Study of heavy metal speciation in branch sediments of Poyang Lake

This study concentrates on the environmental pollution level of sediments in the six branches of Poyang Lake, the biggest fresh water lake in China. This is the first systematic report on the speciation analysis of heavy metals （Cu, Co, Cd, Pb, and Ni） in the six branches of the lake. A reported analytical procedure involving a five-step sequential extraction is used for the partition of particulating heavy metals. The sediment samples are analyzed using flame atomic absorption spectroscopy （FAAS）. Experimental results obtained from five replicate samples of fluvial bottom surface sediments at the sampling points demonstrated that the relative standard deviation of the sequential extraction procedure was generally better than 10% （Cd except）. The average extracted contents of the five elements, analyzed after all five steps, are found to be （mg/kg） for Cu： 26.89, Co： 16.25, Cd： 1.08, Pb： 37.98, and Ni： 20.46. The content of the exchangeable species was generally lower. Except Cu, the percentage of the species bond to organic matter was lower than 20%. The fractions containing the most metal for Cu, Co, and Ni were the residues （52.26%, 45.28%, and 74.82%, respectively）.     

珠江口桂山岛沉积物中重金属的污染评价和形态分布特征

在珠江口东侧航道附近的桂山岛周围7个位点采集表层沉积物样品,采用Hakanson生态危害指数法和污染系数初步考察了表层沉积物中重金属污染状况和生态危害程度,并由重金属富集因子分析了沉积物中重金属污染来源.结果表明,沉积物中Cu、Pb、Cd和Zn的富集达到中等污染水平,而Ni尚处于低污染水平;沉积物中重金属的生态危害目前...     

湘江表层沉积物重金属的赋存形态及其环境影响因子分析

采用BCR三步分级提取法分析了湘江衡阳段与岳阳段表层沉积物中4种重金属（Cd、Pb、Cu、Zn）不同赋存形态的含量,阐述了重金属赋存形态及其环境影响因子的关系,评估了这4种重金属的生物有效性.结果表明,4种元素均以弱酸溶解态、可还原态和可氧化态3种可提取态为主,各元素生物有效性即可提取态含量排序为：Cd〉Pb〉Zn〉C...     

Chemodynamics of heavy metals in long-term contaminated soils：Metal speciation in soil solution

The concentration and speciation of heavy metals in soil solution isolated from long-term contaminated soils were investigated. Thesoil solution was extracted at 70% maximum water holding capacity (MWHC) after equilibration for 24 h. The free metal concentrations(Cd2+, Cu2+, Pb2+, and Zn2+) in soil solution were determined using the Donnan membrane technique (DMT). Initially the DMT wasvalidated using artificial solutions where the percentage of free metal ions were significantly correlated with the percentages predictedusing MINTEQA2. However, there was a significant difference between the absolute free ion concentrations predicted by MINTEQA2and the values determined by the DMT. This was due to the significant metal adsorption onto the cation exchange membrane used inthe DMT with 20%, 28%, 44%, and 8% mass loss of the initial total concentration of Cd, Cu, Pb, and Zn in solution, respectively.This could result in a significant error in the determination of free metal ions when using DMT if no allowance for membrane cationadsorption was made. Relative to the total soluble metal concentrations the amounts of free Cd2+ (3%–52%) and Zn2+ (11%–72%) insoil solutions were generally higher than those of Cu2+ (0.2%–30%) and Pb2+ (0.6%–10%). Among the key soil solution properties,dissolved heavy metal concentrations were the most significant factor governing free metal ion concentrations. Soil solution pH showedonly a weak relationship with free metal ion partitioning coefficients (Kp) and dissolved organic carbon did not show any significantinfluence on Kp.     

重金属污染土壤化学淋洗技术的文献计量学分析

土壤化学淋洗是一项新兴的高效土壤修复技术,近年来得到了快速发展。以化学淋洗技术修复重金属污染土壤为研究对象,对这一领域相关研究论文和专利进行了文献计量学分析。在此基础上,系统梳理了该领域国内外年度发展趋势;分析了论文和专利的重要研究机构、区域及国家分布情况;探讨了该领域我国与世界主要发达国家和地区间存在的差距。分析表明:该领域的研究重点和热点应为淋洗的工艺与设备及淋洗剂。     

Effect of moisture regime on the redistribution of heavy metals in paddy soil

Sequential extraction procedure was applied to assess the dynamics of solid-phase transformation of added Cu, Pb, Cd, and Hg in a typical Chinese paddy soil incubated under three moisture regimes (75% field capacity, wetting-drying cycle, and flooding). The heavy metals spiked in the soil were time-dependently transferred from the easily extractable fraction (the exchangeable fraction) into less labile fractions (Fe-Mn oxide- and organic matter-bound fractions), and thus reduced lability of the metals. No significant changes were found for the carbonate-bound and residual fractions of the heavy metals in the soil during the whole incubation. Change rate of the mobility factor (MF), a proportion of weakly bound fractions (exchangeable and carbonate-bound) in the total metal of soil, reflected the transformation rate of metal speciation from the labile fractions toward stable fractions. It was found that soil moisture regime did not change the direction and pathways of transformation of metal speciation, but it significantly a ected the transformation rate. In general, the paddy soil under flooding regime had higher metal reactivity compared with 75% field capacity and wetting-drying cycle regimes, resulting in the more complete movement of metals toward stable fractions. This might be related to the increased pH, precipitation of the metals with sulfides and higher concentration of amorphous Fe oxides under submerged condition.     

Application of chemometrics methods for the estimation of heavy metals contamination in river sediments

The concentration and speciation of six heavy metals in sediments of eight sampling sites of Haihe River were investigated. The metals, namely Cd, Cu, Co, Ni, Mn and Pb were considered. By using sequential extraction(SE), the total metals were divided into five fractions: exchangeable, carbonate bound, iron/manganese oxide bound, sulfides and organic matter fraction and residual fraction. A multivariate statistical approach( principal component analysis, PCA) was used to evaluate the contamination of heavy metals by the total levels and chemical forms, respectively. The results showed that the total metals concentration(TMC) could not provide sufficient and accurate information because the mobility, bioavailabllity and toxicity of metals depend not only on their total concentration but also on the physicochemical form in which they occur.     

密云水库上游某铁矿区土壤重金属含量及形态研究

应用富集因子法(EF)和风险评估编码方法(RAC)对北京市密云水库上游某铁矿矿区及其周边土壤中重金属的分布状况和潜在生态风险进行了研究.结果表明,各重金属元素含量除As外,其余均明显高于北京市土壤重金属背景值,矿区的选冶活动已经对下游的水体和土壤环境造成一定的影响.富集因子法评价表明Cd、Pb、Cr富集较为严重,达到显著污染水平.形态分析表明,残渣态是重金属元素的主要存在形态, Cd元素可交换态所占比例(2.88%~21.15%)最高,RAC评价结果显示Cd基本处于中等风险水平,Pb为无风险,风险等级由强至弱的顺序为:Cd>Mn>Zn>Cu>Co>Cr>Pb.     

新河污灌区土壤中重金属的形态分布和生物有效性研究

通过野外采样调查和实验分析,对北京市新河污灌区土壤中Cu、Pb、Zn、Cd 4种重金属的含量、形态分布和生物有效性进行了研究.首次尝试运用体外消化法研究了土壤中重金属的生物有效性问题,并与经典的Tessier五步连续提取法的结果进行了对比.结果发现,新河污灌区土壤中,Cd的浓度超过国家二级标准,Cu、Pb、Zn的浓度未超标.土壤中Cu、Pb、Zn主要以残渣态存在,Cd主要以有机结合态存在,且Cd的可交换态比例最高,生物有效性也最高.体外消化法分析得到的重金属生物有效性成分的含量要比利用化学形态分析法分析得到的高,但Cu、Pb、Zn、Cd 4种重金属的生物有效性排序是相同的,即Cd＞Zn＞Pb＞Cu.两种方法提取的重金属含量之间有相关关系.     

土壤重金属测定的前处理的方法的改进

本文根据美国EPA的微波消解标准方法,结合了我国传统的土壤消解方法,解决了传统的土壤消解方法的时间长,试剂消耗量大的问题。     

Microbial diversity of soil bacteria in agricultural field contaminated with heavy metals

In this study we evaluated the bacterial diversity in a soil sample from a site next to a chemical industrial factory previously contaminated with heavy metals. Analysis of 16S rDNA sequences amplified from DNA directly extracted from the soil revealed 17 different bacterial types （genera and/or species）. They included Polyangium spp., Sphingomonas spp., Variovorax spp., Hafina spp., Clostridia, Acidobacteria, the enterics and some uncultured strains. Microbes able to tolerate high concentrations of cadmium （500μmol/L and above） were also isolated from the soil. These isolates included strains of Acinetobacter （strain CD06）, Enterobacter sp. （strains CD01, CD03, CD04 and CD08） （similar strains also identified in culture-independent approach） and a strain of Stenotrophomonas sp. The results indicated that the species identified from direct analysis of 16S rDNA of the soil can be quite different from those strains obtained from enrichment cultures and the microbial activities for heavy metal resistance might be more appropriately addressed by the actual isolates.     

柠檬酸对重金属复合污染土壤的浸提效果研究

以浙江富阳某炼铜厂附近受Cd、Cu、Pb和Zn复合污染的土壤为研究对象,采用振荡、静置和超声3种不同浸提方式,通过研究柠檬酸在不同浸提方式下对重金属的去除效果,筛选出最佳柠檬酸浓度、处理时间及功率,并采用Tessier连续提取法分析浸提前后4种重金属形态变化.结果表明,柠檬酸对4种重金属均具有较好的去除效果,其中对Zn的去除效果最好,Cd的去除效果最差,而Cu和Pb的去除效果相当.Pb和Zn的去除率均随着柠檬酸浓度的增加而增加,但增幅随之减小,Cu的去除率则先增加后基本保持不变,而Cd的去除率变化不明显.综合考虑成本和浸提效果后,选用0.2 mol·L-1柠檬酸浸提2次为最优条件,最佳振荡时间和静置时间分别为4 h和24 h,最佳超声时间和功率分别为30 min和500 W.柠檬酸能够在很大程度上改变土壤中重金属的形态分布,主要去除以可交换态和碳酸盐结合态形式存在的Cd及以碳酸盐结合态和铁锰氧化物结合态形式存在的Cu、Pb和Zn.通过对比3种浸提方式,在同等去除效果的前提下,静置浸提相比振荡浸提需要更长的时间,而将超声波应用于重金属污染土壤淋洗,所需时间较少,因此,超声波辅助浸提土壤中重金属是可行的,具有良好的应用前景.     

丹江口水库沉积物重金属形态分布特征及其迁移能力

以丹江口库区及其支流为研究对象,采用连续分级提取法研究了表层沉积物中Cr、Ni、Cu、Zn、As、Cd、Hg和Pb各形态的空间赋存特征和相对比例,探讨了各形态金属的稳定度并对其进行污染评价.结果表明,表层沉积物各形态金属分布都具有明显的空间差异性,高值集中于库区中部、西部入库支流和丹江库区西北部.沉积物中Pb的可还原态、Cd的弱酸提取态占总量的质量分数较高,分别达到54.91%和42.19%,其余重金属则以残渣态为主.重金属稳定度分析表明,8种金属稳定性顺序为Cr >Pb >As >Ni >Cu >Hg >Zn >Cd,Cd在大部分点位处于不稳定状态,快速解吸释放的风险较大.     

Mobilities and teachabilities of heavy metals in sludge with humus soil

Chemical forms of Zn, Ni, Cu, and Pb in municipal sewage sludge were investigated by adding humus soil to sludge and by performing sequential extraction procedures. In the final sludge mixtures, Zn and Ni were mainly found in Fe/Mn oxide-bound (F3) and organic matter/sulfide-bound (F4) forms. For Zn, exchangeable (F1), carbonate-bound (F2), and F3 forms were transformed to F4 and residual forms (F5). For Ni, Fl and F2 forms were transformed to Fl, F2, and F3 forms. Both Cu and Pb were strongly associated with the stable forms F4 and F5. For Cu, F2 and F3 forms were major contributors, while for Pb, F3 and F4 forms were major contributors to F5. Humus soil dosage and pH conditions in the sludge were strongly correlated with the forms of heavy metals. Five forms were used to evaluate metal mobilities in the initial and final sludge mixtures. The mobilities of the four heavy metals studied decreased after 28 days. The metal mobilities in the final sludge mixtures were ranked in the following order: Ni > Zn > Cu = Pb. Leaching tests showed that the mobilities of Zn and Ni in lower pH conditions (pH 4) were higher than those in higher pH conditions (pH 8).     

Mobilities and leachabilities of heavy metals in sludge with humus soil

Chemical forms of Zn, Ni, Cu, and Pb in municipal sewage sludge were investigated by adding humus soil to sludge and by performing sequential extraction procedures. In the final sludge mixtures, Zn and Ni were mainly found in Fe/Mn oxide-bound (F3) and organic matter/sulfide-bound (F4) forms. For Zn, exchangeable (F1), carbonate-bound (F2), and F3 forms were transformed to F4 and residual forms (F5). For Ni, F1 and F2 forms were transformed to F1, F2, and F3 forms. Both Cu and Pb were strongly associated with the stable forms F4 and F5. For Cu, F2 and F3 forms were major contributors, while for Pb, F3 and F4 forms were major contributors to F5. Humus soil dosage and pH conditions in the sludge were strongly correlated with the forms of heavy metals. Five forms were used to evaluate metal mobilities in the initial and final sludge mixtures. The mobilities of the four heavy metals studied decreased after 28 days. The metal mobilities in the final sludge mixtures were ranked in the following order: Ni > Zn > Cu = Pb. Leaching tests showed that the mobilities of Zn and Ni in lower pH conditions (pH 4) were higher than those in higher pH conditions (pH 8).     

The role of arbuscular mycorrhiza on change of heavy metal speciation in rhizosphere of maize in wastewater irrigated agriculture soil

To understand the roles of mycorrhiza in metal speciation in the rhizosphere and the impact on increasing host plant tolerance against excessive heavy metals in soil, maize ( Zea mays L. ) inoculated with arbuscular mycorrhizal fungus ( Glomus mosseae) was cultivated in heavy metal contaminated soil. Speciations of copper, zinc and lead in the soil were analyzed with the technique of sequential extraction. The results showed that, in comparison to the bolked soil, the exchangeable copper increased from 26% to 43% in non-infected and AM-infected rhizoshpere respectively; while other speciation (organic, carbonate and Fe-Mn oxide copper) remained constant and the organic bound zinc and lead also increased but the exchangeable zinc and lead were undetectable. The organic bound copper, zinc end lead were higher by 15%, 40% and 20%, respectively, in the rhizosphere of arbuscular mycorrhiza infected maize in comparison to the non-infected maize. The results might indicate that mycorrhiza could protect its host plants from the phytotoxicity of excessive copper, zinc and lead by changing the speciation from bio-available to the non-bio-available form. The fact that copper and zinc accumulation in the roots and shoots of mycorrhia infected plants were significantly lower than those in the non-infected plants might also suggest that mycorrhiza efficiently restricted excessive copper and zinc absorptions into the host plants. Compared to the non-infected seedlings, the lead content of infected seedlings was 60% higher in shoots. This might illustrate that mycorrhiza have a different mechanism for protecting its host from excessive lead phytotoxicity by chelating lead in the shoots.     

北京市大兴区土壤重金属含量的空间分布特征

在面积为1039km2的北京市大兴区布设了70个取样点,测定了其表层土壤重金属Cu、Zn、Pb、Cr、Cd、Ni、As、Se、Hg和Co的含量.统计结果表明,除As和Se外,其它重金属平均含量均高于其背景含量.只有个别地方Cd的含量超过了国家二级标准限值,而其余重金属含量均没有超过其二级标准.通过半方差函数分析,发现10种重金属元素在一定范围内均存在空间相关性.采用Kriging最优内插法得到了表层土壤重金属含量的空间分布图,发现土壤重金属含量与土壤质地和有机质含量关系密切.目前大兴区土壤重金属的主要来源是污灌,特别是来自凉水河、新凤河和凤河的污水,应重点对这些河流周围的排污企业进行治理,严格执行达标排放.     

应用化学提取法评价大气颗粒物中重金属的生物有效性

以广州市楼顶降尘为研究对象,在分析其粒度分布和重金属总量的基础上,采用单一化学提取法（DWLP、TCLP）和多级化学提取法（SEP）研究了大气颗粒物中4种重金属元素的生物有效性。结果表明：样品中96％以上颗粒小于100μm,其中10μm和2．5μm以下颗粒分别占33％和11％。大气颗粒物中重金属含量很高,Cu、Pb、Zn和Cd的平均含量分别为362．43、1033．81、830．32和5．80mg／kg,是广东省环境土壤背景值的17～64倍。单一提取法中,TCLP的提取效率明显高于DWLP,表明pH值是影响大气颗粒物中重金属释放的主要因素。SEP法结果显示,Zn和Cd的生物可利用态比例远高于Cu和Pb。经DWLP和TCLP法提取后,颗粒物中重金属的总含量有不同程度的降低,生物可利用态所占比例明显增加。通过综合分析,发现SEP此其他两种方法更适用于评价大气颗粒物中重金属的生物有效性。     

超声辅助EDDS/EGTA淋洗对土壤重金属形态、环境风险的影响及响应面优化

采用响应面法实验设计研究了超声辅助EDDS/EGTA淋洗对Cu、Zn、Pb和Cd等不同重金属的洗脱效果和对残留重金属化学形态分布的影响,以超声功率、初始pH、EDDS投加量、EGTA投加量作为考察对象,以各重金属去除率及其环境风险削减率为响应值进行了模拟和优化.结果表明,EDDS对Pb的洗脱效率最高,Cu、Zn次之,Cd最低;EGTA对Cd的洗脱效率最高,Pb、Zn次之,Cu最低;超声功率对Cu、Pb去除强化效果明显,对Cd影响小,对Zn无显著影响;初始pH值为酸性时,Cu和Zn去除率高,碱性时Pb去除率较高,Cd去除率有所下降.EDDS与EGTA投加量及EGTA投加量与初始pH值对环境风险总削减率存在交互作用.超声辅助EDDS/EGTA对可还原态重金属洗脱效果较好,但容易导致弱酸提取态Cu和Pb残留率有所升高.响应面优化结果表明,当EDDS和EGTA投加量分别为重金属总摩尔数的1.92和2.56倍、超声功率为600 W、淋洗液初始pH值为5.27时,环境风险总削减率达到77.58%,与模拟值相近,模型具有较好的模拟和预测能力.     

污染土壤中重金属的超声波强化EDTA洗脱及形态变化

以EDTA为洗脱剂,对重金属污染土壤进行超声波强化洗脱正交实验,并用Tessier连续提取法研究了洗脱前后Cd、Cu、Pb、Zn的形态变化.结果表明,在EDTA浓度20 mmol·L-1、固液比1∶20、超声波作用时间16 min、超声波功率54%、洗脱次数4次的条件下,对4种重金属洗脱率最大,分别为:Cd 83.6%、Cu 58.8%、Pb 98.0%、Zn 43.0%.在实验所设浓度范围内,随着EDTA浓度的升高,重金属洗脱率均有降低.形态分析结果显示,超声波强化EDTA洗脱能显著降低土壤重金属的残渣态含量.除土壤中Zn残渣态去除率只有5.7%以外,超声波强化EDTA洗脱对土壤中Cd、Cu、Pb的残渣态去除率都很高,分别为81.6%、62.3%、93.8%.