Genesis of Tongchang Copper-Iron Deposit in Mian-Lue-Ning Area: Constraints from Re-Os Isotopic Dating of Chalcopyrite and In-Situ Sulfur Isotope Compositions of Sulfides
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摘要:
铜厂铜-铁矿床在成矿时代、成矿物质来源及矿床成因等方面存在较大争议，限制了其成矿模式的建立以及进一步的找矿实践. 利用黄铜矿Re-Os同位素对该矿床进行定年，并利用LA-MC-ICP-MS技术对黄铜矿、黄铁矿及磁黄铁矿等硫化物开展原位硫同位素研究. 分析结果显示，5件黄铜矿Re-Os同位素等时线年龄为484±34 Ma（MSWD=8.7），表明铜厂铜-铁矿床形成于早古生代加里东期. 铜厂铜-铁矿床上部铜矿床中黄铜矿（+9.75‰~+13.1‰）和黄铁矿（+9.22‰~+13.9‰）的δ34S值略高于下部铁矿床中黄铜矿（+8.66‰~+10.9‰）、黄铁矿（+8.85‰~+11.0‰）和磁黄铁矿（+7.93‰~+9.28‰）. 计算得到早期成矿热液的δ34S∑S值约为+10.6‰，晚期成矿热液的δ34S∑S值约为+12.3‰，说明矿床硫是地幔硫混染海水硫形成的，热化学还原在海水硫酸盐还原过程中起到关键作用. 铜厂铜-铁矿床的形成可分为两期：新元古代晋宁期，Rodinia超大陆裂解导致勉略宁地区发生海底火山喷发形成富含Fe、Cu的初始矿源层；早古生代加里东期，大陆边缘持续的裂解和裂陷形成勉略海槽并导致强烈的岩浆活动，富含挥发分及硫的岩浆热液混合海水硫，并从细碧岩中萃取Fe、Cu等成矿物质，早期成矿热液在铜厂地区深部形成铁矿床，随着磁铁矿和硫化物的沉淀，成矿热液演化到晚期阶段并沿断裂构造带向上运移，在铜厂地区浅部形成铜矿床.
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关键词:
- 勉略宁 /
- 铜厂铜-铁矿床 /
- Re-Os同位素定年 /
- LA-MC-ICP-MS /
- 原位硫同位素 /
- 成矿模式 /
- 矿床学
Abstract:There are great disputes about the metallogenic age, source of ore-forming material and genesis of the Tongchang copper-iron deposit, which limits the establishment of its metallogenic model and further prospecting practice. Re-Os isotope of chalcopyrite is used to date the ore-forming age, and the S isotope compositions of chalcopyrite, pyrite and pyrrhotite are systematically studied by LA-MC-ICP-MS. The Re-Os isotopic isochron age of the five chalcopyrite samples is 484±34 Ma (MSWD=8.7), indicating that the Tongchang copper-iron deposit was formed in the Early Paleozoic Caledonian period. The δ34S values of chalcopyrite (+9.75‰-+13.1‰) and pyrite (+9.22‰-+13.9‰) in the upper part of Tongchang copper-iron deposit are slightly higher than those of chalcopyrite (+8.66‰-+10.9‰), pyrite (+8.85‰-+11.0‰) and pyrrhotite (+7.93‰-+9.28‰) in the lower part. The δ34S∑S value in the early ore-forming hydrothermal solution is about +10.6‰, and that in the late ore-forming hydrothermal solution is about +12.3‰, showing that the sulfur source of the deposit is from mixture of mantle sulfur and seawater sulfur. Thermochemical sulfate reduction (TSR) plays an important role in the process of seawater sulfate reduction. The formation of the Tongchang copper-iron deposit can be divided into two stages. In Neoproterozoic Jinning period, Rodinia supercontinent breakup event leads to submarine volcanic eruption and the formation of initial source bed which was enriched in Fe and Cu. During the Caledonian period of Early Paleozoic, the continuous cracking and rifting of the continental margin formed the Mian-Lue trough and led to intense magmatic activity. The magmatic hydrothermal solution enriched in volatile and sulfur, mixed with seawater sulfur, and extracted Fe, Cu and partial sulfur source from the spilite of the Guojiagou Formation. The early ore-forming hydrothermal solution formed the iron ore body in the deep part of the Tongchang area. With the precipitation of magnetite and sulfide, the ore-forming hydrothermal solution evolved to the late stage and migrated upward along the fault to form the copper deposit in the upper part of the Tongchang area.
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图 1 勉略宁矿集区地质构造略图（据岳素伟等，2013）
Fig. 1. Simplified geological map of the Mian-Lue-Ning area (from Yue et al., 2013)
图 2 铜厂矿田地质简图(a)和铜-铁矿床地质剖面示意图(b)
a.据王瑞廷等(2012); b.据任小华(2008)
Fig. 2. Simplified geological map of the Tongchang ore field (a) and geological cross-section of the Tongchang copper-iron deposit (b)
图 3 铜厂铜-铁矿床矿石手标本及显微照片
a、b.下部铁矿床磁铁矿矿石；c.下部铁矿床硫化物矿石；d~f.下部铁矿床含硫化物的磁铁矿矿石；g~i.上部部铜矿床硫化物矿石. Py.黄铁矿；Po.磁黄铁矿；Mt.磁铁矿；Ccp.黄铜矿；Q.石英；Cc.方解石；Srp.蛇纹石. 圆圈代表原位硫同位素分析点位
Fig. 3. Hand specimens and microphotographs of the ores from the Tongchang copper-iron deposit
图 4 铜厂铜-铁矿床矿化蚀变共生序列
线条的粗细分别代表主要和次要矿物
Fig. 4. Paragenetic sequence of ore and alteration minerals in the Tongchang copper-iron deposit
图 5 铜厂铜-铁矿床黄铜矿Re-Os同位素等时线年龄（a）和187Os/188Os-1/192Os图解（b）
Fig. 5. Re-Os isotope isochrone age (a) and 187Os/188Os vs. 1/192Os (b) of chalcopyrite from the Tongchang copper-iron deposit
图 6 铜厂铜-铁矿床硫化物原位硫同位素组成直方图
Fig. 6. In-situ S isotopic composition histogram of sulfide from the Tongchang copper-iron deposit
图 7 铜厂铜-铁矿床成矿流体δ34S∑S值计算图
Fig. 7. δ34S∑S calculation diagram of the ore-forming fluid of the Tongchang copper-iron deposit
图 8 铜厂铜-铁矿床硫化物原位硫同位素组成
底图据Li and Santosh（2014）
Fig. 8. In-situ S isotopic composition of sulfide from the Tongchang copper-iron deposit
表 1 铜厂铜-铁矿床及岩浆岩形成时代
Table 1. Ages of the Tongchang copper-iron deposit and magmatic rocks
地层/矿体/岩体 方法 年龄（Ma） 资料来源 碧口群 上部浅变质中酸性火山岩 锆石SHRIMP U-Pb同位素年龄 790±15~776±13 闫全人等，2003 下部基性火山岩 840±10 铜厂矿田 铜厂铜矿床 矿化闪长岩中辉钼矿Re-Os同位素模式年龄 889 丁振举等，1998 脉状铜矿石中黄铜矿Rb-Sr等时线年龄 359 铜厂闪长岩 闪长岩 锆石SHRIMP
U-Pb同位素年龄842±6.5 叶霖等，2009 早期闪长岩 锆石LA-ICP-MS
U-Pb同位素年龄879±7 王伟等，2011 中期石英闪长岩 848±5~840±7 含矿钠长岩脉 843±7 晚期花岗闪长岩 824±5 闪长岩 锆石LA-ICP-MS
U-Pb同位素年龄843.7±3.9 宫相宽等，2013 
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表 2 LA-MC-ICP-MS工作参数
Table 2. LA-MC-ICP-MS operation conditions
MC-ICP-MS工作参数 激光工作参数 仪器型号 Nu Plasma 1700 仪器型号 RESOlution M50-LR RF射频功率 1 300 W 激光能量密度 3.5~4 J/cm2 等离子气（Ar）流速 13 L/min 载气（He）流量 280 mL/min 补充气（Ar）流量 0.96 L/min 束斑 20~37 μm 背景时间 30 s 频率 3~4 Hz 积分时间 50 s 剥蚀方式 点剥蚀
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表 3 铜厂铜-铁矿床黄铜矿Re-Os同位素测试数据
Table 3. Re-Os isotopic data of chalcopyrite from the Tongchang copper-iron deposit
样品编号 Re(10-9) ±2σ Os(10-12) ±2σ 187Re/188Os ±2σ 187Os/188Os ±2σ 1/192Os(1012) T17-8 1 110 27 8.763 0.056 1 455.34 37.06 10.74 0.06 0.671 T17-11 3 371 10 19.27 0.10 7 209.31 41.84 58.05 0.39 1.101 T17-12 1 562 30 10.53 0.23 2 184.00 63.49 15.90 0.42 0.717 T17-13 1.298 0.028 21.09 0.14 447.35 10.04 4.03 0.02 0.176 T17-17 0.794 0 0.010 0 63.99 0.37 76.52 1.06 2.28 0.02 0.049 T17-20 4 814 24 31.15 0.19 3 164.05 25.39 25.04 0.28 0.345
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表 4 铜厂铜-铁矿床硫化物原位硫同位素组成
Table 4. In-situ S isotopic composition of sulfide from the Tongchang copper-iron deposit
样品类型 样品编号 δ34S(‰) 样品类型 样品编号 δ34S(‰) 上部黄铜矿 TC15-5 +12.3 上部黄铁矿 T17-8 +13.8 +12.5 T17-9 +12.9 TC15-17 +10.5 T17-11 +12.4 +10.5 T17-13 +12.7 +9.75 T17-16 +12.4 +10.6 T17-19 +12.4 +9.90 T17-20 +12.4 TC15-18 +12.7 T17-22 +13.9 TC15-38 +12.9 T17-23 +12.7 T17-8 +12.8 T17-25 +12.3 T17-9 +12.2 下部黄铜矿 yjb-3 +10.6 T17-11 +12.4 yjb-5 +10.6 T17-13 +12.7 yjb-6 +10.9 T17-16 +12.1 Y17-7 +8.76 T17-19 +12.6 Y17-8 +8.85 T17-20 +12.4 Y17-12 +8.66 T17-22 +12.7 下部黄铁矿 yjb-3 +10.8 T17-23 +12.7 yjb-5 +10.7 T17-25 +13.1 yjb-6 +11.0 上部黄铁矿 TC15-5 +13.6 Y17-7 +8.95 TC15-17 -1.02 +9.48 -0.96 +9.05 +9.22 +8.71 +10.3 +8.97 +12.8 Y17-8 +9.64 +4.51 Y17-12 +9.54 -1.96 下部磁黄铁矿 Y17-7 +9.20 +1.25 +9.28 +11.2 +9.07 +10.9 +7.93 TC15-18 +12.6 +8.74 +12.5 TC15-38 +12.9 +13.0
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