Ore Geology Reviews 140 (2022) 103745

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Ore Geology Reviews

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Carbonates at the supergiant Olypmic Dam Cu-U-Au-Ag deposit, South

Australia part 2: Sm-Nd, Lu-Hf and Sr-Pb isotope constraints on the
chronology of carbonate deposition
Roland Maas a, *, Olga B. Apukhtina b, Vadim S. Kamenetsky b, c, Kathy Ehrig d, Peter Sprung e, f,
Carsten Münker e
a
School of Earth Sciences, University of Melbourne, Parkville, VIC 3010, Australia
b
School of Natural Sciences, University of Tasmania, Hobart, TAS 7001, Australia
c
Institute of Volcanology and Seismology, Petropavlovsk-Kamchatsky, Russia
d
BHP Billiton Olympic Dam, Adelaide, SA 5000, Australia
e
Institute of Geology und Mineralogy, University of Köln, 50674 Köln, Germany
f
Paul-Scherrer Institut, 5232 Villigen PSI, Switzerland

A R T I C L E I N F O A B S T R A C T

Keywords: Mineralization at the supergiant Cu-U-Au-Ag Olympic Dam deposit (South Australia), the ‘uranium endmember’
Olympic Dam of the iron-oxide copper–gold (IOCG) spectrum of ore deposits, is hosted in a breccia complex developed entirely
IOCG within granite of the 1.59 Ga Hiltaba Suite (Gawler Craton). Earlier studies suggested brecciation and miner­
Carbonates
alization occurred within a magmatically-driven hydrothermal system at 1.59 Ga, with a critical role for
Sm-Nd isotopes
Diachronous mineral formation
mafic–ultramafic intrusions. In contrast, recent radiometric dating of the breccia complex indicates a prolonged,
multi-stage history of brecciation and mineralization from 1.59 to 0.5–0.4 Ga. Ca-Fe-Mg-Mn-carbonate gangue
minerals are associated with ore minerals at virtually every stage of mineralization. In a companion study
(Apukhtina et al., 2020), this mineralogically, texturally and compositionally diverse carbonate mineral suite
was assigned to seven associations defined on the basis of host lithology and texture. Here we report Sm-Nd, Pb-
Pb and Lu-Hf isotope ages for these carbonates, which are used to examine the chronology of carbonate depo­
sition. Initial Sr-Nd isotopic compositions are used to place constraints on fluid sources. Sm-Nd and Pb-Pb isotope
systematics of calcite veins in ~1.59 Ga IOCG ore indicate 1.59–1.55 Ga deposition ages. Likewise, locally
abundant laminated siderites have Sm-Nd ages in this age interval. A world-first attempt to apply Lu-Hf dating to
carbonate gangue in an ore deposit yields ages that are 70–100 Ma younger than corresponding Sm-Nd ages,
presumably reflecting isotopic exchange of carbonate Lu-Hf isotope systems with host rocks. Sm-Nd ages for
carbonates assigned to other carbonate associations (hosted in highly altered inferred 1.59 Ga basalt and picrite;
diverse settings within granite-dominated breccia; locally abundant megaclasts of green and red bedded sand­
stone/mudstone sequences; ~0.82 Ga doleritic dykes) are more diverse and range from ~1.59 to 0.5 Ga. The
structurally youngest carbonates (unbrecciated fluorite-barite veins; carbonate matrix in polymict conglomerate
above the breccia complex) yield ~0.50 Ga Sm-Nd ages. Inferred carbonate ages are broadly consistent with
radiometric dates for other hydrothermal minerals (e.g., hematite, uraninite, apatite, fluorite). They suggest that
mineralization initiated at 1.59 Ga was reworked and possibly increased in size in response to large-scale tec­
tonic, magmatic, sedimentary and hydrothermal events. Initial 87Sr/86Sr in the carbonates is higher and more
variable (0.710–0.752, average ~0.721) than could be explained by ore and gangue mineral formation from
magmatic-hydrothermal fluids during a single event at 1.59 Ga, a model favored in several earlier studies. By
contrast, carbonate formation over a long period, as inferred from the Sm-Nd chronology presented here, would
allow ingrowth of 87Sr in the granitic host rocks to develop the heterogeneous initial 87Sr/86Sr recorded in the
carbonates. Carbonate-bearing fluids appear to have sourced Nd (and most likely also Sr) locally, within the host
granite and breccia, with contributions from mafic rocks. The emerging evidence for protracted, multi-stage
mineralization implies that single-stage models for Olympic Dam need to be revisited and that all studies of
sulfide and gangue minerals in this deposit require careful radiometric dating. We speculate that the polymetallic

* Corresponding author.
E-mail address: maasr@unimelb.edu.au (R. Maas).

https://doi.org/10.1016/j.oregeorev.2020.103745
Received 25 May 2020; Received in revised form 23 August 2020; Accepted 27 August 2020
Available online 5 September 2020
0169-1368/© 2020 Elsevier B.V. All rights reserved.
R. Maas et al.
nature and unusually large metal reserves of the Olympic Dam mineralization are related to its multi-stage
formation history.
1. Introduction
Like many other iron-oxide copper–gold (IOCG) deposits, the su­
pergiant Olympic Dam Cu-U-Au-Ag deposit (South Australia) is associ­
ated with significant Ca-Fe-Mg-Mn carbonate gangue (e.g., Ehrig et al.,
2012; Hauck, 1990; Hitzman et al., 1992; Meyer, 1988). Aspects of
carbonate gangue minerals at Olympic Dam were described in Oreskes
and Einaudi (1992) and Ehrig et al. (2012). A more comprehensive
description is provided in Apukhtina et al. (2020) who document the
diversity and multi-stage nature of the carbonates. These authors
distinguish seven associations of carbonates based largely on host rock
lithology. They also note that early suggestions of diachronous car­
bonate deposition at Olympic Dam (Oreskes and Einaudi, 1992) are
supported by mineral isotopic dating which records an apparent multi-
stage ~ 1000 Ma long history of the deposit (McPhie et al., 2011; Maas
et al., 2011, 2015a; Kamenetsky et al., 2015; Kirchenbaur et al., 2016;
Macmillan et al., 2016) following initial IOCG-style mineralization at
~1.59 Ga (e.g., Johnson and Cross, 1995; Skirrow et al., 2007; Ciobanu
et al., 2013 Apukhtina et al., 2017; Cherry et al., 2018b; Courtney-
Davies et al., 2019). Radiometric dating of the carbonates is therefore
required to assess their temporal/genetic position in the mineralization.
Furthermore, simple budget estimates require that carbon, like much of
the Fe and economic metals (Cu, Au, U, Ag), were sourced largely from
outside the host 1.59 Ga granite in which the Olympic Dam Breccia
Complex is developed. While carbon and oxygen isotopes for the car­
bonates suggest a range of fluid sources (magmatic, sedimentary,
Apukhtina et al., 2020), interpretation of these data must account for the
inferred diachronous nature of the carbonate associations.
This paper reports new Rb-Sr and Sm-Nd isotopic results for samples
which represent all seven carbonate associations (see Section 2.2)
defined in Apukhtina et al. (2020). These data were acquired to provide
(i) independent age constraints for hydrothermal carbonate deposition
and (ii) initial Sr-Nd isotope constraints on possible fluid sources and
pathways. We show that many of the carbonates are amenable to Sm-Nd
isochron dating, or can at least be placed in a broad chronologic context
using isochron diagrams. In addition, this study presents U-Th-Pb and
Lu-Hf isotope results for selected carbonate associations. The latter are
among the first published Lu-Hf isotope studies of carbonates.
2. Geological setting and mineralization
2.1. Geology
The supergiant Olympic Dam Cu-U-Au-Ag deposit, one of the largest
known deposits of Cu, Au and U on Earth, is by far the largest of several
IOCG-deposits in the Olympic Cu-Au Province of the eastern Gawler
Craton, South Australia (e.g., Williams et al., 2005; Ehrig et al., 2012;
Reid, 2019). Mineralization is hosted in the voluminous Olympic Dam
Breccia Complex (ODBC) which is developed entirely within the 1593.9
± 0.2 Ma Roxby Downs Granite (RDG), a member of the Hiltaba granite
suite and part of the Gawler Silicic Large Igneous Province (e.g., Hand
et al., 2007; Johnson and Cross, 1995; Allen et al., 2008; Jagodzinski,
2014; Cherry et al., 2018b). The breccia complex, described in detail in
Ehrig et al. (2012), is dominated by clasts of granite, with minor but
locally important clast contributions from non-granitic lithologies
including the ‘bedded clastic facies‘ (packets of interbedded sandstone
and red mudstone, well-sorted quartz-rich sandstone, green sandstone
and mudstone, polymictic volcanic-clast conglomerate, and thinly
bedded green and red mudstone, McPhie et al., 2011, 2016; Cherry
et al., 2017, 2018b), mafic to ultramafic dykes/lavas (Johnson and
McCulloch, 1995; Huang et al., 2015, 2016, 2017) and inferred rhyolitic
2
Ore Geology Reviews 140 (2022) 103745
rocks (e.g., Ehrig et al., 2012; Apukhtina et al., 2017). Strongly altered
mafic–ultramafic (picritic) rocks within the breccia complex have long
been considered equivalents of basaltic rocks in the ~1.59 Ga Lower
Gawler Range Volcanics (e.g., Reeve et al., 1990; Johnson and McCul­
loch, 1995) and this was confirmed by Huang et al. (2016). A clearly
younger generation of less altered dolerite dykes crosscuts the breccia
complex parallel to NW-oriented structures and has been identified as
part of the regional 825 Ma Gairdner Dyke Swarm (GDS, e.g., Huang
et al., 2015; Apukhtina et al., 2016). The eroded breccia complex and
host granite are unconformably overlain by ~320 m of undeformed,
unaltered and unmineralized Neoproterozoic to Cambrian sedimentary
formations of the Stuart Shelf (Reeve et al., 1990).
The Olympic Dam Breccia Complex is lithologically, texturally and
mineralogically diverse, and most minerals (e.g., hematite, Cu minerals,
pyrite, gold, uraninite, REE-fluorocarbonates) show signs of multiple
precipitation and dissolution events (Ehrig et al., 2012; Ciobanu et al.,
2017; Apukhtina et al., 2020 and references therein). Yet, despite the
alteration and mechanical mixing (brecciation), some large-scale zoning
patterns are recognized, such as the deposit-wide orthoclase-sericite-
hematite zoning and a margin-to-center/depth-to-top zoning of Fe-Cu
sulfides (pyrite → chalcopyrite → bornite → chalcocite) described by
Roberts and Hudson (1983) and Oreskes and Einaudi (1992). Sulfide
minerals, chiefly pyrite and the dominant Cu carriers chalcopyrite,
bornite and chalcocite, occur mainly as disseminated grains in granite-
and hematite-rich breccias, or as inclusions in hematite, while U min­
erals (uraninite, coffinite, brannerite) occur as small grains associated
with many other minerals, chiefly hematite, quartz and sericite; signif­
icant U is also found as nanoparticles or lattice-bound within hematite
(Ehrig et al., 2012; Ciobanu et al., 2013). Gold occurs as small grains of
electrum and Au-Ag tellurides attached to or occluded within sulfides, or
associated with sericite, quartz, barite or hematite (Ehrig et al., 2012).
The intensely brecciated core of the complex is dominated by mostly
barren quartz-hematite and is assumed to represent a block of sediments
deposited in a fault-controlled environment (McPhie et al., 2016).
Swarms of crosscutting barite-fluorite-rich veins are common in this part
of the deposit and produce a large-scale carbonate to fluorite-barite
(margin-to-center) zonation within the breccia complex. The veins
themselves are not brecciated (e.g., Ehrig et al., 2012).
U-Pb dating of a marginal magnetite-apatite-pyrite-uraninite
assemblage preserved at depth shows it formed during the initial
stages of IOCG-style mineralization at ~1.59 Ga (Apukhtina et al.,
2017). Similar U-Pb ages were reported for some of the hydrothermal
hematite (Ciobanu et al., 2013; Courtney-Davies et al., 2019). Other
studies provide evidence of protracted - perhaps episodic - brecciation,
mineralization and alteration between 1.4 and 1.1 Ga (Gustafson and
Compston, 1979; Trueman, 1986; Johnson, 1993; McInnes et al., 2008;
Maas et al., 2011; Kamenetsky et al., 2015), local remobilization of Cu
and other elements at the time of dolerite emplacement at 0.825 Ga
(Huang et al., 2015; Apukhtina et al., 2016), and formation of barite-
fluorite-carbonate veins at ~0.5 Ga (Wawryk, 1989; Maas et al., 2011;
Kamenetsky et al., 2015).
2.2. Carbonate gangue minerals
Carbonates (siderite, calcite, ankerite, dolomite) are a generally
minor but locally abundant component of the alteration/gangue
mineralogy in the ODBC. Siderite comprises just under 90% of all car­
bonate (Ehrig et al., 2012) and occurs in breccia clasts, in the breccia
matrix and in veins. Other carbonates (calcite, dolomite, ankerite and
solid solutions of dolomite-ankerite and siderite-rhodochrosite-
magnesite) are far less abundant (Ehrig et al., 2012). The bulk of the
R. Maas et al.
light rare earth elements (LREE) at Olympic Dam is hosted in the car­
bonates bastnӓsite ([Ce,La)(CO3)F], the most abundant REE mineral in
the deposit) and synchysite ([Ca(Ce,La)(CO3)2F]) which together
comprise ~3% of total carbonates (Lottermoser, 1995; Oreskes and
Einaudi, 1990; Ehrig et al., 2012).
The structural/textural diversity of the ODBC greatly complicates the
task of establishing consistent paragenetic mineral sequences. This in­
cludes the carbonate minerals which vary considerably in mineralogy,
texture and infill style. For this reason, Apukhtina et al. (2020) assigned
the carbonate gangue minerals to seven ‘associations‘ based on host li­
thology or texture: (1) coarse-grained calcite veins in weakly-brecciated
granite and rhyolite; (2) carbonates in strongly brecciated granite; (3)
carbonate veins in bedded sediments; (4) carbonates in mafic and ul­
tramafic igneous rocks; (5) carbonates in massive barite-fluorite-
dominated veins (with minor carbonate); (6) laminated siderite; (7)
carbonate matrix in conglomerate and sandstone along the unconfor­
mity between ODBC and Neoproterozoic cover sediments. Each associ­
ation shows a range of carbonate mineralogy and textures, association 2
(dominated by Fe-rich carbonates) being by far the most voluminous
and texturally diverse. Other associations are of local significance but
are mineralogically more variable. Further details can be found in
Apukhtina et al. (2020).
3. Sample selection and analytical methods
3.1. Samples
Based on the carbonate petrographic study of Apukhtina et al.
(2020), 56 samples (from 27 drillcores and 2 underground locations)
representing the seven carbonate associations were selected for isotopic
study. These samples cover the range in carbonate textures (breccia and
conglomerate cement, breccia clasts, crosscutting veins, pore infill,
massive laminated blocks and the ooide-like textures first described in
Roberts and Hudson (1983)). Mineral compositions include calcite,
dolomite, ankerite, siderite, and dolomite-ankerite and siderite-
rhodochrosite-magnesite solid solution mixtures. Anhydrite from
~1.59 Ga magnetite-rich IOCG mineralization in deep drillhole RD2773
was analysed together with the vein calcite of association 1 because like
calcite it postdates the dominant hydrothermal magnetite-apatite-
uraninite-pyrite-quartz IOCG assemblage observed in this drillhole
(Apukhtina et al., 2017). The analysed anhydrite (OD817.1, OD817.2)
fills pockets and veins in magnetite and contains inclusions of fine-
grained hematite, tourmaline and rutile. Minerals for analysis were
handpicked from crushed material or extracted as cleavage fragments
from polished drillcore using a small hand-held drill. Where required,
samples were powdered in an agate mortar.
3.2. Methods
Rb-Sr, Sm-Nd and U-Th-Pb isotopic analyses were carried out at the
University of Melbourne, following techniques adapted from Maas et al.
(2015b). Calcite and dolomite-ankerite were dissolved in dilute nitric
acid while siderite and anhydrite were dissolved in 2 M HCl; sample
weights of 20–50 mg were used throughout. Aliquots of the solutions
were used for trace element analyses on an Agilent 7700 Q-ICPMS, using
methods adapted from Eggins et al. (1997). A discussion of this diverse
trace element data set is beyond the scope of this paper; full trace
element results are compiled in Apukhtina (2016).
Solutions intended for isotope dilution Sm-Nd isotope work were
equilibrated with a 149Sm-150Nd tracer. Sr and LREE were extracted
using Eichrom Sr and TRU resin (Pin et al., 1994) followed by purifi­
cation of Nd and Sm using Eichrom LN resin (Pin and Zalduegui, 1997).
Sr fractions for some Ba-rich (barite-bearing) samples required 3 passes
over Sr resin to minimize interference from BaAr++ (Scher et al., 2014).
Where Pb isotope analysis was required, Pb was extracted first, using a
double pass over 0.1 ml beds of AG1-X8 (100–200 mesh, HBr-HCl
3
Ore Geology Reviews 140 (2022) 103745
technique). Total analytical blanks were <100 pg in all cases, and no
blank corrections were required. Isotopic analyses were carried out on a
Nu Plasma MC-ICPMS with sample uptake through a CETAC Aridus
desolvator and PFA nebuliser operated at ~0.07 ml/min sample uptake,
producing sensitivities in the range 100–150 V/ppm. Analyses were
conducted in static multi-collection mode with signals near 6 V Sr, 15 V
Nd and 10 V Pb, where possible. Instrumental mass bias in Sr isotope
runs was corrected by normalizing to 88Sr/86Sr = 8.37521, using the
exponential law. Data for spiked Nd fractions were normalized to
146
Nd/145Nd = 2.0719425 (equivalent to 146Nd/144Nd = 0.7219), using
the exponential law as part of an on-line iterative spike-stripping/
internal normalization procedure. 87Sr/86Sr and 143Nd/144Nd ratios
are reported relative to SRM987 = 0.710230 and La Jolla Nd =
0.511860 and have external precisions (reproducibility, 2sd) of
±0.000040 (Sr) and ±0.000020 (Nd). External precision for
147
Sm/144Nd obtained by isotope dilution is ±0.2%. 87Rb/86Sr ratios for
age corrections are based on the trace element results for the same
sample solution and have an external precision of ±2–3%. Results for
international standards agree with reference values. For example, long-
term (2011–2014) averages for USGS basalt standard BCR-2 are
0.704997 ± 42 (2sd, n = 44) and 0.512641 ± 24 (2sd, n = 74), and
147
Sm/144Nd is 0.1382 ± 0.0002. Decay constants are 87Rb = 1.395x10-
11
/yr and 147Sm = 6.54x10-12/yr. εNd values were calculated using a
modern CHUR composition of 147Sm/144Nd = 0.1960 and 143Nd/144Nd
= 0.512632 (Bouvier et al., 2008).
Mass bias in Pb isotope analyses was corrected using the thallium-
doping technique of Woodhead (2002). The long-term average for
Broken Hill galena measured with the same technique is 206Pb/204Pb =
16.004 ± 0.038%, 207Pb/204Pb = 15.388 ± 0.057% and 208Pb/204Pb =
35.661 ± 0.076% (n = 73, ±2sd%), consistent with reference values (e.
g., Richards, 1986; Parr et al., 2004) and implying external precisions for
unknowns in the range ± 0.04–0.08% (2sd). 238U/204Pb and
232
Th/204Pb ratios are based on the trace element results for the same
sample solution and have an external precision of ±2%.
Lu-Hf isotopic data for a sub-set of calcites and siderites were ac­
quired at the University of Cologne, Germany. Low Hf concentrations
(<1 to several ppb) and extremely high Lu/Hf make analyses of these
materials very challenging. The powdered samples (up to 2 g) were
dissolved with 3 M HCl − 1 vol% H2O2 or 3 M HNO3 − 1 vol% H2O2 at
room temperature and 80˚C, respectively. A 176Lu-180Hf spike optimized
for high-Lu/Hf materials was added before digestion, and spike and
sample were allowed to equilibrate for 24 h, promoted by heating
(HNO3-H2O2 experiments) and sonication. Although acid was added
slowly, vigorous reaction of the calcite samples led to partial loss of
sample in some cases (see Table 3). As this is likely to be a recurring issue
in Lu-Hf studies of reactive carbonate minerals, analysis of these samples
was continued to allow comparison with uncompromised samples. Prior
to column chemistry, the sample solutions were adjusted to 1 M HCl or 1
M HNO3, respectively, by adding distilled water with 1 vol% H2O2.
These solutions (10 ml total) were loaded onto column 1 of Bast et al.
(2015), in this case rescaled to a 15 ml bed of AG50-X8 (200–400) cation
resin within disposable polyethylene (Biorad EconoPac) columns. Hf
and other high field strength elements were collected in the loading
solution and another 15 ml of 0.1 M HCl-0.1 M HF or 0.1 M HNO3-0.1 M
HF (depending on dissolution type), followed by removal of the Ca/Fe
matrix and collection of a Lu-rich fraction with 2.5 M HCl. Hf was pu­
rified using EICHROM LN-resin (column 2 of Bast et al., 2015). The
procedural blank averaged 7 pg Lu and 36 pg Hf (176Hf/177Hf assumed
as 0.28216) and Hf blank was significant (0.3–38 mol%) in all analyses.
Isotopic data were acquired on a Thermo-Finnigan Neptune MC-ICPMS
equipped with standard nickel sampler and H-type skimmer cones as
well as two 10-12 Ohm Faraday detectors to record signals on 175Lu and
177
Hf during Hf isotope analysis. Hf fractions were picked up in 4%
HNO3-1% HF and aspirated via a PFA nebulizer and Cetac Aridus 2
desolvator (uptake rate 0.1 ml/min). Typical signals were 0.4–0.8 V of
total Hf from solutions with 0.5–1 ppb Hf. Interference from HREE was
 R. Maas et al.
Table 1
Rb-Sr and Sm-Nd isotope results for Olympic Dam carbonate gangue minerals from all 7 carbonate associations.
87
Sample # Fraction # Drill hole Depth, m Mineral Rb ppm Sr ppm Rb/86Sr 87
Sr/86Sr Sm ppm Nd ppm 147
Sm/144Nd 143
Nd/144Nd εNd Age t, Ma 87
Sr/86Srt εNd t
#
association 1 carbonates in felsic unit
OD 817.1 RD2773 2036.3 Anh 0.03 1,690 0.00006 0.720432 6.03 45.91 0.0793 0.511259 − 26.7 1550 0.72043 − 3.6
OD 817.2 RD2773 2036.3 Anh 0.93 1,424 0.0019 0.718045 5.35 41.25 0.0783 0.511226 − 27.4 1550 0.71800 − 4.0
OD 818 11 RD2773 2036.7 Cal 2.49 139.6 0.052 0.723206 4.78 28.17 0.1026 1550 0.72208
OD 819 12 RD2773 2051.3 Cal 0.50 97.5 0.015 0.717110 6.44 25.91 0.1502 0.511937 − 13.5 1550 0.71678 − 4.4
OD 826 47 RD2773 2179.2 Cal 0.12 97.5 0.0037 0.710388 5.54 18.03 0.1854 0.512349 − 5.5 1550 0.71031 − 3.4
OD 826.2 RD2773 2179.2 Cal 0.13 84.06 0.0046 0.712175 5.49 16.76 0.1980 0.512459 − 3.3 1550 0.71207 − 3.7
OD 827 41 RD2773 2182.4 Cal 0.11 93.2 0.0035 0.710819 3.42 17.10 0.1206 0.511684 − 18.5 1550 0.71074 − 3.5
OD 827.2 RD2773 2182.4 Cal 0.16 83.80 0.0057 0.713625 3.91 18.66 0.1264 0.511714 − 17.9 1550 0.71350 − 4.1
OD 829 42 RD2773 2208.5 Cal 0.11 107.4 0.0030 0.712044 19.80 71.35 0.1675 0.512150 − 9.4 1550 0.71198 − 3.7
OD 829.2 RD2773 2208.5 Cal 0.10 103.7 0.0027 0.711527 26.56 97.51 0.1644 0.512100 − 10.3 1550 0.71147 − 4.1
OD 830A 13 RD2773 2238.4 Cal 0.02 87.5 0.0008 0.710094 8.99 54.22 0.1001 0.511458 –22.9 1550 0.71008 − 3.8
OD 830C.1 24 RD2773 2294.5 Cal 0.11 165.8 0.0020 0.716610 7.67 16.13 0.2876 1550 0.71657
OD 830C.2 RD2773 2294.5 Cal 0.42 85.67 0.0143 0.711096 7.04 40.09 0.1061 0.511511 − 21.8 1550 0.71078 − 4.0
OD 830C.3 RD2773 2294.5 Cal 0.27 156.3 0.0050 0.718297 9.18 20.99 0.2640 0.513100 9.2 1550 0.71819 − 4.4

association 2 carbonates in granite-dominated breccia

OD 193 5 RD2773 1172.1 Cal 0.01 39.0 0.0006 0.719175 2.90 20.39 0.0858 0.511445 –23.1 1593 0.71916 − 0.6
OD 667 8 RD2319 760.1 Dol-Ank 0.22 13.4 0.0466 0.716395 1.19 5.39 0.1335 1593 0.71535
OD 835 14 RD2786A 1753.2 Cal 0.15 84.8 0.0050 0.712139 5.83 35.28 0.0998 0.511451 –23.0 1593 0.71203 − 3.4
OD 656 19 RD1172 571.5 Sid 3.74 6.2 1.750 0.751560 0.37 0.91 0.2459
OD 687 27 RD2715 855.7 Sid 0.72 4.2 0.497 0.723364 7.90 43.99 0.1086
OD 674 33 RD2681 718.3 Sid 20.61 20.6 2.890 0.752411 2.71 8.08 0.2029
OD 665 58 RD2143 787.6 Sid 11.21 321.1 0.1009 0.723039 9.93 45.27 0.1324 0.512518 − 2.2 825 0.72187 4.5
OD 659 6 RD1705 493.8 Sid 1.66 11.7 0.4101 0.722635 3.07 20.43 0.0909
OD 661 7 RD2063 680.3 Dol-Ank 0.09 17.6 0.0141 0.729437 3.53 9.69 0.2202 0.512019 − 11.9 500 0.72934 − 13.5
4

OD 660 29 RD2016 622.3 Dol-Ank 0.71 520.5 0.0039 0.715620 1.73 10.29 0.1014 0.511306 − 25.8 1593 0.71553 − 6.5
OD 662 34 RD2143 542.1 Sid 0.14 10.0 0.0416 0.710679 1.16 8.14 0.0862 1593 0.70974
OD 675 59 RD2681 731.8 Sid 0.06 109.5 0.0017 0.713897 483 3236 0.0903 1593 0.71386
OD 1001 55 underground grab sample Sid, oolite 0.57 213.9 0.0077 0.708831 14.53 89.43 0.0981 0.511421 –23.6 1593 0.70866 − 3.6

association 3 carbonates in green sandstone

OD 226.6 vein RD1624 584.2 Dol-Ank 1.73 122.4 0.0408 0.718450 5.06 20.27 0.1508 0.511909 − 14.1 1593 0.71753 − 4.8
OD 187 21 RD2821 627.9 Dol-Ank, (Sid-Mag) 0.36 139.2 0.0075 0.736650 3.65 8.97 0.2460 0.513012 7.5 1593 0.73648 − 2.8

association 3 carbonates in red sandstone

OD 836 39 RD2786A 1796.2 Dol-Ank 0.11 80.8 0.0038 0.70769 0.94 4.79 0.1187 0.511711 − 17.9 1550 0.70761 − 2.6
OD 839 40 RD2786A 1896.5 Dol-Ank 0.50 210.1 0.0068 0.71132 2.25 10.59 0.1281 0.511485 –22.3 500 0.71127 − 18.0
OD 837 45 RD2786A 1847.8 Dol-Ank 0.17 557.5 0.0009 0.72280 4.14 14.10 0.1773 0.511418 –23.6 500 0.72279 –22.5

association 4 carbonates in basalt (~1590 Ma)

OD 95 1 RD2715 836.3 Sid 0.37 24.1 0.0450 0.72404 3.79 14.74 0.1551 0.511962 − 13.0 1593 0.72303 − 4.7
OD 18 3 RD2744 821.2 Dol-Ank 0.22 56.1 0.0112 0.72246 26.36 61.94 0.2570 0.512163 − 9.1 500 0.72238 − 13.0
OD 106 4 RD2031W1 889.1 Dol-Ank 4.30 66.1 0.1880 0.72121 18.91 58.57 0.1950 0.511994 12.4 500 0.71989 − 12.4

Ore Geology Reviews 140 (2022) 103745

−
OD 806 10 RD2773 1263.1 Cal 0.02 123.3 0.0006 0.72064 0.68 3.77 0.1088 0.512284 − 6.7 825 0.72064 2.5
OD 684 35 RD2715 839.2 Sid 2.91 17.1 0.491 0.72864 14.43 60.75 0.1437 1593 0.71761
OD 197 20 RD2773 1248.5 Cal 0.03 34.6 0.0028 0.72006 2.05 8.72 0.1422 0.511754 − 17.1 1593 0.72000 − 6.1
OD 16 22 RD2744 761.4 Dol-Ank 0.30 109.3 0.0081 0.71639 46.82 59.65 0.4740 0.512569 − 1.2 500 0.71634 − 19.0
OD 78 23 RD2773 1255.2 Cal 0.08 58.4 0.0041 0.72454 0.16 0.94 0.1030 1593 0.72444
OD 134 26 RD1763 864.5 Dol-Ank 0.10 58.7 0.0047 0.72063 4.81 36.36 0.0800 1593 0.72052
OD 2 28 RU39-5426 224.4 Dol-Ank 0.19 226.9 0.0024 0.72964 5.74 22.63 0.1531 0.512538 − 1.8 825 0.72962 2.7
OD 102 49 RD2018B 812.8 Dol-Ank 0.27 103.5 0.0074 0.71611 2.10 5.71 0.2225 0.512221 − 8.0 500 0.71606 − 9.7
OD 114 50 RD271 650.5 Cal 1.56 15.0 0.3007 0.72521 0.30 1.00 0.1815 1593 0.71845
OD 82 51 RD2773 1331.7 Cal 77.86 150.8 1.492 0.73940 0.28 5.89 0.0288
OD 199 53 RD2773 1329.2 Cal 0.38 89.0 0.0122 0.72186 0.06 0.21 0.1728 1593 0.72159
(continued on next page)
 R. Maas et al.
Table 1 (continued )
87
Sample # Fraction # Drill hole Depth, m Mineral Rb ppm Sr ppm Rb/86Sr 87
Sr/86Sr Sm ppm Nd ppm 147
Sm/144Nd 143
Nd/144Nd εNd Age t, Ma 87
Sr/86Srt εNd t
OD 914.6 vein RD2715 852.6 Dol-Ank 2.36 13.3 0.514 0.727686 10.56 32.77 0.1963 0.512599 − 0.6 825 0.72173 − 0.6
OD 906 cc RD2715 810.1 Sid 1.36 431.0 0.0092 0.718387 1593 0.71818

association 4 carbonates in picrite (~1590 Ma)

OD 868 43 RD1756 342 Dol-Ank 2.70 40.4 0.193 0.719914 25.63 35.8 0.4337 1593 0.71557
OD 494.6 vein RD3564 368.9 Dol-Ank 3.09 109.13 0.0819 0.713336 13.40 58.49 0.1383 0.512126 − 9.8 1593 0.71149 2.0

association 4 carbonates in mafic/ultramafic rocks (825 Ma dolerite)

OD 857 30 RU39-5426 238 Dol-Ank 6.23 131.6 0.137 0.72488 7.57 20.21 0.2263 0.512851 4.3 825 0.72330 1.1
OD 852 31 RU65-8230 596 Cal 0.17 62.1 0.0079 0.71872 6.38 18.67 0.2064 0.512746 2.3 825 0.71863 1.2
OD 848 15 RU65-8230 529 Dol-Ank 0.22 72.3 0.0088 0.72329 9.00 34.25 0.1590 825 0.72319
OD 186 46 RD2821 608 Dol-Ank 1.07 30.2 0.1025 0.72601 3.93 51.84 0.0458 0.511804 − 16.1 825 0.72482 − 0.3
OD 79 48 RD2773 1271 Cal 0.65 262.6 0.0072 0.71925 825 0.71916

association 5 carbonates in massive barite-fluorite-siderite veins

OD 686 9 RD2715 855 Sid 2.97 7.0 1.227 0.73561 23.73 177.7 0.0808 500 0.72702
OD 831 25 RD2786A 1601 Sid 0.06 2.0 0.0852 0.74123 0.03 0.08 0.1979 500 0.74063
OD 842 2 RD2786A 2160 Sid 0.08 46.8 0.0048 0.75229 0.05 0.12 0.2334 500 0.75225
OD 1005 32 underground grab sample Dol-Ank 2.72 688.0 0.0114 0.71523 5.04 17.07 0.1782 0.511358 − 24.8 500 0.71515 –23.7
OD 841 54 RD2786A 1949 Dol-Ank 0.02 45.8 0.0016 0.72553 0.08 0.2 0.2200 500 0.72552

association 6 laminated carbonate

OD 1006_ core 36 RU36-8834 69 Sid 0.34 79.6 0.0124 0.72297 6.34 52.97 0.0722 0.511182 − 28.2 1593 0.72269 − 3.0
OD 1006_ rim1 37 RU36-8834 69 Sid 0.02 4.4 0.0146 0.71674 0.97 5.61 0.1046 1593 0.71641
OD 1006_ rim2 38 RU36-8834 69 Sid 0.03 39.8 0.0018 0.71784 0.92 4.91 0.1137 0.511425 –23.5 1593 0.71780 − 6.7
5

OD 1045 RU36-8834 62.2 Sid 0.075 18.66 0.0115 0.71772 4.07 27.27 0.0901 0.511380 − 24.4 1593 0.71746 − 2.8
OD 1047 RU36-8834 70.2 Sid 0.087 4.98 0.0503 0.71902 6.95 37.51 0.1118 0.511503 –22.0 1593 0.71789 − 4.8
OD 1048 RU36-8834 71.4 Sid 0.189 13.27 0.0411 0.72383 4.54 29.20 0.0938 0.511272 − 26.5 1593 0.72291 − 5.6
OD 1050 RU36-8771 105 Sid 0.053 6.75 0.0227 0.71680 1.43 4.51 0.1913 0.512412 − 4.2 1593 0.71628 − 3.3
OD 1051 RU36-8771 108.5 Sid 0.080 2.86 0.0804 0.71678 0.78 3.07 0.1526 0.511968 − 12.9 1593 0.71497 − 4.1
OD 1008 RU36-8834 64.6 Sid 0.029 15.88 0.0052 0.71475 5.64 36.00 0.0946 0.511367 − 24.6 1593 0.71464 − 3.9
OD 1008_1 RU36-8834 64.6 Sid 0.11 7.64 0.0426 0.71843 0.61 3.08 0.1207 0.511624 − 19.6 1593 0.71747 − 4.2
OD 1008_3 RU36-8834 64.6 Sid 0.068 4.67 0.0423 0.71649 0.51 2.34 0.1313 0.511708 − 18.0 1593 0.71554 − 4.8
OD 1008_4 RU36-8834 64.6 Sid 0.076 4.63 0.59 2.93 0.1218 0.511637 − 19.4 1593 − 4.2
OD 1008_8 RU36-8834 64.6 Sid 0.059 3.35 0.0513 0.71519 1593 0.71404
OD 1008_10 RU36-8834 64.6 Sid 0.060 3.61 0.0482 0.71577 0.52 2.43 0.1287 0.511712 − 17.9 1593 0.71469 − 4.2

association 7 carbonate matrix in conglomerate at unconformity

OD 425 57 RD3564 364 Dol-Ank 0.85 59.0 0.0418 0.72327 6.07 9.76 0.3752 0.512151 − 9.3 500 0.72298 − 20.8
OD 886_1 fawn 17 RD2972 388 Dol-Ank 0.07 411.8 0.0005 0.71990 3.67 9.31 0.2377 0.511733 − 17.5 500 0.71990 − 20.2
OD 886_2 RD2972 388 Dol-Ank 6.63 11.50 0.3482 0.511883 − 14.6 500 − 24.3
OD 886_3 RD2972 388 Dol-Ank 5.88 10.40 0.3411 0.511819 − 15.8 500 − 25.1
OD 873_1 60 RD1629 330 Dol-Ank 0.07 144.0 0.0014 0.71618 9.58 10.55 0.5484 0.512624 − 0.1 500 0.71617 –22.7

Ore Geology Reviews 140 (2022) 103745

OD 873_2 RD1629 329.6 Dol-Ank 13.21 15.08 0.5290 0.512580 − 1.0 500 –22.3
OD 873_3 RD1629 329.6 Dol-Ank 14.31 16.89 0.5116 0.512550 − 1.6 500 − 21.8

Abbreviations: cal = calcite, dol = dolomite, ank = ankerite, sid = siderite, mag = magnesite, anh = anhydrite.
OD830A and C are from different depths of same drillcore; OD830C1,2,3 refer to different sub-samples of calcite.
OD1008 is a large chip of siderite; OD1008.1 to 0.10 are spot samples obtained by micro-drilling of siderite elsewhere in OD1008.
Sm-Nd concentrations and Sm/Nd ratio by isotope dilution, see text for details.
Rb-Sr concentrations and Rb/Sr ratios from trace element data, see text for details.
R. Maas et al.
Fig. 1. (A) Rb-Sr isochron diagram for carbonates from the seven Olympic Dam
carbonate associations. Most of the measured carbonates have low Rb/Sr and
measured 87Sr/86Sr from ~0.710 to ~0.725 (but reaching >0.750). Samples
with high Rb/Sr (mostly siderite with low Sr concentration) do not form readily
interpretable isochronous arrays. Reference isochrons for 1590, 1000 and 500
Ma (anchored at 0.720) shown for comparison. (B) Measured 87Sr/86Sr in
carbonates with 87Rb/86Sr ≤ 0.2 (i.e. minimal ingrowth regardless of age)
shows large isotopic ranges in all measured examples.
mostly negligible, a result of the excellent separation of Hf from HREE in
the 2-column procedure. Mass bias and spike stripping corrections were
done offline, using 179Hf/177Hf = 0.7325 for internal normalization,
with error propagation as described in Sprung et al. (2013). Hf extracted
from USGS standard BCR-2 was measured with signals similar to those
obtained for the carbonate samples and yielded an average of 0.282872
± 68 (95% CL, n = 8), in excellent agreement with reference values; the
large uncertainty (equivalent to an external precision, 2sd, of ±
0.000162, or ± 5.8 εHf units) reflects the small Hf signals. Lu isotope
dilution runs were done as described in Sprung et al. (2013). The Lu
decay constant used is 1.867 × 10− 11/yr.
4. Results
4.1. Rb-Sr isotope results
Hydrothermal Ca-Fe-Mg-Mn carbonates of all seven carbonate
associtions have highly variable Sr concentrations (2–688 ppm, avg. 98
6
Ore Geology Reviews 140 (2022) 103745
Fig. 2. 147Sm/144Nd vs. Nd ppm for carbonate gangue mineral associa­
tions 1–7.
ppm, Table 1). With some exceptions, Sr concentrations tend to be
lowest in siderite, but otherwise there is little systematic difference
between the various carbonate minerals. Rb/Sr is low in most samples:
58 of 75 samples listed in Table 1 have Rb/Sr ≤ 0.02, while the
remaining 17 samples have Rb/Sr from 0.03 to 1.0. The average for the
entire data set is 0.054 (Fig. 1A). Present-day 87Sr/86Sr varies from
0.70769 to 0.75241 with an average at 0.72076; the Sr-weighted
average is 0.72834. This isotopic range is consistent with 87Sr/86Sr in
barite (0.7093–0.7259), fluorite (0.7127–0.7272), and dolomite
(0.7138–0.7167) from prominent baryte-fluorite-dolomite veins
(Wawryk, 1989). In the Rb-Sr isochron diagram (Fig. 1A), high Rb/Sr
tends to be associated with high 87Sr/86Sr, but there are no consistent,
well-supported linear arrays that could be interpreted as isochrons. For
low-Rb/Sr carbonates (e.g., 87Rb/86Sr ≤ 0.2), local ingrowth is small
(≤0.006 for 1.59 Ga), implying that measured 87Sr/86Sr approximates
initial 87Sr/86Sr. In detail, associations 6 and 7 (laminated siderite;
conglomerate matrix) show relatively limited ranges (~0.715–0.725),
while associations 3 and 5 (sandstone and mudstone; massive fluorite-
barite veins) are the most diverse (Fig. 1B). The lowest 87Sr/86Sr
(<0.710) occurs in associations 1–3. Two samples of anhydrite (~1500
ppm Sr, very low Rb/Sr, Table 1) tought to be broadly cogenetic with
association 1 calcite veins have measured 87Sr/86Sr (0.7180–0.7204)
within the range of the associated calcite (0.7104–0.7232).
4.2. Sm-Nd isotope results
Nd concentrations in the carbonates also vary strongly (0.08–3236
ppm), as do Sm/Nd ratios (147Sm/144Nd = 0.028–0.548, average 0.177,
Table 1, Fig. 2). No consistent correlations exist between carbonate as­
sociation or mineral type and Nd concentration, or between Nd con­
centration and Sm/Nd (Fig. 2). Carbonates of association 4
(mafic–ultramafic) show the greatest variability in Sm/Nd while those
of associations 3, 5, and 6 (sandstone and mudstone; fluorite-barite
veins; laminated siderite, respectively) are more homogeneous.
Consistently high Sm/Nd is observed in association 7 (conglomerate
matrix). In general, Sm/Nd in Olympic Dam carbonates is high relative
to the host granite and the breccia complex (Fig. 2). Two samples of
association 1 anhydrite have 41–46 ppm Nd and the lowest Sm/Nd
observed in this association.
In the Sm-Nd isochron diagram (Fig. 3A), the data show a number of
distinct trends that are interpreted to record depositional ages between
ca.1.6 and ca.0.5 Ga:
R. Maas et al.
Fig. 3. Sm-Nd isochron diagrams for Olympic Dam carbonates. (A) all samples
analysed in this study. The ca. 1590 Ma ‘Main Array‘ broadly fits all data points
for associations 1 and 6. The compositions of some carbonates assigned to as­
sociations 2, 3 and 4 also plot along the Main Array while others from these
associations plot above and/or below the trend. Carbonates in the 825 Ma
dolerite (assoc. 4 dolerite) plot along an 825 Ma reference line that passes
through the field of whole rock analyses for this dolerite. All carbonates from
association 7 have high Sm/Nd (Fig. 2) and define a scattered ca. 500 Ma trend:
a composite regression including the association 7 data points, the single point
for carbonate from association 5, and carbonates OD837 and 839 (assoc.3) and
OD16 (assoc.4) yield a 486 ± 84 Ma age (n = 11, MSWA 131, εNdi − 21.6, see
text). Fields for fluorites from late-stage fluorite-baryte veins are shown with
short 500 Ma reference lines (fluoritea from Wawryk (1989); fluoriteb from
Maas et al. (2011)). Other fields shown are for host Roxby Downs Granite
(‘granite‘), Cu ores and Olympic Dam Breccia Complex (‘ores‘), ca. 1.59 Ga
altered mafic and ultramafic rocks from within the breccia complex (‘M-UM‘)
and the 825 Ma dolerite that cuts the breccia complex (‘GDS dolerite‘). Data
sources: Creaser, 1995; Johnson and McCulloch, 1995; Huang et al., 2015;
Apukhtina et al., 2016, 2017; Maas and Apukthina, unpubl. data). (B) Details
for association 4 carbonates showing the diverse compositions for these sam­
ples. The sole analysed carbonate from association 4 (picrite) plots within the
field of whole rock analyses for the ca. 1.59 Ga mafic and ultramafic rocks (M-
UM). Two (possibly three) of the carbonates assigned to association 4 (basalt)
plot near the Main Array, while two (possibly three) lie near the 825 Ma
reference line for association 4 (dolerite) carbonates. Four other carbonates
from association 4 (basalt) plot below the Main Array and may define their own
0.4–0.5 Ga trend. Shaded data fields (granite, ores/ODBC, M-UM, GDS dolerite)
as for Fig. 3A.
7
Ore Geology Reviews 140 (2022) 103745
Association 1. The compositions of all analysed calcites (10 samples,
87
Sr/86Sr 0.71007–0.72321) and anhydrites (2 samples, 0.72043,
0.71800), and two samples of the host rock (a rhyolitic rock referred to
as ‘felsic unit’ in local mine terminology), define a linear array with an
apparent age of 1546 ± 33 Ma (MSWD = 3.2, εNdi = − 4.0, Fig. 3A; see
Apukhtina et al. (2017)). This trend, which also intersects the compo­
sitional fields for the host Roxby Downs Granite and Cu-rich ores, will be
referred to as ‘Main Array’ hereafter.
Association 2. The compositions of four analysed carbonates in
granite-dominated breccia plot close to that of the host granite and thus
the Main Array, including oolitic siderite OD1001 (Figs. 2B, 3A). Two
other carbonates (OD661, 665) have much higher 143Nd/144Nd and lie
off the Main Array; no direct Sm-Nd age information can be derived from
these data.
Association 3. Dolomite-ankerite in carbonate veins OD187
(87Sr/86Sr 0.7365) and OD226 (87Sr/86Sr 0.7176) in green sandstone-
mudstone show considerable Sm-Nd dispersion and plot within the
Main Array, as does dolomite-ankerite OD836 (87Sr/86Sr 0.7077) from
red sandstone, suggesting a 1.6–1.55 Ga age for these three carbonate
samples (Fig. 3A). Two further vein carbonates, dolomite-ankerite
OD837 and OD839 from red sandstone, plot below the Main Array
(Fig. 3A) and may be part of the ~0.5 Ga trend defined by association 5
and 7 carbonates (see below).
Association 4. Carbonates of this association occur (i) in strongly
altered basaltic rocks (olivine-phyric basalt froming a flat-lying unit of
olivine-phyric basalts near the top of the breccia complex; variably
altered aphanitic, doleritic and porphyritic mafic dykes) believed to be
~ 1.59 Ga old (e.g., Huang et al., 2016), and (ii) in veins within less
altered 0.825 Ga dolerite dykes (Huang et al., 2015). Sm-Nd isotope data
for 10 carbonate samples from the older mafic/ultramafic rocks are
diverse and only some of them plot within the broad linear array (with a
1.70–1.76 Ga slope) defined by 12 analyses of their host lithologies
(Fig. 3B): one plots with its host picrite rocks (OD494), two more (OD95,
197) plot near the Main Array, three (OD2, 806, 914) plot near a trend
defined by the 825 Ma dolerites and carbonates within these dolerites,
and four others plot along a scattered ~0.4 Ga trend controlled by high-
Sm/Nd dolomite-ankerite OD16 (Fig. 3B). Multiple age interpretations
are possible for some of these data points. The compositions of three
carbonates (OD186, 852, 857) from veins in the 0.82 Ga dolerite dykes
lie close to an 825 Ma reference line which also intersects a cluster of
dolerite whole rock data points (Huang et al., 2015; Apukhtina et al.,
2016; Maas and Apukhtina, unpubl.data). As mentioned above, three of
the carbonates within altered 1.59 Ga mafic/ultramafic intrusives also
plot near this 825 Ma reference line (Fig. 3B).
Association 6. Sm-Nd data for laminated siderite consistently plot
within the Main Array (Fig. 3A). Regression of twelve data points yields
an apparent age of 1600 ± 190 Ma (MSWD = 33, εNdi = 4.2), consistent
with formation of the laminated siderite during the early history of the
breccia complex.
Association 5 and 7. The results for carbonates from these associa­
tions consistently yield the youngest ages and are thus presented
together. Siderite and dolomite-ankerite within unbrecciated (and thus
‘late-stage’, Ehrig et al., 2012, p 259) fluorite-barite-siderite veins (as­
sociation 5) are probably ~0.5 Ga old, based on imprecise but consistent
Sm-Nd ages for fluorite reported in Wawryk (1989) and Maas et al.
(2011); these fluorite trends are shown in Fig. 3A. A single carbonate
analysis from one of these veins (dolomite-ankerite OD1005) plots well
below the Main Array (Fig. 3A), within the elongate cluster defined by
the fluorite data of Wawryk (1989). This cluster is broadly colinear with
an extensive trend defined by carbonates from conglomerate cement
(association 7, Fig. 3A) and single samples from associations 3 and 4, see
above. Regression of data for the association 5 and 7 dolomite-ankerites
with data for three carbonate samples from two other associations (3, 4,
see above) produces an apparent Sm-Nd age of 486 ± 84 Ma (MSWD =
131, εNd = 21.6) suggesting renewed carbonate formation during the
Cambrian.
R. Maas et al. Ore Geology Reviews 140 (2022) 103745

Table 2
(U-Th)-Pb isotope compositions for Olympic Dam calcites (Association 1) and laminated siderites (Association 6).
238
U ppm Th ppm Pb ppm U/204Pb 232
Th/204Pb 206
Pb/204Pb 207
Pb/204Pb 208
Pb/204Pb 204
Pb/206Pb 207
Pb/206Pb

association 1 carbonates (calcite) and anhydrite, ’felsic unit’

OD826 RD2773 2179.2 cal pink 0.09 0.14 9.2 0.63 0.98 18.420 15.728 36.965 0.054289 0.8539
OD827 RD2773 2182.4 cal pink 0.08 0.04 12.1 0.42 0.20 17.947 15.660 36.734 0.055720 0.8726
OD829 RD2773 2208.5 cal white 0.09 0.09 6.4 0.87 0.96 18.294 15.681 37.355 0.054664 0.8572
OD830.1 RD2773 2238.4 cal pink 0.23 0.03 14.2 1.01 0.12 19.098 15.768 36.927 0.052361 0.8256
OD830.2 RD2774 2238 cal white 0.03 0.01 17.3 0.10 0.04 24.640 16.391 39.079 0.040584 0.6652
OD817.1 RD2773 2036.3 anh, finegrained, 0.81 0.07 8.6 16.14 1.51 109.653 24.649 62.897 0.009120 0.2248
with apatite

association 6 laminated siderite

OD1045 RU36-8834 62.2 Sid 5.18 0.25 61.7 5.25 0.260 19.248 15.685 36.376 0.051953 0.8149
OD1047 RU36-8834 70.2 Sid 13.83 0.90 48.8 17.93 1.202 19.954 15.779 36.418 0.050116 0.7908
OD1048 RU36-8834 71.4 Sid 165.64 1.22 89.4 116.38 0.884 19.667 15.751 36.300 0.050848 0.8009
OD1050 RU36-8771 105 Sid 0.55 0.02 148.1 0.22 0.009 16.664 15.506 36.202 0.060009 0.9305
OD1051 RU36-8771 108.5 Sid 0.37 0.02 79.1 0.28 0.017 16.853 15.522 36.210 0.059338 0.9211
OD1008 RU36-8834 64.6 Sid 11.22 0.32 60.5 11.53 0.342 19.019 15.661 36.301 0.052578 0.8234
OD1008.1 RU36-8834 64.6 Sid 2.06 0.03 27.2 4.70 0.082 18.868 15.740 36.345 0.053000 0.8342
OD1008.3 RU36-8834 64.6 Sid 1.04 0.02 31.3 2.05 0.039 18.328 15.694 36.313 0.054561 0.8563
OD1008.4 RU36-8834 64.6
OD1008.8 RU36-8834 64.6 Sid 2.41 0.03 30.6 4.89 0.056 18.816 15.723 36.331 0.053145 0.8356
OD1008.10 RU36-8834 64.6 Sid 2.06 0.02 32.1 3.96 0.044 18.449 15.692 36.301 0.054204 0.8506
OD1045 RU36-8834 62.2 Sid 0.99 0.01 30.5 2.00 0.029 18.618 15.730 36.329 0.053712 0.8449

U-Th-Pb concentrations and U/Pb-Th/Pb ratios from trace element data for the sample solutions, see text for details. Pb concentrations were determined by summing
the countrates on the three main Pb.
isotopes in unknowns and standards; this eliminates Pb isotope composiiton as a source of systematic error.
Pb-Pb isochron ages (Fig. 4) were calculated using uncertainties of ± 0.1–0.2% for 206Pb/204Pb, 204Pb/206Pb and 207Pb/204Pb, and ±0.02% for 207Pb/206Pb;
error correlations are 0.8–0.9.

4.3. U-Th-Pb isotope results 4.4. Lu-Hf dating of calcite and siderite

Five calcites from association 1 have low U and Th (0.03–0.23 ppm
and 0.1–0.14 ppm, respectively); Pb concentrations vary from 6.4 to
17.3 ppm. As a consequence, U/Pb and Th/Pb ratios are very low
(238U/204Pb 0.1–1.01, 232Th/204Pb, 0.04–0.98, Table 2). Measured
206
Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios range from 17.94 to
24.64, 15.66 to 16.39 and 36.73 to 39.08, respectively. In the
207
Pb/204Pb-206Pb/204Pb diagram (Fig. 4A) the 5 data points form a
slightly scattered linear array with an apparent age of 1795 ± 150
(MSWD = 5.3). Addition of data for texturally cogenetic anhydrite
OD817.1 (206Pb/204Pb 109.6, Table 2) expands the isotopic range
considerably, producing a 6-point Pb-Pb isochron age of 1585 ± 23 Ma
(MSWD = 25, Fig. 4A). This Pb-Pb isochron age is indistinguishable from
laser-ablation ICP-MS U-Pb ages for other hydrothermal minerals (ura­
ninite, apatite, hematite) in the host rocks of these calcites, and similar
to the Sm-Nd age for the calcites themselves (Apukhtina et al., 2017; this
study). However, the significance of this age remains unclear because
present-day Pb isotope ratios in the calcites and anhydrite are unsup­
ported by their low measured U/Pb (Table 2).
Association 6 laminated siderites have highly variable concentra­
tions of U (0.55–165.6 ppm), Th (0.01–1.22 ppm), and Pb (27.2–148.1
ppm, Table 2). U/Pb ratios (238U/204Pb 0.22–116.4) are controlled by U
while Th/Pb is low throughout (232Th/204Pb ≤ 1.2). Measured
206
Pb/204Pb and 207Pb/204Pb ratios (16.66–19.95; 15.52–15.78) do not
correlate with U/Pb, but the uniformly low 208Pb/204Pb (36.2–36.4) is
consistent with the low Th/Pb. In the 207Pb/204Pb-206Pb/204Pb diagram,
seven of the association 6 siderite data points are broadly colinear with
the association 1 calcite trend, while four others define a separate short
array below the calcite trend (Fig. 4A). Much of this detail is lost in the
‘inverse’ Pb-Pb (207Pb/206Pb-204Pb/206Pb) diagram where all siderite
and calcite data points plot on a single trend, yielding a pooled age of
1601 ± 100 Ma (n = 17, MSWD = 66, Fig. 4B). In the
208
Pb/204Pb-206Pb/204Pb diagram, the siderite data form a single trend
that intersects a crustal Pb growth curve at ca.1.25 Ga (Fig. 4C).
Carbonates minerals can show variable and sometimes strong Lu/Hf
fractionation (Bizimis et al., 2003; Kamber and Webb, 2001). Like gar­
nets and phosphates (e.g., Baxter and Scherer, 2014; Barfod et al., 2005),
carbonate minerals may thus be suitable for Lu-Hf dating. Some Olympic
Dam calcites and siderites show high to very high Lu/Hf ratios were used
to explore the utility of Lu-Hf isotope dating of hydrothermal carbon­
ates. The resulting Lu-Hf ages are broadly consistent with Sm-Nd ages,
implying that Lu-Hf may indeed be a useful addition to the range of
carbonate dating methods.
Six samples of laminated siderite (association 6) have 7 to 1686 ppb
Lu and 0.045 to 9.79 ppb Hf (Table 3). 176Lu/177Hf (4.9–98) and
176
Hf/177Hf (0.349–3.546) ratios are very high and variable, and
therefore favorable for dating. Although the low Hf concentrations in
these analyses result in unfavorable sample/blank ratios, the Lu-Hf
isotopic results presented here were not corrected for blank because
such corrections would have minimal effects on the slopes of any iso­
chrons defined by the uncorrected data (Barfod et al., 2005). Regression
of all 9 data points in the isochron diagram yields a slope equivalent to
an age of 1687 ± 150 Ma (MSWD = 2736). After exclusion of OD1045.2,
the most radiogenic data point and a clear outlier, the pooled age be­
comes 1460 ± 120 Ma (MSWD = 1944). A much more precise apparent
age (MSWD = 1.8, 1428 ± 3 Ma, Fig. 5A) is produced by combining the
results for OD1047.2, OD1048.2, and OD1051.2, all from HCl-H2O2
digestions. The calculated y-axis intercepts of these regressions are
highly imprecise and are therefore not discussed.
Calcites from association 1 have generally higher concentrations of
Lu (633–8248 ppb) than the siderites, while Hf concentrations
(0.54–6.12 ppb) are comparable. 176Lu/177Hf (262–26137) and
176
Hf/177Hf (7.32–847) are therefore even more extreme than in the
siderites. With the exception of one data point (OD830C2), the data form
a near-linear array in the isochron diagram (Fig. 5B). If OD830C2 is
excluded, the remaining 7 points (including some replicates) yield an
apparent age of 1482 ± 61 Ma (MSWD = 74). A more precise age
(MSWD = 0.11, 1472 ± 20 Ma) results from pooling the data for OD826,
829 and 829.2; these are considered the most reliable of the calcite
analyses because there was no sample loss during dissolution.

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R. Maas et al. Ore Geology Reviews 140 (2022) 103745

Table 3
Lu-Hf isotopic compositions for Olympic Dam calcites (Association 1) and laminated siderites (Association 6).
Core Depth, m ppb Lu 2sd% ppb Hf 2sd% 176Lu/177Hf 2sd% 176Hf/177Hf 2sd% rho Molar Model age
sample/blank Ga

association 1 calcite
OD826 RD2773 2179.2 1296 0.6 1.09 0.7 1496 0.8 43.03 0.6 − 0.01 46.4 1.51
OD826.2* RD2773 2179.2 772 0.3 0.9566 0.1 262.41 0.3 7.322 0.1 − 0.01 13.3 1.42
OD827.2* RD2773 2182.4 633 0.4 0.5428 0.2 926.7 0.4 25.39 0.2 − 0.01 21.5 1.43
OD829 RD2773 2208.5 5686 3.4 4.25 2 9633 3.5 271 1.6 − 0.04 174.1 1.49
OD829.2 RD2773 2208.5 8248 1.3 6.129 0.2 9232 1.3 258.5 0.1 0.04 113.6 1.48
OD830C1.2 RD2773 2294.5 1106 0.5 0.911 0 1996 0.6 58.02 0.2 0.03 34.6 1.53
OD830C2 RD2773 2294.5 6729 4.2 5.71 0.7 26,137 4.2 846.9 0.5 0.04 265.5 1.71
OD830C2.2* RD2773 2294.5 5636 2.0 3.941 0.1 2831 2.0 70.92 0.1 0.01 91.2 1.32

association 6 siderite
1008.2 RU36-8834 64.6 99.4 0.4 0.935 0.2 16.71 0.5 0.8753 0.2 − 0.02 13.7 1.87
1045.2 RU36-8834 62.2 230.6 0.3 0.531 0.2 98.46 0.4 3.546 0.2 0.09 7.64 1.75
1047 RU36-8834 70.2 222.3 0.3 2.067 0.05 16.59 0.3 0.7563 0.07 0.02 90.5 1.51
1047.2 RU36-8834 70.2 120.4 0.2 1.881 0.02 9.536 0.2 0.5547 0.06 0.00 31.9 1.51
1048 RU36-8834 71.4 201.6 0.2 5.899 0.04 4.976 0.2 0.4246 0.06 0.00 294 1.52
1048.2 RU36-8834 71.4 92.65 0.2 6.904 0.03 1.928 0.2 0.3494 0.05 0.00 165 1.85
1050.2 RU36-8771 105 166.8 0.5 0.482 0.1 65.67 0.5 2.115 0.2 0.02 7.82 1.47
1051 RU36-8771 108.5 6.960 0.2 0.0624 0.05 17.15 0.2 0.7339 0.08 0.11 2.59 1.39
1051.2 RU36-8771 108.5 1686 0.3 9.858 0.1 27.68 0.3 1.047 0.1 0.00 152 1.46

Suffix .2 denotes second digestion for same powder; * marks digestions affected by sample loss during dissolution.
Lu and Hf ppb measured by isotope dilution; molar sample/blank ratio, see text for details; listed data not corrected for blank.
Lu-Hf model ages are 2-point model ages calculated with a common Hf anchor composition of 176Lu/177Hf 0.015, 176Hf/177Hf 0.28216.

By analogy with other highly radiogenic mineral isotope systems (e.
g., Re-Os molybdenite), single sample Lu-Hf (model) ages can be derived
for the siderites and calcites by combining the Lu-Hf results with an
estimate of the relevant common Lu-Hf system. Although the exact
common Hf anchor composition has little influence, we chose present-
day 176Lu/177Hf and 176Hf/177Hf ratios of 0.015 ± 0.005 and 0.28216
± 0.00002, respectively. This 176Lu/177Hf ratio is an often-cited estimate
for average continental crust (e.g., Griffin et al., 2004) while the
176
Hf/177Hf (fortuitously identical with the nominal composition of the
widely used JMC475 Hf isotope standard) is based on forward calcula­
tion of Hf isotope data for magmatic zircon formed during the 1590 Ma
Hiltaba Suite magmatic event (~0.2817, Belousova et al., 2009) using
an assumed 176Lu/177Hf of 0.015 (this value was also used in Belousova
et al. (2009)). In the absence of published whole rock Lu-Hf isotope data,
the 0.28216 ± 0.00002 figure is the best available estimate of present-
day 176Hf/177Hf in the Roxby Downs Granite and ODBC. Two-point
model ages for the siderites range from 1394 to 1870 Ma (average
1593 ± 179 Ma, 1sd, Table 3), those for the calcites range from 1320 to
1707 Ma (average 1485 ± 111 Ma, 1sd). Model ages for the analyses
considered to be the most reliable are 1460–1850 Ma for siderites and
1477–1510 Ma for calcites.
5. Discussion
5.1. Age constraints for carbonates
5.1.1. Association 1 calcite-anhydrite
Calcite veins (association 1) in paragenetically early magnetite-
apatite-quartz-pyrite-uraninite IOCG mineralization within an unbrec­
ciated porphyritic facies of the RDG (the ‘felsic unit’) provide age con­
straints that are broadly consistent with U-Pb ages for the host granite,
and for apatite (1583 ± 7 Ma) and uraninite (1594 ± 6 Ma) from the U-
rich assemblage (ca.1583–1594, Jagodzinski, 2014; Apukhtina et al.,
2017). The Sm-Nd isochron age of 1546 ± 33 Ma for these calcites
(Fig. 3A; see also Apukhtina et al. (2017)) suggests vein emplacement
coeval with or within tens of Ma after formation of the initial IOCG
mineralization. The Pb isotope results for calcite and anhydrite also
yield a 1585 ± 23 Ma Pb-Pb isochron age (Fig. 4A), indistinguishable
from the U-Pb ages for U-rich minerals in the same host IOCG para­
genesis. As noted earlier, the very low U/Pb ratios in these minerals
could not have produced the observed ingrowth in uranogenic Pb. The
range in 206Pb/204Pb and 207Pb/204Pb in these minerals is therefore
‘unsupported’ and may have been inherited from ca. 1.59 Ga U-rich
minerals. This inheritance may be a natural process (release of radio­
genic Pb from unstable U minerals, e.g., brannerite, coffinite) but could
also be a laboratory artifact (selective leaching of radiogenic Pb from
small uraninite impurities within the calcites and anhydrites during
dissolution with dilute acid). Whatever the process, we suggest that the
1585 ± 23 Ma Pb-Pb isochron age does not date the calcites directly,
despite the close similarity with reference ages.
The Lu-Hf ages for association 1 calcites (1472 ± 20 Ma isochron,
Fig. 5B, model ages 1477–1510 Ma) are younger than the Sm-Nd age.
Given the low Hf concentrations (<0.01 ppm) and extreme Lu/Hf ratios
in the calcites relative to vein host rocks (e.g., trace element data in
Ehrig et al. (2012)), even small degrees of isotopic exchange with host
rocks would strongly affect the calcite Lu-Hf systems and lead to partial
resetting of calcite Lu-Hf ages.
87
Sr/86Sr in the calcites and anhydrites varies from 0.71007 to
0.72208, higher than initial 87Sr/86Sr in the host granite
(0.7088–0.7089 from magmatic apatite, Creaser and Gray, 1992). If Sr
in calcite-forming hydrothermal solutions was derived from the felsic
unit/host granite, their elevated 87Sr/86Sr implies a substantial age gap
between granite emplacement and calcite veining, to allow higher
87
Sr/86Sr in the granite to develop before interaction with the carbonate-
forming fluids (Maas et al., 2015a). The wide range in Rb/Sr within the
host granite (Fig. 6b) could generate 87Sr/86Sr up to 0.715–0.717 by
~1500 Ma, still broadly consistent with the Sm-Nd age constraints for
the calcites (section 4.2). 87Sr/86Sr > 0.720 would not be available to
hydrothermal fluids within the granite until ~1400 Ma except were
fluids are in contact with volumes of highly differentiated granite. A
granitic source of hydrothermal Sr is thus at least partly plausible.
Alternatively, calcite 87Sr/86Sr, like the Lu-Hf isotope systems, may be
affected by post-depositional isotopic exchange. However, there is no
clear correlation between Sr concentrations (85–1690 ppm, Table 1) and
87
Sr/86Sr, suggesting that secondary effects were not important in this
case (see also Section 5.2).
5.1.2. Association 2
Four of the six analysed carbonate samples from granite-dominated
breccia have Sm-Nd isotope compositions that are very similar to
those of the host granite (Fig. 3A). For consistency with the interpreta­
tion of other data points within the Main Array, we suggest these 4

9
R. Maas et al.
Fig. 4. Pb isotope systematics for 1.59–1.55 Ga carbonates from associations 1
(drillhole RD2773, Apukhtina et al., 2017) and 6 (laminated siderite). (A)
207
Pb/204Pb vs. 206Pb/204Pb systematics for association 1 calcites (plus radio­
genic anhydrite OD817.1) define an apparent 207Pb-206Pb isochron age of 1585
± 23 Ma. Data for association 6 siderites show more scatter and possibly two
separate trends. (B) In this ‘inverse‘ Pb-Pb isochron plot, pooled regression of all
data points yields 1601 ± 100 Ma. (C) Measured 208Pb/204Pb in association 6
siderites correlate well with 206Pb/204Pb, defining a trend that may be inter­
preted as a mixing line between radiogenic and common Pb. The line intersects
the crustal Pb growth curves at ~1.25 Ga (Stacey and Kramers, 1975) or ~1.4
Ga (upper crust, Zartman and Doe, 1981, not shown); the significance of these
’intersection dates’ is unclear. The data for association 1 calcites show greater
scatter but a linear trend through the data, including the radiogenic anhydrite,
has a similar ca. 1.2–1.3 Ga intersection with the growth curve.
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Ore Geology Reviews 140 (2022) 103745
Fig. 5. Lu-Hf isochron diagrams for Olympic Dam carbonates. (A) Association
6, laminated siderite. All 9 data points from 6 siderite samples define a
regression with an apparent age of 1687 ± 150 Ma (MSWD 2736). Removal of
the most radiogenic point lowers the age to 1460 ± 120 Ma (MSWD 1944). The
three most reliable analyses yield an age of 1428 ± 3 Ma (MSWD 1.8). (B)
Association 1 calcites. Data for 7 of 8 analyses (OD830C2 excluded) define a
regression with an apparent age of 1482 ± 61 (MSWD 74). The three most
reliable analyses yield an age of 1472 ± 20 Ma (MSWD 0.11).
carbonate samples are 1.60–1.55 Ga in age. Two further examples,
OD661 and OD665, have higher Sm/Nd and 143Nd/144Nd. Their position
outside the 1.60–1.55 Ga Main Array implies they formed from fluids
with non-granitic Nd, or they are younger, or their original Sm-Nd
systems were disturbed. OD665 plots close to a field defined by the
825 Ma dolerite dykes and to some of the association 4 carbonate
samples hosted in 1.59 Ga basalts (Fig. 3) and could thus be related to
basaltic rocks, one of the major non-granite clast components in the
breccia. By contrast, OD661 plots to the right of the Main Array, again
with carbonates from association 4 (1.59 Ga mafic/ultramafic rocks),
apparently forming a trend which runs sub-parallel to the ~0.5 Ga trend
of association 7 carbonates and late fluorite-bearing veins, suggesting
they may all be Cambrian in age (Fig. 3).
87
Sr/86Sr in eight low-Rb/Sr carbonates (siderite, calcite, dolomite-
ankerite) from association 2 shows a wide range (0.7088–0.7294, Rb/
Sr ~ 0, Fig. 1B) while another five with elevated Rb/Sr form a strongly
scattered array with a slope equivalent to 900 ± 400 Ma (initial
87
Sr/86Sr ~ 0.720, not shown in Fig. 1A). One of these samples, OD665,
R. Maas et al.
Fig. 6. Initial Sr-Nd isotope compositions in Olympic Dam carbonates, with
mineral formation ages inferred from Sm-Nd isotope results or direct U-Pb
dating. For clarity, no distinction based on carbonate association is made. (A)
εNd vs. inferred age. The 1.59–1.55 Ga stage of the deposit’s history produced
carbonate with εNdi from ~− 7 to +2, similar to εNdi in host granite and the Cu
ore/breccia complex (ODBC). εNd in 825 Ma carbonates of association 4
(dolerite) is controlled by their host dolerite while ca. 500 Ma carbonates from
associations 7, 5, 4 and 3 have evolved εNd values within the wide isotopic
range of the ODBC, with contributions from the 1.59 Ga basaltic lithologies. (B)
87
Sr/86Sr vs. inferred age (all data shown are for samples with 87Rb/86Sr < 0.2).
87
Sr/86Sri in carbonates inferred to be 1.59–1.55 Ga old shows an unexpectedly
large range, with ratios > 0.715 being quite common; Sr with this isotopic
composition would have been unavailable or uncommon in the host granite so
early in its history (see shaded area). Likewise, carbonates of association 4
(1.59 Ga basalts, picrites) do not show the expected low 87Sr/86Sri (<0.705) of
their host rocks during that time. The 825 Ma carbonates show an even more
pronounced isotopic contrast with their host rocks, recording 87Sr/86Sri ≥ 0.720
in all cases (see also Apukhtina et al., 2016). The ca. 500 Ma carbonates show
the largest isotopic range; black bar shows range of Sr isotope results for baryte,
fluorite and dolomite in late-stage baryte-fluorite veins from Wawryk (1989).
Data sources as in Fig. 3.
plots near the field of 825 Ma dolerite in the Sm-Nd isotope diagram
(Fig. 3B). Sample OD661, a low-Rb/Sr dolerite-ankerite with a possible
Cambrian Sm-Nd age, has 87Sr/86Sr near 0.729. Oolitic siderite OD1001,
which plots within the Sm-Nd Main Array, is the only carbonate found in
this study to have a 87Sr/86Sr similar to the initial 87Sr/86Sr of the host
granite (0.70883 vs. 0.7088–0.7089); this supports a near-1.59 Ga age
for this carbonate clast.
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Ore Geology Reviews 140 (2022) 103745
5.1.3. Association 3
Sm-Nd isotope data for hydrothermal carbonates in rocks of the
bedded clastic facies plot in either Main Array or the ~0.49 Ga trend
(Fig. 3A). This suggests that carbonate veining in these sediment pack­
ages started at 1.59–1.55 Ga, consistent with the depositional age of
these sediments inferred from U-Pb zircon dating (McPhie et al., 2016;
Cherry et al., 2018b), and re-commenced in the Cambrian. The five
analysed carbonate samples from association 3 have low Rb/Sr, and
87
Sr/86Sr ranges from 0.7077 to 0.7367. The wide Sr isotopic range in
these samples does not consistently correlate with ages inferred from
Sm-Nd isotopes, suggesting that even carbonates on the Main Array
formed several tens of Ma after deposition of their high-Rb/Sr host
sedimentary sequences, allowing a rapid build-up of variable 87Sr/86Sr
in host sediment before carbonate formation. By contrast, 87Sr/86Sr in
OD836 (one of the three analysed samples on/near the Sm-Nd Main
Array) is lower than the initial 87Sr/86Sr in the host granite (0.70761 vs.
0.7088–0.7089, Creaser and Gray, 1992) and must reflect a local
basaltic (?) source of fluid-mobile Sr. To preserve such a signature
within thick sandstone composed of crustally-derived material (detrital
quartz, feldspar, granitic/volcanic fragments, detrital hematite) and
lacking basaltic detrital components, this particular carbonate sample
must have formed very close to the time of sediment deposition, when
87
Sr/86Sr in the sandstones and siltstones was still low and relatively
homogeneous.
5.1.4. Association 4
Carbonates collected from the dolerite dykes must be 825 Ma old or
younger. A broadly syn-dolerite origin is supported by their position
near an 825 Ma reference line through a cluster of dolerite whole rock
analyes (Fig. 3B). The Sm-Nd isotope data for carbonates extracted from
inferred 1.59 Ga basalts and picrites are more diverse. The only picrite-
hosted carbonate analysed (OD494) plots with the whole rock data for
some altered picrites and is therefore probably cogenetic, and thus
~1.59 Ga old. Likewise, two of the carbonates from basalt plot on/near
the Main Array (Fig. 3B) and thus probably formed near 1.59 Ga. Three
further carbonates from ~1.59 Ga basalt (OD2, 806, 914) plot within the
Sm-Nd trend defined by the dolerite-hosted carbonates and may thus be
syn-dolerite. Other carbonates from 1.59 Ga basalt form a divergent
shallow trend, which is subparallel to the ~0.50 Ga trend of the asso­
ciation 7 carbonates, and like the latter may thus be of Cambrian age.
The low-Rb/Sr carbonates from association 4 have relatively high
87
Sr/86Sr (0.7115–0.7248, Table 1), implying they formed from fluids
with variably radiogenic Sr derived from the breccia complex (Apukh­
tina et al., 2016).
5.1.5. Association 5
Carbonates in this association should be cogenetic with the associ­
ated fluorite, for which ~0.5 Ga Sm-Nd ages were reported by Wawryk
(1989) and Maas et al. (2011). This is supported by the Sm-Nd isotopic
composition of dolomite-ankerite OD1005 which plots on the shallow
~0.5 Ga Sm-Nd trend defined by fluorite (fluoritea in Fig. 3A) and by
carbonates from association 7. Age-corrected 87Sr/86Sr in five siderite
and dolerite-ankerite samples varies widely (0.715–0.752, Table 1,
Fig. 1A,B) and does not provide any additional age information.
5.1.6. Association 6
Like association 1 calcites, the prominent laminated siderites of as­
sociation 6 show very coherent Sm-Nd isotope systematics within, and
help define, the Main Array (Fig. 3A), implying a 1.59–1.55 Ga age. This
is broadly supported by the 1598 ± 170 Ma Sm-Nd age for the 12 data
points. A ~1600 Ma Pb-Pb isochron for the pooled association 1 and 6
carbonates (Fig. 4B) is problematic because measured Pb isotope vari­
ations are not correlated with measured U/Pb ratios and may thus be
‘unsupported’. Lu-Hf dating of the siderites yields ages in the range
1400–1500 Ma, the most precise being a 1428 ± 3 Ma 3-point age. As
suggested for association 1 calcites, the age deficit relative to Sm-Nd
R. Maas et al.
data for the same samples may indicate disturbance of siderite Lu-Hf
systems.
As a group, these siderites have by far the lowest Sr concentrations
(2.9–79.6 ppm, average 15 ppm) measured here, yet Rb/Sr is uniformly
low. Measured (~initial) 87Sr/86Sr is higher than the initial 87Sr/86Sr of
the host granite and quite diverse (0.7147–0.7238 vs. 0.7088–0.7089).
As inferred for other carbonates with ‘old’ Sm-Nd ages, elevated and
variable 87Sr/86Sr may indicate an age gap between formation of the
granite and siderite deposition, to allow build-up of radiogenic Sr in the
OBDC; in this case the imprecise Sm-Nd isochron allows an gap of up to
170 Ma which would be sufficient to produce 87Sr/86Sr > 0.720
(Fig. 6B). The laminated siderites are interpreted to be former Fe-rich
sandstones (bedded iron stones, BIF) overprinted by hydrothermal
siderite (Apukhtina et al., 2020). They occur preferentially near
Masher’s Fault, which is thought to be a long-lived structure reactivated
during the Delamerian Orogeny in the Cambrian (Sugden and Cross,
1991). However, the Sm-Nd isotope data for the siderites do not show
signs of resetting during the Cambrian.
5.1.7. Association 7
Dolomite-ankerite carbonates (+barite + celestite ± Cu-Fe sulfides)
assigned to this association form the matrix of alternating beds of
conglomerate-breccia and sandstone beds which unconformably overlie
the eroded Olymic Dam Breccia Complex and are estimated to have a
maximum age of ~0.6 Ga (Apukhtina et al., 2020). The Sm-Nd isotope
signatures of these carbonates, with their characteristic high and vari­
able Sm/Nd (Fig. 2), clearly diverge from the Main Array and yield a Sm-
Nd age of ~0.5 Ga (Fig. 3A). Analyses of members from several other
carbonate associations plot within this trend, and the same age is
assigned to them. 87Sr/86Sr in three low-Rb/Sr association 7 carbonates
strongly overlaps the range in association 6 laminated siderites
(0.7162–0.7233 vs. 0.7147–0.7238), despite a potentially 1000 Ma age
difference between these carbonate assemblages.
5.2. Isotopic constraints on fluid sources and pathways
Whole rock Sm-Nd isotope data for Olympic Dam reported in
Johnson and McCulloch (1995) suggested slightly different εNd1.59 Ga in
the host granite (− 5) and various styles of Cu mineralization within the
granite-hosted ODBC (εNd1590 − 3 to − 2, the ‘ore envelope’), with data
points for various types of breccia having intermediate compositions.
This isotopic contrast was used to support ore formation involving two
or more distinct fluids (e.g., Oreskes and Einaudi, 1992) to link Cu
mineralization to isotopically juvenile, perhaps basaltic, sources within
the breccia complex. Breccia components with the requisite juvenile Nd
isotope signatures exist in the form of the ~1.59 Ga mafic and ultramafic
igneous components of the breccia complex (Johnson and McCulloch,
1995; Huang et al., 2015). In a survey of other, much smaller Cu-Au
IOCG mineralizations of the NE Gawler Craton, Skirrow et al. (2007)
did not find equivalent Nd isotopic shifts and concluded that a strong
basaltic influence may have been important in the formation of the
much larger Cu-Au mineralization at Olympic Dam. Such arguments are
based on the assumption that ore-forming activity at Olympic Dam was
initiated during the ~1590 Ma bimodal magmatism recorded in the
Roxby Downs Granite and the wider Olympic Province (e.g., Williams
et al., 2005), and largely completed soon after. It is now clear that
brecciation, alteration and mineral formation continued episodically
over ~1 Ga (e.g., Ciobanu et al., 2013; Cherry et al., 2017, 2018a,
2018b; Kirchenbaur et al., 2016; Huang et al, 2017; Meffre et al., 2010,
2015; Ehrig et al., 2017; Kamenetsky et al., 2015; Maas et al., 2011,
2015a), and this protracted evolution is also recorded in carbonate
gangue.
Initial εNd values reported for ca. 1.6–0.5 Ga carbonates analysed
here show a large range (Table 1). In some cases, these εNd results may
not be robust, possibly because the mineral ages used to calculate initial
εNd in these cases are poorly defined (ages used are listed in Table 1), or
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because of open system behaviour. However, the overall distribution of
most carbonate Sm-Nd isotope data points along geologically realistic
trends (Fig. 3) suggests that disturbance of Sm-Nd isotope systems af­
fects only a small fraction of the analysed carbonates. In the following,
some of the ages assigned to the carbonates are simplifications made for
the sake of Fig. 6.
The εNd vs. time plot (Fig. 6A) shows three distinct clusters. Car­
bonates formed during the 1.59–1.55 Ga stages of the deposit have
initial εNd values from − 6.7 to + 2, broadly similar to the range reported
for whole rocks of granite, breccia, Cu ore and mafic/ultramafic rocks in
Johnson and McCulloch (1995). Association 1 calcites apparently
formed soon after early (1580–1590 Ma) IOCG-style ore (Apukhtina
et al., 2017) and have initial εNd1550 values averaging − 3.9. Association
6 laminated siderites, dated at ~ 1.59 Ga, show similar signatures
(average εNd1593 = -4.3). Association 2 carbonates are more heteroge­
neous: samples assigned a 1.59–1.55 Ga age (see Section 5.1) have
εNd1593 values of − 6.5 to − 0.6 (n = 4). Association 3 carbonates with
assigned 1.59–1.55 Ga ages show a similar range (εNd = − 7.4 to − 2.5),
while those from association 4 (εNd = − 6.1 to + 2.0) are more variable,
reaching the high values observed in some of the 1.59 Ga basalts and
picrites (Johnson and McCulloch, 1995). This suggests that while
granitic Nd (εNd1590 = − 5 to − 3) was dominant in the early stage of the
deposit, an additional more juvenile component was recorded in at least
some early-formed carbonates, as suggested by Johnson and McCulloch
(1995).
Carbonates assigned a 0.82 Ga age tend to have higher εNd825 (up to
− 0.2 to +5, Fig. 6), reflecting the high εNd of the 0.82 Ga dolerites
(Huang et al., 2015; Apukhtina et al., 2016). Interestingly, 87Sr/86Sr in
these carbonates (~0.717 to >0.730) is much higher than in the least
altered dolerite (0.7035–0.7052, Apukhtina et al., 2016), suggesting
they contain a mix of unradiogenic Sr from basalt and radiogenic Sr from
the host breccia complex.
Carbonates formed during the Cambrian occur in several associa­
tions and all show strongly negative εNd500 (− 26 to − 10, Fig. 6A).
Carbonate εNd500 signatures below ~− 16 probably reflect local crustal
sources (host granite, breccia complex, Neoproterozoic cover sediments)
available at the time while higher εNd500 may indicate sources within the
older basaltic components of the breccia complex.
Carbonate 87Sr/86Sr is much less dependent on age assignments than
εNd because age corrections are small in the majority of analysed sam­
ples. On the other hand, Sr is known to be more mobile than Nd in hy­
drothermal and meteoric fluids, which could result in both long-range
transport (e.g., from the Archean-Mesoproerozoic basement of the
Olympic IOCG Province, Reid, 2019) and extensive local reequilibration
along the flow path and at the site of deposition within the ODBC and
host granite where a large range in Rb/Sr generated diverse 87Sr/86Sr
signatures very quickly. If plotted against mineral age, there is a broad
increase of carbonate 87Sr/86Sr towards younger ages but a dominant
0.710–0.725 signature persists throughout (Fig. 6B). Given the generally
high Rb/Sr in the granite (avg. Rb/Sr for samples >80 ppm Sr is 1.09,
present-day mean 87Sr/86Sr = 0.8088, Creaser and Gray, 1992; Ehrig
et al., 2012), successive generations of carbonate would be expected to
have ever-increasing 87Sr/86Sr if fluid Sr is sourced in local granite or
breccia host rocks (Maas et al., 2015a). Against this background, the
recurrence of the 0.710–0.725 signature in all three major carbonate age
groups (including fluorites + barite in the ca. 500 Ma veins) may reflect
buffering by unradiogenic Sr from basaltic rocks.
As noted earlier, diverse 87Sr/86Sr in low-Rb/Sr carbonates could be
a result of isotopic heterogeneity within carbonate separates or grains,
perhaps reflecting the post-depositional textural/mineralogical modifi­
cation reported for virtually all minerals in the breccia complex (Ehrig
et al., 2012; Ciobanu et al., 2017; Apukhtina et al., 2020). In the absence
of spatially-resolved Sr isotope data as provided by in situ isotopic
analysis (e.g., Woodhead et al., 2005), indirect evidence must be used to
evaluate the carbonate 87Sr/86Sr signatures. For example, carbonates of
association 1 do not show the inverse correlation of 87Sr/86Sr with Sr
R. Maas et al. Ore Geology Reviews 140 (2022) 103745

Fig. 7. Chronology of major carbonate forming events within the Olympic Dam Breccia Complex. (A) Summary of major geological events relevant to the Olympic
IOCG Province in the NE Gawler Craton, including magmatism, sedimentary basins, orogenic activity and glaciation events, and their place in the history of
Columbia, Rodinia and Gondwana. (B) Timing of gangue carbonate mineral deposition (green) compared to known/inferred ages for ore minerals (red) and non-
carbonate gangue minerals (blue). Based mainly on Sm-Nd isotope data, Ca-Fe-Mg-Mn carbonate minerals were formed at ~ 1.59–1.55 Ga (assoc. 1, Apukhtina
et al., 2017; this study; assoc. 2, oolite; assoc. 3, 4 and 6, this study), ~0.82 Ga (assoc. 4, Apukhtina et al., 2016; this study), and ~0.6–0.5 Ga (assoc. 3, 4, 5, and 7,
this study). Not all studied carbonate samples provided useable age constraints (e.g., assoc. 3, 4). Sm-Nd data for REE-fluorocarbonates suggest they were formed at
~1.4–1.1 Ga (Maas et al., 2011; Diemar, 2014). Carbonate formation broadly agree with ages for other minerals, and the history of mineral formation at Olympic
Dam generally correlates with large-scale geological events (see panel A). Data sources for panel A: breakup of supercontinent Columbia (~1.6–1.3 Ga, Meert and
Santosh, 2017), Grenville-aged resetting of some ~1.6 Ga old rocks (Wong et al., 2015), amalgamation and breakup of Rodinia (~1.3–0.9 and ~0.8–0.5 Ga,
respectively, Li et al., 1999, 2008), amalgamation of Gondwana (~0.6–0.3 Ga, Veevers, 2004). Data sources for ore mineral ages: chalcopyrite (~1.26 Ga, McInnes
et al., 2008), galena (~1.4–1.2 Ga, Meffre et al., 2010; ~1.1 Ga, Kamenetsky et al., 2015), pyrite (hydrothermal, ~1.59 Ga*, age inferred from U-Pb dating of
associated minerals, Apukhtina et al., 2017; authigenic, ~1.1 Ga, Kamenetsky et al., 2015), uraninite (~1.59 Ga, Apukhtina et al., 2017; ~1.4–1.3, ~1.22, ~0.83
and ~ 0.57 Ga, Johnson, 1993; ~1.4 and ~0.5 Ga, Trueman et al., 1988; ~0.5 Ga, Ehrig et al., 2018). Data sources for non-carbonate gangue mineral ages: anhydrite
(~1.58 Ga, Apukhtina et al., 2017; this study), fluorapatite (hydrothermal, ~1.59 Ga, Apukhtina et al., 2017; ~0.82 Ga, Huang et al., 2015; Apukhtina et al., 2016;
authigenic, hydrothermal, ~0.44–0.48 Ga, Kamenetsky et al., 2015), fluorite (~0.45–0.55 Ga, Wawryk, 1989; Maas et al., 2011), hematite (~1.59–1.58 Ga,
Apukhtina et al., 2017; Ciobanu et al., 2013; Courtney-Davies et al., 2019), magnetite (possibly inherited from older BIF ~1.76 Ga, Courtney-Davies et al., 2019,
Courtney-Davies et al., 2020; magmatic, ~1.59 Ga**, age inferred from U-Pb dating of associated minerals, Apukhtina et al., 2017; hydrothermal, ~0.82 Ga,
age inferred from U-Pb age for associated apatite in dolerite dyke, Apukhtina et al., 2016), monazite (hydrothermal, ~0.48–0.44 Ga, Kamenetsky et al., 2015),
sericite (~1.49 Ga, Craeser, 1989; ~1.31 Ga, Gustafson and Compston, 1979; ~1.1 Ga, Maas et al., in preparation; ~0.45–0.55 Ga, Maas et al., 2011), titanite
(hydrothermal, ~0.82 Ga, Huang et al., 2015; Apukhtina et al., 2016), and zircon (hydrothermal, magmatic, ~1.59 Ga; hydrothermal, ~1.14 Ga, Jagodzinski, 2014).

13
R. Maas et al.
concentration expected if low-Sr calcite is particularly vulnerable to
post-depositional isotopic disturbance. The highest 87Sr/86Sr is found in
anhydrites with very high Sr concentrations (1424–1690 ppm, Table 1).
Siderites of association 6 have very low Sr concentrations, yet their
87
Sr/86Sr range is comparable to that in association 1 carbonates, sug­
gesting that secondary modification of 87Sr/86Sr is not strong even in
low-Sr carbonates. Finally, barytes (a Sr-rich, alteration-resistant min­
eral, e.g., McCulloch, 1994) and fluorites from association 5 fluorite-
baryte veins have a Sr isotope range that is almost identical with that
of carbonates assigned a 0.5 Ga age (black bar in Fig. 6B). While we can
not rule out secondary disturbance of carbonate 87Sr/86Sr entirely, these
observations suggest that diverse Sr isotope signatures in carbonates
may be mostly primary.
6. Summary and conclusions
The results of this study show that carbonates are a rich source of
information on the chronology and geochemical evolution of the Olymic
Dam Fe-oxide Cu-U-Au-Ag mineralization. The Sm-Nd isotope data for
the seven lithologically-constrained gangue carbonate associations at
Olympic Dam document three likely formation ages, at 1.60–1.55 Ga,
~0.82 and ~ 0.5 Ga. This carbonate-based chronology is consistent with
ages measured for other minerals (gangue and ore), providing additional
evidence for a multi-stage history of this large and unusual minerali­
zation. The post-1.59 Ga carbonate ages obtained here might be inter­
preted as a result of episodic or continuous resetting within the long-
lived thermal anomaly of a very large U deposit, as observed else­
where (e.g., Fayek et al., 2002; Skirrow et al., 2016). However, most of
the mineral ages obtained for Olympic Dam show clustering consistent
with mineral deposition in response to regional tectonic controls
(Fig. 7), presumably through changes in local fluid flow regimes brought
on by regional responses to large-scale tectonic events, and/or through
episodic magmatically-driven hydrothermal activity, against a back­
ground of locally elevated temperatures and earthquake activity
(repeated brecciation). Other support for a protracted, multi-stage
evolution of the carbonate minerals comes from their mineralogical,
textural and compositional diversity, and from 87Sr/86Sr ratios which
tend to be much higher and more variable than expected if all carbon­
ates (and associated ore minerals) formed near 1.59 Ga (as inferred in
earlier studies) and remained undisturbed to the present day. The
imprecision of most ages reported here almost certainly masks the true
complexity in carbonate depositional history, as observed in textures.
Similar multi-technique studies of carbonate minerals may produce
important insights on ore formation at other IOCG-deposits, where
carbonates are present but sparsely described and largely ignored in
radiogenic isotope studies.
The strong evidence for diachronous mineral deposition (ore and
gangue) at Olympic Dam (Fig. 7) implies that interpretations of fluid
inclusion, stable and radiogenic isotope or chemical data should be
supported, wherever possible, by radiometric dating, using a combina­
tion of solution-mode and in situ micro-sampling analytical techniques
and isotopic systems. In this context, our study provides yet another
example of the utility of Sm-Nd dating for ore deposits, in particular for
carbonate minerals. Lu-Hf dating of hydrothermal calcite and siderite
with high Lu/Hf ratios, applied here for the first time, yielded apparent
Lu-Hf ages that are some 70–100 Ma younger than those from Sm-Nd.
We infer this reflects isotopic exchange between the extremely radio­
genic carbonate Lu-Hf systems (with ≤ 0.01 ppm Hf) and those in their
host rocks. While we consider it important to report these results here,
further applications of carbonate Lu-Hf isotope studies should be tar­
geted at simpler ore systems and, as was done here, be paired with other
dating systems.
Declaration of Competing Interest
The authors declare that they have no known competing financial
14
Ore Geology Reviews 140 (2022) 103745
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
We are grateful to Alan Greig, Warrick Joe and Serene Paul (Uni­
versity of Melbourne) for assistance with analytical work. The paper
significantly benefited from insightful comments by two reviewers and
efficient editorial handling by Franco Pirajno. This study was funded by
BHP Olympic Dam and the Australian Research Council (Linkage Grant
LP130100438).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.oregeorev.2020.103745.
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