云贵川交界地氟病区煤系黏土-黄铁矿的风化
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摘要
云贵川交界区地氟病流行与拌煤黏土有关已形成共识,新的研究不仅证实当地出露煤系地层黏土高氟且富酸从而加剧原煤-黏土混合物燃烧释放氟化氢.本文在观察到相关黏土样本富黄铁矿基础上,采用飞行时间二次离子质谱(TOF-SIMS)表征了样本中典型的黄铁矿颗粒,检出其表面富HSO~-_4、SO~-_4、FeSO~+_4、FeO~+等特征正负离子,指示相关黏土-黄铁矿已发生风化并产酸,是研究区煤系地层长期自然暴露的后果.另一方面通过氟化氢释放实验证明,风化土中的酸对黏土中氟的释放具有一定促进作用.同时本文也演示了TOF-SIMS在研究天然矿物及其风化中发挥的重要作用.
A popular riff is that the prevalence of endemic fluorosis in the border area of Yunnan,Guizhou and Sichuan is associated with the clay for coal-combustion. The emerging study confirms that efflorescent clay of coal-bearing strata has a high concentration of fluorine and acid, thus intensifing the release of hydrogen fluoride in the combustion of coal-clay mixed fuel. This paper utilized, Time of Flight Secondary Ion Mass Spectrometry(TOF-SIMS) to verify the typical pyrite particles in the coal sample, which are rich in positive and negative ions such as HSO~-_4, SO~-_4, FeSO~+_4 and FeO~+on the basis of observation of the relevant clay samples. The results revealed that the relevant clay-pyrite had been weathered and produced acids as a result of long-term natural exposure of the coal-bearing strata in the study area. At the same time, the experiment of hydrogen fluoride release proved that the acid in the weathered soil enhanced the release of fluorine in the clay. Besides that, this paper also demonstrates the crucial role that TOF-SIMS should play in the study of natural minerals and their weathering.
A popular riff is that the prevalence of endemic fluorosis in the border area of Yunnan,Guizhou and Sichuan is associated with the clay for coal-combustion. The emerging study confirms that efflorescent clay of coal-bearing strata has a high concentration of fluorine and acid, thus intensifing the release of hydrogen fluoride in the combustion of coal-clay mixed fuel. This paper utilized, Time of Flight Secondary Ion Mass Spectrometry(TOF-SIMS) to verify the typical pyrite particles in the coal sample, which are rich in positive and negative ions such as HSO~-_4, SO~-_4, FeSO~+_4 and FeO~+on the basis of observation of the relevant clay samples. The results revealed that the relevant clay-pyrite had been weathered and produced acids as a result of long-term natural exposure of the coal-bearing strata in the study area. At the same time, the experiment of hydrogen fluoride release proved that the acid in the weathered soil enhanced the release of fluorine in the clay. Besides that, this paper also demonstrates the crucial role that TOF-SIMS should play in the study of natural minerals and their weathering.
引文
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[3] DAI S F,LI W W,TANG Y G,et al.The sources,pathway and preventive measures for fluorosis in Zhijin County,Guizhou,China[J].Applied Geochemistry,2007,22 (5):1017-1024.
[4] WU D S,ZHENG B S,WANG A M,et al.A new estimation of fluoride source in coal-burning endemic fluorosis areas of Guizhou Province[J].Chinese Journal of Endemiology,2004,23,135-137.
[5] LYTH O.Endemic fluorosis in Kweichow,China[J].The Lancet,1946,1:233-235.
[6] 李日邦,谭见安,王五一,等.贵州地方性食物性氟中毒氟源探讨[J].中华医学杂志,1982,62(7):425-428.LI R B,TAN J N,WANG W Y,et al.Discussion on fluorosis source for endemic fluorosis caused by food in Guizhou[J].National Medical Journal of China,1982,62(7):425-428(in Chinese).
[7] ZHENG B S,HUANG R G.Prevention and research of fluorosis caused by domestic coal pollution[J].Journal of Practical Local Epidemiology,1986,1:11-13.
[8] ZHENG B S,HONG YT.Geochemical environment related to human endemic fluorosis in China[C].In:Geochemistry and health.Northwood:Science Reviews Limited,1988:93-96.
[9] ZHENG B S,DING Z H,HUANG R G,et al.Issues of health and disease relating to coal use in southwestern China[J].International Journal of Coal Geology,1999,40(2-3):119-132.
[10] 郑宝山,吴代赦,王滨滨,等.导致燃煤型氟中毒流行的主要地球化学过程[J].中国地方病学杂志,2005,24(4):468-471.ZHENG B S,WU D S,WANG B B,et al.Main geochemical processes that cause prevalence of coal-burning fluorosis[J].Chinese Journal of Endemiology,2005,24(4):468-471(in Chinese).
[11] 孙玉壮.黔西煤中氟与燃煤型地方性氟中毒的地球化学研究[J].矿物岩石地球化学通报,2005,24(4):350-356.SUN Y Z.Geochemical study advance about fluorine in coal and "coal-burning" endemic fluorosis from western Guizhou[J].Bulletin of Mineralogy,Petrology and Geochemistry,2005,24(4):350-356(in Chinese).
[12] 刘雪峰,刘楚光,刘晶等.贵州煤中氟赋存形态分析[J].中国电机工程学报,2008,28(8):46-52.LIU X F,LIU C G,LIU J,et al.Analysis on fluorine speciation in coals from Guizhou Province[J].Proceedings of the CSEE,2008,28(8):46-52(in Chinese).
[13] LIANG H D,LIANG Y C,GARDELLA Joseph A.Jr,et al.Potential release of hydrogen fluoride from domestic coal in endemic fluorosis area in Guizhou,China[J].Chinese Science Bulletin.2011,56,2301-2303.
[14] American Association for the Advancement of Science News (AAAS News) [EB/OL].[2011-10-01].http://esciencenews.com/sources/physorg/2011/10/01/hydrogen.fluoride.may.be.major.cause.coal.burning.endemic.fluorosis.
[15] 徐彬彬,何明德.贵州煤田地质[M].徐州:中国矿业大学出版社,2002,5-7.XU B B,HE M D.Coal geology of guizhou [M].Xuzhou:China University of Mining and Technology Press,2002(in Chinese).
[16] 洪秀萍,梁汉东,张玉法,等.云贵川交界地氟病区晚二叠世煤的酸度分布[J].煤炭学报,2016,41(4):964-973.HONG X P,LIANG H D,ZHANG Y F,et al.Acidity characteristic of efflorescent clay in late Permian coal-bearing strata in border area of Yunnan,Guizhou and Sichuan[J].Journal of China Coal Society,2016,41(4):964-973(in Chinese).
[17] 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.HONG X P,LIANG H D,ZHANG Y F,et al.Acidity characteristic of efflorescent clay in late Permian coal-bearing strata in border area of Yunnan,Guizhou and Sichuan[J].Environmental Chemistry,2017,36(8):1831-1841(in Chinese).
[18] 洪秀萍.中国典型富煤区地表氟与酸污染现状与成因[D].北京:中国矿业大学(北京),2018,127-131.HONG X P.Fluorine and acid pollutant within soil around three coal-rich areas in China[D].Beijing:China University of Mining & Technology,Beijing,2018,127-131(in Chinese).
[19] WANG H,SHAO L,HAO LM,et al.Sedimentology and sequence stratigraphy of the Lopingian(Late Permian) coal measures in southwestern China[J].International Journal of Coal Geology,2011,83(1):168-183.
[20] 罗忠,邵龙义,姚光华,等.滇东黔西上二叠统含煤岩系泥岩粘土矿物组成及环境意义[J].古地理学报,2008,10(3):297-304.LUO Z,SHAO L Y,YAO G H,et al.Mudstones in the Upper Permian coal-bearing series in eastern Yunnan and western Guizhou:Clay minerals composition and their environmental significance[J].Journal of Palaeogeography,2008,10(3):297-304 (in Chinese).
[21] 王强,杨瑞东,鲍淼.贵州毕节地区煤层中稀土元素在含煤地层划分与对比中应用探讨[J].沉积学报,2008,26(1):21-27.WANG Q,YANG R D,BAO M.Discussion on the role of REE in stratigraphic subdivision and correlation in coal measures from Bijie City,Guizhou Province[J].Acta Sedimentologica Sinica,2008,26(1):21-27 (in Chinese).
[2] DAI S F,REN D Y,MA S M.The cause of endemic fluorosis in western Guizhou Province,Southwest China [J].Fuel,2004,83(14-15):2095-2098.
[3] DAI S F,LI W W,TANG Y G,et al.The sources,pathway and preventive measures for fluorosis in Zhijin County,Guizhou,China[J].Applied Geochemistry,2007,22 (5):1017-1024.
[4] WU D S,ZHENG B S,WANG A M,et al.A new estimation of fluoride source in coal-burning endemic fluorosis areas of Guizhou Province[J].Chinese Journal of Endemiology,2004,23,135-137.
[5] LYTH O.Endemic fluorosis in Kweichow,China[J].The Lancet,1946,1:233-235.
[6] 李日邦,谭见安,王五一,等.贵州地方性食物性氟中毒氟源探讨[J].中华医学杂志,1982,62(7):425-428.LI R B,TAN J N,WANG W Y,et al.Discussion on fluorosis source for endemic fluorosis caused by food in Guizhou[J].National Medical Journal of China,1982,62(7):425-428(in Chinese).
[7] ZHENG B S,HUANG R G.Prevention and research of fluorosis caused by domestic coal pollution[J].Journal of Practical Local Epidemiology,1986,1:11-13.
[8] ZHENG B S,HONG YT.Geochemical environment related to human endemic fluorosis in China[C].In:Geochemistry and health.Northwood:Science Reviews Limited,1988:93-96.
[9] ZHENG B S,DING Z H,HUANG R G,et al.Issues of health and disease relating to coal use in southwestern China[J].International Journal of Coal Geology,1999,40(2-3):119-132.
[10] 郑宝山,吴代赦,王滨滨,等.导致燃煤型氟中毒流行的主要地球化学过程[J].中国地方病学杂志,2005,24(4):468-471.ZHENG B S,WU D S,WANG B B,et al.Main geochemical processes that cause prevalence of coal-burning fluorosis[J].Chinese Journal of Endemiology,2005,24(4):468-471(in Chinese).
[11] 孙玉壮.黔西煤中氟与燃煤型地方性氟中毒的地球化学研究[J].矿物岩石地球化学通报,2005,24(4):350-356.SUN Y Z.Geochemical study advance about fluorine in coal and "coal-burning" endemic fluorosis from western Guizhou[J].Bulletin of Mineralogy,Petrology and Geochemistry,2005,24(4):350-356(in Chinese).
[12] 刘雪峰,刘楚光,刘晶等.贵州煤中氟赋存形态分析[J].中国电机工程学报,2008,28(8):46-52.LIU X F,LIU C G,LIU J,et al.Analysis on fluorine speciation in coals from Guizhou Province[J].Proceedings of the CSEE,2008,28(8):46-52(in Chinese).
[13] LIANG H D,LIANG Y C,GARDELLA Joseph A.Jr,et al.Potential release of hydrogen fluoride from domestic coal in endemic fluorosis area in Guizhou,China[J].Chinese Science Bulletin.2011,56,2301-2303.
[14] American Association for the Advancement of Science News (AAAS News) [EB/OL].[2011-10-01].http://esciencenews.com/sources/physorg/2011/10/01/hydrogen.fluoride.may.be.major.cause.coal.burning.endemic.fluorosis.
[15] 徐彬彬,何明德.贵州煤田地质[M].徐州:中国矿业大学出版社,2002,5-7.XU B B,HE M D.Coal geology of guizhou [M].Xuzhou:China University of Mining and Technology Press,2002(in Chinese).
[16] 洪秀萍,梁汉东,张玉法,等.云贵川交界地氟病区晚二叠世煤的酸度分布[J].煤炭学报,2016,41(4):964-973.HONG X P,LIANG H D,ZHANG Y F,et al.Acidity characteristic of efflorescent clay in late Permian coal-bearing strata in border area of Yunnan,Guizhou and Sichuan[J].Journal of China Coal Society,2016,41(4):964-973(in Chinese).
[17] 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.HONG X P,LIANG H D,ZHANG Y F,et al.Acidity characteristic of efflorescent clay in late Permian coal-bearing strata in border area of Yunnan,Guizhou and Sichuan[J].Environmental Chemistry,2017,36(8):1831-1841(in Chinese).
[18] 洪秀萍.中国典型富煤区地表氟与酸污染现状与成因[D].北京:中国矿业大学(北京),2018,127-131.HONG X P.Fluorine and acid pollutant within soil around three coal-rich areas in China[D].Beijing:China University of Mining & Technology,Beijing,2018,127-131(in Chinese).
[19] WANG H,SHAO L,HAO LM,et al.Sedimentology and sequence stratigraphy of the Lopingian(Late Permian) coal measures in southwestern China[J].International Journal of Coal Geology,2011,83(1):168-183.
[20] 罗忠,邵龙义,姚光华,等.滇东黔西上二叠统含煤岩系泥岩粘土矿物组成及环境意义[J].古地理学报,2008,10(3):297-304.LUO Z,SHAO L Y,YAO G H,et al.Mudstones in the Upper Permian coal-bearing series in eastern Yunnan and western Guizhou:Clay minerals composition and their environmental significance[J].Journal of Palaeogeography,2008,10(3):297-304 (in Chinese).
[21] 王强,杨瑞东,鲍淼.贵州毕节地区煤层中稀土元素在含煤地层划分与对比中应用探讨[J].沉积学报,2008,26(1):21-27.WANG Q,YANG R D,BAO M.Discussion on the role of REE in stratigraphic subdivision and correlation in coal measures from Bijie City,Guizhou Province[J].Acta Sedimentologica Sinica,2008,26(1):21-27 (in Chinese).