Fluid Sources and Ore Genesis of the Pb-Zn Deposits of Huayuan Ore-Concentrated District, Northwest Hunan Province, China
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摘要: 湘西北花垣矿集区位于扬子地台东南缘，是湘西-鄂西成矿带上最典型的超大型铅锌矿床所在地.通过对花垣矿集区典型铅锌矿床流体包裹体显微测温、成分分析及C、H、O同位素研究，结果表明，该区铅锌矿床闪锌矿与方解石中流体包裹体的均一温度范围集中在120~200℃，盐度范围集中在8%~20% NaCleqv.流体中液相离子成分主要为Ca2+、Na+、Mg2+、SO42-、Cl-，气相成分主要为H2O、N2和CO2及少量的CO、CH4和H2.流体的δDSMOW值范围为-60.4‰~-33.0‰，δ18O流体值范围为3.8‰~9.2‰.以上流体包裹体和稳定同位素分析结果表明，花垣矿集区铅锌矿床的成矿流体具有热卤水的性质，主要来源于建造水和大气降水.成矿期方解石的δ13CPDB值范围为-4.89‰~0.57‰，δ18OSMOW值范围为13.37‰~21.73‰，略低于碳酸盐围岩，说明成矿流体中的碳主要来源于碳酸盐围岩的溶解作用.矿石沉淀机制可能为两种流体的混合，即来自深部的富含金属物质的热卤水与富含有机质和硫酸盐的建造水及下渗大气降水的混合导致了铅锌矿石的沉淀.对地质和地球化学资料的综合结果表明，花垣矿集区铅锌矿床属于密西西比河谷型（MVT）铅锌矿床.Abstract: The Pb-Zn deposits of Huayuan ore-concentrated district in northwest Hunan Province are located on the southeastern margin of the Yangtze Craton. It has been one of the most important giant Pb-Zn deposits in Xiangxi-Exi metallogenic belt. Through the microthermometric and component analysis of the fluid inclusion, and the C, H, O isotope study of the Pb-Zn deposits in Huayuan ore-concentrated district, the results show that fluid inclusions hosted in sphalerite and calcite have total homogenization temperatures concentrated of 120 to 200℃ and calculated salinities concentrated of 8% to 20% NaCleqv. Compositionally, the fluid inclusions are dominated by Ca2+, Na+, Mg2+, SO42- and Cl-, whereas the gaseous species consist of H2O, N2, CO2 with a small amount of CO, CH4, H2. Based on hydrogen isotopes of fluid inclusion waters and oxygen isotopic compositions of calcite, the ore fluids have δDSMOW and δ18O fluid of -60.4‰ to -33.0‰ and 3.8‰ to 9.2‰, respectively. Thus, the isotope data suggest that the ore-forming fluids were mostly derived from formation water, with variable amounts of meteoric water. The δ13CPDB and δ18OSMOW of calcite range from -4.89‰ to 0.57‰ and from 13.37‰ to 21.73‰, respectively, indicating that carbon in the ore-forming fluids was mainly sourced from carbonate wall rocks through water-rock reactions. Precipitation of the sulfide ores was attributed to mixing of two end-member fluids, i.e., metalliferous fluid and organic-and sulfate-rich fluids. Integration of geological and geochemical data suggest that the Pb-Zn deposits of Huayuan ore-concentrated district can be best classified as the MVT Pb-Zn deposit.
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图 1 花垣铅锌矿集区地质简图
F1.花垣-张家界断裂；F2.松桃-水田断裂；F3.麻栗场断裂；据李堃等(2017)修改
Fig. 1. Geological sketch of the Huayuan Pb-Zn ore-concentrated district
图 2 花垣矿集区下寒武统地层柱状图
Fig. 2. Stratigraphic sequence of lower Cambrian in Huayuan ore-concentrated district
图 3 花垣矿集区铅锌矿床的矿物组成及矿石结构构造特征
Sp.闪锌矿；Py.黄铁矿；Gn.方铅矿；Cal.方解石；Fl.萤石；Bit.沥青
Fig. 3. Photographs and photomicrographs showing mineralogical and textural characteristics of the Pb-Zn deposits of Huayuan ore-concentrated district
图 4 花垣矿集区铅锌矿床矿物生成顺序
Fig. 4. Mineral-forming sequence of the Pb-Zn deposits of Huayuan ore-concentrated district
图 5 花垣矿集区铅锌矿床闪锌矿(a、b)和方解石(c、d)中流体包裹体特征
Fig. 5. Characteristics of fluid inclusions in sphalerite (a, b) and calcite (c, d) of the Pb-Zn deposits of Huayuan ore-concentrated district
图 6 花垣矿集区铅锌矿床流体包裹体均一温度、盐度和密度直方图
Fig. 6. Histograms of homogenization temperature, salinity and density of fluid inclusion in the Pb-Zn deposits of Huayuan ore-concentrated district
图 7 花垣矿集区铅锌矿床成矿流体均一温度盐度散点图
MVT.密西西比河谷型；Sedex.喷流-沉积型；VMS.块状硫化物型；底图据Kesler(2005)修改
Fig. 7. Scatter diagram of homogenization temperatures and salinities of ore-forming fluid in the Pb-Zn deposits of Huayuan ore-concentrated district
图 8 花垣矿集区铅锌矿床方解石中流体的δDV-SMOW-δO流体图解
底图据Taylor(1974)
Fig. 8. δDV-SMOW-δO fluid diagram of fluid inclusion in calcite of the Pb-Zn deposits of Huayuan ore-concentrated district
图 9 花垣矿集区铅锌矿床碳酸盐围岩与成矿期方解石δ13CPDB-δ18OSMOW图
Fig. 9. δ13CPDB-δ18OSMOW diagram of carbonate rocks and calcite of the Pb-Zn deposits of Huayuan ore-concentrated district
表 1 花垣矿集区铅锌矿床流体包裹体特征及参数
Table 1. Microthermometric data and characteristics of fluid inclusions in the Pb-Zn deposits of Huayuan ore-concentrated district
采样位置 寄主矿物 大小
(μm)气液比
(%)均一温度(℃) 冰点温度(℃) 盐度
(%NaCleqv)密度
(g/cm3)范围 均值 范围 均值 李梅 闪锌矿 2~10 5~15 93~222(38) 140 -18.5~-9.7(10) -14.0 13.62~21.33 1.02~1.07 方解石 3~15 5~25 111~228(75) 164 -19.6~-3.0(75) -9.9 4.96~22.44 0.90~1.11 土地坪 闪锌矿 3~10 5~10 92~170(9) 132 -16.1~-12.1(8) -14.3 16.14~19.71 1.03~1.10 方解石 4~12 10~20 92~214(46) 160 -19.2~-2.2(25) -11.8 3.69~22.09 0.90~1.12 大石沟 闪锌矿 2~8 5~10 115~152(4) 129 -15.7~-9.7(4) -13.2 13.72~19.40 1.04~1.07 方解石 3~18 5~25 94~232(99) 161 -19.6~-3.4(97) -11.8 5.56~22.44 0.91~1.11 注：温度范围后的括号内为包裹体个数. 
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表 2 花垣矿集区铅锌矿床流体包裹体液相成分分析结果
Table 2. Liquid composition analysis results of fluid inclusions in the Pb-Zn deposits of Huayuan ore-concentrated district
采样位置 样号 矿物 F- Cl- NO3- SO42- Na+ K+ Mg2+ Ca2+ Na+/
K+Na+/
(Ca2++Mg2+)F-/
Cl-(μg/g) 李梅 LM-93 闪锌矿 1.61 20.70 2.06 290.00 7.71 2.39 2.51 112.00 3.23 0.07 0.08 LM-94 方解石 1.88 17.30 1.18 52.00 8.44 1.66 1.60 35.30 5.08 0.23 0.11 土地坪 TDP5-102 闪锌矿 0.93 12.40 1.76 213.00 4.24 1.62 1.53 83.40 2.62 0.05 0.07 TDP5-106 方解石 0.54 47.90 1.17 38.60 20.30 3.59 4.89 25.40 5.65 0.67 0.01 大石沟 DSG-91 闪锌矿 0.46 7.95 1.26 129.00 3.86 1.83 1.24 50.80 2.11 0.07 0.06 DSG--96 闪锌矿 0.20 5.51 1.75 198.00 3.91 3.22 1.37 94.60 1.21 0.04 0.04
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表 3 花垣矿集区铅锌矿床流体包裹体气相成分分析结果
Table 3. Gas compositon analysis results of fluid inclusions in the Pb-Zn deposits of Huayuan ore-concentrated district
采样位置 样号 矿物 H2 N2 CO CH4 CO2 H2O(气相) (μL/g) 李梅 LM-93 闪锌矿 0.552 9.06 0.944 0.288 20.30 2.69×105 LM-94 方解石 1.640 15.80 1.020 0.620 6.61 1.72×105 土地坪 TDP5-102 闪锌矿 0.431 11.30 0.904 0.422 11.80 1.23×105 TDP5-106 方解石 0.920 1.14 0.450 4.110 9.93 7.07×105 大石沟 DSG-91 闪锌矿 0.480 11.70 0.749 0.291 7.39 7.63×104 DSG-96 闪锌矿 0.204 11.60 0.935 0.311 12.50 1.17×105
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表 4 花垣矿集区铅锌矿床碳-氢-氧同位素分析结果
Table 4. Carbon, hydrogen and oxygen isotope analysis results of the Pb-Zn deposits of Huayuan ore-concentrated district
采样位置 样号 测试对象 δ13CPDB
(‰)δ18OPDB
(‰)δ18OSMOW
(‰)δDSMOW
(‰)δO流体
(‰)温度
(‰)数据来源 李梅 LM-62 方解石 0.57 -8.86 21.73 -55.7 9.2 152 本文 LM-63 方解石 -4.89 -16.97 13.37 / / / 本文 大石沟 DSG-51 方解石 0.18 -11.05 19.47 -60.4 6.5 145 本文 DSG-53 方解石 -1.64 -11.69 18.81 -46.9 5.8 145 本文 DSG-55 方解石 -2.68 -13.01 17.45 -56.4 4.4 145 本文 DSG-58 方解石 0.00 -12.66 17.81 -54.9 4.8 145 本文 DSG-60 方解石 -2.67 -13.62 16.82 -38.8 3.8 145 本文 DSG-62 方解石 -2.95 -13.57 16.87 -46.0 3.9 145 本文 DSG-63 方解石 -1.16 -11.28 19.23 -33.0 6.2 145 本文 土地坪 TDP5-102 方解石 -0.74 -12.19 18.29 本文 TDP5-104 方解石 -0.45 -10.69 19.84 本文 TDP5-105 方解石 -0.92 -12.95 17.51 本文 TDP5-107 方解石 -1.64 -14.06 16.37 本文 TDP3-112 方解石 0.17 -12.86 17.60 本文 李梅 L16-4 灰岩 0.29 / 22.06 夏新阶和舒见闻，1995 L16-6 灰岩 0.46 / 21.49 夏新阶和舒见闻，1995 LM-11 灰岩 1.05 -9.11 21.47 蔡应雄等，2014 LM-16 灰岩 0.52 -9.24 21.33 蔡应雄等，2014 13LM-B23 灰岩 1.17 -8.83 21.76 周云等，2017 13LM-B28 灰岩 0.55 -9.44 21.13 周云等，2017 13LM-B30 灰岩 0.62 -9.80 20.76 周云等，2017 大石沟 13DSG-B20 灰岩 0.44 -8.47 22.13 周云等，2017 13DSG-B21 灰岩 0.55 -10.74 19.79 周云等，2017 13DSG-B26 灰岩 0.77 -9.02 21.56 周云等，2017
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表 5 花垣矿集区铅锌矿床与典型MVT型铅锌矿床地质特征对比
Table 5. Comparison of geological characteristics between Pb-Zn deposits of Huayuan ore-concentrated district and MVT Pb-Zn deposit
花垣矿集区铅锌矿床 MVT型铅锌矿床 区域背景 扬子地台东南缘与江南造山带过渡区 造山带边缘前陆环境或靠近克拉通一侧的沉积盆地环境 赋矿围岩 下寒武系统清虚洞组藻灰岩、鲕粒灰岩 台地碳酸盐岩，主要为白云岩，少部分为灰岩 与岩浆岩关系 没有关系 没有关系 矿体形态 主要呈层状、似层状和脉状，少数呈浸染状、透镜状 一般为层状、似层状、透镜状、筒状和不规则状，局部可呈喀斯特形态和角砾状 控矿构造 湘黔断裂带及其次生断裂与背向斜 溶蚀坍塌角砾岩、断层和裂隙、相变过渡位置、白云石化生物礁相 矿物组合 矿石矿物主要为闪锌矿和方铅矿，次为黄铁矿，脉石矿物主要为方解石，次为重晶石、萤石、白云石和沥青 主要为闪锌矿、方铅矿、黄铁矿、白铁矿、方解石和白云石，重晶石与萤石很少 矿石结构构造 自形-半自形、他形、交代残余、脉状穿插、环带、镶边结构；团块状、脉状、网脉状、胶状、浸染状、角砾状构造 细-粗晶结构，各种交代、溶蚀、填隙包含结构；条带状、浸染状、角砾状、脉状构造 围岩蚀变 主要为方解石化，次为重晶石化、白云石化、黄铁矿化及萤石化 普遍为热液碳酸盐化，有机质化，少数还有硅化，极少地区还有粘土化、云母化、长石化 成矿流体 低温、中高盐度热卤水，温度范围集中在120~200 ℃，盐度范围集中在8%~20% NaCleqv 为低温中高盐度盆地卤水，温度一般为50~250 ℃，盐度一般为10%~30% NaCleqv 硫同位素组成 δ34S值变化范围为24.5‰~34.7‰ δ34S值变化范围为-25‰~30‰ 成矿物质来源 硫来源于海水硫酸盐或膏岩溶解，铅锌主要来源于青白口系-下寒武统等下伏地层 硫来源于地壳及海水中的硫酸盐，铅锌来源于上地壳
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