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甘肃毕家山铅锌矿床中镉的赋存状态及矿床成因：来自硫化物LA−ICP−MS微量元素和原位硫同位素的证据

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陈雪锋, 白荣龙, 郭东宝, 刘光贤. 2024. 甘肃毕家山铅锌矿床中镉的赋存状态及矿床成因：来自硫化物LA−ICP−MS微量元素和原位硫同位素的证据. 地质通报, 43(10): 1715-1733. doi: 10.12097/gbc.2023.02.041
引用本文: 陈雪锋, 白荣龙, 郭东宝, 刘光贤. 2024. 甘肃毕家山铅锌矿床中镉的赋存状态及矿床成因：来自硫化物LA−ICP−MS微量元素和原位硫同位素的证据. 地质通报, 43(10): 1715-1733. doi: 10.12097/gbc.2023.02.041
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CHEN Xuefeng, BAI Ronglong, GUO Dongbao, LIU Guangxian. 2024. Occurrence of cadmium and ore genesis in the Bijiashan lead-zinc deposit: Evidence from LA−ICP−MS trace elements and in-situ sulfur isotope of sulfide. Geological Bulletin of China, 43(10): 1715-1733. doi: 10.12097/gbc.2023.02.041
Citation: CHEN Xuefeng, BAI Ronglong, GUO Dongbao, LIU Guangxian. 2024. Occurrence of cadmium and ore genesis in the Bijiashan lead-zinc deposit: Evidence from LA−ICP−MS trace elements and in-situ sulfur isotope of sulfide. Geological Bulletin of China, 43(10): 1715-1733. doi: 10.12097/gbc.2023.02.041
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甘肃毕家山铅锌矿床中镉的赋存状态及矿床成因：来自硫化物LA−ICP−MS微量元素和原位硫同位素的证据

  • 1.

    自然资源部黄河上游战略性矿产资源重点实验室, 甘肃 兰州 730000

  • 2.

    天水师范学院资源与环境工程学院, 甘肃 天水 741000

  • 3.

    甘肃省有色金属地质勘查局兰州矿产勘查院, 甘肃 兰州 730000

  • 4.

    兰州大学资源环境学院, 甘肃 兰州 730000

  • 5.

    东华理工大学, 江西 南昌 330013

  • 基金项目: 甘肃省自然资源厅科技创新项目《甘肃西成铅锌矿田伴生稀散金属元素赋存状态及富集机理、工艺矿物学研究》（编号：2024）、甘肃省高等学校青年博士基金项目《西秦岭造山带云台地区金矿床成矿元素超常富集机制研究》（编号：2022QB-135）、甘肃省青年科技基金计划项目《甘肃六丈山铷矿床中铷的富集机制研究》（编号：21JR7RE185）、甘肃省科技计划资助项目《甘肃省西成铅锌矿田伴生关键金属矿产资源高效利用研究》（编号：22YF7GA073）、天水师范学院 2021年产业支撑引导项目《甘肃西成矿田铅锌矿床中伴生 Cd、Ga、Ge、In 等稀散金属元素赋存状态及富集技术研究》（编号：CYZ2021-03）和天水师范学院教育教学改革研究项目《西秦岭地区地理科学专业野外实习基地和实习路线探索与优选研究》（编号：2021）
详细信息
    作者简介: 陈雪锋（1989− ），男，博士，副教授，从事元素赋存状态及矿床成因研究。E−mail：xfchen2016@126.com
    通讯作者: 白荣龙（1989− ），男，博士，副教授，从事成矿作用与成矿规律研究。E−mail：baironglong@126.com

  • 中图分类号: P595; P618.81

Occurrence of cadmium and ore genesis in the Bijiashan lead-zinc deposit: Evidence from LA−ICP−MS trace elements and in-situ sulfur isotope of sulfide

  • 1.

    Key Laboratory of Strategic Mineral Resources of the Upper Yellow River, Ministry of Natural Resources, Lanzhou 730000, Gansu, China

  • 2.

    College of Resources and Environmental Engineering, Tianshui Normal University, Tianshui 741000, Gansu, China

  • 3.

    Lanzhou Mineral Exploration Institute of Gansu Nonferrous Metal Geological Exploration Bureau, Lanzhou 730000, Gansu, China

  • 4.

    College of Earth and Environmental Sciences, Lanzhou 730000, Gansu, China

  • 5.

    College of Earth and Environmental Science, East China University of Technology, Nanchang 330013, Jiangxi, China

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    摘要

  • 甘肃毕家山铅锌矿床是西秦岭造山带西成矿田发现的首个铅锌矿床，累计探明铅锌资源量120×104t，Pb和Zn的品位分别为1.86%和5.42%。矿床中发育2类矿体，分别是赋存于灰岩中的灰岩型和赋存于千枚岩中的千枚岩型。2类矿体的矿石矿物组合均为闪锌矿+方铅矿±黄铁矿±黄铜矿。毕家山铅锌矿床镉的赋存状态尚不明确。通过激光剥蚀电感耦合等离子质谱仪（LA−ICP−MS）分别对灰岩型和千枚岩型矿石中的硫化物（闪锌矿、方铅矿、黄铁矿和黄铜矿）进行了微量元素及原位S同位素分析。研究结果显示，灰岩型和千枚岩型矿石中闪锌矿的Cd平均含量分别为2076×10−6和1695×10−6，高于矿产工业一般标准（1000×10−6），而方铅矿、黄铁矿和黄铜矿中的Ga、Ge、Se、In、Tl含量均低于矿产工业一般标准（100×10−6）。结合岩相学和LA−ICP−MS分析发现，毕家山铅锌矿床无Cd的独立矿物和以吸附形式存在的Cd，Cd主要以Cd2+↔Zn2+类质同象形式赋存于闪锌矿中，其次为Cd2+ +Fe2+ ↔ 2Zn2+。通过闪锌矿微量元素温度计获得灰岩型和千枚岩型矿石中闪锌矿的形成温度分别为198~254℃（平均值为227℃）和203~245℃（平均值为230℃），与前人通过流体包裹体和矿物对温度计的研究结果一致，表明其成矿温度为中温。此外，原位硫同位素分析结果显示，该矿床中灰岩型和千枚岩型矿石的δ34S平均值分别为+13.64‰和+17.72‰，表明硫来源于海相硫酸盐。综合闪锌矿微量元素数据、同位素地球化学、成矿温度、岩相古地理和矿床地质特征对比分析，推测毕家山铅锌矿床的成因类型属于SEDEX型。

    The Bijiashan deposit is the first lead−zinc deposit discovered in the Xicheng ore field in the West Qinling Orogenic Belt (WQOB), with reserves of 1.2 million tons of lead and zinc, and grades of 1.86% and 5.42%, respectively. This deposit is characterised by the presence of two distinct types of orebodies: limestone−type and phyllite−type, which are located within limestone and phyllite formations, respectively. The mineral assemblages present in both ore types include sphalerite, galena, pyrite, and chalcopyrite. Previous investigations have primarily concentrated on the geological characteristics, petrography, isotope geochemistry, and fluid inclusions associated with the deposit; however, the occurrence of cadmium (Cd) is still uncertain. In this study, laser ablation inductively coupled plasma mass spectrometry (LA−ICP−MS) was employed to analyse various sulfide minerals (sphalerite, galena, pyrite, and chalcopyrite) from both ore types. The analytical results indicate that the average Cd content in sphalerite from the limestone−type and phyllite−type ores is 2076×10−6 and 1695×10−6, respectively, exceeding the general industry standard of 1000×10−6. Conversely, the concentrations of gallium (Ga), germanium (Ge), selenium (Se), indium (In), and thallium (Tl) in galena, pyrite, and chalcopyrite from both ore types are below the mineral industry standard of 100×10−6. Based on petrographic observations and LA−ICP−MS analyses, it is proposed that there are no independent Cd minerals present in the Bijiashan lead−zinc deposit. Instead, Cd is primarily incorporated into sphalerite through the substitution mechanism of Cd2+ ↔ Zn2+, with a minor substitution pathway of Cd2+ + Fe2+ ↔ 2Zn2+. The estimated formation temperature for sphalerite in the limestone type and phyllite type ores are 198–254°C (mean of 227°C) and 203–245°C (mean of 230°C), respectively. These findings are consistent with previous studies utilising fluid inclusion thermometry, suggesting a moderate temperature for ore−forming mineralisation. In−situ sulfur isotope analysis reveals average δ34S values of 13.64‰ and 17.72‰ for the respective ore types, indicating a marine sulfate source. Drawing upon the evidence from LA−ICP−MS trace element data of sphalerite, petrography, geological characteristics of the deposit, isotope geochemistry, and metallogenic temperature, we propose that the Bijiashan lead−zinc deposit is classified as a sedimentary−exhalative (SEDEX) deposit.

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  • 图 1  西成矿田地质图（据王集磊等，1996修改）

    Figure 1. 

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    图 2  毕家山矿区地质图（据王集磊等，1996修改）

    Figure 2. 

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    图 3  毕家山铅锌矿床14号勘探线地质剖面（据王集磊等，1996修改）

    Figure 3. 

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    下载: 全尺寸图片 幻灯片
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    图 4  毕家山铅锌矿床灰岩型矿石中闪锌矿（BJS-16）面扫描微量元素分布

    Figure 4. 

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    图 5  毕家山铅锌矿床中硫化物Cd、Ga、Ge、Se、In、Tl元素含量分布箱状图

    Figure 5. 

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    下载: 全尺寸图片 幻灯片

    图 6  毕家山铅锌矿床中闪锌矿Zn、Cd和Fe关系图

    Figure 6. 

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    图 7  毕家山铅锌矿床成矿温度统计图

    Figure 7. 

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    图 8  西成矿田铅锌矿床中硫同位素组成分布图（*数据据李英，1986；孙省利等，1992；地层表示中泥盆统安家岔组）

    Figure 8. 

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    表 1  毕家山铅锌矿床中闪锌矿、方铅矿、黄铁矿和黄铜矿电子探针成分含量分析结果

    Table 1.  The analytical results of sphalerite, galena, pyrite and chalcopyrite from the Bijiashan Pb−Zn deposit using electron probe %

    类型 矿物 点号 Zn S Pb Fe Cu Cd Ga Ge Tl Cr Se In Te 总和
    灰岩型矿石 闪锌矿 4-1 65.6 32.2 <Bdl 1.13 <Bdl 0.21 0.06 <Bdl <Bdl <Bdl <Bdl 0.03 0.03 98.2
    4-2 65.6 32.3 <Bdl 1.15 <Bdl 0.22 <Bdl <Bdl <Bdl <Bdl <Bdl 0.03 0.02 99.4
    5-1 65.7 32.8 <Bdl 1.97 <Bdl 0.25 <Bdl 0.02 <Bdl 0.01 <Bdl <Bdl <Bdl 100.7
    5-2 64.2 32.5 <Bdl 3.77 <Bdl 0.21 <Bdl <Bdl <Bdl <Bdl <Bdl <Bdl 0.01 100.7
    6-1 65.7 32.1 <Bdl 1.20 <Bdl 0.17 <Bdl 0.04 <Bdl 0.02 <Bdl <Bdl <Bdl 99.3
    6-2 63.9 32.3 <Bdl 2.81 <Bdl 0.17 0.03 <Bdl <Bdl <Bdl 0.01 <Bdl <Bdl 99.3
    12-1 64.5 32.6 0.02 4.75 <Bdl 0.24 <Bdl <Bdl <Bdl 0.02 0.01 0.02 0.04 102.2
    12-2 65.0 32.4 0.04 5.33 0.01 0.18 0.03 0.02 <Bdl 0.01 <Bdl 0.02 0.01 103.0
    14-1 65.7 32.2 0.01 1.75 <Bdl 0.28 <Bdl <Bdl <Bdl 0.01 <Bdl <Bdl 0.02 100.0
    14-2 66.3 32.1 <Bdl 1.26 <Bdl 0.24 <Bdl <Bdl <Bdl 0.01 <Bdl <Bdl 0.03 100.0
    16-1 65.4 32.3 <Bdl 2.62 0.02 0.19 <Bdl <Bdl <Bdl 0.01 <Bdl 0.01 0.01 100.5
    16-2 65.4 32.3 <Bdl 2.63 0.02 0.18 <Bdl <Bdl <Bdl 0.01 <Bdl 0.01 0.01 100.5
    21-1 66.4 32.3 <Bdl 1.41 <Bdl 0.30 0.10 <Bdl 0.01 <Bdl <Bdl <Bdl 0.04 100.5
    21-2 64.9 32.4 <Bdl 2.82 0.03 0.25 0.04 <Bdl <Bdl <Bdl <Bdl <Bdl <Bdl 100.5
    23-1 66.3 32.5 <Bdl 1.79 <Bdl 0.19 0.10 <Bdl <Bdl <Bdl <Bdl <Bdl 0.01 100.8
    23-2 65.8 32.4 <Bdl 3.21 0.02 0.22 <Bdl 0.02 <Bdl <Bdl <Bdl <Bdl 0.01 101.7
    千枚岩型矿石 闪锌矿 25-1 63.0 32.5 <Bdl 3.90 <Bdl 0.17 <Bdl <Bdl <Bdl 0.01 <Bdl <Bdl 0.01 99.6
    25-2 62.9 32.5 <Bdl 3.86 <Bdl 0.17 <Bdl <Bdl <Bdl 0.01 <Bdl <Bdl 0.01 99.4
    28-1 63.5 32.4 <Bdl 5.83 0.01 0.20 0.07 <Bdl <Bdl <Bdl <Bdl 0.02 0.01 102.1
    28-2 62.0 32.5 <Bdl 5.76 0.01 0.21 0.06 <Bdl <Bdl <Bdl <Bdl 0.02 0.01 100.5
    30-1 62.0 32.7 <Bdl 6.94 0.02 0.22 <Bdl <Bdl <Bdl <Bdl <Bdl <Bdl 0.01 101.9
    30-2 62.4 32.5 0.04 4.41 0.32 0.25 <Bdl <Bdl <Bdl 0.01 <Bdl <Bdl 0.02 100.0
    31-1 62.4 32.7 <Bdl 4.58 <Bdl 0.18 0.02 <Bdl <Bdl <Bdl <Bdl <Bdl 0.04 99.9
    31-2 62.4 32.5 <Bdl 4.57 <Bdl 0.19 0.02 <Bdl <Bdl <Bdl <Bdl <Bdl 0.04 99.7
    灰岩型矿石 方铅矿 5-1 0.08 13.4 85.5 <Bdl <Bdl 0.13 <Bdl 0.07 <Bdl <Bdl <Bdl <Bdl 0.04 99.2
    8-1 0.11 13.2 84.7 0.02 <Bdl 0.18 <Bdl 0.01 <Bdl <Bdl <Bdl <Bdl 0.12 98.3
    9-1 0.08 13.2 85.4 0.02 0.01 0.11 <Bdl 0.02 <Bdl <Bdl <Bdl <Bdl 0.08 98.9
    12-1 0.11 13.2 85.6 <Bdl 0.04 0.11 <Bdl 0.03 <Bdl 0.06 <Bdl <Bdl 0.05 99.2
    12-2 0.04 13.2 84.7 <Bdl <Bdl 0.17 0.01 <Bdl <Bdl <Bdl <Bdl <Bdl 0.06 98.2
    14-1 0.06 13.5 85.4 0.01 <Bdl 0.12 <Bdl <Bdl <Bdl <Bdl <Bdl <Bdl 0.05 99.1
    14-2 0.07 13.5 85.4 0.01 <Bdl 0.13 <Bdl <Bdl <Bdl <Bdl <Bdl <Bdl 0.05 99.1
    千枚岩型矿石 方铅矿 22-1 0.10 13.0 84.8 0.02 <Bdl 0.19 <Bdl 0.03 <Bdl <Bdl <Bdl <Bdl 0.12 98.2
    27-1 0.08 13.0 84.9 0.01 <Bdl 0.14 <Bdl 0.05 <Bdl <Bdl <Bdl <Bdl 0.03 98.3
    27-2 0.07 13.0 85.0 0.01 <Bdl 0.14 <Bdl 0.05 <Bdl <Bdl <Bdl <Bdl 0.25 98.5
    灰岩型矿石 黄铁矿 4-1 0.09 53.0 <Bdl 46.5 <Bdl 0.01 <Bdl <Bdl <Bdl <Bdl <Bdl <Bdl 0.02 99.6
    4-2 0.08 53.1 <Bdl 46.5 <Bdl 0.01 <Bdl <Bdl <Bdl <Bdl <Bdl <Bdl 0.02 99.7
    10-1 0.01 52.8 0.01 46.3 <Bdl 0.01 <Bdl <Bdl <Bdl 0.01 <Bdl <Bdl 0.05 99.2
    13-1 0.03 53.0 <Bdl 43.5 4.25 0.02 <Bdl <Bdl <Bdl <Bdl <Bdl <Bdl 0.02 100.9
    13-2 0.02 53.0 <Bdl 43.5 <Bdl 0.02 <Bdl <Bdl <Bdl <Bdl <Bdl <Bdl 0.02 96.6
    13-3 0.04 53.3 <Bdl 46.5 0.17 0.04 <Bdl <Bdl <Bdl <Bdl <Bdl <Bdl <Bdl 100.1
    千枚岩型矿石 黄铁矿 30-1 0.01 51.9 0.01 48.8 0.07 0.02 <Bdl <Bdl <Bdl 0.01 <Bdl <Bdl <Bdl 100.8
    30-2 0.01 53.0 0.01 48.7 0.07 0.02 <Bdl <Bdl <Bdl 0.01 <Bdl <Bdl <Bdl 101.8
    灰岩型矿石 黄铜矿 13-1 0.09 34.8 0.01 30.9 34.5 0.04 <Bdl <Bdl <Bdl 0.03 0.01 <Bdl 0.03 100.5
    13-2 2.47 34.6 0.04 30.0 33.3 0.05 <Bdl <Bdl <Bdl 0.04 <Bdl <Bdl <Bdl 100.4
    千枚岩型矿石 黄铜矿 27-1 0.01 34.9 0.06 30.8 34.5 0.03 <Bdl <Bdl <Bdl <Bdl <Bdl <Bdl <Bdl 100.4
    27-2 0.05 35.0 0.07 30.8 34.6 0.03 <Bdl <Bdl <Bdl <Bdl <Bdl <Bdl 0.01 100.5
    27-3 0.17 34.8 <Bdl 30.9 34.4 0.03 0.06 <Bdl 0.07 <Bdl 0.10 <Bdl 0.03 100.6
    27-4 0.12 34.8 0.02 30.9 34.4 0.02 0.05 <Bdl 0.06 <Bdl 0.02 <Bdl 0.01 100.5
    　　注：“<Bdl”代表低于仪器检测限
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    表 2  毕家山铅锌矿床中闪锌矿、方铅矿、黄铁矿及黄铜矿LA−ICP−MS微量元素成分含量分析结果

    Table 2.  Analytical results of trace element of sphalerite, galena, pyrite and chalcopyrite analyzed by LA−ICP−MS from the Bijiashan Pb−Zn deposit 10−6

    矿石类型 矿物 样号 Li Be Mg P Sc Ti V Cr Mn Co Ni Cu Ga Ge Se Mo Cd In Sn W Tl Pb Bi T/℃
    灰岩型 闪锌矿 4-1 0.01 0.08 0.94 17.3 <Bdl 0.72 0.03 <Bdl 350 5.91 1.58 32.8 2.17 1.17 0.35 0.58 2004 0.23 0.96 <Bdl 0.01 2.72 0.02 254
    4-2 <Bdl <Bdl 0.35 19.6 0.83 1.60 0.06 <Bdl 355 6.06 1.80 37.1 2.65 1.10 0.25 0.19 1779 0.20 1.77 0.02 0.02 4.22 0.03 252
    5-1 0.16 <Bdl 0.21 26.0 0.35 1.41 0.07 <Bdl 48.3 9.10 1.15 6.20 3.02 0.85 0.02 <Bdl 2085 0.04 0.94 0.01 0.04 0.49 0.01 233
    5-2 0.20 0.23 0.27 8.16 <Bdl 0.56 0.05 0.69 52.6 9.59 0.90 8.36 3.12 0.82 <Bdl <Bdl 2648 0.04 1.98 <Bdl 0.01 10.9 0.02 248
    6-1 0.05 0.13 0.09 16.5 <Bdl 0.28 0.05 0.43 36.4 12.4 11.1 12.6 8.10 3.01 1.02 0.03 1877 0.36 0.95 0.01 <Bdl 0.16 0.04 206
    6-2 0.07 <Bdl <Bdl 26.4 <Bdl 0.29 0.05 1.72 33.3 13.4 13.3 15.5 5.11 3.14 1.43 0.38 2354 0.36 1.56 0.01 <Bdl 0.82 <Bdl 228
    12-1 6.61 <Bdl 52.9 16.1 <Bdl 1.37 0.53 0.08 38.5 5.49 1.87 21.6 4.47 2.23 1.02 <Bdl 2178 0.02 0.79 <Bdl <Bdl 11.6 0.05 229
    12-2 0.09 <Bdl 0.50 9.5 <Bdl 0.08 0.06 1.01 33.3 5.81 2.25 13.3 4.48 1.98 0.98 0.06 2397 0.03 0.92 0.02 <Bdl 5.02 0.01 232
    14-1 <Bdl <Bdl <Bdl 26.7 0.10 <Bdl 0.07 1.84 45.0 6.17 0.61 39.0 2.37 2.01 <Bdl <Bdl 2066 0.11 2.31 0.07 <Bdl 8.95 0.02 229
    14-2 <Bdl 0.14 <Bdl 18.1 <Bdl <Bdl <Bdl <Bdl 45.5 5.92 2.11 17.0 1.39 2.10 <Bdl <Bdl 1739 0.10 1.78 <Bdl <Bdl 1.90 0.03 228
    16-1 0.18 0.29 0.95 14.3 0.15 2.35 0.08 <Bdl 42.0 10.2 5.45 17.1 1.20 6.90 0.01 <Bdl 1645 0.08 0.62 0.01 0.01 6.14 0.04 228
    16-2 0.35 0.03 0.03 34.7 <Bdl 0.34 0.11 2.38 46.2 10.4 4.42 18.9 1.64 7.88 <Bdl <Bdl 1866 0.08 2.06 0.01 0.01 18.1 <Bdl 223
    21-1 <Bdl <Bdl 0.84 23.4 <Bdl 1.48 0.18 <Bdl 34.8 3.40 0.08 12.2 2.81 5.24 0.62 <Bdl 2196 0.05 0.94 0.02 <Bdl 6.73 0.04 204
    21-2 <Bdl <Bdl 0.20 26.2 0.06 0.41 0.08 <Bdl 38.0 3.96 0.25 11.5 3.92 31.13 0.45 0.02 2649 0.11 1.14 0.01 <Bdl 2.54 <Bdl 198
    23-1 <Bdl <Bdl 0.44 15.3 <Bdl 0.41 0.06 <Bdl 27.5 15.7 4.75 4.91 2.82 2.26 0.01 0.03 1769 0.06 1.28 <Bdl <Bdl 0.53 0.01 217
    23-2 <Bdl 0.14 <Bdl 11.6 0.10 <Bdl 0.11 0.20 29.8 15.3 3.81 6.10 2.90 2.08 <Bdl <Bdl 1960 0.05 1.45 <Bdl <Bdl 2.16 0.01 228
    千枚岩型 闪锌矿 25-1 <Bdl 0.44 <Bdl 18.2 <Bdl <Bdl 0.04 <Bdl 59.3 41.6 3.48 15.9 5.14 1.26 2.02 0.05 1579 <Bdl 3.03 <Bdl <Bdl 6.92 <Bdl 217
    25-2 <Bdl 0.18 1.30 11.8 <Bdl <Bdl 0.05 <Bdl 59.7 40.9 3.81 14.6 5.19 1.18 2.26 0.02 1670 <Bdl 1.71 <Bdl <Bdl 1.53 <Bdl 203
    28-1 0.33 <Bdl <Bdl 22.4 0.20 0.70 0.09 0.19 26.0 30.7 1.77 16.4 14.6 1.43 4.68 0.07 1495 0.55 1.42 <Bdl <Bdl 0.11 <Bdl 239
    28-2 0.07 <Bdl 1.77 14.6 0.03 0.56 0.01 0.33 26.9 34.3 2.46 39.7 16.0 1.28 4.71 0.02 1675 0.61 1.45 <Bdl <Bdl 0.76 0.02 240
    30-1 <Bdl 0.08 3.48 19.0 0.10 <Bdl 0.11 <Bdl 32.4 45.9 0.19 1117 10.7 2.08 1.71 0.07 1919 0.65 1.65 0.02 0.01 53.6 0.01 245
    30-2 0.54 0.47 4.70 19.4 0.53 <Bdl 0.08 1.82 41.7 46.4 0.41 122 15.6 2.25 1.64 0.03 1796 0.67 1.37 0.01 0.01 45.1 <Bdl 233
    31-1 <Bdl <Bdl 0.54 23.3 <Bdl <Bdl 0.15 0.71 31.2 58.2 7.13 19.6 10.2 1.83 3.20 0.04 1633 0.24 2.32 <Bdl <Bdl 0.37 0.02 232
    31-2 <Bdl <Bdl <Bdl 16.0 <Bdl <Bdl 0.01 0.55 32.3 62.8 7.34 16.3 8.92 1.70 3.25 0.02 1790 0.15 1.63 <Bdl <Bdl 0.34 0.04 232
    灰岩型 方铅矿 5-1 <Bdl 0.11 1.65 4.84 0.14 0.01 0.01 <Bdl 0.01 <Bdl 0.04 0.24 <Bdl 0.44 0.06 <Bdl 24.9 0.03 4.97 0.01 1.95 --- 0.19 ---
    8-1 0.27 0.03 0.05 3.29 0.01 0.23 0.04 1.39 <Bdl 0.03 0.01 1.62 <Bdl 0.52 0.09 <Bdl 40.8 0.05 8.30 <Bdl 2.02 --- 0.61 ---
    9-1 0.13 0.04 0.05 9.01 <Bdl <Bdl <Bdl 0.37 <Bdl 0.03 0.04 0.74 <Bdl 0.56 0.55 <Bdl 11.2 0.07 2.13 0.01 1.23 --- 0.13 ---
    12-1 0.08 0.07 <Bdl 12.3 <Bdl <Bdl 0.02 2.42 0.08 0.04 0.02 <Bdl <Bdl 0.45 0.76 <Bdl 19.2 <Bdl 0.92 <Bdl 1.60 --- 0.08 ---
    12-2 0.29 <Bdl 0.44 24.1 0.07 0.47 0.09 3.03 <Bdl <Bdl 0.14 0.80 <Bdl 0.53 0.79 <Bdl 30.9 <Bdl 3.41 0.01 1.58 --- 0.11 ---
    14-1 0.17 <Bdl <Bdl 10.3 0.43 0.59 0.02 0.09 <Bdl 0.07 0.18 0.22 0.02 0.98 2.00 <Bdl 12.2 0.02 2.33 <Bdl 0.45 --- 0.42 ---
    14-2 <Bdl 0.04 0.02 9.48 <Bdl <Bdl 0.01 <Bdl <Bdl 0.01 0.06 1.46 0.01 0.96 2.09 <Bdl 12.0 0.01 1.46 0.01 0.41 --- 0.38 ---
    千枚岩型 方铅矿 22-1 0.07 0.11 1.03 9.44 <Bdl <Bdl 0.01 <Bdl <Bdl 0.03 <Bdl 14.4 0.01 0.60 43.46 0.01 23.6 0.03 6.09 0.01 2.87 --- 6.52 ---
    27-1 <Bdl 0.15 1.10 10.2 <Bdl 0.63 <Bdl 2.75 <Bdl 0.02 <Bdl 0.43 <Bdl 1.13 5.11 0.02 24.3 0.05 7.17 0.01 0.12 --- 5.15 ---
    27-2 0.02 0.13 0.66 5.40 <Bdl <Bdl 0.10 2.14 <Bdl 0.07 <Bdl 1.37 0.04 1.00 5.93 0.07 26.4 0.04 12.2 <Bdl 0.15 --- 6.23 ---
    灰岩型 黄铁矿 4-1 <Bdl <Bdl 0.45 0.05 0.12 0.17 0.02 <Bdl 0.04 7.45 35.8 599 0.89 2.99 0.45 <Bdl 0.61 0.13 1.74 <Bdl 0.01 232 13.7 ---
    4-2 <Bdl 0.09 0.67 8.76 <Bdl 1.10 0.01 0.09 0.03 14.4 40.1 1144 0.96 2.56 0.45 0.05 0.65 0.13 4.14 <Bdl 0.01 105 5.82 ---
    10-1 <Bdl 0.01 0.71 1.31 0.08 0.06 0.05 <Bdl 0.07 37.5 24.0 15.7 0.01 2.89 1.48 0.07 1.30 0.06 0.07 0.01 0.01 61.9 2.60 ---
    13-1 <Bdl <Bdl <Bdl 2.19 0.03 0.13 0.04 <Bdl <Bdl 113 315 355 0.05 2.90 1.38 0.01 0.27 0.06 2.19 0.02 0.01 19.1 0.36 ---
    千枚岩型 黄铁矿 13-2 0.30 <Bdl 0.15 <Bdl <Bdl <Bdl 0.07 0.56 0.02 635 1013 522 0.08 2.00 3.02 0.03 0.06 0.04 0.92 <Bdl <Bdl 140 0.26 ---
    13-3 0.06 <Bdl <Bdl 0.50 <Bdl <Bdl 0.01 <Bdl <Bdl 1475 35.5 217 0.01 2.20 2.98 0.01 0.01 0.03 <Bdl <Bdl <Bdl 115 0.11 ---
    30-1 <Bdl 0.03 2.95 4.17 0.28 0.69 0.06 1.05 0.13 0.04 40.0 81.2 0.02 2.33 1.12 0.18 0.04 <Bdl <Bdl 0.01 1.22 156 0.01 ---
    30-2 0.25 <Bdl 36.5 6.45 0.02 0.78 0.23 0.53 0.84 0.66 136 250 0.45 2.44 1.20 0.78 0.63 0.01 0.16 <Bdl 1.19 517 0.05 ---
    灰岩型 黄铜矿 13-1 0.16 0.23 0.53 2.09 0.04 0.34 0.04 <Bdl 0.01 <Bdl <Bdl --- <Bdl 3.04 0.74 <Bdl 0.49 0.13 1.25 0.01 <Bdl 1.05 <Bdl ---
    13-2 <Bdl <Bdl 2.21 13.94 <Bdl <Bdl 0.17 <Bdl <Bdl 0.13 0.51 --- 0.81 3.00 0.71 <Bdl 2.70 0.32 15.94 <Bdl <Bdl 10.96 <Bdl ---
    22-1 0.31 <Bdl 3.21 4.86 0.93 <Bdl 0.10 4.63 0.92 1.07 0.19 --- 3.16 5.60 1.00 <Bdl 368.20 0.25 38.89 <Bdl 0.51 19.38 0.10 ---
    22-2 0.69 <Bdl 21.17 <Bdl <Bdl <Bdl 0.07 <Bdl 0.57 0.52 0.19 --- 1.10 5.82 1.04 0.04 184.87 0.21 36.98 <Bdl 0.57 32.54 0.10 ---
    千枚岩型 黄铜矿 27-1 <Bdl 0.12 1.84 8.41 1.09 4.51 0.14 <Bdl <Bdl 0.02 0.91 --- 1.61 5.53 0.01 0.06 4.35 0.52 48.82 0.01 0.03 8.59 <Bdl ---
    27-2 <Bdl <Bdl 2.24 <Bdl <Bdl <Bdl 0.03 <Bdl 0.18 <Bdl 0.04 --- 1.23 5.52 <Bdl <Bdl 20.82 0.47 53.04 <Bdl 0.02 6.36 <Bdl ---
    27-3 0.51 0.45 2.59 12.16 0.65 <Bdl 0.19 4.77 <Bdl <Bdl <Bdl --- 1.19 3.80 <Bdl <Bdl 3.83 0.50 40.63 0.01 0.06 3.48 0.04 ---
    27-4 0.05 0.19 <Bdl 10.81 0.90 <Bdl 0.06 5.77 0.13 0.09 0.62 --- 1.22 3.78 <Bdl 0.04 3.13 0.53 49.10 <Bdl 0.07 12.69 0.03 ---
    　　注：“<Bdl”表示低于检测限；“---”表示无数据
    下载: 导出CSV

    表 3  毕家山铅锌矿床中硫化物硫同位素数据

    Table 3.  Sulfur isotope compositions of sulfides in the Bijiashan lead-zinc deposit

    类型样号矿物δ34SV-CDT/‰
    灰岩型矿石22-1闪锌矿+13.60
    22-3闪锌矿+13.69
    千枚岩型矿石30-1闪锌矿+18.04
    30-2闪锌矿+17.40
    30-3黄铜矿+15.75
    30-4黄铁矿+15.59
    下载: 导出CSV

    表 4  毕家山铅锌矿床相关特征

    Table 4.  Relevant characteristics of Bijiashan Pb−Zn deposit

    类型 密西西比河谷型（MVT）铅锌矿床 喷流沉积型（SEDEX）铅锌矿床 毕家山铅锌矿床
    定义 指赋存于台地碳酸盐岩中，成因与岩浆岩无关的浅成后生层状铅锌矿床，是在50~250℃条件下从密度较高的盆地卤水中沉淀形成的 在水温70~350℃或更高的热水介质（海水、湖水、热泉等）中形成的主体，以沉积的方式形成于水−岩石界面之上水体中的层状、似层状矿体，也包括此界面之下可能存在的以充填和交代形成的筒状、锥状或面型热液矿化蚀变体 ——
    成矿构
    造背景    		 形成与全球板块汇聚事件相一致，主要分布于相对稳定的克拉通边缘或浅水碳酸盐台地边缘，有利构造环境为俯冲碰撞环境靠近克拉通一侧的部位，克拉通边缘沉积盆地内古隆起带之上或附近，与板块俯冲形成的局部伸展环境有关，前陆逆冲推覆环境，大陆伸展的裂谷或裂谷环境 主要形成于拉张性构造环境：离散板块动力学背景下陆内裂谷、坳拉槽、被动大陆边缘裂谷；汇聚板块动力学背景下远离弧后的拉张断陷盆地 中泥盆世秦岭地槽拉张环境
    成矿
    物质    		 Pb上地壳来源；
    δ34S=−25‰~+30‰，沉积地层和海水，壳源特征；
    含硫酸盐的蒸发岩、同生海水、成岩期的硫酸盐、含硫有机质、H2S气体储库、盆地中缺氧水中的还原硫    		 Pb受成矿流体控制，总体壳源特征；
    δ34S=−8‰~+30‰（深源S，海水SO4，生物S），
    主要介于−5‰~+15‰之间，
    S主要来自于海相硫酸盐    		 206Pb/204Pb=18.131，206Pb/204Pb=15.633，206Pb/204Pb=38.284，与赋矿地层一致，来自壳源；闪锌矿：δ34S=+9.2‰~+22.8‰（平均值：+14.6‰），方铅矿：δ34S=+4.7‰~+22.3‰（平均值：+14.6‰），黄铁矿：δ34S=+11.0‰~+24.1‰（平均值：+19.5‰），具有与围岩地层一致的S同位素组成，来自于海相硫酸盐
    成矿
    流体    		 均一温度（50~250℃）主要为75~150℃，盐度NaCleq=15%~30%，成分与油田卤水相似 均一温度（70~350℃）主要为140~280℃，众值225℃，
    盐度NaCleq=15%~20%    		 微量元素温度计：灰岩型闪锌矿189~254℃（平均值218℃），千枚岩型闪锌矿193~245℃（平均值229℃）；硫化矿物对温度计：230℃；成矿温度以中温为主；流体包裹体：140~292℃（平均值219℃），盐度NaCleq= 10.6%~19.8%
    流体
    来源    		 盆地卤水（主要溶质源于海水蒸发或地下蒸发矿物（石盐） 盆地中被埋藏的沉积物在压实过程中释放出多种形式的水及其他组分 流体以原生沉积建造水为主，可能有少量其他水分参与
    成矿
    能量    		 构造挤压运动产生的动能使成矿流体运移，重力引起的梯度热能以及有机生物能促使硫的还原 沿构造从壳源深部传导出的热扩散，可能受地幔柱的影响 西成矿田内礼县−白云−山阳区域性同沉积深大断裂为区域内热水活动提供了通道
    成矿流
    体通道    		 张性断层 同生断裂和长期活动的断裂 礼县−白云−山阳区域性同生沉积断裂
    成矿堆
    积场所    		 以碳酸盐岩为主，碳酸盐岩溶塌角砾岩、断层及构造裂隙、岩相过渡界面、生物礁及障壁体系、 盆地基底的组成了成矿堆积场 以较细粒的碎屑沉积物为主的岩石，其顶部的页岩、粉砂岩和碳酸盐岩及其变质后的产物有效地形成了成矿的地球物理化学障 由礁灰岩、硅质岩、千枚岩构成“礁硅岩套”组合屏障
    矿石矿物 方铅矿、闪锌矿、黄铁矿、黄铜矿为主 方铅矿、闪锌矿、黄铁矿为主 方铅矿、闪锌矿、黄铁矿为主
    脉石矿物 白云石、方解石、少量矿床具有萤石、重晶石 石英、白云石、方解石、重晶石 石英、方解石、少量重晶石
    结构构造 块状、浸染状、脉状 层状、纹层状、条带状、角砾状和致密块状为主，脉状浸染状和星点状 条带状、团块状
    成矿阶段 热液期+表生期 喷流沉积期+后期变形变质 喷流沉积+后期变形变质
    参考文献 Cook et al., 2000; Bradley et al., 2003; Leach et al., 2001, 2005, 2010, 2017, 2019 Cook et al., 2000; Bradley et al., 2003; Goodfellow, 2004; McGoldrick et al., 2010; Maier, 2011; Gadd et al., 2015; Mukherjee et al., 2017; Cugerone et al., 2018; Yuan et al., 2018 陈建民，1986；李英，1986；戴问天，1987；吴廷祥，1991；林兵等，1992；孙省利1992；鲁燕伟，2009；刘红丽，2015
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