黄铜矿微量元素对矿床成因类型的指示

王启林; 张金阳; 严德天; 闵红; 刘曙; 李晨

doi:10.19509/j.cnki.dzkq.2021.0090

黄铜矿微量元素对矿床成因类型的指示

doi: 10.19509/j.cnki.dzkq.2021.0090

王启林^1,,
张金阳^1, ,,
严德天¹,
闵红²,
刘曙²,
李晨²

1.
中国地质大学(武汉)资源学院, 武汉 430074
2.
上海海关工业品与原材料检测技术中心, 上海 200135

基金项目:

国家重点研发计划 2018YFF0215402

国家自然科学基金面上项目 41572048

详细信息

作者简介:
王启林(1995— )，男，现正攻读矿产普查与勘探专业博士学位，主要从事成因矿物学的研究工作。E-mail：wangqilin@cug.edu.cn

通讯作者:
张金阳(1977— )，男，教授，博士生导师，主要从事岩浆岩石学与矿床学研究工作。E-mail：zhangjinyang@cug.edu.cn

中图分类号: P618.4
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- 文章访问数: 652
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- 被引次数: 0
出版历程
- 收稿日期: 2021-07-07

Genesis type of ore deposits indicated by trace elements of chalcopyrite

1.
School of Earth Resources, China University of Geosciences(Wuhan), Wuhan 430074, China
2.
Technical Center for Industrial Product and Raw Material Inspection and Testing, Shanghai Customs, Shanghai 200135, China

摘要

摘要:
金属矿物微量元素对矿床形成过程和成因类型具有重要指示作用，目前对黄铁矿、磁铁矿及闪锌矿研究较多，黄铜矿微量元素特征鲜有报道。根据收集的斑岩型铜矿床(PCD)、岩浆型铜镍硫化物矿床(MSD)、沉积岩型层状铜矿床(SSC)、铁氧化物铜金矿床(IOCG)、喷流沉积型矿床(SEDEX)及火山成因块状硫化物矿床(VMS)铜精矿样品，结合资料，对黄铜矿开展了详细矿相学和LA-ICP-MS微量元素研究，揭示黄铜矿微量元素特征及其与矿床成因类型的关系。黄铜矿中Mn，Co，Ni，Se，Ag，Sn，Pb及Bi质量分数可达1 000×10^-6以上，Ga，Ge，Mo，Cd，In，Sb，Te，Au及Tl质量分数可达100×10^-6以上，说明黄铜矿是很多微量元素的重要载体。黄铜矿Sb-Tl，In-Sn，Pb-Bi及Mn-Ni呈明显的正相关关系，其中Sb，Tl，In及Sn主要以固溶体的形式赋存于黄铜矿，Pb与Bi以方铅矿包裹体的形式赋存于黄铜矿，Mn，Co，As，Te，Ag及Ni 2种赋存状态均有发育。PCD型和VMS型黄铜矿微量元素变化大，MSD型黄铜矿中Ni质量分数高，In质量分数较低，SSC型黄铜矿Ge质量分数高，Sn质量分数较低。Se在MSD型和VMS型黄铜矿中质量分数较高，在SEDEX型和SSC型黄铜矿中质量分数较低。Ni，In，Sn元素差异主要与不同类型岩浆作用有关，Se元素质量分数差异主要受温度控制，SSC型黄铜矿Ge元素质量分数高可能与成矿温度和赋矿围岩有关。因此，基于上述微量元素特征，Ni-Co和Ni-In图解可区分MSD型和其他类型，Ni-Se图解可区分SEDEX型，SSC型及VMS型，Ge-Sn图解可进一步区分SSC型和SEDEX型，Co/Ni-Ag/Bi图解可区分MSD型和PCD型，Zn-Sn/In在一定程度上可区分IOCG型和其他类型。这些首次系统地提出的图解将为判别矿床成因类型提供新的参考。
- 黄铜矿 /
- 微量元素 /
- 矿床成因类型 /
- 赋存状态 /
- LA-ICP-MS /
- 判别图解
Abstract:
Trace elements of metallic minerals are important to constrain the formation processes and genetic types of ore deposits. Trace elements have been mainly focused on pyrite, magnetite, and sphalerite but have rarely been applied to chalcopyrite. To reveal the relationships between chalcopyrite trace elements and ore deposit types, ore petrography and LA-ICP-MS trace element of chalcopyrite in collected copper concentrate samples from porphyry copper deposits (PCD), magmatic copper-nickel sulfide deposits (MSD), sedimentary rock-hosted stratiform copperdeposits (SSC), iron oxide copper-gold deposits (IOCG), sedimentary exhalative deposits (SEDEX) and volcanogenic massive sulfide deposits (VMS) have been carried out. In chalcopyrite, Mn, Co, Ni, Se, Ag, Sn, Pb, and Bi contents are more than 1 000×10^-6, and Ga, Ge, Mo, Cd, In, Sb, Te, Au and Tl contents are up to 100×10^-6, which together indicate chalcopyrite is an important carrier for many trace elements. Antimony-Tl, In-Sn, Pb-Bi, and Mn-Ni in the chalcopyrite are positively correlated.Meanwhile, in chalcopyrite, Sb, Tl, In, and Sn mainly occur in the form of solid solution, Pb and Bi in the form of galena inclusions, and Mn, Co, As, Te, Ag, and Ni are both developed. Trace elements of chalcopyrite from PCD and VMS are variable. The concentrations of Ni and In in chalcopyrite from MSD are high and low, and Ge and Sn from SSC are higher and lower than other types, respectively. Moreover, the concentration of Se in chalcopyrite is higher from MSD and VMS, but is lower from SEDEX and SSC. Different concentrations of Ni, In, and Sn in the chalcopyrite are mainly related to different magmatism, and Se is principally controlled by temperature. The high concentrations of Ge in chalcopyrite from SSC may be related to ore-forming temperature and host rocks.Therefore, based on the above trace elements characteristics, Ni-Co and Ni-In diagrams can distinguish MSD from other deposit types, the diagram of Ni-Se can differentiate SEDEX, SSC from VMS, and the diagram of Ge-Sn is used to isolate SSC from SEDEX. In addition, the diagram of Co/Ni-Ag/Bi can differentiate between MSD and PCD, while Zn-Sn/In can discriminate IOCG from others to some extent.These first systematically proposed diagrams will provide a new reference for distinguishing the genetic types of deposits.
- chalcopyrite /
- trace elements /
- genetic type of deposit /
- occurrence /
- LA-ICP-MS /
- discriminant diagram

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图 1 铜精矿产地分布图

Figure 1. Distribution map of copper concentrate origin

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图 2 铜精矿样品及典型矿相结构照片

a.样品信息牌；b.MSD中镍黄铁矿、磁黄铁矿和黄铜矿共生；c.IOCG中黄铜矿与磁黄铁矿接触边界平直，大致共生；d, e.IOCG中磁铁矿被斑铜矿半包裹；e.SEDEX中磁黄铁矿和磁铁矿被黄铜矿半包裹；f.磁铁矿与黄铜矿接触边界平直，大致共生；g~h.PCD中辉钼矿和斑铜矿多呈单体；i.与粗粒黄铜矿共生的闪锌矿出溶黄铜矿；j.VMS中黄铜矿包裹黄铁矿，又被闪锌矿尖角交代；k.黄铜矿的同心环带结构，环带之间被闪锌矿充填；l.SSC中大量斑铜矿出现。Bor.斑铜矿；Ccp.黄铜矿；Mag.磁铁矿；Mol.辉钼矿；Pn.镍黄铁矿；Po.磁黄铁矿；Py.黄铁矿；Sp.闪锌矿。括号内为样品号

Figure 2. Photos of copper concentrate samples and typical mineragraphy

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图 3 黄铜矿微量元素箱形图

Figure 3. Box diagram of trace elements in chalcopyrite

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图 4 不同类型矿床黄铜矿微量元素箱形图(数据来源见表 3)

Figure 4. Box diagrams of trace elements in chalcopyrite from different types of deposits

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图 5 黄铜矿微量散点图

a~d.Sb-Tl、Pb-Bi、In-Sn和Ni-Mn在VMS、PCD、IOCG等矿床中均呈正相关；e~h.Au-Te、Sb-As、Zn-In、Zn-Mn等主要在VMS和PCD中呈正相关；i.Co-As并没有明显的相关性

Figure 5. Scatter diagrams of trace elements in chalcopyrite

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图 6 黄铜矿典型LA-ICP-MS剥蚀信号剖面图(括号内为质量分数，10^-6)

Figure 6. Representative single-spot LA-ICP-MS spectra for selected elements in chalcopyrite(number in bracket is concentration)

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图 7 黄铜矿微量元素判别图解

Figure 7. Discrimination diagrams of trace elements in chalcopyrite

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表 1 铜精矿产地及矿床成因信息

Table 1. Origin and genesis of samples of copper concentrate

类型	国家	编号	矿床(区)	资料来源
IOCG	澳大利亚	Cu-18	Mim	文献[27]
	澳大利亚	Cu-19	Eloise	文献[27]
	巴西	Cu-26	Antas North	文献[28]
	巴西	Cu-27	Sossego
	巴西	Cu-68-1	Salobo
	秘鲁	Cu-05	Condestable	文献[29]
MSD	澳大利亚	Cu-66-1	Nova	文献[30]
MSD	中国	X11-2	Xiarihamu	文献[31]
PCD	智利	Cu-13	Escondida	文献[32]
	智利	Cu-14	Los Pelambres	文献[33]
	印度尼西亚	Cu-30	Grasberg	文献[34]
	墨西哥	Cu-23	Cananea	文献[35]
	墨西哥	Cu-42	Buenavista	文献[35]
	秘鲁	Cu-06	Antamina	文献[36]
	秘鲁	Cu-07	Las Bambas	文献[37]
	秘鲁	Cu-09	Toromocho	文献[38]
	秘鲁	Cu-10	Cerro Verde	文献[39]
	老挝	Cu-28	Phu Kham	文献[40]
	美国	Cu-24	Sierrita	文献[41]
SEDEX	澳大利亚	Cu-50-1	Kanmantoo	文献[42]
SSC	中国	TD-2	Tangdan	文献[43-44]
SSC	刚果	Cu-51-3	Kinsenda	文献[45]
VMS	澳大利亚	Cu-21	Tritton	文献[46]
	澳大利亚	Cu-22	Cobar	文献[47]
	厄立特里亚	Cu-29	Bisha	文献[48]
	西班牙	Cu-43	Aguas Tenidas	文献[49]
未知	刚果	Cu-100-1	Kapuio	未知
未知	巴西	Cu-93-1	Para	未知

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表 2 黄铜矿LA-ICP-MS微量元素组成

Table 2. Trace element concentrations in chalcopyrite determined by LA-ICP-MS w_B/10^-6

样品	Cu-18				Cu-19					Cu-26						Cu-27
编号	1	2	3	4	1	2	3	4	5	1	2	3	4	5		1
Ti	1.54	2.02	0.41	1.52	12.9	4.42	1.96	BDL	3.36	0.36	BDL	3.51	0.46	2.46		2.06
Cr	28.6	166	51.7	104	14.2	15.9	4.3	1.3	47.1	2.1	52.9	87.0	16.4	35.2		BDL
Mn	0.85	0.05	BDL	0.32	4.84	2.74	2.90	1.30	1.75	1.31	0.98	38.8	BDL	4.54		BDL
Co	4.42	0.84	1.86	3.94	2.27	8.76	1.67	3.09	7.09	1.47	2.82	8.52	0.32	5.20		0.14
Ni	0.15	0.01	0.36	0.10	22.0	18.0	43.1	58.5	44.2	44.6	0.64	85.4	0.47	111		35.9
Zn	79.3	30.6	169	1818	868	525	1 269	653	392	715	923	1295	418	843		179
Ga	0.09	0.02	0.29	0.19	1.20	0.12	0.25	0.21	0.24	0.48	0.14	0.31	0.05	0.11		0.32
Ge	1.83	1.15	1.44	0.64	0.32	0.68	1.32	0.92	BDL	0.94	0.73	0.38	0.72	0.59		1.10
As	24.7	BDL	7.24	BDL	1.24	11.2	11.9	BDL	18.7	1.24	BDL	3.55	BDL	2.94		1.35
Se	164	41.6	44.8	6.72	16.1	17.1	15.9	16.0	14.0	37.8	48.5	67.3	40.3	68.1		23.9
Mo	BDL	BDL	0.36	0.30	BDL	0.80	BDL	BDL	BDL	BDL	BDL	BDL	0.05	BDL		0.11
Ag	2.14	0.08	0.09	42.7	92.0	151	10.4	6.53	160	7.48	100	42.6	23.5	16.8		11.9
Cd	BDL	0.44	0.70	2.33	3.58	3.05	2.01	2.42	3.64	2.60	4.49	6.18	0.58	3.92		BDL
In	5.07	176.1	5.12	14.4	33.0	16.6	33.9	19.3	10.4	3.85	2.79	4.62	1.03	5.04		6.91
Sn	113	0.22	56.9	7.93	44.9	22.8	24.1	18.1	15.5	28.3	1.51	25.0	0.25	5.80		10.6
Sb	0.62	0.59	0.90	2.49	2.45	4.77	0.40	0.42	2.27	0.06	0.52	BDL	0.39	BDL		0.27
Te	2.17	0.57	9.85	0.19	2.36	0.99	0.77	1.32	1.25	1.96	1.53	0.98	1.14	2.71		0.58
Au	BDL	BDL	0.07	BDL	2.16	0.76	0.01	0.03	0.39	0.01	BDL	BDL	BDL	0.04		0.02
Tl	BDL	0.07	0.13	0.21	0.13	0.19	0.02	0.02	0.56	0.06	0.13	0.04	0.03	BDL		0.02
Pb	2.50	0.10	3.57	15.5	41.0	25.4	2.47	14.3	25.9	3.48	20.0	70.2	2.99	11.1		3.42
Bi	1.06	2.42	13.2	4.08	16.8	18.6	1.15	0.92	27.9	0.13	0.48	0.90	0.19	0.27		0.39

样品	Cu-27				Cu-68-1				Cu-05				Cu-66-1
编号	2	3	4	5	1	2	3	4	1	2	3	4	1	2		3
Ti	2.18	1.72	157	2.87	1.85	0.79	3.13	1.48	0.75	0.01	0.79	1 756	17.5	0.20		2.24
Cr	32.5	25.1	143	6.6	1 108	411	456	962	46.5	80.2	35.9	182	3 368	93.5		1 634
Mn	0.67	BDL	13.3	0.85	6.30	11.1	3.70	7.13	.90	6.00	39.2	143	28.4	14.9		6.11
Co	0.09	0.16	2.43	0.01	21.1	1.39	0.52	10.6	0.60	0.45	3.33	1.41	20.6	0.64		4.36
Ni	0.37	0.31	15.2	0.01	2.22	2.05	0.59	11.1	0.92	0.50	0.23	1.91	742	318		176
Zn	87.6	65.5	25.9	187	673	1 730	1 371	1 069	1 201	123	1 654	617	389	531		406
Ga	0.03	BDL	0.60	0.03	24.3	22.1	20.8	0.08	1.43	BDL	1.22	5.87	0.42	0.23		0.23
Ge	0.90	0.66	1.39	0.64	26.2	2.53	2.57	1.49	BDL	1.42	1.88	3.21	3.15	2.47		2.58
As	1.14	0.38	3.78	BDL	22.6	39.5	BDL	16.6	56.3	80.2	10.1	93.9	4.81	2.65		4.36
Se	33.5	25.6	32.7	24.8	26.7	35.2	42.4	5.76	10.5	6.35	12.2	22.6	38.2	42.4		44.4
Mo	0.27	BDL	5.83	BDL	2.48	3.98	0.57	6.47	0.32	0.20	BDL	1.60	2.32	0.11		3.58
Ag	0.23	0.18	4.19	31.4	4.39	44.3	82.6	129	442	14.9	1.98	9.62	26.7	17.7		47.0
Cd	0.61	0.95	BDL	0.09	1.27	7.19	4.93	3.94	9.18	0.95	9.84	6.35	30.5	18.3		14.1
In	1.84	4.96	2.27	2.19	13.2	39.2	42.2	0.17	697.4	2.92	90.6	36.4	1.31	0.91		0.79
Sn	0.15	0.71	0.04	BDL	221	155	171	3.58	1025	0.66	81.6	412	3.36	5.66		2.97
Sb	0.42	0.01	0.42	0.32	14.9	6.04	1.25	8.98	8.20	6.06	3.68	13.3	6.04	2.30		10.6
Te	0.15	0.13	0.83	0.73	0.34	1.31	0.23	0.25	1.65	1.23	2.17	1.41	7.51	8.94		4.28
Au	0.06	BDL	0.31	0.04	0.16	0.07	0.08	0.13	0.07	0.07	0.13	0.15	0.16	BDL		BDL
Tl	0.01	BDL	0.02	0.01	BDL	0.10	0.04	0.11	0.04	0.06	0.34	0.23	0.11	BDL		BDL
Pb	2.07	1.97	10.5	2.62	23.9	472	5.57	330	145	101	44.6	190	15.3	4.18		28.8
Bi	0.24	0.38	0.81	1.73	1.59	42.9	1.38	20.6	24.1	20.8	1.43	41.4	2.22	0.44		2.34

样品	Cu-66-1		X11-2				Cu-13			Cu-14				Cu-30
编号	4	5	1	2	3	4	1	2	3	4	5	6	7	1		2
Ti	2.70	1.32	BDL	BDL	0.65	0.64	2.07	100	62.8	44.5	47.4	28.6	35.1	213		8.42
Cr	2 107	1 145	34.8	25.9	37.2	2.0	72.1	4.7	58.5	213	654	197	77.5	32.0		367
Mn	8.29	3.85	69.3	2.59	1537	3.11	4.88	2.65	15.4	6.58	5.35	12.5	6.36	236		34.6
Co	2.86	4.33	15.9	0.06	32.8	0.01	3.00	0.92	1.08	7.29	1.82	8.89	1.18	18.0		37.8
Ni	147	219	1 289	8.12	2 407	5.64	0.41	0.11	0.55	0.83	1.76	2.28	1.44	2.12		0.70
Zn	334	233	852	455	1 139	358	1 365	347	2 849	29.6	13.4	118	21.5	292		91.6
Ga	0.06	BDL	0.01	0.01	0.11	0.03	0.33	0.59	1.84	0.49	0.77	1.12	0.58	3.85		1.59
Ge	3.08	1.61	3.15	2.65	1.69	3.48	2.56	1.42	4.23	2.46	3.17	0.12	2.83	4.04		3.83
As	2.54	3.63	4.82	1.53	27.4	1.53	59.3	25.1	BDL	83.0	49.6	37.7	280	24.4		BDL
Se	36.6	39.5	30.8	53.1	33.5	20.5	115	62.3	165	65.0	190	200	142	296		163
Mo	3.60	1.22	0.30	0.06	0.27	0.03	1.05	0.82	1.04	25.0	85.7	40.3	14.2	4.01		3.59
Ag	19.4	20.6	4.32	1.05	1.81	0.48	12.3	4.62	30.5	20.8	17.4	112	7.44	49.8		24.1
Cd	13.1	13.6	4.88	2.72	6.90	4.02	6.07	1.17	1.36	1.67	BDL	3.40	1.32	5.71		0.68
In	0.61	0.01	1.55	1.32	1.41	0.32	2.56	9.88	4.71	3.35	2.81	2.79	6.23	13.7		2.45
Sn	2.94	0.54	0.37	0.55	BDL	0.24	1.67	1.09	5.44	22.5	BDL	29.1	1.03	31.0		35.7
Sb	7.58	3.08	0.42	1.50	1.46	0.35	2.94	0.84	1.86	3.50	1.32	5.39	3.78	1.18		2.35
Te	0.92	2.63	0.79	0.52	0.38	0.24	1.59	0.88	2.07	0.81	4.21	0.37	0.83	10.1		2.17
Au	0.05	BDL	0.06	0.04	BDL	0.02	BDL	0.04	0.04	0.03	BDL	0.27	0.01	0.94		0.18
Tl	0.01	BDL	0.07	BDL	0.05	0.03	0.03	0.09	0.04	0.07	0.09	0.09	0.05	0.57		0.07
Pb	18.0	16.6	27.5	29.3	33.3	11.8	213	39.1	255	32.2	49.1	98.7	117	619		303
Bi	1.31	2.71	0.35	0.65	1.30	0.42	3.07	1.11	8.80	6.28	38.9	5.65	6.88	55.1		3.34

样品	Cu-30				Cu-23				Cu-42					Cu-06
编号	3	4	5	6	1	2	3	4	1	2	3	4	5	1		2
Ti	21.5	107	158	29.2	8.21	470	11.2	75.3	0.91	25.8	1.00	0.14	BDL	2.86		3.80
Cr	49.9	828	28.3	524	71.4	1 345	317	430	98.3	291	41.1	1.6	0.5	1.8		54.2
Mn	17.2	48.0	296	111	2.29	107	4.24	13.7	34.7	34.3	21.5	2.69	1.64	6.98		129
Co	29.7	47.5	16.2	27.3	0.53	1.10	1.12	6.27	4.47	3.63	0.84	0.04	0.07	21.4		94.7
Ni	0.42	2.20	4.05	2.12	0.57	2.02	1.22	6.21	56.8	0.92	0.98	0.01	0.01	0.31		74.1
Zn	182	161	324	270	223	1 481	1 311	2 536	2 202	1 271	5 033	1 704	1 483	1 159		3 342
Ga	0.93	2.96	2.43	1.30	0.64	6.40	0.85	4.45	0.42	0.74	0.72	0.53	0.46	0.79		0.61
Ge	2.31	4.60	1.59	BDL	1.62	4.09	4.12	1.24	1.86	2.82	2.14	1.59	2.41	1.11		0.90
As	BDL	BDL	27.3	53.6	62.6	34.0	17.5	57.7	13.7	28.9	36.7	2.21	BDL	2.48		17.8
Se	450	408	375	226	73.3	54.2	74.1	22.4	87.3	57.6	53.7	46.4	46.9	40.6		55.3
Mo	1.35	3.19	9.05	47.2	0.11	8.52	0.82	18.1	1.69	15.3	3.32	BDL	BDL	0.10		16.4
Ag	9.91	11.0	28.1	25.5	44.0	30.5	8.29	24.4	14.5	24.7	34.9	1.65	1.69	217		246
Cd	3.20	1.92	8.02	2.57	6.12	17.1	11.3	19.1	15.8	15.4	21.1	5.57	5.23	5.64		10.9
In	7.21	7.89	8.15	6.04	43.3	28.7	24.2	33.8	12.8	19.8	36.7	27.5	28.7	76.1		24.4
Sn	48.0	46.3	20.3	39.4	3.06	4.26	4.14	4.83	19.5	29.1	7.24	5.09	4.38	44.0		7.66
Sb	1.65	10.8	0.28	1.06	52.3	44.8	6.40	23.0	6.09	109	7.04	0.10	0.41	0.13		11.0
Te	1.11	5.69	6.39	4.71	1.88	9.27	2.41	2.83	0.90	0.49	1.31	0.99	0.70	1.06		3.10
Au	0.14	0.19	0.86	0.21	0.03	0.02	0.01	BDL	BDL	BDL	0.11	0.02	BDL	BDL		0.11
Tl	0.02	0.17	0.40	0.31	0.83	0.90	0.14	1.18	0.13	1.14	0.25	0.02	0.03	BDL		2.19
Pb	155	193	1353	420	12.5	308	36.6	226	24.9	664	77.7	0.93	0.55	3.51		300
Bi	3.23	9.01	11.8	12.0	17.3	46.3	15.0	26.3	5.27	7.66	2.90	0.83	0.76	3.02		130

样品	Cu-06		Cu-07					Cu-09				Cu-10
编号	3	4	1	2	3	4	5	1	2	3	4	1	2	3		4
Ti	7.32	3.75	BDL	0.05	2.43	10.03	BDL	BDL	0.73	44.6	4.65	4.67	1252	4.03		4.65
Cr	11.7	19.1	4.6	2.2	50.5	27.7	7.5	22.5	36.8	28.1	208	95.3	193	54.7		14.8
Mn	18.6	5.79	2.35	0.94	5.08	5.81	2.27	BDL	2.79	0.48	15.2	5.85	16.8	4.02		4.23
Co	0.58	87.5	0.35	2.31	0.46	3.32	0.47	BDL	0.19	BDL	3.50	0.79	0.91	0.12		0.40
Ni	0.42	3.37	0.12	0.01	0.22	0.57	0.01	0.01	0.06	0.29	0.01	0.64	0.57	0.01		0.35
Zn	1 301	8 197	110	BDL	156	23.5	3.61	188	1881	158	1692	310	1085	104		152
Ga	0.33	0.15	0.42	BDL	1.57	0.07	0.10	4.76	22.4	0.61	0.44	0.57	0.18	0.34		0.30
Ge	0.96	1.44	0.75	1.86	1.57	0.55	1.82	0.84	1.62	0.60	0.95	1.14	1.03	0.66		1.22
As	18.1	6.92	2.68	BDL	4.88	29.6	0.97	2.85	33.9	46.2	127	42.3	29.1	4.92		87.9
Se	46.1	21.0	49.3	185	75.9	36.7	118	27.0	15.2	59.4	45.5	54.4	34.5	36.2		17.9
Mo	899	BDL	1.38	BDL	18.6	23.0	BDL	BDL	0.25	0.12	1.54	0.51	1.63	0.05		0.52
Ag	89.0	269	17.0	5.86	18.5	8.11	2.12	0.43	11.9	5.04	8.62	1.37	3.91	5.07		0.29
Cd	4.12	24.0	0.07	0.29	0.60	BDL	0.08	1.61	7.58	4.65	17.4	2.59	10.6	2.40		4.60
In	45.0	23.5	2.19	1.85	2.61	2.20	2.88	13.0	80.8	6.09	13.1	5.22	15.0	9.84		7.08
Sn	4.57	18.4	2.57	9.37	15.4	9.49	4.53	186	273	1.94	38.0	1.12	3.84	1.44		1.45
Sb	4.53	0.54	0.11	BDL	4.63	0.43	0.22	0.14	1.97	2.84	41.4	3.26	4.10	0.49		0.85
Te	1.86	0.54	7.05	2.21	5.41	11.3	2.26	0.93	0.72	BDL	4.05	1.99	1.04	0.27		1.09
Au	BDL	BDL	BDL	BDL	0.18	0.06	BDL	0.04	BDL	BDL	0.03	0.01	0.03	BDL		0.01
Tl	1.46	0.08	BDL	BDL	0.10	1.26	0.04	BDL	1.05	0.17	0.18	0.07	0.19	0.09		0.02
Pb	179	7.62	4.04	2.32	11.6	13.0	16.8	3.59	44.6	10.0	102	58.6	53.1	123		5.01
Bi	73.3	6.75	0.44	BDL	5.37	1.60	0.13	0.79	2.54	3.00	12.1	1.44	3.28	1.73		0.19

样品	Cu-10	Cu-28				Cu-24					Cu-50					TD-2
编号	5	1	2	3	4	1	2	3	4	5	1	2	3	4		1
Ti	23.5	BDL	BDL	3.25	5.53	418	9.51	4.18	46.9	1.46	0.24	0.07	0.34	0.37		BDL
Cr	52.6	167	78.9	731	118	680	108	227	449	14.9	1.1	1.4	0.4	2.4		2.4
Mn	0.95	0.18	0.90	4.02	2.79	0.53	2.63	BDL	10.5	0.41	2.52	2.79	2.81	5.89		0.81
Co	0.05	0.12	BDL	0.33	0.05	1.45	0.31	0.53	4.55	0.02	10.5	4.34	5.25	1474		3.57
Ni	0.01	BDL	0.03	0.75	0.46	0.95	0.02	BDL	2.48	0.11	0.20	1.95	1.45	162		0.53
Zn	129	176	250	1146	203	198	115	99.5	555	262	735	1196	3097	1033		10.7
Ga	0.16	0.03	0.13	0.10	0.10	0.35	5.03	0.29	0.57	0.13	0.28	0.14	0.16	0.17		0.97
Ge	1.80	2.48	1.12	6.45	1.12	0.12	0.57	1.15	0.89	1.20	1.85	2.09	1.95	2.81		49.4
As	29.2	8.52	6.95	37.7	29.2	2.10	5.22	4.86	26.8	1.33	3.74	3.14	2.67	0.95		2.94
Se	33.7	29.5	37.2	29.0	39.9	53.0	59.9	37.6	25.2	32.8	9.07	22.3	20.3	10.9		24.2
Mo	0.09	0.36	0.91	2.02	0.22	48.6	23.0	56.2	741	0.34	BDL	0.01	BDL	BDL		0.08
Ag	1.01	13.0	9.77	28.8	15.6	20.7	146	72.0	78.5	1.29	17.2	52.6	51.0	90.4		2.63
Cd	2.59	2.03	3.13	6.39	1.08	2.28	BDL	0.89	3.55	3.20	1.21	2.72	3.99	1.04		0.08
In	13.8	2.10	1.67	8.02	5.34	10.3	17.6	12.8	11.9	13.0	23.3	42.3	48.2	25.5		0.47
Sn	1.18	BDL	1.25	4.32	0.22	19.4	8.85	2.93	4.56	8.88	19.4	84.1	85.8	78.4		0.88
Sb	1.47	2.02	1.67	5.39	7.11	1.70	4.48	2.32	51.2	0.36	BDL	0.01	0.18	1.23		0.17
Te	0.62	0.87	0.41	3.17	1.28	0.41	0.30	0.39	0.99	0.43	0.10	1.44	1.38	0.10		BDL
Au	BDL	BDL	0.04	0.09	0.22	0.09	BDL	0.08	0.11	BDL	0.09	0.14	0.10	0.16		0.01
Tl	BDL	BDL	0.02	0.04	0.08	0.08	0.05	0.03	0.26	0.06	0.01	0.02	BDL	0.36		BDL
Pb	18.4	23.6	47.1	166	40.6	18.8	55.8	109	190	0.69	1.43	0.38	0.48	7.97		4.81
Bi	1.30	8.19	5.33	6.07	30.7	2.48	4.86	8.35	16.6	0.33	2.84	4.18	3.05	7.30		0.06

样品	TD-2			Cu-51-3		Cu-21						Cu-22
编号	2	3	4	1	2	1	2	3	4	5	6	1	2	3		4
Ti	BDL	21.6	2.04	1.97	0.42	1.17	0.14	BDL	1.13	BDL	BDL	2.25	1.47	BDL		6.39
Cr	1.5	1.2	6.3	260	59.0	116	52.7	62.8	30.9	70.9	65.8	25.0	0.1	0.0		0.9
Mn	1.33	1.51	15.7	4.31	2.52	0.85	BDL	BDL	0.42	1.64	BDL	4.76	BDL	0.26		16.1
Co	2.84	3.11	3.16	1.71	0.44	1.20	9.14	4.92	6.41	19.0	0.19	0.28	1.52	0.59		2.85
Ni	0.60	0.40	1.05	0.29	0.27	1.51	1.06	0.01	0.92	0.37	0.01	0.34	23.9	0.74		17.6
Zn	6.97	13.8	11.0	7.23	102	950	577	1660	493	765	554	442	210	497		498
Ga	0.97	1.62	1.96	0.15	0.06	0.42	0.05	0.04	0.25	0.41	1.00	0.12	0.54	0.03		0.34
Ge	47.0	57.2	66.4	1.20	1.94	2.18	1.39	0.85	0.90	0.89	2.20	0.62	1.32	1.33		1.22
As	BDL	2.69	1.12	BDL	2.43	3.63	3.12	1.62	0.32	3.59	0.48	BDL	0.53	1.23		BDL
Se	7.44	10.8	7.92	3.29	26.9	138	96.4	70.2	98.0	234	33.3	99.2	91.5	83.8		117
Mo	BDL	BDL	1.14	0.30	0.32	0.12	0.43	BDL	0.23	BDL	BDL	BDL	BDL	BDL		BDL
Ag	3.74	4.92	5.03	1.04	5.54	61.9	58.4	66.3	55.7	32.8	124	8.32	1.53	3.93		8.63
Cd	0.10	0.02	BDL	0.10	0.52	12.0	4.52	6.50	4.40	11.6	3.03	0.93	0.46	2.13		1.80
In	1.20	1.29	1.26	0.07	29.7	4.26	3.48	6.33	19.4	12.6	5.34	39.1	12.9	25.7		28.5
Sn	0.33	BDL	BDL	1.28	11.2	10.8	7.31	10.7	49.9	25.8	23.8	196	118	141		1260
Sb	0.09	0.48	0.19	1.94	7.78	3.25	0.71	0.31	1.47	1.52	0.28	0.20	BDL	BDL		0.53
Te	BDL	0.27	BDL	0.22	0.34	0.57	0.29	0.20	0.86	3.38	1.25	0.09	0.17	BDL		0.27
Au	0.03	0.07	0.03	0.02	1.15	0.04	0.04	0.04	0.09	BDL	BDL	BDL	BDL	0.01		0.01
Tl	0.02	0.04	0.21	0.88	BDL	0.05	BDL	BDL	0.22	0.04	0.02	0.02	0.03	BDL		0.01
Pb	1.13	10.9	6.93	11.9	2.87	22.0	1.62	2.09	26.8	1.64	4.35	12.5	1.14	3.87		25.3
Bi	0.12	0.77	1.23	1.48	8.84	0.61	0.03	0.04	0.88	0.13	0.06	5.91	0.03	0.08		9.22

样品	Cu-22		Cu-29				Cu-43		Cu-100-1					Cu-93-1		MDL
编号	5	6	1	2	3	4	1	2	1	2	3	4	5	1	2
Ti	1.46	0.21	1.76	0.68	BDL	2.14	2.01	38.6	1.89	5.05	37.6	111	1907	0.22	0.84	1.20
Cr	4.1	18.4	105	220	134	17.6	53.8	197	824	102	164	293	112	12.5	9.1	5.07
Mn	BDL	4.82	18.7	0.31	BDL	2.25	6.16	314	7.49	7.28	14.1	31.5	58.9	BDL	0.51	1.17
Co	1.28	1.14	0.10	BDL	BDL	0.17	3.54	30.7	0.80	0.98	2.91	6.78	6.97	1.92	0.15	0.21
Ni	13.0	20.5	0.01	0.01	0.16	0.04	2.32	1.05	0.23	0.34	14.6	2.24	0.50	32.8	4.54	0.44
Zn	175	212	5907	742	953	644	1012	4024	213	131	443	663	166	299	360	2.80
Ga	0.03	0.47	26.1	25.3	4.75	37.8	8.19	7.28	0.10	0.03	0.17	0.69	1.79	0.52	0.17	0.03
Ge	0.79	1.44	6.88	48.8	8.06	51.2	5.17	5.01	4.13	1.05	1.21	2.14	2.13	2.09	0.49	1.35
As	0.28	0.21	31.4	BDL	27.4	8.09	149	11.8	8.86	7.27	686	45.0	137	0.14	0.74	10.60
Se	98.9	65.2	17.4	52.2	32.4	14.4	118	126	0.72	2.42	3.22	2.42	7.22	15.6	15.2	3.55
Mo	BDL	BDL	BDL	BDL	BDL	BDL	2.42	17.3	2.55	1.70	6.99	12.1	7.85	BDL	0.04	0.09
Ag	7.83	13.5	16.1	9.44	23.6	16.1	11.8	20.9	9.40	1.93	69.8	7.68	18.5	25.6	15.0	0.04
Cd	0.59	1.57	20.5	1.95	5.02	1.67	4.75	9.48	0.54	0.61	0.59	2.56	0.71	0.84	0.64	0.37
In	16.5	19.0	16.7	9.79	8.13	11.5	1.97	1.66	0.66	1.34	0.50	5.57	5.51	7.34	8.80	0.07
Sn	436	168	201	215	158	787	5.16	1.31	0.02	0.81	2.71	2.12	2.26	5.06	7.01	1.91
Sb	0.38	0.63	7.90	3.21	15.9	17.0	31.1	19.4	3.25	1.55	99.4	1.08	1.89	0.21	0.08	0.41
Te	0.48	0.31	4.32	1.34	1.49	1.17	0.41	0.35	0.28	BDL	0.29	BDL	BDL	1.58	1.74	0.27
Au	0.04	0.03	0.35	0.04	0.30	0.02	0.16	0.19	0.04	0.02	BDL	BDL	BDL	BDL	BDL	0.06
Tl	BDL	0.02	1.84	0.84	1.52	3.84	1.27	1.64	4.53	2.77	37.6	0.83	2.46	0.05	0.23	0.07
Pb	1.52	39.6	205	156	112	8.73	2411	182	202	78.9	1296	257	121	5.46	3.01	0.11
Bi	0.42	18.9	7.90	2.25	2.92	0.13	9.47	0.90	112	46.1	106	171	103	2.21	3.84	0.04
注：BDL表示低于检测限(below detection limits); MDL为平均检测限(mean detection limits); 矿床名和矿床类型见表 1

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表 3 黄铜矿微量元素数据来源统计

Table 3. Statistics table of trace element data sources of chalcopyrite

类型(点数)	矿床(点数)	资料来源
ED (112)	Herja(10), Kochbulak(10), Toroiaga(59), Niuxingba(4), Zhengguang(29)	文献[20, 51-52]
IOCG(82)	Alcaparrosa(2), Las Pintadas(9), Santos(2), Dahongshan(28), Marcona(16), Mina Justa(15), Yinachang(10)	文献[53-57]
MSD(316)	Aguablanca(17), Alexo(10), Beni Bousera(1), Duluth(29), Jinchuan Complex(3), Kharaelakh(59), Mirabela complex(59), Noril′sk I(15), Serranía de Ronda(25), Sudbury Complex(128), Talnakh(5), Voisey′s Bay(20), Yangliuping(3)	文献[58]
HD(46)	Shimensi(11), Shizhuyuan(1), Taoxikeng(17), Weilasituo(12), Xianglushan(5)	文献[51, 59-61]
PCD(205)	109(10), Asarel(30), Baita Bihor(20), Bor(10), Elastite(16), Chagele(32), Fenghuangshan(29), Larong(3), Oravita(40), Zhengguang(15)	文献[20, 52, 62-64]
SEDEX(78)	Bleikvassli(24), Broken Hill(15), Kapp Mineral(9), Mofjell(30)	文献[20]
SMS(50)	Chongsheng(5), Duanqiao(4), Kairei Vent(16), Longqi(6), Wocan(19)	文献[65-68]
VMS(101)	Alexandrinskoye(1), Dergamysh(2), Baiyinchang(27), Buribay(1), Çayeli(42), Hongtoushan(5), Oktyabrskoye(1), Safyanovskoye(3), Sultanovskoye(1), Talgan(1), Tash-Tau(1), Uzelga-1(1), Uzelga-4(1), Valentorskoye(1), Vorta(8), Yaman-Kasy(2), Yubileynoye(3)	文献[65, 69-71]
注：ED为浅成低温热液型矿床；HD为高温热液钨锡型矿床；SMS为现代海底块状硫化物型矿床

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表 4 黄铜矿微量元素最大值统计

Table 4. Statistical of maximum trace elements of chalcopyrite w_B/10^-6

类型	ED	IOCG	MSD	HD	PCD	SEDEX	SMS	SSC	VMS	总计
Mn	73.4	1 758	1 537^*	6 060	1 170	60.5	133	15.7^*	515	6 060
Co	15.7	1 900	10 980	68	94.7^*	1474^*	1781	3.57^*	3 970	10 980
Ni	3.38	163	9 360	14.9	74.1^*	162^*	06	1.05^*	173	9 360
Zn	3 440	1 818^*	2 860	10 913	10 900	3 097	4 093	102^*	10 205	10 913
Ga	4.68	24.3^*	0.42^*	4.08	22.4^*	33.7	175	1.96^*	37.8^*	175
Ge		26.2^*	3.48^*	2.3	7.5	2.81^*	457	66.4^*	51.2^*	457
As	1 752	128	50.2	2 813	735	13.6	1249	2.94^*	1418	2 813
Se	119	394	353	49.2	964	32.9	1283	26.9^*	1536	1 536
Mo	8.06	12.2	4.74	16.9	899^*	0.01^*	216	1.14^*	651	899^*
Ag	959	516	380	1 341	410	1 450	174	5.54^*	718	1 450
Cd	43.4	9.84^*	69.7	215	145	82.1	23.8	0.52^*	55	215
In	376	697^*	5.09	430	539	48.2^*	61.2	29.7^*	112	697^*
Sn	77.3	1 025^*	274	4 077	1 448	1 521	65.5	11.2^*	2 009	4 077
Sb	208	14.9^*	22.2	27.8	109^*	158	108	7.78^*	465	465
Te	263	11.6	70		11.3^*	1.88	110	0.34^*	7 006	7 006
Au	17.9	616	1.28		0.94^*	0.86	3.47	1.15^*	148	616
Tl	0.58	1.22	2.13	1.73	2.19^*	1.74	19	0.88^*	97.1	97.1
Pb	1 425	472^*	247	2 933	1 353^*	98.4	761	11.9^*	7 522	7 522
Bi	1 913	42.9^*	19.7	4 423	130^*	7.3^*	26.3	8.84^*	1 386	4 423
注：空白为无数据，带*来自本研究，其余来自表 3中文献

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表 5 黄铜矿微量元素平均值统计

Table 5. Statistical of average trace elements of chalcopyrite w_B/10^-6

类型	ED	IOCG	MSD	HD	PCD	SEDEX	SMS	SSC	VMS	总计
Mn	7.43	52.9	186	644	25.4	13.5	7.73	4.37	24.9	47.7
Co	2.28	35.8	502	8.24	4.84	18.5	177	2.47	36.4	147
Ni	0.25	10.8	249	2.76	0.97	2.4	10.4	0.52	3.7	65.3
Zn	768	309	424	5 712	716	502	887	25.3	1 189	846
Ga	0.58	1.49	0.12	2.38	0.79	5.84	8.84	0.96	2.96	2.36
Ge		1.58	2.65	0.51	1.96	2.17	34.9	37.2	4.91	8.9
As	29	9.96	4.07	351	13.6	2.45	81	1.53	60.8	31.3
Se	18.3	49.7	89	19.6	60	7.22	255	13.4	156	78.8
Mo	1.31	0.71	0.2	1.81	21	0.001	8.42	0.31	18.6	8
Ag	147	69.2	14.9	322	26	153	54.9	3.82	54.6	61.8
Cd	14	2.41	14.1	83.8	10.7	14.2	5.56	0.14	7.23	14.6
In	27.5	23.3	1.87	148	35.1	10.5	7.85	5.67	21.7	29.1
Sn	18.8	30.3	24.8	640	55.4	362	12.4	2.28	90	92.5
Sb	4.78	1.72	0.57	3.11	2.93	11.9	6.45	1.78	20.6	5.68
Te	6.5	2.21	6.97		0.98	0.21	14.2	0.14	112	15.1
Au	0.34	8.32	0.04		0.05	0.03	0.4	0.22	9.47	2.22
Tl	0.04	0.18	0.22	0.4	0.11	0.1	1.63	0.19	4.07	0.87
Pb	48.2	29.9	25.1	402	43.3	6.98	41.2	6.41	512	112
Bi	67	5.13	0.83	1 056	5.81	0.26	1.07	2.09	52.9	50.3
注：空白为无数据；计算时本文低于检测限的数据赋0值

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