Trace elements of pyrite and S, H, O isotopes from the Laowan gold deposit in Tongbai, Henan Province, China: implications for ore genesis

doi:10.1007/s11707-019-0807-3

Front. Earth Sci.

2020, Vol. 14

Issue (3) : 578-600 https://doi.org/10.1007/s11707-019-0807-3

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 CHEN^1,²(

), 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 $δ 18 O H 2 O$ 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 Issue Date: 04 December 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., 2020, 14(3): 578-600.

URL:

https://academic.hep.com.cn/fesci/EN/10.1007/s11707-019-0807-3
https://academic.hep.com.cn/fesci/EN/Y2020/V14/I3/578

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
Sample No.	Type	/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
Sample No.	Type	/ppm	/ppm	Co/Ni	/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.

Tab.2 Previous studies of d³⁴S isotope characteristics in the Laowan gold deposit

	Sample	d³⁴S_pyrite/‰	T/°C	$δ 34 S H 2 S$ /‰
Ore	Pyrite (PyI)	1.45	/	/
	Pyrite (PyI)	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	d¹⁸O_mineral/‰	$δ 18 O H 2 O$ /‰	$δD H 2 O$ /‰
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

δ 18 O H 2 O

for ore-forming fluids of the Laowan gold deposit (modified by Taylor, 1997). SMOW: standard mean ocean water.

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