贺兰山北段羊氟中毒区氟污染研究
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摘要
宁夏贺兰山煤炭开采和煤层自燃已有300多年历史,该区近30年来开采强度加大,自燃程度趋重。本工作深入调查和系统测试了该区地表土和牧草等共计137件样品中的氟含量,结果显示:地表土中氟含量总均值为707±126μg/g,显著高于当地氟背景值;牧草氟含量为218±42μg/g,表明羊氟中毒可能与地表土及牧草高氟息息相关。地表土中硫酸盐均值为1771±130μg/g,而p H均值为5. 92±0. 82,与当地背景值相比,该区硫酸盐含量显著偏高,酸性明显较强。研究表明,贺兰山北段地表土存在酸污染及硫酸盐污染,并伴随氟污染,可能源于该区域采煤、用煤及煤层自燃历史悠久,导致氟化物、酸性硫酸盐沉降并存,随之污染牧草,进而引发羊氟中毒。
There is a history of 300 years of coal mining and coal seam fire in the Helan Mountain,Ningxia province. The coal mining and spontaneous combustion kept increasing for nearly 30 years and the endemic sheep fluorosis aggravated. A total of 137 samples including topsoil and grass were collected in this area and their fluorine levels were determined. The mean content of fluorine in topsoil samples was 707±126 μg/g( n = 77) and the mean fluorine content of grass was 218±42 μg/g( n = 28),significantly higher than respective background values of the region,suggesting that the sheep fluorosis may be associated with high fluorine contents in topsoil and grass; the sulfate content and p H of topsoil were 1 771±130 μg/g( n = 77) and 5. 92±0. 82( n = 77),respectively,and positively correlated in acidic topsoil samples( r = 0. 72),indicating that the acidity of soil may result from acidic sulfates,such as NaHSO_4 and KHSO_4. The high fluorine,sulfate and acidity in soil may because of the long history of coal mining,coal using and coal spontaneous combustion,which result in fluoride and acidic sulfate coexisting depositions.
There is a history of 300 years of coal mining and coal seam fire in the Helan Mountain,Ningxia province. The coal mining and spontaneous combustion kept increasing for nearly 30 years and the endemic sheep fluorosis aggravated. A total of 137 samples including topsoil and grass were collected in this area and their fluorine levels were determined. The mean content of fluorine in topsoil samples was 707±126 μg/g( n = 77) and the mean fluorine content of grass was 218±42 μg/g( n = 28),significantly higher than respective background values of the region,suggesting that the sheep fluorosis may be associated with high fluorine contents in topsoil and grass; the sulfate content and p H of topsoil were 1 771±130 μg/g( n = 77) and 5. 92±0. 82( n = 77),respectively,and positively correlated in acidic topsoil samples( r = 0. 72),indicating that the acidity of soil may result from acidic sulfates,such as NaHSO_4 and KHSO_4. The high fluorine,sulfate and acidity in soil may because of the long history of coal mining,coal using and coal spontaneous combustion,which result in fluoride and acidic sulfate coexisting depositions.
引文
[1] Meenakshi R C,Maheshwari,Fluoride in drinking water and its removal[J],Journal of hazardous materials. 2006,137:456-463.
[2] Singh B,Gaur S,Garg V K. Fluoride in drinking water and human urine in Southern Haryana,India[J]. Journal of hazardous materials,2007,144:147-151.
[3] Luo K L,Li L,Zhang S X. Coal-burning roasted corn and chili as the cause of dental fluorosis for children in southwestern China. Journal of Hazardous Materials[J],2011,185:1340-1347.
[4] Dai S F,Ren D Y,Ma S M. The cause of endemic fluorosis in western Guizhou province,Southwest China[J]. Fuel,2004,83:2095-2098.
[5] Finkelman R B,William O,Vincent C,et al. Health impacts of coal and coal use:possible solutions[J]. International Journal of Coal Geology,2002,50:425-443.
[6]洪秀萍，梁汉东，张玉法，等．云贵川交界处地氟病区晚二叠世煤的酸度分布[J]．煤炭学报，2016,41(4):964-973.
[7]李康然．家禽氟中毒概述[J]．广西畜牧兽医，1999,5(1):35-37.
[8]陈萍，唐修义．中国煤中氟[J]．中国煤田地质，2002,14(增刊):25-28.
[9]李康然．耕牛慢性氟中毒病例报告[J]．兽医科技通讯，1977(1):42-47.
[10]郑宝山．地方性氟中毒及工业氟污染研究[J]．北京:中国环境出版社，1992.
[11]衣守志，方中心，金峰．稀土精矿酸法冶炼中含氟废气治理技术[J]．天津科技大学学报，2012,27(4):74-78.
[12]云敏瑞，云鹏，高小玲．包头市空气中氟化物污染变化趋势与治理效果分析[J]．内蒙古环境保护，2005,17(4):17-19.
[13]马步君，司红霞．石嘴山地区羊氟中毒病及氟化物污染情况的调查[J]．黑龙江畜牧兽医，2010.
[14]贾恒义，程浦海，雍绍萍，等．黄土高原草地土壤化学元素的特征与生态环境[J]．水土保持学报，1995,9(4):84-73.
[15]刘秉儒，张秀珍，胡天华，等．贺兰山不同海拔典型植被带土壤微生物多样性[J]．生态学报，33(22),7211-7220.
[16]丁培民．贺兰山含煤区[J]．地质学报，1960,40(1):89-109.
[17] Rosema A,Guan H,Veld H. Simulation of spontaneous combustion,to study the causes of coal fires in the Rujigou Basin[J]. Fuel,2001,80(1):7-16.
[18] Prakash A,Vekerdy Z. Design and implementation of a dedicated prototype GIS for coal fire investigations in North China[J]. International journal of coal geology,2004,59(1):107-119.
[19] Voigt S,Tetzlaff A,Zhang J,et al. Integrating satellite remote sensing techniques for detection and analysis of uncontrolled coal seam fires in North China[J]. International Journal of Coal Geology,2004,59(1):121-136.
[20]黄丹青，赵育台，谢志清．宁夏汝箕沟煤火遥感探测与效果[J]．物探与化探，2007,31(增刊):41-43.
[21]林燕．基于avenue的汝箕沟煤火遥感监测信息系统设计与实现[D]．西安科技大学，2006.
[22] DB51/T 1047-2010，粮油作物植物样品田间采集及制备技术规范[S].
[23] GBT 36197-2018，土壤质量土壤采样技术指南[S].
[24] Geng W H,Nakajima T,Takanashi H,et al. Determination of total fluorine in coal by use of oxygen flask combustion method with catalyst[J].Fuel,2007,86:715-721.
[25]潘锋，麦琦．氧瓶燃烧-离子色谱法检测茶叶中总氟的含量[J]．中国卫生检查杂志，2007,17(9):1634-1636.
[26] Hong X P,Liang H D,Y K,et al. Preliminary Survey of fluorine content in soil and plants around Wuda coalfield,Inner Mongolia,China[J].Fluoride,2017,50(4),430-444.
[27]郁冬梅，吴学华，崔向红．从土壤地球化学看宁夏平罗县砷、氟中毒地方病的起因与分布[J]．农业科学研究，2011,32(4):45-47.
[28]闫锦鹏．牧草含氟规律探讨[J]．包钢科技．1999,2:46-49.
[29]高德，刘焕文．大气氟污染对牧草的影响[J]．甘肃环境研究与监测，1985,4(3):5-9.
[30]刘焕文，高德．家畜慢性氟中毒与牧草氟临界范围的探讨[J]．环境科学，1985,6(2):40-45.
[31]刘焕文，高德．牧草氟污染与家畜慢性氟中毒的探讨[J]．环境科学丛刊，1986,11(7):74-78.
[32]周翰信，刘统海，胡义，等．放牧绵羊氟中毒调查及预防对策[J]．青海畜牧兽医杂志，1999,29(6):23-25.
[33]洪秀萍，梁汉东，张玉法，等．云贵川交界区晚二叠世煤系地层出露风化土的酸性特征[J]．环境化学，2017,36(8):1831-1841.
[34]洪秀萍，梁汉东，吕帅，等．贵州织金荷花村拌煤粘土的潜在氟化氢释放[J]．地质论评，2015,61(4):852-860.
[35]黄建成，桂林国．宁夏碱性土壤施肥技术对枸杞生长和土壤的影响[J]．宁夏农林科技，2015,56(11):29-31.
[36]张芬芬，孙娟，谢忠奎．西北碱性土壤施肥对东方百合“索邦”光合作用及种球产量的影响[J]．草业学报，2012,21(4):79-87.
[37]李伟，李飞，毕德．兰州碱性土壤与农产品中硒分布及形态研究[J]．土壤，2012,44(4):632-638.
[38]王华，刘洋，汤笑飞，等．汝箕沟矿区露天开采小窑火区快速治理技术．煤炭技术，2016,35(1):164-166.
[39]任德贻，赵峰华，代世峰，等．煤的微量元素地球化学[M]．北京:科学出版社，2006.
[40]张苗云，王世杰，马国强，等．大气环境的硫同位素组成及示踪研究[J]．中国科学:地球科学，2011,41(2):216-224.
[41]边敏娟，钱骏，刘志红等．四川中东部地区2009年大气硫沉降模拟[J]．环境科学研究，2012,25(10):1115-1119.
[42]李文华，熊飞，姜英．微量有害元素在高硫煤中的存在状态[J]．煤化工，1994,4:20-23.
[43]洪秀萍，张引，梁汉东，等．三道岭露天煤矿外围表土总氟含量研究[C]. 2014年中国地球科学联合学术年会—专题10:流体地球科学与巨型成矿带及重大自然灾害成因论文集，2014.
[2] Singh B,Gaur S,Garg V K. Fluoride in drinking water and human urine in Southern Haryana,India[J]. Journal of hazardous materials,2007,144:147-151.
[3] Luo K L,Li L,Zhang S X. Coal-burning roasted corn and chili as the cause of dental fluorosis for children in southwestern China. Journal of Hazardous Materials[J],2011,185:1340-1347.
[4] Dai S F,Ren D Y,Ma S M. The cause of endemic fluorosis in western Guizhou province,Southwest China[J]. Fuel,2004,83:2095-2098.
[5] Finkelman R B,William O,Vincent C,et al. Health impacts of coal and coal use:possible solutions[J]. International Journal of Coal Geology,2002,50:425-443.
[6]洪秀萍，梁汉东，张玉法，等．云贵川交界处地氟病区晚二叠世煤的酸度分布[J]．煤炭学报，2016,41(4):964-973.
[7]李康然．家禽氟中毒概述[J]．广西畜牧兽医，1999,5(1):35-37.
[8]陈萍，唐修义．中国煤中氟[J]．中国煤田地质，2002,14(增刊):25-28.
[9]李康然．耕牛慢性氟中毒病例报告[J]．兽医科技通讯，1977(1):42-47.
[10]郑宝山．地方性氟中毒及工业氟污染研究[J]．北京:中国环境出版社，1992.
[11]衣守志，方中心，金峰．稀土精矿酸法冶炼中含氟废气治理技术[J]．天津科技大学学报，2012,27(4):74-78.
[12]云敏瑞，云鹏，高小玲．包头市空气中氟化物污染变化趋势与治理效果分析[J]．内蒙古环境保护，2005,17(4):17-19.
[13]马步君，司红霞．石嘴山地区羊氟中毒病及氟化物污染情况的调查[J]．黑龙江畜牧兽医，2010.
[14]贾恒义，程浦海，雍绍萍，等．黄土高原草地土壤化学元素的特征与生态环境[J]．水土保持学报，1995,9(4):84-73.
[15]刘秉儒，张秀珍，胡天华，等．贺兰山不同海拔典型植被带土壤微生物多样性[J]．生态学报，33(22),7211-7220.
[16]丁培民．贺兰山含煤区[J]．地质学报，1960,40(1):89-109.
[17] Rosema A,Guan H,Veld H. Simulation of spontaneous combustion,to study the causes of coal fires in the Rujigou Basin[J]. Fuel,2001,80(1):7-16.
[18] Prakash A,Vekerdy Z. Design and implementation of a dedicated prototype GIS for coal fire investigations in North China[J]. International journal of coal geology,2004,59(1):107-119.
[19] Voigt S,Tetzlaff A,Zhang J,et al. Integrating satellite remote sensing techniques for detection and analysis of uncontrolled coal seam fires in North China[J]. International Journal of Coal Geology,2004,59(1):121-136.
[20]黄丹青，赵育台，谢志清．宁夏汝箕沟煤火遥感探测与效果[J]．物探与化探，2007,31(增刊):41-43.
[21]林燕．基于avenue的汝箕沟煤火遥感监测信息系统设计与实现[D]．西安科技大学，2006.
[22] DB51/T 1047-2010，粮油作物植物样品田间采集及制备技术规范[S].
[23] GBT 36197-2018，土壤质量土壤采样技术指南[S].
[24] Geng W H,Nakajima T,Takanashi H,et al. Determination of total fluorine in coal by use of oxygen flask combustion method with catalyst[J].Fuel,2007,86:715-721.
[25]潘锋，麦琦．氧瓶燃烧-离子色谱法检测茶叶中总氟的含量[J]．中国卫生检查杂志，2007,17(9):1634-1636.
[26] Hong X P,Liang H D,Y K,et al. Preliminary Survey of fluorine content in soil and plants around Wuda coalfield,Inner Mongolia,China[J].Fluoride,2017,50(4),430-444.
[27]郁冬梅，吴学华，崔向红．从土壤地球化学看宁夏平罗县砷、氟中毒地方病的起因与分布[J]．农业科学研究，2011,32(4):45-47.
[28]闫锦鹏．牧草含氟规律探讨[J]．包钢科技．1999,2:46-49.
[29]高德，刘焕文．大气氟污染对牧草的影响[J]．甘肃环境研究与监测，1985,4(3):5-9.
[30]刘焕文，高德．家畜慢性氟中毒与牧草氟临界范围的探讨[J]．环境科学，1985,6(2):40-45.
[31]刘焕文，高德．牧草氟污染与家畜慢性氟中毒的探讨[J]．环境科学丛刊，1986,11(7):74-78.
[32]周翰信，刘统海，胡义，等．放牧绵羊氟中毒调查及预防对策[J]．青海畜牧兽医杂志，1999,29(6):23-25.
[33]洪秀萍，梁汉东，张玉法，等．云贵川交界区晚二叠世煤系地层出露风化土的酸性特征[J]．环境化学，2017,36(8):1831-1841.
[34]洪秀萍，梁汉东，吕帅，等．贵州织金荷花村拌煤粘土的潜在氟化氢释放[J]．地质论评，2015,61(4):852-860.
[35]黄建成，桂林国．宁夏碱性土壤施肥技术对枸杞生长和土壤的影响[J]．宁夏农林科技，2015,56(11):29-31.
[36]张芬芬，孙娟，谢忠奎．西北碱性土壤施肥对东方百合“索邦”光合作用及种球产量的影响[J]．草业学报，2012,21(4):79-87.
[37]李伟，李飞，毕德．兰州碱性土壤与农产品中硒分布及形态研究[J]．土壤，2012,44(4):632-638.
[38]王华，刘洋，汤笑飞，等．汝箕沟矿区露天开采小窑火区快速治理技术．煤炭技术，2016,35(1):164-166.
[39]任德贻，赵峰华，代世峰，等．煤的微量元素地球化学[M]．北京:科学出版社，2006.
[40]张苗云，王世杰，马国强，等．大气环境的硫同位素组成及示踪研究[J]．中国科学:地球科学，2011,41(2):216-224.
[41]边敏娟，钱骏，刘志红等．四川中东部地区2009年大气硫沉降模拟[J]．环境科学研究，2012,25(10):1115-1119.
[42]李文华，熊飞，姜英．微量有害元素在高硫煤中的存在状态[J]．煤化工，1994,4:20-23.
[43]洪秀萍，张引，梁汉东，等．三道岭露天煤矿外围表土总氟含量研究[C]. 2014年中国地球科学联合学术年会—专题10:流体地球科学与巨型成矿带及重大自然灾害成因论文集，2014.
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