无机稳定剂处理重金属污染土壤

以重金属污染土壤为研究对象,比较了铁屑、蒙脱石、碳酸钙和羟基磷灰石4种稳定剂对土壤中Pb,Zn,Cd,Cu 4种重金属的稳定效果。实验结果表明,4种稳定剂稳定效率的大小顺序为:羟基磷灰石碳酸钙蒙脱石铁屑。当稳定剂质量分数为10%时,羟基磷灰石、碳酸钙、蒙脱石和铁屑对Pb,Zn,Cd,Cu 4种重金属的平均稳定效率分别为99.63%,98.53%,97.15%,86.95%。未加稳定剂时,土壤中的Pb以残渣态为主,Zn以残渣态和可交换态为主,Cd以残渣态为主,Cu以残渣态和可交换态为主;加入稳定剂后,土壤中4种金属可交换态的所占比例(简称占比)均显著降低,还原态的占比明显增大,残渣态的占比略有增大,氧化态的占比基本保持不变。     

硫酸锰渣污染土壤中重金属的形态分布及生物活性

测定了硫酸锰渣污染土壤中Cu,Zn,Cd,Pb,Mn的总量和各形态含量.结果表明重金属总量远超过环境背景值和土壤环境二级标准.重金属各形态分布特征:Cu,有机态>残渣态>铁锰氧化态>碳酸盐态>可交换态;Zn,残渣态>铁锰氧化态>有机态>碳酸盐态>可交换态;Cd,铁锰氧化态>可交换态>碳酸盐态>残渣态>有机态;Pb,铁锰氧化态>残渣态>有机态>碳酸盐态>可交换态;Mn,铁锰氧化态>残渣态>可交换态>有机态>碳酸盐态.重金属的生物可利用性系数和迁移系数均为Cd>Mn>Pb>Cu>Zn.     

柠檬酸淋洗去除电子垃圾污染土壤中的重金属

采用柠檬酸溶液对模拟电子垃圾污染土壤（简称污染土壤）中Cu,Pb,Cd 3种重金属进行淋洗实验,考察了柠檬酸溶液的浓度、柠檬酸溶液的pH、淋洗时间等对污染土壤中Cu,Pb,Cd的淋洗效果,探讨了柠檬酸溶液淋洗前后污染土壤中Cu,Pb,Cd 3种重金属各形态含量的变化。研究结果表明,在柠檬酸溶液的浓度0.100 mol/L、柠檬酸溶液的pH 5、淋洗时间1 440 min的适宜条件下,对污染土壤中Cu,Pb,Cd的去除率分别达到89.37%,72.11%,86.39%。柠檬酸溶液对3种重金属的去除主要是通过洗出酸可提取态（R1）和酸可还原态（R2）来实现的,每种重金属的R1和R2之和均占到其淋出总量的95%以上,而酸可氧化态（R3）和残渣态（R4）的含量淋洗前后基本无变化。     

表面活性剂与柠檬酸联合洗涤高黏性土壤中的重金属

以一水合柠檬酸（CA）为洗涤剂,分别采用吐温80（TW80）、十二烷基磺酸钠（SDS）、β-环糊精（BCD）和腐植酸（HA）4种表面活性剂与CA联合洗涤高黏性土壤中的重金属,考察表面活性剂与CA的联合洗脱效果。实验结果表明：添加4种表面活性剂均可提高CA对Cu、Zn和Pb的去除率;处理时无需调节体系pH;在表面活性剂与CA的混合液与土壤的液固比为10:1（mL/g）的条件下,采用一次洗涤即可。经4种表面活性剂与CA联合洗涤后,土壤中Cu、Zn和Pb的离子交换态、碳酸盐结合态和铁锰氧化结合态的占比均下降,而硫化物及有机结合态和残渣态的占比有所提升。     

气化炉渣的重金属浸出特性及化学形态分析

分别采用硫酸硝酸法、水平振荡法和醋酸缓冲溶液法制取气化炉渣的浸出液，考察了不同提取方式对浸出液中重金属质量浓度的影响。采用改进BCR连续提取法对气化炉渣中的重金属Cr，Zn，Cu，Pb，Ni，As，Cd的化学形态进行了分析。实验结果表明：煤气化工艺中的气化炉渣属第Ⅰ类一般工业固体废物;在3种提取方式中，醋酸缓冲溶液法的重金属浸出种类最多，且浸出量最大;Cd和Cr对环境具有较高的潜在危害性，Cu次之，Zn，Pb，Ni，As主要以残渣态形式存在，对环境的直接危害性较低。     

复合重金属污染高岭土的电动修复

根据电子废弃物拆解场地的污染特征,以复合重金属(Cu,Cd,Pb)污染高岭土为研究对象,考察了电动技术对污染土壤的修复效果。实验结果表明:在电压梯度为1 V/cm、阳极液为自来水、阴极液为柠檬酸-柠檬酸钠缓冲液(pH=5)、靠近阴极设置活性炭渗透反应墙(PRB)的条件下电动修复96 h后,Cu,Cd,Pb的平均去除率分别可达79.93%,99.43%,39.36%;土壤的酸碱性对电动修复效果影响显著,通过在阴极添加缓冲液维持土壤偏酸性条件,有利于重金属污染物的电动去除;在靠近阴极设置活性炭PRB可富集重金属,减少阴极液的污染;迁移率大的酸可提取态重金属较易去除,残渣态重金属稳定性强,去除率较低。     

典型磷矿区表层土壤重金属空间分布特征研究

以开阳磷矿区为对象,结合地统计学普通克里金插值法以及单因素分析法,研究了矿区表层土壤重金属的空间分布特征,并对其进行了污染评价。结果表明：以矿区当地土壤重金属背景值为标准,Cu,Zn,Pb,Cd,As含量均存在超标情况;5种元素含量的变异程度均为高度变异,Pb,Cd,As的变异系数远大于Cu,Zn的变异系数;土壤重金属空间分布特征为Cd,As含量在东北部的积累程度大于西南部,东北—东南方向Cu,Zn,Pb,Cd,As的富集程度远大于西北—西南方向;不同土地利用类型对重金属的积累没有显著影响,这很可能与其他因素如背景值、风向、人类干扰（如化工产业）等有关。     

赤泥中重金属元素的浸出性与结合形态

采用等离子体质谱仪分析了拜耳法赤泥(BRM)和烧结法赤泥(SRM)中Cr,Ni,Cu,Zn,As,Cd,Cs,Pb等8种重金属元素的含量。采用逐级提取的方法分析了BRM和SRM中8种重金属元素的浸出情况和形态分布差异。实验结果表明:SRM中水溶态As的质量浓度达到17.3μg/L,BRM和SRM中可交换态Cr的质量浓度均在2 300μg/L以上,对水环境可能存在潜在危害;两种赤泥中不同形态重金属的浸出率有较大差异,SRM中Ni和BRM中Zn的总浸出率分别在60%和50%以上。     

添加CaO对燃煤重金属元素富集效果的影响

选取CaO作为吸附剂,探究了不同燃烧温度下添加CaO对重金属元素在燃煤灰渣中富集效果的影响规律。实验结果表明:添加CaO对重金属元素Cr未起到富集作用,而对Mn,Ni,Cu,Zn,As,Cd,Pb 7种重金属元素的富集效果显著;随燃烧温度的升高,CaO对各赋存形态的Mn,Ni,Cu,Zn,As的富集效果先变好而后变差,对各赋存形态的Cd和Pb的富集效果越来越好;CaO添加比(预处理后的CaO颗粒与预处理后的原煤的质量比)越大,CaO对Mn,Ni,Cu,Zn,As,Cd,Pb的富集效果越好,燃烧温度为850℃时的最佳CaO添加比为4%。     

无患子皂苷与柠檬酸协同洗脱污染土壤中镉铅

以某废弃铅锌矿区重金属污染土壤为研究对象,采用无患子皂苷与柠檬酸（CA）协同洗脱污染土壤中的Cd和Pb。以无患子果皮投加量为20 g/L所得水浸提液和浓度为0.3 mol/L的CA配制复配淋洗剂。在浸提液中添加CA后,能有效提高对土壤中Pb的去除率。在浸提液和CA的体积比为1∶3、淋洗剂pH为5、淋洗时间为12.0 h的条件下,复配淋洗剂对Cd和Pb的去除率分别为75.2%和41.6%。双常数方程和Elovich方程均可较好描述复配淋洗剂对污染土壤中Cd和Pb的淋洗过程,表明Cd和Pb的解吸主要为非均相扩散过程。复合淋洗剂能有效降低土壤中Cd的可交换态和Pb的铁锰氧化态含量,并可促进重金属形态的转变。     

Chemical properties of heavy metals in typical hospital waste incinerator ashes in China

Incineration has become the main mechanism for hospital waste (HW) disposal in China after the outbreak of Severe Acute Respiratory Syndrome (SARS) in 2003. However, little information is available on the chemical properties of the resulting ashes. In the present study, 22HW ash samples, including 14 samples of bottom ash and eight samples of fly ash, were collected from four typical HW incineration plants located across China. Chemical analysis indicated that the HW ashes contained large amounts of metal salts of Al, Ca, Fe, K, Mg, Na with a concentration range of 1.8-315gkg(-1). Furthermore, the ashes contained high concentrations of heavy metals such as Ag, As, Ba, Bi, Cd, Cr, Cu, Mn, Ni, Pb, Ti, Sb, Sn, Sr, Zn with a vast range of 1.1-121,411mgkg(-1), with higher concentrations found in the fly ash samples. Sequential extraction results showed that Ba, Cr, Ni and Sn are present in the residual fraction, while Cd existed in the exchangeable and carbonate fractions. As, Mn, Zn existed in the Fe-Mn oxide fraction, Pb was present in the Fe-Mn oxide and residual fractions, and Cu was present in the organic matter fraction. Furthermore, toxicity characteristic leaching procedure (TCLP) results indicated that leached amounts of Cd, Cu and Pb from almost all fly ash samples exceeded the USEPA regulated levels. A comparison between the HW ashes and municipal solid waste (MSW) ash showed that both HW bottom ash and fly ash contained higher concentrations of Ag, As, Bi, Cd, Cr, Cu, Pb, Ti, and Zn. This research provides critical information for appropriate HW incineration ash management plans.     

Distribution of Cd,Ck, Pb and Zn in Soil and Vegetation Compartments in Stands of Five Boreal Tree Species in N.E. Sweden

Concentrations and total quantity of cadmium (Cd), cupper (Cu),lead (Pb) and zink (Zn) were determined in biomass and soil compartments in a replicated tree species experiment with 27-yr-old stands growing on former farmland in N.E. Sweden. Sequentialextractions of soil samples were performed in order to estimate the exchangeable and an organically bound fraction of each element. The tree species included were Picea abies (L.)H. Karst., Pinus sylvestris L., Pinus contorta Dougl., Larix sibirica Ledeb., and Betula pendula Roth.Tree species influenced the rate of removal of Cu, Pb and Zn incase of stemwood harvesting, and of Cd, Cu and Zn in the case ofwhole-tree harvesting. B. pendula and P. abies had higher quantities and average concentrations of Zn in the biomass. For all species, >50% of the Zn in the stems was found in the bark. P. abies and L. sibirica had higher quantities of Cu in the biomass than the other species.P. abies and P. contorta had high quantities of Cd inthe biomass in relation to the other species. Branches and stembark contained high concentrations of Cd and Pb in relation to foliage and stemwood. Dead branches had especially high concentrations of Pb. The high accumulation rate of Zn in thebiomass of B. pendula was related to a low exchangeable amount of Zn in the A horizon. In the superficial centimeters ofthe A horizon, a depletion similar to that found for Zn was detected for Cu, whereas for Cd and Pb, no correlations were found between quantities of elements in the trees and element pools in the soil.     

Dynamics of Cd, Cu and Pb added to soil through different kinds of sewage sludge

A greenhouse experiment was set up to study the distribution of Cd, Cu and Pb in three typical soils of the Pampas Region amended with sewage sludge. A sequential extraction procedure was used to obtain four operationally defined geochemical species: exchangeable, bound to organic matter, bound to carbonates, and residual. Two kinds of sewage sludge were used: pure sewage sludge and sewage sludge containing 30% DM of its own incinerated ash, at rates equivalent to a field application of 150 t DM ha(-1). Pots were maintained at 80% of field capacity through daily irrigation with distilled water. Soil samples were obtained on days 1, 60, 270 and 360, and then air-dried and passed through a 2 mm sieve for analysis. Results showed that sludge application increased the less available forms of Cd, Cu and Pb. The inorganic forms became the most prevalent forms for Cu and Pb, whereas Cd was only found in the residual fraction. The concentrations of OM-Cu and INOR-Cu in the amended soil samples were closely correlated with soil pH, whereas the chemical behavior of Cd and Pb did not depend on soil physico-chemical characteristics.     

稳定化技术在铅砷复合污染土壤修复中的应用

以铅砷复合污染土壤为研究对象,采用硫酸亚铁和氧化钙作为稳定剂,通过正交实验得出各因素对土壤中铅的稳定率影响程度的大小顺序为：氧化钙添加量>硫酸亚铁添加量=养护周期>两种稳定剂的交互作用。最佳实验条件为硫酸亚铁添加量2 g/kg,氧化钙添加量10 g/kg,养护时间2 d。添加硫酸亚铁后,土壤pH对砷的稳定化效果影响不大,砷的浸出质量浓度均较低。过低和过高的pH均不利于土壤中铅的稳定化,当土壤pH=10.06~12.20时,土壤中铅的浸出质量浓度低于目标值。两种稳定剂对土壤中的砷均有稳定化效果,但硫酸亚铁起主要作用,氧化钙起次要作用;氧化钙在土壤中铅的稳定化过程中起主要作用。     

Metal fractionation in soil profiles at automobile mechanic waste dumps.

Soil profiles at five automobile mechanic waste dumps in Port-Harcourt, Nigeria were investigated to assess the spatial distribution, chemical speciation, and likely mobility of Cd, Cu, Pb, Zn, Cr and Ni in the soil as a function of the soil properties. A sequential fractionation protocol was used that generated six different fractions into which soil metal could partition. Cadmium was associated with non-residual fractions at surface horizons, but at lower depths it was in the residual fractions. Copper and Cr partitioned into organic and residual fractions, while Pb was associated with an Fe-Mn oxide fraction and the residual fractions. Zinc in surface horizons partitioned into an Fe-Mn oxide fraction and a fraction that captured carbonate-bound species, but in subsurface horizons, it was mainly in the residual fractions. Ni was predominantly found in the residual fractions. Mobility factors were calculated, and their values tended to decrease with increasing profile depth, indicating that these metals are relatively mobile in the surface horizons compared the subsurface except for chromium in the 15-30 cm depths. The mobility factors for the heavy metals follow the order: Cd > Zn > Pb > Cu > Cr > Ni. The results suggest that there is serious contamination hazard with Cd, Pb, and Zn in the soil profiles.     

Variations of metal distribution in sewage sludge composting

In the study, the variations of heavy metal distributions (of Cu, Mn, Pb, and Zn) during the sewage sludge composting process were investigated by sequential extraction procedures. The total content of Cu and Zn in the composted mixture increased after the composting process. Mn and Zn were mainly found in mobile fractions (exchangeable fraction (F1), carbonate fraction (F2), and Fe/Mn oxide fraction (F3)). Cu and Pb were strongly associated with the stable fractions (organic matter/sulfides fraction (F4) and residual fraction (F5)). These five metal fractions were used to calculate the metal mobility (bioavailability) in the sewage sludge and composted mixture. The mobility (bioavailability) of Mn, Pb, and Zn (but not Cu) increased during the composting process. The metal mobility in the composted mixture ranked in the following order: Mn>Zn>Pb>Cu.     

Solubility and Potential Mobility of Heavy Metals in Two Contaminated Urban Soils from Stockholm,Sweden

The solubility and potential mobility of heavy metals (Cd, Cu,Hg, Pb and Zn) in two urban soils were studied by sequential andleaching extractions (rainwater). Compared to rural (arable) soils on similar parent material, the urban soils were highlycontaminated with Hg and Pb and to a lesser extent also with Cd,Cu and Zn. Metal concentrations in rainwater leachates were related to sequential extractions and metal levels reported fromStockholm groundwater. Cadmium and Zn in the soils were mainly recovered in easily extractable fractions, whereas Cu and Pb were complex bound. Concentrations of Pb in the residual fractionwere between two- and eightfold those in arable soils, indicatingthat the sequential extraction scheme did not reflect the solidphases affected by anthropogenic inputs. Cadmium and Zn conc. inthe rainwater leachates were within the range detected in Stockholm groundwater, while Cu and Pb conc. were higher, whichsuggests that Cu and Pb released from the surface soil were immobilised in deeper soil layers. In a soil highly contaminatedwith Hg, the Hg conc. in the leachate was above the median concentration, but still 50 times lower than the max concentration found in groundwater, indicating the possibilityof other sources. In conclusion, it proved difficult to quantitatively predict the mobility of metals in soils by sequential extractions.     

Predicting the mobility of Zn, Fe, Cu, Pb, Cd from roasted sulfide (pyrite) residues—A case study of wastes from the sulfuric acid industry in Sweden

Leachates from roasted sulfide residues, which are the wastes from the production of sulfuric acid at Falun, Sweden, have low pH and high concentrations of Zn, Fe, and SO₄. The minerals are mainly hematite and maghemite and, because the various sulfides in the feed behave differently during the roasting process, the residual sulfides minerals are pyrrhotite and sphalerite. Oxidation of the residual sulfides contributes acidity, Zn, Fe, Cu, Cd, and sulfate to the effluents from the waste deposits. The dissolution of sphalerite is most likely accelerated in acid solution rich in Fe (III). The formation of Pb-sulfate coatings on galena may provides an armoring effect which slows the oxidation of the galena. Residual sulfides are source phases controlling long-term contaminant release. Other source minerals for Zn, Fe, Pb, Cu, Cd and SO₄ in the effluents are iron oxides which retained percentage quantities of SO₄, roast-derived alteration rims of Zn oxides on sphalerite, alterated silicates formed during the roasting process, and secondary minerals (e.g. Zn, Fe, Cu sulfates, iron hydroxides) that were precipitated by in-site oxidation in the waste dumps. The Zn, Fe, and Cu sulfates most likely control short-term changes in the chemistry of the leachate, while Pb concentration in the leachates may be controlled predominantly by Pb-release from the altered silicates. The mineralogical and geochemical data provide fundamental information essential for the remedial management of this type of industial waste.     

Fractionation of heavy metals in sludge from anaerobic wastewater stabilization ponds in southern Spain

The analysis of heavy metals is a very important task to assess the potential environmental and health risk associated with the sludge coming from wastewater treatment plants (WWTPs). However, it is necessary to apply sequential extraction techniques to obtain suitable information about their bioavailability or toxicity. In this paper, a sequential extraction scheme according to the Standard, Measurements and Testing Programme of the European Commission was applied to sludge samples collected from ten anaerobic wastewater stabilization ponds (WSPs) located in southern Spain. Al, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Ti and Zn were determined in the sludge extracts by inductively coupled plasma atomic emission spectrometry. In relation to current international legislation for the use of sludge for agricultural purposes, none of the metal concentrations exceeded maximum permitted levels. Overall, heavy metals were mainly associated with the two less-available fractions (34% oxidizable metal and 55% residual metal). Only Mn and Zn showed the highest share of the available (exchangeable and reducible) fractions (25-48%).