Genesis of gold and antimony deposits in the Youjiang metallogenic province, SW China: Evidence from in situ oxygen isotopic and trace element compositions of quartz

Journal Pre-proofs Genesis of gold and antimony deposits in the Youjiang metallogenic province, SW China: evidence from in situ oxygen isotopic and trace element compositions of quartz Jinwei Li, Ruizhong Hu, Jiafei Xiao, Yuzhou Zhuo, Jun Yan, Abiola Oyebamiji PII: DOI: Reference:

S0169-1368(19)30671-7 https://doi.org/10.1016/j.oregeorev.2019.103257 OREGEO 103257

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Ore Geology Reviews

Received Date: Revised Date: Accepted Date:

24 July 2019 8 November 2019 25 November 2019

Please cite this article as: J. Li, R. Hu, J. Xiao, Y. Zhuo, J. Yan, A. Oyebamiji, Genesis of gold and antimony deposits in the Youjiang metallogenic province, SW China: evidence from in situ oxygen isotopic and trace element compositions of quartz, Ore Geology Reviews (2019), doi: https://doi.org/10.1016/j.oregeorev.2019.103257

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1

Genesis of gold and antimony deposits in the Youjiang

2

metallogenic province, SW China: evidence from in situ

3

oxygen isotopic and trace element compositions of quartz

4 5

Jinwei Lia,b, Ruizhong Hua,b,*, Jiafei Xiaoa, Yuzhou Zhuoa,b, Jun Yana, Abiola

6

Oyebamijia,b

7 8 9

a

State Key Laboratory of Ore Deposit Geochemistry, Institute of Geochemistry,

10

Chinese Academy of Sciences, Guiyang 550002, China

11

b

12

Sciences, Beijing 100049, China

College of Earth and Planetary Sciences, University of China Academy of

13 14 15 16 17 18 19 20

* Corresponding author: [email protected] (Ruizhong Hu)

21 22 23 1

24

Abstract

25

Abundant Carlin-type gold deposits and vein-type antimony deposits were

26

discovered in the Youjiang basin of SW China, constituting the Youjiang

27

Metallogenic Province (YMP). Although they had been widely studied by

28

geologists, the genesis of these deposits remains debatable, while both

29

intrusion-linked and non-intrusion linked models have been proposed. In this

30

paper, new data of in situ trace elements (LA-ICP MS) and oxygen isotope

31

(SIMS) analysis of hydrothermal quartz from the Yata Carlin-type gold deposit

32

and the Qinglong vein-type antimony deposit in the province were provided to

33

better understand the origin of ore-forming fluids as well as the genetic

34

mechanism of Au and Sb mineralization. Four quartz generations were

35

identified from the Yata (YTi to YTiv) and the Qinglong (QLi to QLiv) deposits.

36

In the Yata deposit, the fluid inclusions in quartz have varied homogenization

37

temperatures from 140~260℃ and salinities of 2.4~7.4 wt％ NaCleq, while in

38

the Qinglong deposit, the temperatures and salinities ranged from 140~200℃

39

and 0.2~7.2 wt％ NaCleq., respectively. Both of the temperatures and salinities

40

tend to decrease from early to late generations in the two deposits. δ18O values

41

of initial fluids in the Yata (YTi: 7.70~10.56 ‰) and the Qinglong (QLi: 4.66~8.75

42

‰) deposits are similar and suggest that they were mainly from magmatic or

43

metamorphic fluids. The covariability of oxygen isotope and Al concentrations

44

indicate that interaction between fluids and wall rocks is a significant factor in

45

determining the compositions of fluids in Au mineralization, and the meteoric 2

46

water is a key proxy in Sb mineralization, respectively. From these observations,

47

we proposed that the Carlin-type Au deposit and vein-type Sb deposit in YMP

48

were sourced from an analogous ore fluid. Different lithologies of wall rocks and

49

the dilution of meteoric water controlled the compositional evolution of fluids,

50

which might be the main reason for the diversity of Au and Sb mineralization.

51 52

Keywords

53

Quartz, trace elements, oxygen isotopes, gold and antimony deposits, Youjiang

54

metallogenic province

55 56

1. Introduction

57

The Youjiang basin is an important Au-As-Sb-Hg metallogenic province in

58

the South China low-temperature metallogenic domain (LTMD; Tu, 2002; Hu et

59

al., 2017). The Youjiang metallogenic province (YMP) is characterized by the

60

occurrence of several Carlin-type Au, vein-type Sb, Hg, and As deposits.

61

Previous studies have been carried out to determine the sources of the ore-

62

forming fluids of the Carlin-type gold deposits. There still exist an argument

63

related to the origin of ore-forming fluids classified either meteoric (Hu et al.,

64

2002), metamorphic (Hofstra et al., 2005; Su et al., 2009a) or magmatic (Wang

65

et al., 2013; Tan et al., 2015; Large et al., 2016; Pi et al., 2017) fluids.

66

Furthermore, past findings have been documented that Sb mineralization and

67

Carlin-type Au mineralization have a similar age range (Peng et al., 2003; Su 3

68

et al., 2009b), tectonic setting (Hu and Zhou, 2012) and mineral paragenesis

69

(Wang, 2013; Chen et al., 2018), suggesting they may have a possible genetic

70

relationship. In the late mineralization of the Au deposit, a large amount of

71

stibnite is often associated with quartz, calcite, and realgar. Meanwhile, ring-

72

banded arsenian pyrite, which is the main Au-bearing mineral, can be seen in

73

the early quartz veinlets of Sb deposit.

74

Quartz is one of the most common minerals in hydrothermal ore deposits;

75

different generations of quartz record multiple fluids generations. Trace element

76

compositions of hydrothermal quartz have been used to constrain various

77

parameters of ore-forming fluids, such as temperature, pressure, pH and fluid

78

composition (Götze et al., 2004; Landtwing and Pettke, 2005; Rusk et al., 2008;

79

Müller et al., 2010; Tanner et al., 2013; Maydagán et al., 2015; Breiter et al.,

80

2017). Quartz also contains lots of fluid inclusions, and its isotopes are used to

81

determine fluid provenance (Imai et al., 1998; Allan and Yardley, 2007).

82

Traditionally, trace element and isotope analysis of quartz often use bulk

83

analysis, but multiple periods of quartz growing and mixing are widespread in

84

hydrothermal deposits. It is hard to distinguish different generations of quartz

85

by the naked eye or optical microscope. Many results from quartz bulk analysis

86

are multi-stage mixed data.

87

In this study, the scanning electron microscope cathodoluminescence

88

(SEM-CL) was used to identify different generations of quartz. Fluid inclusion

89

microthermometry was used to determine the temperature and salinity of the 4

90

quartz-depositing fluids. The laser ablation-inductively coupled plasma mass

91

spectrometry (LA-ICP MS) trace elements analyses of each generation of

92

quartz were carried out to constrain the various parameters of ore-forming fluids.

93

Also, the δ18O secondary ion mass spectrometry (SIMS) analysis was utilized

94

to reflect the fluid provenance. However, the mechanism of paragenesis and

95

separation of Au and Sb in the YMP is not precise. Thus, we choose a typical

96

Carlin-type Yata Au deposit and the largest vein-type Qinglong Sb-(Au) deposit

97

as a case study to discuss the sources of ore-forming fluids and identify the

98

genetic relationship between Au and Sb deposits in the YMP.

99 100

2. Geology of deposits

101

2.1 Regional geology

102

As shown in Fig. 1, the YMP is located in the southwestern margin of the

103

Yangtze Block. This triangular-shaped region is bounded by the Mile-Shizong

104

Fault to the northwest, the Shuicheng-Ziyun-Bama Fault to the northeast, and

105

the Youjiang Fault to the south. The basin is mainly covered by the strata from

106

Devonian to Triassic. The carbonate platform and deep-water basin

107

sedimentary system appeared from late Lower Devonian to Lower Triassic.

108

Lithologically, the platform facies are carbonate depositions and breccias, and

109

the basin facies are deep-water sedimentary rocks such as pelites and

110

silicolites (Hu and Zhou, 2012; Yan et al., 2018). Magmatic rocks are less

111

outcropped, but only the Late Permian dolerite intrusions (259Ma; Zhang and 5

112

Xiao, 2014), quartz porphyry dykes (140~130Ma; Zhu et al., 2016) and

113

lamprophyre dykes (88~85Ma; Liu et al., 2010) are revealed in the southeastern

114

and northern parts of this area. According to the gravity and magnetic data,

115

igneous intrusions might conceal at depths of 2~5 km (Zhou, 1993). There are

116

many low-temperature hydrothermal Au-Sb-Hg-As deposits, especially

117

numerous Carlin-type deposits, existing in this area, which is collectively

118

referred to as the “Dian-Qian-Gui golden triangle” (Tu, 1992).

119 120

2.2 Yata Au deposit geology

121

The Yata Au deposit is located on the south of the Nanpanjiang Fault. The

122

Middle Triassic Xinyuan Formation (T2x) and Bianyang Formation (T2b) are the

123

main strata exposed at the deposit. The Xinyuan Formation (T2x) contains

124

Member 1 (T2x1) and Member 2 (T2x2), wherein Member 1 comprises of

125

sandstone, siltstone with interbedded limestone, and Member 2 consists of

126

argillite and siltstone only. The Bianyang Formation (T2b) includes Member 1

127

(T2b1) and Member 2 (T2b2), in which Member 1 composes of sandstone with

128

interbedded limestone, and Member 2 is made up of sandstone and argillite.

129

Gold mineralization occurs in the calcareous siltstone and claystone of the

130

Xinyuan Formation and the Bianyang Formation (Su et al., 2009a). The deposit

131

is controlled by regional EW-trending folds and fractures (Fig. 2). The gold

132

mineralization occurs mainly on the southern limb of the Huangchang anticline,

133

extending about a 3 km EW along strike. All ore bodies are EW-trending, and 6

134

the average Au grade is 1~3 g/t. The lenticular, veins and veinlet-disseminated

135

zones within the broader envelope mineralization contain Au of 3~5 g/t. The

136

highest known Au grade of bulk samples is 50.7 g/t from the M1 ore body at

137

present (Zhang et al., 2003). From the hand specimens, there are no apparent

138

differences between gold ore and wall rocks. The gold occurs in arsenopyrite

139

and arsenian pyrite as submicroscopic particles. Based on the hypothesis of

140

previous studies, mineralization is classified into the main ore stage and late

141

stage. The main ore stage formed pyrite, arsenopyrite, arsenian pyrite, quartz,

142

and ferrodolomite, while the late stage includes stibnite, sphalerite, orpiment,

143

realgar, quartz, and calcite (Su et al., 2009a).

144 145

2.3 Qinglong Sb deposit geology

146

The Qinglong Sb deposit is located on the southeast of the Mile-Shizong

147

Fault (Fig. 3). The deposit contains eight ore blocks (Dachang, Shuijingwan,

148

Dishuiyan, Gulu, Houpo, Xishe, Sanwangping, and Heishanjing), which are

149

controlled by a dome structure associated with NE-trending faults (Huayujing

150

fault, Yezhutang fault, Qingshanzhen fault). Strata exposed at Qinglong deposit

151

are the Middle Permian Maokou Formation (P2m), “Dachang layer” (P2d), the

152

Upper Permian Emeishan flood basalt (P3β), and the Upper Permian Longtan

153

Formation (P3l). The Maokou Formation comprises shallow-marine platform

154

carbonate rocks. The Longtan Formation compose of interbedded sandstone

155

and shale. The Dachang layer where the antimony ore bodies exist lies 7

156

between the Maokou Formation and the Emeishan flood basalt. Lithologically,

157

it can be sectioned into lower, middle, and upper units. The lower unit consists

158

of high silicified limestone, siliceous rocks, silicified breccia, and detrital quartz.

159

The middle unit contains high silicified limestone, tuff, and brecciated basalt.

160

The upper unit is made up of tuffaceous clay, basalt, and basalt lens (Peng et

161

al., 2003). Besides, gold mineralization with Au grade 0.1~9.9 g/t developed in

162

the Dachang layer generally shows the co-occurrence of gold and antimony,

163

but antimony mainly (Chen et al., 2018). Based on field crosscutting occurrence

164

and mineral paragenesis, the mineralization of the Qinglong deposit can be

165

divided into the Au-arsenian pyrite ore stage, Sb ore stage, and late stage. The

166

Au-arsenian pyrite ore stage is characterized by pyrite, arsenian pyrite, and

167

quartz. The Sb ore stage is composed of stibnite, pyrite, jasperoid quartz,

168

quartz, fluorite, and kaolinite, while the late-stage consists of quartz, calcite,

169

orpiment, and realgar (Su et al., 2015).

170 171

3. Sampling and analytical methods

172

3.1 Samples

173

Au ore samples of the Yata deposit were collected from an open pit.

174

Samples from late-stage contain quartz-calcite veins of Yata deposit were

175

sampled from 940m adit. Samples of the Qinglong deposits were taken from

176

No. 1 adit and ZK-16 drill core of the Dachang ore block. The sampling locations

177

are marked in Fig. 2, and 3. Fifteen hand specimens (Table 1) were obtained 8

178

and cut into small pieces for thin sections. Each piece was chipped into two thin

179

sections, one for SEM-CL observation, in-situ LA-ICP MS and SIMS analysis,

180

and the other for fluid inclusion microthermometry.

181 182 183

3.2 Scanning electron microscope cathodoluminescence Scanning

electron

microscope

cathodoluminescence

(SEM-CL)

184

observation and imaging were carried out using a JEOL JSM-7800F thermal

185

field scanning electron microscope equipped with a Gantan Mono CL4

186

cathodoluminescence spectroscope at the State Key Laboratory of Ore Deposit

187

Geochemistry, Chinese Academy of Sciences, Guiyang. The polished thin

188

sections were carefully examined using an optical microscope to confirm the

189

positions before SEM-CL observation and imaging. The acceleration voltage

190

and beam-current density were 15 kV and 10 nA, respectively.

191 192

3.3 Fluid inclusion microthermometry

193

The samples were prepared as doubly polished thin sections.

194

Microthermometry was carried out using a Linkam THMSG600 heating-freezing

195

stage attached to an Olympus BX51 microscope at the State Key Laboratory of

196

Ore Deposit Geochemistry, Chinese Academy of Sciences, Guiyang. The

197

calibration of the instrument was regularly monitored using standard artificial

198

inclusion wafers. The estimated temperature measurement accuracy was ±0.1

199

℃. The warming rate was ≤15 ℃/min, and the warming rate was from 0.1 to 9

200

1 ℃/min near the phase transition point.

201 202

3.4 SIMS oxygen isotope

203

High-precision in situ oxygen isotope analyses were performed with a

204

Camerca IMS-1280 Ion Microprobe at the Institute of Geology and Geophysics,

205

Chinese Academy of Sciences, Beijing. Thin sections were made into targets

206

with NBS-28 (Matsuhisa, 1974) and Qinghu (Li et al., 2013) quartz standards,

207

then polished and coated with gold. A primary Cs+ ion beam of 10 kV, 2 nA was

208

rastered over a 10 μm area. The spot size was 10×20 μm in diameter. Oxygen

209

isotopes were counted with two off-axis Faraday cups. Detailed sample

210

preparation and instrument operation conditions are described in Li et al. (2010).

211

The method of calculating the δ18O is the same as Li et al. (2017). The weighted

212

mean δ18O value was calculated by Isoplot 3.70 with a rejection of any data

213

outside of the 2-sigma uncertainty (Ludwig, 2013). The precision is 0.2% (RSD),

214

and the detection limit is about 0.1ppm.

215 216

3.5 LA-ICP MS trace element

217

Targets for SIMS spots and some other thin sections were subsequently

218

analyzed using a GeoLasPro 193 nm ArF Excimer laser system combined with

219

an Agilent 7900 ICP MS instrument at the State Key Laboratory of Ore Deposit

220

Geochemistry, Chinese Academy of Sciences, Guiyang. For some SIMS spots

221

that were not suitable for LA-ICP MS analysis due to different spot sizes, the 10

222

same SEM-CL zones of the same quartz samples were selected to replace

223

them. The laser energy was 15-20 J/cm2, 10 Hz frequency. The spot size was

224

44 μm in diameter. The single spot was ablated for 30 seconds collection of

225

background signal and 60 seconds data. Twenty isotopes signals were

226

collected in this experiment, including 7Li, 9Be,

227

49Ti, 55Mn, 56Fe, 63Cu, 71Ga, 74Ge, 75As, 88Sr, 118Sn, 121Sb, 137Ba,

228

values were calculated by using NIST610 as an external standard and no

229

internal standard. The whole process of the experiment is shown in Lan et al.

230

(2017). The data was processed by ICPMSDataCal (Liu et al., 2008), and two

231

standard deviations (2-sigma) from the range of data were selected for analysis.

232

The precision is 0.1% (RSD). The detection limits of Li, Al, Ti and Ge are

233

0.06ppm, 0.1ppm, 0.08ppm, and 0.08ppm respectively. The detection limits of

234

other elements are listed in Appendix 1.

11B, 23Na, 27Al, 31P, 39K, 44Ca,

and 197Au. The

235 236

4. Results

237

4.1 Quartz textures visualized by SEM-CL

238

Using SEM-CL imagery on thin sections, four major quartz generations

239

were identified in the Yata deposit (YTi to YTiv) and Qinglong deposit (QLi to

240

QLiv), respectively. The mineralization stages related to the quartz generations

241

are indicated in Fig. 4.

242

The YTi stage is the early-stage milky quartz generation. Paragenetically,

243

the YTi quartz, which has a syngenetic relationship with pyrite and arsenopyrite, 11

244

predates the gold mineralization, or they form simultaneously. Some of YTi

245

quartz veins are cut by arsenopyrite-arsenian pyrite-quartz veinlets (YTii; Fig.

246

5A, Fig. 6A) and stibnite-realgar-orpiment-quartz veins (YTiii). In general, YTi

247

quartz luminesces darkly under the SEM beam. It is CL-homogenous with no

248

growth zonation and little variation in CL intensity (Fig. 6A). The YTii quartz

249

contains amounts of jasperoid quartz and arsenopyrite-arsenian pyrite-quartz

250

veinlets (Fig. 5D, Fig. 5E). The YTii jasperoid quartz associates with arsenian

251

pyrite closely and represents the main gold mineralization stage. The YTii

252

quartz is brighter than YTi quartz in CL images. The jasperoid quartz shows a

253

homogenous CL texture, while arsenopyrite-arsenian pyrite-quartz veinlets

254

present spider and cobweb texture alternating with dark and bright, which

255

suggests an activity of hydrothermal fluid (Fig. 6B, Fig. 6C). The YTiii quartz

256

veins that commonly contain fine-grained inclusions of stibnite (Fig. 5F), realgar

257

and orpiment are thicker than YTii veinlets. YTiii quartz shows irregular, wavy

258

CL textures, and the CL intensity is the brightest in the Yata deposit. It is easily

259

observed that YTiii quartz crosscut or overgrow the YTii quartz (Fig. 5B, Fig.

260

6C), which indicates the primary silica source for the precipitated YTiii quartz is

261

probably from the dissolution of YTii quartz. YTiv stage is the generation of

262

translucent crystal clusters (Fig. 5C). A large amount of realgar and orpiment

263

grows into the gap space of quartz crystal. The YTiv quartz show mosaic texture

264

and subhedral-euhedral growth zones of unclear oscillating CL intensity (Fig.

265

6D). 12

266

The QLi quartz always coexists with arsenian pyrite. We chose three ores

267

from the QLi stage and found that the Au grade could reach 5 g/t. Ring-banded

268

arsenian pyrite, which is the main Au-bearing mineral, can be seen in the QLi

269

quartz vein (Fig. 7G, Fig. 7H). Undoubtedly, the QLi stage represents the Au

270

ore stage of the Qinglong deposit. QLi shows dark and unclear oscillatory zones

271

of CL texture in general (Fig. 8A). QLii quartz, which is called jasperoid green

272

quartz, commonly associates with fluorite (Fig. 7A) and contains clumps of

273

stibnite (Fig. 7B). The CL textures of QLii are microcrystalline quartz with

274

irregular and wavy concentric patterns. The luminance of the CL imagery is

275

brighter than QLi quartz (Fig. 8B). QLiii quartz is the main paragenetic mineral

276

associated with stibnite (Fig. 7C, Fig. 7D) and crosscuts the QLii quartz (Fig.

277

7F). QLiii quartz shows CL dark breccias with CL bright overgrowths in general

278

(Fig. 8C). QLiv stage is the late quartz-calcite vein. It commonly cut the stibnite

279

and silicates wall rock (Fig. 7E). The quartz of the QLiv stage shows slightly

280

mottled to homogenous texture with CL dark intensity (Fig. 8D).

281 282

4.2 Fluid inclusion microthermometry

283

The micrographs show that numerous fluid inclusions concentrated at

284

5~12 μm are developed in the samples of the Yata deposit. However, only 32

285

vapour-liquid H2O inclusions and 30 vapour-liquid CO2-H2O inclusions could be

286

related to quartz generations of Yata deposit analyzed. Vapour-liquid H2O

287

inclusions are developed in each generation, and vapour-liquid CO2-H2O 13

288

inclusions are mainly developed in YTii generation and YTiii generation (Fig.

289

9A, Fig. 9B, Fig. 9C, Fig. 9D). Also, realgar and orpiment inclusions could be

290

encapsulated in numbers of regions of YTiii and YTiv quartz (Fig. 9E). There

291

are few fluid inclusions (≤5 μm) in quartz of the Qinglong deposit, only 4 fluid

292

inclusions in QLi quartz and 5 fluid inclusions in QLiii quartz were measured.

293

As mentioned above, fluid inclusions in quartz are microscopic compared to

294

other hydrothermal deposits (Fig. 9F). Therefore, the data are only used to

295

estimate the temperature ranges and salinities listed in Table 2 and may not

296

accurately represent the results. Besides, vapour-liquid H2O inclusions are rich

297

in fluorite, which has an intergrowth relationship with QLii quartz (Fig. 9G).

298

Hence, the microthermometry of fluorite is utilized to represent the QLii

299

generation.

300

Vapour-liquid H2O inclusions from YTi, YTii, and YTiii quartz record

301

homogenization temperatures of 196~263℃, 172~240℃, and 144~199℃

302

respectively. The ice melting temperatures of mentioned above fluid inclusions

303

range

304

Calculated fluid salinities (Hall et al., 1988) range from 3.74~7.43 wt％ NaCleq.,

305

3.35~6.79 wt ％ NaCleq., 2.38~6.79 wt ％ NaCleq. for YTi, YTii, and YTiii,

306

respectively, with averages of 6.1 wt％ NaCleq., 5.42 wt％ NaCleq. and 4.16 wt％

307

NaCleq., for YTi, YTii, and YTiii, respectively (Fig. 10).

from

-3.8~-2℃,

-3.5~-1.8℃,

and

-3.5~-1.3℃

correspondingly.

308

Microthermometric data for vapour-liquid CO2-H2O inclusions in the YTii

309

quartz are melting of CO2 at -60.8~-56.7℃, clathrate melting at 7.8~9.9℃, CO2 14

310

homogenization at 15.5~24.8℃, and final Th of 194~267℃. Microthermometric

311

data for vapour-liquid CO2-H2O inclusions in the YTiii quartz are melting of CO2

312

at -58.7~-56.1℃, clathrate melting at 7.7~9.4℃, CO2 homogenization at

313

18.8~28.2℃, and final Th of 202~231℃. Due to only 4 fluid inclusions in the

314

YTiii quartz, the microthermometric data between YTii and YTiii have no

315

obvious differences (Fig. 11). The calculated CO2 content in fluid inclusion

316

(Parry, 1986) ranges from 11.9~34.67 mol% and 9.08~12.73 mol% for YTii and

317

YTiii correspondingly, with averages of 19.7 mol% and 10.84 mol%,

318

respectively.

319

The homogenization temperatures of fluid inclusions in QLi quartz and QLiii

320

quartz range from 185~198℃ and 155~171℃, respectively. The ice melting

321

temperatures of fluid inclusions in QLi quartz and QLiii quartz range between -

322

3.7~2.4℃ and -1.5~-0.2℃, respectively. The fluid inclusions in fluorite

323

coexisting with QLii quartz have homogenization at 145~183℃ and melting at

324

-2.1~-0.1℃. The calculated fluid salinities (Hall et al., 1988) range from

325

4.53~7.22 wt％ NaCleq., 0.18~3.94 wt％ NaCleq., 0.36~2.77 wt％ NaCleq. for

326

QLi, QLii, and QLiii, respectively, with averages of 5.75 wt％ NaCleq., 1.95 wt％

327

NaCleq. and 1.57 wt ％

328

microspectroscopy analyses of fluid inclusions show that vapor phases of

329

arsenian pyrite-quartz veins consist primarily of H2O with minor CO2, and vapor

330

phases of stibnite-quartz veins are dominated by H2O(Chen et al., 2018).

331

NaCleq., in each case (Fig. 12). Laser Raman

In sum up, the metallogenic fluids of the Yata and the Qinglong deposits 15

332

are both characterized by low temperature and low salinity. Following the

333

mineralization, there is a gradual decline in temperature and salinity. The

334

metallogenic temperature and salinity of the Yata deposit are higher than the

335

Qinglong deposit overall, but the data of QLi are similar to YTi and YTii. CO2 is

336

rich in the Au metallogenic fluids of the Yata deposit and scarcely exists in the

337

Sb metallogenic fluids of the Qinglong deposit.

338 339

4.3 Trace element trends

340

A number of twenty trace elements were analyzed (Appendix 1);

341

specifically, elements of Ti, Li, Al, and Ge are mainly structurally hosted in

342

quartz and they could reflect the physical and chemical conditions of quartz

343

formation according to previous findings (Götze et al., 2004; Larsen et al., 2004;

344

Jacamon and Larsen, 2009; Lehmann et al., 2009; Götte et al., 2011; Audétat

345

et al., 2015; Breiter et al., 2017; Mao et al., 2017; Müller et al., 2018). As other

346

elements are prone to contamination by fluid and mineral inclusions, the main

347

discussions are focused on these four elements mentioned above.

348

Fig. 13 illustrates the variations of Ti, Li, Al, and Ge concentrations among

349

different quartz generations in the Yata and Qinglong deposits. The quartz from

350

the Yata deposit is similar to the Qinglong deposit with very low Ti

351

concentrations ranging from 0 to 2.23 ppm. Lithium concentrations generally

352

increase from early to late generations in the Yata deposit, from (0.1~10.3 ppm,

353

10.1~53 ppm, 14.1~98 ppm, and 33.1~124.9ppm) for YTi, YTii, YTiii, and YTiv 16

354

respectively. However, Li concentrations decrease in the ore-forming process

355

of the Qinglong deposit, from (3.5~63.4 ppm, 33.1~124.9ppm, 7.5~20.4 ppm,

356

and 8.6~14 ppm) for QLi, QLii, QLiii, and QLiv correspondingly. Aluminum

357

concentrations vary widely from a few ppm up to thousands ppm, with an

358

average of (210 ppm, 837.5 ppm, 1165.7 ppm, and 2489.5 ppm) for YTi, YTii,

359

YTiii, and YTiv accordingly. Also, the average contents of Al in the Qinglong

360

samples are (152.9 ppm, 4412.7 ppm, 3373.7 ppm, and 3302.7 ppm) for QLi,

361

QLii, QLiii, and QLiv respectively. Germanium concentrations of quartz from the

362

Yata deposit are one order larger than the Qinglong deposit. Germanium

363

contents range from (1.04~6.18 ppm, 1.77~11.97 ppm, 0.99~11.76 ppm,

364

and0.79~12.59 ppm) corresponding to YTi, YTii, YTiii, and YTiv while

365

approaching or being below the limit of detection in quartz from the Qinglong

366

deposit.

367

To other elements analyzed, B, Be, Mn, Cu, Ga, Sn, and Au are almost

368

undetectable. Quantification of B and P could be severely affected by

369

polyatomic interferences (Müller et al., 2008; Audétat et al., 2015). Sodium, K,

370

and Ca are abundant in fluid and mineral inclusions, Fe, As, and Sb can be

371

contaminated by pyrite, arsenopyrite, realgar, orpiment, or stibnite. Therefore,

372

it is hard to distinguish they are structurally hosted in quartz or contained in tiny

373

inclusions. Strontium and Barium concentrations vary from a few ppm to tens

374

of ppm in QLii, QLiii, and QLiv, but almost below 1 ppm in YTi, YTii, YTiii, YTiv,

375

and QLi. 17

376 377

4.4 Oxygen isotope data

378

In situ oxygen isotope ratios were determined to represent different quartz

379

generations of the Yata and Qinglong deposits (Appendix 2). Average δ18O

380

values in YTi, YTii, YTiii, and YTiv are 20‰, 25.09‰, 29.66‰, and 25.89‰,

381

respectively. Average δ18O values in QLi, QLii, QLiii, and QLiv are 19.49‰,

382

9.49‰, 7.98‰, and 5.93‰, respectively (Table 3). The δ18O values of the Yata

383

deposit increase from YTi to YTiii and decrease in YTiv. For the Qinglong

384

deposit, the δ18O values are elevated in QLi and then decrease sharply in QLii,

385

QLiii, and QLiv (Fig. 13).

386 387

5. Discussion

388

5.1 CL variability and causes of the trace elements diversity

389

The relationship between CL intensity and trace element concentrations in

390

hydrothermal quartz have been discussed in a few studies and they concluded

391

that CL intensity variations are almost always correlated with structurally bound

392

trace elements in quartz (Rusk and Reed, 2002; Götze et al., 2004; Landtwing

393

and Pettke, 2005; Rusk et al., 2011; Frelinger et al., 2015). In some porphyry

394

Cu deposits, CL intensity and Ti concentration are strongly positively correlated,

395

suggesting that the increased CL intensity is mainly caused by the substitution

396

of Ti4+ for Si4+ in high-temperature hydrothermal quartz (Donovan et al., 2011).

397

However, in low-temperature (＜300℃) hydrothermal quartz, owing to the low 18

398

abundance of Ti, CL intensity generally is relevant to the concentrations of Al

399

and correlated monovalent cations such as Li, K, P, and Fe (Rusk et al., 2008).

400

Table 3 shows CL and geochemical characteristics of quartz from each period

401

in the Yata and Qinglong deposits. The most abundant trace element in quartz

402

from these two deposits is aluminum. In relation to the CL images that contain

403

two generations of quartz (Fig.6, Fig.7), it could be inferred that the correlation

404

between Al and CL intensity is positive due to the brighter CL intensity of Al-

405

richer quartz. Other elements are not related to CL intensity.

406

Quartz Al concentrations increased following the ore-forming process in

407

the Yata deposit while they were low in QLi, but Al concentrations were highest

408

in QLii and then decreased following the Sb ore-forming process in the

409

Qinglong deposit. The hydrothermal quartz Al concentration depends on the

410

ionized Al in the fluid. Rusk et al. (2008) and Müller et al. (2010) suggest that

411

the content of the ionized Al increases with decreasing hydrothermal fluid pH.

412

Also, Lehmann et al. (2011) suggested the fluid's CO2 concentration has a more

413

critical impact on Al solubility in fluid rather than pH. The increasing CO2

414

concentration would lead to a decrease in Al solubility. The Au metallogenic

415

fluids contain rich CO2 in the Yata deposit, and CO2 content presents a

416

tendency to decrease during the ore-forming process. Due to the dissolution of

417

carbonate minerals in the wall rocks as the initial process of Carlin-type gold

418

deposition, which caused a lot of CO2 dissolving into fluids in the Yata deposit.

419

Jasperiod quartz and Fe-dolomite are commonly associated with arsenian 19

420

pyrite in the Yata deposit (Fig. 5E). According to Xie et al. (2018), dolomite-

421

stable alteration formed from weak acidic ore fluids in Carlin-type deposits in

422

the north of the YMP. With the gradual release of CO2 and the later formation

423

of carbonate, CO2 of the fluids decreased, and fluid pH went neutral.

424

Hence, the Al concentrations of quartz from the Yata deposit increased due

425

to the decreasing CO2. However, minor CO2 is captured in the fluid inclusions

426

of the Qinglong deposit. Kaolinite is the main gangue mineral identified with

427

stibnite-jasperoid quartz vein (QLii) of the Qinglong deposit (Chen et al., 2018).

428

According to Rusk et al. (2008), in 200℃ hydrothermal fluids, kaolinite is the

429

only stable Al-bearing mineral below the pH of 3.5, and muscovite presents at

430

higher pH. Therefore, the pH value of QLii Sb metallogenic fluids is considered

431

less than 3.5. These strong acidic fluids could be formed by dissolving a large

432

amount of Al-bearing acidic minerals of the Dachang layer. With the

433

neutralization of acidic fluids, the Al concentration decreases in late-stage

434

quartz of the Qinglong deposit. Consequently, quartz Al concentration is

435

strongly influenced by fluid’s CO2 content in the Yata deposit, and fluid’s pH is

436

the main controlling factor in the Qinglong deposit.

437

Rusk (2012) compared Ti and Al concentrations and Al/Ti ratios in

438

hydrothermal quartz among porphyry-type deposits, orogenic Au deposits, and

439

epithermal deposits and suggested that Ti and Al concentrations could

440

fingerprint the type of deposit. Fig. 14 shows the logarithmic Ti and Al plot in

441

quartz from each period of Yata and Qinglong deposits, and the concentrations 20

442

of Ti and Al in the Yata and Qinglong deposits exhibit similarities with those in

443

epithermal deposits. The possible reason is that physical and chemical

444

conditions for quartz crystallization are similar, such as low temperature

445

(<200℃) and/or low salinity and/or acidic pH of the fluid in epithermal deposits

446

(Huang and Audétat, 2012). The compiled data could be divided into the Au

447

mineralization part (YTi, YTii, YTiii, and QLi) and Sb mineralization part (QLii

448

and QLiii). It is noteworthy that data of YTi and QLi are overlapped, suggesting

449

that initial fluids of Yata deposit are similar to the Qinglong deposit, or they are

450

in the same physical and chemical conditions.

451

Lithium concentrations are positively correlated with Al both in the Yata and

452

Qinglong deposits. Generally, Li serves as a charge compensator for Al3+

453

substituting Si4+ in the quartz lattice (Rusk et al., 2011; Gotte et al., 2011). Molar

454

Al/Li ratios of most samples in the Yata deposit range between 1 to 10 and get

455

closer with 10. Meanwhile, the ratios in QLi are near 1, and the proportions in

456

QLii to QLiv are near 100. The differences of Al/Li ratios may be due to the

457

availability of Li+ in the hydrothermal fluid relative to other charge-balancing

458

elements such as H+, Na+, K+, and P5+ (Allan and Yardley, 2007). Besides, Sb

459

is likely to be present in the 5+ valence state, but the molar Sb/Al ratios are so

460

low (＜0.5%) that it has only little effect on charge-balancing (Rusk et al., 2011).

461

The molar (Al+Fe) vs. (Li+Na+K+P) diagram in Fig. 15C, and Fig. 15D

462

illustrates that the amount of substitutional Al3+ and Fe3+ corresponds to the

463

amount of Li+, Na+, K+, and P5+ for YTi and QLi. Comparing the molar ratios of 21

464

YTii-YTiv and QLii-QLiv, the molar ratios of (Al+Fe)/(Li+Na+K+P) in most of the

465

analyzed samples of the Qinglong deposit are larger than those of the Yata

466

deposit. Although the concentrations of Fe, Na, K, and P are not completely

467

accurate due to polyatomic interferences or presence of micro-inclusions, it

468

could be inferred that more H+ ions participate in the charge balancing of quartz

469

in the Qinglong deposit, which suggests that hydrothermal fluid pH of the

470

Qinglong deposit is lower than the Yata deposit.

471

Germanium is compatible with quartz and substitutes for Si4+ (Audétat et

472

al., 2015). Since Ge and Al are not incorporated together in a combined defect,

473

the correlation between Ge and Al is weak (Fig. 15E, Fig. 15F). Therefore, Ge

474

concentrations in quartz of the Yata and Qinglong deposits are strongly

475

controlled by the amount available Ge in the hydrothermal fluids. Germanium

476

cannot be concentrated in the magma process but could be transferred greatly

477

in the hydrothermal fluid system (Rakov, 2015). It is considered that the Ge/Al

478

ratio could distinguish between magmatic quartz and hydrothermal quartz

479

(Müller et al., 2018). Lehmann et al. (2011) proposed that the significant

480

sources of Ge in authigenic quartz cement are from pressure solution of detrital

481

quartz and feldspar. The YTi and QLi are strongly enriched in Ge (average 3.17

482

ppm for YTi and 3.01 ppm for QLi), whereas the average Ge in the upper crust

483

is 1.4 ppm (Rudnick and Gao, 2004). The enrichment could reflect the initial

484

ore-forming fluids of two deposits are Ge-riched and not direct products of

485

magma. During the metallogenic process, Ge concentrations in the Yata quartz 22

486

maintained slight growth, but those in Qinglong quartz decreased sharply. It

487

could be inferred that the variations of Yata quartz are caused by additional

488

sources of Ge from detrital quartz, feldspar or other Ge-bearing minerals (e.g.,

489

micas or illitization of kaolinite, Evans and Derry, 2002) in wall rocks and the

490

variations of Qinglong quartz are according to Pokrovskii and Schott (1998)

491

findings that the decreasing temperature could lead to the decreasing Ge

492

solubility in the hydrothermal fluid.

493

In addition, Sr and Ba contents vary from a few ppm to tens of ppm in QLii,

494

QLiii, and QLiv. A critical domain is that K and Ca concentrations in QLii, QLiii,

495

and QLiv also show one order of magnitude higher than QLi and each

496

generation of Yata deposit. Although these concentrations are easy to be

497

contaminated by micro-inclusions (Rusk et al., 2011), they also correlate with

498

Al contents. At least, it is proposed that these elements in hydrothermal fluids

499

of the Sb ore stage are more abundant than the Au ore stage. Aluminium, K,

500

Ca, Sr, Ba, or other lithophile elements might be injected into hydrothermal

501

fluids by the interaction between fluids and wall rocks that contain high

502

concentrations of soluble elements above in Sb ore-forming process. The levels

503

of these elements reach the highest values in QLii, which indicates that

504

interaction in this period was more drastic.

505 506 507

5.2 Oxygen isotope evaluation The main factors for a range of δ18O values of fluid are varying degrees of 23

508

fluid/rock exchange, temperature variations, fluid salinity, and fluid boiling

509

(Lubben et al., 2012). Fluid inclusion microthermometry indicates that the

510

temperature and salinity of the ore fluid remained constant in different

511

generations. Meanwhile, no evidence for fluid boiling was identified during

512

petrographic and fluid inclusion analysis. Thus, it seems that the variations of

513

oxygen isotope compositions in quartz from the Yata and Qinglong deposits are

514

not mainly caused by temperature variations, fluid salinity, and fluid boiling.

515

Host rock dissolution and fluid mixing may have been responsible for the

516

isotopic variations.

517

Based on the assumption that the fluid was in equilibrium with quartz

518

(Matsuhusa et al., 1979), the δ18O values of fluid were calculated using the

519

temperature of fluid inclusions. This calculation yields a range between

520

(7.70~10.56‰, 11.73~13.4‰, and 12.63~14.87‰) for YTi to YTiii, and

521

(4.66~8.75‰, -6.99~-3.85‰, and -10.06~-6.5‰) for QLi, QLii, and QLiii

522

respectively (Fig. 16).

523

The initial δ 18O values of fluids in Yata deposit (YTi: 7.70~10.56‰) and

524

Qinglong deposit (QLi: 4.66~8.75 ‰ ) are similar and indicate sources from

525

magmatic (5.5~10‰; Taylor, 1974) or metamorphic fluids (2~25‰; Taylor,

526

1974; Sheppard, 1981). In the Yata deposit, when the initial fluids migrated

527

through wall rocks dominated by the calcareous siltstone and claystone，the

528

relatively

529

included in the wall rocks would be decarbonized and dissolved into the ore

18O-enriched

carbonate minerals (24~27‰; Vaughan et al., 2016)

24

530

fluids. It may contribute to the higher δ 18O values in YTii and YTiii quartz. In

531

the Qinglong deposit, although the Dachang layer contains some silicified

532

limestone, the main wall rocks of tuff and brecciated basalt (-8.3~2.5 ‰; Wu,

533

2015) belong to 18O-depleted types. The interaction between ore fluids and the

534

Dachang layer may decrease the δ18O values in QLii and QLiii. In previous

535

studies, the general decrease in δ18O values is common in most Carlin-type

536

deposits, and this is attributed to the variable dilution of hydrothermal fluid by

537

meteoric water during the ore-forming process (Hofstra et al., 2005; Lubben et

538

al., 2012). From the YTii stage to YTiii stage, the variation of δ18Ofluid is slight,

539

but in the Qinglong deposit, it shows a severely decreasing trending. These

540

inferred that the dilution of meteoric water has limited influence on the Yata

541

deposit but plays a positive role in the Qinglong deposit.

542 543

5.3 Implications for interpreting Au and Sb mineralization

544

In previous studies, the Sb deposits and Carlin-type Au deposits in the

545

YMP show many similarities. Two types of deposits all lie in the Youjiang basin

546

and are controlled by a common tectonic setting (Hu and Zhou, 2012). The

547

mineral paragenesis of Au deposits and Sb deposits, which is an assemblage

548

of Au-As-Sb-Hg low-temperature minerals (Wang, 2013; Chen et al., 2018).

549

Peng et al. (2003) used Sm-Nd isotope dating of fluorites from the Qinglong

550

deposit and presented the metallogenic age of about 150 Ma. Although the

551

metallogenic epochs of Carlin-type Au deposits are still in debate, most 25

552

published works show Carlin-type Au deposits in the north of YMP were formed

553

in 148~125 Ma (Su et al., 2009b; Wang, 2013; Hu et al., 2017; Jin, 2017; Pi et

554

al., 2017; Su et al., 2018). Jin (2017) used Rb-Sr isotope dating of fluid

555

inclusions in quartz from the Yata deposit and reported the metallogenic age of

556

148.5±4.1 Ma. The similar geological features and mineralization age show that

557

Au and Sb have a close genetic link in the YMP.

558

By comparing trace elements and O isotope between YTi and QLi, the

559

similar characteristics of these suggest that initial fluids of the Yata and

560

Qinglong deposits are the same. Previous studies have proposed several

561

sources of ore fluids in Carlin-type gold deposits in the Youjiang basin (Hu et

562

al., 2002; Hofstra et al., 2005; Su et al., 2009a; Wang et al., 2013; Tan et al.,

563

2015). Most published conclusions are based on δD-δ18O bulk analysis of

564

quartz, calcite, or dolomite. However, multiple stages of quartz usually grew

565

together, and some quartz veins may or may not be ore-related. Consequently,

566

the bulk analysis would likely obtain mixing values and result in erroneous

567

characterization of the source fluid. In this study, different generations of quartz

568

were distinguished by SEM-CL imagery and analyzed by using in-situ methods,

569

which well avoided the interference of mixing values and could represent the

570

characteristics of fluids. The δ18Ofluid values of YTi and QLi indicate that the

571

initial metallogenic fluids are magmatic or metamorphic fluids. But relatively

572

high Ge concentrations of YTi and QLi do not support the magmatic model or

573

suggest that Ge-riched substances were injected into initial fluids during 26

574

magmatic-hydrothermal activities.

575

Since mixing of different isotopic fluid reservoirs may impart changes in

576

solute composition (Allan and Yardley, 2007), the covariability between

577

isotopes and trace elements of hydrothermal quartz may become markers to

578

record physical and chemical parameters of the fluid. Fig. 17 shows the

579

summary plot of logarithmic Al concentrations versus δ18Ofluid of Yata and

580

Qinglong deposits. These pairs of data were collected from the same positions

581

or the identical SEM-CL zones in the similar quartz samples. Three categories

582

are represented as initial fluid, Au metallogenic fluid, and Sb metallogenic fluid,

583

respectively. The covariability between Al concentrations and δ18Ofluid of Au

584

metallogenic fluid and Sb metallogenic fluid is obvious, suggesting that the

585

variation of δ18Ofluid may be related to the parameters controlling trace element

586

substitution into hydrothermal quartz. As discussed above, the disparities of Al

587

concentrations in the Yata and Qinglong deposits are different, which would be

588

interpreted by the varying CO2 in the Yata deposit and pH in the Qinglong

589

deposit. Meanwhile, the variations of δ18Ofluid in the two deposits are also

590

different, which would be interpreted by fluid-rock interaction in the Yata deposit

591

and involvement of meteoric water in the Qinglong deposit. Combining Al

592

concentrations and δ18Ofluid, it could be proven that interaction between fluids

593

and wall rocks is the primary influence to cause variations in compositions of

594

fluids in Au mineralization, while meteoric water is a major factor in Sb

595

mineralization, respectively. The increasing concentrations of most trace 27

596

elements during Au mineralization and the decreasing concentrations during

597

Sb mineralization could support this conclusion. In Au metallogenic period, the

598

persistent fluid-rock interaction would lead to continuous wall rocks dissolving

599

into fluids, which would increase the concentrations of trace elements. In Sb

600

metallogenic period, the dilution of meteoric water could decrease the

601

concentrations of trace elements. The recent in-situ analyses of sulfur isotope

602

also support this conclusion, the δ34S values of As-rich ring-band in arsenian

603

pyrite from the Yata deposit are 5~8‰ (Jin, 2017), and δ34S values of stibnite

604

and As-rich ring-band in arsenian pyrite from the Qinglong deposit are -6.9~2.9‰

605

(Chen et al., 2018). Besides, fluid inclusion images and concentrations of Al

606

and Li in quartz show that Au metallogenic fluids are CO2-riched and weakly

607

acidic, but Sb metallogenic fluids are CO2-free and strongly acidic. Therefore,

608

the differences in fluid evolution may be the main reason for the diversity of Au

609

and Sb mineralization.

610

6. Conclusions

611

We used coupled trace elements and oxygen isotope data, in conjunction

612

with fluid inclusion microthermometry and SEM-CL techniques, to characterize

613

different generations of quartz from the Yata Au and Qinglong Sb deposits. The

614

main findings of our study are as follows:

615 616 617

1. SEM-CL imagery was used to recognize different generations of hydrothermal quartz representing distinct mineralization stages. 2. The metallogenic fluids of the Yata and Qinglong deposits are both 28

618

characterized by low temperature and low salinity. Fluid inclusion images and

619

concentrations of Al and Li in quartz show that Au metallogenic fluids are CO2-

620

riched and weakly acidic, but Sb metallogenic fluids are CO2-free and strongly

621

acidic.

622

3. By comparing trace elements and O isotope between YTi and QLi, these

623

similar characteristics indicate that initial fluids of the Yata and Qinglong

624

deposits are comparable, which are magmatic fluids or metamorphic fluids. The

625

variations of δ18Ofluid in these two deposits are different, which would be

626

interpreted by fluid-rock interaction in the Yata deposit and involvement of

627

meteoric water in the Qinglong deposit.

628

4. The covariability of oxygen isotope and Al concentrations inferred the

629

interaction between fluids and wall rocks as a proxy to cause variations in

630

compositions of fluids in Au mineralization, and meteoric water is a

631

considerable influence in Sb mineralization, respectively.

632

5. From these, we conclude that the Carlin-type Au deposit and vein-type

633

Sb deposit in YMP have a similar fluid origin. Varied lithologies of wall rocks

634

and the dilution of meteoric water determine the evolution of fluids, which are

635

the main reason for the diversity of Au and Sb mineralization.

636

Acknowledgements

637

This study was jointly funded by the National Natural Foundation of China

638

(41830432,

639

(2014CB440900). We thank Yata Mine Ltd and Qinglong Mine Ltd for fieldwork

U1812402)

and

the

National

29

973

Program

of

China

640

support, Dr. Shaohua Dong for assistance in SEM-CL analysis, Dr. Yanwen

641

Tang for help in LA-ICP MS analysis, and Dr. Xiaoxiao Lin for support in SIMS

642

analysis. This paper is written to show our respect to Prof. Zhai Yusheng for his

643

90th anniversary.

30

644

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behaviour of trace elements in granitic pegmatite quartz from South Norway. Contrib.

705

Mineral. Petrol. 147, 615-628.

706

Lehmann, K., Berger, A., Götte, T., Ramseyer, K., Wiedenbeck, M., 2009. Growth related

707

zonations in authigenic and hydrothermal quartz characterized by SIMS-, EPMA-,

708

SEM-CL- and SEM-CC-imaging. Mineral. Mag. 73, 633-643

709

Lehmann, K., Pettke, T., Ramseyer, K., 2011. Significance of trace elements in syntaxial

710

quartz cement, Haushi Group sandstones, Sultanate of Oman. Chem. Geol. 280, 47-

711

57.

712

Li, X.H., Li, W.X., Li, Q.L., Wang, X.C., Liu, Y., Yang, Y.H., 2010. Petrogenesis and tectonic

713

significance of the similar to 850 Ma Gangbian alkaline complex in South China:

714

evidence from in situ zircon U-Pb dating, Hf-O isotopes and whole-rock geochemistry.

715

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716

Li, Y., Li, J.W., Li, X.H., Selby, D., Huang, G.H., Chen, L.J., Zheng, K., 2017. An Early

717

Cretaceous carbonate replacement origin for the Xinqiao stratabound massive sulfide

718

deposit, Middle-Lower Yangtze Metallogenic Belt, China. Ore Geol. Rev. 80, 985-1003. 32

719

Liu, S., Su, W., Hu, R., Feng, C., Gao, S., Coulson, I.M., Wang, T., Feng, G., Tao, Y., Xia,

720

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721

alkaline ultramafic dikes from southwest Guizhou Province, SW China. Lithos. 114,

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253-264.

723

Liu, Y.S., Hu, Z.C., Gao, S., Günther, D., Xu, J., Gao, C.G., Chen, H.H., 2008. In situ

724

analysis of major and trace elements of anhydrous minerals by LA-ICP-MS without

725

applying an internal standard. Chem. Geol. 257, 34-43

726

Lubben, J.D., Cline, J.S., Barker, S.L.L., 2012. Ore fluid properties and sources from quartz

727

associated gold at the Betze–Post Carlin-type gold deposit, Nevada, United States.

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729 730

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731

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732

Dabaoshan porphyry Mo deposit, South China: Insights from fluid inclusions,

733

cathodoluminescence, and trace elements in quartz. Econ. Geol. 112, 889-918.

734

Matsuhisa, Y., 1974. 18O/16O ratios for NBS-28 and some silicate reference samples.

735 736 737

Geochem. J. 8, 103–107 Matsuhisa, Y., Goldsmith, J., Clayton, R., 1979. Oxygen isotopic fractionation in the system quartz-albite-anorthite-water. Geochim. Cosmochim.Acta 43, 1131-1140.

738

Maydagán, L., Franchini, M., Rusk, B.G., Lentz, D.R., McFarlane, C., Impiccini, A., Ríos,

739

F.J., Rey, R., 2015. Porphyry to epithermal transition in the Altar Cu-(Au-Mo) deposit,

740

Argentina, studied by cathodoluminescence, LA-ICP-MS, and fluid inclusion analysis.

741

Econ. Geol. 110, 889-923.

742

Müller, A., Herklotzc, G., Gieglingc, H., 2018. Chemistry of quartz related to the

743

Zinnwald/Cínovec Sn-W-Li greisen-type deposit, Eastern Erzgebirge, Germany. J.

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Geochem. Explor. 190, 357-373.

745

Müller, A., Herrington, R., Armstrong, R., Seltmann, R., Kirwin, D.J., Stenina, N.G., Kronz,

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Mongolian porphyry-style deposits. Mineral. Deposita. 45, 707-727.

748

Müller, A., Wiedenbeck, M., Flem, B., Schiellerup, H., 2008. Refinement of phosphorus

749

determination in quartz by LA-ICP-MS through defining new reference material values.

750

Geostand. Geoanal. Res. 32, 361-376.

751

Parry, W.T., 1986. Estimation of XCO2, P and fluid inclusion volume from fluid inclusion

752

temperature measurements in the system NaCl-H2O-CO2. Econ. Geol. 81, 1009-

753

1013.

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Peng, J.T., Hu, R.Z., Jiang, G.H., 2003. Samarium-Neodymium isotope system of fluorites

755

from the Qinglong antimony deposit, Guizhou Province: constraints on the

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mineralizing age ore-forming materials’ sources. Acta Petrol Sin. 19, 785-791 33

757

(inChinese with English abstract).

758

Pi, Q.H., Hu, R.Z., Xiong, B., Li, Q.L., Zhong, R.C., 2017. In situ SIMS U-Pb dating of

759

hyrothermal rutile: reliable age for the Zhesang Carlin-type gold deposit in the golden

760

triangle region, SW China. Mineral. Deposita. 52, 1179-1190

761

Pokrovskii, G.S., Schott, J., 1998. Thermodynamic properties of aqueous Ge(IV) hydroxide

762

complexes from 25 to 350 °C: implications for the behavior of germanium and the

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Ge/Si ratio in hydrothermal fluids. Geochim. Cosmochim. Acta 62, 1631-1642.

764 765

Rakov, L.T., 2015. Role of Germanium in isomorphic substitutions in quartz. Geochem. Int. 53, 171-181.

766

Rudnick, R.L., Gao, S., 2004. Composition of the continental crust. In: Holland, H.D.,

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Turekian, K.K. (Eds.), Treatise on Geochemistry. vol. 3. Elsevier, Amsterdam, pp. 1–

768

65.

769

Rusk, B., Koenig, A., Lowers, H., 2011. Visualizing trace element distribution in quartz

770

using cathodoluminescence, electron microprobe, and laser ablation-inductively

771

coupled plasma-mass spectrometry. Am. Mineral. 96, 703-708.

772

Rusk, B., Reed, M., 2002. Scanning electron microscope-cathodoluminescence analysis

773

of quartz reveals complex growth histories in veins from the Butte porphyry copper

774

deposit, Montana. Geology 30, 727-730.

775

Rusk, B.G., 2012. Cathodoluminescence and trace elements in hydrothermal quartz. In:

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Götze, J., Möckel, R. (Eds.), Quartz: Deposits, Mineralogy and Analytics. Springer,

777

Berlin, pp. 307-329.

778

Rusk, B.G., Lowers, H.A., Reed, M.H., 2008. Trace elements in hydrothermal quartz:

779

Relationships to cathodoluminescent textures and insights into vein formation.

780

Geology. 36, 547-550.

781 782

Sheppard, T.M., 1981. Stable isotope geochemistry of fluids. Phys. Chem. Earth. 13, 419445

783

Su, W.C., Heinrich, C.A., Pettke, T., Zhang, X.C., Hu, R.Z., Xia, B., 2009a. Sediment-

784

Hosted gold deposits in Guizhou, China: products of wall-rock sulfidation by deep

785

crustal fluids. Econ. Geol. 104, 73-93.

786 787

Su, W.C., Hu, R.Z., Xia, B., Xia, Y., Liu, Y.P., 2009b. Calcite Sm-Nd isochron age of the Shuiyindong Carlin-type gold deposit, Guizhou, China. Chem. Geol. 258, 269-274.

788

Su, W.C., Zhu, L.Y., Ge, X., Shen, N.P., Zhang, X.C., Hu, R.Z., 2015. Infrared

789

microthermometry of fluid inclusions in stibnite from the Dachang antimony deposit,

790

Guizhou. Acta Petrol Sin. 31 (4), 918-924 (in Chinese with English abstract).

791

Su, W.C., Dong, W.D., Zhang, X.C., Shen, N.P., Hu, R.Z., Hofstra, A.H., Cheng, L.Z., 2018.

792

Carlin-type gold deposits in the Dian-Qian-Gui “golden triangle” of southwest China.

793

Reviews in Economic Geology, 20, 157-185

794

Tan, Q.P., Xia, Y., Xie, Z.J., Yan, J., Wei, D.T., 2015. S, C, O, H, and Pb isotopic studies 34

795

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796

for ore genesis. Chin. J. Geochem. 93, 525-539.

797

Tanner, D., Henley, R.W., Mavrogenes, J.A., Holden, P., 2013. Combining in situ isotopic,

798

trace element and textural analyses of quartz from four magmatic-hydrothermal ore

799

deposits. Contrib. Mineral. Petrol. 166, 1119-1142.

800 801 802 803

Tu, G.C., 1992. Some problems on prospecting of super large gold deposits. Acta Geol. Sichuan Spec. 12, 1-9 (in Chinese with English abstract). Tu, G.C., 2002. Two unique mineralization areas in southwest China. Bull. Mineral., Petrol. Geochem. 21, 1-2 (in Chinese).

804

Vaughan, J.R., Hickey, K.A., Barker, S.L.L., 2016. Isotopic, chemical and textual evidence

805

for pervasive calcite dissolution and precipitation accompanying hydrothermal fluid

806

flow in low-temperature, carbonate-hosted, gold systems. Econ. Geol. 111, 1127-1157

807

Wang, Z.P., 2013. Genesis and dynamic mechanism of the epithermal ore deposits, SW

808

Guizhou, China. A case study of gold and antimony deposits PhD thesis. Institute of

809

Geochemistry, Chinese Academy of Sciences, Guiyang, pp. 1-150 (inChinese with

810

English abstract).

811

Wang, Z.P., Xia, Y., Song, X.Y., Liu, J.Z., Yang, C.F., Yan, B.W., 2013. Study on the

812

evolution of ore-formation fluids for Au-Sb ore deposits and the mechanism of Au-Sb

813

paragenesis and differentiation in the southwestern part of Guizhou Province, China.

814

Chin. J. Geochem. 32, 56-68.

815

Xie, Z.J., Xia, Y., Cline, J.S., Alan, K., Wei, D.T., Tan, Q.P., Wang, Z.P., 2018. Are ther

816

Carlin-type gold deposits in China? A comparison of the Guizhou, China, deposits with

817

Nevada, USA, deposits. Reviews in Economic Geology, 20, 187-233

818

Yan, J., Hu, R.Z., Liu, S., Lin, Y.T., Zhang, J.C., Fu, S.L., 2018. NanoSIMS element

819

mapping and sulfur isotope analysis of Au-bearing pyrite from Lannigou Carlin-type

820

Au deposit in SW China: New insights into the origin and evolution of Au-bearing fluids.

821

Ore Geol. Rev. 92, 29-41

822

Zhang, X.C., Spiro, B., Halls, C., Stanley, C.J., Yang, K.Y., 2003. Sediment-hosted

823

disseminated gold deposits in Southwest Guizhou, PRC: their geological setting and

824

origin in relation to mineralogical, fluid inclusion, and stable-isotope characteristics.

825

Int. Geol. Rev. 45, 407-470.

826

Zhang, X.J., Xiao, J.F., 2014. Zircon U-Pb geochronology, Hf isotope and geochemistry

827

study of the Late Permian diabases in the northwest Guangxi autonomous region.

828

Bull. Mineral. Petrol. Geochem. 33, 163-176 (in Chinese with English abstract).

829

Zhou, Y.F., 1993. The application of regional gravity to the deep geology and mineralization

830

prognosis in Guangxi. Geol. Guangxi. 6, 15-24 (in Chinese with English abstract).

831

Zhu, J.J., Hu, R.Z., Richards, J.P., Bi, X.W., Stern, R., Lu, G., 2017. No genetic link

832

between Late Cretaceous felsic dikes and Carlin-type Au deposits in the Youjiang 35

833

basin, Southwest China. Ore Geol. Rev. 84, 328-337.

834 835 836 837 838 839 840 841 842 843 844 845 846 847 848 849 850

36

851

Figure Captions

852

Fig.1 Geologic map of Youjiang metallogenic province (YMF) in SW China (modified after

853

Hu and Zhou, 2012). NCC: North China Craton; YB: Yangtze Block; CB: Cathaysia

854

Block; IB: Indochina Block; SMS: Song Ma Suture; QL-DB: Qinling-Dabie

855

Fig.2 Geologic map of Yata deposit (modified after Zhang et al., 2003)

856

Fig.3 Geologic map of Qinglong deposit (modified after Chen et al., 2018)

857

Fig.4 Mineral paragenesis and related quartz crystallization sequence in the Yata and

858 859

Qinglong deposits observed in the study samples. Fig.5 Hand specimen photos and photomicrographs of minerals and their relationships in

860

the Yata deposit. Abbreviations: As-Py = arsenian pyrite; Real = realgar; Fe-Dol =

861

ferrodolomite; Stb = stibnite. (A) YTⅱ quartz vein crosscut YTⅰ milky quartz. (B) YTⅲ

862

quartz vein crosscut YTⅱ quartz vein. (C) Realgar filled in YTⅳ translucent crystal

863

quartz clusters. (D) YTⅱ quartz vein crosscut YTⅰ quartz. (E) Intergrowth relationship

864

of YTⅱ jasperoid quartz, arsenian pyrite and ferrodolomite. (F) Stibnite in YTⅲ quartz

865

vein.

866

Fig.6 SEM-CL textures of quartz in the Yata deposit. Abbreviations: As-Py = arsenian pyrite;

867

Real = realgar; Stb = stibnite. (A) YTⅱ quartz vein containing arsenian pyrite crosscut

868

dark CL-homogenous YTⅰ. (B) CL bright YTⅲ quartz-stibnite vein crosscut spider and

869

cobweb textural YTⅱ quartz. (C) CL bright YTⅲ quartz vein crosscut YTⅱ jasperoid

870

quartz. (D) YTⅳ quartz coexisting with realgar showed mosaic texture and subhedral-

871

euhedral growth zones of unclear oscillating CL intensity.

872

Fig. 7 Hand specimen photos and photomicrographs of minerals and their relationships in

873

the Qinglong deposit. Abbreviations: Py = pyrite; Fl = fluorite; Stb = stibnite; Cal =

874

calcite; Real = realgar; As-Py = arsenian pyrite. (A) QLⅱ quartz associating with fluorite

875

crosscut QLⅰ quartz-pyrite vein. (B) QLⅱ jasperoid green quartz contained clumps of

876

stibnite. (C) QLⅱ quartz coexisted with QLⅲ quartz and stibnite. (D) Stibnite in QLⅲ

877

quartz. (E) Realgar filled in the calcite-QLⅳ quartz vein. (F) QLⅲ quartz crosscut QLⅱ

878

quartz. (G) QLⅱ quartz crosscut QLⅰ quartz-pyrite vein. (H) Ring-banded arsenian

879

pyrite in the QLⅰ quartz. (I) QLⅱ quartz coexisted with QLⅲ quartz and stibnite.

880

Fig. 8 SEM-CL textures of quartz in the Qinglong deposit. Abbreviations: As-Py = arsenian

881

pyrite; Stb = stibnite; Cal = calcite. (A) QLⅰ quartz coexisting with arsenian pyrite

882

showed dark and unclear oscillatory zones of CL texture. (B) QLⅱ microcrystalline

883

quartz vein with irregular concentric patterns crosscut QLⅰ quartz. (C) Irregular and

884

wavy QLⅱ quartz coexisted with QLⅲ quartz and stibnite, QLⅲ quartz showed CL dark

885

breccias with CL bright overgrowths. (D) QLⅳ quartz coexisting calcite showed slightly

886

mottled to homogenous texture with CL dark intensity.

887

Fig. 9 Transmitted light images of fluid inclusions in Yata and Qinglong deposits. 37

888

Abbreviations: Real = realgar; Fl = fluorite. (A) LH2O-VH2O fluid inclusion in YTⅰ quartz.

889

(B) LH2O-LCO2-VCO2 fluid inclusion in YTⅱ quartz. (C) LH2O-LC2O fluid inclusions in YTⅱ

890

quartz. (D) LH2O-VH2O fluid inclusion and LH2O-LC2O fluid inclusion in YTⅲ quartz. (E)

891

Realgar inclusions in YTⅲ quartz. (F) LH2O-VH2O fluid inclusion in QLⅰ quartz. (G) LH2O-

892

VH2O fluid inclusions in fluorite coexisting with QLⅱ quartz.

893 894 895 896 897 898

Fig. 10 Histograms of homogenization temperatures and salinities of vapour-liquid H2O inclusions from the Yata deposit. Fig. 11 Histograms of homogenization temperatures and salinities of vapour-liquid CO2H2O inclusions from the Yata deposit. Fig. 12 Histograms of homogenization temperatures and salinities of vapour-liquid H2O inclusions from the Qinglong deposit.

899

Fig. 13 Variations in δ18O and concentrations of Li, Al, Ti, and Ge between different quartz

900

generations. The average concentrations shown as red spots are connected by a red

901

line.

902

Fig. 14 Logarithmic Ti versus Al plot of quartz of Yata and Qinglong deposits compared

903

with data from Rusk (2012) including porphyry-type Cu-Mo-Au deposits, orogenic Au

904

deposits, and epithermal Au deposits.

905 906

Fig. 15 Trace element chemistry of quartz in Yata and Qinglong deposits. Abbreviations: apfu = atoms per formula unit, ppma = parts per million atoms.

907

Fig. 16 Histograms of δ18Ofluid of different generations from Yata and Qinglong deposits.

908

Fig. 17 δ18Ofluid versus logarithmic Al plot of quartz of Yata and Qinglong deposits.

909 910 911 912 913 914 915 916 917 918

Fig. 1 38

919 920 921 922 923 924 925 926 927 928 929 930 931

Fig. 2 39

932 933 934 935 936 937 938 939 940 941 942 943 944 945 946 947

Fig. 3 40

948 949 950 951 952 953 954 955 956 957 958 959

Fig. 4 41

960 961 962 963 964 965 966 967 968 969 970 971 972

Fig. 5 42

973 974 975 976 977 978 979 980 981 982 983 984 985 986 987 988

Fig. 6 43

989 990 991 992 993 994 995 996

Fig. 7 44

997 998 999 1000 1001 1002 1003 1004 1005 1006 1007 1008 1009

Fig. 8 45

1010 1011 1012 1013 1014 1015 1016 1017 1018 1019 1020 1021

Fig. 9 46

1022 1023 1024 1025 1026 1027 1028 1029 1030 1031 1032 1033 1034 1035 1036

Fig. 10 47

1037 1038 1039 1040 1041 1042 1043 1044 1045 1046 1047

Fig. 11 48

1048 1049 1050 1051 1052 1053 1054 1055 1056 1057 1058 1059 1060 1061 1062

Fig. 12 49

1063 1064 1065 1066 1067 1068 1069 1070 1071 1072 1073

Fig. 13 50

1074 1075 1076 1077

Fig. 14 51

1078 1079 1080 1081 1082 1083 1084 1085 1086 1087 1088 1089 1090 1091 1092

Fig. 15 52

1093 1094 1095 1096 1097 1098 1099 1100 1101 1102 1103 1104

Fig. 16 53

1105 1106 1107 1108 1109 1110 1111 1112 1113 1114 1115 1116 1117 1118 1119 1120 1121 1122

Fig. 17 54

1123 1124 1125 1126 1127 1128 1129 1130 1131 1132 1133 1134 1135 1136 1137 1138

Table 1 Details of samples 55

Sample

Description

number Yata

YT-1

deposit

Mikly

quartz

veined

breccia

siltstone

contained

disseminated

arsenopyrite and pyrite YT-4

Thin translucent quartz vein crosscut milky quartz bulk

YT-9

Coarse quartz crosscut thin translucent quartz veins in siltstone

YT-12

Coarse quartz veined siltstone contained disseminated arsenopyrite and pyrite

YT-13

Translucent quartz veinlets in breccia siltstone contained disseminated pyrite

YT-21

Translucent crystal quartz and calcite clusters contained realgar and oripment

YT-22

Coarse quartz vein contained stibnite and little realgar

Qinglong

ZK16-10

Pyrite-baering quartz veinlets crosscut altered basalt

deposit

QL-3

Jasperiod quartz contained clumps of stibnite

QL-4

Translucent crystal quartz clusters contained realgar and oripment

QL-7

Coarse quartz-calcite vein contained little realgar and oripment

QL-11

Jasperiod quartz-fluorite crosscut pyrite-bearing quartz veinlets in altered basalt

QL-15

Jasperiod quartz contained translucent quartz-stibnite aggregation

QL-16

Translucent quartz-stibnite bulk

1139 1140 1141 1142 1143 1144 1145 1146 1147 1148 1149 1150

Table 2 Fluid inclusion microthermometry of different generations in Yata and Qinglong 56

1151

deposits. nr. of

Tm-ice

Th

Tm-CO2

Tm-clath

ThCO2

Th-tot

Salinity

analyse

(℃)

(℃)

(℃)

(℃)

(℃)

(℃)

wt.%NaCle

s YTi

8

quartz YTii

15

quartz

q

-3.8~

196~

-2

263

-3.5~

172~

-1.8

240

26 YTiii

9

quartz

-3.5~

144~

-1.3

199

4 QLi

4

quartz QLii

12

fluorite QLiii quartz

5

-3.7~

185~

-2.4

198

-2.1~

145~

-0.1

183

-1.5~

155~

-0.2

171

3.74~7.43 3.35~6.79 -60.8~

7.8~

15.5~

194~

-56.7℃

9.9

24.8

267

0.21~4.32 2.38~6.79

-58.7~

7.7~

18.8~

202~

-56.1

9.4

28.2

231

1.23~4.51 4.53~7.22 0.18~3.94 0.36~2.77

1152 1153 1154 1155 1156 1157 1158 1159 1160 1161 1162 1163 57

1164

Table 3 Comparison of the characteristic of quartz generations in Yata and Qinglong

1165

deposits. Abbreviations: SC = splatter and cobweb, OGZ = oscillatory growth zones, ICSP

1166

= irregular and wavy concentric patterns, DBBO = dark breccias with bright overgrowths. Yata deposit

Qinglong deposit

quartz

YTi

YTii

YTiii

YTiv

QLi

QLii

QLiii

QLiv

CL

low

low-

moderate-

moderat

low

bright

moderat

low

moderat

bright

e-bright

intensity

e-bright

e CL textures

average

homog

homoge

wavy,

mosaic,

OGZ,

IWCP

DBBO

homog

enous

nous, SC

dissolved

OGZ,

SC

228.38

205.67

162.11

192

169.75

163.6

6.1

5.42

4.16

5.75

1.95

1.57

3.51

28.73

41.15

21.5

14.91

13.85

10.52

enous

temperatur e average fluid salinity average Li

75.31

5 average Al

210

838

1166

2490

153

4413

3374

3303

average Ti

0.09

0.32

0.61

0.38

0.06

1.13

0.36

0.52

average Ge

3.17

6.06

4.21

7.2

0.17

0.32

0.34

0.26

average

20

25.82

27.17

25.89

19.5

9.81

8.52

6.35

8.72

13.13

11.09

5.85

-5.6

-7.43

δ18Oquartz average δ18Ofluid

1167 1168 1169

Highlights:

1170

1. The initial fluids of the Yata and Qinglong deposits are comparable.

1171

2. Interaction between fluids and wall rocks determines variations of

1172 1173

fluids in Au mineralization. 3. Meteoric water is a considerable influence in Sb mineralization.

1174 1175

58

1176 1177 1178 1179 1180 1181 1182

The summary plot of logarithmic Al concentrations versus δ18Ofluid of Yata and Qinglong deposits shows three categories represented as initial fluid, Au metallogenic fluid, and Sb metallogenic fluid. The Carlin-type Au deposit and vein-type Sb deposit in the YMP were similar in origin of ore fluids. Different lithologies of wall rocks and the dilution of meteoric water controlled the compositional evolution of fluids.

1183

Conflict of interest

1184

We declare that we do not have any commercial or associative interest

1185

that represents a conflict of interest in connection with the work

1186

submitted.

1187 1188 1189

59