黑色页岩与土壤重金属污染

本文利用ICP—MS等技术分析了湘中地区黑色页岩及其相应土壤的重金属含量,在对分析结果进行统计分析的基础上,探讨了黑色页岩与土壤重金属污染的关系。研究表明,黑色页岩是富集多种重金属元素的特殊岩石。以黑色页岩岩系为母岩的土壤,不仅明显富集Cu、Cd、Cr、Co、Pb、Zn、Mo、Ni、V、U、Sn、Sb、T1、Th等多种重金属元素,而且受到Mo、Sb、Cd、U、Tl、Cu、V、Sn、Th等重金属的污染,其中以Mo、Cd、Sb、U、Tl等的污染尤为严重。黑色页岩土壤重金属污染在一些地方已产生明显的负面环境效应,值得关注。     

湘中安化黑色页岩土壤玉米的元素地球化学分析

利用等离子质谱(ICP-MS)等分析技术,对产于安化东坪、烟溪黑色页岩土壤上的玉米进行元素地球化学分析.结果.表明:尽管东坪、烟溪黑色页岩土壤重金属元素富集的程度及其元素组合特征明显不同,但生长在其上的玉米有相似的主量元素和重金属元素的富集特征.玉米中Cd、Cr、Sc、Tl、Zn等重金属相对富集,以Cd的富集尤为明显;而Ba、Co、Cu、Fe、Mo、Ni、Pb、Sb、U、V等重金属相对亏损.黑色页岩土壤重金属污染的环境地球化学效应表现为Sc、Cr、Cd、Tl等生物毒性重金属元素在玉米中富集,而Ba、V、Co、Ni、Mo、Rb、Sr等生物必需微量金属在玉米中亏损.     

贵州惠水农作物-土壤剖面重金属污染评价

为研究贵州省惠水县农作物-土壤重金属污染现状,采集农作物-根系土、土壤剖面-成土母岩样品,测定Cd、Hg、As、Pb、Cr、Cu、Ni、Zn和pH的含量,选用富集系数、健康风险评估、单因子污染指数法、地累积指数法对农作物-土壤重金属污染现状进行了评价。研究表明：（1）农作物中水稻、玉米和油菜中以Cd累积为主,其次为Pb、Cr、Hg;金钱橘无重金属超标;农作物富集系数中Cd是Pb、As、Cr的几倍至上百倍;经玉米、油菜、金钱橘摄入重金属的人体健康风险很低;水稻中Cd的THQ大于1,对人体的健康有一定的风险;（2）单因子污染指数研究结果说明根系土以Cd污染为主;Ig揭示根系土中Hg、Cd、Cr超标可能受人类活动影响较大;（3）从土壤剖面-成土母岩系统来看,As、Cd、Cu具有继承性,尤其Cd含量在成土母岩、土壤剖面、根系土、农作物中含量超标,有部分来源于成土母岩高背景值。     

贵州开阳白马洞铀矿化岩层地球化学特征

贵州开阳白马洞铀矿是重要的蚀变型铀矿,通过对白马洞清虚洞组黑色蚀变岩及白云岩风化红粘土和寒武系牛蹄塘组黑色页岩的常量元素、微量元素和稀土元素组成的分析研究,发现铀元素含量与Re、Se、Pb、Cu、As、Sb、Tl、Zn、Ni、Mo、Co、S含量为正相关关系,铀含量高,则Re、Se、Pb、Cu、As、Sb、Tl、Zn、Ni、Mo、Co、S含量也高,其中As、Co、Mo、Ni、Re、Tl、Zn、S具有显著的正相关性,而且地表土壤中Se、V、Mo 等元素的富集是铀矿找矿的主要标志之一。根据白马洞清虚洞组、寒武系牛蹄塘组黑色页岩、灯影组硅化白云岩的稀土元素配分模式分析,硒富集和铀矿化矿源层不仅是牛蹄塘组黑色页岩,可能有更深部的矿源存在。认为硒富集区是铀矿找矿远景区域;古代炼汞矿渣富集铀矿,值得开发利用和治理。     

湘中桃江锰矿废矿堆环境地球化学分析

对湘中桃江锰矿废矿堆的废石进行了主量元素、稀土元素、微量元素和重金属元素的地球化学分析。野外观察及分析结果表明:组成废矿堆的岩石主要是赋矿围岩中奥陶统黑色页岩和原生碳酸锰矿石。这些废石富含Cu、Pb、Zn、Cr、Tl、Sb、U等重金属元素。废石暴露地表而遭受风化分解,导致Sc、V、Cr、U、Cd、Th等重金属元素淋滤释出,在废石样品中均表现出不同程度的迁移特征,且以V、Cd、U的迁移性最为强烈。此外,黑色页岩中Ni、Cu、Zn、Pb、Tl、Sb也明显发生淋失。这些重金属元素如Cd、Tl等毒性极强,进入矿区周围不断积聚,便可能对环境造成严重的影响。故对区内分布的废矿堆作为重金属污染源应高度重视。     

云南典型地质高背景区土壤重金属含量特征及污染风险评价

云南峨眉山玄武岩和碳酸盐岩分布区为典型重金属地质高背景区,选取云南鲁甸县典型地质高背景区为研究对象,采集1406件表层土壤样品,系统研究土壤中重金属含量特征,评价土壤重金属污染风险,重点探讨不同地质岩性对土壤重金属含量的影响,分析土壤重金属的来源。结果表明:(1)表层土壤中Cu、Cr、Cd、Zn和Ni含量均超出云南省背景值,土壤重金属含量明显受成土母质影响,碳酸盐岩明显富集Cd、Cr、Cu、Hg、Ni、Pb、Zn,飞仙关组碎屑岩明显富集Cr、Cu、Ni、Cd,玄武岩明显富集Cu、Cd、Zn、Cr,均为典型的地质高背景区;(2)表层土壤重金属综合评价等级以风险可控为主,碳酸盐岩、飞仙关组碎屑岩和玄武岩土壤中污染风险较高的重金属元素主要为Cd、Cu、Cr、Ni,且明显受玄武岩岩浆活动影响;(3)主成分和空间分析结果显示,地质高背景区土壤重金属高含量主要为成土母岩中重金属高含量及其风化成土过程中次生富集作用导致,人为影响相对较小。     

徐州城市表层土壤中重金属环境风险测度与源解析

研究了徐州城市表层土壤的21个样品中重金属元素富集特征,结果表明,与我国土壤元素的背景值(算术平均值)相比,表层土壤中Zn、Cd、As、Hg、Sb、Sn和Ag等元素富集程度高;Se、Sc、Ba、Bi、Pb、Cu、Ni、Cr、Mn、Mo、Be、Ga和Co等元素的富集程度较低。不同城市表层土壤中重金属元素有着不同的来源,统计分析结果表明,研究区表层土壤样品中重金属元素可分成4种类别:“自然因子”类别元素(Ti、Ga、Li、V、Co、Mn、Be和Pt);“交通因子”类别元素(Ag、Se、Sc、Pb、Cu、Zn、Cd、Br、S、Mo和Au);“燃煤因子”类别元素B(i、Cr、Hg、As、Sb和Pd)和混合源类别元素(Sn和Ba)。环境风险指数的计算结果表明,表层土壤中重金属污染具有较大的环境风险,其中属于中等环境风险级别以上的样品占近40%。     

广西373铀矿床微量元素地球化学特征及其成因探讨

373铀矿床是我国南方典型碳硅泥岩型铀矿床之一,主要发育一套黑色弱硅化泥岩、粉砂岩,硅化生屑灰岩及其过渡型岩类地层,矿床明显受断裂发育影响,铀矿化于次级断裂带中.通过系统地球化学研究表明:3组不同期次脉体普遍亏损过渡元素Ti、Sc、Cr、Cu、Zn和高场强元素Nb、Ta、Zr和Hf;相对较富集Mn、Ni、As、Sr、Mo、Sb、Tl和U等微量元素.后期热液活动使脉体Ba、Sb、As和Mo等元素异常富集.后期热液叠加改造,使得岩石普遍亏损过渡元素Sc、Ti、Cr和高场强元素Nb、Ta、Zr、Hf,普遍富集Co、Ni、Zn、As、Sb、Mo、Cd、W、Tl、Pb、Bi和U,其中As、Sb、Mo、Tl和U尤为富集,富集系数平均达到100左右,U与W、As、Sb和Pb相关系数都在0.9左右,具有高度同源性,铀成矿与热液活动有关.典型剖面微量元素富集与硅化密切相关,当硅化达到一定程度后微量元素富集出现反转,即随着硅化强度增加而富集能力反而降低.V/Cr、V/Sc、Ni/Co、V/(V+Ni)、U/Th、δU、δEu和δCe等特征元素比值反应铀预富集形成于缺氧的古海洋环境.高丰度的As、Sb和Ba等元素,以及U-Th关系图解和Zn-Ni-Co三元图解均显示热水沉积成因.微量元素特征表明碳硅泥岩形成于缺氧的还原环境,铀预富集与热水沉积有关,铀成矿与热液叠加改造有关,后期热液沿运移通道上升进入储集空间,与铀预富集地层热液叠加成矿.     

内蒙古废弃钨钼矿区周围土壤重金属污染生态环境评价及成因分析

为研究内蒙古赤峰市废弃钨钼矿区周围土壤重金属污染特征、潜在生态风险及成因分析，共采集83份表层土壤样品和6个土壤钻孔。采用ArcGIS空间插值分析方法研究As、Cd、Cr、Cu、Ni、Pb、Mo和Zn的空间分布，构建重金属扰动指数函数研究重金属受人类活动的污染程度，利用地累积指数法验证矿区周围土壤重金属污染程度，通过相关性分析判断重金属来源并讨论污染成因。结果表明：矿区周围土壤As、Cd、Cu、Pb、Zn和Mo平均含量明显高于矿区周边背景值，高含量主要分布尾矿库周围，主要来源为矿山采选活动；Cr和Ni基本无污染，主要来源为母岩风化。通过重金属扰动指数函数计算发现：采用区域背景值对矿区周围进行重金属污染评价夸大了矿山采选活动对矿区周围土壤重金属的污染，矿区周围土壤重金属污染是由于天然重金属富集和采矿活动共同作用下的“双驱动模式”导致，尾矿库周围土壤重金属污染程度随着与尾矿库水平距离的增加和深度的加大而逐渐降低。降水量丰富程度是影响重金属迁移能力的关键因素，该矿处于降水量匮乏地区，尾矿库对周围土壤重金属污染范围有限，对生态环境影响轻微。     

浙江省下寒武统荷塘组黑色页岩系地球化学特征

首次根据浙江省西北部荷塘组岩石样品的实测数据,提出了浙江省荷塘组黑色岩系6个岩性层的Pt、Pd、Au、Ag、Cu、As、Sb、Pb、Mo、Ni、V、P、U、B、Cd、Tl、Se、Zn元素的平均值,运用微量元素和稀土元素的配分模式探讨了成岩环境及元素高含量对环境的影响.荷塘组富集元素较多,富集程度高的有Mo、Se、Cd、Ag、Sb、U、As、P;较富集的有V、B、Cu、Tl、Zn,弱富集的为Au、Pt、Pb、Ni.综合地质地球化学特征研究认为,荷塘组黑色岩系具有寻找含钼、磷、矾和有色金属矿产的潜力.     

Metal dispersion in groundwater in an area with natural and processed black shale – Nationwide perspective and comparison with acid sulfate soils

Black shale is often rich in sulfides and trace elements, and is thus a potential environmental threat in a manner similar to acid sulfate soils and active or abandoned sulfide mines. This study aims at characterising how exposed and processed (mined and burnt) black shale (alum shale) in Degerhamn, SE Sweden, affects the chemistry (Al, As, Ba, Cd, Ca, Cr, Co, Cu, Fe, Pb, Mg, Mn, Mo, Ni, K, Si, Na, Sr, S, U, V and Zn) of the groundwater. There were large variations in groundwater chemistry between nearby sampling points, while the temporal variations generally were small. Acidic groundwater (around pH 4), found in deposits of burnt and carbonate-poor shale where the conditions for sulfide oxidation were favourable, was strongly elevated in Al, U and several chalcophilic metals (Cd, Co, Cu, Ni and Zn). Cadmium and U were also, together with Mo, abundant in many of the near-neutral waters, both in the non-mined black shale bedrock and in the deposits of burnt shale. An extrapolation to a national level suggests that the dispersion of Ni from naturally occurring black shale is similar to that from anthropogenic point sources, while for Cd and As it is assessed to be approximately one tenth of that from point sources. The processed shale was, however, a much larger source of metals than the black shale bedrock itself, showing this material’s potential as a massive supplier of metals to the aquatic environment. A comparison of waters in contact with the processed Cambrian–Ordovician black shale in Degerhamn and acid sulfate soils of the region shows that these two sulfide-bearing materials, in many respects very different, delivers basically the same suite of trace elements to the aquatic environment. This has implications for environmental planning and protection in areas where these types of materials exist.     

贵州织金下寒武统黑色页岩矿物岩石成分及资源利用特征

通过野外采样、化学分析、电子探针(EPMA)和X射线衍射(XRD)分析等手段,研究了贵州织金地区黑色页岩矿物成分、化学组分、微量元素、稀土元素特征。研究区矿样化学成分以SiO_2和Al_2O_3为主,且具有高K低Na的特征。电子探针和X射线衍射分析表明,研究区黑色页岩主要矿物组成有石英、粘土矿物、白云石及黄铁矿等。织金黑色页岩中Pb、Ni、U、V、Cr等金属元素存在不同程度的富集,稀土元素总量为153.2×10~(-6)~224.89×10~(-6),属轻稀土元素富集型。同时从多金属层、页岩气、页岩提钾及近底部含磷铀矿资源等方面讨论了织金黑色页岩资源化利用。织金黑色页岩多金属层含有Mo、V、Ni、Ag及U等多金属元素,具综合利用价值;其中有机碳含量达到页岩气开发大于2%的条件,可进一步开展研究;页岩中伊利石含量较多,可提取黑色页岩中的钾制备含钾复合肥;黑色页岩底部与磷矿层接触带产出磷铀矿,主要为胶状磷铀矿,接触带可作为铀矿找矿的标志层。     

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

系统考察了湖南省麻田和桃花江两个不同发育程度的下寒武统黑色页岩风化剖面,并提出了元素在理想剖面中的分布模式(概念模型);通过对比分析这两个剖面中元素的分布特征与理想分布模式的关系,并结合元素相关性研究、等质量图解的判别分析、微量元素的赋存状态及地球化学性质的探讨,认为在黑色页岩风化过程中,Ti为不活动元素,可作为参照系来计算其它元素的相对迁移性,Nb、Ta的活动性较小,Zr与Hf之间存在着共迁移现象;研究表明化学风化程度是影响元素活动性的重要因素.     

Research on the Eco-Geochemical Effects of Black Shales in Pingli County,Shaanxi

This paper presents the results of eco-geochemical research on black rock series enriched in metallic elements in Pingli County,Shaanxi Province,which lies at the northern margin of the Yangtze Platform.There is a suite of bone coal-bearing black carbonaceous rocks in the Cambrian Donghe Formation throughout the region.Soils in Pingli contain high metallic elements derived from the bone coal and carbonaceous rocks.Edible plants growing in the soils contain high Se,Cu and Mo.Two case studies are documented.One is a black shale area with bone coal and Se enrichment,and the other is a black shale area with bone coal mine and copper mineralization.Eco-geochemical effects of metallic element-rich black shales on plants are reported in this paper.     

Behavior of Re and Os during low-temperature alteration: Results from Himalayan soils and altered black shales

Re-Os analyses were performed on five soil profiles developed on silicate lithologies in the Narayani drainage basin of the Himalayas, as well as on several altered black shales and associated alteration phases. The results indicate that all of these samples have lost large amounts of Re. This Re loss approached 100% in the black shale-derived soils, which also most probably lost substantial quantities of Os. The near constancy of Os and Re concentrations with depth indicates that this loss occurred quite early in the alteration process, rather than progressively during the course of soil development. A slight decrease in ¹⁸⁷Os/¹⁸⁸Os was observed toward the surface of the two black shale soil profiles, possibly indicating a minor preferential mobility of radiogenic ¹⁸⁷Os for this lithology. In the black shale-derived saprolite and soils, the loss of Re and Os was related to the loss of organic carbon. The importance of this phase is underscored by the fact that organic material separated from a black shale sample accounted for nearly all of the Os contained in the whole rock. Analysis of alteration phases from the surface of a weathered black shale showed that Os liberated during alteration was partially reprecipitated in Fe oxides, with Os isotopic compositions very similar to that of the original rock, whereas Re was removed with the fluid phase.These results demonstrate the disproportionately large role that black shale weathering may play in determining the Re and Os contents of continental runoff and, thus, ultimately of seawater, but they also emphasize the possible complexity of this process. The data suggest that a large fraction of the Os contained in black shales is released during chemical alteration, which is apparently not the case for most other silicate rocks. Therefore, the potential contribution of black shales to the dissolved Os budget of runoff and river water may be even greater than that expected from the high Os concentrations of these rocks. The extent to which this Os will affect the seawater Os composition depends on how efficiently it is recaptured by secondary phases such as Fe-Mn oxides in situ or during transport. These results also underscore the high mobility of Re with respect to Os at every stage in the erosional process, thus explaining the order of magnitude increase in Re/Os ratio from the black shale source rocks to seawater.     

黔北下寒武统黑色岩系的沉积环境与地球化学响应

下寒武统黑色岩系在我国华北、华南及塔里木盆地等广泛发育,但富有机质泥页岩的分布特征及其控制因素未有定论。本文对黔北地区下寒武统牛蹄塘组(及同时期地层)不同沉积相带典型剖面中的富有机质泥页岩及其上下层位进行了地球化学分析,识别出寒武纪早期不同沉积相带氧化还原环境的明显差异。台内凹陷相主要岩性为黑色页岩,底部为不等厚的薄层磷块岩和硅质岩或硅磷质结核,沉积的黑色页岩厚度大,有机质丰度高,V、Ni、Mo、U等微量元素显著富集,反映了贫氧-缺氧环境,以及短暂动态的硫化环境,Mo/TOC反映了其为局限盆地特征;上斜坡相为贫氧到氧化的沉积环境,但更多地是表现为氧化的沉积环境,其中牛蹄塘期存在局部的硫化环境,沉积的黑色页岩厚度小,但有机质丰度最高,V、Ni、Mo、U等微量元素的富集程度较低;盆地相为黑色硅质岩与富有机质的黑色硅质页岩间互沉积,同期沉积厚度较小,有机质丰度相对较低,V和U的富集程度大于台内凹陷相,而Ni和Mo的富集程度则低于台内凹陷相,指示了缺氧环境,期间伴随有贫氧和短暂的氧化环境存在,且可能存在局部的硫化环境,Mo/TOC反映了中等的局限程度。总的来说,黔北下寒武统黑色岩系的有机质丰度、厚度以及微量元素富集程度等特征主要受控于不同的氧化还原环境。     

Geochemistry of trace and rare earth elements during weathering of black shale profiles in Northeast Chongqing,Southwestern China: Their mobilization,redistribution, and fractionation

In this study, the mobilization, redistribution, and fractionation of trace and rare earth elements (REE) during chemical weathering in mid-ridge (A), near mountaintop (B), and valley (C) profiles (weak, weak to moderate, and moderate to intense chemical weathering stage, respectively), are characterized. Among the trace elements, U and V were depleted in the regolith in all three profiles, Sr, Nb, Ta, Zr, and Hf displayed slight gains or losses, and Th, Rb, Cs, and Sc remained immobile. Mn, Ba, Zn, Cu, and Cr were enriched at the regolith in profiles A and B, but depleted in profile C. Mn, Pb, and Co were also depleted in the saprock and fractured shale zones in profiles A and B and enriched in profile C. REEs were enriched in the regolith and depleted at the saprock zone in profiles A and B and depleted along profile C. Mobility of trace and REEs increased with increasing weathering intensity. Normalized REE patterns based on the parent shale revealed light REE (LREE) enrichment, middle REE (MREE), and heavy REE (HREE) depletion patterns. LREEs were less mobile compared with MREEs and HREEs, and this differentiation increased with increasing weathering degree. Positive Ce anomalies were higher in profile C than in profiles A and B. The Ce fractionated from other REE showed that Ce changed from trivalent to tetravalent (as CeO₂) under oxidizing conditions. Minimal REE fractionation was observed in the saprock zone in profiles A and B. In contrast, more intense weathering in profile C resulted in preferential retention of LREE (especially Ce), leading to considerable LREE/MREE and LREE/HREE fractionation. (La/Yb)_N and (La/Sm)_N ratios displayed maximum values in the saprock zone within low pH values. Findings demonstrate that acidic solutions can mobilize REEs and result in leaching of REEs out of the highly acidic portions of the saprock material and transport downward into fractured shale. The overall behavior of elements in the three profiles suggests that solution pH, as well as the presence of primary and secondary minerals, play important roles in the mobilization and redistribution of trace elements and REEs during black shale chemical weathering.     

贵州开阳磷矿地区下寒武统牛蹄塘组地层层序及其As、Sb、Au、Ag丰度异常与赋存状态研究

贵州开阳磷矿地区出露较为完整的下寒武统黑色岩系层序,这套黑色岩系中富含多种金属元素,但目前对岩系中主要低温成矿元素As、Sb、Au、Ag的地球化学背景异常与分布规律了解极少,对其形成背景与赋存状态无法进行深入讨论。本文以开阳磷矿地区下寒武统牛蹄塘组黑色岩系剖面作为研究对象,通过详细的野外地质调查、系统采样并进行地球化学分析、全岩硫同位素分析及黄铁矿电子探针分析,划分了详细的牛蹄塘组地层层序,对主要低温成矿元素(As、Sb、Au、Ag)的丰度异常、富集特征及赋存状态进行了研究,结果表明,黑色岩系中普遍富集As、Sb、Ag三种主要低温成矿元素,Au也在大部分层位富集。四种元素具有层控性的特点,在牛蹄塘组下部有机质含量较高的黑色白云质粉砂质页岩和黑色页岩层位中具有较高的元素丰度异常,在泥岩和粉砂岩混合层位元素丰度异常较低,钙质成分含量较高的层位元素含量较低。黄铁矿是黑色页岩中金的主要赋存矿物,也是Sb的重要赋存矿物,同时是Ag和As的次要赋存矿物;不同类型的黄铁矿,元素富集规律也不相同:As、Ag更容易富集在不规则集合体和草莓状黄铁矿中,Sb和Au则在散布的单颗粒黄铁矿中富集系数最高。