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
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摘要
选择黔中地区的一条白云岩原位风化剖面(平坝剖面)作为研究对象,通过对岩-土界面之下的岩粉层(砂状碳酸盐岩)动态淋溶过程中高场强元素(HFSE)地球化学行为的研究,并结合其在风化壳剖面的分布特征,获得了以下主要认识:(1)碳酸盐岩风化过程中,HFSE间存在明显的分馏,而且元素分馏主要出现在岩-土界面作用过程中,即碳酸盐岩溶蚀形成残积土阶段;元素的地球化学惰性由强到弱的顺序依次为Zr>Hf>Nb>Sc>Th>Ta>Ti>Y,其中,Zr是最稳定的元素,Hf仅次于Zr,Nb和Sc也相对较为惰性,而Th、Ta、Ti、Y呈现出明显的活性;(2)对于碳酸盐岩风化剖面的质量平衡计算,Zr是理想的参比元素(即惰性元素);(3)由基岩酸不溶物至风化壳剖面,元素对Nb-Ta、Zr-Hf显示出较好的协变性,没有明显分馏,因此,在利用这类元素对岩溶区风化壳的物源进行示踪时,碳酸盐岩作为潜在母岩,宜采用其酸不溶物作为参比对象;(4)碳酸盐岩风化过程中,虽然Sc也是一个较为稳定的HFSE,但在风化母岩中分布不均匀,不宜用于岩溶区风化壳的物源示踪。
It is generally believed that the high field strength elements(HFSE,including Sc,Ti,Y,Zr,Nb,Hf,Ta,Th,etc.) are extremely inert in the epigenetic environment.However,it had been reported that there was a significant variation in the content ratio between above elements during the transition from the rock to soil in weathering profiles developed on carbonate rocks.At present,little is known about whether the fractionation between HFSE occurs or not during weathering of carbonate rocks,which needs further research.The karst area in southwestern China,centered on Guizhou Province,is the largest carbonate rock continuous distribution area in the world,with an area of 5×10~5 km~2.Under the subtropical humid monsoon climate,a set of 1-10 m thick red weathering crusts widely cover over the gently sloping hilly area,which is an ideal place for the above research.In this paper,we selected an in-situ weathering profile derived from carbonate rock(i.e.,dolomite) in central Guizhou Province as the study area,by probing geochemical behaviors of the HFSE due to dynamic leaching of the arenilitic carbonate rock happens at the rock-soil interface and by combining the distribution characteristics of HFSE in the profile to preliminarily reveal geochemical behavior of the HFSE during weathering of the carbonate rocks.This study draws the conclusions as follows,(1) During weathering of carbonate rocks,there is distinct fractionation between HFSE;and their fractionation mainly occurs in the geochemical reaction at the rock-soil interface,i.e.,at the stage of residual soil formation by carbonate dissolution.Geochemical inertia of these elements from strong to weak is in the order of Zr > Hf > Nb > Sc > Th> Ta > Ti > Y.Among them,Zr is the most immobile,while Hf is second only to Zr.Nb and Sc are relatively more immobile and Th,Ta,Ti and Y show obvious mobility;(2) For mass balance calculation of the weathering profile of carbonate rocks,Zr is an ideal reference element(i.e.,inert element);(3) The element pairs such as Nb-Ta and Zr-Hf display good covariances from the acid-insoluble residues of the bedrock to the weathering profile,without evident fractionation.Therefore,when using these elements to trace the provenance of weathering covers in karst areas,and when carbonate bedrocks are used as the potential parent rocks,their acid-insoluble residues should be used as the reference object;(4) Although Sc is also relatively inert during weathering of carbonate rocks,it is not suitable for tracing the source of weathering covers in karst areas owing to its non-even distribution in the parent rocks of the weathering profile.
It is generally believed that the high field strength elements(HFSE,including Sc,Ti,Y,Zr,Nb,Hf,Ta,Th,etc.) are extremely inert in the epigenetic environment.However,it had been reported that there was a significant variation in the content ratio between above elements during the transition from the rock to soil in weathering profiles developed on carbonate rocks.At present,little is known about whether the fractionation between HFSE occurs or not during weathering of carbonate rocks,which needs further research.The karst area in southwestern China,centered on Guizhou Province,is the largest carbonate rock continuous distribution area in the world,with an area of 5×10~5 km~2.Under the subtropical humid monsoon climate,a set of 1-10 m thick red weathering crusts widely cover over the gently sloping hilly area,which is an ideal place for the above research.In this paper,we selected an in-situ weathering profile derived from carbonate rock(i.e.,dolomite) in central Guizhou Province as the study area,by probing geochemical behaviors of the HFSE due to dynamic leaching of the arenilitic carbonate rock happens at the rock-soil interface and by combining the distribution characteristics of HFSE in the profile to preliminarily reveal geochemical behavior of the HFSE during weathering of the carbonate rocks.This study draws the conclusions as follows,(1) During weathering of carbonate rocks,there is distinct fractionation between HFSE;and their fractionation mainly occurs in the geochemical reaction at the rock-soil interface,i.e.,at the stage of residual soil formation by carbonate dissolution.Geochemical inertia of these elements from strong to weak is in the order of Zr > Hf > Nb > Sc > Th> Ta > Ti > Y.Among them,Zr is the most immobile,while Hf is second only to Zr.Nb and Sc are relatively more immobile and Th,Ta,Ti and Y show obvious mobility;(2) For mass balance calculation of the weathering profile of carbonate rocks,Zr is an ideal reference element(i.e.,inert element);(3) The element pairs such as Nb-Ta and Zr-Hf display good covariances from the acid-insoluble residues of the bedrock to the weathering profile,without evident fractionation.Therefore,when using these elements to trace the provenance of weathering covers in karst areas,and when carbonate bedrocks are used as the potential parent rocks,their acid-insoluble residues should be used as the reference object;(4) Although Sc is also relatively inert during weathering of carbonate rocks,it is not suitable for tracing the source of weathering covers in karst areas owing to its non-even distribution in the parent rocks of the weathering profile.
引文
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[16]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(3):403-417.
[17]Liu W,Liu C,Brantley S L,et al.Deep weathering along a granite ridgeline in a subtropical climate[J].Chemical Geology,2016,427:17-34.
[18]Nesbitt H W.Mobility and fractionation of rare earth elements during weathering of a granodiorite[J].Nature,1979,279:206-210.
[19]Wei X,Ji H,Wang S,et al.The formation of representative lateritic weathering covers in south-central Guangxi(southern China)[J].Catena,2014,118:55-72.
[20]Zhang Z-J,Liu C-Q,Zhao Z-Q,et al.Behavior of redox-sensitive elements during weathering of granite in subtropical area using Xray absorption fine structure spectroscopy[J].Journal of Asian Earth Sciences,2015,105:418-429.
[21]Ji H,Ouyang Z,Wang S,et al.Element geochemistry of weathering profile of dolomitite and its applications for the average chemical composition of the upper-continental crust[J].Science in China(Series D),2000,43(1):23-35.
[22]Ji H,Wang S,Ouyang Z,et al.Geochemistry of red residua underlying dolomites in karst terrains of Yunnan-Guizhou PlateauⅠ.The formation of the Pingba profile[J].Chemical Geology,2004,203(1):1-27.
[23]王世杰,孙承兴,冯志刚,等.发育完整的灰岩风化壳及其矿物学与地球化学特征[J].矿物学报,2002,22(1):19-29.
[24]孙承兴,王世杰,刘秀明,等.碳酸盐岩风化壳岩-土界面地球化学特征及其形成过程:以贵州花溪灰岩风化壳剖面为例[J].矿物学报,2002,22(2):126-132.
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[27]Feng J-L.Behaviour of rare earth elements and yttrium in ferromanganese concretions,gibbsite spots,and the surrounding terra rossa over dolomite during chemical weathering[J].Chemical Geology,2010,271(3-4):112-132.
[28]Feng J-L.Trace elements in ferromanganese concretions,gibbsite spots,and the surrounding terra rossa overlying dolomite:Their mobilization,redistribution and fractionation[J].Journal of Geochemical Exploration,2011,108(1):99-111.
[29]Feng J-L,Cui Z-J,Zhu L-P.Origin of terra rossa over dolomite on the Yunnan-Guizhou Plateau,China[J].Geochemical Journal,2011,43(3):151-166.
[30]Feng J-L,Gao S-P,Zhang J-F.Lanthanide tetrad effect in ferromanganese concretions and terra rossa overlying dolomite during weathering[J].Chemie Der Erde-Geochemistry,2011,71(4):349-362.
[31]冯志刚,王世杰,孙承兴,等.岩溶地区缺失原岩残余结构红色风化壳的粒度分布特征及成因指示:以贵州平坝为例[J].矿物学报,2002,22(3):243-248.
[32]季宏兵,王世杰.黔中白云岩风化剖面的钕、锶同位素组成及演化[J].自然科学进展,2008,18(10):1128-1135.
[33]姜立君,王世杰,刘秀明,等.贵州碳酸盐岩风化壳中晶体石英的硅同位素组成及硅质来源探讨[J].地球与环境,2009,37(1):20-27.
[34]刘秀明,王世杰,冯志刚,等.石灰土物质来源的判别:以黔北、黔中几个剖面为例[J].土壤,2004,36(1):30-36.
[35]刘春茹,刘秀明,王世杰,等.贵州碳酸盐岩风化壳物源判别的新证据:石英颗粒形态、表面结构特征[J].矿物学报,2007,27(1):49-56.
[36]孙承兴,王世杰,季宏兵.碳酸盐岩风化成土过程中REE超常富集及Ce强烈亏损的地球化学机理[J].地球化学,2002,31(2):119-128.
[37]Berner R A,Lasaga A C.Modeling the geochemical carbon cycle[J].Scientific American,1989,222(3):74-82.
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