Metallogenic regularity of strontium-rich drinking natural mineral water in Devonian carbonate area in southern Hunan: Taking strontium-rich drinking mineral water in Xinxu town, Xintian county as an example
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摘要: 湘南地区泥盆系碳酸盐岩分布广泛，文章在分析湖南省新田县新圩富锶饮用天然矿泉水形成的岩性、构造、水文地质条件、水文地球化学成因的基础上，通过探究影响锶富集的因素，揭示出泥盆系碳酸盐岩分布区富锶饮用天然矿泉水的成矿规律：泥盆系佘田桥组泥灰岩中锶的高丰度、相对封闭的地下水循环交替条件和弱的水动力条件是形成富锶饮用天然矿泉水的根本条件，循环深度和水温是锶富集的重要影响因素。湘南地区台盆相佘田桥组泥灰岩分布区是寻找富锶饮用天然矿泉水的首选靶区，特别是平缓的溶丘岗地地区的阻水断裂上盘以及靠近岩浆岩岩体和区域导热断裂附近是寻找富锶饮用天然矿泉水的有利地段。Abstract: The study area is located in Xinxu, Xintian county, the middle of southern Hunan, in which Devonian carbonate rocks are widely distributed in the south of N26°30'. 44 samples have been taken from some boreholes and springs in different lithologic distribution areas in different seasons for many years. The sampling sites are located in the marl distribution area of Shetianqiao formation of Devonian interplatform basin (D3s). Testing statistics of these samples show that the strontium content of groundwater in ZK13-10, ZK1601 and ZK1602 boreholes is 1.66 mg·L−1, 6.76 mg·L−1 and 0.41 mg·L−1 respectively, which can prove the existence of strontium-rich drinking natural mineral water.Based on the analysis of lithology, structure, hydrogeological conditions, hydrogeochemical origin and influencing factors of strontium enrichment, the metallogenic regularity of strontium-rich mineral spring water in Devonian carbonate distribution area is preliminarily revealed. According to the statistics of rock and mineral analysis and test results of 80 groups of rock cores at different depths of 5 boreholes, the average content of strontium in marl of Shetianqiao formation of Devonian interplatform basin (D3s) is 524×10−6, peaking at 800×0−6, much higher than that in other rocks.The high abundance of strontium is the material basis for the formation of strontium-rich mineral water in the study area. Primarily, the content variety of strontium in groundwater is closely related to groundwater circulation conditions. Three spots of strontium-rich groundwater in the study area mainly come from strontium-rich water in the zone of deep subsurface flow. High circulation depth, relatively closed groundwater circulation and weak hydrodynamic conditions are the main constraints for the formation of strontium-rich mineral spring. Because the groundwater recharge runoff is restricted by topographic and geomorphic conditions, seepage conditions, fault structure location and water control properties, the farther the distance of groundwater recharge runoff is, the higher the circulation depth will be, and in turn the more conducive will be to the enrichment of strontium and the formation of deep strontium-rich water. The water temperature is another important factor affecting the enrichment of strontium in groundwater because it affects the dissolution and ion replacement of minerals containing strontium, and it also affects the CO2 content and corrosiveness in groundwater, thus affecting the enrichment of strontium in groundwater. Meanwhile, the circulation depth and geothermal field will control the groundwater temperature.The metallogenic regularity of Xinxu strontium-rich drinking mineral water shows that the marl distribution area of Shetianqiao formation of Devonian interplatform basin (D3s) is a favorable area for people to look for the strontium-rich mineral spring in southern Hunan. In particular, the hanging wall of water-blocking faults in gentle karst hills as well as the location close to magmatic rocks and regional thermal conductivity faults are the target areas.
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图 6 研究区ZK13-10、ZK1601水文地质剖面图
Figure 6. Hydrogeological profile of shaft ZK13-10 and shaft ZK1601
图 7 丰水期深潜流带高锶水上升示意图
Figure 7. Runoff sketch of strontium-rich groundwater in the zone of deep subsurface flow during wet season
图 8 研究区机井地下水Sr2+含量与Cl−、SO42−含量关系图
Figure 8. Relationship between the content of Sr2+ and Cl−, SO42− in groundwater of bore holes in Xinxu
图 9 研究区Sr2+含量＞0.2 mg·L−1机井阳离子毫克当量饼图
Figure 9. Statistics of mg equivalent of cation in bore holes (the content of Sr2+＞0.2 mg·L−1)
图 10 研究区Sr2+＜0.2 mg·L−1机井阳离子毫克当量饼图
Figure 10. Statistics of mg equivalent of cation in bore holes (the content of Sr2+＜0.2 mg·L−1)
表 1 研究区地层岩性表
Table 1. Stratum lithology in Xinxu
地层 符号 岩性 厚度/m 分布 泥盆系锡矿山组下段 D3x1 灰岩、白云质灰岩 72~436 研究区西部及南东角局部，出露面积0.56 km2 泥盆系佘田桥组 D3s 泥质灰岩、泥灰岩 551~915 研究区大部，新圩背斜翼部，出露面积16.69 km2 泥盆系棋梓桥组 D2q 厚层状生物碎屑灰岩 193~1048 研究区中部，分布面积12.86 km2，多被第四系覆盖 泥盆系跳马涧组 D2t 石英砂岩、含砾砂岩 165~588 研究区中部新圩背斜核部，无出露，仅在ZK1602孔被揭露 
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表 2 研究区水源点地下水水化学特征统计表
Table 2. Statistics of hydrochemical characteristics for groundwater in Xinxu
指标 单位 ZK13-10 ZK1601 ZK1602 ZK1603 ZK1604 ZK1605 Q15100 水温 ℃ 17.4 23.0 23.8 pH / 7.21 7.26 7.20 7.18 7.09 7.47 6.55 Sr mg·L−1 1.66 6.76 0.41 0.05 0.032 0.067 0.087 K+ mg·L−1 1.37 2.38 1.70 2.56 0.84 3.15 0.28 Na+ mg·L−1 2.84 10.60 8.90 5.05 1.74 3.30 0.50 Ca2+ mg·L−1 93.74 70.20 96.70 96.00 98.40 80.80 104.00 Mg2+ mg·L−1 39.07 44.60 10.50 2.02 6.88 3.60 1.50 Cl− mg·L−1 3.04 6.60 10.20 13.30 4.30 7.50 0.50 ${\rm{SO}}_4^{2-}$ mg·L−1 12.22 22.10 17.40 10.70 7.78 19.90 5.70 ${\rm{HCO}}_3^{-}$ mg·L−1 473 456 348 275 324 235 326 ${\rm{CO}}_3^{2-}$ mg·L−1 0 0 0 0 0 0 0 TDS mg·L−1 639 486 332 300 297 252 286
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表 3 研究区钻孔岩石中Sr平均丰度与地下水中Sr含量表
Table 3. Average abundance of Sr in rock and in groundwater in Xinxu
地层 岩性 岩石中Sr含量/×10−6 地下水Sr含量/mg·L−1 样本数 范围值 平均丰度 D3s 泥灰岩 45 400~800 524 0.08~6.76 D2q 灰岩 26 100~400 239 0.03~0.13 D2t 石英砂岩 9 300~400 322 0.41
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表 4 研究区富锶钻孔水文地质条件对比表
Table 4. Comparison of hydrogeological conditions of strontium-rich shafts in Xinxu
钻孔 Sr含量/mg·L−1 含水段深度/m 地下水补给径流循环条件对比 ZK1601 6.76 87.6~125 补给、径流区岩性为D3s泥灰岩，锶含量高；补给来源较远，径流距离较远；渗透系数为0.05 m·d−1，径流循环条件封闭；c(Cl−)/c(Ca2+)=0.053，水动力条件较弱；水温23 ℃相对较高，循环深度相对较大 ZK13-10 1.66 4.4~167.0 补给、径流区岩性为D3s泥灰岩，锶含量高；部分补给来源和径流距离较远，部分补给来源和径流距离近；渗透系数为0.158 m·d−1，径流循环条件相对较开放；c(Cl−)/c(Ca2+)=0.032，水动力条件相对较强；水温17.4 ℃正常，循环深度相对较小 ZK1602 0.41 232~296 补给、径流区岩性部分为D3s泥灰岩，部分为D2q灰岩和D2t石英砂岩，锶含量较低；补给来源较远，径流距离较远；渗透系数为0.27 m·d−1，径流循环条件相对较开放；c(Cl−)/c(Ca2+)=0.060，水动力条件较弱；水温23.8 ℃相对较高，循环深度相对较大
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表 5 研究区达标水源点不同季节锶含量测试结果统计表
Table 5. Comparison of Sr2+ content in groundwater in different seasons
富锶机井 ZK13-10 ZK1602 测试日期/年.月.日 2014.5.29 2014.7.14 2016.4.11 2016.12.30 2016.8.15 2016.12.30 2017.1.10 2019.1.30 锶元素含量/mg·L-1 3.02 1.68 3.63 1.66 0.96 0.98 0.90 0.41
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表 6 湘南泥盆系碳酸盐岩中Sr元素含量表(据刘文均[18]修编)
Table 6. Sr content in Devonian carbonate area in southern Hunan (modified according to Liu[18])
沉积相 层位 岩性 Sr含量范围值/×10−6 Sr含量平均值/×10−6 台地 局限台地（泻湖） D2q 白云岩 25.94~136.90 64.85 D3s 白云岩 27.47~123.80 77.13 局限台地（潮坪） D2q 灰岩 102.50~259.10 169.44 D3s 灰岩 66.65~370.40 185.09 开放台地 D3s 灰岩 179.40~404.90 297.31 台棚 D2q 泥质灰岩 143.00~523.70 303.40 D3s 泥质灰岩 196.10~402.10 300.78 盆缘斜坡 D3s 灰岩 214.20~1244.00 522.46 台盆 D3s 泥质灰岩 304.60~1158.00 769.72
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