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Ore fluid chemistry in super-giant porphyry


copper deposits
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Jamie J Wilkinson
Natural History Museum, London
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Ore Fluid Chemistry in Super-Giant Porphyry Copper


Deposits
1,2

J J Wilkinson , C C Wilkinson
6
7
M Zentilli and T E Jeffries

2,3

, V H Vry , B G Rusk , J Sguel ,

ABSTRACT
Laser ablation Inductively Coupled Plasma Mass Spectrometry (ICPMS) analysis of
fluid inclusions trapping mineralising solutions in major porphyry-copper deposits
indicates that copper concentrations can reach 103 - 104 ppm in both dilute, CO2-bearing
fluids and in high salinity brines. Non-Cl transport of Cu is implicated. Au has been
determined at 0.2 - 0.4 ppm in the low salinity fluids and may be co-transported with Cu.
In contrast, high concentrations of Fe, Mn, Zn and Pb are only attained in brines and
correlate strongly with Cl-indicating chloride transport. Physical and/or temporal
separation of these fluid types can therefore produce metal fractionation within porphyry
systems. Evidence concerning the behaviour of Mo is less clear but brine transport
appears to be favoured; phase separation is one mechanism that may account for the
fractionation of Mo from Cu and the formation of quartz-molybdenite veins.

INTRODUCTION
Laser ablation ICPMS analysis of fluid inclusions is providing new insights into metal budgets,
sources of metals and depositional mechanisms in porphyry deposits. Initial results are presented
from three porphyry-copper deposits: pre-Mainstage at Butte, Montana; Chuquicamata and El
Teniente, Chile.

BUTTE, MONTANA
Early, low-salinity (3 - 5 wt per cent NaCl equivalent) aqueo-carbonic fluid inclusions from porphyry
Cu-Mo-stage mineralisation at Butte (B35 inclusions: Rusk, Reed and Dilles, 2008) contain Cu
concentrations of up to 1 wt per cent (Figure 1) and Cu is, on average, the most abundant ore metal in
solution in these liquid-like, but intermediate density fluids (cf Rusk et al, 2004). The extremely high
Cu content of such low salinity fluids is anomalous. Two gold analyses of these fluids suggest
concentrations of 0.2 - 0.4 ppm and limited data show Mo concentrations of up to 100 ppm. Results
from quartz-molybdenite veins that contain essentially the same inclusion type show comparable Cu
1.

Reader in Hydrothermal Geochemistry, Department of Earth Science and Engineering, Imperial College London,
Exhibition Road, London SW7 2AZ, United Kingdom. Email: j.wilkinson@imperial.ac.uk

2.

CODES, The Australian Research Councils Centre of Excellence in Ore Deposits, University of Tasmania, Private Bag
126, Hobart Tas 7001.

3.

Department of Earth Science and Engineering, Imperial College London, Exhibition Road, London SW7 2AZ, United
Kingdom.

4.

School of Earth and Environmental Sciences, James Cook University, Townsville Qld 4811.

5.

CODELCO El Teniente, Rancagua, Chile.

6.

Department of Earth Sciences, Dalhousie University, Edzell Castle Circle, Halifax NS B3H 4J1, Canada.

7.

Department of Mineralogy, Natural History Museum, Cromwell Road, London SW7 5BD, United Kingdom.

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Mn

Fe

Cu

Zn

Pb

Mo

Au

Cu (qz-moly)

Mo (qz-moly)

Cu (barren qz)

Mo (barren qz)

Au (barren quartz)

100 000.0
Early magmatichydrothermal fluids

Metal (ppm)

10 000.0
1000.0
100.0
Pegmatite-related fluids

10.0
1.0
0.1
0

50 000

100 000

150 000

200 000

250 000

Cl (ppm)
FIG 1 - Plot of metal content as a function of chloride concentration for early magmatic fluids (B35 inclusions)
from the Butte pre-Main (porphyry) stage and from pegmatite-related fluids in the Butte Quartz Monzonite that
are not directly related to the porphyry mineralisation stage.

and Mo concentrations to vein samples dominated by copper sulfides. This implies that the
quartz-molybdenite veins formed by preferential precipitation of molybdenite from the same fluids
that elsewhere deposited copper-dominant sulfide assemblages. One sample showed evidence for
phase separation associated with molybdenite precipitation suggesting that this could be a
fractionating mechanism. Barren quartz veins also formed from fluids of the same type but which
contained, on average, lower concentrations of Cu and Mo, suggesting that these veins may have
precipitated from spent mineralising fluids. In contrast, Au concentrations in barren veins are similar
to those in Cu mineralised veins so that these fluids may have still been pregnant with Au and capable
of Au precipitation further along the flow path. Higher salinity fluids associated with a pegmatite
sample from the Butte Quartz Monzonite not directly related to the porphyry system contain
somewhat lower Cu concentrations and are particularly enriched in Fe and Mn. Overall, Cu does not
correlate with Cl content and other ore metals, and only weakly with Fe. In contrast, Fe, Mn, Pb and
Zn correlate strongly with salinity.

CHUQUICAMATA, CHILE
At Chuquicamata, intense shearing has destroyed the majority of fluid inclusions in early
magmatic-hydrothermal veins. However, aqueous inclusions are preserved in quartz eyes and in
quartz inclusions in K-feldspar megacrysts. These display wide salinity variations, partly attributable
to boiling. Copper (up to 0.9 wt per cent) is not correlated with Cl (Figure 2) and shows only a weak
correlation with Fe. Potassium, Rb, Zn, Mn, Fe and Pb are strongly correlated with Cl and are
markedly enriched in high salinity brines believed to have been produced via phase separation.

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ORE FLUID CHEMISTRY IN SUPER-GIANT PORPHYRY COPPER DEPOSITS

Mn

Fe

Cu

Zn

Pb

Mo

100 000.0

Metal (ppm)

10 000.0
1000.0
100.0
10.0
1.0
0.1
0

50 000

100 000

150 000

200 000

250 000

Cl (ppm)
FIG 2 - Plot of metal content as a function of chloride concentration for aqueous inclusions hosted by
K-feldspar megacrysts and quartz eyes from Chuquicamata Este and Banco porphyries.

Limited data suggest Mo concentrations may be highest in the brines, ranging up to 140 ppm. Overall,
the comparatively wide scatter of data reflects trapping of fluids over a protracted part of the fluid
evolution history in the deposit.

EL TENIENTE, CHILE
At El Teniente, preliminary analyses from an early magmatic-hydrothermal stage vein have identified
the presence of low, intermediate and high salinity liquids together with vapour-rich inclusions
that indicate boiling at 350 - 400C. Cu concentrations range from 290 - 1400 ppm in the brines,
140 - 550 ppm in the intermediate salinity fluids and 40 - 1300 ppm in the dilute fluids (Figure 3). Mo is
systematically enriched in the more saline fluids (up to 24 ppm) implicating brines as the main agent for
Mo transport. As at Chuquicamata, Cu concentrations are independent of salinity and may be high in
low salinity, liquid-like fluids, although the levels measured so far at El Teniente are significantly lower.

DISCUSSION
Despite some differences in the overall chemistry of the fluids from these systems, a number of
general observations can be made. Cu concentrations are generally independent of salinity and can be
extremely high, even in very dilute and typically CO2-bearing, liquid-like fluids. This implicates an
alternative complexing ligand, possibly a sulfur species (eg Simon et al, 2006). Decoupling of Cu
(and Au?) from the other base metals in all the deposits studied may be related either to direct
separation of a low salinity, CO2-bearing fluid from the melt (preferentially extracting Cu), either as a
low density vapour-like fluid that then contracts to forms a liquid-like fluid, or directly as a liquid; or
brine-vapour separation after degassing of the magmatic volatiles resulting in metal partitioning
between coexisting brine and vapour phases, followed by contraction of the vapour phase to a
liquid-like state (cf Heinrich et al, 2004). The weak covariation of Cu and Fe, and significant

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Mn

Fe

Cu

Zn

Pb

Mo

100 000.0

Metal (ppm)

10 000.0
1000.0
100.0
10.0
1.0
0.1
0

50 000

100 000

150 000

200 000

250 000

Cl (ppm)
FIG 3 - Plot of metal content as a function of chloride concentration in early magmatic-hydrothermal fluids
from El Teniente, early magmatic stage sample ET172.

variations in total concentrations of these elements (up to four orders of magnitude for Cu), can be
modelled in terms of Cu-Fe sulfide precipitation. The other metals determined are always present in
the order of abundance: Fe >Mn >Zn >Pb >Mo >Au and, with the exception of Au, correlate
strongly with salinity, where neutral complexes (MeCl20) probably predominate. These metals
show much less variation than Cu within individual samples consistent with less common sulfide
saturation.
In terms of absolute metal concentrations, both brines and dilute fluids may be equally capable of
Cu transport so it is the relative mass proportions of these fluid types in the system that will influence
Cu mobility and ultimate distribution. For Mo, the limited data suggest that brines appear to be more
important, perhaps explaining the common restriction of Mo to the deeper parts of the system where
these dense fluids may pond. Future work is aimed at distinguishing between fertile and barren
systems on the basis of fluid chemistry and metal budgets as well as identifying potentially anomalous
fluid characteristics that may provide insights into the genesis of these super-giant deposits.

ACKNOWLEDGEMENTS
We are grateful to CODELCO-Norte and the geologists at Chuquicamata, in particular Ricardo Boric,
Mario Vivanco and Armando Sinha for generous access to drillcore and geological data, and
CODELCO El Teniente and Patricio Zuiga for permission to carry out research at El Teniente.
Thanks to David Cooke for providing additional samples from the deposit. John Dilles provided
invaluable advice regarding Butte geology. CCW was supported by an EPSRC PhD studentship, a
grant from the University of London Central Research Fund, and Hugh McKinstry student grants
from the SEG. VV is supported by a Janet Watson Scholarship from the Department of Earth Science
and Engineering at Imperial College and SEG student fellowship and Hugh McKinstry awards.
Laboratory support was provided by Raquel Garcia-Sanchez and Barry Coles.

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REFERENCES
Heinrich, C A, Driesner, T, Stefnsson, A and Seward, T M, 2004. Magmatic vapor contraction and the transport
of gold from the porphyry environment to epithermal ore deposits, Geology, 32:761-764.
Rusk, B G, Reed, M H and Dilles, J H, 2008. Fluid inclusion evidence for magmatic-hydrothermal fluid
evolution in the porphyry copper-molybdenum deposit at Butte, Montana, Economic Geology,
103:307-334.
Rusk, B G, Reed, M H, Dilles, J H, Klemm, L and Heinrich, C A, 2004. Compositions of magmatic
hydrothermal fluids determined by LA-ICP-MS of fluid inclusions from the porphyry copper-molybdenum
deposit at Butte, Montana, Chemical Geology, 210:173-199.
Simon, A C, Pettke, T, Candela, P A, Piccoli, P M and Heinrich, C A, 2006. Copper partitioning in a
melt-vapor-brine-magnetite-pyrrhotite assemblage, Geochimica et Cosmochimica Acta, 70:5583-5600.

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