Chemical Geology 548 (2020) 119674

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Chemical Geology
journal homepage: www.elsevier.com/locate/chemgeo

Fluorite as indicator mineral in iron oxide-copper-gold systems: explaining T

the IOCG deposit diversity
Tobias U. Schlegela,b, , Thomas Wagnerb, Tobias Fusswinkelb,c
⁎

a
CSIRO Mineral Resources, Australian Resources Research Centre, 26 Dick Perry Avenue, Kensington, WA 6151, Australia
b
Institute of Applied Mineralogy and Economic Geology, RWTH Aachen University, Wüllnerstrasse, 2, 52062 Aachen, Germany
c
Department of Geosciences and Geography, University of Helsinki, Gustaf Hällströmin katu 2a, 00014 Helsinki, Finland

ARTICLE INFO ABSTRACT

Editor: Michael E. Boettcher Hydrothermal iron oxide-copper-gold (IOCG) ore deposits are globally important sources of Cu and Au. IOCG
Keywords: systems show many common features, but also considerable diversity in terms of geological setting, miner-
Method development alization style and ore fluid characteristics. The key factors that control ore formation are controversially de-
Indicator mineral bated and no general ore deposit model has been able to explain the diversity of IOCG deposits on the global
Iron oxide-copper-gold scale. Building on previous work that characterized four distinct fluid types at the Prominent Hill IOCG deposit,
IOCG South Australia, we have analyzed the rare earth element (REE) composition of fluorite from the Prominent Hill,
Fluorite Olympic Dam and Ernest Henry IOCG deposits and from two prospects close to Prominent Hill. The REE data of
Rare earth elements
fluorite from Prominent Hill show four distinct chondrite-normalized patterns, which reflect the four fluid types
Fluids
Ore deposit
identified as metalliferous volcanic lake water derived fluid, magmatic-hydrothermal fluid, sedimentary basin
Copper brine, and wall rock-buffered basement brine. Two strikingly similar REE pattern types were found in fluorite
Olympic Dam from the Olympic Dam deposit and one in an exploratory data from the Ernest Henry deposit, demonstrating the
Prominent Hill involvement of the same principal fluid types. We therefore conclude that world-class IOCG deposits can form by
interaction of host rocks with different characteristic types of ore fluids and their combinations, thus IOCG
deposits do not necessarily form by a single sequence of processes.

1. Introduction the significance of fluid-rock interaction involving at least two fluids of

Iron oxide-copper-gold (IOCG) deposits are a globally important but
diverse group of hydrothermal ore deposits showing similarities to
porphyry Cu-Au, sedimentary Cu and skarn deposits, reflecting variable
fluid chemistry, links to intrusions and tectonic settings. Despite con-
siderable research efforts in the last decades, there is no consensus yet
on a consistent ore formation model explaining this diversity.
Nevertheless, it has become clear that IOCG deposits are always char-
acterized by abundant iron oxides, and that structurally controlled
economic Cu-Au ores are hosted by rocks affected by zoned iron oxide-
alkali alteration (Fig. 1; Hitzman et al., 1992; Williams et al., 2005;
Richards and Mumin, 2013; Barton, 2014; Corriveau et al., 2016).
Current formation models for IOCG deposits suggest that iron oxide-
apatite (IOA) deposits may represent the deeper roots of IOCG systems
and highlight the importance of ascending magmatic-hydrothermal
fluids in creating vertically zoned mineralization (Fig. 1; Sillitoe, 2003;
Williams et al., 2005; Knipping et al., 2015a, 2015b; Corriveau et al.,
2016; Reich et al., 2016; Simon et al., 2018). Many studies emphasize
either magmatic, surficial, sedimentary, or metamorphic origin in the
formation of world-class IOCG deposits such as Olympic Dam, Promi-
nent Hill and Ernest Henry, whereas this may not be required for
forming smaller deposits (Fig. 2; e.g. Oreskes and Einaudi, 1992; Mark
et al., 2000; Bastrakov et al., 2007; Williams et al., 2015; Schlegel et al.,
2018). Despite the presence of a range of contrasting fluid types, the
ultimate sources of fluids, metals and sulfur in many deposits of the
IOCG spectrum remain contentious. Therefore, identification of robust
tracers of the fluid sources would make it possible to understand which
processes and ingredients are critical for formation of world-class IOCG
deposits in different provinces, compared to smaller deposits and sub-
economic occurrences.
Extensive studies of diverse hydrothermal mineral deposits have
shown that the REE patterns of fluorite reflect the composition of the
fluid from which it precipitated and permit characterization of the
source rocks (Möller et al., 1976; Bau et al., 2003; Schwinn and Markl,
2005). On this basis we have investigated the REE signatures of fluorite
in ores from the large Prominent Hill, Olympic Dam, and Ernest Henry

⁎
Corresponding author at: CSIRO Mineral Resources, Australian Resources Research Centre, 26 Dick Perry Avenue, Kensington, WA 6151, Australia.
E-mail address: tobias.schlegel@csiro.au (T.U. Schlegel).

https://doi.org/10.1016/j.chemgeo.2020.119674
Received 21 November 2019; Received in revised form 5 May 2020; Accepted 15 May 2020
Available online 19 May 2020
0009-2541/ © 2020 Elsevier B.V. All rights reserved.
T.U. Schlegel, et al. Chemical Geology 548 (2020) 119674

Fig. 1. Synthesis of the hydrothermal origins of selected IOCG systems, their tectonic setting, and fluids involved in economic mineralization (not to scale). The schematic block models are compiled from published
135°25’E 135°30’E
Cloncurry region Ernest Henry,
Monakoff and
E1 IOCG
deposits

29°40’S
Ernest Henry
Ernest Henry

Prominent Hill &

Olympic Dam
IOCG deposits
Gawler
craton

Prominent Hill

29°45’S
lt
Neptune fau
Southern overthrust ia
Triton nn
Major fault lgu
Bu
Intrusion felsic / mafic N
Dolostone

Prominent Hill
Neptune Volcanics
Prominent Hill

5 km
Siliciclastic sedimentary rocks IOCG deposit
and tectonic breccias
Calc-silicate metasedimentary rocks IOCG prospect
Metasedimentary and metavolcanic rocks 135°40’E

Fig. 2. Map showing the locations of IOCG deposits and prospects investigated
in this study and the interpreted geology of the Proterozoic basement in the
studies (see references in the text) and illustrate the geometries of zoned iron oxide-alkali alteration patterns and the location of Cu-Au ore bodies. Prominent Hill area below the Phanerozoic cover.
(After Freeman and Tomkinson (2010).)
Mineralization controlling structures

IOCG deposits, as well as from the small Triton and Neptune prospects
Olympic Dam

by LA-ICP-MS (Fig. 2). Building on recent advances in characterizing

IOCG fluids, the four distinct fluid types identified in the Prominent Hill
deposit (Schlegel et al., 2018) were used to calibrate four characteristic
REE signatures of fluorite. Each signature is specific to one fluid type
involved in IOCG mineralization and can be used as a proxy for the fluid
origins in other IOCG deposits. Comparison with published data con-
firms that interactions between a magmatic-hydrothermal and at least
one additional fluid lead to formation of world-class IOCG deposits.
IOA deposit + IOCG veins
Olympic Dam

Potential fluids involved in IOCG deposit formation include volcanic

lake water derived fluids in areas of active volcanism, magmatic-hy-
drothermal fluids, sedimentary basin brines and rock buffered base-
ment brines including metamorphic fluids.

2. IOCG fluids and mineralization in the Prominent Hill area

We report only the distinctive characteristics of the Prominent Hill

Rock buff. basem. brine

deposit and the Triton and Neptune prospects as a basis to interpret the
Magmatic-hydrot. fluid

REE data; further background information for the Prominent Hill,

Volcanic lake water

Sedim. basin brine

Olympic Dam and Ernest Henry deposits is summarized in Fig. 1 and in

Mineralization (Sulfides)

Cu (Cct, Bn, Ccp)

the literature (e.g. Oliver et al., 2008; Ehrig et al., 2012; Schlegel and
IOCG vein deposit IOA deposit

Heinrich, 2015; Schlegel et al., 2017, 2018).

Cu (Py, Ccp)

The Prominent Hill deposit is located in the footwall of a fault

(Py ± Ccp)

system, which has thrusted metamorphic and in parts magnetite-pyrite

altered rocks over a foreland composed of discontinuous packages of
IOCG fluids

sedimentary rocks and the Neptune Volcanics. The latter are dominated
Au

by andesitic equivalents of the ca. 1.6 Ga Gawler Range Volcanics near

Prominent Hill (Williams et al., 2017a, 2017b). The deposit is hosted by
a package of overturned marine calcareous and siliciclastic sedimentary
rocks, breccias, as well as Neptune Volcanics. Acidic hematite-quartz
Hem-Chl-Ph-Sd-Fl-Brt(-Ap)

alteration resulted in a sub-vertical body forming the Cu-poor but Au-

Ab-Act-Ap-Di(-Scp-Mag)
Kfsp-Bt-Mag(-Ap-Act-Di)

mineralized core of the deposit (Schlegel and Heinrich, 2015). Hematite

Mag(-Ap-Sd-Chl-Qz)

breccias extend upward and westward and host the Cu sulfide ore in
alteration assemblages including chlorite, phengite, siderite, fluorite
Chl-Ph/Ms-Hem
Chl/Kfsp-Ph/Ms

and barite (Fig. 1; Freeman and Tomkinson, 2010).

Hem-Qz-Brt

The Cu ore body preserves abundant, petrographically consistent

Acid sulfate

fluid inclusion assemblages (FIA) hosted in fluorite (quartz and barite)

Ab(-Ttn)

within the hematite breccia matrix and in vein samples. Although veins
Alteration

are rare, they provided important petrographical constrains and fluid

data of samples that pre- and post-dated economic mineralization in the
breccia matrix (c.f. Schlegel et al., 2018). In total, Schlegel et al. (2018)
investigated 64 fluorite-hosted FIA in eight different samples by

2
T.U. Schlegel, et al.
petrography (Roedder, 1984; Goldstein and Reynolds, 1994), and a
combination of microthermometry and LA-ICP-MS microanalysis
(Schlegel et al., 2012). The FIA vary systematically in total salinity
(NaCl + CaCl2), Ca/Na ratios, conservative fluid components such as
Cs, Cl, Br as well as in other major (K and Fe) and trace elements (Mn,
Cu, Pb, U and S). The data of the investigated FIA cluster into four
groups and the compositional variation among the groups is much
larger than the chemical variation of FIA within a single group
(Schlegel et al., 2018; their Table 2). The four clusters show some
compositional overlap in certain elements (e.g. Fe, S, Cu, U), which is
probably due to different extents of fluid mixing and fluid-rock reaction
ratios occurring during hematite precipitation and Cu mineralization.
Importantly, the FIA in each group show a distinct Na-Ca signature, i.e.
Ca/Na ratios and (NaCl + CaCl2) salinity, and well-defined con-
centrations of conservative fluid components (i.e. Cl and Cs) and ha-
logen ratios (i.e. Br/Cl ratio). These compositional signatures, in con-
junction with the textural occurrence of different fluid inclusion types
hosted in hematite breccia matrix and in vein samples, were then used
to define four different fluid types (c.f. Schlegel et al., 2018; their fluids
A to D). Subsequently, the origin of each fluid type was interpreted
from the halogen ratios, used to trace the origin of the salinity sedi-
mentary brines, and global comparison with published fluid composi-
tions that origin from different hydrothermal settings.
Mineralization at Prominent Hill occurred during late stages of the
Gawler Range volcanism and involved degassing of magmatic fluids
into a volcanic lake environment. The acidic and oxidized lake water
was of low to intermediate salinity, dominated by NaCl. The volcanic
lake water contained magmatic derived sulfur (Schlegel et al., 2017),
abundant U (0.5–70 ppm) and became rich in Cu (1000 ppm) by
leaching and likely by dissolving Cu-rich volcanic condensates. It ad-
vected from the surface towards the zone of extreme leaching within
the hematite-quartz alteration boundary. A magmatic-hydrothermal
Na-dominated and Ca-bearing brine was rich in Fe (2 wt%) and con-
tained modest Cu (70 ppm). The third fluid was a Na-Ca sedimentary
basin brine that contributed Cu (200 ppm) and Fe (up to 5000 ppm) to
economic mineralization. Fluid inclusions approaching the composition
of the volcanic lake water and the sedimentary basin brine are present
in fluorite intergrown with Cu sulfides in the hematite breccia matrix
(Fig. 3A, B). The magmatic-hydrothermal brine occurs in early siderite-
bearing veins (Fig. 3C), which crosscut the hematite breccia but also
infiltrate into the porous breccia matrix. Economic Cu-(Fe) sulfide mi-
neralization occurred outside the hematite-quartz alteration zone by
mixing of the volcanic lake water with the Fe-rich magmatic-hydro-
thermal brine and the sedimentary basin brine, and also by interaction
of these fluids with acid-neutralizing and pyrite-bearing host-rock strata
(Fig. 1). Finally, a basement brine (100 ppm Cu) with a very high Ca/
Na ratio comparable to that observed in continental shield or retrograde
metamorphic brines is present in late calcite veins (Fig. 3D) that clearly
postdate mineralization at Prominent Hill.
The Triton and Neptune prospects are hosted by the Neptune
Volcanics showing chlorite + phengite + magnetite/hema-
tite + carbonate altered lavas with an anomalous to low-grade Cu tenor
(Freeman and Tomkinson, 2010). Higher Cu grades occur in replace-
ments of altered lava, hydrothermal breccia intervals, and in locally
abundant iron oxide + apatite + quartz
phengite + fluorite + chalcopyrite ± pyrite + carbonate “Cu feeder”
veins (Fig. 3E). Degassing of volatiles produced amygdales containing
quartz + hematite, locally followed by chalcopyrite + fluorite bearing
infill (Fig. 3F).
3. Methods
3.1. Sampling
Forty-seven fluorite bearing samples were collected mostly from
drill core and they originate from the Prominent Hill, Olympic Dam and
Chemical Geology 548 (2020) 119674
Ernest Henry IOCG deposits as well as the Neptune and Triton prospects
near Prominent Hill. The location of each sample including a summary
description is given in Table A1 in the Electronic supplementary ma-
terial, which also contains specific references to Figures from previous
studies.
Fifteen of the 19 samples from the Prominent Hill deposit were
collected from the hematite breccia ore body, specifically from three
north-south oriented cross sections (Figs. 3A–D, A1 and A2 in the
Electronic supplementary material). These sections sample steep Cu
grade and alteration gradients where zones of hema-
tite + quartz + barite alteration change into zones with hema-
tite + chlorite + phengite + siderite + fluorite + barite alteration
(Fig. 1). Four additional samples were collected from the Malu pit
(stage 1). One of them represents a magnetite-pyrite skarn-like rock,
two others are from dm-wide siderite + quartz + fluorite veins, and
one shows a late fluorite + hematite + barite vein. Finally, one sample
originates from a deep drill hole sampled at 635 m below the present-
day surface (PH08D359, 950.8 m) showing a hema-
tite + fluorite + chalcopyrite breccia. The selection of samples was
focused on specimens with fluorites containing fluid inclusion assem-
blages with previously determined element compositions (Schlegel
et al., 2018). In fact, 15 out of the 19 samples (74 out of 96 LA-ICP-MS
analyses) from Prominent Hill contain fluorite with ore-stage FIA and
known composition (Fig. 3A–D).
Twenty-one samples from the Neptune and Triton prospects
(Figs. 3E, F and A3–4) cover the principal Cu-(Fe) sulfide occurrences in
the volcanic rocks, which are present as disseminations in altered lava,
in veins, and breccia intervals. Several samples were collected from drill
core showing maximum Cu grades (e.g. PH564, PH570, PH571, PH575,
PH578, PH584 in drill hole DD10TRI008, or PH636 in drill hole
DD09TRI007).
Six high-grade ore breccias including one hematite breccia with
3.7 wt% Cu + 0.79 g/t Au originate from the Olympic Dam and one
from the Ernest Henry IOCG deposits (Figs. 3G, H, A5 in the Electronic
supplementary material). Four hematite + fluorite + chalcopyrite
breccia samples from Olympic Dam (OlyD1–4) were sampled in 1989
from mine level 34. The hematite breccias were collected (outside the
Greenfield Fm.) from a zone of high-grade Cu ore located at the tran-
sition between the central hematite-quartz-barite (HEMQ) breccia and
the aluminosilicate-stable hematite breccia. In addition, two samples
(OD1–2) containing fluorite are from the RWTH Aachen University
collection and were sampled in 2004. The magnetite-chalcopyrite
breccia from the Ernest Henry deposit comes from the main ore-pipe of
the underground mine and was collected in 2018.
3.2. Sample preparation and petrography
Petrography was carried out using doubly polished wafers of
200–350 μm thickness permitting the pre-selection of LA-ICP-MS spots
spatially related to fluid inclusion assemblages which were previously
characterized and analyzed by LA-ICP-MS (Schlegel et al., 2018). Pet-
rographic relations between fluorite and the other ore and gangue
minerals including hematite, Cu-(Fe) sulfides, phengite, chlorite, barite,
calcite and dolomite were documented on high-resolution printouts of
± photomicrographic mosaics, scans of rock slabs, and wafers. Fluorite
grains of individual samples from Neptune were extracted from drill
core slabs using a dental micro-saw and examined under a binocular
microscope. Grains which were visibly intergrown with other minerals
were rejected. All sample material was cleaned with deionized water
and ethanol prior to LA-ICP-MS analysis.
3.3. LA-ICP-MS analysis
The major and trace element analyses of 248 pre-selected LA-ICP-
MS spots were performed on doubly polished wafers, thick sections
mounted on glass slides, and on polished fluorite grains. Replicate
3
T.U. Schlegel, et al. Chemical Geology 548 (2020) 119674

A Hem B
Ccp
Bn

Bn+Dg
Fl

Hem Fl
Brt
200 µm 200 µm

part of FIA part of

part of FIA
FIA
C D
Ccp
Ccp
2cm Cal
Sid
Fl with FIA

Fl
Fl with FIA
0.5cm 1 cm

E Qz
F Ccp
Ablation pit
Ccp

Ap Fl Fl
Hem Cal

Fl
Ccp
1 cm Qz 1 cm

G H
Qz Py
Fl
Carb
Fl Ccp
Fl

Ccp Mgt
Hem 500 µm 1mm

Fig. 3. Photomicrographs of representative samples from (A–D) Prominent Hill, (E–F) Triton, (G) Olympic Dam and (H) Ernest Henry IOCG deposits. (A) Fluorite
containing primary fluid inclusions (red arrows) approximating volcanic lake water is intergrown with chalcopyrite and hematite in the breccia matrix. (B) Fluorite
containing a fluid inclusion assemblage resembling the composition of a sedimentary brine, intergrown with bornite and digenite within hematite breccia matrix. (C)
Part of siderite + chalcopyrite bearing vein with fluorite containing primary fluid inclusions approximating the Fe rich magmatic-hydrothermal fluid. (D)
Paragenetically late calcite + barite + fluorite + pyrite + chalcopyrite vein with fluid inclusions representing the composition of the wall-rock buffered basement
brine. (E) Copper feeder vein crosscutting altered andesite. (F) Amygdale filled by hematite + quartz and late chalcopyrite intergrown with fluorite and calcite. (G)
Fluorite intergrown with chalcopyrite in hematite-fluorite breccia matrix from Olympic Dam. (H) Fluorite intergrown with chalcopyrite, magnetite, pyrite and
carbonate in magnetite breccia matrix form Ernest Henry (FIA: fluid inclusion assemblage analyzed in Schlegel et al., 2018). Mineral abbreviations from Whitney and
Evans (2010).

4
T.U. Schlegel, et al.
A B Hem
C Bn
Fl
Py
Py
Ccp
Ccp Ccp
1mm 1mm
Fig. 4. Photomicrographs of textures showing sulfides in the hematite breccia matrix of the Olympic Dam deposit (OlyD1–4) with different Cu-(Fe) sulfides replacing
pre-existing pyrite (A-C) partially and (D) completely. Mineral abbreviations from Whitney and Evans (2010).
measurements of homogeneous fluorite were conducted on the same
crystal, unless this was not possible due to the presence of inclusions,
sulfide intergrowths or compositional zoning.
Laser ablation-ICP-MS analysis in fluorite was done using a
Coherent GeoLas MV 193 nm ArF excimer laser ablation system coupled
to an Agilent 7900s ICP mass spectrometer at the University of Helsinki,
Finland, and a similar analytical system featuring a Coherent GeoLas
HD 193 nm laser ablation system coupled to an Agilent 7900s ICP mass
spectrometer at RWTH Aachen University, Germany. The LA-ICP-MS
system was tuned daily to ensure high signal/blank intensity ratios over
the entire mass range at low oxide and doubly charged interference
production rates (ThO/Th < 0.5%; Ca2+/Ca < 0.3%), as well as
ideal ablation, transport and ionization conditions (U/Th:
1.00 ± 0.02). The instrument was operated at 1500 W plasma power,
Ar plasma gas flow of 15 l/min, Ar auxiliary gas flow of 0.8 l/min and
He carrier gas flow of 1.15 l/min. Analytical accuracy was monitored
daily by measuring the composition of reference material NIST 612
against reference material NIST 610 as external standard (5 repeat
measurements, bracketed by 3 analyses of external standard). The
measured concentrations across the entire mass range were within the
propagated uncertainty intervals for all 38 analyzed elements (2–10%
relative deviation from the reference value). Fluorite analyses included
the isotopes 23Na, 24Mg, 29Si, 39K, 43Ca, 45Sc, 55Mn, 57Fe, 63Cu, 88Sr,
89
Y, 133Cs, 137Ba, 139La, 140Ce, 141Pr, 146Nd, 147Sm, 153Eu, 157Gd, 159Tb,
163
Dy, 165Ho, 166Er, 169Tm, 172Yb, 175Lu, 85Rb, 89Y, 208Pb, 232Th, 238U.
Integration times per isotope were 10 ms for all elements except the
REE from 141Pr to 175Lu with 20 ms. Laser ablation analyses were re-
corded as real-time signals. Sample measurements were bracketed by
repeat ablations of the NIST 610 external reference material, typically
after every hour.
Laser ablation performance of fluorite can be poor due to the perfect
cleavage of fluorite. Under these circumstances, cracking and chipping
can occur during the first few ablation pulses, especially when ablating
with a large and fixed beam diameter, resulting in a spiky ICP-MS signal
at the onset of the analysis. After the first few seconds, typically a well-
shaped ablation crater develops and the ICP-MS signal smoothes out
and stabilizes quickly. The laser spot diameter and the beam fluence
strongly influence the ablation performance of fluorite, and both
parameters were optimized prior to sample ablations. Ablation spot
sizes were also adjusted to match sample features (homogeneity, pre-
sence of mineral inclusions), but spots were always in the range be-
tween 44 and 90 μm. The ideal energy density setting for good ablation
performance was found to be in the range of 15 to 22 J/cm2. Laser pulse
frequency was 10 or 12 Hz, depending on sample ablation behavior.
The SILLS (Signal Integration for Laboratory Laser Systems) soft-
ware (Guillong et al., 2008) was used for signal processing, including
spike elimination and element quantification. Signal intervals showing
5
Chemical Geology 548 (2020) 119674
D Hem
Dg Id
Py
50 µm 500 µm
impurities from fluid inclusions, silicates, carbonates, iron oxides, sul-
fides, and uranium-rich minerals were detected as peaks in Na, Mg, Si,
K, Mn, Fe, Cu and U and subsequently excluded. Fluorite was assumed
to have stoichiometric concentration of Ca and thus, Ca was used as
internal standard element for the quantification of element concentra-
tions from ICP-MS data (counts/s). Strontium, Y and Ce may substitute
for Ca (Gagnon et al., 2003), but their concentrations were generally
below 0.1 wt%, with the exception of two samples where they reached
0.6 wt%. Even in the case of these two samples, the concentrations of
other trace elements would be overestimated by only about 1% when
assuming stoichiometric Ca concentrations. This deviation lies well
within the analytical uncertainty resulting from counting statistical
errors and the uncertainty of the element concentrations in the re-
ference material NIST 610. Data quantification based on stoichiometric
Ca concentration in fluorite is therefore justified and will not result in
any detectable additional source of error, even for the two samples with
slightly higher Y and Ce concentrations.
4. Results
4.1. Petrographic relations in samples across different deposits
Representative mineral textures of samples from each locality are
documented in Figs. 3, 4 and A2–5 (Electronic supplementary material)
and show that fluorite is intergrown with Cu-(Fe)-sulfides as an integral
part of the mineral assemblage. Careful petrography made it possible to
clearly relate fluorite from Prominent Hill to FIA containing one of the
four fluid types (Fig. 3A–D). We consider some of the textural differ-
ences among the hematite breccias from Olympic Dam and Prominent
Hill (i.e. difference in clast types) of minor importance for this study.
The dominant mineralogy and their petrographic relations in the high-
grade breccia matrix from Olympic Dam (samples OlyD1 to OlyD4) and
Prominent Hill are very similar. For example, the hematite breccia
matrices show patchy fluorite intergrown with alteration minerals in-
cluding fine-grained hematite, chlorite, sericite, chalcopyrite, idaite and
chalcocite. Just like in the hematite breccia body at Prominent hill, Cu-
(Fe) sulfides in the samples OlyD1 to OlyD4 commonly occur as partial
to complete replacement of pyrite (Fig. 4A–D). At Prominent Hill, si-
milar Cu-(Fe) sulfides formed by isovolumetric replacement of pyrite
upon reaction with a highly oxidized and acidic Cu-rich fluid and si-
multaneous precipitation of hematite (Schlegel et al., 2017). Addi-
tional, non-essential petrographic observations are documented in a
separate section of the Electronic supplementary material.
4.2. Rare earth element chemistry of fluorites
The analytical results are summarized in the data repository. Four
T.U. Schlegel, et al. Chemical Geology 548 (2020) 119674

A 104
Fig. 3A Type A B 104
Fig. 3G
Type B
103 103 Olympic Dam
Fig. 3F Type C Type D
Fluorite/chondrite

Fluorite/chondrite
102 102
Fig. 3C Fig. 3E

101 101
Monakoff

E1
1 1

Fig. 3D Ernest Henry, Fig. 3H

-1
10 10-1
Fig. 3B
Prominent Hill IOCG deposit This study
Neptune / Triton IOCG prospects Literature data
10-2 10-2
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

C Fig. 3A D Epithermal
(Pegmatitic)
(Magmatic-) (Magmatic-)
Fig. 3F
-5
Hydrothermal -5
Hydrothermal
10 10

Epithermal
(Pegmatitic)
Fig. 3G
Tb/Ca

Tb/Ca

10-6 Fig. 3C 10-6

Fig. 3B

10-7 Sedimentary 10-7 Sedimentary

Fig. 3E

n
n

io
io

at
at

liz
lliz

Fig. 3H

al
Fig. 3D
ta

t
ys
ys

remobilization

cr
remobilization
cr

10-8 10-8
10-3 10-2 10-1 100 101 102 10-3 10-2 10-1 100 101 102
Tb/La Tb/La

E 400 Prominent Hill Olympic Dam Ernest Henry Triton Neptune

Fig. 3E
Fluorite A: VOLCANIC LAKE WATER Fluorite C: SEDIMENTARY BASIN BRINE
High-grade hematite breccia Hematite breccia matrix
matrix (Hem+Fl+CCp/Cct±Dg (Hem+Ph+Chl+Fl±Cct±Dg±Bn±Id
Fig. 3C
100 ±Bn±Id±Py) Mag+Py skarn-like rock
High-grade granite breccia matrix
Fluorite D: ROCK BUFF. BASEMENT BRINE
Sr (ppm)

Fig. 3A (Fl+Hem+Id+Cct)
Magnetite breccia matrix
Fluorite B: MAGM.-HYDROT. FLUID
Hem/Mag+Qz+Ap+Fl+Py+
Hematite breccia matrix (Hem+
Fig. 3G Ccp breccia
Fig. 3H Ph+Chl+Fl+Ccp/Cct±Dg±Bn±Id)
Hematite breccia matrix (Hem+ Qz+Hem/Mag+Fl±Ccp amygdale
Kfsp+Ph+Chl+Fl+Ccp+Id) Qz+Mag+Fl+Py+Ccp vein
Mag+Py±Ccp skarn-like rock Cal+Brt+Fl+Py+Ccp vein (late)
Fig. 3F
Sd+Qz+Fl+Brt+Ccp vein Literature data
10 Monakoff IOCG deposit1
Hem/Mag+Ap+Qz(±Ph)+Fl+
Ccp+Py “Cu feeder“ vein E1 IOCG deposit1
Qz+Mag+Fl+Py+Ccp vein Acid volcanic lake water / fumaroles2
Fig. 3D Gallinas Mountains deposits3
4 Fig. 3B Qz+Hem/Mag+Fl±Ccp amygdale
Volcanogenic epithermal fluorite dep.4
Hem+Fl+Brt+Ccp+Py breccia
(All samples from the Mount Woods area
10-3 10-2 10-1 100 101 102 contain carbonate)
Tb/La

Fig. 5. REE and Sr data of fluorite. (A–B) Representative, chondrite-normalized averages of single and multiple LA-ICP-MS spot analyses from (A) the Prominent Hill
deposit and the Neptune and Triton prospects, (B) the Olympic Dam, Ernest Henry (data from this study), Monakoff and E1 deposits (Williams et al., 2015). (C–D)
Fluorite REE data plotted into the Tb/Ca vs. Tb/La diagram with field names modified after Möller et al. (1976). (E) Sr vs. Tb/La diagram. Mineral abbreviations from
Whitney and Evans (2010). References: 1) Williams et al., 2015; 2) van Hinsberg et al., 2010; 3) Gagnon et al., 2003; 4) Dill et al., 2016.

6
T.U. Schlegel, et al.
principal types of chondrite-normalized (McDonough and Sun, 1995)
REE patterns (Fig. 5A, B) correspond to the four endmember fluids.
These determine four types of fluorite A-D and show clear groupings
within the Tb/Ca–Tb/La diagram (Fig. 5C, D). Fluorites with type A
pattern are highly enriched in LREE, show a negative slope, and contain
FIA resembling the composition of volcanic lake water. They plot in the
epithermal field and occur in ores from the Prominent Hill and Olympic
Dam deposits. Type B fluorites show weak to strong REE enrichment.
The patterns are nearly horizontal between La and Gd, have a positive
Eu anomaly, and are typically followed by a small convex-upward
curvature among the heavy REE. Fluorites with this signature plot in
the magmatic-hydrothermal field and occur in siderite-bearing veins,
Cu feeder veins, and in the hematite breccia matrix at Prominent Hill
and Olympic Dam. Type C fluorites show depletion in the LREE coupled
with a small negative Ce anomaly, and distinct bell-shaped patterns.
They plot in the sedimentary field consistent with the sedimentary
basin brine in fluid inclusions hosted by these fluorites and are common
in the hematite breccia matrix at Prominent Hill. Type D fluorites show
flat REE patterns approaching the REE distribution of C1-chondrites.
Some fluorites of this group show weak enrichment in LREE and HREE.
They occur in breccia intervals at Ernest Henry, Triton, Neptune, and in
the late calcite-bearing veins across the Prominent Hill area. Notably,
the Sr content of all fluorites has a bimodal distribution (Fig. 5E).
Fluorite types A and B contain typically > 40 ppm Sr whereas types C
and D contain < 20 ppm. Importantly, the data of the fluorites in
siderite veins, Cu feeder veins, and in the hematite breccia matrix at
Prominent Hill and Olympic Dam largely overlap with data from vol-
canogenic epithermal fluorite deposits (Fig. 5C, D; Dill et al., 2016).
5. Discussion and conclusions
5.1. Classification of fluorite
The classification of fluorite in this study is strictly based on a
combination of their REE patterns and their position in the Tb/La–Tb/
Ca diagram (Fig. 5; c.f. Möller et al., 1976). The classification diagram
builds up on the earlier works of Schneider et al. (1975), Jacob (1974)
and Fleischer (1969) who analyzed the REE data of fluorite from nu-
merous deposits located in Asia, Bulgaria and the United States. The
following paragraph summarizes its background information originally
published in Möller et al. (1976) and is supported by the results of more
recent studies. The fractionation of REE from a fluid into fluorite at any
given conditions of mineralization is dominated by two processes,
namely the most stable REE-complexation in the fluid, and the in-
corporation of the non-complexed REE-ion into fluorite. The stability of
REE-complexes generally increases from La to Lu with ligands such as
chlorite, fluoride, sulfate and carbonate, and with increasing tempera-
ture (Wood, 1990a, 1990b; Munizaga and Lottermoser, 1992; Haas
et al., 1995; Migdisov et al., 2006, 2009, 2016; Loges et al., 2013). The
incorporation of REE ions from hydrothermal fluids into fluorite de-
pends on several factors including the radius of the REE-ion relative to
the Ca2+ ion, and this process occurs as concentration of LREE during
initial fluorite crystallization, incorporation of REE roughly conforming
to chondritic composition during intermediate stages of crystallization,
and concentration of HREE in late stages of fluorite mineralization. In
consequence, the REE incorporation into fluorite is optimal for Dy and
Tb. The Tb/La ratio therefore indicates the degree of REE remobiliza-
tion during mineralization, whereas the Tb/Ca ratio characterizes the
geochemical environment of fluorite formation, such that low Tb/Ca
indicates the involvement of a calcium-rich carbonate rock, or a calcic
sedimentary brine (c.f. Hanor, 1994). Conversely, a high Tb/Ca ratio
reflects source regions rich in late-stage differentiates and implies
fluorite formation involving relatively Ca-poor fluids such as those that
occur in volcanic lake water (c.f. Sriwana et al., 2000; van Hinsberg
et al., 2010), pegmatitic and epithermal environments, in which Ca is
usually not detected in the mineralizing fluids (Böhlke and Irvine, 1992;
7
Chemical Geology 548 (2020) 119674
Sirbescu et al., 2013; Márquez-Zavalía and Heinrich, 2016; Berni et al.,
2017). Progressive fractionation of La and Tb during crystallization of
fluorite describes a trend with equally increasing Tb/La and Tb/Ca
ratios.
In contrast to the original Tb/La–Tb/Ca diagram, we have re-la-
beled the “pegmatitic” field “epithermal (pegmatitic)” and the “hy-
drothermal” field “(magmatic-) hydrothermal” to stay consistent with
the fluid-types interpreted to be important for IOCG mineralization.
These are namely of magmatic, surficial, sedimentary, or metamorphic
origin (Hitzman et al., 1992; Oreskes and Einaudi, 1992; Barton and
Johnson, 1996; Pollard, 2000; Williams et al., 2005; Chiaradia et al.,
2006; Davidson et al., 2007; Dreher et al., 2008; Chen, 2013; Barton,
2014; Schlegel et al., 2018). Importantly, fluorite in IOCG ores forming
from metamorphic rock-derived fluids and fully rock-buffered basement
brine, important at the Ernest Henry deposit and other deposits of the
Cloncurry area (Oliver et al., 2008), can only be interpreted in com-
bination with their REE patterns. This is because fractionation of REE
during their remobilization results in a decrease of La compared to Tb
and thus in an increase of the Tb/La ratio (Schwinn and Markl, 2005;
Schönenberger et al., 2008). Studies by Dill and Weber (2010) confirm
that the (magmatic-) hydrothermal and sedimentary compositional
fields for fluorite on the original diagram as established by Möller et al.
(1976) are robust for those deposit types. The boundary between the
(magmatic-) hydrothermal and the epithermal (pegmatitic) fields is
potentially less well constrained and may be shifted to somewhat lower
Tb/Ca values as indicated by clearly volcanogenic epithermal fluorite
from the Andean volcanic arc (Fig. 5; Dill et al., 2016). However, we
have not changed the positions of the field boundaries. In summary, the
Tb/La–Tb/Ca diagram, in combination with REE patterns permits a
practical, synoptical, and experimentally-derived but nonetheless em-
pirical classification based on the petrogenetic conclusions of the dif-
ferent fluorites studied.
5.2. REE data in fluorite are proxies of fluids involved in IOCG
mineralization
The REE data of fluorite show clear differences and demonstrate
that they are suitable as proxies for the origin of the fluids involved in
IOCG mineralization. Each of the four REE pattern types (Fig. 5A, B)
and their location in the Tb/Ca-Tb/La diagram (Fig. 5C, D) fingerprints
one of the four fluid types identified at Prominent Hill. The REE data of
fluorites from Prominent Hill hosting volcanic lake water-derived fluid
inclusions (type A) correspond with REE data of fluorite in high-grade
ore from Olympic Dam (Fig. 5C, D), fluorite in REE-fluorite deposits in
the Gallinas Mountains, New Mexico, which are possibly related to al-
kaline magmatism (Williams-Jones et al., 2010; Gagnon et al., 2003)
but were previously considered as epithermal deposits (Perhac and
Heinrich, 1964), and with acidic volcanic lake water (van Hinsberg
et al., 2010). Oxidized volcanic lake water was therefore also a critical
ore fluid for the high-grade mineralization at the Olympic Dam IOCG
deposit (Fig. 1). This interpretation is consistent with conclusions of
Reeve et al. (1990) who suggested that mineralization at Olympic Dam
involved subaqueous venting of hydrothermal fluids, and with the
distribution of iron oxide-alkali alteration exerting the primary control
on the mineralization (Fig. 1). More specifically, the extent of the he-
matite-quartz alteration is controlling the high-grade Cu mineralization
(Schlegel and Heinrich, 2015) which is located immediately outside of
the zone of most intense leaching and within chlorite + phen-
gite + siderite + fluorite and barite stable hematite breccias (Fig. 1).
The reversed propagation of hematite-quartz alteration fronts at
Olympic Dam (downward) compared to Prominent Hill (upward) is
likely a consequence of the different dispersion directions of the vol-
canic lake water derived fluid. Moreover, the similarities among the
type of iron oxide-alkali alteration, its distribution, and sulfide zonation
in both deposits are evident, but they differ significantly from the dis-
tribution of alteration patterns and the dominant sulfide mineralogy at
T.U. Schlegel, et al.
the Ernest Henry deposit and IOA deposits extending into IOCG veins
(Fig. 1).
Positive Eu anomalies (type B) develop in hydrothermal fluids at
temperatures above about 200–250 °C (Bau and Möller, 1992), which
suggests that hot and Fe-rich magmatic-hydrothermal fluids (Schlegel
et al., 2018) are important in IOCG formation. Europium anomalies are
absent in fluorite (type C) hosting the sedimentary basin brine FIA at
Prominent Hill, implying that this fluid never reached higher tem-
peratures. Both interpretations are consistent with the minimum en-
trapment temperatures of relevant FIA in siderite-bearing veins
(240–270 °C) and in the hematite breccia matrix (109–220 °C) at Pro-
minent Hill (Schlegel et al., 2018). The low LREE contents coupled with
negative Ce anomalies in the fluorites of type C are similar to the REE
patterns of fluorites of Mississippi Valley-Type Pb-Zn deposits and are
characteristic for fluids that interacted with marine carbonate rocks
(Bau et al., 2003) such as those present at Prominent Hill.
Our REE data from the Ernest Henry deposit do not contradict an
ore formation model (Oliver et al., 2008) involving a magmatic fluid
that derived some of its metal content by alteration-induced leaching of
metamorphic rocks leading to a rock-buffered basement brine (Fig. 1).
This is because this process produces flat REE patterns in fluorite
(Schwinn and Markl, 2005), which are present in the samples analyzed
in this study. Nevertheless, the direct input of Cu by magmatic-hydro-
thermal fluids (Mark et al., 2000; Baker et al., 2008) cannot be excluded
based on the limited dataset from Ernest Henry. The Ernest Henry de-
posit also formed at greater depth, possibly between 5 and 8 km depth
(e.g. Pollard et al., 1998; Rusk et al., 2010) compared to the Olympic
Dam deposit which formed at a depth estimated to 1.5 km or less
(Oreskes and Einaudi, 1992). However, the one sample form Ernest
Henry is indeed significant because it shows, independently from other
studies, that a rock-buffered basement brine was involved in ore for-
mation at Ernest Henry. In contrast, this type of fluid was not important
during the primary and high-grade Cu mineralization at Prominent Hill
and this fluid signature is also not present in our dataset from Olympic
Dam.
Some of the REE data of fluorites in siderite veins (type B) and late
calcite veins (type D) from the Mount Woods area are very similar to
the REE data of fluorite available from the Monakoff and E1 IOCG
deposits (Figs. 2, 5). They support two conclusions of Williams et al.
(2015), namely that a metal-rich brine of magmatic origin was present
at Monakoff, whereas the influence of a rock-buffered and presumably
late brine involved at the E1 deposit is indicated based on REE data and
lower Sr contents (Fig. 5D). Similarly, the different REE data and much
lower Sr contents of fluorite in breccias (type D) compared to Cu feeder
veins (type B) at the Neptune and Triton prospects (Fig. 5D) is ex-
plained by reaction of a magmatic-hydrothermal fluid with altered and
Sr-depleted lavas. This is because Sr contents in hydrothermal fluids are
very sensitive to fluid-rock interaction involving Ca-rich minerals
(Ridley and Diamond, 2000).
The apatite-bearing Cu feeder veins are evidence for a spatial link
between deeper IOA deposits and shallower IOCG mineralization.
Likewise, magnetite + apatite-rich drill core with Cu contents up to
0.7 wt% present in deep levels of the Olympic Dam breccia complex
(Apukhtina et al., 2017) were interpreted in the same manner (Simon
et al., 2018). However, the presence of a magmatic-hydrothermal fluid
resulting in mineralization with similar ore mineralogy but usually low
Cu tenor (e.g. at the Triton and Neptune prospects) does not unequi-
vocally prove that it was the main metalliferous fluid-type causing
economic mineralization in world-class IOCG deposits such as Promi-
nent Hill and Olympic Dam. Magmatic-hydrothermal fluids may
nevertheless have been the major ore fluid elsewhere as suggested for
the IOA-IOCG transition in the Chilean iron belt (Sillitoe, 2003;
Knipping et al., 2015a, 2015b; Reich et al., 2016; Simon et al., 2018).
In conclusion, our data provides clear evidence for the presence of
volcanic lake water derived fluid present at Olympic Dam (or at least a
highly oxidized epithermal fluid) which was also essential in ore
8
Chemical Geology 548 (2020) 119674
formation at Prominent Hill. The fluorite REE chemistry clearly tracks
the type of ore fluid, thus the character and source of fluids involved in
the complex continuum of IOCG mineralization can now be readily
evaluated using this simple proxy. Furthermore, this study shows that
world-class IOCG deposits form by interaction of host rocks with dif-
ferent fluids such as a metalliferous volcanic lake water, pristine and
wall-rock reacted Fe-rich magmatic-hydrothermal fluids, sedimentary
basin brines and their combinations. Ore formation models empha-
sizing the importance of a single ore fluid type may explain IOCG mi-
neralization in some regions of the world but cannot explain the for-
mation of IOCG deposits globally. Thus, the broader implication of our
study is that IOCG deposits in general probably do not form by a single
sequence of processes, which requires to exercise care when defining
exploration concepts for IOCG deposits.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This project was made possible by funding from the German
Research Foundation (DFG), grants number WA1526/7-1 and
INST222/1235-1. We thank Christoph A. Heinrich for providing sam-
ples from the Olympic Dam and Ernest Henry ore deposits and we thank
Peter Pollard for his insightful comments and constructive review. We
also acknowledge the comments of Adam Simon and Andrew Tomkins
on an early version of this paper.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.chemgeo.2020.119674.
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