Chemical Geology 347 (2013) 175189

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

Trace element heterogeneity in molybdenite ngerprints stages

of mineralization
C.L. Ciobanu a, b,, N.J. Cook a, b, C.R. Kelson c, R. Guerin a, N. Kalleske a, L. Danyushevsky d
a
Centre for Tectonics, Resources and Exploration (TRaX), School of Earth and Environmental Sciences, University of Adelaide, SA 5005, Australia
b
Deep Exploration Technology Cooperative Research Centre (CRC-DET), University of Adelaide, North Terrace, SA 5005, Australia
c
Dept. of Geology, State University of New York College at Potsdam, Potsdam, NY 13676, USA
d
CODES, University of Tasmania, Hobart, Tasmania, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Variations in molybdenite trace element chemistry represent a tool for discriminating discrete events in
Received 8 September 2012 young magmatic-hydrothermal systems and constrain the role of granites in older greenstone belt-hosted
Received in revised form 4 March 2013 gold systems. We show that besides Re and W (typical lattice-bound elements), molybdenite also concen-
Accepted 8 March 2013
trates chalcophile elements with chalcogenide afnity such as Bi, Pb, and Te (CEs). Elements from the latter
Available online 29 March 2013
group form nano- to micron-scale inclusions which also attract Au and Ag incorporation. High concentration
Editor: K. Mezger of all elements is attributable to lattice-defects and coherent intergrowths between molybdenite and
CE-minerals rather than polytypism. If both groups are used, trace element patterns are useful for
Keywords: interpreting superimposed ore-forming processes. We test the validity of this hypothesis by carrying out
Molybdenite Laser-Ablation Inductively-Coupled Mass Spectroscopy spot analysis and element mapping on high-Re mo-
Laser-Ablation Inductively-Coupled Mass lybdenite from the Tertiary Au deposit at Hilltop (NV, USA) and the Archean Boddington CuAu deposit
Spectroscopy (Western Australia). Whereas W and CEs are affected by both deformation and interaction with subsequent
Element mapping uids, Re is only affected by the latter. An epithermal overprint at Hilltop, recorded in a grain with a CE-rich
Bismuth
halo surrounding a core with ReW oscillatory zoning, upgrades Re content and is also traceable by measur-
Gold
able Au. At Boddington, granite-derived uids dilute Re in precursor molybdenite, but both granite and oro-
genic deformation assist CE-mineral coarsening and Au release.
2013 Elsevier B.V. All rights reserved.

1. Introduction Mass Spectroscopy (LAICP-MS) to measure a number of elements in

Molybdenite, the primary source of Mo is long known as a carrier of
rhenium (Re) and tungsten (W) where both elements are incorporated
in the molybdenite lattice due to similar ionic radii of Mo4+ (0.65 ),
Re4+ (0.63 ) and W4+ (0.66 ). One mechanism explaining Re enrich-
ment in molybdenite is expansion of the crystal lattice via polytypism
(Frondel and Wickman, 1970), which is attractive since there are only
two molybdenite polytypes: hexagonal (2H) and the rarer rhombohe-
dral (3R). McCandless et al. (1993) have conrmed that the 3R polytype
is often richer in Re. Newberry (1979) emphasized the correlation
between crystal structure and chemistry noting that other elements
(W, Nb, V, Fe and Ti) are also concentrated in the 3R polytype. Drawing
attention to associations of 3R molybdenite and Bi-minerals in several
deposits and the structuralchemical parameters for analogous MSn
layer compounds, he discussed how Bi and Sn could also be incorporat-
ed. Blevin and Jackson (1998) used Laser-Ablation Inductively-Coupled
Corresponding author at: Centre for Tectonics, Resources and Exploration (TRaX),
School of Earth and Environmental Sciences, University of Adelaide, SA 5005, Australia.
Tel.: +61 405 826 057.
E-mail address: Cristiana.ciobanu@adelaide.edu.au (C.L. Ciobanu).
molybdenite containing both Bi-mineral inclusions and Au. They found
that such chalcophile elements and associated chalcogens (Pb, Bi, Te;
CEs) are indeed present and were the rst to propose that variation in
their abundance could potentially be a valuable petrogenetic tool.
Such dirty molybdenite can be used as a petrogenetic tool and
Norman et al. (2004) point at the usefulness of molybdenite trace
element data, notably including Bi, for ngerprinting mineralization
in granitic settings. This idea, however, has not been widely followed
up and the focus on molybdenite has instead shifted to geochronolog-
ical applications using ReOs isotopic ratios (Stein et al., 2001a). The
method offers a mineralization age and is robust with respect to sub-
sequent overprinting (e.g., Stein et al., 2003; Selby and Creaser, 2004)
except when subject to supergene alteration (McCandless et al.,
1993).
Heterogeneity within single grains of molybdenite has been docu-
mented by Aleinikoff et al. (2012). In their samples from Hudson
Highlands, NY, distinct cores and rims, each with distinct trace ele-
ment compositions, give different ReOs ages suggestive of a process
of dissolution/reprecipitation following peak high-grade regional
metamorphism. Coexisting molybdenite grains giving different ReOs
ages had earlier been reported by Requia et al. (2003) who considered

0009-2541/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.chemgeo.2013.03.011
176 C.L. Ciobanu et al. / Chemical Geology 347 (2013) 175189

this resulted from temporally separated pulses of molybdenite
deposition in the Salobo iron oxide coppergold deposit, Brasil, and
by Wilson et al. (2007) for the Cadia porphyry system, New South
Wales, Australia.
LAICP-MS spot analysis and mapping are used to document and
interpret patterns of trace element distribution in refractory suldes
such as pyrite and arsenopyrite (e.g., Cook et al., 2009, in press;
Large et al., 2009; Sung et al., 2009; Thomas et al., 2011; Ciobanu
et al., 2012; Winderbaum et al., 2012), but have not been applied
to molybdenite which readily undergoes ductile deformation. Here,
we use such methods to document the behavior of a wide range of
trace elements in Re-rich molybdenite attributed to porphyry-style
mineralization from two deposits of very different geological settings
and ages. Our aim is to demonstrate how petrographic study can be
corroborated by trace element analysis of molybdenite to pinpoint
the sequence of ore-forming events in complex geological environ-
ments. These two deposits were selected for study since previous
work has, in both cases, clearly shown the inuence of successive
events.
2. Deposits sampled
The ~2 MOz Hilltop Au deposit, Lander County, NV, USA (Fig. 1a, b),
is one of several Au Ag base metal deposits within the northern
Shoshone Range. Collectively, these deposits formed throughout the
continuum between low-temperature (epithermal) and higher-
temperature (porphyry) regimes (Kelson et al., 2005, 2008). Hilltop
contains mineralization of both types where porphyry-related Mo +
Cu Au-bearing quartz veins are spatially, temporally, and genetically
associated with mostly felsic Eocene intrusive igneous rocks and occur
only within or adjacent to these rocks. Conversely, younger epithermal
Au Ag base metal mineralization is mostly conned to a tectonic
breccia (main zone) composed of highly-fractured Ordovician
Valmy Formation and Eocene intrusive igneous rocks. Kelson et al.
(2005, 2008) give a weighted ReOs molybdenite mean age of
40.23 1.7 Ma for Hilltop molybdenite (n = 4).
Epithermal mineralization at Hilltop occurs as open-space lling
and fracture-ll hosted by both the Ordovician Valmy Formation
(chert, quartzite, siltstone, and argillite) and by Tertiary intrusive
rocks (feldspar and quartzfeldspar porphyry, granodiorite and dio-
rite) that occur as small plugs, dikes, and sills. The Ordovician host
rocks were bleached and recrystallized, presumably by the igneous
rocks associated with molybdenite mineralization, prior to fracturing
and the Au mineralization event. Most of the Au and base-metal min-
eralization at Hilltop is localized within a megabreccia (main zone)
between two sub-parallel, N-trending, W-dipping faults. No molyb-
denite is observed within the main zone. Molybdenite-bearing quartz
veins are only observed in the igneous rocks and in Valmy Formation

Fig. 1. (a) Location of the Hilltop area in central Nevada within the Battle MountainEureka trend and (b) geological sketch map of the Hilltop area (both maps after Kelson et al.,
2005, 2008). (c) Simplied drillcore sections for the two holes from the Hilltop prospect (J and L) sampled in this study.
 C.L. Ciobanu et al. / Chemical Geology 347 (2013) 175189
rocks adjacent to them. The Valmy Formation rocks stratigraphically
below the main zone are unaltered and unmineralized; igneous
rocks are truncated by the main zone faults.
The ages of molybdenite and primary igneous biotite (Ar/Ar; 39.7
38.5 Ma) from Hilltop igneous rocks are given by Kelson et al. (2008);
ReOs ages are slightly older than the Ar/Ar ages, probably due to the
difference in closure temperatures between the two isotopic systems.
Molybdenite-bearing quartz veins, or pieces of them, have not been
observed in direct contact with main zone Au and base-metal miner-
alization, but main zone mineralization frequently incorporates
bleached and recrystallized Valmy Formation rocks; this alteration
presumably occurred during emplacement of the igneous rocks asso-
ciated with molybdenite precipitation. It should be noted that the
molybdenite mineralization at Hilltop cannot strictly be classied as
porphyry-type mineralization, since the usual alteration assemblages
associated with porphyry systems and the typical (volcanic) host
rocks are absent.
The World-Class Boddington CuAu(Mo) deposit, (>26 MOz Au,
>1.2 Mt Cu) is located within Archean felsic to intermediate igneous
rocks belonging to the northern part of the Neoarchean (2714
2665 Ma) Saddleback Greenstone Belt (SGB) in the South West Terrane
of the Yilgarn Craton, Western Australia (Fig. 2). The whole-rock
geochemistry of the SGB suggests formation in an island arc setting
(e.g., Wilde and Pidgeon, 2006). The main magmatic activity in the
SGB appears to have taken place during two distinct episodes (2714
2696 and ~26752665 Ma; Wilde and Pidgeon, 1986, 2006; Allibone
et al., 1998). Syntectonic granitic intrusion at 26502630 Ma (Wilde
and Pidgeon, 1986; Nemchin and Pidgeon, 1997; Qiu and Groves,
Fig. 2. Simplied geological map of the Boddington deposit (after Newmont, unpublished
data and Kalleske, 2010) with sample locations marked. The inset shows the location of
the deposit in the South West terrane of the Yilgarn Craton.
177
1999) postdates terrane amalgamation and a later post-tectonic,
A-type granite event (at ~2612 Ma) is also recorded at Boddington
(Allibone et al., 1998) and elsewhere across the South West Terrane
(Korsch et al., 2011).
The Boddington deposit lies within a steeply-dipping sequence of
metamorphosed and faulted sedimentary, felsic, and mac volcanic
and pyroclastic rocks. Strong structural and lithological control of
the mineralization is evident. Ores are characterized by a pronounced
AuCuMoTeBi association within a generally low-sulde system.
Molybdenite is associated with disseminated and veinlet CuAu min-
eralization in shears, faults and altered rocks (mainly diorite) located
along a 4 km-long NNWSSE-striking zone between two major duc-
tile shear zones.
Genetic models for the deposit have shifted from an Archean
porphyry (Symons et al., 1990; Roth and Anderson, 1993) to an orogen-
ic Au system (Allibone et al., 1998). Stein et al. (2001b) provide two
distinct ReOs ages for Boddington molybdenite (2707 17 Ma and
2623 9 Ma), supporting a two-stage model combining the two. The
error on the second age overlaps with SHRIMP UPb zircon dating of
the barren Wourahming granite (2611 3 Ma; Allibone et al., 1998)
which intrudes southeast of the deposit. McCuaig et al. (2001) attribut-
ed the second ReOs age to intrusion-related AuCu rather than oro-
genic Au. This latest interpretation, based on the intrusion-related
model of Thompson and Newberry (2000) has been taken up by other
authors (Baker et al., 2005; Duuring et al., 2007; Hart, 2007) noting
that Boddington does indeed at least some of the characteristics of an
intrusion-related gold deposit. If correct, Boddington would represent
the rst well-documented occurrence of an Archaean AuCu deposit
associated with post-tectonic granitoids. Despite this, evidence of ex-
tensive reworking of pre-existing mineralization and trace-element sig-
natures in molybdenite from diorite and granite favors a multi-stage
genesis (Kalleske, 2010; Guerin, 2011). Re concentrations show three
distinct populations, attributed to porphyry-style (hundreds of ppm)
and orogenic- and granite-related systems (b 1 to a few ppm, respec-
tively, discriminated from one another by different CoNi, CEs and Au
signatures). Hagemann et al. (2007) sought to support an intrusion-
related model by addressing melt and uid inclusions in the
Wourahming monzogranite. The study demonstrated trapping of
saline, CuAuBiW-enriched magmatic hydrothermal uids during
cooling of the stock. Hagemann et al. (2007) did not rule out other
metal sources but took the data to indicate that the monzogranite con-
tributed at least some metals.
The three molybdenite-bearing samples from Hilltop (HT-X, 97-10
106.1, and 97-12 339) studied here were collected from two different
core holes. Figs. 1c and 3ad show the locations of these samples and
their spatial relationships to intrusive igneous and siliceous/siliciclastic
host rock types, and to main zone mineralization. The Mo-bearing
quartz veins also contain chalcopyrite, Au-bearing arsenian pyrite and
carbonate minerals (Fig. 3a).
In both deposits, a pronounced association between Bi(Pb)-
chalcogenides (tetradymite group and aleksite series), galena and
molybdenite is recognized (Kelson et al., 2005; Kalleske, 2010;
Guerin, 2011; Fig. 3df). This is especially pronounced at Boddington
where Bi(Pb)-chalcogenides are common components of molybdenite;
sub-5 m-sized grains of gold are also seen between molybdenite lamel-
lae (Fig. 3e). By comparing and contrasting trace element patterns in mo-
lybdenite, we address the question of whether grain-scale heterogeneity
reects deposit evolution.
3. Methodology
3.1. Laser-Ablation Inductively-Coupled Mass Spectroscopy
An Agilent 7500 mass spectrometer coupled with a UP-213
laser-ablation system (CODES, University of Tasmania) was used to
acquire the molybdenite trace element data. The following isotopes
178 C.L. Ciobanu et al. / Chemical Geology 347 (2013) 175189

Fig. 3. Photographs illustrating petrographic aspects of molybdenite in the sample suite. (a) Hilltop sample HT-X consisting of porphyritic quartzfeldspar rock containing
molybdenite-bearing quartz veins and thin veinlets of Au-bearing arsenian pyrite. Molybdenite grains analyzed are highlighted in the black circle. (b) Hilltop sample 97-12
consisting of molybdenite-bearing quartz veins in porphyritic quartzfeldspar rock. Analyzed molybdenite grains are highlighted in the black circle. (c) Coarse aggregate of molyb-
denite lamellae with abundant intergrowths and inclusions of chalcopyrite (Hilltop, sample HT-X) (d) Coarse, felted aggregates of molybdenite containing inclusions of
Bi(Pb)-chalcogenides and galena (Hilltop, sample 97-12). (e) Coarse aggregate of molybdenite lamellae containing inclusions of Bi(Pb)-chalcogenides and native gold along
the molybdenite cleavage planes (Boddington, sample 25RG). (f) Detail of larger molybdenite lamellae containing inter-lamellar inclusions of Bi-tellurides (Boddington, sample
60RG).

were measured: 57Fe, 59Co, 60Ni, 65Cu, 66Zn, 75As, 77Se, 107Ag, 118Sn,
121
Sb, 125Te, 182W, 185Re, 197Au, 204Pb, 207Bi, 238U. The in-house stan-
dard STDGL2b2 was used for calibration (Danyushevsky et al., 2011).
Standards were analyzed at 10 Hz laser frequency and 80 m spot
size whereas measurement of molybdenite spots was performed at
5 Hz laser frequency and 35 m spot size. Pre-ablation at 1 Hz was
undertaken to clean the surface of contaminants. Measured isotopes
were selected to avoid isobaric and polyatomic interferences. Analysis
time for each sample was 90 s, comprising a 30 s measurement of
background with laser off, and 60 s measurement with laser-on.

Table 1
Samples used in this study.

Sample Location Host rock Molybdenite morphology Other ore minerals in Inclusions in
the sample molybdenite

Hilltop, Northern Shoshone Range, Battle Mountain-Eureka Trend, Lander County, NV, USA (AuAgCuMo; Eocene)
HT-X Drillcore L, >339 ft QzFds porphyry Along Qz-veins; coarse-grained Py, Cp Cp, Gn,
Bi(Pb)-tell
97-12 Drillcore L, 339.3 ft QzFds porphyry Margin Qz veins, coarse-grained (Py, Cp) Gn
97-10 Drillcore J, 106.1 ft Intrusive matrix breccia (BRIM) Along Qz-veins; ne-grained Ttd

Boddington, Yilgarn Craton, Western Australia (CuAuMo; Archean)

25NK ABreccia, N pit (RL 150 m) Altered diorite (Clz, Qz, Ab, Chl) cm-size sheared veinlet of molybdenite Cp Au
10RG Southern Diorite Deep, Altered diorite (Clz, Qz, Ab, Chl) mm- to cm sized patches Bi, Bi-tell
S pit (RL 108 m)
27RG Southern Diorite Deep, Altered diorite (Bt, Qz, Fds, Mu, Chl, Stb) mm- to cm sized patches, Cp replacement Cp, Po, Cub, Sph, (Stn) Cp, Bi
Drillcore WBD105900002 (339.8 m) along cleavages/lamellae boundaries

Abbreviations: Ab albite; Au gold; Bi native bismuth; Bi-tell Bi-tellurides; Bt biotite; Cb cubanite; Chl chlorite; Clz clinozoisite; Cp chalcopyrite; Fds feldspar;
Gn galena; Mu muscovite; Po pyrrhotite; Py pyrite; Qz quartz; Sph sphalerite; Stb stilbite; Stn stannite; Ttd tetradymite.
Table 2
LAICP-MS spot analysis trace element data for Hilltop samples (ppm).

Fe Co Ni Cu Zn As Se Ag Sn Sb Te W Re Au Tl Pb Bi U

HT-X, drillcore L, >339, grain 1 (inner core)

aHT-X.8 Middle transect 1916 0.47 0.24 2016 5.8 b1.5 458 3.1 0.69 8.0 71 52 101 4.1 0.14 231 28 b0.01
HT-X.2 Middle transect 26 0.69 1.0 3.8 15 b2.3 438 2.0 b0.3 2.6 86 47 99 9.4 0.27 238 50 b0.02
aHT-X.10 Right end 186 0.38 0.79 10 49 1.6 478 2.5 0.22 1.6 120 59 83 11 0.23 192 138 b0.02
HT-X.10 Left end 81 0.48 b0.5 3.2 17 3.7 468 10 0.56 1.1 130 52 76 10 0.09 965 139 b0.02
HT-X.11 Leftdown margin 19 0.42 b0.4 4.4 3.4 3.5 458 4.7 b0.3 1.6 65 53 65 3.1 0.08 409 28 b0.02
HT-X.1 Middle transect 33 0.79 b0.5 3.5 2.9 3.4 539 39 0.94 1.9 196 69 41 3.5 0.38 3789 305 b0.03
Mean (n = 6) 377 0.54 0.67 340 16 3.1 473 10 0.60 2.8 111 55 77 6.9 0.20 971 115
S.D. 757 0.16 0.38 821 17 1.0 35 14 0.30 2.6 49 7.8 22 3.7 0.12 1411 106
Maximum 1916 0.79 0.98 2016 49 3.7 539 39 0.94 8.0 196 69 101 11 0.38 3789 305
Minimum 19 0.38 0.24 3.2 2.9 1.6 438 2.0 0.22 1.1 65 47 41 3.1 0.08 192 28

HT-X, drillcore L, >339, grain 1 (outer core)

aHT-X.11 Transect lower end >10,000 5.0 3.6 13 20 3.4 394 2.0 0.1 12 54 21 1531 3.7 0.23 52 43 0.37
aHT-X.5 Upper border to inner core 568 6.8 4.5 51 6.0 15 558 19 0.49 28 128 142 664 7.0 0.75 893 223 1.1
HT-X.9 Transect upper end 20 1.9 1.1 8.0 2.1 1.9 416 7.1 0.33 8.7 68 29 403 3.7 0.23 352 65 0.02
HT-X.4 Upper border to inner core 34 0.74 0.73 5.0 5.2 b3.0 392 1.0 b0.4 2.6 68 27 367 4.5 0.04 26 32 b0.02
HT-X.7 Upper border to inner core 218 5.8 6.2 28 3.2 8.1 462 17 0.47 16 81 57 314 3.3 0.76 645 109 0.03

C.L. Ciobanu et al. / Chemical Geology 347 (2013) 175189

HT-X.6 Upper border to inner core 17 2.8 2.5 8.8 1.3 b3.3 447 4.7 b0.3 8.5 100 47 281 11 0.22 146 95 b0.02
HT-X.12 Left border to inner core 38 2.9 3.6 20 0.73 4.8 420 4.6 0.36 6.4 107 40 272 13 0.12 77 82 b0.02
aHT-X.9 Transect upper end b10 0.17 0.29 5.2 0.85 1.9 459 1.6 b0.2 0.95 72 22 252 0.51 0.06 181 42 b0.02
HT-X.3 Transect lower end 59 0.10 b0.4 0.89 22 2.4 387 0.33 b0.3 0.50 63 20 232 3.3 0.09 78 18 b0.02
HT-X.8 Transect lower end b17 b0.1 b0.5 1.2 1.8 b3.1 401 1.2 b0.3 0.29 48 28 213 0.15 b0.03 133 4.8 b0.02
HT-X.5 Upper border to inner core b13 0.12 b0.3 1.5 1.1 2.7 386 b0.1 b0.3 0.19 55 18 184 0.12 b0.02 3.7 1.9 b0.02
Mean (n = 11) Not included in summary statistics 136 2.6 2.8 13 5.8 5.0 429 5.8 0.35 7.7 77 41 428 4.5 0.28 235 65 0.4
S.D. 203 2.5 2.0 15 7.7 4.6 51 6.7 0.16 8.6 25 36 389 4.1 0.28 286 63 0.51
Maximum 568 6.8 6.2 51 22 15 558 19 0.49 28 128 142 1531 13 0.76 893 223 1.1
Minimum 17 0.10 0.29 0.89 0.73 1.9 386 0.33 0.09 0.19 48 18 184 0.12 0.04 3.7 1.9 0.02

HT-X, drillcore L, >339, grain 1 (halo)

aHT-X.2 Upper right end 2729 6.4 3.8 2815 6.1 5.5 528 20 1.6 23 114 85 727 2.6 0.73 1192 186 0.07
HT-X.16 Lower right end 4586 5.9 8.2 63 22 10 479 21 0.42 17 154 112 687 0.56 0.38 679 232 0.19
aHT-X.3 Upper right end 474 5.0 4.6 57 3.0 4.3 528 11 1.0 12 129 113 683 5.7 0.79 361 170 0.07
HT-X.17 Lower right end 602 7.5 5.0 337 6.2 5.0 586 24 28 15 181 180 671 5.1 0.66 845 285 0.43
HT-X.19 Middle lower margin >10,000 15 11 >10,000 47 12 511 47 3.1 46 206 113 650 1.9 1.0 4555 409 0.36
HT-X.15 Middle-left lower margin >10,000 26 17 >10,000 333 47 872 46 32 200 213 139 633 14 3.2 1196 546 1.7
HT-X.18 Middle lower margin >10,000 12 12 81 29 7.3 522 36 0.51 20 288 163 623 4.5 1.1 1936 531 0.21
aHT-X.1 Lower right end 1304 3.5 5.1 130 8.1 5.4 529 7.3 0.31 11 95 123 622 0.68 0.43 163 70 0.01
HT-X.13 Left-upper end 177 8.0 6.1 187 3.3 b3.7 585 25 0.73 15 210 105 611 1.7 1.0 1385 378 0.01
aHT-X.7 Left-upper end 3770 5.9 7.6 59 14 5.2 554 29 0.53 12 166 132 593 3.8 1.1 2180 287 0.04
aHT-X.6 Upper middle margin 100 7.2 5.0 162 2.8 11 561 35 0.27 18 300 152 581 5.2 1.2 2378 576 0.06
HT-X.22 Left middle end 15 3.4 2.4 42 2.4 5.9 497 21 0.09 10 619 115 575 1.8 0.41 2025 1053 0.05
HT-X.20 Middle upper margin 740 8.6 6.5 29 32 8.9 509 13 1.5 27 83 156 573 3.0 2.3 290 147 0.35
HT-X.14 Left middle end 1339 5.6 5.0 1753 3.2 6.5 491 14 0.86 15 160 122 546 5.0 0.75 470 262 b0.02
HT-X.21 Upper middle margin 7535 7.9 6.5 60 7.5 18 510 18 1.4 16 132 195 541 1.3 1.3 1191 223 0.15
HT-X.23 Left lower end b16 0.23 b0.5 2.5 1.02 b2.7 391 0.49 0.29 1.1 62 19 363 0.21 b0.04 31 30 b0.02
aHT-X.4 Upper middle margin 16 0.33 b0.2 3.5 2.7 2.0 422 0.39 0.14 0.65 68 24 172 6.9 0.02 17 21 b0.01
Mean (n = 17) Not included in summary statistics 1799 7.6 7.1 385 31 10 534 22 4.3 27 187 120 580 3.8 1.0 1229 318 0.26
S.D. 2274 6.1 3.8 801 79 11 101 14 10 46 131 47 132 3.4 0.77 1150 255 0.44
Maximum 7535 26 17 2815 333 47 872 47 32 200 619 195 727 14 3.2 4555 1053 1.7
Minimum 15 0.23 2.4 2.5 1.0 2.0 391 0.39 0.09 0.65 62 19 172 0.21 0.02 17 21 0.01

HT-X, drillcore L, >339, grain 1a

aHT-X.17 Kinks and decussate twins 4.7 0.47 1.3 1.6 0.78 0.73 411 0.61 0.20 3.0 69 13 1673 0.05 0.18 49 65 b0.01
aHT-X.14 Clear middle part of one lamella in the 6.3 0.28 0.28 2.2 0.78 0.85 376 0.34 0.06 1.3 52 21 954 0.30 0.04 13 16 b0.01
aggregate
aHT-X.12 Edge of above with rosette 8.0 0.13 0.11 0.26 0.69 0.38 406 0.26 0.09 1.1 51 17 605 0.02 0.02 16 12 b0.01
lens-shaped twins

(continued on next page)

179
 180
Table 2 (continued)
Fe Co Ni Cu Zn As Se Ag Sn Sb Te W Re Au Tl Pb Bi U

HT-X, drillcore L, >339, grain 1a

aHT-X.15 Twinned moir texture at another 54 2.9 4.5 4.2 0.89 1.9 438 4.9 0.13 14 93 21 593 0.42 0.6 131 100 0.04
edge
aHT-X.16 Centre of radial lens-shaped twins and 1474 1.7 2.6 9.3 4.7 3.6 427 1.7 4.4 6.3 70 34 478 2.6 1.0 30 51 0.03
kinks
aHT-X.13 Twinned moir texture, ne gangue 7859 5.0 2.8 6.5 8.3 4.0 447 1.6 1.0 8.0 68 34 301 1.4 0.2 88 44 0.06
inclusions

C.L. Ciobanu et al. / Chemical Geology 347 (2013) 175189

HT-X, drillcore L, >339, grain 2
HT-X.26 Knotted grain, outer margin 32 8.2 11.8 14 1.9 3.3 443 7.3 1.0 36 76 46 724 0.36 4.3 98 102 b0.04
HT-X.24 Same area, inner margin, twins 44 3.2 4.1 28 2.5 b3.2 429 5.7 0.65 11 95 23 591 4.6 0.52 70 71 0.02
HT-X.25 Opposite edge, twins b17 1.0 3.9 b1.2 0.71 b2.9 495 0.2 b0.3 0.8 55 64 34 b0.1 b0.05 15 8.0 b0.03

HT-X, drillcore L, >339, grain 3

HT-X.27 Coarse lamella, edge, twins 7.0 1.4 1.1 2.1 0.65 2.1 375 1.4 0.20 7.0 71 10 3370 0.07 0.29 60 64 b0.01
HT-X.28 Further diagonal transect 4.1 0.29 0.31 0.85 0.37 0.56 358 0.19 0.19 1.7 39 12 1208 0.43 0.06 8.6 8.9 b0.01
HT-X.29 Further diagonal transect b3.6 0.04 b0.06 0.98 0.86 b0.4 367 b0.02 0.38 0.11 48 14 552 b0.01 b0.01 0.74 0.83 b0.01
HT-X.30 Other edge transect across lamella 13 0.06 0.10 10 4.5 1.1 393 0.09 0.79 0.16 54 45 143 0.20 b0.01 8.3 8.5 b0.01

HT-X, drillcore L, >339, grain 4

HT-X.31 Middle, knotted aggregate 18 0.66 0.85 6.5 0.92 4.8 369 0.80 b0.07 3.4 46 16 1697 0.25 0.08 22 15 b0.01

HT-X, drillcore L, >339, grain 5

HT-X.35 Fine lamella on edge with gangue 146 2.8 1.2 119 8.1 8.2 469 3.0 0.50 12 82 13 3024 5.3 0.40 89 78 b0.04
inclusions
HT-X.34 Towards edge, kinks 176 8.7 5.1 51 6.9 21 925 26 2.8 30 197 40 2766 25 0.90 192 143 b0.03
HT-X.36 Lobe of ne lamellae 31 2.9 3.5 22 1.8 13 502 2.8 0.29 10 69 39 1183 3.7 0.23 58 46 b0.04
HT-X.32 Middle with gangue inclusions 43 2.9 1.7 32 0.66 5.8 502 2.0 0.40 7.6 95 116 941 2.5 0.12 18 33 b0.03
HT-X.37 Middle with gangue inclusions b23 3.0 2.5 4.3 0.50 8.0 429 3.9 0.07 19 72 36 586 0.83 0.49 107 79 b0.04
HT-X.33 Middle of the lamellar aggregate b19 0.34 b0.5 1.9 0.26 b2.9 435 0.15 b0.4 0.79 60 30 316 b0.12 b0.06 4.6 2.8 b0.03

HT-X, drillcore L, >339, grain 6

HT-X.39 Apex of kinked edge 67 7.5 6.6 18 1.7 13 483 7.5 0.30 26 188 29 2644 20 1.4 164 297 0.04
HT-X.40 Along the same apex as above 406 7.8 9.0 36 4.3 13 485 10 4.6 24 260 30 1456 53 2.2 242 369 0.03
HT-X.38 Edge of large lamella b14 0.38 b0.4 3.4 1.4 3.3 399 0.44 0.43 2.3 43 27 1389 1.1 0.12 2.9 8.7 b0.02
HT-X.41 Further apex of kinked edge 49 1.4 1.1 25 3.0 b2.5 487 1.7 0.60 3.9 87 13 1231 2.0 0.95 101 103 0.05
Mean gr,1a6 550 2.6 3.1 17 2.4 5.7 452 3.6 0.9 10 85 31 1186 5.9 0.7 66 72 0.04
(n = 24)
S.D. 1802 2.8 3.1 26 2.5 5.7 111 5.6 1.3 10 54 23 932 13 1.0 65 90 0.01
Maximum 7859 8.7 12 119 8.3 21 925 26 4.6 36 260 116 3370 53 4.3 242 369 0.06
Minimum 4.1 0.04 0.10 0.26 0.26 0.38 358 0.09 0.06 0.11 39 10 34 0.02 0.02 0.74 0.83 0.02
Mean all (n = 58) 892 4.3 4.4 129 12 7.2 474 10 2.2 15 117 62 827 4.9 0.7 482 151 0.2
S.D. 1903 4.7 3.7 466 46 7.9 105 12 6.3 28 96 53 736 8.6 0.85 845 197 0.39
Maximum >10,000 26 17 >10,000 333 47 925 47 32 200 619 195 3370 53 4.3 4555 1053 1.7
Minimum 4.1 0.04 0.10 0.26 0.26 0.38 358 0.09 0.06 0.11 39 10 34 0.02 0.02 0.74 0.83 0.01

97-12 drillcore L, 339

a97-12.4 Short, wide lamella b2.2 0.05 0.06 1.3 0.83 1.7 510 0.06 0.07 0.21 24 28 318 b0.1 0.03 1.1 0.34 b0.01
97-12.4 Short lamellar aggregate 102 7.8 2.4 5.9 2.1 29 648 3338 368 8.5 967 69 157 0.08 0.50 >10,000 759 4.8
 Fe Co Ni Cu Zn As Se Ag Sn Sb Te W Re Au Tl Pb Bi U

97-12.3 Kinked short lamellar aggregate 27 0.30 0.45 2.9 b1.3 b2.8 472 12 1.1 5.7 42 104 131 b0.1 0.11 727 16 b0.02
a97-12.2 Basal section, rough surface 5819 1308 218 19 17 3125 872 >10,000 2093 27 6219 79 122 1.0 11 >10,000 1718 0.07
a97-12.1 Thin, long wispy lamella, galena 7354 0.71 1.5 0.95 21 1.2 519 2.14 0.18 1.47 37 91 114 0.47 0.02 50 8.1 b0.01
inclusions
a97-12.7 Kink along set of long lamella 36 0.03 0.12 2.9 0.92 0.56 526 1.1 0.05 0.95 33 102 110 0.02 0.03 33 6.2 b0.01
97-12.8 Middle of short lamella 39 0.04 b0.4 b1.6 b1.7 b3.0 464 b0.15 0.60 0.24 31 66 106 b0.1 0.09 6.7 0.88 b0.03
97-12.6 Kinked lamellar aggregate with 216 0.62 b0.8 2.7 2.6 b3.4 485 28 3.7 3.5 37 140 104 b0.1 0.54 960 86 0.08
gangue between
97-12.7 Close to pt. 97-12.6 686 1.1 1.0 19 8.9 4.5 435 26 1.9 3.9 61 119 98 5.1 0.40 379 77 0.18
a97-12.3 Thin, long wispy lamella 23 0.21 0.24 1.9 0.69 3.0 526 1.2 0.29 2.7 39 111 91 0.32 0.07 17 4.5 b0.01
97-12.9 Wispy lamella b22 1.3 1.0 5.5 1.5 3.1 576 14 b0.4 5.5 49 168 81 0.80 0.22 174 51 b0.04
97-12.5 Gentle kink in same area as pt. 31 0.12 b0.4 6.0 b1.4 b2.3 466 5.7 0.38 1.6 33 80 81 1.5 0.12 106 23 b0.02
97-12-4
97-12.2 Wispy lamella 99 0.92 1.4 4.5 1.3 b2.8 466 12 1.1 16 44 141 73 0.27 1.0 183 14 b0.02
97-12.10 Wider part of wispy lamella b22 0.07 b0.5 b1.5 b1.7 b3.0 466 1.7 0.36 0.88 26 55 55 b0.1 b0.04 37 3.5 b0.02
a97-12.5 Thin decussate lamellae, edge of wispy 206 0.79 0.87 5.2 2.0 1.8 523 50 3.2 8.3 34 97 85 0.09 1.4 2137 128 0.03
aggregate
a97-12.6 Basal section, rough surface 829 0.69 1.3 3.7 6.2 2.7 514 12 12 7.7 26 40 54 b0.1 1.8 488 46 0.26
97-12.1 Short lamellar aggregate 88 0.5 b0.5 9.1 b1.9 4.7 596 5.9 1.1 5.4 38 165 37 0.14 0.33 168 11 0.04
Mean (n = 17) Not included in summary statistics 1111 78 19 6.0 5.4 289 533 234 155 5.9 455 97 107 0.89 1.1 364 174 0.78
S.D. 2352 317 63 5.7 6.9 941 103 859 525 6.8 1502 41 62 1.5 2.7 568 437 1.8
Maximum 7354 1308 218 19 21 3125 872 3338 2093 27 6219 168 318 5.1 11 2137 1718 4.8

C.L. Ciobanu et al. / Chemical Geology 347 (2013) 175189

Minimum b2.2 0.03 0.06 1.0 0.69 0.56 435 b0.15 b0.4 0.21 24 28 37 b0.1 0.02 1.1 0.34 b0.01

97-10 and a97-10 drillcore J, 106.1 m

97-10.7 Coarser wispy aggregate, transversal 25 8.0 17 3.7 b2.1 4.6 353 4.1 b0.5 24 67 84 130 0.23 4.0 66 126 b0.02
twins
97-10.8 Same aggregate as pt. 97-10.7 b28 2.6 8.3 6.1 b2.1 b4.2 373 2.0 1.1 12 61 59 115 b0.1 0.67 36 63 b0.02
97-10.6 Same aggregate as pts. 97-10.7 & -.8 b19 1.5 3.6 2.6 b2.1 b3.7 355 2.3 b0.4 6.5 60 67 108 0.14 0.32 122 72 0.05
97-10.3 Thin lamella in a wispy aggregate b26 0.15 0.54 2.0 b2.8 b4.7 361 0.38 b0.5 2.4 56 62 103 b0.1 0.10 14 40 0.03
97-10.4 Same lamella as pt. 97-10.3 b29 14 26 11 b3.4 b5.0 359 21 1.2 31 72 75 88 0.78 3.7 167 180 b0.02
97-10.1 Thin lamella with transversal twins b27 0.11 b0.5 1.4 b2.9 b4.2 376 0.72 b0.4 1.8 275 70 62 b0.09 b0.06 22 428 b0.02
97-10.5 Same lamella as pt. 97-10.3 b22 2.6 6.7 4.9 b2.3 b3.7 345 1.8 0.55 11 58 108 61 b0.1 1.1 44 58 b0.02
97-10.2 Same lamella as pt. 97-10.1 58 8.3 17 11 b2.3 b3.7 389 6.5 b0.4 23 82 78 29 0.53 2.3 88 171 b0.02
a97-10.2 Middle part of wispy lamella 37 3.8 7.9 5.0 b3.0 b4.8 384 3.9 1.2 18 57 46 139 b0.15 1.1 212 132 b0.03
a97-10.7 Similar type of lamellae as py. 97-10.6 192 50 73 17 2.3 17 432 31 0.81 120 135 47 126 0.94 9.5 1252 905 0.62
a97-10.4 Rounded lamellar aggregate, gangue 25 7.8 12 6.4 1.2 3.8 363 6.3 0.16 16 56 48 112 0.25 1.3 178 161 0.03
inclusions
a97-10.5 Edge of same as pt. a97-10.4 6.6 1.3 2.2 2.1 0.66 0.89 341 1.2 0.27 3.4 40 52 90 0.07 0.19 37 36 b0.01
a97-10.6 Thin tangled lamellae with gangue 30 8.8 15 4.5 0.67 3.8 353 6.5 0.19 31 68 70 84 0.15 1.9 321 221 0.03
inclusions
a97-10.3 Edge of wispy lamellae b18 0.09 0.75 5.2 b2.5 b4.9 424 1.0 0.88 1.6 496 51 69 b0.08 b0.04 129 863 b0.02
a97-10.1 Thin edge, wispy lamellae 48 20 30 16 b2.5 10 395 11 1.8 56 84 47 62 0.36 4.5 538 359 0.21
a97-10.8 Next to pt. A97-10.7 120 31 46 12 2.4 11 386 19 1.0 65 88 59 54 0.64 5.1 675 513 0.45
Mean (n = 16) 60 10 18 6.9 1.4 7.3 374 7.4 0.84 26 110 64 90 0.41 2.6 244 270 0.20
S.D. 59 14 20 4.9 0.84 5.7 26 8.9 0.51 31 117 17 31 0.30 2.6 328 277 0.24
Maximum 192 50 73 17 2.4 17 432 31 1.8 120 496 108 139 0.94 9.5 1252 905 0.62
Minimum 6.6 0.09 0.54 1.4 0.66 0.89 341 0.38 0.16 1.6 40 46 29 0.07 b0.04 14 36 b0.01

Mo used as internal standard (60 wt.% Mo).

97-10 and a97.10 are two different polished blocks prepared from the same hand specimen.
Locations (left, right, up, down etc.) on the mapped grain refer to Fig. 5; transect was through the middle of the grain, excluding halo; two lines of spots followed the boundary between inner and outer core.
indicates value not included in statistical calculation.

181
 182
Table 3
LAICP-MS spot analysis trace element data for Boddington samples (ppm).

Fe Co Ni Cu Zn As Se Ag Sn Sb Te W Re Au Tl Pb Bi U

Abreccia, North Pit, RL 150 m

NK25.A1 Coarse lamella, mechanical twins 1448 5.5 13 135 3.7 8.5 821 2.2 0.11 12 119 89 143 18 3.1 241 335 0.01
NK25.A2 Stepwise kinks along deformed lamella 3977 21 44 100 5.6 19 645 2.8 0.33 22 151 218 541 7.5 14 257 641 0.19
NK25.A3 Diagonal fracture, gangue inclusions >10,000 8.1 28 101 21 40 683 3.1 0.37 12 123 107 328 9.4 2.8 217 365 0.52
NK25.A4 Roll-over stepwise kinks, fracture >10,000 12 44 74 32 29 701 7.2 0.86 21 139 207 206 23 5.1 244 504 0.07
NK25.A5 Apex of tight fold 813 1.7 5.8 111 2.7 5.1 516 1.0 0.85 3.3 47 239 905 7.8 1.6 57 162 b0.004
NK25.A6 Kinked and decussate shears 3086 1.8 6.6 72 5.8 6.4 666 1.3 1.2 2.9 81 86 288 11 1.1 50 115 0.02

C.L. Ciobanu et al. / Chemical Geology 347 (2013) 175189

NK25.A7 Large bend, pitted surface 4536 1.9 8.5 68 8.4 4.9 634 1.3 2.2 5.8 45 125 232 17 0.31 70 82 0.01
NK25.A8 Decussate shears, edge 1387 2.2 6.5 391 10 7.5 930 2.3 4.9 8.4 133 69 94 27 0.35 123 282 b0.005
NK25.A9 Decussate shears, edge >10,000 6.6 31 152 33 18 710 3.3 1.9 12 94 216 360 18 2.0 134 259 0.02
NK25.A10 Kinks & shears pitted by gangue inclusions >10,000 24 66 76 47 48 673 5.3 1.9 30 143 262 646 10 5.6 440 685 2.9
25NK.1 Patchy edge >10,000 20 240 212 33 372 569 6.5 b0.9 58 115 201 1066 8.3 8.6 633 422 0.30
25NK.2 Curved edge limb, gangue inll 1881 6.4 19 834 7.4 10 732 3.4 b0.7 12 107 88 245 6.4 4.5 381 441 b0.04
25NK.3 Second narrower edge limb next to pt. 2 >10,000 15 37 66 19 23 488 7.0 b0.6 27 110 506 624 54 4.7 694 577 b0.03
25NK.4 Along the same edge as pt. 3 5138 16 34 102 8.2 19 731 2.4 b0.8 24 131 189 367 15 6.2 863 559 b0.02
25NK.5 Margin of same area as pts. 14; deformation 4325 10 26 286 7.3 12 634 2.6 b0.6 14 148 140 315 12 8.4 296 602 b0.03
twins
25NK.6 Same area as pts. 16, across deformation twins 185 2.3 7.4 47 0.9 4.8 773 0.72 b0.6 5.9 90 61 152 6.0 2.9 117 160 b0.04
25NK.7 Into the coarser part of lamella in pts.17 1466 7.9 20 423 5.0 11 783 7.2 b0.6 29 129 110 319 37 3.6 461 431 b0.03
25NK.8 Across sets of thin deforamtion twins 117 5.7 16 43 2.1 4.2 697 0.53 b0.7 7.5 84 56 229 3.2 6.6 150 191 b0.04
25NK.9 Similar to pt. 8, another area 5348 22 48 83 7.5 19 660 3.1 b0.6 31 129 291 405 15 9.2 621 609 b0.03
25NK.10 Next to pt. 9, constrating twin orientation 795 2.8 5.7 115 3.9 7.1 668 0.89 b0.6 7.7 82 60 1181 11 2.4 107 161 b0.04
25NK.11 Constriction sheared domains, fractures with >10,000 7.0 48 36 58 14 568 2.3 b1.2 6.9 74 342 502 16 1.3 150 204 0.59
gangue
25NK.12 Along lamella with scalloped inversion 8335 2.0 13 79 16 10 630 1.0 b0.6 2.8 65 197 343 6.4 0.30 107 72 b0.05
boundary
25NK.13 Along the same boundary as in pt. 12 >10,000 5.3 22 180 19 23 680 3.0 b0.8 8.7 147 186 419 12 1.3 228 470 3.7
25NK.14 Scalloped domain crosscutting deformation 3959 7.4 18 167 25 19 734 2.3 b0.7 9.2 105 170 417 12 6.9 208 307 0.01
twins
25NK.15 Swell part of sheared domain 5078 2.4 10 32 6.3 11 642 1.2 b0.8 5.2 66 273 401 7.3 0.64 72 117 0.02
25NK.16 Lamellar domain crosscutting deformation 4406 1.6 6.3 80 5.1 27 656 108 b0.7 6.1 140 89 719 360 0.72 87 164 b0.03
25NK.17 Pinch and swell domains >10,000 11 34 50 24 34 683 1.9 b0.9 14 108 307 990 11 5.5 178 357 0.04
25NK.18 Hexagonal domain with internal twin 928 0.75 1.6 14 2.7 42 647 8.6 b0.7 0.50 130 139 247 114 b0.07 5.2 22 b0.04
deformation
25NK.19 Marginal small lobe 1158 3.7 7.6 152 3.3 5.8 802 0.69 b0.9 4.4 78 67 110 7.6 2.1 137 128 b0.04
25NK.20 Marginal lobe with pitted surface 2741 0.65 3.3 712 19 3.8 597 0.35 b0.9 2.7 50 52 1170 5.1 0.07 27 26 b0.07
25NK.21 Small patch outside main veinlet 3825 1.8 6.0 902 9.3 98 567 1.8 b0.9 3.6 501 206 392 13 0.47 128 1190 b0.04
25NK.22 Short lamellar patch outside main veinlet 2428 1.4 4.6 68 5.6 3.4 734 2.6 b0.6 6.1 118 105 374 44 0.35 83 310 b0.03
25NK.23 Wide lamella 2938 6.3 13 316 11 13 725 2.3 b0.8 11 92 91 477 17 1.6 182 285 b0.04
25NK.24 Close to deformation twins along lamella in pt. 766 0.27 1.3 11 2.3 b3.5 962 0.19 b0.6 1.0 64 28 849 6.9 0.04 17 44 b0.03
23
25NK.25 Close to pts. 2324, no visible deformation 338 1.2 3.9 175 5.1 1.7 707 0.38 b0.6 2.7 86 36 287 4.8 0.17 125 137 b0.03
Mean (n = 35) 2746 7.0 26 185 14 29 687 5.7 1.46 12 115 160 467 27 3.4 225 326 0.60
S.D. 2044 6.7 41 220 14 63 98 18 1.4 12 74 104 299 61 3.3 207 245 1.2
Maximum >10,000 24 240 902 58 372 962 108 4.9 58 501 506 1181 360 14 863 1190 3.7
Minimum 117 0.27 1.3 11 0.9 b3.5 488 0.19 b0.6 0.50 45 28 94 3.2 b0.07 5.2 22 b0.03
 Fe Co Ni Cu Zn As Se Ag Sn Sb Te W Re Au Tl Pb Bi U

Southern Diorite Deep, South Pit, RL 108 m

RG10.1 Flank kink on edge lamella with gentle bend 821 4.1 7.2 12 8.2 11 1358 27 3.6 7.1 245 79 304 46 5.3 378 599 0.10
RG10.2 Boundary shear domains in small patch >10,000 5.6 12 15 36 21 1016 115 2.1 11 273 536 248 126 4.5 323 600 0.07
RG10.3 Flank of fold in small lamellar patch 1050 0.67 1.5 9.4 4.1 5.2 1068 11 1.5 3.8 231 89 437 4.5 0.58 41 366 0.02
RG10.4 Edge small kink close to larger kink 568 1.6 1.6 24 3.7 5.5 1191 29 0.35 7.2 634 29 150 18 0.64 322 1338 b0.003
RG10.5 Margin lamella, change to pitted surface 4500 2.4 3.4 51 29 15 1256 14 2.1 20 370 105 232 23 1.9 402 662 0.005
RG10.6 Edge lamella in point 4 7379 3.3 6.0 15 24 12 779 8.2 0.47 6.5 170 392 212 18 1.5 321 353 0.01
RG10.7 Middle lamella in point 4 5821 2.0 4.5 21 21 10 1165 6.4 1.4 7.6 249 72 286 25 0.6 203 401 0.01
RG10.8 Apex fold in long lamellae 1137 1.1 1.6 9.9 7.3 6.3 1337 7.9 0.12 2.2 300 44 368 11 0.8 179 524 b0.004
RG10.9 Second apex fold in lamella parallel to pt. 8 2692 1.6 2.6 8.8 11 16 1543 13 0.24 3.3 371 25 392 12 2.4 231 578 0.12
RG10.10 Wedged edge of lamella in pt. 9, pitted surface 58 0.41 0.55 6.4 1.5 30 1302 6.6 0.91 1.3 307 8.1 713 20 0.37 106 528 0.05
RG10.11 Middle part of long lamella 167 0.15 0.25 2.7 1.9 32 1288 0.16 0.13 0.33 161 50 578 0.63 0.03 16 34 b0.006
RG10.12 Dislocation within lamella in pt. 11 >10,000 4.6 9.0 27 43 10 892 12 0.65 22 174 162 247 18 2.6 361 371 0.01
RG10.13 Long lamella, rod-like gangue inclusions 1103 0.51 0.91 8.8 4.0 3.6 995 1.1 0.18 1.3 145 92 416 7.9 0.06 95 167 b0.003
RG10.14 Gentle bent edge of lamella in pt. 13 1829 1.2 2.1 5.7 9.6 5.1 893 3.3 0.15 4.1 133 91 325 11 1.4 146 201 b0.005
RG10.15 Moir-deformed surface pitted with gangue 212 0.44 0.73 13 9.5 5.3 1153 27 0.44 1.7 670 57 337 11 0.5 126 1230 b0.003
Mean (n = 15) 2103 2.0 3.6 15 14 13 1149 19 0.95 6.7 295 122 350 24 1.6 217 530 0.04
S.D. 2352 1.7 3.5 12 13 8.9 208 28 1.0 6.6 163 146 146 30 1.6 128 354 0.04
Maximum >10,000 5.6 12 51 43 32 1543 115 3.6 22 670 536 713 126 5.3 402 1338 0.12
Minimum 57.6 0.15 0.25 2.7 1.5 3.6 779 0.2 0.12 0.33 133 8.1 150 0.63 0.03 16 34 b0.003

C.L. Ciobanu et al. / Chemical Geology 347 (2013) 175189

Southern Diorite Deep, drillcore WBD105900002, 339.8 m
RG27.1 Set short lamellae 1662 1.1 11 91 16 3.8 428 1.1 3.1 0.27 23 133 26 3.9 0.34 58 40 0.13
RG27.2 Stepwise-kink & fold, lamella with Cp along 4477 6.7 26 4267 30 2.8 786 2.8 10 1.0 85 54 131 14 0.82 155 94 b0.006
cleavages
RG27.3 Boundary pitted to normal surface, edge 3068 3.9 8.8 1368 17 1.8 605 1.0 2.8 1.1 72 51 234 5.2 0.38 304 132 0.01
lamellae
RG27.4 Edge lamella with Cp along cleavages 6338 5.2 14 1357 66 2.2 492 3.1 89 1.2 64 112 46 22 0.52 181 247 0.28
G27.5 Middle lamella, between cleavages with Cp 4921 0.83 2.8 110 16 3.0 750 0.14 3.5 0.16 69 60 117 0.49 0.09 9.1 12 0.03
RG27.6 Apex large kink across lamella; Cp along 283 0.74 2.1 191 13 2.7 465 0.50 0.65 0.07 25 98 79 3.6 0.01 6.5 18 b0.006
cleavages
RG27.7 Lamella with surface inversion as above, tiny Cp 5137 3.9 20 1767 80 5.0 502 2.1 8.4 0.95 57 78 22 13 1.1 198 175 0.02
RG27.8 Next to gentle bend in lamalla; wedged Cp 4962 1.5 6.4 13 11 7.6 392 0.58 0.47 0.14 54 76 162 0.2 0.52 16 70 0.01
inclusions
RG27.9 Wedged grains at triple junction; change in 7051 29 104 199 64 11 439 129 5.4 0.39 40 162 98 14 0.81 57 363 0.03
orientation & surface inversion
RG27.10 Boundary surface inversion 3069 1.5 3.6 3430 16 10 376 2.8 4.5 0.38 41 56 8.4 12 0.07 42 65 b0.003
RG27.11 Stepwise-kink & fold at lamella edge >10,000 13 30 3211 165 4.9 467 10 55 4.2 69 280 122 43 1.2 399 361 0.43
RG27.12 Displacement boundary 5526 2.4 8.5 1112 36 2.2 436 1.2 7.4 0.71 20 99 347 4.4 0.45 71 41 0.08
RG27.13 Apex wedged kink, adjacent Cp along cleavages 9601 4.3 15 1200 123 4.0 397 0.97 5.7 0.76 41 107 48 6.2 0.91 112 132 0.30
RG27.14 Apex kink on wedged grain with pitted surface 7493 3.6 24 1242 38 4.5 292 1.1 13 0.41 22 119 291 7.5 0.80 53 39 0.02
RG27.15 Wide part of short lamella, shard-like Cp 3.9 0.14 0.17 2.8 0.41 15 390 0.05 0.12 b0.04 22 135 59 0.20 0.01 4.4 6.8 b0.004
inclusions
RG27.16 Clean side of lamella with Cp along cleavages 573 0.27 2.4 618 2.2 1.4 539 0.16 0.69 0.22 25 42 221 0.21 0.01 12 6.0 b0.003
Mean (n = 16) 4278 4.9 17 1261 43 5.1 485 9.8 13 0.80 46 104 126 9.4 0.50 105 113 0.12
S.D. 2823 7.3 25 1326 46 3.8 132 32 24 1.0 22 59 101 11 0.40 116 118 0.15
Maximum >10,000 29 104 4267 165 15 786 129 89 4.2 85 280 347 43 1.2 399 363 0.43
Minimum 3.9 0.14 0.17 2.8 0.41 1.4 292 0.05 0.12 b0.04 20 42 8.4 0.17 0.01 4.4 6.0 b0.003
indicates value not included in statistical calculation.

183
184 C.L. Ciobanu et al. / Chemical Geology 347 (2013) 175189

An integration time of 0.02 s was used for each of the elements
measured. The raw analytical data in each spot analysis is plotted
as a time-resolved depth spectrum and the integration times for
background and sample signal selected. Counts for each element are
then corrected for instrument drift and converted to concentration
values using known values of a major element in the analyzed
minerals as an internal standard in this case Mo. Standards were
run before and after each set of spots on a given sample (typically
1220 unknowns).
The uncertainty on the Mo concentration in standard STDGL2b2 is
~ 6% (Danyushevsky et al., 2011). As Mo is used as the internal stan-
dard, this uncertainty is propagated to all other elements analyzed.
The uncertainty for the Re concentration in the standard is less well
constrained but is likely to be of a similar magnitude. The extent of
possible Re/Mo fractionation during ablation of molybdenite relative
to the standard has not been assessed in detail but is unlikely be
> 20% based on the results of Danyushevsky et al. (2011). We thus es-
timate the total error on reported Re concentration to be 2040%.
Consistent with this, the measured Re concentrations are at the
same order of magnitude as published Re concentrations for samples
from both Hilltop and Boddington as measured by Carius-tube
methods during the course of ReOs dating. Irrespective of any errors in-
troduced in analysis, the observed small difference between those con-
centration values and the ones given here (our values tend to be
somewhat higher) is also consistent with substantial variation between
grains in the same sample and between samples from the same locality.
The element maps of molybdenite in the Hilltop sample (Fig. 5)
were made using the same LAICP-MS instrumentation. Images were
acquired using laser frequency of 10 Hz, laser beam size of 6 m, and
a rastering rate of 10 m/s. Further details of the methodology are
given by Large et al. (2009). Element maps on the Boddington material
(Figs. 68) were acquired with laser beam sizes of 10 m, 8 m and
15 m, respectively.
3.2. Focused Ion BeamScanning Electron Microscopy and Transmission
Electron Microscopy
A FEI-Helios nanoLab Focused Ion BeamScanning Electron Micros-
copy (FIBSEM) system at Adelaide Microscopy was used to prepare
samples for Transmission Electron Microscopy (TEM) foils. Methodolo-
gy is described by Ciobanu et al. (2011). The TEM study was performed
on a Philips 200CM instrument operated at 200 kV. The instrument is
equipped with a double-tilt holder and Gatan digital camera. Measure-
ments on the diffractions were performed using DigitalMicrograph
3.11.1.
4. Results
4.1. Molybdenite trace element heterogeneity
Molybdenite in analyzed samples from both deposits (Table 1) oc-
curs mostly as up to cm-sized, lamellar or knotted aggregates as well
as single wispy lamellae with common kinks and folding. Inclusions of
Bi-minerals and galena in molybdenite, often associated with native
gold at Boddington, are ubiquitous throughout the samples (Fig. 3df).
LAICP-MS spots were selected to characterize homogeneous areas,
targeting key intragranular fabrics to understand variation with respect
to textures.
Molybdenite shows highly-variable Re concentrations (Tables 2
and 3), ranging from tens to >1000 ppm (Fig. 4a). At Hilltop, one

Fig. 4. (a) Plot showing Re variation in the samples. Individual spot analyses are arranged in decreasing order within each sample or zone; mean sample concentrations (ppm)
are given in red. Mean Re in the BRIM sample (97-10; 90 ppm) agrees well with concentrations given by Kelson et al. (2005) (51 ppm; n = 2). Similarly, values given here compare
with those reported by Stein et al. (2001b) for Re-rich molybdenite at Boddington (328, 344, 435, 832 ppm). Abbreviations: BRIM intrusive matrix breccias; Fds feldspar; Qz
quartz. (b) Positive correlation between (Au + Ag) and CEs (Bi + Pb + Te) for all samples. (c) and (d) Representative time-resolved LAICP-MS depth proles for molybdenite
from Hilltop and Boddington to show noisiness for CEs (and W on (d)) contrasting with at signals for lattice-bound elements. Element concentrations (ppm) are given in brackets.
 C.L. Ciobanu et al. / Chemical Geology 347 (2013) 175189
sample (HT-X) has much higher Re than the others and one of the
grains stands out in having a coarse lamellar core surrounded by a
ner-grained halo cemented by chalcopyrite, silicates and with inclu-
sions of Bi-chalcogenides and galena. Re concentration is low in the
inner core but higher and irregular in the outer part of the core whereas
the halo has remarkably constant values. Other grains in this sample
have still higher Re values. Tungsten is typically tens of ppm but up to
195 ppm in the grain halo. CEs range up to several hundred ppm; Bi,
Pb and Te are high in the grain halo; Au is highest (mean 4.8 ppm) in
HT-X. At Boddington, Re variation is highest in molybdenite from the
granite aureole and W varies across two orders of magnitude in all sam-
ples. Mean Bi and Pb concentrations are hundreds of ppm but Te is
lower and displays greater variance; Au is up to 360 ppm but typically
tens of ppm. In both deposits, Au + Ag and CEs show a good correlation
(Fig. 4b). Time-resolved LAICP-MS depth proles reect two groups of
elements in the atness (Re, Se and in most cases W) or noisiness (CEs)
of the proles (Fig. 4c). In Boddington molybdenite, W can also show
irregular proles similar to CEs (Fig. 4d).
Mapped grains were selected to reect corehalo relationships at
Hilltop and response to deformation and replacement at Boddington.
Trace element maps for Fe, Cu, CEs and U outline the corehalo texture
at Hilltop (Fig. 5). Re displays oscillatory zonation in a depleted
inner-core and no marked boundary between the outer-core and halo
whereas W shows an inverse pattern to Re in the core and is highest
in the halo. Expected Re depletion in areas highest in Cu is not seen
due to pervasive molybdenite inclusions in chalcopyrite.
Fig. 5. Reected light photomicrograph and LAICP-MS element maps for molybdenite in HT-X (Hilltop). Scales represent 10n counts-per-second values. Cp chalcopyrite, Qz quartz.
185
All element maps of Boddington samples show grain-scale hetero-
geneity. Patterns in part of a lamella framed by kinks (Fig. 6) show
that Re is homogeneously distributed, thus contrasting with W which
is concentrated in kinks and along grain margins. CE-rich spots correlate
with cleavages and kinks; Au and Ag show clustered spots along the CE
patterns. Similar patterns are seen in a strongly-deformed molybdenite
aggregate (Fig. 7) where W is enriched in intensely-deformed domains
but Re is unaffected. A distinct Re pattern is mapped on a lamella from a
diorite sample in the granite aureole (Fig. 8), 200 m below the sample
mapped in Fig. 7. Here, molybdenite features a subtle ne-grained tex-
ture when adjacent to chalcopyrite inlling cleavages and both Re and
W are concentrated along such replacement zones.
4.2. Crystal-structure and defects
Whether local trace element enrichment correlates with polytypism
in molybdenite was checked by preparing TEM foils from the core-halo
grain using the FIBSEM approach (Ciobanu et al., 2011) and method.
Slices were cut at site-specic locations (Fig. 9a): (i) outer core; and
(ii) halo. High-resolution FIBSEM imaging shows nanoporosity associ-
ated with hairpin folding (Fig. 9b) and sub-m galena inclusions
(Fig. 9c) in foil (i). CE-mineral inclusions reach several m in the halo
(Fig. 9d). Electron diffraction patterns indicate the presence of the 2H
polytype only in both foils (Fig. 9e). Abundant nanoscale fractures
with terminations sealed by curvature of lattice fringes in both foils
may be associated with stacking disorder (Fig. 9f and inset).
186 C.L. Ciobanu et al. / Chemical Geology 347 (2013) 175189

Fig. 6. Reected light photomicrograph and LAICP-MS element maps for molybdenite in RG10 (Boddington). Scales represent 10n counts-per-second values. Contoured areas are
AuAg-rich spots.

Fig. 7. BSE image and LAICP-MS element maps for molybdenite in sample 25NK (Boddington). Scales represent 10n counts-per-second values. Scales represent 10n
counts-per-second values.
 C.L. Ciobanu et al. / Chemical Geology 347 (2013) 175189
Fig. 8. Reected light photomicrograph and LAICP-MS element maps for molybdenite in sample 27RG (Boddington). Scales represent 10n counts-per-second values. Note abun-
dant inter-lamellar inclusions of chalcopyrite.
5. Discussion
Complementary to previous studies that have distinguished
co-existing generations of molybdenite with implications for evalua-
tion of deposit evolution (Requia et al., 2003; Wilson et al., 2007;
Aleinikoff et al., 2012), the data presented here shows trace element
patterns that can be used to interpret mineralization histories. CEs are
an important element set for constraining either deformation or replace-
ment, particularly when compared with the patterns of lattice-bound
elements in the same grain. The persistent noisiness of CE signals, con-
trasting with Re, Se and (largely) W in both study cases, suggests a dis-
tinct trapping and release behavior for inclusion- and lattice-bound
elements. However, W can behave differently to other lattice-bound ele-
ments under similar conditions, e.g., the ragged signal mimicking CEs
(Fig. 4d).
Observed CE-minerals and their size down to nanoscale, indicate
that whichever the trapping mechanism, CEs readily coarsen out of
smaller impurities attached to crystal defects or lamellae surfaces.
Crystal-chemical modularity in Bi-chalcogenides (Cook et al., 2007a,b;
Ciobanu et al., 2009a) may attract coherent intergrowths with other
minerals that have mixed-layer conguration such as molybdenite. The
presence of the 2H polytype in both outer-core and halo molybdenite
from Hilltop indicates that cell expansion by polytypism is not sensitive
to order-of-magnitude differences in trace element concentrations,
even if observed stacking disorder can be related to lattice-scale defects
initiating 2H 3R transformation. Sub-grain-scale trace element trap-
ping mechanisms discussed for molybdenite (Stein et al., 2003) extend
to the nanoscale. Furthermore, crystal-structural defects and porosity
enhance uid inltration and promote incorporation, nucleation and
coarsening of impurities.
Despite the abundance of such defects, element maps and narrow
concentration ranges in 2 of the 3 cases from Boddington show Re
187
remains locked in molybdenite under deformation. However, in the
granite aureole, Re-enrichment along replacement boundaries sug-
gests local dissolution and reprecipitation of molybdenite behind
the chalcopyrite-forming reaction front. Replacement by coupled dis-
solutionreprecipitation reaction (CDRR; Putnis, 2002) results in a
precipitate that, even if the same as the parent mineral, will differ in
trace element concentration and grain size (ne-grained Re-rich mo-
lybdenite in this case).
A stronger case for trace element redistribution via CDRR,
expressed best by Re, is Hilltop. The steady, inwards advance of reac-
tion is seen in formation of a well-dened molybdenite halo with
characteristic ne-grain size and constant Re concentration. The wan-
ing stage, when coupling between dissolution and reprecipitation is
no longer sustained, is seen as replacement limited to cleavages and
fractures (erratic Re values in the outer-core). These relationships
point to a second molybdenite generation, also carrying a CE-U signa-
ture, as a halo superposed onto a preserved oscillatory-zoned core.
Second stage molybdenite at Hilltop suggests an epithermal overprint
linked to an unidentied Re-rich, MoCuAu-bearing intrusion, or
upgrading precursor molybdenite. Such superposition of events is com-
mon in young, relatively short-lived magmatic-hydrothermal systems.
Understanding the molybdenite history from an Archean Au deposit
within a granite-greenstone belt such as Boddington, centers on the ge-
netic role of granite as a metal source or heat engine. We show here that
early, Re-rich molybdenite, attributable to the porphyry-stage, occurs
across the deposit. Unlike W and CEs, Re is largely unaffected by the oro-
genic event. Granite-derived uids, although low in Re (as seen in
granite-hosted molybdenite itself; Kalleske, 2010; Guerin, 2011) affect
pre-existing diorite-hosted molybdenite, resulting in an overall dilution
but retention of higher Re along replacement zones.
The analytical datasets from both deposits show that molybdenite
concentrates Au and Ag if CEs are present. This can be attributed to the
188 C.L. Ciobanu et al. / Chemical Geology 347 (2013) 175189

Fig. 9. (ad) Secondary electron FIB images of molybdenite showing location of FIB cuts (a), nanopores in hairpin fold (b) and CE-mineral inclusions ranging in size from several
hundred nm (c) to m (d). (e) Selected area of electron diffraction (SAED) on [1100] zone in molybdenite showing the c spacing (12 ) characteristic of the 2H polytype. (f) Dis-
tortion of lattice fringes (white arrows) closing in a nanofracture. SAED (inset) shows streaking of reections (arrowed) along rows parallel to c*.

role of Bi-chalcogenides as scavengers and hosts for Au (Ciobanu et al.,
2009b). Coarsening of CE-minerals with subsequent Au release and
reconcentration are attributable to both orogenic and granitic events at
Boddington. Aleinikoff et al. (2012) have demonstrated that multiple
ages can be measured in individual molybdenite grains. Here we show
that such zonation is also reected by trace element distributions.
Acknowledgments
The authors thank Newmont Asia-Pacic for supporting two B.Sc.
Hons. projects at Boddington, and Barrick Cortez for their support
with the Hilltop material and for permission to publish. AMMRF is
thanked for use of the FEI Helios nanoLab Dual Beam FIB/SEM system.
Partial funding for this project was provided by the Department of
Geology, State University of New York at Potsdam. We appreciate
the helpful comments from the two anonymous journal reviewers,
as well as those of Marc Norman on an earlier version of this manu-
script. This is TRaX contribution no. 288.
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