Wall rock alteration and trace elements of pyrite in Qiyugou No.189 porphyry gold deposit in western Henan Province and their constraints on metallogenic process
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摘要:
豫西祁雨沟189号金矿床是华北陆块南缘熊耳山矿集区近年新发现的中型金矿床。金矿体赋存于早白垩世角闪二长花岗岩体内，上部为细脉浸染状金矿化，下部为岩浆热液角砾岩型金矿化，总体具有斑岩型矿床特征。尽管前人开展过研究工作，但对于矿床蚀变分带和成矿过程仍存在较大的争议。在野外调查划分蚀变分带的基础上，运用微区分析技术对不同蚀变带中的黄铁矿主、微量元素和硫同位素组成开展了测试分析。结果表明，围岩蚀变具有面型分带特征，由矿体中心到外围发育钾长石化带、绢英岩化带和青磐岩化带。金主要以裂隙金、粒间金和包体金的形式赋存于黄铁矿等硫化物中，不可见金的含量低。从钾长石化带，经绢英岩化带到青磐岩化带，Ag、Bi含量整体呈上升趋势，As、Sb、Zn、Mn、Mo、Sn等总体变化不明显。原位硫同位素组成表明成矿物质来源于深部岩浆。对金矿成矿过程进行了探讨，指出络合物和Te-Bi熔体对Au的迁移富集起着重要作用。
Abstract:The Qiyugou No.189 gold deposit in western Henan is a medium-sized one newly discovered in the Xiong'ershan ore-concentrated area on the southern margin of the North China Block in recent years.The gold orebodies are hosted in the Early Cretaceous hornblende monzonitic granite.The upper part is veinlet disseminated gold mineralization, and the lower part is hydrothermally mineralized Au-bearing breccia, which shows porphyry mineralization characteristics.Although predecessors carried out research work, there are still big controversies about the alteration zonation and mineralization process of the deposit.Based on the field investigation and analysis of alteration zonation, micro-area analysis technology was used to test and study the main-trace elements and sulfur isotopic compositions of pyrite in different alteration zones.The wall rock alteration zonation is characterized by potassium feldspar zone-sericitization zone-propylitization zone from the center to the periphery of the orebody.Gold mainly occurs in the form of fissure gold, intergranular gold and inclusion gold in pyrite and other sulfide, and the content of invisible gold is low.From the potassic zone, through the phyllic zone, to the propylitic alteration zone, the contents of Ag and Bi tend to increase, while the contents of As, Sb, Zn, Mn, Mo and Sn, etc.show no obvious changes.The in-situ sulfur isotope composition indicates that the ore-forming material originates from deep magma.The analysis of its metallogenic process indicates that complexes and Te-Bi melts play an important role in the migration and enrichment of gold.
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表 1 祁雨沟189号金矿床各蚀变带黄铁矿电子探针分析结果
Table 1. EPMA analysis of pyrite in each alteration zones of Qiyugou No.189 gold deposit
样品号 蚀变带 Se As Ge S Ga Pb Sb Fe Co Bi Ni Zn Te Cu Ag Au 总计 δS δFe N(S)/N(Fe) ZK032H11-1 钾长石化带 0.03 0.02 - 53.34 - 0.02 - 46.35 0.08 - - 0.05 - - 0.02 0.02 99.93 -0.206 -0.430 2.014 ZK032H11-2 - 0.07 - 52.96 - 0.03 - 45.54 0.06 - - - - - - 0.03 98.69 -0.913 -2.163 2.035 ZK032H21-1 - 0.05 - 53.24 - 0.08 - 46.29 0.05 - - - - - - 0.03 99.74 -0.393 -0.556 2.013 平均 0.03 0.05 - 53.18 - 0.04 - 46.06 0.06 - - 0.05 - - 0.02 0.03 99.52 -0.504 -1.050 2.021 ZK032H11-5 绢英岩化带 - 0.01 - 52.95 - - 0.01 46.29 0.11 - - 0.02 0.02 - - - 99.41 -0.93 -0.561 2.002 ZK032H11-6 0.02 - 0.02 52.81 - - - 46.37 0.06 - - - 0.04 0.02 - - 99.34 -1.196 -0.385 1.993 ZK032B26-2 - - - 52.73 - - - 46.62 0.03 - - 0.03 0.01 - - - 99.42 -1.351 0.146 1.979 ZK032B26-3 - 0.06 - 53.55 0.01 0.06 - 46.40 0.09 - - - - 0.01 - - 100.18 0.183 -0.329 0.020 ZK032B26-4 - - - 52.70 - 0.03 - 46.28 0.05 - - 0.02 - - - 0.04 99.12 -1.398 -0.582 1.993 ZK032B26-5 0.03 - - 52.78 - 0.02 0.01 46.15 0.02 - - 0.04 - - - 0.03 99.08 -1.257 -0.857 2.001 ZK032B26-1 - 0.05 - 52.99 0.05 - 0.03 46.58 0.05 - - - 0.02 - 0.01 - 99.78 -0.895 0.062 1.991 平均 0.02 0.03 0.02 52.93 0.03 0.04 0.02 46.38 0.06 - - 0.03 0.02 0.02 0.01 0.03 99.64 -0.978 -0.358 1.997 ZK022H63-9 青磐岩化带 - - - 53.27 - - - 46.28 0.06 - - - 0.03 - - - 99.64 -0.754 -0.694 2.008 ZK022H63-10 0.02 - - 53.44 - 0.10 - 46.6 0.11 - 0.01 0.03 - - - - 100.31 -0.664 0 1.996 ZK032H21-5 - 0.03 - 52.82 - - - 46.04 0.07 - - - - - - - 98.96 -0.453 -0.206 2.004 ZK032H21-6 - 0.04 0.03 53.02 0.02 0.14 0.03 45.85 0.04 - - 0.02 - - - 0.04 99.23 -1.182 -1.096 2.008 ZK032B144-1 0.04 - - 53.05 - - - 46.23 0.03 - 0.02 - 0.02 0.01 - 0.02 99.42 -0.812 -1.495 2.023 ZK032B144-2 - 0.03 - 53.10 - 0.06 - 46.55 0.07 - - - 0.04 - - 0.05 99.90 -0.311 -0.591 2.015 ZK032B144-3 0.04 0.01 - 53.21 - 0.05 - 46.45 0.06 - - 0.02 0.05 0.03 - - 99.92 -0.024 0.112 2.007 平均 0.04 0.03 0.03 53.05 - - 0.03 46.23 0.06 - - 0.02 0.04 0.02 - 0.03 99.58 -0.600 -0.567 2.009 ZK032B208-1 与方解石共生 - - - 54.04 - - - 46.16 0.12 - 0.03 - - - - 0.01 100.36 1.111 -0.831 2.049 ZK032B208-2 - 0.04 - 53.72 - 0.03 - 46.42 0.03 - 0.01 - - 0.02 - 0.04 100.31 0.503 -0.290 2.025 ZK032B208-3 - - - 53.36 - 0.06 - 45.86 0.03 0.04 0.03 0.03 0.01 - - - 99.42 0.167 -1.473 2.036 ZK032B208-4 - - - 53.98 - 0.06 - 46.37 0.08 - - - 0.03 - 0.01 0.03 100.6 0.995 -0.397 2.037 ZK032B115-1 - 0.02 - 52.56 - - - 46.20 0.07 - - 0.03 - - - 0.07 98.95 -1.665 -0.763 1.991 ZK032B115-2 - - - 52.84 - 0.07 0.03 46.09 0.05 - - - 0.04 - - 0.01 99.13 -1.133 -0.995 2.007 ZK032B115-3 0.06 - - 52.71 - 0.10 - 46.22 0.02 - 0.01 - 0.02 - - - 99.14 -1.381 -0.715 1.996 平均 0.03 0.03 - 53.32 - 0.06 0.03 46.19 0.06 0.04 0.02 0.02 0.03 0.02 0.01 0.03 99.89 -0.248 -0.781 2.020 ZK022B215-1 与硫铅铋矿共生 - - - 52.73 - 0.01 - 46.17 0.12 - - 0.01 0.03 - - - 99.07 -1.355 -0.825 1.999 ZK022B215-2 - - - 53.35 - - - 46.79 0.04 - - - - - - - 100.2 -0.193 0.520 1.995 ZK022B215-3 0.02 0.06 - 53.03 - - - 46.40 0.07 - - - - - 0.02 - 99.60 -0.79 -0.324 2.000 平均 0.02 0.06 - 53.03 - 0.01 - 46.45 0.08 - - 0.01 0.03 - 0.02 - 99.71 -0.779 -0.210 1.998 注：“一”表示元素含量低于检测限, 元素含量单位为% 
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表 2 祁雨沟189号金矿床各蚀变带黄铁矿LA-ICP-MS微量元素分析结果
Table 2. LA-ICP-MS analysis of trace elements in pyrites from different alteration zones of Qiyugou No.189 gold deposit
10-6 样品编号 Py产状 As Sb Au Ag Cu Pb Zn Mn Mo Co Ni Sn Bi Co/Ni ZK32H21-K1 Py1 nd nd - nd nd 10.71 - nd - 18.98 - 1.55 22.02 - ZK32H21-K2 Py1 42.48 nd - 0.61 nd - 7.51 nd - 2122 80.71 nd - 26.29 ZK22H2-1-1 Py1 17.99 nd - - nd 1.53 - - nd 2053 - nd 0.34 - ZK22H2-1-2 Py1 - nd nd nd nd 9.47 20.42 - nd 7031 17.96 nd 26.96 391.4 ZK22H44-1 Py1 22.14 nd - 1.13 nd nd 10.35 nd nd 1132 - 1.83 - - 平均(钾长石化带) Py1 27.54 nd - 0.87 nd 7.24 12.76 - - 2471 49.33 1.69 16.44 208.9 ZK22H44-2 Py2 nd 0.34 0.28 nd nd 34.90 27.47 14.25 - 587.1 - nd 74.12 - ZK32B11-SM1 Py2 - - 0.06 0.74 nd - 12.57 - nd 152.9 - nd nd - ZK32B11-SM2 Py2 - - - 0.10 nd 0.87 15.77 - 6.51 56.39 46.66 0.61 nd 1.21 ZK32B26-SM1 Py2 164.9 nd 0.07 nd nd nd 16.57 4.90 nd 24.67 - nd 0.27 - ZK32B26-SM2 Py2 37.80 0.38 - nd nd 1.70 10.42 nd 10.82 212.9 - 1.05 0.65 - ZK32B77-1-1 Py2 nd 0.18 nd - nd nd 11.42 nd nd 599.7 60.83 1.12 - 9.86 ZK32B77-1-2 Py2 - nd nd nd nd - 20.17 - nd 142.8 nd 1.10 - - ZK32H9-1 Py2 8.63 2.35 3.97 318.1 nd 4986 24.60 - nd 127.7 306.7 - 3355 0.42 ZK32H9-2 Py2 - - - 0.40 nd - 9.24 - nd 417.2 207.2 - - 2.01 ZK32H9-3 Py2 40.06 0.42 nd 3.87 nd 412.7 - - nd 50.56 2861 nd 5.25 0.02 ZK22H21-1 Py2 15.88 0.35 - 11.31 nd 2179 15.37 nd nd 781.9 nd - 45.72 - ZK22H21-2 Py2 19.01 - - 0.26 nd 1.76 17.57 5.13 - 263.9 - 0.56 0.24 - ZK22H21-3 Py2 19.51 - - - nd 1.31 72.68 - nd 144.7 - - nd - ZK32H19-S2 Py2 44.89 nd nd nd - - - nd nd - nd - - - ZK32H19-S3 Py2 130.6 nd - nd - - - - nd - nd - - - ZK32H19-S4 Py2 44.88 0.14 0.02 nd - 0.90 17.12 nd - - - - - - 平均(绢英岩化带) Py2 47.83 0.46 0.88 47.82 - 846.6 20.84 6.07 5.78 274.0 580.4 0.89 435.1 2.70 ZK32H20-1 Py3 nd nd nd nd nd nd - - nd 15.66 - nd nd - ZK32H20-2 Py3 - nd 0.10 nd nd nd 12.30 - - 175.7 - nd nd - ZK32H20-3 Py3 - nd nd nd nd - 12.49 nd - 401.5 - - 2.27 - ZK32H20-4 Py3 - - nd - nd 21.53 25.88 12.25 - 301.5 - nd 22.76 - ZK32H20-5 Py3 - nd nd nd nd 4.43 16.41 nd - 962.9 nd nd 5.75 - ZK32H21-CM2 Py3 49.39 nd 0.18 17.80 nd 362.4 9.73 nd nd nd nd 1.87 198.6 - ZK22H10-1 Py3 23.04 nd 0.16 nd nd 1.96 16.67 21.46 nd 403.1 nd nd 6.63 - ZK22H10-2 Py3 47.33 0.76 nd 5.38 nd 52.66 19.44 - - 192.3 394.6 - 81.70 0.49 ZK22H18-CM1 Py3 - 0.63 0.07 nd nd 2.68 14.88 nd nd 39.51 nd nd nd - ZK22H18-CM2 Py3 nd - nd nd nd 1.70 24.87 nd nd - - 2.52 0.93 - ZK22H22-1 Py3 66.88 nd nd nd nd 3.52 12.34 nd nd 2396 nd nd 8.89 - ZK22H22-2 Py3 86.84 0.22 nd nd nd nd - nd - 2111 - 2.47 nd - ZK22H43-1 Py3 55.22 nd 0.07 - nd 2.88 16.82 - nd nd - - 1.38 - ZK22H43-2 Py3 167.7 0.37 0.09 1.24 nd 4.17 25.16 - nd nd 151.1 nd 1.05 - ZK32B144-1 Py3 - 0.13 nd nd - - - nd nd 387.5 nd 0.50 - - ZK32B144-2 Py3 nd - 0.02 - nd nd 6.66 2.09 - 477.9 - - nd - ZK32B144-3 Py3 83.50 0.16 - 0.55 - 9.56 nd 9.57 - 137.3 nd - 0.89 - 平均(青磐岩化带) Py3 72.49 0.38 0.10 6.24 - 42.50 16.43 11.35 - 615.5 272.9 1.84 30.08 0.49 ZKO32B115-1 Py4 24.56 0.06 - - - 1.74 13.10 1.44 nd 1.57 - - 0.45 - ZKO32B115-2 Py4 14.69 nd 0.20 7.10 11.11 121.8 14.98 1.58 - 12.84 nd - 18.57 - ZKO32B115-3 Py4 - nd - - - nd 16.38 nd - 229.3 21.38 nd nd 10.73 ZKO32B115-4 Py4 - nd nd - 4.73 nd - nd - 29.35 - - nd - ZKO32B115-5 Py4 26.93 0.32 - 0.67 4.19 22.91 16.82 nd nd 4.09 nd nd 0.74 - ZK32H18-1 Py4 - - 0.05 nd - - 8.67 - - 13.07 - - 0.03 - ZK32H18-2 Py4 - nd nd - - 1.02 15.96 - nd 8.13 - nd 0.13 - ZK32H18-3 Py4 nd nd 0.05 nd 5.57 2.56 11.10 2.01 - 8.29 - - 0.15 - ZK32H18-4 Py4 - - - 0.61 - - 8.78 - nd 6.69 - - 0.06 - ZK32H18-5 Py4 - - nd nd 5.03 0.43 13.22 - - 729.3 nd - 0.19 - ZK32H19-F1 Py4 64.93 nd - - - 1.70 16.06 - nd - nd nd 0.14 - ZK32H19-F2 Py4 77.46 5.34 0.15 53.26 432.2 5361 447.3 nd nd nd - - 151.1 - ZK32H19-F3 Py4 2768 - 0.15 0.73 7.90 50.79 13.12 nd - 13.90 157.8 - 1.57 0.09 ZK32H19-F4 Py4 853.9 - 0.07 - - 0.57 - - - 236.9 19.53 0.26 - 12.14 ZK32H19-F5 Py4 nd - - 1.93 10.01 112.8 9.37 - - nd nd nd 0.24 - 平均(与方解石共生) Py4 547.2 1.91 0.11 10.72 60.09 516.2 46.53 1.68 - 107.8 66.22 0.26 14.44 7.65 注：“nd”表示元素未检测出；“-”表示元素含量低于检测限
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表 3 祁雨沟189号金矿床黄铁矿原位硫同位素分析结果
Table 3. In-situ sulfur isotope analysis of pyrite of Qiyugou No.189 gold deposit
样品编号 蚀变带 黄铁矿世代 δ34S值/‰ ZK022H2-1 钾长石化带 Py1 -0.1 ZK022H2-2 Py1 -3.2 ZK032H11-1 Py1 1.9 ZK032H11-2 Py1 3.5 ZK022H44-1 Py1 0.0 ZK022H44-2 Py1 0.3 平均 Py1 0.4 ZK032B26-1 绢英岩化带 Py2 -0.5 ZK032B26-2 Py2 1.3 ZK032H19-1 Py2 0.1 ZK032H19-2 Py2 -2.1 ZK032H19-4 Py2 -7.3 ZK022H21-1 Py2 -7.4 ZK022H21-2 Py2 -2.2 平均 Py2 -2.6 ZK022H18-1 青磐岩化带 Py3 0.7 ZK022H18-3 Py3 -4.7 ZK022H22-1 Py3 -6.2 ZK022H22-2 Py3 -4.2 ZK022H22-3 Py3 -0.2 ZK032H20-1 Py3 -5.1 ZK032H20-2 Py3 -7.8 ZK032H20-3 Py3 -6.4 平均 Py3 -4.2 ZK032B115-1 与方解石共生 Py4 1.8 ZK032B115-2 Py4 1.3 ZK032B208-1 Py4 0.6 ZK032B208-2 Py4 -0.3 ZK032H18-1 Py4 -5.7 ZK032H18-3 Py4 -1.0 平均 Py4 -0.6
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① 姚书振. 河南省嵩县祁雨沟金矿床成矿规律研究报告. 武汉: 中国地质大学, 2012.
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