ORE SYSTEM STUDIES

147
ORE SYSTEM STUDIES
The Centre for Advanced Studies of Ore Systems (CASOS) is a joint initiative between
RSES and the ANU Department of Geology (The Faculties). CASOS links together
researchers with a common research and training focus on themes dealing with various aspects
of the formation of ore systems.
The CASOS mission is:
To advance fundamental understanding of processes involved in the genesis of large
and economically significant mineral resource systems on a lithosphere and province
scale.
In collaboration with the international minerals industry, to develop and apply new
techniques and new models to drive the development of new minerals exploration
concepts, as well as strategies to direct resource definition and mine development more
effectively.
To provide high level training of graduate students and postdoctoral fellows so that
Australian scientists are at the international forefront of ore systems research and
minerals exploration technology.
Expertise at ANU in the development and application of new microanalytical techniques,
high-pressure/high-temperature experimental facilities, and modelling capabilities, provide
unique opportunities to explore some of the fundamental physical and chemical processes
involved in ore genesis from metal source, through the transport path, to resource accumulation
sites. Ore Systems research at ANU is conducted within six programs:
Ore Fluids
Deformation and Fluid Pathways
Magmatic Processes
Stable Isotope Studies
Radiogenic Isotope Systems
Diamond Systems
During 1999 at RSES, Ore Systems research was conducted across a number of the
Schools Groups, but principally in Ore Genesis, Petrochemistry and Experimental Petrology,
Petrophysics and Geophysical Fluid Dynamics.
A major focus of our activities continues to be the relationship between gold
mineralisation and the evolution of Archaean, granite-greenstone terrains in the Yilgarn craton of
Western Australia. Dr M. Palin and Ms Y. Xu have been using stable isotopes to study the
genesis of the gold deposits in the Kalgoorlie-Kambalda area of Western Australia. It has been
known for some time that mesothermal gold deposits are commonly hosted by Fe-rich host
rocks, and this has lead to the suggestion that the gold precipitated as a consequence of
desulphidation, when sulphur in the ore fluid reacted with Fe in the wall rocks. However many
important gold deposits are not hosted by Fe-rich wall rocks. Palin and Xu have found that the
sulphides associated with the highest gold grades at Kambalda have the lightest sulphur
isotopes. They have shown that this relationship results from oxidation of the ore-forming fluid
which converts sulphur in the auriferous fluid from sulphide to sulphate, destabilising the gold-
carrying sulphide complexes in the fluid and causing gold to precipitate. Destabilisation of the
gold-carrying complex and precipitation of gold can therefore occur both as the consequence of
reduction or oxidation of sulphur in the ore fluid. It appears that it is the second of these
mechanisms that is the more important, because many of the worlds giant gold deposits,
including the Golden Mile, Hemlo, Kirkland Lake and Hollinger-McIntyre, have sulphides with
light sulphur isotopes, indicative of oxidised ore fluids. Oxygen isotopes have been used to
show that formation of the gold deposits also involves mixing between a high-temperature deep-
crustal fluid and a low-temperature, presumably oxidised, fluid that is probably seawater or
RESEARCH SCHOOL OF EARTH SCIENCES ANNUAL REPORT 1999
148
meteoric water. The conclusions of Palin and Xu are being further tested at the Golden Mile by
Mr C. Heath as part of a new PhD project that is being funded through the SPIRT program with
Kalgoorlie Consolidated Gold Mines. Finally, Dr Loucks has found a relationship between
Archaean mesothermal gold deposits and anticlines which has lead to the suggestion that
anticlines act as a focussing mechanism for metamorphic fluid flow.
Professor S. Cox, in collaboration with WMC Resources Ltd and University of Newcastle
PhD student, Mr K. Ruming, is investigating structural and deformational controls on fluid flow
associated with gold mineralisation in faults, shear zones and associated fracture systems at the
St Ives Goldfield, near Kambalda in Western Australia. Fluid-pressure-driven growth of faults
and reaction-weakening in the gold-hosting structures has been found to influence their
localisation. Accordingly, current work is focussing on understanding how the distribution of
vein-rich and vein-poor mineralisation across the 20 km long, 5 km wide goldfield relates to the
distribution of fluid pressure regimes in the fault/shear controlled hydrothermal system that
generated gold mineralisation. A contractional jog on a major shear system is recognised as
playing a key role in nucleating low displacement structures which host some of the major
mineralisation at St Ives. The ore-hosting structures are being interpreted as aftershock
structures associated with major slip events on adjacent, crustal-scale shear systems.
A principal focus of research in the Ore Genesis Group is the development of copper and
gold deposits at convergent plate margins. This research program involves three PhDs and Dr
R. Loucks. Mr B. Rohrlach has been analysing oxygen isotopes in hydrothermally altered
volcanic samples from the Tampakan stratovolcano, which hosts a major porphyry copper-gold
deposit in the Philippines. The isotopic study examines the interaction between magmatic
hydrothermal fluids and meteoric water, as influenced by volcanic topography on the hydrology
of the ore-forming system, and the relationship of the fluid mixing to ore deposition. Mr B.
Setiabudi has analysed samples from Kelian gold mine in Indonesia for major elements and for
a wide range of trace elements. The major elements and some of the trace elements have been
affected by the extreme hydrothermal alteration of the mine area, so samples from the unaltered
and petrological similar Magerang area to the northwest were also analysed for comparative
purposes. Trace element ratios, for elements that are normally regarded as immobile in
hydrothermal fluids, are the same for the two areas, suggesting that the Magerang data provide a
good analog for the Kelian volcanics and can be used to study the chemical evolution of the ore
forming system without the complication of alteration. Mr J. Ballard has been studying the
giant Chuquicamata copper deposit in Chile. This year he used the excimer laser (ELA) ICP-
MS to date igneous zircons in the three porphyries in the mine and showed that they span a
resolvable age range, consistent with the hypothesis that Chuquicamata owes its enormous size
to three superimposed porphyry systems. He also used variations in the Ce anomaly in zircons
to show that the productive porphyries in the Chuquicamata area crystallised from a more
oxidised magma than the barren intrusions.
A feature of the Tampakan, Chuquicamata and Kelian studies is that Y and the heavy rare
earth elements decrease with increased magmatic differentiation in the felsic suites associated
with the ore deposits. This is unexpected because these elements are usually incompatible in
major igneous minerals, and so accumulate in the residual melt as magmatic differentiation
proceeds. The unusual depletion trend is attributed to extensive amphibole fractionation and
implies that the ore-producing systems are unusually water-rich. The addition of water to a
magma expands the stability field of amphibole at the expense of plagioclase. As a
consequence, it should be possible to use variations in Sr, which partitions strongly into
plagioclase, and Y, which partitions into amphibole, to distinguish ore-bearing and barren felsic
systems. Dr Loucks has shown that the Sr/Y ratio in fertile segments of convergent margins
increases with fractionation but decreases in barren segments. Furthermore, within ore-bearing
segments, the productive stocks and porphyries have higher Sr/Y ratios than barren intrusions.
This study suggests that Sr/Y ratios will be a valuable aid to mining companies in the exploration
for copper and gold deposits at convergent plate margins.
Professor Cox, in collaboration with Dr S. Munroe (SRK Consulting), has been
examining the coupling between stress states and fluid pressure regimes in generating the
ORE SYSTEM STUDIES
149
fault/fracture system which hosts the giant intrusive-related gold deposit at Porgera in PNG.
The development of suprahydrostatic fluid pressures, and a change in the stress regime during
the evolution of this intrusive-related hydrothermal system, is a key factor controlling a change
from distributed fluid flow to highly localised, fracture-controlled flow. Early distributed fluid
flow produced high-tonnage, low grade mineralisation, whereas the later fault-hosted flow
regime produced extremely rich mineralisation.
Activities in the Petrochemistry Group complement the field-based and analytical
approaches on convergent margin Cu-Au deposits. PhD student, Mr A. Hack, and
Dr J. Mavrogenes are conducting an experimental campaign to explore Cu solubility in
supercritical and two-phase aqueous solutions, Cu solubility in silicate melts, and the critical
issue of Cu partitioning between silicate melts and co-existing vapour. Significant advances are
being made using high pressure/high temperature laboratory facilities at RSES and the ANU
Geology Department, in conjunction with ELA-ICP-MS techniques. The study is providing
fundamental information on the processes leading to the formation of porphyry-type mineral
deposits at convergent plate margins.
Using the high temperature laboratory facilities in the Petrochemistry Group,
Drs Mavrogenes and H. ONeill are studying sulphur solubilities in silicate melts under
controlled fO
2
and fS
2
conditions. The results indicate that FeO has a stronger influence on
sulphide capacities in haplobasaltic and basaltic melts than indicated by previous work. The
results have implications for understanding the genesis of magmatic Ni and platinoid deposits.
High tenor mesothermal gold ores with low
34
S
J.M. Palin and Y. Xu
Experimental studies conducted previously at the RSES show that gold is present in
sulphide-saturated hydrothermal solutions at temperatures above 300C and at near neutral pH
principally as AuHS(H
2
S)
3
or AuHS. Gold solubility under such conditions is described by
the general reaction:
Au + n H
2
S = AuHS(H
2
S)
n-1
+ 1/2 H
2
where n is 1 or 4. Variable and low
34
S of pyrite in high tenor ores of the Victory mesothermal
gold deposit of Western Australia indicate progressive oxidation of initially reduced ore-forming
solutions. Lowering of the activity of dissolved hydrogen gas, a(H
2
), increases gold solubility
according to the above reaction leading to an apparent contradiction between observation and
theory.
Changes in fluid chemistry and sulphur isotope values that accompany carbonation and
sulphidation of wall rock can be estimated for incremental reaction of magnetite with CO
2
and
H
2
S in a pyrite-saturated fluid according to:
Fe
3
O
4
+ 3 CO
2
+ H
2
= 3 FeCO
3
+ H
2
O
Fe
3
O
4
+ 6 H
2
S = 3 FeS
2
+ 4 H
2
O + 2H
2
Calculated reaction paths are shown in Figure 1 for two different fluid starting compositions.
Solution pH is assumed to remain neutral (near the quartzK-feldsparmuscovite buffer) in this
simplified model, which is consistent with observed mineral assemblages. The stoichiometry of
the carbonation and sulphidation reactions produces changes in H
2
that are the same order of
those in CO
2
or H
2
S, although these two species are several orders of magnitude more abundant
than H
2
in the fluids. Thus, shifts in a(H
2
) are proportionally much larger than those in a(H
2
S)
or a(CO
2
) for each increment of reaction progress. The resulting vertical reaction paths cross
contours of gold solubility at steep angles (Figure 1). In the case of carbonation, gold solubility
increases as the solution becomes increasingly oxidized until the HSO
4
-

predominance field for
RESEARCH SCHOOL OF EARTH SCIENCES ANNUAL REPORT 1999
150
dissolved sulphur is encountered. From there to the point where the solution reaches hematite or
magnetite saturation, conversion of H
2
S to HSO
4
-

causes a rapid decrease in a(H
2
S) relative to
a(H
2
), which results in flattening of the reaction paths and a precipitous drop in gold solubility.
This is because the sulphide complex that carries the gold is destabilised when sulphur in the ore
fluid is oxidised to sulphate. The largest decreases in a(H
2
S) and a(Au) occur around the
H
2
S/HSO
4
-

equal-activity boundary and thus coincide with the point where sulphide sulphur
isotope compositions are most strongly shifted to negative values (Figure 1). Wall-rock
carbonation thus provides a straightforward explanation for the negative correlation observed
between gold content and pyrite
34
S in the Victory deposit. In contrast, sulphidation of wall
rock results in a decrease in gold solubility as the fluid undergoes progressive reduction until
pyrrhotite stability is reached, whereupon further changes in a(H
2
S) and a(H
2
) are buffered by
pyrite-pyrrhotite equilibrium up to magnetite saturation. No sulphur isotope shifts occur during
sulphidation because the fluids remain entirely within the H
2
S predominance field for dissolved
sulphur.
P o
P y
AuHS(H
2
S )
3
H t
AuHS
1 0
-5
1 0
-4
1 0
-3
1 0
-2
1 0
-3
1 0
-2
1 0
-1
1 0
0
a(H
2
)
a(H
2
S)
log a(Au) = -7 - 4 - 6 - 5
-0.1
- 1
- 5
-13
-17
-17.6
400C
1000 b
neutral pH
1
2
M t
H
2
S
HSO
4

- 3
CH
4
C O
2

3
4
S

H
2
S

S
Figure 1: Reaction paths showing changes of a(H
2
S) and a(H
2
) in aqueous solution during
wall rock carbonation (solid lines) and sulphidation (dashed lines) at 400C, 1000 bars and
neutral pH from two initial fluid compositions with X(CO
2
CH
4
) = 0.1. Also shown are
contours of total gold solubility (a(Au)); shifts of
34
S H
2
S relative to bulk sulphur in
solution; equal activity boundaries for H
2
S/HSO
4
-
, CO
2
/CH
4
, and AuHS/AuHS(H
2
S)
3
; and
stability fields for magnetite (Mt), hematite (Ht), pyrite (Py), and pyrrhotite (Po). Unit
activity coefficients assumed for all dissolved species.
It is interesting to note that a high proportion of giant and supergiant mesothermal gold
deposits worldwide exhibit variably negative sulphur isotope values and extensive carbonate
alteration. In the Golden Mile, Hemlo (Canada), Kirkland Lake (Canada), Hollinger (Canada),
and McIntyre (Canada) deposits, the sulphur isotope compositions have been interpreted as
recording involvement of oxidized ore-forming fluids. As shown here, fluid oxidation
accompanying carbonation of wall rock magnetite can be an efficient means of gold
precipitation. We speculate that it may play a key role in generating very large mesothermal
gold deposits.
ORE SYSTEM STUDIES
151
Gold deposition by mixing of deep and surficial fluids: Inferences from stable isotope and
experimental studies
J.M. Palin, Y. Xu, I.H. Campbell and R.R. Loucks
The mesothermal gold deposits of Western Australia include some of the richest gold ores
in the world and account for a significant portion of total historic gold production of Australia.
The deposits were generated by focused flow of hydrothermal fluids within fault and shear
zones in the middle to upper crust. Determining the source and large-scale flow paths of these
hydrothermal fluids is vital to understanding the processes responsible for gold mineralisation
and has important consequences for developing successful exploration strategies.
Oxygen-isotope geochemistry of hydrothermal vein minerals from the Mt Charlotte
deposit at Kalgoorlie and the Hunt, Junction, Revenge and Victory deposits at Kambalda suggest
that quartz veins, and by inference their associated gold mineralisation, formed during influx and
mixing of cooler surficial water with greenstone-buffered hydrothermal fluid. Experimental
studies at the RSES indicate that such a process would lead to very efficient precipitation of gold
and quartz, as both minerals exhibit strongly temperature-dependent solubility in aqueous
solutions.
Equilibrium fractionation of oxygen-isotopes among minerals depends solely upon
temperature, and thus the temperature of vein formation can be calculated from oxygen-isotope
differences among coprecipitated minerals. The resulting temperature can be combined with the
measured
l8
O values for the vein minerals to calculate the oxygen isotopic composition of the
hydrothermal fluid from which the minerals precipitated. Using this method, we determined
temperatures and
18
O H
2
O values of vein-forming fluids for albite-, scheelite- and magnetite-
bearing quartz veins from the Mt Charlotte deposit at Kalgoorlie and the Hunt, Junction,
Revenge and Victory deposits at Kambalda. The range of oxygen-isotope temperatures from
each deposit is very similar to those estimated from fluid inclusions, indicating that the oxygen-
isotope temperatures for the quartz veins are accurate. The relatively uniform quartz
18
O values
require that the oxygen-isotope compositions of vein-forming fluids varied systematically with
temperature. When the data for the veins examined in this study are plotted, a positive
correlation between precipitation temperatures and
18
O H
2
O values is clearly evident (Figure 2).
Previous investigators noted the small spread of quartz
18
O values for veins in many
mesothermal gold deposits, including those from Western Australia, and assumed that the
parental hydrothermal fluids must have had constant oxygen isotopic compositions. However,
such an interpretation is valid only if the veins were precipitated over a narrow temperature
interval. More recent work has established that hydrothermal activity occurred over a substantial
range of temperatures (250600C). A temperature spread of this magnitude requires a
significant variation in
18
O values for the auriferous fluid.
Further examination of Figure 2 reveals that above about 450C, the data lie along a
greenstone-buffer curve; that is, the trend expected for equilibrium between a hydrothermal fluid
and greenstone at variable temperature and low water to rock ratio (W/R). Such a fluid could
have been generated by metamorphic dehydration reactions within the greenstone sequence or it
could have originated from an external source and exchanged oxygen-isotopes during flow
through the greenstones. In either case, this deep hydrothermal fluid maintained thermal and
oxygen isotopic equilibrium with the enclosing greenstones due to a combination of low W/R,
long residence times, and rapid oxygen-isotope exchange at high temperatures.
Below 450C, the vein data delineate a different trend, extending away from the
greenstone-buffer curve toward lower temperatures and oxygen isotopic compositions (Figure
2). These fluids lie to the left of the greenstone-buffer curve and suggest mixing with an
additional fluid with a low
18
O value. Previous workers have demonstrated that hydrothermal
fluids in the Wiluna and Racetrack deposits contained a major component of seawater or low-
latitude meteoric water. The estimated fluid temperatures and oxygen-isotope compositions for
both Wiluna and Racetrack lie on the low temperature extension of our Kalgoorlie-Kambalda
RESEARCH SCHOOL OF EARTH SCIENCES ANNUAL REPORT 1999
152
data array, allowing us to conclude that low
18
O fluid was derived from the surface. This fluid
probably descended along normal or trans-tensional faults, flowed up the ambient temperature
gradient into structures hosting the deposit, and mixed with deep, greenstone-buffered
hydrothermal fluid.
0
100
200
300
400
500
600
T

(

C
)
10 = W/R
1
0.1
down-T flow
greenstone-buffer
- 4 0 4 8 12
0
100
200
300
400
500
600

18
O H
2
O
W/R = 10
1
0.1
up-T fluid flow
T
(

C
)
Figure 2: (Top): Temperatures and
18
O H
2
O values of fluids in the Mt Charlotte gold
deposit (solid dots) and several deposits at Kambalda (open dots) based on oxygen-isotope
partitioning in quartz-albite and quartz-scheelite veins. Also shown are expected trends for
buffering of a fluid by greenstone and rate-controlled oxygen-isotope exchange between
water and rock assuming an average flow velocity of 1 m/y and a geothermal gradient of
50/km for down-T flow of a deep hydrothermal fluid initially in equilibrium with
greenstone. (Bottom): Same as (top) with expected trend for up-T flow of
18
O-depleted
surficial water.
Gold solubility in aqueous solutions buffered by magnetite-pyrrhotite-pyrite-K-feldspar-
muscovite-quartz and containing 01 m Cl has recently been determined at elevated temperature
and pressure at the RSES. The experiments involve trapping fluid at peak T and P in synthetic
inclusions in quartz and subsequently measuring their compositions by ELA-ICP-MS. The
results show that the solubility of gold in a likely greenstone-buffered hydrothermal fluid
increases exponentially with temperature in a manner similar to that for quartz (Figure 3). As a
consequence, if a deep, greenstone-buffered hydrothermal fluid encounters and mixes with much
ORE SYSTEM STUDIES
153
cooler water, the resulting hybrid will be supersaturated with both gold and quartz, even if the
initial gold concentrations of the fluid end-members lie below saturation. Mixing between fluids
of contrasting temperature therefore provides a simple explanation for the ubiquitous spatial
association between gold mineralization and quartz veins in mesothermal gold deposits and can
explain the occurrence of mesothermal gold ores in a wide variety of rock types.
0
1000
2000
3000
4000
0
100
200
300
0 100 200 300 400 500 600
T(C)
S
i
O
2

(
m
g
/
k
g

f
l
u
i
d
)
A
u

(
n
g
/
k
g

f
l
u
i
d
)
fluid mixing line
supersaturated
undersaturated
2000 bars
Figure 3: Hydrothermal solubility of quartz (black) and gold (grey) as function of
temperature at 2000 bars. Hydrothermal fluid in equilibrium with altered, quartz-bearing
greenstone at 450C will lie on the quartz saturation curve. As a consequence of the steep
temperature dependence of gold solubility in sulphur-bearing aqueous solutions, the
concentration of gold in such a fluid is likely to be determined by the W/R and labile gold
content of the source region. The value shown is for 1 wt% H
2
O interacting with a
greenstone containing 3 ppb (ng/kg) extractable gold. Mixing of this deep hydrothermal
fluid with 50C surficial water will result in hybrids that are quartz supersaturated
throughout and strongly gold supersaturated below 350C.
Greenstone-belt gold lodes localised by anticline focussing of metamorphic fluid flow
R.R. Loucks
Discussions of structural controls on localisation of hydrothermal gold ore deposition in
Archean greenstone belts, such as Western Australias Eastern Goldfields region, almost
invariably focus on large-scale faults as the main conduits for delivery of metalliferous fluid to
sites of gold accumulation. In the context of the RSES Fluids in the Crust strategic research
initiative (19941999), an effort has been made to better characterise the evidence for, and the
mechanisms of, aqueous fluid migration through deep crustal regimes hotter than 350C which
generally deform in a plastic fashion in response to moderate tectonic stresses applied on
geologic time scales. The prevailing view has been that, during heat-induced metamorphic
recrystallisation of hydrous minerals to form volatile-poor mineral assemblages, the liberated
buoyant fluids escape via sub-vertical hydraulic fractures generated by intermittent build-up of
fluid overpressures.
Metamorphic rocks hot enough to undergo plastic deformation have generally been considered
incapable of sustaining the long-range continuity of permeability needed to conduct kilometre-
scale fluid flow with a substantial lateral component. That traditional view that flow of buoyant
fluids through metamorphic rocks is essentially vertical warrants reassessment in light of
improved understanding of how percolation networks develop in deforming successions of
layered rocks that contain contrasts in plasticity or brittleness. Thick successions of layered
RESEARCH SCHOOL OF EARTH SCIENCES ANNUAL REPORT 1999
154
volcanic and sedimentary rock were deposited in subsiding Archean greenstone trough-basins,
and were deformed as corrugation-folds with kilometre-scale amplitudes and tens of kilometres
fold length. Of special interest are layered rock successions that contain extensive layers of
komatiite, which is converted by fluids into serpentinite (soapstone), a rock type too plastic to
retain a percolation network of open pores and cracks essential to fluid flow. Therefore,
extensive, thick layers of extremely plastic serpentinite should be barriers to fluid flow and divert
fluids through more brittle, cracked layers of basalt and shale.
M
t


P
le
a
s
a
n
t
1
3
L
e
f
r
o
y
Major Gold Deposits by Number
Kambalda
1. Junction
2. Victory-
Defiance
3. Orchin
4. Revenge
5. Red Hill-Hunt
6. Cave Rocks
NewCelebration
7. Jubilee
8. New
Celebration
9. Mt. Martin
Anticline
Syncline
Thrust
Fault
Other
Coolgardie
Kambalda
K
a
l
g
o
o
r
l
i
e
A
n
t
ic
lin
e
A
n
t
ic
lin
e
K
a
m
b
a
l d
a
B
a
rd
o
c
F
a
u
lt
F
a
u
lt
F
a
u
l t
F
a
u
l
t
R
e
p
u
b
l ic
a
n
F
a
u
lt
H
u
n
t
M
o
u
n
t
A
n
t
ic
lin
e
Coolgardie
12. Burbank
13. Tindals
14. Bayleys
15. Three Mile Hill
Kalgoorlie
16. Golden Mile
17. Mt Charlotte
18. Mt. Percy
Mt Pleasant
19. Lady Bountiful
20. Golden
Kilometre
21. Racetrack
Paddington
22. Paddington
23. Panglo
Kanowna
10. White Feather
11. Kanowna Belle
B
o
u
ld
e
r


F
.
A
n
tic
lin
e
K
a
n
o
w
n
a
B
o
u
l d
e
r
19
22
23
10
11
16
17
18
20
21
4
6
2
9
5
7
8
12
13
14
15
Figure 4: Geologic map of part of the Norseman-Wiluna greenstone belt in Western
Australias Yilgarn Craton, showing major early D1 folds and coeval thrusts in relation
to locations of all known gold deposits containing >10 tonnes of gold. Production +
reserves in the map area exceed 2100 tonnes gold. Fold and fault distributions in the
goldfields and this lithologic base-map are compiled from many published sources. Nearly
all published studies discussing structural controls on ore location in this region have
postulated that formation of major gold deposits requires major faults as hydrothermal
plumbing. The Boulder and Lefroy Faults are generally supposed to be the main fluid
conduits along the Kalgoorlie-Kambalda trend. Simplified maps showing all major gold
deposits from Victory to Paddington lined up on the Boulder-Lefroy Fault may seriously
mislead exploration based on assumed structural controls. Of 23 gold deposits on the map,
20 lie on or near the crests of anticlines, including all four giant deposits having 100
tonnes contained gold (Victory-Defiance, Kanowna Belle, Golden Mile, and Mt Charlotte),
and including the largest 6 of the 7 goldfields. No deposit is on the Lefroy Fault; the
Boulder Fault encounters only New Celebration and Jubilee where it intercepts the crest
of the D1 anticline. Except for three shear-zone deposits not on anticlines (Cave Rocks,
Paddington, Panglo), the deposits formed in minor faults on or near crests of early, major
anticlines generated penecontemporaneously with diapiric emplacement of major granitoid
batholiths. Coeval synclines are conspicuously unproductive.
ORE SYSTEM STUDIES
155
Chert is another common rock type that behaves more plastically than interlayered basalt and
shale. Chert and komatiite units typically were deposited with lateral extents of hundreds or
thousands of square kilometres in subsiding Archean volcano-sedimentary trough-basins. Their
broad extent and relatively plastic mechanical properties permit those rock types to play
important roles in focussing regional-scale fluid flow by diverting fluids into permeable rock
layers. The flow up both sides of a kilometre-scale fold converges in the crest of the fold, so
fold crests should be sites of fluid accumulation, and sites of gold accumulation if the fluids
carry dissolved gold.
A global survey seeking field evidence in support of this conjecture has identified many
persuasive examples of fold-focussed fluid migration in gold-producting granite-greenstone
terrains of Archean cratons, wherein the geochronologic, geochemical and structural data are
consistent with a predominantly metamorphic origin of the gold-mineralising hydrothermal
fluids. An example from the main producing region of Australia is shown here as Figure 4.
Other major producers from fold crests (anticlines) in Western Australia include the Norseman
and Mount Magnet goldfields. With >1800 tonnes of recoverable gold, the Porcupine goldfield
in Ontario is Canadas most important; its major producers Hollinger-McIntyre and Dome-
Preston, as well as lesser mines are located along the crest of the Central and South Tisdale
anticlines. In Ontarios other two largest goldfields, Hemlo (~630 tonnes gold) and Red Lake
(>600 tonnes), the main lodes are on kilometre-scale anticlines. Most gold production from the
Zimbabwe craton has come from the Midlands greenstone belt, wherein the major producers
the Cam and Motor, Golden Valley, Globe and Phoenix, Gaika, and others lie along the ~100-
km-long Kadoma anticline. Most of South Africas greenstone gold production is from the
Barberton goldfields (>250 tonnes gold), mainly from the Sheba and Fairview mines, which lie
along a shear system following the axial trace of the Sheba-Barbrook anticline. In the Archean
So Francisco craton, Brazils most important gold deposits Morro Velho, Raposas, and
Cuib (~630 tonnes of gold) lie atop the 80-km-long Rio das Velhas-Mariana anticline, and the
So Bento and Santa Quiteria mines (~100 tonnes gold) lie atop the next anticline eastward in
the fold series.
Structural and deformation controls on fluid flow and ore genesis, St Ives Goldfield,
Western Australia
S.F. Cox and K. Ruming
1
Ongoing structural, microstructural and hydrothermal alteration studies of a major group
of Archaean gold deposits in the St Ives Goldfield (south of Kambalda, WA) aim to advance our
fundamental understanding of the coupling between crustal deformation processes, crustal-scale
fluid flow and ore genesis. The project is also providing new understandings of the influence of
high fluid fluxes on mechanics of faults and shear zones at depths at which major earthquakes
nucleate in continental crust.
Major developments in the past year include:
Recognition of kilometre-scale variations in intensity of veining associated with
mineralised shear systems. These variations are interpreted to reflect variations in the
pore fluid factor (the ratio of pore fluid pressure to overburden pressure) in the gold-
producing hydrothermal system in response to lateral and vertical variation in fluid
flow rates.
Increasing recognition of the role of competence contrast between rock units as a key
factor localising fracture growth, permeability enhancement and ore deposition.

1
Department of Geology, The University of Newcastle, NSW
RESEARCH SCHOOL OF EARTH SCIENCES ANNUAL REPORT 1999
156
The recognition of multiple styles and episodes of hydrothermal alteration in some of
the major ore-hosting structures, together with documentation of overprinting
relationships between alteration assemblages, are providing insights about the
dynamics of fluid flow and interactions between various fluid reservoirs during gold
mineralisation.
A 3D visualisation of all the geological (outcrop and drill core) data and gold assay
data for the Victory Complex has been completed and will form the basis for
numerical modelling and analysis of fluid flow in this major gold system.
An important result has been the recognition that contractional jogs, and not just dilational
jogs, can be a key factor localising fluid flow to restricted parts of fault systems. In the St Ives
goldfield, low displacement imbricate thrust systems have developed around a contractional jog
on the much larger displacement, strike-slip Playa Fault. Intense shearing and associated
fracturing has generated a high permeability damage zone around the contractional jog and
localised some of the major gold deposits in the St Ives goldfield. The damage zone of low
displacement reverse faults and shear zones extends up to several kilometres away from the jog
on the Playa Fault.
By analogy with the modern distribution of seismic activity around major fault systems,
low displacement structures which host gold mineralisation in the St Ives area are interpreted to
be aftershock structures generated in association with major slip events on the Playa Fault and
the nearby Boulder-Lefroy Fault. Modelling of stress transfer associated with seismogenic slip
on modern active faults has recently been used successfully to predict the distribution of
aftershocks around larger seismogenic faults (Stein, 1999). We are exploring the application of
stress transfer modelling in analysing the distribution of low displacement, gold-hosting fault
systems around crustal-scale shear zones.
Origin and composition of ore-forming fluids in the giant Golden Mile gold deposit,
Kalgoorlie Western Australia
C.J. Heath, J.M. Palin and I.H. Campbell
Archaean greenstone-hosted mesothermal gold deposits are an important source of gold
throughout the world. The Yilgarn craton in Western Australia is host to many significant
deposits of this style, with the giant Golden Mile deposit by far the largest. Although the
Golden Mile is often referred to as the type example for this style of mineralisation in Australia,
it is fundamentally different in size, metal budget, mineralogy and structural control on lodes
from other Archaean mesothermal gold deposits.
The aim of this study is to acquire fundamental scientific data from the giant Golden Mile
deposit and establish the origin and composition of the auriferous ore forming fluids. Proposed
analytical techniques include; fluid inclusion studies, mineral trace element geochemistry by
laser ablation ICP-MS, hydrogen, oxygen, sulphur stable isotopes and lead radiogenic isotopes.
A geochronological study to determine absolute age of gold mineralisation is also proposed.
Multiple mining leases have previously limited research at the Golden Mile to areas
controlled by separate companies. This project will be the first to examine the Golden Mile in
its entirety. The project is supported through the SPIRT program in collaboration with
Kalgoorlie Consolidated Gold Mines.
ORE SYSTEM STUDIES
157
Reversed magmatic differentiation trends of strontium and yttrium in water-rich magmas
parental to magmatic-hydrothermal copper-gold ore deposits
R.R. Loucks and B.D. Rohrlach
In most volcano-plutonic belts along convergent margins of tectonic plates, strontium (Sr)
is preferentially incorporated in plagioclase feldspar crystals and depleted in the residual silicate
melt as crystallisation of the magma proceeds from SiO
2
-poor basaltic starting compositions to
SiO
2
-enriched derivatives. Conversely, yttrium (Y) accumulates in the residual liquid as
crystallisation of Y-poor olivine, pyroxenes, magnetite, and feldspars proceeds. Figure 5
illustrates typical trends in representative segments of the Chilean volcanic chain. Marked
decrease of the Sr/Y ratio with increasing SiO
2
is characteristic of most other segments of the
Andes and Central America, the North American Cascade volcanoes, the Aleutian island chain,
and most volcanic chains along the western Pacific margin.
However, some segments of volcano-plutonic belts, often lying at the intersection of the
arc with transform faults or thickened plateaus in the subducting oceanic plate, are exceptionally
enriched in water and water-soluble elements that presumably are released by the hydrated
oceanic crust as it dives into the planets interior. Published laboratory experiments by other
scientists have demonstrated that elevated content of water dissolved in magma disrupts the
melts polymer structure and thereby selectively retards the crystallisation of feldspars and
promotes calcium-rich feldspar compositions that are less hospitable to strontium. So we
anticipated that the Sr depletion trend illustrated in Figure 5 might become flat or reversed
during differentiation of H
2
O-rich magmas.
Conversely, published experiments have shown that, with increasing supply of dissolved
water in the magma, hornblende crystallises earlier and in greater abundance, at the expense of
pyroxenes, feldspars and magnetite. Among the major rock-forming igneous minerals,
hornblende has a singular ability to concentrate yttrium and impose an Y-depletion trend upon
the crystallising magma. So we expected that in H
2
O-rich magmatic crystallisation-
differentiation series, Y may decline as SiO
2
is enriched in successive fractions of residual melt.
In that case, the Sr/Y ratio would amplify the signal from waters role-reversal effect on Sr and Y
individually. The Sr/Y ratio is expected to evolve toward higher values during chemical
differentiation of H
2
O-rich magmas, rather than decrease as in the regions represented in Figure
5.
This expectation is confirmed in Figure 6, which shows atypical Sr/Y increase in two
regions selected from several examples we have developed in a hypothesis-testing global survey
of the trace-element geochemistry of young volcanic provinces along circum-Pacific plate
margins. This trace-element identifier of igneous rocks that represent the crystallisation-
differentiation series of exceptionally water-rich mantle-derived basaltic magmas will be of
special interest in exploration for hydrothermal ore deposits of gold, silver, and copper. Those
ores develop when the crystallising magma has accumulated sufficient residual water to exceed
its capacity to dissolve it, causing release of a water-rich fluid that scavenges the magmas
accumulation of sulphur, chlorine and trace metals such as gold, copper, silver and others, and
then carries the dissolved chemicals via fracture plumbing systems to sites where the metallic
minerals precipitate in minable concentrations.
Prospective segments in chains of volcano-plutonic complexes can be efficiently identified
using the Sr/Y index in regional reconnaissance surveys, as illustrated in Figure 6. Follow-up
exploration effort and expenditure can focus on those selected segments or individual
complexes, using the local-exploration procedure illustrated in the following article.
RESEARCH SCHOOL OF EARTH SCIENCES ANNUAL REPORT 1999
158
10
20
30
40
50
60
70
100
200
300
400
500
600
700
800
45 50 55 60 65 70 75 80
45 50 55 60 65 70 75 80
22-26S Central Volcanic Zone
39-43S Southern Volcanic Zone
Chilean Andes
Quaternary Volcanoes
Crustal thickness
~30-35 km
Crustal thickness
~50-60 km
SiO
2
(wt %)
S
r

(
p
p
m
)
Y

(
p
p
m
)
Figure 5: (Top) A compilation of data from many published studies shows that the
strontium content (parts per million) in volcanic rocks decreases as weight percent silica
increases during crystallisation-differentiation of magmas in two segments of the Chilean
Andes. (Bottom) Yttrium measurements in the same samples show that Y accumulated as
the magma evolved to higher SiO
2
in sub-volcanic magma chambers that were sampled by
volcanic eruptions at varied stages of the magmas chemical evolution. Each black or grey
array represents 810 major volcanic centres, each of which spans a substantial range of
SiO
2
content. Mantle-derived basaltic magmas are thought to pause and partially
crystallise at the crust-mantle boundary. In the Southern Volcanic Zone (black symbols),
the boundary is at relatively shallow depth, and the modest pressure there permits early
saturation with plagioclase feldspar, which depletes Sr from the residual magma as
crystallisation proceeds. In contrast, magma pausing at 5060 km depth in the central
Andes (grey symbols) crystallises less plagioclase and later, due to the higher pressure.
That retardation shifts the Sr-depletion trend to higher SiO
2
values. The black array in the
bottom diagram illustrates efficient residual accumulation of Y during magma
crystallisation at modest depth in and beneath thin continental crust. The grey array in the
bottom diagram illustrates diminished efficiency of Y accumulation. The diminished
efficiency is attributable to extraction of some Y into crystallising aluminium-rich
clinopyroxene, hornblende, and possibly garnet. Those minerals are stabilised by the
higher pressures at the base of thicker crust in the Central Volcanic Zone of the Andes.
Nevertheless, the erupted magmas (mainly pyroxene-andesites and -dacites, with minor or
no hornblende) show similar trends of Sr depletion and Y enrichment in both segments,
regardless of the different crustal thickness.
ORE SYSTEM STUDIES
159
H
2
O
-
r
i
c
h
m
a
g
m
a
s
0
50
100
150
200
Mindanao North of Cotabato Suture
Mindanao South of Cotabato Suture
Sangihe Intra-Oceanic Island Arc
SiO
2
(wt %)
H
2
O
-
r
i
c
h
m
a
g
m
a
s
H
2O
-
magmas
trend
p
o
o
r
Tampakan-T'Boli
Unmineralised
0
50
100
150
200
45 50 55 60 65 70 75
22-26S Unproductive
26-30S MaricungaEl Indio
Tambo Gold-Copper Belt
32.5-34.5S Los Pelambres
El Teniente Porphyry Copper Belt
36-43S Unproductive
Central Chile
Miocene Gold-
Copper Belt
North & South Chile
Unproductive Mioc. Belts
H
2 O
-
m
a
g
m
a
trend
p
o
o
r
45 50 55 60 65 70 75
Chilean Andes
Southern Philippines
Copper-Gold Belt
S
r
/
Y
S
r
/
Y
Figure 6: The upper diagram shows two contrasting trends of the Sr/Y ratio in three
segments of the 770-km-long Central Mindanao/Sangihe island-arc volcanic chain. The
north Mindanao and southerly Sangihe island-arc segments contain no known significant
hydrothermal gold-copper ore deposits, but they bracket an intervening segment comprising
several volcanic complexes in southern Mindanao that contains major copper and gold ore
deposits produced by hydrothermal fluids exsolved from crystallising magmas. The
contrasting behaviour of the Sr/Y ratio in the productive (black diamonds) and unproductive
(circles and crosses) arc segments indicates that the productive magmas were exceptionally
rich in dissolved water throughout the course of magma crystallisation. (Most black
symbols represent Tampakan volcano samples analysed by laser-ablation ICPMS by B.D.
Rohrlach; other data points are analyses compiled from many literature sources.) The
bottom diagram illustrates a similar case in the Chilean Andes, where a rich mineral belt
with many gold mines in the 2630S latitude interval and 3 giant porphyry-copper mines
at 32.534.5S is bracketed to the north and south by long chains of igneous complexes
of similar age that formed no known minable ore deposits during the Miocene epoch (24 to
5 million years ago). All available published analyses of fresh volcanic and sub-volcanic
rocks along the Miocene arc front within each latitude interval are included in the plot.
RESEARCH SCHOOL OF EARTH SCIENCES ANNUAL REPORT 1999
160
Application of the Sr/Y ratio to exploration for intrusion-related copper-gold ore deposits:
discrimination of productive from unproductive stocks in sub-volcanic intrusive complexes
R.R. Loucks, J. Ballard and I.H. Campbell
At scales on the order of 100 km or so encompassing several nearly volcano-plutonic
complexes, eruptive rocks often show similar trends in the behavior of the Sr/Y ratio during
magmatic crystallisation-differentiation preceding eruption. But contemporaneous intrusive
rocks in the same regions display much less coherence in their Sr/Y trends, so attention to the
differences among individual intrusions is required for discrimination of the prospective ones.
The greater regional coherence of volcanic rocks, which simplifies regional target selection,
probably reflects a tendency of volcanic eruptions to provide a sampling bias toward eruption of
water-rich magmas. Exsolution of hydrothermal fluid from a crystallising magma is
accompanied by a substantial expansion of the magmas volume as melt melt+bubbles, which
often triggers volcanic eruptions, spewing the sulphur and metals into the atmosphere and across
the landscape, instead of making an ore deposit. Infrequently, exsolution of magmatic
hydrothermal fluid occurs in a shallow magma body that is sufficiently small, or in a larger
magma body that is buried sufficiently deep that the magmas volume expansion is
accommodated by deformation of enclosing rocks, without triggering a volcanic eruption. Such
bodies of un-erupted magma can generate ore deposits that are usually associated regionally and
temporally with areally extensive volcanic rocks sharing the elevated Sr/Y chemical signature of
ore-productive magma in the same volcanic-intrusive composite igneous complexes. Magma
bodies can also fail to erupt if they contain too little dissolved water to exsolve a significant
volume of hydrothermal fluid at any stage of crystallisation. These become barren intrusives. In
other cases, relatively H
2
O-poor magmatic differentiation series may eventually exsolve a
magmatic hydrothermal fluid after the magma has already precipitated most of its copper and
precious metals as igneous sulphide crystals, in which case the hydrothermal fluid exsolving late
from metal-stripped silicate melt may be too impoverished in ore metals to make an ore deposit.
We show here that the Sr/Y ratio in intrusive granitoid rocks is useful in discriminating those
bodies incapable of making ore from those that contained sufficient H
2
O over the course of
igneous crystallisation to have a high probability of releasing an ore-producing magmatic
hydrothermal fluid.
Figure 7 shows our ICPMS measurements of the whole-rock Sr/Y ratio in 19 samples
from ore-productive and barren intrusives spatially and temporally associated with the giant
Chuquicamata porphyry copper deposit in northern Chile. The three productive stocks (black
squares) are distinguished from unproductive intrusives at Chuquicamata (open squares) by low
contents of whole-rock yttrium and generally higher Sr/Y ratios. The Chuquicamata data are
compared with our compilation of data from many published literature sources describing
productive and barren intrusives associated with other porphyry copper-gold deposits in the
Andes and in Arizona and the South Pacific. Figure 7 shows that plots of Sr/Y against Y are
remarkably successful in sorting ore-productive intrusives from spatially associated intrusives of
similar age that failed to generate ore. Most productive intrusives (black symbols) have low
contents of whole-rock Y and Sr/Y > 40, whereas unproductive intrusives (blank symbols) plot
in the lower right-hand side of the array. Comparison of this plot with Figures 5 and 6 of the
previous article indicates that the arrays in Figure 7 are composites of two opposing magmatic
differentiation trends. Parental basaltic magmas with initial Sr/Y 30 and relatively low initial
H
2
O evolved toward lower Sr/Y and higher Y as crystallisation-differentiation proceeded toward
derivative magmas of granitoid compositions. Parental basaltic magmas with initial Sr/Y also
around 30 but with relatively high initial H
2
O contents evolved toward granitoid derivatives with
low Y and high Sr/Y, due to the effects of dissolved magmatic H
2
O on hornblende and
plagioclase stability, as described in the preceding article.
Having selected a prospective region according to Sr/Y criteria described in the previous
article, the explorationist could conduct follow-up sampling of those regions at higher spatial
resolution for chemical analysis of intrusive rocks, and then select specific drilling targets using
the Sr/Y indicator in the manner shown in Figure 7.
ORE SYSTEM STUDIES
161
0
50
100
150
200
0 5 10 15 20 25 30 35 40
Y (ppm)
Cerro Verde
El Abra
Chuquicamata
El Salvador
Potrerillos
Rio Blanco-Los Bronces
El Teniente
Bagdad
Ray-Christmas
Safford
Copper Creek
Diamond Joe
Tombstone
Chile & Peru Arizona
UNPRODUCTIVE STOCKS
PRODUCTIVE
STOCKS
0
50
100
150
200
0 5 10 15 20 25 30 35 40
Plesyumi
Kulu
Usilau
Yandera
Frieda River
Panguna
Koloula
New Guinea Mobile Belt
New Britain
Solomon Islands
UNPRODUCTIVE STOCKS
PRODUCTIVE STOCKS
S
r
/
Y
S
r
/
Y
Figure 7: The ratio of parts per million strontium to yttrium is plotted against parts per
million yttrium in whole-rock analyses of representative, relatively alteration-free samples
of intrusive igneous rocks spatially and temporally associated with porphyry copper-gold
ore deposits in three of the worlds most productive regions. Black symbols identify
samples of intrusives that released an ore-forming magmatic-hydrothermal fluid during
crystallisation. Blank symbols of the same shape identify samples in the same district of
spatially and temporally associated intrusives that failed to make ore. Data for
Chuquicamata were generated for this study (J. Ballard, analyst), whereas other data are
compiled from many published sources. Although there is some overlap of the data arrays
for barren and ore-productive intrusives, the Sr/Y ratio is shown to be remarkably effective
in sorting prospective intrusives from ones likely to be a waste of exploration
expenditures.
RESEARCH SCHOOL OF EARTH SCIENCES ANNUAL REPORT 1999
162
Fluid flow within a volcanic-centred, magmatic hydrothermal system A district-scale
whole-rock oxygen-isotope study
B.D. Rohrlach, J.M. Palin and R.R. Loucks
The Tampakan porphyry-epithermal copper-gold deposit in southern Mindanao
(Philippines) is hosted by a Pliocene age, erosionally truncated stratovolcano. This andesitic
volcanic centre was the focus for a large magmatic hydrothermal system which formed both
porphyry and epithermal copper-gold mineralisation. Current models for formation of high-
sulphidation epithermal copper-gold ores involve condensation of metalliferous volcanic vapours
and mixing of those magmatic fluids with overlying, shallow, meteoric ground-water flow
systems high in the superstructure of volcanic edifices. Widespread intensive alteration of
volcanic rocks by sulphuric-acid-rich fluids accompanies silicification and metal deposition by
these shallow-level fluid mixing processes.
This study is utilising oxygen-isotope data from 137 whole-rock samples collected over
an area in excess of 200 square kilometres, to investigate the interaction between magmatic fluids
and meteoric ground-water in a volcanic-centred magmatic hydrothermal system. Oxygen-
isotope (
18
O) data are being acquired on a conventional oxygen line using bromine
pentafluoride as the reaction agent to extract O
2
gas. The oxygen-isotope data is being
integrated with major-element compositional data acquired by electron microprobe analyses of
synthetic glasses made from fused aliquots of the whole-rock powders, and with district-scale
alteration mineralogy defined by whole-rock infra-red spectroscopic analyses. The study seeks
to understand the hydrological structure of a volcano-centred magmatic hydrothermal system
though determination of the relative influence of isotopically contrasting magmatic versus
meteoric water induced alteration in different portions of the volcanic centre, by mapping of
regions where fluids are migrating up or down a thermal temperature gradient, determination of
the total fluid flux required to shift
18
O values to those observed, and by understanding the
spatial variation in time-integrated cumulative fluid-rock ratios.
Whole-rock major-element compositional data for each sample are being used to estimate
an oxygen isotope fractionation factor for each whole-rock sample, thus allowing
mineralogical/oxide compositional variability to be taken into account during interpretation of
oxygen-isotope (
18
O) variation within the district. Preliminary data acquisition indicates there
is sufficient variability in the whole-rock data-set to enable a district-scale oxygen stable isotope
study of the Tampakan hydrothermal system and the effects of palaeo-topography on magmatic-
meteoric ground-water interaction.
Magmatic oxidation state inferred from REE systematics in zircon
J. Ballard, J.M. Palin and I.H. Campbell
The western margin of the South American Plate has been associated with continental
subduction since the early Jurassic. This tectonic setting has produced magmatic belts of calc-
alkaline character in north Chile. In the Chuquicamata area, crustal scale structures may have
acted as suitable conduits for these magmas to reach shallow levels in the crust where they
produced large magmatic-hydrothermal systems.
This study sets out to understand the conditions that are favourable to the formation of
world class copper deposits and in particular, the role of the oxidation state of the magma in ore
formation. To achieve this, zircons were analysed by ELA-ICP-MS using NIST 612 as the
standard. Ten grains from each sample were analysed from the three mineralised Chuquicamata
mine porphyries and six barren regional intrusive units. The concentration of divalent, trivalent
and tetravalent cations were measured in each of the zircons. The estimated Ce
4+
to Ce
3+
ratios
in zircons from the various units were calculated from the observed Ce concentration (from
ELA-ICP-MS) and the predicted concentration for Ce
3+
from the trivalent REE trend and Ce
4+
from the tetravalent hafnium-thorium-uranium trend. Similarly, the Eu
3+
:Eu
2+
ratio was
ORE SYSTEM STUDIES
163
calculated from the measured Eu concentration and the predicted concentrations of pure Eu
3+
and Eu
2+
based on the trivalent and divalent trends respectively.
Initial findings support a positive correlation between the mineralised ore-bearing units in
the Chuquicamata mine and the oxidised magmas, as illustrated by Figure 8. Based on these
observations, the oxidation state of the magma appears to exert a control on the fertility of calc-
alkaline magma systems. If this control proves to be critical, it may be possible to use zircon
geochemistry to distinguish between ore-bearing and barren systems. This is potentially of
great economic significance because zircon is a resistate mineral which survives weathering and
is resistant to abrasion.
0
20
40
60
80
100
30 33 36 39 42 45
Ore-bearing
Z
i
r
c
o
n

C
e
4
+
/
C
e
3
+
Age (Ma)
Unproductive
Figure 8: Zircon Ce
4+
:Ce
3+
ratios in three ore-bearing intrusives and five unmineralised
intrusives from the Chuquicamata district of northern Chile. Each point represents the
average of 10 replicate ELA-ICP-MS analyses of zircon from the 8 units studied.
High precision U-Pb zircon geochronology of multiple igneous events in the super-giant
Chuquicamata porphyry copper deposit, Chile, byELA-ICP-MS and SHRIMP methods
J. Ballard, J.M. Palin, I.H. Campbell and I. Williams
The Chuquicamata mine is historically the worlds largest copper producer and has been
in operation for the last 85 years. The deposit is located in the Precordillera of north Chile at the
southern end of the 12 by 11.5 km northerly trending Chuquicamata Intrusive Complex. The
mineralised eastern section of the mine consists of three intrusives the East, West and Bench
porphyries. Barren Fortuna Complex is juxtaposed against the productive section of the deposit
by the West Fissure, a 37 km net sinistral displacement strike-slip fault.
Previous
39
Ar-
40
Ar studies suggest that more than one hydrothermal event may have
affected Chuquicamata. However, there are no precise igneous ages on the three mineralised
porphyries and therefore the time evolution of the igneous system remains unclear. The purpose
of this study was to test an hypothesis that Chuquicamata is a super-giant deposit because two
or more discrete igneous and hydrothermal events have contributed to its formation. That is,
Chuquicamata is two, and possibly three, superimposed porphyry copper deposits.
The technique used to date the porphyries in this study was U-Pb dating of zircons by
ELA-ICP-MS. This method has three important advantages over alternative techniques. Firstly,
RESEARCH SCHOOL OF EARTH SCIENCES ANNUAL REPORT 1999
164
U-Pb systematics in young zircon are highly resistant to hydrothermal resetting. Secondly, the
ELA-ICP-MS is a micro-beam technique that allows grains with inherited cores, which have
been found in the Chuquicamata porphyries, to be identified and rejected. Finally, the ELA-ICP-
MS is a fast and low cost method for dating young igneous rocks at high precision.
The reliability of the data produced by this technique are confirmed by comparison with
SHRIMP dating of the same samples, as illustrated in Figure 9. The results for the two methods
are comparable but ELA-ICP-MS consumes more material and more analyses are required to
achieve equivalent precision.
Bench Porphyry
140 150 160 170 180 190 200 210 220
2
0
7
P
b
/
2
0
6
P
b
0.02
0.04
0.06
0.08
40 30 35
0.10
0.00
238
U/
206
Pb
Figure 9: A Tera-Wasserburg plot of Chuquicamatas Bench Porphyry. SHRIMP
204
Pb
corrected and EELA-ICP-MS
208
Pb corrected data compared.
The identification of ancient mantle plumes
I.H. Campbell
Ancient mantle plumes can be recognized from uplift prior to volcanism, the orientation of
dikes that feed the volcanism, the nature of the physical volcanism, age progressions along
volcanic chains and the chemistry of the magmas they produce. The thermal anomaly
introduced by arrival of a plume head beneath continental crust leads to widespread uplift. A
plume head, with an average temperature excess of 100C, will produce 500 to 1000 m of uplift
prior to volcanism over an area slightly smaller than the flattened plume head. During
volcanism, the surface onto which the lavas erupt subsides due to deflation of the underlying
mantle as melt is removed to produce the basalts. However, this is balanced by the eruption of
basalt onto the surface so that the net additional change in the surface level due to volcanism is
small, and may be positive or negative depending on geometric considerations. Uplift is
followed by gradual subsidence as the mantle thermal anomaly decays over a period of ~1 Ga.
The domal uplift associated with emplacement of a plume head leads to extension around
the circumference of the dome and to the formation of radial dyke swarms, provided there is no
external force acting on the region. If there is a pre-existing external force, the dikes will tend to
partially reorientate perpendicular to that force to produce radiating dikes.
The physical volcanology of plume basalts is characterized by massive flows that can be
correlated over large distance. They contrast with island arc basalts, which consist dominantly of
pyroclastics that are difficult to correlate over large distances, and with MORBs, which are found
ORE SYSTEM STUDIES
165
only in ophiolite sequences. Chains of volcanoes, which are produced by melting plume tails,
show systematic age progressions that are diagnostic of mantle plumes.
The chemistry of plume magmas reflects their origin in anomalously hot zones in the
mantle. High temperature magmas, such as picrites and komatiites, and high-pressure magmas
such as alkali basalts, nephelinites and type-1 kimberlites, are characteristic of plumes. The high
liquidus temperatures also leads to high Cr in olivines and to high Ni at a given MgO content in
plume basalts. Chondrite normalized trace element patterns that are strongly LREE enrichment,
with no Nb, Ta or Ti anomaly, are found only in plume basalts, but not all plume basalts share
these features.
Geochemistry of the igneous suite associated with the Kelian gold deposit, Indonesia
B. Setiabudi and I.H. Campbell
The Kelian gold deposit is an intrusive-related low sulphidation system, situated within the
Central Kalimantan Continental Arc which consists of andesitic-trachyandesitic volcanics and
intrusives of Late Oligocene Middle Miocene age. The hydrothermal mineralisation is
hosted by a series of intercalated felsic tuff and volcaniclastic sediments intruded by andesite
stocks. One of the aims of the study was to test a hypothesis that the auriferous fluid at Kelian
is the product of fractional crystallisation of an igneous body at depth which is the parent to the
felsic rocks that host the ore. Unfortunately it is not possible to make such a study of rocks
from the mine area because they are highly altered so that many major elements, including Si, Na
and K, have been extensively mobilised. However, similar rock sequences occur in the
southwestern area (Nakan) and the northwestern areas (Magerang and Imang) which show little
evidence of alteration and are suitable for a detailed geochemical study.
The Magerang-Imang intrusives are of low K to medium K andesite and have well-
defined, linear trends when major and trace elements are plotted against SiO
2
over an SiO
2
range
of 56 to 64 wt%, suggesting that chemical variations within the suite are controlled by crystal
fractionation. MgO, Fe
2
O
3
, TiO
2
and CaO decrease and Na
2
O, K
2
O and P
2
O
5
increase with
increasing SiO
2
. Highly incompatible elements such as La, Th, Zr and Hf also increase with
increasing SiO
2
, but weakly incompatible elements show no increase and some, such as Sm, Ho
and Y actually decrease.
Within the mine area, silica has been mobilised by hydrothermal alteration so it can not be
used to monitor fractional crystallisation. However, in the unaltered samples from Magerang,
highly incompatible elements, such as Th correlate with SiO
2
. Because Th is much less mobile
than SiO
2
during hydrothermal alteration it has been used as monitor of fractionation for the
altered mine samples. In the least altered samples from Magerang immobile elements, such as
U, Zr, Hf, Y, Nb, Ta and REE, increase with increasing Th concentration. The plots for Kelian
samples show similar trends for immobile trace elements, suggesting that the two suites are
closely related. However, the data are much more scattered in the altered andesite from the mine
area indicating that alteration has produced some mobility for elements that are normally
regarded as immobile. The range of Th values is much greater in the mine sequences and is
probably a factor of 10 greater than that in the unaltered samples. This suggests that the Kelian
rocks have undergone a much greater range of fractional crystallisation than the Mayerang
samples. Quantitative modelling of the effects of fractional crystallisation on the trace elements
is in progress.
Future laboratory works will include geochemical analysis on the other least altered
samples from Magerang and Kelian mine areas to extent the fractionation range in both areas
and to test the correlation between the regions. The correlation will be further tested by U-Pb
dating of zircons from both areas. PGE and gold analysis will be carried out to study the effect
of fractional crystallisation in concentrating PGE and gold.
RESEARCH SCHOOL OF EARTH SCIENCES ANNUAL REPORT 1999
166
The sulphide capacities (C
S
) of haplobasaltic and basaltic silicate melts at 1400C and 1 bar
J.A. Mavrogenes and H.StC. ONeill
Fincham and Richardson (1954) showed that sulphur dissolves in silicate melts at low
oxygen fugacities (fO
2
< QFM) as S
2-
, and does so by replacing O
2-
on the anion sublattice, as
described by the reaction: O
2-
+ 1/2 S
2
= S
2-
+ 1/2 S
2
. This suggests the relationship: [S] = C
S
(fS
2
/fO
2
)
0.5
where [S] is the sulphur content of the melt (conveniently in ppm) and C
S
is the
sulphide capacity of the melt, which may be thought of as an equilibrium constant, and is a
function of melt composition as well as temperature and pressure. Fincham and Richardson
(1954) experimentally verified the (fS
2
/fO
2
)
0.5
relationship for simplified metallurgical slag
compositions in the system CaO-Al
2
O
3
-SiO
2
(CAS) by varying fS
2
. and fO
2
independently at
1 atm. Subsequent work has repeatedly confirmed the validity of the Fincham and Richardson
model for other simple metallurgical slag compositions, but there is only limited information on
the solubility of sulphur in silicate melts relevant to geology.
Obviously C
S
only has meaning if the (fS
2
/fO
2
)
0.5
dependence shown by Fincham and
Richardson (1954) is obeyed. While this relationship has been confirmed for an Hawaiian
tholeiite composition by Katsura and Nagashima (1974), other studies (Haughton, D. et al.,
Economic Geology, 1974; Buchanan, D.L. and Nolan, J., Can. Mineral., 1979) have shown
disturbing deviations from the relationship, which, if real, would demand a fundamental
rethinking of the sulphide solubility theory as developed by the metallurgists. Moreover, there
are apparent inconsistencies in the geological studies that presently preclude the development of
a quantitative model relating sulphide solubility to melt composition.
Accordingly we have embarked on a program to study experimentally sulphur solubilities
in silicate melts under controlled fO
2
and fS
2
, firstly to test the (fS
2
/fO
2
)
0.5
relationship over a
wide range of silicate melt compositions, and hence, if the relationship is confirmed, to determine
the compositional dependence of Cs. Initially experiments have been undertaken at the relatively
high temperature of 1400C to access as wide a range of compositions as possible.
Experiments were conducted in a conventional vertical tube furnace equipped for gas
mixing, using CO
2
-CO-SO
2
mixtures to impose fO
2
and fS
2
, delivered by commercial mass
flow controllers. The performance of the controllers was tested repeatedly during the
experimental campaign by calibrating their flow rates using the moving bubble method, and the
CO
2
and CO flows were further tested in situ using zirconia oxygen sensors. The oxygen
sensors deteriorate rapidly in the S atmosphere at 1400C and could not be used to monitor gas
mixtures continuously. In fact, the major experimental problem in studies of this type is
condensation of solid sulphur on the cool parts at the top of the furnace, which may then fall off
into the hot part of the furnace, greatly increasing fS
2
over that calculated from the gas mixture.
To minimise this, we established for a range of compositions the time needed to reach steady
state S solubilities, and took care not to exceed this time too much. The furnace was cooled
down and the inside of the muffle tube cleaned between each run.
Four strategies were used for investigating the effect of melt composition on sulphur
solubility. For the first strategy, we selected for study seven near-eutectic compositions in the
CMAS system, plus compositions along the join CaAl
2
Si
2
O
8
-CaMgSi
2
O
6
(anorthite-diopside).
Secondly, starting with anorthite-diopside eutectic as the base composition, we added the
following components: SiO
2
, MgSiO
3
, CaSiO
3
, Mg
2
SiO
4
, FeO, Fe
2
SiO
4
, TiO
2
, NaAlSi
3
O
8
. The
compositional range of these pseudo-binary joins extended either to the pure component where
this melts below 1400C, or to the level at which the melt becomes saturated in the component at
1400C (eg ~15% for Mg
2
SiO
4
, ~60% for CaSiO
3
). Thirdly, we studied an assortment of
natural melt compositions spanning a range of FeO contents. Lastly, we have attempted to
replicate some measurements on melt compositions studied by previous investigators.
Samples were hung on Pt loops (or Re or Fe-Ir loops for Fe-bearing compositions), and
run generally six at a time. Quenching was by dropping into water. Samples were analysed by
electron microprobe using WDS and a troilite standard for S. EDS was used to confirm major
ORE SYSTEM STUDIES
167
element compositions. As expected, alkali loss and Fe loss into Pt loops were pervasive
problems.
The results were fitted by a global non-linear least squares regression to an expression of
the form: [S] = (fS
2
/fO
2
)
0.5
A
M
[MO
x
] where MO
x
are the oxide components of the melt (in
wt%), and the coefficients A
M
are used to describe the compositional dependence of C
S
. The fit
to the data shows that the (fS
2
/fO
2
)
0.5
relationship is followed by all compositions. We find A
Fe
> A
Ca
>> A
Mg
> A
Ti
with the coefficients for other oxide components (SiO
2
, Al
2
O
3
, Na
2
O) being
effectively zero. The magnitude of AM correlates roughly with the magnitude of the free
energies for the reactions: MO
x
+ 1/2x S
2
= MS
x
+ 1/2x S
2
for M = Fe, Ca, Mg, Ti, Al and Si,
but this relationship breaks down completely for the alkalis, for which it would predict A
Na
or A
K
to be large, rather than negligible as observed.
Our results are not in good agreement with the previous work of Buchanan and Nolan or
Haughton et al. (1974), although allowance needs to be made for the different temperature of the
latter study. Nevertheless, we find a much higher value of A
Fe
, indicating that FeO has a stronger
influence on CS than hitherto thought. Our very high value of A
Fe
helps explain the empirical
observation that the Sulphur Content at Sulphide Saturation (SCSS) of natural melts increases
with increasing [FeO] in the melt, despite the simple prediction from the law of mass action for
the reaction: FeO
(melt)
+ S
2-
(melt)
= FeS
(sulphide)
+ O
2-
(melt)
that increasing FeO in the melt should
correlate with lower SCSS.
Experimental investigations of Cu in magmatic-hydrothermal systems
A.C. Hack and J.A. Mavrogenes
Cu solubility in supercritical and two-phase aqueous solutions
It has long been recognised that supercritical hydrothermal fluids must play a major role
in fractionating and transporting metals in geological systems. Unfortunately, the nature of the
high-temperature fluid is poorly understood. This is primarily because of the difficulties in
constructing high-temperature experimental reaction cells for in situ analysis that can withstand
high vapour pressures. New techniques, such as ELA-ICP-MS of fluid inclusions, now allow
this region of pressure-temperature space to be investigated (eg Loucks and Mavrogenes 1999).
The limited data for Cu solubility in supercritical fluids come from analysis of quenched
experimental solutions. The possibility of modification of these solutions during the quenching
process means that it is not known if they truly are representative of the experimental
conditions. Fluid inclusion synthesis gets around this problem by isolating the solution at the
run conditions (Figure 10). An experimental project to investigate the solubility and partitioning
of Cu under a range of conditions by trapping supercritical, and coexisting vapor- and liquid
inclusions, combined with analysis by LA-ICPMS, is currently being undertaken.
RESEARCH SCHOOL OF EARTH SCIENCES ANNUAL REPORT 1999
168
Figure 10: Synthetic fluid inclusions trapped in quartz at 700
o
C and 2.9 kb under
supercritical conditions.
Cu partitioning between silicate melt and co-existing vapor
Our understanding of hydrothermal systems originating from magmatic volatile
exsolution, such as porphyry-type ore deposits, is limited by data for the initial melt-vapor
fractionation of metals. A series of experiments to quantify melt-vapor partitioning is currently
in progress. The method involves the synthesis of coexisting melt- and vapor inclusions at
various experimental conditions and subsequent analysis by ELA-ICP-MS and electron
microprobe. Examples of synthetic fluid- and melt inclusions are shown in Figures 11 and 12.
Controls on Cu solubility in silicate melts
A large proportion of worldwide Cu production comes from a class of magmatic-
hydrothermal ore deposits known as porphyries. In these systems, the entire hydrothermal
metal budget is sourced from and thus ultimately controlled by the quantity of Cu dissolved in
the melt. However, Cu dissolution mechanisms in silicate melts are not well understood and
synthetic melt inclusions are being used to investigate the relative effects of fO
2
, fS
2
, fH
2
O, and
Cl (Figure 11).
Figure 11: Synthetic melt inclusions trapped in quartz at 715
o
C and 3.0 kb under vapor-
saturated conditions.
ORE SYSTEM STUDIES
169
Speciation of ore-forming solutions at high temperature and pressure
A.J. Berry, J.A. Mavrogenes, E.R. Krausz
2
and R.R. Loucks
Hydrothermal ore deposits are the worlds principal source of most metals. The deposits
form as a result of ore-metal transport by aqueous solutions at high temperatures and pressures.
To understand the formation of these deposits, it is necessary to determine both the solubility
and speciation of each metal complex in solution. Progress in this area has been limited by the
inability of existing experimental methodologies to sample solutions at supercritical
temperatures. This problem is being addressed by studying ore-bearing fluid trapped
experimentally as fluid inclusions in quartz.
The importance of metal speciation can be illustrated by our limited understanding of the
relationship between porphyry and epithermal type deposits. The ores may derive from a single
source by partitioning of metals between a brine and vapour associated with changes in
speciation determined by ligand availability. For example, the porphyry ore may form from
copper transported as a chloride complex in a high-density brine and the epithermal from a
vapour phase volatile sulphide species. The mechanism of deposition may also be linked to the
type of metal complex dissolved in solution; boiling (loss of H
2
S) or the formation of pyrite
(loss of dissolved S) may be important precipitation mechanisms for sulphide complexes, while
cooling or dilution may result in the breakdown of chloride complexes.
Optical absorption spectroscopy is a well-established method for determining the
speciation of metal ions. The absorption bands are characteristic of each complex, or in the case
of mixed species may be deconvoluted by fitting procedures. Variations in the absorbance data
as a function of ligand concentration and temperature can be used to derive thermodynamic
properties such as the equilibrium formation constants. We are constructing a micro-optical
imaging spectrometer to obtain absorption spectra from single fluid inclusions at elevated
temperatures. This system acquires images of an inclusion at a series of illumination
wavelengths. An absorption value can be determined at each wavelength from the referenced
light intensity passing through a region inside the inclusion. Spectra have been acquired for
cobalt(II) and nickel(II) solutions in glass capillaries with an internal diameter of < 50 m.
A research program has also been established at the Advanced Photon Source, Argonne
National Laboratory, USA, to investigate speciation in fluid inclusions by extended X-ray
absorption fine structure (EXAFS) spectroscopy. Spectra have been recorded at room
temperature from individual fluid inclusions and modelled to obtain bond lengths and
coordination numbers. A heating stage has recently been commissioned and preliminary spectra
recorded at temperatures up to 500C.

2
Research School of Chemistry, ANU
RESEARCH SCHOOL OF EARTH SCIENCES ANNUAL REPORT 1999
170