土壤中有效态重金属的化学试剂提取法研究进展

土壤重金属污染是国内外关注的热点问题，针对采用全量重金属评价土壤污染存在的问题，本文综述了近年来土壤有效态重金属的化学提取方法研究进展，比较分析了各种单一提取法和影响土壤重金属提取率的因素。在此基础上，评价了各类提取方法的特点及其在应用上的优势和局限，指出了筛选通用提取剂的原则和依据。结合实验初步提出以去离子水作为通用提取剂的可行性及尚需研究解决的问题。     

鞍山市郊蔬菜基地土壤重金属污染状况调查

通过对鞍山市郊蔬菜基地土壤中重金属含量的分析表明,所采集的菜地土壤中Cd的超标率为44．4％,Cu、Pb、Cr、As、Hg无超标现象。大田菜菜地土壤中As、Hg、Pb含量比大棚菜菜地略高,Hg、Pb、Cu、Cr、Cd含量超背景值。     

大冶龙角山地区土壤中重金属污染现状与评价

为了研究大冶龙角山地区尾砂坝内尾砂排放对下游耕地土壤中重金属含量的影响,本文对尾矿坝及河流两岸的耕地进行布点采样,通过等离子体发射光谱仪（ICP—OES）测定土壤中A5、Cd、Cr、Cu、Pb、Zn6种重金属的含量,并用污染指数法进行分析评价。旨在调查研究的基础上,使人们认识当地重金属污染的严重性,加大环境保护力度。     

濮阳工业园区土壤重金属背景值及质量评价

为了研究濮阳工业园区土壤重金属背景值,采集了该园区及周边土壤46个样品,测定了土壤中重金属Cu、Zn、Pb、Cr、Cd和Ni的含量,并采用污染负荷指数法和潜在生态危害指数法对土壤质量进行了评价。结果表明:工业园区土壤中Cu、Zn、Pb、Cr、Cd、Ni的背景值分别为36.2、118、49.2、40.6、0.125、15.3 mg/kg;Cu、Zn、Pb、Cd的含量高于河南省土壤重金属背景值;Pb为极强污染,Cu、Zn、Cd为中等污染,重金属污染程度从重到轻的排序为PbZnCuCd,表明濮阳工业园区土壤重金属具有轻微的潜在生态危害。     

Leaching Characteristics of Arsenic and Heavy Metals in Urban Roadside Soils Using a Simple Bioavailability Extraction Test

Regular ingestion of soils could pose a potential health threat due to long-term toxic element exposure. In order to estimate the human bioavailability quotients for As and heavy metals, 12 urban roadside soil samples were collected and analyzed for As, Pb, Cu, Zn, Ni, Co, and Cr using Simple Bioavailability Extraction Test (SBET). The quantities of As, Pb, Cu, Zn, Ni, Co, and Cr leached from soils within the simulated human stomach for 1 h indicated, on average, 27.3, 71.7, 40.4, 59.3, 17.7, 27.2 and 5.6% bioavailability, respectively. Significant positive correlations were observed between the amounts leached using SBET and the total amounts dissolved with HNO₃-HCl-HF acid mixtures. Stepwise multiple regression analysis indicated that the amounts leached with SBET for As, Pb, Zn, Ni, and Co were not related to any of the physic-chemical parameters measured (i.e., soil texture, pH, total organic matter). These results may be valuable for providing input data for risk assessment at sites subject to anthropogenic soil contamination.     

Leaching Characteristics of Heavy Metals and As from Two Urban Roadside Soils

The leaching tests, including the Toxicity Characteristic Leaching Procedure (TCLP), EDTA extraction and BCR sequential extractions before and after EDTA treatments, were performed on two specific soils to elucidate heavy metal-associated mineral fractions and general leachability. The TCLP illustrated the low leachability of heavy metals in soils from two sites. EDTA is a strong chelator and therefore had higher extraction efficiency compared to that of TCLP. The lower extraction percentages by EDTA for As and Sb were found compared to the other heavy metals derived from anthropogenic sources. Sequential extractions showed that the importance of acid-extractable, organically-bound and Fe–Mn oxide fractions was identified for anthropogenic heavy metals with the exception of As and Ni while the importance of residual fraction was identified for endogenous metals. Changes in sequential fractions of heavy metals after leaching with EDTA are very complex and it is difficult to generalize on which fraction was more mobile than the others. These combined results are helpful in elucidating the association of heavy metals to soil fractions and the mobility characteristics of heavy metals under certain environmental conditions.     

Metal Fractionation Studies in Surfacial and Core Sediments in the Achankovil River Basin in India

The Fractionation of Fe, Zn, Cu, Pb, Mn and Cd in the sediments of the Achankovil River, Western Ghats, India using a sequential extraction method was carried out to understand the metal availability in the basin for biotic and abiotic activities. Spatial distribution of heavy metals has been studied. Sediment grain size has significant control over the heavy metal distribution. The fluctuations in their concentration partly depend upon the lithology of the river basin and partly the anthropogenic activities. The sediments are dominated by sand and are moderately to strongly positively skewed and are very leptokurtotic in nature. The quartzite and feldspars are abundant minerals along with significant amount of mica with low clay content. The core sediments show increasing trend of heavy metal concentration with depth due to the recent addition of anthropogenic sources and post-diagenic activities. Significant amount of Cd (18%) was found in carbonate fraction, which may pose environmental problems due to its toxic nature. Small concentrations of metals, except Cd and Cu, are in exchangeable fraction, which indicate low bio-availability. Enrichment Factor (EF) for individual metals shows the contribution from terrregious and in part from anthropogenic sources. Selective Sequential Extraction (SSE) study shows the variation in specific metal distribution pattern, their distribution in different phases and their bio-availability. Maximum amount of the metals were bound to the non-residual fractions (mainly Fe-oxides). Overall, bio-availability of these micronutrients from sediments seems to be very less. Non-residual phase is the most important phase for majority of heavy metals studied. Among the non-residual fraction, maximum amount of the heavy metals bound to Fe-oxides. The study high lights the need for in-depth study of heavy metals distribution and fractionation in the smaller river basins to get precise information on the behavior and transport of heavy metals in the fluvial environment and their contribution to the world ocean.     

基于Hakanson潜在生态风险指数的某垃圾填埋场土壤重金属污染评价

将Hakanson提出的潜在生态风险指数法应用于垃圾填埋场及周边土壤重金属污染评价,扩充了评价因子,确定了各重金属的毒性系数及参比值。研究结果表明,评价区土壤中Hg的潜在生态风险较重,其后依次为Cd、As、Ni、Cu、Pb、Co、Cr、Mn和Zn。对污染场地的风险评估及生态修复有一定的指导意义。     

山区土壤重金属空间插值性能的改进

山区土壤重金属监测中,密集均匀的布点采样困难大,成本高。根据稀疏非均匀样本数据准确预测山区土壤重金属空间分布,对可视化描述检测元素的分布及趋势具有重要意义。基于云南省楚雄市南部山区表层土壤中重金属锰、钒的采样数据,对集成径向基函数神经网络(IRBFANNs)和传统插值方法:反距离(IDW)、普通克里格(OK)、径向基函数神经网络(RBFANNs),进行了不同等级采样密度下的插值性能比较。结果表明,样本点数量减少时,传统预测方法的插值精度都有所下降,而IRBFANNs算法在样本点较少情况下能够保持最好的插值精确度和稳定性,有效改进了空间插值性能。     

Heavy Metals Fractionation in Ganga River Sediments, India

The Ganga River is the largest river in India which, originates in the Himalayas and along with the Brahmaputra River, another Himalayan river, transports enormous amounts of sediments from the Indian sub-continent to the Bay of Bengal. Because of the important role of river sediments in the biogeochemical cycling of elements, the Ganga river sediments, collected from its origin to the down stretches, were studied in the present context, to assess the heavy metals associated with different chemical fractions of sediments. The fractionation of metals were studied in the sediments using SM&T protocol for the extraction of heavy metals and geo-accumulation index (GAI) (Muller, Schwermetalle in den sedimenten des rheins – Veranderungen seit. Umschau, 79, 778–783, 1979) and Metal Enrichment Factor (MEF) in different fractions were calculated. As with many river systems, residual fractions constitute more than 60% of total metals, except Zn, Cu and Cr. However, the reducible and organic and sulfide components also act as major sinks for metals in the down stretches of the river, which is supported by the high GAI and MEF values. The GAI values range between 4 and 5 and MEF exceed more than 20 for almost all the locations in the downstream locations indicating to the addition of metals through urban and industrial effluents, as compared to the low metals concentrations with less GAI and MEF in the pristine river sediments from the rivers in Himalayas.     

Ecotoxicological Assessment of the Impact of Residual Heavy Metals on Soil Nematodes in the Guadiamar River Basin (Southern Spain)

On 25 April 1998, as a consequence of the breaking of a dam containing the tailings of a pyrite mine, a land strip of approximately 43 km in length was covered with a layer of black sludge, containing high levels of heavy metals, along the Guadiamar River Basin (southern Spain). In this investigation we carried out an ecotoxicological assessment (field and laboratory studies) of the impact of residual heavy metals (Cu, Pb, Zn, Ni) on soil nematodes in the impacted riparian zone, two years after the huge mine spillage. Concentrations of residual heavy metals were significantly (P<0.05) higher at the impacted sampling sectors (S-2, S-3, S-4, S-5) than at the unpolluted (reference) sampling sector (S-1). Nickel however exhibited the lowest increases at the impacted sectors. As a consequence, correlation coefficients between concentrations of heavy metals and values of ecological indices were not significant for Ni. In contrast, copper, lead and zinc exhibited significant (P<0.05) negative correlation coefficients with ecological indices, particularly with diversity indices (including the~number of taxa). In addition, the toxicity of Cu and Pb to nematode test species (Aphelenchus avenae and Cephalobus persegnis) during short-term toxicity bioassays was much higher than the toxicity of Zn and Ni. We conclude that residual heavy metals were still influencing adversely the community of soil nematodes in the impacted riparian zone of the Guadiamar River Basin. Cu, Pb and, to a lesser extent, Zn would be major responsible for the observed impact.     

河北曹妃甸农田土壤重金属污染及潜在生态风险评价

以河北曹妃甸项目区农田土壤为研究对象,分析测定土壤基本性质和Zn、Cu、Pb、Cd含量,并依据有关标准和模型对土壤环境质量和潜在生态风险进行评价。结果表明:农田土壤总体偏碱性,属壤质和黏壤质水稻土,有机质含量低;土壤中Cu的污染指数最大,Zn、Pb次之,Cd虽没超过国家标准但已出现污染累积现象。在单因子评价中,有76%的土样中Cd元素呈中等或强潜在生态风险,其余元素均无潜在生态风险;在多因子评价中,有95%的土样属于无生态危害或一般生态危害,只有5%是强生态危害。项目区农田土壤质量虽总体良好,但个别区域存在严重生态危害问题,尤其是Cd元素的潜在生态风险十分突出。在今后的土地整理和污染修复工程中,应注意保护清洁农田,防止污染交叉转移,促进农业可持续发展。     

土壤重金属元素检测国际实验室比对研究

IERM和CNAS合作组织开展了亚太实验室合作组织(APLAC)能力验证计划"APLAC T066土壤重金属元素检测",其目的是评价参加实验室定量分析土壤重金属元素总量的能力。研究所用的能力验证样品为IERM研制的土壤标准样品。结果表明,参加实验室检测土壤砷、铜、汞、镍、铅和锌的结果满意率分别为85.7%、95.8%、77.1%、83.3%、93.5%和91.7%。样品消解过程加入氢氟酸时,铅和锌的检测结果与标准值更加接近,说明检测土壤重金属元素总量时氢氟酸的加入非常关键。文章还对比对实验室结果评价的统计方法进行了探讨。     

土壤中重金属可提取态(氯化钙法)分析质量控制样品的研制

为真实反映土壤中重金属的生态风险和环境效应,全国农用地土壤污染状况详查土壤检测要求测定土壤中重金属可提取态(氯化钙法)指标。针对农用地土壤污染状况详查分析质量控制工作要求,研制了土壤中重金属可提取态(氯化钙法)分析质量控制样品。土壤样品为采自江西省旱地农田的红壤,经除杂、干燥、球磨、筛分(0.250 mm)、混匀等加工处理后装瓶。采用重金属总量和重金属可提取态(氯化钙法)两大类指标评价土壤样品的均匀性,均匀性分析结果同时采用单因素方差分析法(F检验法)和相对标准偏差法(RSD法)评价。结果表明:土壤样品均匀性良好,样品最小取样量为4.0g。8家实验室对土壤中As、Cd、Cr、Cu、Hg、Ni、Pb和Zn等8种元素开展联合定值。标准值为联合定值结果的总平均值(X-),标准值上、下限值分别为(X-+3S)和(X--3S),S为联合测定平均值的标准偏差,低于《全国土壤污染状况详查土壤样品分析测试方法技术规定》中分析方法检出限的元素不做量值评定。As、Cd、Cu、Ni和Zn等5种元素评定了标准值,含量范围为0.190 ～ 13.6 mg/kg。Cr、Pb和Hg等3种元素分析结果低于分析方法检出限,未能定值。研制的土壤分析质量控制样品已应用于土壤详查工作,在保证土壤详查检测结果准确可比等方面发挥了重要作用。     

典型沼肥灌施农田重金属的时间多尺度特征分析

长期对农田进行沼肥灌施对土壤养分及重金属累积、迁移产生何种影响,尚缺乏系统的调查和研究。选取7—10年灌施沼肥的农田为研究对象,分析耕层土壤中Cu、Zn、Cr、Cd、Pb、Ni、Hg和As的全量及Cu、Zn各形态含量,并对污染水平及生态风险进行评价和预测。结果表明:持续灌施沼肥改变土壤的EC、pH等理化性质,造成P、K等营养元素和重金属Cu、Zn的显著累积。Cu、Zn平均积累速率分别为5.70~6.15、12.13~18.7 mg/(kg·年)。Cu和Zn含量之间具有显著相关性,表明它们同源。外源输入的稀释作用及形态转化使原土壤Cu、Zn赋存形态发生改变。综合污染指数法研究结果表明,养殖场土壤重金属均处于警戒水平。潜在生态风险指数法研究结果表明,养殖场土壤重金属危害程度整体表现为轻微生态危害。Cu、Zn年积累通量分别为10.26~11.07、21.83~33.66 kg/(hm²·年)。预测土壤中Cu、Zn浓度超出风险筛选值时间分别为10.19~11.01、9.16~14.14年。连续多年灌施沼肥将对土壤生态环境造成潜在风险。     

上海、乌鲁木齐与昌吉三市城市土壤重金属富集特征比较研究

选择上海、乌鲁木齐、昌吉3个城市,通过对其城市土壤重金属含量水平、分布特征及活性的比较研究,发现城市土壤中Cr、Cu、Pb、Zn含量均远高于背景值,但Mn、Fe含量与背景值差别不大;上海市Cr、Pb、Zn含量最高,而昌吉市Cu含量最高,城市规模的大小并不能直接反映土壤重金属含量的高低,工业污染物排放量、交通量、城市规模大小、城市发展历史、工业区位置及变迁、土壤背景值等因素均会影响土壤重金属含量水平。除Mn、Fe无明显的功能区分布差异外,各城市重金属功能区分布规律并不相同,城市污染来源的不同可能是主要原因。重金属活性并未与其含量分布规律完全一致,上海土壤重金属活性大于乌鲁木齐、昌吉,上海土壤pH值小于乌鲁木齐、昌吉可能是主要影响因素,但也存在上海土壤中个别重金属活性小于乌鲁木齐、昌吉的现象,污染物来源存在差异等可能是主要原因。也可能较强,反之亦然。     

奎屯市北郊蔬菜污灌区土壤重金属污染调查

通过对奎屯市北郊污灌区菜地土壤中重金属含量的分析表明，所调查的污灌菜地土壤中铅、锌、镉、砷和汞均未超标，部分地块铜超标，说明多年来因工业废水的浇灌，已造成铜对局部区域土壤的污染。     

乌鲁木齐市米东污灌区农田土壤重金属污染评价

对米东污灌区农田土壤重金属含量进行监测分析,利用不同的评价方法和标准对土壤重金属的环境质量进行评价。结果表明:米东污灌区农田土壤重金属含量分别为Cd(0.12±0.06)mg/kg,Cu(40.43±5.30)mg/kg,Zn(78.38±11.04)mg/kg,Pb(11.66±11.79)mg/kg,Ni(20.24±8.05)mg/kg,Cr(75.81±8.05)mg/kg。以国家土壤环境质量标准(二级)为标准评价,各元素的污染指数排序为Cu>Ni>Cr>Zn>Cd>Pb,综合污染指数为0.337,污染程度为安全。以食用农产品产地土壤环境质量要求为标准评价,各元素的污染指数排序为Cu>Ni>Cr>Zn>Cd>Pb,综合污染指数为0.343,污染程度为安全。表明米东污灌区农田土壤重金属含量尚能达到食用农产品产地土壤环境质量要求。Pb、Cu、Zn的平均含量超过乌鲁木齐市土壤背景值,这说明污灌区土壤重金属Pb、Cu、Zn近年来已有所累积,存在一定的污染风险。     

石河子燃煤电厂重金属排放研究

选取石河子市典型燃煤电厂,对其燃煤烟气重金属排放浓度及飞灰、底渣、脱硫石膏重金属的富集进行定量分析。结果表明,烟气中各重金属排放浓度从高到低依次为Zn、Ni、Cr、Pb、Cu、Hg、Co、Cd、As。各重金属元素在飞灰中的富集程度较高,除Hg、Cd、Ni外,其他重金属元素在飞灰的富集因均值均大于5。其中,As在飞灰的富集因子均值为5.76。研究结果可为石河子重金属污染控制提供基础数据。     

土壤中7种重金属和砷测定的精密度控制指标研究

通过对浙江省近700组实际土壤样品进行分析,研究了土壤中铜、铅、锌、铬、镍、镉、砷、汞7种重金属和砷测定的精密度控制指标(实验室内相对偏差和实验室间相对偏差),并与行业标准分析方法和文献进行了比较,旨在为环境监测质量控制与质量保证工作提供参考。经统计分析,建议实验室内相对偏差控制指标如下:铜,≤15%;铅,≤15%;锌,≤15%;铬,≤15%;镍,≤15%;镉,≤20%;砷,≤15%;汞,≤50%。建议实验室间相对偏差控制指标如下:铜,≤25%;铅,≤25%;锌,≤20%;铬,≤20%;镍,≤25%;镉,≤35%;砷,≤25%;汞,≤55%。