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Geochemistry and Metallogenic Model of Carlin-Type Gold

Deposits in Southwest Guizhou Province, China
Chapter · May 2012

DOI: 10.5772/31742
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7
Geochemistry and Metallogenic

Model of Carlin-Type Gold Deposits in
Southwest Guizhou Province, China
Yong Xia, Wenchao Su, Xingchun Zhang and Janzhong Liu
State Key Laboratory of Ore Deposit Geochemistry, Institute of Geochemistry
Chinese Academy of Sciences, Guiyang
China
1. Introduction
Carlin-type gold deposits, also known as sediment-hosted gold deposits are among the
largest hydrothermal gold deposits in the world, currently being sought and mined in the
United States and China (Tretbar et al., 2000; Hu et al., 2002). The region of southwestern
Guizhou (SW Guizhou), which is a region where the Carlin-type gold deposits were found
for the earliest time in China, is an important component of the Yunnan-Guizhou-Guangxi
“gold triangle” province. Carlin-type gold deposits in SW Guizhou, China, are hosted in late
Paleozoic and early Mesozoic sedimentary rocks along the southwest margin of the
Precambrian Yangtze craton. They can be classified as two types, i.e., the fault type and the
strata-bound type, on the basis of their occurrence, shape and structural controls (Zhang et
al., 2003; Xia, 2005). The former type includes the Lannigou, Yata, Banqi, Zhimudang (the
upper orebodies), etc. with gold ores mostly occurring in high-angle compresso-shear faults.
The ore-hosted strata are generally Middle and Lower Triassic in age, ore-bearing rocks are
dominated by muddy siltstones and silty mudstones. The strata-bound gold deposits
include the Shuiyindong, Taipingdong, Zhimudang (the lower orebodies), Getang, Nibao,
etc. Gold ores are hosted mainly in the interbeded rupture zone at the karst discontinity
surface of the Upper-Lower Permian and the Upper Permian strata. The deposits are mostly
concealed ones at depth, the orebodies occur as stratiform, stratoid and lenticular ones and
are developed along the strata, characterized by multi-layer distribution. Ore-hosted rocks
are mainly impure bioclastic limestones and carbonate rocks in organic-rich coal series
formations, with obvious anticline ore-controlling features. They have characteristics similar
to Carlin-type gold deposits in Nevada, including notable enrichment in As, Sb, Hg, and Tl
(Hu et al., 2002; Xia, 2005). Typical characteristics include impure carbonate or calcareous
and carbonaceous host rock that contains disseminated pyrite and arsenopyrite. Gold occurs
either as submicrometer-sized particles or invisibly as solid solution in As-rich rims of pyrite
and arsenopyrite. Late stibnite, realgar, and orpiment fill fractures on the periphery of gold
mineralization. Hydrothermal alteration caused decarbonation, silicification, argillization,
and sulfidation, similar to Carlin-type gold deposits in Nevada (Hofstra and Cline, 2000;
Emsbo et al., 2003; Kesler et al., 2003). Detailed studies in recent years have shed much light
on the geochemistry and metallogenic mechanisms of the Carlin-type gold deposits in the
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128 Geochemistry – Earth's System Processes
region, promoted metallogenic prognosis and exploration, thus making the Shuiyindong
gold deposit become a typical super-large Carlin-type gold deposit. On the other hand, a
great breakthrough has been made in metallogenic prognosis and exploration of Carlin-type
gold deposits on a regional scale.
2. Regional geologic setting

2.1 Stratigraphy in SW Guizhou
The Carlin-type gold mineralization area in southwestern SW Guizhou Province (Fig.1) lies
on the southwestern edge of the Yangtze Paraplatform which is composed of crystalline
rocks of Proterozoic age overlain mainly by shallow-marine platform deposits of Devonian
through Triassic age. After the Caledonian tectonism, from Devonian to Triassic, this area
subsided and formed a large sedimentary basin filled with thick sedimentary strata.
Outcrops of Devonian, Carboniferous, Permian and Triassic strata occur in the area with
sporadic outcrops of Jurassic and Cretaceous strata in this area.
The Carlin-type gold in SW Guizhou are located in sedimentary rocks of Permian and
Triassic age, and the environment of sedimentation changed from continental, to marine
platform to marine basin facies across the area from the northwest, to the central and to the
southeastern part.
The Permian strata are mainly limestones of the Lower Permian with EW-trending facies
distribution, and clastic sediments and thinly-bedded limestones of the Upper Permian with
NS-trending facies distribution. Late Permian strata change from the northwest to the
southeast across the line of Anshun-Anlong-Xingyi. On the northwest side of the line, there
are interbedded continental margin facies, where the Getang deposit is located on the
palaeokarst surface which separates Early and Late Permian sequences. On the southeast
side, there are mainly platform carbonates, and reef facies along the platform margin.
Further to the southeast, sedimentation took place in a deep-sea trough-like basin near
Ceheng-Zhenfeng-Ziyun-Wangmo and shingle fine-grained clastic sediments of the marine
basin were deposited.
Triassic strata were developed extensively in the area. The Late Permian framework of
sedimentation continued into the Early Triassic period. The Early Triassic platform facies,
mainly marl and claystone interbedded with bioclastic limestone, in which the Zimudang
deposit is located, is situated on the northwest side of the Anshun-Zhenfeng-Ceheng line.
However, a slope facies of platform margin, mainly calcirudite and micritic limestone,
occurs on the southeast side, and the marine basin facies, micritic limestone and shale,
occurs further to the southeast. The Banqi and Ceyang deposits are located in slope facies
which surrounded the Permian island reef.
The pattern of sedimentation of the Early Triassic continued through the Middle Triassic.
The Middle Triassic slump deposits of conglomerate/psephite which crop out in the belt
between the platform margin and the deep-sea trough-like basin further indicate that it was
an active fault-trough basin. The Lannigou and Yata deposits are located on the boundary
between that belt and deep-sea facies. There were Middle Triassic platform facies on the
northwest side of the platform margin along the line of Anshun-Zhenfeng-Ceheng, and
marine basin facies on the southeast side.
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Model of Carlin-Type Gold Deposits in Southwest Guizhou Province, China 129
Fig. 1. Simplified geologic map of southwestern Guizhou (modified after Zhang et al., 2003),
showing the locations of the major Carlin-type gold (e.g., Shuiyindong and Yata) and
antimony and mercury deposits.
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2.2 Igneous rocks in SW Guizhou

Outcrops of both intrusive and extrusive igneous rocks including basalts, diabase, vitric tuff
and meta-alkaline ultrabasic rocks occur in the area (Fig.2). Several sequences of basalts
from Carboniferous to Late Permian are exposed in in the northwest corner of the area.
Explosion-type basalts of Early Carboniferous and Early Permian only crop out locally in
shallow marine environment, whereas Late Permian Emeishan basalts of the continental
flood-type are widely exposed on the northwest corner of the area with the thickness of the
basalt sequence decreasing from west (500-1250m in Panxian/Puan) to east (<150m in
Anshun/Qinglong) (Bureau of Geology and Mineral Resources of Guizhou Province, 1987;
Yang et al., 1992; Li et al., 1989). From the results of petroleum exploration drilling, it is
known that a thick sequence of Late Permian Emeishan basalts, reaching one thousand
metres, lies buried several hundred metres beneath the western area of Xingyi and Luoping
(Huang, 1986). Late Permian diabases are generally exposed as sills and dykes in limited
areas (Mei, 1973, 1980). Thin seams of Late Permian acidic vitric tuffs are locally distributed
within Triassic dolomite and claystone. Small pipes and dykes of meta-alkaline ultrabasic
rocks are exposed in the belt of transitional sedimentary facies along the line of Zhenfeng-
Ziyun (Mei, 1973). It is believed that the Puding-Ceyang Fracture provided a pathway for
their intrusion (Yang et al., 1992).
Fig. 2. (a) Distributions of the major terranes in China (modified after Chung and Jahn,
1995); (b) geological map of the SW Guizhou area and the distribution of the sedimentary
rocks, Permian basalts, tectonic elements, ultramafic dykes and gold deposits.
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2.3 Regional structures in SW Guizhou

The SW Guizhou lies on the southwestern edge of the Yangtze Paraplatform. The adjacent
southeast area (mainly northwestern Guangxi) belongs to Youjiang geosyncline which is
believed to be the northwest part of the South China Fold System. However, with the
discovery of characteristic Yangtze paraplatform-type sedimentary associations, fossils and
Caledonian folds in covering strata, it is believed that the Youjiang geosyncline was
developed on the southwestern edge of the Yangtze Paraplatform by continental rifting
activation during the Variscan cycle (Lu, 1986).
Several deep fractures or fracture zones cut through the area (Fig.1, Fig.2). The movements
on these fractures provided an important control on geological development including
sedimentation and folding in this area from Late Palaeozoic to Triassic time (Li et al., 1989,
Yang et al., 1992, Hou and Yang, 1989). The NE-trending Mile-Shizhong Fracture cut
through the nortwestern part of the area and separates the outcrop of Upper Proterozoic
sediments and Permian continental flood basalts on its northwest side from the Triassic
sediments on its southeast side. The NW-SE-trending Shuicheng-Ziyun-Bama Fracture Zone
(Hezhang-Ziyun) cut through the northeast part of the area. The NEE-trending Nanpanjiang
Fracture (Kaiyuan-Pingtang) cut through the southern part of the area with the character of
different Triassic sedimentary facies on its two sides. The NS-trending Puding-Ceyang
Fracture is believed to be a concealed fracture with the characteristic outcrop of meta-
alkaline ultrabasic pipes and the characteristic sedimentary transition of Permian and
Triassic strata along the line (Yang et al., 1992). However, Wang et al. (1994) indicated that
the boundary between clastic rocks and carbonates along the line of Anshun-Zhenfeng-
Ceyang-Nidang was not a real sedimentary transition boundary but a SW Guizhou Thrust
formed by thrusting of the shallow-water carbonates onto the calstic sediments from
nothwest to southeast after the main gold mineralization, with possible maximum thrusting
distance of 80 km at peak of the thrust arc near Ceyang.
As a result of the reactivation of these fractures during the Yanshanian orogeny from
Middle Triassic to the end of the Cretaceous, a series of subsidiary fractures were formed. It
was with these that the gold, mercury, antimony and arsenic mineralization were
associated. According to the characteristic sedimentary associations, the structural
deformation of the sedimentary cover and the distribution of regional deep fracture zones in
this area, two structural units are identified by the Bureau of Geology and Mineral
Resources of Guizhou Province (1987). The Puan Rotational-Shear Deformation Area, which
is bordered by the Nanpanjiang Fracture to the south, the Puding-Ceyang Fracture to the
east and the Shuicheng-Ziyun Fracture to the northeast, mainly has rotational-shear folds
associated NW-, NE- and NNE-trending structures, carbonates and calcareous clastic
sediments with coal seams of carbonate platform facies in which the gold deposits of
Getang, Zimudang, Sanchahe, Xiongwu, the Lamuchang mercury-thallium deposit and the
Dachang antimony deposit are located. The Wangmo Deformation Area, which is bordered
by the Ziyun-Bama Fracture to the northeast and the Puding-Ceyang Fracture on the west,
mainly has NW-trending shear structures and EW- and NS-trending compressive structures,
turbidites of marginal slope facies and marine basin facies in which the gold deposits of
Banqi, Yata, Baidi, Lannigou, Daguan are located.
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3. Geology of the gold deposits

There are two kinds of Carlin-type gold deposits: stratabound and fault-controlled in the
southwestern Guizhou Province. The stratabound Carlin-type gold deposits such as
Shuiyindong, Taipingdong, Zimudang (lower orebodies), Getang, Nibao gold deposits,
etc. are controlled by anticlines and hosted in silty bioclastic limstones of Upper Permian
(e.g., Shuiyindong). The fault-controlled Carlin-type gold deposits such as Lannigou,
Yata, Banqi, Zimudang (upper orebodies) gold deposits, etc. are localized at the
compressive shear faults and hosted in siltstones and silty mudstones of Middle or Lower
Triassic (e.g., Yata).
3.1 Geology of the Shuiyindong (Stratabound Carlin-type gold deposit)

The Shuiyindong deposit is located about 20 km northwest of the town of Zhenfeng in
southwestern Guizhou (Fig. 3). It lies on the eastern limb of the Huijiabao anticline
(Fig. 3A), which also hosts a cluster of deposits on its western limb, including the
Zimudang deposit. Recent exploration and mining at Shuiyindong has proven gold
reserves of 55 metric tons (t) Au (1.8 Moz), with average gold grades from 7 to 18 g/t (Xia,
2005). All of the gold is refractory, occurring in arsenian pyrite and arsenopyrite (Xia,
2005; Su et al., 2008).
Sedimentary rocks in the district consist of bioclastic limestone, siltstone, and argillite of the
Middle and Upper Permian and Lower Triassic. The Middle Permian Maokou Formation, a
massive bioclastic limestone, is overlain by the Upper Permian Longtan, Changxing, and
Dalong and Lower Triassic Yelang Formations. The Longtan Formation is about 300 m thick
in the Shuiyindong district and has been divided into three stratigraphic units (Liu, 2001).
The lowest unit consists of calcareous siltstone, which grades into fine-grained sandstone at
the top. The second unit consists of silty argillite intercalated with bioclastic limestone and
coal seams. The third unit includes calcareous siltstone, sandstone, and muddy and
bioclastic limestone. Gold mineralization is preferentially disseminated in bioclastic
limestone and calcareous siltstone of the first and second units of the Longtan Formation at
depths of 100 to 300 m below the surface (Fig. 3B). These rocks were deformed into an east-
trending anticline with limbs that dip 10° to 20°. Strata-bound gold orebodies are located
mainly on the flanks of the anticline (Fig. 3B). The limbs of the anticline are cut by reverse
faults F101 and F105, respectively, which strike east-west and dip steeply to the north and
south, respectively (Fig. 3A). The reverse faults host small orpiment and realgar bodies with
low-grade gold mineralization and are cut by a series of near northsouth–trending normal
faults with steep dips (70°–80°). The normal faults contain mercury-thallium deposits, such
as Lanmuchang (Fig. 3A).
The three main orebodies at Shuiyindong (IIIa, IIIb, IIIc; Fig. 3B) contain approximately half
of the gold reserves. They are 100 to 400 m long, 50 to 350 m wide, 1.7 to 1.9 m thick, and
have an average gold grade of 16 g/t (Xia, 2005). A lower grade orebody (Ia) is hosted in
silicified, brecciated argillite and limestone at the unconformity between the Maokou
Limestone and the first unit of the Longtan Formation. This unconformity controlled the
distribution of other gold deposits regionally in the southwestern Guizhou, such as Getang
and Nibao (Fig. 1), suggesting that it may have been a feeder conduit for gold
mineralization.
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Note the stratiform nature of the numbered orebodies.

Fig. 3. Simplified geologic plan (A) and cross section (B) along the A-A' exploration line of
Shuiyindong (modified from Liu, 2001).
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Wall-rock alteration at Shuiyindong caused decarbonation, silicification, sulfidation, and

dolomitization. Of the alterations, silicification, dolomitization, pyritization (associated with
arsenopyritization) are most closely connected with gold mineralization. In the ores metallic
minerals include pyrite, arsenopyrite, hematite, stibnite (occasionally seen), cinnabar
(occasionally seen), realgar (occasionally seen), and native gold (occasionally seen, found for
the first time in this study) (Su Wenchao et al., 2006). Gangue minerals are quartz, dolomite,
calcite, hydromica, sericite, kaolinite, and organic carbon. As viewed from the compositional
characteristics of ore minerals and phase analyses, it is known that pyrite and arsenopyrite
are the carrier minerals of gold.
3.2 Geology of the Yata (Fault-controlled Carlin-type gold deposit)

The Yata gold deposit is located about 15 km southwest of the town of Ceheng in
southwestern Guizhou (Fig. 1). The deposit had been mined for arsenic (realgar) at a small
scale for many years. Gold mineralization was discovered as a result of reconnaissance
sampling around the old realgar pits in the early 1980s. Intensive exploration was carried out
by the Guizhou Bureau of Geology and Mineral Resources in the late 1980s. This resulted in
the definition of more than 10 t of gold reserves, with an average gold grade of 3 to 5 g/t (Tao
et al., 1987). Geologic descriptions of the deposit were given by Zhang et al. (2003).
Sedimentary rocks exposed in the district are mainly siltstone, sandstone, argillaceous
limestone, and shale of the Middle Triassic Xuman Formation, which is divided into four
members based on sand grain size and bedding thickness (Tao et al., 1987). Gold
mineralization occurs in Member 2, which is composed of interbedded sandstone, fine-
grained sandstone, siltstone, and mudstone. Unmineralized carbonaceous shale in this
formation contains quartz, biotite, ferroan dolomite, illite, calcite, and minor fine-grained
diagenetic pyrite.
Gold mineralization (Fig.4) occurred along a narrow easttrending zone and comprises more
than 40 orebodies. Most of them occur along high-angle and strike-slip faults that cut the
south limb of the east-trending Huangchang anticline and subsidiary folds. Limbs of the
anticline dip at 35° to 70°, contain chevron folds and mesoscopic compressive fracture zones.
Faults F1, F2, F3, and F6 controlled mineralization within the zone. The F2 and F3 faults,
which have easterly trends and dip south at 65° to 85°, controlled the largest mineralization
zone (M1) in the district. The M1 zone is 1,500 m long, 40 to 60 m wide, and 200 m thick,
with average gold grades varying from 1 to 3 g/t (Zhang et al., 2003). Smaller orebodies
with average gold grades of 3 to 5 g/t occur as lenticular zones, veins, and vein stockworks
within the larger envelope of mineralization. Gold orebodies are preferentially hosted in
altered calcareous siltstone and shale at intersections with high-angle faults that focused
fluid flow during gold mineralization.
Despite the stronger structural control than at Shuiyindong, wall-rock alteration at Yata is
similar and extends well away from faults and fractures along more reactive or permeable
clastic strata or calcareous shale and siltstone. Carbonate dissolution mostly occurred in
carbonate strata. In proximal zones of carbonate dissolution, disseminated irregular or
euhedral crystals of orpiment or realgar formed locally in porous decarbonated rocks.
Silicification typically produced small bodies of jasperoidal quartz within the larger areas of
altered rocks. Coarser quartz crystals occur in veins and veinlets. Argillization has mainly
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produced illite or illite-quartz veinlets, many of which contain pyrite and arsenopyrite. The
dominant primary ore minerals at Yata are arsenian pyrite, arsenopyrite, marcasite, stibnite,
orpiment, and realgar (Zhang et al., 2003). Trace amounts of sphalerite, galena, and
chalcopyrite also occur. Gangue minerals include quartz, dolomite, calcite, and clay
minerals (e.g., illite). Pyrite is the dominant sulfide in the ores (3–5 vol %). It occurs
disseminated in the host rocks as rounded pentagonal, dodecahedral, octahedral, and cubic
Fig. 4. Simplified geologic plan (A) and cross section (B) along the A-A' exploration line of
Yata (after Zhang et al., 2003). Note the vertical (± fault-controlled) orientation of the
orebodies.
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crystals, or as aggregates of all morphologies. EMPA showed that gold is predominantly in

arsenian pyrite (540 ppm Au, 10.73 wt % As: Ye et al., 1994), but a few gold grains (0.3–0.8
μm) have been observed in arsenian pyrite using scanning electron microscopy (Ye et al.,
1994). Arsenopyrite is generally disseminated in the ore as tiny acicular to prismatic crystals.
Some arsenopyrite occurs as rims on pyrite. Marcasite occurs as rare, tiny grains
surrounding pyrite grains. Some stibnite formed early, although later than the gold-bearing
pyrite, because stibnite crystals have overgrown on gold-bearing pyrite crystals at their
margins. Most of the stibnite formed euhedral crystals filling fractures on the periphery of
gold mineralization, local overgrowths of realgar and orpiment (Fig. 4B). Orpiment and
realgar are also commonly observed in open cavities with euhedral quartz crystals (Fig. 4K)
and fractures in the ore zones or their vicinities. Some calcite-orpiment-realgar veinlets cut
pyrite-arsenopyrite-jasperoidal quartz veinlets.
4. Geochemistry of elements and isotope

4.1 Geochemistry of elements
The mineralized rocks in gold deposits in SW Guizhou, are chiefly bioclastic limestone ,
fine-grained sandstone, siltstone and shale. The gold concentrations are variable for
different rock types in different deposits, even within sedimentary rocks of similar type.
Generally, siltstones contain higher concentrations of gold than sandstones and shales. As,
Sb, Hg, Pb and Zn are generally enriched in weakly mineralized rocks compared to the
country rocks in SW Guizhou. However, not only As, Sb and Hg, but also Tl, Mo, and Ag
are highly enriched in gold-rich ores compared to the country rocks (Zhang et al., 2003).
This phenomenon is particularly noticeable for the ore rocks at Shuiyingdong.
Weakly altered or unaltered samples in Shuiyingdong were selected from various types of
rocks for trace element analysis and comparisons were made between their trace element
compositions with those of the same type of rocks in the ore-bearing series (Table 1).
As can be seen clearly, the contents of Au, As, Cu, Sb, Tl and Pb in the ore-bearing series are
remarkably increased relative to those of unaltered rocks of the same type, reflecting that the
trace elements had been brought in by mineralizing hydrothermal solutions. Ti, Sc, Nb, Ta,
Zr, Hf, V, Cr, Co, Sn, Ga, Ge, Cd, Rb, Cs, Ba, Mn, Zn, Th and REE showed a little variation in
their contents. According to the element geochemical analysis, the former elements belong
to the relatively inert elements without having been reworked by hydrothermal solutions,
while the latter elements were affected by hydrothermal solutions, slightly influenced by
hydrothermal superimposition and reworking processes.
There is no significant difference in primary contents of Au, As, Cu, Sb and Tl for various
types of rocks (with unaltered rock samples for reference), and their variation is much less
obvious than what was caused by mineralization alteration. As can be seen more clearly
from the values of Table 1, the average cotents of Au, As, Cu, Sb and Tl in various types of
mineralized rocks are several tens to one hundred times those of the elements in the normal
rocks of the same type. Of those elements, the contents of Au, As and Tl are the highest. It
may be considered that the contens of these elements in the mineralized rock series were
generally affected by mineralizing hydrothermal activities. Relatively speaking, their
primary contents in the protoliths can be ignored. These elements are the basic
hydrothermal elements in the Shuiyindong gold deposit. Their ratios can be used as the
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basic parameters for measuring the hydrothermal alteration intensity. As, Cu, Sb and Tl,
especially As, can be employed as the indicator elements for ore exploration.
Average value of ore-bearing Average value of ore-bearing

rocks/normal rocks rocks/normal rocks
Limestone
Limestone
Claystone
Claystone
limestone
limestone
siltstone
siltstone
Element Element
Muddy
Muddy
Muddy
Muddy
Au 79.80 55.14 69.33 82.50 Zr 1.15 1.34 1.32 0.70
Sc 1.06 1.14 1.15 0.50 Nb 1.32 1.42 1.29 0.68
TiO2 1.25 1.04 1.19 0.62 Mo 1.59 6.56 1.42 1.48
V 0.65 1.46 1.23 0.66 Cd 1.87 2.76 2.67 6.31
Cr 0.55 2.32 1.01 0.54 Sn 0.57 2.20 1.79 0.97
MnO 1.25 1.69 0.45 1.20 Sb 2.91 7.95 11.73 32.80
Co 1.30 1.41 1.86 0.62 Cs 1.94 1.39 1.05 0.32
Ni 1.22 1.12 1.06 0.72 Ba 1.01 0.73 1.14 3.07
Cu 3.74 2.27 2.47 1.57 Hf 0.95 1.29 1.29 0.73
Zn 2.07 1.92 1.04 0.82 Ta 1.17 1.29 1.28 0.73
Ga 1.32 1.18 1.38 0.63 Tl 109.0 53.27 69.07 34.92
Ge 0.50 1.17 1.20 0.71 Pb 1.53 1.52 1.62 1.30
As 22.00 19.39 94.26 63.08 Th 0.96 1.04 1.21 0.79
Rb 1.60 1.14 1.51 0.87 U 0.70 3.34 1.47 2.01
Sr 0.25 0.60 0.51 0.86 ree 0.95 1.52 1.42 0.72
Y 0.84 1.61 1.31 0.74
Table 1. Average values of elements in ore-bearing rock seires and content ratios of elements
of normal rocks of the Shuiyindong gold deposit (unit: wt% for TiO2, MnO, and 10-6 for the
others).
The result of elements analysis of rocks and ores indicates that the contents of Au, As, Cu,
Sb, Tl in rocks are similar and original differences of their contents in rocks is much smaller
than the differences caused by hydrothermal alteration. The average contents of these
elements in mineralized rocks are tens times even hundred times higher than
nonmineralized rocks. So, the contents of these elements are controlled by action of ore-
forming fluids. These elements are most basic elements representing action of ore-forming
fluids and indicator elements of prospecting.
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4.2 Stable Isotopes

The sulfur isotopic composition of pyrite in the ore varies significantly, with δ34S values
varying within the range of +27.17‰– -8.64‰, with a range value of 35.81‰, indicanting a
high measure of dispersion. There would be shown the characteristics of sulfur of
sedimentary origin and the involvement of other sources of sulfur. Electron microscopic
analysis of pyrite monomineral (Fig. 5) indicated that pyrite in the ore contains fram-boid
(irregular) pyrite powder crystals and zonal pyrite with arsenopyrite surface (hydrotheral
origin) and framboid (irregular) pyrite core (primary sedimentary origin). The sulfur isotope
values can only represent those of pyrite of primary sedimentary origin and hydrothermal
origin. In most cases the volume of pyrite inner core (petrogenesis) is much larger than that
of the girdles of arsenopyrite formed during the metallogenic period. Therefore, the sulfur
isotope values obtained mainly represent the sulfur isotopic composition of pyrite of
petrogenic origin, but can not fully represent the sulfur isotopic composition of ore-forming
fluids (Zhang et al., 2010).
However, the δ34S values of realgar range from 0.81‰ to 3.03‰ and close to the value of
mantle with the range 2.22‰, mean value 1.6‰, indistinctive variation and high
homogenization, indicating that the ore-forming substance was probably derived mainly
from the deep place (Zhang et al., 2010).
The δ13CV-PDB values of calcite which is the main gangue mineral vary from -8.473～0.866‰,
with two main distribution from -4～-9‰ and around 0‰. According to the previous
literatures, carbon derived from the mantle and the formation (Zhang et al., 2010).
As La Au La
Pyrite outer zone
Pyrite core Gold circle
Arsenopyrite
A B
Fig. 5. Scan images of As La(A) and Au La(B) compositions of fine-grained pyrite by electron
microprobe spectral scaning.
5. The Sm-Nd isotopic composition of the Shuiyindong gold deposit and its
ore-forming geochronological study
In the Carlin-type gold deposits there are usually no minerals suitable for traditional dating,
so the problem of metallogenic time has not yet been solved. In the past the fission track
method, the quartz fluid inclusion Rb-Sr method and the pyrite Pb-Pb method were used to
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constrain the metallogenic ages, giving a larger age range of 80–170 Ma (Hu et al., 2002).
Studies by researchers from the Institute of Ore Deposits Geology showed that there are
usually developed carbonate veins or realgar (orpiment)-stibnite-carbonate veins in the fault
zones exposed on the surface or the hanging-wall of orebodies in the Carlin-type gold
mining districts of SW Guizhou. The extensive development of such carbonate veins may
imply that there had occurred such geochemical processes as interactions between Au-
bearing hydrothermal solutions and Fe-bearing carbonate strata or cements (decarbonation)
and they would be the most direct macroscopic geological manifestion of decarbonation
during gold metallogenesis.
REE analyses indicated that there are significant differences between the calcite veins closely
associated with gold metallogenesis and those with no connection with gold metallogenesis
on a regional scale (Table 2, Figs. 6 and 7). The analytical results of Sm-Nd isotopic
composition for calcite veins which have close genetic connections with gold mineralization
are listied in Table 4 and the calculated results of Sm-Nd isotopic ages are shown in Fig.8.
All the results showed that the considerably reliable mineralization age of the super-large
Shuiyindong strata-bound Carlin-type gold deposit is 134–136 Ma (Early Cretaceous), just
corresponding to the tectonic background of the regional lithosphere expansion(Su
Wenchao et al., 2009).
Sample No. La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Cal-08 0.43 1.77 0.45 3.33 2.38 1.08 3.99 0.7 3.07 0.49 1.05 0.1 0.57 0.07
Cal-11 0.73 3.08 0.73 5.58 3.82 1.89 5.85 0.96 4.32 0.65 1.3 0.14 0.72 0.09
Cal-16 0.18 0.68 0.15 1.05 0.48 0.19 0.57 0.1 0.44 0.08 0.21 0.02 0.14 0.02
Cal-03 6.54 17.1 3.1 16.06 3.81 1.87 3.46 0.46 1.96 0.3 0.61 0.06 0.29 0.04
Cal-17 0.63 2.1 0.4 2.4 0.95 0.41 1.51 0.26 1 0.14 0.22 0.02 0.12 0.02
Cal-10 0.64 1.58 0.38 2.26 0.85 0.28 1.2 0.2 1.02 0.2 0.5 0.05 0.31 0.04
Cal-05 1.66 3.96 0.71 3.5 0.85 0.6 0.95 0.12 0.51 0.09 0.21 0.02 0.1 0.01
Cal-20 1.28 4.18 0.67 3.4 1.04 0.34 1.06 0.18 0.75 0.13 0.3 0.04 0.21 0.03
Cal-21 0.99 3.46 0.59 3.16 1 0.37 1.16 0.18 0.89 0.15 0.35 0.04 0.23 0.03
Cal-12 0.09 0.32 0.07 0.46 0.22 0.09 0.32 0.06 0.29 0.05 0.12 0.01 0.07 0.01
Cal-14 0.67 0.25 0.2 0.99 0.21 0.07 0.24 0.03 0.16 0.03 0.07 0.01 0.05 0.01
ZK1648-14 0.45 0.89 0.17 0.95 0.3 0.12 0.46 0.08 0.36 0.07 0.14 0.02 0.09 0.01
ZK3101-22 0.17 0.55 0.12 0.81 0.81 0.17 0.43 0.07 0.31 0.05 0.1 0.01 0.05 0.01
ZK2002-31 0.21 0.7 0.16 1.23 0.32 0.47 2.72 0.64 3.37 0.55 1.02 0.09 0.47 0.07
NN-03 2.06 3.1 0.49 2.357 0.565 0.182 0.961 0.171 1.009 0.221 0.609 0.085 0.5 0.074
NN-04 0.63 1.26 0.22 1.13 0.339 0.0178 0.45 0.064 0.361 0.068 0.149 0.018 0.087 0.011
NN-05-1 2.3 4.41 0.71 3.368 0.795 0.227 1.018 0.18 0.971 0.203 0.569 0.078 0.449 0.071
NN-05-2 1.49 2.47 0.34 1.234 0.2 0.046 0.192 0.032 0.189 0.036 0.103 0.015 0.087 0.013
Table 2. REE data (×10-6)
for calcite samples in the orebodies and wall rocks of the
Shuiyindong gold deposit.
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Fig. 6. The chondrite-normalized REE patterns for the calcite veins associated with Au
mineralization in the Shuiyindong gold deposit. All data are normalized according to the
chondrite REE values of Sun and McDonough (1989).
Fig. 7. The chondrite-normalized REE patterns for the calcite veins which have no genetic
connection with gold mineralization. All the data are normalized according to the chondrite
REE values of Sun and McDonough (1989).
Sm Nd 147Sm/144Nd 143Nd/144Nd(2σ)
Sample No. 87Sr/86Sr(2σ)
(×10-6) (×10-6) (atomic) (atomic)
Cal-08 2.3002 3.0752 0.4522 0.512762±6 0.707083±10
Cal-11 3.8689 5.5334 0.4227 0.512735±5 0.707203±21
Cal-16 0.4683 1.0775 0.2628 0.512593±9 0.707482±13
Cal-03 3.6978 14.5286 0.1539 0.512496±7 0.707251±25
Cal-17 0.9178 2.2416 0.2475 0.512579±6 0.707991±11
Cal-10 0.8437 2.1825 0.2337 0.512567±8 0.707217±13
Cal-05 0.8203 3.2117 0.1544 0.512497±8 0.707152±16
Cal-20 0.9776 3.2226 0.1834 0.512523±12 0.707125±13
Cal-21 0.9602 2.8964 0.2004 0.512537±7 0.707143±10
Cal-12 0.2227 0.457 0.2946 0.512064±6 0.707729±8
Cal-14 0.2044 0.9306 0.1328 0.511922±15 0.707614±10
ZK1648-14 0.2869 0.8801 0.1971 0.511978±20 0.708003±24
ZK3101-22 0.812 0.9904 0.4957 0.512241±18 0.707610±11
ZK2002-31 0.39 0.9459 0.2493 0.512024±7 0.706620±18
Table 3. Sm, Nd and Sr isotopic compositions of calcite veins from the Shuiyindong gold
deposit.
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Fig. 8. The chondrite-normalized REE patterns (A and C) and corresponding Sm-Nd

isochron ages (B and D) for the calcite veins from the Shuiyindong deposit. All data are
normalized using the chondrite REE values of Herrmann (1970).
6. Geochemistry of fluid inclusions

6.1 Fluid inclusion types and petrographic relationships
Eight samples used in this study were collected from the main orebodies in the
Shuiyindong and Yata deposits (Figs.3B, 4B). Three are barren milky quartz veins that
have early horizontal dips in the ore zones at Shuiyindong and fill fractures at Yata. Some
of the milky quartz veins are colored orange or gray by inclusions of realgar or stibnite or
are cut by stibnite-realgar-orpiment-quartz veinlets. A sample (YT-5) from Yata contains
arsenian pyrite, arsenopyrite, and quartz; other samples from Yata contain stibnite,
realgar, orpiment, calcite, and quartz, filling in fractures on the periphery of gold
mineralization.
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Fluid inclusions observed in this study have negative crystal, elongate, or irregular shapes
(Fig. 9). Fluid inclusions types were classified based on their appearance at 25°C andby their
Raman spectra and occur in successive stages of the vein and alteration paragenesis.
Type Ia inclusions are two-phase, liquid-rich aqueous inclusions with 10 to 20 vol percent of
a low-density vapor bubble at room temperature. They occur in early barren milky quartz
veins at Shuiyindong and Yata. Primary inclusions of this type occur along growth zones of
quartz and have negative crystal shapes, generally less than 25 μm in diameter (Fig. 9B, E).
Secondary inclusions are elongate or irregular and occur along trails crosscutting quartz
grains or grain boundaries (Fig. 9C, F). Raman spectroscopy analysis has failed to accurately
determine the composition of the vapor phase of this type of inclusion because the bubble
moved as the laser beam was focused on it. Raman peaks of CO2, N2, and CH4 have,
however, been detected.
Type Ib inclusions are two- or three-phase aqueous-carbonic inclusions with a dominant
aqueous liquid phase and a relatively constant carbonic (vapor + CO2 liquid) fraction of 15
vol percent (Fig. 9H). They are commonly observed in quartz veinlets with arsenian pyrite
and arsenopyrite of the main stage of gold mineralization at Yata and in jasperoidal quartz
of the main stage at Shuiyindong. Primary inclusions are typically 20μm in diameter, occur
along growth zones of quartz, and have negative crystal shapes (Fig. 9G, H). Some
inclusions along microfracture planes within quartz grains are pseudosecondary based on
their spatial relationship to the growth zones and healed fractures. Both microthermometry
and Raman spectroscopy analyses have revealed that the main component of the volatile
phase of the inclusions is CO2, with minor N2 and trace CH4.
Type II inclusions are rare, two-phase, aqueous-carbonic inclusions with variably high
proportions of a carbonic phase ranging from 45 to 90 vol percent (Fig. 9K). In samples from
Yata, they occur in late drusy quartz with realgar, stibnite, and calcite.
Type III inclusions are monophase carbonic inclusions (Fig. 9L) and generally less than 15
μm in diameter. They are restricted to late quartz-realgar veins or veinlets at Yata and occur
along trails crosscutting quartz grains. Both microthermometry and Raman spectroscopy
have revealed that the volatile phase is mainly composed of CO2 and N2, with trace CH4.
Petrographic relationships indicate that CO2-poor aqueous inclusions of type Ia can be
interpreted to approximate the mineralizing fluid, which was responsible for precipitation
of early ore minerals in veins but predates the deposition of the bulk of disseminated gold-
bearing arsenian pyrite and arsenopyrite deposition in both deposits. CO2-rich fluids of type
Ib are interpreted to correspond to the main gold-bearing fluid in both deposits. The same
aqueous-carbonic fluids also occur together with type II and III carbonic fluids in the late
quartz-realgar veins at Yata. Type II and III fluids are interpreted to represent the waning or
outflow stage of economic gold mineralization.
6.2 Quantitative fluid inclusion results

6.2.1 Microthermometry and Raman data
Microthermometric measurements were made on primary, pseudosecondary, and
secondary inclusions in quartz crystals from milky quartz veins, replacement-style quartz
veinlets, and late drusy quartz. Three distinctive fluid compositions are interpreted to be
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representative of the different mineralization stages. Microthermometric data and Raman

spectroscopy analyses of representative fluid inclusions are given in Table4.
Fig. 9. Microphotographs of fluid inclusions in quartz. A. Early milky quartz (thin section)
from Shuiyindong. B. Primary and C. Secondary type Ia aqueous inclusions in the milky
quartz from Shuiyindong. D. Photograph and sketch of early milky quartz from Yata. E.
Primary and F. Secondary type Ia aqueous inclusions in the milky quartz from Yata. G.
SEM-CL image of a main ore-stage quartz crystal, and H. Photographs of type Ib
aqueous-carbonic inclusions from Yata. Circles denote the positions of inclusions analyzed
by LA-ICP-MS. I. to L. Late drusy quartz crystal with types Ib, II, and III aqueous-carbonic
and carbonic-rich inclusions from Yata, respectively. Note that two end-member fluid
inclusion assemblages are cogenetic in (L). Scale bar is 20 μm unless defined otherwise.
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Microthermometry Raman data

Stage Quartz type Inclusion Tm (CO2) Th(CO2) Tm(cl) Th (ºC)
Mode Mode CO2 N2 CH4
(ºC) (ºC) (ºC)
Main-stage Veinlet quartz 41 –56.7 20.5 L 9.4 228 L 97.5 1.5 1.0
crystals 42 –57.7 17.6 L 9.3 227 L 95.7 3.3 1.0
55 –56.7 21.6 L 9.4 220 L 97.0 3.0 n.d.
60 –56.8 22.2 L 8.8 215 L 96.8 2.0 1.2
61 –56.6 22.9 L 9.4 210 L 99.5 0.5 n.d.
65 –56.9 21.4 L 238 L 96.0 3.5 0.5
66 –56.8 22.3 L 217 L 97.0 3.0 n.d.
76 –56.7 23.4 L 9.6 223 L 96.8 2.5 0.7
80 –56.7 23.3 L 206 L 98.2 1.8 n.d.
93 –56.6 24.8 L 8.6 225 L 98.7 1.3 n.d.
94 –56.7 24.5 L 9.4 210 L 97.5 1.8 0.7
99 –56.7 17.9 L 9.0 247 L 96.5 2.7 0.8
107 –56.7 20.8 L 9.8 216 L 97.2 1.9 0.9
Late stage Veinlet quartz 34 –58.7 6.3 L 9.5 2321 86.5 13.5 n.d.
crystals 35 –58.6 7.8 L 9.3 2281 89.2 10.0 0.8
11 –60.5 –24.3 L 71.0 27.2 1.8
12 –60.3 –24.0 L 73.0 27.0 n.d.
14 –60.2 –23.3 L 75.0 25.0 n.d.
15 –60.2 –23.2 L 77.0 23.0 n.d.
(Notes: Tm (CO2) = final melting temperature of CO2, Th(CO2) = homogenization temperature of CO2,
Tm = melting temperature of ice, Tm(cl) = final melting temperature of clathrate, Th = homogenization
temperature; L = homogenize to liquid; 1 Decrepitation temperature; n.d. = not detected; Composition is
given in mol percent)
Table 4. Chemical Compositions of Representive Aqueous–Carbonic and Carbonic–Rich
Inclusions Obtained by Raman Spectroscopic Analysis and Corresponding
Microthermometric Data from Yata.
Type Ia primary and secondary aqueous inclusions (Fig.9B-C, E-F) have initial ice-melting
temperatures (Te) from –22.2° to –21.0°C, which is similar to the eutectic melting
temperature in the NaCl-H2O system (Hall et al., 1988) but does not exclude more complex
systems such as the NaCl-KCl-H2O system (Sterner et al., 1988). Final ice-melting
temperatures (Tm) of primary aqueous inclusions range from –3.0° to –4.3°C, corresponding
to salinities of 5.0 to 6.9 wt percent NaCl equiv (Bodnar, 1993) with an average of 6.0 wt
percent NaCl equiv (Fig. 10B, D). Homogenization of these fluid inclusions was to the liquid
phase at temperatures ranging from 190° to 258°C with a mode around 230°C (Fig. 10A, C).
The Tm of secondary inclusions range from –1.2° to –4.5°C, corresponding to salinities of 2.1
to 7.2 wt percent NaCl equiv (Fig. 10B, D). Secondary inclusions of type Ia also
homogenized into the liquid phase at temperatures ranging from 151° to 261°C with a mode
around 190°C (Fig. 10C). No evidence of other phases, such as clathrate, liquid, or solid CO2
were observed, suggesting that this type of inclusion may contain as much as 2.4 mol
percent CO2 dissolved in the aqueous phase without developing a separate CO2 liquid
phase at room temperature (Bodnar et al., 1985).
Type Ib primary and secondary aqueous-carbonic inclusions (Fig. 9H, J) always develop a
vapor phase in the carbonic bubble, even if they are two-phase at room temperature. The
melting temperature of CO2 (Tm (CO2)) ranges from –58.1° to –56.6°C with the majority of
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Final CO2 melting temperature (℃) CO2 homogenization temperature (℃)

Fig. 10. Histogram of homogenization temperature, final CO2 melting temperature, and
salinity of fluid inclusions from Shuiyindong (A-B) and Yata (C-H).
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CO2 melting occurring at –56.6°C (Fig. 10G). The carbonic phase always homogenized to the
liquid (Th (CO2)) at temperatures ranging from 10.2° to 26.1°C with a mode around 24.0°C
(Fig. 10H). Clathrate observed in these inclusions exhibits a typical Q2 melting behavior
(Bakker and Brown, 2003). The clathrate melting temperatures (Tm(cl)) of primary
inclusions range from 8.3° to 9.2°C, corresponding to salinities of 1.6 to 3.3 wt percent NaCl
equiv (Diamond, 1992), with an average of 2.3 wt percent NaCl equiv (Fig. 10F), which is
two to three times lower than the salinity of the type Ia aqueous inclusions. The Tm(cl) of
secondary inclusions range from 9.4° to 9.8°C, corresponding to salinities of 0.4 to 1.2 wt
percent NaCl equiv (Fig. 10F). These inclusions commonly decrepitated at temperatures
below 200°C, before total homogenization was attained.
The 35 inclusions that did not decrepitate homogenized into the liquid phase at
temperatures from 190° to 245°C, with a mode around 220°C (Fig. 10E). Raman spectroscopy
of the carbonic phase in individual fluid inclusions showed that CO2 is the dominant
volatile (>96 mol %), N2 is always detected (0.5–3.5 mol %), and CH4 has been detected (up
to 1.2 mol%) in a few inclusions (Table 4).
Type II aqueous-carbonic inclusions (Fig. 9K) also always develop a vapor phase in the
carbonic bubble during cooling runs. Their Tm(CO2) ranged from –59.6° to –58.1°C
(Fig.10G). Homogenization of the CO2 was always to the liquid phase between 6.3° to
20.9°C. The Tm(cl) range from 9.5° to 10.7°C, corresponding to salinities of 0 to 8.9 wt
percent NaCl equiv (Bakker and Brown, 2003). Total homogenization temperatures were not
obtained because these inclusions decrepitated when heated to above 200°C. Raman
spectroscopy revealed that their volatile phases contain major CO2 (87–89 mol %), minor N2
(10–14 mol %), and trace CH4 (0.8 mol %; Table 4).
In the process of freezing (down to –180°C) and subsequent heating, type III carbonic
inclusions (Fig. 9L) underwent the following sequence of phase transitions: S + V → L + V →
L. The Tm(CO2) range from –60.5° to –59.6°C with the majority at –60.1°C (Fig. 10G). The
Th(CO2) of this type of inclusion range from –24.3° to –22.5°C (Fig. 10H) and were always
into the liquid phase. Total homogenization temperatures could not be measured reliably
owing to optical limitations (Diamond, 2003). Raman spectroscopy showed that the volatile
phase of type III inclusions contains major CO2 (71–77 mol %), minor N2 (23–27 mol %), and
trace CH4 (up to 1.8 mol %; Table 4).
6.2.2 Bulk compositions of aqueous-carbonic and carbonic-rich fluids

Aqueous-carbonic inclusions in the main stage of pyrite-arsenopyrite-quartz veins and late
stage of stibnite-realgar-orpiment-quartz veins at Yata have 10 to 15 vol percent volatile
phase (nearly pure CO2), regardless of the sample localities. Calculated density of the
volatile phase varies from 0.72 to 0.82 g/cm3, with an average of 0.75 g/cm3. Calculated
bulk compositions showed that the fluids are dominated by H2O (91–92 mol %) and CO2
(6.3–8.4 mol %, with an average of 7.6 mol %). Their bulk densities range from 0.97 to 0.99
g/cm3. Their average salinities vary from 0.9 to 2.3 wt percent NaCl equiv. Calculated bulk
compositions of carbonic-rich inclusions in the late stage of stibnite-realgar-orpiment-quartz
veins at Yata are dominantly CO2 (58–64 mol %), N2 (19.2–23.7 mol %), and H2O (12.5–22.8
mol %), and trace CH4 (up to 1.6 mol %), with volatile phase densities and bulk densities of
0.75 to 0.80 and 0.77 to 0.82 g/cm3, respectively.
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6.3 Pressure and temperature estimation

The compositions of type Ib inclusions plot close to the solvus of the H2O-CO2 system at 1.0
kb in Figure 8A. It is possible that the fluids of these inclusions may represent one end
member produced by unmixing of H2O-CO2 fluids. The compositions of a few type II
inclusions plot in the two-phase field in Figure 11A. These inclusions may represent
mechanical mixtures of two immiscible fluid phases. The local occurrence of type II
inclusions at Yata indicates that the hydrothermal fluid reached a state of immiscibility at
some time in its history (Diamond, 1990). Type III inclusions plot close to the 1.0 kb solvus
in Figure 8A. If they coexisted with type Ib inclusions, then these inclusions may represent
another end member produced by unmixing of H2O-CO2 fluids.
Fig. 11. A. T-X diagram of the H2O-CO2 system at 1.0 kbar based on experimental data from
Tödheide and Franck (1963)and Takenouchi and Kennedy (1964). B. P-T diagram showing
the range of possible P-T conditions during mineralization at Yata. The miscibility
boundaries for fluids with 6 and 7.6 mol percent CO2 are from experimental data of the
H2O-CO2 system of Tödheide and Franck (1963) and Takenouchi and Kennedy (1964).
The minimum P-T conditions of inclusion entrapment are constrained by intersecting points
using the range of homogenization temperatures of type Ib inclusions (190°–245°C) and the
minimum of the bubble curves of 6 mol percent CO2 (Fig. 11B). The defined area in Figure
8B (shaded) ranges from 450 to 1,150 bars, corresponding to a depth of 1.7 to 4.3 km under
lithostatic load, using the average density of sedimentary rocks in southwestern Guizhou
(2.67 g/cm3: Wang et al., 1995) and 4.5 to 11.5 km assuming hydrostatic pressure. As Yata
was controlled by a fault, the estimated pressure may have been fluctuating between
hydrostatic and lithostatic pressures. Decompression associated with episodes of faulting
may have caused the immiscibility in the late stage of stibnite-realgar observed in this
deposit. Zhang et al. (2003) previously estimated pressures for the Lannigou deposit ranging
from 600 to 1,700 bars based on the CO2-bearing fluid inclusions, corresponding to a depth
of 2.2 to 6.3 km under lithostatic conditions or an unlikely 6 to 17 km under hydrostatic
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load. CO2 contents of fluid inclusions at Yata (6–8 mol %) are somewhat lower than those of
many orogenic lode gold deposits (10–25 mol % CO2: Ridley and Diamond, 2000) but higher
than those of Carlin-type gold deposits in Nevada (2–4 mol % CO2: Hofstra and Cline, 2000).
It is, therefore, reasonable to infer that the Yata deposit may have formed at depths
intermediate between orogenic-type gold deposits and those of the Carlin trend in Nevada.
6.4 Source of fluids

Oxygen and hydrogen isotope compositions of early barren milky quartz veins and clay
minerals (<2 μm) in the mineralized rock from Shuiyindong have been reported by Hofstra
et al. (2005). The milky quartz veins have a narrow range of high δ18O values (21–27‰).
Calculated δ18O(H2O) values for fluids in these samples vary from 10.5 to 16.5 per mil, using
a homogenization temperature of 230°C from this study and the quartz-water isotopic
equilibrium fractionation equation of Friedman and O’Neil (1977). Calculated δ18O(H2O)
and δD(H2O) values for fluids in equilibrium with clay minerals in the mineralized rocks at
Shuiyindong range from 4 to 10 and –56 to –68 per mil, respectively (Hofstra et al., 2005).
Similar fluid calculations for clay minerals in the mineralized rocks from the Zimudang
deposit, located 15 km west of Shuiyindong on the same large-scale dome structure, indicate
δ18O(H2O) and δD(H2O) values from 13 to 16 and –35 to –40 per mil, respectively (Hofstra et
al., 2005).
Li et al. (1989) and Zhu et al. (unpub. data) reported oxygen for the main ore quartz and the
late ore calcite from Yata. The main ore quartz has a narrow range of δ18O values (20.9–
26.1‰), similar to milky quartz veins at Shuiyindong. The calculated δ18O(H2O) values for
the main ore fluids from Yata vary from 9.9 to 15.1 per mil at 220°C. The δ18O(H2O) values
of late ore fluids (8.1–10.9‰) were calculated from measured δ18O calcite values (18.2–
20.8‰), the minimum homogenization temperature of 190°C for CO2-bearing fluid
inclusions within calcite (Zhang et al., 2003) and the calcitewater isotopic equilibrium
fractionation equation of Friedman and O’Neil (1977). The δD(H2O) values of water
extracted from inclusion fluids in the main ore quartz at Yata range from –51.1 to –78.8 per
mil (Li et al., 1989), significantly higher than the average δD(H2O) value of local meteoric
water during the Jurassic and Cretaceous (–85‰: Han et al., 1999). The δ18O(H2O) and
δD(H2O) values plot within or close to the metamorphic-water box (Hofstra et al., 2005, fig.
3), suggesting that the ore fluids are characterized by a predominantly metamorphic
component. There is no evidence for meteoric water involvement, but a deep magmatic
component cannot be excluded.
6.5 Processes of gold deposition

Recent studies of Carlin-type deposits in Nevada have concluded that gold-rich arsenian
pyrite precipitated from H2S rich fluids, which sulfidized iron-bearing minerals in the host
rocks (Hofstra et al., 1991; Hofstra and Cline, 2000). The chemical reaction of cooling H2S-
rich fluids in contact with iron-poor carbonate-bearing sedimentary rocks has been
calculated from thermodynamic data by Heinrich (2005). An important prediction is that Au
solubility may remain high to temperatures as low as 150°C, provided that an excess of H2S
over Fe is maintained in a moderately oxidized hydrothermal fluid, the pH of which is kept
close to neutral by carbonate dissolution (Heinrich, 2005, fig. 6). This fluid-chemical
evolution path can equally apply to fluids of magmatic or metamorphic origin but clearly
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matches the low Fe contents of fluids measured in the inclusions from the Shuiyindong and
Yata deposits. At the strata-bound Shuiyindong deposit, there is no evidence for significant
phase separation during the main mineralization stage. At the fault-controlled Yata deposit,
phase separation was minor during gold mineralization and common in the late stibnite-
realgar stage. This fluid inclusion evidence suggests that phase separation was not the key
process for deposition of gold and arsenian pyrite. The low Fe contents in the ore fluids
(below 400 μg/g) measured by LA-ICPMS of fluid inclusions and many relict inclusions of
ferroan carbonate (with up to 7.0 wt % Fe determined by EMPA: Su et al., 2008) enclosed in
the jasperoidal quartz crystals suggest that iron in sulfide minerals was probably derived
from dissolution of ferroan carbonate in the host rocks, as has been documented in Carlin-
type gold deposits in Nevada by lithogeochemistry of ores (Hofstra et al., 1991; Hofstra
and Cline, 2000). Sulfidation of ferroan carbonate-rich host rocks by H2S-rich ore fluids
containing Au(HS)–2 or Au(HS)0 (Seward, 1973, 1991), along with arsenic as H3AsO3
(aq) complex (Heinrich and Eadington, 1986; Pokrovski et al., 2002), would have effectively
extracted gold from solution and transformed primary ferroan carbonate to secondary
gold-bearing arsenian pyrite, possibly by a coupled reaction such as the following:
2FeCO3 + 2H3AsO3 (aq) + H2S(aq) + 2Au(HS) 2－(aq) + H2 (g)
= Fe(S, As)2 · Au2S0 + FeS2 + CO–23(aq) + CO2 (g) + 7H2O.

Any loss of CO2 by fluid phase separation would further promote the formation of gold-
bearing arsenian pyrite by such a reaction. This is consistent with petrographic observations
that gold-bearing arsenian pyrite and arsenopyrite occur together with Fe-poor
hydrothermal dolomite (Fig. 4C). Moreover, it can explain the covariance of Au, As, Sb, and
Sr contents of the ore fluids (Fig. 9). The reaction involves reduction of As (+III) and Au (+I)
by consumption of H2 (g), which can be provided by reaction of the metal-transporting
fluids with the local organic-rich sediments. This situation is likely to occur where fluids are
channeled into a fluid conduit (e.g., along the unconformity between the Maokou Limestone
and the Longtan Formation at Shuiyindong or the reverse faults at Yata). Here, they reacted
with carbonaceous and Fe carbonate-rich host rock, or were mixed with Fe+2- and
CH4-bearing pore fluids previously equilibrated with the reduced host-rock package, to
deposit arsenian pyrite and arsenopyrite that host most of the gold in the deposits. The
generation of secondary pervasive permeability and porosity by carbonate dissolution from
the host rocks favors fluid focusing and the formation of strata-bound orebodies (Heinrich,
2005), as is the case in the Shuiyindong. Therefore, fluid reduction and sulfidation of wall-
rock iron by H2S-rich ore fluids are proposed to be the most important mechanism of gold
deposition as auriferous arsenian pyrite in the Chinese Carlin-type gold deposits.
Genetic models previously proposed for Carlin-type deposits in Nevada fall into three
groups involving magmatic (Radtke et al., 1980; Ressel et al., 2000), metamorphic (Groves et
al., 1998; Hofstra and Cline, 2000), and deeply or shallowly circulated meteoric waters
(Ilchik and Barton, 1997; Emsbo et al., 2003). Our study of Carlin-type deposits in Guizhou
indicates that the ore fluids are of low salinity but rich in highdensity CO2, and stable
isotope data are consistent with a dominant metamorphic fluid source. The ore-forming
fluids have extremely high contents of the characteristic ore elements (As, Sb, and Au), and
the mineralogical characteristics and high gold grade of the deposits can be explained by
interaction of such fluids with chemically reactive carbonate-, iron-, and carbon-rich
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sedimentary host rocks. The deposits formed at similar temperatures as epithermal gold
deposits, but at significantly higher pressure and greater depths (4–6 km), consistent with
regional-metamorphic temperature gradients. Their thermal regime and ore fluid
characteristics are similar to those of the broad group of orogenic gold deposits, raising the
possibility that the Carlin-type deposits in Guizhou might be the basin-hosted and relatively
cool end member of the crustal continuum of orogenic gold deposit formed from fluids
liberated by deep metamorphic dehydration or magmatism (Groves, 1993; Groves et al.,
1998; Pettke et al., 2000).
7. Metallogenic model
Through comprehensive geological-geochemical studies and discusion on the problems
concerning metallogenesis, the metallogenic model of the Shuiyindong gold deposit can be
summarized as follows(Xia 2005; Zhang et al., 2010):
Late Indosinian to Early Yanshanian tectonic movements put the end to the history of basin
evolution in this region. Development of strata folds, faults, deep giant faults and
magmatism, abnormally high geothermal temperature, and deeper burial resulted in the
formation of ore fluids with abundant volatile elements in the deep interior of the crust and
upper mantle. In addition, the fluids also became the overpressured fluids after extracting
ore-forming elemens in the Au-, Hg-, Sb-, As- and Tl-rich rocks in the basement and at great
depth.
At that time, as the crust was in the compressive sealed stress state, the overpressured ore
fluids were sealed at depth and were in strong equilibrium with the lithosphere. During the
Yanshanian period this region was in the extensional state. With the injection of alkaline
ultrabasic dykes (tubes), resurvival of the faults had occurred at the basement, which,
together with cover-strata faults, cut through the crust. As a result, the sealing conditions of
overpressured ore fluids were destroyed, the fault system, like a pump, made ore fluids find
their way into the upper crust. Gold in the ore fluids would be rapidly precipitated and
accumulated as gold deposits in the favorable loci where metallogenic conditions changed
suddenly. Meanwhile, Hg, Sb, As, Tl and other ore-forming elements would be precipitated
as ores in the proper locations. All these led to what we see today in Southwest Guizhou,
where the Carlin-type gold deposits are characterized by close Au-Hg-Sb-As-Tl paragenesis
or association on a regional scale, while various gold deposits show the phenomenon of
differentiation. At that time, as for the Shuiyindong gold deposit, due to the formation of the
Huijiabao short-axis anticline and that of the favorable Upper Permian Longtan Formation
assemblage of claystone→bioclastic limestone→claystone, volatiles with abundant CH4, N2
and CO2, which found their way into the anticline core along the karst and non-kart
unconformability at the bottom of the Longtan Formation, and gold overpressured ore
fluids were gathered. The fluids contained no iron (Su Wenchao et al., 2006), gold can be
exist in the form of Au-S coordination compound (Seward, 1973; Hofstra and Cline, 2000;
Zhang Jun et al., 2002). Relatively high pressure and high volatiles made ore fluids move
laterally and infiltrate to some extent in bioclasstic sandy limestones in the favorable
lithologic assemblage. Sometimes, the overpressured ore fluids would hydrodynamically
destroy the country rocks. With the structural development, the faults destroyed the traps
constituted by the anticline and favorable lithologic assemblage, making volatiles in the
fluids escape out rapidly. As a result, the fluid pressure dropped suddenly, followed by the
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decrease of reductivity and the local or partial involvement of iron, some other components
and meteoric water in the strata, leading to significant differences in ore-forming conditions.
The ore-forming conditions thus rapidly turned favorable for gold deposition, and gold
would be rapidly precipitated with the crystallization of arsenopyrite (partly in the inner
core of pyrite of sedimentary origin) or fine-grained cinnaba.
Run-through of the faults and the repeated occurrence of favorable lithologic assemblages
led to the multi-layer orebody occurrence of the Shuiyindong gold deposit (Fig. 14). And Hg
and Tl in metallogenic hydrothermal solutions possess much higher mobility, thus forming
ore deposits in high-angle tensional-shear faults in the priphery of the gold deposit.
Therefore, there appeared anticline core and low-angle compresso-shear fault strata-bound
gold deposits and slightly later high-angle tensional-shear strata-bound Hg and Hg-Tl
deposits.
Fig. 11. The ‘’two-stories’’ gold orebodies distribution and metallogenic model of the Carlin-
type gold deposit in SW Guizhou (after Xia, 2005). 1. Stratum boundary; 2. Maokou Formation;
3. alteration zone; 4. Longtan Formation; 5. Changxin Formation; 6. Dalong Formation; 7. the
first member of the Yelang Formation; 8. the second member of the Yelang Formation; 9. deep
giant fault; 10. fault; 11. gold orebody; 12. migration direction of ore-forming fluid.
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Studies showed (Su Wenchao et al., 2006) that the mineralization experienced
decarbonation, gold and sulfur precipitation and the formation of carbonate veins, The
chemical reactions involved in these three processes are presented as follows:
1. Decarbonation:
CO2+H2O=H2CO3 (1)
H2CO3 +(Ca, Fe)CO3=Fe2+ + Ca2+ +2 HCO3－ (2)
2. Precipitation of gold and sulfides:
Au(HS) 2－+0.5 H2=Au0+H2S+HS－ (3)
2H2S + Fe2+=FeS2十2H+ +H2 (4)
3. Formation of carbonate veins:
2HS－+ Fe2+ = FeS2十2H+ (5)

－
Ca2+ + CO32 =CaCO3 (6)
a. Weak acidity of Au-bearing hydrothermal solutions made Fe-carbonate minerals in ore-

hosted wall rocks dissolve, followed by the release of Fe and Ca into the hydrothermal
system [Reactions (1) and (2)], i.e., decarbonation. b. Au(HS)2－ in hydrothermal solutions
－
was decomposed under relatively reducing conditions, making H2S and HS enter into the
hydrothermal system [Reaction (3)], both of them together with Fe-carbonate minerals
were dissolved, releasing Fe2+-bound pyrite (sulfidation) and producing H+ [Reactions (4)
and (5)].
The acidic environment resultant from sulfidation may further promote Fe-carbonate
minerals in the wall rocks to dissolve, followed by the release of a large amount of Fe2+
into the hydrothermal system. Sulfidation would finally lead to the over-saturation of Au
in hydrothermal solutions and its precipitation as native gold grains and accumulation on
the surface of arsenopyrite grains or their margins. c. Dissolution of Fe-carbonate minerals
led to the release of Ca [Reaction (6)], which would be involved in the formation of late
calcite veins, accompanied by Au pyrite veinlets or cutting through the latter. Therefore,
high-grade Fe-carbonate ore-hosted wall rocks are one of the important factors for the
formation of large-sized Carlin-type gold deposits. Carbonate veins associated with
decarbonation may be one of the important indicators for search of large-sized Carlin-
type gold deposits.
8. Acknowledgments
The project was supported jointly by the State Science and Technology Supporting Program
(2006BAB01A13), the self-research project funded by the State Key Laboratory of Ore
Deposit Geochemistry (Ore Deposit Special Research Project), and Guizhou Provincial
Bureau of Geology and Mineral Resource Exploration and Development [Qian Di Kuang Ke
(2009) No. 11].
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Geochemistry and Metallogenic Model of Carlin-Type Gold

Chapter · May 2012

Yong Xia Su Wenchao

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Geochemistry and Metallogenic

2. Regional geologic setting

2.2 Igneous rocks in SW Guizhou

2.3 Regional structures in SW Guizhou

3. Geology of the gold deposits

3.1 Geology of the Shuiyindong (Stratabound Carlin-type gold deposit)

Note the stratiform nature of the numbered orebodies.

Wall-rock alteration at Shuiyindong caused decarbonation, silicification, sulfidation, and

3.2 Geology of the Yata (Fault-controlled Carlin-type gold deposit)

crystals, or as aggregates of all morphologies. EMPA showed that gold is predominantly in

4. Geochemistry of elements and isotope

Average value of ore-bearing Average value of ore-bearing

4.2 Stable Isotopes

Fig. 8. The chondrite-normalized REE patterns (A and C) and corresponding Sm-Nd

6. Geochemistry of fluid inclusions

6.2 Quantitative fluid inclusion results

representative of the different mineralization stages. Microthermometric data and Raman

Microthermometry Raman data

Final CO2 melting temperature (℃) CO2 homogenization temperature (℃)

6.2.2 Bulk compositions of aqueous-carbonic and carbonic-rich fluids

6.3 Pressure and temperature estimation

6.4 Source of fluids

6.5 Processes of gold deposition

2FeCO3 + 2H3AsO3 (aq) + H2S(aq) + 2Au(HS) 2－(aq) + H2 (g)

= Fe(S, As)2 · Au2S0 + FeS2 + CO–23(aq) + CO2 (g) + 7H2O.

H2CO3 +(Ca, Fe)CO3=Fe2+ + Ca2+ +2 HCO3－ (2)

2. Precipitation of gold and sulfides:

Au(HS) 2－+0.5 H2=Au0+H2S+HS－ (3)

2H2S + Fe2+=FeS2十2H+ +H2 (4)

3. Formation of carbonate veins:

2HS－+ Fe2+ = FeS2十2H+ (5)

a. Weak acidity of Au-bearing hydrothermal solutions made Fe-carbonate minerals in ore-

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