Characterization of Yellow-Green Hetian Jade in Qiemo—Ruoqiang, Xinjiang
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摘要:
新疆且末—若羌一带的和田玉，以带有黄绿色调为特征，针对该种和田玉的颜色成因和特性表征研究较少，影响了对这种和田玉的颜色和矿床成因的认识。本文利用电子探针(EPMA)、背散射电子图像(BSE)、X射线荧光光谱(XRF)、高分辨电感耦合等离子体质谱(HR-ICP-MS)分析技术对且末黄口料的矿物组成和化学成分进行测试，采用滴定法测试FeO含量，探究其颜色成因和成矿类型，并采用锆石SHRIMP U-Pb同位素定年约束其成矿时代。结果表明：该地区和田玉主要由磷灰石、方解石、白云石、透辉石、绿帘石、榍石和锆石组成。其稀土总量低(∑REE=2.61~19.1μg/g)，稀土配分模式呈现出明显Eu负异常(δ Eu < 0.05)、LREE右倾、HREE平坦，根据稀土配分模式和Cr、Ni元素含量，推测是一种镁质矽卡岩型和田玉。且末黄口料和田玉Fe3+/Fe2+平均值(0.16)与其他地区和田玉有重叠，但该比值稍高(0.07~0.26)，而Fe3+、Fe2+含量与其他地区和田玉之间差异并不明显。因此，推测且末—若羌和田玉的颜色成因与Fe3+/Fe2+比值有关，与Fe3+、Fe2+含量并无明显关系; 该地区和田玉中锆石SHRIMP U-Pb同位素定年获得的两个加权平均年龄为461.7±6.1Ma (MSWD=1.6)和498.1±4.6Ma (MSWD=1.16)，代表了该地区黄绿色和田玉的形成时代，并可以进一步约束西昆仑的构造演化。
Abstract:BACKGROUND The Hetian nephrite belt in Xinjiang is the largest nephrite ore belt in the world, with a length of about 1300km. In addition to white, gray, black and brown nephrite, the Qiemo—Ruoqiang zone, Xinjiang also produces a yellow-green nephrite. There are few studies on the color origin and characterization of this kind of Hetian nephrite, which affects the understanding of the color and genesis of this kind of Hetian nephrite.
OBJECTIVES To understand the color genesis, genetic types and formation age of the yellow-green nephrite in Qiemo—Ruoqiang deposit.
METHODS Electron probe microanalysis (EPMA), backscattered electron (BSE) image, X-ray fluorescencespectrometry (XRF), and high resolution inductively coupled plasma-mass spectrometry (HR-ICP-MS) were used to investigate mineral and chemical composition. The FeO content was determined by titration method to explore its color origin and genetic type, and the zircon U-Pb isotope dating by sensitive high-resolution ion microprobe (SHRIMP) was used to constrain its mineralization age.
RESULTS Yellow-green nephrite in Qiemo—Ruoqiang was predominately composed of apatite, calcite, dolomite, diopside, epidote, sphene and zircon. The yellow-green nephrite whole rock had low total REE (∑REE=2.61-19.1μg/g) with obvious Eu negative anomaly (δEu < 0.05), LREE right dipping, and HREE flat pattern. According to the distribution pattern of rare earth and the content of Cr and Ni, it was inferred that it was a magnesia skarn type Hetian nephrite. Compared with other nephrite in the world, the average value of Fe3+/Fe2+ of the yellow-green nephrite in Qiemo—Ruoqiang (average=0.16) overlapped with nephrite in other regions. The ratio is slightly higher (0.07-0.26), while the content of Fe3+ and Fe2+ was not significantly different between the yellow-green nephrite and other color nephrite. The SHRIMP U-Pb dating of zircon in the yellow-green nephrite yielded ages of 461.7±6.1Ma (MSWD=1.6) and 498.1±4.6Ma (MSWD=1.16).
CONCLUSIONS The color genesis of the yellow-green nephrite in Qiemo is probably related to the ratio of Fe3+/Fe2+, but not to the content of Fe3+ and Fe2+. The SHRIMP U-Pb dating results of zircon in yellow-green nephrite represent the formation age of the yellow-green nephrite. These new data provide geochronological constraints for the magmatism of Hetian nephrite belt and the tectonic evolution of the West Kunlun orogenic belt.
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图 4 (a) 且末—若羌黄绿色和田玉的REE模式；(b)且末—若羌黄绿色和田玉的原始地幔原始标准化微量元素图(稀土和微量元素标准化数值依据Sun和McDonough，1989)
Figure 4.
表 1 且末—若羌地区黄绿色和田玉中的透闪石化学成分EPMA分析结果
Table 1. Chemical composition measured by EPMA of tremolite in the yellow-green nephrite from Qiemo—Ruoqiang area
成分 QM20-4-2-12 QM20-4-2-13 QM20-4-2-14 QM20-8-9 QM20-8-12 QM20-2-1 QM20-2-2 QM20-11-6 QM20-3-1-18 QM20-8-5 QM20-11-5 SiO2 58.31 58.02 57.86 58.43 59.24 57.98 56.06 57.45 55.10 55.74 56.98 TiO2 0.04 0.03 0.00 0.04 0.06 0.06 0.01 0.05 0.12 0.07 0.03 Al2O3 0.78 0.87 0.68 0.79 0.10 0.05 0.58 0.66 2.36 1.11 0.66 Cr2O3 0.10 0.00 0.01 0.05 0.00 0.00 0.02 0.00 0.03 0.00 0.01 FeO 0.16 0.27 0.37 0.73 0.13 0.14 0.08 1.79 0.08 5.30 1.86 MnO 0.00 0.01 0.00 0.07 0.00 0.02 0.00 0.13 0.00 0.01 0.12 MgO 23.76 23.69 23.46 23.36 24.39 23.97 23.84 22.43 23.38 20.42 22.15 CaO 12.70 12.47 12.92 13.02 13.05 13.09 13.07 13.36 13.27 12.98 13.24 Na2O 0.15 0.16 0.09 0.15 0.04 0.02 0.26 0.08 0.86 0.17 0.12 K2O 0.07 0.09 0.16 0.05 0.04 0.03 0.07 0.05 0.23 0.04 0.05 NiO 0.01 0.00 0.01 0.01 0.02 0.00 0.03 0.02 0.06 0.00 0.00 总和 96.18 95.61 95.56 96.75 97.07 95.35 94.04 96.00 95.52 95.84 95.23 TSi 8.01 8.00 8.01 8.00 8.05 8.03 7.91 7.98 7.69 7.89 7.98 TAl 0.00 0.00 0.00 0.00 0.00 0.00 0.09 0.02 0.31 0.11 0.02 T位阳离子数 8.01 8.00 8.01 8.00 8.05 8.03 8.00 8.00 8.00 8.00 8.00 CAl 0.13 0.14 0.11 0.13 0.02 0.01 0.01 0.09 0.08 0.07 0.09 CFe3+ 0.00 0.00 0.04 0.08 0.01 0.02 0.00 0.21 0.01 0.59 0.22 CCr 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 CMg 4.86 4.86 4.84 4.77 4.94 4.95 5.00 4.64 4.87 4.31 4.62 CFe2+ 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 CMn 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.02 0.00 0.00 0.01 C位阳离子数 5.00 5.00 4.99 4.99 5.00 4.98 5.01 4.96 4.96 5.00 4.94 BMg 0.00 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 BFe2+ 0.02 0.03 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.04 0.00 BMn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 BCa 1.87 1.84 1.92 1.91 1.90 1.94 1.98 1.99 1.99 1.96 1.99 BNa 0.04 0.04 0.02 0.04 0.01 0.01 0.00 0.01 0.01 0.00 0.01 B位阳离子数 1.93 1.92 1.94 1.95 1.91 1.95 2.00 2.00 2.00 2.00 2.00 ACa 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 ANa 0.00 0.00 0.00 0.00 0.00 0.00 0.07 0.01 0.22 0.05 0.02 AK 0.01 0.02 0.03 0.01 0.01 0.01 0.01 0.01 0.04 0.01 0.01 A位阳离子数 0.01 0.02 0.03 0.01 0.01 0.01 0.08 0.02 0.26 0.07 0.03 阳离子总和 14.95 14.94 14.97 14.95 14.97 14.97 15.09 14.98 15.22 15.07 14.97 Mg/(Mg2++Fe2+) 1.00 0.99 0.99 0.98 1.00 1.00 1.00 0.96 1.00 0.87 0.95 注：数据单位为%。 
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表 2 且末—若羌地区黄绿色和田玉中的次要矿物组成电子探针(EPMA)分析结果
Table 2. Compositions measured by EPMA of associate minerals in the yellow-green nephrite from Qiemo—Ruoqiang area
元素 角闪石(%) 透辉石(%) 绿帘石(%) QM20-8-7 QM20-8-8 QM20-8-10 QM20-4-1-1 QM20-3-1-1 QM20-3-1-4 QM20-3-1-9 QM20-3-1-14 QM20-11-1 QM20-8-11 QM20-8-3 SiO2 45.69 43.27 47.16 55.27 54.99 55.00 54.94 55.16 55.36 38.72 38.47 TiO2 0.42 0.61 0.59 0.00 0.02 0.04 0.03 0.08 0.05 0.59 0.08 Al2O3 14.10 15.02 11.67 0.18 0.36 0.26 0.28 0.24 1.63 28.71 28.18 Cr2O3 0.08 0.00 0.31 0.00 0.00 0.00 0.03 0.00 0.02 0.05 0.00 FeO 0.52 0.71 0.50 0.02 0.02 0.06 0.11 0.06 1.65 3.43 5.45 MnO 0.05 0.01 0.00 0.02 0.00 0.00 0.06 0.00 0.08 0.06 0.05 MgO 19.63 19.13 20.70 18.16 18.25 18.35 18.98 18.12 16.12 0.55 0.10 CaO 12.91 13.03 13.03 25.31 25.36 25.19 23.88 25.24 24.11 23.48 23.46 Na2O 2.11 2.21 2.14 0.10 0.14 0.14 0.09 0.10 0.43 0.02 0.00 K2O 1.48 1.60 1.05 0.00 0.00 0.00 0.03 0.00 0.00 0.01 0.00 NiO 0.01 0.00 0.02 0.01 0.03 0.08 0.03 0.00 0.00 0.02 0.00 总和 97.00 95.59 97.17 99.07 99.17 99.12 98.46 99.00 99.45 95.64 95.79 Si 6.43 6.22 6.61 2.01 2.00 2.00 2.00 2.01 2.01 3.04 3.03 Al 2.34 2.54 1.93 0.01 0.02 0.01 0.01 0.01 0.07 2.65 2.61 Mg 4.11 4.09 4.32 0.98 0.99 1.00 1.03 0.98 0.87 0.06 0.01 TFe 0.06 0.09 0.06 0.00 0.00 0.00 0.00 0.00 0.05 0.23 0.36 Ca 1.94 2.00 1.95 0.98 0.99 0.98 0.93 0.98 0.94 1.98 1.98 Na 0.58 0.62 0.58 0.01 0.01 0.01 0.01 0.01 0.03 0.00 0.00 K 0.27 0.29 0.19 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 总和 15.73 15.85 15.64 3.99 4.01 4.00 3.98 3.99 3.97 7.96 7.99
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表 3 且末—若羌地区黄绿色和田玉中的全岩主微量XRF和HR-ICP-MS分析结果
Table 3. Analytical results of major and trace elements measured by XRF and HR-ICP-MS in the yellow-green nephrite from Qiemo—Ruoqiang area
主量元素 含量(%) QM20-1 QM20-2 QM20-3 QM20-4 QM20-7 QM20-8 SiO2 57.76 57.63 56.93 58.06 57.54 56.16 TiO2 0.01 0.02 ＜0.01 0.01 ＜0.01 0.12 Al2O3 0.91 0.48 0.71 0.90 0.96 1.01 Cr2O3 0.01 0.02 0.01 0.02 0.02 0.01 Fe2O3 0.02 0.04 ＜0.01 0.04 0.02 0.09 FeO 0.24 0.22 0.18 0.20 0.37 0.94 MnO 0.03 0.03 0.03 0.03 0.04 0.06 MgO 24.50 24.10 23.20 24.70 24.10 22.10 CaO 13.10 14.20 15.15 12.95 14.25 16.35 Na2O 0.26 0.26 0.23 0.25 0.23 0.23 K2O 0.17 0.08 0.06 0.12 0.06 0.08 P2O5 0.01 0.01 ＜0.01 ＜0.01 0.01 0.03 LOI 2.98 3.22 3.18 3.66 2.81 2.61 总和 100.00 100.31 99.68 100.94 100.41 99.79 Fe3+/Fe2+ 0.11 0.23 低于检测限 0.26 0.07 0.12 微量元素 含量(μg/g) QM20-1 QM20-2 QM20-3 QM20-4 QM20-7 QM20-8 Cr 3.00 3.00 2.00 3.00 2.00 5.00 Ni 1.20 1.20 0.90 1.40 1.00 3.80 Rb 16.0 2.70 2.80 11.6 1.70 4.90 Ba 7.80 5.10 18.7 15.4 9.20 13.9 Th 0.22 0.12 0.12 0.17 0.59 0.73 U 1.01 0.47 0.94 0.87 0.57 0.83 Nb 0.40 0.30 0.10 0.30 0.20 3.00 Ta ＜0.05 0.10 ＜0.05 0.05 0.06 0.21 La 0.80 0.60 0.60 1.00 ＜0.50 2.80 Ce 1.81 1.41 1.23 2.01 0.75 6.53 Pr 0.21 0.17 0.14 0.22 0.09 0.84 Sr 12.3 10.1 16.5 14.1 8.50 24.9 Nd 0.90 0.70 0.50 0.80 0.40 3.40 Zr 4.00 4.00 ＜2.00 3.00 3.00 17.0 Hf 0.10 0.10 ＜0.10 0.10 0.10 0.50 Sm 0.19 0.16 0.11 0.14 0.09 0.83 Eu ＜0.03 ＜0.03 ＜0.03 ＜0.03 ＜0.03 0.11 Gd 0.20 0.16 0.13 0.14 0.14 0.97 Tb 0.03 0.03 0.02 0.02 0.03 0.18 Dy 0.21 0.17 0.15 0.15 0.20 1.23 Y 1.40 1.10 1.30 1.20 1.90 7.20 Ho 0.04 0.04 0.03 0.04 0.05 0.27 Er 0.13 0.11 0.11 0.10 0.16 0.83 Tm 0.02 0.02 0.02 0.01 0.02 0.13 Yb 0.11 0.13 0.09 0.07 0.13 0.83 Lu 0.02 0.02 0.01 0.01 0.02 0.13 Li 12.8 7.20 7.40 9.20 9.90 14.3 Be 16.2 6.10 9.31 14.6 9.67 18.3 Mn 204 181 197 216 254 390 Co 1.60 1.70 1.70 1.60 4.60 5.70 Cu 2.50 5.00 3.10 3.00 2.50 6.20 Zn 106 72.0 119 113 102 96.0 Ga 2.44 2.09 2.01 1.84 2.02 2.54 Cu 2.50 5.00 3.10 3.00 2.50 6.20 Zn 106 72.0 119 113 102 96.0 Ga 2.44 2.09 2.01 1.84 2.02 2.54 Mo ＜0.05 0.14 ＜0.05 0.05 ＜0.05 ＜0.05 Cd 0.03 0.04 0.03 0.04 0.03 0.04 In 0.01 ＜0.005 ＜0.005 ＜0.005 ＜0.005 0.04 Cs 2.27 0.20 0.71 2.17 0.65 0.65 Tl 0.11 0.04 0.03 0.09 ＜0.02 0.04 Pb 3.20 1.40 2.70 2.20 2.30 1.70 Bi 0.01 0.01 0.03 0.02 0.02 0.09 Sn 1.00 1.00 0.20 0.80 0.20 1.80 Sb 0.36 0.20 0.82 0.63 0.51 0.44 Ti 0.01 0.02 0.01 0.01 0.01 0.07 W 0.60 0.20 0.80 1.30 1.10 0.70 As 3.60 4.20 5.60 2.40 3.00 3.10 V 29.0 27.0 15.0 29.0 23.0 36.0 Sc 0.50 0.60 0.20 0.20 0.20 3.70 LREE 3.94 3.07 2.61 4.20 1.86 14.5 HREE 0.76 0.68 0.56 0.54 0.75 4.57 ∑REE 4.70 3.75 3.17 4.74 2.61 19.1
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表 4 且末—若羌地区黄绿色和田玉中锆石SHRIMP U-Pb年龄
Table 4. SHRIMP U-Pb zircon ages of the yellow-green nephrite from Qiemo—Ruoqiang area
测点号 206Pbc
(%)U
(μg/g)Th
(μg/g)232Th/238U 206Pb*
(μg/g)Th/U 207Pb*/206Pb* 207Pb*/235U 206Pb*/238U 206 Pb/238U
年龄(Ma)QM20-2-1 0.04 656 7 0.01 45.6 0.01 0.0568±0.99 0.6340±1.4 0.0809±1.4 501.4±4.7 QM20-2-2 0.07 436 36 0.08 41.0 0.08 0.0648±1.1 0.9770±1.5 0.1094±1.4 669.4±6.5 QM20-2-3 0.02 470 69 0.15 49.9 0.15 0.0706±0.01 1.203±1.3 0.1235±1.4 750.9±6.8 QM20-2-4 0.03 518 7 0.01 36.8 0.01 0.0564±1.1 0.6432±1.5 0.0827±1.4 512.3±4.7 QM20-2-5 0.00 590 8 0.01 42.6 0.01 0.0573±0.96 0.6643±1.3 0.0840±1.4 520.1±4.7 QM20-2-6 0.05 547 70 0.13 43.6 0.13 0.0689±0.97 0.8810±1.4 0.0928±1.4 572.0±5.4 QM20-2-7 0.04 564 141 0.26 73.9 0.26 0.0731±0.68 1.536±1.2 0.1525±1.4 914.7±8.1 QM20-2-8 0.00 511 274 0.55 112 0.55 0.1019±0.58 3.592±1.1 0.2558±1.4 1468±12 QM20-2-9 0.04 661 643 1.01 70.6 1.01 0.0684±0.67 1.173±1.2 0.1244±1.4 755.7±6.7 QM20-2-10 0.03 548 28 0.05 91.5 0.05 0.0998±0.53 2.673±1.2 0.1942±1.4 1144±11 QM20-8-1 0.15 191 15 0.08 12.4 0.08 0.0562±2.0 0.5840±2.3 0.0754±1.1 468.3±5.0 QM20-8-2 0.35 116 31 0.28 7.40 0.28 0.0551±3.5 0.5620±3.7 0.0739±1.2 459.7±5.4 QM20-8-3 0.34 123 13 0.11 8.40 0.11 0.0576±3.5 0.6290±3.9 0.0792±1.6 491.2±7.7 QM20-8-4 0.21 116 10 0.09 8.10 0.09 0.0560±2.6 0.6270±2.9 0.0813±1.2 503.7±5.9 QM20-8-5 0.16 154 15 0.10 10.7 0.10 0.0588±2.5 0.6530±2.7 0.0806±1.2 499.8±5.6 QM20-8-6 0.22 109 7 0.07 7.40 0.07 0.0556±3.7 0.6070±4.0 0.0792±1.5 491.3±7.3 QM20-8-7 0.07 201 12 0.06 14.1 0.06 0.0574±2.0 0.6460±2.3 0.0817±1.1 506.2±5.5 QM20-8-8 0.26 104 11 0.11 7.00 0.11 0.0568±3.1 0.6170±3.4 0.0788±1.3 489.2±6.2 QM20-8-9 0.28 154 46 0.31 9.70 0.31 0.0555±3.2 0.5600±3.4 0.0732±1.3 455.6±5.6 QM20-8-10 0.00 165 20 0.13 11.4 0.13 0.0568±2.0 0.6280±2.3 0.0802±1.2 497.4±5.6 注：206Pbc和206Pb*分别表示普通铅和放射成因铅, 普通铅根据实测204Pb进行校正，误差为1σ。
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