吉林大学学报(地球科学版) ›› 2019, Vol. 49 ›› Issue (2): 548-558.doi: 10.13278/j.cnki.jjuese.20170224

• 地质工程与环境工程 • 上一篇    下一篇

西藏搭格架高温热泉中砷的地球化学异常及其存在形态

严克涛, 郭清海, 刘明亮   

  1. 中国地质大学(武汉)生物地质与环境地质国家重点实验室/环境学院, 武汉 430074
  • 收稿日期:2017-09-05 出版日期:2019-03-26 发布日期:2019-03-28
  • 通讯作者: 郭清海(1978-)男,教授,博士生导师,主要从事高温地热流体地球化学领域的研究工作,E-mail:qhguo2006@gmail.com E-mail:qhguo2006@gmail.com
  • 作者简介:严克涛(1992-)男,博士研究生,主要从事高温地热流体地球化学领域的研究工作,E-mail:904188340@qq.com
  • 基金资助:
    国家自然科学基金项目(41572335,41772370)

Geochemical Anomalies of Arsenic and Its Speciation in Daggyai Geothermal Springs, Tibet

Yan Ketao, Guo Qinghai, Liu Mingliang   

  1. State Key Laboratory of Biogeology and Environmental Geology/School of Environmental Studies, China University of Geosciences, Wuhan 430074, China
  • Received:2017-09-05 Online:2019-03-26 Published:2019-03-28
  • Supported by:
    Supported by National Natural Science Foundation of China(41572335,41772370)

摘要: 西藏搭格架高温热泉是我国大陆少有的大型间歇性喷泉,砷元素作为对人类威胁极大的环境问题普遍存在于热泉之中,搭格架高温热泉中砷元素质量浓度最高已达到了9.75 mg/L,其对地表水和浅层地下水的污染不容忽视。硫代砷是富含硫化物热泉中砷的存在形态之一,鉴于国内相关研究较少,本文对西藏搭格架地热区的热泉样品进行了水化学分析,并利用水文地球化学模拟软件PHREEQC开展了对热泉中砷元素存在形态的地球化学模拟。结果表明:西藏搭格架热泉中砷元素的存在形态有亚砷酸盐、砷酸盐和硫代砷,其中亚砷酸盐与砷酸盐是砷的主要存在形态,且在pH影响下两者之间存在相互转化关系;各种硫代砷按质量浓度由高至低依次为一硫代砷酸盐、三硫代砷酸盐、二硫代砷酸盐、一硫代亚砷酸盐、四硫代砷酸盐;硫代砷形态占总砷浓度比例主要受热泉中硫化物质量浓度、Eh(氧化还原电位)和pH等因素的控制,在硫化物质量浓度总体偏低的情况下,硫化物质量浓度的上升可促进其他形态的砷向硫代砷形态转化,强还原性环境有利于硫代砷形态的存在;此外,在中性环境下,硫代砷占总砷浓度比例随pH上升亦有上升趋势。

关键词: 热泉, 硫代砷, 搭格架热田, 地球化学

Abstract: Daggyai geothermal system in Tibet includes the biggest geyser in mainland China. Arsenic, as one of the most harmful substances, commonly exists in geothermal water, and the highest arsenic concentration detected in Daggyai geothermal springs reaches 9.75 mg/L, unneglectable potential arsenic pollution in shallow groundwater and rivers should be noticed. Thioarsenic usually exists as the dominant species of arsenic in sulfide-rich thermal springs;however there are few related studies in China. We focused on Daggyai geothermal system, and analyzed the chemical components of the geothermal spring samples. Thioarsenic species in each sample were calculated by using the hydro-geothermal simulation software PHREEQC. The results are as follows:Arsenic in Daggyai geothermal water consists of arsenate, arsenite, and thioarsenic, among which the arsenate and arsenite are the main species. There are interchanges between arsenate and arsenite when pH changes. The descending order of thioarsenic species in terms of their average ratio is monothioarsenate, trithioarsenate, ditthioarsenate, monothioarsenite and tetrathioarsenate. The proportion of thioarsenic to total arsenic concentration is mainly controlled by sulfide concentration, pH and Eh in geothermal water. High concentration of sulfide can promote the process of arsenic changing into thioarsenic, and strong reducing environment is required for the existence of thioarsenic. Moreover, the percentage of thioarsenic seems to have a positive correlation with pH value.

Key words: geothermal spring, thioarsenic, Daggyai geothermal system, geochemistry

中图分类号: 

  • X142
[1] 孙贵范.我国地方性砷中毒研究进展[J].环境与健康杂志,2009,26(12):1035-1036. Sun Guifan. Research Progress of Endemic Arsenism in China[J]. Journal of Environment and Health,2009,26(12):1035-1036.
[2] Craigmile P F,Calder C A,Li H,et al.Hierarchical Model Building,Fitting,and Checking:A Behind-the-Scenes Look at a Bayesian Analysis of Arsenic Exposure Pathways[J]. Bayesian Analysis,2009,4(1):1-35.
[3] Figueira R,Sérgio C,Lopes J L,et al.Detection of Exposition Risk to Arsenic in Portugal Assessed by Air Deposition in Biomonitors and Water Contamination[J]. Int J Hyg Environ Health,2007,210(3/4):393-397.
[4] Whanger P D,Weswig P H,Stoner J C.Arsenic Levels in Oregon Waters[J]. Environ Health Perspect,1977,19:139-143.
[5] Subramanian K S,Kosnett M J.Human Exposures to Arsenic from Consumption of Well Water in West Bengal,India[J]. Int J Occup Environ Health,1998,4(4):217-230.
[6] Anawar H M.Arsenic Poisoning in Groundwater:Health Risk and Geochemical Sources in Bangladesh[J].Environment International,2002,27(7):597-604.
[7] Das D,Chatterjee A,Mandal B K,et al.Arsenic in Ground Water in Six Districts of West Bengal,India:The Biggest Arsenic Calamity in The World:Part 2:Arsenic Concentration in Drinking Water,Hair,Nails,Urine,Skin-Scale and Liver Tissue (Biopsy) of the Affected People[J].Analyst,1995,120(3):917-24.
[8] 金银龙,梁超轲,何公理,等.中国地方性砷中毒分布调查:总报告[J].卫生研究,2003,32(6):519-540. Jin Yinlong,Liang Chaoke,He Gongli,et al. Study on Distribution of Endemic Arsenism in China[J]. Journal of Hygiene Research,2003,32(6):519-540.
[9] 卞建民,查恩爽,汤洁,等.吉林西部砷中毒区高砷地下水反向地球化学模拟[J].吉林大学学报(地球科学版),2010,40(5):1098-1103. Bian Jianmin,Cha Enshuang,Tang Jie,et al.Inverse Geochemical Modeling of Arsenic Groundwater at Arseniasis Area in the Western of Jilin Province[J].Journal of Jilin University (Earth Science Edition),2010,40(5):1098-1103.
[10] 赵娟,李育松,卞建民,等.吉林西部地区高砷地下水砷的阈值分析及风险评价[J].吉林大学学报(地球科学版),2013,43(1):251-258. Zhao Juan,Li Yusong,Bian Jianmin,et al. Threshold Analysis and Health Risk Assessment of Arsenic in Groundwater in Western Jilin Province[J]. Journal of Jilin University (Earth Science Edition),2013,43(1):251-258.
[11] Cortecci G,Boschetti T,Mussi M,et al.New Chemical and Original Isotopic Data on Waters from El Tatio Geothermal Field,Northern Chile[J].Geochemical Journal,2015,39(6):547-571.
[12] Khorasanipour M,Esmaeilzadeh E.Geogenic Arsenic Contamination in the Kerman Cenozoic Magmatic Arc,Kerman,Iran:Implications for the Source Identification and Regional Analysis[J].Applied Geochemistry,2015,63:610-622.
[13] Birkle P,Bundschuh J,Sracek O,et al. Mechanisms of Arsenic Enrichment in Geothermal and Petroleum Reservoirs Fluids in Mexico[J].Water Research,2010,44(19):5605-5617.
[14] Arnold Y P,Cabassi J,Tassi F,et al.Fluid Geochemistry of a Deep-Seated Geothermal Resource in The Puna Plateau (Jujuy Province,Argentina)[J].Journal of Volcanology & Geothermal Research,2017,338:121-134.
[15] Kaasalainen H,Stefánsson A. The Chemistry of Trace Elements in Surface Geothermal Waters and Steam,Iceland[J]. Chemical Geology,2012,330/331:60-85.
[16] Smedley P L,Kinniburgh D G.A Review of the Source,Behaviour and Distribution of Arsenic in Natural Waters[J].Applied Geochemistry,2002,17(5):517-568.
[17] 丁爱中,杨双喜,张宏达.地下水砷污染分析[J].吉林大学学报(地球科学版),2007,37(2):319-325. Ding Aizhong,Yang Shuangxi,Zhang Hongda.Analysis of Groundwater Arsenic Pollution[J]. Journal of Jilin University (Earth Science Edition),2007,37(2):319-325.
[18] Bostick B C,Fendorf S,Brown G E. In Situ Analysis of Thioarsenite Complexes in Neutral to Alkaline Arsenic Sulphide Solutions[J].Mineralogical Magazine,2005,69(5):781-795.
[19] Helz G R,Tossell J A.Thermodynamic Model for Arsenic Speciation in Sulfidic Waters:A Novel Use of Ab Initio,Computations[J].Geochimica Et Cosmochimica Acta,2008,72(18):4457-4468.
[20] Parkhurst D L.User's guide to PHREEQC:Version 2:A Computer Program for Speciation,Batch-Reaction,One-Dimensional Transport,and Inverse Geochemical Calculations[R].Water Resources Investigations Report,1999:99-4259.
[21] Zakaznova-Herzog V P,Seward T M.A Spectrophotometric Study of the Formation and Deprotonation of Thioarsenite Species in Aqueous Solution at 22℃[J].Geochimica Et Cosmochimica Acta,2012,83(1):48-60.
[22] Thilo E,Hertzog K,Winkler A.Vber Vorgänge bei der Bildung des Arsen(V)-Sulfids Beim Ansäuern von Tetrathioarsenatlösungen[J].Zeitschrift Für Anorganische Und Allgemeine Chemie,1970,373(2):111-121.
[23] Guo Q,Planer-Friedrich B,Liu M,et al.Arsenic and Thioarsenic Species in the Hot Springs of the Rehai Magmatic Geothermal System,Tengchong Volcanic Region,China[J]. Chemical Geology,2017,453:12-20.
[24] 郭清海,刘明亮,李洁祥.腾冲热海地热田高温热泉中的硫代砷化物及其地球化学成因[J].地球科学,2017,42(2):286-297. Guo Qinghai,Liu Mingliang,Li Jiexiang.Thioarsenic Species in the High-Temperature Hot Springs from the Rehai Geothermal Field (Tengchong) and Their Geochemical Geneses[J]. Earth Science,2017,42(2):286-297.
[25] 庄亚芹,郭清海,刘明亮,等.高温富硫化物热泉中硫代砷化物存在形态的地球化学模拟:以云南腾冲热海水热区为例[J].地球科学,2016,41(9):1499-1510. Zhuang Yaqin,Guo Qinghai,Liu Mingliang,et al.Geochemical Simulation of Thioarsenic Speciation in Hgh-Temperature,Sulfide-Rich Hot Springs:A Case Study in the Rehai Hydrothermal Area,Tengchong,Yunnan[J]. Earth Science,2016,41(9):1499-1510.
[26] 朱弟成,莫宣学,赵志丹,等.西藏南部二叠纪和早白垩世构造岩浆作用与特提斯演化:新观点[J].地学前缘,2009,16(2):1-20. Zhu Dicheng,Mo Xuanxue,Zhao Zhidan,et al.Permian and Early Cretaceousc Tectonomagmatism in Southern Tibet and Tethjy and Evolution:New Perspective[J]. Earth Science Frontier,2009,16(2):1-20.
[27] 郑绵平,王秋霞,多吉.水热成矿新类型西藏铯硅华矿床[M].北京:地质出版,1995. Zheng Mianping,Wang Qiuxia,Duo Ji. New Types of Hydrothermal Mineralization,Tibet Cesium Silicate Deposit[M].Beijing:Geological Publishing House,1995.
[28] 赵元艺,聂凤军,侯增谦,等.西藏搭格架热泉型铯矿床地质特征及形成时代[J].矿床地质,2006,25(3):281-291. Zhao Yuanyi,Nie Fengjun,Hou Zengqian,et al.Geological Characteristics and Formation Age of Hot Spring Cesium Deposit Area,Tibet[J].Mineral Deposits,2006,25(3):281-291.
[29] 赵元艺,聂凤军,侯增谦,等.西藏搭格架热泉型铯矿床地球化学[J].矿床地质,2007,26(2):163-174. Zhao Yuanyi,Nie Fengjun,Hou Zengqian,et al.Geochemistry of Targejia Hot Spring Type Cesium Deposit in Tibet[J]. Mineral Deposits,2007,26(2):163-174.
[30] 沈立成,伍坤宇,肖琼,等.西藏地热异常区CO2脱气研究:以朗久和搭格架地热区为例[J].科学通报,2011,56(26):2198-2208. Shen Licheng,Wu Kunyu,Xiao Qiong,et al.Carbon Dioxide Degassing Flux from Two Geothermal Fields in Tibet,China[J].Chinese Science Bulletin,2011,56(26):2198-2208.
[1] 任宪军, 石云倩. 松辽盆地南部下白垩统火石岭组钙碱性火山岩地球化学特征及成因[J]. 吉林大学学报(地球科学版), 2026, 56(3): 818-834.
[2] 王常东, 董小宇, 郝晓飞, 姜山, 于兵, 周舰, 王天奇. 广兴—芝瑞盆地上伙房地段流纹斑岩地球化学特征及其地质意义[J]. 吉林大学学报(地球科学版), 2026, 56(3): 835-851.
[3] 刘宇泰, 李碧乐, 陈晓琳, 李浩然, 史雨凡, 孙亚明.  东昆仑沟里地区瓦勒尕南矿区花岗闪长岩地球化学特征、锆石U-Pb年代学及其地质意义[J]. 吉林大学学报(地球科学版), 2026, 56(3): 875-895.
[4] 张海洪, 乔锦燃, 陈国强, 薛晓刚, 邓馨卉, 苗长盛, 李 雪, 郜春生. 张广才岭南部早侏罗世两类I型花岗岩成因:年代学、地球化学和锆石Hf同位素证据[J]. 吉林大学学报(地球科学版), 2026, 56(3): 896-914.
[5] 赵振, 秦光雄, 闫佰忠, 马苗苗. 青海省互助土族自治县地热田水化学特征及成因机制[J]. 吉林大学学报(地球科学版), 2026, 56(3): 986-1001.
[6] 何天鑫, 柳蓉, 刘强浩, 宁婷, . 银额盆地下白垩统巴音戈壁组纤维状方解石脉成因机制——热水沉积与同位素证据[J]. 吉林大学学报(地球科学版), 2026, 56(2): 497-510.
[7] 李阳, 周文博, 王长虹, 刘娜, 苟军, 孙文博, 孙家兴, 孙德有. 海拉尔盆地克鲁伦凹陷赋铀地层沉积物源#br#[J]. 吉林大学学报(地球科学版), 2026, 56(2): 522-539.
[8] 徐骏, 高阳, 刘军, 王晓彤, . 大兴安岭北段三矿沟铁铜矿床成因——来自石榴子石U-Pb定年及元素地球化学证据[J]. 吉林大学学报(地球科学版), 2026, 56(2): 540-556.
[9] 陈卓, 周建波, 李功宇, 辛中华, 王红燕, 孙宁辰. 北方造山带东段微陆块构造属性与超大陆重建[J]. 吉林大学学报(地球科学版), 2026, 56(1): 1-16.
[10] 张佳琦, 王志新, 梁琛岳, 郑常青, 刘永江. 吉中地区范家屯组变沉积岩碎屑锆石年代学与Hf同位素示踪——对古亚洲洋东段闭合的约束[J]. 吉林大学学报(地球科学版), 2026, 56(1): 149-172.
[11] 高心如, 梁琛岳, 郑常青, 刘永江, 周建波, 宋志伟, 贾祥鹤, 殷浚哲, 洪雨萱, 谭卓, 张佳琦. 蒙古—鄂霍茨克构造域东段晚中生代演化历史——来自岩浆岩和沉积岩的证据[J]. 吉林大学学报(地球科学版), 2026, 56(1): 36-65.
[12] 柳蓉, 何天鑫, 张浩然, 刘强浩, 张苡铭. 中国典型含油气盆地热液作用及其对沉积环境的影响[J]. 吉林大学学报(地球科学版), 2025, 55(6): 1785-1805.
[13] 张万仁, 吴保祥, 韦枫, 杨维刚, 刘杰. 甘肃省宕昌—崖湾地区水系沉积物地球化学特征与锑找矿预测[J]. 吉林大学学报(地球科学版), 2025, 55(5): 1462-1480.
[14] 郑伟, 刘东宏, 吴晓东, 孙煜恒, 邢波. 粤西石菉Cu-Mo矿床石榴子石与符山石地球化学特征及其对成矿流体演化的制约[J]. 吉林大学学报(地球科学版), 2025, 55(5): 1481-1505.
[15] 杨维刚, 李永胜, 任文秀, 王玉玺, 黄增保, 牛鹏飞, 王怀涛, 张家瑞, 贾志磊, 李小强. 西秦岭九寨沟县下草地村含金花岗斑岩特征及其金矿找矿指示意义[J]. 吉林大学学报(地球科学版), 2025, 55(5): 1506-1524.
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed   
[1] 吴远坤, 刘成林, 于春勇. 松辽盆地双城断陷深层原油成藏模式[J]. 吉林大学学报(地球科学版), 2024, 54(5): 1443 -1456 .
[2] 马荣,石建省,刘继朝. 人工内分泌网络模型在水文地质参数研究中的应用[J]. 吉林大学学报(地球科学版), 2013, 43(3): 914 -921 .
[3] 李宁, 王成文. 东北及邻区晚古生代地层接触关系与佳-蒙地块的形成和演化[J]. 吉林大学学报(地球科学版), 2017, 47(5): 1331 -1340 .
[4] 胡大千,初凤友,姚 杰. 中太平洋YJA海山富钴结壳矿物组成与元素地球化学[J]. J4, 2006, 36(01): 32 -0037 .
[5] 姜 雪, 程日辉,于民凤. 裂谷地层的气候和构造控制:Zscape模型分析与在松辽盆地北安断陷的应用[J]. J4, 2006, 36(01): 54 -0059 .
[6] 李春柏,张新涛,刘 立,任延广,孟 鹏. 布达特群热流体活动及其对火山碎屑岩的改造作用--以海拉尔盆地贝尔凹陷为例[J]. J4, 2006, 36(02): 221 -0226 .
[7] 孟宪纲,薄万举,刘志广,刘勇,畅柳,李朝柱,王子平. 芦山7.0级地震与巴颜喀拉块体中东段的活动性[J]. 吉林大学学报(地球科学版), 2014, 44(5): 1705 -1711 .
[8] 陈欢庆, 梁淑贤, 舒治睿, 邓晓娟, 彭寿昌. 冲积扇砾岩储层构型特征及其对储层开发的控制作用——以准噶尔盆地西北缘某区克下组冲积扇储层为例[J]. 吉林大学学报(地球科学版), 2015, 45(1): 13 -24 .
[9] 贾大成,邢立新, 潘 军, M. J. van Bergen, H. van Roermund. 伊通上地幔剪切带捕虏体中富铝尖晶石的地球化学特征[J]. J4, 2006, 36(04): 497 -502 .
[10] 谢忠雷,杨佰玲,包国章,董德明. 茶园土壤不同形态镍的含量及其影响因素[J]. J4, 2006, 36(04): 599 -604 .