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Making Metal Super-Charged Ore Fluids: The

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Making Metal Super-Charged Ore Fluids: The Key to
Hydrothermal Base-Metal Ore Formation?
Jamie J. Wilkinson, David R. Cooke
CODES ARC Centre of Excellence in Ore Deposits, University of Tasmania, Private Bag 126, Hobart, TAS 7001,
Australia
Dominik J. Weiss, Helen L. Crowther, Barry J. Coles
Department of Earth Science and Engineering, Imperial College London, Exhibition Road, London SW7 2AZ, UK
Teresa E. Jeffries
Department of Mineralogy, Natural History Museum, Cromwell Road, London SW7 5BD, UK
Chris G. Ryan, Jamie Laird
CSIRO Exploration and Mining, School of Physics, University of Melbourne, VIC 3010, Australia
Abstract. The formation of large hydrothermal ore
deposits is optimized by several factors: efficient
extraction of metals from the source region, elevated
metal concentrations in hydrothermal fluids, high fluid
flux, effective focusing of fluids into a limited rock volume
and efficient precipitation. Of these parameters, metal
solubility displays the widest variability (up to 4 orders of
magnitude) and is potentially the most important. A case
study tracing metal transport in the Irish orefield suggests
that efficient extraction from the source rocks is critical for
the formation of economic deposits. The observation that
ore fluids trapped in sphalerite contain orders of
magnitude more metal than those in quartz implies that
ore deposition is related to the influx of metal super-
charged brines produced by this efficient leaching
process. Large parts of the hydrothermal system in space
and time may be barren due to a failure to attain efficient
extraction and transport conditions.
Keywords. Hydrothermal, ore, metal, solubility, source,
leaching
1 Introduction
Hydrothermal ore deposits are products of flow regimes
that extract metals from source rocks, transport them as
complexes in solution and precipitate them in a limited
rock volume. Of the parameters that govern the total
metal deposited, metal solubility varies over the widest
range (up to 4 orders of magnitude) and it is suggested
that this is the most important variable in the formation
of large deposits. This hypothesis is supported by results
from a recent laser ablation ICPMS study comparing
fluid inclusions trapped in sphalerite with those trapped
in gangue from two major Zn-Pb systems (Wilkinson et
al. 2009). The fluids responsible for ore mineral
precipitation were anomalously enriched in metals
compared to those forming gangue and had chemical
fingerprints of a distinct origin. This led to the
conclusion that episodic influxes of specialized fluids
were critical for ore formation. Here, we present results
of a case study tracing the Zn pathway from source to
trap in the Irish carbonate-hosted Zn-Pb-Ba orefield. The
aim was to test the idea that processes occurring in the
extraction zone are key controls on the formation of
large base-metal ore deposits.
2 Mineralogical Hosts for Metals in the
Source Rocks
Pb isotope studies in the Irish orefield have convincingly
demonstrated that the main source for metals is the
Lower Paleozoic, very weakly metamorphosed volcano-
sedimentary succession that is unconformably overlain
by a thin clastic wedge and the mineralized ramp and
nearshore carbonate facies of Carboniferous age
(Caulfield et al. 1986; O'Keeffe 1986, 1987; LeHuray et
al. 1987; Dixon 1990; Dixon et al. 1990; Everett 1999;
Everett et al. 2003). There may also be a contribution
from the underlying Precambrian high grade basement
(Walshaw et al. 2006). Although it is inferred that K-
feldspar is likely to have been the principal mineral host
for Pb in these rocks (Everett et al., 2003), no detailed
studies have been carried out on trace metal speciation.
Proton-induced X-ray emission (PIXE) analyses of
greywackes, the dominant rock type in the Lower
Paleozoic source rock sequence (~60 ppm Zn, ~19 ppm
Pb), were carried out at the CSIRO-GEMOC Nuclear
Microprobe facility, Melbourne University, to identify
principal host minerals for ore-forming metals and their
concentrations in these phases (Ryan et al. 1990; Ryan
2000). In these rocks the predominant clastic grains are
quartz with lesser plagioclase and K-feldspar, in a
matrix dominated by Fe-chlorite and subordinate
muscovite (Fig. 1). Fe and Zn are principally hosted by
chlorite as shown by the spatial association between Fe
and Zn in rock scans (Fig. 1), and illustrated by the
strong covariance of Fe and Zn in individual pixel data
(Fig. 2). The linear correlation is produced by
covariation in X-ray yield as a function of mineral grain
thickness in polished thin section. The average
concentration of Zn in chlorite is ~215 ppm (Table 1).
Mn 0.30 % As <45 ppm
Fe 18.03 % Rb 42 ppm
Ni 225 ppm Sr 53 ppm
Cu <39 ppm Ba 45 ppm
Zn 215 ppm Pb 27 ppm
Table 1. Average L. Paleozoic chlorite composition (sample
no. 01-0108)

Figure 1. PIXE X-ray intensity maps showing metal distribut-
ions within Lower Paleozoic greywacke source rocks (sample
no. 01-0110). Q: quartz, P: plagioclase, K: K-feldspar. Bright
grains on the Fe image are chlorite. Width of images: 4 mm.
Zn also occurs in higher concentrations (~500-1500
ppm) in a minor secondary phase, possibly an
oxyhydroxide (Fe ~11.5 wt%, Mn ~8.6 wt%). Pb occurs
at ~40 ppm in K-feldspar (crustal average ~50 ppm;
Patterson and Tatsumoto 1964) but the Pb budget
appears to be dominated by a minor unknown phase in
which Pb occurs at high concentrations (0.24-0.47 wt%),
together with elevated Fe, As and Cu – possibly a
sulphide. It is known that the dominant Pb-bearing
phase(s) are very easily leached or dissolved in low
temperature acid-leach and high temperature
hydrothermal experiments (Bischoff et al. 1981; Everett
et al. 2003; Crowther 2007). Ba is elevated in K-feldspar
(~900-1500 ppm) but also occurs at relatively high
concentrations in minor phases, possibly barite and/or
carbonates. Mn, substituted in hydrothermal dolomite or
occurring with hematite in oxide facies mineralization in
the deposits, is enriched in chlorite (~0.3 wt%).
Figure 2. Left: element covariation plot showing strong Fe-Zn
association in chlorite. Right: Threshold image, using data
contained by ellipse on left, maps out chlorite grains. Zn-rich
grain (white, top right) corresponds to circle in left image.
Ni, a minor metal in the deposits, also occurs
principally in chlorite. Arsenic appears to coexist with
Pb and also with Ba (Fig. 1) in minor phases. Cu and
Mo principally occur in rare, accessory phases.
3 Metal Extraction Efficiency
The region from which the hydrothermal fluids extracted
metals in the Irish hydrothermal system is currently
inaccessible, probably located at palaeodepths of >5 km
(Wilkinson et al. 2005a). Consequently, it is only
possible to infer the processes that occurred in this
region from isotopic and experimental data.
Zinc isotope data acquired from wholerock samples
of Lower Palaeozoic greywacke gave 66Zn values of
-0.01 to 0.26‰ (Lyon JMC Zn), slightly below average
crustal values. This range is identical to the Zn isotope
composition of sphalerite from the principal orebodies
(average 0.13±0.28‰, 2; Wilkinson et al. 2005b In
contrast, samples leached in sealed polystyrene test
tubes using 6N HCl at 25°C for two hours produced
isotopically heavy leachates with 66Zn values of 0.60 to
0.80‰ containing 11-32% of the total Zn budget (Fig.
3). This result indicates that a minor, isotopically heavy,
cold acid-leachable fraction exists in the samples that
can be correlated with the non-silicate (?oxyhydroxide)
Zn component identified in the PIXE analyses. Because
this component is likely to be extracted more easily
during hydrothermal interaction, fluids that only weakly
leached the source rocks would probably acquire an
isotopically heavy Zn isotope signature. Conversely, to
attain an isotopic composition consistent with the
dominant ore signature, >80% of the wholerock
(dominantly chlorite) Zn would need to be extracted.
This assumes that negligible bulk fractionation occurred
during precipitation of sphalerite in the deposits which is
probable based on current knowledge. This
interpretation is consistent with the tendency for
subeconomic prospects to contain isotopically heavy
sphalerite (66Zn 0.03-0.64‰) that can be explained by
their formation from fluids that only interacted weakly
with the source rocks.
Leachates
WKH siltstone 01-0110 greywacke 01-0108 greywacke
0.78
0.80
Residues
0.60
-0.30 0.17 0.05
Wholerock 66Zn= -0.01‰ 66Zn=0.26‰ 66Zn=0.14‰
Figure 3. Pie charts showing proportions of total Zn extracted
in cold acid leachates in three Lower Palaeozoic metasediment
samples and the Zn isotope composition of these fractions.
4 Metal Super-Charged Ore Fluids
Laser ablation ICPMS analyses of fluid inclusions have
provided new insights into the chemistry of Irish ore
fluids (Wilkinson et al. 2007, 2009). Results from the
Silvermines district show that sphalerite-hosted inclus-
ions contain Pb (and by inference Zn) concentrations up
to two orders of magnitude higher than in Lower
Palaeozoic-hosted feeder veins distal to deposits (Fig. 4).
 12
10 Sphalerite (P)
Quartz (P)
Frequency
8
Sphalerite (S)
6 RWA, Finlay S, Pennell WM, Pyne J, eds, Geology and
Quartz (S)
4
2
0 isotope study of the Irish Zn-Pb orefield. Unpub PhD thesis,
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6
Log Pb concentration (ppm)
Figure 4. Frequency histogram showing Pb concentrations in
individual inclusions in sphalerite and quartz from the Irish
orefield. P: primary inclusions, S: secondary inclusions.
The relationship between metal-rich fluids trapped in
sphalerite and metal-poor fluids in gangue phases has
also been observed in MVT deposits (Stoffell et al.
2008; Wilkinson et al. 2009). This implies that influx of
metal-enriched batches of fluid may be responsible for
ore formation. Intervening periods of time, or different
parts of the system, such as feeder veins distal to
deposits (Everett et al. 1999), may be characterized
largely by precipitation of gangue phases from metal-
poor fluids.
5 Conclusions
Based on the results of the case study in the Irish
orefield and data from other systems (e.g., Stoffell et al.
2008), we suggest that hydrothermal ore formation may
commonly be episodic, driven by influxes of
anomalously metal-rich fluids. For the Irish Pb-Zn
deposits, we propose that, at certain times, specific parts
of the hydrothermal system reached a critical threshold
in the reaction zone that allowed substantial leaching of
metals to take place, thereby producing significantly
more metal-rich fluids for a limited period. For the
principal ore metal Zn, together with Mn and Ni, this
process required breakdown of chlorite at assumed
temperatures of ~300 °C. This conclusion places a much
greater emphasis on the nature of the source region and
metal extraction processes as primary controls on the
generation of fertile hydrothermal systems with ore-
forming potential.
Acknowledgements
Some of the samples for this study were collected under
NERC grant GR9/03047. We are grateful to the
Department of Earth Science and Engineering, Imperial
College London, Anglo American plc, the University of
London Central Research Fund and CODES for
additional financial support. Isotope and laser ablation
analyses were made in the Joint Analytical Facility of
Imperial College and the Natural History Museum,
London.
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