Zircon U-Pb Geochronology, Geochemistry and Sr-Nd-Hf Isotopes of Diorite in Heishishan Copper Polymetallic Deposit, East Kunlun
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摘要: 黑石山铜铅锌矿床位于东昆仑造山带中段的五龙沟地区，矿区内中三叠世的侵入岩十分发育，与矿体近平行产出的闪长岩为限定东昆仑地区古特提斯洋闭合时间提供了很好的研究对象.对黑石山闪长岩进行了LA-ICP-MS锆石U-Pb定年、全岩地球化学和Sr-Nd-Hf同位素分析.定年显示，黑石山闪长岩形成于241.6±1.0 Ma.样品的SiO2含量为52.23%~56.19%，全碱含量为K2O+Na2O=3.99%~6.26%，Na2O=2.79%~3.63%，K2O=1.06%~2.71%，样品富铝、钙、铁，MgO=2.55%~4.84%，TiO2=1.11%~1.43%；样品富集大离子亲石元素如Rb、Ba、K，明显亏损Nb、Ta、Ti、P等高场强元素，富集轻稀土元素，亏损重稀土元素，大多具有较为明显的Eu负异常，δEu为0.39~0.59.锆石εHf（t）值为-4.1~+0.7；全岩（87Sr/86Sr）t为0.708 860~0.708 960，εNd（t）为-4.5~-4.3.综合研究认为，黑石山闪长岩为壳幔混合成因，结合区域构造演化历史，认为其形成于俯冲构造背景，指示东昆仑地区古特提斯洋闭合晚于241.6 Ma.Abstract: The Heishishan copper polymetallic deposit is located in Wulonggou area, middle part of the East Kunlun orogen belt. The Middle Triassic intrusions in the mining area are very developed, and the diorite produced nearly parallel to the ore bodies provides a good research object for limiting the closure time of the paleo-Tethys ocean in the East Kunlun area. In this article, investigations in terms of zircon U-Pb dating, geochemistry, and Sr-Nd-Hf isotope data were carried out on the Heishishan diorite. Zircon U-Pb dating of the diorite yields magmatic crystallization ages of 241.6±1.0 Ma. The diorite samples contain SiO2=52.23%-56.19%, K2O+Na2O=3.99%-6.26%, Na2O=2.79%-3.63%, K2O=1.06%-2.71% and MgO=2.55%-4.84%. The diorites are rich in Al, Ca and Fe. Also, they are enriched in light rare earth elements and large ion lithophile elements (Rb, Ba, K), and depleted in heavy rare earth elements and high field strength elements (Nb, Ta, Ti, P). Most samples have obvious negative Eu abnormality (δEu=0.39-0.59). Hf isotopic analysis shows that the zircon εHf(t) values of the diorite are from -4.1 to +0.7. The samples have whole-rock (87Sr/86Sr)t ratios from 0.708 860 to 0.708 960, εNd(t) of -5.0 to -4.9. The comprehensive analysis shows that the Heishishan diorite is of crust-mantle mixing origin. Based on the regional tectonic evolution history, the diorites were formed in a subduction tectonic setting, indicating that the closure of the paleo-Tethys ocean in the East Kunlun area was later than 241.6 Ma.
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Key words:
- East Kunlun /
- diorite /
- zircon U-Pb dating /
- Sr-Nd-Hf isotope /
- crust-mantle mixing /
- ore deposit /
- geochronology
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图 1 东昆仑地图(a)、东昆仑地质草图(b)和东昆仑造山带地质简图(c)
a和b利用GeoMapApp制作（
http://geomapapp.org ）；c.据Xia et al.（2015）修改Fig. 1. Map of the East Kunlun (a), geological sketch map of the East Kunlun (b) and simplified regional geological map of the East Kunlun orogen belt (c)
图 2 黑石山矿区地质图(据姜芷筠, 2021修改)
Fig. 2. Geological map of the Heishishan deposit (modified from Jiang, 2021)
图 3 黑石山矿床闪长岩野外照片(a, b)、手标本照片(c)、镜下照片(d~f)和地质剖面图(g)
a.闪长岩与内矽卡岩化花岗岩的接触照片；b.闪长岩与成矿花岗岩的接触部位可见冷凝边和烘烤边；c.闪长岩手标本照片，可见斜长石和角闪石；d.闪长岩的角闪石和长石存在弱定向（-）；e，f.闪长岩的斜长石发育聚片双晶和环带结构（+）；矿物缩写：Pl.斜长石；Hbl.角闪石；Qr.正长石（矿物缩写据Whitney and Evans, 2010）
Fig. 3. Field photographs (a, b), hand specimen photo (c), microphotographs (d-f) and geological profile (g) of the Heishishan diorite
图 4 黑石山闪长岩锆石CL图像(a)、U-Pb年龄谐和图(b)和频数图(c)
Fig. 4. Cathodoluminescence (CL) images (a), U-Pb ages concordia diagram (b), and frequency diagram of zircons from the Heishishan diorite
图 5 黑石山闪长岩(Na2O+K2O)-SiO2图解(a)和K2O-SiO2图解(b)
a.据Middlemost（1994）；b.据Peccerillo and Taylor（1976）
Fig. 5. (Na2O+K2O)-SiO2 diagram (a) and K2O-SiO2 plot (b) of the Heishishan diorite
图 6 黑石山闪长岩稀土元素球粒陨石标准化配分曲线(a)和微量元素原始地幔标准化蛛网图(b)
球粒陨石和原始地幔标准化值引自Sun and McDonough（1989）
Fig. 6. Chondrite-normalized REE (a) and primitive mantle-normalized multi-element (b) diagrams of the Heishishan diorite
图 7 黑石山闪长岩的锆石年龄-εHf(t)值相关图(a)和全岩εNd(t)-(87Sr/86Sr)t图解(b)
b.据Xiong et al.（2013）修改，数据来源：黑石山正长岩、花岗岩和花岗闪长岩为数据李治华等（2023）和Li et al.（2023），富集地幔成因的中基性岩石数据熊富浩等（2011）；Ding et al.（2014）；Xiong et al.（2019）
Fig. 7. εHf(t) vs. t diagram for zircons (a) and εNd(t) vs. (87Sr/86Sr)t diagram (b) from Heishishan diorite
图 8 黑石山闪长岩Zr/Nb-Zr图解(a)、TFeO-MgO图解(b)、MgO-SiO2图解(c)和Mg#-SiO2图解(d)
b.据Zorpi et al.（1991）；c.据Defant and Drumond（1990）；d.据Rapp et al.（1999）和Wang et al.（2006）
Fig. 8. Zr/Nb vs. Zr diagram (a), TFeO vs. MgO diagram (b), MgO vs. SiO2 diagram (c) and Mg# vs. SiO2 diagram (d) of Heishishan diorite
图 9 黑石山闪长岩TFeO-MgO-Al2O3图解(a)、Zr/Yb-Nb/Yb图解(b)和Th/Yb-Ta/Yb图解(c)
a.据Pearce et al.（1977）；b和c.据Pearce and Peate（1995）
Fig. 9. TFeO-MgO-Al2O3 diagram (a), Zr/Yb vs. Nb/Yb diagram (b) and Th/Yb vs. Ta/Yb diagram (c) of Heishishan diorite
表 1 黑石山闪长岩锆石U-Pb同位素定年数据
Table 1. Zircon U-Pb isotopic dating results of the Heishishan diorite
样品 Th/U 207Pb/206Pb 207Pb/235U 206Pb/238U 207Pb/206Pb 207Pb/235U 206Pb/238U 比值 1σ 比值 1σ 比值 1σ t(Ma) 1σ t(Ma) 1σ t(Ma) 1σ HSS-N1-01 0.68 0.050 15 0.002 31 0.264 90 0.011 94 0.038 22 0.000 65 202 103 239 10 242 4 HSS-N1-02 0.62 0.052 62 0.002 89 0.272 88 0.01 460 0.037 53 0.000 72 312 120 245 12 238 4 HSS-N1-03 0.68 0.051 59 0.003 44 0.267 24 0.017 33 0.037 49 0.000 81 267 146 241 14 237 5 HSS-N1-04 0.46 0.050 94 0.003 69 0.266 63 0.018 75 0.037 89 0.000 87 238 159 240 15 240 5 HSS-N1-05 0.90 0.050 87 0.002 46 0.267 64 0.012 65 0.038 10 0.000 67 235 108 241 10 241 4 HSS-N1-06 0.61 0.051 25 0.003 86 0.270 87 0.019 83 0.038 28 0.000 88 252 164 243 16 242 5 HSS-N1-07 0.58 0.050 70 0.003 15 0.271 02 0.016 45 0.038 73 0.000 77 227 138 244 13 245 5 HSS-N1-09 0.38 0.051 92 0.005 26 0.268 49 0.026 32 0.037 47 0.001 14 282 216 242 21 237 7 HSS-N1-10 0.44 0.050 45 0.002 33 0.266 07 0.01 20 0.038 23 0.000 66 216 103 240 10 242 4 HSS-N1-11 0.94 0.051 72 0.002 29 0.271 40 0.011 75 0.038 05 0.000 65 273 98 244 9 241 4 HSS-N1-12 0.64 0.050 71 0.003 15 0.268 19 0.016 18 0.038 36 0.000 80 228 137 241 13 243 5 HSS-N1-13 0.43 0.051 28 0.002 89 0.266 32 0.014 62 0.037 68 0.000 74 253 125 240 12 238 5 HSS-N1-15 1.01 0.049 14 0.002 42 0.258 91 0.012 43 0.038 24 0.000 68 155 111 234 10 242 4 HSS-N1-17 0.38 0.050 32 0.001 93 0.266 06 0.010 04 0.038 39 0.000 61 210 87 240 8 243 4 HSS-N1-18 0.55 0.050 68 0.004 38 0.263 79 0.0220 8 0.037 81 0.000 99 226 188 238 18 239 6 HSS-N1-19 0.89 0.051 70 0.002 38 0.272 31 0.012 22 0.038 27 0.000 67 272 102 245 10 242 4 HSS-N1-22 0.96 0.050 87 0.002 17 0.268 67 0.011 21 0.038 40 0.000 64 235 95 242 9 243 4 HSS-N1-24 0.37 0.050 49 0.002 50 0.265 99 0.012 85 0.038 33 0.000 69 217 111 240 10 243 4 HSS-N1-25 0.45 0.051 32 0.004 61 0.268 87 0.023 38 0.038 12 0.001 04 255 194 242 19 241 6 HSS-N1-26 0.96 0.050 96 0.002 64 0.269 96 0.013 60 0.038 56 0.000 72 239 115 243 11 244 4 HSS-N1-27 0.48 0.049 90 0.002 85 0.268 05 0.014 90 0.039 11 0.000 78 190 128 241 12 247 5 HSS-N1-28 0.72 0.051 46 0.005 37 0.272 56 0.027 46 0.038 57 0.001 21 261 223 245 22 244 8 HSS-N1-30 0.76 0.051 32 0.004 12 0.266 20 0.020 71 0.037 79 0.000 96 255 175 240 17 239 6 
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表 2 黑石山闪长岩样品主量元素、稀土元素和微量元素含量及有关参数
Table 2. Major, REE and trace element content and parameter of the Heishishan diorite
样品号 HSS-N1-Y1 HSS-N1-Y2 HSS-N1-Y3 HSS-N1-Y4 HSS-N1-Y5 HSS-N1-Y6 HSS-N1-Y7 SiO2 52.23 53.95 53.73 52.96 52.53 56.19 52.68 TiO2 1.25 1.11 1.28 1.33 1.43 1.19 1.31 Al2O3 18.86 15.80 18.36 18.11 17.12 18.82 17.07 Fe2O3T 10.30 11.59 9.72 9.52 11.00 8.28 10.86 FeO 8.66 8.82 7.49 7.18 9.27 6.41 8.38 MgO 4.02 3.78 3.35 3.25 4.84 2.55 4.04 MnO 0.19 0.24 0.17 0.18 0.21 0.15 0.25 CaO 8.82 7.77 7.64 8.03 8.61 6.93 8.29 K2O 1.06 2.17 1.98 2.71 1.26 1.92 1.83 Na2O 2.94 3.39 3.48 3.55 2.79 3.63 3.37 P2O5 0.33 0.22 0.30 0.36 0.22 0.34 0.29 LOI 1.79 0.95 1.19 1.09 1.18 1.07 2.09 Total 99.33 99.56 99.36 99.35 99.36 99.36 100.53 K2O/Na2O 2.78 1.56 1.75 1.31 2.21 1.89 1.84 Mg# 43.59 39.24 40.59 40.32 46.56 37.87 42.45 Sc 23.55 39.68 29.69 38.23 40.50 28.67 29.48 V 185 303 170 258 281 132 200 Cr 7.64 8.71 3.61 9.12 10.60 4.59 8.95 Co 21.55 19.91 20.15 22.85 23.07 14.31 22.54 Ni 8.01 8.56 8.83 9.54 9.82 6.17 8.62 Cu 12.75 12.30 26.03 11.47 11.90 11.20 12.61 Zn 96 113 167 116 121 91 110 Ga 23.17 22.60 23.06 21.79 21.16 23.73 22.72 Rb 46.39 46.30 93.90 47.59 48.28 108.33 50.43 Sr 437 412 490 361 345 443 428 Y 63.13 68.60 47.74 68.48 72.49 50.89 69.47 Zr 329 314 256 312 299 637 319 Nb 15.85 15.70 16.89 15.76 15.90 20.58 15.91 Cs 3.39 6.50 6.52 8.22 9.21 5.05 5.23 Ba 205 256 680 346 295 661 229 La 28.12 30.32 42.77 30.10 28.88 42.87 28.34 Ce 69.05 71.41 89.68 76.30 78.32 93.53 71.42 Pr 9.79 11.72 11.50 10.20 11.32 11.97 10.15 Nd 46.32 47.33 48.04 49.30 51.25 48.73 48.54 Sm 11.45 10.63 10.31 12.50 13.33 10.38 11.88 Eu 1.80 1.56 1.99 1.77 1.74 1.81 1.78 Gd 11.84 11.93 10.38 12.36 14.02 10.70 12.52 Tb 1.89 2.22 1.52 2.23 2.31 1.53 1.95 Dy 11.94 14.12 9.11 12.83 13.70 9.41 12.40 Ho 2.42 2.63 1.63 2.68 2.80 1.69 2.62 Er 7.08 7.64 4.67 8.02 8.09 4.92 7.38 Tm 0.88 0.95 0.60 0.98 1.02 0.65 0.95 Yb 5.73 6.52 4.13 6.23 6.74 4.55 5.87 Lu 0.77 0.83 0.55 0.85 0.89 0.60 0.84 Hf 7.59 7.29 5.85 7.41 7.22 14.13 7.44 Ta 0.80 0.79 0.78 0.78 0.80 1.00 0.77 Pb 16.52 13.40 25.19 13.40 11.68 15.70 15.20 Th 3.93 2.54 3.18 2.46 2.15 3.81 3.42 U 1.15 0.98 1.31 1.22 0.92 1.32 1.57 ΣREE 209.08 219.81 236.88 226.35 234.40 243.35 216.64 LREE/HREE 3.91 3.69 6.27 3.90 3.73 6.14 3.87 (La/Yb)N 3.52 3.34 7.43 3.47 3.07 6.76 3.46 δEu 0.47 0.42 0.59 0.44 0.39 0.53 0.45 Nd/Th 11.79 18.63 15.09 20.04 23.81 12.78 14.19 Rb/Sr 0.11 0.11 0.19 0.13 0.14 0.24 0.12 注：表中主量元素为去烧失量之后的结果，主量元素单位为10-2；微量、稀土元素单位为10-6，FeO采用容量滴定法测得，Fe2O3利用Fe2O3T和FeO计算得到(Fe2O3=Fe2O3T-FeO×1.111)，Mg#=100×(MgO/40.31)/(MgO/40.31+Fe2O3T×2/159.7).
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表 3 黑石山闪长岩锆石Lu-Hf同位素组成
Table 3. Zircon Lu-Hf isotopic compositions of the Heishishan diorite
样品 t (Ma) 176Yb/177Hf 176Lu/177Hf 176Hf/177Hf 2σ εHf(0) εHf(t) 2σ tDM1(Hf) tDM2(Hf) fLu/Hf HSS-N1-001 241.6 0.056 052 0.001 528 0.282 512 0.000 017 -9.2 -4.1 0.6 1 062 1 280 -0.95 HSS-N1-004 241.6 0.021 454 0.000 679 0.282 607 0.000 014 -5.8 -0.7 0.5 906 1 102 -0.98 HSS-N1-006 241.6 0.036 948 0.001 153 0.282 639 0.000 015 -4.7 0.4 0.5 872 1 048 -0.97 HSS-N1-010 241.6 0.018 666 0.000 577 0.282 615 0.000 011 -5.6 -0.3 0.4 892 1 086 -0.98 HSS-N1-011 241.6 0.024 032 0.000 759 0.282 599 0.000 013 -6.1 -0.9 0.5 918 1 116 -0.98 HSS-N1-013 241.6 0.032 173 0.001 027 0.282 646 0.000 015 -4.4 0.7 0.5 858 1 033 -0.97 HSS-N1-017 241.6 0.031 941 0.001 035 0.282 576 0.000 014 -6.9 -1.8 0.5 957 1 160 -0.97 HSS-N1-019 241.6 0.028 283 0.000 904 0.282 598 0.000 015 -6.1 -1.0 0.5 923 1 119 -0.97 HSS-N1-022 241.6 0.032 989 0.001 101 0.282 623 0.000 018 -5.3 -0.1 0.6 893 1 075 -0.97
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表 4 黑石山闪长岩全岩Sr-Nd同位素组成
Table 4. Whole rock Sr-Nd isotope results of the Heishishan diorite
样品 t (Ma) 87Rb/86Sr 87Sr/86Sr (87Sr/86Sr)t 147Sm/144Nd 143Nd/144Nd εNd(t) (143Nd/144Nd)t HSS-N1-01 241.6 0.106 2 0.709 914 0.708 860 0.149 5 0.512 333 -4.5 0.512 097 HSS-N1-03 241.6 0.191 6 0.710 869 0.708 960 0.129 8 0.512 313 -4.3 0.512 108
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