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。     

Heavy metal pollution in freshly deposited sediments of the Yamuna River (the Ganges River tributary): a case study from Delhi and Agra urban centres, India

 The Yamuna River sediments, collected from Delhi and Agra urban centres, were analysed for concentration and distribution of nine heavy metals by means of atomic adsorption spectrometry. Total metal contents varied in the following ranges (in mg/kg): Cr (157–817), Mn (515–1015), Fe (28,700–45,300), Co(11.7–28.4), Ni (40–538), Cu (40–1204), Zn (107–1974), Pb (22–856) and Cd (0.50–114.8). The degree of metal enrichment was compared with the average shale concentration and shows exceptionally high values for Cr, Ni, Cu, Zn, Pb and Cd in both urban centres. In the total heavy metal concentration, anthropogenic input contains 70% Cr, 74% Cu, 59% Zn, 46% Pb, 90% Cd in Delhi and 61% Cr, 23% Ni, 71% Cu, 72% Zn, 63% Pb, 94% Cd in Agra. A significant correlation was observed between increasing Cr, Ni, Zn, and Cu concentrations with increasing total sediment carbon and total sediment sulfur content. Based on the Müller's geoaccumulation index, the quality of the river sediments can be regarded as being moderately polluted to very highly polluted with Cr, Ni, Cu, Zn, Pb and Cd in the Delhi and Agra urban centres. The present sediment analysis, therefore, plays an important role in environmental measures for the Yamuna River and the planning of these city centres. Received: 21 June 1999 · Accepted: 1 October 1999     

Heavy metals pollution in the soil of an irregular urban settlement built on a former dumpsite in the city of Tijuana, Mexico

The aim of this study was to evaluate soil pollution by heavy metals in an irregular settlement built on a dumpsite. The soil samples were analyzed for Cd, Cr, Cu, Pb and Ni. None of the concentrations found for the heavy metals analyzed were higher than the established Mexican official standards for contaminated soils. The mean concentrations found for the analyzed metals were as follows: 1.4 mg kg⁻¹ for Cd, 4.7 in mg kg⁻¹ for Cr, 304 mg kg⁻¹ for Cu, 74 mg kg⁻¹ for Pb and 6 mg kg⁻¹ for Ni. The results of the geoacummulation index values show that the site was very polluted with Cu and Pb (class 7), polluted to strongly polluted with Ni (class 4); moderately polluted to polluted with Cd (class 3), and moderately polluted with Cr (class 1). The correlation analysis shows a high correlation between Pb and Cu (r ² = 0.98), which would be explained if the main source of the polluting heavy metals was the result of electrical wire burning to recover Copper. Principal component analysis shows three principal components. The first main component (PC1) encompasses Cr, Cd, Pb and Cu. These heavy metals most likely have their origins from the open burning of municipal solid waste, tires and wire. The other two components are encompassed by Cr (PC2) and Ni (PC3). The sources of these pollutants are more likely related to the corrosion of junk metal objects and automobile use.     

云南省宣威市农耕区土壤重金属元素分布影响因素及生态风险评价

为探究云南省碳酸盐岩风化区重金属污染特征及分布影响因素,选取云南省宣威市农垦区为研究对象,利用1:5万土地质量地球化学调查成果,通过分析表层土壤重金属元素累积特征及分布规律,并结合土壤理化性质及地形因素等数据,研究驱动农垦区土壤重金属元素富集的影响因素,并利用富集指数法(EF)和潜在生态风险评价(RI)进行污染评价.结...     

Experimental modeling of the immobilization of heavy metals at the carbonate adsorption–precipitation geochemical barrier

Experimental data obtained on the adsorption–precipitation immobilization of heavy metals (Cu, Zn, Pb, Cd, Co, and Ni) from acidic and neutral solutions by calcite and dolomite demonstrate that interaction of solutions of heavy metals with these minerals at pH > 7.8–8.1 leads to a significant decrease in the concentrations of the metals because of the crystallization of carbonates of these metals. Except Pb, which is equally removed from solutions by both minerals, the immobilization efficiency of the metals on dolomite is greater than on calculate at the same pH. Residual Zn, Cd, Co, and Ni concentrations are immobilized by chemosorption, which is the most efficient for Cd and less significant for Co, Ni, and Zn. It is proved that artificial geochemical barriers on the basis of carbonate rocks can be efficiently applied to protect environment from contamination with heavy metals.     

包头市典型工业区表层土壤中重金属污染状况及其潜在生态风险研究

为了解包头市典型工业企业对其所在地土壤中重金属含量的影响及污染现状,利用相关性系数对其表层土壤中7种重金属(Cu、Zn、Pb、Cr、Cd、Mn、Ni)来源进行研究,并采用内梅罗综合污染指数法和潜在生态危害指数对其污染状况进行评价。结果表明,7种重金属含量平均值均高于内蒙古土壤背景值,其中Cd、Mn、Ni超标率已达100%,而Cu、Pb、Zn的超标率分别为97%、93%和93%,只有Cr超标率较低(53%),污染程度依次为CdPbCuNiZnMnCr,其中Pb和Cd为重度污染,Cu、Zn、Ni为中度污染,Cr、Mn为轻度污染;Cu、Zn、Cr、Mn、Ni可能同时来自工业生产和交通运输两个源,而Pb和Cd除上述来源外,燃煤烟气的排放有较大贡献。潜在生态危害依次为CdPbCuNiCrZnMn,其中Cd的潜在生态风险最大,应予以高度重视,其他金属的风险均为轻微。     

Spectroscopic study of heavy metals sorption on clinoptilolite

Sorption of heavy metal cations (Pb(II), Cr(III), Cd(II), Ni(II)) from aqueous solutions on natural Na-clinoptilolite was studied using atomic absorption spectrometry (AAS) and FT-IR spectroscopy. It was found that the sorption capacity of clinoptilolite decreases in the following order: Pb(II) (22,600 mg/kg), Cr(III) (21,200 mg/kg), Cd(II) (10,400 mg/kg) and Ni(II) (6,200 mg/kg). In the FT-IR spectra of the samples, in the region of pseudolattice vibrations (500–800 cm^–1), systematic changes connected with the type of cation and its concentration in the initial solution were observed. The proportions of ion exchange and chemisorption in the whole process of sorption were also estimated. It was found that the amount of cations sorbed on clinoptilolite depended on the concentrations and pH of the solutions used as well as on the contact time of zeolite-solution system. After 120 min of the reaction, despite the metal type, 90–100% of the total amount of cations were immobilized.     

大亚湾表层沉积物重金属元素形态特征、控制因素及风险评价分析

为了解大亚湾表层沉积物中重金属的污染状况,对大亚湾海域23个点位表层沉积物中7种重金属元素（Cr、Ni、Cu、Pb、Zn、Cd、As）的质量分数、形态特征、来源控制因素以及潜在生态风险进行了研究。采用优化BCR提取法分析重金属元素赋存形态,并依据各种重金属元素的形态特征与沉积物基质属性进行了相关因子分析,了解其分布的控制因素。结果表明：大亚湾沉积物重金属元素呈现环带状分布特征,从岸向湾内逐渐减小;重金属元素质量分数的高值区主要分布于大鹏澳、哑铃湾及范和港附近;重金属元素赋存形态中Cr、Ni、Cu、Zn、As主要以残渣态存在,Pb主要以可还原态存在,Cd主要以酸提取态存在;7种重金属元素各自非残渣态所占比率从大到小为Pb(78.83%)、Cd(78.65%)、Cu(48.54%)、Zn(48.10%)、Ni(38.31%)、Cr(28.43%)、As(27.76%),即Pb最高,As最低,表明Pb的迁移性最强;通过因子分析,大亚湾重金属主要为沿岸自然风化产物的输入,其次为工业废水及养殖污水。运用酸提取态风险评估法对重金属元素潜在生态风险进行评价,发现研究区所选重金属元素综合风险评价Cd为高风险,其余重金属为中-低风险等级。     

Background levels and baseline values of available heavy metals in Mediterranean greenhouse soils (Spain)

This study determines extractable levels of Cd, Cu, Pb, Zn, Ni and Co in western Almería (Spain) greenhouse surface soil horizons using EDTA solution, which is identified as the fraction available for organisms and plants. It also establishes background levels, geochemical baseline concentration and reference values (RV), and investigates the possible relationships between soil properties and elemental concentrations. The results show that the soil concentration of these extractable heavy metals was high as those reported by other authors for Spanish agricultural soils. The available RV concentrations obtained (mg kg⁻¹) were: Cd 0.17, Cu 1.6, Pb 13.8, Zn 5.0 Ni 1.7 and Co 2.9. Using the upper baseline criterion, 95% of greenhouse soils present a relatively higher content of extractable heavy metals given their Cd and Cu concentration. Significant correlations between total and EDTA-extractable metal levels were found for Zn, Pb, Cu, Cd and Ni. Soil properties also related to heavy metals content, suggesting that Cd, Cu, Pb and Zn are of similar origin and relate to anthropic activities, and implies the same interactions and/or relationships among these metals.     

某矿区土壤重金属分布特征及来源解析

为探究赣南某矿区土壤重金属污染状况及来源,以该矿区内40个土壤样品为研究对象,分析了土壤中Cu、Pb、Zn、Cr、Ni、Cd、As和Hg等8种重金属元素的含量,并采用频率直方图、相关性分析、主成分分析等多种统计方法探究了土壤重金属含量的分布特征及来源。研究结果表明:(1)研究区8种重金属中有7种不同程度地超过了江西省土壤重金属元素背景值;(2)Pb、Zn、As和Hg的含量接近正态分布,而Cu、Cr、Ni和Cd的含量则呈现出右偏分布的趋势,这可能与研究区矿山开采活动及土地利用类型等因素有关;(3)矿区土壤重金属相关性分析表明,Cu、Cr、Ni的同源性较高,可能具有相同的污染源,而Pb、Zn、Cd等元素与Cu、Cr、Ni相比,其来源可能存在一定的差异;(4)主成分分析结果显示,矿区内土壤中8种重金属元素含量可以由2个主成分来解释,所代表的实际意义按贡献率排序分别是成土母质和人为采矿活动;(5)矿区内土壤重金属污染物主要为Pb、Zn、Cd,人为采矿活动是这三种重金属污染的主要来源。     

渤海西部表层沉积物中重金属的环境地球化学特征

为探讨渤海西部在多重环境因素变化下沉积物中重金属的环境地球化学行为,分析了渤海西部44个站位表层沉积物样品中8种重金属元素含量,研究了重金属元素的分布特征、环境影响因素及其生态风险。结果表明,渤海西部表层沉积物中As、Cu、Cd、Cr、Hg、Ni、Pb、Zn的平均含量分别为117 mg/kg、255 mg/kg、014 mg/kg、689 mg/kg、0037 mg/kg、303 mg/kg、223 mg/kg、757 mg/kg;Cu、Cr、Ni、Zn含量与有机碳含量、小于63 μm细粒沉积物呈显著正相关,其在表层沉积物中的分布明显受到有机质含量和沉积物粒径的控制,而As、Hg分布没有明显受到有机质含量的影响。富集系数显示,Cr、Ni、Pb和Zn为无富集,Cu、As为轻度富集,Cd和Hg为中度富集。与多种背景值和一致性沉积物质量基准相比较,渤海西部表层沉积物Pb、Cd的含量超出背景值,而Cu、Zn、Ni、Cr、As、Hg含量也存在一定的异常,但其含量水平引发有害生物效应的可能性不大,尽管重金属元素含量偏高,但生态风险较小。     

固体聚合膜电解浓集法测量天然水中低含量氚的化学淬灭效应研究

固体聚合膜电解浓集法是浓缩氚含量较低(1 Bq/m~3)的天然水样的常用方法,但因水样自身含有杂质离子或电解装置聚合膜带入杂质进入浓集液,使浓集液偏酸性,在测量过程中易产生化学淬灭效应,导致氚的测量值偏低。本文研究了水样自身存在的杂质离子和聚合膜上残留的杂质离子、样品溶液的pH值及其电导率所产生的化学淬灭效应的影响,实验表明,为减少化学淬灭效应,提高测量低含量氚的准确性,需保证水样溶液呈中性,电导率≤1μS/cm,同时避免杂质沉积在聚合膜上。如果水样溶液的pH值偏酸性、电导率大于1μS/cm,可采用酸碱混合型离子交换树脂去除水样中自身的杂质;对于聚合膜引入的杂质,可在电解后的水样中加入微量氨水将其pH值调节至中性。     

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。     

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.      

Application of multivariate geostatistics in the investigation of heavy metal contamination of roadside dusts from selected highways of the Greater Toronto Area, Canada

A good understanding of roadside soil contamination and the location of pollution sources is important for addressing many environmental problems. The results are reported here of an analysis of the content of metals in roadside dust samples of four major highways in the Greater Toronto area (GTA) in Ontario, Canada. The metals analyzed are Pb, Zn, Cd, Ni, Cr, Cu, Mn, and Fe. Multivariate geostatistical analysis [correlation analysis (CA), principal component analysis (PCA), and hierarchical cluster analysis (HCA)] were used to estimate soil chemical content variability. The correlation coefficient shows a positive correlation between Cr–Cd, Mn–Fe, and Fe–Cu, while negatively between Zn–Cd, Mn–Cd, Zn-Cr, Pb–Zn, and Ni–Zn. PCA shows that the three eigenvalues are less than one, and suggests that the contamination sources are processing industries and traffic. HCA classifies heavy metals in two major groups. The cluster has two larger subgroups: the first contains only the variables Fe, Mn, Cu, Cr, Ni, and Pb, and the second includes Cd and Zn. The geostatistical analysis allows geological and anthropogenic causes of variations in the contents of roadside dust heavy metals to be separated and common pollution sources to be identified. The study shows that the high concentration of traffic flows, the parent material mineralogical and chemical composition, and land use are the main sources for the heavy metal concentration in the analyzed samples.     

内江市双桥乡土壤重金属含量及风险评价

以四川省内江市双桥乡为研究区域,调查分析各类土壤中重金属（Cu、Pb、Zn、Cd、Cr、As、Hg、Ni）含量情况。采用单因子污染指数、内梅罗综合污染指数和富集因子评价方法,对土壤重金属污染状况进行评价。研究结果表明,该地区Cd、Cr、Cu、Ni、Pb、Zn元素平均含量高于成都经济区、四川省、中国土壤背景值,有一定程度的Cd、Cr、Cu、Ni、Pb、Zn富集,Hg元素有个别样点含量偏高,并且单因子重金属的污染程度依次为：Cd〉Ni〉Zn〉Cu〉Cr〉Pb〉As〉Hg,Cd在绝大部份区域存在轻微污染,由内梅罗污染指数和富集因子评价得出区域综合污染程度为轻度。     

Heavy metals in mangrove sediments of the central Arabian Gulf shoreline,Saudi Arabia

To assess heavy metals in mangrove swamps of Sehat and Tarut coastal areas along the Arabian Gulf, 18 sediment samples were collected for Al, V, Cr, Mn, Cu, Zn, Cd, Pb, Hg, Sr, As, Fe, Co, and Ni analysis. The results indicated that the distribution of some metals was largely controlled by anthropogenic inputs, while others were of terrigenous origin and most strongly associated with distribution of aluminum and total organic carbon in sediments. Mangrove sediments were extremely severe enriched with Sr (EF?=?67.59) and very severe enriched with V, Hg, Cd, Cu, As (EF?=?44.28, 37.45, 35.77, 25.97, and 11.53, respectively). Average values of Sr, V, Hg, Cd, Cu, Ni, As, and Cr were mostly higher than the ones recorded from the Mediterranean Sea, the Red Sea, the Gulf of Aqaba, the Caspian Sea, the Arabian and Oman gulfs, coast of Tanzania, sediment quality guidelines, and the background shale and the earth crust. Landfilling due to coastal infrastructure development around mangrove forests, oil spills and petrochemical and desalination effluents from Al-Jubail industrial city to the north were the anthropogenic activities that further enhanced heavy metals in the studied mangrove sediments.     

安徽铜陵水木冲尾矿重金属赋存状态及污染特征研究

为探讨富硫化物尾矿酸化及重金属污染特征,选择安徽铜陵水木冲尾矿库浅层(0～90 cm)剖面为研究对象,对其结构特点、矿物组成、重金属(Pb、Cd、Zn、Ni、Cr、Mn、Cu和As)含量及赋存形态进行研究。结果表明,该尾矿库浅层出现分层现象,即表层为强硬化层,向下依次为弱硬化层和松散层,且呈酸性;矿物主要以辉石、长石、云母和石膏为主,由浅及深,金属硫化物及碳酸盐型矿物特征峰呈现增强的趋势;重金属呈现两种富集类型:表层(0～30cm,As、Pb)富集和中部(40～60 cm,Cd、Cu、Mn、Ni、Zn和Cr)富集型,其中Cu、Cd、As污染较为严重。由相关性分析可知,部分金属之间存在一定的伴生性,且p H值是影响重金属迁移的重要因素之一。该尾矿重金属主要以残渣态为主,其中Pb的潜在迁移能力最强,As最弱,顺序为Pb Cd Zn Ni Cr Mn Cu As。     

Simultaneous adsorption of divalent and trivalent metal cations by iron oxide-coated gravel

Reducing heavy metal concentrations to allowable levels in landfill leachate before discharge is an extremely important process to prevent environmental pollution. Iron oxide-coated gravel was used in order to remove Cd(II), Cu(II), Pb(II), Fe(III) and Al(III) simultaneously in high-strength synthetic leachate samples. Batch and column studies were performed to determine the kinetics and mechanism of adsorption process. The experimental data obtained from batch study satisfactorily fitted to the Freundlich model indicating surface heterogeneity and multilayer adsorption process. The data obtained from kinetic studies followed the pseudo-second-order kinetics indicating adsorption governed by chemisorption. The metal adsorption order observed in the batch study was Pb(II)(99.72%) ≈ Cu(II)(99.61%) ≈ Cd(II)(99.51%) ≈ Fe(III)(99.3%) > Al(III)(93.3%) at pH 7. Average metal removals in the fixed-bed column were found to be 96.5% for Cu(II), 94.8% for Pb(II), 90% for Cd(II), 84% for Fe(III) and 67% for Al(III). Iron oxide-coated gravel column adsorption capacity ranged from 0.56 to 66.82 mg/g. Recovery efficiency of adsorbed metals via desorption was between 5–97.75% in first cycle and 2–80.3% in second cycle.     

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.