典型铜镍矿区周围环境介质中重金属及其化学形态分布特征

重金属污染是金属矿山开采和冶炼所引起的主要环境问题。对甘肃省典型矿业城市金昌市周围农田土壤、废渣堆表面风化物及降尘、尾矿坝尾矿砂和尾矿坝旁排污沟沉积物中Cr、Cu、Ni、Pb、Zn含量及其化学形态进行分析。结果表明:不同区域环境中重金属呈现不同程度累积,其中以Cu、Ni最为显著,含量由高到低依次为尾矿坝排污沟>尾矿坝>废渣堆>农田土壤;尾矿砂和沉积物中重金属分布以Ni含量显著高于Cu含量为特征;而农田土壤和风化物及降尘中重金属分布以Cu含量高于Ni含量为特征,前者Cu、Ni主要来源于尾矿,后者与冶炼烟尘排放有很大关系;样品中除Cr、Zn以残渣态为主外,Cu、Ni、Pb化学形态分布有较大差异,Cu以可氧化态和残渣态为主,Ni以可还原态为主,其次为弱酸提取态,Pb以可还原态为主,其次为残渣态。土壤理化性质是影响重金属化学形态分布的重要因素。     

基于形态学分析铅锌矿不同功能区土壤重金属元素的分布特征及污染评价

为掌握尤溪铅锌矿区土壤重金属元素分布特征和污染现状,通过采集尤溪铅锌矿不同功能区0~20cm表层土壤样品,测定土壤中Pb、Zn、Cd、Cu、Cr 5种重金属元素的总量及其化学形态,分析不同功能区土壤重金属污染及分布特征,同时采用次生相与原生相比值法(RSP)进行污染评价。结果表明,尤溪铅锌矿不同功能区土壤中Pb、Zn、Cd含量均超过国家土壤环境质量三级标准,废弃冶炼区土壤Cd、Cu、Pb、Zn含量均最高,分别为标准值的14.78、1.13、3.73、1.34倍,采矿区Cr含量最高,但未超过标准限值。重金属形态结果表明,相比其他元素,Cd弱酸提取态所占比例最高,Cu可交换态比例最高,Pb、Zn、Cr以残渣态为主。RSP法评价表明,不同重金属的污染程度表现为:Cu(1.15)Cd(0.80)Pb(0.59)Zn(0.57)Cr(0.54);不同功能区土壤重金属污染表现为:尾矿库区冶炼区废弃冶炼区采矿区。SPEF法评价表明,尤溪铅锌矿区受人为污染明显,采矿区和尾矿库区Zn污染最为严重,冶炼区和废弃冶炼区Pb污染最为严重,功能区污染顺序为:尾矿库区冶炼区废弃冶炼区采矿区。     

成都经济区黄壤土壤剖面Pb形态分布特征及其影响因素

土壤剖面中不同形态铅迁移转化及其影响因素的研究对于了解Pb的土壤地球化学行为具有非常重要的意义。以四川省成都经济区农田生态系统黄壤剖面中不同形态Pb分布特征为例,探讨黄壤剖面中不同形态Pb的迁移转化影响因素及其生态危害性。结果表明:在黄壤剖面中,Pb总量表现为表层富集、深层稳定的特点;弱有机结合态含量表现为表层富集、深层稳定的特点,其他形态Pb含量剖面分布特征不明显;土壤中的Pb主要是以铁锰氧化态和残渣态为主,其他形态Pb含量所占比例较小;成土过程中,随着Pb总量的增加,稳定态Pb含量增加,而活动态相对减少;土壤pH值对各形态Pb含量分布影响较大,尤其是对碳酸盐结合态的影响显著;土壤总有机碳也是影响土壤中各形态Pb含量分布的重要因素之一,尤其是对有机结合态Pb含量影响显著;而随着土壤熟化程度的增加,黄壤剖面中的活动态含量增加,稳定态减少;剖面中的Pb迁移系数和生物可利用系数均较小,说明Pb不易向下迁移,容易在表层富集,对植物及人类有一定的危害。     

珠江三角洲平原区土壤Pb元素地球化学特征及其影响因素研究

以珠江三角洲平原为研究区域,对其7个区县102件水稻根系土样品进行土壤理化参数及Pb形态分析,探讨在第四系分布区土壤Pb全量及Pb活动态含量的特征及影响因素。结果表明:全部供试土壤样品中Pb元素平均含量为46.47mg/kg,略高于广东省土壤Pb含量背景值(36mg/kg),表现出一定的累积趋势。研究区自西北陆相沉积区至南部海陆交互相沉积区,元素含量增高。Pb元素主要以残渣态和铁锰氧化物形态赋存在土壤中,迁移能力弱。影响土壤Pb全量的因素主要有Al2O3、K2O、Tl、Mo;影响土壤Pb活动态的因素有Pb全量、pH、有机质、CEC、P、TFe2O3、Mn;其中,p H是控制Pb元素活动性的最主要因素。     

山东烟台金矿区及城镇周边土壤重金属化学形态分布及转化

土壤中不同形态重金属及其转化的影响因素研究对于了解重金属的地球化学行为具有重要意义。以山东烟台金矿区及城镇周边典型土壤为例,探讨了土壤中不同形态重金属与土壤有机质、黏粒、磁化率和pH值的关系及其生态危害性。结果表明:土壤中大多数重金属以残渣态和铁锰氧化态存在,而Cd以离子交换态为主;土壤酸化可使Ni、Zn、Cd、Hg的活动态含量增加;对于Pb污染严重的土壤,使土壤pH维持在中碱性环境,可以降低Pb危害;防止土壤盐碱化是消除土壤As污染的有效措施;土壤有机质含量增加可明显降低Pb、Hg、Ni等活动态含量,随黏粒含量增加,Pb、Zn等离子交换态含量占总量的比例略有减小;土壤磁化率对了解土壤酸化的状况和土壤污染程度有较好的指示作用。     

南京城市土壤某些元素的富集特征及其对浅层地下水的影响

本研究以南京市的公园、校园绿地、道路绿地和郊区菜地等不同功能区的土壤为对象,对土壤的磷素和重金属以及一些土壤剖面点位的地下水组成进行了分析.研究发现城市土壤构成了区别于自然背景的某些元素(如磷和重金属)的地球化学垒,形成了明显的元素富集区域,其中磷素含量是背景土壤的数倍甚至十数倍,Pb含量也远高出背景土壤,60%以上样品达到中等污染程度以上.从磷素在剖面中的积累模式可以看出,城市土壤中磷含量最高的层次出现在表层以下的不同深度,说明土壤经历了不同的扰动过程,这意味着在城市发展过程中,土壤的性质遭受强烈的人为活动影响,元素在土壤中的分布形态可以指示不同的利用历史.质量改变后的土壤对地下水等环境产生影响,使地下水的组成发生改变,其中磷素含量直接受到土壤的影响,效区菜地地下水中硝态氮含量极高,而本研究尚未发现地下水中的重金属含量与土壤有显著相关.     

河北平原农田土壤重金属元素Pb、Hg地球化学行为的影响因素

土壤重金属元素地球化学行为是目前国内外研究的热点。研究显示重金属元素地球化学行为与土壤理化性质有密切关系。本文选择河北平原农田为研究区,采集了325个根系土样品,测定了Pb、Hg有效态含量,并探讨了影响其地球化学行为的主要因素。研究表明:(1)Pb、Hg水溶态和离子交换态与土壤p H值呈显著负相关关系,土壤酸化使Pb、Hg有效性增加,直接导致农作物中Pb、Hg含量增加,保持土壤p H值在弱酸性至弱碱性范围,防止土壤酸化,可以降低重金属危害。(2)土壤中有机质含量与Pb、Hg全量呈显著的正相关性,但与水溶态和离子交换态呈负相关。所以土壤中有机质的增加可以降低Pb、Hg元素水溶态和离子交换态含量。(3)随着土壤黏粒的增加,Pb、Hg水溶态和离子交换态含量降低,说明黏粒可以吸附一定量的重金属离子,与重金属元素Pb、Hg地球化学行为存在一定关系。土壤p H值、有机质、黏粒是控制重金属元素Pb、Hg地球化学行为的重要因素。     

广东省揭阳市土壤铅的空间分布特征及影响因素

以广东省揭阳市土壤为研究对象,采集了表层土壤(0~20 cm)样1 330个和深层土壤(>150 cm)样331个,测定了土壤Pb含量。利用GIS空间分析技术、半变异函数拟合和方差分析等方法研究土壤Pb含量的空间结构、特征和影响因素。结果显示: 揭阳市不存在明显的土壤Pb污染,表层土壤Pb含量平均值39.26 mg/kg,低于揭阳市土壤Pb背景值(43.71 mg/kg),略高于广东省土壤Pb背景值(36.00 mg/kg);富集因子表明研究区表层土壤Pb富集程度主要为无富集和轻微富集,分别占52.11%和42.63%,Pb富集不明显;研究区表层土壤Pb空间分布呈中等自相关性;表层土壤Pb高值区主要分布在人类活动影响强烈的东部和南部地区。按土地利用、成土母质、土壤类型及其理化性质的分类统计表明,林地及未利用地表层土壤Pb含量最高;页岩风化形成的土壤Pb含量显著高于其他成土母质区土壤;黄壤Pb含量相对较高;有机碳和pH值均与土壤Pb含量呈显著正相关。     

长春市城市土壤铅同位素组成特征及其来源解析

为查明长春市土壤铅的污染来源,采集了长春市表层(0～20 cm)土壤及城市环境污染端元(燃煤尘、汽车尾气尘,建筑尘)样品,采用X荧光光谱法(XRF)测定土壤Pb含量,用质谱仪测定各样品的铅同位素组成.分析结果表明,长春市表层土壤Pb平均质量分数44.72×10-6,是长春市土壤背景值(19.06×10-6)的2.35倍,已受到一定程度铅污染;长春市土壤铅同位素208Pb/207Pb和206Pb/207Pb比值变化较大,分别为2.249～2.473和1.158～1.213;各污染端元物质铅同位素组成差异较大,能很好区别各端元物质.运用铅同位素示踪技术追踪土壤铅的污染来源结果表明,长春市中心城区土壤铅污染主要来源于以热电二厂为代表的工业燃煤排放和历史汽车尾气残留,而与当前汽车尾气排放关系不大;建筑尘也一定程度上对城市土壤产生了影响.     

改进BCR法-电感耦合等离子体发射光谱法测定矿产品堆场土壤中镉砷铅的化学形态

矿产品堆场土壤中重金属在环境中富集,随着元素的迁移、转化及地下水的循环,成为环境污染问题。本文将改进的顺序提取法(BCR)应用于矿产品堆场土壤中Cd、As、Pb的化学形态分析,结合这三种元素的性质,将堆场土壤中Cd、As、Pb分为可交换态、可还原态、可氧化态和残渣态,并利用电感耦合等离子体发射光谱法测定其含量。采用形态分析标准参考物质GBW 07436验证了三步提取态的准确性,并对6个矿产品堆场土壤中Cd、As、Pb形态含量进行分析,三步提取态加上残渣态质量分数之和与重金属总量进行了比较,回收率为85.54%~102.88%。通过对矿产品堆场土壤实际样品分析,Cd、As、Pb三种元素非残渣态含量顺序为Cd(79.40%~94.94%)Pb(24.27%~37.73%)As(22.89%~31.51%),表明Cd元素较为容易进入生物圈。该方法解决了港口堆场土壤中重金属化学形态提取问题,对污染土壤的治理具有指导意义。     

Heavy metal contamination of urban soils and street dusts in Hong Kong

Due to rapid urbanisation and scarcity of land, most of the urban parks and recreational areas in Hong Kong are built close to major roads or industrial areas, where they are subject to many potential pollution sources, including vehicle exhaust and industrial emissions. An extensive soil survey was conducted in urban parks of Hong Kong to study the current conditions of heavy metals contamination in soils. Soil samples and associated street dusts were collected from more than 60 parks and public amenity areas in old urban districts, industrial areas and New Towns of the territory. Soils were also sampled in the remote country parks to establish the baseline conditions. The total concentrations of heavy metals and major elements in the samples were determined. The results indicate that urban soils in Hong Kong have elevated concentrations of Cd, Cu, Pb and Zn. The parks with high metal concentrations are located in old urban commercial districts and industrial areas, indicating that the major contamination sources in these soils are traffic emissions and industrial activities. In addition, the application of Cd containing phosphate fertilizers may be an important source of Cd in urban park soils. The street dusts have highly elevated Zn concentration, particularly along the main trunk roads. The high Zn content in the street dusts may come from traffic sources, especially vehicle tyres. Selective soil and road dust samples were also analysed for potential chemical speciation by a sequential chemical extraction method. The chemical partitioning results show that Pb and Zn are mainly in the carbonate/adsorbed and Fe–Mn oxide phases, while Cu is largely associated with the organic and sulphide fractions. The high exchangeable Cd in urban soils and high concentration of Zn in street dusts need further investigation for their ecological and health implications.     

Characteristics of distribution and chemical speciation of heavy metals in environmental mediums around Jinchang mining city,Northwest China

Heavy metal contamination was the main environmental problem around the Jinchang Ni–Cu mine area of Gansu, Northwest China. The concentration of heavy metals (Cr, Cu, Ni, Pb, and Zn) in various environmental mediums around the Jinchang Ni–Cu mine area were analyzed using atomic absorption spectrometry (AAS). The different chemical speciation of heavy metals was extracted using BCR (European Community Bureau of Reference) sequential extraction procedure, and the concentration of chemical speciation of each heavy metal was measured by inductively coupled plasma-atomic emission spectrometry. The results showed that Cu and Ni were the most important heavy metal pollutants in various mediums including cultivated soils, dust on slagheap surfaces, tailings, and sediments in waste water drains. In the tailings and sediments, the concentrations of Ni were obviously higher than those of Cu, whereas, in the soil and dust, the concentrations of Cu were higher than those of Ni. Analysis of chemical speciation indicated that Cr and Zn were mainly in residual fraction; Cu was mainly in oxidizable fraction; Ni was mainly in reducible fraction and acid soluble fraction; and Pb was mainly in reducible fraction and residual fraction. The extent of contamination of various environmental mediums was different because the heavy metals were derived from different sources. Furthermore, the mobility of various heavy metals was different because of the different distribution of chemical speciation.     

冻融作用对黑土和棕壤中Pb、Cd吸附/解吸特征的影响

冻融作用对土壤理化性质具有重要影响,进而影响了土壤中重金属迁移转化过程和环境效应。通过实验模拟研究了冻融作用对黑土和棕壤中Pb、Cd吸附/解吸特征的影响。结果表明：黑土对Pb和Cd的吸附能力大于棕壤;冻融作用降低了土壤对Pb和Cd的吸附能力,这与冻融作用改变了土壤的理化性质有关;随着Pb和Cd吸附量的增大,黑土和棕壤中Pb和Cd的解吸量和解吸率也相应增大;冻融作用促进了黑土和棕壤中Pb和Cd的解吸,并且在同一冻融条件下黑土的解吸能力小于棕壤;冻融作用使得黑土和棕壤对Pb和Cd的解吸量大于未冻融土壤,这与冻融作用使解吸溶液pH的下降幅度增大有关。冻融作用降低了土壤对Pb和Cd的固持能力,增加了土壤中Pb和Cd的生态风险。     

The effect of traffic on levels,distribution and chemical partitioning of harmful metals in the street dust and surface soil from urban areas of Tehran,Iran

Due to the explosive industrialization and rapid expansion of the population in many parts of the world, heavy metals are released into the environment continuously and pose a great risk on human health. Street dust and surface soil samples from very heavy, heavy, medium and low traffic areas and a natural site in Tehran, Iran, were analyzed for some physicochemical features, total and chemical fractionating of selected metals (Zn, Al, Sr, Pb, Cu, Cr, Cd, Co, Ni and V) to investigate the influence of traffic on their mobility and accumulation in the environment. The pH, electrical conductivity (EC), carbonates and organic carbon contents were similar in soil and dust samples from the areas with same traffic. The traffic increases EC contents in dust/soil matrixes, but has no effect on concentrations of metals in soil samples. Rises in metal levels with traffic were found in dust samples. Moreover, the traffic increases the percentage of both acid-soluble and reducible fractions, which are related to Pb and Zn. The mobilization of Cu, Zn, Pb, Cr in dust samples was easier than in soil. The speciation of metals except Cd is mainly affected by physicochemical features in soil, though total metals affected the speciation in dust samples (except chromium and nickel).     

TEM-EDX investigation on Zn- and Pb-contaminated soils

Lead and zinc contaminated soils from a smelter area in the northern part of France have been studied by transmission electron microscopy (TEM). This study was carried out with 4 different soils contaminated by Pb and Zn but with different chemical and physical characteristics. Two soils are tilled and have a neutral or slightly basic pH, one is a wooded soil and the last one is a meadow soil with acidic pH and high total organic content . TEM images of the soil samples have been coupled with focused energy dispersive X-ray (EDX) analyses and chemical mapping on a few micron-sized windows. This study demonstrates that TEM is a particularly efficient method to investigate metal speciation in the fine fractions of the contaminated soils. Zinc could be detected locally in sulphide minerals probably coming from the smelter emissions, but the major phases retaining Zn are Fe-oxyhydroxides and smectites. Lead could be detected in small aggregates which were characterized by EDX and selected area electron diffraction. Their structural formulae correspond to a pyromorphite-like mineral in which Pb is partly substituted by Ca and Na. Pyromorphite is present only in the wooded and meadow soils where it forms partly from amorphous Si-rich phases (slags) coming from the smelter. These results are compared with data previously obtained by spectroscopic methods on the same samples.     

Geochemistry of lead contaminated wetland soils amended with phosphorus

To remediate Pb contaminated soils it is proposed that phosphorus can be amended to the soils to transform the Pb into poorly soluble Pb-phosphate mineral phases. However, remediation strategies must account for variable Pb speciation and site-specific factors. In this study soil mineralogy and Pb speciation in soils from P-amended field trials at sites within the Coeur d’Alene River Basin in Idaho, USA were investigated. The soils are contaminated from mining activities and are enriched with Fe and Mn. Selective extraction of the soils indicated that the Fe oxides are poorly crystalline. XRD of the soil clay size fractions identified quartz, muscovite, kaolinite, siderite, lepidocrocite, and chlorite minerals. Amendment with P fertilizer dissolved the siderite. No Pb–phosphate minerals were detected by XRD. Electron microprobe analysis showed direct correlations between Pb, Fe, and Mn in the unamended soils, and negative correlations between Pb and Si. Lead and Mn were strongly correlated. In the amended soils Fe and P were strongly correlated. Results indicate that the Pb is associated with poorly crystalline Fe and Mn oxides, and that added P is primarily associated with Fe oxide phases. Comparisons of pore water Pb concentrations with chloropyromorphite and plumbogummite solubility suggest that in the phosphate-amended soils the pore waters are undersaturated in these phases, whereas several of the control soil pore waters were oversaturated, indicating the added phosphate suppressed the Pb solubility. Results from this research provide insight into the geochemistry occurring in the P-remediated soils that will help in making management and remediation decisions.     

土壤重金属连续提取方法的优化

重金属在污染土壤中的形态分布决定着重金属的迁移性和危害的程度。土壤重金属形态分析应用最多的是Tessier和BCR连续提取法。Tessier和BCR连续提取法没有考虑土壤样品的特征。美国环保署危险废物浸出毒性鉴别标准法虽然考虑土壤pH值,但没有划分形态。采集不同pH土样,结合Tessier、BCR和毒性浸出鉴别方法的特征,优化出针对不同pH值土壤的连续提取方法,将土壤中重金属划分为活性态、次生碳酸盐结合态、次稳定态和稳定态。用优化的连续提取方法对土样进行连续提取,重金属回收率为85%~115%。优化连续提取方法的结果与Tessier和BCR结果对比显示优化连续提取方法克服了Tessier连续提取法对非石灰质土壤提取过量BCR连续提取法对石灰质土壤提取不足的缺点。优化后的连续提取方法数据稳定可靠,可作为重金属形态分析方法使用。     

The mobility,bioavailability, and human bioaccessibility of trace metals in urban soils of Hong Kong

Trace metals in soils may pose risks to both ecosystem and human health, especially in an urban environment. However, only a fraction of the metal content in soil is mobile and/or available for biota uptake and human ingestion. Various environmental availabilities of trace metals (Cu, Pb and Zn) in topsoil from highly urbanized areas of Hong Kong to plants, organisms, and humans, as well as the leaching potential to groundwater were evaluated in the present study. Forty selected soil samples were extracted with 0.11 M acid acetic, 0.01 M calcium chloride, 0.005 M diethylenetriaminepentaacetic acid, and simplified physiologically based extraction tests (PBET) for the operationally defined mobilizable, effectively bioavailable, potentially bioavailable, and human bioaccessible metal fractions, respectively. The metals were generally in the order of Zn > Cu ∼ Pb for both mobility (24%, 7.6%, 6.7%) and effective bioavailability (2.8%, 0.9%, 0.6%), Pb (18%) > Cu (13%) > Zn (7.4%) for potential bioavailability, and Pb (59%) ∼ Cu (58%) > Zn (38%) for human bioaccessibility. Although the variations in the different available concentrations of metals could mostly be explained by total metal concentrations in soil, the regression model predictions were further improved by the incorporation of soil physicochemical properties (pH, OM, EC). The effectively bioavailable Zn and Pb were mostly related to soil pH. Anthropogenic Pb in urban soils tended to be environmentally available as indicated by Pb isotopic composition analysis. Combining various site-specific environmental availabilities might produce a more realistic estimation for the integrated ecological and human health risks of metal contamination in urban soils.     

Anthropogenic Pb accumulation in forest soils from Lake Clair watershed: Duchesnay experimental forest (Québec, Canada)

Mineral soil horizons (Ae, Bhf1, Bhf2, Bf, BC and C) were carefully collected from two podzolic soil profiles in the Lake Clair watershed (Québec) in order to assess anthropogenic trace metal accumulation. Petrographic and selective analyses were performed to establish the soil mineralogy and properties. Furthermore, a complete sequential extraction procedure has been applied to help understanding the complex chemical speciation of Pb in forest soils. Chemical speciation of Pb showed a strong vertical gradient: 85% of this metal is mainly partitioned in refractory minerals in the C-horizon whereas in the upper Bhf1 and Ae-horizons, less than 50% of Pb is associated with this fraction. In the Ae-horizon, for example, 35%, 30% and 12% of total Pb, respectively, is associated with the exchangeable, labile organic matter and amorphous Fe-Mn oxides fractions. The distribution of Pb and Cr in the studied forest soils mainly reflects progressive contamination of the watershed by anthropogenic atmospheric sources. The anthropogenic source is indicated by elevated Cr and Pb concentrations in the topsoil (Bhf and Ae) horizons and by strong negative correlation between ²⁰⁶Pb/²⁰⁷Pb ratios and total Pb concentrations. According to these isotopic values, penetration of anthropogenic Pb does not exceed 10 cm in both soil profiles. Below this depth, both Pb concentrations and isotopic ratios remain nearly constant and similar to values observed in pre-anthropogenic sediments from Lake Clair. These values are interpreted as the natural geochemical backgrounds of the watershed. Based on that behaviour, calculated anthropogenic Pb net inputs amounted to between 1.24 and 1.8 g/m².     

用微生物对单一碳源利用方法探讨重金属在城市土壤中积累的环境效应

Biolog研究表明，英国阿伯丁市城市土壤的微生物群落结构显著有别于农村土壤，并使微生物对碳源的消耗量增加，消耗速度加快。城市土壤中不仅重金属Cu,Pb,Zn,Ni的含量明显高于农村土壤，而且其化学形态的主成分分析表明，有效态Pb,Zn,Cu及有机态Ni和Cu是导致城市土壤区分于农村土壤的主要因子。相关性分析表明，Biolog的这种变化规律与重金属的上述化学形态密切相关；典型变量分析表明，重金属对城市土壤微生物群落结果的这种损伤具有长期性效应及不可恢复性。