大型金属矿山不同环境介质中重金属元素化学形态分布特征——以甘肃金昌市和白银市为例

重金属元素在环境介质中的存在形态及各形态比例是决定其迁移性和生物可利用性的重要因素.采用BCR法连续提取过程对大型金属矿山周围土壤和水体沉积物中Cd、Cr、Cu、Ni、Pb和Zn化学形态的分析结果表明,土壤和水体沉积物中不同重金属元素化学形态分布有很大差异.总体而言,Cd以弱酸提取态为主(约占60%),Cr以残渣态为主,占90%以上,Cu以可氧化态为主(约占60%),Ni和Pb以可还原态为主,分别约占50%和60%,Zn以残渣态为主,约占45%.不同区域土壤中重金属元素各形态质量分数之和依次为厂区外围>尾矿坝旁>农田,各形态分布也与总量具有相似的变化趋势.金昌市矿山环境介质中重金属以Cu和Ni为主,白银市以Cd、Cu和Pb为主,重金属元素的生物可利用态和潜在可利用态质量分数高,平均约占各金属,总量的60%～90%,对周围环境具有很大的潜在生态危害性.     

巢湖沉积物镉等重金属地球化学分布、赋存特征及危害性研究

对巢湖表层沉积物中8种重金属元素的分布特征和生态风险进行了研究和评价。结果表明：沉积物中Hg、Cd含量总体高于背景值,其中西部沉积物中重金属含量明显高于中东部湖区,并表现出多元素复合污染特征;Hakanson潜在生态危害指数表明巢湖沉积物重金属生态危害变化于轻微-强危害程度,以西北部湖区最为严重,Hg和Cd是主要影响因子,其它元素生态危害性较小;沉积物中As、cd、Hg、Pb元素主要以残渣态（非有效态）形式存在,但沉积物中腐殖酸态的As和Hg、铁锰氧化态的Pb、离子态的Cd占总量比例较高,其中又以Cd易利用态比例最高,生物有效性最强,具有较高的生态危害风险。     

土壤重金属污染现状及检测分析技术研究进展

土壤重金属污染是中国当前最突出的环境污染问题。污染调查公报显示全国土壤重金属总超标率为16.1%,其中镉的点位超标率为7%,对粮食安全产生威胁。本文介绍了中国土壤重金属污染的现状,梳理了土壤重金属污染检测分析的传统和新兴方法技术,包括重金属全量、化学形态和生物可利用态含量等。同时阐述了土壤重金属污染检测分析技术发展趋势,如分子水平上的重金属元素检测和生物传感技术应用于重金属元素检测。考虑到土壤系统的复杂性,未来发展的重点应实现地学、化学和生物学的交叉,加强重金属生物有效性的理论研究,形成土壤重金属污染的生物有效度分析检测指标体系,使评价方法科学化、标准化、统一化。进一步推动我国的有关分析测试技术标准与国际标准接轨。     

长江口吴淞-浏河滨岸带沉积物AVS和SEM含量的空间分布特征

对长江口吴淞-浏河滨岸带37个站位沉积物中酸可挥发性硫化物（AVS）和同时可提取态重金属（SEM）含量及其空间分布特征进行了研究。结果表明,SEM在37个站位沉积物中浓度范围为0．20～1．37μmol／g,平均值为0．74μmol／g;AVS的浓度范围为0．20—0．80μmol／g,平均值为0．23μmol／g;沉积物中AVS含量与总有机碳（TOC）和含水率呈显著正相关关系,而SEM分别与TOC和含水率呈显著正相关关系,与沉积物中值粒径呈显著负相关关系。依据SEM／AVS比值评价方法以及美国EPA（SEM—AVS）差值评价方法对沉积物中重金属的生物有效性的判断表明,除了B2站点无显著生物毒性外,吴淞-浏河滨岸带沉积物中重金属对水生生物均处于中等毒性水平。     

土壤中重金属有效态分析方法研究

土壤中重金属的不同形态决定了对于生物的有效性。自然界的重金属元素参与生态迁移能够被生物吸收利用的部分为生物有效态。土壤重金属可交换态的研究可以为其生物有效态研究提供参考。本文对于土壤中砷、汞、铬、镉、铅和铊的酸溶态、络合态和盐溶态这几种单一提取方式的可交换态的分析方法进行了研究比较,以其提取效率高的为有效态的表现方式,以p H值7.5为土壤酸碱度的界限,建立了土壤中的砷、汞、铬、镉、铅和铊在不同酸碱度下的分析方法。本方法的Cr的方法检出限为4.65ng/g;Cd的方法检出限为0.49ng/g;Pb的方法检出限为9.73ng/g;As的方法检出限为21.89ng/g;Hg的方法检出限为0.30ng/g;Tl的方法检出限为0.54ng/g。采用GBW7412,GBW7413,GBW7416这三个国家一级标准物质样品测得的方法精密度范围6.01%~19.3%。本方法适用于土地质量评估的要求。     

土壤重金属生物有效性研究进展

土壤重金属污染具有巨大环境风险。笔者围绕土壤重金属元素生物有效性(可给性)概念、元素形态与有效性影响因素、有效态(可给态)实验技术,综述了国内外研究现状。土壤金属元素形态和生物有效性取决于其地球化学行为、元素成因来源、土壤理化条件(p H值、有机质、粘土矿物与化学活性矿物、土壤粒级组成等)以及植物根际效应等。选择性单步提取和连续提取是检测土壤元素形态、有效态的有效和可行方法。针对手—口是土壤铅等污染物在儿童群体暴露的重要途径,发展了生物可给态体外试验方法。土壤污染物生物有效性和可给性已成为土壤污染风险评价的重要指标参数,实验成果也为土壤污染修复提供了重要依据。     

矿区土壤中重金属活动性评估方法的研究进展

在过去很长一段时间里重金属含量的高低一直都被看作是土壤污染程度的一个重要指标。当化学相的概念被引入到环境科学领域后，人们才逐渐地认识到重金属在环境中的行为和作用，如活动性、生物可利用性、毒性等，用这些金属在环境中的总量来预测和解释是不确切的。为此，许多化学和生物的方法被用来描述土壤与沉积物中重金属的活性。文章对近年来在该领域内的主要研究工作进行了总结，并对其未来可能的发展方向提出了自己的见解。     

海南土壤中Zn、Pb、Cu、Cd四种重金属含量及其生物有效性的研究

对海南0个土壤样品中的nl、Pb、Cu、0四种重金属的总量和生物有效态含量以及45个植物样(根、茎、叶)中的重金属含量分别进行了测定，采样点基本上覆盖了海南全省，测定结果表明，土壤中nl总量低于全国平均值，而Pb、Cu、Cd高于全国平均值，土壤中重金属生物有效态含量一般低于其总量的10％，其中Pb最高为7．71％，而Cu仅为1．13％，具有较大的变异性；植物中重金属含量与土壤中重金属总量呈现负相关性，但与土壤中有效态重金属含量一般呈现正相关性，叶中的重金属含量与土壤中有效态重金属含量之间的相关性更为显着，叶中的重金属含量与土壤中有效态重金属含量之间的相关系数分别为：Zn(0．726)，Cu(0．626)，Pb(0．n4)，Cd(0．512)。这说明土壤中重金属总量并不能全面的评价土壤的环境效应和重金属的生物有效性，应该把重金属总量和生物有效态含量结合起来加以研究，并应将土壤中重金属的含量与植物中该元素含量之间作相关分析，根据其相关系数的大小来判断其生物有效性的程度。     

土壤中重金属有效态分析技术研究进展

土壤重金属有效态含量作为评价土壤污染程度的指标越来越被认可,为了更好地研究土壤中重金属有效态的分析测试方法,本文综述了近年来土壤中重金属有效态分析技术研究进展。重点阐述了单步提取法、连续提取法,对单步提取法中中性盐、络合剂、酸溶液三类提取剂、电感耦合等离子体等仪器分析方法进行综述。建立有效、准确的土壤中重金属有效态的测试方法,以及标准物质等方面的研究,将为土壤污染风险评估及土壤污染修复工作起到指导作用。     

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。     

Evaluation of phosphorus bioavailability in sediments of the shallow lakes in the middle and lower reaches of the Yangtze River region,China

Phosphorus (P) fractions and their bioavailability in the sediments from the middle and lower reaches of the Yangtze River region were investigated using different chemical extraction methods. The results show that the contents of bioavailable P in the sediments extracted by different extraction procedures varied greatly. But their rank order was similar. Potentially releasable P (PRP) was the largest, followed by algal available P (AAP), NaHCO₃ extractable P (Olsen-P), water soluble P (WSP), and readily desorbable P. PRP contributed approximately 60% to total P (TP) in most sediments, AAP 20%, Olsen-P 15%, WSP 2%, and readily desorbable P (RDP) 0.5%. For the heavily polluted sediments, their bioavailable P extracted from TP mainly originated from inorganic P (IP), IP mainly originated from NaOH–P, the bioavailable P concentrations can be evaluated by measuring the concentrations of TP, NaOH–P, and IP. For the slightly polluted sediments, the bioavailable P can only be evaluated by different chemical extractable methods.     

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.     

Screening of extraction methods for Cd and As bioavailability prediction in rhizospheric soil using multivariate analyses

Heavy metals in tailings and mining wastes from abandoned mines can be released into adjacent agricultural field and bioaccumulated in crops or vegetables. Therefore, prediction of metal bioavailability has become an important issue to prevent adverse effect of bioaccumulated metals on human health. In this study, single and sequential extraction methods were compared using multivariate analysis to predict the bioavailability of Cd and As in contaminated rhizosphere soils. Single extraction using 0.1 M HCl for Cd and 1.0 M HCl for As had an extraction efficiency of 8–12% for soil Cd and 14–17% for soil As compared to total concentration extracted with aqua regia. Using sequential extraction, Fe–Mn-bound Cd (FR3) and residual Cd (FR5) were the dominant fractions representing 43 and 41% of total Cd concentration. For As, the strongly absorbed form (FR2) was the most abundant chemical fraction showing 45–54% of the total As concentration in soil. Multivariate analyses showed that single extraction with HCl and total concentration of Cd and As in soil were significantly correlated to potato and green onion plant tissue metal concentration. Although little information was obtained with multiple regression analysis because of multicollinearity of variables, the result of principle component analysis (PCA) revealed that the highest positive loading was obtained using total concentration of Cd and As in soil in the first principle component (PC1). In addition, total concentration of Cd and As in soil was independently grouped with other chemical fractions by cluster analysis. Therefore, the overall result of this research indicated that total concentrations of Cd and As in rhizosphere soils were the best predictors of bioavailability of heavy metals in these contaminated soils.     

土地利用方式下岩溶湿地土壤无机磷形态特征及分析方法适用性探讨

本研究利用SMT法和七步连续提取法对桂林市会仙岩溶湿地中典型土地利用方式（水稻田、果园、荒地）的土壤以及河流底泥中磷的赋存形态进行研究。结果表明:岩溶土壤总磷含量大小为底泥＞果园＞水稻田＞荒地;底泥中Ex-P和Fe-P所占比例较大;荒地土壤中Or-P和Res-P为主要磷形态;水稻田和果园土壤中Fe-P所占比例较高。人为干扰明显的果园表层土壤有较大的磷淋溶风险;荒地土壤中磷的生物可利用性低,体现了其缓冲固持湿地水体中磷的生态功能。大量可溶性磷经淋溶迁移富集于底泥中,是河流富营养化的风险源。七步法表现出在提取多种复杂结合态磷上的优势,对岩溶土壤中Ca-P的提取更充分有效,更适用于研究岩溶土壤不同形态的磷分布特征。      

德安锑矿区土壤中锑的形态分析及生物可给性初探

按Tessier连续浸提法对德安锑矿区土壤样品进行了分析,得出锑的存在状态主要以残渣态为主,其次是Fe/Mn结合态,有机/硫化物结合态和碳酸盐结合态,可交换态和水溶态占的比率最小。矿区土壤中锑生物可利用态锑占0.52%~3.51%,其浓度一般在1.78~17.48μg/g,中等可利用态占1.04%~5.56%,生物难利用态锑的浓度占92.1%~98.4%。     

应用梯度扩散薄膜技术评价天然富硒土壤中硒的生物有效性

有效硒是评价土壤中硒对植物供给能力的重要指标,中国目前尚无测定土壤有效硒的统一方法.化学提取法、土壤溶液法常用于测定土壤有效硒含量,但存在缺乏普遍适用提取剂类型、目标态提取不完全和对非目标态溶解等问题.梯度扩散薄膜(DGT)技术是一种基于解离、扩散动力学的有效态测定方法,已有学者将其应用于土壤有效硒的测定并取得良好效果...     

Specific detection of bioavailable phenanthrene and mercury by bacterium reporters in the red soil

Genetically engineered Pseudomonas putida reporters (BMB-PL and BMB-ME), which, respectively, carried phnS-luxCDABE and merR-egfp cassette, were used to determine bioavailable phenanthrene and mercury. Over a spiked range of concentrations and aged for 6 days in red soil samples, the reporters were tested to determine the optimal assay conditions and the bioavailable phenanthrene (0–60 mg kg^?1) and Hg²⁺ (0–240 μg kg^?1) were evaluated by the signal of the relative fluorescent units and relative luminescence units. Single contamination was carried out and good correlations were obtained between signal strength and pollutant concentrations, whereas interference and bioavailability repression were observed in dual-contamination experiments. Other heavy metal ions at nanomolar level did not interfere with BMB-ME measurement while BMB-PL showed some response to other polycyclic aromatic hydrocarbons or their intermediate products during degradation. Comparing high-performance liquid chromatography methods with the bacterial reporters, both BMB-ME and BMB-PL appeared to have a detection limit (mercury <40 μg kg^?1; phenanthrene <24 mg kg ^?1) similar to the instrumental analysis. Although physical parameters may affect the interaction of pollutants with bioreporter cells, advantages include the inherent biological relevance of the response, rapid response time, and potential for field deployment. Our results strongly suggest that the BMB-ME and BMB-PL bioreporters constitute an adaptable system for easily detecting the bioavailability of mercury and phenanthrene in the red soils.     

Mercury, copper and zinc contamination in soils and fluvial sediments from an abandoned gold mining area in southern Minas Gerais State, Brazil

Mercury, zinc and copper contamination was evaluated in soils and fluvial sediments from an abandoned gold mining site at Descoberto Municipality (southern Minas Gerais State, Brazil). Metals bioavailability and potential mobility were studied through physical, chemical and mineralogical characterization, geoaccumulation indexes calculations, mercury speciation and determination of potentially bioavailable contents of zinc and copper. Values of pH were in the neutral range, while organic matter concentrations were very low. Mineralogical characterization, in the total samples, indicated the presence of quartz, kaolinite and gibbsite for all samples. Total mercury, zinc and cooper concentrations were higher than the limits recommended by Brazilian documents. Geoaccumulations indexes revealed that most of the sediment samples were low to moderately polluted by zinc and copper, while just one sample was very strongly polluted by mercury. Mercury speciation revealed the predominance of the elementary form for all samples, and low concentrations for exchangeable, strongly bound and residual fractions. Zinc and copper behavior was strongly controlled by iron and aluminum concentrations, while their bioavailable contents were very low in comparison with the total concentrations.     

Phosphorus fractions and bioavailability in relation to particle size characteristics in sediments from Lake Hongfeng, Southwest China

Information on the chemical composition of phosphorus (P) fractions in sediments is fundamental to understanding P bioavailability and eutrophication in lake ecosystems. Phosphorus fractions and its bioavailability in sediments cores of Lake Hongfeng, southwest China, were investigated using a chemical sequential extraction scheme. Relationships between P fractions, P bioavailability and particle sizes were discussed. P fractions concentrations were ranked in the order: Residual-P > NaOH–rP > NaOH–NRP > HCl–P > BD–P > NH₄Cl–P, and all of them decreased with increasing sediment depth. Statistical analysis showed that concentrations of bioavailable P (BAP) which includes the NH₄Cl–P, BD–P, NaOH–rP and NaOH–NRP fractions ranged from 404.68 to 1,591.99 mg/kg and accounted for 26.8–71.8 % of the concentrations of total phosphorus (TP) in the top 5 cm sediments, whereas in the whole sediment cores, their concentrations ranged from 239.70 to 1,591.99 mg/kg and accounted for 26.8–76.0 % of TP. The results suggested that the sediments were a large potential source of P for algae blooms in Lake Hongfeng. Phosphorus fractions and their potential bioavailability were influenced by the sediment particle sizes, especially the bioavailability of the NH₄Cl–P fraction, which was strongly affected by the presence of fine particle sizes in the sediments.