Mineral saturation index characteristics, sources of Sr2+, SO42− and development potential of strontium−rich karst water in Xintian County, Hunan Province
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摘要:研究目的
湖南新田县发现大型富锶矿泉水田，然而锶元素来源及锶矿泉开发利用潜力研究相对薄弱，此外探究富锶岩溶水水化学特征及锶元素来源可为岩溶区寻找富锶地下水提供一定的理论支撑。
研究方法通过开展水文地质调查，富锶地下水水化学指标检测分析，利用PHREEQC软件、水化学计量法、端元法、水文地质参数等揭示富锶岩溶水矿物饱和指数特征，Sr2+、SO42−来源及富锶地下水开发潜力。
研究结果方解石在下降泉和机井中均主要处于饱和状态，白云石由下降泉中未饱和状态转为机井中的饱和状态，菱锶矿在机井中出现饱和状态，石膏在下降泉和机井中均为未饱和状态。下降泉中矿物饱和指数随泉水溶解性总固体增加而升高，两者呈较好的正相关关系，但在机井中两者相关性较差。下降泉SO42−和大气降水SO42−具有较好的拟合关系，根据Ca2+、Mg2+、Sr2+、HCO3−、SO42−化学计量关系，机井中SO42−可能来源于石膏溶解。下降泉中Sr2+主要来源于石灰岩中以类质同像置换钙的锶，机井中Sr2+较大可能来源于含水层中菱锶矿。研究区85.2%水点的地下水符合国家生活饮用水卫生标准，超标水点多为单指标超标。经计算，枯水年富锶地下水天然补给资源量、可开采资源量和地下水资源潜力分别为3.83×107 m3/a、1.05×107 m3/a、7.28×106 m3/a。
结论新田县富锶地下水中锶主要来源于泥盆系佘田桥组地层含锶矿物（类质同像置换钙的锶和菱锶矿）的溶解，富锶地下水资源量及资源潜力可观，具有较大的开发利用潜力与价值。
创新点:（1）运用矿物饱和指数、水化学计量法、端元法探究岩溶地下水中Sr2+、SO42−来源及贡献量；（2）根据新田县气象水文资料、研究区可开采地下水现状，分析富锶地下水资源量及资源潜力，评价富锶地下水开发潜力与价值。
Abstract:This paper is the result of hydrogeological survey engineering.
ObjectiveThere is limited research on the sources of strontium elementand the potential for the development and utilization of karst water in the large−scale strontium rich mineral water field in Xintian County, Hunan Province. Exploring the hydrochemical characteristics of strontium−rich karst water and the sources of strontium element can provide theoretical support for searching for strontium rich groundwater in karst areas.
MethodsPHREEQC software, water stoichiometry, end element method and hydrogeological parameters were used in this study to reveal the mineral saturation index characteristicsof strontium−rich karst water, as well as the sources of Sr2+ and SO42− and its development potential through the hydrogeological investigation and hydrochemical testson groundwater in this strontium−rich mineral water field.
ResultsCalcite is mainly saturated both in the springs and shafts, while dolomite changes from unsaturated in the springs to saturate in the shafts. Strontium is saturated in the shafts, and gypsum is unsaturated both in the springs and the shafts. In the springs, mineral saturation index increases with the total dissolved solids, and they areof a good positive correlation, but of a poor correlation in the shafts. The correlation of SO42− betweenthe springs and shaftsare positive. According to the stoichiometric relation of Ca2+, Mg2+, Sr2+, HCO3− and SO42−, SO42− in the shafts may come from gypsum dissolution. The Sr2+ in the springsare mainly derived from strontium which replaces calcium with isomorphism in limestone, while Sr2+ in the shafts probably come from strontium siderite in the aquifer. 85.2% of the groundwatersamplings in the research area meet the national standard for drinking water quality, and the excess water samplings are mostly single indicator exceeding the standard. Through calculation, the natural recharge resources, exploitable resources and groundwater resource potential of strontium−rich groundwater in dry years are 3.83×107 m3/a、1.05×107 m3/a、7.28×106 m3/a respectively.
ConclusionsStrontium in the strontium−rich groundwater in Xintian County is mainly derived from the dissolution of strontium−containing minerals in Shetianqiao Formation strata of Devonian. Those minerals, including strontianite, were form by isomorphicly substitute of calcium with strontium. The amount and resource potential of strontium−rich groundwater are considerable, with a great value for development and utilization.
Highlights:(1) The sources and contributions of Sr2+ and SO42− in karst groundwater were studied by using mineral saturation index, water stoichiometry and end element method; (2) The amount and development potential of strontium−rich groundwater in the research area are analyzed based on the meteorological and hydrological information and the current exploitable groundwater resource.
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1. 研究目的（Objective）
湘中坳陷作为南方复杂构造区页岩气勘探的热点地区之一，也是中国油气勘探久攻未克的地区。前期在湘中地区北部的涟源凹陷泥盆系和石炭系获得了页岩气突破和发现，证实了湘中地区上古生界页岩气资源丰富。但对湘中地区南部的邵阳凹陷调查程度较为薄弱，针对邵阳凹陷二叠系仅开展了少量基础地质调查工作，页岩气资源潜力评价方面的工作尤为欠缺。本次研究依托邵阳湘邵地1井（XSD1井）钻探工程建立了邵阳凹陷二叠系地层层序序列，揭示了主要含气页岩层系的分布特征，获取了含气性评价参数，对湘中地区二叠系页岩气勘探开发和重新评价湘中坳陷页岩气资源潜力具有重要的现实意义。
2. 研究方法（Methods）
中国地质调查局武汉地质调查中心在收集分析区域地质相关资料的基础上，结合邵阳凹陷短陂桥向斜的煤田浅钻、非震物探等资料开展页岩气地质综合评价，采用页岩埋深500~4500 m，页岩有机碳含量≥1.0%，页岩厚度≥15 m，页岩有机质热演化程度1.0%~3.5%的评价参数在短陂桥向斜区优选页岩气远景区，论证部署了1口小口径页岩气地质调查井—XSD1井，湖南煤田地质勘查有限公司组织实施钻探（图 1a）。该井采样全井段取心钻井工艺，测井选取PSJ-2数字测井系统，录井采用SK-2000G气测录井，钻获二叠系大隆组156.05 m（暗色硅质页岩、钙质泥岩94.48 m），龙潭组349.95 m（暗色泥岩216.93 m，粉砂质泥岩36.9 m），对这两套层系共采集暗色泥岩样品33件，进行解析气含量测定分析，落实了含气性评价参数。
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图 1 湘邵地1井构造位置图（a）、主要含气层段岩性和含气性参数柱状图（b）、以及富集模式图（c）Figure 1. Structural location of Xiangshaodi 1 well (a), lithology and gas-bearing parameters of main gas bearing zones (b), and enrichment mode (c)3. 结果（Results）
本次样品分析工作由武汉地质调查中心古生物与生命-环境协同演化重点实验室完成，采用YSQ-IIIA岩石解析气测定仪（燃烧法）对含气段岩心共计33件样品进行分析。该井钻获二叠系大隆组厚度156.05 m，为一套硅质岩、硅质页岩、炭质钙质泥岩地层。其中在井深842~930.2 m硅质页岩、钙质泥岩段，气测全烃值从1.06%上升至16.54%，甲烷值从1.01%上升至14.04%，13件大隆组硅质页岩现场解析总含气量为1.29~9.97 m3/t，平均4.85 m3/t。实现了湘中坳陷二叠系页岩气新发现，有效拓展了华南地区大隆组勘探范围。
钻获龙潭组厚度349.95 m，上段为一套细砂岩、粉砂岩夹泥岩潮坪相沉积地层，下段为一套炭质泥岩、粉砂质泥岩夹薄层细砂岩泻湖相沉积地层。在井深1013.4~1048 m泥岩与粉砂岩互层段气测全烃值最高可达19.87%，甲烷值最高为16.94%，7件泥岩与粉砂岩样品现场解析总含气量0.57~3.42 m3/t，平均1.78 m3/t；井深1088.10~1199.75 m泥岩夹泥质粉砂岩含气层111.6 m，气测全烃值最高可达28.2%，甲烷值最高为23.6%，13件泥岩、粉砂质泥岩样品现场解析总含气量0.90~4.55 m3/t，平均2.01 m3/t（图 1b），首次查明了湘中坳陷二叠系龙潭组非常规油气分布特点。
通过区域地质背景分析，并结合煤田区域地质资料，本研究认为滑脱断裂（F9）上下盘具有不同的页岩气聚集条件。滑脱断裂之上由一系列的同向逆断层形成的逆冲推覆体，地层变形强烈，且裂缝发育，导致页岩气保存条件变差。滑脱断裂下盘是页岩气主要富集区，地层平缓，不发育次级通天断裂，与下盘地层形成反向遮挡，易形成封闭，保存条件良好（图 1c）。
4. 结论（Conclusions）
（1）二叠系大隆组岩性以硅质岩、硅质页岩为主，夹少量灰岩。主要含气段存在于上段硅质页岩段，厚88.2 m，含气量平均为4.85 m3/t，含气性优越，资源潜力大。
（2）二叠系龙潭组上段以致密砂岩气为主，含气量平均为1.78 m3/t；下段以页岩气为主，泥岩厚达177.47 m，含气量平均为2.01 m3/t，具有泥岩厚度大，含气性好等特征。
（3）保存条件是页岩气富集关键，构造改造弱的封闭演化环境有利于页岩气保存，研究区滑脱断裂下盘是页岩气主要富集区，易形成封闭，保存条件良好。
（4）湘邵地1井在二叠系大隆组和龙潭组获得良好的页岩气显示，证实了湘中地区二叠系具有良好的页岩气资源潜力，对湘中地区页岩气资源潜力评价具有重要意义。
5. 基金项目（Fund support）
本文为中国地质调查局项目“中扬子地区油气页岩气调查评价”（DD20221659）资助的成果。
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图 1 湖南新田县富锶地下水采样点分布图（据夏日元等, 2017修改）
Figure 1. Map showing distribution of sampling sites of strontium−rich groundwater in Xintian County, Hunan Province (modified from Xia Riyuan et al., 2017)
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图 2 湖南新田县地下水矿物饱和指数（a—下降泉；b—机井）
Figure 2. Mineral saturation index in groundwater of Xintian County, Hunan Province (a–Spring；b–Shaft)
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图 3 湖南新田县地下水中矿物饱和指数与TDS关系（a—下降泉；b—机井）
Figure 3. Relationship between mineral saturation index and TDS in groundwater of Xintian County, Hunan Province (a–Spring；b–Shaft)
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图 4 湖南新田县地下水中Sr2+、SO42−与Mg2+/(Ca2++Mg2+) 关系（a—下降泉；b—机井）
Figure 4. Relationship between Sr2+, SO42− and Mg2+/(Ca2++Mg2+) in groundwater of Xintian County, Hunan Province (a–Spring；b–Shaft)
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图 5 湖南新田县地下水中外源酸、TDS与SO42−关系（a—下降泉；b—机井）
Figure 5. Relationship between exogenous acid, TDS and SO42−in groundwater of Xintian County, Hunan Province (a–Spring；b–Shaft)
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图 6 湖南新田县机井中Ca2+、SO42−与石膏饱和指数关系
Figure 6. Relationship between Ca2+, SO42−and gypsum saturation index in shafts of Xintian County, Hunan Province
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图 7 湖南新田县机井中主要离子当量浓度关系
Figure 7. Equivalent concentration relationship of the main ion in shafts of Xintian County, Hunan Province
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图 8 湖南新田县机井中Sr2+与Na+、SO42−关系
Figure 8. Relationship between Na+, SO42−and Sr2+ in shafts of Xintian County, Hunan Province
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图 9 湖南新田县机井中Sr/Ca、Sr/Mg与TDS关系
Figure 9. Relationship between Sr/Ca, Sr/Mg and TDS in shafts of Xintian County, Hunan Province
表 1 湖南新田县大气降水、下降泉、机井水化学指标含量统计结果
Table 1 Statistics of hydrochemical indicator content in springs, shafts and precipitation
分类 统计量 pH Sr2+ K+ Na+ Ca2+ Mg2+ HCO3− SO42− Cl− TDS 下
降
泉最小值 6.76 0.03 0.07 0.37 39.38 1.73 132.50 4.29 1.40 136.91 最大值 7.81 0.67 16.44 15.68 131.14 13.41 398.43 57.71 27.45 411.50 平均值 7.13 0.26 1.69 3.39 94.31 4.27 277.41 19.19 6.10 286.00 标准差 0.27 0.16 2.94 4.14 22.76 2.66 62.59 14.55 6.12 74.65 机
井最小值 6.90 0.20 0.28 0.76 33.10 1.86 182.98 5.18 1.68 186.56 最大值 7.62 8.47 16.04 105.52 159.42 58.22 581.31 98.43 88.78 618.82 平均值 7.33 2.64 2.57 31.63 91.83 22.92 393.74 40.36 19.96 428.27 标准差 0.21 2.48 2.94 35.96 37.79 16.31 80.89 25.33 22.00 105.02 大气降水 7.53 0.00771 0.77 0.19 8.92 0.37 31.49 5.53 0.9 36.27 注：除pH外所有指标含量单位均为mg/L；大气降水样品数1组，下降泉样品数33组，机井样品数28组。 
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表 2 富锶地下水部分常规指标含量统计结果
Table 2 Statistics of some conventional indexes content in strontium−rich groundwater
指标 下降泉 机井 最大值 平均值 最小值 最大值 平均值 最小值 Al/(μg/L) 178 / − 670 / − Cu/(μg/L) 1.52 / − 8.66 / − Pb/(μg/L) 0.76 0.42 0.25 15 1.85 0.32 Zn/(μg/L) 15.8 / − 437 / − Cr/(μg/L) 10.4 5.41 1.47 8.99 6.19 2.36 Cd/(μg/L) 0.2 / − 0.4 / − Mn/(μg/L) 190 / − 571 / − As/(μg/L) 1.38 / − 5.03 / − Hg/(μg/L) 0.14 / − 1.87 / − Se/(μg/L) 1.98 / − 2.04 / − Fe/(mg/L) 0.27 / − 1.1 / − NO3−−N/(mg/L) 78.94 / − 64.46 / − CODMn/(mg/L) 2.51 / − 1.37 / − 注：“−”表示含量低于检测线；“/”表示无数据。
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