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Frontiers of Earth Science

Front. Earth Sci.
RESEARCH ARTICLE
Trace elements of pyrite and S, H, O isotopes from the Laowan gold deposit in Tongbai, Henan Province, China: implications for ore genesis
Yuehua ZHAO1, Shouyu CHEN1,2(), Jianli CHEN3, Shuaiji WU1
1. Faculty of Earth Resources, China University of Geosciences, Wuhan 430074, China
2. State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, China
3. No. 1 Geological Exploration Institute, Henan Bureau of Geo-exploration and Mineral Development, Zhengzhou 450001, China
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Abstract

The Laowan deposit is a large gold deposit in the Qinling-Dabie orogenic belt where pyrite is the main Au-bearing mineral phase. We present results from the occurrences of gold, trace elements and sulfur isotopes of pyrite, and hydrogen and oxygen isotopes of quartz and calcite to elucidate the sources of ore-forming fluid; the genesis of pyrite and the ore-forming process.

From field observations, five generations of pyrite are identified; one formed in a metamorphic-diagenetic epoch (PyI), and the others during four mineralization stages: 1) the coarse-grained pyrite-quartz stage (PyII), 2) the quartz and medium- to fine-grained pyrite stage (PyIII), 3) the polymetallic sulfide stage (PyIV), and 4) the carbonate-quartz stage (PyV). Gold mainly occurs in PyIII and PyIV. We find that Au, Ag, Pb, and Cu are incorporated into pyrite as micro-/nano-inclusions and that Co, Ni, As, and Se enter the pyrite lattice via isomorphous replacement.

The Co/Ni values and Se concentrations indicate that PyI formed from metamorphic hydrothermal fluids and that pyrites (PyII, PyIII, and PyIV) from the ore-forming stages typically reflect a hydrothermal genesis involving magmatic fluid.

The d34S values of PyI (1.45‰–2.09‰) are similar to that of plagioclase amphibole schist, indicating that S was primarily derived from wall rock, while those of PyII, PyIII, and PyIV (3.10‰–5.55‰) suggest that S was derived from the Guishanyan Formation and the Laowan granite. The four mineralization stages show a systematic decrease in dD (from −77.1‰ to −82.8‰, −84.7‰, and −102.7‰), while the δ18 O H 2O values showed a gradual decrease from 5.7 to 2.7‰, 1.0‰, and −1.3‰. These data show that the ore-forming fluid was similar to a mixture of magmatic and meteoric waters. Thus, we conclude that the Laowan gold deposit is related to magmatic-hydrothermal fluid.

Keywords pyrite      trace elements      S-H-O isotopes      genesis      Laowan gold deposit     
Corresponding Author(s): Shouyu CHEN   
Online First Date: 30 July 2020   
 Cite this article:   
Yuehua ZHAO,Shouyu CHEN,Jianli CHEN, et al. Trace elements of pyrite and S, H, O isotopes from the Laowan gold deposit in Tongbai, Henan Province, China: implications for ore genesis[J]. Front. Earth Sci., 30 July 2020. [Epub ahead of print] doi: 10.1007/s11707-019-0807-3.
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http://journal.hep.com.cn/fesci/EN/10.1007/s11707-019-0807-3
http://journal.hep.com.cn/fesci/EN/Y/V/I/0
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Yuehua ZHAO
Shouyu CHEN
Jianli CHEN
Shuaiji WU
Fig.1  Regional geological map of the Laowan gold belt (modified from Liu et al., 2011; Yang et al., 2014b). 1—Nanwan Formation; 2—Guishanyan Formation; 3—Kuanping Group; 4—Erlangping Group; 5—Qinling Group; 6—Xionger Group; 7—Tongbai metamorphic gneissic complex; 8—High pressure rock pile; 9—Diorite; 10—Granite; 11—Fault; 12—Gold-silver deposit; 13—Study areaF1—Youfangzhuang fault; F2—Waxuezi fault; F3—Zhuxia fault; F4—Laowan-Songpa fault (Gui-Mei fault); F5—Tongbai-Shangcheng fault; F6—Xincheng-Huangpi fault
Fig.2  Geological map of the Laowan gold deposit (modified after Kou et al., 2016).
Fig.3  Mineral geological map of (a) W10 exploration line and (b) 204 exploration line (after preliminary report of No. 1 Geological Exploration Institute Henan Bureau of Geo-exploration and Mineral Development).
Fig.4  Stages of mineralization and mineral paragenesis in the Laowan gold deposit.
Fig.5  Mineral assemblage characteristics of the Laowan gold deposit in different metallogenic stages. Metamorphic-diagenetic epoch: (a) plagioclase amphibole schist hand specimen (LW01); (b) irregularly shaped pyrites aggregates; (c) pyrites present mineral orientation. Mineralization Stage I: (d) milky, massive and barren quartz veins with little pyrite (LW02); (e) pyrites present star-like or spot-like distributions in milky quartz veins; (f) cubic pyrite crystals. Mineralization Stage II: (g) quartz vein, mainly consisting of quartz and fine-grained pyrite; (h) hand specimen of quartz and sulfides (LW03); (i) chalcopyrite in cracks or along the edges of pyrites; (j) anhedral pyrrhotite with a light rose color encloses the earlier pyrite; (k) chalcopyrite and electrum in the fissure of pyrite. Mineralization Stage III: (l) quartz vein (Stage II) coexisting with polymetallic sulfides (Stage III); (m) polymetallic sulfide ore hand specimen (LW04); (n) Pyrite is bordered by chalcopyrite, and chalcopyrite exists as inclusions in sphalerite; (o) sphalerite appears as irregular shapes and are intergrown with pyrite, galena and chalcopyrite and arsenopyrite; (p) chalcopyrite, galena, sphalerite and native gold are in the crack of pyrite. Mineralization Stage IV: (q) the early quartz veins (Stage I) cut by the latest barren calcite-quartz vein (Stage IV); (r) calcite hand specimen (LW05); (s) calcite with little pyrite; (t) calcite and quartz. Py-pyrite, Elc-electrum, Gn-galena, Sp-sphalerite, Ser-sericite, Qz-quartz, Gl-gold, Amp-amphibole, Apy-arsenopyrite, Ccp-chalcopyrite, Po-pyrrhotite, Cc-calcite.
Fig.6  The occurrence of visible gold. PyII: (h) oval gold inclusions in pyrite. PyIII: (a) gold inclusion in chalcopyrite; (b) and (c) gold inclusions in the boundaries of sulfides. PyIV: (d) gold in the fissure of pyrite; (e) and (f) gold in cracks of sulfides; (g) and (i) anhedral granular, acicular and flake gold inclusions. Gl – gold, Py – pyrite, Qz – quartz, Ccp – chalcopyrite, Gn – galena, Sp – sphalerite
Fig.7  SEM images of PyII. (a) and (b) electrum in PyII. Elc – electrum, Py – pyrite, Qz – quartz.
Fig.8  SEM images of PyIII. (a), (b) and (c) irregular electrum in PyIII. Elc – electrum, Py – pyrite, Qz – quartz, Ccp – chalcopyrite.
Fig.9  SEM images of PyIV. (a), (b) and (c) gold inclusions in PyIII. Gl – gold, Sp – sphalerite, Elc – electrum, Py – pyrite, Qz – quartz, Ccp – chalcopyrite.
Sample No. Type S Fe As Au Ag Cu Zn Pb Co Ni Ge Bi Ti
/wt% /wt% /ppm /ppm /ppm /ppm /ppm /ppm /ppm /ppm /ppm /ppm /ppm
LW01-1 PyI 47.71 51.66 2988 0.04 0.19 2.4 0.5 14.6 1275 430 11.9 0.33 628
LW01-2 47.47 51.8 2415 0.1 2.4 3.7 0.42 28.2 194 159 11.6 2.6 11.1
LW01-3 45.69 53.91 1470 0.97 13.8 4.2 0.57 36.4 499 665 12 3.6 12.7
LW01-4 42.62 57.03 1636 0.15 0.09 5.5 0.69 8 690 907 11.6 0.18 11.1
LW02-1 PyII 41.06 58.74 218 11.2 49 22.3 0.08 279 342 39.1 13.2 37.2 8.9
LW02-2 39.28 60.43 806 16.5 53.5 11.8 0.68 188 123 748 15.2 8.1 8
LW02-3 42.86 57.01 409 6 19.5 4.2 0.19 61.9 44 67 14.2 7.2 10.2
LW02-4 42.06 57.67 761 96.3 337 29.4 0.3 282 163 245 12.7 16.4 8.9
LW02-5 42.45 57.29 965 14.1 56.9 41.5 0.06 263 23.8 227 13.6 11.3 9.4
LW02-6 44.54 55.22 539 10.8 33.3 98.3 0.18 364 83.6 548 11.3 18.3 8.6
LW02-7 40.82 58.9 324 47.8 125 30.3 0.01 734 80.9 176 12.4 30.4 7.3
LW02-8 44.98 54.72 592 24.2 80.5 162 1 744 206 201 10.8 32 10
LW03-1 PyIII 47.38 52.21 2534 0.77 9.2 120 0 88.8 83 23.4 13.6 1.5 10.5
LW03-2 44.36 54.72 2270 1159 1952 2568 1.6 199 97.2 44.6 13.4 3.3 7.1
LW03-3 45.44 54.26 2181 0.16 0.56 2.8 0 12.9 43.2 28.5 12.5 0.07 8.1
LW03-4 46.68 53 2077 0.3 2.2 3.6 0.54 57.1 39.3 27.3 12 0.82 8.4
LW03-5 47.72 51.86 812 19.6 21 1911 1.2 205 1.1 8.8 11.6 3.6 9.4
LW03-6 48.68 51.11 956 0.31 1.5 3.2 0.46 46.5 8.8 35.2 13.3 0.81 7.9
LW03-7 51.56 47.75 511 4.9 80.1 3616 1.7 160 12.5 18.5 10.5 5.8 9.6
LW03-8 50.24 49.67 175 1.7 9.5 3.4 0.44 26.4 76.2 4 11.4 1.4 8.9
LW03-9 52.34 46.78 532 8.1 132 7129 4.6 213 32.9 28.7 11.3 9.9 10.4
LW03-10 50.97 48.86 543 6.6 27.5 2.4 0 47.7 9.3 26.5 11.1 4.1 5.3
LW03-11 51.93 47.89 619 9.9 38.1 32.1 0.12 150 87 37.6 11.8 9.8 8.4
LW04-1 PyIV 53.58 45.85 673 4.9 90 2313 1.1 390 16.8 328 10.7 6.3 25.8
LW04-2 56.67 43.07 327 7.3 65.8 93 0.2 589 35.4 236 10.5 6.3 7.2
LW04-3 53.02 46.65 989 20.8 182 96.8 0.27 464 83.8 890 10.6 2.4 6.9
LW04-4 56.15 43.56 912 22.5 155 139 1.2 239 77 356 10.9 3.1 7.5
LW04-5 55.49 41.89 2302 10.6 279 3044 622 15221 3.3 77.3 9.6 19.9 5.7
LW04-6 57.56 40.57 1705 8.9 40.6 42.2 0.48 16392 0.98 41 11.2 16 6.5
LW04-7 55.64 43.9 1796 8.2 94.3 1116 0.84 603 0.4 34.9 10.9 2.8 8.2
LW04-8 59.97 39.79 980 2.5 14.6 33.8 0.13 124 25 297 10.1 1.1 8.5
LW04-9 57.92 41.77 2283 0.14 0.48 1.7 0 14.5 4.5 56.2 9.1 0.03 5.5
LW04-10 60.04 37.5 670 10.3 167 5437 14.9 16872 32.4 448 10 31.1 6.6
LW04-11 59.83 37.69 683 21.1 975 6715 1120 8797 164 305 9 48.3 3.8
LW04-12 60.48 38.65 188 4.1 42.9 807 2.4 5888 110 730 11.2 10.8 6
Sample No. Type Se Sb Co/Ni Mg Al Cr Tl Mn Sn Ba V W Zr
/ppm /ppm /ppm /ppm /ppm /ppm /ppm /ppm /ppm /ppm /ppm /ppm
LW01-1 PyI 9.9 0.3 2.97 32 69.2 5.5 0 0.4 0.67 0.41 0.5 0.29 0.36
LW01-2 0 0.84 1.22 41 709 5.3 0.03 2.1 11.6 1.9 0.27 0 0.05
LW01-3 18.5 0.25 0.75 45.4 124 9.4 0.05 0.66 14.5 0.73 0.1 0.01 0.13
LW01-4 4.4 0.11 0.76 9.6 39.6 28.8 0 1.2 1.2 0.52 0.21 0.04 0.08
LW02-1 PyII 0 9.6 8.75 0.59 5.6 3.8 0.03 0.65 0 0 0.19 0 0
LW02-2 3.1 5.2 0.16 0.39 2 3.5 0.05 0 0 0.21 0.04 0 0.01
LW02-3 12.5 3 0.66 0.22 2.6 3.4 0.06 0 0 0.14 0.01 0 0.08
LW02-4 14.8 9.3 0.67 0.69 2.1 1.2 0.03 2.2 0.25 0.56 0.03 0.01 0
LW02-5 20.5 10.6 0.1 0.13 43.8 3.9 0.05 0.11 0.46 0.12 0.02 0.01 0.03
LW02-6 20.8 12.8 0.15 0.42 1.4 0.43 0.02 1.7 0.35 0.11 0 0 0.02
LW02-7 3.7 13.9 0.46 1.5 10.4 8 0.04 0.06 0.06 0.04 0 0.25 0
LW02-8 13.2 22 1.02 2.9 1.9 0.83 0.08 4.6 0.44 0.53 0 0.13 0
LW03-1 PyIII 29.8 6.2 3.55 0.32 0 1.6 0 0.83 0.22 1.1 0 0 0.01
LW03-2 21.7 12.2 2.18 1.5 15.7 3.4 0.05 0 0.15 0.11 0.02 0 0.3
LW03-3 20.1 0.39 1.52 0.77 1.3 5.4 0.01 1.3 0.1 0 0.07 0 0
LW03-4 6.7 3.1 1.44 0.48 1.8 4.3 0 0 0.29 0.18 0 0.02 0.06
LW03-5 6.1 13.5 0.13 0.66 1.4 6.2 0.04 0 0.24 0.16 0 0 0.04
LW03-6 17.3 3.2 0.25 0.31 1.5 2.7 0.01 0.59 0.45 0.07 0.04 0.01 0.06
LW03-7 0 11.4 0.68 0 1.7 1.2 0.06 16.4 0 0.27 0.09 0.02 0
LW03-8 27.2 1.4 19.05 0 0.28 9.2 0 26.7 0.32 0 0.02 0 0
LW03-9 26.9 16.7 1.15 0.59 0.71 0.22 0.05 33.3 0 0.05 0.02 0.01 0.01
LW03-10 18.3 2.5 0.35 0.63 0.72 0 0 0.68 0.09 0.04 0.1 0.01 0.01
LW03-11 7.2 6.4 2.31 0 1 1.3 0.04 0.27 0.18 0 0.06 0.03 0.03
LW04-1 PyIV 12.9 14.4 0.05 2 20.3 4.3 0.04 3.6 0.38 0.06 0.18 4.3 0.05
LW04-2 24.3 17 0.15 0.85 1.8 0.25 0.04 0 0.13 0.17 0.05 0 0.01
LW04-3 5.7 8.6 0.09 1.3 5.6 1.4 0.04 0.32 0 0.06 0 0 0.01
LW04-4 41.9 9.3 0.22 1.4 13.5 19.3 0.03 0.8 1.2 0.06 0.05 0 0.01
LW04-5 0 2883 0.04 0.05 0.13 0 0.14 52.9 0 0.28 0.04 0.02 0
LW04-6 11.1 20 0.02 1.2 4.2 0.64 0.03 0 1.1 0.03 0 0.01 0.01
LW04-7 35.1 10.6 0.01 0.24 1.9 4.5 0.01 0.44 0.18 0.06 0 0 0.02
LW04-8 16 4.6 0.08 0.4 0.16 1.9 0.02 0 0.07 0.06 0 0 0
LW04-9 0 0.66 0.08 0.82 0.25 0.87 0 0 0.23 0 0.06 0.03 0.02
LW04-10 20.5 88.4 0.07 0.41 0.05 0.81 0.09 1.7 0.63 0.04 0.04 0 0.02
LW04-11 1.8 4808 0.54 0.48 0.74 0 0.2 2.5 0.55 0.42 0 0 0
LW04-12 26.75 13.8 0.15 0.51 2.7 6.5 0.03 0 0.66 0.1 0.04 0.01 0.03
Tab.1  LA-ICPMS analyses of selected pyrite grains from the Laowan gold deposit
Fig.10  Representative time-resolved depth profiles for pyrite analyzed in this study indicating the occurrences of gold and other major metal elements.
Fig.11  Binary plots of (a) Ag vs. Au, (b) As vs. Au, (c) Bi vs. Au, (d) Ni vs. Au, (e) Pb vs. Au, (f) Cu vs. Au, (g) Sb vs. Au, (h) Pb vs. Ag, (i) Bi vs. Ag, (j) Sb vs. Ag, (k) Ni vs. Co, (l) Zn vs. Cu in different pyrite types. The trace element concentrations are from Table 1.
Fig.12  Binary plots of Co/Ni vs. Au/Ag.
Fig.13  Correlation diagrams of Pb/Co and Au/Co, Ag/Co and Bi/Co ratios for all the LA-ICP-MS analyses showing good correlations. Correlation coefficients (R) are given in the figures.
Objects Samples d34S/‰ (n) Reference
Ore Pyrite 1.43.8 (4) Chen (2017)
Guishanyan Formation Whole rock 2.5 (1)
Laowan Granite Whole rock 3.7 (1)
Ore Pyrite 2.9–5.8 (17)
Ore Galena 1.9–4.4 (3)
Ore Sphalerite 3.3 (1)
Ore Chalcopyrite 4.9 (1)
Guishanyan Formation Pyrite 3.6–4.3 (5)
Ore Pyrite 2.9–6.0 (21) He and Wang (2005)
Ore Galena 1.69–2.69 (3)
Ore Sphalerite 3.33 (1)
Ore Chalcopyrite 4.9 (1)
Guishanyan Formation Pyrite 3.63–4.26 (5)
Guishanyan Formation Galena 2.78 (1)
Alterated rocks-quartz vein Pyrite 2.9–5.9 (29) Yang et al. (2014b)
Galena 1.7–2.8 (4)
Sphalerite 3.3 (1)
Chalcopyrite 4.9 (1)
Tab.2  Previous studies of d34S isotope characteristics in the Laowan gold deposit
Sample d34Spyrite/‰ T/°C δ34 S H 2S/‰
Ore Pyrite (PyI) 1.45 / /
2.09 / /
Pyrite (PyII) 3.49 337 2.42
3.40 337 2.33
3.10 337 2.03
4.21 337 3.14
Pyrite (PyIII) 5.17 256 3.74
5.48 256 4.05
4.43 256 3.00
5.55 256 4.12
Pyrite (PyIV) 4.12 225 2.51
3.87 225 2.26
4.04 225 2.43
3.95 225 2.34
4.02 225 2.41
Tab.3  d34S isotope characteristics of pyrites and fluid in the Laowan gold deposit
Fig.14  d34S of the pyrites in Laowan gold deposit.
Sample No. Mineral Stages of mineralization Homogenization temperature*/°C d18Omineral/‰ δ18 O H 2O/‰ δDH2 O/‰
LWB-1-2 quartz I 337 11.8 6.1 −76.8
LWB-1-4 quartz 10.9 5.2 −77.4
Average 11.35 5.65 −77.1
LWB-2-1 quartz II 256 11 2.3 −85.6
LWB-2-5 quartz 11.8 3.1 −83
LWB-2-6 quartz 10.8 2.1 −79.4
LWB-2-11 quartz 11.8 3.1 −83.2
Average 11.35 2.65 −82.8
LWB-3-1 quartz III 225 10.8 0.6 −77.8
LWB-3-2 quartz 11.5 1.3 −86.3
LWB-3-3 quartz 11.4 1.2 −90
Average 11.23 1.03 −84.7
LWB-4-1 calcite IV 153 11 −0.9 −108.9
LWB-4-2 calcite 10.2 −1.7 −96.5
Average 10.6 −1.3 −102.7
Tab.4  H and O isotope characteristics of different stages of mineralization in the Laowan gold deposit
Fig.15  Plot of dD versus δ18 O H 2O for ore-forming fluids of the Laowan gold deposit (modified by Taylor, 1997). SMOW: standard mean ocean water.
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