Pyrite and Pyrrhotite Textures and Composition in Sediments, Laminated Quartz Veins

Economic Geology
BULLETIN OF THE SOCIETY OF ECONOMIC GEOLOGISTS
VOL. 106
JanuaryFebruary 2011
NO. 1
Pyrite and Pyrrhotite Textures and Composition in Sediments, Laminated Quartz Veins,
and Reefs at Bendigo Gold Mine, Australia: Insights for Ore Genesis
HELEN V. THOMAS,1, ROSS R. LARGE,1 STUART W. BULL,1 VALERIY MASLENNIKOV,2
RON F. BERRY,1 ROD FRASER,3 SHANE FROUD,3 AND ROBERT MOYE1
1CODES
ARC Centre of Excellence in Ore Deposits, Private Bag 126, University of Tasmania, Australia 7001
2Institute
of Mineralogy, Russian Academy of Science, Urals Branch, Miass
3Bendigo
Mining Limited, 66 Ham St, Bendigo, Victoria, Australia 3555
Abstract
The various types, textures, and compositional zoning of pyrite in the gold-bearing saddle reefs, quartz veins,
and surrounding sedimentary rocks provide new information on the potential source and timing of gold and
arsenic and related fluid processes responsible for mineralization at Bendigo. Nodular diagenetic pyrite in the
black shale tops to sandstone turbidites is enriched in invisible gold and arsenic with mean values of 0.61 ppm
Au, 1,300 ppm As, and Au/Ag <1, based on LA-ICPMS analyses. Other elements enriched in the diagenetic
pyrite within the organic-rich shales are Mn, Zn, Mo, Cu, V, Ba, Ag, Cd, Tl, Co, Ni, Bi, Pb, and Te. In contrast,
euhedral- and growth-zoned hydrothermal pyrite in the turbidites and bedding-parallel laminated quartz veins
contains lower contents of most trace elements but has higher contents of invisible Au and As, especially on
the outermost rim of the pyrite. The gold-rich pyrite rims generally become thicker (a few to hundreds of
microns) in proximity to the gold-bearing saddle reefs. Pyrite in the reef commonly has the highest levels of
invisible Au and As and the lowest levels of other trace elements. It is characterized by Au/Ag >1 and Au/Pb
>0.01. In the deepest stratigraphic levels, below known productive gold reefs, diagenetic pyrite in the most carbonaceous shales has been replaced by pyrrhotite during metamorphism. LA-ICPMS analyses reveal that the
disseminated pyrrhotite contains similar levels of Ni and Co to the diagenetic pyrite but is strongly depleted in
As and Au. The spatial relationships between organic-rich shales, folded bedding-parallel laminated quartz
veins, and gold-arsenicbearing saddle reefs, combined with the consistent trends in the trace element composition of pyrite hosted by these three geological elements, is interpreted to indicate that the black shales were
an initial source of Au and As, and the laminated quartz veins acted as the initial pathways for hydrothermal
fluid flow carrying Au and As from the source shales to the saddle reefs. Maximum gold and arsenic input into
the reefs, principally as free gold plus arsenopyrite, occurred late during deformation toward the end of the
hydrothermal cycle and is expressed by the Au-Asrich rims to hydrothermal pyrite in the sedimentary host
rocks, laminated quartz veins, and reefs. This corresponds with final fold lockup and the development of
through-going fault arrays linking adjacent anticlines. The source of Au and As for this final, and most economically important, fluid-flow event is considered to be from carbonaceous shales deeper in the basin, where
original gold-bearing diagenetic arsenian pyrite reacts with organic matter and is converted to pyrrhotite, with
release of Au, As, and S to the metamorphic fluid.
Introduction
Pyrites were acid etched prior to petrographic study, then

subjected to LA-ICPMS 4500 analysis at CODES (Hobart,
Tasmania) and were analyzed to quantify trace elements using
a combination of laser spots and lines. Samples exhibiting
zoning were mapped using a technique developed in house
(Danyushevsky et al., in press; Large et al., 2009). This technique is a powerful tool in defining separate pyrite growth
zones and hence mineralizing fluid events, giving an immediate overview into concurrent trace element availability in an
accessible format.
This study shows that pyrite growth occurred from sedimentation to late metamorphism, and because later pyrite
GOLD AT Bendigo is hosted in quartz veins and saddle reef

associated with both folds and faults emplaced in a series of
Ordovician turbidites. This study investigates whether pyrite
textures, chemistry, and trace element zonation can be used
to assist in understanding the sequence of ore-forming
events. Polished thin sections and polished section blocks enabled petrographic analysis of sulfide minerals and their host
rock, both under the microscope and using the laser ablationinductively coupled plasma mass spectrometer (LA-ICPMS).
Corresponding
author: email, Helen.thomas@utas.edu.au
2011 by Economic Geology, Vol. 106, pp. 131
0361-0128/11/3933/1-31
Submitted: March 9, 2010

Accepted: October 5, 2010
THOMAS ET AL.
often overgrows earlier generations of pyrite, with careful

petrography, a near-complete sequence of fluid-flow events
has been determined. Samples of pyrite from sedimentary
rocks were taken from drill core within and around the reefs,
but surficial weathering proved too pervasive to recover viable pyrite grains from surface exposures. We show that different generations of pyrite have characteristic trace element
patterns, which can be used as a proxy for fluid-flow events.
Early diagenetic pyrites are characterized by a low Au/Ag
ratio with elevations in Bi, Ni, Cu, Mo, V, and Pb, whereas
late hydrothermal pyrites are commonly zoned, with a higher
Au/Ag ratio and a distinct Au-As correlation. Hydrothermal
pyrite in the sedimentary rocks and laminated quartz veins
close to gold reefs has distinct Au-As rims that increase in
thickness in proximity to the reefs. This new information has
enabled a reinterpretation of the source of gold and the
hydrothermal fluid-flow processes that formed the gold-bearing saddle reefs at Bendigo.
suspension deposited mudstone and shale, termed the Castlemaine Group (Fergusson and VandenBerg, 2003). Together
with the contemporaneous Adaminaby Group in eastern Victoria, these form the Ordovician mud pile (Vandenberg et
al., 2000) that records Late Cambrian to Late Ordovician
basin plain sedimentation outboard of the Gondwanan continental landmass (Cas, 1983). Despite the widespread nature
of these units and the diversity of graptolite fauna they host,
the Castlemaine Supergroup is largely undifferentiated stratigraphically, with laterally discontinuous channelized structures common, preventing correlation over more than a few
kilometers (Cas et al., 1988). The current across-strike extent
of this deep water succession is >500 km, and the pervasive
development of chevron folds during Late Ordovician to
Early Silurian east-west contractional deformation of the Benambran orogeny has resulted in overall shortening of up to
70 percent (Gray, 1997).
In western Victoria, the turbidite pile is exposed in two
structural elements separated by the north-southtrending
Avoca fault (Fig. 1). The western Stawell zone comprises a
Cambro-Ordovician succession termed the St Arnaud Group,
and the eastern Bendigo zone the Lower and Middle Ordovician succession termed the Castlemaine Group. The base of
Regional Geology
The host rocks to the Bendigo goldfields in western Victoria
are an ~3-km-thick Lower and Middle Ordovician succession
of mass-flow deposited sandstone and mudstone, with lesser
FIG. 1. Map showing location of the Bendigo gold deposit, Victoria, Australia, with major structural zones and terranes
labeled. Modified from Vandenberg et al. (2000).
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PYRITE AND PYRRHOTITE AT BENDIGO MINE, AUSTRALIA
the Castlemanian is defined by the Lancefieldian Group of

compositionally variable, laterally extensive lithic sandstones
interbedded with silicious shales (Cas et al., 1988). Provenance data indicate that both successions were derived from
convergent tectonic activity that affected the adjacent Gondwanan continental margin; the Delamerian and Ross orogenies in South Australia and Antarctica, respectively (Gray and
Webb, 1995; Turner et al., 1996; Fergusson and Tye, 1999).
The most comprehensive study of the Castlemaine Group is
that of Cas et al. (1988). The sandstone beds that characterize
the Ordovician succession have been widely interpreted as turbidites due to their broadly lensoidal geometry, and the range
and arrangement of primary sedimentary structures that are
consistent with the Bouma sequence (Cas et al., 1988). The
lack of subsequent reworking and preservation of intervening
fine-grained suspension deposits indicates that they record an
entirely deep water environment on the basin plain outboard
of the continental rise and slope. In a regional sense, one aspect of the sedimentology of the Castlemaine Group that
stands out is the thickness and abundance of graptolitic black
shales. In the turbidite sequences to the west and east of the
Bendigo zone such black shales are relatively rare and finegrained interbeds are more commonly cherts that have faunal
assemblages consistent with a truly pelagic origin (Cas et al.,
1988). It has been suggested that the Castlemaine Group was
deposited in an area of oceanic upwelling that favored organic
productivity, while anoxic bottom conditions favored organic
preservation (Fergusson and VandenBerg, 2003).
1992; Gao and Kwak, 1995a, b; Arne et al., 1998; Bierlein et

al., 1998, 2001, 2004; Foster et al., 1998; Ramsay et al., 1998;
Jia et al., 2000, 2001; Schaubs and Wilson, 2002; Schaubs and
Zhao, 2002; Willman, 2007; Wood and Large, 2007; Boucher
et al., 2008) and only a summary of the major features and
current genetic ideas are presented here.
Gold at Bendigo occurs as nuggets and/or hydrothermal
grains of free gold in quartz saddle reefs and associated spur
veins. Alluvial gold was exploited in the early history of the
deposit (18511853), but resources were soon exhausted and
reef mining began in 1853 (Willman and Wilkinson, 1992).
Gold in quartz reefs is often associated with pyrite, arsenopyrite, galena, sphalerite with minor chalcopyrite, and pyrrhotite
(Sharpe and MacGeehan, 1990). Historically, most of the gold
came from the hinge zones and eastern limbs of three anticlines, the Garden Gully, New Chum, and Hustlers Lines,
with the Deborah Line mined mainly from the 1940s onward
(Willman and Wilkinson, 1992). The best mineralized areas
correspond to domal culminations in the fold axes especially
on the eastern limbs (Fig. 2), however, west-dipping fault and
associated extensional veins also host significant gold (Sharpe
and MacGeehan, 1990). The latter comprise bedding-parallel
laminated quartz veins (locally termed LQ veins) that often
join quartz saddle reefs forming legs (Fig. 2; Willman and
Wilkinson, 1992). These usually occur at the boundary between sandy and shaly intervals (Tanner, 1989) due to the inherent competency contrast. They are thought to form early
in the deformation and/or metamorphic history as beddingparallel zones of flexural slip (Cox et al., 1991; Jessell et al.,
1994), and it is likely that they acted as fluid pathways early in
the deposit history before being overprinted by crosscutting
structures. These veins can be correlated over kilometers of
stratigraphy along relict bedding planes and commonly develop into saddle reefs (Schaubs and Wilson, 2002).
The turbidite host rocks at the mine consist of thick sandstone packages from 10 to 120 m thick, separated by packages
of shale, siltstone, and minor sandstone from less than 5 to 50
m thick. At least 15 cycles of sandstone to shale have been defined in the mine drilling (Fig. 3). Individual turbidites and
turbidite packages generally exhibit an upward fining from
0.3- to 4-m-thick sandy turbidites, to 5- to 20-cm shale-rich
turbidites, and then into a sequence of black and gray shale
up to 30 m thick, which define the major named shale units
(Figs. 23; Sharpe and MacGeehan, 1990; Boucher et al.,
2008). In the current mining area in the Kangaroo Flat section, productive gold-bearing quartz reefs are confined to the
Railway Shale and Big Blue Shale (Fig. 2) but in other areas
of the mine gold reefs are developed in Rowes Shale, Inner
Shale, and Royal Albert Shale (Fig. 3). The siltstones and
shales vary from gray to black, depending on grain size and
organic carbon content (Fig. 4). Mineralogy consists of
quartz, sericite with minor carbonate, chlorite, graphite, and
pyrite. The gray siltstones and shales contain 0.04 to 0.20 wt
percent organic carbon and 0.5 to 2 wt percent pyrite, whereas
the black shales contain 0.2 to 2.0 wt percent organic carbon
and 1.0 to 6.0 wt percent pyrite. The sandstones are light gray
massive units (Fig. 4) with a quartz, albite, sericite mineralogy
and contain <0.05 wt percent organic carbon and <1.0 wt percent pyrite. In addition to the high organic carbon, the black
shales contain elevated trace metals, including V (100500
Deformation and mineralization in the Bendigo zone

The Bendigo zone is characterized by classic upright open to
tight chevron folds with wavelengths of 150 to 500 m, indicating relatively simple east-west compression during the Benambran orogeny (Gray and Foster, 1998; Fergusson and VandenBerg, 2003). Narrow zones of stronger deformation and
cleavage development occur in the hanging walls of the four
major north-southtrending high-angle reverse faults that subdivide the zone (Fig. 1) and are interpreted as a linked system
of imbricates that splay off a midcrustal detachment zone (Cox
et al., 1991; Gray and Willman, 1991). A recent seismic survey
shows that the original depth of the sedimentary pile may have
been >4,000 m, now shortened to its present depth of over 10
km (Willman et al., 2010; Cayley et al., in press). The Heathcote fault zone at the eastern edge of the Bendigo zone represents the exhumation of the detachment zone (Fig. 1).
The Bendigo goldfield is the largest in Victoria and has produced 529 metric tons (t) of vein-hosted gold (Willman and
Wilkinson, 1992; Fig. 1). It is hosted by symmetric and persistent north-southtrending chevron folds that have controlled the geometry of the gold reefs (e.g., Vandenberg et al.,
2000). The eastern edge of the field is sharply bounded by the
more deformed succession in the hanging wall of the westdipping Whitelaw fault, but there is a gradational decline in
grade and abundance of mineralized structures to the west
(Willman and Wilkinson, 1992).
Geology of the Bendigo Deposit
There have been many studies on the geology and mineralization at Bendigo (e.g., Cas et al., 1988; Sharpe and MacGeehan, 1990; Cox et al., 1991, 1995; Willman and Wilkinson,
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THOMAS ET AL.
Garden Gully
Anticline
Scale
1:500
Stratigraphic
column and
legend
Harris Sand
-700 z
Western Shale
Gill Reef
Western Sand
Big Blue Shale
Christine Unit
True Grit
NBD
161
-800 z
Alexandria Sand
Railway Shale
Noah Sand
NBD
238
Emily Shale
Grace Sand
Gold Reef
-900 z
Laminated
Quartz Vein
Anticline/
Syncline trace
Drill hole
trace
NBD
171
Fault
48600 E
48700 E
48800 E
FIG. 2. Mine stratigraphic section Garden Gully anticline, Kangaroo Flat, Bendigo, redrawn from drill sections provided
by Bendigo Mining Ltd. The majority of samples were taken from drill holes shown in the diagram by thick solid lines. Red
lines represent laminated quartz veins; a gold reef is located in the anticlinal axis of the Railway shale (colored red). Syncline
and anticline axes are indicated with dotted lines, faults are indicated with dashed lines. Additional samples were taken
throughout the entire stratigraphy drilled at Bendigo and are discussed in Thomas et al. (in prep). Units are Bendigonian in
age.
ppm), Zn (1001000 ppm), Cu (50150 ppm), Ni (50140

ppm), As (5140 ppm), U (412 ppm), Mo (140 ppm), and
Ag (0.10.5 ppm). Previous workers (e.g., Cas et al., 1988)
have suggested that the regional turbidite pile at Bendigo
fines upward, with sandstones dominating the lower stratigraphy. This is not supported by recent drilling, which has intersected a package consisting of more than 500 m of turbidites
which contains over 30 percent shales and siltstones below
the stratigraphic level of the Railway Shale (Fig. 3).
Alteration halos around the veins and reefs are controlled
by the porosity and permeability of the immediate host rock
and can comprise minor disseminated porphyroblasts of
pyrite and rare arsenopyrite up to several 10s of meters
away from lodes as well as more widespread sericite and
chlorite alteration and carbonate poikioblasts (Cox et al.,
1991; Li et al., 1998; Bierlein et al., 2004). Chlorite geothermometry performed by Li et al. (1998) suggested that the
chlorite alteration took place in temperatures of 260 to
290C. Recent work by Dugdale et al. (2009) suggested that
carbonate spots at Bendigo initially formed during diagenesis
of the sediments by anaerobic oxidation processes associated
with a fluid containing methane. During metamorphism, the
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diagenetic spots were overgrown by a second stage of metamorphic carbonate.

Previous sulfur isotope studies (Jia et al., 2001; Bierlein et
al., 2004) demonstrate that sulfides in the gold reefs are narrowly constrained from 7 to +8 per mil with a median of
+2.5 per mil, compared to pyrite in the sedimentary host
rocks, which shows a larger spread from 23 to +12 per mil.
They interpreted this to reflect variable exchange of ore fluids with synsedimentary-diagenetic sulfides present in wall
rocks during transport of ore fluid to the site of deposition.
Jia et al. (2000) analyzed fluid inclusions in quartz from the
Central and North Deborah mine at Bendigo. They found that
fluid inclusions from the Au-bearing quartz veins are generally
reduced in the CH4-CO2-H2O-NaCl system, whereas fluid inclusions in non Au-bearing quartz veins are more oxidized with
compositions in the CO2-H2O-NaCl or H2O-NaCl systems
only. Recent fluid inclusion studies by Fu et al. (2009) show
that fluid Br/Cl and I/Cl values reflect interaction with, or derivation from, sedimentary rocks enriched in organic matter
and provide no evidence of mantle or deeply derived components. Illite b-spacing index studies indicate peak metamorphic
temperatures were around 300C (Wilson et al., 2009), which
4
Royal Albert
Shale
Inner Shale
Rowe Shale
Western Shale
Big Blue Shale
*
*
*
Railway Shale
Methodology and Analytical Techniques

Analytical instrumentation employed in this study consists of
a New Wave 213-nm solid-state laser microprobe coupled to an
Agilent 4500 quadrupole ICPMS. One pyrite sample (NBD
171-544.8 fish) was mapped on a slightly different set-up utilizing the New Wave 213-nm solid-state laser microprobe coupled to an Agilent 7700 quadrupole ICPMS; both housed at
the CODES LA-ICPMS facility at the University of Tasmania.
The method is described in detail in Large et al. (2009) and
(Danyushevsky et al., in press) and summarized here below.
The laser microprobe is equipped with a small volume ablation cell (~2.5 cm3) characterized by <1-s response time and <2s washout time. Ablation was performed in pure He (0.7 l m1).
The aerosol carried by the He gas was immediately mixed with
Ar (1.23 l m1) after leaving the cell, passed through a pulse-homogenizing device, and then directly introduced to the torch.
ICPMS optimization took place daily in order to maximize
sensitivity to mid- to high-mass isotopes (ranging 130240
a.m.u.); production of molecular oxide species (e.g., 232Th16O/
232Th) and doubly charged ion species (e.g., 124Ce2+/140Ce+)
was maintained at <0.2 percent. No correction was warranted
for the analyte signal intensities caused by the presence of
these interfering species as they occurred at a low level. Each
analysis was performed in time-resolved mode, which involves sequential peak cycling through the mass spectrum.
Pyrite analyses were performed by laser-ablating spots 40
m in diameter, repetition rate was 5 Hz, and laser beam energy was maintained between 4 and 5 Jcm2. Analysis time
was restricted to 90 s, comprising 30-s background (laser
shutter closed) and 60-s analysis (laser shutter open). Acquisition times are as follows: major silicate elements (i.e., Mg,
Al, Si, Ca) and S = 0.005 s; trace silicate elements (i.e., Zr, Ba,
La, Th, U) and Cd = 0.01 s; Se, Mo, and Ag = 0.1 s; Te = 0.2
s; Au = 0.4 s; other elements = 0.02 s; with a total sweep time
of approximately 1.5 s.
Data reduction took place according to standard methods
(Longerich et al., 1996) with Fe the internal standard. The
primary calibration standard consisted of a Li borate fused
glass of pyrite and/or sphalerite mixture developed inhouse
(Danyushevsky et al., in press) and was analyzed twice every
one and a half hours with a 110-m beam size at 10 Hz to correct for instrument drift.
Imaging of sulfides was performed by ablating a set of parallel
lines arranged in a grid over the sample so that the space between the lines was the same as the size of the beam. Beam size
was chosen as 12, 15, 22, 25, 30, or 55 m depending on sample
size. In order to identify zoning in small pyrites of less than 500
m, a beam size of 12 or 15 m was used. This is in contrast to
coarser grained pyrites (>2,000 m), for which beam sizes of 22
to 55 m were employed. The beam was rastered over the lines
at the same speed as the beam size (i.e., spot = 25 m, speed =
25 m/s1), at 10-Hz repetition rate. Therefore, every position in
the sample was ablated 10 times, contributing to five consecutive pixels in the image. This results in an unprocessed effective
resolution which matches the beam size. Each individual sweep
forms a single pixel in the image, about 5 m in size, assuming
a sweep time of ~0.2 s and a speed of 25 m/s1. Samples were
ablated to a depth of approximately 5 m, estimated from the
depth of ablation in a single shot (0.5 m) and the number of
shots in a single point of the sample (repetition rate = 10).
Jude Shale
pyrrhotite present
Emily Shale
Ethan Shale
Owen Shale
20 m
FIG. 3. Stratigraphic column of turbidite package, Bendigo mine. Sandstone units are shown in white, shale and siltstone units in black. The zone
where pyrrhotite is present in the shales is indicated by the dashed line. Shale
units which contain gold-bearing quartz reefs are shown with an asterisk.
is somewhat lower than the hydrothermal fluid inclusion temperatures of 350 25C determined by Jia et al. (2000).
Ar/Ar dating of sericite from a gold-bearing extensional vein
from the Central Deborah mine gave an age of 439 2 Ma
(Foster et al., 1998). Arsenopyrite and pyrite grains from an
auriferous quartz vein in the Deborah anticline were dated as
438 6 Ma, using the Re-Os method by Arne et al. (2001).
Despite the long history of mining of these deposits, there
is no consensus on the source of gold. Workers, including
Crawford and Keays (1987) and Keays (1987), suggested that
gold may have been sourced from deep in the Cambrian
boninites in the lower part of the greenstone pile that underlies the turbididic succession, whereas Bierlein et al. (1998)
suggested that the gold may have been sourced from Cambrian
metatholeiites and interflow sediments that form the upper
part of the greenstone pile. Suggested sources for the oregenerating fluids are metamorphic fluids originating from the
greenschist-amphibolite boundary at depths >12 km (Phillips
et al., 2003), or released from a subduction slab break-off at
depths >200 km (Vos et al., 2007). These previous studies, focused on the source of the gold, have omitted to consider the
source of arsenic, which is in far greater abundance in the
ores than gold. We provide evidence in this paper that the
source of both gold and arsenic was most likely the thick pile
of Ordovician turbiditic sediments that also host the deposits.
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THOMAS ET AL.
5 cm
1 cm
1 cm
1 cm
1 cm
FIG. 4. Rock lithologic units at Bendigo. A. Core tray from drill hole NBD 212W1, showing lithologic units in the Railway Shale. Dark bands are carbonaceous shale, light bands are gray siltstone. A bedding-parallel laminated quartz vein occurs in the middle of the tray. B. Gray sandstone, typical of the massive sandstones in the basal parts of thick turbidite packages. C. Carbonaceous and pyritic shale, typical of the fine tops to the sandstone turbidites. D. Black shale and gray siltstone,
with euhedral pyrite developed in the base of the siltstone. E. Example of a bedding-parallel laminated quartz vein (LQ),
typical of those which connect to the saddle reefs. These veins are characterized by their laminated texture, consisting of
white quartz and dark-colored selvage (chlorite, sericite, graphite). Pyrite present in laminated quartz veins is hydrothermal
in origin, typically euhedral and coarse grained. F. Underground photograph of the Gill reef, a typical gold-rich saddle reef
at Bendigo (Mine Northing 124357 MN; provided by Bendigo Mining).
A set of 20 elements was chosen for analysis, with acquisition time for the majority of elements set to 0.002 s; exceptions were Se (0.004 s), and Ag, Te, and Au (0.04 s). Total
sweep time was ~0.2 s. A 13-s delay was left after each line to
allow for cell washout. Background levels and drift were measured on the primary standard before and after every image
(Danyushevsky et al., in press). Maps were generally generated over a period of 1 to 2 h where drift in sensitivity is minimal. Occasionally, larger maps were generated and a drift
correction was undertaken, with instrument drift considered
to be linear between the standards. Image processing involved drift correction (if necessary), application of a median
filter to remove artefacts generated during processing, subtraction of background from filtered counts, replacement of
filtered counts less than background with the standard deviation value for that element; finally, images were produced for
each element using a logarithmic color scale. Redeposition of
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sample back onto the surface as an ablation plume was kept

to a minimum by preablating each line immediately prior to
analysis. Some elements are particularly prone to redistribution; this is especially evident in the noise present around native gold inclusions.
Pyrite and Pyrrhotite Types and Textures
Based on methods developed in previous studies on pyrite
in sediment- and volcanic-hosted gold deposits (e.g., Mumin
et al., 1994; Huston et al., 1995; Large et al., 2007, 2009), the
morphology and internal structure and zoning of pyrites have
been used here as a guide to the timing relationship between
pyrite growth and gold events.
Diagenetic pyrite in the sedimentary rocks occurs as finegrained rounded or nodular aggregates aligned parallel to bedding, comprised of intergrowths of acicular and very fine cubic
pyrite and marcasite (Figs. 5A-C, 6, 7). Diagenetic pyrite is
6
Diagenetic pyrites
Diagenetic pyrite cores with euhedral hydrothermal overgrowths
Hydrothermal pyrites
Laminated quartz vein pyrites

FIG. 5. Photomicrograph of pyrite types at Bendigo. A. NBD161-437.15, fine acicular-grained pyrite, diagenetic py1 after
marcasite? B. NBD171-531.5, fine-grained diagenetic pyrite in shale (Py1). C. NBD238-186.5, fine-grained pyrite nodule
py1 (after marcasite?). D. BD171-544.8, partially recrystallized diagenetic py1 nodule, with euhedral hydrothermal pyrite
py3 developed in pressure shadows on edges of nodule. E. NBD180W3-338.8, fine-grained cluster of diagenetic py1 overgrown by coarse euhedral hydrothermal py3. F. NBD177-377E, early diagenetic core of py1, followed by a later diagenetic
overgrowth nodule (py2), overgrown by euhedral hydrothermal py3. G. NBD005-104.1, coarse-grained euhedral hydrothermal py3, with an outermost rim. H. NBD161-431.3, coarse-grained euhedral hydrothermal py3 aggregate overgrowing a siltshale boundary. I. NBD186-517.4, zoned euhedral hydrothermal py3, showing the metamorphic fabric of the shale preserved
in the overgrowth pyrite; revealed by acid etch. J. NBD171-521.7, euhedral laminated quartz vein pyrite, showing vein selvage overgrowth texture. K. NBD180W3-341.6, subhedral laminated quartz vein pyrite exhibiting vein selvage overgrowth
texture. L. NBD238-164.8, euhedral laminated quartz vein pyrite, showing vein selvage overgrowth texture. Scale bars are
all 500 m except for pyrites C and I, for which the scale bar is 200 m.
preferentially hosted in black shale units, which provide the

anoxic-reducing environment necessary for their growth. No
framboidal pyrite was observed in this study at Bendigo, but it
has been previously reported by Li et al. (1998).
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Hydrothermal pyrite in the sedimentary rocks is euhedral

and commonly internally zoned (Fig. 5D-I), in places overprinting the metamorphic fabric of the host shale which is
very apparent after acid etching (Fig. 5I). In many cases the
7
THOMAS ET AL.
FIG. 6. Photomicrograph of sulfide textures in a gold-rich sample from the Gill reef. Subhedral pyrite and arsenopyrite
show a fractured texture. Sphalerite and gold are present within pyrite and interstitial to pyrite grains.
euhedral pyrites have an anhedral porous core composed of

original diagenetic pyrite recrystallized during metamorphism, surrounded by euhedral hydrothermal pyrite, with
growth zoning commonly overprinting internal metamorphic
fabric (e.g., Fig. 5F, I). In these cases the term metamorphichydrothermal pyrite is used. Hydrothermal and metamorphic-hydrothermal pyrite is not confined to any lithology at
Bendigo, with the pyrites exhibiting the most evidence of
growth zoning occurring in sandstone units, presumably reflecting their relatively high effective porosity.
Pyrite from laminated quartz veins is euhedral to anhedral
and commonly displays a pervasive structural overprint,
which is parallel to the lamination in the veins (Fig. 5J-L).
This texture of pyrite growth, overprinting the laminated
quartz bands, indicates that the pyrite has grown late in the
history of vein development.
In the quartz-rich gold-bearing saddle reefs, arsenopyrite is
more abundant than pyrite, with lesser sphalerite, minor
galena, and chalcopyrite. Reef pyrite occurs as euhedral crystals in association with arsenopyrite. Free gold is present as
blebs, from 10 m to several millimeters across, commonly
associated with sphalerite and galena, or occurring at the contact between pyrite and arsenopyrite crystals (Fig. 6). Sharpe
and MacGeehan (1990) reported that 95 percent of the reef
gold production at Bendigo has been free gold, with 5 percent
from roasted sulfide concentrates; most probably gold-bearing arsenian pyrite. The highest gold grades are commonly
present toward the margins of the reef where wall-rock selvages and graphitic material are more abundant (Cox et al.,
FIG. 7. Photomicrographs of disseminated pyrrhotite in black shales. A.

Disseminated pyrrhotite aligned parallel to cleavage. B. Different textural
styles of pyrrhotite in shales: LHS = rounded pyrrhotite after framboidal aggregate of pyrite, RHS = blocky pyrrhotite after aggregates of coarse cubic
pyrite.
0361-0128/98/000/000-00 $6.00
1995). In these zones the reef has a laminated texture similar

to the laminated quartz veins, and after acid etching the arsenopyrite shows an overprinting relationship analogous to
that observed in the laminated quartz vein pyrite.
Recent deep drilling at the Kangaroo Flat mine at Bendigo
has revealed that carbonaceous shales intersected in the
lowest stratigraphy contain fine-grained cleavage-parallel
pyrrhotite, rather than pyrite. Magnetic susceptibility readings on the drill core indicate that this pyrrhotite-bearing interval is about 300 m thick (Fig. 3). Disseminated pyrrhotite
is concentrated in the most carbonaceous black shales,
whereas the light-colored siltstones and sandstones contain
disseminated pyrite. Some shale beds contain both disseminated pyrite and pyrrhotite. Under the microscope (Fig. 7A),
the pyrrhotite commonly occurs in elongate patches about 0.5
to 2 mm long, aligned parallel to cleavage. Minor inclusions
of chalcopyrite and sphalerite are common within the elongate pyrrhotite patches. Textural relationships indicate that
the pyrrhotite has replaced diagenetic pyrite in the shales
(Fig. 7B). Because the pyrrhotite is softer than pyrite, it is
more easily recrystallized and deformed during the metamorphism and deformation and is aligned in the cleavage.
type are given in Table 1 and selected analyses for each major
pyrite type are given in Table 2. The full suite of analyses includes 41 for nodular diagenetic pyrite in sediments, 272 for
euhedral hydrothermal pyrite in sediments, 43 for laminated
quartz vein pyrite and 25 for gold reef pyrite. In addition to
the spot analyses a further 45 pyrite grains have been mapped
by LA-ICPMS to determine trace element zonation and relationships to timing of gold. Six of the pyrite trace element
maps are presented here (Figs. 813).
Trace metals in pyrite may occur in several ways: (1) as invisible solid solution within the pyrite structure, (2) within invisible nanoinclusions of other sulfides or elements, (3) within
visible micron-sized inclusions of other sulfides, or (4) within
visible micron-sized inclusions of silicate or carbonate minerals. There has been no attempt in this study to remove the effects of micron-sized inclusions on the pyrite analyses in Tables 1 and 2. However, inspection of the LA-ICPMS output
traces from each laser spot analysis enables an estimation of
whether a particular trace element occurs within a homogeneous invisible or nano-sized inclusion, or alternatively as
larger isolated micron-sized inclusions in the pyrite (Fig. 12;
Maslennikov et al., 2009). However it is not possible to determine by LA-ICPMS whether a particular element is present as nanoparticles in pyrite or as solid solution in the pyrite
structure. As with previous studies (e.g., Large et al., 2007,
2009), this study has found that As, Mn, Co, Ni, Se, and Mo
are commonly homogeneously distributed in the pyrite, either within the pyrite structure or as nanoinclusions, whereas
Au, Ag, Cu, Zn, Sb, Te, Tl, Pb, and Bi may be either invisible,
as in group (1) above, or present within metallic or sulfide
Trace Element Associations and Zoning

within the Sulfide Types
A total of 371 quantified LA-ICPMS spot and line analyses
have been completed on pyrite from Bendigo for the following suite of elements: Mg, Al, Ca, Ti, V, Cr, Mn, Fe, Co, Ni,
Cu, Zn, As, Se, Sr, Zr, Mo, Ag, Cd, Sn, Sb, Te, Ba, La, W, Pt,
Au, Tl, Pb, Bi, Th, and U. Mean values for each major pyrite
TABLE 1. Mean Trace Element Values for Each Major Pyrite Type Determined by LAICPMS
Pyrite type
Rim/core
No. of analyses (ppm)
Au
Al
Ti
V
Cr
Mn
Co
Ni
Cu
Zn
As
Se
Zr
Mo
Ag
Sn
Sb
Te
Ba
La
W
Pt
Tl
Pb
Bi
Th
U
0361-0128/98/000/000-00 $6.00
Reef
(all)
25
5.65
5022.27
902.19
7.27
17.16
8.41
65.16
385.55
65.16
5.67
6581.14
13.95
18.72
0.20
1.11
0.44
25.86
0.36
47.63
3.76
2.40
0.01
0.20
290.14
38.91
1.21
0.52
Hydrothermal
(rim)
167
1.24
3538.88
995.06
5.72
16.68
36.34
198.06
537.08
97.18
28.42
1852.55
33.73
36.16
0.74
1.25
0.54
92.08
1.94
30.72
12.20
1.72
0.05
0.17
426.06
33.86
3.70
1.70
Hydrothermal
(core)
96
0.65
3717.30
1335.09
7.29
20.02
12.61
200.34
404.97
108.05
128.15
1546.89
56.62
21.07
2.56
4.52
0.57
82.14
2.95
34.15
5.54
1.96
0.05
0.16
2079.45
38.37
2.32
0.75
Laminated
quartz vein (rim)
23
4.37
453.68
449.68
1.97
6.96
4.00
36.08
442.73
73.24
2.93
4961.71
20.74
9.17
0.73
0.70
0.50
75.72
3.07
4.70
4.79
1.93
0.03
0.08
315.42
14.58
1.27
0.26
Laminated
quartz vein (core)
20
2.44
1092.84
339.61
3.85
11.27
7.41
169.76
171.32
15.40
3.30
3974.50
33.32
10.13
0.21
0.82
0.20
47.49
1.40
9.99
0.18
0.96
0.04
0.11
138.99
11.44
2.21
0.48
Diagenetic
(all)
43
0.61
23910
2775.73
35.18
46.69
1065.73
765.19
1236.17
1127.44
499.11
1325.79
66.88
26.56
11.47
4.53
1.89
215.21
5.08
216.47
35.85
2.96
0.06
0.75
1156.76
81.07
13.94
4.66
10
THOMAS ET AL.
TABLE 2. Selected Trace Element Analyses for Each Major Pyrite Type and Free Gold from Reef Determined by LA-ICPMS
Sample no.
Py type
Au
0911-83.80A
0911-79.65
0911-83.40
0911-83.40
161-437.15
161-437.15
180W3-349.2
186-594.6
177-377
161-449.8
161-449.8
238-177.525
161-449.8
161-449.8
161-437.15
171-544.8
171-531.5
180W3-338.8
186-273.3
0911-80.90
0911-80.90
0911-83.80
0911-76.65
0911-85.85
Reef
Reef
Reef
Reef
Hydrothermal
Hydrothermal
Hydrothermal
Hydrothermal
Hydrothermal
Laminated quartz vein
Diagenetic
Diagenetic
Diagenetic
Diagenetic
Diagenetic
Arsenopyrite
Arsenopyrite
Arsenopyrite
Arsenopyrite
Arsenopyrite
4.51
4.04
4.71
5.32
0.57
0.42
0.41
0.58
0.71
8.71
6.54
0.80
2.29
2.67
0.91
0.33
0.87
0.52
0.38
1.84
2.19
1.72
3.18
1.79
13.64
5.12
9.95
0.55
0.20
641.05
1020.29
2457.04
109.44
5.75
73.01
10105.95
14.10
334.63
18658.45
18351.05
33835.78
9571.16
1406.92
444.70
0.40
21.94
5447.67
1408.31
FDD0911 = 80.90
Free Au
940000.00
Sample no.
Py type
0911-80.90
0911-83.80
0911-83.80
0911-80.90
161-437.15
161-437.15
180W3-349.2
186-594.6
177-377
161-449.8
161-449.8
238-177.525
161-449.8
161-449.8
161-437.15
171-544.8
171-531.5
180W3-338.8
186-273.3
0911-80.90
0911-80.90
0911-83.80
0911-76.65
0911-85.85
Reef
Reef
Reef
Reef
Hydrothermal
Hydrothermal
Hydrothermal
Hydrothermal
Hydrothermal
Diagenetic
Diagenetic
Diagenetic
Diagenetic
Diagenetic
Arsenopyrite
Arsenopyrite
Arsenopyrite
Arsenopyrite
Arsenopyrite
FDD0911 = 80.90
Zn
Al
Cr
6.12
2.41
3.50
1.51
5.22
390.70
1393.01
994.50
997.31
604.56
6.64
2114.51
101.33
664.74
1242.75
1702.90
3951.56
1811.25
1908.50
14063.51
96.25
131.86
630.85
1154.12
<0.12
<0.17
0.24
<0.18
0.13
3.74
2.17
7.01
1.17
1.24
0.15
16.24
0.15
2.04
27.12
25.18
50.03
14.59
3.40
19.40
0.10
0.12
7.66
3.89
<5.36
<2.91
5.84
<1.73
5.00
19.35
12.29
23.68
5.93
5.00
6.00
53.66
5.00
14.67
80.21
62.35
61.01
20.63
5.53
22.05
1.70
0.64
9.93
7.00
6.96
9.53
0.88
As
Se
Zr
Ni
Cu
519.50
374.40
24.67
1.04
1784.20
350.90
175.88
72.94
246.23
275.26
18.93
249.33
66.90
53.46
423.78
249.41
372.10
1113.34
4165.70
398.96
54.40
48.71
247.60
10.23
3.18
2.35
20.19
2.17
22.36
59.33
67.63
250.62
16.20
4.62
17.60
67.81
9.97
3.48
78.20
76.00
134.15
113.82
3725.96
2.33
1.53
2.00
14.35
9.27
9.32
0.45
1.55
83.72
Mo
Ag
Sn
Sb
Te
0.00
0.00
0.15
0.00
0.10
3.14
4.19
6.57
84.76
13.65
0.19
77.00
0.19
61.21
73.70
12.40
10.11
108.11
1.36
116.84
0.62
1.04
77.14
24.44
0.17
<0.02
0.66
<0.02
0.10
0.20
0.10
0.64
0.97
0.10
0.20
0.36
0.20
0.53
52.98
5.85
0.20
3.60
0.12
1.45
1.34
1.89
9.98
6.94
<0.03
1.17
1.08
1.11
0.16
2.40
1.31
4.32
1.38
0.04
0.05
1.11
0.05
0.04
0.80
6.48
1.91
5.28
7.78
0.14
0.06
0.05
2.18
0.95
0.67
<0.09
<0.14
<0.15
0.16
0.16
0.21
0.21
0.48
0.14
0.18
0.89
0.18
0.14
1.70
1.22
5.84
0.98
0.66
1.96
0.72
1.38
2.22
1.02
1.48
0.37
93.63
2.44
36.02
84.04
249.70
188.26
85.37
5.23
1.65
314.84
2.57
4.97
327.52
291.01
140.42
81.83
291.17
182.09
113.77
90.43
218.04
192.12
<0.47
0.93
<0.39
1.98
0.17
0.96
0.21
0.53
3.46
0.19
1.33
23.06
0.27
0.19
4.14
1.94
8.02
4.83
4.64
3.50
6.39
2.82
5.08
5.63
54023.45
2.96
1.25
3.44
Bi
Th
0.00
0.00
0.04
0.00
0.01
2.14
0.82
0.20
0.39
0.16
0.02
0.02
0.00
2.62
0.00
0.01
0.61
0.21
0.15
0.93
0.22
0.01
15601.55
5507.21
256.00
7069.28
5489.29
762.56
106.75
355.96
4355.98
1400.78
x
x
x
x
x
Free Au
157.93
10.82
25.78
0.74
Sample no.
Py type
Ba
La
Pt
Tl
0911-80.90
0911-83.80
0911-83.80
0911-80.90
161-437.15
161-437.15
180W3-349.2
186-594.6
177-377
161-449.8
161-449.8
Reef
Reef
Reef
Reef
Hydrothermal
Hydrothermal
Hydrothermal
Hydrothermal
Hydrothermal
0.06
0.00
0.00
0.00
0.01
0.02
0.41
0.11
0.15
0.01
0.02
0.05
0.00
0.90
0.06
0.03
0.60
3.67
2.13
0.82
4.56
0.04
<0.04
<0.01
0.01
<0.01
0.04
0.03
0.04
0.01
0.17
0.04
0.04
<0.02
0.05
0.96
<0.01
0.03
0.12
0.12
0.47
0.21
0.04
0.05
10
Co
0.82
<0.01
3.27
0.09
23.73
188.08
46.50
3.77
13.79
24.79
0.40
13.76
15.21
7.52
873.61
725.96
461.81
1156.83
3252.89
25.91
5.56
10.35
3.03
2.24
8.75
36.78
<1.96
14.35
27.27
28.77
13.93
108.03
68.67
4.15
22.07
44.94
30.45
22.99
61.72
92.56
19.06
81.28
7.87
115.28
69.39
64.51
112.86
85.97
0361-0128/98/000/000-00 $6.00
Mn
<3.51
<0.96
<0.82
<0.82
0.88
1.28
9.14
17.74
2.17
1.24
1.34
37.09
1.34
1.24
70.65
78.88
73.66
33.82
2807.90
0.76
0.76
0.00
2.54
0.08
11.65
0.83
10.65
<0.74
2.00
3.00
4.10
7.41
2.29
2.00
3.00
11.09
3.00
2.00
49.20
42.59
34.51
2946.12
41.08
0.53
0.33
0.18
1.83
0.72
0.37
<0.04
1.26
3.64
0.10
6.28
5.75
23.89
0.40
0.12
0.39
4759.63
6690.81
6983.69
7450.63
1219.41
846.72
1525.28
82.75
Ti
Pb
8.55
313.86
108.61
25.97
199.39
1944.10
1042.16
1637.49
176.10
5.75
2.00
2.98
12.71
11.63
2.86
30.15
64.75
2.18
18.57
23.81
0.99
0.63
11

TABLE 2. (Cont.)
Sample no.
Py type
238-177.525
161-449.8
161-449.8
161-437.15
171-544.8
171-531.5
180W3-338.8
186-273.3
0911-80.90
0911-80.90
0911-83.80
0911-76.65
0911-85.85

Diagenetic
Diagenetic
Diagenetic
Diagenetic
Diagenetic
Arsenopyrite
Arsenopyrite
Arsenopyrite
Arsenopyrite
Arsenopyrite
FDD0911 = 80.90
Free Au
Ba
101.31
0.39
2.99
104.82
134.71
321.19
118.60
11.07
4.86
0.15
0.53
58.50
15.79
x
La
0.20
0.07
0.35
1.60
0.44
0.31
0.14
4.73
0.34
0.01
0.02
0.12
0.45
x
Pt
Tl
3.56
0.37
3.21
2.61
3.74
3.64
2.15
1.11
43.99
0.28
0.51
1.72
2.84
0.03
0.04
0.04
0.03
0.08
0.04
0.04
0.01
0.01
0.01
0.00
0.02
0.00
1.64
0.05
0.04
1.79
1.19
0.71
0.25
0.07
0.04
0.01
0.00
1.25
0.64
0.38
0.38
Pb
Bi
Th
916.46
4.70
14.55
585.82
884.83
860.64
1628.08
1535.52
24.65
5.46
15.74
615.50
76.41
253.32
2.49
3.66
188.78
23.84
227.43
53.46
69.92
28.33
8.56
21.92
280.24
88.28
0.23
0.21
1.00
39.55
1.06
3.02
2.63
1.27
2.96
0.01
0.02
0.49
3.67
0.96
5.79
Trace element concentrations in ppm
FIG. 8. Trace element LA-ICPMS map of diagenetic pyrite NBD238-164.6. This aggregate has a rounded nodular morphology common to diagenetic pyrites. It exhibits some zoning, with the pyrite core displaying elevated Ag, Au, Co, Mo, and
Cu. The next internal zone is characterized by elevated Se, Te, Bi, and patchy Pb. Au is present throughout the pyrite nodule but is more elevated in the core. These elements are all part of a suite commonly enriched in diagenetic pyrites at
Bendigo. Arsenic is enriched as a small inclusion of arsenopyrite in the core which has smeared out during laser ablation. Ni,
Co, and As form an outer most rim.
0361-0128/98/000/000-00 $6.00
11
U
0.24
0.01
1.60
9.06
1.24
1.08
3.03
0.16
3.05
0.01
0.02
1.61
3.74
x
12
THOMAS ET AL.
FIG. 9. Trace element LA-ICPMS map of diagenetic pyrite in the center of a quartz nodule in an organic-rich shale
(NBD177-377C). The pyrite is enriched in Ag, Ni, Bi, Pb with lesser Cu, As, Au, and Se. The Pb, V, and Ti maps show the
outline of the quartz nodule that surrounds the pyrite.
microinclusions; the suite V, Ti, Al, Cr, Zr, Sn, Ba, W, Th, and
U is present in pyrite within nonsulfide microinclusions (Fig.
14).
prehensive study here the list of elements enriched in diagenetic pyrite has been extended to include: Mn, Zn, Mo, Cu,
V, Ba, Ag, Cd, Tl, Co, Ni, Bi, and Pb (Fig. 15).
Gold content in diagenetic pyrite in the shales varies from
0.02 to 1.73 ppm with a mean of 0.61 ppm. Arsenic content
varies from 20 to 6,500 ppm with a mean of 1,300 ppm. In a
given LA-ICPMS spot analysis the As and Au counts are relatively uniform, with no spikes, suggesting that the Au and As
are present in solid solution, or as invisible nanoparticles in
the pyrite (Fig. 14). However, the contents of As and Au do
not exhibit any obvious correlation (Fig. 16A). The only trace
Composition of nodular diagenetic pyrite in sediments

The fine aggregates of nodular diagenetic pyrite in the
black shale facies are commonly enriched in a full range of
chalcophile elements (Figs. 89). A previous preliminary
study, reported in Large et al. (2009), found that diagenetic
pyrite at Bendigo was enriched in Ni, Cu, Mo, Ag, Bi, and Pb
compared to later hydrothermal pyrites. In the more com0361-0128/98/000/000-00 $6.00
12
13
FIG. 10. Trace element LA-ICPMS map of euhedral hydrothermal pyrite from a siltstone, sample NBD171-544.8. Cyclic
zoning present in most elements indicates a protracted growth history associated with changes is hydrothermal fluid composition. Round spots defining a v-shape enrichment pattern in Ni, Cu, and Zn are laser burn holes and should be disregarded.
element which shows a clear positive correlation with gold in

diagenetic pyrite is Bi (Fig. 16B). Trace element mapping
shows that some nodular diagenetic aggregates have a core
0361-0128/98/000/000-00 $6.00
enriched in Au, Ag, Mo, Cu, Se, and sometimes Bi, Te, and
Pb, compared to the outer bulk of the pyrite aggregate (e.g.,
Fig. 8).
13
14
THOMAS ET AL.
FIG. 11. Trace element LA-ICPMS map of pyrite in sample NBD180W3-345.8. The euhedral outline and cyclic growth
zoning indicate a hydrothermal origin for this pyrite. The pattern of the growth zoning and trace element distribution are
complicated by the fact that the crystal overgrows a siltstone-shale boundary. The boundary is aligned E-W and occurs approximately in the center of the pyrite, with the upper uniformly zoned shale portion defined by elevated Co, Ni, V, and Bi,
and the lower sandstone portion by elevated Pb. Gold is highest in the core of the pyrite, with later growth cycles also elevated in Au, As, Pb, Bi, and Cu.
0361-0128/98/000/000-00 $6.00
14
FIG. 12. Trace element LA-ICPMS map of pyrite crystal NBD171-521.7. This pyrite is from a laminated quartz vein distal to a productive gold reef, as shown in Figure 2, drill section. Pyrite in this laminated quartz vein overgrows the internal
vein selvages and shows an inherited fabric, revealed by acid etching. The mapping highlights both growth zoning in the
pyrite and the internal vein selvage structure. Gold is elevated on some crosscutting selvage bands (also Pb, Bi, V, Ag, Co,
and Ni) and also as an outermost narrow rim (with As).
0361-0128/98/000/000-00 $6.00
15
15
16
THOMAS ET AL.
FIG. 13. Trace element LA-ICPMS map of pyrite in sample FDD0911-79.65 from the gold-rich Gill reef. The euhedral
pyrite is zoned from an Ni-rich core to an Au-Asrich outer zone. Spotty elevated Ag, Pb, Bi, Se, Te on the lower right-hand
side of the pyrite is due to inclusions of galena carrying Pb, Bi, Se, and Te.
Composition of euhedral hydrothermal pyrite in sediments
elements (e.g., As, Ag, Co, Pb, Bi, Te, and Au; Figs. 10, 11),
indicating fluctuating composition of the hydrothermal fluid.
Au content varies from 0.01 to 21.6 ppm with a mean of 1.03
ppm, whereas As varies from 1 to 12,900 ppm with a mean of
1,740 ppm As. Spot analyses conducted on both the rims and
the cores of euhedral pyrites (Table 1) show that some rims
are enriched in both Au and As compared to the cores (Fig.
17). The pyrite rims average 1.24 ppm Au and 1,850 ppm As,
The euhedral pyrites, which occur in the sedimentary rocks

surrounding both the gold reefs and the bedding parallel laminated quartz veins, are enriched in Au and As but depleted
in all other elements compared to the nodular diagenetic
pyrite (Fig. 15). The LA-ICPMS mapping shows that most of
the hydrothermal pyrites exhibit cyclic zoning of certain trace
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counts
seconds
FIG. 14. LA-ICPMS counts for a laser line burn across a pyrite aggregate (AP02A58), showing the various types of response possible for major and minor elements in the pyrite and matrix. Fe and S exhibit a relatively flat response typical of
major elements in homogeneous pyrite. Au and As show elevated counts on the margins of the pyrite and decrease toward
the center. They clearly define an Au-Asrich rim on the pyrite. The relatively smooth pattern of the counts for Au and As
(with no spikes), and their parallel trends, suggest that these elements are zoned, either in solid solution in the pyrite or as
nanoparticles. Zircon shows a very spiky pattern indicating presence of many microinclusions of a Zr-rich mineral such as
monazite. Lead is elevated and spiky, suggesting abundant microinclusions of galena in the pyrite, with a larger inclusion evident toward the end of traverse. Silver is three orders of magnitude less than Pb, but shows a very similar pattern, suggesting the Ag is present in the structure of the galena inclusions. Antimony is elevated in the center of the pyrite and lower on
the margins, indicating zonation in the reverse order to As. The relatively smooth profile suggests that Sb is in the structure,
or as nanoparticles in the pyrite. For most of the traverse Bi parallels Sb, but toward the end it shows a major spike similar
to Pb and Ag. This suggests some Bi is in the structure of pyrite (same as Sb, As, Au), but some is present in the galena inclusions (same as Pb and Ag).
compared to an average 0.65 ppm Au and 1,550 ppm As for

the cores. Conversely the average cores are significantly enriched in Ag, Zn, Mo, and Pb relative to the average rims. The
euhedral pyrite cores have a similar mean As/Au ratio, Au/Ag
ratio, and Au, Ag, Se, and Pb content to the nodular diagenetic pyrites (Fig. 18A-B), indicating that within the shales,
the cores to the euhedral pyrites most probably formed by recrystallization of diagenetic pyrite. In contrast, the euhedral
overgrowth and rim pyrite has a markedly different chemistry,
suggesting that it was precipitated from a hydrothermal fluid.
The LA-ICPMS trace element map in Figure 11 is of a hydrothermal pyrite that has grown across a shale-sandstone
bedding plane. The zoned pyrite on the shale side of the contact is relatively enriched in Co, Ni, Bi, and V compared to
the other half of the pyrite on the sandstone side of the contact. Lead is the only trace element enriched on the sandstone side of the contact. These differences suggest that certain elements in hydrothermal pyrite, such as Co, Ni, V, Bi,
and Pb, are partly sourced from the immediate surrounding
sedimentary matrix.
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Composition of pyrite and arsenopyrite in

the gold quartz saddle reefs
Pyrite in the gold reefs is commonly the most enriched in
invisible gold and arsenic of all the pyrite types, with a similar
As/Au ratio to that shown by euhedral pyrite in both laminated quartz veins and the sedimentary rocks proximal to the
gold reefs (Fig. 17A). Although enriched in Au and As, the
reef pyrite is commonly low in most other trace elements, in
particular, Co, Cu, Zn, Mo, Sb, and Te (e.g., Fig. 13). It is
generally characterized by a high Au/Ag ratio (90% of the reef
pyrite has Au/Ag >1, Fig. 17B) and a high Au/Pb ratio (67%
of the reef pyrite has Au/Pb >0.01; Fig. 18A), with low Se and
Te contents (Fig. 18C).
Compared to the pyrite, arsenopyrite in the reefs is only
marginally more enriched in invisible gold (mean of 2.15 ppm
Au in arsenopyrite vs. mean of 1.66 ppm Au in pyrite, Table
1). Other elements elevated in the arsenopyrite are Co (mean
315 ppm), Ni (770 ppm), Mo (14 ppm), Sb (168 ppm), Te (5
ppm), W (6 ppm), and Pb (190 ppm). LA-ICPMS mapping
17
18
THOMAS ET AL.
FIG. 15. Spidergram illustrating the mean enrichment of trace elements in diagenetic pyrite compared with metamorphic
hydrothermal pyrite in the sediments at Bendigo. Note the most enriched elements are Mn, Cu, Mo, Zn, Ba, Tl, V, and U.
As and Au are the only two elements that are more enriched in the metamorphic hydrothermal pyrite.
shows no clear growth zoning in this arsenopyrite. However,

some trace elements (e.g., Bi, Ag, V, Cu) are concentrated in
inclusion-rich zones, which follow the lamination of the reef
(Fig. 19), whereas others are enriched in fine cracks that cut
across the lamination (e.g., Pb, Co, Ni).
tion (Fig. 12) quite unlike that of the other pyrite types. The
pyrite is euhedral but commonly fractured parallel to the lamination in the veins. Many of the trace elements (Pb, Bi, Ag,
Co, and Au) are aligned along the fractures and appear to
overprint the growth zoning in the pyrite (Fig. 12). The LAICPMS spot data shows that their composition overlaps the
fields for pyrite in the quartz saddle reefs and pyrite in the
sediments (Figs. 17, 18). Commonly the pyrite in laminated
quartz veins that are within 50 to 70 m of the saddle reefs has
distinct Au-Asrich rims (Fig. 20) with Au/Ag >1, Au/Pb
>0.01, and low Se and Te, similar to pyrite in the saddle reefs.
Composition of pyrite in
the laminated bedding-parallel quartz veins
Pyrite in the laminated quartz veins, which form legs off the
saddle reefs and extend down the fold limbs parallel to bedding, has a characteristic texture and trace element distribu-
2
y = 0.58149 + 2.2153e-5x R 2 = 0.0087031
y = 0.3021 + 0.0037552x R2 = 0.5241
1.5
Au ppm
Au ppm
1.5
0.5
0.5
0
0
1000
2000
3000
4000
5000
6000
7000
50
100
150
200
Bi ppm
As ppm
FIG. 16. LA-ICPMS spot analyses for diagenetic pyrite. A. Au-As shows that no clear relationship is present in the diagenetic pyrite data. B. Au-Bi shows a rough linear relationship, with R2 = 0.5241.
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250
300
19

Diagenetic sedimentary pyrite
Metamorphic hydrothermal core pyrite
Metamorphic hydrothermal rim pyrite
Laminated quartz vein core pyrite
Laminated quartz vein rim pyrite
Gold reef pyrite
100
1000
A
100
10
Au ppm
Au ppm
g=
/A
u
A
10
0.1
0.1
0.01
0.01
0.001
1
10
100
1000
104
0.001
0.001
105
As ppm
0.01
0.1
10
100
Ag ppm
FIG. 17. LA-ICPMS spot analyses on pyrite. A. Au-As: Diagenetic pyrite field (black) overlaps with the broader metamorphic pyrite core field (blue). The pyrite in saddle reefs (red) forms a distinct field with good As-Au correlation. The metamorphic hydrothermal rim pyrite proximal to gold reefs also plots in this field. B. Au-Ag: Diagenetic pyrite (black) forms a
relatively tight field, with 86 percent of data having Au/Ag <1. Reef pyrite (red) shows a broader field, with 90 percent of
data having Au/Ag >1. The metamorphic pyrite (blue) forms a diffuse field that overlaps the diagenetic and reef pyrite.
Laser traverses at right angles to the laminations in the

veins (Fig. 21) show that the narrow 0.1- to 2-mm black bands
that define the laminations are composed of very fine grained
chlorite, sericite, and graphite (Fig. 4D). They are enriched in
Au, Zn, Pb, Mn, Mo, As, Ni, Ag, and Bi, the same suite of elements enriched in diagenetic pyrite in the sediments. In Figure 21 it is evident that Au is enriched by a factor of 10 to 100
times in the black chloritic bands compared to the white
quartz bands. Although these laminated quartz veins rarely
contain ore-grade gold, there is a strong gold signature in the
chloritic bands that likely represents the passage of gold-bearing fluids along the veins.
pyrrhotite compared to diagenetic pyrite are Ti, V, Co, Ni, Se,

Mo, Ag, Sn, and W. (Fig. 23).
Discussion of Pyrite Composition and Ore Genesis
This study has revealed a number of features concerning
the pyrite developed in the quartz reefs, veins, and sedimentary rocks at Bendigo that need to be taken into account in
formulating a genetic model for the deposit:
1. The black shales that are interleaved with turbidite
sandstone beds at Bendigo contain syngenetic invisible gold,
which is present within bedding-parallel diagenetic arsenianpyrite aggregates or nodules (Fig. 24A). The Au and As content of this pyrite averages 0.61 and 1,325 ppm, respectively.
These diagenetic pyrites are also enriched in a suite of trace
elements, including Mn, Zn, Mo, Cu, V, Ag, Tl, Co, Se, Ni, Bi,
and Pb, which are commonly enriched in diagenetic goldbearing pyrite from some other gold provinces, for example,
Carlin, Nevada, and Lena province, Siberia (Large et al.,
2009).
2. Similar shale units stratigraphically below the known
gold-bearing quartz reefs contain both disseminated pyrite
and pyrrhotite. Textural evidence indicates that the pyrrhotite
formed during metamorphism by the replacement of diagenetic pyrite in specific organic-rich beds (Fig. 22). In contrast
to pyrite, the pyrrhotite is devoid of invisible gold and arsenic.
3. Both the sandstones and the shales contain euhedral
hydrothermal pyrite that is concentrated around the saddle
reefs and related bedding-parallel laminated quartz veins. The
cores of many of these euhedral pyrites have trace element
Composition of pyrite and pyrrhotite in

lower stratigraphy below currently mined gold reefs
In contrast to the upper stratigraphy at Bendigo which hosts
the currently mined gold reefs, the lower stratigraphy below
the Ethan Shale (Fig. 3) contains both disseminated pyrite and
pyrrhotite. This is despite the similarity in lithologic units to
the upper stratigraphic sandstone-shale turbidite package.
Diagenetic pyrite (n = 90) from the lower carbonaceous turbidites contains a similar range and mean of gold to diagenetic
pyrite in the upper stratigraphy but a lower level of arsenic
(Table 3). In contrast, metamorphic pyrrhotite developed in
the carbonaceous shales by the replacement of diagenetic
pyrite is depleted in several trace elements, in particular Au
(mean 0.04 ppm) and As (mean 4 ppm; Fig. 22). Other elements that are depleted relative to the diagenetic pyrite, include Cu, Zn, Sb, and Te (Fig. 23; Table 3). The trace elements that are not significantly depleted in metamorphic
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THOMAS ET AL.
106
100
Diagenetic sedimentary pyrite

Metamorphic-hydrothermal core pyrite
Metamorphic-hydrothermal rim pyrite
Laminated quartz vein core pyrite
Laminated quartz vein rim pyrite
Gold reef pyrite
105
Pb ppm
Au ppm
10
0.1
104
1000
100
10
1
0.01
0.1
0.001
0.01
0.1
10
100
1000
104
105
0.01
0.001
106
0.01
0.1
100
1000
Bi ppm
Pb ppm
105
1000
104
Ni ppm
Se ppm
10
100
1000
100
10
10
i=
/N
Co
0.1
1
0.01
0.1
10
0.01
0.01
100
0.1
10
100
1000
104
Co ppm
Te ppm
FIG. 18. LA-ICPMS spot analyses on pyrite. A. Au-Pb: Reef pyrite has a significantly higher Au/Pb ratio than diagenetic
pyrite. B. Pb-Bi: Diagenetic pyrite forms a tight cluster, compared to reef pyrite and LQ vein pyrite which is spread over a
wide Pb and Bi range but with a consistent Pb/Bi ratio. C. Se-Te: Diagenetic pyrite commonly displays the highest Se and
Te values, compared with reef pyrite which has the lowest values. Metamorphic and LQ vein pyrites are between the two extremes. D. Ni-Co: Reef and LQ vein pyrites consistently have Co/Ni ratio <1.
affinities with the diagenetic pyrite, whereas the outer zones

and particularly the pyrite rims have a closer textural and
chemical affinity to the pyrite in the laminated quartz veins
and gold-bearing saddle reefs (Fig. 24B).
4. In the sediments and laminated quartz veins close to
gold-bearing saddle reefs (within 5075 m), the pyrite has
Au-Asrich rims of similar composition to the pyrite within
the saddle reefs (Fig. 24C). These rims are similar, although
thicker and of lower gold tenor, to those seen in Carlin deposits, Nevada (Hofstra and Cline, 2000).
5. The black graphite-bearing bands in the laminated quartz
veins are enriched in Au, As, and the same suite of trace elements that characterize the diagenetic pyrite in the shales.
6. Although some of the hydrothermal pyrite in the sediments and veins shows weak internal zonation of gold and arsenic, by far the highest concentrations of Au and As occur in
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the rims of the hydrothermal pyrite, laminated quartz vein

pyrite and saddle reef pyrite (Fig. 20).
It is inferred that the Au-Asrich rims on pyrite within or
proximal to the gold reefs are a result of the same gold-precipitating event that formed the free nugget gold in the reefs
This could be possible with the pressure changes between the
reef and the sediments causing free gold and arsenopyrite deposition in the reefs, whereas the availability of iron, which
would be higher in the sedimentary rocks, leading to arsenian
pyrite with invisible gold formation in the wall rocks. Some
euhedral hydrothermal pyrites in sedimentary units distal to
productive gold reefs also show this phenomenon, however,
in this case Au-As rims are much thinner and less well developed (Fig. 20). Pyrite euhedra that formed earlier in the paragenetic sequence do not show rims; instead minor gold may
20
FIG. 19. Trace element LA-ICPMS map of an aggregate of arsenopyrite in quartz from the Gill reef, Bendigo (sample
number FDD0911-84.25). The inclusion-rich arsenopyrite, which outlines the structure of the laminated quartz reef, contains elevated Ag, Ni, Pb, Bi, V, Cu, and Ti. The complex patterns indicate that some elements are concentrated in inclusionrich zones (Ag, Bi, V, Mo, Cu), whereas other elements are also elevated in cracks (Co, Ni, Pb).
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THOMAS ET AL.
FIG. 20. Variation of Au-As rims on various types of pyrite at Bendigo. Rims are thicker proximal to gold-bearing quartz
reef structures, particularly in the 0- to 50-m range. Pyrites distal to reef in unmineralized sedimentary units display much
thinner Au-As rims. Sample NBD161-446.05 is from a laminated quartz vein adjacent to a reef, whereas sample NBD171521.7 is from a laminated quartz vein approximately 100 m from the same reef. Sample NBD177-377E is from a synclinal
axis in the poorly mineralized Western Shale (not shown in drill section). NBD171-544.8 is interpreted as a hydrothermal
pyrite, possibly with a diagenetic core from a sedimentary unit more than 100 m from a gold reef. NBD186-775.8 is interpreted as a hydrothermal pyrite found in the Jude Shale deep in the mine stratigraphy. It shows a diffuse zone of internal Au
enrichment on the edge of a zone of As enrichment.
be concentrated in the core of the pyrite, in internal zones

or evenly throughout the crystal (e.g., Figs. 10, 11). This
suggests that multiple gold-introducing events occurred
throughout the deposit history at Bendigo, starting with gold
introduced during sedimentation and diagenesis of the sedimentary rocks.
may provide clues regarding the genesis of the gold ores at

Bendigo. Although there is a significant variation in mean
Au and As content for the six pyrite groups, they all plot
close to a mean trend line of As/Au = 1,700. The mean Au
and As values for nodular diagenetic pyrite are very similar
to the mean for the euhedral hydrothermal core pyrite (Fig.
25A), supporting the interpretation that the euhedral cores
are recrystallized diagenetic pyrite. Also the mean Au and
As values for the saddle reef pyrite is similar to that for the
Au-Asrich rim pyrite in the laminated bedding-parallel
Trends in Au, As, and Ag content of pyrite and native gold

Plots of the mean values of Au versus As and Au versus Ag
for the main pyrite types (Fig. 25) show systematic trends that
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2 cm
quartz bands
chlorite-sericite
graphite bands
counts
seconds
FIG. 21. A. Drill core of typical bedding-parallel laminated quartz vein at the contact of black shale and gray siltstone in
the Railway Shale, drill hole NBD 215 at 379 m; the white bands are quartz and black bands are graphite-chlorite-sericitepyrite. B. LA-ICPMS traverse of 5 mm across a laminated quartz vein, showing the trace element counts for Si, V, Fe, Ni,
As, Mo, Au, and Pb along the traverse. Note the black graphite-chlorite-sericite bands are enriched in Au, Mo, As, Ni, and
Pb compared to the quartz bands.
TABLE 3. Comparison of the Trace Element Composition of Diagenetic Pyrite and Metamorphic Pyrrhotite from the Upper Stratigraphy
(Ethan Shale to Inner Shale) and Lower Stratigraphy (below Ethan Shale)
LA-ICPMS
Trace element
Au
Au
V
Co
Ni
Cu
Zn
As
Se
Mo
Ag
Sb
Te
Pb
Bi
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No. of analyses
Range
Mean
Mean
Mean
Mean
Mean
Mean
Mean
Mean
Mean
Mean
Mean
Mean
Mean
Mean
Diagenetic pyrite
upper stratigraphy
Diagenetic pyrite
lower stratigraphy
Pyrrhotite
lower stratigraphy
43
49
63
<0.02-1.73
0.61
35
765
1236
1127
499
1325
67
11
4.53
215
5
1157
81
<0.02-2.86
0.57
36
570
746
395
104
261
48
29
2.9
269
4
920
94
23
0.002-0.91
0.04
72
788
3175
18
9
4
34
18
2
8
0.7
173
17
% loss ((gain))
when pyrite is replaced
by pyrrhotite
93.0
((100))
((38.2))
((325.6))
95.4
91.3
98.5
29.2
37.9
31.0
97.0
82.5
81.2
81.9
24
THOMAS ET AL.
PYRITE
ppm
Au = 0.42
As = 590
Ag = 17
Te = 14.8
The trends of mean values on the Au versus Ag plot (Fig.

25B) give a very different picture, with a systematic increase in
Au/Ag ratio across the diagram from 0.13 in diagenetic pyrite
to 43 in saddle reef pyrite. The mean value for diagenetic pyrite
is virtually identical to the mean for hydrothermal core pyrite,
supporting our previous contention that the hydrothermal
cores are recrystallized diagenetic pyrite.The systematic increase in Au/Ag ratio from hydrothermal rim pyrite, to laminated quartz vein pyrite to saddle reef pyrite, supports a model
of preferential fractionation of gold, compared with silver, into
the hydrothermal fluid, during metal leaching and transport.
There are two factors involved which lead to a decoupling of
gold from silver. First, the LA-ICPMS data in Table 3 show
that conversion of pyrite to pyrrhotite in the deep shales releases on average 93 percent of the Au from the pyrite but only
31 percent of the Ag. The remaining silver is retained in the
pyrrhotite structure in the sedimentary rocks. Second, the released gold was most likely transported as a soluble bisulfide
complex due to the generation of an H2S-rich, but chloridepoor, neutral metamorphic and/or hydrothermal fluid, whereas
the silver would be more likely transported as the relatively
less soluble chloride complex (Phillips et al., 1984). Both
these process lead to an increase in the Au/Ag ratio in the hydrothermal fluid compared to the source sedimentary rocks.
Previous studies by Morrison et al. (1991) reported that the
free gold in the reefs at Bendigo has a gold fineness of about
950, which equates to an Au/Ag ratio of 19, comparable to the
Au/Ag ratio of the reef pyrite of around 41. Recent LA-ICPMS
analyses on free gold from the Gill Reef (reported in Table 2)
show a fineness variation of 942 to 967 (Au/Ag = 1630), similar to Morrisons early data. No free gold has been identified
in the sedimentary rocks adjacent to the saddle reefs, and the
question arises, why is the gold in the reefs principally free
gold, whereas the gold in the sedimentary wall rocks is invisible gold in arsenian pyrite? This probably relates to the availability of nonsulfide iron in the sedimentary rocks compared
PYRRHOTITE
ppm
Au = 0.05
As = <16
Ag = 1.9
Te = <0.6
500
FIG. 22. Photomicrograph of a pyrite-pyrrhotite aggregate from Ordovician carbonaceous shales west of Bendigo. The black spots mark LA-ICPMS
analytical sites. Note the significantly lower values of Au, As, Ag, and Te in
the pyrrhotite compared with the pyrite.
quartz veins, suggesting that they precipitated from the same

hydrothermal fluid. Overall the similar mean As/Au ratio of
around 1,700 for all pyrite types is compatible with the theory
that the hydrothermal fluid that precipitated Au-Asbearing
pyrite in the saddle reefs and laminated quartz veins derived
the Au and As from the diagenetic and recrystallized metamorphic pyrite in the sediments. This is predicated on the assumption that the Au and As are leached from the diagenetic
pyrite at similar rates and transported together in the same
fluid, probably as bisulfide complexes. The mean trend line
on the Au-As plot (Fig. 25A) allows for minor fractionation of
gold into the reef pyrite, as the As/Au ratio decreases systematically from 2,120 for diagenetic and hydrothermal core
pyrite to 1,150 for saddle reef and laminated quartz vein
pyrite.
Ti
Ni
Element in pyrrhotite
Element in pyrite
Fe Co
Sn
Mo
Se Ag
Cr
La
Tl
Ba
Mn
Pb
Te
Bi Th U
Au
Sb
Zn
Cu
As
FIG. 23. Ratio of mean trace element composition of pyrrhotite to mean trace element composition of pyrite based on
multiple LA-ICPMS analyses of diagenetic pyrite and metamorphic pyrrhotite from shales in the lower stratigraphy at
Bendigo. In order, the most depleted elements in pyrrhotite, compared with pyrite, are As, Cu, Zn, Sb, Au, Mn, and Te.
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A.
B.
Rounded, porous
diagenetic pyrite
Cyclic zoned hydrothermal py

(weak Ni, Co, As, Bi, Pb, Cu)
Au, As, Mo, Ag,

Cu, Se core
C.
low trace
element
inner zones
Au-As-rich rim
Recrystallised
diagenetic py
(Ag, Zn, Se, Mo,
Pb core)
Ni, Zn, Pb, Te,

Ag, Cu, Co, Mn
FIG. 24. Schematic of textural and chemical evolution of pyrite in shales adjacent to laminated quartz veins and gold-bearing saddle reefs at Bendigo.
to the quartz saddle reefs. Minor gold in the wall rocks is most
likely deposited within arsenian pyrite by the process of sulfidation (e.g., Kesler et al., 2003). This process is controlled by
the availability of excess Fe, most likely present within iron
carbonate, chlorite, or phengitic muscovite in the sedimentary rocks that reacts with H2S in the fluid to form the goldbearing arsenian pyrite rims. By contrast, in the dilatant
quartz-rich reefs there is no excess Fe, except possibly where
wall-rock fragments and slivers are present along the margins
of the reef. The shortage of available Fe in the quartz reefs
means that sulfidation to form arsenian pyrite is not the main
pathway for gold precipitation, but rather free gold and arsenopyrite are the ultimate precipitation products.
The first, synsedimentary to diagenetic gold event, is accompanied by a characteristic suite of trace elements (e.g.,
Ni, Zn, Ag, Mn, Mo, Cu, V, U) that are known to be elevated
in organic-rich anoxic to euxinic sedimentary environments
(Huyck, 1989; Quinby-Hunt and Wilde, 1994; Algeo and
Maynard, 2004; Rimmer, 2004; Tribovillard et al., 2006). The
observation from the laser ICPMS mapping, that some diagenetic pyrite nodules (e.g., Fig. 8) have the highest values of
Au, Mo, Ag, and Cu in the core, supports the concept that
the nodules nucleate on organic-rich patches in the shale
matrix.
The later, syndeformation gold event shows a strong AuAs association, with no other consistently elevated trace
element in the pyrite, although Zn, Pb, and Cu occur in
other sulfide minerals in the reefs (sphalerite, galena, and
chalcopyrite). It is not possible, based on the data presented here, to decide whether the metamorphic hydrothermal gold-arsenic event introduced new gold and arsenic to the Bendigo vein system from an external source or
simply that remobilized and reconcentrated gold and arsenic leached from the preenriched sediments of the first
event. However, the similar As/Au ratio for pyrite associated with the two events supports (but does not prove) the
latter hypothesis.
Number of gold fluid events

The presence of invisible gold in both the diagenetic pyrite
in the black shales, and in the rims of the hydrothermal
pyrite, which have markedly different trace element associations, suggests at least two gold events at Bendigo. Weak
internal cyclic zonation of Au, As, Ag, Pb, and Bi in some hydrothermal pyrite (e.g., Fig. 11) suggests that the early synmetamorphic hydrothermal fluids carried minor gold-arsenic
in pulses, but at a much lower level than the late hydrothermal fluids that formed the Au-Asrich pyrite rims.
100
10
10
mean laminated
quartz vein pyrite
/A
As
mean metamorphic
hydrothermal pyrite
u=
0
17
mean rim
mean core
rim
mean gold
reef pyrite
mean diagenetic
pyrite
104
105
u/A
g=
1
mean diagenetic
pyrite
0.1
0.1
As ppm
mean metamorphic
core pyrite
mean metamorphic
rim pyrite
A
1000
mean laminated
quartz vein pyrite
core
mean rim
mean core
0.1
100
mean gold
reef pyrite
Au ppm
Au ppm
Ag ppm
FIG. 25. A. Au-As plot of mean LA-ICPMS spot analyses for the six pyrite groupsshows that the mean Au and As values in the diagenetic pyrite and cores to the metamorphic pyrites are very similar. Also shows the contents for reef pyrite and
pyrite rims to LQ vein pyrite are very similar. B. Au-Ag plot of mean LA-ICPMS spot analyses for the six pyrite groups. The
data show a consistent trend from very low Au/Ag ratio in diagenetic pyrite to very high Au/Ag ratio in reef pyrite.
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THOMAS ET AL.
Significance of organic-rich black shales at Bendigo

Gold-bearing saddle reefs and related bedding-parallel
laminated quartz veins are generally confined to the shale
units in the sandstone-shale turbidite package at Bendigo
(Thomas, 1953; Willman, 2007; Boucher et al., 2008). The
Railway Shale and Big Blue Shale host most of the productive
reefs in the current mining operations (Figs. 23). These
shale units are dominantly comprised of gray siltstone and
black shale but also contain thin beds of sandstone. The reefs
and laminated quartz veins are commonly developed either
within a black shale bed or at a shale-sandstone or shale-siltstone contact within or at the margins of the shale package.
Organic-rich, pyritic black shales are most common along at
least one margin of the reefs and laminated quartz veins. This
relationship is considered to reflect flexural slip during early
folding having initiated along the weak bedding-parallel black
shale-sandstone contacts or within weak and thin organic-rich
shale beds. Bedding-parallel fluid-flow and laminated quartz
veining was initially confined to these zones of flexural slip in
the shales (e.g., Cox et al., 1991; Ramsay et al., 1998). Many
previous workers (e.g., Cox et al., 1991; Phillips et al., 2003)
considered that the black shales have also acted as chemical
traps for the gold. This model involves reaction between the
hydrothermal fluid and organic matter in the shales to produce a secondary CH4-bearing fluid, which then mixes with
the gold-bearing hydrothermal fluid to precipitate native gold
by reduction of the soluble gold bisulfide complex (Cox et al.,
1991).
Rather than the black shales acting as a chemical trap, we
suggest that the black shales may have acted as a source for
gold, arsenic, and other trace metals (Zn, Pb, Cu, Sb, Bi, Te)
in the reefs. There are several lines of evidence to support
this proposal: (1) the organic-rich black shales are the principal host for the diagenetic pyrite which is enriched in gold, arsenic, and a range of other trace elements; (2) no other potential source rocks in the district (e.g., mafic volcanics,
granites) contain anomalous levels of both gold and arsenic;
(3) the bedding-parallel laminated quartz veins are preferentially developed either within or at the contacts with thin beds
of organic-rich black shale and are thus proximal to the potential Au-As source rocks; (4) metamorphic hydrothermal
pyrite in the bedding-parallel laminated quartz veins and the
adjacent shales and sandstones have Au-As rims with an
As/Au ratio similar to that of the diagenetic pyrite in the
shales; and (5) the laminated quartz veins are folded and link
to the saddle reefs which contain native gold and pyrite with
similar Au-As rims to those in the veins and shales.
arsenic and sulfur and generation of an orogenic gold ore

fluid. At Bendigo, however, pyrrhotite is developed in the carbonaceous shales below the gold reefs, at much lower temperatures, associated with lower greenschist facies metamorphism around 250 to 300C (Wilson et al., 2009).
In a detailed study of the petrology of sulfide-rich graphitic
shales and schists from south-central Maine, Ferry (1981)
concluded that the metamorphic conversion of sedimentary
pyrite to pyrrhotite does not form a clearcut isograd, as suggested by Carpenter (1974), but is rather smeared out
across several metamorphic grades from the chlorite to the
sillimanite zone. Ferry (1981) found that on average about 40
percent of pyrite was converted to pyrrhotite in the chlorite
zone, about 75 percent in the biotite zone, and over 90 percent in the sillimanite zone. He thus concluded that increasing temperature is not the sole mechanism that drives the
pyrrhotite-pyrite transition, but that reduction of pyrite to
pyrrhotite by reaction with organic carbon or graphite was a
contributing process (eq. 2). These conclusions match our observations at Bendigoa combination of increasing metamorphic temperature in the lower parts of the stratigraphic
section only enables the pyrite to pyrrhotite conversion to
take place in the most organic-rich black shale units.
2FeS2 + 2H2O + C(graphite) 2FeS + 2H2S + CO2. (2)
Although graphite is used in this equation, at lower greenschist facies and below, organic matter or CH4 may be the active reductant. In typical pelitic rocks, with water generated
by dehydration of chlorite, this reaction is limited by the solubility of H2S, which is relatively low (Connolly and Cesare,
1993). An alternative way to drive this reaction is by introduction of meteoric or formation waters during deformation
(e.g., Nesbitt et al., 1989), although there is no direct evidence that meteoric or formation waters were involved in ore
genesis at Bendigo. Most of the transition to pyrrhotite is controlled by Fe availability, from Fe-rich silicates or carbonates.
Studies by Hoschek (1984) demonstrated that pyrite is only
reacted to pyrrhotite in carbonaceous rocks that were relatively Fe rich:
FeS2 + Fe2+ + 0.5C + H2O 2FeS + 2H+ + 0.5CO2. (3)
In the case of diagenetic arsenian pyrite with 0.0999 mol
percent As and 0.0001 mol percent Au, as observed in the
graphitic shales at Bendigo, equation (2) can be rewritten as
follows:
2Fe(S0.9As0.099Au0.001)2 + 0.492C + 2.192H2O <=>
2FeS + 1.592H2S +0.004Au(HS)2 +
0.396H3AsO3 + 0.004H+ + 0.492CO2.
Significance of disseminated pyrrhotite in

the lower stratigraphy
At upper greenschist and lower amphibolite facies the
breakdown of pyrite to pyrrhotite in sedimentary rocks and
greenstones is facilitated by release of metamorphic water associated with dehydration of chlorite at 450 to 600C.
FeS2 + H2O FeS + H2S + 0.5O2.
Equation 4 records the reduction of gold-bearing arsenian

pyrite by reaction with carbon, during prograde metamorphism, to form pyrrhotite and H2S, accompanied by the release of gold as the soluble bsulfide complex, and arsenic as
the soluble arsenate species (Heinrich and Eadington, 1986),
plus minor hydrogen ions and CO2, to the metamorphic fluid.
As shown by Cooke and Simmons (2000), a near-neutral
(very slightly acidic) fluid, buffered by equation (4), would
have the capacity to carry significant gold (10100 ppb). Such
(1)
Previous workers (e.g., Buryak, 1984; Pitcairn et al., 2006;

Procenko, 2008; Large et al., 2009; Tomkins, 2010) consider
this to be a key metamorphic reaction for the release of gold,
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(4)
26
which indicate that the reef pyrite has an isotopic signature

identical to the mean value for the sedimentary host rocks
(Thomas et al., in prep); (3) Br/Cl and I/Cl values of fluid inclusions in the quartz reefs reflect fluid interaction with, or
derivation from, sedimentary rocks enriched in organic matter, and suggest negligible input of fluids from juvenile mantle or deeply derived components (Fu et al., 2009); and (4)
initial Re/Os ratios of 187Os/188Os = 1.04 0.16 (2), measured on pyrite and arsenopyrite from an auriferous quartz
vein, suggest derivation from a crustal source with very little
mantle component (Arne et al., 2001).
fluids could move laterally, or upsection, away from the zones

of pyrite to pyrrhotite conversion, to deposit the gold and arsenic in favorable structural sites such as the saddle reefs at
Bendigo.
In this discussion, we have concentrated on gold and arsenic, however our LA-ICPMS results indicate that the sedimentary pyrite to pyrrhotite conversion is accompanied by
depletion in certain trace elements (Cu, Zn, Sb, Mn, and Te),
and retention or increase in other trace elements (Ag, Ti, Ni,
W, V, Co, Sn, and Mo) in the resultant pyrrhotite (Fig. 15). In
the case of Cu and Zn, petrological studies have shown that
these elements, on release from the diagenetic pyrite, form
discrete sulfide phases, chalcopyrite and sphalerite, which are
retained as inclusions and intergrowths in the pyrrhotite.
Other elements (Au, As, S, Sb, Mn, and Te) are likely to be
released into the metamorphic fluid and subsequently precipitated as free Au, arsenopyrite, Au tellurides, stibnite, and
Mn carbonate in and around the ore deposits.
A new genetic model for the gold-rich saddle reefs

Our model for development of the gold-bearing saddle
reefs (Figs. 26, 27) builds upon previous research (particularly that of Cox et al., 1991; Willman, 2007) and incorporates
deductions based on this pyrite study. The process starts during diagenesis with preconcentration of Au, As, and other
trace elements (Mn, Zn, Mo, Cu, V, Ag, Cd, Tl, Te, Co, Ni, Bi,
and Pb) in the organic-rich shale tops of turbidite cycles,
where they become locked in diagenetic arsenian pyrite (Fig.
26A). At the onset of compressional deformation and folding,
flexural slip either within the thin organic-rich and structurally weak black shales, or at black shale-sandstone contacts, creates high permeability zones which focus silica-saturated metamorphic hydrothermal fluids to produce
bedding-parallel laminated quartz veins within the shale
packages (Fig. 26B). The fluids dissolve diagenetic arsenian
pyrite from the shales to release Au and As into the hydrothermal fluid for passage along the permeable laminated
quartz veins. Continued flexural slip during folding promotes
dilation at the fold hinge zones. The hydrothermal fluids are
focused along the laminated quartz veins into the hinge zones
to form the saddle reefs (Fig. 22C; Cox et al., 1991). Gold and
arsenic are transferred from the black shales to the reefs via
the laminated quartz veins by this process. However, the thick
Au-As rims on pyrite within and proximal to the reefs indicate
that the main episode of hydrothermal gold and arsenic transfer occurred during the final stages of deformation. Based on
previous work (e.g., Cox et al., 1991; Schaubs and Wilson,
2002; Willman, 2007), this probably occurred during maximum shortening, with the development of throughgoing fault
arrays linking adjacent anticlines and finally accompanying
fault lockup.
At this stage a larger hydrothermal fluid reservoir would
have become available to source gold and arsenic from shales
deeper in the Ordovician basin (Fig. 26D). The release of
metals from these deeper sedimentary rocks was driven by
the pyrite to pyrrhotite metamorphic conversion, contributing Au, As, and S to the fluid reservoir that was accessed by
the throughgoing fault array (Fig. 27).
Source rocks for gold and arsenic

The ultimate source of gold and arsenic in the Victorian
goldfield is not well constrained. Previous workers have suggested that the Cambrian mafic volcanics that underlie the
turbidite package may have been originally enriched in gold
and thus were a viable source (Crawford and Keays, 1978;
Keays, 1987). Phillips et al. (2003) and Phillips and Powell
(2010) suggested that the gold-bearing metamorphic fluids
were generated at the greenschist-amphibolite boundary, at a
depth of 12 to 15 km, whereas Vos et al. (2007) considered
that fluids released from a subduction slab break-off at over
200 km is the most likely gold source. Li et al. (1998) suggested that pyrite framboids may have acted as a source of
gold when recrystallized during metamorphism but assert
that arsenic must have had a different source. No framboids
were observed as part of this study. None of these studies
have considered the source of the arsenic, which is far more
abundant than gold in the ores.
We maintain that the source of both gold and arsenic is the
black shales in the thick Ordovician turbidite package that
hosts and underlies the ore deposits in the Bendigo district.
There is over 10 km of structurally thickened turbiditic strata
(Willman, 2007) that could have supplied gold and arsenic to
the reefs during metamorphism and deformation. The fact
that the final Au-rich rims on the late-stage hydrothermal
pyrite are also strongly enriched in As, suggests that this final
gold pulse came from Au-Asbearing source rocks. The AuAs association in the reefs and sedimentary rocks is too intimate and coincident to accommodate a model involving different source rocks for each metal. Tompkins (2010)
demonstrated that mafic volcanics produce one to two orders
of magnitude less H2S than carbonaceous sediments during
metamorphism. These lines of evidence appear to preclude
the mafic volcanic rocks deep in the basin, because they are
not a suitable source rock for As and S, even if they were a
possible Au source. Supporting evidence for this sedimentary
source model is (1) oxygen isotope data for over 400 quartz
vein samples across the Victorian goldfield (Gray et al., 1991),
which indicate a homogeneous hydrothermal fluid in equilibrium with the local turbidite package; (2) sulfur isotope data
on 150 samples from pyrite in the sediments and quartz reefs
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27
Mass-balance calculation for gold and arsenic

Our LA-ICPMS analyses on diagenetic pyrites in shales
away from the ore zones at Bendigo (Table 2) average 0.61
ppm Au and 1,300 ppm As, giving an As/Au ratio of 2,131.
The background As content of the shale whole rocks, away
from ore zones and visible alteration, is 23.4 ppm (Large,
unpub. data). Using this value, and the mean measured As/Au
ratio in the diagenetic pyrite, it is possible to estimate the
27
28
THOMAS ET AL.
A. Syngenetic-diagenetic low-level Au-As in shales

shale
sandstone
METEORIC
RE-CHARGE ?
B. Initial deformation-flexure slip nucleates LQ

veins in shales, which act as main fluid pathways
Au
As
LQ veins
Au
As
py po
releases Au and
As to fluid
200 m
C. Continued shortening, Au and As leached from

shales and transported via LQ veins to saddle reefs
saddle
reef
Zone where pyrite is replaced by

pyrrhotite in carbonaceous shales
Gold saddle reefs
Pyrite stable in shales and sandstones
Laminated quartz veins
Faults and related

laminated quartz veins
Fluid-flow pathways
FIG. 27. Geologic two-dimensional model, showing the relative positions

of the interpreted Au-As source rocks, Au-bearing saddle reefs, and significant structures that have focused fluid flow from the source rocks to the reefs
(compiled using sections from Cox et al., 1991; and Willman et al., 2007).
original gold content of the shales prior to metamorphism and

hydrothermal leaching (23.4 1,000)/2,131 = 10.98 ppb Au.
These estimated whole-rock values of about 11 ppb Au and
23 ppm As for the premetamorphic Bendigo shales compare
favorably with recent data from Ketris and Yudovitch (2009),
who report mean values of 7 ppb Au and 30 ppm As for carbonaceous black shales generally. Assuming that the complete
Lower to Middle Ordovician turbiditic sedimentary package
at Bendigo is composed of 20 percent carbonaceous shales
containing 7 ppb Au, and 50 percent of the diagenetic pyrite
in the shales becomes recrystallized and converted to
pyrrhotite during metamorphism, releasing all its contained
gold and arsenic, then 1.9 t of gold (plus 6,270 t of As and
35,000 t of S) is released to the metamorphic fluid per cubic
kilometer of sedimentary rock during the pyrite to pyrrhotite
transition. This means about 370 km3 of turbidites are needed
to source the 700 t of gold produced from the Bendigo goldfield. Considering the area of the goldfield (7 20 km2), this
equates to sourcing the gold from a total of about 2.7-km
thickness of turbiditic sediments below the deposits. This
source volume appears feasible, based on an inferred stratigraphic thickness of about 3 km and a structural thickness of
over 10 km for the Lower to Middle Ordovician turbidite
package (Willman, 2007).
A local sedimentary Au-As source for Bendigo may also explain why the major gold deposits in the Victorian goldfields
are all contained in the Lower to Lower Middle Ordovician
(Lancefieldian to Castlemanian stages; Phillips et al., 2003).
This may relate to the original syngenetic gold and arsenic
content of this interval being greater than that in the younger
D. Final stages: through-going fault array links to

deeper metamorphic basin fluids for final Au-As pulse
40 m
deeper
basin
fluids
FIG. 26. Schematic evolution of mineralized reefs at Bendigo (modified

from Cox et al., 1991; Willman, 2007). A. Syngenetic accumulation of Au and
As in organic-rich shale. Gold becomes locked in diagenetic arsenian pyrite.
B. Initial deformation: Flexural slip on black shale contacts nucleate laminated quartz veins, which act as main fluid pathways. C. Continued folding:
Au and As are leached from shales and transported via laminated quartz veins
to saddle reefs. D. Final stages of deformation: Throughgoing faults link adjacent anticlines and tap deeper metamorphic basin fluids leading to final,
and major, Au-As pulse(s).
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28
and older strata. Productive gold deposits may be absent to

the east of the Bendigo zone in the Melbourne zone, if the
shales and cherts to the east are lacking in syngenetic gold, or
alternatively, as suggested by Wilson et al. (2009), the underlying Selwyn block shielded the overlying strata from pervasive metamorphism, deformation, and faulting.
gold-arsenic deposition. It is not possible, based on the data

presented here, to resolve whether the later hydrothermal
gold events introduced new gold to the Bendigo vein system
from a different genetic source, or simply remobilized and
reconcentrated gold leached from the preenriched sediments
of the first event. However, we believe that the coupled AuAs relationship observed throughout the pyrite paragenesis in
both the host rocks and the gold reefs at Bendigo is strong evidence for a sedimentary source.
Conclusions
This study further establishes the value of conducting an LAICPMS study into the trace element composition of sulfides
(especially pyrite) at the ore-deposit scale. Pyrite is formed
throughout the ore-deposit evolution and enables a near-total
documentation of fluid-flow events to be captured, from early
diagenesis through to peak- and postmetamorphic events.
Our work has demonstrated the effects of host-rock composition and texture on the enclosed pyrite. Shales are often
more favorable hosts for diagenetic pyrite due to their high
organic content and generally anoxic, reducing conditions; it
is inferred that diagenetic and/or early hydrothermal pyrites
scavenged trace elements from their immediate organic-rich
vicinity, due to shales low effective porosity and the early paragenetic timing of the pyrite. Sandstones and siltstones are
host to later hydrothermal pyritewith a more pervasive
fluid flow accommodated by their higher effective porosity.
The pyrite present in the sandstones generally exhibits pervasive growth zoning and as such can provide a better record of
later fluid-flow events through the sedimentary rocks. In organic-rich black shale beds deeper in the section pyrite is partially to completely replaced by metamorphic pyrrhotite
which becomes aligned in the metamorphic fabric.
Diagenetic pyrites present in shale horizons exhibit a consistent association of elevated Bi, Ni, Cu, Mo, Ag, V, and Pb,
with a lower Au/Ag ratio than demonstrated in hydrothermal
pyrites. Hydrothermal pyrites are commonly euhedral,
growth zoned, and exhibit a simpler trace element association, exemplified by a strong gold-arsenic relationship where
the concentration of gold retained in the structure of pyrite is
directly proportional to the arsenic concentration. They also
exhibit higher Au/Ag ratios, similar to the Au/Ag ratio (or
fineness) of the free gold in the saddle reefs. Pyrites adjacent
to productive saddle reefs have gold-arsenic rims analogous
to the fine (220 m) gold rims seen at Carlin, Nevada (Hofstra and Cline, 2000; Large et al., 2009). Disseminated
pyrrhotite, formed by the replacement of pyrite in the shales
below the gold reefs, is totally devoid of gold and arsenic
which have been lost to the metamorphic fluid.
The consistent complex trace element association present
in early pyrite leads to some interesting questions with regards to the origin of some of the elements responsible for
generating the ore deposit in question. Many workers have
postulated that the source of the gold for the Bendigo gold
deposits is the Cambrian mafic volcanics which underlie the
turbidite pile at a depth of greater than 3 km but neglect to
consider the source of the arsenic and sulfur. We propose
that the initial source of gold, arsenic, and sulfur is from the
shale host rocks, generated by the recrystallization and destruction of early diagenetic pyrite to pyrrhotite. The deeper
sedimentary strata reaccessed only after fold lockup and the
formation of throughgoing structures during the later stages
of the hydrothermal events, which correspond to the peak in
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29
Acknowledgments
Leonid Danyushevsky is thanked for his help and support
in leading the analytical developments at the CODES LAICPMS laboratory. The authors would like to thank Bendigo
Mining Ltd. for access to samples and information about the
deposit, particularly mine cross sections. This research was
funded by Bendigo Mining Ltd. and the Australian Research
Council through the ARC Centre of Excellence program.
Peter Schaubs and Robert Hough are thanked for their thorough and constructive reviews of the manuscript.
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Pyrite and Pyrrhotite Textures and Composition in Sediments, Laminated Quartz Veins

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Economic Geology

BULLETIN OF THE SOCIETY OF ECONOMIC GEOLOGISTS

of Mineralogy, Russian Academy of Science, Urals Branch, Miass

Mining Limited, 66 Ham St, Bendigo, Victoria, Australia 3555

Pyrites were acid etched prior to petrographic study, then

GOLD AT Bendigo is hosted in quartz veins and saddle reef

author: email, Helen.thomas@utas.edu.au

2011 by Economic Geology, Vol. 106, pp. 131

Submitted: March 9, 2010

often overgrows earlier generations of pyrite, with careful

PYRITE AND PYRRHOTITE AT BENDIGO MINE, AUSTRALIA

the Castlemanian is defined by the Lancefieldian Group of

1992; Gao and Kwak, 1995a, b; Arne et al., 1998; Bierlein et

Deformation and mineralization in the Bendigo zone

ppm), Zn (1001000 ppm), Cu (50150 ppm), Ni (50140

diagenetic spots were overgrown by a second stage of metamorphic carbonate.

PYRITE AND PYRRHOTITE AT BENDIGO MINE, AUSTRALIA

Methodology and Analytical Techniques

sample back onto the surface as an ablation plume was kept

PYRITE AND PYRRHOTITE AT BENDIGO MINE, AUSTRALIA

Diagenetic pyrite cores with euhedral hydrothermal overgrowths

Laminated quartz vein pyrites

preferentially hosted in black shale units, which provide the

Hydrothermal pyrite in the sedimentary rocks is euhedral

euhedral pyrites have an anhedral porous core composed of

FIG. 7. Photomicrographs of disseminated pyrrhotite in black shales. A.

PYRITE AND PYRRHOTITE AT BENDIGO MINE, AUSTRALIA

1995). In these zones the reef has a laminated texture similar

Trace Element Associations and Zoning

PYRITE AND PYRRHOTITE AT BENDIGO MINE, AUSTRALIA

Laminated quartz vein

Trace element concentrations in ppm

Composition of nodular diagenetic pyrite in sediments

PYRITE AND PYRRHOTITE AT BENDIGO MINE, AUSTRALIA

element which shows a clear positive correlation with gold in

PYRITE AND PYRRHOTITE AT BENDIGO MINE, AUSTRALIA

Composition of euhedral hydrothermal pyrite in sediments

The euhedral pyrites, which occur in the sedimentary rocks

PYRITE AND PYRRHOTITE AT BENDIGO MINE, AUSTRALIA

compared to an average 0.65 ppm Au and 1,550 ppm As for

Composition of pyrite and arsenopyrite in

shows no clear growth zoning in this arsenopyrite. However,

y = 0.3021 + 0.0037552x R2 = 0.5241

PYRITE AND PYRRHOTITE AT BENDIGO MINE, AUSTRALIA

Laser traverses at right angles to the laminations in the

pyrrhotite compared to diagenetic pyrite are Ti, V, Co, Ni, Se,

Composition of pyrite and pyrrhotite in

Diagenetic sedimentary pyrite

affinities with the diagenetic pyrite, whereas the outer zones

the rims of the hydrothermal pyrite, laminated quartz vein

PYRITE AND PYRRHOTITE AT BENDIGO MINE, AUSTRALIA

be concentrated in the core of the pyrite, in internal zones

may provide clues regarding the genesis of the gold ores at

Trends in Au, As, and Ag content of pyrite and native gold

PYRITE AND PYRRHOTITE AT BENDIGO MINE, AUSTRALIA

The trends of mean values on the Au versus Ag plot (Fig.

quartz veins, suggesting that they precipitated from the same

PYRITE AND PYRRHOTITE AT BENDIGO MINE, AUSTRALIA

Cyclic zoned hydrothermal py

Au, As, Mo, Ag,

Ni, Zn, Pb, Te,

Number of gold fluid events

Significance of organic-rich black shales at Bendigo