Trace Element Geochemical Characteristics of the Shangshuiqiao Fluorite Deposit in Eastern Jiangxi with Implications for the Genesis of the Deposit
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摘要:
赣东黎川上水桥萤石矿床位于华南褶皱系武夷成矿带北端，产于燕山期黑云母花岗岩的断裂破碎带内。笔者对该矿床的地质特征、不同颜色萤石及围岩黑云母花岗岩的微量元素地球化学特征进行了研究。结果表明，萤石整体上呈现Eu正异常和Ce负异常，但不同颜色的萤石REE配分模式特征有差异，浅绿色、深绿色和紫色萤石为轻稀土富集型，白色萤石为重稀土富集型。围岩的REE配分模式为轻稀土富集型，整体呈现Eu负异常。Y/Ho-La/Ho关系图和REE配分模式图显示，萤石成矿过程中Y-REE发生了分馏，白色萤石成矿时期最晚。Tb/Ca-Tb/La关系图显示，研究区萤石矿床为热液成因。围岩黑云母花岗岩的微量元素配分曲线变化趋势与萤石基本一致，且围岩和萤石的Sm/Nd值十分接近。越靠近矿体的围岩F含量越高，且近矿围岩发生硅化、绢云母化等蚀变，推测萤石矿中的Ca和F主要来自围岩。矿区内萤石形成于中低温氧化环境，矿床成因类型为多期次的中低温热液充填型萤石矿床。
Abstract:The Shangshuiqiao fluorite deposit in Lichuan, eastern Jiangxi, is located at the northern end of the Wuyi metallogenic belt in the South China fold system and is produced in the fractured fracture zone of Yanshanian biotite granite. This paper investigates the geological characteristics of the deposit, as well as the trace element geochemical features of different-colored fluorites and the surrounding biotite granite. The results show that fluorite shows positive Eu anomalies and negative Ce anomalies as a whole, but the REE distribution pattern characteristics of different colors of fluorite are different. Light green, dark green and purple fluorite are light rare earth enriched types, and white fluorite is heavy rare earth enriched type. Enriched type. The REE distribution pattern of the surrounding rock is light rare earth enriched type, and the overall negative Eu anomaly is present. The Y/Ho-La/Ho relationship diagram and REE partitioning model diagram show that Y-REE fractionation occurred during the fluorite mineralization process, and the white fluorite mineralization period was the latest. The Tb/Ca-Tb/La relationship diagram shows that the fluorite deposits in the study area are of hydrothermal origin. The change trend of the trace element distribution curve of the surrounding rock biotite granite is basically the same as that of fluorite, and the Sm/Nd values of the surrounding rock and fluorite are very close. At the same time, the F content in the surrounding rocks closer to the ore body is higher, and the surrounding rocks near the ore undergo alterations such as silicification and sericitization. It is inferred that Ca and F in the fluorite ore mainly come from the surrounding rocks. The fluorite in the mining area was formed in a medium-low temperature oxidation environment, and the deposit formation type is a multi-stage medium-low temperature hydrothermal filling type fluorite deposit.
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图 1 华南地区构造简图（a）与武夷北地区地质简图（b）（改自Yu et al., 2012）
Figure 1.
图 4 上水桥萤石矿床围岩及萤石球粒陨石标准化稀土元素配分曲线图（标准数据引自Sun et al.，1989）
Figure 4.
图 5 上水桥萤石矿床围岩及萤石原始地幔标准化微量元素配分曲线图（标准数据引自Taylor et al.，1985）
Figure 5.
图 7 上水桥萤石矿床不同颜色萤石Tb/Ca-Tb/La关系图（a）（底图据Möller et al.，1976）与上水桥萤石矿床不同颜色萤石La/Ho-Y/Ho关系图（b）（底图据Bau et al.，1995）
Figure 7.
表 1 黎川上水桥萤石矿床围岩微量元素（10−6）和CaF2（%）分析结果
Table 1. Analysis results of trace elements (10−6) and CaF2 (%) in the surrounding rocks of the Shangshuiqiao fluorite deposit in Lichuan
样品号 ZK4602 ZK5405 ZK3402 ZK2601 ZK5004 ZK1004 ZK3403 ZK3404 样品名 花岗岩 花岗岩 花岗岩 花岗岩 花岗岩 花岗岩 花岗岩 花岗岩 Rb 252 275 292 252 304 243 252 254 Ba 2070 1500 2020 1640 1820 2170 2080 2010 Th 50.6 63.3 46.6 48.7 55.9 53.3 62.6 10.0 U 7.56 10.3 8.10 8.36 9.25 8.83 9.93 9.14 Nb 18.6 23.2 20.0 20.4 20.3 19.9 20.4 22.5 Sr 761 336 477 625 643 777 730 689 Zr 184 274 246 227 247 263 254 251 Ti 2001 2634 2269 2144 2105 2462 2190 2302 La 102 107 98.7 109 117 91.0 118 91.6 Ce 159 186 161 178 211 196 210 250 Pr 17.1 18.9 16.5 17.6 18.6 16.6 19.3 16.7 Nd 53.6 67.3 57.1 59.6 61.0 63.9 66.0 60.9 Sm 8.44 10.60 9.16 8.87 9.50 9.57 9.41 9.63 Eu 1.61 1.83 1.72 1.83 1.91 2.11 1.87 1.97 Gd 5.59 7.46 6.15 6.31 6.55 6.70 6.41 6.52 Tb 0.72 0.94 0.80 0.77 0.82 0.88 0.85 0.85 Dy 3.54 4.60 3.76 3.89 4.12 4.30 4.03 4.28 Ho 0.65 0.85 0.73 0.76 0.77 0.78 0.74 0.82 Er 1.84 2.35 2.02 1.97 2.00 2.04 2.03 2.14 Tm 0.25 0.32 0.26 0.28 0.28 0.31 0.30 0.31 Yb 1.53 2.14 1.78 1.72 1.78 1.84 1.82 1.98 Lu 0.23 0.30 0.25 0.27 0.27 0.28 0.27 0.29 Y 19.1 24.3 22.0 19.9 20.6 21.4 20.8 22.2 ΣREE 356.10 410.58 359.94 390.88 435.61 396.30 441.03 447.99 LREE 341.75 391.63 344.18 374.90 419.01 379.18 424.58 430.80 HREE 14.35 18.95 15.76 15.98 16.60 17.12 16.45 17.19 LREE/HREE 23.81 20.67 21.84 23.46 25.24 22.14 25.82 25.07 （La/Yb）N 47.82 35.86 39.77 45.46 47.15 35.48 46.51 33.18 δEu 0.72 0.63 0.70 0.75 0.74 0.81 0.74 0.76 δCe 0.93 1.01 0.98 1.00 1.11 1.24 1.08 1.57 CaF2 2.06 9.34 5.18 1.44 3.66 0.74 1.50 0.51 
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表 2 黎川上水桥萤石矿床萤石微量元素（10−6）分析结果表
Table 2. Analysis results of fluorite trace elements (10−6) in the Shangshuiqiao fluorite deposit in Lichuan
样品号 样品名 Rb Ba Th U Nb Sr Zr Ti La Ce Pr Nd Sm Eu Gd ZK3402-1 白色萤石 — — 0.008 — 0.003 67.20 — — 1.00 2.51 0.43 2.78 1.99 0.81 4.97 ZK3402-2 白色萤石 — — — — — 84.23 — — 1.61 3.13 0.64 3.51 2.61 0.97 4.92 ZK3402-3 白色萤石 — 0.017 — — — 87.33 — — 2.40 5.99 1.13 6.26 3.35 1.54 6.00 ZK3402-4 白色萤石 — — — 0.002 — 45.17 — — 1.29 4.18 0.76 4.93 3.28 1.32 6.33 ZK3402-5 白色萤石 — 0.064 0.015 — — 98.35 0.026 — 3.68 8.60 1.46 6.72 4.27 1.70 7.68 ZK3402-6 白色萤石 0.023 — 0.001 — — 103.2 — — 2.16 4.54 0.89 4.49 2.41 1.09 4.96 ZK3402-7 白色萤石 0.017 — — — 0.008 84.43 0.018 — 1.24 2.07 0.33 1.58 0.53 0.40 1.27 ZK3402-8 白色萤石 — — — — — 100.6 0.012 — 1.96 4.27 0.72 4.69 2.00 1.01 4.67 ZK3402-9 白色萤石 0.016 0.092 0.013 0.004 — 100.7 — — 3.07 6.67 1.11 6.30 3.69 1.73 7.81 ZK3402-10 白色萤石 — — — 0.013 — 111.3 — — 1.60 2.88 0.47 3.12 1.84 0.79 3.69 ZK3402-11 白色萤石 — — — 0.017 — 100.2 — — 1.02 2.24 0.37 2.23 1.28 0.35 2.13 ZK3402-12 白色萤石 0.022 — — — — 86.81 0.005 0.903 3.34 6.94 0.96 5.69 3.94 1.81 7.32 ZK3402-13 白色萤石 0.005 — — — — 115.2 — — 3.01 6.51 1.18 6.14 3.31 1.36 6.83 ZK3402-14 白色萤石 0.033 0.084 0.034 — — 94.09 0.055 — 3.25 6.68 1.17 8.03 5.35 2.76 12.9 ZK3403-1 紫色萤石 0.149 0.134 0.016 0.005 — 104.4 — — 8.62 12.8 1.12 4.98 0.76 0.48 1.10 ZK3403-2 紫色萤石 — — 0.003 0.006 — 92.66 — — 5.46 7.49 0.78 3.84 0.98 0.47 1.62 ZK3403-3 紫色萤石 0.003 0.053 0.002 0.006 — 95.80 — — 5.37 7.03 0.93 4.39 0.92 0.69 1.05 ZK3403-4 紫色萤石 — — — 0.006 0.008 73.80 — 0.444 5.85 7.86 0.91 3.94 1.17 0.48 1.49 ZK3403-5 紫色萤石 0.014 0.070 — 0.012 — 83.55 — — 5.78 8.53 1.17 5.90 1.89 0.75 1.87 ZK3403-6 紫色萤石 — — — — — 84.04 — — 4.94 6.75 0.93 3.45 1.48 0.74 1.50 ZK3403-7 紫色萤石 — — — — — 67.33 — — 4.92 6.59 0.81 3.47 1.31 0.59 2.36 ZK3403-8 紫色萤石 0.005 0.065 — 0.001 — 75.19 — 0.610 5.93 7.96 0.97 3.92 1.09 0.68 2.57 ZK4602-1 深绿色萤石 — 0.074 0.004 0.114 — 152.9 0.012 — 141 314 44.0 165 31.3 25.4 27.9 ZK4602-2 深绿色萤石 0.073 0.041 — 0.255 — 180.2 — — 156 374 49.4 191 32.7 24.1 23.6 ZK4602-3 深绿色萤石 — — — 0.107 — 150.4 — 0.334 108 247 36.7 151 28.5 20.9 28.3 ZK4602-4 深绿色萤石 0.017 0.302 — 0.094 — 127.0 — — 55.4 127 19.8 95.7 24.8 13.9 25.6 ZK4602-5 深绿色萤石 — — — 0.131 — 128.5 — — 72.1 164 28.5 136 36.6 17.7 40.6 ZK4602-6 浅绿色萤石 0.258 0.192 — 0.090 — 180.2 — 0.106 7.55 9.83 1.10 3.57 0.53 0.94 0.26 ZK4602-7 浅绿色萤石 0.270 0.190 — 0.084 0.005 175.3 — — 7.63 7.69 0.82 3.00 0.63 0.85 0.42 ZK4602-8 浅绿色萤石 0.145 0.467 — 0.088 — 177.5 — 0.515 8.18 9.93 1.04 3.41 0.71 0.69 0.35 ZK4602-9 浅绿色萤石 0.314 0.410 — 0.136 — 187.8 0.045 — 15.3 18.5 1.74 2.79 0.45 1.16 0.45 ZK4602-10 浅绿色萤石 0.025 0.139 — 0.182 — 173.4 — — 87.5 135 11.4 26.5 1.55 5.66 1.15 ZK4602-11 浅绿色萤石 — 0.121 0.008 0.124 0.010 162.0 0.220 — 25.3 53.4 4.08 11.5 1.45 2.87 1.00 ZK4602-12 浅绿色萤石 0.118 0.216 — 0.211 — 173.5 — — 31.9 42.7 3.52 8.22 0.96 1.63 0.99 ZK4602-13 浅绿色萤石 0.027 0.037 — 0.120 — 141.7 0.010 — 14.5 23.3 2.69 7.44 0.64 4.05 0.31
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续表2 样品号 样品名 Tb Dy Ho Er Tm Yb Lu Y ΣREE LREE HREE LREE/
HREELaN/YbN δEu δCe ZK3402-1 白色萤石 1.10 8.71 1.89 6.11 0.75 4.80 0.598 85.1 38.46 9.52 28.94 0.33 0.15 0.78 0.94 ZK3402-2 白色萤石 0.87 7.16 1.73 4.74 0.68 4.28 0.593 79.3 37.44 12.47 24.97 0.50 0.27 0.83 0.76 ZK3402-3 白色萤石 1.34 11.3 2.45 7.06 1.12 7.72 0.952 95.5 58.60 20.67 37.94 0.54 0.22 1.05 0.89 ZK3402-4 白色萤石 1.34 10.4 2.35 7.39 1.19 8.23 1.308 80.7 54.25 15.75 38.49 0.41 0.11 0.88 1.04 ZK3402-5 白色萤石 1.61 12.5 3.07 8.78 0.92 5.85 0.801 152 67.65 26.43 41.23 0.64 0.45 0.91 0.91 ZK3402-6 白色萤石 1.06 8.20 1.77 4.73 0.61 4.03 0.500 81.5 41.46 15.59 25.86 0.60 0.39 0.96 0.80 ZK3402-7 白色萤石 0.31 1.93 0.34 1.41 0.14 1.22 0.131 21.0 12.90 6.15 6.76 0.91 0.72 1.49 0.80 ZK3402-8 白色萤石 0.81 6.33 1.35 4.21 0.65 3.29 0.381 68.5 36.35 14.66 21.69 0.68 0.43 1.01 0.88 ZK3402-9 白色萤石 1.60 11.6 2.82 7.98 0.90 5.86 0.776 151 61.90 22.57 39.32 0.57 0.38 0.98 0.89 ZK3402-10 白色萤石 0.67 4.60 1.27 3.44 0.41 2.43 0.364 56.6 27.55 10.69 16.86 0.63 0.47 0.92 0.82 ZK3402-11 白色萤石 0.45 3.05 0.71 2.26 0.22 1.48 0.295 27.7 18.10 7.49 10.60 0.71 0.50 0.65 0.89 ZK3402-12 白色萤石 1.55 9.90 2.62 7.86 1.02 5.52 0.783 137 59.25 22.68 36.57 0.62 0.43 1.03 0.95 ZK3402-13 白色萤石 1.54 8.69 2.34 7.65 0.93 5.11 0.631 148 55.24 21.51 33.73 0.64 0.42 0.88 0.85 ZK3402-14 白色萤石 2.67 17.3 4.29 11.8 1.61 9.28 1.112 257 88.22 27.25 60.97 0.45 0.25 1.02 0.84 ZK3403-1 紫色萤石 0.15 1.01 0.17 0.47 0.05 0.33 0.051 6.66 32.04 28.72 3.32 8.64 18.67 1.60 1.01 ZK3403-2 紫色萤石 0.16 0.96 0.13 0.33 0.03 0.14 0.058 8.46 22.44 19.02 3.42 5.56 28.46 1.15 0.89 ZK3403-3 紫色萤石 0.14 0.68 0.12 0.35 0.02 0.33 0.053 7.94 22.06 19.32 2.74 7.05 11.64 2.15 0.77 ZK3403-4 紫色萤石 0.31 1.04 0.29 0.66 0.07 0.46 0.094 10.3 24.63 20.22 4.41 4.59 9.15 1.12 0.84 ZK3403-5 紫色萤石 0.32 2.25 0.36 1.10 0.17 1.09 0.146 15.6 31.33 24.02 7.31 3.29 3.81 1.22 0.80 ZK3403-6 紫色萤石 0.22 1.52 0.28 0.57 0.09 0.60 0.088 8.94 23.14 18.28 4.86 3.76 5.89 1.51 0.77 ZK3403-7 紫色萤石 0.18 1.27 0.25 0.64 0.09 0.29 0.080 10.3 22.85 17.69 5.16 3.43 12.20 1.02 0.81 ZK3403-8 紫色萤石 0.30 1.76 0.30 0.80 0.16 0.78 0.162 14.0 27.37 20.55 6.82 3.01 5.48 1.25 0.81 ZK4602-1 深绿色萤石 3.03 18.1 3.06 7.43 0.90 8.33 1.565 231 791.3 721.0 70.24 10.26 12.18 2.63 0.98 ZK4602-2 深绿色萤石 2.36 12.3 1.92 4.99 0.69 6.40 1.027 138 879.7 826.4 53.27 15.51 17.48 2.66 1.04 ZK4602-3 深绿色萤石 3.24 20.1 3.64 9.21 1.42 12.1 2.027 216 671.7 591.7 79.99 7.40 6.40 2.25 0.96 ZK4602-4 深绿色萤石 3.98 22.5 4.07 11.1 1.62 13.3 2.638 249 421.6 336.8 84.81 3.97 2.98 1.69 0.94 ZK4602-5 深绿色萤石 5.85 38.4 8.19 22.3 3.08 25.6 4.408 428 603.6 455.2 148.4 3.07 2.02 1.40 0.89 ZK4602-6 浅绿色萤石 0.01 0.14 0.02 0.04 — 0.01 — 2.86 24.02 23.52 0.50 46.93 440.9 7.68 0.84 ZK4602-7 浅绿色萤石 0.03 0.16 0.05 0.06 — 0.10 — 6.13 21.44 20.62 0.82 25.03 54.14 5.04 0.75 ZK4602-8 浅绿色萤石 0.06 0.34 0.03 0.07 0.05 0.10 0.020 3.95 24.98 23.96 1.02 23.59 57.49 4.18 0.84 ZK4602-9 浅绿色萤石 0.04 0.25 0.02 0.01 — — 0.004 2.34 40.67 39.89 0.78 50.90 — 7.86 0.88 ZK4602-10 浅绿色萤石 0.04 0.10 — 0.02 — 0.01 0.004 3.40 268.5 267.2 1.34 199.1 4397 12.96 1.04 ZK4602-11 浅绿色萤石 0.01 0.29 — 0.04 — 0.01 — 3.37 99.96 98.58 1.38 71.66 1489 7.27 1.29 ZK4602-12 浅绿色萤石 0.06 0.33 0.06 0.23 0.01 0.24 0.004 6.92 90.85 88.93 1.92 46.39 95.04 5.11 0.99 ZK4602-13 浅绿色萤石 0.05 0.23 — 0.02 — 0.10 0.002 2.99 53.32 52.60 0.72 72.76 103.4 27.70 0.91 注：“—”为低于检测限。
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