Calcite U-Pb Dating and Micro-XRF Analysis Constraint on Formation of Bawang Zn-Fe-Sn Deposit in Danchi Metallogenic Belt, South China
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摘要: 广西丹池成矿带是我国重要的有色金属产业基地，锡矿床成因及锡锌与锑成矿关系一直是地质学界的研究热点.由于锑矿床缺少精确的年代学数据，导致二者关系不清.拔旺锌铁锡矿床是近年发现产于丹池成矿带南段五圩矿田西部古溶洞中的新类型锡矿床.前人研究显示五圩矿田经历锌→锡→锑成矿演化，获得了锡成矿阶段锡石U⁃Pb年代为90 Ma左右.在前期矿田构造、矿物学和锡石U⁃Pb年代学研究基础上，开展了与辉锑矿共生阶段方解石U⁃Pb年代学和矿石微区X射线荧光光谱仪面扫描（μ⁃XRF mapping）研究.μ⁃XRF面扫描显示拔旺矿床经历了闪锌矿→石英-锡石→毒砂的矿物生成顺序，该特征与以往矿相学研究结果一致.上述结果表明，μ⁃XRF面扫描可以作为矿物生成顺序研究的快速分析手段之一.方解石U⁃Pb年代学研究显示，辉锑矿-方解石脉形成年龄62.8±1.1 Ma（MSWD=2.6；2σ）.年代学、矿相学及μ⁃XRF面扫描研究证实拔旺矿床经历了早期锌锡成矿作用，晚期经历了锑成矿作用，二者相差~30 Ma.前人H⁃O同位素及闪锌矿微量元素研究显示，锌锡成矿流体以岩浆流体为主，锑成矿流体为盆地卤水.在此次年代学和前人研究基础上，总结了拔旺锌铁锡多金属矿床的成因，提出其可能为与深部隐伏岩体有关的远端热液矿床，隐伏岩体与围岩中成矿流体压力差可能是形成远端热液矿床的驱动力.五圩背斜西翼乃至丹池断裂-褶皱带西翼能干性差异显著的Si⁃Ca界面是形成古喀斯特充填型矿床有利部位之一.Abstract: Danchi metallogenic belt is one of the most important nonferrous metal industry bases. It is to be the research focus owing to the large scale of Sn and Sb metal budget. The genesis of Sn-polymetallic mineralization during the Late Cretaceous and the relationship between Zn-Sn and Sb mineralization in the belt remain unclear. The Bawang deposit, a recently discovered paleokarst infilled type deposit, occurs in the west limb of the Wuxu anticline. Basing on the earlier study of structural analysis, mineralogy, and cassiterite U-Pb ages, in this study it presents element mapping of ores by micro-XRF (μ-XRF) analysis, and in situ U-Pb laser ablation-magnetic sectorfield-inductively coupled plasma mass spectrometer (LA-SF-ICP-MS) ages of calcite during the antimony mineralization stage. Micro-XRF analysis revealed that the sphalerite, cassiterite-quartz, and arsenopyrite mineralization have taken place in order in the Bawang deposit. Calcite U-Pb dating provides a lower intercept ages of 62.8±1.1 Ma (MSWD = 2.6; 2σ). Combined with previous ages of Zn-Sn mineralization, mineralogy, and μ-XRF analysis, the Zn-Sn mineralization is 30 Ma earlier than Sb mineralization. The pressure contrast existed between the fluid pressure at the site of ore deposition and the fluid pressure within the concealed intrusion is the key dynamics of fluid flow for the tin mineralization.
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图 1 古亚洲构造简图(a)、研究区位置图(b)和右江盆地地质简图及典型钨锡、金矿床分布图(c) (改自Xiao et al.，2022)
Fig. 1. Tectonic map of Asia (a), geological location of the studied area (b) and schematic geological map of the Youjiang basin and the distribution of Sn and W polymetallic deposits and gold deposits (c) (modified after Xiao et al., 2022)
图 2 丹池褶断带地质示意图及岩浆岩、矿田分布(a)，五圩矿田地质图及Zn⁃Sn多金属、Sb、Hg矿床分布(b)(修改自Xiao et al.，2022)
Fig. 2. Schematic geological map of the Danchi fold⁃and⁃thrust belt and the distribution of magmas and districts (a), schematic geological map of the Wuxu district and the distribution of Zn⁃Sn polymetallic deposits, Sb deposits and Hg deposits (b) (modified after Xiao et al., 2022)
图 3 拔旺矿床示意图(修改自Xiao et al.，2022)
Fig. 3. Geological map of the Bawang deposit (modified after Xiao et al., 2022)
图 4 拔旺矿床Ⅰ号矿体剖面图(a, 修改自Xiao et al.，2022)，南丹组与四大寨组层间含矿溶洞示意图(b)，氧化矿石(c, 采自地表Ⅱ号脉体)，块状硫化物-锡石矿石(d, 采自PD5；其中白框代表微区XRF面扫描的范围)和块状磁黄铁矿(e, 采自ZK2703(150 m))
Fig. 4. Cross section of No. Ⅰ orebody from the Bawang deposit (a, modified after Xiao et al., 2022), schematic of the proposed mechanism for the ore⁃bearing cavities formed between the Nandan Formation and the Sidazhai Formation (b), oxidized ores from orebody Ⅱ (c), massive sulfide⁃cassiterite ore from PD5 (d, the white rectangle represents the scope of micro⁃XRF analysis) and massive pyrrhotite from ZK2703 (150 m) (e)
图 5 拔旺矿床矿物组合
a.PD5中产于南丹组砾屑灰岩中辉锑矿方解石脉；b.黄铁矿-菱铁矿交代块状磁黄铁矿；c.自形锡石-闪锌矿-石英交代第一期粗粒闪锌矿；d.自形锡石-黄铁矿交代第一期粗粒闪锌矿，自形毒砂-菱铁矿交代上述矿物；e.自形黄铁矿溶蚀孔中可见细粒辉锑矿；f.第三期闪锌矿-毒砂-菱铁矿充填交代自形黄铁矿；g.放射状的辉锑矿（黑色）与方解石共生（BW2013）
Fig. 5. Mineral assemblages of the Bawang deposit
图 7 拔旺矿床(a)与辉锑矿共生方解石和标样WC⁃1(b)T⁃W U⁃Pb年龄图
Fig. 7. Tera⁃Wasserburg plots for calcite which intergrew with stibnite from the Bawang deposit (a) and reference sample WC⁃1 (b)
图 8 拔旺矿床块状硫化物-锡石样品μ⁃XRF单元素面分布图(a~h)和多元素组合图(i~j)
Fig. 8. Single⁃element μ⁃XRF maps (Ca, Si, Sn, S, Fe, Zn, Mn, As), photograph (a-h), and multi⁃element map of sample BW1702 (i-j) from the Bawang deposit
表 1 拔旺矿床方解石LA-SF-ICP-MS U-Pb数据
Table 1. LA-SF-ICP-MS U-Pb dating results and compositions of calcite from the Bawang deposit, South China
分析点位 U-Th-Pb含量(10-6) U-Th-Pb同位素比值 Total Pb 238U 207Pb/
206Pb2σ 207Pb/235U 2σ 206Pb/238U 2σ 238U/
206Pb百分比(%) 207Pb/
206Pb百分比(%) bw2013-1-01 0.07 2.62 0.306 4 0.014 4 0.635 4 0.032 4 0.015 1 0.000 3 66.75 2.29 0.31 4.72 bw2013-1-04 0.06 2.59 0.286 7 0.015 0 0.563 8 0.030 4 0.014 3 0.000 3 70.20 2.34 0.29 5.25 bw2013-1-11 0.07 2.60 0.267 8 0.016 1 0.543 9 0.026 9 0.014 4 0.000 3 69.58 2.05 0.27 6.01 bw2013-1-18 0.64 9.05 0.413 5 0.046 0 1.755 1 0.386 4 0.018 9 0.002 9 53.20 15.45 0.41 11.13 bw2013-1-19 0.05 2.66 0.215 7 0.016 1 0.360 7 0.025 6 0.012 2 0.000 2 82.11 1.99 0.22 7.46 bw2013-1-20 0.09 4.73 0.212 8 0.007 6 0.373 2 0.012 2 0.012 8 0.000 2 78.45 1.65 0.21 3.59 bw2013-1-21 0.06 2.79 0.216 7 0.015 6 0.383 1 0.024 2 0.013 0 0.000 3 77.12 2.16 0.22 7.21 bw2013-1-25 0.06 2.41 0.295 3 0.012 9 0.562 2 0.023 6 0.013 9 0.000 3 72.20 2.07 0.30 4.35 bw2013-1-26 0.05 1.88 0.254 3 0.023 7 0.514 7 0.049 2 0.014 6 0.000 4 68.69 2.47 0.25 9.31 bw2013-1-28 0.10 8.69 0.097 9 0.005 7 0.141 3 0.009 5 0.010 3 0.000 2 97.28 2.18 0.10 5.85 bw2013-1-29 0.04 2.57 0.127 9 0.009 4 0.203 7 0.010 7 0.011 6 0.000 2 86.39 1.89 0.13 7.36 bw2013-1-31 0.03 1.52 0.141 0 0.011 8 0.216 4 0.015 9 0.011 1 0.000 4 88.22 3.87 0.14 8.40 bw2013-1-32 0.04 3.59 0.079 7 0.006 6 0.107 5 0.007 3 0.010 0 0.000 3 98.04 3.00 0.08 8.29 bw2013-1-33 0.04 3.69 0.074 8 0.006 0 0.100 4 0.007 1 0.009 8 0.000 2 99.82 2.19 0.07 8.06 bw2013-1-34 0.05 3.88 0.096 4 0.005 7 0.138 2 0.007 7 0.010 5 0.000 3 93.21 2.50 0.10 5.87 bw2013-1-35 0.05 1.84 0.268 3 0.019 3 0.528 8 0.022 5 0.013 7 0.000 4 71.56 2.96 0.27 7.19 bw2013-1-37 0.18 2.94 0.501 3 0.013 5 1.574 4 0.039 5 0.023 0 0.000 6 42.66 2.44 0.50 2.69 bw2013-1-42 0.08 6.98 0.073 7 0.004 4 0.100 5 0.005 1 0.010 0 0.000 3 97.66 2.53 0.07 5.95 bw2013-1-43 0.05 2.31 0.205 3 0.011 9 0.356 1 0.016 2 0.012 9 0.000 4 76.07 2.84 0.21 5.81 bw2013-1-44 0.09 5.03 0.183 9 0.008 9 0.299 2 0.011 9 0.011 9 0.000 2 82.35 1.75 0.18 4.82 bw2013-1-45 0.12 2.65 0.421 8 0.017 7 1.127 9 0.032 1 0.019 2 0.000 4 50.98 2.16 0.42 4.20 bw2013-1-47 0.02 0.85 0.165 7 0.019 4 0.262 0 0.026 3 0.011 5 0.000 5 85.52 4.32 0.17 11.72 bw2013-1-56 0.04 1.95 0.264 4 0.016 9 0.458 3 0.034 2 0.012 5 0.000 5 78.62 3.93 0.26 6.39 bw2013-1-58 0.03 1.49 0.181 2 0.015 8 0.278 1 0.022 8 0.011 2 0.000 4 87.15 3.48 0.18 8.71 
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