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.     

湖南水口山多金属矿区废石堆重金属污染评价及赋存形态分析

湖南水口山及周边是湖南省重金属污染较为严重的地区之一,龙王山金矿床是该区中部的一个重要金矿床.为调查该矿床废石堆污染状况、是否为周边环境的污染源、污染途径、重金属迁移能力和潜在的危害,对矿区FS17废石堆进行了自然淋滤水和24 m浅钻系统取样,开展重金属元素总量分析,利用单因子指数法和内梅罗综合污染指数法对其重金属污染程度进行污染评价,采用四步改良BCR提取法分析废石堆中8种重（类）金属元素（Pb、Zn、Cd、Cu、Cr、Ni、As和Fe）的赋存形态,并利用迁移指数量化废石堆重金属元素迁移能力;发现废石堆中Cd、Cu、Pb、As、Zn、Ni重金属元素严重超标,且在垂向上分布极不均匀;其自然淋滤水样中重金属元素Cd、Ni、Zn、Cu也严重超标;废石堆浅层重金属元素潜在迁移能力顺序为:Cd＞Ni≈Zn＞Cu＞Pb＞As＞Cr＞Fe,深层重金属元素迁移能力顺序为:Cd＞Zn＞Cu＞Ni＞Cr＞Pb＞As＞Fe,浅层重金属元素的迁移性大于深层;说明该废石堆重金属元素含量高,是周围环境重要污染源,酸性废水排放为其释放污染元素的主要途径;Cd、Cu、Zn、Ni迁移能力强,是周围环境的主要污染元素;Pb、Ni、As的迁移性在深层明显降低,可以通过埋深来削弱其迁移性,而Cr不会对周边环境产生污染.      

湘中HJC铀矿区黑色页岩土壤重金属污染地球化学分析

本文以湘中HJC铀矿区黑色页岩土壤为研究对象,对黑色页岩土壤重金属污染进行了地球化学分析。通过测制A、B、C、D等土壤剖面并系统取样,借助ICPMS等分析技术,对土壤、成土母岩、玉米等进行了系统的主量元素、重金属和其他微量元素（稀土元素）分析。结果表明,矿区黑色页岩土壤具富Al2O3、Fe2O3,而贫CaO、Na2O的化学组成特征,其化学风化指数CIA值在79~84之间。土壤因继承成土母岩的元素富集特征而富集V、Cr、Co、Ni、Cu、Zn、Mo、Cd、Sn、Sb、Tl、Pb、Th、U等多种重金属,其中Mo、Cd、Sb、U的富集最强。土壤重金属综合富集指数（EI值）在3~9之间,各剖面EI值大小顺序是：D>A>B>C, 以D剖面土壤重金属综合富集最强。土壤重金属污染富集因子（F）评价结果显示：矿区土壤普遍存在Cd、Mo、Sn、Sb、U等重金属污染,其中Mo、Cd、Sb等的污染最强,达显著（3级,2 < F < 20）污染程度以上。重金属污染效应既表现为Sc、Cd、Sn、Sb、U、Tl、Pb等生物毒性重金属在玉米中的富集,又表现为Mo、Co、Ni、Cu、Zn等生物有用金属在玉米中的明显亏损。黑色页岩即为土壤重金属污染的污染源。土壤重金属污染与重金属在成土母岩和土壤中的富集程度(Ks、EI、F)、重金属的活动性（Change%）等多种因素有关。重金属污染主影响因子的Pearson相关系数分析显示：Cd对土壤构成持久性污染,Mo、Sn、Sb、U等的污染程度可随土壤风化的进行因淋失而趋于降低,而Zn、Mn、Ba、Co、Ni、Th等目前未达到污染水平的重金属则可因次生富集而在未来引发污染。     

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.     

涡阳花沟西10号煤中微量元素的有机亲和性

为研究淮北矿区涡阳花沟西勘查区10号煤中微量元素的有机亲和性,共采集10个勘探钻孔煤样品,采用电感耦合等离子质谱仪ICP-MS分析了12种微量元素的含量;应用LECO碳硫分析仪测定了煤的总有机碳TOC,并通过两者的相关关系分析了元素的有机亲和性,结合元素的地球化学特征和煤样XRD物相鉴定结果,通过聚类分析进一步推断元素的赋存状态。结果表明:V、Cr、Co、Ni、Mo、Cd、Sb、Pb和Zn元素含量低于全国均值,没有异常富集,Be、Cu和Tl略高于全国均值;Cd具有较强的有机亲和性,Co、Zn、Be和Cr的有机亲和性较弱,V、Ni、Cu、Mo、Sb、Pb和Tl不具有机亲和性;V、Sb、Cu、Cr、Pb、Co和Ni主要以铝硅酸盐吸附态赋存,Cd主要以有机结合态赋存。      

黔北地区下寒武统底部黑色页岩沉积环境条件与源区构造背景分析

为了深入探讨黔北地区下寒武统底部黑色页岩的沉积环境条件和源区构造背景,对黔北地区下寒武统牛蹄塘组黑色页岩进行系统采样,对其微量元素和稀土元素地球化学特征进行了系统分析。研究表明,微量元素中高的WV/(WNi+WV)和U/Th比值等反映该区黑色页岩形成于海域开阔的还原环境。区内黑色页岩样品中Mo、Sb、U、Cd、 V、Ba、Tl、Ni、W、 Cr、Cs、Cu、Zn、Bi等元素的高富集以及正Eu异常和较低的Co/Zn比值均反映了黔北下寒武统底部黑色页岩受到深部热液活动的影响。根据主、微量和稀土元素组合及比值特征可以看出黔北地区下寒武统底部黑色页岩的源岩具有花岗岩、沉积岩和玄武岩等多成因性质。源区构造背景以被动大陆边缘为主,由于受深部热液活动的影响,也显示大陆岛弧构造背景的特征。     

湘西北早寒武世黑色岩系微量元素地球化学特征

对湘西北杆子坪剖面牛蹄塘组黑色岩系进行了系统的微量元素地球化学研究，结果表明：牛蹄塘组底部黑色岩系Ni、Mo、V、U、Cu、Pb、Zn、Cd、Tl、Ba等亲硫元素与过渡元素高度富集，U／Th大于1，稀土元素具有明显的正Eu异常与正Y异常，是海底热水沉积作用的结果。牛蹄塘组上部碳质页岩与泥质页岩亲硫元素与过渡元素明显降低，而Nb、Ta、Zr、Hf、Rb等高场强与大离子元素明显增高，表明陆源碎屑来源越来越多。     

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.     

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。     

Mineralogical and geochemical constraints on environmental impacts from waste rock at Taojiang Mn-ore deposit,central Hunan,China

The mineralogy and geochemistry of the waste rocks distributed at Taojiang Mn-ore deposit, central Hunan province, China, were studied using X-ray powder diffraction (XRD), electron microprobe analysis (EMPA) fitted with energy dispersive spectrometer (EDS) and inductively coupled plasma mass spectrum (atomic emission spectra) ICP-MS (AES), with the aim of predicting the environmental impacts of weathering of the waste rocks. The mineralogical results from microscope observation and XRD and EMPA studies show that the waste rock is composed of black shale and minor Mn carbonates. The oxidation of sulfide minerals such as galena, pyrite and chalcopyrite is accompanied by decomposition of Mn carbonates and K-feldspar during exposure to atmospheric O₂. The geochemical characteristics of major, rare earth elements (REE) and trace elements of the waste rocks also show that the waste rock can be divided into black shale and Mn carbonate, and both of them are currently under chemical weathering. The major alkalies and alkaline elements (Ca, Mg, Na, K, Rb, Sr and Cs) and major elements (Fe, S and P) and heavy metals (Sc, V, Cr, Th, U, Sn, Co, Ni, Cu, Zn, Pb, Mo, Cd, Sb, an Tl) are being released during weathering. The mobility of alkalis and alkaline elements Ca, Mg, Na, K, Rb, Sr and Cs is controlled by decomposition of Mn carbonates. The dispersion of Cr, Sc and Th (U) might be related to weathering of K-feldspar, and the release of the heavy metals Co, Ni, Cu, Zn, Pb, Mo, Cd Sb and Tl is dominated by the breaking of sulfide minerals. The REE of the waste rocks and surrounding soils and the spidery distribution patterns of heavy metals in the waste rocks, the surrounding soils and the surface waters show that weathering of the waste rocks and bedrock might be the sources of heavy metal contamination for the surrounding soils and surface water system for the mining area. This is predicted by the mass-balance calculation by using Zr as an immobile element. Therefore, it is urgently necessary take measures to treat the waste rocks distributed throughout the area for the local environmental protection.     

Release of heavy metals during weathering of the Lower Cambrian Black Shales in western Hunan,China

Weathering of heavy metal enriched black shales may be one of the most important sources of environmental contamination in areas where black shales are distributed. Heavy metal release during weathering of the Lower Cambrian Black Shales (LCBS) in western Hunan, China, was investigated using traditional geochemical methods and the ICP-MS analytical technique. Concentrations of 16 heavy metals, 8 trace elements and P were measured for samples from selected weathering profiles at the Taiping vanadium ore mine (TP), the Matian phosphorous ore mine (MT), and Taojiang stone-coal mine (TJ). The results show that the bedrock at these three profiles is enriched with Sc, V, Cr, Co, Ni, Cu, Zn, Pb, Th, U, Mo, Cd, Sb, Tl, and P. Based on mass-balance calculation, the percentages of heavy metals released (in % loss) relative to immobile element Nb were estimated. The results show significant rates of release during weathering of: V, Cr, Co, Ni, Cu, Zn, U, Mo, Cd, Sn, Sb, and Tl for the TP profile; Sc, Cr, Mn, Co, Ni, Cu, Zn, Pb, Th, Cd, and Sn for the MT profile; and Sc, Mn, Co, Ni, Zn, Th, Cd, Sn, and Tl for the TJ profile. Among these heavy metals, Co, Ni, Zn, Cd, and Sn show very similar features of release from each of the three weathering profiles. The heavy metals released during weathering may affect the environment (especially topsoil and surface waters) and are possibly related to an observed high incidence of endemic diseases in the area.     

Heavy metal geochemistry of the acid mine drainage discharged from the Hejiacun uranium mine in central Hunan,China

The acid mine drainage (AMD) discharged from the Hejiacun uranium mine in central Hunan (China) was sampled and analyzed using ICP-MS techniques. The analyzing results show that the AMD is characterized by the major ions Fe_Total, Mn, Al and Si, and is concentrated with heavy metals and metalloids including Cd, Co, Ni, Zn, U, Cu, Pb, Tl, V, Cr, Se, As and Sb. During the AMD flowing downstream, the dissolved heavy metals were removed from the AMD waters through adsorption onto and co-precipitation with metal-oxhydroxides coated on the streambed. Among these metals, Cd, Co, Ni, Zn, U, Cu, Pb and Tl are negatively correlated to pH values, and positively correlated to major ions Fe, Al, Si, Mn, Mg, Ca and K. The metals/metalloids V, Cr, Se, As and Sb are conservative in the AMD solution, and negatively-correlated to major ions Na, Ca and Mg. Due to the above different behaviors of these chemical elements, the pH-negatively related metals (PM) and the conservative metals (CM) are identified; the PM metals include Cd, Co, Ni, Zn, U, Cu, Pb and Tl, and the CM metals V, Cr, Se, As and Sb. Based on understanding the geochemistry of PM and CM metals in the AMD waters, a new equation: EXT = (Acidity + PM)/pH + CM × pH, is proposed to estimate and evaluate extent of heavy-metal pollution (EXT) of AMD. The evaluation results show that the AMD and surface waters of the mine area have high EXT values, and they could be the potential source of heavy-metal contamination of the surrounding environment. Therefore, it is suggested that both the AMD and surface waters should be treated before they are drained out of the mine district, for which the traditional dilution and neutralization methods can be applied to remove the PM metals from the AMD waters, and new techniques through reducing the pH value of the downstream AMD waters should be developed for removal of the CM metals.     

Chemistry and Sulfur Isotopes in a Chert-dominant Sequence around the Stratiform Manganese Deposit of the Noda-Tamagawa Mine, Northern Kitakami Terrane, Northeast Japan: Implication for Paleoceanographic Environmental Setting

Abstract. Chemistry and sulfur isotopes are analyzed for a series of rocks in the chert‐dominant sequence around the stratiform manganese ore deposit of the Noda‐Tamagawa mine in the northern Kitakami Terrane, northeast Japan. The sequence is litholog‐ically classified into six units in ascending order: lower bedded chert, lower black shale, massive chert, manganese ore, upper black shale, and upper bedded chert. The rocks around the manganese ore deposit exhibit anomalous enrichment in Ni (max. 337 ppm), Zn (102) and U (30) in the upper part of lower bedded chert, Mo (122), Tl (79) and Pb (33) in the lower black shale, MnO, Cu (786) and Co (62) in the manganese ore, and As (247) and Sb (17) in the upper black shale. The aluminum‐normalized profiles reveal zonal enrichment of redox‐sensitive elements around the manganese bed: Zn‐Ni‐Fe‐Mo‐U(‐Co), Tl‐Pb(‐Mo), Mn‐Fe‐Cu‐V‐Cr‐Co(‐Zn) and As‐Sb in ascending order. The uppermost part of the lower bedded chert and black shale exhibit negative Ce/Ce* values, whereas the massive chert, manganese ore and lower part of the upper bedded chert display positive values. The isotopic δ³⁴S values are 0±6 % in the lower part of the lower bedded chert, ‐19 to ‐42 % in the upper part of the lower bedded chert, ‐36 to ‐42 % in the lower black shale, ‐28 to ‐35 % in the massive chert, manganese ore and upper black shale, and ‐23±5 % in the upper bedded chert. Thus, there is a marked negative shift in δ³⁴S values in the lower bedded chert, and an upward‐increasing trend in δ³⁴S through the manganese ore horizon. The present data provide evidence for a change in the paleoceanographic environmental resulting from inflow of oxic deepwater into the stagnant anoxic ocean floor below the manganese ore horizon. This event is likely to have triggered the precipitation of manganese oxyhydroxides. The redistribution of redox‐sensitive elements through the formation of metalliferous black shale and manganese carbonate ore may have occurred in association with bacterial decomposition of organic matter during early diagenesis of initial manganese oxyhydroxides.     

Geochemistry of trace metals and Pb isotopes of sediments from the lowermost Xiangjiang River, Hunan Province (P. R. China): implications on sources of trace metals

This paper reports a geochemical study of trace metals and Pb isotopes of sediments from the lowermost Xiangjiang River, Hunan province (P. R. China). Trace metals Ba, Bi, Sc, V, Cr, Mn, Co, Ni, Cu, Zn, Mo, Cd, Sn, Sb, Pb, Tl, Th, U, Zr, Hf, Nb and Ta were analyzed using ICP-MS, and Pb isotopes of the bulk sediments were measured by MC-ICP-MS. The results show that trace metals Cd, Bi, Sn, Sc, Cr, Mn, Co, Ni, Cu, Zn, Sb, Pb and Tl are enriched in the sediments. Among these metals, Cd, Bi and Sn are extremely highly enriched (EF values >40), metals Zn, Sn, Sb and Pb significantly highly (5 < EF < 20), and metals Sc, Cr, Mn, Co, Ni, Cu and Tl moderately highly (2 < EF < 5) enriched in the river sediments. All these metals, however, are moderately enriched in the lake sediments. Geochemical results of trace metals Th, Sc, Co, Cr, Zr, Hf and La, and Pb isotopes suggest that metals in the river sediments are of multi-sources, including both natural and anthropogenic sources. Metals of the natural sources might be contributed mostly from weathering of the Indosinian granites (GR) and Palaeozoic sandstones (PL), and metals of anthropogenic sources were contributed from Pb–Zn ore deposits distributed in upper river areas. Metals in the lake sediments consist of the anthropogenic proportions, which were contributed from automobile exhausts and coal dusts. Thus, heavy-metal contamination for the river sediments is attributed to the exploitation and utilization (e.g., mining, smelting, and refining) of Pb–Zn ore mineral resources in the upper river areas, and this for the lake sediments was caused by automobile exhausts and coal combustion. Metals Bi, Cd, Pb, Sn and Sb have anthropogenic proportion of higher than 90%, with natural contribution less than 10%. Metals Mn and Zn consist of anthropogenic proportion of 60–85%, with natural proportion higher than 15%. Metals Sc, Cr, Co, Cu, Tl, Th, U and Ta have anthropogenic proportion of 30–70%, with natural contribution higher than 30%. Metals Ba, V and Mo might be contributed mostly from natural process.     

湘江入湖河段沉积物重金属污染及其Pb同位素地球化学示踪

湘江是我国重金属污染最严重的河流之一.本次工作利用等离子质谱(ICP-MS)和多接收同位素质谱(MC-ICP-MS)等技术,对湘江入湖河段沉积物进行了系统的重金属微量元素和Pb同位素分析.结果表明,湘江河床沉积物明显富集Bi、Sc、V、Mn、Ni、Cu、Zn、Pb、Cd、Sn、Sb等多种重金属微量元素,而湖盆沉积物重金...     

Multi-matrix environmental monitoring to assess heavy element distribution around a municipal solid waste landfill in Italy

Multi-matrix environmental monitoring was used to evaluate the influence of a municipal solid waste landfill (Ginestreto, Emilia Romagna, Italy) on the level and distribution of heavy elements in the surrounding environment (air, soil and soil biota). Concentrations of As, Cd, Co, Cr, Cu, Hg, Ni, Pb, Sb, Tl and Zn were measured by inductively coupled plasma-mass spectrometry in transplanted lichens, topsoils and isopods. The highest accumulation levels found for Cd, Cr, Pb, Sb and Zn in lichens transplanted within the Ginestreto landfill. However, similar concentrations of these heavy elements were also found in lichens exposed in monitoring sites influenced by other man-made sources, such as vehicle traffic and truck movements. The fallout of heavy elements emitted by the landfill had low impact on their levels in topsoil: Cd, Cr, Pb, Sb and Zn showed higher contents in topsoil collected close to the landfill and a slight decrease in concentrations with increasing distance from the landfill. There was no variation in heavy element accumulation in isopods in relation to distance from the landfill. The results of this study indicate that the Ginestreto municipal solid waste landfill had limited impact on the environmental distribution of heavy elements, since accumulation and enrichment in lichens and topsoils were only detected close to the landfill, up to about 100 m from its border.