Pyrite and Pyrrhotite Textures and Composition in Sediments, Laminated Quartz Veins
Pyrite and Pyrrhotite Textures and Composition in Sediments, Laminated Quartz Veins
Pyrite and Pyrrhotite Textures and Composition in Sediments, Laminated Quartz Veins
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
3Bendigo
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deepest stratigraphic levels, below known productive gold reefs, diagenetic pyrite in the most carbonaceous shales has been replaced by pyrrhotite during metamorphism.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
0361-0128/11/3933/1-31
THOMAS ET AL.
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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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.
Royal Albert
Shale
Inner Shale
Rowe Shale
Western Shale
Big Blue Shale
*
*
*
Railway Shale
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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Diagenetic pyrites
Hydrothermal pyrites
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.
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
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
Laminated quartz vein
Laminated quartz vein
Laminated quartz vein
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
Laminated quartz vein
Laminated quartz vein
Laminated quartz vein
Laminated quartz vein
Laminated quartz vein
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
Laminated quartz vein
Laminated quartz vein
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
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
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
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.
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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
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.
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.
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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).
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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.
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,
16
17
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).
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.
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
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
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.
19
20
THOMAS ET AL.
106
100
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.
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.
22
23
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
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.
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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25
A.
B.
Rounded, porous
diagenetic pyrite
C.
low trace
element
inner zones
Au-As-rich rim
Recrystallised
diagenetic py
(Ag, Zn, Se, Mo,
Pb core)
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.
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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10
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THOMAS ET AL.
(1)
(4)
26
27
28
THOMAS ET AL.
METEORIC
RE-CHARGE ?
Au
As
LQ veins
Au
As
py po
releases Au and
As to fluid
200 m
Fluid-flow pathways
40 m
deeper
basin
fluids
28
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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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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