湘西北黑色泥灰岩风化剖面重金属富集的地球化学机制
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摘要
通过对湘西北地区黑色泥灰岩风化剖面(DM剖面)中Cr、Ni、Cu、Zn、Cd、Pb、Th、U 8种重金属元素地球化学特征的研究,并与区域上发育于黑色页岩的2条风化剖面的对比分析,初步揭示了黑色泥灰岩风化剖面中重金属富集的地球化学机制。结果表明:(1)与黑色页岩相比,黑色泥灰岩风化成土过程中重金属元素普遍呈现出低背景、高富集的地球化学特征。(2)黑色泥灰岩风化剖面的形成,是在基岩中碳酸盐快速溶蚀的基础上(基岩的酸溶相含量为78. 57%),由酸不溶相进一步演化的结果。在此过程中,对于无明显外源输入的元素Cr、Ni、Cu、Zn、Pb、Th、U,一方面,赋存在酸溶相的部分随碳酸盐的淋失而亏损甚至强烈亏损(其中Th相对惰性);另一方面,残余在酸不溶相的部分因基岩中大量碳酸盐的淋失而显著富集,且随风化剖面的演化未显示出进一步的亏损。因此,这些元素在风化剖面中的富集是绝对(强烈)亏损和显著相对富集的综合结果。对于Cd,存在明显的外源输入,可能主要以水溶态形式带入并大量淀积在剖面下部。(3)在黑色泥灰岩风化剖面,有机质(OM)不是重金属元素的主要赋存介质,其对重金属元素地球化学行为的影响有限。(4)黑色泥灰岩发育的土壤中,Cu和Cd的平均含量分别为54. 58 mg/kg和0. 58 mg/kg,高于农用地土壤污染风险筛选值,特别是Cd,对土壤生态环境可能形成不利影响,应引起关注。
To understand the underlying geochemical mechanism of the heavy metal element( HME) enrichment in weathering profiles of black marlstone,this study characterized 8 kinds of HME,including Cr,Ni,Cu,Zn,Cd,Pb,Th and U,along a weathering profile of black marlstone( DM profile) in the northwestern Hunan Province,China,and compared with two weathering profiles of black shales( XT and HZ profiles) from the same region. The results showed that:( 1) Geochemical characteristics of HMEs in processes of black marlstone weathering and pedogenesis could be summarized as relatively low background values and high enrichment,compared to black shale cases.( 2) The weathering profile of black marlstone was the outcome of further evolution of acid-insoluble material after the rapid dissolution of carbonate bedrock,in which the acid-soluble content occupied 78. 57%. In this process,HEM without exogenous inputs,such as Cr,Ni,Cu,Zn,Pb,Th and U,would be leached or even strongly leached if they existed in the acid-soluble component of the bedrock( among them,Th is relatively inert),or would be enriched remarkably due to large amounts leaching of carbonates from the bedrock if they existed in the acid-insoluble component,therefore,the enrichment of these elements in the profile was a comprehensive result of both their absolute( strong) loss and significant relative enrichment during weathering and pedogenesis of black marlstone. Cd,the exogenous origin element,might be entered as water-soluble form and deposited in the lower part of the profile.( 3) In the weathering profile of black marlstone,organic matter( OM) was not the main medium associated heavy metals,therefore its impact on the geochemical behaviors of HME might be limited.( 4) The average contents of Cu and Cd in soils developed from black marlstone were 54. 58 mg/kg and 0. 58 mg/kg,respectively,which are higher than the risk screening values for soil contamination in agricultural lands,especially Cd,which has adverse effects on soil ecological environment and should be paid more attention.
To understand the underlying geochemical mechanism of the heavy metal element( HME) enrichment in weathering profiles of black marlstone,this study characterized 8 kinds of HME,including Cr,Ni,Cu,Zn,Cd,Pb,Th and U,along a weathering profile of black marlstone( DM profile) in the northwestern Hunan Province,China,and compared with two weathering profiles of black shales( XT and HZ profiles) from the same region. The results showed that:( 1) Geochemical characteristics of HMEs in processes of black marlstone weathering and pedogenesis could be summarized as relatively low background values and high enrichment,compared to black shale cases.( 2) The weathering profile of black marlstone was the outcome of further evolution of acid-insoluble material after the rapid dissolution of carbonate bedrock,in which the acid-soluble content occupied 78. 57%. In this process,HEM without exogenous inputs,such as Cr,Ni,Cu,Zn,Pb,Th and U,would be leached or even strongly leached if they existed in the acid-soluble component of the bedrock( among them,Th is relatively inert),or would be enriched remarkably due to large amounts leaching of carbonates from the bedrock if they existed in the acid-insoluble component,therefore,the enrichment of these elements in the profile was a comprehensive result of both their absolute( strong) loss and significant relative enrichment during weathering and pedogenesis of black marlstone. Cd,the exogenous origin element,might be entered as water-soluble form and deposited in the lower part of the profile.( 3) In the weathering profile of black marlstone,organic matter( OM) was not the main medium associated heavy metals,therefore its impact on the geochemical behaviors of HME might be limited.( 4) The average contents of Cu and Cd in soils developed from black marlstone were 54. 58 mg/kg and 0. 58 mg/kg,respectively,which are higher than the risk screening values for soil contamination in agricultural lands,especially Cd,which has adverse effects on soil ecological environment and should be paid more attention.
引文
[1]范德廉,杨秀珍,王连芳,等.某地下寒武统含镍钼多元素黑色岩系的岩石学及地球化学特点[J].地球化学,1973(3):143-164.
[2]高振敏,罗泰义,李胜荣.黑色岩系中贵金属富集层的成因:来自固定铵的佐证[J].地质地球化学,1997(1):18-23.
[3]杨宗玉,罗平,刘波,等.塔里木盆地阿克苏地区下寒武统玉尔吐斯组两套黑色岩系的差异及成因[J].岩石学报,2017,33(6):1893-1918.
[4] Mao J,Lehmann B,Du A,et al. Re-Os dating of polymetallic Ni-Mo-PGE-Au mineralization in lower Cambrian black shales of south China and its geologic significance[J]. Economic Geology,2002,97(5):1051-1061.
[5]李苗春,姚素平,丁海,等.湘西牛蹄塘组黑色岩系的地球化学特征及其油气地质意义[J].煤炭学报,2013,38(5):857-863.
[6]赵瞻,谢渊,刘建清,等.渝东南下寒武统黑色岩系稀土元素地球化学特征与沉积环境[J].沉积与特提斯地质,2011,31(2):49-54.
[7]吴蓓娟,彭渤,张坤,等.黑色页岩化学风化程度指标研究[J].地质学报,2016,90(4):818-832.
[8]杨恩林,吕新彪,鲍淼,等.黔东下寒武统黑色页岩微量元素的富集及成因分析[J].地球科学进展,2013,28(10):1160-1169.
[9]余昌训,彭渤,唐晓燕,等.黑色页岩与土壤重金属污染[J].矿物岩石地球化学通报,2008,27(2):137-145.
[10] Tang X,Zhang J,Liu Y,et al. Geochemistry of organic matter and elements of black shale during weathering in Northern Guizhou,Southwestern China:Their mobilization and inter-connection[J]. Chemie der Erde,2018,78:140-151.
[11] Perkins R B,Mason C E. The relative mobility of trace elements from short-term weathering of a black shale[J]. Applied Geochemistry,2015,56:67-79.
[12] Yu C,Lavergren U,Peltola P,et al. Retention and transport of arsenic,uranium and nickel in a black shale setting revealed by a long-term humidity cell test and sequential chemical extractions[J]. Chemical Geology,2014,363:134-144.
[13] Ling S,Wu X,Ren Y,et al. Geochemistry of trace and rare earth elements during weathering of black shale profiles in Northeast Chongqing,Southwestern China:Their mobilization,redistribution,and fractionation[J]. Chemie der Erde,2015,75:403-417.
[14] Lee J S,Chon H T,Kim J S,et al. Enrichment of potentially toxic elements in areas underlain by black shales and slates in Korea[J]. Environmental Geochemistry and Health,1998,20(3):135-147.
[15] Yu C,Peng B,Peltola P,et al. Effect of weathering on abundance and release of potentially toxic elements in soils developed on Lower Cambrian black shales,P. R. China[J]. Environmental Geochemistry Health,2012,34:375-390.
[16] Tuttle M L W,Fahy J W,Elliott J G,et al. Contaminants from Cretaceous black shale:I. Natural weathering processes controlling contaminant cycling in Mancos Shale,southwestern United States,with emphasis on salinity and selenium[J]. Applied Geochemistry,2014,46:57-71.
[17] Peng B,Song Z,Tu X,et al. Release of heavy metals during weathering of the Lower Cambrian black shales in western Hunan,China[J]. Environmental Geology,2004,45:1137-1147.
[18] Bradshaw P M D,Thomson I,Smee B W,et al. The application of different analytical extractions and soil profile sampling in exploration geochemistry[J]. Journal of Geochemical Exploration,1974,3:209-225.
[19] Baeza A,del Río M,Jiménez A,et al. Influence of geology and soil particle size on the surface area/volume activity ratio for natural radionuclides[J]. Journal of Radioanalytical and Nuclear Chemistry,1995,189:289-299.
[20] Rao Z X,Huang D Y,Wu J S,et al. Distribution and availability of cadmium in profile and aggregates of a paddy soil with 30-year fertilization and its impact on Cd accumulation in rice plant[J]. Environmental Pollution,2018,239:198-204.
[21] Williams P N,Lei M,Sun G,et al. Occurrence and partitioning of cadmium,arsenic and lead in mine impacted paddy rice:Hunan,China[J].Environmental Science&Technology,2009,43:637-642.
[22] Ma L,Sun J,Yang Z,et al. Heavy metal contamination of agricultural soils affected by mining activities around the Ganxi River in Chenzhou,Southern China[J]. Environmental Monitoring&Assessment,2015,187(12):731.
[23] Wang M,Chen W,Peng C. Risk assessment of Cd polluted paddy soils in the industrial and township areas in Hunan,Southern China[J].Chemosphere,2016,144:346-351.
[24]宋照亮,彭渤,刘丛强.黑色页岩风化过程中元素的活动性及参照系的选取初探——以湖南省麻田、桃花江剖面为例[J].地质科技情报,2004,23(3):25-29.
[25]谢淑容,彭渤,唐晓燕,等.湘中地区发育于黑色页岩上的土壤重金属污染特征[J].土壤通报,2008,39(1):137-142.
[26]余昌训,彭渤,唐晓燕,等.湘中下寒武统黑色页岩土壤的地球化学特征[J].土壤学报,2009,46(4):557-570.
[27] Oliveira D P,Sartor L R,Júnior V S S,et al. Weathering and clay formation in semi-arid calcareous soils from Northeastern Brazil[J]. Catena,2018,162:325-332.
[28] Wang S,Ji H,Ouyang Z,Zhou D,et al. Preliminary study on weathering and pedogenesis of carbonate rock[J]. Science in China(Series D),1999,42(6):572-581.
[29] Nesbitt H W,Young G M. Early proterozoic climates and plate motions inferred from major element chemistry of lutite[J]. Nature,1982,299:715-717.
[30] Mc Lennan S M. Weathering and global denudation[J]. Journal of Geology,1993,101:295-303.
[31] Babechuk M G,Widdowson M,Murphy M,et al. A combined Y/Ho,high field strength element(HFSE)and Nd isotope perspective on basalt weathering,Deccan Traps,India[J]. Chemical Geology,2015,396:25-41.
[32] Mahmoodi M,Khormali F,Amini A,et al. Weathering and soils formation on different parent materials in Golestan Province,Noethern Iran[J].Journal of Mountain Science,2016,13(5):870-881.
[33] Fralick P W,Kronberg B I. Geochemical discrimination of clastic sedimentary rock sources[J]. Sedimentary Geology,1997,113:111-124.
[34]黄镇国,张伟强,陈俊鸿,等.中国南方红色风化壳[M].北京:海洋出版社,1996:1-312.
[35] Wedepohl K H. The composition of the continental crust[J]. Geochimica et Cosmochimica Acta,1995,59:1217-1232.
[36]中国环境监测总站.中国土壤元素背景值[M].北京:中国环境科学出版社,1990:87-89.
[37]生态环境部国家市场监督管理总局. GB 15618—2018中国环境质量农用地土壤污染风险管控标准(试行)[S].北京:中国环境科学出版社,2018.
[38] Brimhall G H,Dietrich W E. Constitutive mass balance relations between chemical composition,volume,density,porosity,and strain in metosomatic hydrochemical systems:Results on weathering and pedogenesis[J]. Geochimica et Cosmochimica Acta,1987,51:567-587.
[39] Brimhall G H,Lewis C J,Ague J J,et al. Metal enrichment in bauxites by deposition of chemically mature aeolian dust[J]. Nature,1988,333:819-824.
[40] Egli M,Fitze P. Quantitative aspects of carbonate leaching of soils with differing ages and climates[J]. Catena,2001,46:35-62.
[41]冯志刚,刘炫志,韩世礼,等.碳酸盐岩风化过程中高场强元素的地球化学行为研究:来自碳酸盐岩淋溶实验的证据[J].中国岩溶,2018,37(3):315-329.
[42] Aley T J,Kirkland S L. Down but not straight down:Significance of lateral flow in the vadose zone of karst terrains[J]. Carbonates Evaporites,2012,27:193-198.
[43] Yang Q,Chen H,Li B. Source identification and health risk assessment of metals in indoor dust in the vicinity of phosphorus mining,Guizhou Province,China[J]. Archives of Environmental Contamination and Toxicology,2015,68:20-30
[44] Tang Y,Han G,Li F,et al. Natural and anthropogenic sources of atmospheric dust at a remote forest area in Guizhou karst region,Southwest China[J]. Geochemistry Exploration Environment Analysis,2016,16:159-163.
[2]高振敏,罗泰义,李胜荣.黑色岩系中贵金属富集层的成因:来自固定铵的佐证[J].地质地球化学,1997(1):18-23.
[3]杨宗玉,罗平,刘波,等.塔里木盆地阿克苏地区下寒武统玉尔吐斯组两套黑色岩系的差异及成因[J].岩石学报,2017,33(6):1893-1918.
[4] Mao J,Lehmann B,Du A,et al. Re-Os dating of polymetallic Ni-Mo-PGE-Au mineralization in lower Cambrian black shales of south China and its geologic significance[J]. Economic Geology,2002,97(5):1051-1061.
[5]李苗春,姚素平,丁海,等.湘西牛蹄塘组黑色岩系的地球化学特征及其油气地质意义[J].煤炭学报,2013,38(5):857-863.
[6]赵瞻,谢渊,刘建清,等.渝东南下寒武统黑色岩系稀土元素地球化学特征与沉积环境[J].沉积与特提斯地质,2011,31(2):49-54.
[7]吴蓓娟,彭渤,张坤,等.黑色页岩化学风化程度指标研究[J].地质学报,2016,90(4):818-832.
[8]杨恩林,吕新彪,鲍淼,等.黔东下寒武统黑色页岩微量元素的富集及成因分析[J].地球科学进展,2013,28(10):1160-1169.
[9]余昌训,彭渤,唐晓燕,等.黑色页岩与土壤重金属污染[J].矿物岩石地球化学通报,2008,27(2):137-145.
[10] Tang X,Zhang J,Liu Y,et al. Geochemistry of organic matter and elements of black shale during weathering in Northern Guizhou,Southwestern China:Their mobilization and inter-connection[J]. Chemie der Erde,2018,78:140-151.
[11] Perkins R B,Mason C E. The relative mobility of trace elements from short-term weathering of a black shale[J]. Applied Geochemistry,2015,56:67-79.
[12] Yu C,Lavergren U,Peltola P,et al. Retention and transport of arsenic,uranium and nickel in a black shale setting revealed by a long-term humidity cell test and sequential chemical extractions[J]. Chemical Geology,2014,363:134-144.
[13] Ling S,Wu X,Ren Y,et al. Geochemistry of trace and rare earth elements during weathering of black shale profiles in Northeast Chongqing,Southwestern China:Their mobilization,redistribution,and fractionation[J]. Chemie der Erde,2015,75:403-417.
[14] Lee J S,Chon H T,Kim J S,et al. Enrichment of potentially toxic elements in areas underlain by black shales and slates in Korea[J]. Environmental Geochemistry and Health,1998,20(3):135-147.
[15] Yu C,Peng B,Peltola P,et al. Effect of weathering on abundance and release of potentially toxic elements in soils developed on Lower Cambrian black shales,P. R. China[J]. Environmental Geochemistry Health,2012,34:375-390.
[16] Tuttle M L W,Fahy J W,Elliott J G,et al. Contaminants from Cretaceous black shale:I. Natural weathering processes controlling contaminant cycling in Mancos Shale,southwestern United States,with emphasis on salinity and selenium[J]. Applied Geochemistry,2014,46:57-71.
[17] Peng B,Song Z,Tu X,et al. Release of heavy metals during weathering of the Lower Cambrian black shales in western Hunan,China[J]. Environmental Geology,2004,45:1137-1147.
[18] Bradshaw P M D,Thomson I,Smee B W,et al. The application of different analytical extractions and soil profile sampling in exploration geochemistry[J]. Journal of Geochemical Exploration,1974,3:209-225.
[19] Baeza A,del Río M,Jiménez A,et al. Influence of geology and soil particle size on the surface area/volume activity ratio for natural radionuclides[J]. Journal of Radioanalytical and Nuclear Chemistry,1995,189:289-299.
[20] Rao Z X,Huang D Y,Wu J S,et al. Distribution and availability of cadmium in profile and aggregates of a paddy soil with 30-year fertilization and its impact on Cd accumulation in rice plant[J]. Environmental Pollution,2018,239:198-204.
[21] Williams P N,Lei M,Sun G,et al. Occurrence and partitioning of cadmium,arsenic and lead in mine impacted paddy rice:Hunan,China[J].Environmental Science&Technology,2009,43:637-642.
[22] Ma L,Sun J,Yang Z,et al. Heavy metal contamination of agricultural soils affected by mining activities around the Ganxi River in Chenzhou,Southern China[J]. Environmental Monitoring&Assessment,2015,187(12):731.
[23] Wang M,Chen W,Peng C. Risk assessment of Cd polluted paddy soils in the industrial and township areas in Hunan,Southern China[J].Chemosphere,2016,144:346-351.
[24]宋照亮,彭渤,刘丛强.黑色页岩风化过程中元素的活动性及参照系的选取初探——以湖南省麻田、桃花江剖面为例[J].地质科技情报,2004,23(3):25-29.
[25]谢淑容,彭渤,唐晓燕,等.湘中地区发育于黑色页岩上的土壤重金属污染特征[J].土壤通报,2008,39(1):137-142.
[26]余昌训,彭渤,唐晓燕,等.湘中下寒武统黑色页岩土壤的地球化学特征[J].土壤学报,2009,46(4):557-570.
[27] Oliveira D P,Sartor L R,Júnior V S S,et al. Weathering and clay formation in semi-arid calcareous soils from Northeastern Brazil[J]. Catena,2018,162:325-332.
[28] Wang S,Ji H,Ouyang Z,Zhou D,et al. Preliminary study on weathering and pedogenesis of carbonate rock[J]. Science in China(Series D),1999,42(6):572-581.
[29] Nesbitt H W,Young G M. Early proterozoic climates and plate motions inferred from major element chemistry of lutite[J]. Nature,1982,299:715-717.
[30] Mc Lennan S M. Weathering and global denudation[J]. Journal of Geology,1993,101:295-303.
[31] Babechuk M G,Widdowson M,Murphy M,et al. A combined Y/Ho,high field strength element(HFSE)and Nd isotope perspective on basalt weathering,Deccan Traps,India[J]. Chemical Geology,2015,396:25-41.
[32] Mahmoodi M,Khormali F,Amini A,et al. Weathering and soils formation on different parent materials in Golestan Province,Noethern Iran[J].Journal of Mountain Science,2016,13(5):870-881.
[33] Fralick P W,Kronberg B I. Geochemical discrimination of clastic sedimentary rock sources[J]. Sedimentary Geology,1997,113:111-124.
[34]黄镇国,张伟强,陈俊鸿,等.中国南方红色风化壳[M].北京:海洋出版社,1996:1-312.
[35] Wedepohl K H. The composition of the continental crust[J]. Geochimica et Cosmochimica Acta,1995,59:1217-1232.
[36]中国环境监测总站.中国土壤元素背景值[M].北京:中国环境科学出版社,1990:87-89.
[37]生态环境部国家市场监督管理总局. GB 15618—2018中国环境质量农用地土壤污染风险管控标准(试行)[S].北京:中国环境科学出版社,2018.
[38] Brimhall G H,Dietrich W E. Constitutive mass balance relations between chemical composition,volume,density,porosity,and strain in metosomatic hydrochemical systems:Results on weathering and pedogenesis[J]. Geochimica et Cosmochimica Acta,1987,51:567-587.
[39] Brimhall G H,Lewis C J,Ague J J,et al. Metal enrichment in bauxites by deposition of chemically mature aeolian dust[J]. Nature,1988,333:819-824.
[40] Egli M,Fitze P. Quantitative aspects of carbonate leaching of soils with differing ages and climates[J]. Catena,2001,46:35-62.
[41]冯志刚,刘炫志,韩世礼,等.碳酸盐岩风化过程中高场强元素的地球化学行为研究:来自碳酸盐岩淋溶实验的证据[J].中国岩溶,2018,37(3):315-329.
[42] Aley T J,Kirkland S L. Down but not straight down:Significance of lateral flow in the vadose zone of karst terrains[J]. Carbonates Evaporites,2012,27:193-198.
[43] Yang Q,Chen H,Li B. Source identification and health risk assessment of metals in indoor dust in the vicinity of phosphorus mining,Guizhou Province,China[J]. Archives of Environmental Contamination and Toxicology,2015,68:20-30
[44] Tang Y,Han G,Li F,et al. Natural and anthropogenic sources of atmospheric dust at a remote forest area in Guizhou karst region,Southwest China[J]. Geochemistry Exploration Environment Analysis,2016,16:159-163.
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