The Petrogeochemistry and Zircon U-Pb Age of Nephrite Placer Deposit in Xiuyan, Liaoning
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摘要: 河磨玉是产于辽宁省岫岩县细玉沟沟谷及白沙河河谷底部和两岸阶地的和田玉,目前仅依据产出位置判断河磨玉来源于细玉沟沟头的原生和田玉矿床,但河磨玉的矿物组成、地球化学特征、年龄等并不清楚,与原生和田玉是否一致有待深入研究。本文主要通过电子探针成分分析、全岩主微量分析、氢氧同位素分析、锆石SHRIMP U-Pb定年等测试方法对河磨玉的矿物组成、地球化学特征及年龄进行研究,确定河磨玉与老玉是否为相同成因。结果表明:①河磨玉中主要矿物为透闪石、阳起石,次要矿物为透辉石、磷灰石、绿泥石、绿帘石、石英、榍石、锆石、磁铁矿、菱锌矿等。②河磨玉的成因类型为大理岩型。河磨玉稀土总量低,相对富集轻稀土,普遍显示Eu正异常。③河磨玉中透闪石δ18O值为8.00‰~10.60‰,δD值为-94.95‰~-75.20‰,成矿流体中的水主要为岩浆水。④河磨玉中的岩浆锆石U-Pb年龄为220.8±7.6Ma(n=4,MSWD=2.3),代表河磨玉成玉年龄的上限。本文提出河磨玉的稀土分配特征、氢氧同位素组成、成矿流体来源及形成年龄均与原生和田玉不一致,河磨玉并非来源于细玉沟沟头的原生和田玉。
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关键词:
- 和田玉 /
- 岩相学 /
- 地球化学特征 /
- 电子探针 /
- 电感耦合等离子体质谱 /
- SHRIMP锆石U-Pb年龄 /
Abstract:BACKGROUNDThe Xiuyan placer nephrite is located in the Xiyu gully, Baisha river valley and terrace, located in Xiuyan, Liaoning Province. Currently, the primary nephrite in the Xiyu gully is regarded as the Xiuyan placer nephrite's primary deposit according to location. However, the mineral composition, geochemical characteristics and age of the placer nephrite is unknown; whether they are consistent with primary nephrite needs to be studied further. OBJECTIVESTo confirm whether the Xiuyan placer nephrite is from primary nephrite by investigating the mineral composition, geochemical characteristics and age of the Xiuyan placer nephrite. METHODSElectron microprobe analysis (EMPA), inductively coupled plasma-mass spectrometry (ICP-MS), X-ray fluorescence spectrometry (XRF), stable isotope mass spectrometry and zircon SHRIMP U-Pb dating were employed. RESULTSPrimary minerals of the Xiuyan placer nephrite were tremolite, actinolite, whereas secondary minerals were diopside, apatite, chlorite, epidote, quartz, titanite, zircon, magnetite, and smithsonite. The Xiuyan placer nephrite was dolomite-related nephrite. Its total rare earth element (REE) was low with LREE enrichment and positive Eu anomaly. The δ18O and δD isotope compositions of nephrite were from 8.00‰ to 10.60‰ and from -94.75‰ to -75.20‰, respectively. Water in ore-forming fluids was mainly magmatic water. Zircon U-Pb age of the placer nephrite was 220.8±7.6Ma, which suggested that the placer nephrite formed after this time. CONCLUSIONSThe Xiuyan placer nephrite is different from primary nephrite in bulk-rock REE pattern, hydrogen and oxygen isotope compositions, and source of ore-forming fluids and age, which may indicate that the placer nephrite is not derived from the original nephrite in the Xiyu gully. -
表 1 河磨玉中透闪石-阳起石化学成分电子探针分析结果
Table 1. Chemical component analysis of tremolite and actinolite in Xiuyan placer nephrite obtained by EMPA
样品编号 颜色 SiO2(%) TiO2(%) Al2O3(%) FeO(%) Cr2O3(%) MnO(%) MgO(%) CaO(%) Na2O(%) K2O(%) 总计(%) BFe2 BMg BCa CFe2 CMg Mg/(Mg+Fe2+) Mg/(Mg+Fe2+)平均比值 矿物定名 LHM15-8-1 54.71 0.36 3.06 5.28 0.01 0.08 18.92 13.31 0.25 0.25 96.32 0.11 0.00 1.87 0.52 4.05 0.86 LHM15-8-2 56.93 < 0.05 1.74 5.67 0.03 0.06 19.14 13.30 0.12 0.06 97.08 0.00 0.00 1.94 0.66 4.00 0.86 LHM15-8-3 57.40 0.07 1.01 7.52 < 0.05 0.09 18.26 13.30 0.10 0.02 97.9 0.00 0.00 1.91 0.88 3.83 0.81 LHM15-8-4 56.59 < 0.05 1.36 5.47 0.02 0.09 18.68 12.91 0.06 0.05 95.36 0.03 0.00 1.95 0.64 4.11 0.86 LHM15-8-5 墨绿 56.28 0.03 1.83 5.57 < 0.05 0.15 18.92 13.30 0.13 0.05 96.38 0.06 0.00 1.91 0.60 4.07 0.86 0.87 阳起石 LHM15-8-6 57.56 0.01 1.08 4.52 0.01 0.05 19.84 13.59 0.08 0.05 96.94 0.03 0.00 1.96 0.51 4.29 0.89 LHM15-8-7 57.35 < 0.05 1.45 5.74 0.01 0.11 19.38 12.88 0.08 0.02 97.26 0.30 0.00 1.68 0.41 4.32 0.86 LHM15-8-8 56.01 < 0.05 1.95 5.68 < 0.05 0.17 18.85 13.09 0.12 0.05 96.13 0.3 0.00 1.67 0.41 4.23 0.86 LHM15-8-9 54.15 0.10 3.55 6.50 0.04 0.09 18.10 13.22 0.27 0.08 96.13 0.02 0.00 1.96 0.76 3.86 0.83 LHM15-9-1 57.34 0.04 1.23 0.25 0.01 < 0.05 22.77 13.72 0.15 0.20 96.06 0.03 0.46 1.50 0.00 4.76 0.99 LHM15-9-2 58.56 < 0.05 0.69 1.65 0.01 0.01 22.22 13.30 0.07 0.01 96.69 0.10 0.00 1.89 0.09 4.78 0.96 LHM15-9-3 57.41 < 0.05 1.25 1.37 < 0.05 0.10 21.84 13.12 0.12 0.07 95.63 0.18 0.32 1.48 0.00 4.76 0.97 LHM15-9-4 浅绿 57.83 < 0.05 0.31 1.00 < 0.05 0.07 22.39 13.62 < 0.05 0.03 95.47 0.12 0.05 1.80 0.00 4.94 0.98 0.96 透闪石 LHM15-9-5 54.56 < 0.05 0.16 0.15 0.02 < 0.05 17.96 25.52 0.01 < 0.05 98.38 0.00 0.00 2.00 0.01 3.76 0.99 LHM15-9-6 57.49 < 0.05 0.62 1.59 < 0.05 0.02 21.72 13.34 0.07 0.03 95.24 0.21 0.21 1.57 0.00 4.88 0.96 LHM15-9-7 57.36 0.02 0.66 1.40 < 0.05 < 0.05 21.98 13.40 0.05 0.03 95.15 0.17 0.05 1.76 0.00 4.87 0.97 LHM15-10-1 57.27 0.05 0.41 2.59 0.05 0.05 20.99 13.93 0.05 0.02 95.53 0.00 0.00 2.00 0.31 4.59 0.94 LHM15-10-2 灰黑 56.80 < 0.05 0.44 3.41 0.01 0.07 21.10 13.88 0.01 0.01 95.83 0.01 0.00 1.97 0.39 4.52 0.92 0.94 透闪石 LHM15-10-3 57.16 < 0.05 0.66 1.84 < 0.05 0.07 21.30 14.01 0.07 0.06 95.42 0.03 0.00 1.95 0.19 4.691 0.95 LHM15-11-1 黄白 56.33 0.03 2.13 1.98 < 0.05 0.19 20.79 13.37 0.18 0.06 95.3 0.25 0.06 1.65 0.00 4.61 0.95 0.95 透闪石 LHM15-11-2 57.99 0.10 0.34 1.94 0.01 0.28 21.63 13.38 0.02 0.02 95.92 0.06 0.00 1.89 0.17 4.75 0.95 LHM15-11-3 58.34 0.03 0.75 1.69 < 0.05 0.22 22.00 13.30 0.07 0.01 96.44 0.00 0.00 1.83 0.19 4.52 0.96 LHM15-11-4 57.14 0.11 1.13 2.12 0.01 0.14 21.68 12.81 0.08 0.06 95.43 0.18 0.00 1.79 0.07 4.72 0.95 表 2 河磨玉全岩主量元素分析结果
Table 2. Analytical results of major elements in Xiuyan placer nephrites
主量元素 测定值(%) LHM15-1 LHM15-2 LHM15-3 LHM15-4 LHM15-5 LHM15-6 LHM15-7 SiO2 59.37 57.95 58.72 58.96 58.92 59.50 59.39 Al2O3 0.63 1.62 0.40 0.52 1.03 0.49 0.46 CaO 12.72 11.94 12.63 11.97 12.28 12.59 12.87 Fe2O3 < 0.05 < 0.05 0.49 0.11 0.05 < 0.05 < 0.05 FeO 0.46 0.49 0.32 0.28 0.99 1.53 0.47 K2O 0.10 0.09 0.05 0.06 0.06 0.05 0.06 MgO 23.12 23.74 23.46 24.38 25.61 23.15 23.45 MnO 0.05 0.06 0.06 0.06 0.05 0.06 0.05 Na2O 0.10 0.05 0.07 0.13 0.10 0.05 0.05 P2O5 0.04 0.03 0.07 0.12 0.07 0.07 0.03 TiO2 0.02 0.01 < 0.05 < 0.05 0.01 < 0.05 0.01 CO2 0.97 1.20 0.53 1.28 1.01 1.15 1.10 H2O+ 1.66 1.98 1.86 2.04 1.54 1.18 1.12 LOI 3.25 3.78 3.59 3.80 1.52 3.31 3.14 表 3 河磨玉全岩微量元素分析结果
Table 3. Analytical results of trace elements in Xiuyan placer nephrites
微量元素 测定值(μg/g) LHM15-1 LHM15-2 LHM15-3 LHM15-4 LHM15-5 LHM15-6 LHM15-7 Li 1.30 4.91 0.95 1.06 2.42 1.83 0.89 Be 17.00 14.50 13.80 15.20 15.80 15.60 13.10 Cr 6.26 2.93 0.91 2.32 1.72 1.68 12.20 Mn 409 461 502 503 417 466 444 Co 0.79 1.24 1.51 1.06 0.73 1.35 0.79 Ni 1.08 0.81 < 0.05 1.11 0.86 0.74 6.19 Cu 11.20 8.17 6.73 7.15 6.85 8.72 4.36 Zn 30.10 56.70 53.80 44.10 37.90 29.40 41.30 Ga 1.29 2.42 0.87 1.09 1.59 1.12 0.93 Rb 1.82 1.22 0.56 1.34 1.01 1.00 0.93 Sr 10.60 7.60 7.22 11.10 9.04 12.90 12.20 Mo 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 Cd < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 In < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 Cs 0.52 0.39 0.26 0.56 0.33 0.49 0.32 Ba 4.31 2.29 5.02 5.98 5.54 6.87 3.92 Tl < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 Pb 1.75 0.49 0.64 1.45 4.09 1.35 0.39 Bi < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 Th 0.45 0.10 < 0.05 0.05 < 0.05 < 0.05 < 0.05 U 1.12 1.11 1.14 1.47 1.19 1.17 1.21 Nb 0.56 0.53 0.67 0.49 0.47 0.49 0.38 Ta 0.11 0.12 0.12 0.10 0.10 0.09 0.09 Zr 5.31 0.77 1.12 0.83 0.95 0.48 0.50 Hf 0.18 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 Sn 0.73 0.62 1.30 0.88 0.72 1.21 0.69 Sb 5.09 5.18 1.52 4.72 2.78 2.86 2.12 Ti 99.60 41.60 36.40 24.70 31.20 16.30 15.40 W 0.26 0.17 0.48 0.34 0.19 0.25 0.25 As 3.37 1.50 0.68 3.78 0.80 0.75 0.72 V 11.40 15.80 8.25 11.20 9.56 10.10 9.17 La 0.69 0.37 0.63 0.49 0.42 0.51 0.41 Ce 1.59 0.81 1.56 1.09 1.03 1.08 0.96 Pr 0.21 0.10 0.21 0.14 0.15 0.13 0.12 Nd 1.04 0.48 1.12 0.70 0.82 0.67 0.64 Sm 0.26 0.11 0.33 0.21 0.22 0.16 0.18 Eu 0.08 0.07 0.14 0.12 0.07 0.08 0.08 Gd 0.35 0.13 0.58 0.36 0.30 0.22 0.29 Tb 0.08 < 0.05 0.15 0.10 0.07 0.06 0.08 Dy 0.61 0.21 1.23 0.83 0.53 0.43 0.62 Ho 0.14 0.05 0.30 0.21 0.12 0.10 0.15 Er 0.38 0.15 0.93 0.63 0.32 0.31 0.41 Tm 0.05 < 0.05 0.14 0.09 < 0.05 < 0.05 0.05 Yb 0.29 0.12 0.90 0.55 0.22 0.25 0.29 Lu < 0.05 < 0.05 0.16 0.08 < 0.05 < 0.05 < 0.05 Sc 2.21 2.70 2.37 2.11 1.93 1.82 1.81 Y 4.66 1.79 10.30 6.80 4.63 4.02 5.21 表 4 河磨玉的氢氧同位素数据
Table 4. Hydrogen and oxygen isotope data in Xiuyan placer nephrite
样品编号 样品名称 δD(‰) δ18O(‰) δD水(‰) δ18O水(‰) 330℃ 390℃ 450℃ LHM15-1 透闪石 -88.23 8.40 -66.53 8.89 9.52 9.92 LHM15-2 透闪石 -75.20 8.50 -53.50 8.99 9.62 10.02 LHM15-3 透闪石 -93.29 8.80 -71.59 9.29 9.92 10.32 LHM15-4 透闪石 -94.95 9.30 -73.25 9.79 10.42 10.82 LHM15-5 透闪石 -78.51 10.60 -56.80 11.09 11.72 12.12 LHM15-6 透闪石 -93.78 8.20 -72.07 8.69 9.32 9.72 LHM15-7 透闪石 -86.58 8.00 -64.88 8.49 9.12 9.52 -
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