Occurrence of Silver in the Shagou Ag-Pb-Zn Deposit, Luoning County, Henan Province: Implications for Mechanism of Silver Enrichment
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摘要: 位于河南洛宁境内的沙沟热液脉型Ag-Pb-Zn矿床是熊耳山地区近年来新发现的大型矿床.野外观察和矿相学研究表明成矿过程包含4个阶段, 分别为石英-菱铁矿阶段(Ⅰ)、石英-闪锌矿阶段(Ⅱ)、石英-银矿物-方铅矿阶段(Ⅲ)和石英-碳酸盐阶段(Ⅳ), 其中Ⅱ、Ⅲ阶段为主成矿阶段.扫描电子显微镜-能谱分析(SEM-EDS)和电子显微探针微区成分分析(EMP)结果显示, 沙沟矿床中的银以不可见银和可见银两种形式存在, 但以可见银为主.不可见银主要以次显微包体(< 1 μm)的形式被包裹在黄铜矿和闪锌矿等硫化物中, 而可见银通常以各种银的独立矿物形式交代方铅矿和黄铜矿等硫化物或充填在硫化物和石英的显微裂隙内.结合本文研究和前人对沙沟矿床流体包裹体的研究认为, 银和铅、锌等金属离子在成矿早期高温阶段以氯络合物的形式搬运, 随着成矿热液温度和氧逸度的降低以及pH值的升高, 氯络合物因稳定性降低而解体, 硫氢络合物成为银、铅、锌的主要迁移形式.随着成矿热液温度的继续降低, 铅、锌等金属硫氢络合物开始分解, 方铅矿、黄铜矿和闪锌矿等硫化物得以沉淀, 此时部分银以显微和次显微包体银的形式被包裹于这些硫化物中.铅锌硫化物的大量沉淀引起成矿热液组成和性质的显著变化, 最终导致银从硫氢络合物中彻底解体, 并与Cu+、Sb3+等离子结合形成大量独立银矿物(如含银黝铜矿、硫锑铜银矿和辉铜银矿等), 而溶液中过饱和的银则以自然银的形式沉淀.Abstract: The Shagou Ag-Pb-Zn vein-type deposit, located in the Luoning county of Henan Province, is hosted in amphibolite facies metamorphic rocks of the Archean Taihua Group and consists of four stages of mineralization: the quartz-siderite stage (Ⅰ), the quartz-sphalerite stage (Ⅱ), the quartz-silver minerals-galena stage (Ⅲ), and the quartz-carbonate stage (Ⅳ), with stages Ⅱ and Ⅲ being the main mineralization stages. Scanning electron microscopy-energy dispersive spectrometry (SEM-EDS) and electron microprobe (EMP) analysis suggests that both visible and invisible Ag are present in the ores. Invisible Ag occurs mainly as sub-micron inclusions (< 1 μm) within chalcopyrite, sphalerite and other sulphide minerals, whereas visible Ag occurs as silver minerals that replaced galena, chalcopyrite and other sulphides, or fills microfractures in sulphides and quartz. Combined with existing fluid inclusion data, our results indicate that Ag+, Pb+, Zn+ and other metal ions were transported as chloride complexes at the early high-temperature stage. When temperature and oxygen fugacity of the fluids descended, coupled with increasing pH, chloride complexes started to decompose to liberate Ag+, Pb+, Zn+ to form HS- complexes. Continuous drop of temperature and likely degassing of ore fluids, led to separation of Pb+ and Zn+ from HS- to form galena and sphalerite, into which some amounts of Ag+ were incorporated, forming sub-microscopic to microscopic silver inclusions. With the changes of composition and property of ore-forming fluids caused by precipitation of voluminous sulfide, Ag+ was released from HS- complex to combine with Cu+ and Sb3+, forming silver minerals (e.g. polybasite, jalpaite and native silver).
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Key words:
- Xiong'er mineral district /
- Ag-Pb-Zn deposit /
- mineralogy /
- occurrence of silver /
- enrichment mechanism
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图 1 沙沟Ag-Pb-Zn矿床地质构造简图(据毛景文等, 2006, 略有简化)
Fig. 1. Geological and tectonic map of the Shagou Ag-Pb-Zn deposit
图 2 沙沟矿床Ag-Pb-Zn矿脉野外产状特征
a.典型矿脉及其外围的围岩蚀变.其中矿脉自内向外依次为石英、铁白云石、闪锌矿、菱铁矿,呈细脉状对称分布;b.宽厚的条带状矿脉中多期矿化叠加;c.含硫化物石英脉切割早期含菱铁矿粗晶闪锌矿脉;d.石英和方解石晶簇充填在方铅矿脉的裂隙中;e.矿脉及叠加矿化特征,围岩被分支复合的矿脉捕获并发生蚀变.菱铁矿常分布于矿脉边部,闪锌矿与石英关系密切.方铅矿呈细脉充填菱铁矿脉,或是呈宽厚脉体将菱铁矿、闪锌矿捕获至其内部;Sd.菱铁矿;Ank.铁白云石;Sp.闪锌矿;Gn.方铅矿;Py.黄铁矿;Cp.黄铜矿;Cal.方解石;Qz.石英
Fig. 2. Field attitudes of Ag-Pb-Zn lodes in the Shagou deposit
图 3 银铅锌矿石的矿物组成和结构构造
a.菱铁矿脉穿插绢英蚀变岩,前者又被闪锌矿细脉充填;b.块状粗粒闪锌矿脉被石英细脉穿插;c.黄铜矿、石英和粗晶方铅矿的共生关系;d.细粒致密块状方铅矿呈脉状充填蚀变带;e.菱铁矿沿脉壁向中心生长(箭头所示),闪锌矿紧随菱铁矿生长(透射光,正交偏光);f.毒砂被包裹于闪锌矿中并被方铅矿切割,在其周围有辉砷镍矿呈自形晶粒产出(反射光,单偏光);g.方铅矿被含银黝铜矿交代,二者共同产于闪锌矿与石英的接触裂隙内,黄铜矿呈乳滴状分布于闪锌矿中(反射光,单偏光);h.含银黝铜矿交代黄铜矿和方铅矿(反射光,单偏光);i.方铅矿和黝铜矿交代闪锌矿,方铅矿也可被黝铜矿交代;含银黝铜矿呈包裹体产出在方铅矿中(反射光,单偏光);Ger.辉砷镍矿;Apy.毒砂;Ttr.黝铜矿;Ag-Ttr.含银黝铜矿;Ser.绢云母;其他矿物代号缩写同图 2
Fig. 3. Mineral compositions and structures of the sulfide ores
图 4 主要银矿物组成和产状及其与硫化物的结构关系
a.含银黝铜矿和硫锑铜银矿交代方铅矿,三者共同产于闪锌矿与石英之间的显微裂隙内(反射光,单偏光);b.硫锑铜银矿交代黄铜矿和含银黝铜矿,三者共同产于闪锌矿裂隙内(反射光,单偏光);c.黄铜矿、含银黝铜矿及方铅矿呈细脉状充填在绢英岩化蚀变带内(左侧反射光,单偏光;右侧透射光,正交偏光);d.黄铜矿呈不规则状分布于黝铜矿内,自然银及辉铜银矿呈细脉状穿插二者(反射光,单偏光);e.辉铜银矿呈镶边状包裹自然银,二者交代黄铜矿、黝铜矿及方铅矿(反射光,单偏光);f.自然银及其外侧镶边状辉铜银矿共同呈脉状穿插交代黄铜矿(反射光,单偏光);Pol.硫锑铜银矿;Jal.辉铜银矿;Arg.辉银矿;Ag.自然银;矿物代号缩写同图 2和图 3
Fig. 4. Compositions and attitudes of the silver minerals and their relations with sulfides
图 6 代表性样品SG80(a, b)和SG68(c, d)中主要银矿物的背散射电子图像
a.含银黝铜矿和硫锑铜银矿呈共结边结构,它们共同交代方铅矿,三者呈集合体状共同产于闪锌矿与铁白云石之间的裂隙内;b.含银黝铜矿和硫锑铜银矿交代或切割方铅矿和闪锌矿,闪锌矿中可见硫锑铜银矿的显微包体;c.硫锑铜银矿呈不规则状产于闪锌矿裂隙内,含银黝铜矿交代方铅矿或呈显微包体分布于闪锌矿内;d.硫锑铜银矿、含银黝铜矿和石英呈脉状充填在闪锌矿的显微裂隙内.矿物代号缩写同图 2、图 3和图 4
Fig. 6. BSE images of silver minerals from the representative samples SG80 (a, b) and SG68 (c, d)
图 9 银的氯络合物和硫氢络合物及主要银矿物的logf(O2)-pH稳定场(据尚林波等, 2004, 略有修改)(a)和沙沟矿床部分银矿物的Ag-Cu-Sb三角图解及银矿物的生成顺序和演化趋势(b)
图a中粗实线区分Ag、Ag2S、AgCl固相稳定场;细实线区分各种溶解硫稳定场;虚线区分AgCl2-和Ag(HS)2-的稳定场;点线表示AgCl2-和Ag(HS)2-的溶解度等值线,浓度均为10-6 mol/L.实验和热力学计算表明(尚林波等, 2003, 2004),在相同的环境中Ag(HS)2-在中低温条件下比Pb+, Zn+硫氢络合物的溶解度要高.随着温度的降低,铅、锌硫化物发生饱和并沉淀,银则以硫氢络合物形式继续稳定存在于热液中,从而造成银与铅、锌的分离.当物理化学条件超出Ag(HS)2-的稳定场,Ag+可直接从溶液中沉淀形成辉银矿和自然银等独立银矿物;图b的数据来源于主要银矿物的电子探针分析
Fig. 9. Logf(O2)-pH predominance area of Ag-complexes and major silver minerals at 200 ℃ (a) and Ag-Cu-Sb triangular diagram indicating the deposit sequence and evolutionary tendency of silver minerals in the Shagou deposit (b)
表 1 沙沟矿床SEM-EDS和EMP研究样品简要描述
Table 1. Brief description of the samples for SEM-EDS and EMP from the Shagou deposit
样品号 矿脉 中段(m) 阶段 位置 样品描述 SG37 S14 450 Ⅲ CM105南沿脉50 m处方铅矿脉中部 伴有硅化的块状细粒方铅矿 SG39 S14 450 Ⅱ CM105南沿脉80 m处闪锌矿脉中部 被后期石英脉充填的粗粒闪锌矿 SG40 S14 450 Ⅲ CM105南沿脉80 m处方铅矿脉中部 中-细粒方铅矿呈脉状充填细粒闪锌矿脉 SG43 S14 450 Ⅱ CM105南沿脉90 m处闪锌矿脉边部 沿菱铁矿脉内侧生长的粗粒闪锌矿 SG68 S6 570 Ⅲ CM102北沿脉25 m处方铅矿脉边部 细粒方铅矿交代闪锌矿细脉 SG80 S6 570 Ⅲ CM102北沿脉120 m处矿脉中部 条带状多金属硫化物矿石 SG17 S16 490 - CM105南沿脉30 m处矿脉边部 与石英共生的粗粒方铅矿集合体 SG88 S8 570 - CM102北沿脉上山15 m处矿脉边部 细粒多金属硫化物矿石 表 2 沙沟矿床硫化物的电子探针分析结果(%)
Table 2. EMP data of sulfides from the Shagou deposit
矿物 分析点号 Ag Fe Cu Zn Pb S As Sb Co Ni Total 闪锌矿 SG37-1-3 b.d. 0.20 0.21 66.31 n.d. 32.53 0.04 b.d. n.d. n.d. 99.28 SG39-1-5 b.d. 2.18 0.45 64.36 n.d. 32.01 b.d. b.d. n.d. n.d. 99.00 SG43-1-3 0.02 3.59 0.78 62.54 n.d. 32.76 b.d. b.d. n.d. n.d. 99.69 SG40-2-4 0.59 0.52 1.37 63.98 n.d. 32.17 0.10 0.85 n.d. n.d. 99.58 SG68-1-3 0.04 0.43 0.18 66.86 n.d. 32.31 b.d. b.d. n.d. n.d. 99.82 SG88-1-4 b.d. 0.15 0.16 66.73 n.d. 32.68 b.d. b.d. n.d. n.d. 99.72 方铅矿 SG37-1-2 b.d. 0.07 0.14 0.44 86.49 12.36 b.d. b.d. n.d. n.d. 99.50 SG37-2-4 b.d. 0.07 0.14 0.22 87.22 12.18 b.d. b.d. n.d. n.d. 99.82 SG39-1-4 b.d. 0.67 0.14 1.01 85.97 12.09 b.d. b.d. n.d. n.d. 99.88 SG40-2-3 b.d. 0.09 0.23 0.59 86.55 12.46 b.d. b.d. n.d. n.d. 99.92 SG17-1-2 b.d. 0.07 0.15 0.23 86.85 12.41 b.d. b.d. n.d. n.d. 99.71 SG17-2-3 b.d. 0.08 0.24 0.27 86.61 12.53 b.d. b.d. n.d. n.d. 99.72 SG17-3-2 b.d. 0.11 0.18 0.19 87.03 12.31 b.d. b.d. n.d. n.d. 99.82 SG88-1-5 b.d. 0.08 0.14 0.21 86.89 12.32 b.d. b.d. n.d. n.d. 99.63 SG88-2-6 0.08 0.08 0.17 0.19 86.83 12.44 b.d. b.d. n.d. n.d. 99.79 黄铁矿 SG37-2-3 0.01 46.54 0.07 0.08 n.d. 52.29 0.19 b.d. 0.10 0.04 99.32 SG37-3-2 b.d. 46.36 0.35 0.06 n.d. 52.45 b.d. b.d. 0.09 0.06 99.38 SG39-2-2 0.03 46.05 0.04 0.45 n.d. 52.12 0.02 b.d. 0.30 0.44 99.45 SG39-3-1 b.d. 45.45 0.06 0.33 n.d. 52.35 0.95 b.d. 0.32 0.32 99.78 SG80-5-2 b.d. 46.45 0.06 0.08 n.d. 52.23 b.d. b.d. 0.10 0.13 99.05 SG88-3-3 0.04 45.73 0.24 0.08 n.d. 53.60 b.d. b.d. 0.08 0.03 99.79 黄铜矿 SG37-2-2 b.d. 30.95 33.82 0.09 n.d. 34.88 b.d. b.d. 0.05 0.05 99.83 SG37-3-1 0.01 30.93 33.32 0.12 n.d. 35.46 b.d. b.d. 0.06 0.03 99.93 SG40-2-5 1.12 28.26 32.78 0.86 n.d. 35.09 0.03 1.57 0.08 0.03 99.82 SG68-1-5 0.08 29.57 32.48 2.05 n.d. 35.51 0.00 b.d. 0.06 0.06 99.81 SG17-4-1 0.37 30.01 32.96 0.41 n.d. 35.44 b.d. 0.02 0.07 0.03 99.30 SG88-1-2 0.90 30.74 33.37 0.10 n.d. 34.49 b.d. b.d. 0.07 0.04 99.72 SG88-2-2 1.74 29.74 33.54 0.14 n.d. 34.00 b.d. b.d. 0.06 0.03 99.25 毒砂 SG39-1-1 0.01 35.70 0.05 0.59 n.d. 22.85 39.90 0.13 0.12 0.10 99.45 SG39-3-2 0.03 34.15 0.05 0.74 n.d. 20.15 43.37 0.14 0.55 0.41 99.59 SG39-3-4 b.d. 35.75 0.08 0.49 n.d. 24.45 38.30 0.00 0.24 0.20 99.51 SG39-3-5 b.d. 34.94 0.09 1.58 n.d. 22.70 40.45 0.08 0.08 0.05 99.97 SG39-4-1 b.d. 35.81 0.08 0.62 n.d. 23.80 39.08 0.23 0.13 0.05 99.78 SG43-2-1 0.02 35.87 0.10 0.09 n.d. 22.67 40.57 b.d. 0.14 0.08 99.53 铁辉砷镍矿* SG39-1-6 b.d. 10.84 b.d. 1.14 n.d. 19.98 41.41 b.d. 3.64 21.38 98.39 SG39-1-7 b.d. 10.31 b.d. 0.53 n.d. 20.53 43.04 b.d. 3.21 21.70 99.32 注:“b.d.”表示低于检测限;“n.d.”表示未进行检测;*矿物命名据於晓晋等(1997). 表 3 沙沟矿床银矿物的电子探针分析结果(%)
Table 3. EMP data of silver minerals from the Shagou deposit
矿物 分析点号 Ag Fe Cu Zn S As Sb Se Te Sn Co Ni Total 自然银 SG88-1-1 99.13 n.d. 0.28 n.d. 0.20 b.d. b.d. n.d. n.d. n.d. n.d. n.d. 99.61 SG88-2-1 99.26 n.d. 0.21 n.d. 0.11 b.d. b.d. n.d. n.d. n.d. n.d. n.d. 99.58 SG88-2-4 99.10 n.d. 0.23 n.d. 0.11 b.d. b.d. n.d. n.d. n.d. n.d. n.d. 99.44 硫锑铜银矿 SG40-2-1 69.44 0.06 6.12 0.51 14.73 2.35 5.92 b.d. 0.04 b.d. 0.06 0.08 99.30 SG43-1-2 70.70 0.69 4.31 0.47 14.89 1.98 6.36 b.d. 0.03 b.d. 0.06 0.06 99.55 SG68-1-1 66.98 0.07 5.12 1.92 15.63 2.18 7.36 b.d. 0.02 b.d. 0.07 0.08 99.42 SG68-2-1 70.21 0.05 4.89 0.77 14.37 1.31 7.76 b.d. b.d. b.d. 0.05 0.08 99.49 含银黝铜矿* SG37-1-1 11.80 1.40 29.38 5.99 23.75 1.61 25.41 b.d. b.d. 0.21 0.04 0.06 99.65 SG37-2-1 13.49 1.32 28.18 6.12 23.19 0.69 26.45 b.d. b.d. 0.18 0.05 0.06 99.73 SG40-1-1 15.32 1.74 26.88 6.10 23.20 2.27 23.50 b.d. b.d. 0.33 0.05 0.05 99.45 SG40-2-2 15.42 2.01 27.09 5.93 23.49 2.63 22.96 b.d. b.d. 0.17 0.04 0.08 99.81 SG40-3-1 15.46 1.90 26.07 7.66 22.84 1.78 24.03 b.d. b.d. 0.20 0.05 0.06 100.05 SG43-1-1 16.88 2.33 25.41 5.83 23.36 3.24 22.15 b.d. b.d. 0.18 0.04 0.07 99.49 SG68-1-2 17.04 2.45 24.45 6.02 23.02 1.33 24.85 b.d. b.d. 0.24 0.02 0.08 99.51 SG80-5-1 16.05 1.59 26.40 5.62 23.34 1.21 25.14 b.d. b.d. 0.23 0.07 0.07 99.71 黝铜矿* SG17-1-1 4.52 0.82 34.64 6.89 24.42 1.56 25.77 b.d. b.d. 0.28 0.05 0.06 99.00 SG17-3-3 3.05 0.78 36.23 6.94 25.12 3.18 24.02 b.d. b.d. 0.24 0.05 0.06 99.66 SG88-1-3 3.29 0.45 35.97 7.38 24.18 0.85 26.84 b.d. b.d. 0.25 0.07 0.07 99.33 SG88-2-3 3.58 0.51 35.99 7.39 24.01 0.59 27.15 b.d. b.d. 0.23 0.06 0.07 99.58 SG88-2-5 4.88 0.44 35.28 7.18 24.19 1.19 26.02 b.d. b.d. 0.23 0.07 0.08 99.55 SG88-3-1 5.78 0.38 33.61 7.28 24.14 1.13 26.78 b.d. b.d. 0.21 0.07 0.06 99.43 SG88-3-2 6.02 0.38 34.30 7.22 24.34 1.38 25.69 b.d. b.d. 0.24 0.04 0.07 99.69 SG88-3-4 2.09 0.44 36.60 7.43 24.38 0.87 27.23 b.d. b.d. 0.26 0.06 0.06 99.41 注:“b.d.”表示低于检测限;“n.d.”表示未进行检测;*矿物命名据黄典豪(2000). -
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