, Foland, 1996; Shaw,
Penczak, 1996; Greenwood, 1998; Kogarko et al., 2005; Krivdik, Mikhailov, 2007). Here we present new data on
chemistry and substitutions of Ba-Ti-micas from the Udokan olivine melanephelinites.
Ba-Ti-phlogopite forms xenomorphic grains in the groundmass and rarely occurs as daughter phase of olivine-
hosted melt inclusions. According to EMPA and SIMS data micas studied contain low H2O (0.1-0.3 wt.%), Li (30-50
ppm) and high BaO (6.7-11.5 wt.%), TiO2 (10-13.3 wt.%), F (to 3 wt.%), Nb (460-920 ppm), Cr (180-420 ppm), Sr
(940-1970 ppm), Zr (60-150 ppm) and REE (100-120 ppm) (Table 1). In general, most mica grains do not show
essential zonation in chemical composition. The core-to-rim variations in rare grains indicate the enrichment in K2O and
depletion in BaO.

Table 1. Chemical composition (EMPA+SIMS, wt.%) of Ba-Ti-phlogopites from the Udokan olivine
melanephelinites.

Sample Lv-18 Le23/1 Le23/2 Le24/1 Le24/2 Le26

core rim core rim core rim core rim core rim core rim
SiO2 30.95 31.19 31.03 32.82 31.49 32.82 31.20 31.81 31.26 31.92 31.93 33.46
TiO2 13.25 12.96 11.52 11.27 11.96 11.66 12.26 12.37 12.89 12.77 12.75 12.46
ZrO2 0.01 0.01 0.02 0.02 0.02 0.01
Nb2O5 0.17 0.21 0.26 0.16 0.13 0.15
Cr2O3 0.11 0.05 0.06 0.08 0.12 0.05
Al2O3 14.55 14.57 13.99 13.65 13.86 13.74 13.70 13.27 13.63 13.45 13.51 13.46
Nd2O3 0.01 0.01 0.01 0.01 0.02 0.01
Fe2O3 2.11 2.88 0.57 2.09 1.82 4.14 0.15 1.84 0.58 0.55 0.48 3.19
FeO 11.18 10.20 11.15 9.84 10.51 8.90 12.23 11.13 12.74 12.45 11.68 9.67
MnO 0.09 0.08 0.08 0.06 0.07 0.08 0.07 0.10 0.09 0.08 0.07 0.06
MgO 10.67 10.90 12.51 12.42 12.43 12.51 11.65 11.31 11.26 10.88 12.10 12.42
CaO 0.02 0.13 0.01 0.10 0.01 0.04 0.02 0.04 0.00 0.04 0.09 0.11
BaO 9.37 9.14 11.20 8.98 10.58 8.60 11.46 9.21 10.08 9.77 9.83 6.68
SrO 0.23 0.11 0.11 0.15 0.15 0.12
Na2O 0.77 0.73 0.57 0.57 0.53 0.40 0.63 0.62 0.57 0.55 0.64 0.53
K2O 5.33 5.34 5.10 5.63 5.40 6.31 4.87 5.72 5.40 5.48 5.43 6.71
Li2O 0.01 0.02 0.02 0.02 0.02 0.02
F 1.28 1.29 1.91 1.80 1.73 1.78 1.75 1.83 1.63 1.63 1.70 1.80
H2O 0.11 0.29 0.21 0.17 0.21 0.19
100.2 100.7 100.5
Total 99.41 100.35 99.23 101.10 100.97 100.59 99.25 100.80 99.56
4 6 5
O=F2 0.54 0.54 0.80 0.76 0.73 0.75 0.74 0.77 0.69 0.69 0.72 0.76
100.0
Total 99.70 98.87 99.54 98.47 100.37 100.22 99.86 98.48 100.11 98.88 99.79
4
Note: Lv - Munduzhyak volcano; Le - Ingamakit volcano. ZrO2, Nb2O5, Cr2O3, Nd2O3, SrO, Li2O and H2O were analyzed by
SIMS, others - by EMPA. FeO and Fe2O3 are calculated by stoichiometry for formula on the basis of 16 cations and 24 anions.
 135

The complete chemical compositions (with H2O and F) show the following formulas: K1.5Ba0.5(Mg,Fe)4.5Ti1.5
[Al2.5Si5.5O20]O3F - K1.25Ba0.75(Mg,Fe)4.5Ti1.5[Al3Si5O20]O3.25F0.75 - K1.5Ba0.5(Mg,Fe)4Fe3+0.5Ti1.5[Al2.75Si5.25O20]O3.25F0.75
and indicate that studied micas are related to intermediate members of the theoretical solid solution
K(Mg,Fe)6[Al2Si6O20]F4 - KBa(Mg,Fe)4Ti2[Al3Si5O20]O4 via complex isomorphic substitution K+2(Mg,Fe2+)+2Si+4F
→ Ba+2Ti+Al+4O. In general, composition of the Udokan mica approaches oxykinoshitalite KBa(Mg,Fe) 3.5Fe3+Ti1.5
[Al3Si5O20]O3F0.5(OH)0.5 (Kogarko et al., 2005) differing in lower Ba, Fe 3+, H2O and higher K and F. In addition to the
main substitution, K+2Si+(Mg,Fe2+)+F  Ba+2Al+Ti+O and K+2Fe3++O  Ba+2(Mg,Fe2+)+F are not excluded in the
Udokan micas. The latter scheme explains the positive correlation of Ba with F, Fet and antipathetic relations of Ba with
Mg, K (Fig. 1), showing the incorporation of octahedral Fe 3+ in the mica structure. The above substitutions strongly
suggest that specific change in chemical composition does not lead to the appearance of vacancy sites in the structure of
the Udokan micas.

Figure 1. Compositional variations (in apfu) for Ba-Ti-micas from the Udokan olivine melanephelinites.
Note: 1 - Ingamakit volcano; 2 - Munduzhyak volcano; 3 - Peremychka volcano. Formula is calculated on the basis of 16
cations.

Like apatite, the Udokan Ba-Ti-phlogopite contains very low H2O what strongly illustrates that melanephelinite
magma and its derivates were virtually dry. The presence of Fe 3+ in mica possibly indicates the gradual increasing in
fO2 during evolution of melanephelinite melt.
This study was financially supported by RFBR (grant 08-05-00134).

References:
Edgar A.D. Barium-rich phlogopite and biotite from some Quaternary alkali mafic lavas, West Eifel, Germany //
European Journal of Mineralogy. 1992. Vol. 4. P. 321-330.
Greenwood J.C. Barian-titanian micas from Ilha da Trindade, South Atlantic // Mineralogical Magazine. 1998.
Vol. 62. P. 687-695.
Henderson C.M.B., Foland K.A. Ba- and Ti-rich biotite from the Brome alkaline igneous complex, Monteregian
Hills, Quebec: mechanism of substitution // Canadian Mineralogist. 1996. Vol. 34. P. 1241-1252.
Kogarko L.I., Uvarova Yu.A., Sokolova E., Hawthorne F.C., Ottolini L., Grice J.D. Oxykinoshitalite, a new
species of mica from Fernando de Noronha Island, Pernambuco, Brazil: occurrence and crystal structure // Canadian
Mineralogist. 2005. Vol. 43. P. 1501-1510.
 136

Krivdik S.G., Mikhailov V.A. Geochemical and mineralogical features of potassic rocks of the Urmia Lake, Iran
// In: Shcherbak N.P. (Ed.), Alkaline magmatism of the Earth and its ore potential. Kiev, Logos. 2007. P. 133-134 (in
Russian).
Litasov Yu.D. Alkali basaltic volcanoes Ingamakit and Munduzhyak (Udokan plateau, North Transbaikal):
peculiarities of evolution // In: Simonov V.A., Kolobov V.Yu. (eds.): Thermobarogeochemistry of mineral formation
processes. Issue 2. Problems of magmatism and metamorphism. UIGGM, Novosibirsk. 1992. P. 16-29 (in Russian).
Mansker W.L., Ewing R.C., Keil K. Barian-titanian biotites in nephelinites from Oahu, Hawaii // American
Mineralogist. 1979. Vol. 64. P. 156-159.
Seifert W., Kampf H. Ba-enrichment in phlogopite of a nephelinite from Bohemia // European Journal of
Mineralogy. 1994. Vol. 6. P. 497-502.
Shaw C.S.J., Penczak R.S. Barium- and titanium-rich biotite and phlogopite from the Western and Eastern
Gabbro, Coldwell alkaline complex, northwestern Ontario // Canadian Mineralogist. 1996. Vol. 34. P. 967-975.
Stupak F.M. Cenozoic volcanism of the Udokan ridge // Novosibirsk, Nauka. 1987. 168 p. (in Russian).
Zhang M., Suddaby P., Thompson R.N., Dungan M. Barian titanian phlogopite from potassic lavas in northeast
China: Chemistry, substitutions, and paragenesis // American Mineralogist. 1993. Vol. 78. P. 1056-1065.

Fe-rich delhayelite from nephelinite lavas, Oldoinyo Lengai, Tanzania

Sharygin V.V.
* V.S.Sobolev Institute of Geology and Mineralogy SB RAS, Novosibirsk, Russia

“Delhayelite” from the Oldoinyo Lengai volcano were firstly described by Dawson (1998) and Dawson and Hill
(1998) in combeite and wollastonite-combeite nephelinites. During study of the the Oldoinyo rocks we also observed
the delhayelite-group mineral in nepheline-hosted melt inclusions and in the groundmass of wollastonite-combeite
nephelinite. The rock studied (sample Ol7-2000, 1917 eruption) are porphyritic and contain abundant euhedral
phenocrysts (>1-5 mm) of nepheline and clinopyroxene, and rarer euhedral combeite, titanite, Ti-andradite and apatite.
The groundmass consists of microphenocrysts (<1 mm) of the above mentioned minerals and green to brown glass.
Delhayelite, perovskite, magnetite, wollastonite with combeite corona, pyrrhotite, K-feldspar, Sr-bearing barite and
calcite are minor or accessory in the groundmass.
Delhayelite occasionally occurs in large silicate melt inclusions (>40 µm) in the core of nepheline phenocrysts.
They are partly crystallized and also contain green glass, gas-carbonate globule, unidentified K-rich (20.3 wt.% K2O)
alumosilicate and fluorite (Fig. 1). Delhayelite within inclusions forms colorless radial aggregates or individual acicular
crystals (up to 10-20 µm). In groundmass association this mineral forms acicular crystals (up to 50 µm) in green or
brown glass (Fig. 1). Some groundmass crystals indicate the presence of alteration rim. It is most common of
delhayelite occurring in brown glass, up to complete replacement by water-bearing mineral of the delhayelite group.
The same alteration processes were observed for delhayelite from Shahery, DR Congo (Sahama, Hytonen, 1959) and
Khibini (Dorfman, Chiragov, 1979) and delhayelite-like mineral from Pian di Celle, Italy (Stoppa et al., 1997).

Fig. 1. Delhayelite in nepheline-hosted inclusions and groundmass of wollastonite-combeite nephelinite,

Oldoinyo Lengai, sample Ol7-2000, 1917 eruption (ordinary light and scanning microscopy, SEM).
Note: Gl - silicate glass; Dlh - delhayelite; g - gas bubble; Fl - fluorite; Kp - unidentified K-alumosilicate; Cmb - combeite;
Ne - nepheline, Alt - altered delhayelite (hydrodelhayelite ?); Cal - calcite; Po - pyrrhotite; SiC - abrasive. Scale bar - 10 µm.

New EMPA data confirmed very specific composition of the Oldoinyo delhayelite obtained previously by
Dawson (1998) and Dawson and Hill (1998). This mineral contains high concentrations of Fe2O3, TiO2, MgO and S and
low amounts of Al2O3 (Table 1). These compositional features are remarkable in comparison with the Khibini
 137

delhayelite (Dorfman et al., 1961; Stoppa et al., 1997; Ageeva, 2002; Sharygin, 2002; Sokolova et al., 2005). It should
be noted that delhayelite from nepheline-hosted inclusions are richer in F, S and poorer in Cl than groundmass mineral
(Table 1). Altered rims on the groundmass crystals differ from fresh samples in lower alkalis, F, Cl and higher SiO 2 and
seem to be hydrodelhayelite or other water-bearing mineral of the delhayelite group (rhodesite, macdonaldite, Chiragov,
Dorfman, 1981). The high Fe2O3 and low Al2O3 strongly suggest that iron is incorporated into tetrahedral site. The
calculations on the basis of (Si+Al+Fe3+)=8 indicate formula for the Oldoinyo fresh delhayelite close to
K4Na2Ca2[(Al,Fe3+)Al7O19]F2Cl, where Fe3+ is up to 0.6 apfu, K is 3.3-3.7 apfu, Ca is 2.1-2.4 apfu and Na is near 2.0
apfu. In general, this approaches formula, proposed for the Khibini delhayelite: HxK8-xNa4Ca4[AlSi7O19]2F4Cl2, where
x=0.5-1.5 (Sharygin, 2002). The possible incorporation of iron as Fe 3+ in delhayelite is consistent with mineralogy of
the Oldoinyo nephelinites, where the groundmass minerals contain high abundance of Fe2O3 and some of them
(sodalite, nepheline) may bear Fe3+ in tetrahedral site (Dawson, 1998; Dawson, Hill, 1998).
At present day, the studies for the crystal structure of delhayelite were provided for the Shahery holotype,
K7(Na3Ca)Ca4[AlSi7O19]2F4Cl2 (Cannillo et al., 1970), and the Khibini holotype, K 3Na2Ca2[AlSi7O19](F,Cl)2 (Chiragov,
Mamedov, 1974). However, both structural formulae are so far from real compositions of fresh delhayelite, especially
in lower contents of K2O (Stoppa et al., 1997; Ageeva, 2002; Sharygin, 2002; Sokolova et al., 2005). The composition
of the Khibini delhayelite with highest content of K 2O (20.75 wt.%, Sokolova et al., 2005) shows K up to 3.94 apfu. In
addition, structural study of the Khibini delhayelite indicated the presence of domains with composition
K4Na2Ca2[Al2Si6O19](Cl,F)2·H2O (Chiragov, Mamedov, 1983), which is very close to delhayelite-like mineral from
Pian di Celle (Stoppa et al., 1997; Sharygin, 2002). Apparently, the crystal structure of delhayelite requires refinement,
especially in respect to positions of K, F, Cl, S, H 2O and possible incorporation of Fe3+. Recent chemical data for the
Khibini delhayelite show variable contents of K2O, F and Fe2O3 (Stoppa et al., 1997; Ageeva, 2002; Sharygin, 2002;
Sokolova et al., 2005). The concentrations of SO3 in different samples of the Khibini fresh delhayelite varies from 0.0 to
1.05 wt. % (author’s data), whereas the Oldoinyo samples contain up to 2.3 wt.% SO 3 (Table 1). However, the
specification of sulfur in the delhayelite structure is not clear. Based on IR spectra of delhayelite from Khibini,
Sokolova et al. (2005) suggest the possible incorporation of sulfur as (SO 4)-group. Nevertheless, the existence of S2-
should not be excluded like in minerals of the hauyne-sodalite group.

Table 1. Representative analyses (wt.%) of delhayelite from the Oldoinyo Lengai wollastonite-combeite
nephelinite in comparison with fresh minerals from other nephelinites of Oldoinyo Lengai and rocks of Khibini and Pian
di Celle.

n SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO BaO SrO Na2O K2O F Cl S H2O O=F,Cl,S Total
1 2 44.87 0.56 3.69 4.82 0.05 0.41 14.58 0.00 6.79 18.38 5.33 2.64 0.36 3.02 99.45
2 1 45.00 0.35 2.99 4.59 0.05 0.34 14.64 0.23 7.02 16.92 5.15 1.30 0.93 2.92 96.57
3 1 43.21 0.58 4.64 5.51 0.15 0.57 12.75 0.00 6.42 18.99 4.45 4.75 0.25 3.07 99.20
4 1 43.87 0.18 5.35 3.50 0.08 0.46 13.86 0.00 6.76 18.80 4.55 4.46 0.06 2.96 98.97
5 1 43.98 0.43 5.11 4.45 0.09 0.58 14.30 0.08 6.77 18.59 4.16 4.35 0.10 2.78 100.19
6 1 54.08 0.30 4.93 5.28 0.19 0.55 11.06 0.05 0.24 4.88 3.05 0.32 0.04 1.38 83.59
7 1 51.61 0.30 4.10 5.49 0.16 0.55 15.87 0.22 1.63 6.75 3.38 2.25 0.12 1.99 90.44
8 1 54.07 0.30 5.93 3.33 0.18 0.68 15.88 0.05 0.27 2.80 3.97 0.99 0.02 1.90 86.58
9 9 44.60 0.11 6.18 1.83 0.09 0.09 14.70 6.94 18.00 4.09 3.87 0.05 2.62 97.93
10 1 45.60 0.19 4.71 3.17 0.09 0.48 14.90 7.13 17.80 4.76 3.86 0.04 2.89 99.83
11 4 47.31 0.00 5.88 0.59 0.12 0.03 12.78 0.30 7.25 20.25 2.45 3.85 1.90 98.89
12 31 47.58 0.01 6.11 0.14 0.11 0.04 13.40 0.02 0.27 6.77 19.95 4.58 3.74 0.13 0.75 2.84 100.76
13 16 42.74 0.05 11.94 1.36 0.05 0.40 10.99 0.03 0.15 3.57 22.59 3.63 4.98 0.01 1.18 2.65 101.01
Note. 1-10 - Oldoinyo Lengai: 1-8: wollastonite-combeite nephelinite, sample Ol7-2000, 1917 eruption (this work): 1-2 -
from nepheline-hosted inclusions; 3-8 - from groundmass: 3-5 - fresh mineral; 6-8 - altered mineral; 9-10 - from groundmass of
combeite and wollastonite-combeite nephelinites, respectively (Dawson, Hill, 1998; Dawson, 1998); 11-12 - Khibini massif: 11 -
veinlets in ristschorrite, Rasvumchorr (Sokolova et al., 2005); 12 - pegmatite, Yukspor (this work); 13 - delhayelite-like mineral, Pian
di Celle volcano, Italy (this work). H2O is determined by SIMS, n means number of analyses.

References:
Ageeva O.A. Typomorphism of accessory minerals and evolution of mineral formation in rocks of ristschorrite
complex (Khibini massif) // PhD Thesis. Moscow 2002. 187 p. (in Russian).
Canillo E., Rossi G., Ungaretti L. The crystal structure of delhayelite // Rendiconti Societa Italiana di
Mineralogia e Petrologia. 1970. Vol. 26. P. 63-75.
Chiragov M.I., Dorfman M.D. Crystal chemistry of minerals of the delhayelite group // Doklady Akademii Nauk
SSSR. 1981. Vol. 260. P. 458-461 (in Russian).
Chiragov M.I., Mamedov Kh.S. Crystal structure of delhayelite, Ca2Na2K3[(Si,Al)8O19](F,Cl)2 //
Mineralogicheskii Sbornik L'vovskogo Gos. Universiteta. 1974. No. 28. Pt. 1. P. 3-7 (in Russian).
Chiragov M.I., Mamedov Kh.S. Crystal structure of new mineral of the delhayelite group // Abstracts of IX
Vsesouznogo soveshchaniya po rentgenografii mineral’nogo syr’ya, Kazan, 1983. P. 24-25 (in Russian).
 138

Dawson J.B. Peralkaline nephelinite-natrocarbonatite relationships at Oldoinyo Lengai, Tanzania // Journal of

Petrology. 1998. Vol. 39. P. 2077–2094
Dawson J.B., Hill P.G. Mineral chemistry of a peralkaline combeite lamprophyllite nephelinite from Oldoinyo
Lengai, Tanzania // Mineralogical Magazine. 1998. Vol. 62. P. 179–196.
Dorfman M.D., Belova Ye.N., Neronova N.N. Delhayelite from Khibini // Trudy Mineralogicheskogo Muzeya
Akademii Nauk SSSR. 1961. V. 12. P. 191-195 (in Russian).
Dorfman M.D., Chiragov M.I. Hydrodelhayelite (product of hypergene alteration of delhayelite) // Novye
Dannye o Mineralakh SSSR. 1979. Vol. 28. P. 172-175 (in Russian).
Sahama Th.G., Hytonen K. Delhayelite, a new silicate from Belgian Congo // Mineralogical Magazine. 1959.
Vol. 32. P. 6-9.
Sharygin V.V. Delhayelite from pegmatites of the Khibiny massif and delhayelite-like mineral from melilitolites
of the Pian di Celle volcano (San Venanzo, Italy) // In: Geokhimiya magmaticheskikh porod. Vserossiiskii seminar s
uchastiem stran SNG, Moscow. 2002. P. 105 (in Russian).
Sokolova M.N., Smol’yaninova N.N., Golovanova T.I., Chukanov N.V., Dmitrieva M.T. Delhayelite crystals
from ristchorrites of the Rasvumchorr plateau (Khibiny massif) // New Data on Minerals. 2005. Vol. 40. P. 115-118.
Stoppa F., Sharygin V.V., Cundari A. New mineral data from the kamafugite-carbonatite association: the
melilitolite of Pian di Celle, Italy // Mineralogy and Petrology. 1997. Vol. 61. P. 27-45.

Immiscible melt inclusions in nepheline phenocrysts from nephelinite lavas, Oldoinyo Lengai: heating
experiments and compositional constraints
Sharygin V.V.*, Kamenetsky V.S.**, Zaitsev A.N.***, Kamenetsky M.B.**
* V.S.Sobolev Institute of Geology and Mineralogy SB RAS, Novosibirsk, Russia;** School of Earth
Sciences, University of Tasmania, Hobart, Australia; *** Saint Petersburg State University, Saint
Petersburg, Russia

Silicate melt inclusions with immiscibility have been found in nepheline phenocrysts of peralkaline nephelinite
lavas at the Oldoinyo Lengai volcano, Tanzania. The host rocks are porphyritic and contain abundant euhedral
phenocrysts (>1-5 mm) of nepheline and clinopyroxene, and rarer euhedral combeite, titanite, Ti-andradite and apatite.
The groundmass consists of microphenocrysts (<1 mm) of the above mentioned minerals and green to brown glass.
Delhayelite, perovskite, magnetite, wollastonite with combeite corona, pyrrhotite, K-feldspar, Sr-bearing barite,
lamprophyllite, sodalite and calcite are minor or accessory in the groundmass. In general, all studied nephelinite species
are similar to those described by Dawson (1998) and Dawson and Hill (1998).
Silicate melt inclusions outline the growth zones in host nepheline phenocrysts. Other inclusion types (fluid,
carbonate, sulfide and chloride) are scarce. Clinopyroxene is abundant among crystallites in nepheline, whereas other
crystallites (apatite, titanite, Ti-andradite, magnetite and perovskite) occur occasionally.
Silicate melt inclusions (10-100 µm) in nepheline are very specific in phase composition: green glass + gas-
carbonate globules + daughter crystals + trapped crystals + fluorite +/- other salts (Fig. 1).

Ol- Ol- Ol- Ol-

004/05 004/05 004/05 4421
C S
ph L L
cg G
m m
l G
L g
g l
m G
G g C
l
l C c
c C
c
Ol- Ol- Ol- Ol-
003/05 003/05 7/2000 7/2000
g C
g c C g
L gc
m C C
g G C
c g c
C l Gc
c G G
l
l l

Fig. 1. Immiscible melt inclusions in nepheline phenocrysts from different samples of nephelinites, Oldoinyo
Lengai. Notes: Gl - silicate glass; Cc - natrocarbonatite globule; g - gas bubble; Lm - leucocratic mineral; Sph - titanite. Scale bar -
10 µm.
 139

The most typical inclusions contain glass and one gas-carbonate globule. In some inclusions gas and carbonate
components are separated into individual phases, and gas bubble always contains some amounts of salt crystals on the
walls. According to optical observations, SEM and EMPA, trapped crystals are clinopyroxene, apatite, Ti-andradite and
titanite, whereas daughter phases are Na-Fe-rich clinopyroxene, fluorite, delhayelite, K-feldspar and unidentified K-rich
(20.3 wt.% K2O) alumosilicate. Fluorite occurs both in carbonate globule and in silicate glass. Carbonate globule is
commonly fine-devitrified and some individual phases (calcite, nyerereite, Na-carbonate, fluorite) are sometimes fixed
in it, like in gregoreyite-hosted inclusions from the Oldoinyo natrocarbonatite (Mitchell, Belton, 2004; Mitchell, 2006).
Same immiscible nepheline-hosted inclusions were previously described in nephelinites of the Mosonik carbonatite-
related volcano, which is neighboring with the Oldoinyo Lengai volcano (Bazarova et al., 1975).
Preliminary heating experiments with the Oldoinyo nepheline-hosted inclusions (silicate glass + gas-carbonate
globule) were provided for the 20-900oC range. First changes within inclusions are observed in a gas-carbonate globule
at 470-510оС and assigned to recrystallization of phases. The carbonate component of gas-carbonate globules melts
instantaneously at 550-570оС. Silicate glass melts at 600-670oC. Further increasing of temperature (670-810оС) led to
the appearance and then disappearance of blebs of salt liquid (fluoride, chloride or sulfate composition ?) both in silicate
and in carbonate melts. Salt liquid blebs occurring in the silicate melt disappear by coalescence with the carbonate melt.
In the same temperature range individual carbonate melt globules amalgamate into one large globule, which then
gradually decreases in size and gas bubble in it also decreased in size at 800-900oC. The gas-carbonate melt globule
homogenizes at 900oC. At this temperature phase composition of the melt inclusions is silicate melt + carbonate melt.
Quenching of inclusions showed silicate melt-glass transition at 600oC, appearance of gas bubble in a carbonate globule
at 530-540oC and crystallization of phases within carbonate globule at T<500 oC (Fig. 2).

4 5 5 7 8
40oC T 10oC T 70oC T 25oC T 00oC T
↑ ↑ ↑ ↑ ↑
C C C C C
c c c melt c melt c melt
g
g g
g g

S S S S S
i glass i glass i glass i melt i melt
8 9 6 5 4
95oC T 00oC T 00oC T 37oC T 00oC T
↑ hom ↓ ↓ g C↓
C C
c melt C C c melt c
g c melt c melt g
g

S S S S S
i melt i melt i glass i glass i glass

Fig. 2. Heating experiment with a nepheline-hosted inclusion from nephelinite, sample Ol7-2000, 1917 eruption,
Oldoinyo Lengai. Note. Si glass - silicate glass; Si melt - silicate melt; Cc - natrocarbonatite solid; Cc melt - natrocarbonatite melt;
g - gas bubble. Size of inclusion is 40 µm. Initial phase composition is similar to that on photo at 440 oC.

Silicate peralkaline glass of nepheline-hosted inclusions strongly vary (in wt.%): SiO2 - 43.6-53.0; TiO2 - 1.0-
2.0; Al2O3 - 2.7-7.1; FeOt - 7.5-18.6; MnO - 0.5-1.2; MgO - 0.2-1.8; CaO - 1.0-7.2; BaO - 0.1-1.1; Na2O - 4.4-10.6;
K2O - 9.0-19.3; P2O5 - 0.1-0.3; SO3 - 0.6-1.8; F - 0.4-2.0; Cl - 0.0-0.5. The most Si-undersaturated compositions in
partly crystallized inclusions approach the groundmass glasses (author’s data; Peterson, 1989; Dawson, 1998; Dawson,
Hill, 1998). Unfortunately, we were unable to fully quantify composition of carbonate globules due to their rapid
decomposition after exposing at the surface. After opening they gradually reacted with air to form Na-water-bearing
carbonate (trona ?), aphthitalite and Na-K-chlorides. The qualitative analyses by EDS and EMPA show that the
carbonate globules are natrocarbonatite in composition and Na, Ca, K, C, Cl, F, S and P are prevailed components,
which are common for natrocarbonatite lavas of Oldoinyo Lengai.
Thus, study of nepheline-hosted inclusions in nephelinite lavas advocates very complicated history during
cooling of initial silicate melt as suggested by Dawson (1998). The silicate-natrocarbonatite immiscibility took place at
temperature above 900oC. In the 900-600oC range the gas phase and salt liquids of different compositions may be
separated from natrocarbonatite melt. The carbonate-carbonate immiscibility cannot be excluded (Mitchell, 1997). The
enrichment of peralkaline silicate melt in Fe and alkalis was favorable to crystallization of minerals rich in these
components and poor in Al. Unlike inclusions (closed system), during crystallization of nephelinite lavas (open system)
the silicate-natrocarbonatite immiscibility phenomenon is commonly hidden, owing to degassing of silicate melt,
separation of carbonate melt from silicate melt and/or reaction of carbonate melt with primary silicate minerals
(combeite coronas around wollastonite, etc.). Evidences of immiscibility were observed only in the Oldoinyo hybrid
rocks intermediate between silicate rocks and natrocarbonatites (Church, Jones, 1995; Dawson et al., 1996).

References:
 140

Bazarova T.Yu., Bakumenko I.T., Kostyuk V.P., Panina L.I., Sobolev V.S., Chepurov A.I. Magmatic
crystallization based on the study of melt inclusions // Transactions of the Institute of Geology and Geophysics, SB
USSR Academy of Sciences. Nauka. Novosibirsk. 1975. Iss. 264. 258 p. (in Russian).
Church A.A., Jones A.P. Silicate-carbonate immiscibility at Oldoinyo Lengai // Journal of Petrology. 1995. Vol.
36. P. 869-889.
Dawson J.B. Peralkaline nephelinite-natrocarbonatite relationships at Oldoinyo Lengai, Tanzania // Journal of
Petrology. 1998. Vol. 39. P. 2077–2094
Dawson J.B., Hill P.G. Mineral chemistry of a peralkaline combeite lamprophyllite nephelinite from Oldoinyo
Lengai, Tanzania // Mineralogical Magazine. 1998. Vol. 62. P. 179–196.
Dawson J.B., Pyle D.M., Pinkerton H. Evolution of natrocarbonatite from a wollastonite nephelinite parent:
evidence from the June, 1993 eruption of Oldoinyo Lengai, Tanzania // Journal of Geology. 1996. Vol. 104. P. 41-54.
Mitchell R.H. Carbonate-carbonate immiscibility, neighborite and potassium iron sulphide in Oldoinyo Lengai
natrocarbonatite // Mineralogical Magazine. 1997. Vol. 61. P. 779-789.
Mitchell R.H. Sylvite and fluorite microcrysts, and fluorite-nyerereite intergrowths from natrocarbonatite, Oldoinyo
Lengai, Tanzania // Mineralogical Magazine. 2006. Vol. 70. P. 103-114.
Mitchell R.H., Belton F. Niocalite-cuspidine solid solution and manganoan monticellite from natrocarbonatite, Oldoinyo
Lengai, Tanzania // Mineralogical Magazine. 2004. Vol. 68. P. 787-799.
Peterson T.D. Peralkaline nephelinites. I. Comparative petrology of Shombole and Oldoinyo L'engai, East Africa
// Contributions to Mineralogy and Petrology. 1989. Vol. 101. P. 458-478.

Features of Proterozoic alkaline and subalkaline magmatism in Ukrainian shield: dependence on

geodynamic position
Sheremet E.M.
Ukrainian State Research and Design Institute of Mining Geology, Rock Mechanics and Mine Surveying
National Academy of Science of Ukraine, Donetsk, Ukraine

The Late Proterozoic subalkaline and alkaline magmatism of Ukrainian shield has manifested itself
approximately at the same time (1.9 – 1.7 milliard years ago) in different megablocks united with each other by suture
zones. The latter are considered from the position of plate tectonics as sutures of closed in the past intermicrocontinental
basins. Fragments of the Early Pre-Cambrian microcontinents among which those basins were located are the present
megablocks of Ukrainian shield. From east to west one can distinguish: the Orekhovo-Pavlograd suture zone located
between the megablocks of the Azov Sea Region and the Middle-Dnieper Region; the West Ingulets-Krivoi Rog suture
zone located between the megablocks of the Middle-Dnieper Region and the Ingul Region; the Golovanevsko-Yadlovo-
Traktemirov suture zone located between the megablocks of the Ingul Region and the Belotserkovian-Bug Region; the
Nemirov-Kocherovsk suture zone located between the megablocks of the Belotserkovian-Bug Region and the
Volhynia-Podolsk Region.
Subalkaline and alkaline magmatism of the megablock of the Azov Sea Region (the Khlebodar granite–
granosyenite complex, the South Kalchik gabbro-syenite complex, the Oktyabr nepheline-granosyenite complex, the
Kamennye Mogily complex of subalkaline less-common metal granites) was formed at the final stage of sinking of the
paleosubduction zone (the Orekhovo-Pavlograd suture zone). The absorption of the oceanic lithosphere under the
megablock of the Azov Sea Region was accompanied by transformation of its epi-Archean continental crust as it
penetrated deep into the mantle. Heat and fluids that generated melts escaped from the excited mantle. This is
confirmed by lateral magmatic zoning of the Proterozoic magmatism from calcareous-alkaline magmatites to
subalkaline-alkaline ones, their ages being rejuvenated from front to rear parts of the zoning.
Subalkaline Upper Proterozoic (1.75 milliard years) granitoids in the megablock of the Ingul Region are
represented by rapakivi-granite Korsun-Novy Mirgotod pluton. We have a good reason to believe that its generation
was connected with the final stage of formation of the Proterozoic granite-gneiss megablock of the Ingul Region which
was arisen in place of the oceanic basin that separated microcontinents – megablocks of the Belotserkovian-Bug Region
the Middle-Dnieper Region. West Ingulets-Krivoi Rog and the Golovanevsko-Yadlovo-Traktemirov suture zones are
sutures of that oceanic basin. Collision histories accompanied by the junction of the above megablocks began formation
in the Proterozoic of structural-material complexes of the Ingul Region megablock directly after closure of the basin.
While oceanic sediments sunk into the mantle, more deep-laid parts of it had been generating. The deepest fluids have
led to formation of the basic-based melts (anorthosites, norites, monzonitoids) and subalkaline acid rapakivi-granites
(the Korosten pluton).
Subalkaline Upper Proterozoic (1.76 – 1.73 milliard years) magmatites in the megablock of the Volhynia-
Podolsk Region are represented by the Korosten and the Perzhanian complexes. The Korosten pluton is composed of
association consisting of rapakivi granites, rapakivi-like granites, granite-porphyrys, anorthosites, gabbronorites,
syenites, alkaline syenites and others. The Perzhanian complex is represented by subalkaline granites. The Korosten
pluton is a kind of a cap over the north part of the Nemirov-Kocherovsk suture zone which is a boundary structure
between the Volhynia-Podolsk Region megablock and the Belotserkovian-Bug Region megablock. The latter does not
manifest subalkaline magmatism as younger as milliard years. It can be expected that in place of the Nemirov-
Kocherovsk suture zone there was an oceanic basin indirect confirmation of the existence of which are carbonaceous
 141

rocks in its north part. Closure of that basin was accompanied by plunging of oceanic sediments towards the Volhynia-
Podolsk Region megablock and forming, as a consequence, of palingenic melts due to activation of the mantle. At the
final stage of closure of the oceanic basin deep parts of the activated mantle have led to generation of subalkaline melts
responsible for formation of the Korosten and the Perzhanian complexes.
Thus, manifestations of the Upper Proterozoic subalkaline magmatism in different megablocks of Ukrainian
shield depend on the same reasons, namely, on the excitation of relatively deep parts of the mantle due to sinking of
oceanic sediments deeply down as a result of collision of geotectonic histories. It appears that this is one of possible
version for explanation of identity of petrochemical, geochemical, accessory-mineralogical compositions of the Late
Proterozoic magmatites in separate megablocks of Ukrainian shield.

Modeling distribution of polymerized anions on the liquidus of the Na2O-SiO2 system

Shildt A.V.*, Ariskin A.A.**, Polyakov V.B.***
* Department of Geology, Moscow State University, Moscow, Russia;
** Vernadsky Institute of Geochemistry and Analytical Chemistry, Moscow, Russia;
*** Institute of Experimental Mineralogy, Chernogolovka, Russia
In previous studies, we have presented a STRUCTON computer program designed for statistical simulations of
molecular-size distribution of Si-anions in polymerized silicate melts (Polyakov, Ariskin, 2008). The INPUT file of this
model includes proportions of five Qn- structons– “SiO4-groups” (0 ≤ n ≤ 4, Q0 corresponds to the SiO44- ion) which are
distinguished by the number of bridging oxygen. A system of OUTPUT files includes statistical characteristics for the
modeled ensembles of the chain, branched, and ring complexes corresponding to a general formula (SiiO3i+1-j)2(i+1-j)-,
where i is the size of an anion, j is the number of the ring bonds. First calculations were conducted for the compositions
ranging from ortho- to metasilicates based on a random distribution of Qn-structons suggesting an equal reactivity of
various atoms of non-bridging oxygen. According to our calculations, the number of polymerized anion species varies
from 3 (SiO44-, Si2O76-, Si3O108-) in Na4SiO4 composition to 153 in metasilicate, whereas the average size of polymer
species varies from 1 to 7.2 (Ariskin, Polyakov, 2008). Further development of the model accounts for the non-equal
reactivity of Qn-species which are known to disproportionate in silicate melts and glasses due to three structure-based
reactions:
Qn-1 + Qn+1 = 2Qn ,
kn=[Q ] /[Q ][Q ] (1 ≤ n ≤ 3).
n 2 n-1 n+1
(1)
These reactions cause fractions of Q1, Q2 and Q3-structons to increase with respect to fractions of “end-member”
Q0- and Q4-structons, The distribution of Qn-structons observed from Raman and NMR spectroscopy is never coincides
with the random distribution for a given melt composition (Mysen, Richet, 2005) Such deviation of the real Q4-structon
distribution from the random one affects the distribution of polymer species and should be taken into account in correct
models. For this purpose, a special subroutine of the STRUCTON program was developed. It calculates the distribution
of Qn-structons for a given composition using values of constants of the disproportionation reactions (1). The
spectroscopic data on these constants were rationalized using the following Arrhenius temperature dependence:
kn  sn exp   H / RT  , (2)
where sn is the entropic factors; H is the enthalpy; n = 1,2,3; and R and T have a common meaning. s1 = s3 = 8/3 and s2 =
9/4 are the same for silicate systems in our model, whereas the enthalpy depends on a cation type. The realistic
distribution of Qn-structons calculated using the disproportination constants (2) is used as an INPUT information for the
STRUCTON model. This allows one to estimate distribution of (SiiO3i+1-j)2(i+1-j)- species more correctly than in the the
scope of the random model. Since the random distribution of Qn-structons corresponds to infinite temperature in (2),
one can conclude that accounting for the disproportionation reactions provides evaluations of the effect of temperature
on the distribution of anion polymer species in the melt.
As an example, we have carried out a set of testing calculations for the Na 2O-SiO2 system in the range of 33.3-
50.0 mol% of SiO2. Results of these calculations along the liquidus of the binary system have demonstrated a
systematic decrease in the proportion of Q0-species with respect to that following from stochastic modeling. Na 6Si2O7
(40 mol% SiO2) and Na2SiO3 (50 mol% SiO2) melts are enriched in Q1- and Q2-structons, respectively (see Shildt et al.,
2009). This results in the predominance of Si2O76- dimers in the Na6Si2O7 melt and “flat” rings SinO3n2n-(Si3O96-, Si4O128-
, Si5O1510-, etc.) in the Na2SiO3 melt. Such predominance of stoichiometric polymeric compounds in the melts follows
directly from our modeling.

References:
Ariskin A.A., Polyakov V.B. Simulation of molecular mass distributions and evaluation of O 2- concentrations in
polymerized silicate melts // Geochemistry International. 2008. Vol. 46. P. 429-447.
Mysen B., Richet P. Silicate glasses and melts: properties and structure. Amsterdam: Elsevier, 2005. 560 p.
Polyakov V.B., Ariskin A.A. Simulation of the composition and proportions of anions in polymerized silicate
melts // Glass Physics and Chemistry. 2008. Vol. 34. P. 50-62.
Shildt A.V., Polyakov V.B., Ariskin A.A. Calculation of distributions of Q-species on the liquidus of the Na2O-
SiO2 system: Updating the STRUCTON model // Abs. of Annual seminar on experimental mineralogy, petrology, and
geochemistry (Moscow, Vernadsky Institute, 2009).
 142

This study was supported by the RFBR grant 08-05-00194-a.

The peculiarities of plume-tectonic processes in the Early Proterozoic Pechenga Area from the isotope
Sm-Nd and Rb-Sr data.
Skuf’in P.K.
Geological Institute of the Kola Science Centre, RAS, Apatity, Russia
The Early Proterozoic Pechenga Area is formed by volcanic and sedimentary rocks of the Northern Pechenga and
Southern Pechenga Complexes. The first one is generated by four volcanic suites (VS), at which basis sedimentary
suites (SS) occur. Sedimentation and volcanism occurred in this region during the Sarioli (I SS and I VS), Jatuli (II SS
and II VS) and Ludikovi (III SS, III VS, IV SS and IV VS) times. Andesite-basalts and andesites of the most ancient I
VS have the characteristics of the enriched mantle (Т = 2324 Ма; εNd(Т): from –3.39 to –4.19) with varying T(DM) in
the range of 2844-2878 Ma). Subalkalic rocks of the overlying II VS have the characteristics of the partially enriched
mantle (Т = 2214 Ma, εNd(T): from –1.56 to –2.83; T(DM) = 2590-2789 Ma). Younger tholeiitic basalts of the III VS are
representatives of the depleted mantle (Т = 2114 Ma, εNd(T): from +1.99 to +2.90; T(DM) = 2161-2273 Ma). Basalts and
ferropicrites of the youngest IV VS have the characteristics of the partially enriched mantle (Т = 1980-1956 Ma;
εNd(T): from +1.43 to –0.48) with varying T(DM) in the range of 2142-2470 Ma). The young South Pechenga complex is
generated by volcanic suites (VS), tuff-volcanic suites (TVS) and tuffaceous suites (TS) (from bottom to top): Kalevian
time – Kallojarvi TS and Bragino TVS; Vepsian time – Menel VS, Kaplja VS and Kassesjoki TS. Picrites and
picrobasalts of the Menel VS have the attributes of the partially enriched mantle (Т = 1960 Ма; εNd(T): from +0.18 to
+0.62; T(DM) = 2317-2762 Ma), while andesites and dacites of the Kaplja VS are typical products of the enriched mantle
(Т = 1950 Ма; εNd(T): from –3.32 to –6.07; T(DM) = 2539-2574 Ma), as well as granites of the Shuoni-javr massif from
the southern frame of the Pechenga Area (Т = 1940 Ма; εNd(T) = –5.06; T(DM) = 2519 Ma).
Taking into account volcanic isotope data, and also modern ideas about consistency of plume-tectonic activity,
we offer the following scenario of evolution of plume-tectonic processes in this region. Sarioli is the time of display of
the shallow super-plume of the first generation (effusion of the Mg-rich “boninitic” andesites, enriched in the lithophile
elements – K, Rb, Ba, Th, Sr). Jatuli is the time of the life termination of this super-plume (effusion of the alkalic Ti-
Fe-rich trachybasalts and trachyandesites, enriched in K, Rb, Ba, Th, Sr, P, Nb, Zr). Ludikovi, Kalevi and Vepsi are the
time, accordingly, of the beginning and termination of activity of the deep super-plume of the second generation
(effusion of the Ti-Fe-rich tholeiites of III and IV VS, and later effusion of the bimodal picrite-andesite volcanites of the
Menel and Kaplja Suites).
The certain composition inheritance is typical for the Southern Pechenga magmatism, that is manifested in the
inheritance petrochemical signs in Kalevian basalts (Bragino Suite) as compared with the Northern Pechenga basalts.
The received Sm-Nd isochrone of the Southern Pechenga picrites (1894±40 Ma) dates the beginning of the Vepsian
time in the Southern Pechenga zone (Fig. 1 and Table 1).
This isochrone confirmes the earlier Rb-Sr isochrone age of Vepsian events in the Pechenga Area (Balashov,
1996). The received dates correlate with granite events in the Lapland Belt from the southern frame of the Pechenga
Area – 1884±18 Ma (Bibikova et al., 1993), and with the U-Pb age of the syenites from the Soustov and Gremjacha-
Virmes massifs (1872±8 Ma and 1884±6 Ma, respectively) (Bea et al., 2001).
The received Rb-Sr isochrone of the Southern Pechenga volcanites (1260±73 Ma) show the age of the Middle
Riphean thermal events in this area (Fig. 2 and Table 2). The received date correlates with the age of Kostomuksha
Area lamproites (1230±5 Ma) (Marchenko, 1997).

Table 1. Isotopic Sm-Nd data for the Menel Suite volcanites.

Contents, ppm Isotopic ratio

Sample Rock T, Ma εNd(T)
147
Sm Nd Sm/144Nd 143
Nd/144Nd
89-76 Picrite 3.31 10.97 0.181832 0.512473±10 1850 0.37
89-81 Picrite 22.37 126.21 0.107142 0.511545±10 1850 0.43
89-88 Picrite 2.24 7.63 0.177815 0.512430±15 1850 0.51
89-95 Picrite 3.31 12.82 0.156087 0.512157±6 1850 0.47
89-62 Mg-basalt 3.24 12.47 0.157121 0.512164±5 1850 0.35
 143

Fig. 1. Sm-Nd isochrone for Menel Suite volcanites.

Table 2. Isotopic Rb-Sr data for the Menel and Kaplja Suites volcanites.
Contents, ppm Isotopic ratio
Sample Rock Suite
87 86 87
Rb Sr Rb/86Sr 87
Sr/86Sr
89/78 Menel 0.34 37.40 0.0273 0.70441±18
Picrite
89/77 Menel 62.70 0.70 0.0322 0.70465±22
Picrite
89/88 Menel 2.70 97.00 0.0827 0.70494±20
Picrite
YP-1 Kahusite Menel 2.70 9.10 0.3726 0.71072±21
YК Kahusite Menel 0.70 4.00 0.5194 0.71274±19
88/130 Andesite Kaplja 140.00 563.00 0.7399 0.71741±15

Fig. 2. Rb-Sr isochronе for Menel and Kaplja Suites volcanites.

References:
Balashov Yu.A. Geochronology of the Early Proterozoic rocks of the Pechenga-Imandra Varzuga Area //
Petrology. 1996. Vol. 4, № 1. P. 3-25. (in Russian).
Bea F., Arzamastsev A., Montero P., Arzamastseva L. Anomalous alkaline rocks of Soustov, Kola: evidence of
mantle-derived metasomatic fluids affecting crustal materials // Contrib. Mineral. Petrol. V. 140. 2001. P. 554-566.
Bibikova Ye.V., Melnikov V.F., Avakjan K.H. Lapland granulites: petrology, geochemistry and isotopic age //
Petrology. 1993. Vol. 1, № 2. P. 215-234. (in Russian).
Marchenko A.G. Geochemical data of the Kostomuksha lamproites in Karelia. Precambrian of Northern Europe.
St.-Petersburg. 1997. P. 59-60. (in Russian).
Skuf’in P., Bayanova T. The Early Proterozoic volcano of the central type in the Pechenga Area and its connection
with the ore gabbro-wehrlitic complex (Kola Peninsula). // Petrology. 2006. Vol. 14, № 6. P. 649-669. (in Russian).
 144

The luminescence of apatite from phlogopite and rare metal-apatite-magnetite ores of the Kovdor
massif
Sokolov S.V. ([email protected]), Rassulov V.A. ([email protected])
All-Russian scientific-research Institute of Mineral Resources named after N.M. Fedorovsky (VIMS),
Moscow, Russia

In the limits of the Kovdor massif (Kola Peninsula, Russia) two large deposits are situated – phlogopite and rare
metal-apatite-magnetite. Coarse-grained diopside-phlogopite-olivine rocks and restricted to them vein-like pegmatoid
bodies with commercial mica compose phlogopite complex (Rimskaya-Korsakova, Krasnova, 2002). Rare metal-
apatite-magnetite mineralization is presented by calcite(±dolomite)-bearing phoscorites and analogous with them by
mineral composition carbonatites (Sokolov, 1983).
A number of researches (V.I.Ternovoy, E.M.Epshtein and some others) considered, that both deposits arised
simultaneously as a result hydrothermal-metasomatic process and have similar mineral composition. However,
comparison analysis of geological, geochronological and mineralogy-geochemical data along with results of
thermobarogeochemical study of melt and fluid inclusions in rock-forming minerals of ores displayed considerable and
important distinctions between these deposits, that allowed us to relate them to magmatic formations, but different
genetic type (Sokolov, 2006).
The luminescence investigation techniques is used successfully for revealing such mineral features, which could
be used as diagnostic signs or are typomorphic for definite geologic environments. With the aim of supporting of
different nature of the mentioned deposits were studied X-ray luminescence (XL) and laser-induced photoluminescence
(PL) of apatite. This mineral is wide distributed in the cited ores, and, as known (Portnov, Gorobets, 1969), is
characterized by definite luminescence spectra in deposits of different genetic (formation) type.
Spectra of X-ray luminescence (n = 16), were obtained using monofractions of apatite with mass of 20-50 mg,
collected from phlogopite ores with modify ratio of rock-forming minerals (olivine, diopside, phlogopite, apatite) and
various by composition phoscorites (apatite-forsterite, apatite-forsterite-magnetite, calcite-forsterite-magnetite) and
carbonatites (forsterite-calcite and phlogopite-calcite). Spectra of photoluminescence (n = 44) were measured on apatite
grains from the same samples. Spectra contain luminescence bonds of optic-active centres of rare-earth elements and
manganese: Ce3+ (390 nm), Eu2+ (450 nm), Dy3+ (485 and 575 nm), Tb3+ (490 and 550 nm), Sm3+ (565, 600, and 642
nm), Mn2+ (585 nm), Eu3+ (620 and 628 nm). Initiation of a REE-centres, probably, is caused by the presence of
isomorphic sodium, which manifests itself as a compensator of superfluous positive charge, created by the lanthanides.
X-ray luminescence spectra of apatite from phlogopite ores differ from apatite spectra from phoscorites and
carbonatites: 1) by a greater amounts of bonds of REE luminogens (Tb 3+, Sm3+); 2) reduced intensity of a luminescence,
attaining correspondingly, 350-1900 и 2450-4770 relative units (Fig. 1, 3, 4). At the same time they are identical with
spectra of apatite from calcite ijolites, enclosing apatite-magnetite deposit (Fig. 1 and 2), which corresponds with their
mutual belonging to silicate system, while rare metal-apatite-magnetite ores by their composition represent silicate-
phosphate-oxide and carbonate rocks.
Photoluminescence of apatite was generated by laser radiation (exc = 337.1 nm), under influence of which the
mineral displays blue (or lilac-blue) luminescence with vary intensity. According to the used method (Rassulov, 2005),
in one point of each grain were measured two PL-spectra – integral by time and with registration delay of 180 s later
on laser impulse, what allow to fix the weak lines of the centers with long afterglow (Sm3+, Dy3+). Photoluminescence
spectra, like X-ray luminescence spectra, make up also two groups, corresponding to apatites: 1) from rocks of
phlogopite complex and calcite ijolites and 2) from phoscorites and carbonatites. The first group possess luminescence
bonds of Eu2+, Dy3+, Tb3+, Eu3+, Sm3+ (Fig. 5 and 6) and the second one has distinct manifested only bonds of Ce3+ and
Mn2+ (Fig. 7 and 8).
Conclusions: the results of investigation of apatite luminescence confirm difference of ores of phlogopite and
rare metal-apatite-magnetite deposits and testify to genetic unity of phoscorites and carbonatites in composition the last.

References:
Portnov A.M., Gorobets B.S. The luminescence of apatite from different types of rocks // Doklady of the
Academy of Sciences USSR. 1969. Vol. 184. № 1. P. 199-202. (in Russia).
Rassulov V.A. Local laser luminescent spectroscopy of minerals (on example of zircon). Methodical
recommendations № 156. М. VIMS. 2005. 16 p. (in Russia).
Rimskaya-Korsakova O.M., Krasnova N.I. Geology of the deposits of the Kovdor massif. St.-Petersburg. 2002.
146 p. (in Russia).
Sokolov S.V. The genetic unity of apatite-magnetite ores and carbonatites in alkali-ultrabasic intrusions //
Geochem. Internat. 1983. Vol. 20. P. 86-98.
Sokolov S.V. Genetic relationships between apatite-magnetite and phlogopite deposits of the Kovdor massif
(Kola Peninsula, Russia). 12th Quadrennial IAGOD Symposium 2006. Moscow. 2006. Abstracts e-book, №356.
 145

650
3+
2500 Dy
3+ Sm
3+
1 3+ 5
Tb 3+ Eu
550 Tb
2000
3+ 3+
Tb Dy 3+
2+
Eu
450 O* Eu 2+
1500 Mn
3+
Sm
350 2+
Mn 1000

250 500

Z
150 0
300 400 500 600 700 390 490 590 690 790

2500
3+ 3+
Tb Dy
800
3+ 2 Eu
3+ 6
Sm
2000
O* 3+ 3+
Tb Tb
600 3+ 3+
Dy Eu
1500 2+
Eu 2+
Mn 3+
Sm
400
1000
2+
Mn

200 500

Z
0 0
300 400 500 600 700 390 490 590 690 790

5000
3+
Sm 2000
3 7
4000 3+
3+ Dy
Ce
1500
2+
3000 Mn
2+
Mn
O* 1000
2000

500
1000
3+
Dy Z

0 0
300 400 500 600 700 390 490 590 690 790

1600
3+
Sm 3+
4 Ce
8
4500
1200 2+
Mn

2+
3000 Mn
800

O*
1500
400

3+
Dy Z
0 0
300 400 500 600 700 nm 390 490 590 690 790 nm

Representative spectra of X-ray luminescence (1-4) and laser-induced photoluminescence (5-8) of apatite from
phlogopite deposit (1 and 5), calcite ijolites (2 and 6), and rare metal-apatite-magnetite deposit – phoscorites (3 and 7)
and carbonatites (4 and 8); z – spectra, resulting from registration delay of 180 s. Spectra given without taking into
account spectral function of the register.
 146

Fluid and melt inclusions in minerals of West Greenland lamprophyres

Solovova I., Girnis A., Kopylova M.
Institute of Ore deposits, petrography, mineralogy and geochemistry RAS (IGEM),
Moscow, Russia

We report a reconnaissance study of melt and fluid inclusions in the rocks of West Greenland (Manitsoq area)
assigned to transitional varieties between ultramafic lamprophyres and kimberlites. The lamprophyres are massive dark
gray rock with no less than 50% olivine phenocrysts (mg up to 0.9) and less abundant laths of phlogopite, ilmenite, and
Cr spinel embedded in an altered fine-grained groundmass of carbonate-dominated composition. The presence of
phlogopite indicates that the rock can be classified as a minette or a mica lamprophyre. The groundmass contains
euhedral microphenocrysts (~50 micron across) of Mg-Fe carbonate with up to 0.16 wt % F. At least half of the olivine
crystals are strongly fractured rounded grains, which are probably xenocrysts. A glomerophyric olivine-phlogopite
aggregate almost without groundmass was observed in one sample. This aggregate is considered as a cumulate of
liquidus crystals of the lamprophyre. Irrespective of the origin, the olivine grains are strongly altered; however, there
are relics of fresh olivine containing melt inclusions.

Table. Compositions of lamprophyre minerals, wt %

1 2 3 4 5
SiO2 40.75 36.24 0.93 0.15 0.08
TiO2 0.00 2.18 51.11 4.33 0.04
Al2O3 0.00 15.11 0.11 8.70 0.00
FeO 11.06 6.59 34.81 27.15 19.28
MnO 0.15 0.11 1.20 0.54 0.72
MgO 48.77 21.72 8.30 11.73 35.57
CaO 0.10 0.00 0.49 0.00 0.80
Na2O - 0.22 0.00 0.00 0.12
K 2O - 9.11 0.00 0.00 0.00
Cr2O3 - 0.00 0.00 46.0 0.00
BaO - 0.23 0.00 0.00 0.00
SrO - 0.10 0.00 0.61 0.00
ZrO2 - - 0.12 0.00 0.00
F - 0.59 0.00 0.00 0.16
Total - 92.20 97.07 99.21 56.88
mg 0.89 0.85 - - -
Note. 1 – olivine, 2 – phlogopite, 3 – ilmenite, 4 – chromite, 5 – secondary (?) carbonate.

Figure. Primary melt inclusion in olivine. The inclusion is

almost fully crystallized and includes daughter carbonate
and mica crystals. The olivine zone adjacent to the
inclusions contains numerous small secondary inclusions
produced by partial decrepitation of the main inclusion
during cooling and decompression

Primary melt inclusions 10-20 micron in size were observed in the olivine phenocrysts. The inclusions are often
partly decrepitated and surrounded by halos of small satellite inclusions (figure), which indicates high fluid pressure.
The melt inclusions consist of daughter minerals, a small amount of residual glass, and a gas bubble. Carbonates and
mica were identified among the daughter crystals. The mica is compositionally similar to the phlogopite phenocrysts
and contains up to 4 wt % TiO2, 0.7 wt % ВаО, and 0.5 wt % F. The residual glass is rich in TiO 2 (up to 4 wt %) and F
(up to 0.65 wt %) and contains significant amounts of SrO, BaO, and Cl. Secondary fluid inclusions were observed in
olivine along healed fractures. The obtained data suggest that the primary magmas of ultramafic lamprophyres
contained considerable amounts of volatiles (CO2, F, Cl, H2O) and incompatible elements (Ba, Sr, Ti, etc.). The high
 147

mg values of host olivine phenocrysts suggest that the enrichment of the melts is an intrinsic property of their primary
mantle melts rather than the result of extensive crystal fractionation.

Trace element partitioning between immiscible silicate and carbonate melts from primary melt
inclusions
Solovova I.P., Girnis A.V. and Ryabchikov I.D.
Institute of Ore deposits, petrography, mineralogy and geochemistry RAS (IGEM),
Moscow, Russia

We investigated silicate-carbonate melt inclusions (Fig. 1) in clinopyroxene phenocrysts from the fergusite of the
Dunkeldyk potassic alkaline basaltoid complex in the Eastern Pamirs (Tajik Republic). The presence of silicate and
carbonate melts in coexisting hermetic inclusions allowed us to evaluate trace element partitioning between these melts.
The pressures and temperatures of melt equilibration were constrained by heating and cooling experiments. Both
carbonate and silicate melts homogenized at 1150–1180оC, and their subsequent cooling resulted in the formation a
fine-grained quench aggregate and a silicate glass. The maximum pressure of host clinopyroxene crystallization and
melt inclusion entrapment was constrained as 0.4–0.6 GPa.

Fig. 1. Photomicrograph of a quenched melt inclusion in clinopyroxene containing two immiscible liquids,
silicate melt (S) with carbonate melt globules (C), at 1150°C.

Fig. 2. Primitive mantle-normalized trace element contents in silicate and carbonate melts.
 148

Fig. 3. Trace element partition coefficients between carbonate and silicate melt inclusions homogenized at
1180°C.

The silicate melt from inclusions is alkali-rich (up to 16.5 wt % Na2O + K2O) at K2O/Na2O up to 4.3. The least
evolved melts (SiO2 < 46 wt %) are agpaitic, (K2O+Na2O)/Al2O3 > 1. The composition of carbonate melt quenched
from a temperature of 1180°C was estimated as (wt %) 10.4 SiO 2, 0.3 TiO2, 2.6 Аl2O3, 5.0 FeO, 2.6 MgO, 16.2 CaO,
0.2 SrO, 5.8 Na2O, 14.1 K2O, 0.2 Cl, 1.1 F, 41.5 СО2. Noteworthy is the very high content of K2O, which is in line with
the K-rich composition of coexisting silicate melt.
The silicate melt inclusions show high contents of REE (up to 1000 ppm in total), especially LREE, Ва, Th, U,
Li, B, and Be. The primitive mantle-normalized (La/Yb)N ratio is up to 68. Both the melt inclusion and bulk rock
compositions have high Th/U (up to 5.0 and 6.7, respectively). The carbonatite melt exhibits the same geochemical
features but has more pronounced negative anomalies of Zr, Nb, Ti, and V.
The partition coefficients of trace elements were estimated on the basis of the SIMS analyses of two carbonatite
inclusions and 2 silicate inclusions quenched from 1150–1180°C. The compositions of the carbonate inclusions were
similar (except for Zr) and their average was used for the calculation of partition coefficients.
The rare earth elements and most trace element (e.g., Nb, Hf, Y) show negligible fractionation between the two
melts (D ≈ 1), i.e., the geochemical effect of silicate-carbonate liquid immiscibility under the P-T conditions of
inclusion entrapment is very small. The carbonate melt is somewhat enriched in Gd, Ba, Sr, and U, whereas the silicate
melt is enriched in Pb, Ti, and Li. The experiments of Hamilton et al. (1989) showed that the partition coefficients of
REE between immiscible carbonate and silicate melt are close to 1 at 1150°C and 0.35–0.60 GPa. They suggested that
carbonate melts could be enriched in trace elements at high pressures (>0.6 GPa), which makes them potent agents of
mantle metasomatism. On the other hand, the enrichment of carbonate melts in trace elements was observed at low
temperatures (Jones et al., 1995; Veksler et al., 1998). This trend may have a bearing on the formation of carbonatite-
related rare metal deposits. In addition, the enrichment of natural carbonatites in rare elements can be related to the high
mobility of carbonate melt and its separation from crystalline residue at very low melt fractions.
References:
Veksler I.V., Petibon C., Jenner G. A. et al. Trace element partitioning in immiscible silicate–carbonate liquid
systems: an initial experimental study using a centrifuge autoclave // J. Petrol. 1998. V. 39. N 11/12. P. 2095–2104.
Jones J.H., Walker D., Pickett D.A et al. Experimental investigations of the partitioning of Nb, Mo, Ba, Ce, Pb,
Ra, Th, Pa and U between immiscible carbonate and silicate liquids // Geochim. Cosmochim. Acta. 1995. V. 59. P.
1307– 1320.
Hamilton D. L., Bedson P., Esson J. The behaviour of trace elements in the evolution of carbonatites // In: Bell,
K. (ed.) Carbonatites. Genesis and Evolution. 1989. London: Unwin Hyman, pp. 405–427.

The behavior of Cl, F, and H2O during the late evolution of alkaline magmas on the Island of
Pantelleria
Solovova I.P., Kovalenko V.I., Girnis A.V.
Institute of Ore deposits, petrography, mineralogy and geochemistry RAS (IGEM),
Moscow, Russia
The Island of Pantelleria is situated in the Straight of Sicily within the Sicily continental rift. The island is made
up of a bimodal basalt–pantellerite volcanic association. The formation of the main caldera separates the development
of pre- and post-caldera volcanic suites. Ignimbrites with an age of 114 ka mark the boundary between the early (325–
124 ka) and late (106–47 ka) sequences. The last eruption of subalkali basalts was documented in 1891. The volcanic
rocks are rich in Cl, which was interpreted as an indicator of the “dryness” of pantellerite magmas.
 149

This study is based on the analysis of melt inclusions in minerals. The investigation of inclusions included
heating/cooling experiments, electron microprobe analysis, secondary ion mass spectrometry, and Raman spectroscopy.
It was shown that volatile components (CO2, H2O, Cl, F) played a significant role during all stages of magma
formation of differentiation. Carbon dioxide was the main volatile component in the source region of subalkaline
(hawaiite) magmas. The analysis of glasses from melt inclusions in hawaiites showed no more than 0.07 wt % F and Cl.
The low content of H2O in the deep fluids is supported by the investigation of a gas phase in melt inclusions.
The more evolved plumasitic trachytes inherit the enrichment of melts in CO 2 fluids, which were observed in
fluid inclusions. In contrast to the hawaiite magmas, inclusions in the trachytes contain up to 1 wt % Cl. The direct
analysis of hydrogen (SIMS) in inclusions in anortoclase phenocrysts homogenized at 985°C showed an H 2O content of
~0.3 wt %.
Melt inclusions from the agpaitic trachytes and pantellerites also contain CO 2. Fluid inclusions dominated by
CO2 were found in anorthoclase phenocrysts. Solid CO2 was obtained during cooling of these inclusions and sublimated
at temperatures from –75 to –62°C, which correspond to densities of 0.0037–0.010 g/cm3 and fluid pressures of 9–24
bar at 950°C.
During the examination of some melt inclusions in clinopyroxene from the pre-caldera volcanic rocks, unique
evidence was found for the loss of H 2O from inclusions during the process of rock formation. Numerous tiny hematite
crystals (identified by EPMA) were observed on the walls of such inclusions (fig 1, a). They were formed owing to FeO
oxidation accompanying H2 diffusion through the host mineral in response to a temperature increase. Based on the
composition of anomalous inclusions (~7 wt % FeO in normal inclusions and no more than 1.1 wt % FeO in the
inclusions with hematite crystals), the maximum amount of H2O that escaped from such inclusions is estimated as ~1 wt
%. According to SIMS analysis, the quenched glasses contain ~0.9 wt % H 2O, which implies that the primary melts
contained approximately 2 wt % H2O. Similar inclusions were also observed in some anorthoclase phenocrysts.
There are two types of melt inclusions in anorthoclases. The first type comprises completely crystallized
inclusions with grains of a Zr-bearing amphibole-like mineral. The inclusions of the second type are dominated by
glass. In addition, euhedral and skeletal fluorite crystals were observed in these inclusions. The complete melting of
fluorite was observed at 840–890°C The content of F in the melts of the amphibole-bearing inclusions is twice that of
the fluorite-bearing inclusions (0.58 and 0.26 wt %, respectively). The daughter amphibole contains up to 1.55 wt % F.
Fluorite in melt inclusions closely associates with salt globules dominated by NaCl and containing minor
amounts of Ca and Fe (fig 1, b). The fluid of silicate inclusions also contains NaCl crystals, which rim a gas bubble.
The melting temperatures of the salt globules in the glasses of inclusions are 760–740°C in the pre-caldera rocks and
640–600°C in the post-caldera rocks, which correspond in the NaCl–H2O system to salinities of 93–91 и 71–69 wt %,
respectively. Correspondingly, the content of H 2O in the salt globules is 7–9 wt % for the pre-caldera pantellerites and
29–31 wt % in the post-caldera rocks.

Figure.
Photomicrography of
inclusions. (a) black points
on the walls of the inclusion
in clinopyroxene are Fe2O3;
(b) globule of NaCl + CaF2 +
ore phase in the melt
inclusion from anorthoclase.

Similar salt aggregates were observed in the groundmass glass of agpaitic trachytes and pantellerites, where they
coexist with low-density gas vesicles. The salt aggregates are polycrystalline and include approximately 90 vol % NaCl.
In addition to Na and Cl, their analysis yielded up to 10 wt % Ca, 0.3 wt % K, 0.4 wt % Fe, and 0.3 wt % F. The salt
aggregates contain an opaque phase (less than 1 vol %) and a gas bubble (3–8 vol %), in which liquid water was
occasionally observed.
The coexistence low-density fluids and salt melts (brines) in the glasses of melt inclusions and rock groundmass
indicates that a fluid phase separated from the melt and unmixed into two phases (brine + vapor) during the late
magmatic stage of the evolution of the magmatic system.
Thus, the investigation of melt and fluid inclusions in minerals and groundmass glasses showed that the primary
basic (hawaiite) magmas were saturated with respect to CO2, which remained to be the main fluid component until the
formation of agpaitic trachytes in the course of crystallization differentiation. The composition of fluid changed
significantly in more evolved silicic melts, which contained considerable amounts of Н2О, Сl, and, to some extent, F.
The formation of such melts could not be related to crystal fractionation alone and required mixing/contamination
phenomena.
 150

Albitites of the Kryvyi Rig-Kremenchug Zone

Syomka V.A, Velikanov Ju.F, Velikanova O.Ju.
N.P. Semenenko Institute of Geochemistry, Mineralogy and Ore Formation National Academy of Sciences of
Ukraine, Kyiv

Deposits of sodium-uranium formation occur in all Precambrian shields of the world. They are confined to the
tektono-metasomatic zones developed among the rocks different in composition of amphibolite facies, they are
considerably granitized and are of Paleoproterozoic age. Uranium ores are formed by metasomatic way among albitites
or albititesated crystalline slates, gneisses, migmatites, granites and ferriferrous quartzite's. Age of ore mineralization by
different definitions is from 1.6 billion years to 1.8 billion years, depth more than 2-2.5 km, scope from 0.9-1.0 km to
1.2-1,5 km [1].
Uranium deposits of sodium-uranium formation are widely developed within the Kryvyi Rig-Kremenchug
synclinal structure [2]. Processes of albites metasomatism are most intensively shown in the northern part of the
structure – in the Lenin, Pervomaisk mines in the East Annove strip and Zhovta Richka iron-ore deposit. Albititesation
is displayed in metasomatic albite replacement of various rocks on Gdantsevo and Saksahan' suites of Paleoproterozoic
Kryvyi Rig series, metamorfized in the conditions of green-slate and epidot-amphibolite facies.
Albitites formed during metasomatic replacement of micaceous slates of the Gdansk suite are homogeneous in
their mineral structure and are composed by albite, glaucophane, and hydrobiotite; minor ones – by actinolite, tremolite,
chlorite; accessory – by apatite, zircon, grothite and rutile. In the rocks of Saksahan′ suite processes albititesation are
confined to ferriferrous quartzites and magnetite-amphibolous, amphibolous, garnet-amphibolous and micaceous slates
dividing them. The basic varietes of sodium-metasomatites are albitites, aegirinites, riebeckitisated and albititesated
magnetite-amphibol slates. Albitites consist from albitite, by 80-90%, alkaline amphiboles, aegirine, quartz, magnetite,
biotite, hydrobiotite, chlorite, calcite and accessory malacon, apatite and grothite (sphene) are present in them in
subordinate quantity.
Formation of uranium ores which occur, not only in albititesated rocks but also in more cold products of
calcium-magnesian and silicium-alkaline metasomatism is connected with albititesation processes in the rocks of
Kryvyi Rig series [3]. Albititesated rocks are transitive ones between albitites and enclosing ferriferrous quartzites. Both
minerals of initial rocks (magnetite, cummingtonite) and neogenic ones (albite, crossite, rodusite, aegirine, chlorite,
hydromicas) in them are noted. The uranium mineralization is presented by silicates and uranium oxides in them.
Products of calcium-magnesian metasomatism are developed at average depths. They form large lenticular bodies on
magnetite-amphibole slates and ferriferrous quartzites. Their mineral composition – magnetite, martite, hematite,
dolomite, alkaline amphiboles, talc, biotite, chlorite, garnet. Industrial uranium ferriferrous-carbonate ores in which the
main mineral is uraninite are connected with calcium-magnesian metasomatism. The latest metasomatites fill cracks,
secant sodium-carbonate metasomatites and metamorphic rocks and consist of quartz, and biotite, muscovite, feldspars,
calcite, chlorite, hydromicas, graphite and organic substance occur in subordinate quantity. The ore mineralization is
presented in them by nasturan, coffinite, magnetite, mushketovit, iron hydroxides, pyrite, marcasite, chalcopyrite.
Some deposits of sodium-uranium formation are characterised by complex ore mineralization, for example,
uranium ores of the Zhovta Richka deposit are substantially enriched with V, Sc and TR and have the age of 1.77 billion
years [4, 5]. Concerning the age of other uranium deposits defined by K-Ar method, they change in the limits from 1.7
billion years by riebeckite from the Frunze mine [6] to 1.82 billion years on hydrobiotite from Northern Kryvyi Rig
Region [7].
Deposits of sodium-uranium formation of Kryvyi Rig-Kremenchug synclinale structure were formed at
Paleoproterozoic stage of tektono-magmatic activization of the Ukrainian Shield in the subduction zone of Archeane
Middle-Dnieper megablock under Paleoproterozoic Ingul megablock.

References:
1.Geology and Genesis of Deposits of Uranium in Sedimentary and Metamorphic Thicknesses. — Moscow:
Nedra, 1980. — 270 p. (in Russian).
2.Belevtsev Ya.N., et al. Genetic Types and Laws of Placing of Uranium Deposits of Ukraine. — Kiev: Nauk.
Dumka, 1995. — 397 p. (in Ukrainian).
3.Belevtsev Ya.N., et al. Laws of Placing and Search of Criteria of Metamorphic deposits. — Kiev: Nauk.
Dumka, 1995. — 397 p. (in Ukrainian).
4.Anderson Е.B., Barhanov L.V., Zaslavsky V.G. Ages of a Parity of Uranium Mineralization and Regional
Metamorphism on the Zheltaya Rechka Deposit / The Soviet Geology. — 1987. — No 12. — P. 64-69 (in Russian).
5.Tarhanov A.V., et al. Zheltaya Rechka Vanadium-Scandium's Deposit // Geology of Ore Deposits. — 1991. —
No 6. — P. 50-56 (in Russian).
6.Shcherbak N.P., et al. The Catalogue of Isotope Dates of Rocks of the Ukrainian Shield. — Kiev: Nauk.
Dumka, 1978. — 224 p. (in Ukrainian).
7.Vinogradov A.P., et al. The Age of Precambrian Rocks of Ukraine. Works of V Session of the Commission on
Definition of Absolute Age of Geological Formations. — Moscow: АS USSR. — 1958. — P. 111-134 (in Russian).
 151

Mineralogy of alkaline ultrabasic rocks in Bolyarka intrusion (North-Western area of the Ukrainian
Shield)
Tsymbal S.N.*, Kryvdik S.G.*, Tsymbal Yr.S.*, Geiko Ju.V.**, Baran A.N.**
* N.P. Semenenko Institute of Geochemistry, Mineralogy and Ore formation, NAS of Ukraine, Kyiv,
Ukraine; ** "Pivnichgeologia" regional geological enterprise of Ukrainian geological survey, Kyiv, Ukraine

It is known four alkaline ultrabasic intrusions in North-Western part of the Ukrainian Shield (Novograd-
Volynsk block): Gorodnitsa, Glumcha, Pokoshevo, Bolyarka. Three of these intrusions have been discovered and
studied earlier [1, 2, 3]. The Bolyarka intrusion was discovered in 2005. Its studying is continuing. In papers [4, 5] the
data on this intrusion has been first concerned.
According the geological and the geophysical data the intrusion is up to 10 m width, its hade is steep (more than
80о), hade's direction is South-Western. This body intrudes biotite-microcline-plagioclase granitoides contained a small
quantity of garnet (spessartine-almandine) and zircon. The granitoids are intensively altered by fenitization. The
fenitization zone is 5-7 m.
The intrusion is composed predominantly by melteigites and subordinately by ijolites and jacupirangites which
have been amphibolized to different degree. The rock texture is medium-grained; close to granitoid's contact one is
fine-grained. The main rock-forming minerals are clinopyroxenes, magnesian amphiboles, olivines and nepheline.
Cancrinite, zeolite; apatite and phlogopite occur seldom. Zircon, chrome-spinelides, chrome-magnetite, sphene, rutile,
ilmenite, sulphides and also xenogenic minerals such as garnet, biotite, crome-diopside, orthopyroxene, chrome-
spinelides, high-magnesium olivine are detected in crashed samples.
The clinopyroxenes are usually zonal. Their composition corresponds chrome-diopside with different amount of
jadeite and aegirine minals: the central grain zone is enriched in jadeite minal, margin zone in aegirine one. At the same
time aegirine minal and accordingly Fe2O3 increasing occur in accordance with TiO2 increasing and MgO decreasing.
Judging from Ca/(Ca+Mg) ratio the chrome-diopside enriched in jadeite minal is more high-temperatured in
comparison with the aegerine-bearing one. As a rule the latter grew on the previous and includes amphibole, nepheline,
chrome-magnetite and chrome-spinelides enriched in manganese. The most enriched in iron (FeO - 6,0-8,5 %)
diopsides are enriched in Na2O (1,9-2,3 %), MnO (0,15-0,20 %) and are depleted in Al2O3 (0,4-0,7 %), Cr2O3, TiO2.
They had been crystallized in a final stage of the intrusion formation by increased potential of natrium and oxygen.The
olivine is usually intensively altered. This notice concerns the nepheline too. It is altered to zeolites and cancrinite.
The amphiboles are posterior magmatic and autometasomatic. They are represented by calcium and calcium-
natrium amphibole types. The Na2O contents vary from 3,3 to 7,8 %, K2O - from 0,1 to 0,7 %. A composition of the
most of the amphiboles varies from hastingsite to edenite, from edenite to kathophorite, from edenite to richterite. On
AlIV - (Na+K) diagram they have distinct hastingsite-richterite trend. Some of their compositions correspond
kathophorite and winchite one, or close to arfvedsonite one. They are high-magnesium (70-80 %), low-titanian (TiO2 -
0,1-1,0 %, up to 1,5-1,7 % seldom), low chromian (Cr2O3 - 0,0-0,8 %, sometimes 1,0-1,6 %) and high-alumina (Al2O3 -
до 13,5 %). The high-TiO2 amphiboles occur seldom. As a rule they are enriched in Al 2O3 and K2O, in comparison
with less titanian amphiboles (low-temperature) they are depleted in Na2O.
The phlogopite is rare mineral. It is low-titanian (TiO2 is up to 0,6 %) and with increased chrome (Cr2O3 up to
0,5 %).
The ilmenite often forms aggregates with alkaline amphibole and sphene. It is represented by high-manganic
type (MnO - 12,1-13,2 %) with low MgO (< 0,5 %), Cr2O3 (< 0,15 %) and Nb2O5 (0,05-0,15 %). Earlier manganic
ilmenites of the similar composition have been discovered in jacupirangites in Gorodnitsa intrusion [1].
Among sulfides pyrrhotite and pyrite predominate, the pentlandite and the chalcopyrite relatively often occur
too. Mostly they form inclusions in amphiboles; their origin is autometasomatic.
The apatite belongs to fluorine type (F - 1,7-3,0 %) with low MnO (<0,1 %), Cl and rare-earth elements of
cerium groupe. It often forms inclusions in amphibole and nepheline.
The zircon crystals occur as fine-grained prismatic ones and as light-brownish aggregates. In crystal's margin
the zoning has noted. A xenogenic core is absent. On crystal's surface occurs a dilution sculpture.
The xenogenic minerals have been discovered in meltiegites and jakupirangates of the Bolyarka intrusion. They
originate from crust and upper mantle.
The spessartine-almandine (Mn - 8.6 %), the spessartine-grossular-almandine garnets (Mn - 2,1-2,5 %, CaO -
7,3-12,0 %) and the biotite have a crust origin. Sometimes they have inclusions of quartz, ilmenite and magnetite. The
upper mantle minerals are represented by pyrope, pyrope-almandine, chrome-spinelides, orthopyroxene, magnesian
clinopyroxene and olivine.
Pyrope contains 2,1 % Cr2O3 and 4,3 % CaO. By its composition it belongs to paragenesis of granular
Iherzolites from graphite-pyrope facies of the upper mantle. Pyrope-almandine (MgO - 5,8 %, Cr2O3 - 0,03 %) belongs
toeclogitic upper mantle paragenesis.
Orthopyroxene forms grains of irregular shapes to 0,6 mm size which has reaction contacts with amphiboles. By
chemical composition they corresponds alumina enstatite and bronzite (Al 2O3 - 2,3-4,1 %, Mg# - 86-90) with increased
contents CaO (0,3-1,0 %) and Cr2O3 (0,19-0,27 %). It may be as a result of disintegration of upper mantle chrome-
spinel peridotites.
 152

Among rock-forming pyroxenes of the Bolyarka intrusion the chromian (Cr2O3 - 0,4-1,1 %) diopside with
increased amount of aluminium Al2O3 (2,5-4,5 %), FeO (3,0-4,5 %) and Na2O (0,6-1,0 %) and low - TiO2 (less 0,12 %)
are discovered. These pyroxenes have reaction contacts with nepheline and alkaline amphiboles. Their relation with
other clinopyroxenes is not finally clear. On diagram Al 2O3 - Na2O, Cr2O3 - Na2O and FeO - TiO2 they separates from
diopside enriched in aegierine minal.
Chrome-spinelides have no perfect crystals. They are usually represented by oval grains with reaction keliphytic
rims that consist of chrome-magnetite with increased contents of MnO. Presence of these keliphytic rims evidence on
long being in nonequilibrium relationship with alkaline-ultrabasic melts, so they are products of desintagration of upper
mantle chrome-spinel peridotites. The composition of non-altered chrome-spinelides vary in wide range: amount of
Cr2O3 varies from 33 to 60 , MgO - 10-18 , TiO2 -0,1-0,6 %. On the diagram MgO - Cr2O3 they lies in field of chrome-
spinelides from mantle peridotites in kimberlites. They contain inclusions of diopside with increased Cr 2O3 (0,7-1,8 %)
and Na2O (1,3-1,8 %).
Among the studied chrome-spinelids the chromite crystal (Cr2O3 - 60,3 %) that close to chromites of diamond-
bearing association in kimberlites and lamproites has been found. In this chromite the inclusions of high-magnesian
forsterite with 0,4 % NiO was discovered. It is identical to olivine (inclusions) in diamond. That mineral paragenesis
may consider them as a product of desintagration of dunites from diamond facies. It is possible to guess that initial
alkaline-ultrabasic magma for the Bolyarka intrusion has been generated in upper mantle in field of diamond stability.
The rocks of studied intrusion can be diamond-bearing and are worthy of detail investigation.
The age of amphiboles from early generation is 2000 ± 25 Ma, later one - 1885 ± 40 Ma (K-Ar method), and
zircon age is about 2100 Ma (thermoemission method).

References:
Tsymbal S.N., Scherbakov I.B., Kryvdik S.G., Labusniy V.F. Alkaline-ultrabasic rocks of the Gorodnitsa
intrusion (North-Western of the Ukrainian Shield) // Mineral. Journ. (Ukraine). 1997. Vol. 19, № 3. P. 61-80. (in
Russian)
Kryvdik S.G., Tsymbal S.N., Geiko Yu. V. Proterozoic Ultrabasic Magmatism of the North-Western of the
Ukrainian Shield as an Indicator of Kimberlite Formation // Mineral. Journ. (Ukraine). 2003. Vol. 25, № 5/6. P. 57-69.
(in Russian)
Tsymbal S.N., Shumlyanskyy L.V., Bogdanova S.V., Bisllstrom K. Alkaline-ultrabasic rocks in North-Western
of the Ukrainian Shield: Age, Isotope, Geochemistry // Proc. of seminar "Alkaline magmatism of the Earth and their
ore-bearing ability". Donetsk (10-16 Sept. 2007). P. 248-250. (in Russian)
Tsymbal S.N., Geiko Yu.V., Kryvdik S.G., Baran A.N., Tsymbal Yr.S. The Bolyarka intrusion of alkaline-
ultrabasic rocks (North-Western of the Ukrainian Shield) // Proc. of seminar "Actual problems of geology of Belarus
and neighbor territories". Minsk (8-9 Dec. 2008). P. 35-40. (in Russian)
Geiko Yu. V., Prychodko V. L., Tsymbal S.N., Baran A.N. Alkaline-ultrabasic rocks of Novograd-Volyn
region and possible their relationship with kimberlitic magmatism // Abst. of seminar "Parental and placer deposits of
diamond and main metals". Simpheropol (15-21 Sept. 2008). P. 13-15. (in Ukrainian)

Alkaline granites of the Syadatoyakhinsky massif (Polar Urals)

Udoratina O.V.
Institute of Geology of Komi SC UB RAS, Syktyvkar, Russia

In Polar Urals among numerous acidic magmatic rocks of the Kharbey block of preuralides the alkaline
granitoids of the Syadatayakhinsky massif are found. The granitoids are related to the Syadatayakhinsky complex
(Correlation …, 1985). The rocks of the massif are rare exception - they are poorly affected in this zone by metasomatic
silica-alkaline processes and actually magmatic (intrusive formations) (Okhotnikov, 1985).
In this zone the alkaline metasomatites with rare metal specificity are widespread (Taykeyusky ore knot). The
ore rocks are related to the formation of alkaline metasomatites of fault zones and have paragenetic relation with
magmatites. Recently the material has been collected, which allow relating genetically the rare metal deposits with
alkaline source. The magmatic rocks of such bias are also included in the studied massif, which does not yield,
however, ore load.
The granitoids, exposing in source of the Zaozerny brook, comprise sheet bodies among green shales
metamorphites of the Middle Riphean Nyarovey suite. The absolute age of massif rocks on the basis of Rb-Sr (bulk)
and U-Pb (zircon) datings corresponds to Middle Cambrian (Andreichev, 2007). It should be noted that figures of age of
rocks, determined by different methods, are close. The initial 87Sr/86Sr ratio makes 0.70490±41 and specifies the abyssal
nature of the matter.
The massif is composed by arfvedsonite-biotite, biotite and micropegmatite granites, as well as granophyres and
granite-porphyries. The ratio with host rocks – layered intrusion into metamorphite strata. The arfvedsonite-biotite
granites are the deepest, other varieties of rocks are located hypsometrically higher and represent endocontact facies.
Lenticular or rhythmical zoning is observed near endocontacts and in apophysis bodies. The observable geological
ratios – intertransitions of rocks specify their near-simultaneous formation that allows relating them to the products of
one phase of intrusion (t– 600–700) (Okhotnikov, 1985).
 153

Table. Chemical composition (weight %) and content of rare elements (g/t).

Component 368/1 368/3 368/4 368/5 368/7 368/8 368/9
SiO2 66.78 71.12 71.38 71.50 70.94 70.82 73.90
TiO2 0.10 0.15 0.19 0.14 0.18 0.20 0.13
Al2O3 21.85 13.12 14.36 14.18 15.95 15.67 12.72
Fe2O3 0.99 1.34 1.31 1.05 1.58 1.47 1.08
FeO 0.45 0.76 0.73 0.68 0.56 0.76 0.58
MnO 0.02 0.02 0.04 0.03 0.03 0.05 0.02
MgO 0.07 0.80 0.20 0.70 0.33 0.31 0.31
CaO 0.56 0.56 0.69 0.67 0.62 0.48 0.67
Na2O 3.88 4.64 4.60 4.80 3.90 4.62 4.17
K2O 4.59 5.84 5.47 5.39 4.58 5.49 4.95
P2O5 – – 0.03 – 0.02 0.02 0.01
LOI 0.88 1.27 0.90 0.83 0.85 0.61 1.04
Total 100.17 99.62 99.90 99.97 99.54 100.50 99.58
Na2O+ K2O 8.47 10.48 10.07 10.19 8.48 10.11 9.12
Na2O/ K2O 0.85 0.80 0.84 0.90 0.85 0.84 0.84
P.I. 0.52 1.06 0.94 0.97 0.71 0.86 0.96
La 38.0 23.2 19.7 48.5 95.4 83.4 3.87
Ce 65.3 35.0 30.1 71.0 150.0 138.0 5.0
Pr 6.35 3.08 2.74 6.9 13.1 12.2 0.4
Nd 21.7 9.88 8.52 20.4 40.3 40.2 1.03
Sm 4.76 2.0 1.82 4.2 8.43 8.19 0.19
Eu 0.26 0.046 0.22 0.036 0.53 0.23 0.11
Gd 4.2 2.22 2.02 4.98 11.1 10.1 0.23
Tb 0.53 0.29 0.3 0.71 1.73 1.58 0.037
Dy 2.53 1.6 1.77 4.11 10.1 9.03 0.24
Ho 0.44 0.33 0.39 0.87 2.24 2.0 0.054
Er 1.01 0.82 1.02 2.26 6.26 5.58 0.16
Tm 0.13 0.11 0.15 0.33 0.93 0.81 0.026
Yb 0.56 0.57 0.8 1.71 5.03 4.5 0.14
Lu 0.076 0.085 0.13 0.27 0.85 0.7 0.026
(La/Yb)N 46.75 27.44 16.60 19.12 12.78 12.49 18.63
EuN/Eu*N 0.17 0.07 0.35 0.02 0.17 0.08 0.61
Cs – 0.042 0.049 – 2.4 – 1.14
Ba 45 20 33 165 125 265 69
Sc 2.57 1.1 1.33 3.31 4.87 4.61 0.48
Cr 3.36 3.23 1.05 1.25 8.93 8.61 0.92
Co 0.54 0.26 0.22 1.69 0.99 4.2 0.13
Ni 410 570 110 260 380 360 140
Zn – 46.1 – – 46.4 – 14.4
Se 2.01 0.53 0.38 0.44 3.91 1.66 2.73
As 6.68 – 3.37 3.17 5.95 2.35 2.96
Sb 1.17 0.4 0.62 0.37 1.04 0.18 0.35
Th 9.07 4.07 3.04 10.0 14.5 11.2 0.97
U 2.97 0.39 2.57 2.72 4.92 2.17 2.1
Br 1.02 0.5 0.4 2.36 0.89 0.54 0.33
Hf 10.5 3.15 3.12 14.0 17.5 0.92 0.31
Ta – 0.58 – 0.88 4.31 2.12 –
Au – 0.019 – – 0.026 0.05 –
Ag 1.76 – – – – – –
Nb* 13 21 18 17 19 22 19
Zr* 207 450 411 274 428 422 248
Y* 24 37 34 29 39 36 31
Rb, мкг 97.5 95.3 87.8 108.9 98.3 102.7 88.0
Sr, мкг 85.2 75.7 27.0 9.2 25.4 12.3 14.8
Note. Rare and rare earth elements are determined in the Institute of Geochemistry RAS by neutron-activation
and X-ray-radiometric (*) methods. The chemical contents and Rb, Sr data are according to [1].

The ore load of the granitoids of the Syadatoyakhinsky massif, as N. Okhotnikov emphasizes, does not represent
practical value; generally it is a fine scattered sulphidic mineralization (molybdenite, sphalerite, pyrite, pyrrotyne). He
also stated that the granites of lower and upper levels have different geochemical specialization - atop the magmatic
chamber tin, molybdenum and tungsten, and below - tantalum-bearing granites with niobium (!) accumulated.
The tested rocks of the massif (V. L. Andreichev’s collection) are represented by medium-grained, massive
alkaline arfvedsonite-biotite and biotite granites. Microscopic studies reveal granite hypidiomorphic-granular texture,
locally cataclastic.
 154

The rocks are composed (%) of potassic feldspar (40-45), plagioclase (25-30), quartz (20-25) and biotite (3-5).
The constant presence of arfvedsonite is characteristic. Accessory minerals are presented by allanite, sphene, zircon
(rarer by apatite). Ore minerals – magnetite, pyrite; secondary - epidote, limonite.
Salic minerals are presented by potassic feldspar and plagioclase and quartz. Potassic feldspar is presented by
pertitized orthoclase and neogenic microcline replacing orthoclase. Plagioclase - albite-oligoclase (An10–15)
idiomorphous prismatic, it forms hypidiomorphic-granular texture. It is often sericitized. Quartz is poorly cataclized.
Chemical compositions of plagioclase and potassic feldspar are without impurities. Widespread femic minerals are
represented by micas (biotite and phengite), and also amphibole (arfvedsonite). In arfvedsonite-biotite reveal taxitic
distribution of dark minerals. The amphibole is dark green, pleochroic from dark green to yellowish green; it is optically
negative. The biotite is presented by thin scale stilpnomelane. Often biotite is a unique dark mineral in the rocks. At
transition to micropegmatitic granites and also granophyres and granite-porphyries muskovite (phengite) is found.
Epidote and allanite are observed as small isometric grains forming accumulations. Among accessory the structures of
zircons and sphene have been studied. Apatite and garnet, described by V.N.Okhotnikov, are not found. Zircon is
observed as small crystals of prismatic yellow-brownish habitus. According to V. L. Andreichev the catode-luminescent
survey reveals concentric magmatic zoning (Andreichev, 2007). It is characterized by HfO 2 presence, which content
vary from 1.75 to 2.51 weight %. Sphene is observed as individual small extended brown crystals.
Petrochemically the rocks of the massif correspond to the family of alkaline granites. The content (table) of silica
acid varies (weight %) from 67 to 74, and alkalis from 8.5 to 10.5, at the alumina content at 14-15, but can reach 21 in
granosyenites (Okhotnikov, 1985; Andreichev, 2007). The agpaite index varies from 0.7 to 1 except for one test.
The geochemically studied rocks are characterized by the raised content in relation to clarke for acid rocks Rb,
Zr, Hf, reduced content of all the light (except for La) and medium rare earths, also Cr, Sr, Ba, Zn, Th, Y, the contents
of heavy rare earths Y, Nb and U are observed at the clarke level. The rocks are characterized by low REE content with
predominance of light over heavy and distinct europium anomaly, (La/Yb) N varies from 13 to 47. By the substrate type
the studied rocks are related to A-granites. Thus, the geochemical features of the rocks, their abyssal nature and age
values specify that the geodynamic conditions of formation correspond to postcollision settings prior to riftogenesis in
the north Urals.
The work is performed under financial support of project НШ-3763.2008.5 Leading scientific schools.

References
Andreichev V. L., Larionov A. N., Litvinenko A.F. New Rb-Sr and U-Pb data on the age of granitoids of
Syadatayakhinskya intrusion (Polar Urals) // Lithosphera, 2007, №1, pp. 147-154. (in Russia).
Correlation of magmatic complexes of European northeast of the USSR / V.N. Okhotnikov, V.I.Mizin,
L.T.Belyakova et al. // Series of pre-prints «Scientific recommendations for the national economy». Syktyvkar, 1985.
edition 53.24 pp. (in Russia).
Okhotnikov V. N. Granitoids and ore formation (Polar Urals). Leningrad: Nauka, 1985.184 pp. (in Russia).

Multi-scale numerical modeling of carbonatite-silicate magma interaction

Valentini L., Moore K.R.
Department of Earth and Ocean Sciences, National University of Ireland Galway, Galway, Ireland

In the last decade, an ever increasing number of carbonatite occurrences has been documented. Nonetheless, the
abundance of this peculiar type of rocks is still relatively scarce with respect to the more common silicatic rocks and a
single active carbonatitic volcano exists. This results in a limited knowledge about the mechanisms of carbonatite
magma ascent and emplacement dynamics with respect to the silicatic counterpart. Moreover, although carbonatites and
silicatic rocks often occur in spatial and temporal association, little is known about their modes of mechanical and
thermodynamical interaction. In this contribution, we utilize Computational Fluid Dynamics in order to study the
interaction dynamics of theoretical liquids to which the physico-chemical characteristics (viscosity, density, diffusivity
etc.) of carbonatite and silicate magmas are assigned. Numerical models are performed at different scales of analysis in
order to infer the kind of mechanisms resulting in the textural features that are commonly observed in natural samples.
The formation of microstructures such as micron-scale carbonatitic globules surrounded by a silicatic matrix is
simulated by means of a set of advection-diffusion equations with Korteweg Stress (i.e. gradient induced stress). At a
larger scale of analysis, the effect of viscosity contrasts on the extent of mechanical interaction is investigated.
Implications for processes such as mechanical intermingling, magma hybridization and immiscible separation are
discussed on the basis of our numerical results. It is highlighted how textural observation should be integrated by
geochemical data and considerations about the physics of the system in order to infer reliable conclusions about the
mode of carbonatite-silicate interaction.

This presentation was financially supported by INTAS project 05-1000008-7938.

 155

Mantle Plumes and Lithosphere Thickness Are Factors Governing Magma Formation in the Yakutian
Diamondiferous Province
Vasilenko V.B.
Institute of Geology and Mineralogy, Siberian Branch of the Russian Academy of Sciences, Novosibirsk,
630090 Russia

The Yakutian Kimberlite Province includes 24 volcanic rock fields. Their compositions vary from deep
diamondiferous kimberlites in the south to ultrabasic–alkalic rocks with carbonatites in the north. The decrease of
depths of melt generation tend to correspond to the decrease of the depth of the lithosphere bottom (see figure).

Location of kimberlite fields in the Yakutian Diamondiferous Province.

1, Mirny; 2, Nakyn; 3, Alakit-Markha; 4, Daldyn; 5, Verkhne-Muna; 6, Chomurdakh; 7, Ogoner-Yuryakh; 8,
West Ukukit; 9, East Ukukit; 10, Merchimden; 11, Molodo; 12, Toluop; 13, Kuoik; 14, Khorbusuon; 15, Tomtor; 16,
Ebelyakh; 17, Yargin; 18, Starorechenskoe; 19, Ary-Mastakh; 20, Dyuken; 21, Luchakan; 22, Birigindin; 23, Kuranakh;
24, Anabar.

Kimberlites. Melting of peridotites saturated with carbon dioxide occurs by transfer to the liquidus of the
clinopyroxene–olivine cotectic. The composition of the first drops of the selective melt corresponded to calcite, whose
amount could be as large as 80% of the parental melt volume. Higher contents of calcite in the parental melt resulted in
metasomatism of syngenetic olivine and restite peridotite. During further melting, the proportion of olivine in
kimberlites increased up to the formation of high-olivine varieties. Olivine accumulation occurred step-by-step;
therefore, 12 varieties can be recognized in kimberlites according to the CaO : MgO ratio. The volume ratio between
carbonate and olivine varieties can be different, depending on the composition of the magma-producing matter.
Predominance of calcite-rich rocks results in formation of carbonate kimberlites. They constitute no less than 15% in
major diamond fields of Yakutia. As a rule, they are prepipe or postpipe carbonate-rich rocks. The typochemical feature
of these rocks is the inverse correlation between MgO and CaO. This phenomenon reflects the evolution of thermal
conditions of the melting of kimberlite parental melts at temperatures within 900–1500°. Melts of diamondiferous
kimberlites form at depths within approximately 100–200 km or, possibly, even deeper. Part of diamonds may be of
xenogenous origin, but the majority of them formed concurrently with kimberlite parental melts, whose composition
determined the amount of idiogenous diamonds.
Above the aforementioned depths, the lithosphere section is geochemically heterogeneous even in the model
with uniform peridotite composition. Under increasing pressure, admixing elements are redistributed over peridotite
minerals. In peridotite clinopyroxene, the titanium admixture is redistributed to other minerals, whereas potassium is
accumulated. Each range of the lithosphere section is characterized by a certain TiO 2 : K2O ratio in clinopyroxenes.
Hence, the contents of titanium and potassium in kimberlite parental melts depend on the depth ranges where they
formed.
Thousands of chemical analyses of Yakutian kimberlites were considered and subdivided into seven populations,
the first of them being the deepest, and the seventh, the shallowest. They differed in the contents of TiO2 and K2O.
Ranking of the mean contents of these oxides in the populations shows that TiO 2 contents form a sequence within 3.0–
0.3%. Correspondingly, the mean K2O contents form an inverse sequence. The population with the lowest TiO2 content
 156

contains 0.85% K2O. Higher K2O contents in kimberlites are produced by subducted oceanic crust fragments entering
the magma formation zone. The thermal factor, namely, the inverse correlation between CaO and MgO, is clearly
observable in each population. The deepest populations have the highest diamond potential.
Mean TiO2 contents over all kimberlite bodies within each kimberlite field form sequences from the deepest to
shallowest populations. This phenomenon results from vertical migration of magmatic chambers and sequential
formation of kimberlite bodies. The deepest (1 and 2) kimberlite populations are absent from some kimberlite fields
(Daldyn and Verkhne-Muna) because of the rise of the lithosphere bottom and reduction of its thickness. Thus, the
geochemical zoning of the lithosphere is responsible for type geochemical indices of the P–T conditions of kimberlite
formation and diamond potential.
Picrites. This statement is confirmed by the occurrence of picrites, rocks different from kimberlites, in northern
fields of the province, where they are often present in the same bodies as kimberlites. The maximum contents of picrites
are recorded in the Ary-Mastakh and Dyuken fields of the Anabar group of fields and in the West Ukukit and Ogoner-
Yuryakh fields of the Olenek group. The predominance of picrites in northern fields of the province indicates that the
lithosphere is thinner there. The depths of the formation of the picrite parental melts vary approximately from –100 to –
70 km. Picrites show the same features as kimberlites except for higher TiO 2 contents and absence of diamonds and
their associates. Carbonate varieties are typical for picrites, as well as for kimberlites. However, their proportion is
larger there.
Alkalic–ultrabasic rocks with carbonatites occur most often in the Tomtor field of the province. The depth of the
formation of their parental melts is estimated to be 60–70 km. They are characterized, first of all, by separate bodies of
carbonate rocks (carbonatites) enriched in rare earths. The silicate and silicate–carbonate rocks of the Tomtor field can
be subdivided into two groups: rich in CaO and rich in Al 2O3. The former can be assigned to the carbonatite association,
and the other, to ultrabasic foidolites (see table). In our opinion, these rocks form in a way similar to that of kimberlites.
In both cases lime is leached from silicate minerals of basaltoid rocks in the course of carbonate metasomatism.
The variation of rock compositions from diamondiferous kimberlites in the south to carbonatites of the Tomtor
field in the north is characterized by higher contents of TiO2 and Fe2O3 in kimberlites of northern fields, dramatic
increase of TiO2 and Fe2O3 contents in picrites of the same fields. The typochemical feature of the carbonate rocks,
kimberlites and picrites, is the inverse correlation between CaO and MgO, whereas in the carbonate rocks of the Tomtor
field the typochemical feature is the inverse correlation between CaO и Al 2O3.
A common feature of rocks of all assemblages is the presence of carbonate matter and predominance of
potassium. These features may have arisen from widespread subduction of the oceanic crust from the Upper Yana fold–
thrust belt. This subduction favored the emergence of mantle plumes and their penetration to the lithospheric mantle
beneath the Yakutian Diamondiferous Province.

Table. Composition of rocks of various assemblages in the Yakutian Diamondiferous Province

Oxides Kimberlites of Rocks of the Olenek Representative compositions of the Tomtor field
the Vilyui group of fields
Subprovince Kimberlites Picrites 1 2 3 4 5 6 7
n 7537 174 124 213 95 133 55 130 51 140
SiO2 26.73 23.93 27.51 4.73 29.23 32.12 46.86 35.73 7.48 5.79
TiO2 1.34 1.59 4.06 0.40 2.70 3.35 3.41 4.94 6.55 2.54
Al2O3 2.70 3.17 4.11 1.01 7.62 10.79 25.25 20.68 19.63 5.94
Fe2O3 6.78 8.31 12.12 6.41 9.43 11.98 4.45 9.61 11.87 35.87
MnO 0.12 0.13 0.15 1.38 0.55 0.50 0.14 0.37 0.77 3.59
MgO 25.42 19.11 21.70 2.29 7.83 8.44 0.75 2.92 0.35 0.95
CaO 14.64 19.96 13.19 44.05 15.18 11.93 1.05 2.50 3.12 3.78
Na2O 0.13 0.21 0.19 0.16 0.85 0.95 0.29 0.27 0.20 0.13
K2O 0.58 0.92 1.34 0.64 5.38 4.71 6.90 4.91 0.38 0.30
P2O5 0.50 0.61 0.69 7.37 2.69 2.68 1.10 2.45 14.34 6.01
LOI 21.84 21.84 15.44 32.61 18.50 12.60 10.09 15.73 35.40 35.21

Conditions of polylithionite formation by experimental data

Vasil'ev N.V.*, Zaraisky G.P.**, Schuriga T.N.***.
*-The Institute of Mineralogy, Geochemistry, and Crystal Chemistry of Rare Elements Moscow, Russia.
** - The Institute of Experimental Mineralogy (IEM RAS), Chernogolovka, Russia.
*** - N.M. Fedorovsky Russian Institute of Mineral Materials, Moscow, Russia.

Lithium is very important component of granites, syenites and nepheline syenites. In contrast to the widespread
occurrence of lithian muscovite and lepidolite in granitic pegmatites, polylithionite K(Li 2Al)Si4O10(F,OH)2 is restricted
to alkalic and peralkaline paragenesis. The well-known localities of polylithionite are the Ilimaussaq massif in
Greenland; Mount St. Hilaire in Canada; the Lovozero massif in Kola Peninsula, Dara-i-Pioz massif in Altai, and in
Tajikistan region. Polylithionite stage was one of the main metasomatic stages of Ulug-Tanzek rare metal deposit
formation (Grechishev et al. 1998) and the polylithionite greisens are complex Li-Ta-Nb-REE ores.
 157

At the previous stage of our works, during studying the equilibrium of Kfs - Lepidolite reaction, the wide field of
polylithionite stability is established at LiF, SiO2 saturated conditions. All experiments have been carried out in
hydrothermal conditions (T=400°С, P = 1.0 kbar) in presence of HF solutions. Then we decided to investigate the
interaction of LiF saturated solutions with two types of rocks from Ulug-Tanzek rare-metal deposit (samples 1-Rib and
268/85).
Experiments by duration of 2 weeks were carried out in autoclaves in sealed big platinum capsule (10x100 mm).
Small open Pt capsules (5x25 mm) with rock powder, SiO 2, LiF, natural columbite (Ta2O5 ≈ 8-10 wt. %) were placed
on a bottom of a big platinum capsule, filled with solution. HF concentration of solution was 0,1 m. As a result of
metasomatic interaction with a solution by diffusuion way the rock in small open capsule was transformed into quartz-
polylithionite greisen. The metasomatic column received in the small capsule was taken and studied by a microprobe
analysis. Figure 1 shows photo (BSE) of new-forming polylithionite in experimentally obtained quartz-polylithionite
metasomatite.

Figure 1. New-forming polylithionite (19 and others

grey elongated crystals), cryolite (17) and rare-metal
fluoride (18 and others white separations) in rock
(sample 1-Rib) after experiment.

Then polylithionite zone (2-3 mm length) was selected for the ICP-MS/AES analysis for major and trace elements
(Table 1).

Table 1. Comparison of chemical composition of Ulug-Tanzek rocks before and after experiment.
El-t 1-Rib 1-Rib after 268/ 268/85 after PolGr
85
experiment experiment
Wt. %
Na2 4,37 0,37 1,90 0,38 0,18
O
K2 3,43 7,52 4,43 2,83 7,86
O
Ca 0,03 0,07 1,68 1,03 0,01
O
Al2 9,70 8,36 8,76 3,56 13,41
O3
Mn 0,04 0,05 0,01 0,02 0,23
O
Fe2 1,70 1,51 0,26 0,46 5,86
O3
ppm
Li 736,0 25560,29 28,6 10460,21 22816,1
4 7 4
Rb 1255, 1310,89 145, 242,57 2411,79
01 04
Be 17,91 13,04 3,05 8,05 180,74
Zn 917,8 887,05 47,5 127,79 156,99
0 0
Zr 640,5 200,93 43,3 52,50 323,97
5 2
 158

Hf 29,71 21,31 3,68 9,88 30,89

Y 124,8 198,24 23,9 23,29 13,24
8 5
RE 114,4 182,24 38,2 42,43 99,49
E 1 5
Nb 664,2 713,75 17,2 168,07 1017,94
6 9
Ta 138,7 116,30 1,92 15,68 309,24
6
Th 191,7 180,62 11,0 76,72 744,50
4 5
U 58,01 61,12 2,36 8,88 21,25

The sample of natural Ulug-Tanzek polylithionite greisen (PolGr) was analyzed for comparison.
Concentration of lithium in fluorine rich solutions is controlled by excess of poorly soluble LiF. Presence of even
small amount of lithium (0.01 m) in hydrothermal solution strongly reduces area of quartz-topaz greisen stability and
expands the area of quarts-Li-mica greisen. The saturated by LiF solutions produce quartz-polylithionite metasomatites.
Polylithionite replaces not only Kfs, but it effectively replaces albite with removing sodium. Small amount of residual
sodium produces cryolite Na3AlF6 in our experiments. Simultaneously precipitation of Ta and Nb in metasomatic zones
of greisen column is observed. It is shown that Ta and Nb in conditions of experiments can be gained in a column by
HF solutions and be precipitated in greisen.
Our experiments shows that polylithionite can easily replace feldspars and/or other phases like riebeckite and topaz.
Presence of Li and F volatiles and SiO2 saturation are necessarily. They play a key role for polylithionite formation.
Acknowledgements: Authors thank the Russian Foundation for Fundamental Research (No. 08-05-00835) and
the President RF Grant of Leading Research Schools (SS-3763.2008.5) for the financial support.

References:
Grechishev O.K., Sherbakov Yu. O., Obolenskiy A.A.. The geochemical trend and the evolution regularities of the
Ulug-Tanzek rare-metal deposit (Tuva). // Large and unique deposits of rare and noble metals: 101-109. Nauka. 1998.
(in Russian).

The Zr-Ti mineralization in carbonatites of the Samchampi alkaline carbonatite complex, Assam,
India
Viladkar S.G.*, Sorokhtina N.V.**, Senin V.G.**
* Carbonatite Research Centre, Amba Dongar Kadipani, India; ** Vernadsky Institute of geochemistry and
analytical chemistry, Moscow, Russia

The Zr-Ti minerals are widespread in carbonatites of a many alkaline provinces - Kola Peninsula, Polar Siberia,
Ukrainian, Canada, Brazil et al. We have found calzirtite and zirconolite in calcite carbonatites of the Samchampi
alkaline complex (India). The Samchampi-carbonatite alkaline igneous intrusion is a roughly circular and stock-like
body cropping out in Archaean of the Mikir Hills massif of Assam (eastern India). The Samchampi complex is
composed of syenitic fenite, magnetite-perovskite-apatite rock, phoshatic rock, ijolite-melteigite, carbonatites of varied
dimensions, chert breccia, nepheline syenite, alkali pyroxenite, phonoliteand volcanic tuff [1].
Carbonatites the first generation are presented with olivine-phlogopite sovite and sovite with pyrochlore. The
second generation’s carbonatites are olivine-biotite sovite, beforsite and silicocarbonatites and they are changed
metasomatically often. Carbonatites forms discontinuous dykes and veins intruding silicate rocks of massif.
Representative microprobe analyses of Zr-Ti minerals are listed in Table 1, 2. The chemical composition of
zirconolite grains is inhomogeneous (table 1). Single crystals are commonly zoned with respect to REE, Ca, and Nb.
The composition of zirconolite from the Samchampi has been plotted in terms (according to isomorphic scheme (Th4+
+ U4+) + Ti4+ = REE3+ + (Nb5+ + Ta5+) [2]) together with data of different deposits for comparison (fig. 6). Chemical
compositions for zirconolites from the Samchampi carbonatites follow the general trend typical of syenites and differ
from those recorded for this mineral from the intrusive carbonatites.
 159

Fig.1 (a) backscattered electron images of euhedral zirconolite showing chemical zoning and (b) replacement of
calzirtite (Cz) with zirconolite (Zr) and baddeleyite (Bd) from the Samchampi complex.

Table 1 Microprobe analyses of zirconolite, calzirtite and baddeleyite (wt.%)

1 2 3 4 5 6 7 8 9
N one grain Zr another grain
D-R C L-R L-R Zr Cz Cz Bd Bd
CaO 14.76 12.96 11.37 7.57 12.77 11.95 11.92 0.85 0.16
SrO 0.07 0.11 0.1 0.01 0.15 0.13 0.15 0.18 0.21
BaO 0.21 0.08 b.d. b.d. 0.23 b.d. 0.06 b.d. b.d.
Ce2O3 0.87 1.22 3.01 6.48 1.16 b.d. b.d. b.d. b.d.
La2O3 0.06 b.d. 0.32 0.71 0.09 b.d. b.d. b.d. b.d.
Nd2O3 0.84 1.64 3.27 7.32 1.22 b.d. b.d. b.d. b.d.
ΣREE 1.77 2.86 6.6 14.51 2.47 b.d. b.d. b.d. b.d.
ThO2 b.d. b.d. 0.14 b.d. 0.16 b.d. 0.08 0.16 b.d.
UO2 b.d. 0.15 b.d. b.d. b.d. 0.17 0.06 0.15 b.d.
PbO 0.21 0.2 0.25 b.d. 0.21 0.18 b.d. b.d. b.d.
ZrO2 38.54 37.18 34.95 31 37.48 69.08 69.09 98.45 99.26
HfO2 0.63 0.8 0.97 0.77 0.72 1.36 0.54 0.47 b.d.
TiO2 37.33 39.52 36.94 32.69 36.06 17.04 16.8 0.51 0.31
Nb2O5 0.62 0.96 0.27 0.32 1.5 0.14 0.29 b.d. b.d.
Ta2O5 b.d. 0.07 0.15 0.32 0.16 0.23 0.2 b.d. b.d.
FeO 3.86 4.32 4.88 7.84 4.53 0.83 0.7 b.d. 0.09
MgO 0.08 0.1 0.14 0.13 0.1 0.12 0.1 b.d. b.d.
SiO2 0.11 b.d. 0.13 0.17 0.15 b.d. b.d. b.d. b.d.
Total 98.19 99.31 96.89 95.33 96.69 101.23 99.99 100.77 100.03
b.d.= below detection; R – rim, C – center, D – dark and L - light in backscattered electron
Sovite of the second generation with Zr-Ti mineralisation has been investigated in our studies. Carbonatite is
represented with a medium-grained, magnetite-rich variety, which consists of aegirine, biotite, orthoclase, fluorapatite,
ilmenite, baddeleyite, hematite, calzirtite, zirconolite, chevkinite-(Ce) and sulphides. Calzirtite is a first Zr-Ti mineral
of this association, it forms small (up to 100 µm), euhedral grains, which are replied with zirconolite and baddeleyite
(fig.1). The zirconolite occurs also as small (up to 50 µm) idiomorphic zoned crystal.
 160

4 1

Fig. 2 Y+REE-U+Th-Nb+Ta ternary diagram (wt.%) for Fig. 3 Backscattered electron images of
zirconolites in genetically different rocks. Triangles – Samchampi ilmenite (Ilm) replaced by chevkinite-
carbonatites; circles – syenites (different deposits) and silicocarbonatites (Ce) (Chvk)
(Afrikanda); field 1is for zirconolites of intrusive continental and ocean
carbonatites; field 2 is for zirconolites of chromitites (Finero); field 3 is for
zirconolites of lamproite (Peruvian Altiplano); field 4 is for zirconolites of
hydrothermal rocks; field 5 is for zirconolites of metasomatic rocks; field 5 is
for zirconolites of lunar rocks. Data are from our data base “Carbonatite”
N0220611462.

Table 2 Microprobe analyses of magnetite, ilmenite and chevkinite-(Ce) (wt.%)

1 2 4 5 6 7 8 10
N
Mgt Ilm Chvk
FeO 93.45 90.43 41.98 38.59 4.97 5.67 7.78 5.93
MgO 1.02 2.04 5.48 8.13 3.02 2.20 2.26 2.00
TiO2 1.32 3.11 49.87 51.75 17.42 16.43 15.81 17.66
CaO 0.05 b.d. 0.43 0.03 4.08 2.96 2.37 4.47
MnO - 0.44 - 1.79 0.08 0.08 b.d. 0.07
La2O3 b.d. b.d. b.d. 0.12 14.52 14.61 15.67 14.32
Ce2O3 0.02 0.08 0.31 0.08 26.14 25.20 26.54 24.69
Pr2O3 - 0.13 - b.d 2.50 1.90 2.26 1.92
Nd2O3 0.05 0.07 b.d. b.d. 6.60 6.74 6.27 5.48
Sm2O3 - b.d. - b.d. 0.46 0.51 0.53 0.35
Σ REE 0.07 0.28 0.31 0.21 50.22 48.96 51.27 46.76
Nb2O5 b.d. b.d b.d. b.d b.d. 0.12 b.d 0.04
Ta2O5 0.07 b.d. 0.26 b.d. b.d. 0.22 b.d b.d.
ZrO2 b.d b.d. 0.05 0.08 0.21 0.00 0.33 0.20
HfO2 0.41 b.d. 0.68 0.12 b.d. b.d. b.d. b.d.
SiO2 0.06 0.05 0.04 0.36 20.54 20.50 19.57 20.57
Total 96.46 96.38 99.10 101.07 100.54 97.14 99.43 97.70
b.d.= below detection, - not determined

Chevkinite-(Ce) is the only REE-bearing accessory mineral in carbonatites of the Samchampi massif (fig.3) . The
minerals of the chevkinite group are widespread in pegmatites of peralkaline granites and syenites, mafic gabbros,
fenites, granulite facies gneisses, but occur occasionally in carbonatites [3]. Chevkinite-(Ce) forms a thin corona around
ilmenite and magnetite grains. Apparently the chevkinite-(Ce) was formed by hydrothermal alteration of ilmenite or
magnetite in the late stage of carbonatite.
Calzirtite, zirkelite and baddeleyite are primary Ti-Zr minerals of the Samchampi carbonatites. During the
transformation of the calzirtite, Zr was liberated to produce baddeleite and zirconolite. Thus, hydrothermal alteration of
 161

carbonatites in the Samchampi massif causes evolutional changes of mineral associations. The trends of the
transformation of primary Ti and Zr-minerals can be presented as: calzirtite - baddeleyite + zirconolite and ilmenite
(magnetite) - chevkinite-(Ce).
Research covered by the RFFI grant

References:
1 Nag S., Sengupta S.K., Gaur R.K., Absar A. Alkaline rocks of Samchampi-Samteran, District Karbi-Anglong,
Assam, India // Proc. Indian Acad. Sci. (Earth Planet Sci.). 1999. V. 108. N 1. P. 33-48.
2 Bellatreccia F., Della Ventura G., Williams C.T., Lumpkin G.R., Smith K.L., Colella M. Non-metamict
zirconolite polytypes from the feldspathoid-bearing alkali-syenitic ejecta of the Vivo volcanic complex (Latinum, Italy)
// Eur. J. Mineral. 2002. V. 14. P. 809-820.
3 Macdonald R., Belkin H.E. Compositional variation in minerals of the chevkinite group // Min. Mag. 2002. V.
66. N 6. P. 1075-1098.

Geochemistry of isotopes (Sr-Nd) and TR of lamproites from the Aldan shield

Vladykin N.V.
Institute of Geochemistry SB RAS, Irkutsk, Russia

Lamproites of the Aldan Shield were found (Vladykin 1985) at the beginning of 80-es (for the first time in the
USSR), being mainly the intrusive varieties of lamproites, though there occur among them some dyke and volcanic
varieties. The general geological and geochemical features of lamproites of the Aldan shield were reported at the VI
International Kimberlite Conference at Novosibirsk in 1995 (Vladykin 19971).
As of now, on the Aldan Shield there are known 14 deposits of lamproites in the following massifs. Twelve of
the lamproites objects are connected with the Mesozoic rift magmatism of the Aldan Shield. This zone stretches out
over all Aldan Shield, from the Murun massif in the Western part of the shield up to the Konder massif in the Eastern
part of the shield. These occurrences of lamproites are of Jurassic age (120-150 m.a.). Only lamproites of Khani massif
in the SW part of the Aldan Shield are more ancient. At first (according to the data of V.V.Arkhangelskaya) the Khani
massif was considered to be Paleozoic, then using K-Ar method (VSEGEI) it was established Proterozoic age of biotite
pyroxenites of the massif 1800 m.a. We found the dyke of olivine lamproites of the massif that crosses the biotite
pyroxenites. We obtained even more ancient age – 2700 m.a. by zircons from these lamproites with a device SHRIMP
(VSEGEI) (Vladykin, Lepekhina - 2005).
New data on Sr-Nd – systematization of the lamproites of the Aldan Shield have been obtained. The ratios
87Sr/86Sr in lamproites of Aldan vary from 0.703 to 0.708, whereas έ Nd – from -6 to -25. The source of Aldan Shield
lamproites is enriched mantle ЕМ-1 (fig. 1), that is consistent with their geological position (Vladykin -1997). They are
situated between the Aldan Shield and the Siberian platform, where did not occur subduction. The North American
lamproites (Leucite Hills, Smoky Bewt, Prery Creak ecc) have similar position between the Canadian shield and the
North-American platform and the same mantle source.

Fig. 1. Diagram of ratios of epsilon Nd and 87Sr/86Sr in lamproites and carbonatites.

 162

(Circles- carbanatites of the framing of the Siberian Platform, Squares – lamproites of Aldan, Russia and USA,
Triangles-carbonatites and lamproites –Australia, Spain of folded areas)

Compared to the Australian lamproites, the lamproites of the Aldan Shield have lower concentrations of rare-
earth elements. The TR spectra for the Aldan lamproits (fig. 2) are rather uniform. A slight slope of the spectrum curves
and slight Eu-anomaly are typical for them. For the earlier olivine lamproites lower TR concentrations are typical as
compared with more differentiated leucite and sanidine lamproites.

Fig. 2. TR spectra in lamproites of Aldan Shield : 1-Fsp- lamproite, 2- 3-olivine lamproites

The lamproites of the Aldan Shield originated from the enriched mantle source ЕМ-1, the age of that, according
to Pb isotopic data, obtained for the rocks of the Murun massif (Vladykin 1997 2) is estimated as 3200 m.a. The dykes of
the olivine lamproites of the Khani massif are the oldest lamproites in the world (2700 m.a.). The TR spectrum of the
same type is indicative of similar genesis of the lamproites from various massifs of the Aldan Shield. In spite of the
deep mantle source of the Aldan lamproites, they don’t bear diamonds actually, since the diamonds were likely burnt
during their crystallization (at t- 1200-1000o C).
The studies were supported by Russian Foundation for Basic Research, grants 09-05-00116, 08-05-9000.

References:
Vladykin N.V. First occurence of lamproites in the USSR.//Doklady Academii Nauk SSSR, 1985, Vol..208, N 3,
p.718-722. (in Russia).
Vladykin N.V. Geochemistry and genesis of lamproites of the Aldan shield // Geology and Geophysics. 6 Inter.
Kimber. Conf., Russia, Novosibirsk, 19971, Vol. 38, № 1, p. 130-145. (in Russia).
Vladykin N.V. Petrology and ore potential of K-alkaline rocks of the Mongol-Okhotsk magmatic area. Thesis as
scientific report, 19972, p.1-80. (in Russia).
Vladykin N.V Lepekhina E.N. Age of xenogenic zircons from kimberlites of Yakutia.//Evolution of Continental
Lithosphere, Origin of Diamonds and Diamond Depsits. Novosibirsk, 2005, p. 158.

Study of the nature of magmatic complexes using NRE ratio values

Volodkova T.V.
Yu. A. Kosygin Institute of Tectonics and Geophysics, Khabarovsk, Russia

The major part of ore regions of Priamurye is covered by aerogeophysical survey (aeromagnetic prospecting,
aerogammaspectrometry) scale of 1:50000-1:10000, using complex aerogeophysical station devices SKAT—77 an
STK-11. Measurement accuracy of the natural radioactive elements (NRE) content attains to the following values: for
uranium - (0.1-0.15)*10-4%,–for thorium – (0.55-0.65)*10-4%, for potassium – (0.05-0.10)%. Magmatic complexes are
characterized by average background U/Th, K/Th, U/K ratio values; as compared to NRE contents, these are less
dependent on survey errors and are commensurable with the results obtained by ground survey. The confidence level
values (±σ) attain to: U/Th – 0.1; K/Th – 0.1; U/K – 0.25.
In terms of isotopic geology, uranium, thorium and potassium are a part of a group of extremely incompatible
elements-indicators of magmatic processes. Unaltered rocks, formed due to processes of crystallization differentiation
 163

in closed magma chambers are characterized by constant NRE ratios irrespective of the composition. They are close in
age, being related to the main stages of a single magmatic cycle, which is comparable with the time of existence of
magma chamber. Hydrothermally-metasomatically altered rocks (degree of alteration of more than 10-20 %) are
distinguished by the anomalous NRE ratios. In the open magma chambers conditions for crystallization vary from phase
to phase due to deep fluid inflow, therefore, the average NRE ratio values will vary regularly for magmatic rocks. The
background NRE ratio values vary sharply for magmatic complexes due to affecting hydrothermal-metasomatic
processes, mantle metasomatism and geodynamic environments. It has been elaborated methodology taking into
consideration the influence of hydrothermal-metasomatic processes on NRE ratio characteristics, such data are
eliminated from sampling when making statistical reports. The mantle metasomatism and juvenile fluidization are
typical of plume magmatism; intrusion of exclusively subalkali and alkali rocks is associated with it. In Priamurye
magmatic rocks of plume nature are associated with hot spot areas and the Maya-Selemdzha plume which are
distinguished from geological-geophysical data. The NRE ratio characteristics for subalkali rocks are weakly
anomalous (weak fluid inflow); these may reach “hurricane” values for alkali rocks (the Ingili, Arbarastakh massifs).
The U/K ratio can be used as a geodynamic criterion. Purely subduction (Andean) amphibole-bearing biotite
granitoids as well as those transitional to collisional (early collisional) can be referred to I-type (U/K≥ 0.75). Taking
into consideration the U/K ratio value, one can refer calcareous plagiogranites, the Kurile island arc granites to I-type.
The category of collisional granitoids of S-type (U/K=1.30-1.75) includes syncollisional and late collisional
granitoids; we can distinguish post-collisional and proper intraplate ones among the magmatic rocks of А-type. The
post-collisional granitoids are characterized by U/K=0.75-1.30 values; as for intraplate rocks with increased
alkalinity, associated with plume effect, U/K≤0.75 values are typical. Taking into consideration the U/K ratio the
island-arc granitoids (the Kuriles), namely: quartz diorites, diorites, calc-alkali gabbroids are referred to М-type.
From geophysical data, the Kurile subduction calcareous granitoids are associated with the crustal magma sources,
while those of М-type –with the mantle ones being formed due to the Kurile mantle diapir (plume) (Volodkova,
2008). Granitoids formed due to the mantle sources, the intraplate continental (A-type) and island-arc (M-type) ones,
are not differentiated from the U/K ratio criterion; for the granitoids of both categories increased alkalinity is typical
and the U/K ratio values are significantly lower as compared to characteristics of depleted mantle. By all appearances,
both categories of granitoids are formed due to the mantle metasomatism processes.
Geodynamic types of magmatic rocks are determined by the processes occurring within the lithosphere and
asthenosphere; magmas of plume nature reflect deeper physical-chemical conditions. The formation of EM I, EM II,
HIMU mantle reservoirs is related to the plume influence (Weaver, 1991); EM I and HIMU reservoirs are
contrastingly distinguished, while EM II one is close to the crustal parameters according to NRE ratios. It is in
consistency with the well-known point of view on the formation of EM II from the continental crust due to recycling.
Taking into account the NRE ratio values, the magmatic complexes with increased alkalinity are to either
extent formed due to the following sources (Volodkova, 2008):
1. EM I source (U/K <0.75);
2. HIMU source (U/K >1.75);
3. Rocks with intermediate characteristics of NRE ratio of 1.25<U/K<1. 75 more rarely occur; they are formed
based on substrate with ingreased basicity, recycled by deep fluids;
4. Probably, EM I and HIMU sources characterize two mantle levels of different depth;
5. Geodynamic types of magmatic rocks are related to the plume processes and can be formed as follows: I-
type –due to HIMU mantle source, A-type – due to EM I mantle source.

Table Characteristics of average NRE ratio values for normal granitoids in different geodynamic environments.

Name of intrusive (IC) and volcanic NRE ratio values Notes*2

(VC) complexes*1 U/Th K/Th U/K
Continental crust CC 0.23 0.25 0.85 Nikolaeva, 1997; Ryabchikov, 1997
Sedimentary layer 0.20 0.20 0.20 Smyslov, 1974
Granite-metamorphic layer 0.25 0.20 1.28 Smyslov, 1974
Andesite-metamorphic layer 0.21 0.21 1.00 Smyslov, 1974
Granulite-basic 0.33 0.50 0.66 Smyslov, 1974
Primitive mantle РМ 0.26 0.30 0.94 Ryabchikov,1997; Flerov,2001
Depleted mantle DM 0.40 0.53 0.80 Ryabchikov, 1997; Khain, 2002
Enriched mantle EM I 0.08 0.17 0.45 Woodhead, 1989; Weaver, 1991
Enriched mantle EM II 0.49 0.49 1.00 Wilson, 2001; Weaver, 1991
Enriched mantle HIMU 0.25 0.10 2.51 Chauvel, 1992
Ultrabasic rocks 0.37 1.7 0.20 Bazilevsky, 1985
Alaskite granites 0.50 0.28 1.75 Bazilevsky, 1985
Meimechites, ijolites 0.27 0.18 1.45 Bazilevsky, 1985
Nepheline agpaite syenites 0.36 0.18 2.04 Bazilevsky, 1985
Basalts, trachydacites, J3-K1 0.33 0.57 0.80 Subalkali range, Mongolia and Trans-Baikal,
 164

Plateaubasalts, basalt-comendite- 0.32 0.58 0.56 Yarmolyuk, 2003

pantellerite associations, PZ3-MZ1
Alkali basalts, source is close to DM, 0.25 1.01 0.20 Mongolia, Khubsugul, Genschaft, 2006
KZ1
Alkali basalts, source is DM+HIMU, 0.23 0.48 1.10 Mongolia, Deriganga, Genschaft, 2006
KZ1
Alkali basalts, source is DM+EM, KZ1 0.33 0.90 0.63 Mongolia, Khangai, Genschaft, 2006
Konder IC, ultrabasic alkali rocks, PR1 0.45 0.25 1.3 Subalkali range, Konder massif,
Quartz subalkali diorites, K1 0.45 1.10 0.75
Granites, porphyry-like monzodiorites, 1.05 0.80 1.15 Kalar massif, normal-subalkali range of Na-
PZ1 series
Leucocratic syenites, PZ1 1.25 0.50 0.85
Ingili IC, alkali-ultrabasic rocks, PR3 0.28 0.08 4.75 Ingili and Arbarastakh massifs, alkali range of
Arbarastakh IC, alkali-ultrabasic rocks, 0.82 0.13 15.0 K-Na series
PR3
Amphibole-bearing calc-alkali 0.25 0.14 1.73
Australia, Rozen, 2001
granitoids of I-type
Porphyry-like biotite granites of I-type 0.29 0.14 2.10 Tyrnauz, Rozen, 2001
Felsic rocks with decreased alkalinity 0.40 0.30 1.90
The Kuriles, Volodkova, 2007
of subduction I-type
High aluminous collisonal granitoids of 0.26 0.18 1.47
Australia, Rozen, 2001
S -type
Felsic calc-alkali island-arc rocks of 0.20 0.30 0.65
The Kuriles, Volodkova, 2007
М-type
Monzonites of А-type 0.11 0.17 0.66 Trans Baikal, Tsigankov, 2007
Quartz syenites of A-type 0.16 0.08 0.16 Trans Baikal, Tsigankov, 2007

References
1. Volodkova T.V. Characteristics of alkali rocks of Priamurye from aerogammaspectrometry data // Alkali
magmatism of the Earth. St. Petersburg, 23-26 May, 2008. (in Russian). P. 27.
2. Volodkova T.V. Granites and Earths Evolution: geodynamic Position, Petrogenesis and Ore Content of
Granitoid Batholiths. Ulan-ude, 26-29 August 2008. (in Russian). P. 68-71.
3. Barry L. Weaver. The origin of ocean island basalt end-member compositions trace element and isotopic
constraints // Earth and Planetary Science Letters. 1991. Vol. 104. P.381-397.

First data on composition of volcanic rocks from the northern part of Sredinny Range, Kamchatka
Volynets A.O.*, Pevzner M.M.**
*Institute of volcanology and seismology FED RAS, Petropavlovsk-Kamchatsky, Russia
**Geological Institute RAS, Moscow, Russia

This study is focused on composition of volcanic rocks from the northernmost part of Sredinny Range of
Kamchatka. Sredinny Range (SR) represents a back-arc of the present Kamchatka subduction system according to the
most researches’ opinion (Avdeiko et al., 2002; Churikova et al., 2001, etc.); Benioff zone is located at 350 km depth in
the southern part of SR, beneath Khangar volcano, and is not observed further to the north (Gorbatov et al., 1997).
Active volcanic front ends on the latitude of Shiveluch volcano. Nevertheless, recent geochronologic research revealed
Holocene eruptions in SR up to 180 km to the north-north-west from Shiveluch: Spokojny volcano (N 58° 08’, E
160°49’) was active in early and middle Holocene, last eruption 5400 14C years B.P.; Nilgimelkin monogenetic lava
field (N 57° 58’, E 160° 39’) was formed during fissure eruption 5500 14C years B.P.; X cinder cone (N 58° 10’, E 160°
48’) erupted 4000 14C years B.P.; and the youngest edifice, Tobeltsen cinder cone and lava flow (N 58 ° 15’, E 160° 44’),
were formed around 3500 14C years B.P. (Pevzner, 2006). Here we present first data on composition of major and some
microelements of the volcanic rocks produced by Pleistocene eruptions of Spokojny volcano and surrounding
monogenetic lava field, Pleistocene Snegovoj shield volcano; Holocene Nilgimelkin and Tobelsten monogenetic cinder
cones and underlying Neogene lava flows.
All studied rocks belong to calc-alkaline medium- to high-K series and fall into the field of previously studied
volcanic rocks from the other parts of Sredinny Range (Volynets et al., submitted; Volynets, 2006; Churikova et al.,
2001). Most samples are basaltic andesites, with some basalts and andesites; products of Pleistocene Spokojny volcano
and Neogene lavas, exposed in the upper part of Cherpokvejem River, are represented by dacites. Plateau-basalts are
exposed in the upper part of Voyampolka River. Two trends can be identified on K 2O-SiO2, MgO-CaO, Rb-MgO
diagrams (Fig.1A)
 165

Holocene Tobeltsen and Nilgimelkin basaltic andesites, Pleistocene Snegovoj andesites, monogenetic lavas of
the Voyampolka headwaters and andesitic monogenetic lava flow near Spokojny volcano compose first trend. These
rocks belong to medium-K series; they have rather low Mg content (3.17-4.59 wt.% for basaltic andesites and 3.15-3.51
wt.% for andesites). Pleistocene monogenetic lavas of Spokojny volcano surroundings compose second trend. It is
characterized by higher K2O content (the samples are actually located on the margin between medium and high-K
rocks), higher MgO (3.51 wt.% (andesite) -7.32 wt.% (basalt)). At the same MgO content, rocks, forming second trend,
are slightly more CaO-rich. Spokojny’ dacites are more alkali-rich and lye on the boundary of dacites and trachydacites
on the classification diagram Na2O+K2O – SiO2. A single sample of Neogene plateau-basalts from Voyampolka River
is located on Harker diagrams between plateau-basalts from Left and Right Ozernaya Rivers and is similar to Right
Ozernaya plateau-basalts by microelements content (Volynets et al., submitted, Volynets, 2006). In general, analyzed
samples have the same concentrations of V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Ba, Nb, and Y as previously studied volcanic
rocks of Sredinny Range (Volynets et al., submitted; Volynets, 2006). Concentrations of fluid-mobile elements are more
or less constant in all samples from basalts to andesites: Ba 400-700 ppm, Sr ~500 ppm, Rb 8-22 ppm. Due to the fact
that Ba and Nb have similar partition coefficient in melt, but behave quite opposite way in fluid, Ba/Nb ratio does not
depend on partial melting processes and immediately increases at fluid presence, so it can be used as indicator of fluid
involvement. Most studied rocks have Ba/Nb 30-80 (Fig.1B), what means that these rocks contain moderate amount of
fluid in the source. Neogene lavas and Pleistocene monogenetic lava flow in the Cherpokvejem River headwaters have
higher Ba/Nb ratio: 168-202 and 123, respectively; this indicated substantial fluid influence to magma genesis in a zone,
where no active subduction is registered by modern geophysical data. Nb/Y ratio in studied volcanic rocks varies in a
wide range from 0,14 to 0,74 (Fig.1B). Lowest values are typical for Neogene lavas, both acid and basic. Higher Nb/Y
ratio, observed in Pleistocene surroundings of Spokojny volcano and northernmost sampled sites, may be connected
either with lower degrees of melting in the source, or with enrichment of the source with HFSE (which is also reflected
in high Nb content in these samples: 13-18 ppm). Previous studies have shown, that OIB-like mantle source
involvement in magma generation is necessary for explanation of the specific features (i.e. HFSE enrichment) of the SR
volcanic rocks (Volynets et al., submitted, Volynets, 2006, Churikova et al., 2001). Available data for the north of SR
do not allow making a well-reasoned conclusions regarding mantle, slab and/or other sources in magma genesis, and
further research should be done; nevertheless, similarity of the geochemistry of the volcanic rocks from the north part of
SR with the volcanic rocks from the rest of SR suggests relatively similar source composition and uniform melting
process within the whole Sredinny Range. Therefore, presence of young (Late Pleistocene and Holocene) volcanic
 166

centers in the north SR and geochemical characteristics of their products, indicating involvement of slab component and
OIB-like source in their genesis, again raise up a question of the geodynamic situation in this region.
This study was financially supported by RFBR grant 07-05-00536, 08-05-00092, FED RAS 09-III-В-08-465,
Program 16 of RAS Presidium.

References:
Avdejko G.P., Popruzhenko S.V., Palueva A.A. Tectonic Evolution and Volcano-Tectonic Zoning of Kurile-
Kamchatka Island-arc System // Geotectonic, 2002. Volume 4, p. 64-80 (in Russian)
Churikova T., Dorendorf F., Woerner G. Sources and fluids in the mantle wedge below Kamchatka, evidence
from across-arc geochemical variation // Journal of Petrology, 2001. Volume 42 (8), p. 1567-1593
Gorbatov A., Kostoglodov V., Suarez G. Seismicity and structure of the Kamchatka subduction Zone // Journal
of Geophysical Research, 1997. Volume 102 (B8), p. 17883 – 17898
Pevzner M. Holocene volcanism of the Northern Kamchatka: space and time aspects // Dokladi RAS, 2006.
Volume 409, #5. P. 648-651 (in Russian)
Volynets A. Pleistocene-Holocene volcanism of Sredinny Range, Kamchatka: composition of rocks and
geodynamic model. PhD thesis, Moscow, 2006, 145 p. (in Russian).
Volynets A., Churikova T., Woerner G., Gordeychik B., Layer P. Mafic Late Miocene - Quaternary volcanic
rocks in the Kamchatka back arc region: implications for subduction geometry and slab history at the Pacific-Aleutian
junction // submitted to Contributions to mineralogy and petrology.

Occurrence and compositional variation of high-Na-Al melilites at Oldoinyo Lengai, Tanzania

Wiedenmann D.*,**, Keller J.***, Zaitsev A.N.****
* Department of Geoscience, University of Fribourg, Pérolles, 1700 Fribourg, Switzerland
** Swiss Federal Laboratories for Material Testing and Research, Hydrogen and Energy,
Überlandstrasse 129, 8600 Dübendorf, Switzerland
*** Institute of Geoscience, University of Freiburg, Albertstrasse 23b, 79104 Freiburg, Germany
**** Department of Mineralogy, St. Petersburg State University, University Emb. 7/9, St. Petersburg
199034, Russia
* Corresponding author Tel.: +41 44 823 48 62; fax: +41 44 823 40 22; Email address:
[email protected]

Oldoinyo Lengai is the only active carbonatite volcano in the world and is located in the Gregory Rift Valley, the
northern Tanzanian sector of the East African Rift System. The volcano is famous for its unique low-temperature and
low-viscosity natrocarbonatites, however silicate lavas and pyroclastics dominantly build up the 3000 m high cone
(phonolites and nephelinites). Detailed fieldwork at Oldoinyo Lengai and the volcanic centres around showed melilite
as a widespread mineral in silicate lavas of the province. Extraordinary Na-rich melilites (> 6 wt.% Na2O; > 9 wt.%
Al2O3) from younger explosive eruptions range among the most Na-rich åkermanites ever reported. Their unusual
mineral chemistry leads to unusual optical properties with vivid birefringence colours of the 2 nd and 3rd order under
crossed nicols. In this context, a new mineral named Alumoåkermanite (Ca,Na) 2(Al,Mg,Fe2+)(Si2O7), was described and
accepted by IMA in December 2008. The mineral (space group P421m) has straight extinction, positive elongation,
and is nonpleochroic. Alumoåkermanite occurs as tabular phenocrysts (up to 1.5 mm) and microphenocrysts in evolved
olivine free melilite-nephelinitic ashes and lapilli-tuffs. Alumoåkermanite has a Mohs' hardness from 4.5 to 6 and is
uniaxial (–) with ω = 1.635(1) and ε = 1.624-1.626(1). The variation in mineral chemistry ranging from sodium
enriched åkermanites to high sodium-melilites (alumoåkermanites) reflects the peralkaline evolution trend from
primitive olivine melilitites to highly evolved, melilite-bearing combeite-wollastonite nephelinites. Melilite
compositions extend the magmatic field in the Ca2FeSi2O7 - Ca2MgSi2O7 - CaNa(Al,Fe3+)Si2O7 endmember triangle
(figure 1).
 167

Fig. 1: Classification of Oldoinyo Lengai melilites in terms of åkermanite Ca 2MgSi2O7, sodium-aluminium

melilite CaNa(AlFe3+)Si2O7, and ferro-åkermanite Ca2FeSi2O7. Filled circles: melilite data of this study. Squares:
publishes Lengai data.
This work was supported by Deutsche Forschungsgemeinschaft (grant Ke 136/40) and Alexander von Humboldt
Stiftung.

References:
Dawson J.B. Peralkaline nephelinite-natrocarbonatite relationships at Oldoinyo Lengai, Tanzania // Journal of
Petrology. 1998. Vol. 39. P. 2077-2094.
Dawson J.B., Pyle D.M., Pinkerton H. Evolution of natrocarbonatite from a wollastonite nephelinite parent: evidence
from the June 1993 Eruption of Oldoinyo Lengai, Tanzania // Journal of Geology. 1996. Vol. 104 P. 41-54.
Dawson, J.B., Smith, J.V. and Jones, A.P. A comparative study of bulk rock and mineral chemistry of olivine melilitites
and associated rocks from East and South Africa // Neues Jahrbuch Mineralogischer. Abhandlungen. 1985. Vol. 152. P.
143-175.
Donaldson, C.H. and Dawson, J.B. Skeletal crystallization and residual glass compositions in a cellular alkalic
pyroxenite nodule from Oldoinyo Lengai // Contribution to Mineralogy and Petrology. 1987. Vol. 67. P. 139-149.
Donaldson, C.H., Dawson, J.B., Kanaris-Sotiriou, R., Batchelor, R.A. and Walsh J.N. The silicate lavas of Oldoinyo
Lengai, Tanzania // Neues Jahrbuch fuer Mineralogie. Abhandlungen 1987. Vol. 156. P. 246-279.
Keller, J. and Krafft, M. Effusive natrocarbonatite activity of Oldoinyo Lengai, June 1988 // Bulletin of Volcanology.
1990. Vol. 52. P. 629-645.
Keller, J., Zaitsev, A.N. and Wiedenmann, D. Primary magmas at Oldoinyo Lengai: The role of olivine melilitites //
Lithos. 2006. Vol. 91. P. 150–172.
Klaudius, J. and Keller, J. Peralkaline silicate lavas at Oldoinyo Lengai, Tanzania // Lithos. 2006. Vol. 91, 173–190.
Wiedenmann, D. Vulcanological position and petrological interpretation of biotite-pyroxene-olivine-tuffs from
Oldoinyo Lengai, Tanzania // Diploma thesis (in German language), University of Freiburg im Breisgau, 2004, 89 pp.
Wiedenmann, D., Keller, J., Zaitsev, A.N. and Vogt, U. (2009) Occurrence and compositional variation of high-Na-Al
melilite group minerals at Oldoinyo Lengai, Tanzania. 2009. (in preparation).
Wiedenmann, D., Zaitsev A.N., Britvin S.N., Krivovichev, S.V., Keller, J. Alumoåkermanite,
(Ca,Na)2(Al,Mg,Fe2+)(Si2O7), a new mineral from the active carbonatite-nephelinite-phonolite volcano Oldoinyo
Lengai, northern Tanzania // Mineralogical Magazine, 2009 (submitted).

Genesis of carbonatites: inferences from a world map and database

Woolley A.R.
Department of Mineralogy, Natural History Museum, London, United Kingdom.

A recently published world map and database of carbonatites (Woolley and Kjarsgaard, 2008) includes data that
provide insights, some new, into the spatial and temporal distribution and petrogenesis of carbonatites. 527 carbonatite
occurrences are briefly described and their plotting on a world geology base map demonstrates (a) that in many
provinces there has been repeated emplacement of carbonatites over geological time, (b) that there are few carbonatites
in oceanic areas, most of which lie close to continental margins, (c) that there is an overwhelming concentration in
Precambrian cratons (perhaps as much as 86%), including occurrences of Phanerozoic age, and (d) that many of these
cratonic areas are ‘domed’ i.e. are topographically elevated. The repetition of carbonatite emplacement in restricted
areas of continental lithosphere/plate, which have generally drifted considerable distances between episodes of
carbonatitic volcanism, must preclude any genesis involving mantle plumes, and underlines the crucial role that the
 168

lithosphere undoubtedly plays in carbonatite generation. The doming of the carbonatite-bearing cratonic areas is
interpreted as reflecting metasomatism of the lithosphere, the metasomatism being concentrated, initially at least, by
structural features leading to ‘lithosphere focussing’.
The database comprises short descriptions of all 527 carbonatites together with tabulated information on
economic aspects, including working deposits, and a range of subsidiary maps. Some 50 occurrences include extrusive
carbonatite and these are particularly significant because 20 of them contain mantle xenoliths and/or xenocrysts, with
none found in intrusive carbonatites, which gives direct evidence of a mantle origin and metasomatism, and pressure
(depth) and temperature data. The igneous silicate rocks found in association with carbonatites are tabulated and form
an extensive range of rock types which fall into six series i.e. kimberlite, melilitite (melilitolite), nephelinite (ijolite),
phonolite (foid syenite), basanite (alkali gabbro) and trachyte (syenite). About 20% of carbonatites have no associated
silicate rocks. The extrusive carbonatites demonstrate one major difference from the intrusive ones in that nearly half of
them are associated with melilite-bearing rocks, whereas the equivalent association in the intrusives is found in <10% of
occurrences. The relative abundance of melilite-bearing rocks amongst the extrusive carbonatites is believed to reflect
one of the major, if not the main, paths of carbonatite evolution, while the relative paucity of these rocks amongst
intrusive carbonatites is considered to be owing to loss during multiple high-level emplacement and volcano growth as
well as reflecting the instability of melilite in later melt fractions. Finally, essentially utilising the evidence of the map
and database, a model is presented in the form of a lithosphere section, metasomatised in the lower part, in which
carbonatites are either generated at depth directly in the mantle or at higher levels by fractionation from at least five of
the six silicate series. The silicate series vary in depth of origin from kimberlite at the base of the lithosphere, or within
the uppermost asthenosphere, through melilitites and nephelinites to relatively shallow originating phonolites and
basanites. Some cognisance is also taken of known alkali silicate differentiation series. All the silicate series rocks also
occur in carbonatite-free associations so that the impression is gained that carbonatites are only generated when a
particular type of metasomatism is superimposed on lithosphere mantle which, in its absence, has the potential to
produce the silicate rocks anyway. However, the silicate rocks, being essentially alkaline, themselves probably have
antecedants involving mantle metasomatism, albeit chemically distinct from that leading to carbonatite generation.

Reference:
Woolley, A.R. and Kjarsgaard, B.A. 2008. Carbonatite occurrences of the world: map and database. Geological
Survey of Canada, Open File 5796. 1 CD-ROM and 1 map.

Mineralogical and geochemical features of high-alumina fenites of the Mont Saint-Hilaire alkaline
complex, Québec, Canada
Yakovleva O.S.*, Pekov I.V.*,**, Bryzgalov I.A.*, Horváth L.***, Yapaskurt V.O.*, Guseva E.V.*
1
Moscow State University, Faculty of Geology, Moscow, Russia; 2Institute of Geochemistry and Analytical
Chemistry of RAS, Moscow, Russia; 3Hudson Heights, Québec, Canada.

The Mont Saint-Hilaire complex, part of the Monteregian Hills alkaline province, is situated 40 km east of
Montréal, Québec, Canada, forming a roughly circular intrusion emplaced in Ordovician shales and limestones. Total
area of the massif is about 8 km2. The Mont Saint-Hilaire complex was formed by three separate igneous intrusion
phases, which resulted in three distinct suites of intrusive rocks; the oldest (western) one is represented by basic and
alkaline ultrabasic rocks such as several varieties of gabbros and jacupirangites; the second suite includes nepheline
gabbros, diorites and monzonites and biotite trachygabbro; the youngest (eastern), alkali-rich intrusive suite consists of
nepheline syenites (including their peralkaline varieties), their pegmatites, igneous breccias and various xenoliths. Thick
hornfels aureole surrounding the massif is a product of the contact metamorphism (Currie et al., 1986). High-alumina
rocks found at Mont Saint-Hilaire have not been studied before, only the occurrence of corundum, columbite and
hercynite were noted. This paper is the first systematic characterization of these rocks, considered by us as specific
fenites.
High-alumina rocks, uncovered in the Poudrette quarry, form small bodies at the contact of alkaline pegmatites
with hornfels and granites. Also they replace granite veins. These fenites are fine- to medium-grained rocks consisting
substantially of feldspars (albite, K,Na feldspar and potassic feldspars are abundant, albite-oligoclase is subordinate).
Hercynite (in all the rocks discussed below) and biotite (in almost all rocks) are the other rock-forming minerals.
Typically biotite is high-alumina annite close to siderophyllite. Sporadically nepheline becomes a rock-forming mineral.
We have subdivided the high-alumina oxide-silicate rocks of Mont Saint-Hilaire to four types:
(1) A rock with significant biotite content (to 15%). Isolated spessartine crystals (up to 1 cm) are typical for this
rock. Concentrically-zonal polymineral rims surround spessartine crystals. Internal part of a rim consists of biotite with
Mn-rich hercynite inclusions, whereas the outer part is composed of pyrrhotite with chalcopyrite and pyrophanite
inclusions. Corundum is a typical accessory mineral.
(2) A rock with corundum-hercynite intergrowths surrounded by annite rims (sometimes with muscovite).
Siderite is typically observed in cores of hercynite grains. The rock contains rare impregnation of pyrrhotite and
manganocolumbite.
(3) A rock with Zn-rich hercynite grains with annite rims and intergrowths of biotite and muscovite. A lot of
zoned well-shaped and skeletal zircon crystals occur there. The rock is strongly altered and contains different
 169

carbonates: siderite–magnesite series members, ankerite, dolomite; calcite, mckelveyite, Ca,REE fluorocarbonates are
subordinate; late natrolite and fluorite are also present. Accessory minerals are members of the ferrocolumbite–
manganocolumbite series, ilmenite, Nb-bearing rutile (var. ilmenorutile), uedaite-(Ce), pyrrhotite, monazite-(Се),
xenotime-(Y), and a Ti-free REE niobate, probably fergusonite-(Ce). Isolated inclusions consisting of quartz (60%) and
biotite (typically annite) (40%) are observed in a rock. Some biotite crystals contain inclusions of metacrystals of Ti-
bearing spinelides of the magnetite-chromite series.
(4) A rock with equal impregnation of Zn-rich hercynite (up to 20%), accessory zircon and ilmenite (with
ferrocolumbite microinclusions). Sporadically, hercynite forms aggregations containing clusters of zircon with thorite
inclusions. There are big (up to 6 mm) equant idiomorphic crystals of Fe-rich spessartine, as well as isolated corundum
crystals (up to 1 mm) intergrown with muscovite in the rock. Pyrophanite, pyrrhotite, chalcopyrite, sphalerite, galena
and rhodochrosite are also present in this rock.
Similar rocks are known in large fenitized xenoliths in the Khibiny massif (Kola Peninsula, Russia) (Shlyukova,
1986; Yakovenchuk et al., 2005; Yakovleva et al., 2006). High-alumina rocks in two agpaitic massifs, Mont Saint-
Hilaire and Khibiny, have a lot of common mineralogical and geochemical features. These rocks are Si-poor in silica
and, as a result, oxides became rock-forming minerals: hercynite at first and corundum in some cases (Khibiny). The
main rock-forming minerals in both Mont Saint-Hilaire and Khibiny are alkali feldspars, hercynite, biotite (typically
annite), quite often muscovite; corundum and Al-garnets occur and accessory minerals are similar. Pyroxenes and
amphiboles are absent in Mont Saint-Hilaire high-alumina rocks that is also typical for the majority of the Khibiny
high-alumina fenites.
Besides the common mineralogical features, we note some differences. Majority of Khibiny high-alumina
fenites contain nepheline that is not typical for the high-alumina Mont Saint-Hilaire rocks. Carbonates are widespread at
Mont Saint-Hilaire unlike at Khibiny.
The oxide-silicate rocks of Mont Saint-Hilaire and Khibiny are characterized by high contents of Al, Fe, Na, and
K while concentrations of Ca and Mg are low. Similar rare-element speciality of high-alumina rocks of both massifs
should be noted: the majority of accessory minerals contain Nb (+Ta), Zr, Ce (+ other LREE), and Th, less Y (+HREE),
Sr, Ba, and U.
When the geochemistry of high-alumina rocks of both alkaline massifs are compared, we noted the higher
alkalinity (especially Na) for Khibiny and relative enrichment in CO2 and Mn for Mont Saint-Hilaire rocks. Content of
S in high-alumina rocks of Mont Saint-Hilaire is lower compared to Khibiny, while contents of rare elements are close.
The important common feature at both localities is the reducing conditions of mineral formation, that is shown by the
abundance of hercynite (both massifs), and the presence of native iron (Khibiny) or Fe 2+ carbonates (Mont Saint-
Hilaire).
Geochemically, the high-alumina fenites contrast sharply with relatively Al-poor host agpaitic rocks. It can be
explained by the nature of a protholite that coud be initially Al-rich. In Khibiny, the protholite is most likely
metamorphic rocks (muscovite shales or gneisses) formed after clays, whereas in Mont Saint-Hilaire it was hornfels or
granite. High-alumina rocks of Khibiny were altered by alkaline fluids more strongly compared to their Mont Saint-
Hilaire analogues. In the Khibiny xenoliths, nepheline-bearing rocks are typical products of the fenitization unlike the
majority of Mont Saint-Hilaire high-alumina rocks, in which almost all Na is concentrated in feldspars. Note that
nepheline-free varieties of high-alumina fenites, very similar to Mont Saint-Hilaire ones, are common also at Khibiny.
This study was supported by grant of President of Russain Federation No. 863.2008.5, grant of RFBR No. 08-
05-00077-a and grant of Russian Science Support Foundation (I.V.P.).

References
Currie K.L., Eby G.N., Gittins J. The petrology of Mont St-Hilaire complex, southern Quebec: An alkaline
gabbro-peralkaline syenite association // Lithos, 1986, 19, pp. 65-81.
Shlyukova Z.V. Mineralogy of Contact Formations of the Khibiny Massif. Moscow: Science , 1986, 97 pp. (in
Russian).
Yakovenchuk V., Ivanyuk G., Pakhomovsky Ya., Men'shikov Yu. Khibiny. Apatity: Laplandia Minerals, 2005,
468 pp.
Yakovleva O.S., Pekov I.V., Kononkova N.N. Hercynite from alkaline alumina rocks of fenitized xenoliths in
the Khibiny massif // Proc. All-Russian Conference Geochemistry, Petrology, Mineralogy and Genesis of Alkaline
Rocks, Miass, 2006, pp. 310-313 (in Russian).

Sheet dike complex of the forearc ophiolite

Yurkova R.M., Voronin B.I.
Institute of oil and gas problems RAS, [email protected]

This research was conducted in the northwest Pacific active continental margin: Sakhalin, Kamchatka, Koryaks
range, Karagin Island, Shirshova range in Bering Sea. The formation of ophiolite is related to the development of
magmatic-metamorphic diapir in the lithospheric wedge above Benioff zone [Yurkova, Voronin, 2006]. Magmatism
evolution is traced from abyssal facies (lherzolite, gabbro-norite) to hypabyssal (dike series of diabase and gabbro-
diabase, plagiogranite intrusions) and further to effusive underwater facies (spilite, quartz keratophyre). Ophiolite
associations are noted for the following.
 170

The early pseudomorphic harzbugite serpentinization has been shown as a result from the effect of reducing
fluids with the formation of structural serpentine water and methane in the presence of nickel catalyst according to
thereaction 2Mg2Si04+Mg2Si206+4CO+12H2→Mg6Si4010(OH)8+4CH4. This yielded antigorite-serpentine (with a lattice
constant a=35.5Å) and taenite (a natural alloy of Fe-Ni composition) scattered in antigorite as tiny (2-5 mk) inclusions.
Experimental, thermodynamic (T=450-600°C, P=13-16 kbar), and balance calculations have confirmed that antigorite
has formed in the mantle, at the depth of 40-50 km.
The bimetasomatic contact-reactional units emerged at diffrent stages of formation of ophiolite suite both in high
(T=900°C) and low (T=160°C) temperature conditions realised respectively during the 30-40 km deep magmatic rock
intrusions into serpentinite and during the contacts of ultramafic and brecciated volcanic-sedimentary rocks. Thus the
following different-temperature bimetasomatic layers are formed: 1. apogabbronorite (T=900°C) composed with
bronzite diopside and the pargasitic hornblende; 2. apolherzolite (T=550-700°C) typically comprising diopside,
pargasitic hornblende, grossular, andradite and hertzinite; 3. aposerpentinite, including antigorite, lizardite, pentlandite,
chromespinellide.
There have been synchromsn of seirpentinite rise and dike packets injection. Dike series serve the joining of a
heterogenous ophiolite complexes. They are presented link packets and swarms of dikes and semidikes and locally
single dikes of diabase and gabbro-diabase. They cut across all ophiolite complexes starting with dunite and harzburgite
and in this case are significant indicators of the conditions of ophiolite association formation in the single magmatic-
metamorphic geothermal system. On the assumption of petrologic and geochemical similarity of dike rocks and rocks of
boninite and intermediate tholeiitic magmatic series.
The dike complex formation is reconstructed in the base of the frontal part of the primitive island arc in the
conditions of the mantle diapir upriase in the third and second seismic layers. The interrelations between the dike
complex and the rest of the members of ophiolite association do not suggest significant horizontal movements of
ophiolite before semidikes packets intrusion. The concentration of semidikes packets is observed in the central inherited
magmatogene part where bipyroxene anorthite gabbro crystallized. Thin packets of semidikes cross the serpentinous
ultrabasite of the diapir banks. In dike complexes "dike-in-dike", two series (generations) of dikes are combined. One of
them consists of subvertical or highly dipping weakly winding semidikes leaning against enclosing gabbroid blocks in
magma chilling zone. They are not always parallel to each other. In a number of cases they are slightly displaced
relative to each other by subvertical dislocations. In a number of cases the dykes of this series thin out at different levels
inside amphibolite blocks. The other series of packets consists of arching curved or straight parallel
semidikes crossing semidikes of the former series at acute angle. Semidike rocks of the former
series have a more melanocratie composition (see the table 1). Packets of a thickness from 3 to 10 meters contain from
2 to 5 semidikes. Chill zones from 5 to 15 cm are distinguished and successive inequigranular layers from edge to the
center that is fine- and coarse-grained layers (0.3-0.5 m) in the inner parts of semidikes are noted.
Glomeroporphyritic structures are characteristic of dike diabase and gabbro-diabase. In porphyritic growths
plagioclase, clinopyroxene (Wo40En50Fs10), and amphibole-chlorite pseudomorphism by orthopyroxene (Wo 3En67Fs30)
are combined. Autometamorphic minerals for the major part are represented by the titanic hornblende and sphene.
Apogabbro and apodiabase thermal and dynamiothermal amphibolite and the major part of rodingite formed at the
expense of heat and fluids related to the injection of dike magmatic series (T=550-700°C, P>5kbar). Zonal structure of
semidikes is inherited with rodingite formation.
At the expense of rocks of the dyke series formed large group of low- and medium-temperature (500-550°C)
rodingites. Noteworthy is that Ca - and other chemical components necessary to form rodingites were derived from the
magmatic rocks and magmatism-related fluids. The Ca-enriched hydrothemal solutions circulating through contact
zones form early plagioclase albitization occurring in diabases. The formation of rodingites at the expense of effusive-
tuff rocks of the spilite-keratophyre complex lying above the dyke series was related to serpentinite protrusion in early
post-volcanic environments.
There as an injection of ophiolite blocks in marginal volcanic sedimentary complexes formed by autokinetic
lows. At the contact of serpentinites with turbidites and hemipelagites in forearc flyschoid island complexes associated
with ophiolites there emerged bimetasomatuc layers are comprising either or xonotlite (T=160°C) and chlorite.

Table 1. Chemical composition of rocks of sheet dike and lava complexes.

1 2 3 4 5 6 7 8
 171

SiO2 48,74 50,00 54,64 52,80 49,83 54,78 39,26

TiO2 0,61 0,93 0,74 0,77 0,66 0,70 1,37
Аl2Оз 16,12 15,20 14,71 15,29 15,84 16,46 12,12
Fe2O3 3,62 3,51 3,68 3,32 4,16 2,92 2,72
FeO 5,30 5,84 5,42 4,96 5,40 6,83 7,15
MnO 0,16 0,20 0,13 0,10 0,13 0,19 0,38
MgO 8,00 7,78 6,12 6,18 6,99 4,72 9,06
CaO 9,32 8,59 5,74 7,09 8,14 2,60 19,20
Na2O 4,28 4,00 6,28 5,95 3,45 5,95 1,58
K 2O 0,19 0,38 0,10 0,27 0,43 0,54 0,00
P2O5 0,18 0,18 0,13 0,12 0,20 0,12 0,40
H2O+ 3,37 2,28 1,85 2,33 - 3,52 6,14
H 2O - 0,32 0,27 0,20 0,31 - 0,36 0,50
C 0,00 0,26 0,15 0,19 - 0,00 0,12
Sum 100,21 99,42 99,89 99,68 95,23 99,69 100,00
V 172 148 168 157 142 232 120
Cr 133 54 42 52 50 24 165
Co 36 28 22 33 26 18 42
Ni 71 48 28 39 32 24 110
Cu 130 98 44 68. 80 147 65
Zn 70 63 55 62 50 80 250
Rb <5 <5 <5 <5 3 5 5
Sr 63 184 148 127 377 76 101
Y 20 26 26 28 23 22 22
Zr 15 51 38 65 78 25 56
Nb <5 <5 <5 <5 5 5 5
Ba <100 40 25 <100 30 30 30

Annotation. 1 – oxides (wt %) and chemical elements (g/t). 2-5 – sheet dike complex: 2-3 – early dikes; 4-5 –
late dikes; 2, 4 – chilling zone; 3, 5 – central part; 6-7 – spilitizate lava: 6 – basalt, 7 – andesite basalt; 8 – hyaloclastite;
- no result.
Reference:
1. Yurkova R.M., Voronin B.I. Uplift and transformation of mantle hydrocarbon fluids connected with ophiolitic
diaper formation//Genesis of the hydrocarbon fluids and deposits.M.:GEOS, 2006. C 56-67. (in Russian).

Mineralogical and geochemical changes of natrocarbonatites due to fumarolic activity at Oldoinyo

Lengai volcano, Tanzania
Zaitsev A.N.*, Keller J.**, Jones G.***, Grassineau N.****
* Department of Mineralogy, St. Petersburg State University, St. Petersburg, Russia; ** Institute für
Mineralogie, Universität Freiburg, Freiburg, Germany; *** Department of Mineralogy, Natural History
Museum, London, UK; **** Department of Geology, Royal Holloway University of London, London, UK.
Modern Oldoinyo Lengai natrocarbonatites from the Gregory Rift in northern Tanzania. are well known for their
instability under normal atmospheric conditions (Dawson et al 1987, Keller & Krafft 1990). Fresh rocks can be
observed for a short time only after eruption and after a few days of exposure to the atmosphere the natrocarbonatite
lavas change color to gray or brown and contain abundant subsolidus minerals such as the hydrous carbonates
thermonatrite, trona and nahcolite. Extended periods of low-temperature alteration of the natrocarbonatites leads to the
formation of rocks, which contain pirssonite, calcite, and rarely shortite in various proportions (Zaitsev & Keller 2006,
Zaitsev et al 2008).
Surprisingly, fumarolic activity at Oldoinyo Lengai has not received much attention. Measurements of fumarolic
gas temperatures vary from 49 to a maximum of 312 C (Dawson, 1962; Keller and Krafft, 1990; Koepenick et al.,
1996). The composition of gas from fumaroles at Oldoinyo Lengai has been studied by Javoy et al. (1989) and
Koepenick et al. (1996) who reported CO2-H2O gases containing 64-74 mol.% CO2, 24-34% H2O (48.7% and 49.2%,
respectively, in Javoy et al., 1989) with traces of H 2, CO, H2S, HCl, HF and CH4. Study of gases by Oppenheimer et al.
(2002) and Burnard et al (2006) revealed a much higher water content of about 75-77 mol.%, however, the observed
high water content may be attributed to a mixing of magmatic and meteoric water or contamination by old hydrated
natrocarbonatites. Data on abundances and isotopic composition of the gases (N, He, Ne, Ar, Xe) are reported by
Teague et al (2008) and Fischer et al (2006).
Subsolidus minerals in altered natrocarbonatites were studied from four active fumarolic fields: (1) in the north-
western part of the crater near hornito T49, (2) in the central part of the crater, hornito T46, (3) in the northern area of
the crater near the same hornito T49 and (4) in the southern area of the crater near hornito T30. The temperature of the
 172

gases from second locality was measured as 54.5 °C (at the surface), 73.8 – 74.7 °C (25 cm down the crack) and 141.1
°C (1 m down the crack). The measured pH and Eh of natrocarbonatite were pH = 6.1 and Eh = 87 mV for a sample
from a 1 cm surface layer and pH = 8.6 and Eh = 240 mV for a sample 20 cm down from the surface (for pH and Eh
measurement both samples were cooled to a temperature of 20 °C).
Sulphur is the only mineral previously reported from fumaroles (Keller and Krafft, 1990; Koepenick et al.,
1996). The mineral typically occurs as prismatic crystals up to 3 mm in size and covers the surface of natrocarbonatite
in contact with fumarolic gases. The natrocarbonatites are soft (they can be easily kneaded by hand), porous, water-
saturated and are characterised by various shades of white, grey, fawn, black or even red.
Two mineral assemblages were distinguished in the samples studied by XRD and SEM/EDS with reference to
published studies of fresh and altered natrocarbonatite. The first assemblage, represents relicts of primary magmatic
natrocarbonatite minerals and the second assemblage, represents the subsolidus minerals formed during alteration of
natrocarbonatite. In addition to sulphur, calcite and gypsum are major subsolidus minerals in altered natrocarbonatites.
The natrocarbonatites in fields of fumarolic activity undergo as well substantial chemical transformation. The
rocks contain between 0.1 and 23.9 wt.% Snative, 0-32.9 wt.% SO3, 0.8-30.7 wt.% CO2 and 0.6-12.9 wt.% H2O.
Compared to fresh natrocarbonatites they are strongly depleted in K (0.1-2.4 wt.% K2O), Na (0.2-6.8 wt.% Na2O) and
Cl (<0.5 wt.%) and show enrichment in Ca (21.0-41.7 wt.% CaO) and F (1.7-14.8 wt.%). Sr and Ba are also high with
up to 4.7 wt.% SrO and 9.2 wt.% BaO.
Three samples of native sulphur, collected in 1999, 2000 and 2005, have been analysed for S isotopic
composition – the 34S values are –5.3 (1999), +0.1 (2000) and +2.2 ‰ CDT (2005).
Conclusions. Fumarolic activity in the northern active crater produce previously unrecognized mineral
assemblage of subsolidus minerals at Oldoinyo Lengai that consist of native sulphur, gypsum, calcite, anhydrite, barite
and celestine in various proportions. Hot H2O-rich fumarolic gases emitting from numerous vents and cracks cause
complete dissolution of primary natrocarbonatite minerals gregoryite, nyerereite and sylvite. Fluorite and khanneshite
are stable minerals during alteration.
The mineralogy and bulk rock geochemistry show nearly complete removal of Na, K and Cl. In contracts Ba and
Sr, leached from gregoryite and nyerereite, were immobile and involved in formation of barite and celestine. High
content of fluorine in studied rocks is attributed to relative enrichment of residual in fluorite. Enrichments of some
altered natrocarbonatites in sulphate component, up to 32.9 wt% SO 3, may indicate oxidation of native sulphur,
deposited around the vents, to SO42- and sulphate involvement in formation of gypsum.
Isotopic composition of native sulphur, 34S = -5.3 to +2.2 ‰ CDT, indicate deep-seated, mantle source of the
element.
This research was supported by a Marie Curie International Fellowship within the 6th European Community
Framework Programme, Alexander von Humboldt-Stiftung and German Research Foundation (DFG).
References:
Dawson J.B. The geology of Oldoinyo Lengai // Bulletin Volcanologique. 1962. Vol. 24. P. 348-387.
Dawson J.B., Garson M.S., Roberts B. Altered former alkalic carbonatite lava from Oldoinyo Lengai, Tanzania:
inferences for calcite carbonatite lavas // Geology. 1987. Vol. 15. P. 765-768.
Fischer T., Burnard P., Marty B., Palhol F, Mangasini F., Shaw A.M. The 2005 and 2006 eruptions of Ol Doinyo
Lengai: assessing deep and shallow processes at an active carbonatite volcano using volatile chemistry and fluxes //
EOS Transactions. 2006. Vol. 87(52). P. V14B-04.
Keller J., Krafft M. Effusive natrocarbonatite activity of Oldoinyo Lengai, June 1988 // Bulletin of Volcanology.
1990. Vol. 52. P. 629-645.
Keller J., Zaitsev A.N. Calciocarbonatite dykes at Oldoinyo Lengai: the fate of natrocarbonatite // Canadian
Mineralogist. 2006. Vol. 44. P. 857-876.
Koepenick K.W., Brantley S.L., Thompson J.M., Rowe G.L., Nyblade A.A., Moshy C. Volatile emissions from
the crater and flank of Oldoinyo Lengai volcano, Tanzania // Journal of Geophysical Research. 1996. Vol. 101. P.
13819-13830.
Oppenheimer C., Burton M.R., Durieux J., Pyle D.M. Open-path Fourier transform spectroscopy of gas
emissions from Oldoinyo Lengai volcano, Tanzania // Optics and Lasers in Engineering. 2002. Vol. 37. P. 203-214.
Teague A.J., Seward T.M., Harrison D. Mantle source for Oldoinyo Lengai carbonatites: evidence from helium
isotopes in fumarole gases // Journal of Volcanology and Geothermal Research. 2008. Vol. 175. P. 386-390.
Zaitsev A.N., Keller J. Mineralogical and chemical transformation of Oldoinyo Lengai natrocarbonatites,
Tanzania // Lithos. 2006. Vol. 91. P. 191-207.
Zaitsev A.N., Keller J., Spratt J., Perova E.N., Kearsley A. Nyerereite – pirssonite – calcite – shortite
relationships in altered natrocarbonatites, Oldoinyo Lengai, Tanzania // Canadian Mineralogist. 2008. Vol. 46. p. 843-
860.

Zr garnet from intrusive carbonatites of Kerimasi volcano, Tanzania

Zaitsev A.N.*, Williams C.T.**, Kuznetsova I.V.***, Britvin S.N.*, Spratt J**., Petrov S.V.*
* St. Petersburg State University, St. Petersburg, Russia; ** The Natural History Museum, London, UK;
*** St. Petersburg University of Technology and Design, St. Petersburg, Russia.
 173

Kerimasi is an extinct carbonatite-nephelinite volcano located in the Gregory rift in northern Tanzania. It is
composed of nephelinitic pyroclastic rocks with carbonatite agglomerates and tuffs (Mariano, Roeder 1983, Hay 1983,
Church 1995).
Carbonatites here are represented by both intrusive and extrusive types. They occur as blocks up to 0.5 m in
diameter. Intrusive carbonatites are calcitic in composition and contain forsterite pseudomorphs, magnetite and apatite
as minor mineral phases and pyrochlore, baddeleyite and calzirtite as accessory minerals.
Zr-rich garnet was found in some samples of calcite carbonatites as well as in eluvial deposits on the eastern
slope of the volcano and from explosive craters of Loluni, Kisete and Lulmurwak. The Zr-rich garnet occurs as
spherical crystals up to 40 m in carbonatite blocks and as euhedral to subhedral crystals up to 80 m in carbonatite
eluvium (Fig. 1). Microscopically the mineral is light to dark-brown, transparent with vitreous luster. It is isotropic with
n = 1.945(5).

Microprobe analyses of the mineral show some variations in chemical composition and it contains 32.6-36.6
wt.% ZrO2, 26.6-28.0 CaO, 15.0-17.8 Fe2O3, 7.4-10.0 SiO2 and 3.1-7.4 Al2O3. The mineral is also Nb-rich with Nb2O5
ranging from 2.1 to 4.8 wt.%.
The average empirical formula of the mineral is
(Ca2.996Mn0.010)3.006(Zr1.719Nb0.139Ti0.078Mg0.024Y0.016Ce0.012Nd0.009La0.003)2.000(Fe3+1.234Si0.857Al0.825Ti0.084)3.000O12.000
The crystal structure of the mineral is very similar to the structure of Zr garnet kimzeyite with the ideal formula
Ca2Zr2(Al2Si)O12 (Milton et al. 1961) or Ca2(Zr,Ti)2(Si,Al,Fe3+)O12 (http://pubsites.uws.edu.au/ima-cnmnc/) (Munno et
al. 1980, Schingaro et al. 2001). It is cubic, space group Ia3d and a = 12.549(1) Å.
The mineral can be considered as the ferrite-dominant member of zirconium garnet series with ideal formula
Ca2Zr2(Fe3+2Si)O12.

References:
Church A.A. The petrology of the Kerimasi carbonatitevolcano and the carbonatites of Oldoinyo Lengai with a
review of other occurrences of extrusive carbonatites // PhD thesis. 1996. London: University of London. 384 p.
Hay R.L. Natrocarbonatite tephra of Kerimasi volcano, Tanzania // Geology. 1983. Vol. 11. P. 599-602.
Mariano A.N., Roeder P.L. Kerimasi: a neglected carbonatite volcano // J. Geology. 1983. Vol. 91. P. 449-455.
Milton C., Ingram B.L., Blade L.V. Kimzeyite, a zirconium garnet from magnet Cove, Arkansas // American
Mineralogist. 1961. Vol. 46. P. 533-548.
Munno R., Rossi G., Tadini C. Crystal chemistry of kimzeyite from Stromboli, Aeolian Islands, Italy // American
Mineralogist. 1080. Vol. 65. P. 188-191.
Schingaro E., Scordari F., Capitanio F., Parodi G., Smith D.C., Mottana A. Crystal chemistry of kimzeyite from
Anguillara, Mts. Sabatini, Italy // European Journal of Mineralogy. 2001. Vol. 13. P. 749-759.

Chemical differentiation of products of crushing by the grain-size fractions: example of Kovdor

magnetite ore
Zaitsev V.A., Rosсhina I.A.
Vernadsky Institute of Geochemistry and Analytical Chemistry
 174

«Sample selection and sample preparation are the most critical stages in the analysis of a rock » - this sentence
has become a truism of geochemistry. The process of quartering, reducing the weight of a sample without reducing
representativeness of this sample was many times described in textbooks for students. However it sometimes happens,
that after the crushing of a sample only the fine fraction is used for the chemical analysis, and the coarse one is used for
the separation of pure mineral fractions.
The danger of this approach was emphasized in many publications but it was never done in terms of quanttive
analyses. In this connection it is interesting to compare the composition of different grain-size fractions and to estimate
the possible error resulting from the irregular sample preparation.
For example, we carried out the experiment with a magnetite ore from the Kovdor deposit. The ore consists of
magnetite and calcite (the main minerals), phlogopite and apatite (minor) and baddeleyite (accessory).
The sample was crushed in an iron mortar and divided into the grain-size fractions: +1 mm, -0.5+1 mm and -0.5
mm. Each fraction was powdered in an agate mortar. The results of the X-ray fluorescent analyses are given in Table 1.

Table 1. The chemical compositions of grain-size fractions after the crushing of one sample of a magnetite ore.
Rock/
fractions "+1" "+0.5-1" "-0.5" max/min
SiO2 4.35 6.63 7.28 1.7
TiO2 0.24 0.16 0.15 1.7
Al2O3 2.13 1.86 1.49 1.4
Fe2O3* 73.71 57.81 43.45 1.7
MnO 0.30 0.28 0.25 1.2
MgO 9.14 11.92 14.30 1.6
CaO 5.03 11.33 17.13 3.4
Na2O 0.23 0.24 0.21 1.2
K2O 0.07 0.11 0.09 1.4
P2O5 0.14 0.05 0.07 2.6
SO3* 0.11 0.16 0.13 1.5
CO2 (as LOI) 4.40 9.78 15.21 3.5
V 0.031 0.029 1.1
Co 0.0131 0.0115 0.0083 1.6
Sr 0.037 0.073 0.1052 2.8
Zr 0.0195 0.0383 0.0773 4.0
Nb 0.005
Cu 0.0105 0.0175 0.007 2.5
Zn 0.0304 0.0233 0.0157 1.9
Ni 0.0107 0.0103 0.0079 1.4
Y 0 0.0008 0.0003
Ba 0.024 0.0313 0.077 3.2
As 0.0009 0.0008 0.0007 1.3
Pb 0.0019 0.0018 0.0011 1.7
Cr 0.0078
100.03 100.54 100.08
* All iron as Fe2O3

If one looks at this table he can decide that it contains the analyses of three different samples. The coarsest
fraction is enriched in iron, alumina, titanium and zinc (mainly concentrated in magnetite) and also in phosphorous
(mainly concentrated in apatite). The finest fraction is enriched in magnesia, calcium, strontium and CO 2, mainly
concentrated in calcite and in zirconium, which forms its own mineral – baddeleyite. The medium-size fraction is
enriched in potassium, sulphur and copper – the elements, concentrated in phlogopite and sulphides.
The last column of the table characterizes the degree of elements distribution as the ratio of maximum
concentration/ minimum concentration.
The most contrast distribution show the elements, which concentrate in the finest fraction: Zr concentrates four
times as much, Ca, Ba, CO2 – more than triple. For other elements the concentration ratio is rarely less than 50 %.
After all, we can conclude, that the difference of composition of the grain-size fractions can result in bigger and
more significant errors in estimation of a rock composition than any analytical errors of chemical analyses. Our
experiment shows that grain-size separation after the crushing can be effective mechanism for mineral concentration, at
least for carbonatite-related ores, and can be regarded as effective way of ore-dressing.
 175

This study was funded by grants of President of Russian Federation MK-860.2008.5, grant RFBR 09-05-90436
and 08-05-00054.

Graphite-bearing carbonatite of Guli massif

Zaitsev V.A., Sorokhtina N.V., Kogarko L.N.
Vernadsky Institute of Geochemistry and Analytical Chemistry

The Guli massif is a word-largest alkaline-ultrafic complex, located in a Nord of Siberian platform. Carbonatites
form two separate bodies, named Nord carbonatite massif and South carbonatite massifs. First time for this massif we
have found graphite in carbonatite from the South carbonatite massif.
This carbonatite is anhimonomineral calcitic rock (sevite) with minor amounts of dolomite, phlogopite,
amphibole and K-feldspar. Accessory minerals are apatite, pyrite, graphite, and Nb-bearing rutile.
Wall-rock composition was estimated by X-ray fluorescent analyse: SiO2–0.95 % Al2O3–0.14 % Fe2O3*–0.48
% MnO–0.12 % MgO–1.46 % CaO–53.72 % Na2O–0.14 % K2O–0.07 % P2O5–0.02 % S2-–0.03 % Sr–0.02 % LOI–
42.9 % Total –100.05 %.
Neutron-activation analyse shows relatively-low contens Sr and Ba for carbonatites (2415 и 240 ppm,
respectively). Similar concentrations of Sr и Ba are reported by Egorov for «dolomitic metacarbonatites» from Guli
massif. This rock is strongly depleted by the rare-earth elements (total content of REE is 28 ppm). The REE pattern
shows gentle slope from La to Lu with positive Eu-anomaly.
Graphite forms the crusts on the carbonate crystals and intergrowth with phlogopite (fig. 1-2).
Raman spectra of graphite samples from the Guli carbonatite are largely similar to published spectra of
crystalline graphite. The G band exhibited notable band broadening, with G band FWHMs in the range 24-34 cm1 in
compare with graphite form Gremiakha-Vyrmes and Pogranichnoe. This band FWHMs correspond to temperature 320-
500 °C of graphite formation.
The mineral composition was estimated by the electron-microprobe analyses.
Calcite contain 2-3% of dolomite component and up to 1% of siderite component. Dolomite contain 3-4 % of
calcite component. The calcite-dolomite solvus curve (Anovitz Essene 1987) shows that dolomite composition
correspond to the temperature as 550-600° C, and calcite near 300° C.

Fig 1 Fig 2
Graphite (Grph) cover carbonate (Ca). Secondary Graphite (black) intergrowth with phlogopite
electron image (light-grey) in calcite (grey).
Back-scattered electron image

Amphybole (richterite) composition correspond the formula (K0.1-0.3Na0.5-0.8)0.9(Na1-1.3Ca0.1-1)2(Mg4.5-4.7Fe0.1-

phlogopite – K(Mg2.8Fe0.06Ti0.05)Si3.2Al0.9O11(OH)2 and K-feldspar - K0.95Na0.04Ca0.01AlSi3O8.
0.3Al0.1Ti0.05)5Si8O22(OH)2,
The formations conditions of association including dolomite, calcite, K-feldspar and phlogopite can be estimated
from the reaction 3 Do +1 H2O +1Kfs =3 CO2+3 Cc +1Phl. This equilibrium depends on temperature, pressure and
proportion of CO2/H2O in fluid.
E.M. Epstein has estimated depth of Guly carbonatites formation by the fluid inclusions and by
paleoreconstruction of erosion level as 2.1-2.7 km. It correspond the pressure approximately 1 Kbar. If fluid contents
 176

80-95% CO2, equilibrium 3 Do +1 H2O +1Kfs =3 CO2+3 Cc +1Phl coresponds 450-500 °C. If fluid was richer in CO2,
the temperature estimation might be higher.
700 -10
Gr+O2=CO2
3Do+H2O+Kfs
95% CO2 5% H2O Hem
90% CO2 10% H2O 3Do+H2O+Kfs= Mt 3Cc+3Grph+Phl
80%CO2 20% H2O 3Cc+3Grph+O2
600 +Phl
-20
Temperature, C

log(fO2)
Wu
500 Iron

CO2
3 Do +1 H2O +1Kfs =3 CO2+3 Cc +1Phl -30 Grph

400

QFM

300 -40
0 1000 2000 bar
Presure, 3000 4000 300 500 Temperature, C 700 900

Fig. 3. P-T and f(O2)-T conditions for dolomite+K-feldspar+calcite+phlogopite+graphite association estimated

by thermochemical calculations with program complex BAYES (Chatterjee et al., 1998).

We have estimated the conditions of equilibrium 3 Do +1 H2O +1 Kfs = 3 Cc +3 Grph +3 O2 +1 Phl (fig.3).
Eqilibrium line Do+H2O+Kfs=Cc+Grph+Phl crosses lines of CO2-graphite and QFM – buffers at 500-500°C. The
topology of T-f(O2) diagram show that cooling in the closed system Dol+Kfs+Cc+Phl+Grph+H2O results in disappear
of calcite, phlogopite or graphite, but cooling along the QFM-buffered line result in formation of graphite, calcite and
phlogopite after K-feldspar and dolomite at temperature lower than 500-550°.
It mean that graphite in this rock can be formed only due to addition of reduced fluid, including the fluid,
equilibrated with QFM-buffered rock at the tempetatures lower than 500° C.
This study is supported by the INTAS project 05-1000008-7938
References:
Anovitz L. M., Essene E. J. Phase Equilibria in the System CaCO3-MgCO3-FeCO3 Joumal of Petrology, Vol.
28, Put 2, pp. 389-414, 1987
Egorov, L.S. (1991) Ijolite Carbonatite Plutonism. Nedra, Leningrad, 260 pp.
Epstein E.M. Geologo-Petrological model and genetic features of ore-bearing carbonatite complexes.// M:
Nedra, 1994, 256 pp. ( in Russian).
Chatterjee N.D., Krüger R., Haller G. & Olbricht W. (1998): The Bayesian approach to an internally consistent
thermodynamic database: theory, database, and generation of phase diagrams. Contrib. Mineral. Petrol., 133, 149-168
Zaitsev V.A., Sorokhtina N.V., Nasdala L. Kogarko L.N Raman spectroscopic investigation of graphite from the
Gremyakha Vyrmes and Pogranichnoe carbonatites, Russia Geophysical Research Abstracts, Vol. 11, EGU2009-134-3,
2009.

Spinel group minerals in dunites of Guli massif. I Spatial variations.

Zaitsev V.A. Senin V.G.
Vernadsky Institute of Geochemistry and Analytical Chemistry

Guli massif is a world-largest alkaline-ultramafic complex. It located in transition zone between Siberian
platform and Khatanga syncline. Dunites are the first intrusive phase of Guli massif. They cover approximately 60% of
present-day surface of the massif (Egorov, 1991).
Chromite-spinel-magnetite solid solutions are supposed to be the most informative minerals of olivine-
ultramafic and mafic rocks. They are widely used for determination of formation type of ultramafic and mafic rocks and
estimation of rock-forming conditions.
Composition vatiations of spinel-group minerals in Guli massif was previously studied by Egorov (1991), who
attributed the olivine rocks of Guli massif as dunites instead of olivinites, and Malich with co-authors (Malich, 1999),
who found that spinel-minerals composition depend on type of rocks, serpentinization ratio and ontogeny character of
spinel minerals.
We have studied the spatial variations of spinel minerals composition. The mineral composition was estimated
by electron-microprobe analyse in GEOKHI RAS (Cameca-100). The samples collection was kindly given by L.N.
Kogarko and A.M. Asavin.
According with the data of previous investigators, compositions of spinel minerals vary between ferrichromite and
titanomagnetite with minor but variable amount of aluminium and titanium components. Spinel-minerals composition
can be shown in Al3+-Cr3+-Fe3+ diagram (fig 1).
 177

Cr
Left tributary of r. Vostochny (1985-142,
1985-152)
Maimechite

Ingarynga (Гх-40)

Episkin hill (Гх-35, Гх-36)

Iolite hill (Гх-12, Гх-16)

Khaluda (1985-87, 1982-82, 1985-84)

1 South part of massif (1985-39)

3+
Al Fe
Fig. 1. Variations of spinel-group minerals from Guli massif. Numbered arrows show: 1- core-rim zoning in chromite
from maimechite(Kogarko, Ryabchikov, 1999); 2-evolution of chromspinel composition during fraction crystallisation
of maimechite melt; 3 – evolution of chromspinel composition during equilibrium crystallisation of maimechite melt; 4-
chromspinel composition variation in Khaluda hill, from bottom to top.

We hasn’t found the noticeable core-rim zonation and chemical difference between compositions of spinel-
minerals crystals included in olivine, subhedral crystals between olivine and euhedral crystals between serpentine in the
same sample. At the same time some samples contain compositionally contrast spinel minerals. Some grains are
ferrichromite or chrom-magnetite and some grains are titanomagnetite. It result in bimodal distribution of compositions
in Cr3+/Fe3+ ratio.
We can see the accordance between aluminium content in ferrochromite and in magnetite from the same
sample or series of samples from one place of massif.
The richest in aluminum are a ferrichromite and magnetite from Ingarynga valley, the next are samples from
district of r.Vostochny and mt. Khaluda (they are similar to the external part of chromite grains in maimechite by Al
content), the next - from Epishkin Hill and from the South part of massif. The lowest aluminum content we have found
in samples from Iolite hill.
Samples of dunites from mt. Khaluda show chrome-spinel composition variations depending on vertical
position: on the bottom part of mountain present only the ferrichromite and Cr-free magnetite, in the medium part of
slope – ferrichromite with lower average Cr/Fe3+ ratio and chrom-magnetite and in the top of mountain – only chrome-
magnetite. This composition trend conform to the crystallization differentiation of ultramafic magma.
We cannot explain the difference in aluminum content in spinel-group minerals from the different parts of Guli
massif by the fractionation in single magma portion, because differentiation trends are sub-parallel to the Cr-Fe side of
the diagram. On the other hand, we cannot explain this difference by the postmagmatic reequilibration, because the
diffusion coefficients of Al and Cr in chrome-spinels are very low, therefore their concentrations practically not change
in post-crystallisation processes unlike Fe and Mg concentrations (Roeder, Cambell, 1985).
The only explanation we can propose that different parts of dunite-core of Guli massif were formed from
different portions of primary melt. It means that we have to consider the dunite core of Guli complex as combination of
dunite massifs.

References
Egorov L.S. Ijolite-carbonatite plutonism (on the sample of Maymecha-Kotuy complex, Polar Siberia) //
Leningrad: Nedra, 1991. 260 p.
Malich K.N. Platinoides of clinopyroxenite-dunite massifs of East Siberia // St. Peterburg: VSEGEI, 1999. 293
p.
 178

Roeder P.L. Cambell I.H. The effect of pustcumulus reaction of chrome-spinels from the Jimberlana intrusion
// J. of Pertrology. 1985. Vol. 26. Part 3. Pp.763-786.
Kogarko L.N., Ryabchikov I.D. Geochemical evidence for meimechite magma generation in the subcontinental
lithosphere of Polar Siberia // Journal of Asian Earth Sciences. 1999. P. 1-9.

Spinel group minerals in dunites of Guli massif. II Numerical modeling of maimechite, pictite and
khatangite crystallization.
Zaitsev V.A. Ermolaeva V.N.
Vernadsky Institute of Geochemistry and Analytical Chemistry

The spinel-group minerals are believed to be the most informative phase of ultramafic rocks. Their composition
is a complex function depending of the magma composition, volatile elements concentration, oxygen fugacity, P-T
parameters of crystallization, cooling rate and history of postmagmatic reequilibration (Kamenetsky et al., 1991).
In this study we try to answer the question about the possible primary melt for Guli massif, comparing the
composition of spinel-group minerals from the dunites of Guli massif with model compositions of spinel-group
minerals, which are in equilibrium in system, chemically corresponding with primary melt. We consider three
candidates to be a primary melt for Guli massif: meimechite, picrite and khatangite.
Using the MELTS Web-applet (Ghiorso, Sack, 1995, Asimow, Ghiorso 1989) we carried out the numerical
experiment of equilibration of systems with meimechite, picrite and khatangite bulk composition in wide range of
conditions: T=1200-1400ºC, P=1-10 kbar, Fe2+/FeTotal = 0.99-0.50 (it is correspond to log(fO2) = –15.50 +4.48 relative
QFM buffer) and H2O content 1% (for meimechite composition we also used also 0.2, 2 and 5%). The average
compositions of meimechite, picrite and hatangite were estimated from published analyses (Kogarko, Ryabchikov,
1999).
The results of modeling allow to estimate the influence of the main parameters of magma crystallisation to the
composition of spinel-minerals. In all cases the temperature decreasing results in the decrease of chromium
concentration in the spinel minerals, this trend is subparallel to the Fe-Cr side. System oxidation leads to the Fe3+
enrichment of chromite at a constancy or slightly reduction of the Al/Cr ratio. Pressure increasing results in increasing
of Fe3+ content in chrome-spinels together with slight increasing of Al-content. Increasing of water content results in
decreasing of Al-content in spinel minerals with slight increasing of Fe3+ content. The influence of this factor is strongly
limited by the H2O solubility in the melt.
Comparing of composition fields of model chrome-spinels and chrome-spinel from the Guli massif shows, that
model compositions are much richer in Mg: all of they are Mg-dominant, unlike the natural compositions which are Fe-
dominant (except the central part of chromite crystals in maimechite and the shlire chromite in one dunite). We can
explain this fact by the post-crystallization re-equilibration, because the diffusion coefficient of Mg and Fe in chromite
are quite high, to provide the noticeable changing of Fe/ Mg ratio in conditions of subaeral lava cooling (Kamenetsky et
al., 1991). The diffusion coefficients for Cr and Al are much lower, and Cr/Al ratio is preserving practically constant in
postcrystallization history even for intrusive bodies (Roeder, Cambell, 1985). It is reason, why Al-Fe-Cr diagram is
very convenient for chromite.

Cr Cr Cr
M-.99, 1Kbar
П-99, 10 Kbar X-.99, 1Kbar
M-.99, 3Kbar
П-90, 1Kbar X-.99, 3Kbar
M-.99, 10 Kbar X-.99, 10 Kbar
П-90, 3 Kbar
M-09,1 Kbar X-09,1 Kbar
П-90, 10 Kbar
M-09,3 Kbar X-09,3 Kbar
П-70, 1 Kbar
M-09,10 Kbar X-09,10 Kbar
П-70, 3 Kbar
Iron oxidation M-08,1 Kbar
П-70, 10 Kbar X-07,1 Kbar
M-08,3 Kbar X-07,3 Kbar
П-50, 1 Kbar
M-07,1 Kbar X-07,10 Kbar
П-50, 3 Kbar
M-07,3 Kbar X-05,1 Kbar
П-50, 10 Kbar
M-07,10 Kbar X-05,3 Kbar
H2O content incr.
M-08,1 Kbar (0.2% H2O) X-05,10 Kbar
M-08,3 Kbar (5% H2O)
Temperature Pressure incr. Iron oxidation
decr. Pressure incr.
Pressure Temperature
incr. decr.
Temperature decr.

Iron oxidation

Al Fe3+
Fe3+ Al0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
Fe3+ 0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
Al0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1

A B C
Fig.1 The model compositions of spinel-group minerals in the systems with meimechite (A), picrite (B) and
khatangite (C) bulk composition on the Al-Fe-Cr diagram

The composition field of model composition of spinel-minerals (see fig.1) in system with picritic bulk
composition corresponds to the most aluminum-rich part of natural chrome-spinels from the Guli massif (fig. 1 from
part I). The composition fields of model composition of spinels in systems with maimechite and khatahgite bulk
composition are much closer to the Al-angle of diagram.
At the same time, Al content in the real chromite from meimechite decrease from core to rim. This difference in
composition can be result from joint changing of pressure of crystallization and water content in the melt. For example,
it can be explained by crystallization of central parts of chromite grains in the high depth with further moving to upper
 179

horizon and covering here by the chromite with lower Al-content. The composition of such chromite is similar to the
composition of chromites from r. Vostochny, Ingarynga, Khaluda regions of Guli massif.
Thus both two-stage meimechite crystallization with melt separating from earlier chromite crystals (formed in
high-pressure and low water-content conditions), and crystallization of pictrite may result in formation of chrome-spinel
composition, which is observed in Guli massif.

References
Egorov L.S. Ijolite-carbonatite plutonism (on the sample of Maymecha-Kotuy complex, Polar Siberia) //
Leningrad: Nedra, 1991. 260 p.
Roeder P.L. Cambell I.H. The effect of pustcumulus reaction of chrome-spinels from the Jimberlana intrusion
// J. of Pertrology. 1985. Vol. 26. Part 3. Pp.763-786.
Kogarko L.N., Ryabchikov I.D. Geochemical evidence for meimechite magma generation in the subcontinental
lithosphere of Polar Siberia // Journal of Asian Earth Sciences. 1999. P. 1-9.
Kamenetsky V.S. Craford A.J., Meffre S. Factors controlling chemistry of magmatic spinel: an empirical study
of associated olivine, Cr-spinel and melt inclusions from primitive rocks.// J. Of petrology, 2001, vol.42 No 4 pp. 655-
671.
Ghiorso, M. S., Sack R. O. Chemical Mass Transfer in Magmatic Processes. IV. A Revised and Internally
Consistent Thermodynamic Model for the Interpolation and Extrapolation of Liquid-Solid Equilibria in Magmatic
Systems at Elevated Temperatures and Pressures. Contributions to Mineralogy and Petrology, 1995 Vol. 119, pp. 197-
212.
Asimow P.D, Ghiorso M.S. Algorithmic Modifications Extending MELTS to Calculate Subsolidus Phase
Relations. American Mineralogist, 1998, Vol. 83, pp. 1127-1131.

Is a magma of subalkaline monzo-granodiorite series parental to Late Jurassic calc-alkaline granites

of the Eastern Transbaykaliya and associated rare-metal mineralization?
Zaraisky G.P.
Institute of Experimental Mineralogy RAS, Chernogolovka, Russia, [email protected]

The Kukulbey complex (J3) of rare-metal granites in Eastern Transbaikalia belong to postorogenic reactivation
calc-alkali granite-leucogranite series. Hypabyssal intrusions of these granites are checked deep seated faults which
crossing thickness of earlier consolidated regions. At the watershed between the Turga and Borzya rivers Kukulbey
granite massifs extend for 110 km in the NE–SW direction in the following order: Belukha, Bukuka, Turga, Achikan,
Etyka, Oldonda, Soktuy, Sherlovaya Gora, Adun-Chelon, and Ary-Bulak massifs. On this territory, sometimes within
one and same massifs, are present granites several more early monzo-granodiorite Shakhtama complex (J2-3). Majority
of the researchers links origin of Kukulbey granites mainly with Continental Crust source, but Shakhtama serits with the
Mantle participation (Kovalenko et al., 1999; Troshin, 1985; Syritso, 2002).
Together with that question about a role of the Crust-Mantle interaction in origin of the Kukulbey granite magma
and, especially in genesis lithium-fluorine granites and connected with them rare-metal mineralization remains rather
discussion. The Kukulbey granites are characterized by a uniquely high degree of fractionation of the parental granitic
magma, forming three intrusive phases. The biotite granites of phase 1 are barren, the leucogranites of phase 2 are
accompanied by greisen Sn-W mineral deposits (Spokoininskoe and others), and the final dome-shaped stocks of
amazonite Li–F granites of phase 3 host Ta deposits of the “apogranite” type: Orlovka, Etyka, and Achikan. All granitic
rocks of the complex are roughly simultaneous and have an age of 142 0.6 Ma (Kostitsyn, 2004). The rare-metal
specification of Kukulbey complex in Shachtama granite is absent. With broadly wide-spread in Transbaykalia monzo-
granodiorite (latite) series are usually associated the Mo, Pb-Zn and Au mineralization. However, uncertainty available
data allows expect different degree of the Shakhtama latite magma participation in genesis Kukulbey granite-
leucogranite complex and associated with him rare-metal mineralization (Sn, W, Be, Ta, Nb,Li). This promotes the
small time gap between Shachtama and Kukulbey complexes (near 10 Ma), close weakly negative values εNd, and
practically alike 87Sr/86Sr ratio at a rate of 0.705-0.708 (Kostitsyn et al., 2004; Syritso et al., 2007). Different variants
participation of the mantle latite magmas are proposed for genesis of Kukulbey rare-metal mineralization: from as
energetic factor (only as source of the heat) up to suggestion of crucial role of mantle fluid in the melting of Crust
substrate and even up to suggestion that latite magma is the paternal source for Kukulbey granites (Kovalenko et al.,
1999; Syritso, 2002; Syritso et al 2007; Kozlov and Efremov, 1999; Troshin, 1985).
All of the intrusive massifs, stocks, and dikes of rocks of the Kukulbey and Shakhtama complexes were sampled
during our fieldwork in the Kukulbey and Khangilay ore areas (1995-2005. The samples were analyzed for major
elements and F by conventional “wet” chemical techniques and by XRF. Minor and trace elements were determined by
ICP/MS-AES. The analytical database includes near 300 samples (Zaraisky et al., 2009). Figures 1 and 2 presents a
SiO2–Zr/Hf diagrams for the rocks of Shachtama and Kukulbey complexes with the evolutionary trends of the
crystallization fractionation (Zaraisky et al., 2009). In the diagrams Fig.1 the granitoids of the Shakhtama
complex,which do not bear elevated concentrations of rare metals, display a well pronounced trend of usual
crystallization differentiation due to an increase in the content of silica according to a decrease in the (FeO + MgO
+CaO) contents in the course of melt crystallization. The Zr/Hf ratio systematically decreases from 45 in diorite to 25 in
 180

granite. The Shakhtama complex contains no leucocratic granites. This trend is weakly pronounced in the granites of the
Kukulbey complex because the original composition of the granites was close to the eutectic (Fig. 2). Their
differentiation trend is thus nearly vertical and almost perpendicular to the differentiation trend of the Shakhtama rocks.
A decrease in the Zr/Hf ratio generally points to a systematic fractionation sequence: the Zr/Hf ratio of the rocks
systematically decreases from intrusive phase 1 (40–25) to phases 2 (20–30) and 3 (10–2).

Fig. 1. Zr/Hf-SiO2 diagram for Shakhtama Fig. 2. Zr/Hf-SiO2 diagra m for Kukulbey granites
granites

Fig. 3. Spaidergram of Kukulbey granites Fig. 4. Spaidergram of Shakhtama granites

The Kukulbey Li–F granites of phase 3 are the most strongly enriched in rare metals and other incompatible
elements and inherit geochemical tendencies toward enrichment or depletion in the same groups of elements from the
parental biotite granites of the Kukulbey complex with respect to the Upper Crust (Fig. 3). They are enriched in Rb, Li,
Cs, Be, Sn, W, Mo, Ta, Nb, Bi, and F but are depleted in Mg, Ca, Fe, Ti, P, Sr, Ba, V, Co, Ni, Cr, Zr, REE, and Y. The
Zr/Hf ratio of rocks serves as a reliable indicator of the concentrating level of rare elements during the fractional
crystallization of Kukulbey granites. Compared to the clarkes of trace elements in the Upper Crust, the Ta, Li, and Sn,
concentrations in Li–F granites increase by factors of 75–35, the W, Rb, Be, and Pb concentrations are 20 to 12 times
higher, and the F, Cs, Mo, Nb, and Hf concentrations are 10–2 times as high.
Shakhtama basites and monzonites are impoverished in rare metal typical for granite of Kukulibey complex (Ta,
Nb, Mo, Rb, Pb) but are enriched in elements peculiar to mantle rocks such as, Mg, Ti, Cr, V, Sr, Ba (Fig.4). Only in
their more late differentiates - Q-syenites and Bt-Hbl granites is noted weak enrichment in Li, Mo, Ta, Rb, Ba, which,
possible, is explained by greisenization connected with granites of Kukulbey complex.
Thereby, mismatch of the crystallization differentiation trends and of the geochemical particularities do not
allow speak about genetic relationship of the Kukulibey granite with Shakhtama latite magmatism. In ditto time heat
influence of the latite magmas could promote anatexsis melting of Kukulbey anhieutectic magma from silica-rich
substratum of Upper Continental Crust (Zaraisky, 2004).
This study was financially supported by RFBR grant 08-05-00865 and Project 3763.2008.5 of the Program of
Leading Research Schools.

References:
Kostitsyn Yu. A., Zaraiskii G.P., Aksyuk, A. M., and Chevychelov V. Yu. Rb–Sr evidence for genetic links
between biotite and Li–F granites: An example of the Spokoinoe, Orlovka, and Etyka deposits, Eastern
Transbaikalia // Geokhimiya. 2004. No. 9. P. 940–948 [Geochem. Int. 2004. Vol. 42. P. 822–830 (2004)].
Kovalenko V. I., Kostitsyn Yu. A., Yarmolyuk V. V., et al. // Magma sources and the isotopic (Sr and Nd)
evolution of Li–F rare-metal granites // Petrologiya, 1999 Vol. 7 No. 4. P. 401–429 [Petrology 1999. Vol. 7. P. 383–
409].
Kozlov V.D and Efremov S.V. Potassic alkali basaltoids and geochemical specification of associated rare-metals
granites // Russian Geology and Geophysics. 1999. Vol. 40. No. 7. P. 973-985 (in Russian).
 181

Syritso L. F. Meosozoic granitoids of the Eastern Transbaikalia and problems of rare-metal ore formation (Izd-vo
SPbU, St. Petersburg, 2002. 357 p. (in Russian).
Syritso L. F., Badanina E.V.,Abushkevich V.S., Volkova T.V. Ways of the decision of the problem of rare-metal
Li-F granite origin and formation conditions // Problems of the geochemistry of the endogenic processes and
environment // Conference materials. Irkutsk, 2007. Vol. 2. P. 227-231 (in Russian)
Troshin Yu. P. Petrochemical specification of basite and medium magmatites with which rare-metal plumasite
granite are associated // Petrochemistry, genesis, and ore productivity of the magmatic formations //, Novosibirsk:
Nauka. 1985. P. 216-225 (in Russian). [in Russian].
Zaraisky G. P. Conditions of the formation of rare-metal deposits related to granitoid magmatism // Proceedings
of Academician V.I. Smirnov’s Memorial Conference. M.: MSU, 2004. P. 105-192 (in Russian).
Zaraiskii G.P., Aksyuk, A. M., Devyatova, V. N. Udoratina O. V., and Chevychelov V. Yu. The Zr/Hf ratio as a
fractionation indicator of rare-metal granites // Petrologiya, 2009. Vol. 17. No. 1. P. 28-50 [Petrology. 2009, Vol. 17.
No. 1. P.. 25–45].

Fairchildite K2Ca(CO3)2 in carbonatites at Loolekop mine, Phalaborwa Igneous Complex

Zhitova L.M.*, Sharygin V.V.*, Nigmatulina E.N.*, Zhitov E.Yu.**
*V.S.Sobolev Institute of Geology and Mineralogy SB RAS, Novosibirsk, Russia; **Novosibirsk State
University, Novosibirsk, Russia

Fairchildite and buetschliite, the high- and low-temperature polymorphs of K2Ca(CO3)2, were described in
wood-ash clinkers formed during forest fires, firstly in western United States (Milton, Axelrod, 1947) and then in
Canada (Dawson, Sabina, 1958). At present day, there are three natural occurrences of fairchildite: the North America
forest fires and slags of Rosenberg mine, W.Germany (Schnorrer-Kohler, David, 1991). High-temperature K2Ca(CO3)2
was indicated in burning (>600oC) ash products of biomass and agricultural waste, in different glasses and cement
clinkers. The experimental study of the system Na2CO3-K2CO3-CaCO3 at 1 kb (Cooper et al., 1975) has shown that
fairchildite is stable from its melting point (809°C) down to 547°C, where it inverts into buetschliite, and the nyerereite-
fairchildite solid solutions are real. All this strongly assume the possible appearance of fairchildite in carbonatites, but it
has never observed previously in them. Nyerereite enriched in K is the major mineral in natrocarbonatites of Oldoinyo
Lengai and occasionally occurs as daughter phases of mineral-hosted inclusions in calciocarbonatites and related
silicate rocks (Le Bas, Aspden, 1981; Kogarko et al., 1991, Veksler et al., 1998; Zaitsev, Chakhmouradian, 2002;
Kogarko, Turkov, 2007; Stoppa et al., 2008). Here we report fist occurrence of magmatic fairchildite found in
magnetite-hosted inclusion of carbonatite from the Loolekop mine, Phalaborwa. The previous inclusion studies for
carbonatites and silicate rocks of this complex were provided by Aldous (1986) and Solovova et al. (1998).
The Phalaborwa igneous complex (age >2060 Ma), located in the Archean Shield of northeastern Transvaal,
South Africa, is the unique in that its carbonatites are host of an economic deposit of copper ores with considerable
resources of magnetite, apatite, vermiculite, uranothorianite and baddeleyite (Hanekom et al., 1965, Palabora MC,
1976). The complex (area - 16.5 km2, depth - up to 5 km) is a ring shaped pipe-like structure, which resulted from the
four intrusive cycles: 1 - pyroxenites; 2 - syenites; 3 - phoscorites and banded carbonatites; 4 - transgressive
carbonatites. The specific feature of all rocks of the Phalaborwa complex is low abundance of Na 2O. Studied samples
were collected from deep horizons of the Loolekop mine, where phoscorites and early carbonatites form a banded ore
body, and represent coarse-grained combined phoscorite-carbonatites. They contain variable amounts of coarse-grained
magnetite, partially serpenitized olivine (Fo80), fluorapatite and phlogopite in fine-, medium-grained matrix, consisting
of Mg-calcite and dolomite. Sulfide mineralization is represented mainly by chalcopyrite and bornite. Brucite,
chondrodite, baddeleyite, uranothorianite, Ba-Sr-carbonates, barite, celestine, Na-REE-apatite are minor or accessory.
Magnetite forms coarse grains (up 3 cm) and contains abundant solid inclusions different in mineral composition
and origin. Host magnetite in chemical composition approaches ideal FeFe2O4 with minor TiO2 (1.0-1.7), MgO (1.2-
1.7), Al2O3 and MnO (up to 0.2 wt.%). Solid decay microstructure of magnetite-ilmenite-ulvospinel and individual
large lamellae of picroilmenite (TiO2 - 58.3-58.6; FeO -22.2-28.0, MgO -12.1-16.9, MnO - 1.1-2.5 wt.%) are common.
Discrete euhedral grains (size - 100-300 µm) and intergrowths of fluorapatite, dolomite, calcite, olivine, baddeleyite,
and phogopite also occur. Unlike solid inclusions, multiphase primary inclusions have rounded or irregular shape (size -
10-300 µm) and vary in mineral composition from carbonate to carbonate-silicate-oxide. Dolomite, calcite, apatite,
picroilmenite, phlogopite, magnesite, brucite are essential minerals in such inclusions. Minor phases are interstitial in
respect to the essential minerals. According to scanning microscopy, there are baddeleyite, uranothorianite, strontianite,
witherite, barite, celestine, siderite, Ca-Ba-carbonate, bastnaesite-(Ce), Na-REE apatite, halite and Fe-Ni-Co-Cu
sulfides. The carbonate inclusions usually vary in calcite-dolomite ratio and calcite sometimes contains perthitic
dolomite. In addition, minute (5-10 µm) inclusions enriched in halite, sylvite and Mg-Fe chlorides occur in magnetite.
They are similar to secondary inclusions described in apatite of the Loolekop phoscorites by Solovova et al. (1998).
In the core of magnetite crystal we have been found a multiphase inclusion (size - 60 µm) with K-Ca-carbonate
K2Ca(CO3)2. This inclusion also contains dolomite, picroilmenite (geikielite-ilmenite), phlogopite, brucite, witherite and
halite (Fig. 1, Table 1). The relationships of phases within inclusion have shown that K-Ca-carbonate crystallized after
phlogopite and picroilmenite and before dolomite. Estimations for the magnetite-ilmenite and dolomite-calcite pairs
gave equilibrium temperatures higher than 650-700oC. The study of fluid and salt inclusions in apatite of the Loolekop
 182

phoscorites (Solovova et al., 1998) has shown homogenization temperatures in the 630-750oC range. Judging mineral
relations and temperature estimations, K-Ca-carbonate seems to be high-temperature polymorph of K2Ca(CO3)2 -
fairchildite. The existence of brucite and phlogopite in multiphase magnetite-hosted inclusions suggests the presence of
some water in the initial carbonatite melt, what can provoke the fairchildite-buetschliite inversion with decreasing
temperature. However, experiments of Cooper et al. (1975) has shown that neither presence of water nor pressure
changing lead to a drastic shift in the fairchildite-buetschliite inversion temperature. Fairchildite may convert slowly to
buetschliite at room temperature and in air conditions (Mrose et al., 1966). Possibly, the same phenomenon of
fairchildite decomposition was observed by us during one month after opening of the inclusion on the surface.

W
B S A F
P
ith
hl SE i l e
D
B
ol F
rc I
air
lm I
P
hl lm

F
air F
air
2
0 µm
K C M T
a g i

Figure 1. BSE image and elemental maps for fairchildite-containing inclusion in magnetite, phoscorite-
carbonatite. Note: Fair - fairchildite; Dol - dolomite; Phl - phlogopite; Ilm - geikielite-ilmenite; Brc - brucite; With - witherite.

Table 1. Chemical composition (EMPA, in wt.%) of minerals of fairchildite-containing inclusion and host
magnetite, phoscorite-carbonatite, Phalaborwa complex.

Phase n SiO2 TiO2 Al2O3 FeO MnO MgO CaO BaO SrO Na2O K2O F Total
Mgt-
1 0.00 0.95 0.10 90.34 0.16 1.74 0.00 0.00 0.00 0.00 0.00 0.00 93.29
host
Ilm 3 0.00 58.60 0.00 21.58 2.98 16.55 0.00 0.00 0.00 0.00 0.00 0.00 99.70
Phl 2 38.27 2.85 12.11 5.91 0.13 27.13 0.59 0.13 0.00 0.12 10.91 0.76 98.90
Dol 6 0.00 0.00 0.00 1.87 0.17 21.19 29.48 0.07 0.47 0.02 0.00 0.00 53.28
Fair 5 0.00 0.00 0.00 1.47 0.01 0.00 23.15 0.00 0.00 0.63 38.54 0.00 63.80
Brc 3 0.00 0.00 0.00 3.80 0.22 65.85 0.31 0.00 0.03 0.02 0.00 4.22 74.45

Thermobarogeochemical studies of Solovova et al. (1998) have shown that the Phalaborwa carbonatites and
phoscorites have been formed at 850-870oC and 4-4.5 kb and calciocarbonatite melt contains up to 7 wt.% SiO2, 11.5
wt.% P2O5, 0.8 wt.% K2O and very low concentration of Na2O (<0.1 wt.%). In phoscorite-carbonatites the traces of
Na2O are fixed as an accessory Na-REE-apatite (groundmass, inclusions) and as halite in salt inclusions. Unlike
calciocabonatite worldwide, the drastic predominance of K2O over Na2O was promoted the appearance of fairchildite
instead of nyerereite during crystallization of the Phalaborwa calciocarbonatite melt.
This study was financially supported by RFBR (grant 07-05-00685).

References:
Aldous R.T.H. Copper-rich fluid inclusions in pyroxenes from the Guide Copper Mine, a satellite intrusion of
the Palabora igneous complex, South Africa // Economic Geology. 1986. Vol. 81. P. 143-155.
Cooper A.F., Gittins J., Tuttle O.F. The system Na2CO3-K2CO3-CaCO3 at 1 kilobar and its significance in
carbonatites petrogenesis // American Journal of Science. 1975. Vol. 275, P. 534-560.
Dawson K.R., Sabina A.P. A Canadian occurrence of fairchildite and buetschliite, Ontario // Canadian
Mineralogist. 1958. Vol. 6. P. 290-291.
Hanekom H.J., van Staden C.M.v.H., Smith P.J., Pike D.R. The geology of the Palabora igneous Complex:
South Africa Geol. Survey Mem. 1965. Vol. 54, 179 p.
Kogarko L.N., Plant D.A., Henderson C.M.B., Kjarsgaard, B.A. Na-rich carbonate inclusions in perovskite and
calzirtite from the Guli intrusive Ca-carbonatite, polar Siberia // Contributions to Mineralogy and Petrology. 1991. Vol.
109. P. 124-129.
 183

Kogarko L.N., Turkov V.A. Crystallization features of ultrabasic alkaline melts based on study of inclusions (Kugda
massif, Polar Siberia) // In: Shcherbak N.P. (Ed.), Alkaline magmatism of the Earth and its ore potential. Kiev, Logos.
2007. P. 116-118 (in Russian).
Le Bas M.J., Aspden J.A. The comparability of carbonatitic fluid inclusions in ijolites with natrocarbonatite lava
// Bulletin of Volcanology. 1981. Vol. 44-3. P. 429-438.
Milton C., Axelrod J. Fused wood-ash stones: fairchildite (n. sp.) K2CO3·CaCO3, buetschliite (n. sp.)
3K2CO3·2CaCO3·6H2O and calcite, CaCO3, their essential components // American Mineralogist. 1947. Vol. 32. P.
607-624.
Mrose M.E., Rose H.J., Marinenko J.W. Synthesis and properties of fairchildite and buetschliite: their
relationship in wood-ash stone formation // GSA Special Papers. 1968. Vol. 101, P. 146.
Palabora Mining Company Limited Mine Geological and Mineralogical Staff. The Geology and the economic
deposits of copper, iron, and vermiculite in the Palabora igneous complex: a brief review // Economic Geology. 1976.
Vol. 71, P. 177-192.
Schnorrer-Kohler G., David W. Die Blei- und Silberhutte Braubach in ihre Haldenminerale // Lapis. 1991. Vol.
16 (1). P. 38-53.
Solovova I.P., Ryabchikov I.D., Kogarko L.N., Kononkova N.N. Study of inclusions in minerals of the
Phalaborwa carbonatite complex, S. Africa. Geokhimiya. 1998. P. 435-447 (in Russian).
Stoppa F., Sharygin V.V., Jones A.P. Mantle metasomatism and alkali carbonatite silicate phase reaction as
inferred by nyerereite inclusions in Vulture volcano carbonatite rocks // CD edition of Extended abstracts of 9th IKC.
2008. No. 9IKC-A-00068.
Veksler I.V., Nielsen T.F.D., Sokolov S.V. Mineralogy of crystallized melt inclusions from Gardiner and Kovdor
ultramafic alkaline complexes: implications for carbonatite genesis // Journal of Petrology. 1998. Vol. 39. P. 2015-2031.
Zaitsev A.N., Chakhmouradian A.R. Calcite-amphibole-clinopyroxene rock from the Afrikanda complex, Kola
Peninsula, Russia: mineralogy and possible link to carbonatite. II. Oxysalt minerals // Canadian Mineralogist. 2002.
Vol. 40. P. 121-136.

Geochemical constraints on the genetic relationship between A-type peralkaline granite and
anorthosite from the Neoarchean Keivy alkaline province, NE Baltic Shield
Zozulya D.R.*, Eby G.N.**
* Geological Institute, Kola Science Centre, Apatity, Russia; ** University of Massachusetts Lowell, USA.

The genetic relationship of anorthosites and of A-type granites and intermediate alkaline rocks is debated for well
known localities from Gardar province (Greenland), Air ring complex (N. Niger), Younger Granite province (Nigeria),
Pikes Peak batholith (Colorado) (Barker et al., 1975; Bonin, 1996; Demaiffe & Moreu, 1996; Upton, 1974, 1996).
A suite of massif-type anorthosites and peralkaline granites is found in the Archean Keivy terrane of the NE
Baltic shield. The Keivy terrane is mainly composed of mafic (minor) - intermediate - felsic (most abundant)
metavolcanic and metasedimentary rocks that overlie the oldest tonalite-trondhjemite-granodiorite (TTG) basement of
the Central Kola Block. According to the geochronological data, the oldest basement of the Central Kola Block was
formed during several stages of the Neoarchean endogenic activity and has an isotopic age of 3.0-2.7 Ga. The felsic
metavolcanics of the Keivy terrane, which completed the extrusive succession, represent orogenic rocks with a U-Pb
zircon age of 2870 Ma, forming from geochemical constraints in island-arc environment. Interformational sheet-like
intrusive bodies of peralkaline granites, and spatially confined to them gabbro-anorthosite lopolithes are present in the
margins of the Keivy terrane.
The Keivy alkaline province consists of 2650-2660 Ma aegirine-arfvedsonite granites (six massifs of a few
hundred meters thicknesses and with the total exposure area of ca. 2500 km2; the largest ones are the West Keivy,
Ponoj, White Tundra), 2670 Ma aegirine-augite-lepidomelane-ferrohastingsite syenogranites in margins of some
massifs, and 2680 Ma lepidomelane-ferrohastingsite syenite dykes cutting the TTG basement (Zozulya et al., 2005).
Small dike-like bodies of 2610 Ma nepheline syenite cut the West Keivy peralkaline granite massif.
The Keivy anorthosite complex consists of several (the largest Tsaga massif is up to the 170 km2) lopolithes and
fault-type intrusions composed mainly of anorthosite and gabbro-anorthosite and marginal gabbro-norite and
titanomagnetite-rich troctolite bodies. The formation age for them range from 2670 Ma to 2660 Ma (Zozulya et al.,
2005).
The Keivy anorthosites have low REE abundances (Ce 5-23 and Yb 1.5-6.8 times chondrites), fractionated REE
distributions (chondrite-normalized La/Yb ratios are 4-10) and positive Eu anomalies (Fig. 1). The comagmatic gabbro-
norites have similar REE patterns, but no or negligible positive Eu anomalies. As the chondrite-normalized La/Yb ratios
do not correlate with REE abundances, an enriched source for the primary magmas is proposed. The Keivy peralkaline
granites are extremely enriched in REE (100-1000 times chondrites), show negative Eu anomalies, have normalized
La/Yb ratios of 1.5-13 (Fig. 1).
 184

Fig. 1. Chondrite normalized REE distribution patterns for the Keivy gabbro-anorthosite and peralkaline granite.

The granites of the Keivy alkaline province are extremely enriched in Zr (300-1900 ppm), Y (40-150 ppm), Nb
(20-150 ppm) and Rb (160-900 ppm), have associated Zr-REE ore occurrences, are very low in Sc (0.3-1.3 ppm) and Sr
(10-30 ppm), and high Ga/Al ratios. On standard trace element discrimination diagrams (Whalen et al., 1987; Pearce et
al., 1984; Eby, 1990) the Keivy peralkaline granites plot as within-plate or post-collisional A-type granitoids, and
nepheline syenites fall to OIB field. The least evolved syenogranites plot in the EM2-field on the εSr - εNd diagram.
The anorthosites show high compatible element (Sc, 25-40 ppm and Sr, 460-670 ppm) abundances and very low
incompatible elements (Zr, 60-100 ppm, Y, 4-15 ppm, Nb, 8-12 ppm, Rb, 15-30 ppm), but the same Y/Nb, Ce/Nb,
Yb/Ta ratios as the granites (Fig. 2). The enriched source for the Keivy anorthosites has low εNd (-0.15 to -0.24) and
low Y/Nb (0.6-1.3) and Ce/Nb (1-3) ratios. The OIB-like source for anorthosites is enhanced also by the similar Nb/Zr
and Ba/Zr ratios (Fig. 2).
The close temporal and spatial association of the gabbro-anorthosites and the peralkaline granites and their
similar magma sources suggest a genetic relationship. One possible model is protracted fractional crystallization of a
primary subalkaline/alkaline basalt magma with removal of plagioclase during the early stages of crystallization
(forming a Ca- and Al-enriched cumulate, anorthosite) and alkali, iron and HFSE enrichment of the residual melt
leading to the peralkaline granites (Fig. 3). In cases, this fractionation has been accompanied by simultaneous crustal
contamination. “Plagioclase effect” was favored by anorogenic tectonic environment.

Fig. 2. Trace element discrimination diagrams for Keivy anorthosites (peralkaline granite field shown for comparison).
 185

Fig. 3. Schematic illustration of mineral fractionations and inferred sequence of crystallization

for the Keivy anorthosite – peralkaline granite – nepheline syenite anorogenic suite.

References:
Barker F., Wones D.R., Sharp W.N., Desborough G.A. The Pikes Peak batholith, Colorado Front Range and a
model for the origin of gabbro-anorthosite-syenite-potassic granite suite // Precambrian Research. 1975. V.2. P. 97-160.
Bonin B. A-type granite ring complexes: mantle origin through crustal filters and the anorthosite-rapakivi
magmatism connection. In: Petrology and geochemistry of magmatic suites of rocks in the continental and oceanic
crusts. Bruxelles: 1996. P. 201-218.
Demaiffe D, Moreau C. Crustal growth in Air (Niger, West Africa): significance of the Palaezoic anorthosite-
bearing anorogenic province. In: Petrology and geochemistry of magmatic suites of rocks in the continental and oceanic
crusts. Bruxelles: 1996. P. 35-50.
Eby G.N. The A-type granitoids: a review of their occurrence and chemical characteristics and speculations on
their petrogenesis // Lithos. 1990. Vol. 26. P. 115-134.
Pearce J., Harris N., Tindle A. Trace element discrimination diagrams for the tectonic interpretation of granitic
rocks // Journal of Petrology. 1984. Vol. 25. P. 956-983.
Upton B.G.J. The alkaline province of south-west Greenland. In: The alkaline rocks (Ed. H. Sǿrenson). London -
New York – Sydney – Toronto: 1974. P. 221-238.
Upton B.G.J. Anorthosites and troctolites of the Gardar magmatic province. In: Petrology and geochemistry of
magmatic suites of rocks in the continental and oceanic crusts. Bruxelles: 1996. P. 19-34.
Whallen J., Currie K., Chappell B. A-type granites: geochemical characteristics, discrimination and petrogenesis
// Contributions to Mineralogy and Petrology. 1987. Vol. 95. P. 407-419.
Zozulya D.R., Bayanova T.B., Eby G.N. Geology and age of the Late Archean Keivy alkaline province,
Northeastern Baltic Shield // The Journal of Geology. 2005. Vol. 113 (5). P. 601-608.

Lithospheric roots and asthenospheric upwarps of the NE Baltic Shield: spatial controls for
kimberlitic and alkaline magmatism
Zozulya D.R.*, Peltonen P.**, O’Brien H.***, Lehtonen M.***
* Geological Institute, Kola Science Centre, Apatity, Russia; ** Northland Exploration Oy, Espoo, Finland;
*** Geological Survey of Finland, Espoo, Finland.

The NE Baltic Shield can be considered as prospective on diamondiferous magmatism at a whole. The more
general structural-tectonic condition is met for it – confinement to the platform with Precambrian basement. This part of
the Shield represents the oldest continental crust with cool lithosphere (<40 mWt/m2) of 170-240 km thickness. The
petrological and mineralogical criteria for kimberlitic magmatism are also fulfilled. The region is characterized with
abundant dykes and explosive pipes of alkaline and alkaline-ultramafic composition. The numerous indicator
kimberlitic minerals and diamonds are recovered from the Quaternary sediments of the region. Based on their findings
the inferred kimberlitic fields are predicted in the region (Makeevka, Pyalitsa, Pulonga, Snezhnitsa fields in the south-
east, Zarechensk field in the south-west (Zozulya et al., 2008)). In the southern part of region the two Ermakovsky low-
grade kimberlitic pipes are found (Kalinkin et al., 1993).
More than 600 pyrope and chrome diopside grains recovered from the Quaternary sediments (till, alluvium,
coastal sediments) of the southern, central and northern parts of the Kola craton were analyzed in order to determine
their P-T parameters. Representing either mantle xenocrysts or constituents of mantle xenoliths, the pyropes and
chrome diopsides contain valuable information on the composition of the lithospheric mantle and its thermal properties.
It is established (Hirvas, 1977) that in the glaciated areas the main portion (75-90%) of the transported detrital
material has rather local (0-5 km) than distal sources. So the samples studied mostly characterize the closest areas. As
the sediments could contain the shallower pyropes and diopsides from crustal eclogites and eclogitic xenoliths and
 186

xenocrysts from non-kimberlitic dykes and pipes the thorough discrimination of minerals originally derived from the
deep lithospheric peridotites was done (G9 (lherzolitic) and G10 (harzburgitic) pyropes; chrome diopsides with
Al2O3<4.5 wt%, Cr2O3>0.5 wt%, Na2O<2 wt% and MgO>15 wt%). Ni-thermometry of Ryan et al. (1996) on pyropes
gives a range of temperatures between 650-1250°C, corresponding to a sampling interval of ca. 75-190 km. From the
distribution of the different pyrope groups and their trace element compositions, stratified structure of the SE Kola
craton lithospheric mantle is inferred: G10-pyropes are absent in the shallow mantle horizon (75-110 km) which is the
main source of G9-pyropes, while deeper mantle horizon between 110 and 190 km has contributed abundant G10-
pyropes to magmas. Ca. 20 % of these pyropes are derived from the stability field of diamond, i.e. from the depth of
130-190 km. The stratified structure is established also for major part of Karelian craton with Kaavi-Kuopio and
Kuhmo kimberlitic and lamproitic fields (Lehtonen et al., 2004; Peltonen & Brügman, 2006; Peltonen et al., 2008).
P-T values for peridotitic chrome diopsides using the single-grain thermobarometer of Nimis & Taylor (2000)
imply that most of grains from SE Kola fall into the graphite stability field within 20-45 kbar and 700-1300 °C. These
grains apparently originated from non-diamondiferous ultramafic xenoliths in alkaline-ultramafic dykes of the region
and located to the west from sampled area. Nevertheless, ca. 15% of SE Kola diopsides yield values of 40-60 kbar and
700-1100 °C and have been derived from the stability field of diamond. Diopsides from SW Kola yield P-T estimates
within of 45-65 kbar and 850-1100°C, and mostly fall into diamond stability field. Diopsides from the central Kola
yield P-T values of 20-55 kbar and 700-1150°C, ca. 20% of them being derived from the diamond field. Diopsides from
the northern Kola region, in turn, yield P-T values of 20-45 kbar and 600-1300°C, them all falling within the stability
field of graphite. The maximum depth of xenocryst sampling varies from up to 200 km in the south-eastern and south-
western Kola, to 170 km in central Kola, and down to 140 km in the northern Kola region.
The P-T values for chrome diopsides thus imply significant regional variations in the heat flow. Within the
southern part of the Kola, adjacent to the Kandalaksha graben, the chrome diopside data is consistent with the 38-46
mW/m2 model geotherm of Pollack & Chapman (1977). Importantly, towards east and west, away from Kandalaksha
graben, the lithosphere appears to become thicker and the heat flow corresponds to the cool cratonic model geotherm of
35-38 mW/m2. The central Kola, in turn, is characterized by more elevated heat flow of ca. 38-44 mW/m2. The highest
heat flow values (up to 50 mW/m2), are observed in the northernmost Kola craton, adjacent to the Barents rift system.
Pyropes and chromites from Ermakovsky kimberlite (southern Kola craton) show a range of temperatures
between 650-1000°C, corresponding to a sampling interval of ca. 75–150 km. This is in accordance with the low
diamond grades determined for these pipes. The data show a different lithosphere mantle composition beneath area; one
that is relatively uniform in its harzburgite-lherzolite distribution. The similar lithospheric composition is observed for
the NE segment of Karelian craton with Kuusamo kimberlitic field (Peltonen et al., 2008). This could be explained by
the spatial proximity of the Ermakovsky area to the Kandalaksha graben of the Belomorian rift system. Paleozoic
reactivation of the rift may have altered the stratified Archean lithospheric mantle. Additionally, melt metasomatism is
confirmed for this mantle, based on higher TiO2 contents in pyropes (average value 0.21 wt%) relative to those from the
south-eastern area (average value 0.11 wt%).
Based on the whole data on xenocryst thermobarometry from Karelia and Kola cratons the follow structure of the
lithosphere could be outlined along the ca. 1000 km transect “Karelian craton-Kandalaksha graben-Kola craton” (Fig.
1). For the major part of Karelia craton (Kaavi-Kuopio and Kuhmo areas) and for the SE part of the Kola craton the
deep lithospheric roots are inferred, up to 240 and 200 km, correspondingly. The lithospheric mantle here is stratified:
the shallow horizon (75-110 km) is of mainly werhlitic (Kaavi-Kuopio) or lherzolitic (Kuhmo and SE Kola) content; the
middle horizon (110-190 km) is of lherzolitic-harzburgitic content; and the deepest horizon (190-240 km) is of
lherzolitic (Kaavi-Kuopio) or lherzolitic-harzburgitic (Kuhmo) content and presented only in Karelian craton. The roots
are of Archean age (Peltonen & Brügman, 2006) and cratonic geotherm is cool (34-38 mW/m2). These areas are most
promising for diamondiferous kimberlitic magmatism.
 187

Fig. 1. Simplified geological cross-section of the lithosphere along the “Karelian craton - Kandalaksha graben -
Kola craton” transect with kimberlitic occurrences shown.

Asthenosphere uplift is observed in the NE part of Karelia craton (Kuusamo area) and in southern Kola craton
(Ermakovsky area, adjacent to Kandalaksha graben) up to 180 and 140-150 km, correspondingly. The lithospheric
mantle of this segment is of homogeneous lherzolitic-harzburgitic composition and characterized by elevated heat flow
values (38-46 mW/m2). Apparently, the regeneration of mantle occurred here during 1.2 and 0.36 Ga rifting. This area
is characterized with the abundant occurrences of rift-related alkaline and ultrabasic-alkaline dykes and pipes and has
low/no diamond potential.
The data obtained indicate also on the shallower thickness of the northern part of the Kola craton down to 140
km. This area is also characterized by the elevated heat flow values (up to 38-50 mW/m2) and by the presence of non-
diamondiferous alkaline-ultrabasic rocks.
The study is supported by the Department of Earth Science RAS (Priority programs 6 & 8).

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