绿洲土Cd、Pb、Zn、Ni复合污染下重金属的形态特征和生物有效性

通过模拟基于干旱区绿洲土壤Cd-Pb-Zn-Ni复合污染下的油菜盆栽试验,采用Tessier五步连续浸提法探究了重金属复合污染对油菜生长的影响及其各形态的转化归趋和生物有效性.结果显示,随着Cd-Pb-Zn-Ni复合胁迫水平的升高,油菜的干重先增加后减小,根系的生长由促进作用转变为抑制作用;对照土壤中4种重金属元素均以残渣态为主要赋存形态,可交换态的含量均很小;随着外源重金属的添加,油菜种植土壤中4种重金属元素的各形态含量随之增加,Cd、Pb、Zn的可交换态和Ni的碳酸盐结合态对外界胁迫响应强度最大,Cd、Pb、Zn、Ni的活性增加,且Cd、Pb的主要赋存形态迅速转变为碳酸盐结合态和铁锰氧化态,Zn的主要赋存形态由残渣态和碳酸盐结合态过渡到碳酸盐结合态和铁锰氧化态,Ni的主要赋存形态为碳酸盐结合态;Cd、Zn在茎叶中的含量大于根系,Pb、Ni反之,油菜能将Cd、Zn更多的运输至茎叶,Pb、Ni则主要积累在根系;油菜茎叶吸收Cd和油菜各部位吸收Zn的主要贡献形态为可交换态,根吸收Cd的主要贡献形态由可交换态转变为有机结合态,根吸收Pb和油菜各部位吸收Ni的主要贡献形态为碳酸盐结合态.     

Cd、Pb投加浓度对其在黑土中化学形态分布及油菜生长和吸收Cd、Pb的影响

采用室内模拟实验和连续形态分级方法研究了Cd、Pb投加浓度对其在黑土中化学形态分布及油菜生长和吸收Cd、Pb量的影响.结果表明:随Cd、Pb投加量的增加,土壤中Cd交换态含量增幅较大,Pb碳酸盐结合态、Fe-Mn氧化物结合态含量增幅较大;外源Cd在土壤中的存在形态以交换态和残留态为主,Pb的交换态比例相对较低,其存在形态主要为残留态;土壤Cd、Pb投加浓度较低时,促进了油菜的生长,投加浓度较高时,对油菜生长的抑制作用较为明显;地下部分Cd、Pb含量远高于地上部分,与Cd相比,Pb向地上部的迁移率相对较小;土壤中Cd、Pb各形态含量与油菜地下、地上部分吸收的Cd、Pb量均呈显著正相关,与干质量呈负相关;交换态Cd、Pb对油菜干质量影响最大,碳酸盐结合态对油菜吸收Cd、Pb的贡献最大.     

露地栽培向设施栽培转变对菜田土壤重金属含量及形态的影响

为了研究露地栽培向设施大棚栽培转变对土壤重金属含量的影响,对武汉市郊区露地和设施塑料大棚两种栽培条件下菜田土壤重金属Cd、Cr和Pb各形态含量及分布特征进行了研究。结果显示,露地和大棚栽培条件下土壤重金属元素Cr和Pb各种形态含量之间没有明显差异,但Cd各种形态含量间有显著差异;从露地到大棚,土壤中Cd酸可提取态含量从露地的0.62 mg/kg上升到大棚的1.19 mg/kg,其次是Cd残渣态、有机结合态、氧化态和碳酸盐结合态;Cd总含量从露地的0.79 mg/kg升高到大棚的1.58 mg/kg,显著超过土壤环境质量标准中的Cd含量标准值(0.3 mg/kg),达到严重污染水平。Cd碳酸盐结合态和氧化态占总量的比例有所降低,而酸可提取态占总量的比例有所升高。说明从露地到设施大棚栽培,促使了土壤中部分Cd碳酸盐结合态和氧化结合态向酸可提取态转变,提高了土壤中Cd的生物有效性。因此,在设施大棚栽培快速发展的情况下,要加强重金属Cd对土壤污染的治理,减少重金属Cd对蔬菜的毒害。     

稻麦轮作下水稻土重金属形态特征及其生物有效性

在成都平原稻麦轮作下86个土样中重金属全量和各形态含量分析的基础上,采集分析相应点位上种植的主要粮食作物小麦和水稻籽粒的重金属含量,通过描述性统计分析、相关性分析及线性回归方程的模拟,研究了土壤中重金属的形态分布特征及其生物有效性。统计分析结果表明：土壤中Cr、Cu、Pb、Zn各形态含量的分配顺序为：残渣态〉有机物结合态〉铁锰氧化物结合态〉碳酸盐结合态〉可交换态,而Cd各形态含量的分配顺序为：铁锰氧化物结合态〉残渣态〉碳酸盐结合态〉有机物结合态〉可交换态。若以活性态（非残渣态含量）而论,Cd的活性最高,Cr的活性最低。除Cr外,各元素全量与各活性形态之间的关系较为密切。土壤中全Cd含量与4种活性形态Cd含量间的相关性均达极显著水平;Cu、Zn全量分别与其铁锰氧化物和有机物结合态含量,Pb全量分别与其可交换态和铁锰氧化物含量间的相关系数达显著或极显著水平。用卫生部颁布的食品中重金属限量卫生标准评价稻麦籽粒重金属累积情况,其结果表明,小麦籽粒（旱作）中的Cd、Cr、Cu、Pb分别超标14.71%、8.70%、6.50%和17.40%,而水稻籽粒（水作）仅有Pb和Cd含量超标10.90%和8.70%。不同形态重金属对水稻和小麦籽粒中重金属累积的影响效应不同，从多元线性回归方程的回归系数来看：稻一麦籽粒中Cd含量受到土壤中各活性形态Cd含量的影响。除铁锰氧化态Cd和有机物结合态Cd含量分别对小麦和水稻籽粒中Cd的累积表现出负效应外，其余均为正效应。可交换态Cu含量对稻-麦籽粒Cu累积的效应最大，其次受碳酸盐结合态Cu含量的影响。稻一麦籽粒Pb含量的累积受土壤各活性态Pb含量影响效应的差异不甚明显。稻-麦籽粒Zn含量与土壤各活性态Zn含量间无显著线性关系。     

芜湖钢铁厂周边土壤及油菜籽中镉、铜、锌、铅含量和形态分布研究

研究了污染土壤、油菜籽中Cd、Cu、Zn、Pb含量、形态分布特征和重金属富集状况及可能存在的生物毒性.结果表明,土壤中Cd、Zn、Pb以铁锰氧化物结合态、Cu以残留态占5种形态最高比例,分别为31.1%、39.3%、53.79%、46.24%;Cd、Pb交换态比例较高,为23.47%、16.32%,Cu、Zn的交换态比例较小,为3.14%、0.54%;土壤中不同重金属与各重金属形态相关关系有差别,5种重金属形态转化为有效态重金属难易程度不同;油菜籽和油菜籽壳中不同重金属累积趋势有差异,Cu易在油菜籽壳中累积,Cd、Zn、Pb易在油菜籽中累积;油菜籽中不同重金属累积率不同,Cd累积率最高,为0.56.油菜籽中重金属累积率与土壤中重金属总量呈显著负相关关系(P＜0.05),土壤中重金属的形态、转化差异是此种负相关关系的主要原因;油菜籽中Cd、Cu、Pb以氯化钠态为主,分别为32.50%、22.94%、34.69%,Zn以EDTA态为主,为45.97%.油菜籽中重金属形态可能影响其毒性,但其毒性的人类膳食风险还需进一步研究证实.油菜籽中重金属形态与油菜中重金属总量相关性不好.     

环境重金属污染物的生物有效性

利用生态系统研究了白银有色金属冶炼矿区周围环境中重金属的分布及生物有效性。结果表明 ,工厂在冶炼过程中已造成 Pb、Cd、Cu、Zn对周围环境不同程度的污染 ,其含量与距工厂的距离呈负相关 ;重金属在各种生物体内均有不同程度的吸收和累积 ,其吸收累积量随重金属和生物种类的不同而有差异 ;土壤的污染 ,使农作物和牧草中 Pb、Cd含量超过动物的最大耐受量和中毒的临界值 ;动物研究发现 ,肾脏、骨骼和肝脏是机体内重金属蓄积的主要器官。因此 ,放牧动物可作为环境重金属污染状况的标识 ,对评价重金属环境污染对当地人群的危害也有重要意义     

利用乙二胺四乙酸淋洗修复重金属污染的土壤及其动力学

通过室内模拟试验,采用振荡淋洗的方法研究了乙二胺四乙酸(EDTA)浓度、pH、淋洗时间对重金属去除效果的影响.利用一级反应动力学模型对试验数据进行拟合,并测定了EDTA处理前后土壤中重金属形态的变化.结果表明,EDTA溶液在浓度为0.1 mol·L^-1、pH 7、淋洗时间1 d的条件下能达到对污染土壤重金属的最大去除率,去除率分别为Cd 89.14%、Pb 34.78%、Cu 14.96%、Zn 45.14%.模型拟合结果表明,Cd的质量转移系数最大,其次是Zn、Pb和Cu.说明在土壤淋洗过程中,Cd和Zn最先达到质量转移的平衡状态,然后是Pb和Cu.形态分级结果表明,EDTA能有效地去除交换态、碳酸盐结合态和氧化物结合态重金属,而对有机态和残余态部分重金属作用效果不明显.     

施污土壤重金属有效态分布及生物有效性

以城市污泥为研究对象,将城市污泥与土壤按照一定的质量比配成污泥混合土壤.采用6种不同性质提取剂(0.05mol/L EDTA、0.1 mol/L CH3 COOH、0.01 mol/L CaC12、1 mol/L CH3COONH4,0.05 mol/L NaHCO3和0.05 mol/L Tris-HCl)分别对污泥混合土壤中重金属(Cd、Pb、Cu和Zn)的螯合态、酸溶态、中性交换态、中性结合态、碱性交换态和蛋白质结合态进行提取,考察污泥的添加对土壤中不同形态重金属的消长规律.通过黑麦草盆栽试验,探究污泥混合土壤中不同形态重金属的植物可利用性.结果表明:污泥混合土壤中重金属螯合态比例较大,占总量的20.3％-40.0％;其次为酸溶态和中性结合态,而中性交换态、碱性交换态和蛋白质结合态的含量较低.污泥的添加促进了黑麦草对Cd、Cu和Zn的吸收,在污泥添加率为44.4％时根部对其吸收量达最大,分别较CK处理增加了0.3、2.3和6.5倍.抑制了对Pb的吸收,在污泥添加率为37.5％时,根部对Pb的吸收较CK处理下降0.4倍.Pearson相关系数分析结果表明:污泥混合土壤中以螯合态、酸溶态和中性结合态存在重金属可被黑麦草吸收利用.     

贵阳花溪区石灰土林地土壤重金属含量特征及其污染评价

选取贵阳市花溪区典型石灰土林地土壤作为研究对象,分析了林地石灰岩和土壤中7种重金属(Cu、Zn、Mn、Cd、Ni、Pb、Co)的含量特征,以贵州省土壤背景值和全国石灰(岩)土类背景值为评价标准进行林地土壤重金属污染评价和潜在生态风险评价.结果表明:林地石灰岩以Pb的平均含量(40.21mg·kg-1)最高,Zn的(5.78 mg·kg-1)最低,7种重金属平均含量高低顺序为:Pb＞Ni＞Mn＞Co＞Cu＞Cd＞Zn;林地土壤中以Mn的平均含量(451.16 mg·kg-1以上)最高,Cd的(2.87mg·kg-1以下)最低,7种重金属含量的变异系数在8.57%～63.10%之间,Zn的平均含量明显低于贵州省土壤背景值和全国石灰(岩)土类背景值,Cu、Mn、Cd、Pb、Ni、Co的平均含量高于或接近于贵州省土壤背景值和全国石灰(岩)土类背景值.Cu、Zn、Mn、Ni、Co,Ni与Pb,Cd与Pb,Cd与Co来源相同的可能性较大,而Cd与Cu、Ni,Pb与Mn、Cu、Co的来源不同;石灰土偏碱性,富含Ca、Mg元素,有利于重金属Cd、Pb的累积.单因子污染指数和多因子综合指数(内梅罗指数法)与Hakanson潜在生态危害指数的评价结果一致,林地土壤重金属综合污染指数在3.67以上,达到重污染程度,以Cd的污染指数(4.94以上)最高,污染程度最为严重,其次是Pb(1.82以上),Zn、Mn污染程度最低,林地土壤重金属潜在生态危害指数(RI)为173.75以上,为中度生态危害程度,产生最大生态危害的是Cd,其次是Pb、Ni、Co、Cu,危害程度最小的是Mn、Zn,在相同的成土母岩和人为活动影响下,无林地土壤重金属的综合污染指数和潜在生态危害指数均明显高于有林地.     

强还原过程对设施菜地土壤重金属形态转化的影响

设施菜地由于污水灌溉、粪肥施用等导致重金属污染.本文通过土柱淹水同时添加玉米秸秆培养和后期通水淋洗,研究强还原法对设施土壤重金属(Cd、Cu、Pb和Zn)形态转化的影响.结果表明: 强还原处理使土壤pH显著降低,玉米秸秆处理变化更显著;土壤氧化还原电位(Eh)迅速下降至-280 mV左右.玉米秸秆处理可以促进土壤中Cd、Cu、Pb和Zn活化,第9天土壤中有机物及硫化物结合态和残渣态Cd、Cu、Pb和Zn含量比重下降;至15 d培养结束,土壤中4种重金属含量较对照分别减少18.1%、19.0%、16.1%和15.7%.玉米秸秆处理可以增加土壤中Cd和Zn的溶出量,但是Cu的溶出量减少;胶体结合态Cd和Pb含量较对照增加、Cu较对照显著减少、Zn没有显著变化.强还原可以引起设施土壤重金属活化,提高蔬菜积累重金属的风险,而且其随土壤水分的运移可能导致水体的污染.     

镉与豆磺隆复合胁迫下小麦根－土界面镉形态的变化

通过根际箱试验,研究了Cd与豆磺隆复合胁迫下小麦根 土界面Cd形态变化的空间和时间效应.在空间上将根－土界面(0～5 mm)细化到1 mm,在时间上将取样时间分为14、21、28、35和42 d,并将小麦体吸收的Cd与根 土界面各形态Cd作相关分析,从而得出影响小麦体生长的Cd形态.结果表明,在小麦不同的生长时间内,可交换态Cd表现出的空间效应明显不同.在小麦生长的第14天,根－土界面可交换态Cd大体上由根中心区(6.186 mg·kg^-1)向根外区(6.482 mg·kg^-1)逐渐增加;从小麦生长第21天到42天,根-土界面可交换态Cd呈现出由根中心区到某一层升高,之后又由该层到土体下降的趋势.根-土界面各层碳酸盐和铁锰结合态Cd向可交换态Cd转化的趋势由根中心区向根外区逐渐减弱,而向残留态Cd转化的趋势逐渐加强,有机结合态Cd浓度变化在近根区较大.碳酸盐结合态Cd、铁锰结合态Cd、有机结合态Cd浓度随时间而逐渐下降;残留态Cd浓度则表现出明显的上升趋势.相关分析表明,近根层的可交换态Cd和有机结合态Cd是小麦能直接利用的两种Cd形态.豆磺隆对可交换态Cd含量变化以及碳酸盐和铁锰结合态Cd的转化有明显影响.     

Spatial Variation and Fractionation of Bed Sediment-Borne Copper,Zinc, Lead,and Cadmium in a Stream System Affected by Acid Mine Drainage

An investigation was conducted to examine the spatial variation and fractionation of bed sediment-borne Cu, Zn, Pb, and Cd in a stream system affected by acid mine drainage. The pH had a major control on the spatial variation pattern of soluble, exchangeable, and carbonate-bound Cu, Zn, and Cd. There was a prominent concentration peak of carbonate-bound, oxide-bound, and organic-bound metals at the 29 km station, as controlled by the abundance of organic C, carbonate C, and oxides of manganese and iron. In general, the residual fraction was the dominant form for all four investigated metals. It was likely that oxide-Mn played a more important role in binding Zn and Cd than oxide-Fe did. In contrast, Cu had a higher affinity for iron hydrous oxides than for manganese oxide. Pb had a higher affinity for oxides of iron and manganese than for carbonates and organic matter. The presence of organic-bound metals in both the acidic upstream reach and non-acidic downstream reach suggests that the binding of these metals by organic matter was not markedly affected by pH, while the correspondence of organic C peak and organic-bound metal peaks at the 29 km station indicates a strong control by organic matter abundance on the quantity of organic-complexed metals.     

铜尾矿库区土壤与植物中重金属形态分析

对铜陵铜尾矿区土壤和植物中重金属形态进行了研究.结果表明,尾矿库区种植地极端贫瘠,有机质含量仅2.6～.8 g·kg^-1,而土壤Cu、Cd、Pb、Zn含量皆高于对照土壤,其中Cu含量达809.30～1 39.4 mg·kg^-1,Cd含量达3.2～6.3 mg·kg^-1,达到对照土壤30～60倍.结缕草和三叶草体内重金属含量与土壤重金属交换态及有机结合态含量成正相关,与碳酸盐结合态、铁锰氧化物结合态成显著或极显著负相关,与矿物态含量相关性不显著.在两种优势植物中,Cu、Zn、Pb均以活性较低的醋酸提取态、盐酸提取态和残渣态为主;Zn在根系和茎叶中,NaCl提取态占有较大比例,而Cd均以NaCl提取态为主.     

Experimental Assessment of Using Soluble Humic Substances for Remediation of Heavy Metal Polluted Soils

Since heavy metals are nondegradable and strongly bonded in soils, remediation of heavy metal polluted soils by extraction is difficult and current extraction techniques require harsh chemicals such as ethylenediaminetetraacetic acid (EDTA). However, use of EDTA is environmentally problematic because of costs, persistence, toxicity and deterioration of soil structure. Therefore, the potential of soluble natural humic substances (HS) to extract heavy metals from contaminated soils is tested as an environmentally friendly substitute for EDTA. A strongly polluted, calcareous urban soil (CRC soil) and a moderately polluted agricultural soil (CUP soil) were extracted at neutral pH in batch mode by three HS solutions from beech and Norway spruce litter (Beech-HS and Spruce-HS) and processed cow slurry (Bio-HS), all containing 25 mM dissolved organic carbon (DOC). After 10 extractions with a solution to soil ratio of 5:1 (L/kg), 8% to 39% of the total Cd, Cu, Ni and Pb soil contents, lowest for Ni and highest for Cu/Pb, were extracted. Natural and processed HS samples had comparable capacities to extract the heavy metals. A comparison of 100 mM DOC of Bio-HS and EDTA as extractants for Cu from the CRC soil showed extraction of 67% by EDTA and 41% by Bio-HS, indicating somewhat higher efficiency of EDTA than of HS. Sequential extraction of the CRC soil after Bio-HS and EDTA extraction showed removal of exchangeable, carbonate- and metal oxide-bound Cu but also of some residual Cu. It is therefore concluded that HS appears to be an attractive and promising alternative to EDTA as remediation agent for heavy metal polluted soils provided cheap HS of good quality is easily available.     

Preliminary study on heavy metals contamination of soil using solid phase speciation and the influence on groundwater in Bozanta–Baia Mare Area,Romania

Abstract

A preliminary study on soil contamination with heavy metals and As based on solid phase speciation according to the Tessier scheme and the influence on groundwater in an area under anthropogenic influence (Bozanta-Baia Mare, Romania) was conducted. The partitioning of Al, As, Cd, Cu, Fe, Mn, Pb and Zn in five fractions is discussed in relation to soil characteristics, pH, organic matter content, mineralogical composition and distribution of the same elements in airborne particulate matter. The airborne particulate matter contains high quantities of As, Cd, Cu, Pb and Zn as exchangeable fraction. The sequential extraction carried out on soil samples revealed the main role of Fe-Mn oxides surface in the immobilization of metals. Organic matter has a specific role in complexation of Cu, Pb, As and Al, since high contents of these metals were recovered in the oxidizable fraction. Cadmium has a high selectivity for carbonate minerals. The amendment of soil with natural fertilizer increases the exchangeable fraction of metals with the highest toxicity. The available fraction for plants (exchangeable + carbonate-bound species) exceeded the alert values in soil, therefore the continuous monitoring of the area is necessary. The soil is unsuitable for agricultural use due to high contamination on surface with toxic elements resulted from anthropogenic activities. Groundwater is contaminated with very toxic elements (As, Cd and Pb) but also with Cu, Mn and Zn and is unsuitable as supply for drinking water.     

The migration and transformation regular study of metal manganese in surface soil of Yiwang Industrial Park in Shanxi Province,China

All kinds of industries can produce a large amount of the heavy metal Mn emission, especially in the Mn steel plant production process. The assessment of Mn pollution in industrial areas is vital to human health and soil conservation. First, there are 120 samples of 0–5 cm and samples 9 of 0–40 cm of the surface soil collected from outside. Next, the soil column test is applied to study the migration and speciation regularity of Mn in 0–40 cm of soil layer, and then a forecasting model is established to verify and evaluate the Mn pollution in the study area. After the exogenous Mn enters the soil, Mn soon transforms into a more stable form in soil at 0–20 cm depth. But the residual amounts of Mn in deep soil increases with the increase of exogenous Mn. The main speciation of Mn in surface soil includes residual, oxide-bound, and organic-bound forms. Carbonate-bound form is sensitive to the increase of exogenous Mn. The exogenous Mn content has less influence on the content of oxide-bound and organic-bound forms in soils below 20 cm. The prediction model can be used to evaluate the degree of pollution of Mn in surface soil of the study area.     

新疆焉耆盆地辣椒地土壤重金属污染及生态风险预警

从新疆加工辣椒主产地(焉耆盆地)采集105个辣椒地典型土壤样品,测定其中As、Cd、Cr、Cu、Mn、Ni、Pb和Zn等8种重金属元素的含量。采用污染负荷指数(Pollution load index,PLI)、潜在生态风险指数(Potential ecological risk index,RI)和生态风险预警指数(Ecological risk warning index,I_(ER))对辣椒地土壤重金属污染及生态风险进行评价。结果表明:(1)焉耆盆地辣椒地土壤Cd、Cr、Ni、Pb和Zn含量的平均值分别超出新疆灌耕土背景值的1.65、1.40、1.32、3.21、6.42倍。辣椒地土壤Pb和Zn呈现重度污染,Cd、Cr和Ni轻度污染,As、Mn和Cu无污染。(2)土壤PLI平均值为1.40,呈现轻度污染。各重金属元素单项生态风险指数从大到小依次为:Cd、Ni、As、Cu、Pb、Cr、Zn。土壤RI平均值为18.40,属于轻微生态风险态势,IER平均值为-4.78,属于无警态势;博湖县辣椒地污染水平、潜在生态风险程度与生态风险预警等级最高,焉耆县污染水平、潜在生态风险程度与生态风险预警等级最低。(3)辣椒地土壤As、Cd、Pb与Zn主要受到人类活动的影响,Cr、Cu、Mn和Ni主要受到土壤地球化学作用的控制。Cd是焉耆盆地辣椒地生态风险等级最高的重金属元素,研究区农业生产过程中要防范Cd的污染风险。