环境样品中铊的提取、形态分布与定量分析技术研究进展

<正>铊(Thallium,Tl)是一种剧毒的重金属元素,对哺乳动物的毒性高于泵、镉、铅和锌等元素,为美国环保署规定的优先控制污染物之一[1]。为加深了解Tl的环境化学行为,笔者对其提取方法、化学形态与定量分析技术的研究进展和最新动态进行简要的综述。土壤、沉积物和市政污泥等包括Tl的重金属元素提取方法主要采用"BCR连续提取法"。自Perez-Cid等[2]和Martin,R等人[3]使用Tessier等[4]提出的"连续提取法对"分别对市政污泥和河道沉积物的重金属进     

类芽孢杆菌对铜陵新桥矿区土壤中Cu化学形态的影响

采用Tessier五步连续提取法和红外光谱技术,研究类芽孢杆菌对铜陵新桥矿区重金属污染土壤中Cu化学形态的影响,初步探讨了Cu形态变化的机理。结果表明,不同投入量的类芽孢杆菌接种到土壤培养一周后,土壤溶液pH值降低,土壤中可交换态、有机结合态Cu含量增加,碳酸盐结合态、铁锰氧化物结合态和残渣态Cu的含量降低。土壤中可交换态、铁锰氧化物结合态和残渣态Cu含量的变化主要受土壤溶液的pH值控制;有机结合态升高主要与类芽孢杆菌菌数及其代谢产生的低分子量有机酸有关。类芽孢杆菌可以改变矿区土壤中Cu的化学形态,影响Cu的生物有效性。     

德兴矿区土壤中铜的地球化学形态及影响因素

土壤中铜的地球化学形态决定了其在环境中的释放、变化形式、迁移规律及生物效应。通过对德兴铜矿及周边地区82件表层土壤样品,采用改进的BCR提取方法测定铜的地球化学形态,了解其区域分布特征,结果表明:(1)德兴地区土壤中酸可溶态的铜≈可还原态铜<可氧化态铜≈残渣态铜,酸可溶态 可氧化态 可还原态的铜平均质量分数为45.07×10-6,较中国土壤背景值全铜的质量分数(22.6×10-6)高,这些活动态的铜易于进入食物链,对人体健康和生态安全构成潜在的威胁,不同形态铜的区域分布特征相似,主要位于采矿和选矿活动区附近;(2)采用改进的BCR方法提取的土壤中铜的酸可溶态和可氧化态和采用EDTA提取的可交换态具有明显的正相关关系,土壤pH值增大时酸可溶态铜的比例降低,土壤TOC含量增加时可氧化态铜的比例增大,而土壤CEC对BCR方法提取铜的形态影响不大。     

土壤和沉积物中元素的化学形态及其顺序提取法

介绍了形态分析的概念和化学形态分析方法，探讨了广泛应用于土壤、沉积物重金属形态分析中的Tessier和BCR顺序提取方案及其异同，综述了顺序提取方法在地球化学、环境科学、农业科学等方面的应用及中国相关标准物质的研制现状。     

天然及改性凹凸棒对稀土尾矿土壤中重金属铅的钝化效果研究

赣南离子型稀土矿的大肆开采,以及尾矿废渣不合理处置,造成矿区周边环境中重金属铅含量超标,破环矿区生态环境。本文利用不同剂量（质量分数分别为5%、10%和15%）的天然及改性凹凸棒作为钝化剂,利用扫描电镜和傅里叶红外光谱对两种钝化剂的表面特征和官能团进行分析,采用BCR重金属连续提取法对钝化能力和效果进行评价,并以此研究土壤中铅的形态变化,借鉴国外的重金属TCLP提取法评估重金属污染土壤的环境质量。结果表明：经过50d的培养,土壤pH值从4.76显著升高至接近7.0。改性后凹凸棒使铅的酸提取态含量从25.69mg/kg降低至7.42mg/kg,并促进其向残渣态转化,残渣态含量比对照组增加了1.38倍,TCLP提取态含量比对照组降低了65.70%,从而显著降低了铅的生物可利用度和生态风险。与天然凹凸棒相比,改性后凹凸棒对稀土尾矿土壤修复具有较为良好的效果。     

淮南潘集采煤沉陷区土壤及煤矸石镉环境地球化学特征

以淮南潘集采煤沉陷区土壤、煤矸石为研究对象,采用电感耦合等离子体质谱(ICP-MS)测定样品中重金属镉(Cd)含量,探讨其空间分布特征;利用Tessier五步形态提取法,研究样品中Cd赋存形态,分析其生物可利用性;最后采用地累积指数法评价沉陷区土壤和煤矸石中Cd污染程度。结果表明:潘集采煤沉陷区土壤Cd含量是淮南土壤背景值4.17倍,煤矸石中Cd含量是淮南土壤背景值和煤背景值5.33倍;潘集采煤沉陷区土壤和煤矸石中残渣态Cd占绝大部分,可交换态Cd含量低,但潜在生物可利用态含量高;地累积指数法结果表明,淮南潘集采煤沉陷区土壤和煤矸石中Cd中度污染,应采取措施优先治理控制。     

典型稀土矿区周边土壤中稀土元素含量及赋存形态研究

研究不同类型稀土矿区周边土壤中稀土元素(REE)的含量与形态特征,可为矿区周边污染环境治理提供理论支持与科学建议。本文采用欧盟BCR顺序提取法、电感耦合等离子体质谱测定的方法,对内蒙古白云鄂博稀土尾矿区和江西赣南稀土矿区周边6个土壤样品中15种稀土元素进行了含量及形态分析测定。结果表明:矿区周边土壤中稀土元素总量约为264～15955μg/g,明显高于全国土壤背景值(186μg/g),白云鄂博尾矿区周边土壤富集轻稀土元素,稀土元素主要以残渣态富集,占总含量的64.0%～89.4%,生物有效性较低,对环境影响较小;赣南矿区周边土壤富集重稀土元素,稀土元素的主要存在形式是弱酸提取态和可还原态,占总含量的70%以上,易发生迁移转化及对周边环境造成污染。土壤中稀土元素的形态分布与pH值有显著相关性,随着土壤pH值的降低,稀土元素的弱酸提取态含量不断升高,残渣态含量不断降低。     

泉州城市表层土壤重金属的赋存形态及污染评价

本文采用改进的BCR连续提取法研究泉州市区表层土壤中17种重金属的形态分布特征,并运用地积累指数Igeo法、潜在生态危害指数法、次生相与原生相分布比值法(RSP)评价土壤中重金属元素的潜在生态危害。结果表明,Li,Ti,Fe,Sc,V,As,Sb,Sn主要以残渣态存在;Cr,Ni,Cu,Zn,Bi在可氧化态中占有大比例,但仍以残渣态为主;Pb以可还原态为主;Mn,Cd,Co在可还原态和残渣态中占有较大比例。根据地累积指数法和RSP,泉州土壤受到不同程度的Sc,Co,Ni,Cu,Cd,Sb,Pb污染;潜在生态危害指数表明泉州市城区受到轻微生态危害。     

沈阳细河沿岸土壤中重金属垂直分布特征与形态分析

研究了沈阳细河沿岸翟家、彰驿和黄腊坨地区13个土壤剖面样品中重金属的垂直分布特征,对土壤环境危害较大的3种重金属元素Cd、Hg、As进行了重点分析。采用改进的Tessier连续萃取法研究了5个表层土壤中7种重金属元素的形态分布。研究表明土壤重金属元素形态分布具有以下特点:As、Cu、Cr、Zn和Pb主要以残渣态存在;Cd主要以离子交换态存在,残渣态所占的比例较低,表明表层土壤中Cd的活动性较强,容易迁移进入生态食物链。大部分样品中Hg以残渣态为主。除Cd外,土壤中其余6种重金属的可交换态含量都比较低。7种重金属的潜在迁移能力顺序为:CdHgPbZnCrCuAs。     

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.     

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.     

冻融循环下含磷材料固化锌铅污染土的强度及溶出特性研究

采用新型含磷材料（KMP）及水泥（PC）固化稳定化锌（Zn）、铅（Pb）重金属污染土,研究试验土经冻融循环后的毒性浸出（CLP）、无侧限抗压强度（UCT）、压汞试验（MIP）及化学形态分析（BCR）,探究固化污染土的力学特性及耐久特性。试验结果表明,经冻融循环后,未处理污染土Zn、Pb浸出值均超过中国土壤标准;采用KMP和PC固化后,Zn、Pb浸出浓度明显低于未处理污染土;KMP固化污染土比PC固化污染土重金属固化效果更为显著,并能达到中国土壤标准;与常规养护相比,冻融循环之后的固化土体强度明显减小;经过12级冻融循环的KMP固化复合Zn、Pb重金属污染污染土强度高于PC固化试样8.6倍。压汞试验表明,经12级冻融循环后固化污染土孔隙体积增大,化学形态分析结果表明,采用KMP、PC固化重金属污染土中可交换态Zn随着养护龄期的增长而减少,残渣态Zn增加。     

改进BCR法在分析水系沉积物样品铅形态中的应用

研究了超声波水浴提 BCR顺序提取法在铅形态分析中的应用,优化了水系沉积物样品铅的各分步提取时间。与传统的BCR法相比,改进BCR法所用的提取时间由原来的几十小时缩短为几十分钟。氢化物 原子荧光法测定样品中3种形态铅含量的统计结果显示,改进BCR法分析精度好,各形态铅的提取效率高,是一种快速、定量铅形态分析方法。     

A comparison between heavy metals released from soil and its efficient speciation extracted by sequential extraction procedure

A simulating experiment was carried out on the interaction between natural precipitation and soil. The results demonstrated that the contents of heavy metals （V, Co, Cr, and Ni） released from soil into the solution under Earth＇s surface conditions are higher than the contents of those metals bonded to exchangeable species, which were extracted by sequential extraction procedure recommended by Tessier and others in 1979. It is demonstrated that the metals bonded to other 3 species （carbonate, Fe-Mn oxide, and organic matter） except those bonded to the exchangeable species in efficient speciation can be released under the Earth＇s surface conditions, when pH=4 in the reaction system, and the higher correlation coefficient indicated that the concentrations of heavy metals released from soil into the solution vary approximately with reaction time in terms of index regulations.     

Heavy metals deposited from the atmosphere on upland Scottish soils: Chemical and lead isotope studies of the association of metals with soil components

Three soil profiles taken from the Hartwood Research Station in Central Scotland have been analyzed using chemical digestion and extraction techniques to investigate the chemical association of heavy metals deposited from the atmosphere. Total digestion, EDTA extraction and the BCR (Bureau Communitaire de Reference) sequential extraction procedure were used. In addition, lead isotope ratios in the whole soils and in the fractions from the sequential extraction procedure were measured using thermal ionisation mass spectrometry. All the digestion and extraction procedures gave clear indication of enhanced concentrations of heavy metals in surface soils, in particular for lead and zinc. Whereas total digestion gave a good indication of the heavy metal status of the soils, the extraction procedures were necessary to provide information on chemical association of the metals with soil components, information needed to understand the soil processes involved in mobilization of metals. Lead isotope analysis of the whole soils revealed a consistent picture of lower ²⁰⁶Pb/²⁰⁷Pb ratios in surface soils (1.140-1.147) than in soils at 20-30 cm depth (1.182-1.190). The steady progression from the lower to higher ratios down the profile was clear indication that anthropogenic lead had penetrated to some degree into the deeper soils. The combination of sequential extraction and lead isotope analysis proved to be a powerful approach to studying this effect in more detail and showed that the fractions extractable from 20 to 30 cm soils contained lead with much lower ²⁰⁶Pb/²⁰⁷Pb ratios (1.174-1.178) than the residual fraction (1.196-1.200). As the extractable fractions contained ≥85% of the lead in the soil, a substantial portion of lead at 20-30 cm depth was of anthropogenic origin. The ²⁰⁶Pb/²⁰⁷Pb ratios of 1.174-1.178 found in the extractable fractions suggested that the mobile component of the anthropogenic lead was that deposited before the introduction of leaded petrol.     

Sequential extraction and leaching characteristics of heavy metals in abandoned tungsten mine tailings sediments

The chemical speciation of potentially toxic elements (As, Cd, Cu, Pb, and Zn) in the contaminated soils and sulfides-rich tailings sediments of an abandoned tungsten mine in Korea was evaluated by conducting modified BCR sequential extraction tests. Kinetic and static batch leaching tests were also conducted to evaluate the potential release of As and other heavy metals by acidic rain water and the leaching behaviors of these heavy metals. The major sources of the elements were As-, Zn- and Pb-bearing sulfides, Pb carbonates (i.e., cerussite), and Pb sulfates (i.e., anglesite). The biggest pollutant fraction in these soil and tailing samples consists of metals bound to the oxidizable host phase, which can be released into the environment if conditions become oxidative, and/or to residual fractions. No significant difference in total element concentrations was observed between the tailings sediments and contaminated soils. For both sample types, almost no changes occurred in the mobility of As and the other heavy metals at 7 days, but the mobility increased afterwards until the end of the tests at 30 days, regardless of the initial pH. However, the mobility was approximately 5–10 times higher at initial pH 1.0 than at initial pHs of 3.0 and 5.0. The leached amounts of all the heavy metal contents were higher from tailings sediments than from contaminated soils at pH > 3.0, but were lower at pH < 3.0 except for As. Results of this study suggest that further dissolution of heavy metals from soil and tailing samples may occur during extended rainfall, resulting in a serious threat to surface and groundwater in the mine area.     

太湖MS岩芯重金属元素地球化学形态研究

采用BCR三步提取法对太湖MS岩芯沉积物中Cu、Fe、Mn、Ni、Pb和Zn等6种重金属元素的化学形态进行了研究.结果表明,有效结合态的Cu、Ni和Pb主要以有机物及硫化物结合态、Fe-Mn氧化物结合态存在,Fe和Zn主要以Fe-Mn氧化物结合态存在,Mn主要以可交换态及碳酸盐结合态存在;Fe-Mn氧化物结合态的Ni、Pb和Zn与可还原态的Mn有较好的正相关关系,有机物及硫化物结合态的Cu、Mn、Ni、Pb和Zn与有机碳含量有较好的正相关关系;重金属形态分布体现了重金属元素地球化学性质的差异,以及重金属形态含量与沉积物理化性质的关系.沉积岩芯重金属元素形态垂向变化规律及次生相富集系数表明,Cu、Mn、Ni、Pb和Zn在沉积岩芯13～4 cm有效结合态含量较稳定,为自然沉积;4～0 cm有效结合态含量明显升高,存在一定程度的人为污染.根据137Cs测年结果判断,沉积岩芯Cu、Mn、Ni、Pb和Zn等重金属污染开始于20世纪70年代末期,主要污染元素及污染历史与太湖流域污染工业类型及经济发展阶段相吻合.     

干旱区绿洲土壤共存重金属元素形态变化及生物有效性实验分析——以Cd、Zn、Ni元素为例

采用盆栽试验,初步研究了干旱区绿洲土壤—胡萝卜系统中镉、锌、镍3种重金属的形态变化特征及其生物有效性问题。结果表明:供试绿洲土壤原状土中,Cd、Zn、Ni均以稳定的残渣态形式存在,而处理土壤中重金属被钝化的量有限,Cd的存在形式主要以碳酸盐态为主,Zn、Ni则主要以铁锰氧化态为主;3种元素的活性大小依次为Cd>Ni>Zn。根据回归分析,元素Zn对胡萝卜块茎和茎叶吸收Zn量贡献最大的分别是Zn的碳酸盐结合态和铁锰氧化态;元素Ni对胡萝卜各部位吸收贡献最大的均为Ni的铁锰氧化态。