In-situ sulfur isotope characteristics of pyrite and chalcopyrite from the Naruo porphyry Cu (Au) deposit in Xizang: Implications for geological significance
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摘要:
拿若矿床是目前西藏多龙矿集区内第三大斑岩型铜（金）矿床，前人针对成岩成矿地质年代学、成矿地质背景等开展了大量研究，但对于其成矿物质硫的来源等成矿机制尚不明确。本文针对拿若矿床中广泛发育的黄铁矿和黄铜矿，利用镜下鉴定、LA-MC-ICP-MS同位素测试分析等方法，开展了矿相学特征和同位素地球化学研究，以期查明其原位硫同位素特征，揭示其矿床成因并指示找矿勘查。研究结果显示，黄铁矿主要分为三类，从早到晚分别为：Py-Ⅰ→Py-Ⅲ→Py-Ⅱ→Py-Ⅲ，除Py-Ⅰ外，其他均与黄铜矿的形成密切相关。黄铁矿δ34S值介于－4.05‰～3.49‰（均值为－0.2‰，n=53），黄铜矿表现出更小的δ34S值特征，即δ34S=－7.24‰～0.32‰（均值为－2.44‰，n=24），测试结果与矿集区内其他矿床数值相近。计算所得成矿流体总硫值（δ34SΣ）为－3.06‰，表明硫的来源主要与岩浆硫有关。硫同位素黄铁矿–黄铜矿矿物对显示成矿温度介于255℃～590℃之间，成矿中心温度为320℃，证实了中温成矿环境。硫同位素空间分布特征表明，从矿化中心到外围，δ34S值呈逐渐降低的趋势，这与某些碱性斑岩型矿床明显不同。本次研究认为，拿若矿床的成矿主要与中温环境和远端SO2的脱气作用有关，该特征可作为拿若矿床重要的找矿勘查指示标志。本次研究丰富了对于拿若矿床硫的来源和成矿温度等成矿机制的认识，为下一步成矿理论和找矿勘查研究奠定了基础。
Abstract:The Naruo deposit is the third largest porphyry Cu (Au) deposit within the Duolong ore district in Xizang. Previous studies have extensively investigated the petrogenesis, metallogenetic geological chronology, and metallogenic geological background. However, the ore-forming mechanism, including the source of sulfur, remains unclear. This study focuses on the widespread occurrence of pyrite and chalcopyrite in the Naruo ore deposit. Through methods such as optical microscopy identification and LA-MC-ICP-MS isotopic analysis, mineralogical characteristics and isotopic geochemistry were investigated. The aim is to elucidate the in-situ sulfur isotope characteristics, reveal the ore genesis of the deposit, and provide guidance for mineral exploration. Based on microscopic observations, three types of pyrite are categorized, from earlier to later: Py-Ⅰ→Py-Ⅲ→Py-Ⅱ→Py-Ⅲ. Except for Py-Ⅰ, all others are closely associated with the occurrence of chalcopyrite. Pyrite exhibits δ34S values ranging from －4.05‰ to 3.49‰ (with a mean of －0.2 ‰, n=53), while chalcopyrite demonstrates smaller δ34S values, ranging from －7.24‰ to 0.32‰ (with a mean of －2.44‰, n=24). These test results closely approximate values found in other deposits within the ore cluster. The total sulfur value of the ore-forming fluid (δ34SΣ) is －3.06‰, indicating that the source of sulfur is primarily associated with magmatic sulfur. The sulfur isotope mineral pairs of pyrite-chalcopyrite indicate ore-forming temperatures ranging from 255℃ to 590℃, with a central ore-forming temperature of 320℃, revealing a mesothermal ore-forming environment in the ore deposit center. The spatial distribution patterns of sulfur isotopes indicate a gradual decrease in δ34S values from the mineralization center to the periphery, which is notably different from some alkaline porphyry-type deposits. This study suggests that such variation is attributed mainly to ore formation in a mesothermal environment and the degassing of remote SO2, thus serving as crucial exploration indicators for the Naruo deposit. This study has enriched our understanding of the sources of sulfur and ore-forming temperatures, among other ore-forming mechanisms, in the Naruo ore deposit. It lays the foundation for further research in ore-forming theories and mineral exploration.
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Keywords:
- pyrite /
- chalcopyrite /
- in-situ S isotope /
- Naruo deposit /
- Duolong ore district /
- Xizang
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图 1 多龙矿集区地质、构造、矿产简图
Figure 1. Sketch map of geology, structure, and mineral resources in Duolong ore district
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图 2 拿若斑岩型铜矿床地质简图（修改自方向等，2014）
Figure 2. Sketch map of Naruo porphyry copper deposit (modified from Fang et al., 2014)
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图 3 拿若矿床典型矿石组构显微照片
a、b. 结晶结构：黄铁矿、黄铜矿粒状结晶结构，可见自形晶黄铁矿发生断裂被黄铜矿充填；c. 交代结构：沿裂隙充填的黄铜矿边缘被铜蓝交代；d. 交代结构：黄铁矿被闪锌矿、方铅矿充填交代，可见港湾状交代结构，后期黄铜矿以包裹体和交代矿物边缘相方式形成；e. 固溶体分离结构：黄铜矿以固溶体分离方式存在于闪锌矿边缘；f. 压碎结构：早期黄铁矿受外力作用发生碎裂，后期黄铜矿沿裂隙充填发育；Py—黄铁矿，Ccp—黄铜矿，Cv—铜蓝，Sp—闪锌矿，Gn—方铅矿
Figure 3. Micrographs of typical ore texture from Naruo deposit
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图 4 拿若矿床不同类型黄铁矿显微镜下照片
a. Py-Ⅰ期早期黄铁矿颗粒，呈椭圆状，发育于岩体基质中，受后期热液影响内部多发育硅酸盐矿物、黄铜矿等的包裹体，从内到外发育三期环带，S同位素先降低后升高；b. Py-Ⅱa期含矿物包裹体的热液成因粒状黄铁矿，与黄铜矿脉伴生；c. Py-Ⅱb期含矿物包裹体热液成因脉状黄铁矿，包裹体颗粒较大，主要为硅酸盐矿物、黄铜矿、硫砷铜矿等；d. Py-Ⅲa表面光滑黄铁矿脉，与黄铜矿共生；e. Py-Ⅲb表面光滑黄铁矿颗粒，呈半自形—他形粒状，裂隙被后期黄铜矿脉填充，S同位素多呈正值；f. 热液黄铁矿，发育于基质或围岩中，右下角黄铁矿可见3阶段，早期为光滑黄铁矿，中期为麻点+含矿物包裹体黄铁矿，晚期为光滑黄铁矿，左上黄铁矿中心发育为麻点+含矿物包裹体黄铁矿，外围发育光滑黄铁矿，总体从中心到外围S同位素逐渐升高；Qtz—石英，Py—黄铁矿，Ccp—黄铜矿，Eng—硫砷铜矿
Figure 4. Microscopic photos of different types of pyrite in Naruo deposit
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图 5 拿若矿床AA’剖面及样品采集位置图
Figure 5. AA’ profile and sample location map of the Naruo deposit
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图 6 拿若黄铁矿和黄铜矿δ34S频率分布直方图（a）及δ34SΣ Pinckney法图解（b）
Py—黄铁矿，Ccp—黄铜矿
Figure 6. Histogram of δ34S frequency distribution of pyrite and chalcopyrite (a) and diagram of δ34SΣ Pinckney method (b) in the Naruo deposit
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图 7 多龙矿集区硫同位素值分布图（修改自高轲等, 2023）
图中拿若已有硫同位素数据引自吕丽娜, 2012；高轲等, 2023；铁格隆南数据引自王艺云等，2017，2018；多不杂数据引自李金祥，2008；肖剑波，2012；波龙数据引自周玉等，2013；郭硕，2013；拿顿数据引自王松等，2017；色那、尕尔勤、铁格山数据引自吕丽娜，2012；斑岩型铜矿床数据引自Stefanova et al., 2023；地幔硫范围引自Chaussidon et al., 1989
Figure 7. Distribution of sulfur isotope values in the Duolong ore district (modified from Gao et al., 2023)
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图 8 拿若AA’剖面黄铁矿δ34S等值线图（a）及低δ34S值处发育硬石膏微观照片（b）
Hem—赤铁矿，Anh—硬石膏
Figure 8. Contour map of δ34S values for pyrite in AA’ profile of the Naruo deposit (a) and microphotographs of anhydrite development at low δ34S values (b)
表 1 拿若矿床金属硫化物原位S同位素测试结果及矿物对温度计
Table 1 In-situ S isotope test results and mineral pair thermometers of sulfides in the Naruo deposit
测试样品编号 δ34S/‰ 2σ 矿物类型 温度/℃ 测试样品编号 δ34S/‰ 2σ 矿物
类型0701-74.2-01-2 0.90 0.20 Py-Ⅱb 1504 -495.1-053.49 0.21 Py-Ⅲb 0701-74.2-01-3 0.57 0.27 Py-Ⅱb 1504 -495.1-062.35 0.12 Py-Ⅲb 0701-74.2-02-1 1.94 0.16 Py-Ⅱb 1504 -495.1-072.52 0.13 Py-Ⅲb 0701-74.2-02-2 0.74 0.20 Py-Ⅱb 1504 -495.1-082.03 0.12 Py-Ⅲb 0701-74.2-03-1 －0.84 0.09 Py-Ⅱa 0801-404.63-03 －0.69 0.09 Py-Ⅲa 0701-148.7-01 0.66 0.09 Py-Ⅲa 0801-593.97-03 －1.81 0.11 Py-Ⅱa 0701-217.4-01-1 －0.17 0.14 Py-Ⅱb 2301 -132.3-01－3.70 0.12 Py-Ⅱb 0701-217.4-01-2 －0.71 0.22 Py-Ⅱb 2301 -132.3-03－0.59 0.09 Py-Ⅱa 0701-411.3-01 0.37 0.08 Py-Ⅱb 2301 -257.6-010.31 0.14 Py-Ⅱa 0701-411.3-02 －0.38 0.08 Py-Ⅱb 2301 -257.6-030.53 0.11 Py-Ⅱb 0701-411.3-03 －0.27 0.09 Py-Ⅱb 2301 -257.6-04－4.05 0.10 Py-Ⅱb 1504 -158.5-01－0.41 0.13 Py-Ⅰ 2301 -400.7-010.56 0.09 Py-Ⅱb 1504 -158.5-02－0.99 0.09 Py-Ⅰ 2301 -400.7-02－1.24 0.08 Py-Ⅱb 1504 -158.5-03－2.21 0.10 Py-Ⅰ 2301 -400.7-03－2.26 0.08 Py-Ⅱa 0001-81.42-02 －0.49 0.12 Py-Ⅲa 437 0001-81.42-03 －1.38 0.14 Ccp 0001-155.4-01 1.05 0.09 Py-Ⅱa 320 0001-155.4-02 －0.23 0.22 Ccp 0001-400.5-02 1.94 0.10 Py-Ⅲa 255 0001-400.5-03 0.32 0.18 Ccp 0701-880.4-02 0.31 0.13 Py-Ⅱa 420 0701-880.4-03 －1.37 0.14 Ccp 0701-880.4-04 －0.44 0.10 Py-Ⅲa 264 0701-880.4-05 －1.25 0.15 Ccp 0801-593.97-02 －1.14 0.12 Py-Ⅲa 590 0801-593.97-01 －1.74 0.14 Ccp 0001-81.42-01 0.03 0.09 Py-Ⅲa 0001-31.2-01 －1.76 0.13 Ccp 0001-155.4-03 －0.73 0.18 Py-Ⅱb 0001-81.42-04 －1.33 0.15 Ccp 0001-280.6-01 1.09 0.10 Py-Ⅱb 0001-81.42-05 －1.38 0.13 Ccp 0001-280.6-02 －2.64 0.15 Py-Ⅱb 0001-155.4-04 0.26 0.53 Ccp 0701-669.5-01 －0.05 0.08 Py-Ⅱb 0001-400.5-06 －6.24 0.97 Ccp 0701-669.5-03 －1.14 0.13 Py-Ⅱa 0701-148.7-02 －2.87 0.14 Ccp 0701-669.5-04 －1.23 0.13 Py-Ⅱa 0701-411.3-04 －0.56 0.20 Ccp 0701-669.5-05 －1.01 0.11 Py-Ⅱa 0701-669.5-02 －2.27 0.14 Ccp 0701-880.4-01 0.04 0.08 Py-Ⅱa 0801-60.6-01 －3.67 0.15 Ccp 0801-60.6-03 －1.20 0.09 Py-Ⅲa 0801-60.6-02 －4.64 0.15 Ccp 0801-152.45-01 －2.92 0.16 Py-Ⅱb 0801-152.45-02 －2.37 0.18 Ccp 0801-196.15-01 －0.63 0.11 Py-Ⅱb 0801-196.15-02 －7.24 0.15 Ccp 0801-257.2-01 0.71 0.09 Py-Ⅱa 0801-257.2-02 －3.21 0.17 Ccp 0801-404.63-01 －0.77 0.12 Py-Ⅲa 0801-404.63-02 －1.35 0.22 Ccp 0001-400.5-01 2.18 0.09 Py-Ⅲa 0801-593.97-04 －2.35 0.16 Ccp 0001-400.5-04 －1.13 0.09 Py-Ⅱa 0801-593.97-05 －3.20 0.15 Ccp 0001-400.5-05 －0.51 0.13 Py-Ⅱa 2301 -132.3-02－4.06 0.20 Ccp 0701-74.2-01-1 1.37 0.29 Py-Ⅱb 2301 -257.6-02－4.69 0.20 Ccp 1504 -158.5-04－0.21 0.10 Py-Ⅰ 注：黄铁矿–黄铜矿S同位素矿物温度计（t）计算方法见公式(1)，含温度的单元格左右两侧的黄铁矿–黄铜矿即为计算该温度的矿物对。 
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