1

Microbiallyinduced
sulphurandcarbonateauthigenesis
inMessiniansulphaterichstrata
DissertationzurErlangungdesDoktorgradesindenNaturwissenschaften
Dr.rer.nat.

vorgelegt
imFachbereichGeowissenschaftenderUniversitätBremen
von
DiplomGeowissenschaftlerinSimoneZiegenbalg
Januar2011

TagdesöffentlichenKolloquiums
02.März2011
GutachterderDissertation
Prof.Dr.JörnPeckmann
Dr.TimothyG.Ferdelman
Prüfer
Prof.Dr.KaiUweHinrichs
Prof.Dr.WolfgangBach
WeitereMitgliederderKommission
Dr.DorotheeWilhelmsDick
KevinBecker
…dasGeheimniseinesSteines,
außengrauundunscheinbar,
weißerdochinseinemInneren
einKristallsternenklar…
GerhardSchöne
(aus„DiesiebenGaben“)*

5

PREFACE
ThethesispresentedherewasfinancedbytheGermanResearchFoundationthroughthe
InternationalGraduateCollegeProxiesinEarthHistory(“EUROPROX”),whichprovidednotonlymy
scholarshipbutalsofinancedthetwosamplingcampaignsinSicily,myparticipationonnationaland
internationalscientificmeetings,myattendanceontopicrelatedandsoftskillcourses,mystay
abroadforthreeweeksatthedepartmentofsedimentologyoftheVrijeUniversteitAmsterdamas
wellashalfayearatthedepartmentofgeodynamicsandsedimentologyoftheUniversityofVienna
andofferedmeapleasantandeffectivetimefordoingmyPhD.

6

7
TABLEOFCONTENTS
Abstract
Kurzfassung
1 Introduction 13
1.1 Sulphur 13
1.1.1 Sulphurandthesulphurcycle 13
1.1.2 Applicationofsulphurandoxygenisotopesinsulphurspecies 14
1.2 Authigeniccarbonates 17
1.3 AuthigenicsulphurandcarbonatedepositswithfocusonSicilyandSpain 19
2 Objectivesofthethesis 22
Manuscripts
3 Firstmanuscript– 26
FormationofsecondarycarbonatesandnativesulphurinsulphaterichMessinian
strata,Sicily
4 Secondmanuscript– 52
AnaerobicoxidationofmethaneinhypersalineMessinianenvironmentsrevealedby
13
Cdepletedmolecularfossils
5 Thirdmanuscript– 66
GypsumwhiskersinMessinianevaporitesidentifiedbyμXRD2
6 Fourthmanuscript– 73
Authigenesisofnativesulphuranddolomiteinalacustrineevaporiticsetting(Hellín
basin,LateMiocene,SESpain)
7 Concludingremarksandperspectives 93
8 References 96
9 Danksagung 114
Erklärung 117

8

ABSTRACT 9

ABSTRACT
Authigeniccarbonatesaccompaniedbynativesulphurarepresentwithinsulphaterichdeposits
allaroundtheworld,forexampleassociatedtosaltdomecaprocksortheevaporiticsuccessionof
theMessiniansalinitycrisisintheMediterranean.Severalauthorsproposed theinvolvementof
sulphatereducingbacteriaincarbonateandsulphurauthigenesis,butthepathwaysofsulphurand
carbonateformationarestillunderdiscussionandtheorganismsinvolvedinthesediagenetic
processescouldnotbedeterminedsofar.Becausenumerousabandonedsulphurminesstill
demonstratetheformereconomicimportanceofnativesulphurforthisisland,Siciliansulphur
depositswereselectedtostudythegenesisofauthigeniccarbonateandsulphur.Theresultsare
presentedinthefirstandsecondmanuscript:
Microbialsulphatereductionresultsinlargesulphurisotopefractionationbetweenthesulphate
sourceandtheproducedsulphide,reflectedinfractionationofupto60‰betweensulphateand
sulphurintheSiciliansamples.Theobservedvariabilityincarbonandoxygenisotopiccompositionof
thecarbonatesbetweenthefivesampledlocationswasunexpected.Althoughthereductionof
sulphateledinalllocationstodepositionofauthigeniccarbonateandaccompanyingnativesulphur,
twodistinctmodesofthatprocessaredifferentiable.A)Duringepigenesist(latediagenetic)gypsum
oranhydritewasdissolvedbymeteoricwaters,providingasulphatesourceforbacteriatooxidize
mainlycrudeoilcarbon,resultingincarbonatesdepletedin13C(13C:aslowas29‰)and
characterizedbylow18Ocarbonatevalues.B)Duringsyngenesis(earlydiagenetic)dissolvedsulphate
wasconsumedtooxidizeorganiccarbon,mainlymethane,resultinginhighly13Cdepleted
carbonates(13C:aslowas52‰).High18Ovaluesandpseudomorphsafterlenticulargypsum
withinthecarbonaterevealevaporiticconditions,whichisverifiedbylipidbiomarkersnamely
tetrahymanol,extendedarchaeolandpossiblyphytanylglycerolmonoethersaswellasnon
isoprenoidalmacrocyclicglyceroldiethers.Thepresenceof13CdepletedarchaeallipidssuchasPMI
andsn2hydroxyarchaeolaswellas13Cdepletedmolecularfossilsofsulphatereducingbacteria(e.g.,
isoandanteisofattyacids)inthesesyngeneticcarbonatesledtotheconclusionthatthese
carbonatesareinducedbysulphatedependentanaerobicoxidationofmethane(AOM)andthat
AOMfunctionsalsoinhypersalinesettings.
ThethirdmanuscriptdescribestheapplicationofamodernXraydiffractometercombinedwith
focussingXrayopticsandalarge2dimensionaldetector(μXRD2),whichallowsthedetermination
ofminutemineralsdirectlyonuncoveredthinsection.IncontrasttoconventionalXRDandelectron
microscopyincludingEDX,thatmethodallowedtheidentificationofpeculiarhairlikecrystalsina

10 ABSTRACT

sulphurbearinganhydritesamplefromSicilyasgypsumwhiskers.Thesedelicatecrystalsare
successfullyprotectedagainstdestructionbyembeddinginnativesulphur.Whiskercrystalshadnot
beendescribedbeforeinsuchsettings,accordingtoavailableliterature.Furthermorethestudy
emphasisestheutilityofμXRD2forsedimentologicalstudies.
Lacustrinesettingsareusuallylowinsulphateandthereforenotthoughttobeinfluencedby
sulphatereduction.Nevertheless,nativesulphuraccompaniedbydiageneticcarbonateispresentin
thelacustrineHellínbasininsoutheasternSpain,asreportedinthefourthmanuscript.Here
microbialsulphatereductioniscrucialforthesulphurprecipitationaswell,revealedbylowsulphur
isotopevaluesofthenativesulphur(aslowas17‰).Theaccompanyingcarbonate,mainly
dolomite,ischaracterizedbylamination,whichpartlyresemblesbiomatstructures,andby
spheroidaldolomitecrystalswhichindicateamicrobialorigin,corroboratedbylow13Cvalues(as
lowas11‰).Mostinterestinglytheoxidationofsulphide,whichresultedfromsulphatereduction,
tonativesulphur,wasmostlikelycarriedoutbysulphurbacteria,indicatedbyspheroidalstructures
beddedinsulphur,whichresembleThiomargaritasp.orAchromatiumsp..Thisisimportantasthe
oxidationofsulphidetosulphurisstillpuzzlinginmostofthesulphurdepositsandsofarnomethod
isavailabletoclearlysolvethatquestion.
Kurzfassung 11

KURZFASSUNG
SchwefelführendeauthigeneKarbonatekommenweltweitinvielensulfatreichenAblagerungen
vor,zumBeispielindenDeckgesteinenvonSalzstöckenoderindenevaporitischenAblagerungender
MessinischenSalinitätskriserundumdasMittelmeer.DerEinflusssulfatreduzierender
MikroorganismenaufdieKarbonatundSchwefelbildungwurdeinmehrerenStudienanHandvon
petrographischenundstabilenIsotopendatendargelegt.DerZeitpunktundAblaufder
Sulfatreduktionkonntejedochbishernochnichtabschließendgeklärtwerden.Ebensowurdendie
beteiligtenMikroorganismenbishernichtnäherbestimmt.InSizilienweisendutzendeverlassene
Schwefelminendaraufhin,dassderSchwefelabbaubiszuBeginndesletztenJahrhundertsinSizilien
einegroßeBedeutunghatte.FünfLokationen,alleaufdemGebietoderinderNäheehemaliger
Schwefelminenwurdenausgewählt,umdieGenesederauthigenenKarbonateunddesSchwefelszu
untersuchen.DieErgebnissesindindenManuskripteneinsundzweidargestellt.
MikrobielleSulfatreduktionführtzueinerstarkenFraktionierungderSchwefelisotopezwischen
derSulfatquelleunddemproduziertenSulfid.DasspiegeltsichineinerFraktionierungvonbiszu
60‰zwischenSulfatundSchwefelindenSizilianischenProbenwieder.DieVariabilitätinder
KohlenstoffundSauerstoffisotopiederKarbonatezwischendeneinzelnenLokationenwar
unerwartetgroß.ObwohlSulfatreduktioninallenLokationenzurBildungvonauthigenemKarbonat
undSchwefelführte,lassensichzweiverschiedeneEntstehungswegeunterscheiden.A)Währendder
Epigenese(spätdiagenetisch)werdenGipsoderAnhydritedurchmeteorischeWässergelöstund
stehensomitdenMikroorganismenalsSulfatquellezurVerfügungumorganischenKohlenstoff,z.B.
Rohöl,zuoxidieren.DiedarausresultierendenKarbonatesindcharakterisiertdurcheine
Abreicherungan13Cundniedrige18OWerte(13C29‰;18O4‰).B)Währendder
SyngenesenutzendieMikroorganismenimPorenwassergelöstesSulfatumhauptsächlichMethanzu
oxidieren.DasführtzurBildungvonsehrstarkan13CabgereichertemKarbonat(52‰).Hohe18O
Werte(+8‰)undPseudomorphosennachGipsindenKarbonatenzeigenevaporitische
Bedingungenan.LipidBiomarker(Tetrahymanol,verlängertesArchaeol,sowiehöchstwahrscheinlich
auchPhytanylglycerolMonoetherundmakrozyklischeGlycerolDiether)bestätigendieExistenzvon
salzliebendenMikroorganismenwährendderKarbonatbildung.DerNachweisvonArchaeenlipiden
mitniedrigen13CWerten(105‰),wiezumBeispielPMIundsn2Hydroxyarchaeol,sowie
molekularenFossiliensulfatreduzierenderBakterienmitähnlichniedrigen13CWerteninden
syngenetischgebildetenKarbonatenführtzuderSchlussfolgerung,dassdieKarbonatbildungdurch
denProzessdersulfatabhängigenanaerobenMethanoxidation(AOM)induziertwurdeunddasAOM
auchinhypersalinarenMilieusablaufenkann.

12 KURZFASSUNG

DasdritteManuskriptbeschreibtdieAnwendungeinesmodernenRöntgendiffraktometersin
KombinationmiteinerfokussierendenRöntgenoptikundeinemgroßenzweidimensionalenDetektor
(μXRD2).DieseTechnikerlaubtdieUntersuchungvonsehrkleinenMineralendirektaufdem
Dünnschliff.VerglichenmitherkömmlicherRöntgendiffraktometrie,sowiederAnalysemit
ElektronenmikroskopundenergiedispersiverRöntgenspektroskopiewarnurdieseneueMethodein
derLagefeinehaarartigeKristalleinschwefelführendenAnhydritprobenausSizilienalsGipsWhisker
zuidentifizieren.DiesefiligranenKristallesinddurchihreEinbettunginSchwefeleffektivgeschützt.
BisherwurdensolcheGipsWhiskerinevaporitischenAblagerungennichtbeschrieben.Darüber
hinausunterstreichtdieseArbeitdieBedeutungderMikroXRD2fürsedimentologischeStudien.
ElementarerSchwefelunddiagenetischeKarbonateausdemlakustrinenHellínBeckenim
SüdostenSpanienssindimviertenManuskriptbeschrieben.WeillakustrineMilieusnormalerweise
niedrigeSulfatkonzentrationenaufweisen,spieltdiebakterielleSulfatreduktionhiermeisteine
untergeordneteRolle.ImHellínBeckenallerdingsdienenimUntergrundbefindlicheTriassischeGipse
alsSulfatquelle.NiedrigeSchwefelisotopedesSchwefels(17‰)zeigendasSulfatreduziererander
Schwefelbildungbeteiligtwaren.DasKarbonat,hauptsächlichDolomit,zeigteinebiomattenartige
Lamination.SpheroidaleDolomitkristallelegenebensoeinenmikrobiellenUrsprungnahe.Daswird
untermauertdurchniedrige13CWerte(11‰).DieOxidaonvonSul dzuSchwefelerfolgte
höchstwahrscheinlichdurchSchwefelbakterien,daessichbeidenimSchwefeleingebetteten
spheroidalenStrukturenhöchstwahrscheinlichumfossilisierteZellenvonThiomargaritasp.oder
Achromatiumsp.handelt.DasistvongroßerBedeutung,dafürdiemeistenSchwefelvorkommen
nachwievorungeklärtist,aufwelchemWegdasSulfidzuSchwefeloxidiertwird.

INTRODUCTION 13

1INTRODUCTION
1.1 Sulphur
1.1.1 Sulphurandthesulphurcycle
SulphuristhefourteenthmostabundantelementintheEarth’scrust.Itmainlyoccursas
sulphideorsulphatewithvalencestates2and+6respectively,butitisalsopresentasnative
sulphur(S0)orintermediatelyinvalencestatesof+2and+4.Thisvariabilityinvalencestatesallows
itsparticipationinvariousreactionsandmakessulphuranimportantredoxpartnerforbiochemical
processes.Sulphateisthesecondmostabundantanioniccomplexinseawater(behindchloride)with
averageconcentrationsofabout2649ppm.Ifoxygenisdepletedduetomineralizationoforganic
matterinthewatercolumnortheuppersediment,otherelectronacceptorstakesuptheroleof
oxygenasprincipalelectronacceptor,namelynitrate,manganeseandiron.Mainlysulphatereducing
bacteriaundertakethetaskfromaerobicheterotrophicorganismsunderanaerobicconditions,due
totheubiquitouspresenceofsulphateinseaandporewater(e.g.,Jørgensen,1982;Ferdelmanet
al.,1999).Sulphatereducingbacteriaareabletooxidiseorganicmatterincludingcrudeoil
compounds(Rueteretal.,1994;Heideretal.,1999;Rabus,2005andreferencestherein).The
sulphateisreducedtosulphide,andbicarbonateisproducedaccordingtothefollowingnetequation
([I];e.g.,ColemanandRaiswell,1995).
[I] 2CH2O+SO42Æ2HCO3+H2S
Sulphatereducingbacteria,whichareabletousemethaneascarbonsourcedirectly,arenot
knownsofar.Theprocessofsulphatedependentanaerobicoxidationofmethane(AOM)mediated
byaconsortiumofmethanotrophicarchaeaandsulphatereducingbacteriacouplestheoxidationof
methanewithsulphatereductionaccordingtothefollowingnetequation([II];e.g.,Hoehleretal.,
1994;Boetiusetal.,2000).
[II] CH4+SO42ÆHCO3+HS+H2O
Sulphateisabiologicallyreducedbythermochemicalsulphatereduction(TSR)insettings
characterizedbytemperaturesabove80°C(mainlybetween100and140°C;Macheletal.,1995;
Wordenetal.,1995,1997;Machel2001).

14 INTRODUCTION

Subsequentlysulphideiseitherprecipitatedasmetalsulphide,ifsufficientmetalionsare
available,oritisoxidizedbiologicallyorabiologicallytonativesulphurorfurthertosulphate.Purple
sulphurbacteriaoxidizehydrogensulphidebyanaerobicphotosynthesistonativesulphurwhichis
storedassmallglobulesinsidethecells(MadiganandMartinko,2009).Chemolithotrophicsulphur
oxidizingbacteriaorsocalledcolourlesssulphurbacteria,e.g.,thesphericalAchromatiumand
ThiomargaritaorthefilamentousBeggiatoa,oxidizehydrogensulphidetonativesulphurwith
oxygenornitrate(SchulzandJørgensen,2001).Likethephotosyntheticsulphurbacteria,theystore
nativesulphurwithinthecellandmayfurtheroxidizeittosulphateifsulphideistemporarynot
sufficientlyavailable(Ferdelmanetal.,1997;SchulzandJørgensen,2001).Withouttheactivityof
microorganismssulphurissuggestedtobeproducedbysynproportionation,whichisthereactionof
hydrogensulphidewithsulphate(FeelyandKulp,1957).Davisetal.,(1970)querieshowever,that
synproportionationoccursattemperaturesbelow70°C.Instead,theseauthorssuggestedabiological
sulphideoxidationwithoxygenleadingtosulphurprecipitation.
1.1.2 Applicationofsulphurandoxygenisotopesinsulphurspecies
Sulphurhasfourstableisotopes32S,33S,34S,36Swithrelativeabundancesof94.99%,0.75%,
4.25%and0.01%,respectively(DeLaeteretal.,2003).Forstudiesconcerningisotopefractionation
betweennaturallyoccurringsulphurcontainingphases,the32Sand34Sisotopesaremainly
considered.Recently,higherprecisiontechniquesincreasetheimportanceof33Sand36S(e.g.,Ono,
2008).Sulphurisotopiccompositionisgiveninnotationaccordingtothefollowingequation
relativetothestandardmaterial,atroilite(i.e.,ironmonosulphide)fromtheCañonDiabolo
meteorite(CañonDiabolotroilite,CDT;Dingetal.,2001):
[III] 34SCDT(‰)=[(34S/32S)sample/(34S/32S)CDT1]*103
TheCDTwasrecentlysubstitutedbyViennaCDT,whichisbasedonthenewsulphidereference
materialIAEAS1(DeLaeteretal.,2003).Theratiobetweentheisotopiccompositionsoftwophases
AandB(RAandRB)isgivenasfractionationfactor
,whichisdefinedas:
[IV]
AB=RA/RB
Theisotopeenrichmentorseparationfactordescribesthedifferencesbetweentheisotopic
compositionsoftwophasesinpermill,givenas:
[V] =
1*1000
Ithaslongbeenknownthatsulphatereducingbacteriaareabletofractionatesulphurisotopes
(e.g.,JonesandStarkey,1957;HarrisonandThode,1958;KaplanandRittenberg,1964).They
INTROD
DUCTION 15

preferen
ntiallyusesulphateconta
ainingtheligghtsulphurissotopeandrreduceittossulphide,ressultingin
anenrich
hmentoflightsulphurisotopesinth ereducedsu
ulphurspecie
esrelativetoothesulphatte.A
fractionaationofupto
o46‰betw
weensulphideeandthesulphatesourcceinculture studieswas
suggesteedtobetheupperlimito
ofbacterialssulphatereduction(KaplanandRitte nberg,1964;Kemp
andThode,1968;HaabichtandCa
anfield,19966).Sedimenttarysulphide
e,however,issevenmore
e
depleted
dcomparedtomarinesu
ulphateinsoomelocations(e.g.,Fryettal.,1991;W
Wortmannettal.,
2001).So
omeauthorssrecommendanoxidativvesteptobe
eresponsible
efortheseh ighfractiona
ation
effects,n
namelythed
disproportionation(Jørgeensen,1990;;CanfieldandThamdrupp,1994;Habichtand
Canfield,2001).Sulp phurintermeediatesasnative
phurdisproportionatingbbacteriausevarioussulp
sulphur,sulphiteortthiosulphate
etoproduce contemporaaneouslybotthoxidizedaandreducedsulphur
species((Canfieldand
dThamdrup,,1994;Cypioonkaetal.,1
1998;Finster etal.,1998;;Habichteta
al.,1998;
Böttcherretal.,2001
1).Iffollowed
dbysulphideeoxidation,aacyclingisin
nitiatedwhicchmaycause
ehuge
fractionaationbetweeenthesulphatesourceaandreducedsulphurspeccies(Jørgenssen,1990;Ca
anfield
andTham
mdrup,1994
4).Nevertheless,arecen tmodelbyB
BrunnerandBernasconi((2005)propo
osed
thatbactterialsulphaatereduction
nalonecanaachieveafractionationasshighas70‰
‰.
Fig.11SSulphurflux esinandou
utofasystem
mofinterestt(bycourtessyofBenBruunner,Brem
men)
Theexpressiono
ofisotopefra
actionationeeffectsbysulphatereducctioninsulphhurbearingp
phases
phates,sulph
(i.e.,sulp hides,native
esulphur)strronglydepen
ndsonthesu
ulphurfluxessinandouto
ofthe
systemo
ofinterest,w
wherethesulphatereducctiontakesp
place(Figure11).Iftherrateofsulphate
reductio
onissimilarttothefluxoffsulphateinttotheinvesttigatedsystem(Fsulphide Finput),thesu
ulphur
isotopiccomposition esulphatesoource(34Ssulphide
noftheresultingsulphid eissimilartothatofthe

16 INTRODUCTION

34Sinput).Fractionationduringsulphatereductionenrichesthesulphateinthesystemin34S
34 34
comparedtothesulphatesource( SSO42> Sinput).Ifthoughtherateofsulphatereductionis
muchsmallerthantheinfluxofsulphateintothatsystem(Fsulphide<Finput),fractionationbetween
34
sulphateandsulphideislarge,leadingto34Sdepletedsulphide(34Ssulphide< SSO42).Thesulphur
isotopiccompositionofthesulphateinthesystemisnearlyunchangedcomparedtothesulphate
34 34
source( SSO4234Sinput).Thefractionationduringsulphatereduction( SSO42—H2S)cantherefore
beestimatedbythedifferenceinsulphurisotopiccompositionbetweentheproducedsulphideand
thesulphatepresentinthesystem.Tostudythegenesisofnativesulphurdeposits,itisworthwhile
toanalysetheisotopiccompositionofsulphateenteringthesystem,sulphateinthesystemandthe
producedsulphide.
Evaporiticgypsumoranhydritemayprovidethesulphurisotopiccompositionofthesulphate
source.Thesulphurisotopiccompositionofsulphidecanbederivedfromthesulphurisotopic
compositionofnativesulphur,ifnotpreservedinformofpyriteorothersulphideminerals.Thereis
onlyasmallfractionationeffectduringbacterialoxidationfromsulphidetonativesulphur(Fryetal.,
1986).Thesulphurisotopeexchangebetweennativesulphurandsulphideisrapid(Fossing,1995)
andcomprisesonlyasmallisotopeequilibriumfractionation(OhmotoandRye,1979).Asthe
sulphateinthesystemcannotbemeasureddirectly,the34Sofcarbonateassociatedsulphate(CAS)
isappliedasproxyhere.CASoccursintraceamountsincarbonates.Thereitsubstitutescarbonate
ionsinthecrystallattice(Pingitoreetal.,1995).AlthoughtheconcentrationofCASinthecarbonates
maybeinfluenced,thesulphurisotopiccompositionisfoundtobestablealsoincaseofdiagenetic
processes(Lyonsetal.,2004;Gilletal.,2008).Therefore,CASisavaluableandelegantproxyofthe
sulphurisotopiccompositionofsulphatepresentintheseaorporewatercontemporaneousto
carbonateprecipitation.
Theoxygenisotopesofsulphatespeciesaregiveninnotation,calculatedrelativetothe
standardViennaStandardmeanoceanwater(VSMOW)correspondingtoequation[III].Similarto
34S,the18Oofsulphatealsomirrorsbacterialsulphatereductionsincebothfractionationprocesses
arepositivelycorrelated.Sulphatereducingbacteriapreferentiallyutilizesulphatewith16O,leading
to18Oenrichmentintheresidualdissolvedsulphate(Lloyd,1968;MizutaniandRafter,1973;
Böttcheretal.,1998,1999;Brunneretal.,2005).Gypsumandanhydrite,whichprecipitatefroma
solutionthatisinfluencedbyintensemicrobialsulphatereduction,arethereforecharacterizedby
elevated34Sand18Ovalues.

INTRODUCTION 17

1.2 Authigeniccarbonates
Theinfluenceofmicroorganismsoncarbonateprecipitationhaslongbeenproposed.In
laboratoryexperimentstheactivityofsulphatereducingbacteriaincreasedthebicarbonateand
carbonateconcentrationandtherewiththealkalinity(AbdelMalekandRizk,1962a,b).Some
authorsremarkthattheabilityofdissimilatorysulphatereductiontoprecipitatecarbonateis
dependentonthepresenceandbehaviouroftheproducedsulphide(Castanieretal.,2000,Soetaerd
etal.,2007).Ifsulphideisneitherusedbye.g.,sulphideoxidizingmicroorganismsnorprecipitatedas
metalsulphidesordegassed,itleadstoadecreaseinpHandhenceinhibitscarbonateprecipitation
(Castanieretal.,2000;cf.,Soetaerdetal.,2007).Neverthelessculturestudiesofsulphatereducing
bacteriasubstantiatedtheircrucialroleintheproductionofbicarbonateandsubsequentcarbonate
precipitationinavarietyofenvironments(VanLithetal.,2003;Duprazetal.,2004;Aloisietal.,
2006).ForthesulphurbearingsettingsIsupposethatthetransformationofsulphideintonative
sulphurlikewisepreventstheloweringinpH,andconsequentlypermitscarbonateprecipitation.
SulphatedependentAOM,however,inanycasefavourscarbonateauthigenesisasthisprocessin
generalincreasesthealkalinity(Soetaerdetal.,2007).
Theinfluenceofmicrobialprocessesoncarbonateauthigenesisisreflectedbythecarbon
isotopiccompositionofthecarbonateminerals.The13Ccarbonateisdependentonthepoolofcarbon
fromwhichthecarbonateprecipitated.Marinedissolvedinorganiccarbon(DIC)ischaracterizedbya
13Cofapproximately+1‰(Kroopnicketal.,1972).Thisvaluefitsquitewellto13Cvaluesmeasured
foranumberofdifferentmarinecarbonates(13C:3to+2‰;Craig,1953).Ifheterotrophic
processesproduceadditionalbicarbonate,the13Ccarbonatewillbeshiftedtowardsthecarbonisotopic
compositionofthecarbonsources,whicharetypifiedbyspecific13Cranges.Marineorganicmatter
showsacharacteristicdepletionin13CcomparedtoDICbyabout20to25‰(13Cformarine
planktonfrommidlatitudes:25to20‰;Sackettetal.,1965).Themajorityofcrudeoilsiseven
moredepletedin13C(13C:30to26‰;Eckelmannetal.,1962).Methaneisthemostdepleted
carboncompoundwith13Cof50to20‰forthermogenicand110to50‰forbiogenic
methane(Whiticar,1999).Carbonate,whichresultedfromtheoxidationofmethanebyAOM,is
characterizedby13Cvaluesaslowas76‰(Campbell,2006).
Stableisotopecompositionofcarbonatesandsulphurcompoundscanbeconsideredasindirect
biologicalmarkersofbiologicalprocesses.Comparedtothat,lipidbiomarkersaredirectbiological
markersofbiosyntheticorigin.Dependingontheirtaxonomicspecificityandtheirpreservation
potential,theycanberegardedasmolecularfossils.Someofthemareevenstableenoughtooutlast
hundredsofMillionsofyears(e.g.,Brocksetal.,2003).Lipidbiomarkersalsoprovideinformation
aboutenvironmentalparametersastemperature,salinity,pH,andnutrients,towhichtheorganisms

18 INTRODUCTION

areadaptedto.Additionallytheycanbeappliedtoidentifychemicalprocesses,inwhichthe
organismsparticipate(seetable11).Lipidbiomarkersarepotentiallywellpreservedinauthigenic
carbonates.Heretheyofferinformationabouttheorganismswhichinducedthecarbonate
precipitationandmoreovertheyarchivethemicrobialecosystemthatwasactivecontemporaneous
toauthigenesis(e.g.,PeckmannandThiel,2004;Birgeletal.,2006a,2008b).
Table11:Examplesoflipidbiomarkersandtheirputativesourceorganisms.
Lipid Putativesource Reference

Pentamethylicosane halophilicmethanogenicarchaea Holzeretal.,1979;Tornabeneet
(PMI) al.,1979
PMI,13Cdepleted methanotrophicarchaea Elvertetal.,1999;Peckmannet

al.,1999b,2009;Thieletal.,
1999,2001;Pancostetal.,2000;
Birgeletal.,2008b
Crocetane,13Cdepleted methanotrophicarchaea Elvertetal.,1999;Thieletal.,
1999;Blumenbergetal.,2004
Archaeol archaea,e.g.,halophilic TornabeneandLangworthy,
methanogenicarchaea 1979;DeRosaandGambacorta,
1988;Kates,1993;Kogaetal.,
1993,1998
Archaeol,13Cdepleted methanotrophicarchaea, Hinrichsetal.,1999
Methanosarcinales
Hydroxyarchaeol,13Cdepleted methanotrophicarchaea Hinrichsetal.,1999,2000;
Pancostetal.,2000;Blumenberg
etal.,2004;NiemannandElvert,
2008
Extendedarchaeol(OphytanylO halophilicarchaea Teixidoretal.,1993
sesterterpanylglycerolether)
Monoalkylglycerolethers(MAGEs), sulphatereducingbacteria Hinrichsetal.,2000;Orphanet
Dialkylglycerolethers(DAGEs) al.,2001a;Pancostetal.,2001a;
Werneetal.,2002
isoandanteisoC15:0andC17:0fatty sulphatereducingbacteria TaylorandParkes,1983;Edlund
acid etal.,1985;Dowlingetal.,1986;
Hinrichsetal.,2000;Orphanet
al.,2001a;Rüttersetal.,2001,
2002;Elvertetal.,2003;Könneke
andWiddel,2003;Papeetal.,
2005;Birgeletal.,2006a;
NiemannandElvert,2008
isoC16:0fattyacid sulphatereducingbacteria TaylorandParkes,1983;Dowling

etal.,1986;Colemanetal.,1993;
KönnekeandWiddel,2003;
Londryetal.,2004;Hinrichset
al.,2000;Elvertetal.,2003
INTRODUCTION 19

Molecularfossilsareespeciallyusefultodetectrecentandancientbacterialsulphatereduction
aswellassulphatedependentAOMasbothsulphatereducingbacteriaandmethaneoxidizing
archaeaproducespecificlipids(seetable11;e.g.,TaylorandParkes,1985;Hinrichsetal.,1999;
Thieletal.,1999;Rüttersetal.,2002;Elvertetal.,2003;PeckmannandThiel,2004;Niemannand
Elvert,2008).LipidsderivedfrommicroorganismsinvolvedinAOMarefurthermorecharacterizedby
asignificantdepletionin13Cduetotheuptakeofmethane(e.g.,Elvertetal.,1999;Hinrichsetal.,
1999;Thieletal.,1999;PeckmannandThiel,2004andreferencestherein).
1.3 AuthigenicsulphurandcarbonatedepositswithfocusonSicilyandSpain
Biogenicnativesulphurdepositsarewidelydistributedonearth(Fig.12).Theyareusually
associatedtoauthigeniccarbonatesandoccuralwaysinsulphaterichsettingsorstrata.Most
prominentareasofsulphurdepositsaretheGulfofMexicoarea,withitsvarioussaltdomes(Fig.12,
no.3a,band4;e.g.,FeelyandKulp,1957;DavisandKirkland,1979;Ruckmicketal.,1979)andthe
Mediterraneanarea(Fig.12,no.5,8,9,12;e.g.,Rouchyetal.,1998;NissenbaumandKaplan,1966;
Nissenbaum1980;Hunt,1915;Dessauetal.,1962;Decimaetal.,1988).WhileintheGulfofMexico
areasulphurformationiscloselyrelatedtotheformationanddiagenesisofsaltdomecaprocks,in
theMediterraneanareaitisboundtoevaporiticdepositsoftheMessinian.
TheMessiniansalinitycrisis,oneofthemostimportantevaporiticeventsinearthhistory,had
hugeimpactontheMediterraneanarea.ThedepositionoftheLowerEvaporitesmarkstheonsetof
thecrisisat5.9Ma(Krijgsmanetal.,1999),whichwasinitiatedbyaprogressiveseparationofthe
MediterraneanSeafromtheAtlanticOcean(e.g.,Duggenetal.,2003;Jolivetetal.,2006),
superimposedbyeccentricitycontrolledregionalclimatechanges(Krijgsmanetal.,1999,2007).The
subsequentdevelopmentofrestrictedandevaporativeconditionsledtothedepositionofcomplete
evaporiticseries,includingcarbonates,sulphates,haliteandbitternsaltsinthedeepMediterranean
basins(Hsüetal.,1973a)aswellasinSicily(DecimaandWezel,1973).InSicilythetransitionfrom
preevaporiticconditionstowardspronouncedevaporiticconditionsismarkedbyadiatomiteunit
(Tripoli).Thecarbonate,whichisdescribedasfirst,basalevaporiticdepositisnamed‘Calcaredi
Base’.ItisoverlainbyhugeamountsofMessiniangypsum.Thesulphurbearinglimestone(‘Calcare
Solfifero’)isdescribedassubunitofthebasallimestoneorrestingontopofit(Dessauetal.,1962;
Decimaetal.,1988).

20 INTR
RODUCTION

Fig.12 Globaldistriibutionofde
escribedbioggenicsulphu urdeposits;1)WesternCCanadian
Sedimen ntaryBasinoofAlbertaan ndBritishCo lumbia:Hor aandHamilton,1992;22)PermianR ocksof
theDelaawareBasin,WestTexas,Culberson County,Cas tile,SaladoandRustler Formation: Davis
andKirk land,1970; Kirklandand dEvans,197 6;Davisand dKirkland,19
979;Ruckmiicketal.,1979;
Klemmicck,1992;Sal isbury,1992 2;WallaceanndCrawford ,1992;3a,b b)Saltdomeecaprocksalongthe
northern nandsoutheerncoastoftheGulfofM Mexico:Fee lyandKulp,1957;DavisandKirklan d,1979;
Ruckmiccketal.,197 9;Samuelso on,1992;4)CChallengerK Knollsaltdom
me:DavisanndKirkland,1979;5)
Messiniaanbasinsin southernSpain(Lorca,H Hellín,Terueel):ServantV
Vildaryetal .,1990;Anadónet
al.,19922;Rouchyet al.,1998;Ortíetal.,20 10;6)Saltd
diapirofWeeenzen,Germ many:Schneiderand
Nielsen,1965;7)NoorthernCarpathianforeddeepinPola nd;CisCarpathianarea,,Ukraine:Ivanov,
1968;Paawlowskiet al.,1979;Niec,1992,BötttcherandP Parafiniuk,1998;Gasiew wicz,2000;8))
Northern nApenniness,Perticara:Roverietal..,2006;9)Siicily:Hunt,11915;Dessa uetal.,1962;
Decimaeetal.,1988; 10)KerchPeninsula,Ukkraine:Lein etal.,1975; 11)Turkey :Tekinetal.,1999;
Tekin,20006;12)the southeasterncoastofttheMediterrraneanSea,southernIsrrael(e.g.,Beeri)and
northern nEgypt(Sinaaipeninsula)):NissenbauumandKaplaan,1966;Nisssenbaum19980;Druckm mannet
al.,19944;Burhanet al.,2002;133)RasGems apeninsula,,Egypt:Schn nellmann19559;Youssef, 1989;
14)Strattabounddep positsofnorthernIraq,ee.g.,Mishraq q:Barkeretal.,1979;Jaassimetal., 1999;
15a,b,c) someoftheesulphurdepositssituattedinthearreaoftheformerUSSR: Ivanov,1968 8a)
Vodinod deposits,Ru ssia,b)Krasnovodsk,Tu rkmenistan,,c)ShorSu,Usbekistan
Refeerringtoafirrstdetailedla
aboratoryst udyofsulph
hatereducing
gbacteriabyyBeyerinck(1895),
nfortheSiciliansulphur deposits(Figg.12,
Hunt(19910)suggestedforthefirrsttimeaba cterialorigin
no.9).Laaterthisinteerpretationw
wasappliedttomanyothe
ersulphurde w34Svaluesofnative
eposits.Low
d34Svaluessofassociateedgypsumm
sulphuraandelevated mirrorsulphu
urisotopicfraactionationb
by
sulphateereducingbaacteria(e.g.,Thodeetal..,1954;FeelyyandKulp,1
1957;Schnei derandNiellsen,
ow13Cvalu
1965).Lo uesofsulphurassociateddcarbonaterrevealitsoriginfrom13C depletedcarbon
derivedffromtheoxiidationoforgganicmatterrorcrudeoil(Peckmannetal.,1999aa)orevenm
methane
(CheneyandJensen,,1965;Kirkla
andandEvanns,1976;BötttcherandParafiniuk,19998).
Twodifferentmodelsofsulp
phurandcar bonateprecipitationaredefined(Ruuckmicketal.,1979):
A)Syngeeneticdeposition:Duringgsedimentattionorearlydiagenesissulphatereduucingbacteriamight
INTRODUCTION 21

haveusedsulphatethatisdissolvedintheseaorporewaters,similartoprocessesinrecent
sediments(cf.,Jørgensen,1982).Evaporationmayhaveevenincreasedthesulphateconcentration.
Sulphatereducersoxidizeorganicdetritus(see[I])ortheyjoinanaerobicmethanotrophicarchaeato
mediatesulphatedependentAOM(see[II]).Themethanemaythereforederiveeitherfrom
thermogenicsources(cf.,Orphanetal.,2004)orfrommethanogens,activeinthesedimentsbelow
(cf.,Hoehleretal.,1994).B)Epigeneticdeposition:Muchlaterafterburialandsubsequentuplift,
gypsum,anhydriteorevencelestinemaybedissolvedbymeteoricwaters,providingsulphateions
forbacterialsulphatereduction(e.g.,FeelyandKulp,1957;DavisandKirkland,1970;Böttcherand
Parafiniuk,1998;Peckmannetal.,1999a;Tekinetal.,1999).Herebytheyoxidizemostlikelycrudeoil
compounds.Theepigeneticmodelobviouslydescribestheformationofsaltdomecaprocksulphur
deposits.Thismodelwasappliedtomostofthefossildeposits,whilethesyngeneticmodelis
assumedtobeonlytrueforrecentsedimentarysystems(Wessel,1994).IncontrastDessauetal.,
(1962)favouredasyngeneticoriginformostifnotallSiciliansulphurdeposits.Theydescribethe
sulphurbearinglimestonebedsasmainlyuniformlybedded,lackingintergrowthsbetween
limestoneandunreducedsulphate,whichwouldbeexpectedforepigeneticdeposits.Amostrecent
paper,however,describedthe‘Calcaresolfifero’tobeformedbybacterialreductionofclastic
gypsuminalatediageneticstage(Manzietal.,2010).
InSpainsulphurbearingcarbonatesarepresentinsmallmarginalNeogenebasinscharacterized
byeithermarineorlacustrinedeposits(Fig.12,no.5).InthemarineLorcabasinthemicrobially
inducedsulphurandsecondarycarbonateprecipitationisassociatedwithmeteoricdissolutionof
abundantgypsumpresentintheorganicrichdiatomiticsuccession(Rouchyetal.,1998).Sulphurin
thelacustrineTeruelbasinisreportedtobeearlydiageneticbutderivedfromthedissolutionof
primarygypsumandassociatedtothereplacementofsulphatemineralsbycarbonate(Anadónetal.,
1992;Ortíetal.,2010);andthusmustberegardedasepigeneticdepositaswell.IntheHellínbasin,
anotherlacustrinebasin,nativesulphurwasproducedfromdissolvedsulphateduringanoxic
conditionsinthewatercolumn(ServantVildaryetal.,1990).IncontrasttoLorcaandSicilyfor
examplenomarineevaporitesareprecipitatedduringtheMessinianinthatlacustrinebasin.Instead,
thesulphateforbothgypsumprecipitationandbacterialsulphatereductionderivedfromthe
weatheringofTriassicgypsumlocatedinthebasement(ServantVildaryetal.,1990;Utrillaetal.,
1992).

22 OBJECTIVES&OUTLINE

2Objectivesandoutlineofthethesis
Nativesulphurdepositshavebeenintensivelystudiedinthefirsthalfofthelastcentury,atime
whennaturalsulphurdepositswereeconomicallyimportantandsulphurmineswereinuse.
Nowadayssulphurisabyproductofnaturalgasandpetroleumrefining.Thesulphurminesare
closed,butthescientificinvestigationofnativesulphurisagainofrisinginterestasmeanwhile
methodsevolvedliketheanalysisofmolecularfossilsandcompoundspecificcarbonisotope
measurements,whichareproposedtoincreasetheunderstandingofthegenesisofnativesulphur
deposits.Themicrobiallydrivensulphurcycleisnotonlyoneofthemostimportantelementcyclesin
marinesedimentsbutalsoaveryancientone(Wagneretal.,1998;CanfieldandRaiswell,1999,Shen
etal.,2001;ShenandBuick,2004).Shenetal.(2001)suggestedthatmicrobialsulphatereduction
wasactiveasearlyas3.47Ga.Thebiogenicnativesulphurdepositspresentonearthareobviously
veryimpressivesignsofthehugeimpactofsulphurcyclinginthegeologicalrecord.However,
althoughtherearemanyrecentstudiesaboutbacterialsulphatereductioninalltypesofsediments,
thenativesulphurdepositswerecurrentlynotinvestigatedinsuchadetail.Researchonthe
microbialcommunityinvolvedinsulphurandcarbonateprecipitationbyapplicationoflipid
biomarkermethodsarescarce(Peckmannetal.,1999a;Burhanetal.,2002).
SinceSicilyusedtobetheworld’sleadingsulphurproduceratthebeginningofthelastcentury,
whichisstillvisiblebymeansofnumeroussulphurmines,wedecidedtoexaminetheSiciliansulphur
depositsforanewstudyonmicrobialsulphurdeposition.Forthepresentstudy,fivelocationsin
Sicily,allrelatedtoformersulphurmines,werestudied.Samplesweresubjectedtoamultiproxy
study,includingpetrography,stablecarbon,oxygenandsulphurisotopesaswellaslipidbiomarker
studiesandcompoundspecificcarbonisotopeanalysestoachievethefollowingmainobjectivesof
thepresentedtheses:
x Verifythebiogenicityofbothnativesulphurandauthigeniccarbonate,concerningallindirect
anddirectbiomarkersasdescribedaboveanddeterminethemicroorganisms,whichare
responsibleforsulphurandcarbonateprecipitation,includingtheirmetabolicpathwaysand
carbonsources.
x SolvethecontroversyaboutthepathwayandtimingofprecipitationoftheSiciliansulphur
andcarbonatedeposits:aretheyeithersyngeneticasproposedbyDessauetal.(1992)or
epigeneticasproposedbyothers(Ruckmicketal.,1979;Manzietal.,2010).
x Describethemicrobialecosystem,inwhichtheseprocessesoccurred.
x Compareauthigenicsulphurandcarbonatedepositsofmarineandlacustrineorigin.
OBJECTIVES&OUTLINE 23

Theseobjectivesareaddressedinfourmanuscriptspresentedinthefollowingchapters.
Chapter3:
FormationofsecondarycarbonatesandnativesulphurinsulphaterichMessinianstrata,Sicily.
ZiegenbalgSB,BrunnerB,RouchyJM,BirgelD,PierreC,BöttcherME,CarusoA,ImmenhauserA,
PeckmannJ,SedimentaryGeology2273750.
Inafirstoverviewthefivesamplinglocationsandthepetrographyofthesampleswere
described.Thebiogenicityofthenativesulphurwasprovenbymeansofstrongsulphurandoxygen
isotopefractionationbetweencarbonateassociatedsulphateandsulphatemineralsontheonehand
andnativesulphurontheotherhand.Themicrobialimpactontheauthigenesisofthecarbonatesis
obviousbymeansoflow13Cvalues.Mostsurprisingwasthevariabilityin13Ccarbonateand18Ocarbonate
betweenthedifferentlocations.LeadingtotheconclusionthatdependentonthelocationI)the
carbonsourcesforbacterialsulphatereductionvariedfromorganicmatterandcrudeoilstohighly
13
CdepletedmethaneandII)sulphurandcarbonateweredepositedduringsynandepigenesis,
whichisalsodisplayedbythepetrography.Whilesyngenesisoccurredwithinrestricted,hypersaline
conditions,mirroredbyenrichmentin18Oandpseudomorphsafterlenticulargypsumwithinthe
carbonate,epigeneticdepositsarecharacterizedbymeteoricdissolutionofgypsum,asrevealedby
low18Ovalues.
Iperformedandinterpretedthepetrographicalanalyses,preparedsamplesforXRDand
electronmicroscopyanalysesaswellasforthedeterminationofelementalandisotopiccomposition.
IinterpretedtheXRD,element,electronmicroscopeand13Ccarbonateand18Ocarbonatedata.I
interpretedthe34Ssulphurandsulphateand18OsulphatedatawithsupportofBenBrunnerandwrotethe
manuscriptwiththehelpofJörnPeckmannandBenBrunnerandwitheditorialcommentsofallco
authors.
Chapter4:
AnaerobicoxidationofmethaneinhypersalineMessinianenvironmentsrevealedby13Cdepleted
molecularfossils.ZiegenbalgSB,BirgelD,HoffmannSellL,PierreC,RouchyJM,PeckmannJ,tobe
submittedtoChemicalGeology.
Lipidbiomarkersandcompoundspecificcarbonisotopesfromsamplesoftwoselectedlocations
fromSicilywereanalyzedandcomparedtoanothersiteofMessiniandepositsinthenorthern
Apennines,wherecarbonatewasdepositedundersimilarrestrictedconditions.Resultsverifythe
conclusionsofthefirstmanuscript,thatsulphatereducingbacteriaareinvolvedintheprecipitation

24 OBJECTIVES&OUTLINE

ofthecarbonates.Furthermoretheresultselucidatetheprocessbywhichmethanederivedcarbon
wasincorporatedintothecarbonate,namelythesulphatedependentanaerobicoxidationof
methane.ThisstudyrevealsthatsulphatedependentAOMwasoccurringinhypersalineconditions.
Ipreparedsamplesforanalyses,performedlaboratoryworkoftheSiciliansampleswiththehelp
ofDanielBirgel,processedandinterpretedthedatawithsupportedbyDanielBirgelandwrotethe
manuscriptsupportedbyDanielBirgelandJörnPeckmann,andwitheditorialcommentsofallco
authors.
Chapter5:
GypsumwhiskersinMessinianevaporitesidentifiedbyμXRD2.ZiegenbalgSB,BertholdC,
KapplerA,PeckmannJ,Facies,DOI10.1007/s103470100237x.
Delicatehairlikemineralspresentinsamplesfromoneoftheformerdescribedlocationswere
identifiedasgypsumwhiskerswithanewsophisticatedmethod,theμXRD2.Thistechniqueallows
thenondestructivedeterminationofthemineralogyofsmallcrystalswithintheircontextdirectlyon
thethinsection.Noteventheunevennessofthethinsections,duetothepriordissolutionofnative
sulphurinterferedwiththemeasurements,makingthattechniqueausefultoolnotonlyforour
studies.
IpreparedsamplesforXRD,electronmicroscopyandμXRD2analyses,interpretedthedata,with
supportofChristophBertholdconcerningtheμXRD2dataandwrotethemanuscriptwiththehelpof
JörnPeckmannandeditorialcommentsofallcoauthors.
Chapter6:
Authigenesisofnativesulphuranddolomiteinalacustrineevaporiticsetting(HellínBasin,Late
Miocene,SESpain).LindtkeJ,ZiegenbalgSB,BrunnerB,RouchyJM,PierreC,PeckmannJ,Geological
Magazine(accepted).
Assulphatereductionusuallyoccursinmarinesettingsduetotheubiquitouspresenceof
sulphate,itwasofhighinteresttoinvestigateabiogenicsulphurdepositinalacustrinebasin,where
sulphateistypicallyrare.Sulphurisotopevaluesofnativesulphurarelowcomparedtothesulphate
source,whichisderivedfromtheweatheringofTriassicgypsum,providingevidencethatthe
precipitationofnativesulphurisinducedbysulphatereducingbacteria.Sulphatepresentinthe
samplesissecondaryderivedfromtheoxidationofnativesulphur,partiallyaccompaniedby
replacementofcarbonatesbygypsum.Thepresenceofputativefossilizedsphericalbacteria,
OBJECTIVES&OUTLINE 25

enclosedinnativesulphur,indicatethattheoxidationofsulphide,producedbybacterialsulphate
reduction,tonativesulphurmightbeperformedbysulphideoxidizingbacterialikeAchromatiumsp..
Icontributedtotheinterpretationofpetrographicalandstableisotopedata,helpedsubstantially
preparingtheoutlineandwritingthemanuscript,andgaveeditorialcomments.

26 FIRSTMANUSCRIPT

3FIRSTMANUSCRIPT
Formationofsecondarycarbonatesandnativesulphurinsulphaterich
Messinianstrata,Sicily
S.B.Ziegenbalg1,B.Brunner2,J.M.Rouchy3,D.Birgel1,C.Pierre4,M.E.Böttcher5,A.Caruso6,A.
Immenhauser7,J.Peckmann1
1
MARUM,UniversitätBremen,28359Bremen,Germany
2
MaxPlanckInstitutfürMarineMikrobiologie,28359Bremen,Germany
3
DépartementHistoiredelaTerre,MuséumNationald’HistoireNaturelle,75005Paris,France
4
CNRSUMR7159,LOCEAN,Univ.P.etM.Curie,75252ParisCedex05,France
5
LeibnizInstitutfürOstseeforschungWarnemünde,18119Warnemünde,Germany
6
DipartimentodiGeologiaeGeodesia,UniversitàdegliStudidiPalermo,90123Palermo,Italy
7
RuhrUniversitätBochum,InstitutfürGeologie,MineralogieundGeophysik,44801Bochum,
Germany
Correspondingauthor:JörnPeckmann([email protected])
Keywords:authigeniccarbonate,nativesulphur,microbialsulphatereduction,Messiniansalinity
crisis,Sicily
Abstract
Microbiallyformedauthigeniccarbonatesaccompaniedbynativesulphurarepresentinthe
‘CalcareSolfifero’belowathicksuccessionofgypsumdepositedduringtheMessiniansalinitycrisisin
Sicily.Wesampledthesecarbonatesandassociatedsulphurinfiveformersulphurminestosubject
themtoadetailedpetrographicandgeochemicalstudyinordertoexploretheirdifferentmodesof
formation.Nativesulphurformedinconjunctionwithmicrobialsulphatereduction,whichis
reflectedinitsdepletionin34S(34Svaluesaslowas2‰vs.VCDT)andanenrichmentof34Sinthe
residualsulphate(34Svaluesashighas+61‰).Theoxidationoforganicmatterbysulphate
reductionincreasedalkalinity,inducingprecipitationofsecondarycarbonateminerals.Asetof
authigeniclimestoneslackingsulphateminerals,butcharacterizedbypseudomorphsaftergypsum
andhigh18Ovalues(ashighas+9‰vs.VPDB)reflectssyngeneticmineralformationwithin
evaporiticsettings.Low13Cvalues(aslowas52‰vs.VPDB)revealthatthesecarbonatephases
formedbymicrobialsulphatereductioncoupledtotheoxidationofbiogenicmethane.Anothersetof
FIRSTMANUSCRIPT 27

authigeniccarbonatesthatreplacedsulphatemineralsistypifiedbylow18Ovalues(aslowas4‰).
Thesecarbonatesformedepigeneticallyduringlaterdiagenesisfollowingcompaction.Dissolutionof
gypsumoranhydritebymeteoricwatersdeliveredsulphateformicrobialsulphatereduction.Low
carbonisotopevaluesofthesecarbonates(29to5‰)indicatethatcarbonatewasderivedfrom
theoxidationofcrudeoilandpossiblyminormethane,partlyinvolvingdifferentdegreesof
admixtureofdissolvedcarbonatefromothersources.Althoughthestudiedrockswiththeirvast
amountsofsecondarycarbonatemineralsandsulphurseemtoindicateasimilargenesisatfirst
glance–havingformedbybiogeochemicaltransformationsofsulphateandhydrocarbons–this
studyrevealsthattheseprocessescanoccuratdifferenttimesinvariablegeologicalenvironments.
3.1Introduction
Evaporitesareoftenlocallyassociatedwithnativesulphurdepositsanddiageneticcarbonate
minerals.ExamplesincludecaprockdepositslikethoseofthesaltdomesalongthecoastoftheGulf
ofMexico(Thodeetal.,1954;FeelyandKulp,1957)orthePermiansaltdomeoftheHilssyncline,
northernGermany(SchneiderandNielsen,1965),butalsostratabounddepositslikethosefromthe
westernmarginoftheGulfofSuez,Egypt(Schnellmann,1959;PierreandRouchy,1988),theCastile
Formation,Texas(DavisandKirkland,1970),thePolishCarpathianforedeep(Pawlowskietal.,1979;
BöttcherandParafiniuk,1998),northernIraq(Barkeretal.,1979;Jassimetal.,1999),orZechstein
strataofGermany(Peckmannetal.,1999).Thereareseveralotheroccurrencesofnativesulphurand
associatedcarbonatesworldwide(Wessel,1994),whoseoriginhasnotbeeninvestigatedtodate.
Theexamplesoftheparagenesisofevaporites,nativesulphur,anddiageneticcarbonatemineralsin
theMessinianofSicilybelongtothestrataboundtype(Wessel,1994).TheSiciliansulphurand
secondarycarbonatesareintercalatedinthethickevaporiticsuccessionthatformedduringthe
Messiniansalinitycrisis.Numerousabandonedsulphurminesreflecttheformereconomic
importanceandthevastmassesofnativesulphurinSicily(Hunt,1915).
Microbialsulphatereductionisconsideredtobethekeyprocessfortheprecipitationofnative
sulphurandaccompanyingcarbonatesinevaporiticlithologies(FeelyandKulp,1957;Davisand
Kirkland,1970;Anadónetal.,1992;BöttcherandParafiniuk,1998;Peckmannetal.,1999).Sulphate
reducingbacteriausesulphatetooxidizeorganicmatter,includingcrudeoil(FeelyandKulp,1957;
Rueteretal.,1994;Aeckersbergetal.,1998;Heideretal.,1999;Rabus,2005),whichleadstothe
productionofreducedsulphurspeciessuchashydrogensulphide(FeelyandKulp,1957;Sagemann
etal.,1999)andanalkalinityincrease(AbdElMalekandRizk,1963a).Thisalkalinityincreaseis
responsiblefortheprecipitationofcarbonateminerals(AbdElMalekandRizk,1963b),mainly
calcite(Machel,2001),butalsoaragoniteanddolomite(PierreandRouchy,1988;Anadónetal.,

28 FIRSTMANUSCRIPT

1992;BöttcherandParafiniuk,1998;Peckmannetal.,1999).Hydrogensulphideiseither
abiologicallyorbiologicallyoxidizedtonativesulphur(Machel,1992),buttheexactmechanismsare
stillunknown.
Ruckmicketal.(1979)classifiedrockscontainingbiogenicsulphurintobioepigeneticand
biosyngeneticdeposits.Mostoftheabovementionedexamplesareattributedtothebioepigenetic
pathway(seeWessel,1994).Accordingtothisscenario,meteoricwatersdissolvegypsumor
anhydrite,whichserveassulphatesourceformicrobialsulphatereduction.Thisonlyhappensafter
burialandsubsequentupliftofthehostrocks,oftenhundredsofmillionsofyearsafterdeposition
(e.g.,FeelyandKulp,1957;SchneiderandNielsen,1965;DavisandKirkland,1979;HentzandHenry,
1989).Anepigeneticoriginisobviousforsaltdomecaprocks(SchneiderandNielsen,1965;Davis
andKirkland,1979).Stratabounddepositshavealsobeendescribedasproductsofepigenesis,e.g.
theLatePermianSaladoandCastileFormations(DavisandKirkland,1970;1979;HentzandHenry,
1989).Dissolutionofhaliteandsulphatemineralsbymeteoricwatersisthoughttohaveincreased
theporosity,permittingtheinfluxofcrudeoilbearingwatersfromunderlyingformations,which
thenfuelledmicrobialsulphatereduction(e.g.,KirklandandEvans,1976;DavisandKirkland,1979).
Basedontheobservationthathydrogensulphideisstillpresentinwatersfromsulphurwellsnear
saltdomecaprocks,FeelyandKulp(1957)inferredthatmicrobialsulphatereductionisnot
necessarilyterminatedinthesesulphaterocks,dependingonthepresenceofanoxicconditions,
meteoricwaters,andasourceofreducedcarbon.
Withrespecttosomepreviouslydescribedoccurrences(Dessauetal.,1962;Gasiewiecz,2000),
carbonateprecipitationandsulphurauthigenesisaresuggestedtobeinducedinafashionsimilarto
theepigeneticpathway,butduringsedimentationandveryearlydiagenesis(biosyngeneticpathway;
Ruckmicketal.,1979;Wessel,1994).Interestingly,highMgcalciteanddolomiteformationinduced
bysulphatereducingbacteriaisawellstudiedphenomenoninmodernhypersalinelakesand
lagoons(e.g.,Vasconcelosetal.,1995;Duprazetal.,2004).Intheseenvironments,however,no
accumulationofnativesulphurhasbeendescribed.Activeproductionofnativesulphurwasreported
fromlagoonallakesinCyrenaica,Libya(ButlinandPostgate,1954;Thodeetal.,1954).Inthese
lagoonallakes,hydrogensulphideisproducedlocallybymicrobialsulphatereductionanddissolved
sulphideisapparentlyoxidizedbyanoxygenicphototrophicbacteria(ButlinandPostgate,1954).It
seemslikely,however,thatregionalspringscontributeadditionalsulphide(Ivanov,1968).Todate,
onlyfewancientoccurrencesofnativesulphurandassociatedsecondarycarbonates,likethe
MiocenedepositsfromthePolishCarpathianforedeep,havebeenattributedtobiosyngenetic
processes(Gasiewicz,2000).AbacterialoriginoftheSiciliansulphurdepositswasfirstputforwardat
thebeginningofthe20thcenturybyHunt(1915).Theisotopedataonsulphurandcarbonatesfrom
FIRSTMAN
NUSCRIPT 29

SicilianssulphurmineespresentedbyDessaueetal.(1962)cconfirmedth
hissuggestioon.Theseautthors
favoured
dbiosyngeneeticformatio
onoftheSici liansulphurdeposits.Th
hisassumptioonwaschalle
enged
lateron(e.g.,Ruckm 979;Wessel, 1994),buttheproblemwasneveradddressedbya
micketal.,19
detailedstudyoftheesecondarymineralphasses.
Heree,weanalyseesamplesoffsulphurbeaaringlimesto
onesfromfivveabandoneedminesofSSicilyin
ordertoreconstructthegenesisofnativesu lphurandasssociatedcarrbonates,usiingpetrography,
elementtpatterns,asswellascarb
bon(C),oxyggen(O),andsulphur(S)sstableisotoppesignaturess.Our
datacon
nfirmthemiccrobialorigin
nofthesecoondaryminerralsandreve
ealthattiminngandmode
esof
authigen
nesisaremorevariablethanpreviousslyrecognize
ed.
3.2Geollogicalconteext
Fig.31 InterpretativvecrosssectionthroughhtheCentra lSicilianBassinillustratinngthestratigraphic

position oftheCalcaarediBase,modifiedaftterRouchyaandCaruso(2 2006).
ThesulphatebearingstrataofSicilyresuultedfromon
neofthegre
eatestevapo riticeventsiinEarth
history,tthesocalled
dMessinianssalinitycrisiss.Severalsce
enariosoftheonset,timiing,and
developm beencontrovversiallydiscussedduring
mentofthiscrisishaveb gthelastdeccades(seeRouchy
andCaru
uso,2006;Brriand,2007;Roverietal .,2008a).DepositionoftheLowerEEvaporitesmarksthe
onsetof
fthesalinitycrisisat5.96
6Ma(Krijgsm
manetal.,19
999).Thisonsetwascaussedbythese
ealevel
ducedbythecutoffofth
dropind heMediterraaneanSeafro
omtheAtlan
nticOcean(ee.g.,Krijgsma
anetal.,
1999;Du eferencestheerein).Thedevelopment ofrestricteddconditionsledto
uggenetal.,2003andre
thedepo
ositionofanevaporiticseriesincludi ngevaporiticccarbonate,sulphate,haalite,andbitttersalts
inthedeeepestMessinianbasins(Hsüetal.,11973)aswellasintheCe
entralSiciliannBasin(e.g.,Decima
andWezzel,1973).

30 FIRSTMANUSCRIPT

DuringtheMessinian(LateMiocene)theMediterraneanareawassegmentedintoseveral
interconnectedbasins,largelyvaryinginsize.TheCaltanissettaorCentralSicilianBasininthemiddle
tosouthernpartofSicilywastectonicallyseparatedintoseveralsubbasins(Butleretal.,1995).The
NeogenestratigraphicsuccessionofSicilyincludesMessinianevaporitesofthesocalled‘Formazione
GessosoSolfifera’(gypsumsulphurformation;Fig.31).Thetransitionfromthepreevaporitic
diatomiteformation(TripoliFormation)totheoverlyingevaporitesismarkedbytwotypesof
limestone.Thefirsttypeisnamed‘CalcarediBase’(basallimestone),whichwasstudiedbyMcKenzie
(1985a)andDecimaetal.(1988).Thisunitisformedofmassivelimestonebeds,whichusuallyconsist
ofirregular,peloidal,orclottedmicritetomicrospar.Thebedsareseparatedbylayersoflaminar
limestone,dolomite,calcareousmarl,orrarelygypsum.Insomeplacesstromatolitesoccuratthe
transitionfromtheTripoliFormationtotheCalcarediBase(Oliverietal.,2010)oratthetopof
massiveCalcarediBaselimestonebeds(Decimaetal.,1988).Thetotalthicknessofthisunitisquite
variable,rangingfrom20to60m.TheCalcarediBasewasinterpretedasevaporiticlimestone
(Decimaetal.,1988).Diageneticalterationresultedinpseudomorphsaftergypsumandmouldic
poresthatwereprimarilyfilledwithhalitecrystals.
The‘CalcareSolfifero’(limestonewithsulphur)representsalocalsubunit,whichisintercalated
intheupperpartoftheCalcarediBaseorisfoundontopofit(Decimaetal.,1988).Sometimes,the
CalcareSolfiferoisdescribedasanindependentunit,whichrestsontheCalcarediBaseordirectlyon
thediatomiteunit,wherethebasallimestoneismissing(Dessauetal.,1962).TheCalcareSolfiferois
adiageneticlimestone.Theoccurrencesofnativesulphurarenotcontinuousinthisunit,butare
confinedtosomeisolatedsites(Hunt,1915).AccordingtoRouchyandCaruso(2006)bothtypesof
limestone,theCalcarediBaseandtheCalcareSolfifero,passbasinwardsintothelowergypsumand
saltunitsandareoverlainbytheuppergypsumunits(Fig.31).Thisstratigraphicrelationship,
however,isstillunderdiscussion(RouchyandCaruso,2006;Briand,2007;Roverietal.,2008a).
Therefore,weusetheterm‘CalcareSolfifero’descriptivelyforthesulphurcontaininglimestone.The
Messiniansalinitycrisisendedwiththedepositionofthebrackishandfreshwater‘LagoMare’facies
andthesubsequentreturntomarineconditions(TrubiFormation)duringtheEarlyPlioceneflooding.
ThedistributionoftheuppergypsumandtheLagoMarefaciesaswellastheconditionsunderwhich
theyweredepositedarestilldiscussed(RouchyandCaruso,2006;Roverietal.,2008b;Manzietal.,
2009).
3.3Samples
Forthisstudy,rocksweresampledfromfivelocations(Fig.32).Theformercarbonatequarryof
MontedeDrasiandtheformersulphurmine,LaMuculufa,aresituatedinthesouthofSicilynear
FIRSTMAN
NUSCRIPT 31

Gela.Theabandoned
dsulphurmiineofCozzo DisiissituattedclosetotthetownofCCasteltermin
ni.
ContradaaGaspaandtheformersulphurminee,MonteCapodarso,are
elocatedinccentralSicilyycloseto
Ennaand
dCaltanissettta,respectivvely.Theevaaporiticsuccessionsatth
hefivelocatioonsdisplaya
awide
varietyo
oflithologiessandfacies,o
outofwhichhonlyrocksw
withnativessulphurorcaarbonateswe
ere
sampled
d.
Fig.32 MapofSicilyywiththefivesampleloocations.
3.3.1Mo
ontedeDrassi
Thisoutcropissituatedonth
heslopeoft hemountain
nMontedeD
Drasi,eastofftheroadfrom
oRavanusa.Itrepresentssaformersuulphurminetthatwassub
Licatato bsequentlyussedasacarb
bonate
quarry.TThetransitio
onfromtheu
uppermostcyyclesoftheTTripoliFormationtothe CalcarediBaseis
exposedinthisoutcrrop.TheCalccarediBase isamassive peloidaltoffilamentous limestonecrrosscut
bysulphurfilledvein
ns(Fig.33A,,Fig.34A).
3.3.2LaMuculufa
ountainMonteMuculufaa.Messinianstrata
Thisformerquarrryissituatedonthesloppeofthemo
cropouttclosetotheeabandoned
dsulphurminne,LaMucullufa.Thesed
dimentaryseequenceisinverted
duetoteectonicactivvity.Thereforre,Calcared iBase,which
hisextremelyrichinpseeudomorphsafter
halite,ovverliesgypsu
um.Bothuniitsarecoverredbyapproximately100
0mofTortonnianmarls.LLoose
blocksoffsulphurrichcelestinea
associatedw
withcarbonatte(Fig.33B)weresamplledfromthebaseof
thegypssumquarry.

32 FIRSTMANUSCR
RIPT

Fig.33SSamplesofC CalcareSolfi fero,i.e.,lim

mestoneconntainingnativvesulphur.AAn=anhydrite;Cc=
calcite;C
Cel=celesti ne;Gyp=gyypsum;mi= micrite;S= nativesulphhur.(A)Sulp hurinveins
between nmicriteclassts;Monted deDrasi;sca nnedslab.( B)Sulphuraccompanieddbymicritic and
sparitic calciteince lestinematrrix;MonteM Muculufa;scaannedslab.((C)Sulphur, gypsum,and
dplaty
aggregattionsofseco ondarycalcitte(arrow);CCozzoDisi;cooin=23.3mmindiametter.(D)Sulphurand
dolomitee(arrow)em mbeddedina anhydritemaatrix;Monte eCapodarso;;scannedslaab.
3.3.3CozzoDisi
ThesulphurmineofCozzoD
DisiissituateddsoutheastofCastelterm
mini.Inthem
middleofthe
elast
centuryitwasoneofthemostproductivesuulphurminessinSicily.The
eminewascclosedinthe
e1980s,
resultingginfloodingofthelowerrlevels.The sulphurbearinglimestoneisunderlaainbymarineclays
andpasssesupwardsintomassive
etonodular gypsumbed
ds(Dessauettal.,1962).SSamplesofm
micriticto
spariticllimestonesw
withsomeacccessorysulpphatemineraalsandnative
esulphurfroomdeeper,ccurrently
notacceessiblelevelsoftheminehavebeenpprovidedbyprivatecolle
ectorsforthissstudy.Apartfrom
that,sulphurbearingggypsumcarbonateassoociations(Figg.33C)andlimestoneshhavebeensa
ampled
fromtheeuppermosttlevel,which
hiscurrentlyytheonlylevvelthatcanb
beaccessedssafely.
3.3.4ContradaGaspa
ousandbreccciatedCalcareSolfiferow
Poro wassampled estonecliff,ssituatedclosetothe
dfromalime
streetS230fromEnnatoAlimen
na,betweenCasaRealmesiandCasaBastione.Thhelimestone
ecliffis
closetoanancientsulphurmine
e,whichislarrgelycoveredbysoiland
dwood.Duri ngtheonsettofthe
salinityccrisistheareaofContrad
daGaspawasssituatedinalocaldepo
ocenterinassynclinalpossition,
FIRSTMANUSCRIPT 33

wheremorethan80mofdiatomiticlaminitesoftheTripoliFormationweredeposited(Butleretal.,
1995).ThediatomitesarefollowedbylayeredlimestonesoftheCalcarediBasepassingintothe
CalcareSolfifero.Laterallythesecarbonatefaciespassintogypsumassociatedwithcarbonates.The
sampledsectionconsistsofdiageneticlimestonesfollowedbyathinlayerofwhitishdetrital
mudstonecappedbyyellowishforaminiferalpackstone.
3.3.5MonteCapodarso
Theoutcrop,situatedwithinthenaturalreserve,MonteCapodarsoeValledellImera
Meridionale,northeastofCaltanissetta,isaformersulphurmine.TheTripoliFormationisexposed
alongthefootpathtothemine.Inthissectionitisonly25mthick(Sucetal.,1995),suggestinga
moremarginalsettingthanfortheGaspalocation.Thesedimentarysuccessionofthemine
representsthetransitionfromtheupperTripoliFormationintotheCalcareSolfifero.Inthe
uppermostpart,cavernousCalcareSolfiferocropsout,whichispartlycoveredbypowderlikenative
sulphurandbitumen.LooseblocksofCalcareSolfiferoandsulphurbearinganhydrite(Fig.33D)
weresampledfromadumpingsiteintheformerminearea.
3.4Methods
Thinsectionswerestudiedwithtransmittedlightandfluorescencemicroscopycarriedoutona
ZeissAxioskop40opticalmicroscope(lamp:HBO50;filters:BP365/12FT395LP397andBP450490
FT510LP515).Thinsectionswerestainedwithacombinedpotassiumferricyanideandalizarinred
solution,dissolvedin0.1%HClsolution(Füchtbauer,1988).Feigl’ssolutionwasusedtotestfor
aragonite(Feigl,1960).Magnesiumcontentofthecarbonatewasassessedbythetitanyellow
(Claytonyellow)stain(ChoquetteandTrusell,1978).ALEO1530Geminiandanattachedenergy
dispersiveXrayspectrometer(EDX)OxfordInca400wereusedforfieldemissionscanningelectron
microscopy(FESEM)andqualitativeelementrecognition.MineralogywasdeterminedbyXray
diffractionperformedonaPhilipsX’PertProMD.
Samplesforelementandstableisotopeanalysesweretakenfromthesurfaceofslabsusinga
handheldmicrodrill.Individualphases,whichweredistinguishedbymicroscopeanalysis
beforehand,wereusedforanalysis.Mineralpowdersweredissolvedbymicrowavedigestionwitha
MLSEthos1600.Measurementswereperformedwithaninductivitycoupledplasmaopticalemission
spectrometer(PerkinElmerOptima3300equippedwithacrossflownebulizer).Carbonandoxygen
isotopemeasurementswereperformedwithaFinniganMAT251massspectrometerusingthe‘Kiel’
carbonatedevicetype‘Bremen’.ASolenhofenlimestonewasusedasinhousestandard,whichwas
calibratedagainsttheinternationalstandardNBS19.Analyticalstandarddeviation(1 )wassmaller

34 FIRSTMANUSCRIPT

than±0.07‰for18Ovaluesand±0.05‰for13Cvalues.Carbonandoxygenisotoperatiosfor
carbonatesaregiveninthenotationrelativetotheViennaPeedeeBelemnite(VPDB)standard.
Becauseofundeterminedadmixtureofminorcalcite,oxygenisotopedataofdolomitesampleswere
notcorrectedfortheirdifferentfractionationcomparedtocalciteduringprecipitation(McKenzie,
1981)orduringtheanalyticalprocedure(SharmaandClayton,1965).
Table31:Elementcontentsofindividualmineralphases.
Sample Mineralogy Crystalhabit Ca [%] Mg[ppm] Sr[ppm]
Fe[ppm] Mn [ppm]
MontedeDrasi
MD1a1_E1 calcite microcrystalline 38 2846 17170 755 103
MD1a1_E2 calcite sparitic 36 2182 38085 630 92
MD2d1_E1 calcite microcrystalline 37 2500 28147 873 209
MD2d1_E2 calcite microcrystalline 39 3827 839 326 41
LaMuculufa
LMd_E1 calcite&celestine microcr./acicul. 14 1254 135494 39 109
LMd_E2 celestine acicular 1 31 133526 19 3
LMf_E1 calcite microcrystalline 36 4606 5767 4332 624
LMf_E2 celestine acicular 0 0 246663 13 0
CozzoDisi
CD5_E1 calcite microcrystalline 37 2001 1077 162 310
CD5_E3 aragonite prismatic 36 0 7744 28 1
CD7_E1 calcite radiaxialfibrous 37 6393 713 152 7
CD7_E2 calcite scalenohedral 36 8679 16093 90 54
CD7_E3 calcite microsparitic 34 3559 653 3755 181
CD9_E1 dolomite microcrystalline 21 108069 185 3067 386
CD9_E2 calcite microsparitic 36 4121 2364 1209 31
CD9_E3 calcite scalenohedral 39 3764 664 22 77
CD9_E4 calcite radiaxialfibrous 38 5774 458 61 19
CD18_E2 calcite sparitic 33 3340 459 392 84
CD20_E1 calcite sparitic 38 2805 205 20 78
CD20_E2 gypsum selenitic 29 1091 186 10 28
ContradaGaspa
GAf_E1 calcite microcrystalline 39 2893 479 1557 70
GAf_E2 calcite sparitic 39 3022 645 47 26
GAi_E1 calcite microcrystalline 39 2465 512 1001 34
MonteCapodarso
MCa_E1 anhydrite acicular 29 1039 1009 2 1
MCa_E2 anhydrite&dolomite acicular 25 12270 1175 1454 69
MCc_E1 calcite microcrystalline 37 6237 397 3132 322
MCc_E2 calcite sparitic 39 6335 979 595 62
Forsulphurisotopeanalysis,anhydritewasdissolvedandprecipitatedasbariumsulphateby
additionofbariumchloridesolution.Nativesulphur,gypsum,andcelestineweredirectlyanalyzed
fortheirsulphurisotopecompositionwithoutpretreatment.Foroxygenisotopeanalysisofsulphate,
gypsum,andanhydriteweredissolvedinasodiumchloridesolutionandprecipitatedasbarium
sulphatebyadditionofbariumchloridesolution.Theoxygenisotopecompositionofcelestinewas
analyzeddirectlywithoutpretreatment.Forthedeterminationofcarbonateassociatedsulphate,
FIRSTMANUSCRIPT 35

carbonatesampleswerepowderedandsubmergedinasodiumchloridesolutionovernight.This
treatmentremovedeasilysolublesulphatephases(i.e.,gypsumandanhydrite).Afterwashingwith
deionizedwater,thesamplewasdissolvedwithhydrochloricacid.Liberatedcarbonateassociated
sulphatewasprecipitatedasbariumsulphatebyadditionofbariumchloridesolutionthatwas
furtherwashedanddried.
SulphurandoxygenisotopesweremeasuredincontinuousflowwithaThermoFinniganDeltaV
Plus(viaEurovector3000;MaxPlanckInstitute,Bremen)oraThermoDeltaV(viaThermoflashEA;
ThermoBremen)gasmassspectrometer.Forsulphurisotopeanalysis,samplesandV2O5(asa
catalyst)wereweighedintotincapsulesandcombustedinanelementalanalyzer(EuroVector3000)
toproduceSO2.Foroxygenisotopeanalysis,bariumsulphatewastransferredtoasilvercapsuleand
thermochemicallypyrolizedtoCOgasinaThermoFinniganThermalConversion/ElementalAnalyzer
(TC/EA;ThermoFisherScientific;GehreandStrauch,2003).Sulphurisotopecompositionofsulphur
andsulphatesandoxygenisotopecompositionofsulphatesaregiveninthenotationrelativeto
theViennaCanyonDiabloTroilite(VCDT)standardandViennaStandardMeanOceanWater(V
SMOW),respectively.InternationalstandardNBS127andinhousestandardswereusedforthe
calibrationtowardstherespectivemassscales.Thestandarderrors(1 )ofreplicatemeasurements
werelessthan±0.3‰for18Oand34Svalues.
3.5Results
3.5.1Petrography
3.5.1.aMontedeDrasi
Abundantsulphurfilledveinscrosscutprimaryfilamentouslimestonesconsistingoflow
magnesiumcalcite(Fig.33A).Themicriticmatrixenclosesmicrosparandspar(Fig.34A)aswellas
calciticpseudomorphsaftergypsumandhalite(Fig.34B).Thestrontiumcontentofthemicritic
matrixisexceptionallyhigh(Table31),whichiscausedbynumeroussmallcelestinecrystals
enclosedinthelimestone(Fig.34C).Somesamplesoflimestonecontaintracesofmicrocrystalline
aragonite.Possibly,recrystallisationofaragonitetocalciteprovidedthestrontiumforcelestine
precipitation(cf.,Decimaetal.,1988).Thelimestonesalsoencloseminoramountsofgypsum.Veins
crosscuttingthelimestonearefilledwithsparrycalciteorasequenceofmicrospar,sparrycalcite,
andelementalsulphurtowardsthecentreofthevein(Fig.34D).Occasionally,celestineisembedded
inthesparrycalcite.Thecelestineiseitherbladed,rhombshaped,orappearsasfanshapedcrystal
aggregates.

36 FIRSTMANUSCR
RIPT

Fig.34 MontedeD rasi.Cel=ce elestine;mi =micrite;S =nativesulp

phur;sp=caalcitespar.( A)
Filamenttouslimesto one;planepoolarizedlighht.(B)Sparf illedpseudo
omorphafterrhalite;plan ne
polarized dlight.(C)C
Celestinecrystalsbeddeddincalcitemmicrospar;FEscanningeelectronmicrograph.
(D)Veinwithinthem micriticlimestonefilled byasequen nceofcalcite
espar,celesttine,andnative
sulphur; crosspolar izedlight.
3.5.1.bLLaMuculufa
Samplessfromthissittedisplayaccomplexfabrric.Theirlith
hologyisvolu
umetricallyddominatedby
secondarycelestineandgypsum.Thecelesti neformsfan
nshapedcryystalaggregaates.Crystalssare
prismatictoacicular,butrhombiiccrystalhabbitsoccuraswell.Celestinecrystalsoofupto0.5ccmin
openvoids(FFig.35A).Se condarygyp
lengthprojectintoo psumappearsasafelted massofcrysstal
needles..Thesulphattephasesenclosemicritee,whichissp
patiallyassocciatedwitheelementalsu
ulphur
(Fig.35B).Micriteissaccompanie
edbymicrossparandspar(Fig.35C).Itisorganiccrichandsho
owshigh
contentssofironandmanganese (Table31). Thesulphurrnodulesare
eoftencorroodedattheirrrims.
Minoram
mountsofch
halcedonyarrefinelydisppersedinthelimestonem
matrix.
3.5.1.cC
CozzoDisi
Thelimestonesaamplesaswe
ellasthegyppsumcarbon
nateassociattions(Fig.333C)fromthisssite
containlargeaggreggatesofnativvesulphur.L imestonesco
onsistofmiccriticlowMggcalciteandsparry
calcite(FFig.36A).Th
heorganicrichmicriteis occasionallyylaminateda
andenclosesssparfilled
pseudom
morphsafterrlenticulargyypsum.One sampleconttainsfewsca
atteredforam
minifera(Orb
bulina
FIRSTMAN
NUSCRIPT 37

Fig.35 LaMuculufaa.Cc=calcite
e;Cel=cele stine;mi=m
micrite;S=n
nativesulphuur;sp=sparr.(A)
Celestin eneedlesgrrowingintoa avoid.(B)N ativesulphuurnoduleasssociatedwit hcalciteencclosedin
celestinee;planepolaarizedlight.(C)Closerv iewofthec alcitemadeofmicriticrremnantsand
microspaartosparsuurroundedbyycelestine; planepolariizedlight.
sp.,Glob
bigerinoidessp.,Globigerrinabulloidess).Microcrysstallinedolomiteisanacccessorymineral
phase(TTable31).Sm
mallcelestine
ecrystalsin thelimeston
nematrixacccountfortheehighstronttium
contentss(Table31).Muchoftheformerporrespaceisfilledbynativvesulphur(F ig.36A).Wiithinthe
gypsumcarbonateaassociations,thecarbonaateismostlysparitic,som
metimesencllosingmicrite.The

38 FIRSTMANUSCR
RIPT

Fig.36 CozzoDisi.GGyp=gypsumm;mi=micrrite;rfCc= radiaxialfibrouscalcite cement;scCc=

scalenohhedralcalcit e;S=nativeesulphur;spp=spar.(A) Micritesurrooundedbym microspartospar
andsulpphurasporefilling;planepolarized light.(B)Ca lcitesparpaartlyreplacinngseleniticggypsum;
planepoolarizedlightt.(C)Largeidiomorphic sulphurcrysstalsfillingvveins;planepolarizedligght.(D)
Veincro ssingmicriteefilledbyasuccessionoofscalenohe edralcalcite(arrow),sul phurandlarrge
pseudo hexagonala ragonitecryystals;staineedwithFeigl ’ssolution;scannedthinnsection.(E )Vein
crossing micritefilleedbyasucce
essionofscaalenohedral calcite,sulphur,andraddiaxialfibrou uscalcite
cement; stainedwit hpotassiumferricyanideeandalizari nred;scann nedthinsecttion.(F)Micrite,
sparite, andsecondaarygypsumtthatappearssassmallne eedlesinafeeltedmass;pplanepolarized
light.
secondarysparform
medalongcryystalmarginssofprimaryseleniticgyp
psum,appareentlyreplacingthe
sulphateemineral(Figg.36B).Thisstypeofrep lacementresultedinaplatyhabitoffaggregation
nsof
secondarycalcitecryystals(Fig.33C).Inplacees,subseque
entdissolutio
onofselenitiicgypsumprroduced
areticulaatefabric.Beesidesfillingporespace,,sulphurocccursasinclussionrichnoddulesenclose
edinthe
limeston
neandaslargge,transluce
ent,idiomorpphiccrystals withinveinss(Fig.36C). Somelimesttones
FIRSTMAN
NUSCRIPT 39

showassuccessionoffmicrite,sca
alenohedralccalcite,large
ecrystalsofssulphur,and largecrystalsof
pseudohexagonalaragonite(Figg.36D).Inst eadofthelaatter,radiaxialfibrousca lcitecementtisthe
terminallphaseoftheparageneticsequence insomeothersamples(Fig.36E).Seecondarygypsum
appearsassmallneeedles,formin
ngafeltedm
mass(Fig.36F).
ContradaGasspa
3.5.1.dC

Fig.37 ContradaGaaspa.(A)Lim
mestonemaddeofplanarffragments.C Coinforscalee.(B)Planarr
fragmen tsandchun ksofmicrite eseparated bysparcem ent;scanned dslab.(C)Laayersofmic rite
(dark)anndspar(brigght);planep
polarizedlighht.(D)Spar filledpseudomorphsaftterlenticularr
gypsum; planepolarrizedlight.
ThecliffofContrradaGaspaisformedby limestonem
madeofplanarfragmentss(Fig.37A)that
consisto
oflowmagneesiumcalcite eparatedby laterformed
e.Thesefraggmentsandcchunksarese dsparry
calcite,ffringingthem
micrite,andoblongcavitties(Fig.37B
B).Someoftthemicriticffragmentsarre
laminateed.Microspaartosparsep
paratesthem
micritefragm
mentsparalle
eltotheinteernallaminattion(Fig.
37C).Th
hemicriteco
ontainscalcittepseudomoorphsafterle
enticulargyp
psum(Fig.37D).Themiccrite
showshighironbutlowmanganesecontent s,whilethesparrycalciteexhibitslow
wcontentso
ofthese
elementts(Table31)).Nativesulp
phurhasnottbeenfoundintheselimestones,neiitherduringfield
worknorduringmicroscopicalan
nalysis.Extraactionofthe
elimestoneswithorganiccsolvents,ho
owever,
yieldedh hurisapparentlyfinelydiisseminatedwithin
highamounttsofsulphur.Therefore, nativesulph
thematrrixofthelim
mestone.Thelimestoneaalsocontains minoramou
untsofquarttz,whichwasonly

40 FIRSTMANUSCR
RIPT

detected
dbyXRDanaalysis.Eventhoughtraceeamountsoffcelestinewe
ereidentifieddbyelectron
microsco
opy,thestro
ontiumconte
entisrather low(Table31).
3.5.1.eM
MonteCapod
darso
From
mthissite,lim
mestoneand
danhydritessampleswereanalyzed.T
Thelimestonneconsistso
ofsmall
remnanttsofmicrite,,whicharesurroundedbbyamatrixo
ofmicrospartospar(Fig. 38A).Thed
dense
micriteisdarkbrown,exhibitinggonlyminor fluorescence
e.Itshowselevatedconttentsofironand
manganeese(Table31).Calcitep
pseudomorphhsafterlenticulargypsum
m(Fig.38A andB)are
abundan omite.Itshowstabulartooacicularcrystal
nt.Anhydriteeisaccompaniedbysulpphuranddolo
habits(FFig.38C).Largeanhydritecrystalsprrojectintocaavities,which
harefilledbyynativesulp
phur.
Locally,aanhydriteisreplacedbyalabastrineggypsum(Fig..38D).Occa
asionally,dollomiteisassociated
Fig.38 MonteCapo odarso.An=anhydrite;G Gyp=gypsum m;mi=micrrite;S=sulp hur.(A)Limestone

withmiccriticremnan nts,containingsparfilleedpseudomo orphsafterlenticulargy psum(arrow ws);
planepoolarizedlightt.(B)Closer viewofoneepseudomorrph;planepolarizedlighht.(C)Acicular
anhydrittepartlyrec rystallizedto
ogypsum;suulphurisfill ingporespa
ace.(D)Anhyydritepartlyy
recrysta llizedtoalab
bastrinegyppsumandpo rosityfilling sulphur;pla
anepolarizeedlight.
withsecondarygypssum;thedolo
omiteisrich iniron(Table31)andp
partlyaccomppaniedbycla
ay
mineralss.Dolomiteaalsooccurs,d
dispersedbeetweenanhydritecrystalss.Themagneesiumcontentin
pureanh
hydriteishiggh,whilethe strontiumccontentisunusuallylow((Table31;cff.,Dworkina
and
Land,19994).
FIRSTMAN
NUSCRIPT 41

3.5.2Staableisotopess
3.5.2.aC
Carbonando
oxygenisotopesofcarboonates
ntedeDrasiccarbonatessshowthehigghest13Cvaluesranging
Mon gfrom25too5‰(Table
e32;
Fig.39)..Therespecttive18Ovaluesvaryfrom
m4to+1‰
‰.Therangeofthecarboonisotopeva
aluesof
micriteaandmicrospaarfromLaM
Muculufaisraathernarrow 2‰);thecorrresponding18O
w(29to22
valuesraangefrom4
4to+2‰.Co dedlow13Cvalues(50
ozzoDisilimeestonesyield C 0to29‰)a
andhigh
18Ovalu
ues(0to+7‰ omitesampleeismoreenrichedin18O(+9‰)than
‰).Thedolo O ncalciteasexpected
forthed
differenceofoxygenisoto
opefraction ationbetweenthetwoccarbonatem inerals.The
18Odolommitevaluewou
uldbe+5‰,ifcorrectedfordifferentfractionatio
onfactorsduuringprecipitation
(H18Odolommitecalcite=+3
3.2‰,FritzandSmith,19970;McKenzie,1981)and
dforfractionnationduringg
analyticaalproceduree(H18Odolomitecalcite=+0.8‰
‰at25°C,Sh
harmaandC
Clayton,19655).Withresp
pectto
epletedin13Candlessen
ContradaaGaspalimeestones,micritetendstoobemorede C richedin18Othan
O
edoveralllow13Cvaluees(46to41‰)and
thelaterrsparphasess(Table32).Theselimesstonesyielde
high18O
Ovalues(+3to+5‰).On
nlyaforaminniferalpackstonereveale
edasomewhhatdifferent pattern
(13C:228to23‰,18O:+2to+ west13C
+3‰;Table 32).MonteCapodarsolimestoness howthelow
values(52to46‰ e18Ovaluessarehigh(+44to+5‰).
‰)ofalllimesstonesstudieed,whilethe
Fig.39 Carbonand oxygenstableisotopecoompositionssofindividua alcarbonateephases.One

dolomiteesamplefroomCozzoDissiisindicate dbythelettterd,twosa
amplesofforraminiferal
packston nesareindiccatedbytheletterf.

42 FIRSTMANUSCRIPT

Table32:Carbonandoxygenisotopecompositionsforindividualcarbonatephases,samples
containingforaminiferaaremarkedwith*.
sample mineralogy crystalhabit 13C 18O sample mineralogy crystalhabit 13C 18O
MontedeDrasi [‰] [‰] CozzoDisi [‰] [‰]
MD1aI_1 calcite microcrystalline 23.6 0.1 CD04_1 calcite sparitic 45.2 5.5
MD1aI_2 calcite microcrystalline 24.4 0.2 CD04_2 aragonite prismatic 47.7 5.5
MD1aI_3 calcite microcrystalline 18.0 0.9 CD05_1 calcite microcrystalline 39.2 4.9
MD1aI_4 calcite sparitic 20.8 0.3 CD05_2 calcite microsparitic 45.7 5.3
MD1aI_5 calcite sparitic 14.8 0.7 CD05_3 aragonite prismatic 48.9 5.6
MD1aI_6 calcite microcrystalline 23.1 0.1 CD05_4 aragonite prismatic 49.0 5.6
MD1aI_7 calcite microsparitic 24.8 0.1 CD05_5 calcite microsparitic 47.9 5.2
MD1aI_8 calcite sparitic 15.5 1.0 CD05_6 calcite microcrystalline 40.7 5.2
MD1aI_9 calcite sparitic 23.1 0.3 CD07_1 calcite microspar 36.9 4.9
MD1aI_10 calcite microcrystalline 24.3 0.0 CD07_2 calcite scalenohedral 36.7 4.9
MD1aII_1 calcite microcrystalline 19.7 0.2 CD07_3 calcite radiaxialfibrous 33.7 4.3
MD1aII_2 calcite sparitic 19.2 0.1 CD08_1 calcite microspar 36.5 4.8
MD1c_1 calcite microcrystalline 23.3 0.2 CD08_2 calcite scalenohedral 36.4 5.0
MD2dI_1 calcite microcrystalline 5.5 3.0 CD08_3 calcite radiaxialfibrous 36.1 4.0
MD2dI_2 calcite sparitic 8.1 1.4 CD09_1 dolomite microcrystalline 34.2 8.8
MD2dI_3 calcite microcrystalline 5.5 3.2 CD09_2 calcite microsparitic 29.4 5.0
MD2dI_4 calcite microcrystalline 6.8 2.8 CD09_3 calcite radiaxialfibrous 29.5 5.2
MD2dI_6 calcite sparitic 9.5 1.0 CD10_2 aragonite prismatic 36.5 5.0
MD2dI_8 calcite microcryst. 7.2 2.8 CD14_2 calcite sparitic 37.7 1.9
MD2dI_9 calcite microcrystalline 5.9 3.5 CD14_3 calcite sparitic 32.4 0.2
MD2dI_11 calcite microcrystalline 7.7 1.3 CD18_1 calcite microcrystalline* 33.8 0.1
MD2dI_12 calcite microcrystalline 15.2 0.5 CD18_2 calcite sparitic* 35.0 0.2
MD2dI_13 calcite microsparitic 9.6 2.0 CD20_1 calcite sparitic 36.9 0.1
MD2dII_1 calcite microcrystalline 5.9 2.4 CD20_2 calcite microsparitic 35.7 0.2
MD2dII_2 calcite microcrystalline 9.2 1.6
MD2dII_3 calcite microsparitic 14.7 0.9 ContradaGaspa
MD2dII_4 calcite microcrystalline 8.0 1.4 GA2f_1 calcite microcrystalline 45.0 3.5
MD2dII_7 calcite microcrystalline 7.4 2.0 GA2f_4 calcite microsparitic 45.1 3.6
GA2f_5 calcite microcrystalline 42.6 3.5
LaMuculufa GA2f_6 calcite sparitic 38.6 5.3
LMd_1 calcite sparitic 28.7 3.2 GA2f_7 calcite microsparitic 45.1 3.1
LMd_2 calcite sparitic 27.8 3.1 GA2f_8 calcite sparitic 36.6 6.7
LMd_3 calcite sparitic 27.2 1.0 GA2f_9 calcite microcrystalline 33.5 7.5
LMd_4 calcite sparitic 28.1 3.9 GA2i_1 calcite sparitic 44.4 3.5
LMd_5 calcite microcrystalline 28.4 1.5 GA2i_2 calcite microsparitic 45.6 3.5
LMd_6 calcite sparitic 28.6 1.5 GA2i_3 calcite sparitic 39.3 6.4
LMf_1 calcite microcrystalline 21.7 1.5 GA2i_4 calcite sparitic 40.4 6.3
LMf_2 calcite microcrystalline 22.3 1.4 GA2i_5 calcite sparitic 39.9 5.3
LMf_3 calcite sparitic 28.0 4.0 GA2k_1 calcite packstone* 28.2 3.3
LMf_4 calcite micrite 25.8 0.0 GA2k_2 calcite packstone* 23.1 1.9
LMf_5 calcite sparitic 27.1 2.1 GA2n_1 calcite mudstone* 37.1 4.6
LMf_6 calcite sparitic 28.4 0.4 GA2n_2 calcite mudstone* 35.1 5.3

FIRSTMAN
NUSCRIPT 43

Table3 2:continued
d
sample mineralogy crystalhabit 113C 18O
MonteCapod
darso [‰‰] [‰]
MCc_1 calcitee sparitic 447.6 4.6
MCc_2 calcitee microccrystalline 445.5 4.5
MCc_5 calcitee sparitic 5 0.3 4.0
3.5.2.bSSulphurisoto
opesandoxyygenisotopessofsulphate
e
Thesulp
phurisotopecomposition
nsofnativessulphurfrom
mMontedeD
Drasi,celestinneandnativve
sulphurffromLaMucculufa,gypsu
um,carbonatteassociated
dsulphate,a
andsulphurffromCozzoD
Disi,
carbonatteassociatedsulphateandsulphurffromGaspa,andsulphur andanhydriitefromMonte
ed(Table333;Fig.310).TThe34Svalu
Capodarrsohavebeendetermine uesofMonteedeDrasisu
ulphur
varybetw d+14‰.LaM
ween+3and onglyenrichedin34S(+444to+48‰)
Muculufacellestineisstro
compareedtonativesulphur(2tto+1‰).Sullphurisotopecomposio
onsofCozzoDisisamplesdisplay
hilesomese leniticgypsu
acompleexdiageneticchistory.Wh umrevealshigh34Svaluues(+36to+4
45‰),
laterseccondarygypssumformingafeltedmasssofneedless(+7to+10‰
‰)aswellasssulphur(+4
4to
310).Somennativesulphurexhibits34Svaluesasshighas+22
+10‰)sshowlowervvalues(Fig.3 2‰and
carbonatteassociatedsulphatefrromthesam
mesamplehaasvaluesash
highas+61‰
‰(Fig.310).
Fig.3100Sulphuriso
otopecompo
ositions.

44 FIRSTMANUSCR
RIPT

Finelydisseminaatednativesulphur,whicchwasgainedbysolvent extractionooftheContra
ada
mestone,yieeldeda34Svvalueof+13‰
Gaspalim ‰.Carbonateassociatedsulphatereecoveredfro
om
nrichedin34SS(+52‰).Th
ContradaaGaspalimeestonesisen he34SvaluesofMonteCCapodarsoan
nhydrite
rangefro
om+26to+2
27‰,whilen
nativesulph urshowslow
wervalues(+
+1to+8‰).
Corrrespondingo
oxygenandsulphurisotoopeswereme
easuredonccelestinefrom ufa,
mLaMuculu
gypsumandcarbonaateassociate
edsulphateffromCozzoD
Disi,carbona
ateassociateedsulphateffrom
Gaspa,aandanhydriteefromMontteCapodarsoo(Table33;;Fig.311).T
Thedatashow
wapositiverelation
n34Sand18
between 1
Ovalues.In plesareenricchedinboth 34Sand18O
ngeneral,su lphatesamp
compareedtoMessin
nianseawate essiniangypsum(Fig.3111).Onlyseco
ersulphateasswellasMe ondary
sulphateefromCozzo etedin34Sannd18Orelativvetomarine gypsum.
oDisiisdeple
Fig.3111Sulphuran doxygeniso
otopecompoositionsofsu ulphatescommparedwith literatured
data
(marked with*).Meessiniangypssumfromth eMediterra nean: 34 S:++22‰, 18 O::+16‰(Stenniand
Longinellli,1990).M essinianseawatersulph atecalculate edafterMesssiniangypsuumfromthee
Mediter ranean(see above)with hfractionatiooneffectsfo
orsulphuroff1.6‰(ThoddeandMonsster,
1973)an ndoxygenoof2to6‰Lloyd(1967,11968).

FIRSTMANUSCRIPT 45

Table33:Sulphurisotopecompositionsofnativesulphurandsulphurandoxygenisotope
compositionsofcelestine,gypsum,anhydrite,andcarbonateassociatedsulphate(CAS).
Sample Mineralogy 34S 18O Sample Mineralogy 34S 18O
[‰CDT] [‰VSMOW] [‰CDT] [‰VSMOW]

MontedeDrasi CozzoDisi
MD1_S1a sulphur 7.3 CD04_CAS CAS 61.2 32.4
MD1_S1b sulphur 7.5 CD04_S sulphur 22.9
MD1_S2a sulphur 14.1 CD05_CAS CAS 53.8 32.4
MD1_S2b sulphur 14.1 CD05_S sulphur 22.2
MD1_S3a sulphur 13.1 CD08_S1 sulphur 4.5
MD1_S3b sulphur 14.0 CD08_S2 sulphur 4.3
MD1_S4a sulphur 12.7 CD13_G gypsum 40.0 21.6
MD1_S4b sulphur 11.6 CD13_G1 gypsum 8.9
MD1_S5a sulphur 11.5 CD13_G2 gypsum 38.4
MD2_S1a sulphur 4.7 CD13_S sulphur 5.9
MD2_S2a sulphur 3.2 CD15_G gypsum 6.8
MD2_S2b sulphur 3.8 CD15_G1 gypsum 7.6 3.5
MD2_S3b sulphur 2.8 CD15_G2 gypsum 7.8 3.6
MD2_S4a sulphur 4.5 CD15_Sa sulphur 6.9
MD2_S4b sulphur 5.5 CD15_Sb sulphur 6.9
LaMuculufa CD20_G gypsum 44.9 21.0
LMi_C1 celestine 46.7 21.5 CD20_G gypsum 35.6
LMi_C2 celestine 47.3 21.3 CD20_S sulphur 7.7
LMf_C1 celestine 43.9 23.2 Contrada
LMf_C2 celestine 44.5 23.6 GA2JCAS CAS 52.0
LMf_C3 celestine 47.6 24.3 GA2JS sulphur 13.2
LMf_S1b sulphur 1.2 Monte
LMf_S3a sulphur 0.7 MCa_S1b sulphur 4.8
LMf_S3b sulphur 1.8 MCa_S2b sulphur 7.7
LMd_S1a sulphur 1.9 MCa_S3a sulphur 1.3
LMd_S1b sulphur 0.4 MCa_S3b sulphur 0.8
LMgS1 sulphur 0.2 MCa_S4a sulphur 4.7
LMgS2 sulphur 0.3 MCa_A1 anhydrite 26.4 19.0
MCa_A2 anhydrite 27.0 19.4
MCa_A3 anhydrite 27.0 19.5
3.6Discussion
3.6.1Isotopecompositionofsulphurspecies–implicationsonthegenesisofnativesulphur
Thesulphurandoxygenisotopecompositionofsulphurspeciescanbeusedtotraceredox
processes(e.g.,Pierre,1985;vanStempvoortandKrouse,1994;Böttcheretal.,1998;Brunneretal.,
2005),includingtheidentificationofmicrobialsulphatereductionthatstronglydiscriminatesagainst
34
S(KaplanandRittenberg,1964).TheisotopiccompositionofMessiniangypsumfromthe
Mediterraneanwasapproximately+22‰forsulphurand+16‰foroxygen(StenniandLonginelli,
1990).Onlyasmallisotopefractionationeffectof1.6‰forsulphur(ThodeandMonster,1973)and2
to6‰foroxygen(Lloyd,1967;1968)isobservedduringthecrystallizationofgypsumfrommarine
sulphate.ThereforetheisotopiccompositionforMediterraneanseawatersulphateintheMessinian
wasapproximately+20‰forsulphurand+10to+14‰foroxygen(Fig.311).Asnootherthan
MessinianevaporitesareknowninSicily,Messinianseawatersulphateandgypsumarethelikely
sourcesofsulphateforsulphatereductionprocessesthatleadtothesecondarymineralformationin
theMessinianstrataofSicily.

46 FIRSTMANUSCRIPT

Carbonateassociatedsulphateistrappedincarbonatesastheyform,thusitrecordsthesulphur
isotopecompositionofsulphatefromthefluidinwhichprecipitationtookplace(Burdettetal.,1989;
Lyonsetal.,2004;Newtonetal.,2004),andisonlynegligiblycompromisedbydiageneticalteration
(Gilletal.,2008).Becauseitisusuallyassumedthatsecondarycarbonateprecipitationinlithologies
richinsulphatemineralsisinducedbymicrobialsulphatereduction(e.g.,PierreandRouchy,1988),
theisotopecompositionofcarbonateassociatedsulphatecanbeusedasaproxyfortheisotope
compositionofsulphateduringongoingsulphatereduction.Celestinemayformupontransformation
reactionsinthecarbonatesystemandfixestheisotopiccompositionofdissolvedinterstitialwater
sulphate(BöttcherandParafiniuk,1998).Duetoitslowsolubilityinsulphaterichenvironments,
celestinehasahighpreservationpotential.ComparedtoMessiniangypsum,carbonateassociated
sulphate(ContradaGaspa,CozzoDisi)isenrichedby30to39‰in34S.CelestinefoundatLa
Muculufaisenrichedby22to26‰in34ScomparedtoMessiniangypsum.Theenrichmentof34Sin
bothsulphatephasesreflectstheisotopiccompositionofresidualsulphateafterintensesulphate
reduction(cf.,BöttcherandParafiniuk,1998;Taberneretal.,2002).
Nativesulphurlikelyformedbyoxidationofsulphide(e.g.,Machel,1992).Sincethereislittle
sulphurisotopefractionationforoxidativeprocesses(Fryetal.,1986)andthereisrapidsulphur
isotopeexchangebetweennativesulphurandsulphide(Fossing,1995)withasmallsulphurisotope
equilibriumfractionation(OhmotoandRye,1979),thesulphurisotopecompositionofnativesulphur
reflectsthesulphurisotopecompositionofsulphideproducedbysulphatereduction.Withone
exception,nativesulphurfromtheinvestigatedsitesinSicilyisdepletedbyapproximately5to25‰
comparedtoMessiniansulphates(Fig.310).
UsingMessiniangypsumasaproxyfortheisotopecompositionofthesourceofsulphate,
carbonateassociatedsulphateandcelestineasproxiesforresidualsulphateaffectedbyintense
sulphatereduction,andnativesulphurasproxyforproducedsulphide,weinferthatthesulphur
isotopefractionationduringsulphatereductionrangedfrom5to60‰.Thisiswithintherangeof
sulphurisotopefractionationsobservedinpureandnaturalmixedcultures(KaplanandRittenberg,
1964;HabichtandCanfield,1997;Bolligeretal.,2001).Thisobservationcorroboratesthatthe
investigatednativesulphurdepositsinSicilyresultedfromintensemicrobialsulphatereduction.The
prominenceofsulphatereductionisalsodemonstratedbythecoupledsulphurandoxygenisotope
enrichmenttrends(Figure11;MizutaniandRafter,1973;Fritzetal.,1989;Böttcheretal.,1998;
Brunneretal.,2005)forcelestine,aswellascarbonateassociatedsulphateandgypsum.Thehighest
oxygenisotopevalueofcarbonateassociatedsulphateis32.4‰(Table33),whereasthe
correspondingoxygenisotopecompositionofthecarbonateisapproximately5.5‰(Table32).
Usingtheoxygenisotopecompositionofthiscarbonateasaproxyfortheoxygenisotope
FIRSTMANUSCRIPT 47

compositionofwateratthetimethecarbonateformed,itcanbeconcludedthatthisheavysulphate
isotopecompositionwasclosetotheapparentoxygenisotopeequilibriumbetweensulphateand
water(Fritzetal.,1989).
AlatephaseofgypsuminsomeCozzoDisisamples,representedbysmallneedlesforminga
feltedmass(Fig.36F),mostlikelyderivedfromtheoxidationofsulphideornativesulphur.The
sulphurisotopecompositionofthissecondarygypsum(+8‰)issimilartothatofnativesulphurfrom
thesamesamples,inaccordwithonlyminorsulphurisotopefractionationduringoxidationof
sulphur(KaplanandRittenberg,1964;NakaiandJensen,1964;MizutaniandRafter,1973).The
oxygenisotopecompositionofsulphateproducedduringtheoxidationofsulphurcompoundsis
likelytobeslightlyenrichedin18Ocomparedtoambientwater(e.g.,Lloyd,1967;Balcietal.,2007;
Brunneretal.,2008),whichagreeswellwiththe18Ovalueofsecondarygypsumofapproximately
+4‰.
3.6.2Carbonsourcesofsecondarymicrobialcarbonates
Microorganismsareknowntoinducecarbonateprecipitationthroughrespirationprocessesby
increasingcarbonatealkalinity(KnorreandKrumbein,2000;Castanieretal.,2000;WrightandOren,
2005).Amongdifferentrespirationprocesses,microbialsulphatereductionisoftenconsideredtobe
acrucialfactorfortheformationofsecondarycarbonatesinavarietyofenvironments(VanLithet
al.,2003;Duprazetal.,2004;PeckmannandThiel,2004;Aloisietal.,2006).Organicmatter,crude
oil,andmethaneareknowntoactasreducingagentsformicrobialsulphatereduction(e.g.,Rueter
etal.,1994;Boetiusetal.,2000;Rabus,2005).Thesecarbonsourcesaretypifiedbydistinctcarbon
isotopiccompositions.Methaneisextremelydepletedin13C(110to50‰forbiogenicmethane
and50to20‰forthermogenicmethane;Whiticar,1999).Crudeoilislessdepletedwith13C
valuesof35to25‰(RobertsandAharon,1994).Marineorganicmattertendstohaverelatively
higher13Cvaluesofapproximately–25to–20‰(Hofmannetal.,2000).Becausemicroorganisms
preferentiallytakeupcompoundsdepletedin13Cduringthedegradationoforganicmatter,the
productsoftheseprocessesareevenmore13Cdepletedthanthesource.Butbecausecarbonateions
derivedfromtheoxidationoforganicmatterareusuallyaddedtoapoolofdissolvedinorganic
carbon,thecarbonisotopiccompositionoftheresultantmixturewillfallonamixinglinebetween
theisotopiccompositionsofthedifferentsources.Whilecarbonatesresultingfromtheoxidationof
crudeoilarelessdepletedin13C,methanederivedcarbonatesformingatmarineseepsshow13C
valuesaslowas76‰(Campbell,2006).Limestonesassociatedwithstrataboundsulphurdeposits
likethosefromtheCarpathianforedeep(13Cvaluesaslowas54‰;BöcherandPara niuk,1998;
Gasiewicz,2000)ortheLimestoneButtesinTexas(13Cvaluesaslowas39‰;KirklandandEvans,
1976),butalsosaltdomecaprockcarbonatesfromtheGulfofMexicoarea(13Cvaluesaslowas

48 FIRSTMANUSCRIPT

55‰;Thodeetal.,1954;FeelyandKulp,1957)showsimilarlylow13Cvalues,pointingtomethane
asthepredominantcarbonsource.
CarbonisotopecompositionsoftheSicilianlimestonesvarywidely(52to5‰).Limestones
withcarbonatephasesmostdepletedin13CweresampledatContradaGaspa,MonteCapodarso,and
CozzoDisi.Decimaetal.(1988)describedthesulphureouslimestoneswithlow13Candhigh18O
valuesasdiageneticconcomitantsofbacterialsulphatereduction.Nonsulphureouslimestoneswith
similarisotopiccomposition,however,wereinterpretedastheresultoftheconversionofaragonite
tocalciteinthepresenceof13Cdepletedand18Oenrichedwaters,whichwerethoughttooriginate
fromunderlyingorganicrichdiatomites(Decimaetal.,1988).Weconsideritunlikelythatpore
watersareabletochangethecarbonisotopecompositionofcarbonatestosuchadegree.Although
smallcelestinecrystalsembeddedwithinthenonsulphureouslimestonesfromContradaGaspa
agreewithaconversionofaragonitetocalcite,itismorelikelythatall13Cdepletedcarbonatesare
secondarymineralsthatprecipitatedinthecourseofmicrobialalterationprocessesthataffectedthe
hostlithologies.Thelowest13Cvaluesobserved(CozzoDisi,Gaspa,MonteCapodarso)revealthata
largefractionofthecarbonatewasderivedfromtheoxidationofbiogenicmethane,probablyin
additiontootherlessdepletedcarbonsourcesincludingmarinesourcedbicarbonate.
LaMuculufacarbonatesarelessdepletedin13Cthanthecarbonatesofthethreebefore
mentionedsites.Thiseitherreflects(1)oxidationofmethanewithahigherproportionofmarine
bicarbonate,(2)oxidationoffreshorganicmatterwithvirtuallynoadmixtureofothercarbon
sources,or(3)theoxidationofcrudeoil.Oxidationofmethaneseemsunlikely,assignificant
admixtureofmarinebicarbonateislikelytoresultinawiderspreadof13Ccarbonatevalues(Fig.39).
Oxidationoffreshorganicmatterisalsonotlikely,asthelowest13Ccarbonatevalues(29‰)are
probablytoolowtobeexplainedbythisprocess(cf.,Hofmannetal.,2000).Remineralisationof
pristineorganicmatteralsousuallyoccursduringearlydiagenesis,whichnecessarilyleadstothe
admixtureofmarinebicarbonate,resultinginawiderspreadof13Ccarbonatevaluesandalsohigher
valuesthanthoseoftheorganicsource.Consequently,oxidationofcrudeoilduringlatediagenesisis
mostlikely,asthe13Cvaluesshowlessvariabilitythanwouldbeexpectedifmixingprocesseswere
significantandmatchtheisotopiccompositionofcrudeoil(cf.,RobertsandAharon,1994).The18O
valuesofthesecondarycarbonatesandthedominanceoflaterspariteoverearlymicriteagreewith
alatediageneticformationundertheinfluenceofmeteoricwaters.Therefore,theseobservations
indicatethatLaMuculufacarbonatesresultedfromtheoxidationofcrudeoilwithlittleinputfrom
othersources.MontedeDrasilimestonesmostlyconsistofmarinecarbonateswithdifferentdegrees
ofadmixtureofsecondarycarbonates(13C:25to5‰),reflectingacontributionfromanunknown
sourceoforganiccarbon.
FIRSTMANUSCRIPT 49

3.6.3Epiversussyngeneticpathways
Epigeneticdepositsarecharacterizedbyreplacementofsulphateminerals(anhydriteorgypsum)
bysecondarysulphurandcarbonatesasaresultofdissolutionbymeteoricwatersandtheactionof
sulphatereducingprokaryotessubsequenttoearlydiagenesisandcompactionofthesedimentary
rock.Syngeneticdepositsformbysimilar,ifnotthesameprocesses,buteitherduringsedimentation
orearlydiagenesis.Inthiscase,sulphatereductionmayoccurinsulphateandorganicrich
sedimentsinevaporativesettingssuchaslagoons.AccordingtoWessel(1994),syngeneticsulphur
depositionoccursonlyinmodernspatiallyconfinedmarinetolacustrinesedimentaryenvironments
andisnotconsideredtobeeconomicallysignificant.However,Dessauetal.(1962)suggestedthat
theeconomicallysignificantSiciliandepositsaremainly,ifnotcompletelyofsyngeneticorigin.
ThesecondarycarbonatephasesinthelimestonesfromContradaGaspaandMonteCapodarso
aswellassomeofthelimestonesfromCozzoDisihaveincommonthattheyallformedinan
evaporiticenvironmentwheremethaneoxidationwasapparentlycoupledtosulphatereduction.
Evaporationisnotonlyindicatedbyhigh18Ocarbonatevalues(ashighas+8‰),butalsobyabundant
pseudomorphsafterlenticulargypsum.Someoftheselimestones,mostlyconsistingoforganicrich
micrite,stillexhibitaprimarylamination,agreeingwithsyngeneticformation.
ThesuiteofsamplesfromCozzoDisiprovidesevidenceforseveralstagesofgypsum,native
sulphur,andcarbonateformation.CozzoDisisecondarycarbonatephasescanbedividedintotwo
groupsbytheiroxygenisotopecomposition:Thefirstgroupwasaffectedbyevaporation.During
syngeneticmineralformationinevaporiticenvironments,thesystemvariedbetweenclosedand
moreopenconditions.Closedconditionsarecharacterizedby(a)nearlycompletereductionof
sulphate,resultinginhigh34Svaluesofthecarbonateassociatedsulphate(+54to+61‰)andnative
sulphurwithsulphurisotopecompositioncorrespondingtoMessiniangypsum(34Ssulphur:
approximately+22‰),(b)intenseevaporationindicatedby18Ocarbonatevalueshigherthan+5‰,and
(c)intensemethaneoxidationreflectedbylow13Cvalues(49to40‰).Moreopencondionsare
characterizedby(a)thelowest34Ssulphurvalues(+4‰),(b)lesspronouncedevaporation(18Ocarbonate:
<+5‰),and(c)apparentlyreducedmethaneoxidationorstrongeradmixtureofcarbonatefrom
othersources(13Ccarbonate:37to30‰).ThesecondgroupofsecondarycarbonatephasesofCozzo
Disiformedlaterduringepigenesis.Thesecarbonates,with18Ovaluesofaround0‰,reflectan
increasinginfluenceofmeteoricwaters.Thecarbonatespartlyreplacegypsum(Fig.36B)thatis
typifiedbyhigh34Svalues(+40to+45‰).Apparently,thisgypsumprecipitatedinanearlystage
fromasulphatepoolaffectedbysulphatereduction.Thenativesulphurinthesesamplesformedlate
intheparageneticsequence.Itsrelativelylow34Svalues(+6to+8‰)maythusindicateachange
towardsmoreopenconditions.

50 FIRSTMANUSCRIPT

TheMontedeDrasisamplesrepresentmostlyprimarylimestones,resemblingprimaryCalcaredi
Base(cf.,Decimaetal.,1988),asrevealedbynumerouspeloidaltofilamentousstructures.Similar
structuresinMessinianlimestoneshavebeeninterpretedtorepresentfaecalpellets(Guidoetal.,
2007)ormicrobialfilaments(Oliverietal.,2010).Hypersalineconditionsduringdepositionofthe
MontedeDrasilimestonesarereflectedbypseudomorphsafterhaliteandgypsum.Thedissolution
ofevaporitemineralsoccurredduringmeteoricdiagenesis,asrevealedbylow18Ocarbonatevalues.
Duringdiagenesis,aragonitewasalmostcompletelyrecrystallizedtocalcite,likelydeliveringthe
strontiumfortheprecipitationofcelestine(seeFig.34C).Nativesulphurisnotassociatedwithany
oftheearlydiageneticphases,butonlyoccursinveins,whichcrosscutthelimestone.The
parageneticsequencealongwiththeisotopepatternsrevealthattheMontedeDrasisulphurformed
epigenetically.
ThelocalsourceofstrontiumofcelestinepresentinsamplesfromLaMuculufaismostlikelythe
dissolutionofcalciumsulphateminerals(anhydriteorgypsum;seeSanzMonteroetal.,2009),asno
evidenceforabundantrecrystallizationofaragonitetocalcitewasfound.Basedonisotopepatterns,
anhydriteorgypsumweredissolvedbymeteoricwaterscarryingcrudeoil,favouringepigenetic
sulphurandcarbonateformationinarestricted,probablysubterraneansetting.Likewise,thenarrow
rangeof13Cvalueselucidatesthatthesecondarycarbonatesprecipitatedmostlyfromonecarbon
source(i.e.,crudeoil)withverylittleadmixtureofcarbonfromothersources.
WhiletheepigeneticprocessesthatledtosecondarymineralformationatLaMuculufawere
apparentlyfuelledbycrudeoil,syngeneticmineralauthigenesisatthesitesCozzoDisi,Contrada
Gaspa,andMonteCapodarsowasfuelledbymethane.Themethanesourcewaseithertheorganic
richdiatomiteoftheTripoliFormationasproposedbyDecimaetal.(1988)orcontemporaneous
biogenicmethanogenesis,takingplaceintheunderlyingsediments.
3.7Conclusions
AbundantsecondarycarbonatemineralsandnativesulphurenclosedinMessiniansedimentary
rocksfromCentralSicilyformedasaconsequenceofmicrobialsulphatereduction.Incontrastto
previousstudies,thisstudyrevealsthatdifferentSiciliansulphurandcarbonatedepositsformed
alongbothsyngenetic(i.e.,duringearlydiagenesispriortocompaction)andepigenetic(i.e.,during
latediagenesissubsequenttocompaction)pathways.Thisstudyreestablishesthatsyngenetic
formationandnotonlyepigeneticformationcanyieldeconomicallysignificantamountsofsulphur.
DuringtheevaporationoftheMediterraneanSeaseveralsmallsubbasinsdevelopedinthe
studyarea.Insomeofthesebasinssulphatereducingmicroorganismsflourishedtosuchanextent
FIRSTMANUSCRIPT 51

thatcarbonatemineralsandsulphurformedasaconsequenceofmicrobialmetabolism.Microbial
respirationprocesseswerefuelledbybiogenicmethane,whichmayhavebeenproducedby
methanogenicmicroorganismswithintheunderlyingsediments,butadeepersourceofmethane
cannotbeexcluded.Carbonatemineralsthatformedalongthissyngeneticpathwayare
characterizedbyverylow13Cvalues(52to30‰),reflectingoxidationofmethane,andhigh18O
values(+3to+9‰),reflectingevaporation.
Epigeneticsulphurandcarbonateauthigenesistookplaceafterdepositionofgypsumand
compaction.Epigenesiswascontrolledbydissolutionofsulphatemineralsprovidingsulphatefor
sulphatereducingmicroorganismsandthepresenceofcrudeoilladenmeteoricwaters.Carbonate
mineralsthatformedalongtheepigeneticpathwayarecharacterizedbylow13Cvalues(29to
5‰),reflectingoxidationofcrudeoilandpossiblyminormethaneandbylow18Ovalues(4to
+1‰),reflectingmeteoricconditions.
Acknowledgements
WethankW.KootandB.Lacet(VUAmsterdam),RalfBätzel,aswellasSebastianFlotow(both
Bremen)forthinsectionpreparation,ChristophVoigt(Bremen)forXRDmeasurements,TillHeinrichs
(Göttingen)forhelpwithFESEMandEDXanalysis,SilvanaPapeandKarstenEnneking(bothBremen)
forgeochemicalmeasurements,MonikaSegl(Bremen)forcarbonandoxygenisotopeanalysis,
ThomasMax(MaxPlanckInstituteforMarineMicrobiology,Bremen)andOliverKracht(Thermo,
Bremen)formassspectrometricsupport,MarieMadeleineBlancValleron(Paris)forhelpful
discussions,aswellasGailLeeArnold(Bremen)andthejournalreviewersStefanoLugli(Modena)
andananonymousrefereefortheircomments.ThisprojectwassupportedbytheDFGthroughthe
internationalgraduatecollegeEUROPROX,theDFGResearchCenter“TheOceanintheEarth
System”,theMaxPlanckSociety,andtheLeibnizIOW.

52 SECONDMANUSCRIPT

4SECONDMANUSCRIPT
AnaerobicoxidationofmethaneinhypersalineMessinianenvironments
revealedby13Cdepletedmolecularfossils
S.B.Ziegenbalg1,D.Birgel2,L.HoffmannSell1,C.Pierre3,J.M.Rouchy4,andJ.Peckmann2
1
2
DepartmentfürGeodynamikundSedimentologie,ErdwissenschaftlichesZentrum,UniversitätWien,
Althanstraße,1090Wien,Austria
3
CNRSUMR7159,LOCEAN,Univ.P.andM.Curie,75252ParisCedex05,France
4
Dept.EarthHistory,MuséumNationald'HistoireNaturelle,75005Paris,France
Abstract
TheMessiniansequenceofevaporiticdepositsinItalyincludesauthigeniccarbonatesthathave
beensuggestedtoderivefromthemicrobialdegradationoforganiccompounds,butthe
biogeochemicalmechanismsthatledtotheirformationremainedunknown.Tounravelthese
mechanisms,13Cdepletedcarbonaterocksincludingnativesulphurbearinglimestone(Calcare
Solfifero)fromtwolocationsinSicilyandbeddedlimestonefromthenorthernApennineshavebeen
studied.Their13Cvaluesaslowas48‰reflectincorporationofcarbonderivedfromtheoxidation
ofmethane,whichwaspreviouslysuggestedtohavebeenlinkedtobacterialsulphatereduction.
Molecularfossilsextractedfromthelimestonesrevealthatmethanewasindeedoxidizedinan
anaerobicprocessbyarchaeaandsulphatereducingbacteria.Theobservedbiomarkerpatterns
resemblethoseofmethaneseepcarbonates,whichformasaconsequenceoftheanaerobic
oxidationofmethane(AOM).AOMspecific,13Cdepletedbiomarkersincludingarchaeallipidssuchas
PMI(92to75‰)andsn2hydroxyarchaeol(94‰)aswellascompoundsderivedfromsulphate
reducingbacteria(isoandanteisofattyacids;13Caslowas85‰)wereiden edintheMessinian
carbonates.AlthoughthebiomarkerresultsclearlypointtoAOM,thecompoundinventoryalso
revealeddistinctdifferencestopatternsfoundatmarinemethaneseeps.Forexample,sn3
hydroxyarchaeolisinsomesamplestheonlyhydroxyarchaeolpresent,somethingusuallynotfound
atseeps.Archaeolrevealedintermediate13Cvaluesatmostsites(55to30‰),poinngtoother
archaeathanthoseinvolvedinAOM.Thepresenceofpseudomorphsafterlenticulargypsum,high
SECONDMANUSCRIPT 53

18Ovalues,andthebiomarkersextendedhydroxyarchaeol,tetrahymanol,andpossibly
phytanylglycerolmonoethersaswellasnonisoprenoidalmacrocyclicglyceroldiethersconfirmsthat
carbonateformationtookplaceunderevaporiticconditions.AOMhaspreviouslybeenshowntobe
inhibitedinsomebrinepoolsonthemodernseafloor.Ourobservations,however,demonstratethat
AOMfunctionsinhypersalineenvironmentsaswell.
4.1Introduction
Sulphurbearingcarbonateswithlow13Cvaluesweredescribedfromseveralregionsworldwide
includingtheCarpathianforedeep(13Cvaluesaslowas54‰vs.VPDB;BöttcherandParafiniuk,
1998;Gasiewicz,2000),theLimestoneButtesinTexas(aslowas39‰;KirklandandEvans,1976),
andthe‘CalcareSolfifero’inSicily(aslowas52‰;Decimaetal.,1988;Ziegenbalgetal.,2010).
Thesecarbonateswereinterpretedtoresultfrombacterialreductionofsulphatecoupledto
oxidationofmethane.Therationaleofthissuggestionisthatonlytheincorporationofcarbon
derivedfromtheoxidationofmethane,whichisusuallyverydepletedin13C,canresultinsuchlow
13Ccarbonatevalues(seePeckmannandThiel,2004forareview).Thisinterpretation,however,hasnot
beenfurthervalidatedbyotheranalyticalapproaches.
TheSiciliansulphurbearinglimestones(CalcareSolfifero)areassociatedwithabundantgypsum,
whichprecipitatedinthecourseofoneofthegreatestevaporiticeventsinEarthhistory,the
Messiniansalinitycrisis(DecimaandWezel,1973).Asealeveldropcausedbythecutoffofthe
MediterraneanSeafromtheAtlanticOceanresultedinrestrictedconditionsandthedepositionofan
evaporiticseries,includingevaporiticcarbonate,sulphate,halite,andbitternsaltsbetween5.96and
5.33millionyearsago(e.g.,Hsüetal.,1973a,b;Krijgsmanetal.,1999;Duggenetal.,2003).A
previousstudyonthepetrographyandstableisotopecompositionofthe‘CalcareSolfifero’
confirmedthatsulphurprecipitationresultedfrombacterialsulphatereduction,asrevealedbylow
sulphurisotopevaluesofnativesulphurandhighsulphurisotopevaluesoftheaccompanying
sulphateminerals(34Svaluesaslowas2‰andashighas+61‰vs.VCDT,respectively;
Ziegenbalgetal.,2010).Sulphurbearingcarbonatesformedeitheralongan(i)epigeneticpathwayor
a(ii)syngeneticpathway.Epigeneticcarbonatesarecharacterizedbylow13Cvalues(aslowas
29‰vs.VPDB)duetomicrobialoxidationoforganiccompounds(e.g.,crudeoil)bysulphate
reductioninthepresenceofmeteoricwaters(asindicatedby18Ovaluesaslowas4‰vs.VPDB).
Syngeneticcarbonatesarecharacterizedby18Oenrichment(valuesashighas+9‰),reflecting
evaporiticconditionsduringprecipitation.Thisinterpretationissupportedbypseudomorphsafter
lenticulargypsum,whichgrewintheunconsolidatedsediment.Thelow13Cvaluesofsyngenetic

54 SECONDMANUSCRIPT

carbonates(aslowas52‰)havebeeninterpretedtoreecttheoxidaonofmethane(Decimaet
al.,1988;Ziegenbalgetal.,2010).
Onewaytotestthishypothesisistheanalysisofmolecularfossils(i.e.,lipidbiomarkers).Todate,
onlyepigeneticcarbonatesassociatedwithnativesulphurenclosedinZechsteincarbonatesofthe
HarzMountains,Germany,havebeenanalyzedfortheirbiomarkercontent.Thesecondaryaragonite
(13C:10‰),whichformedinrecentmes,wasfoundtocontainpristinebiomarkersofsulphate
reducingbacteria(Peckmannetal.,1999a).Here,wesubjectedsyngeneticcarbonatesofthe‘Calcare
Solfifero’fromSicilytoabiomarkerstudyinordertoinvestigatetheinventoryofmicroorganisms
thatprevailedintheevaporiticsetting.ForcomparisonaMessiniancarbonatelayerfrombelowthe
baseofthegypsuminthenorthernApennineswasanalyzed.Wealsodeterminedcompoundspecific
carbonisotopecompositionstoidentifythedominantcarbonsourcesoftheMessinianmicrobial
community.
4.2Geologicalcontext,rocksamples,andmethods
CarbonatesoftheMessinian‘Gessososolfifera’FormationinSicilyfromthelocalitiesofCozzo
Disi(CD)andContradaGaspa(GA)aswellasofthenorthernApenninesfromtheMonticinolocality
(MO)werestudied.Petrographyaswellasstablecarbon,oxygen,andsulphurisotopedataof
carbonates,sulphates,andsulphurfromCDandGAwerepresentedbyZiegenbalgetal.(2010).The
formersulphurmineofCDissituatedsoutheastofCasteltermini.TheCDsamplesstudiedhere
comprisemicritictospariticlimestonewithsomeaccessorysulphatemineralsandcontainlarge
aggregatesofnativesulphur.Thelimestoneenclosescalcitepseudomorphsafterlenticulargypsum
andexhibits18Ovaluesashighas+6‰.Thecorresponding13Cvaluesrangefrom48to45‰.
TheabandonedsulphurmineofGAissituatedclosetothestreetS230fromEnnatoAlimena,
betweenCasaRealmesiandCasaBastione.TheGAmicrite,sampledfromalimestonecliff,contains
calcitepseudomorphsafterlenticulargypsum.Itisenrichedin18O(18O:+3to+8‰)anddepletedin
13
C(13C:46to34‰).Navesulphuris nelydisseminatedwithinthelimestone(Ziegenbalgetal.,
2010).TheMOcarbonate,sampledfromtheMonticinoSanctuarynearBrisighella(northern
Apennines,Italy;Roverietal.,2006,p.45f),ishomogenousandconsistsoffinegraineddolomite.It
isless13CdepletedthantheSiciliancarbonates,butalsoenrichedin18O(13C:27to23‰;18O:
+7‰;unpublishedresults).Nonativesulphurwasdetectedinthestudiedsample.
Samplepreparation,dissolution,extraction,andanalyseswereperformedaccordingtomethods
reportedbyBirgeletal.(2006b).Briefly,limestoneswerecarefullycleanedwithacetoneandHCl.
AfterwardsthecarbonatewasdissolvedinHCl.Theremainingsedimentwassaponifiedand
extractedwithamicrowaveextractionsystem(CEMMARSX)at80°Cand300WwithCH2Cl2:MeOH
SECONDMANUSCRIPT 55

(3:1).Theresultingextractwasseparatedintofourfractionsofincreasingpolaritybycolumn
chromatography(hydrocarbons,ketones/esters,alcohols,fattyacids).Inthefollowingwediscussthe
hydrocarbon,alcohol,andfattyacidfractions.Compoundswereexaminedbycoupledgas
chromatographymassspectrometry(GCMS)withaThermoElectronTraceGCMS.Moleculeswere
identifiedbasedonretentiontimesandincomparisonwithpublishedmassspectra.Contentsare
giveninng/gdryweightofthenondecalcifiedsample.Compoundspecificcarbonisotopeanalysis
(irmGC/MS)wasperformedwithaThermoElectronGCcombustionIIIinterfacelinkedtoaThermo
ElectronDeltaplusXPmassspectrometer.Carbonisotopevaluesaregiveninthenotationrelative
totheViennaPeedeeBelemnite(VPDB)standard.SeveralpulsesofCO2gasofknownisotopic
compositionatthebeginningandtheendoftherunswereusedforcalibration.
4.3Results
4.3.1Hydrocarbonfraction
ThesampleGAjshowsmuchhighercontentsoftotalhydrocarbons(1046ng/g;Table41)than
samplesCDandGAb(260and284ng/g,respectively).IntheSiciliansamples,nalkanesarethe
prevalentcompoundclassinthehydrocarbonfraction,rangingfromnC17tonC33.Theyrepresent
morethan50weight%ofallhydrocarbons.ShortchainhydrocarbonsarepredominantintheCD
sample,peakingatnC20,whichaccountsfor12%ofthehydrocarbons.Longchainhydrocarbons
dominateintheGAjsample,withnC31aspredominantcompound(13%).GAbdisplaysabimodal
pattern,peakingatnC20andnC31(8and9%,respectively).
Table41:Contentsandstableisotopecompositionsofmolecularfossils.Datainbracketsgivethe
percentageofthecomponentwithrespecttotheparticularfraction;cont.:contaminated;n.a.:not
analyzed;n.d.:notdetected;tr.:traces.a)Hydrocarbonfraction.ThehydrocarbonfractionofGAp
couldnotbequantified,duetocontaminationoftheusedstandard.Thehydrocarbonfractionof
MOgotlostduringsamplepreparation.
Hydrocarbonfraction CD GAb GAj GAp MO
ng/g(%) ‰ ng/g(%) ‰ ng/g(%) ‰ ng/g ‰ ng/g(%)
nC20 32.5(12) 29 22.8(8) 27 10.9(1) tr.
nC31 4.2(2) tr. 24.5(9) 33 136.8(13) 29
nalkanes(sum) 182.0(70) 29 159.7(56) 27 646.5(62) 28 cont.
PMI 13.6(5) 75 21.7(8) 92 60.4(6) 92 101
Squalane(tailtotail) 17.2(6) 57 n.d. 53.6(5) tr. 24
n.a.
Squalane(headtotail) n.d. n.d. 44.8(4) tr. n.d.
Biphytane n.d. n.d. 17.4(2) tr 95
Pristane n.d. n.d. 8.9(1) tr. n.d.
Phytane 18.7(7) 29 tr. tr. 9.4(1) 33 cont.
Sumhydrocarbons 260.4 284.4 1045.9
Tailtotaillinkedpentamethylicosane(PMI;Table41)isoneofthemainisoprenoidal
compoundsinthehydrocarbonfractionsofCDandGAlimestones,accountingfor5to8%.Exceptfor

56 SECONDMANUSCRIPT

GAb,itisaccompaniedbythetailtotaillinkedC30isoprenoidsqualane.Anaccessorycompoundin
GAjisheadtotaillinkedsqualane.TheheadtotaillinkedC20isoprenoidphytaneisthemain
isoprenoidalcompoundinthehydrocarbonfractionoftheCDsample,accountingfor7%ofthe
hydrocarbons.ItisalsopresentinlowerproportionsintheGAjsampleandintracesintheGAb
sample.Moreover,theGAjlimestoneshowsminoramountsoftheheadtotailC19isoprenoid
pristane.IntheGAjandpsamplestheheadtoheadlinkedacyclicC40isoprenoidbiphytaneis
present.
Table41:continued.b)Alcoholfraction.
Alcoholfraction CD GAb GAj GAp MO
ng/g(%) ‰ ng/g(%) ‰ ng/g(%) ‰ ng/g(%) ‰ ng/g(%) ‰
nC16 34.3(19) 49 22.8(3) 44 98.1(5) 39 18.7(4) tr. 4.0(6) tr.
nC18 21.9(12) 28 18.3(3) 32 77.5(4) 30 21.2(5) 33 4.2(7) tr.
nC24 4.5(3) tr. 115.7(17) 17 268.3(15) 18 103.3(24) 18 2.7(4) tr.
nalcohols(sum) 105.0(60) 35 453.4(66) 23 1123.6(61) 24 305.9(70) 22 21.9(35)
Phytanol 9.9(6) 32 52.1(8) 36 135.7(7) 27 62.3(14) 20 2.0(3) tr.
Archaeol 19.3(11) 34 80.3(12) 55 254.1(14) 52 25.6(6) 30 13.4(21) 89
sn2OHarchaeol 4.9(3) 94 9.8(1) tr. n.d. n.d. n.d.
sn3OHarchaeol n.d. tr. tr. 26.7(1) 79 n.d. 25.6(41) 95
Extendedarchaeol n.d. tr. tr. n.d. n.d. n.d.
sn2phytanylglycerol 3.3(2) tr. 14.3(2) 29 36.7(2) 21 8.6(2) tr. n.d.
monoether
sn3phytanylglycerol 1.8(1) tr. 10.6(2) tr. 18.4(1) 20 2.8(1) tr. n.d.
monoether
MAGE16:0 7.1(4) tr. 2.4(<1) tr. 9.7(1) tr. n.d. n.d.
MAGE17:0 1.8(1) tr. n.d. n.d. n.d. n.d.
C30DAGE n.d. 15.0(2) tr. n.d. n.d. n.d.
C31DAGE 6.4(4) tr. n.d. 35.0(2) 89 n.d. n.d.
C32macrocyclicglycerol 5.2(3) tr. 4.9(1) tr. 5.0(<1) tr. n.d. n.d.
C33macrocyclicglycerol 6.0(3) tr. 7.2(1) tr. 16.6(1) tr. n.d. n.d.
C34macrocyclicglycerol 5.3(3) tr. 6.1(1) tr. 15.7(1) tr. n.d. n.d.
Tetrahymanol n.d. 28.0(4) 19 105.7(6) 28 24.5(6) 21 n.d.
Cholesterol 3.6(2) tr. 7.4(1) tr. 66.2(4) 29 5.0(1) tr. n.d.
Sumalcohols 179.3 691.1 1848.9 434.7 62.9
4.3.2Alcoholfraction
ThenalcoholsrangefromnC12tonC32withanevenoveroddpredominance.ExceptfortheMO
sample,theyrepresent60to70%ofthealcoholfraction(Table41).Shortchainnalcoholsfromn
C14tonC20arepredominantintheCDlimestone,withnC16asmaincompoundaccountingfor19%
ofallcompoundsinthealcoholfraction.InGAsamples,themidandlongchainnalcoholsare
prominent,peakingatnC24(15to24%ofallalcoholcompounds;Fig.41a).
ThealcoholfractionoftheMOlimestonecontainslesslipids(63ng/g)thantheSiciliansamples
(179to1849ng/g).Theisoprenoidalcompoundsarchaeolandsn3hydroxyarchaeolarebyfarthe
mostabundantcompoundsinthealcoholfractionoftheMOsample,accountingfor21and41%,
SEECONDMAN
NUSCRIPT 57

respectivvely.Thesn3
3hydroxyarcchaeolconteentevendou
ublesthatofarchaeol,whhileother
compoundslikenalccoholsandp
phytanolare presentinm
muchlowera
amounts(2tto4ng/g).
Figure4 1Gaschrom matogramso ofsampleGA Ab.a)Alcohholfraction,blackdots:ssaturatedn

alcohols ;blackarrow whead:mon noalkylglyceerolether(MMAGE);whitearrowheadds:dialkyl
glyceroleethers(DAG Es);whitediamonds:phhytanylglyce rolmonoethers(Phme) ;blackarrow ws:
macrocyyclicglycerol diethers;Ar:archaeol; Chol:cholessterol;cont.:contaminannt;IS:intern nal
standard d;OHar:hyddroxyarchaeol;Ph:phytaanol;THM:ttetrahymano ol.B)Carboxxylicacidfraction;
blackdo ots:saturate dnfattyacids;blackstaars:isoand anteisofattyacids;
C 32 :17
(H),21(H)
C 32 hopaanoicacid;
C 32 :17(H
H),21(H)C 332 hopanoic acid;Bp0,B
Bp1,Bp2:bbiphytanicdiacids
with0,11or2cycloppentanerings;IS:internaalstandard; Ph:phytaniccacid;Pr:prristanicacid.
Inth
heSiciliansam
mples,archa
aeolispresenntinsubstan
ntialamounts,represent ing6to14%
%ofall
compoundsoftheallcoholfractio untsofthesnn2hydroxyarchaeol
on.Itisacco mpaniedbyminoramou
Dsample,sn3hydroxyarrchaeolintheeGAjsampleandbybothcompounndsintheGA
intheCD Ab

58 SECONDMANUSCRIPT

sample.TheGAblimestonecontainstracesofOphytanylOsesterterpanylglycerolether(extended
archaeol).Phytanolaccountsfor6to14%.IntheGAplimestone,itscontentexceedsthatof
archaeol.Phytanolisaccompaniedbysmalleramountsofsn2andsn3phytanylglycerolmonoethers
intheCDandGAsamples.Monoalkylglycerolethers(MAGEs)anddialkylglycerolethers(DAGEs)are
presentintheCDlimestone,wheretheyaccountfor1to4%.Inthesamesample,nonisoprenoidal
C32,C33,andC34macrocyclicglyceroldiethers(cf.,Blumenbergetal.,2007)represent3%ofall
compoundsinthealcoholfraction.MAGEs,DAGEs,andmacrocyclicglyceroldiethersarealsopresent
inminoramountsintheGaspabandjsamples.ThemostabundantpentacyclicterpenoidintheGA
samplesistetrahymanol.ThiscompoundwasnotdetectedintheCDandMOlimestones.Cholesterol
wastheonlytetracyclicterpenoidpresent,butitscontentsareonlyminor.
Table41:continued.Carboxylicacidfraction;Bp0,Bp1,Bp2:biphytanicdiacidswith0,1or2
cyclopentanerings.
Carboxylicacids CD GAb GAj GAp MO
ng/g(%) ‰ ng/g(%) ‰ ng/g(%) ‰ ng/g(%) ‰ ng/g(%) ‰
nC15:0 26.8(3) 31 24.4(1) 41 112.5(2) 36 56.6(3) 30 7.8(3) 37
nC16:0 245.2(26) 34 186.1(10) 36 775.7(15) 34 516.8(23) 30 46.3(19) 28
nC17:0 8.4(1) 31 16.7(1) 33 83.3(2) 30 28.1(1) 27 5.1(2) 24
nC18:0 62.7(7) 27 74.0(4) 28 357.3(7) 29 186.6(8) 28 23.8(10) 25
nC22:0 225.6(24) 24 97.6(5) 18 360.5(7) 22 195.0(9) 20 22.6(9) 20
nC28:0 51.7(6) 14 291.4(15) 21 392.5(8) 22 214.1(9) 21 5.8(2) 29
ncarboxylicacids 719.2(76) 25 1205.3(62) 24 3516.3(69) 25 1856.2(81) 23 198.9(81) 26
(sum)
isoC15:0 20.9(2) 83 58.5(3) 80 136.2(3) 81 39.7(2) tr. 4.2(2) 33
anteisoC15:0 11.6(1) 53 24.9(1) 68 69.4(1) 70 27.1(1) tr. 3.5(1) 27
isoC16:0 15.0(2) 85 28.3(2) 70 71.3(1) 68 20.2(1) tr. 3.1(1) 26
isoC17:0 17.42) 84 39.1(2) 55 92.8(2) 55 22.2(1) tr. 2.8(1) 34
anteisoC17:0 tr. tr. 28.3(1) 70 58.0(1) 61 13.6(1) tr. 1.5(1) 31
10MeC16:0 48.4(5) 90 n.d. 28.4(1) tr. n.d. 2.7(1) 69

C32hopanoic n.d. 20.7(1) 52 tr. tr. n.d. n.d.
acid
C32hopanoic 46.0(5) 87 238.0(12) 77 648.3(13) 76 100.4(4) 65 11.5(5) 31
acid
Bp0 tr. tr. 59.4(3) 97 n.a. n.a. 17.9(1) 78 7.3(3) 73
Bp1 tr. tr. 53.3(3) 104 n.a. n.a. 9.5(<1) 100 5.5(2) 93
Bp2 tr. tr. 95.0(5) 105 n.a. n.a. 14.0(1) 103 3.9(2) 99
Phytanicacid 25.7(3) 97 99.2(5) 42 227.5(5) 32 157.1(7) 21 n.d.
Pristanicacid tr. tr. n.d. 32.0(1) tr. 19.1(1) tr. n.d.
Sumcarboxylic 946.8 1950.1 5070.1 2297.0 245.0
acids
4.3.3Carboxylicacidfraction
Thisfractionrevealedthehighestcontentsofcompoundsforallsites.TheGAjsampleshowsthe
highesttotalcontents(5070ng/g;Table41).Saturatednfattyacidsarethepredominant
components,accountingfor62to81%.TheyrangefromnC12tonC30withanevenoverodd
predominance,peakingeitheratnC16(CD,GAjandp,MO),oratnC28(GAb;Fig.41b).The
SECONDMANUSCRIPT 59

terminallybranchedisoandanteisoC15:0andC17:0fattyacids,aswellasisoC16:0fattyacidare
presentinallsamples,representing1to3%.TheratioofanteisoC15:0relativetoisoC15:0isbetween
0.4and0.8.Thecontentsofthebranchedfattyacidsevenpartlyexceedsthesaturatedunbranched
homologues(isoC15:0>nC15:0andisoC17:0>nC17:0inGAbandj).AmidchainmethylbranchedC16:0
fattyacid,namely10MeC16:0,ispresentinsubstantialamountsintheCDlimestone,accountingfor
5%ofallcompoundsinthecarboxylicacidfraction(Table41).Thiscompoundispresentinlower
amountsintheGAjandMOlimestones.17(H),21(H)C32hopanoicacidisfoundinallsamples.It
accountsfor4to5%ofthecarboxylicacidsintheCD,GAp,andMOsamples.IntheGAbandj
limestonesitisamongthemajorcompounds,representing12to13%(Table41).IntheGAb
limestone,theisomerisaccompaniedbyminoramountsofthe
isomer.Sparsepristanic(CD,
GAjandp)andmoreabundantphytanicacid(allsamplesexceptMO)weredetected.Biphytanic
diacidswith0,1,or2cyclopentaneringsarepresentinalmostallsamples(notdetectedintheGAj
sample).Theyaccountforupto5%intheGAblimestone.
4.3.4Compoundspecificstablecarbonisotopedata
Thenalkanes,nalcohols,andnfattyacidsdisplay13Cvaluesfrom49‰to20‰(Table41;
Fig.42).ThebranchedfattyacidsfromtheCDandGAlimestone,showlow13Cvalues(90to
53‰).Similar13Cvalueswereobtainedforthe17(H),21(H)C32hopanoicacidfortheCDandGA
samples(87to65‰).IntheMOsample,the13Cvaluesoftheterminallybranchedfattyacidsas
wellasthe17(H),21(H)C32hopanoicacidareinthesamerangeasthenfattyacids.
Amongtheisoprenoids,biphytanicdiacids(105to73‰)andPMI(101to75‰)arethe
most13Cdepletedcompoundsinallsamples.Interestingly,biphytanicdiacidsshowadecreasein
their13Cvaluewithincreasingnumberofrings.Biphytane(95‰)andsn2andsn3
hydroxyarchaeol(94to79‰)belongtothegroupof13Cdepletedcompounds.Theisotopic
compositionofarchaeolvariessignificantlyamongthevarioussamples.Intermediate13Carchaeol
valueswereobtainedfortheGAbandjsamples(55and52‰,respecvely),whilehighervalues
weremeasuredfortheCDandGApsamples(34and30‰,respectively).OnlyintheMO
limestone,archaeolexhibitsastrong13Cdepletion(89‰).Valuesofirregularsqualanevary
between57‰(CD)and24‰(GAp).Thetwoisoprenoidssn2andsn3phytanylglycerol
monoethers(13C:29to20‰)aswellasthepentacyclicterpenoidtetrahymanol(13C:28to
19‰)revealed13Cvaluestypicalformarinelipids.

60 SECO
ONDMANUSSCRIPT

Figure4 2Carbonis otopiccomp positionofseelectedmole ecularfossils,illustratin gashifttow

wards
higher 13 Cvvaluesfrom markersofaanaerobicm ethanotroph
slightlyh hicarchaea((ANME)tom markers
ofsulph atereducinggbacteria(SRB)andthe widespano of 13 Cvalue
esreflecting amixturefrrom
ANMEso ourcedarchaaeolandarcchaeolderiveedfromothe er,nonmeth hanotrophicarchaeacarrrying
theisotoopicsignaturreoforganiccmatterfrom mthewaterrcolumn(arcchaea–mix)).Notethat SRB
lipidsfro
omMonticin noclusterathigherG 13 C values(blacckcrosses).
4.4Discu
ussion
4.4.1Mo
olecularfossilsofMessin
nianauthigenniccarbonate
esresemblethoseofmeethaneseep
carbonattes
Sulphatedepend
dentanaerobicoxidationnofmethane
e(AOM)isperformedbyyaconsortiumof
bicmethaneoxidizingarcchaea(ANMEE)andsulphatereducing
anaerob gbacteria(SRRB;Boetiuse
etal.,
2000;Hinrichsetal.,,2000;Orphanetal.,20001a;Thielet al.,2001;M
Michaeliseta l.,2002;Knitttelet
ow13Cvalueesisamongtthemostperrsistentmoleecularfossilssof
al.,20033).PMIwitheextremelylo
ANMEin
nmethaneseeepsdepositts(e.g.,Peckkmannetal.,1999b,2009
9;Thieletal .1999;Birge
eletal.,
2008b).Thepresencceof13CdepletedPMI(13Cvaluesasslowas101‰)inallSicciliansample
es
revealstthatANMEw
werepresenttinthesedim
mentduringcarbonatefo
ormation,coonfirmingtha
at
methaneewasoxidizeedanaerobiccallyintheM
Messinianhypersalineenvironment.W
Whenfoundinseep
settings,,13Cdepletedarchaeolh
hasbeenattrributedtoAN
NMErelated totheorderrMethanosa
arcinales
9).Thestronggly13Cdepleetedarchaeo
(Hinrichssetal.,1999 olintheMOsamplewas mostlikelyssourced
SECONDMANUSCRIPT 61

exclusivelyorpredominantlybyANME.Incontrast,inallSiciliansamplesarchaeolshowsasignificant
variationin13CvaluescomparedtoPMI(Fig.42).Sincearchaeolisacommonmembranelipidin
manyeuryarchaeaincludingmethanogensandhalophiles(TornabeneandLangworthy,1979;De
RosaandGambacorta,1988;Kates,1993;Kogaetal.,1993,1998),thiscompoundapparentlyderived
fromvariousarchaealsources,causingthewidescatterofitsisotopiccomposition.Incontrastto
archaeol,thedietherssn2andsn3hydroxyarchaeolyielded13CvaluesinthesamerangeasPMI,
pointingtoANMEasexclusivesourceorganisms.Whereassn2hydroxyarchaeoliscommonly
observedespeciallyinANME2(e.g.,Hinrichsetal.,1999,2000;Pancostetal.,2000;Blumenberget
al.,2004;NiemannandElvert,2008),sn3hydroxyarchaeolisnotcommoninseepdwellingANME;if
present,itisaccompaniedbysn2hydroxyarchaeol(Pancostetal.,2001b;Elvertetal.,2005).Likein
GAjandMOlimestones,sn3hydroxyarchaeolwasfoundasthesolehydroxyarchaeolonlyin
methaneseepcarbonatesfromtheSorokinTrough(BlackSea)andEocenecarbonatecemented
tubularsandstones,agreeingwithitsoriginfromyetunknownANMEinthesesettings(Stadnitskaia
etal.,2005;DeBoeveretal.,2009).Stadnitskaiaetal.(2005)proposedthatitssourceorganismsare
closelyrelatedtoANME1.TheabsenceofcrocetaneintheMessiniansamples,amolecularfossil
indicativeofANME2(Blumenbergetal.,2004),alsosuggeststhattheMessinianmethaneoxidizing
archaeawererelatedtoANME1ratherthantoANME2archaea.Furthermore,13Cdepleted
biphytanicdiacidswithnototwocyclopentaneringswerefoundinalmostallsamples(Fig.42).
Althoughthesourceofbiphytanicdiacidsisyettobedetermined,theyhavebeenregularlyfoundin
ancientseeplimestones(Birgeletal.,2008a),includingtheEocenecarbonatecementedtubular
sandstonesthatalsoyieldedsn3hydroxyarchaeolasthesolehydroxyarchaeolhomologue(De
Boeveretal.,2009).Thispatternindicatesthatthe13Cdepletedbiphytanicdiacidsderived
exclusivelyfrommethanotrophiceuryarchaea,makingthemexcellentcandidatestotracethe
endmemberisotopiccompositionoflipidsderivedfrommethaneoxidizingarchaea(cf.,Birgeletal.,
2008a).
SRBofthegeneraDesulfosarcina/Desulfococcus(DSS)arethesyntrophicpartnersofANME1
and2(e.g.,Orphanetal.,2001a;Knitteletal.,2003).BiomarkersofDSS,includingtherelative
persistentterminallybranchedfattyacidsisoandanteisoC15:0(Birgeletal.,2006a),havebeen
identifiedinvariousmethaneseepenvironments(NiemannandElvert,2008).AsallSiciliansamples
yielded13Cdepletedterminallybranchedfattyacids(Table41),SRBwereapparentlyinvolvedinthe
oxidationofmethaneintheMessiniansediments.Likewise,theobservationthattheSRBmarkers
areabout10to30‰lessdepletedin13Cthanthearchaealmarkersindicatesthatmethanewas
oxidizedinasimilarfashionlikeatmethaneseeps(Fig.42;cf.,Hinrichsetal.,2000;Orphanetal.,
2001a).

62 SECONDMANUSCRIPT

AlthoughthebiomarkerpatternoftheMessinianlimestonesrevealedremarkablesimilarities
withthatofmethaneseepdeposits,therearealsodistinctdifferences.Apreponderanceofanteiso
C15:0overisoC15:0fattyacidhascommonlybeenobservedinseepdeposits(e.g.,Hinrichsetal.2000;
Elvertetal.2003;Papeetal.2005;NiemannandElvert,2008).Thispatternwasalsorecognizedin
culturesofDesulfosarcinaandDesulfococcus(Rüttersetal.,2001,2002),generarepresentingthe
syntrophicpartnersofANME(Boetiusetal.,2000;Orphanetal.,2001a,b,2002;Knitteletal.,2003).
Incontrasttothis,theanteisoC15:0toisoC15:0ratiosvaryfrom0.4(GAb)to0.8(MO)inthe
Messinianlimestones.Suchratioshavebeenreportedfromculturedsulphatereducingbacteria,
whicharenotcommonlyassociatedtoANME,asforexampleDesulfobacterandDesulfovibrio(Taylor
andParkes,1983;Edlundetal.,1985;Dowlingetal.,1986;Londryetal.,2004).Similarandeven
lowerratioswerefoundinreefmicrobialitesfromoffTahiti,whereSRBhavebeensuggestedto
drivecarbonateprecipitation(Heindeletal.,2010).
ApartfromisoandanteisoC15:0fattyacidsofisoandanteisoC17:0fattyacidswerefoundinall
GAsamples.ContentsofterminallybranchedC15:0andC17:0fattyacidsmostlyexceedthoseofthe
correspondingnCfattyacidsintheGAsamples.AlthoughisoandanteisoC17:0fattyacidsoccurin
DSS,theyarenotasprominentinthesebacteriaasinothersulphatereducingbacterialike
DesulfobacterandDesulfovibrio(TaylorandParkes,1983;Rüttersetal.,2001;KönnekeandWiddel,
2003).Furthermore,10MeC16:0fattyacid,oneofthemostabundantandmost13Cdepletedfatty
acidsintheCDlimestone,isaveryprominentcompoundinthegenusDesulfobacter(Taylorand
Parkes,1983;Dowlingetal.,1986;Colemanetal.,1993;KönnekeandWiddel,2003;Londryetal.,
2004),butithasnotbeenreportedtobesynthesizedbyDSS.Liketheterminallybranchedfatty
acids,ithasbeendetectedatmodernmethaneseepsandwassuggestedtobederivedfromyet
unknownsulphatereducersinvolvedinAOMbasedonits13Cdepletion(e.g.,Hinrichsetal.2000;
Elvertetal.2003).Thenonisoprenoidalmonoanddialkylglycerolethers(MAGEsandDAGEs)
detectedintheMessinianlimestoneshavecommonlybeeninterpretedasmolecularfossilsof
sulphatereducingbacteriainvolvedinAOMwhenfoundatseeps(cf.,Hinrichsetal.,2000;Orphanet
al.,2001a;Pancostetal.,2001a;Werneetal.,2002).EvensothecontentsofMAGEsandDAGEsare
low,andonlyone13Cvalueof89‰wasobtainedforDAGEC31(GAj),theirpresenceintheCD,
GAb,andGAjsamplescontributestothelineofevidencethatsulphatereducingbacteriawere
involvedinmethaneoxidationintheMessinianevaporiticsettings.
ThebishomohopanoicacidispresentinallSiciliansamplesinsubstantialamounts,especially
intheGAsamples.Itslow13Cvaluesdemonstratetheincorporationofmethanederivedcarbon.
Pancostetal.(2000)interpreted13Cdepletedhopanoidsaccompanyingother13Cdepletedbacterial
markersaslipidsderivedfromsulphatereducingbacteriainvolvedinAOM.Similarly,hopanoicacids
SECONDMANUSCRIPT 63

foundinmicrobialmatsfromtheBlackSeahavebeeninterpretedtobederivedfromanaerobic
bacteria(Thieletal.,2003).Blumenbergetal.(2006),studyingenrichmentculturesfromtheBlack
Seamats,confirmedthatDesulfovibriostrainsareabletoproducebacteriohopanepolyols.Todate,
DesulfovibrioaretheonlySRBknowntosynthesizehopanoids.The13Cvaluesofthe
bishomohopanoicacidsintheSiciliansamplesfallintherangeofSRBderivedbranchedfattyacids
(Table41),whichwouldagreewithanassignmentofthiscompoundtoSRB,butanotherbacterial
sourceincludingaerobicbacteriacannotbeexcluded.
InthesamplefromthenorthernApennines,thelipidsderivedfromsulphatereducingbacteria
(terminallybranchedfattyacids,possiblybishomohopanoicacid)arenotstrongly13Cdepleted,in
contrasttothearchaealmarkers(Fig.42).Themajorityofsulphatereducingbacteria,whichwere
presentinthatecosystem,wereapparentlynotinvolvedinAOM.DeducedfromFISHSIMSdata,
Orphanetal.(2002)statedthatANME1appearnottobeasdependentontheirSRBpartnersas
ANME2.Accordingly,somemethanotrophicarchaeaseemtobeabletorunsulphatedependent
AOMcompletelyautonomousasreportedfromasubzerohypersalinemethaneseep(Niederberger
etal.,2010).Thelackof13CdepletedbacteriallipidsinthesamplefromthenorthernApenninesmay
consequentlyindicatethatAOMwasperformedbyarchaeaalone,asapreservationalbiasseem
unlikely,giventhatAOMlipidstendtobeverywellpreservedinmethanederivedcarbonates(Birgel
etal.,2008b).
4.4.2TheMessinianmicrobialecosystemcharacterizedbymolecularfossils
InapreviousstudyontheMessinianlimestones,includingtheGAandCDsamples,verylow
13
Ccarbonatevalueswereinterpretedtoreflectmethaneoxidationcoupledtothereductionof
sulphate(Ziegenbalgetal.,2010).Thenewbiomarkersnowshowthatcarbonateprecipitationwas
inducedbytheactivityofanAOMconsortiumsimilartothatatmethaneseeps.Butincontrastto
seepcarbonates,high18OvaluesandpseudomorphsaftergypsumintheCDandGAsamplesreflect
hypersalineconditions(Ziegenbalgetal.,2010).AlthoughsulphatedependantAOMhasbeen
suggestedtooccurinhypersalineenvironments(Pancostetal.,2000,2001b;Daffonchioetal.,2006;
Huguenetal.,2009;Omoregieetal.,2009;Wankeletal.,2010),Joyeetal.(2009b)arguedthathigh
chlorideconcentrationssuppresstheactivityofmethaneoxidizingarchaea.
Additionalevidenceforthepresenceofhypersalineconditionsduringtheformationofthe
Messiniancarbonatesstemsfromsomeoftheobservedmolecularfossils.Althoughthepentacyclic
terpenoidtetrahymanol,whichispresentinallGAsamples,wasdetectedinvariousorganisms
includingferns(Zanderetal.,1969),rumenfungus(Kempetal.,1984),bacteriovorousciliates
(HarveyandMcManus,1991),andinanoxygenicphototrophicbacteria(Kleemannetal.,1990;

64 SECONDMANUSCRIPT

Rashbyetal.,2007),thiscompoundoritsputativediageneticproductgammaceraneisparticularly
abundantinhypersalineenvironments(tenHavenetal.,1988,1989).Extendedarchaeolisamong
themostspecificmolecularfossilsofhalophilicarchaea(Teixidoretal.,1993).Thiscompoundis
presentinGAb.Otherthanextendedarchaeol,sn2andsn3hydroxyarchaeolareubiquitously
distributedinmethanogenic,methanotrophic,andfacultativehalophilicarchaeaoftheorders
MethanosarcinalesandMethanococcales(Sprott,1992;Sprottetal.,1990,1993;Kogaetal.,1993).
Sincesn2andsn3hydroxyarchaeolrevealedsignificant13Cdepletion,amethanotrophicsource
organismseemslikely.OnlyinsampleGAjsn3hydroxyarchaeolisabout10‰lessdepletedin13C
thanPMI,possiblysuggestinganadditionalcontributionfromnonmethanotrophicarchaea.
AlthoughPMIisnowcommonlyusedasabiomarkerformethanogenicormethanotrophic
archaea,PMIwasoriginallyaccountedasmarkerforhypersalineconditions(Waplesetal.,1974).
Thisreasoningwasbasedontheabilityofhalophilicmethanogenicarchaeatosynthesizethis
compound(Holzeretal.,1979;Tornabeneetal.,1979).However,basedonthelow13Cvaluesof
PMIintheanalyzedsamples,asignificantcontributionfrommethanogenicarchaeaisunlikely.In
contrasttoPMIandthehydroxyarchaeols,archaeolrevealedawiderangeof13Cvalues.Inall
SiciliansamplesitislessdepletedthantheAOMlipids(Table41,Fig.42),pointingtoadditional
sourcestomethanotrophicarchaea.
ThephytanylglycerolmonoethersidentifiedinallSiciliansampleshavebeensuggestedto
representhydrolysisproductsofhydroxyarchaeolbasedonlabcultures(Kogaetal.,1993;Obaetal.,
2006).Theonlyreportfromenvironmentalsamplesstemsfrommodernseeps,whereahighly13C
depletedsn1phytanylglycerolmonoether(equivalenttooursn3phytanylglycerolmonoether)was
suggestedtoderivefromdiethersofmethanotrophicarchaea(Hinrichsetal.,2000).Withrespectto
theSiciliansamplesthestrongdifferenceof13Cvaluesbetweenthephytanylglycerolmonoethers
(13C:29to20‰)andthetwohydroxyarchaeols(13C:95and79‰)disagreeswithacommon
sourceofthesecompounds.Instead,phytanylglycerolmonoethersderivedfromnon
methanotrophicarchaea,possiblyhalophiles.
ThenonisoprenoidalmacrocyclicglyceroldiethersfoundintheCDandGAbandjsamples
(Table41)weredescribedfromhydrothermalsystems(Pancostetal.,2006;Blumenbergetal.,
2007),butwereneverextractedfromculturedbacteria.Recently,Baudrandetal.(2010)described
thesecompoundsfromahypersaline,nonhydrothermalsettingfromtheMessinianofEgyptand
Spain.Althoughevaporiticsettingsmaybehot,thereisnoindicationthattherocksanalyzedhereor
thoseanalyzedbyBaudrandetal.(2010)formedunderhydrothermalconditions.Itseems,therefore,
mostlikelythatthesecompoundsderivedfromunknownhalophilicbacteria(cf.,Baudrandetal.,
2010).
SECONDMANUSCRIPT 65

4.5Conclusions
13
Cdepletedmolecularfossilsofanaerobicmethaneoxidizingarchaeaandsulphatereducing
bacteriaarepresentinauthigeniccarbonates,whichoccurinsedimentsdepositedduringthe
MessiniansalinitycrisisinSicilyandthenorthernApennines.Thecarbonatesprecipitatedduring
evaporiticandhypersalineconditionsasconfirmedbyhigh18Ovalues,pseudomorphsafter
lenticulargypsum,andbiomarkersindicatinghypersalineconditionsincludingextendedarchaeol,
tetrahymanol,phytanylglycerolmonoethers,andnonisoprenoidalmacrocyclicglyceroldiethers.
Theseresultsconfirmthatsulphatedependentanaerobicoxidationofmethanefunctionsunder
hypersalineconditionsaswell.Theobservedbiomarkerpatternshowsthatthemicrobialconsortium
thatmediatedanaerobicoxidationofmethane(AOM)wassimilarbutnotidenticaltoAOMconsortia
atmethaneseeps.Some13CdepletedlipidslikePMI,sn2hydroxyarchaeol,isoandanteisoC15:0fatty
acid,MAGEsandDAGEspointtothepresenceofANMEandtheirsyntrophicpartnersDSS,typically
inhabitingmethaneseeps.Otherlipidsincludingsn3hydroxyarchaeol,and10MeC16:0fattyacidas
wellastheratiobetweentheisoandanteisofattyacidssuggestthatdifferentmethanotrophic
archaeaandsulphatereducingbacteriawereinvolvedinmethaneoxidationintheMessinian
hypersalineenvironment.
Acknowledgements
WethankSebastianFlotow(Bremen)forsamplepreparation,SarahJanoschekandKarsten
Hellwig(bothBremen)foranalyticalsupport,aswellasAdrianImmenhauser(Bochum),Marie
MadeleineBlancValleron(Paris),AntonioCaruso(Paris),BenoBrunner(Bremen),andPatrick
Meister(Bremen)forhelpcollectingthesamples.ThisprojectwassupportedbytheDeutsche
ForschungsGemeinschaftthroughtheinternationalgraduatecollegeEUROPROXandtheDFG
ExcellenceClusterMARUM,Bremen.

66 THIRDMANUSCRIPT

5THIRDMANUSCRIPT
GypsumwhiskersinMessinianevaporitesidentifiedbyμXRD2
S.B.Ziegenbalg1,C.Berthold2,A.Kappler3,J.Peckmann4
1
UniversityofBremen,MARUM–CenterforMarineEnvironmentalSciences,28359Bremen,
Germany
2
EberhardKarlsUniversityTübingen,InstituteforGeoscience,ABMineralogy&Geodynamics,
AppliedMineralogy,72074Tübingen,Germany
3
EberhardKarlsUniversityTübingen,CenterforAppliedGeoscience,Geomicrobiology,72076
Tübingen,Germany
4
DepartmentofGeodynamicsandSedimentology,CenterforEarthSciences,UniversityofVienna,
Althanstrasse14,1090Vienna,Austria
Keywords:Gypsumwhisker;Anhydrite;Nativesulphur;Gypsumefflorescence;MicroXRD
Abstract
Thegypsummineralogyofhairlike,socalledwhiskercrystalswasdeterminedbymicroXray
diffractometryequippedwithafocussingXrayopticanda2dimensionaldetector(μXRD2).Gypsum
whiskerstypicallyformbyefflorescenceonsurfacesthatareincontactwithwater.Thedelicate
whiskersstudiedhereformedwithinaMessinianevaporitemostlyconsistingofanhydrite.They
projectfromalabastrinegypsumintoformercavities.Thegypsumresultedfromhydrationof
anhydrite.Whiskerswerefinallyengulfedbybiogenic,nativesulphur,whichfilledthecavitiesinthe
courseofmicrobialalterationofthehostlithology.Thesulphurprotectedthedelicatewhisker
crystalsfromdestruction,includingaperiodofexposuretoweatheringonadumpingsiteofaformer
minewheretherockshavebeensampled.Tothebestofourknowledge,thisisthefirstreportof
gypsumwhiskersinevaporites.Moresignificantly,thisstudyrevealsthatμXRD2hasgreatpotential
forsedimentarypetrology,allowingtheinsituidentificationofminutemineralphasesthatcannotbe
identifiedwithconventionaltechniques.

THIRDMANUSCRIPT 67

5.1Introduction
Gypsumcrystalsexhibitvariousgrowthformsincludingtabular,prismatic,andacicularhabits,
butalsogranularandfibrousmasseshavebeendescribed(Nesse2004).Fibresorfilaments,usually
composedofgypsum,havebeenrecognisedasspeleothemsformingcavehair,cavecotton,and
otherdelicatecrystalforms(HillandForti1997).Hairlikecrystalsarecommonlyreferredtoas
whiskers,whicharedefinedasfilamentarysinglecrystalswithalengthtodiameterratioofatleast
fiveandadiameterbetween20nmand100μm(Evans1972).Gypsumwhiskershavebeenfoundto
growfromaqueoussolution(StricklandConstable1968;HüngerandHenning1988),particularly
fromsolutionswithlowsupersaturation(
2;HüngerandHenning1988)wheregrowthisinhibited
intwodimensions(StricklandConstable1968).
WithinMessinianevaporiticrocksfromSicily,werecognisedsimilarpeculiarhairlike,fibrous
crystals,closelyresemblinggypsumwhiskers.Thewhiskerlikecrystalsareassociatedwithanhydrite
andalabastrinegypsumandaresurroundedbynativesulphur.Becausesuchwhiskershavenotbeen
previouslyrecognisedinevaporites(pers.comm.C.Pierre,J.M.Rouchy,andB.C.Schreiber),wetried
todeterminetheirmineralogy,applyingopticalandelectronmicroscopy,conventionalXray
diffractometry(XRD),aswellasenergydispersiveXrayspectrometry(EDX)forqualitativeelement
analysis.Unfortunately,noneofthesetechniqueswassuccessfulduetothesizeofcrystalsandtheir
entombmentinnativesulphur.Becauseofthesedifficulties,weusedamicroXraydiffractometer
equippedwithafocussingXraypolycapillarymicrolense,whichprovidedtheopportunitytoanalyze
mineralphaseswithalocalresolutioninthehundredμmrange(cf.,Bertholdetal.2009).Thisnew
techniqueallowedtheidentificationofthewhiskersasgypsumcrystals.
5.2Geologicalcontextandmaterials
Looseblocksofsulphurbearinganhydriteweresampledfromadumpingsiteoftheformer
sulphurmineatMonteCapodarso,northeastofthetownofCaltanissetta,Sicily.Theevaporites
belongtothesulphatebearingstrataofSicily,whichformedduringtheLateMiocene(Messinian)
salinitycrisis(ColalongoandPasini1997andreferencestherein).Asealeveldropcausedbythecut
offoftheMediterraneanSeafromtheAtlanticOceanresultedintheapparentdesiccationofthe
MediterraneanSeabetween5.96and5.33millionyearsago(Hsüetal.1973b;Krijgsmanetal.1999;
Duggenetal.2003).Thedevelopmentofrestrictedconditionsledtothedepositionofevaporitic
seriesincludingevaporiticcarbonate,sulphate,halite,andbitternsaltsindeeperMessinianbasins
(Hsüetal.1973a)aswellasinSicily(DecimaandWezel1973).Besidesprimaryevaporiticcarbonate,
asecondtypeofcarbonaterockispresentintheMessiniansequenceofSicily.Apartfromcarbonate
minerals,rocksofthistypecontainvariableamountsofsulphatemineralsandinsomeplaces,native

68 THIR
RDMANUSCR
RIPT

Fig.51Photomicroggraphsofgypsumwhiskeersandassociatedphase es.Ananhyddrite;Gypgyp psum,S
sulphur.(A)Gypsumwhiskers(blackarrowheead)associattedwithdolomite(whiteearrows)witthina
sulphurffilledcavityssurroundedbygypsumaandanhydrite;planepola arizedlight.((B)Gypsumwhiskers
(black)ooriginatingonngypsumanndprojectinggintoaformercavitynow
wfilledbynaativesulphurrand
minordo olomite(whiitearrow);planepolarizeedlight.(C)G
Gypsumwhiskersbetweeenanhydrite e;FE
scanninggelectronmicrograph.(D D)Gypsumw whiskersshow wanangularrprofile.Circclesmarktw
wo
angularccrystaltermiinationswith
hhighwidth toheightratios;FEscan
nningelectroonmicrograp ph
sulphur.Suchparageeneseshavebeendescribbedinevapo
oriticstrataw
worldwideanndarelinked
dtothe
presenceofccrudeoilorm
formerp methane.Thhecarbonatemineralsandnativesulpphurhavebe
een
foundto
oresultfrommicrobialsu
ulphatereduuctionusingllocallyderive
edsulphate ionsandorgganic
compoundsthatinfiltratedtheh
hostlithologyy(Thodeetaal.1954;FeelyandKulp11957;Davisa
and
Kirkland1970;PierreeandRouchyy1988;BöttccherandParrafiniuk1998
8;Peckmannnetal.1999)).Such
secondarycarbonateesandnative
esulphurareeparticularlyyabundantinMessinian strataatdifferent
uetal.1962;;Ziegenbalg etal.2010).WithrespeccttothelocaationMonte
sitesinSSicily(Dessau
Capodarrso,microbiaalsulphatere
eductionwassfoundtohaavebeencou
upledtooxiddationofme
ethane
diagenesis,rresultinginsecondarycarbonateswitth13Cvalue
duringseedimentationandearlyd esaslow
‰VPDB(Zieggenbalgetal.2010).Theeaccompanyyingnativesu
as52‰ w34S
ulphuryieldeedratherlow
values(aaslowas+1‰
‰VCDT),co
orroboratinggthatitform
medasaconssequenceof microbialsu
ulphate
reductio
on(Ziegenbalgetal.2010
0).

THIRDMAN
NUSCRIPT 69

5.3Meth
hods
Thinsectionsweerestudiedw
withtransmitttedlightandfluorescen
ncemicroscoopyusingaZe
eiss
Axioskop
p40opticalm P365/12FT395LP397aandBP4504
microscope((lamp:HBO550,filters:BP 490FT
510LP5515).StandarrdXraydiffrraction(XRD))wasperform
medonpow
wderedsamppleswithaPh
hilips
X’PertPrroMD.ALEO
O1530GemiiniandanatttachedenerrgydispersiveXrayspecttrometer(ED
DX)
OxfordInca400werreusedforfieldemissionnscanningelectronmicroscopy(FESSEM)andqualitative
elementtidentificatio
on.Themicro
oscalephassedeterminaationofthew
whiskercrysttalswasperfformed
directlyo
onuncovereedthinsectio
onsbymicroXraydiffracction.Inorde
ertomaket hecrystals
accessibleforthean
nalysis,thesu
ulphurentom
mbingthewhiskerswasd
dissolvedbeeforehandwith
GADDSXRD2microdiffracctometeratttheIFGTübiingen
hexane.WeusedtheeBrukerD8DISCOVERG
equippedwithafocu
ussingpolyca
apillarymicr olensand2dimensionallHISTARdettector(cf.,B
Berthold
etal.20009).Thespotsizeoftheu
usedmicroleenswasapprroximately50
0μm.Duetoothefixedin
ncident
angleof10°andsam
mplerotation
n,theanalyzeedareaonth
hethinsectionhadadiaameterof
mately400μ
approxim μm.
5.4Resu
ults
Tabu
ulartoacicullaranhydrite dominantphaseinthesttudiedrocks.
ecrystalsreppresentthed
Anhydritteispartlyalteredtoalabastrinegyppsum(Fig.51AandB).Bundlesoffluuorescent,th
hin
fibrousccrystalsprojeectfromthealabastrine gypsuminto
oformercaviities,whichaarenowfilledby
nativesu
ulphurandm
minorsphero
oidaldolomitte.Electronm
microscopyindicatesthaatthethinfib
brous
crystalsaarealsodireectlyassociattedwithanh ydrite(Fig.5
51C).Thecryystalfibresaareapparenttlysingle
crystals,whichareseeveralhundrredμmlong (Fig.51B),fflatshapedw
withawidth ofapproxim
mately1
μmandaheightinthenmscale(Fig.51CanndD).Theyaareconseque
entlycharactterizedbyallengthto
widthratioconsideraablyhighertthanhundreddandarethereforereferredtoaswhhiskercrysta
als.

Fig.52 EDXspectru mofgypsum

mwhiskers

70 THIR
RDMANUSCR
RIPT

BulkkXRDmeasurementsofp
powderedsaamplesreveaaledthepressenceofanhyydrite,gypsu
um,and
sulphur(datanotsho
own).EDXanalysesshow
wedthatwhiiskerscontaincalcium,ooxygen,andssulphur
(Fig.52)).FormicroX weenanhydrite
Xrayanalysis,theXray spotwasfoccussedoncrotchesbetw
crystals((Fig.53A),w
wherewhiske
ersareparticcularlyabundant,formin
ngbundlesofffibres.Anhydriteas
wellasggypsumwereedetected(FFig.53B),buutnootherm
minerals.The
esetwomineeralsshowed
d
distinctlyydifferentdiffractionpatternsonthee2dimensio
onalHISTAR
Rdetector.Thheanhydrite
e
generateedonlyfewiintensespotsonthecorrrespondingp
peakposition
ns(Fig.53C)),typicalforlarge
singlecrystals.Incon
ntrasttothiss,thegypsum
mshowedapatternwith
htypicaldiffrractionringsofa
powderforeach(hkl)reflection(Fig.53C),ccausedbytherandomorrientationoffmanysmallwhisker
crystals.
Fig.53 (A)Position oftheXrayyspotontheethinsectio n.(B)Diffracctionpatternnofthespo tshown

inAwithhpeaksofgyypsumwhiskkersandanhhydrite.(C)D Diffractionimmagefromthhe2dimenssionalHI
STARde tectorwithaaspottydifffractionofannhydrite(II) andevenlyfilleddiffracctionringsof
gypsum whiskers(I) intheconesection

THIRDMANUSCRIPT 71

5.5Discussion
Conventionaltechniquesincludingopticalmicroscopy,electronmicroscopycoupledwithEDX,
andstandardXRDfailedtoidentifythemineralogyofwhiskercrystalsenclosedinMessinian
evaporitesfromSicily.Opticalmicroscopydidnotallowthemineralogytobedetermineddueto
limitedcrystaldiameterandtheentombmentofcrystalsinnativesulphur.AlthoughEDX
measurementsrevealedthatthewhiskersarecomprisedofcalcium,oxygen,andsulphur,thisdid
notunequivocallyconstrainmineralogy.BasedontheparageneticsequenceandEDXresults,
differentmineralogiesstillappearedfeasible,includinganhydrite,bassanite(calciumsulphate
hemihydrate;cf.,AllenandKramer1953;Bundy1956;Peckmannetal.2003),andgypsum.Under
thesecircumstances,conventionalXRDtechniquesrequireeithersufficientamountsoffineground
materialoftherespectivemineralphaseorseparationofsinglecrystals.Becausethewhiskerswere
onlyrecognisedinlimitedamountsinfewthinsections,neitherbulkanalysesnortheirseparation
werefeasible.
WiththeadventofμXRD2equippedwithfocussingmicrolensesitisnowpossibletoidentify
evensmallamountsofmineralphasesinsituonuncoveredthinsections(Bertholdetal.2009).A
problemthatneededtobeovercomewithrespecttothewhiskersintheSiciliansampleswastheir
entombmentinnativesulphur.Surficialdissolutionofsulphurbyhexanecausedthesurfaceofthe
thinsectiontobecomeuneven,withthewhiskersnowbeingexposed,butsituatedwithina
depression.ThissituationwasnotidealforμXRD2,whichbenefitsfromevenandpolishedsurfaces,
butnorelevantnegativeeffectwasobservedbythissurfacetopology,confirmingthegreatpotential
ofthistechnique.
Tothebestofourknowledge,thisstudyisthefirstreportofgypsumwhiskersinevaporitic
lithologies.Similarhairlikestructures,however,havebeenrecognisedingypsumandhalitedeposits
ofmodernandPermianacidsalinelakes(Benisonetal.2008).Thesestructureswerefoundtobea
compositeofgypsumandcarbon,promptingBenisonetal.(2008)tointerpretthemasremainsof
acidophilicmicroorganisms.NocarbonwasfoundtobeassociatedwiththeSicilianwhiskers.Despite
theirdistinctfluorescence,whichappearstobecausedbycrystalboundaries,amicrobialorigin
seemsunlikely.Gypsumwhiskersaretypicallyformedbyefflorescenceonmoistporoussurfaces
(Evans1972)orasspeleothems(VidalRomaniandRodriguez2007).IntheSicilianevaporites,the
gypsumwhiskersformedpredominantlyonalabastrinegypsum,growingintocavityspaces.The
gypsumobviouslyoriginatedfromthehydrationofanhydrite(Fig.51).Waterconsequently
penetratedintotheporespaceoftheMessinianevaporitesandthiswatermostlikelycontained
significantamountsofdissolvedsulphate.Aspartofthewaterwasconsumedinthegypsificationof
theanhydrite,thesulphateconcentrationofthesolutionnecessarilyincreased.Astheformationof

72 THIRDMANUSCRIPT

gypsumwhiskersstartsevenatverylowratesofsupersaturation(cf.,StricklandConstable1968;
HüngerandHenning1988),gypsificationofanhydritemayhavebeensufficienttoinducecrystal
growth.Whiskerprecipitationapparentlyprecededsulphuremplacement,asindicatedbythe
parageneticsequencewithsulphurfillingtheresidualporespaceafterwhiskergrowth.Because
sulphurformationwassyngeneticatthestudiedlocation,occurringduringearlydiagenesis
(Ziegenbalgetal.2010),thewhiskerswouldhavetobeofNeogeneage.Alaterformationof
whiskers,however,cannotbeexcluded.Ifthesulphurwasremobilizedatsomepoint,thewhiskers
mayhaveformedepigenetically,possiblyeveninthecourseofminingactivitiesorafterwards.
Independentonthetimeofwhiskerformation,theentombmentbyhydrophobicsulphurefficiently
protectedthedelicategypsumcrystalsfromdissolutionduringtheexposureoftheevaporitesonthe
dumpingsite.
5.6Conclusions
Becausemicronsizedmineralphasesareoftendifficulttoanalyseandidentifywithconventional
techniques,theuseofmicroXraydiffractometrywithfocussingmicrolensesanda2dimensional
detectorpromisesasubstantialadvancementforsedimentpetrology.WeappliedμXRD2to
uncoveredthinsectionsofMessinianevaporitesfromSicilythatcontainpeculiardelicatehairlike
crystals,revealingtheirgypsummineralogy.Withalengthtowidthratioconsiderablyhigherthan
hundred,thesecrystalscanbereferredtoasgypsumwhiskers.Thewhiskersformedbyefflorescence
fromalabastrinegypsum,whichresultedfromthehydrationofanhydrite.Theentombmentby
biogenicsulphurfinallyenabledthepreservationofthedelicatewhiskercrystals.
Acknowledgements
WethankSebastianFlotow(Bremen)forthinsectionpreparation,ChristophVoigt(Bremen)for
standardXRDmeasurements,TillHeinrichs(Göttingen)forhelpwiththeFESEMandEDXanalyses,
aswellasB.CharlotteSchreiber(Seattle)andananonymousrefereeforcommentsonthe
manuscript.DanielBirgel(Bremen),MarieMadeleineBlancValleron(Paris),AntonioCaruso
(Palermo),AdrianImmenhauser(Bochum),CatherinePierre(Paris),andJeanMarieRouchy(Paris)
participatedinthefieldtripduringwhichthestudiedrockshavebeensampled.Thisprojectwas
supportedbytheDeutscheForschungsgemeinschaftthroughtheinternationalgraduatecollege
EUROPROXandtheResearchCenter“TheOceanintheEarthSystem”.
.
FOURTHMANUSCRIPT 73

6FOURTHMANUSCRIPT
Authigenesisofnativesulphuranddolomiteinalacustrineevaporiticsetting
(Hellínbasin,LateMiocene,SESpain)
J.Lindtke1,S.B.Ziegenbalg1,B.Brunner2,J.M.Rouchy3,C.Pierre4andJ.Peckmann5
1
2
MaxPlanckInstitutfürMarineMikrobiologie,28359Bremen,Germany
3
DépartementHistoiredelaTerre,MuséumNationald’HistoireNaturelle,75005Paris,France
4
CNRSUMR7159,LOCEAN,Univ.P.andM.Curie,75252ParisCedex05,France
5
DepartmentfürGeodynamikundSedimentologie,ErdwissenschaftlichesZentrum,Universität
Wien,Althanstraße14,1090Wien,Austria
Keywords:nativesulphur,authigenicdolomite,bacterialsulphatereduction,lacustrinesetting
Abstract
AbundantsulphurispresentintheLateMioceneevaporiticsequenceofthelacustrineHellín
basininSESpain.WeatheringofTriassicevaporitescontrolledthechemicalcompositionofthe
Miocenelake.Thelacustrinedepositscomprisegypsum,marlstones,diatomites,andcarbonate
beds.Sulphurbearingcarbonatedepositspredominantlyconsistofearlydiageneticdolomite.
Abundantdolomitecrystalswithaspheroidalhabitareinaccordancewithanearlyformationand
pointtoamicrobialorigin.Thecarbonisotopiccompositionofthedolomite(13Cvaluesbetween
11to4‰)indicatesmixingoflakewatercarbonateandcarbonatederivedfromthe
remineralisationoforganicmatterbyheterotrophicbacteria.Dolomiteprecipitatedsyngenetically
underevaporiticconditionsasindicatedbyhighoxygenisotopevalues(18Obetween+6and+11‰).
Nodulesofnativesulphurarefoundingypsum,carbonatebeds,andmarlstonelayers.Sulphur
formedinthecourseofmicrobialsulphatereduction,asreflectedbyitsstrongdepletionin34S(34S
valuesaslowas17‰).Neartothesurfacemanyofthesulphurnoduleswereinpartorcompletely
substitutedbysecondarygypsum,whichstillreflectsthesulphurisotopiccompositionofnative
sulphur(18to11‰).Thisstudyexempli estheroleofbacterialsulphatereductioninthe
formationofdolomiteandnativesulphurinasemienclosedlacustrinebasinduringtheLate
Miocene.

74 FOURTHMANUSSCRIPT

Fig.61W
Workingareea.(a)LocationoftheHeellínbasinin
ntectoniccontextoftheeBeticChain ;
modifieddafterCalvo
oandElizagaa(1989).(b) Subbasins oftheHellín
nbasinwith Neogenesediments;
modifieddafterCalvo
oandElizagaa(1989).(c) Locationof thesamplingareaintheeformersulphur
mineof LasMinas.
6.1Intro
oduction
Nativesulphuro
occurrencesa
arecommonnlycloselyassociatedwithevaporitessandauthige
enic
carbonattes(e.g.Desssauetal.,19
962;DavisanndKirkland,1979;Pierre andRouchyy,1988;Yousssef,
1989).Exxamplesoftthisparagene
esisarefounndincaprocksofsaltdiapirs(Ruckmiicketal.,197
79)and
stratabo
ounddepositslikethoseofnorthernIraq(Jassim
metal.,1999),theDelawaarebasin(Hentzand
Henry,11989),theCaarpathianforredeep(Bött cherandParrafiniuk,199
98),andtheM
Mediterrane
eanarea
FOURTHMANUSCRIPT 75

(Dessauetal.,1962;Anadónetal.,1992;Rouchyetal.,1998;Ortíetal.,2003;Ziegenbalgetal.,
2010).Bothnativesulphurandassociatedauthigeniccarbonatemineralsarecommonlyconsidered
asproductsofbacterialsulphatereduction(FeelyandKulp,1957;Dessauetal.,1962;Davisand
Kirkland,1979;Peckmannetal.,1999;Ziegenbalgetal.,2010).Inthisprocess,theheterotrophic
bacteriaoxidizelocallyabundantcrudeoil,methane,ormorepristineorganicmatterandproduce
sulphideions,facilitatingsubsequentbiologicalorabiologicalsulphideoxidationtonativesulphur
(Machel,1992).Anothercommonconsequenceofbacterialsulphatereductionisanincreaseof
alkalinity,whichresultsintheprecipitationofcarbonateminerals(Castanieretal.,1999).
Dependingonthetimeofformationofauthigenicminerals,Ruckmicketal.,(1979)distinguished
betweensyngeneticandepigeneticprocesses.Syngenesistakesplaceduringsedimentationand
earlydiagenesis.Notably,precipitationofcarbonatemineralsinducedbysulphatereducingbacteria
hasbeendescribedinmodernhypersalineenvironmentsaswellasinlaboratoryexperiments(Lalou,
1957;VasconcelosandMcKenzie,1997;vanLithetal.,2003;WrightandWacey,2005).Epigenesis,
ontheotherhand,takesplaceafterdepositionduringlatediagenesis.Inthecaseofepigenetic
mineralformation,sulphate,theelectronacceptorfortheinvolvedheterotrophicbacteria,is
deliveredbydissolutionofsulphatemineralsbymeteoricwaters.
Becausebacterialsulphatereductionisdependentonahighsupplyofsulphateions,itis
favouredinmarineratherthaninlacustrineenvironments.Inlacustrinesettings,methanogenesis
tendstoactasthemainprocessoforganicmatterremineralisation(Cerlingetal.,1988;Talbotand
Kelts,1990).Nevertheless,someexamplesofcarbonatemineralformationinducedbysulphate
reductioninlacustrinedepositsareknown,includinglakesinSWAustralia(Wright,1999)andthe
easternUSA(Riccionietal.,1996).Sulphurbearingauthigeniccarbonateshavebeenreportedfrom
thelacustrineTeruelbasininSpain(Anadónetal.,1992),whereweatheringofTriassicmarine
evaporitesprovidedthesulphateforbacterialsulphatereduction(Utrillaetal.,1992).Asimilar
occurrenceofnativesulphurandassociatedauthigeniccarbonatesisknownfromtheLateMiocene
HellínbasininSESpain(ServantVildaryetal.,1990).Thisrestrictedbasinwastypifiedbylacustrine
conditionswithonlyepisodicinflowofmarinewaters(ServantVildaryetal.,1990).Although
dolomiteandnativesulphurhavebeensuggestedtoderivefrombacterialsulphatereductionusing
sulphatethatoriginatedfromthedissolutionofTriassicgypsum(ServantVildaryetal.,1990),these
authigenicmineralshavenotbeenstudiedindetailtodate.Herewepresentapetrographicand
isotopicstudyontheevaporiticsedimentarysequenceoftheHellínbasin,focussingonauthigenic
carbonatesandnativesulphur.Ourstudyconfirmsthatsulphatereducingbacteriacanbemajor
playersintheearlydiagenesisoflacustrinesettingsaswell,providedthatsufficientsulphateionsare
available.


Fig.662Nativesu
ulphur.(a)Su
ulphurencloosedinsecon
ndarygypsum
m;overlying laminargypsum
bedsareebentandfaaulted(seein
ndication),LaasMinas.(b))Sulphurencclosedincarrbonatedepo
osits,Las
Minas.(cc)Sulphurno
odulesembe
eddedinacaarbonatebed
d,Cenajo.
6.2Geollogicalsettin
ngandmate
erial
TheHellínbasinofSESpainiisanintramoontanebasin
nintheexterrnalpartofttheBeticcha
ain(Fig6
1a).CrettaceouslimeestonesandT
Triassicevapporitesrepresentthebassementoftheebasin(Servvant
Vildaryeetal.,1990).Basindevelo
opmentisatttributedtossubsidencerelatedtoassystemoftra
ansform
faultsof
f anextensionalregime,w
whichwasacctiveduringtheNeogene
e;subsidencceterminatedinthe
LateTorttonian(Gieseetal.,1982
2;SanzdeGaaldeano,199
90;Krijgsman
netal.,20000;Joliveteta
al.,
FOURTHMANUSCRIPT 77

2006).Initiallythebasinwasfilledbymarinesedimentsdominatedbymarlsandmarlycarbonate
beds.ThelastmarinesedimentationoccurredintheMiddleTortonian(Calvoetal.,1978).Alate
phaseofnorthsouthorientedcompressionstartedintheTortonianandledtoregionalupliftofthe
crust(Rouchyetal.,1998;Jolivetetal.,2006).Subsequently,foldingofMesozoictoCainozoicrocks
endedinthedevelopmentofseverallocalswellsthatdividedtheHellínbasinintoseveralsubbasins
(Fig.61b).FormationofaswelltothesouthclosetoCalasparraledtothesuccessiveisolationofthe
Hellínbasinfromthemarineenvironment(CalvoandElizaga,1989;ServantVildaryetal.,1990).The
changetolacustrineconditionsresultedintheaccumulationofevaporitesandcarbonatedepositsof
theLasMinasdeHellínformation,whichareoverlainbycarbonatedeposits,marls,anddiatomite
(ServantVildaryetal.,1990).Theevaporites,mainlyrepresentedbygypsum,derivedfromthe
dissolutionofTriassicevaporites;continueddissolutionofgypsumoftheTriassicbasement(Garcia
Domingoetal.1980)isreflectedbykarstphenomenaintheHellínbasin(NavarroHervásand
RodríguezEstrella,1985).InthesubbasinsofCenajoandLasMinas,theLasMinasdeHellín
formationcontainsnativesulphur,whichwasmineduntil1960.
Forthisstudy,carbonateandgypsumrockscontainingnativesulphurwerecollectedfromthe
miningareanortheastofthesmallminer’svillageLasMinas(Fig.61c).Sectionsofevaporitesand
carbonatesarewellexposed,butstronglyweathered;thesamplesstudiedherederivedfromthe
upperpartofthestratigraphicintervaldescribedbyServantVildaryetal.,(1990).Stratabound
nodulesofnativesulphurarepredominantlyembeddedinlaminatedgypsumbeds(Fig.62a)andto
alesserdegreeincarbonatebeds(Fig.62b).AsimilarsedimentarysequenceisfoundintheLas
MinasdeHellínformationoftheCenajosubbasin.TheaggregatesofnativesulphurintheCenajo
sequenceresemblethoseoftheLasMinassequence,althoughballshapednodulesofsulphurhave
onlybeenrecognizedincarbonatedepositsfromCenajo(Fig.62c).
6.3Methods
ThinsectionswerestudiedwithtransmittedlightandfluorescencemicroscopyonaZeiss
Axioskop40APol,equippedwithanAxioCamMRcdigitalcamera(lamp:HBO50,filter:BP365FT
395LP397andBP450490FT510LP515).Thinsectionswerepartlystainedwithcombined
potassiumferricyanideandalizarinredsolution(Füchtbauer,1988).Scanningelectronmicroscopy
withqualitativeelementrecognitionwasperformedwithaZeissSupra40REMequippedwithan
OxfordEDXdetector(IncaPentaFETx3).MineralogywasdeterminedwithaPANalyticalX’PertPro
diffractometerusingaNifilteredCuanode,equippedwithamultichanneldetector(X’cellerator).
Mineralcontentwasestimatedsemiquantitativelyusingthepeakareas.Proportionsofmagnesium


tocalciumindolomitewerecalculatedafter Lumsden(1979)byquarrtzcorrectedddvalues.A
ALECOCS
200wasusedfordetterminationofcontents oftotalorgaaniccarbon.
Fig.63 Laminatedccarbonatebe ed.(a)Carboonatebedwiithvarvedlamination,w whichisbent around

asulphu urnodule;arrrowheadsin ndicatelaminnaeofseconndarygypsum m;scannedsslab.(b)Detailof
(a),carb
bonatelamin naeandsmalllsulphurnoodule(arrowwhead);plane epolarizedllight.(c)Dettailof
(a),benttlamination aroundasu ulphurnodulle(S),which ispartlydisssolvedandrreplacedby
diagenetticgypsum( arrowheads);planepolaarizedlight. (d)Matlikelamination;;planepola rized
light.(e))Irregularlaaminationwiithtwocherttlaminae(a rrowheads);planepolarrizedlight.
Forstableisotopean
nalysesmine
eralphasesw
weredrilledffromthesurffaceofslabsswithahand
dheld
microdrrill.Measurementsofcarrbonandoxyygenisotope
es(sampleweight:0.02tto0.10mg)w
were
performedwithaFin
nniganMAT251masssppectrometerusingtheKie
elcarbonateedevicetype
e
“Bremen omBurgboh l/Rheinland.ASolenhofe
n“againstnaaturalCO2fro enlimestoneewasusedas
FOURTHMANUSCRIPT 79

internalstandard,whichwascalibratedagainsttheinternationalstandardNBS19.Valuesare
reportedinthenotationrelativetoViennaPeeDeeBelemnite(VPDB)standard.Longtime
standarddeviation(1 )forthismeasurementwas±0.05‰for13Cand±0.07‰for18Ovalues.
Oxygenisotopevaluesofdolomitewerenotcorrectedforitsdifferentfractionationcomparedto
calciteduringprecipitation(McKenzie,1981)orduringtheanalyticalprocedure(SharmaandClayton,
1965)becauseofanundeterminedadmixtureofminorcalcite.
Foroxygenisotopeanalysisofsulphate,gypsumwasdissolvedwithsodiumchloridesolution.
Afteracidificationofthesolution,sulphatewasprecipitatedasbariumsulphatebyadditionof
bariumchloride.Sulphurisotopesofgypsumweremeasuredeitherongypsumwithoutpre
treatmentoronbariumsulphateprecipitatedasabove.Samplesofsulphurreceivednopre
treatmentforsulphurisotopemeasurements.Sulphurandoxygenisotopemeasurementswere
performedwithaThermoFinniganmassspectrometerDeltaVinacontinuousflowsetup.For
sulphurisotopeanalysis0.3mgofbariumsulphate,0.4mgofcalciumsulphate,or0.05mgofnative
sulphur(with1mgofV5O5ascatalyst,respectively)wereweightedintotincapsulesandcombusted
inanEuroEAElementalAnalyzer(EuroVector,Milan,Italy).Thesulphurisotopemeasurementswere
calibratedwithreferencematerialsNBS127andIAEASO6.Thesulphurisotopiccompositionis
reportedinthenotationrelativetoViennaCañonDiabloTroilite(VCDT)standard.Thestandard
errors(1 )werelessthan±0.2‰for34Svalues.Foroxygenisotopeanalysis0.16mgofbarium
sulphatewasweightedintosilvercapsules.Underpresenceofgraphiteandglassycarbonoxygen
fromsulphatewastransferredtocarbonmonoxidewithinanelementalanalyzer(TC/EA,Thermo
FisherScientific).NBS127,IAEASO5,andIAEASO6wereusedasreferencesforcalibration.The
oxygenisotopiccompositionisreportedinthenotationrelativetoViennaStandardMeanOcean
Water(VSMOW).Thestandarderrors(1 )werelessthan±0.3‰for18Ovalues.
6.4Results
6.4.1Petrography
6.4.1.aCarbonatelithology
Sampledcarbonatebedsconsistpredominantlyofdolomitewithvaryingamountsofgypsum,
calcite,andaccessoryminerals,includingclayminerals,feldspars,andquartz.Onlyfewcarbonate
bedscontainmorecalcitethandolomite.TheMgCO3contentofdolomiteisgenerallyhigh(47to
50%).Thetotalorganiccarboncontentofcarbonatedepositsislowtomoderate(0.2to0.7%).Most
ofthecarbonatedepositsexhibitadistinctlamination,whichcanbegroupedintothreetypes(Fig.6
3).(1)Averyregular,varvelikerhythmiclaminationischaracterizedbythinlaminae,approximately


0.5mminthicknessthatconsistoflightcolooureddolomiticmicrospa
aranddarkoorganicrich
dolomicrrite,respectively(Fig.63
3a,b).Wherresulphurno
odulesoccur,thelaminattionisbenta
and
occasion olvedorrepllacedbygypsum,
nallyfaulted(Figs62a,63ac).Theddolomicriteisspartlydisso
especiallyinthesurrroundingsoffsulphurnoddules.Lessco
ommonlydo
olomiticmicrrosparisreplacedby
gypsum..(2)Asecond
dtypeoflam
minationisleessregular,resemblingla
aminationin microbialm
mats(Fig.
hecarbonateelaminae,w
63d).Th evensurface,,andwedge out
whichdifferinnthickness,sshowanune
laterally.Theyareinterbeddedw
withdisconti nuousclaylaayers.Theprredominant mineralisdo
olomite.
Fig.64 Carbonateddeposits;planepolarizeddlight.(a)C lotteddolom

micritetomi crospar.(b)
Irregularralternation
nofdolomicriteandmic rospar.(c)P Peloidalcarbonatewithaaformersulphur
nodulessubstitutedbbygypsumsurroundedbbyadarkrim m(blackarrowheads).W hitearrowhe eads
pointto largepeloid
ds;crossedn
nichols.
FO
OURTHMAN
NUSCRIPT 81

(3)Athiirdtypeoflaaminationco
omprisesdoloomiteandgyypsumlamin
naeofirregullarthicknesss,ranging
fromafeewto300μm
m,accompan
niedbylateddiageneticcaalciteandch
hertlaminae (Fig.63e).P
Plant
fragmen
ntsarecomm
moninthislitthology.
Fig.65SSpheroidald
dolomite.G= =gypsum,(aa)Spheroidaaldolomitewwithgypsum ;planepolarized
light.(b))Spheroidal dolomitean
ndassociate dclayminerrals(Cl);SEM
Mmicrographhofthinsecction;
circledissplaysareao
ofEDXmeassurement,sppectrumwith hcountsfrom0to5keVV,goldpeak from
coating. (c)Spheroiddaldolomiteewithgypsu m,planepo larizedlight.(d)Samed etailas(c); note
autofluo orescenceof spheroids;ffluorescenceeimage.(e) Aggregateoofspheroidalldolomite;SSEM
micrograaph.(f)Closeeupviewofftwospherooids;SEMmi crograph.


Besidelaminated
dcarbonatebeds,denseebedsofdolomicriteoccur,whichareeuptoafew
w
centimettresinthickn
ness.Theseb
bedscommoonlyrevealaclotted(Fig..64a)orpelloidalmicroffabric.
Formerccavities,now
wfilledbyauthigenicminnerals,areab hislithology (Fig.64a).Inplaces
bundantinth
thedolo
omicriteisaltternatingwitthdolomitic spar(Fig.64
4b).Dolomiccriticpeloidssareupto30
0min
diameterandarepartlyrecrystallizedtomic rosparalonggtheirmargins.Peloidst endtoformdense
fringesaaroundsulph
hurnodules,whicharecoommonlypartlyorcompletelyreplaccedbygypsu
um(Fig.
64c).Blockycalcitesparwithcryystalsupto2200mindiameterisan
naccessorypphaseinthis
olomiticbedssspheroidaldolomiteisobservedin rockforming
lithologyy.Indifferenttypesofdo
quantitiees.Theporespaceleftbyyspheroidsiisfilledbygyypsum(Fig.6
65a).Insom
meofthevuggs,
interlayeers,andsurroundingsofspheroidssuubmicroscop
picaggregate
esofclayminneralsareprresent
(Fig.65b
b).Thefluorrescentspheroidsreveal adarkcoreo
ofunknowncompositionnsurrounded
dby
concentrricringsofdolomite(Fig.65c,d).Sppheroidsvaryybetween5and10mi ndiametera
andare
composeedofirregulaarlyarranged
dcrystals(Fiig.65e,f).
Fig.66 Nativesulph
hur.C=carbonate;D=ddolomite;G=
=gypsum;S=nativesul phur.(a)We ell
preserveedsulphursu urroundedbbyspheroida ldolomite( arrowheads));gypsumfillledfissureiinthe
lowerpaartoftheph otomicrograaph;planeppolarizedligh
ht.(b)Samedetailas(a)),notefluore
escence
ofspherroidaldolom ite(arrowheeads);fluoreescenceimagge.(c)Slightlyweathere daggregateof
sulphur witharimoofgypsum(arrowhead);pplanepolari zedlight.(d)Minoraccuumulationoffsulphur
inalamiinatedcarboonatebed;planepolarizzedlight.

FO
OURTHMAN
NUSCRIPT 83

6.4.1.bN
Nativesulphu
ur
Nativesulphuro
occursaslarggebrightora ngetoyellow
wcrystalswithsharpcryystalboundaries(Fig.
66a,b);thecrystalsaretransluccentintransm
mittedlight.Sulphuriscommonlyclooselyassocia
atedwith
daldolomiteandvugsorfissuresfilleedbysecond
spheroid darygypsum(Fig.66a,b)).Weathered
d
sulphurisbrightyellowtowhitisshincolour((Fig.62a),showsapowderyconsisteency,isblurryin
transmitttedlight,an
ndisabundan
ntlysurrounddedbysecon m(Fig.66c) .Incarbonattebeds
ndarygypsum
withavaarvelikelam
mination,sulp
phuraggregaatestendtobeparticularround(Fig.63ac).In
carbonattebedsofth
hetypes2an
nd3describeedabove,lam
minationisp
partlyinterruuptedbysulp
phur
nodules..Nativesulphuralsoapp
pearsasameeboidalaggre
egates(Fig.6
66c),possibllyfillingform
mer
cavitiesaandastinyaaccumulation
nsfinelydisppersedinthe
ehostrock(F
Fig.66d).Veeryregular,
fluoresceentglobuleswithadiam
meterofapprroximately20
0mwererecognizedinnonesample
eofwell
preserveedsulphur(FFig.67).
Fig.67 (a)Putative fossilizedba

acteriaencloosedinsulph
hur;planepolarizedlighht.(b)Same detailas
(a);fluo rescenceim age.
6.4.1.cG
Gypsum
Gypssumisubiqu
uitousinthestudiedsediimentaryroccks.Insomecarbonatebbeds,gypsum
misfinely
disperseedintherockkmatrix.Else
ewhere,itreepresentsassecondarymineral,growiingaslargeccrystals
perpend
diculartobed
dding.Secondarygypsum
m,whichhassbeendescribedindetai lbyServantVildary
etal.,(1990),iscommonlyreplaccingsulphur(Figs63c,6
64c,66c)an
nddolomitic microspar.Italso
fillsfissu
uresandvugssincarbonattedeposits( Fig.68).Gro
owthofpalissadelikegyppsumcommo
only
disturbedtheprimarrylamination
n.Theseconndarygypsum
moftheLasM
MinasdeHeellínsequenceclosely
resembleesdiageneticgypsumfro
omtheMioccenelacustrin
nesequence
eoftheTerueelbasininNESpain
(cf.,Ortííetal.,2010)).


Fig.68 Fissurefilled
dwithfibrou
usgypsum(ccentre),blocckygypsum(right),andm
minordolom
mite(D)
derived fromtherocckmatrix.
6.4.2Staableisotopess
Fig.69SStablecarbo
onandoxygeenisotopevaaluesofcarb
bonatedepo MinasdeHellín.
ositsofLasM
Trendlin
neindicates linearregressionofdoloomitevaluess.Fieldsdefinedbydotttedlinesindicate
composi tionofcarb onatesfrommtheLorcaa ndCenajob asin.

FOURTHMANUSCRIPT 85

Table61:Stableisotopesofcarbon( 13 C)andoxygen( 18 O)incarbonatedepositsandstable
isotopesofsulphur( 34 S)innativesulphurandstableisotopesofsulphur( 34 S)andoxygen( 18 O)
insecondarygypsumofLasMinasdeHellínandonesampleofTriassicgypsumfromnearCenajo.
Carbonate sulphate&sulphur
sample 13C 18O texture/mineralogy 34S 18O texture/mineralogy
[‰ [‰ [‰ [‰
H1 7.9 10.2 peloidaldolomite 14.4 4.7 gypsumfilledfissure
H1 7.9 9.9 peloidaldolomite
H1 7.1 9.7 spheroidaldolomite
H3 13.0 8.1 gypsum,substitutedsulphur
H3 17.1 gypsum,substitutedsulphur
H5A 7.0 10.3 laminateddolomite 3.7 nativesulphur
H5A 7.1 10.1 laminateddolomite 7.0 nativesulphur
H5A 7.2 9.8 laminateddolomite
H5B 7.1 10.1 laminateddolomite 4.3 nativesulphur
H5B 7.2 10.1 laminateddolomite 3.7 nativesulphur
H5B 7.1 10.1 laminateddolomite
H6A 5.0 6.8 microspariticdolomite 11.1 6.0 gypsumfilledfissure
H6A 5.7 7.1 microspariticdolomite 12.8 6.3 gypsumfilledfissure
H6A 6.0 7.9 spheroidaldolomite
H6A 5.8 7.4 spheroidaldolomite
H6B 5.3 6.5 spheroidaldolomite 18.2 gypsum,rimaroundnative
H6B 5.0 6.5 spheroidal dolomite 6.7 nativesulphur
H6B 6.3 nativesulphur
H7 8.6 9.5 micriticdolomite
H7 8.9 9.6 micriticdolomite
H8 8.5 9.9 microspariticdolomite
H8 8.5 9.5 microspariticdolomite
H8 7.3 9.3 clotteddolomite
H8 7.5 9.1 clotteddolomite
H8 7.6 8.9 microsparitic/clotted
H8 7.7 9.1 microsparitic/clotted
H9A 6.6 0.3 matrixcalcite&dolomite 13.5 nativesulphur
H9A 6.2 0.3 matrixcalcite&dolomite 12.3 gypsum,rimaroundnative
H9A 6.4 0.6 peloidaldolomite
H9A 5.3 0.7 clotteddolomite
H12 6.5 8.3 peloidaldolomite 15.3 gypsum,insidechertlayer
H12 4.2 6.2 microspariticdolomite 14.3 7.6 gypsumfilledfissure
H12 15.0 7.6 gypsumfilledfissure
H13A 5.6 7.2 clotteddolomite 9.5 gypsumfilledcavity
H14 11.1 2.2 matrixcalcite
H14 9.6 1.1 matrixcalcite
H14 3.6 3.9 microspariticcalcite
H15 2.3 0.2 matrixcalcite(marine
H15 2.3 0.5 matrixcalcite(marine

86 FOURTHMANUSCRIPT

Table61:continued
Carbonate Sulphate&sulphur
sample 13C 18O texture/mineralogy 34S 18O texture/mineralogy
H16 8.1 0.2 matrixcalcite&dolomite 11.3 5.2 gypsum,insidelamination
H16 8.6 1.5 matrixcalcite&dolomite 12.6 6.1 gypsum,insidelamination
H19 6.8 3.2 microspariticcalcite 15.7 nativesulphur
H20.1 9.8 10.0 microspariticdolomite
H20.1 9.9 9.7 microspariticdolomite 7.8 nativesulphur
H20.1 9.6 9.1 microspariticdolomite 11.4 5.0 gypsumfilledfissure
H20.1 6.8 3.4 spariticcalcite 11.9 5.2 gypsumfilledfissure
H20.1 6.6 5.2 spariticcalcite 13.4 gypsumfilledfissure
H21 17.1 nativesulphur
H21 14.2 nativesulphur
H21 11.9 7.5 gypsum,substitutedlamination
H21 11.6 7.9 gypsum,substitutedlamination
Triassicgypsum(nearCenajo) 12.0 11.7 gypsum
6.4.2.aCarbonandoxygenisotopesofcarbonates
Oxygenisotopevaluesscatterwidelyfrom5.2to+10.5‰(Table61;Fig.69).Dolomiteismore
enrichedin18Othancalcite.Spheroidaldolomiteshowsslightlylower18Ovalues(+6.2to+9.7‰)
thanothervarietiesofdolomite(+6.8to+10.5‰).Agroupofsampleswithamixeddolomiteand
calcitecompositionexhibitsoxygenisotopevaluescloseto0‰.Thelowestoxygenisotopevalues
arefoundforlatediageneticcalcite(5.2to3.2‰).
Mostcarbonisotopevaluesrangefrom11.1to3.6‰.Twosampleswithslightlyhighervalues
(2.3‰)probablyreflectreworkedmarinecarbonate.The13Cvaluesofsampleswithamixed
calciteanddolomitecomposition(5.3to11.1‰)aswellasthe13Cvaluesofdolomite(4.2to
10.0‰)scaerwidely.The13Cvaluesofdolomitearenegativelycorrelatedwiththe18Ovalues,
correspondingtoacorrelationcoefficientofr=0.75(Fig.69).
6.4.2.bOxygenisotopesofgypsumandsulphurisotopesofgypsumandnativesulphur
Oxygenisotopevaluesofgypsumrangefrom+4.7to+8.1‰(Table61;Fig.610).Nativesulphur
andsecondarygypsumshowmuchlower34Svalues(18.3to3.7‰,Table61;Figs610,611)
thanprimarygypsumoftheLasMinassequence(+13to+19‰;ServantVildaryetal.,1990;Fig.6
10).Sulphurisotopevaluesofnativesulphurfallintotwogroups(Fig.611).Onegroupisless
depletedin34S(7.8to3.7‰),whereastheothergroupshowsverylow34Svalues(17.1to
13.5‰),whichareinthesamerangeasvaluesofsecondarygypsum(18.2to11.1‰).Triassic
FO
OURTHMAN
NUSCRIPT 87

gypsumsampledfromtheperiph
heryoftheCCenajosubb
basinexhibitssapositivessulphurisoto
opevalue
(+12.0‰
‰),inaccordwithdataoffClaypoolettal.,(1980).
Fig.6610Stablessulphurandoxygenisotoopevaluesofsecondarygypsumfrom
mLasMinasdeHellín
andTriasssicgypsumfromCenajo
o.Triassican dCainozoicmarinesulph
hateforcom
mparison.
Fig.6111Stablesulp
phur(34S)isotopevalueesofNeoge nesecondarygypsumanndnativesullphur
fromLassMinasdeH HellínandTriassicgypsum
mfromCenaajo.

88 FOURTHMANUSCRIPT

6.5Discussion
6.5.1Formationofauthigeniccarbonateminerals
Inlacustrineenvironments,carbonatemineralscanprecipitatefromdissolvedinorganiccarbon
(DIC)intheupperwatercolumnandaccumulateatthelakebottom(Stabel,1986;TalbotandKelts,
1990).Thecarbonisotopiccompositionofdissolvedcarbonateinalacustrineenvironmentis
influencedbyseveralfactorsincludingtheamountandthecompositionofinflowingwater,residence
time,andlakesize(TalbotandKelts,1990;Leeetal.,1987).Furthermore,the13CvaluesofDICcan
shifttowardshighervaluesduetoprimaryproductioninsidethelakeandevaporation(Talbot,1990).
Inclosedlakes,13Cvaluesofprimarycarbonatesusuallyrangefrom–5to+3‰(McKenzie,1985b;
Talbot,1990;TalbotandKelts,1990,Tenzeretal.,1997).TheMioceneHellínlakewasmostlikely
hypersaline,becauseLateMioceneclimaticconditionsfavouredevaporationintheMediterranean
area(vanDamandWeltje,1999;GarcíaAlixetal.,2008)andabundantMioceneevaporitesare
presentintheHellínbasin.Thevariable18Ovaluesofthestudiedcarbonatesreflectthestrong
influenceofinflowandevaporation,whichistypicalforhydrologicallyclosedlakes(cf.,Talbotand
Kelts,1990).
Apartfromformationinthewatercolumn,earlydiagenesisinlacustrinesedimentscaninduce
carbonateprecipitationaswell.Asaconsequenceofanaerobicremineralisationoforganicmatter,in
particularbacterialsulphatereduction,carbonatealkalinityiscommonlyincreasing(AbdElMalek
andRizk,1963a;AbdElMalekandRizk,1963b;vanLithetal.,2003).Theresultingauthigenic
carbonatemineralsarecharacterizedbylow13Cvaluesdependingonthesourceoffreshorganic
matterorfossilhydrocarbons(Irwinetal.,1977;PeckmannandThiel,2004).The13Cvaluesof
higherlandplants(aslowas34‰)tendtobelowerthanthatoffreshwateralgae(23‰;Smith
andEpstein,1971).Becauseofthepreferentialuptakeof12Cenrichedcompoundsduringmicrobial
remineralisation,theproducedcarbonateisevenmoredepletedin13Cthanthesourcematerial(e.g.
Leeetal.,1987).ThecarbonisotopiccompositionoftheHellínbasincarbonatedeposits(aslowas
11.‰;Fig.69),thus,reflectsacombinationoflakewaterDICandcarbonatealkalinityproducedby
theremineralisationoforganicmatter.DolomitefromtheCenajosubbasinoftheHellínBasinand
theLorcabasinrevealssimilar13Cvalues,whichhavebeenattributedtobacterialsulphate
reduction(Bellancaetal.,1989;Rouchyetal.,1998).
AdditionalevidenceforamicrobialoriginoftheHellínbasindolomitesstemsfromthe
anticorrelationbetween13Cand18Ovalues(Fig.69).Duringphasesofenhancedevaporationthe
sulphateconcentrationinthelakewaterincreased,allowingsulphateionstopenetratedeeperinto
thesediment,whichconsequentlyexpandedthesulphatereductionzone(cf.,KastenandJørgensen,
FOURTHMANUSCRIPT 89

2000).Whenthishappened,sulphatereductionoverprintedcarbonatebedsbyinducingthe
interstitialprecipitationof18Oenrichedand13Cdepleteddolomite,with18Oenrichmentreflectinga
highdegreeofevaporationand13Cdepletioncorrespondingtoahighcontributionofcarbonate
derivedfrombacterialsulphatereductioncoupledtooxidationoforganicmatter,crudeoil,or
methane.
AnanoxicmilieuinthelacustrinesedimentsoftheHellínbasin,whichisrequiredforsulphate
reduction,agreeswiththelackofbioturbationasrevealedbytheundisturbedlaminationinthe
sulphurbearingstrata.Theabsenceofreplacivegrowthsupportsanearlyoriginofdolomite(cf.,
ServantVildaryetal.,1990).Thebiologicaloriginofthestudieddolomite–resultingfrom
microbiallyinducedprecipitationandnotfromdolomitisation–isevidencedbymicrofabricssuchas
matlikelamination,aggregatesofclottedorpeloidaldolomicrite,andparticularlyspheroidal
dolomite.Thestrongfluorescenceofthespheroidsindicatesahighcontentoforganicmatter(cf.,
DravisandYurewicz,1985).Notably,spheroidaldolomitehasbeensuggestedtoresultfromthe
bacterialremineralisationoforganicmatter(Lalou,1957;Gunatilaka,1989;AyllónQuevedoetal.,
2007;SanzMonteroetal.,2009),indicatingthatthisfabricistypicalformicrobialdolomite.Similar
fabricshavebeenobservedinmicrobialdolomiteforminginmodernlagoonalenvironments
(VasconcelosandMcKenzie,1997;Wright,1999).Theshapeofspheroidsisbelievedtoreflect
microenvironmentsofmineralprecipitation,wherecellsandextracellularpolymericsubstancesact
asnucleationsites(Vasconcelosetal.,1995;Burnsetal.,2000;vanLithetal.,2003;AyllónQuevedo
etal.,2007;Duprazetal.,2008).
Highsulphateconcentrationswerefoundtoinhibitdolomiteprecipitation(e.g.Bakerand
Kastner,1981;foranopposingviewseeSánchezRománetal.,2009).Dolomiteformsundersurface
conditionswhenbacterialsulphatereductioneffectivelyreducessulphateconcentration(Bakerand
Kastner,1981;VasconcelosandMcKenzie,1997;WrightandWacey,2005).Sulphatereducing
bacteriaarebelievedtofavourdolomiteformationbytheliberationofmagnesiumions,whichare
efficientlycomplexedbysulphateions(SlaughterandHill,1991;Vasconcelosetal.,1995;
VasconcelosandMcKenzie,1997).Amagnesiumtocalciumratioof5:1to10:1hasbeenfoundtobe
necessaryfordolomiteprecipitation(e.g.FolkandLand,1975;Warren,2000).Inlacustrine
environmentssuchhighMg:Caratioscanbeachieved(1)byconsumptionofcalciumionsduring
gypsumprecipitation(FolkandLand,1975;Hardie,1987),(2)byprecipitationofcalcite(Land,1998),
or(3)duringearlydiagenesisofclaymineralswithareleaseofmagnesiumions(Kahle,1965;Weaver
andBeck,1971).Whereasthelatterprocesshasbeensuggestedtohaveplayedasignificantrole
duringtheprecipitationofdolomitespheroidsinKuwait(Khalaf,1990),thefirstfactorand,toa
lesserdegree,thesecondfactorprobablyfavoureddolomiteformationintheHellínbasin.

90 FOURTHMANUSCRIPT

Variationsinlakewaterchemistryareapossiblecauseforthechangesfromcalcitetodolomite
lithologiesinthesedimentarystrataoftheHellínbasin(cf.,ServantVildaryetal.,1990).Sucha
scenariohasbeendescribedfortheDevonianOrcadianbasinandthemodernLagoaVermelha,
wheredolomiteformationisbelievedtobelinkedtoperiodsofenhancedevaporationandcalcite
formationsupposedlytakesplaceduringperiodsofenhancedfreshwaterinput(JanawayandParnell,
1989;VasconcelosandMcKenzie,1997).High18OvaluesofHellínbasindolomites(+6.2to+10.5‰)
confirmthatdolomiteprecipitatedinanenvironmenttypifiedbyevaporation(cf.,TalbotandKelts,
1990),asthehighestvalueforacalculatedcalcitewouldstillbe+7.1‰afterthecorrectionfor
differentfractionationfactorsduringprecipitation(H18Odolomitecalcite=+2.6‰,Vasconcelosetal.,
2005)andforfractionationduringtheanalyticalprocedure(H18Odolomitecalcite=+0.8‰at25°C,Sharma
andClayton,1965).Carbonatedepositswithamixedcompositionofcalciteanddolomiteand18O
valuescloseto0‰probablyreflectperiodsofdilutionofthelakebyfreshwater,whereascalcite
sparwithnegative18Ovaluesprecipitatedfrommeteoricwatersduringlatediagenesis.
6.5.2Formationofnativesulphurandsecondarygypsum
Microbialsulphatereductionreleaseshydrogensulphide,whichisfurtheroxidizedtonative
sulphurinsomesettings(e.g.Machel,1992).Sulphatereducingbacteriadiscriminateagainst34S,
resultingintheformationofhydrogensulphidewithlow34Svalues(e.g.KaplanandRittenberg,
1964;Canfield,2001).SimilartootherbasinsinSpainliketheTeruelbasin,theEbrobasin,orbasins
intheeasternBetics(Anadónetal.,1992;Utrillaetal.,1992;Playàetal.,2000),Triassicevaporitic
rockswithanaverage34Svalueof+12‰arepresentinthedrainageareaoftheHellínbasin
(ServantVildaryetal.,1990).DuringtheMiocene,theTriassicevaporitesweredissolvedbymeteoric
watersandtheresultantsulphateionsweresubjectedtobacterialsulphatereductionintheHellín
basin.TheprimarygypsumofthelacustrinesedimentarysequenceoftheHellínbasinisslightly
enrichedin34ScomparedtoTriassicgypsum(+13to+19‰,ServantVildaryetal.,1990),reflecting
theremovalofisotopicallylightsulphatebybacterialsulphatereduction.Theoxidationofsulphide
tosulphurinvolvesonlyanegligiblefractionationeffectforsulphurisotopes(Canfield,2001;Hoefs,
2004).Therefore,thelow34SvaluesofnativesulphurfromtheHellínbasin(17.1to3.7‰)reflect
theisotopiccompositionofsulphideproducedbybacterialsulphatereduction.Theaccordant
fractionationofsulphurisotopesbetweensulphateandsulphide(14to30‰)iswellwithinthe
knownrangeofbacterialsulphatereduction(HartmannandNielsen,1969;GoldhaberandKaplan,
1974,Bolligeretal.,2001;Detmersetal.,2001).
Theoxidationofhydrogensulphidetonativesulphuroccursabiologicallyorbiologically(Machel,
1992).OneobservationsuggeststhatatleastpartofthenativesulphuroftheHellínbasinresults
frombiologicaloxidation.Thefluorescentglobulesenclosedinnativesulphur(Fig.67)probably
FOURTHMANUSCRIPT 91

representfossilizedbacterialcells.TheyresemblethesulphideoxidizingbacteriaThiomargaritasp.
orAchromatiumsp.(writtencomm.H.N.SchulzVogt,2009).Thiomargaritasp.havebeen
exclusivelydescribedfrommarinesediments(SchulzandSchulz,2005).Theirmetabolismisbasedon
oxidationofsulphidewithoxygenornitrate(SchulzandJørgensen,2001;Schulz,2002).
Achromatiumsp.,however,preferlacustrineconditionsandgainenergybytheoxidationofsulphide
tosulphatewithnativesulphurasintermediate(Grayetal.,1999).Thebendingofsedimentlayers
aroundsulphurnodulespointstoasyngeneticformationofsulphurandthus,agreeswithbiological
oxidationofhydrogensulphide.
MostofthegypsumintheLasMinasdeHellínformationisobviouslyofadiageneticorigin,
resemblingdiageneticgypsumoftheMioceneTeruelbasin(cf.,Ortíetal.,2010).Suchanoriginis
revealedbythereplacementofsulphurnodulesorcarbonatelaminaeandtheinfillingoflate
fissures.Theoxidationofreducedsulphurspeciesproducessulphuricacid,whichcausesadropinpH
leadingtocarbonatedissolution(Boudreau,1991;Walteretal.,1993;Kuetal.,1999,Pirletetal.,
2010).Thegypsumthattendstoprecipitateundertheseconditionsreplacescarbonateandnative
sulphurinthesedimentarysequence(ServantVildaryetal.,1990).Thefractionationeffectfor
sulphurisotopesduringtheprecipitationofgypsum(1.6‰)issmall(NakaiandJensen,1964;Thode
andMonster,1973;Claypooletal.,1980).Thelow34Svalues(–11.1to–18.2‰)ofdiagenetic
gypsumconsequentlyconfirmitsoriginfromtheoxidationofnativesulphur.Thissecondarygypsum
isalsocharacterizedbylow18Ovalues,reflectingtheuptakeofoxygenderivedfrommeteoric
waters(cf.,TaylorandWheeler,1984;Brunneretal.,2005).
6.6Conclusions
Thenativesulphurandauthigenicdolomitepresentinthelacustrineevaporiticsequenceofthe
LateMioceneLasMinasdeHellínformationoftheHellínbasininSESpainformedasaconsequence
ofbacterialsulphatereduction.ThehighsulphateconcentrationoftheMiocenelakeledtothe
depositionofprimarylacustrinegypsumandservedasanelectronacceptorforbacterial
remineralisationoforganicmatter.Amicrobialoriginofauthigenicdolomiteisconfirmedbyits13C
valuesaslowas11‰andtexturalevidenceincludingspheroids,clottedandpeloidalfabrics,aswell
asmatlikelamination.Microfossilspreservedinnativesulphurindicatethathydrogensulphide
producedbythesulphatereducingbacteriawasatleastpartiallyoxidizedbiologically,resultingin
sulphurformation.Theputativebacterialfossilsresemblethesulphideoxidizingbacteria
ThiomargaritaandAchromatium.AsignificantamountofthenativesulphurintheLasMinasde
Hellínformationwaslateroxidizedto34Sdepletedsecondarygypsum(34Svaluesaslowas18‰),
stillreflectingthesulphurisotopecompositionofthebiogenicsulphur(34Svaluesaslowas17‰).

92 FOURTHMANUSCRIPT

Acknowledgements
WethankSebastianFlotow(Bremen)forthinsectionpreparation,BritKockisch(Bremen)for
TOCmeasurements,ThomasMax(MPIBremen)forhelpwithsulphurandoxygenisotopeanalysis,
MonikaSegl(Bremen)forcarbonandoxygenisotopeanalysis,ChristophVogt(Bremen)forXRD
measurements,PetraWitte(Bremen)forhelpwithREManalysis,andHeideSchulzVogt(MPI
Bremen)forcommentsonsulphideoxidizingbacteria.CommentsbyFedericoOrtí(Barcelona)and
ananonymousrefereehelpedimprovingthemanuscript.ThisprojectwassupportedbytheDFG
ResearchCenter“TheoceanintheEarthsystem”,theinternationalgraduatecollegeEUROPROX,and
theMaxPlanckSociety.

CONCLUDINGREMARKSANDPERSPECTIVES 93

7CONCLUDINGREMARKSANDPERSPECTIVES
Themainconclusionsofthepresentedthesisare:
I)Allexamineddepositsofnativesulphurandaccompanyingcarbonatearetheresultofmicrobial
activity,withbacterialsulphatereductionasmainandmostimportantprocess.Thisisevidencedby
largesulphurisotopefractionationbetweensulphateandreducedsulphurspecies(upto60‰),best
visibleinthelargedifferencebetween34SCASand34Ssulphur.The34SCASisregardedasgoodmeasure
forthesulphurisotopiccompositionofsulphatecontemporaneouslytocarbonateprecipitation.The
lowcarbonisotopicratiosofthecarbonatesrevealstheincorporationofcarbonderivedfrom
microbialprocessesasthedegradationoforganicmatterorcrudeoilortheoxidationofmethane.
Thepresenceofmicrofabricslikebiomatresemblinglaminationandspheroidaldolomitefurther
supportsthebiogenicityofthesedeposits.
II)Althoughthesemicrobialprocessesledtothesametypeofsulphurandcarbonatedeposits,very
similaratfirstglance,therearetwodifferentpathwaysofdeposition.Duringsedimentationorvery
earlydiagenesis,withintheunconfinedsediment,sulphatereducingbacteriausedissolvedsulphate
tooxidizemainlymethane.Theresultingcarbonatecontainspseudomorphsafterlenticulargypsum
andisenrichedin18O,displayingevaporiticconditionsduringauthigenesis,whichisfurthermore
evidencedbythepresenceoflipidbiomarkersputativelyderivedfromhalophilicorganisms.So,in
accordancewithDessauetal.(1962)andinoppositiontootherpublications(Ruckmicketal.,1979;
Manzietal.,2010)thepresentedresultsshowthatnotallbutsomeoftheSiciliansulphurand
carbonatedepositsprecipitatedsyngenetically.ThesamepathwayisobviousforHellíndeposits,
especiallybecauseofthepresenceofnativesulphurnodulesembeddedinlaminatedcarbonate.In
contrasttothatsyngeneticpathwaytheepigeneticpathwayoccurslatediagenetic.Sulphate
mineralsasgypsumoranhydritearedissolvedbymeteoricwaterstoprovidethesulphatesource.
Thecarbonatesderivedfromthatarecharacterizedbylow18Ovalues.Partlythereplacementof
gypsumbycarbonateisnicelyvisible(seeFig.36B).Overallithastobepointedouthere,that
syngeneticdepositsdonotonlyaccountforsmalloccurrencesinmodernsettingsasproposedby
Wessel(1994)butseemtobemorewidespreadthanformerlythought.
III)Carbonateswhicharemostdepletedin13CareindeedinducedbysulphatedependentAOM,
substantiatedbymolecularfossilsandtheircompoundspecificverylowcarbonisotopevalues.Two
groupsoforganismsareinvolvedinAOM.Anaerobicmethanotrophicarchaeaaredisplayedbylipids
asPMI,sn2hydroxyarchaeolandbiphytanicdiacidswith13Cvaluesaslowas105‰.Thesulphate

94 CONCLUDINGREMARKSANDPERSPECTIVES

reducingbacteriaarerepresentedbye.g.,bishomohopanoicacid,isoandanteisoC15:0andC17:0
andthe10MeC16:0fattyacids,alllikewisesubstantiallydepletedin13C(13Caslowas90‰).
InterestinglythelipidbiomarkerinventorydiffersslightlycomparedtostudiesofconsortiaofANME
andSRBtypicallyassociatedtomethaneseepage.Thereforeanassignmenttooneofthecommon
ANMEgroupswasnotpossible.Nonethelesstheseresultsclearlydemonstratethatsulphate
dependentAOMwasoccurringinevaporiticsettingsoftheMessinian,despiterecentstudieswhich
suggestedthatAOMisinhibitedbyhighchlorideconcentrations(Joyeetal.,2009a,b).
Someaspectsarestilltobediscussed:
Theprocessofsulphideoxidationtonativesulphurremainsratherenigmatic.Samplesfromthe
Hellínbasinindicatethatsulphideoxidationmighthaveoccurredbiologically,asfossilspreservedin
thesamplesresemblesulphideoxidizingbacteria.Unfortunatelylipidsderivedfromtheseorganisms
arenotveryspecific,especiallyinsedimentswheresulphatereducingbacteriaareubiquitous(Arning
etal.,2008).Synproportionationshouldproduce34Ssulphurvaluesplottingexactlybetween34Ssulphate
and34Ssulphide.InSiciliansamplesnosulphidemineralscouldbeobtained.As34Ssulphateisashighas
+60‰andthe34Ssulphurismainlyabout0to10‰,thesulphidefromwhichthesulphurwasformed
wouldhavebeenaslowas50‰,resulnginafraconaonofmorethan100‰,whichisfaroutof
therangeofpublisheddata.Synproportionationisthereforeanunlikelyprocessforgenerationof
nativesulphurfromsulphidefortheSiciliandeposits.Theabiologicaloxidationofsulphidetonative
sulphurwithoxygenwouldhaverequiredalternationbetweenreducingandoxidizingconditions.
Developingmethodstodeterminetheoxidativepathofsulphurdepositionwouldbehighly
necessary.ArecentstudybyZerkleetal.(2009)forexampleproposedthepotentialofmultiple
sulphurisotopestudies(33Sand34S)fordiscriminationofdifferentoxidationpathways,as
phototrophic,chemotrophicandabiologicalsulphideandsulphuroxidation.Theinvestigationof
modernsulphurprecipitatingenvironmentswouldbeofgreathelp.ButlinandPostgate(1954)
describedactivemicrobialsulphurprecipitationinlagoonallakesinCyrenaica,Libya.Similar
occurrencesarealsopresentinanalpinelakecalledAlatsee(pers.com.UlrichStruck).Furthermore
theinvestigationofancientsulphurdepositswithabetterconstrainedgeologicalframe(e.g.,salt
domecaprocks,orsmalllacustrinesulphurcontainingbasins)couldbecombinedtotheapplication
ofaboxmodel,whichintegratesthestabilityanddissolutionofgypsumtocalculatethegypsumto
sulphurtransformationandtheaccompaniedprecipitationofcarbonates.Inaclosedsystemthe
distributionofsulphurisotopesbetweenthedifferentsulphurphasescouldbecalculatedand
comparedtonature.Thatoffersconclusionsaboutthepossiblepathwaysofsulphidetosulphur
oxidationandthepossibilitytocompareittothelesswellconfinedSiciliansulphurdeposits.
CONCLUDINGREMARKSANDPERSPECTIVES 95

Althoughfractionationbetweensulphateandnativesulphurisashighas60‰,animportant
contributionofbacterialdisproportionationisunlikelyfortheSiciliandeposits,firstbecauseofthe
largeamountsofnativesulphurstillpresentandsecondlybecausedisproportionationproduces
protonswhichwouldhaveinhibitedcarbonateprecipitation(cf.,Cypionkaetal.,1998;Finsteretal.,
1998).Neverthelessitwouldbeinterestingtoinvestigatetheinfluenceofdisproportionationin
thesetypesofsettingsandtoevaluatetheconditionswhichfavourdisproportionation.Mass
dependentprocesseslikesulphatereductionshouldproducea33Sthatisabouthalfthe34Svalue
(33S=0.515*34S;Farquharetal.,2003).Recentexperimentsandmodelcalculationsshowthat
althoughbothprocessesaremassdependent,bacterialsulphatereductionanddisproportionation
aredistinguishablebymeansofrelationshipbetween34Sand33Sofsulphateandsulphide
(Farquharetal.,2003;Johnstonetal.,2005a,b,2007,2008).
BöttcherandBrunner(pers.com.)suggestedaveryelegantmethodtoinvestigatethe
temperatureconditionsduringcarbonateprecipitationwiththehelpof18OvaluesofCAS.The
differencein18Obetweencarbonateandwaterinequilibriumisdescribedbythetemperature
dependentseparationfactor.Theoxygenisotopiccompositionofwatercanbecalculatedfromthe
18Ovaluesofthecarbonateanddifferswithchangingtemperature(Zheng,1999).Theoxygen
isotopiccompositionofsulphateinasolutionthatisinfluencedbymicrobialsulphatereductioncan
beassumedfromtheoxygenisotopiccompositionofthewater(Fritzetal.,1989)andappearstobe
temperaturedependentaswell.The18OvalueofCAScoincideswitha18Ovalueofdissolved
sulphateatacertaintemperature,whichrepresentsthetemperatureofthesolutionfromwhichthe
carbonateprecipitated.Thismethodprovidesnotonlyinformationaboutenvironmentalconditions
duringcarbonateprecipitation;itmayalsoofferawaytodistinguishbacterialfromthermochemical
sulphatereduction.AlthoughTSRcanbeexcludedfortheSiciliandepositsandforHellín,becausea)
thereisnoindicationthatthedepositswereexposedtoelevatedtemperatures,b)thesulphur
isotopefractionationissubstantiallyhigherthanproposedforTSR(cf.,Macheletal.,1995;Worden
etal.,1997)andc)thelipidbiomarkerdatagaverobustevidenceformicrobiallymediationinthe
Siciliansamples,Iwouldrecommendthatmethodforothersulphurdeposits,e.g.,saltdomecap
rocks,whereelevatedtemperaturemighthaveoccurred.
Furthermorethestudyofsofarpurelyinvestigateddepositsofmostlikelybiogenicnative
sulphurandauthigeniccarbonates,asforexampleinRomania(pers.com.EugenGradninaru)could
providefurtherinsidesintosulphurandcarbonategenesis.Themolecularfossilapproachshouldbe
appliedalsotootherlocationstofurthercorroboratetheimportanceofmicroorganismsin
carbonateandsulphurauthigenesisandtoextendourunderstandingaboutthemicrobesthatare
flourishingextremeenvironments.

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*„DieSiebenGaben“,TextundMusik:GerhardSchöne,veröffentlichtaufderCD„DieSieben
Gaben.LiederimMärchenmantel.”,Buschfunk1992.

114

9DANKSAGUNG
MeinallerherzlichsterDankgehtanJörn,zunächstmaldafür,dassermichinseinenVorlesungen
undderExkursionindenHarzaufdenGeschmackgebrachthat,unddannnatürlichdafür,dassermir
diesesThemaanvertraut,michbetreutundgefördertundzuletztmitnachWiengenommenhat.
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GanzherzlichmöchteichmichauchbeiAdrianbedanken,fürseineUnterstützungbeim
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116

117

ERKLÄRUNG
Name:SimoneZiegenbalg
Anschrift:Bonygasse55,1120Wien,Österreich
Hiermiterkläreich,dassich:
1)dieArbeitohneunerlaubtefremdeHilfeangefertigthabe,
2)keineanderen,alsdievonmirangegebenenQuellenundHilfsmittelbenutzthabe
und
3)diedenbenutztenWerkenwörtlichoderinhaltlichentnommenenStellenalssolchekenntlich
gemachthabe.
Wien,
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1 Introduction 13

1.1 Sulphur 13

1.1.1 Sulphurandthesulphurcycle 13

1.1.2 Applicationofsulphurandoxygenisotopesinsulphurspecies 14

1.2 Authigeniccarbonates 17

1.3 AuthigenicsulphurandcarbonatedepositswithfocusonSicilyandSpain 19

Lipid Putativesource Reference

PMI,13Cdepleted methanotrophicarchaea Elvertetal.,1999;Peckmannet

isoC16:0fattyacid sulphatereducingbacteria TaylorandParkes,1983;Dowling

Fig.31 InterpretativvecrosssectionthroughhtheCentra lSicilianBassinillustratinngthestratigraphic

Fig.33SSamplesofC CalcareSolfi fero,i.e.,lim

Fig.34 MontedeD rasi.Cel=ce elestine;mi =micrite;S =nativesulp

Fig.36 CozzoDisi.GGyp=gypsumm;mi=micrrite;rfCc= radiaxialfibrouscalcite cement;scCc=

Fig.38 MonteCapo odarso.An=anhydrite;G Gyp=gypsum m;mi=micrrite;S=sulp hur.(A)Limestone

Fig.39 Carbonand oxygenstableisotopecoompositionssofindividua alcarbonateephases.One

[‰CDT] [‰VSMOW] [‰CDT] [‰VSMOW]

Figure4 1Gaschrom matogramso ofsampleGA Ab.a)Alcohholfraction,blackdots:ssaturatedn

Figure4 2Carbonis otopiccomp positionofseelectedmole ecularfossils,illustratin gashifttow

Fig.52 EDXspectru mofgypsum

Fig.53 (A)Position oftheXrayyspotontheethinsectio n.(B)Diffracctionpatternnofthespo tshown

Fig.63 Laminatedccarbonatebe ed.(a)Carboonatebedwiithvarvedlamination,w whichisbent around

Fig.64 Carbonateddeposits;planepolarizeddlight.(a)C lotteddolom

Fig.67 (a)Putative fossilizedba

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