土壤重金属的形态分布特征及其影响因素

土壤重金属元素在介质中的存在形态是衡量其环境效应的关键参数.选择长江三角洲地区的江苏省昆山市为研究区,采集了126个土壤表层样品,通过欧共体标准司提出的BCR 3步提取法对土壤中Cd、Cr、Cu、Co、Ni、Pb和Zn等7种重金属元素的形态分布特征进行了分析,并采用逐步回归法探讨了影响重金属化学形态的影响因素.研究结果表明,Cd主要以可还原态存在,Pb主要以有机结合态存在,而Cr、Cu、Ni、Zn和Co 5种元素主要以残渣态存在,不同重金属元素的次生相态所占总量百分比由大到小的顺序为Cd、Pb、Co、Cu、zn、Ni、Cr.重金属总量是影响重金属形态含量的最主要因素,其次为有机质和pH值,FeOx含量是影响残渣态含量的主要因素,粘粒含量是影响Zn各形态的主要因素,MnOx含量是影响Pb各形态的主要因素.     

宁波市回龙河表层沉积物重金属的形态分析及风险评价

为了解回龙河表层沉积物中重金属的污染状况,采集了表层沉积物样品,测定了重金属Zn、Cu、Pb、Cr、Cd和Ni的总量及其化学形态,并采用潜在生态风险指数法对重金属进行了生态风险评价。结果显示,回龙河表层沉积物中Zn、Cu、Pb、Cr、Cd和Ni均有一定程度的累积,总量分别为286.4～1277.9mg/kg、21.71～146.0mg/kg、10.33～44.20mg/kg、25.13～90.40mg/kg、0.07172～0.3901mg/kg、13.27～157.2mg/kg,其中Cu、Cr、Pb与Ni 4种重金属具有一定的同源特性;形态分析表明,Cu的形态分布以有机结合态为主,最容易迁移释放,Zn、Cr和Ni除残渣态外,铁锰氧化结合态和有机结合态占一定比例,具有潜在风险;潜在生态风险指数法分析表明,沉积物中重金属元素的单一潜在生态风险指数顺序为Cd〉Cu〉Ni〉Zn〉Pb〉Cr,潜在生态危害指数RI均小于150,总体上回龙河处于轻微的生态风险等级。     

黔西北炼锌矿区土壤重金属形态分析及风险评价

为研究黔西北炼锌矿区土壤和矿渣中重金属总量及形态分布特征,采用Tessier五步连续提取法和风险评价编码法(RAC)探讨其污染程度。结果表明,除Cr和Ni外,其他各重金属平均值均超出贵州省的土壤背景值,其中Pb、Zn、Cd污染严重。形态分析表明,土壤和矿渣样品中Pb、Zn、Mn以残渣态(分别占其总量的45.91%、55.11%、42.71%)和铁锰结合态(分别占其总量的33.33%、28.26%、41.78%)为主;Cd的可交换态和碳酸盐结合态之和占总量的30.63%;Cu的有机结合态为65.11%,其次是残渣态30.79%;Cr和As则以残渣态为主要形态,平均占比均超过90%。RAC评价结果表明,矿区周边土壤中Cd元素具有极高的潜在生态风险,其他重金属潜在生态风险水平较低。     

耕地土壤铜、镉、锌形态及生物有效性研究

土壤重金属总量常被用来评估土壤质量安全，但是大量事实说明单纯用土壤重金属总量并不能完全说明土壤重金属的生物有效性及其环境风险。相对于国内外常用的Tessier的五态方法，欧共体标准物质局提出的三步提取法（BCR法1，中国地质调查局地质连续提取法的七态标准少见报道。本研究选取河南平原耕地样品，采用中国地质调查局地质连续提取法（DD2005．03）进行耕地中重金属元素（Cu、Cd、Zn）的形态分布，结果表明：Cu、Zn主要以残渣态存在，其残渣态分别占全量的55．80％和67．35％。Cd以离子交换态为主，占全量的27．30％。Cu、Cd、Zn各态含量占全量比例的顺序是，Cu：残渣态〉弱有机结合交换态〉铁锰氧化态〉碳酸盐结合态〉强有机结合态〉水溶态〉离子交换态。Cd：离子交换态〉弱有机结合交换态〉强有机结合态〉残渣态〉碳酸盐结合态〉铁锰氧化态〉水溶态。Zn：残渣态〉铁锰氧化态〉弱有机盐结合态〉离子交换态〉强有机结合态〉碳酸盐态〉水溶态。从生物可利用性系数k来看，Cd主要以活动性较大的状态存在，很容易被作物吸收。     

青岛城市土壤重金属的形态分布及影响因素分析

选取青岛市不同功能区63个代表性的表层土壤样品,分析了其重金属元素的含量和存在形态.结果表明,青岛城市土壤中Cu、Zn、Pb、Cd均受到不同程度的污染,其中Cd属于重度污染,土壤重金属累积污染程度为Cd>Zn>Cu>Pb.Cu和Zn主要以残渣态为主,Pb主要以残渣态和铁锰氧化态为主,Cd主要以残渣态和有机结合态为主;土...     

填埋场内重金属总量及其形态分布对迁移性的影响

以杭州市天子岭填埋场为例，对不同深度填埋层中的重金属总量、重金属迁移率和重金属形态分布进行了研究．结果表明，尽管填埋层中的重金属总量是土壤背景值的数十倍，超出土壤环境质量标准，但是重金属的迁移率却很低．另外，重金属迁移率与可交换态含量相关；Cd，Cu，Pb，Cr，Ni和Zn在填埋层中均以残渣态为主，填埋场中重金属都得到了有效固定，迁移性很差；各元素的易还原态与难还原态是重金属除残渣态之外主要的结合态(除Cr)，铁锰氧化物循环是控制填埋场中重金属转化行为的主要机制之一；Cu的酸可溶态与易还原态具有较好的相关性，说明cu这两种形态的转化行为相似．     

南京城市土壤中重金属的化学形态分布

采取Tessier连续提取法，研究了南京市不同城区表层土壤中Fe,Mn,Cr,Ni,Co,V,Cu,Zn,Pb的化学形态分布。结果表明，南京城市土壤中Fe,Mn,Cr,Ni,Co,V,Zn,Pb以残渣晶格态为主，可交换态比例极低；Cu在城市道路旁的土壤中有机物结合态所占的比例最高，其他区域残渣晶格态所占的比例最高，与非城区自然土壤相比，主要来源于人为输入的Mn,Cu,Zn,Pb残渣晶格态所占的比例低，活性态比例大；Cr和主要来源于原土壤物质的Fe,Ni,Co,V在城市土壤与非城区自然土壤中各形态所占的比例相似，残渣晶格态比例大，活性态比例极低。     

深圳市内某河表层沉积物重金属含量及污染评价

2008年11月,从广东省深圳市内某河采集9个(0—5cm)表层沉积物样品,分析其Cu,Cd,Cr,Pb,Zn,Ni,As和Hg的含量和前6种元素的形态分布,并采用潜在生态风险指数法进行污染评价.结果表明,沉积物中Cu和Zn的含量普遍较高,为5.27—1865mg.kg-1和198.4—1275mg.kg-1,其次是Cr,Ni和Pb,为54.39—908.7mg.kg-1、31.3—445.5mg.kg-1和11.63—814.9mg.kg-1,As,Cd和Hg的含量较少;Cd的残余晶格态、Cr的铁/锰氧化态和残余晶格态、Cu的有机结合态和残余晶格态,以及Ni,Pb和Zn的铁/锰氧化态为各元素的主要存在形态;沉积物中Cd和Cu的潜在生态风险普遍较大,9个样品中6个达到Cd极强生态危害,4个达到Cu很强生态危害,有5个样品的重金属混合污染潜在生态风险达到极强生态危害.     

青岛市冬季降尘中重金属的形态分析及其环境风险评估

在2017年冬季采集青岛市交通区、居民区、高教区和工业区等功能区的降尘样品,研究了金属元素(Al、Fe、Cd、Cr、Cu、Pb、Zn)的赋存形态和环境风险.结果表明,Cd、Cr、Cu、Pb、Zn的平均含量为0.5、56.4、231.2、143.5、394.1 mg·kg~(-1),均超出了青岛土壤背景值,Cu的含量是背景值的12.8倍.Cd的可交换态(24.5%)和碳酸盐结合态(19%)所占比例较高,Pb、Zn的铁锰氧化态含量高,分别为23.7%、44.6%;Cu以有机态(70.2%)为主,Al、Fe、Cr、Pb金属主要赋存于残渣态中(46%—83%).功能区中的Cd、Pb、Zn的交换态和碳酸盐结合态以交通区和居民区比重较大,且与总量呈极显著相关(P0.01);Cu、Cr的可交换态在居民区和交通区含量较高,两种金属的碳酸盐结合态分别在工业区和高教区含量较高,Cu的可交换态与总量呈正相关(P0.05).风险评价编码法(RAC)表明降尘对环境构成的风险排序为CdZnPbCuCr,Cd在各功能区处于高风险,Pb和Zn属于中等风险,Cr属于低风险.Cu在工业区处于中等风险,在其他3个功能区处于低风险.     

外源重金属在珠江河口湿地土壤中的形态转化

采集珠江口湿地土壤,采用室内培养和Tessier化学逐级连续浸提方法研究了外源重金属在珠江河口湿地土壤中的化学形态转化,探讨了盐分变化对重金属形态转化的影响.试验结果表明,外源重金属进入珠江河口湿地土壤后主要以可利用态和潜在可利用态存在,Ni、Zn、Cu、Cr和Pb主要向铁锰氧化物结合态转化,而Cd主要向可交换态和碳酸盐结合态转化.土壤盐分含量递增对重金属Cu、Zn、Ni和Cr的形态分布无显著影响,对重金属Pb和Cd的影响主要体现在可交换态.在土壤盐分添加量不超过80 g·kg-1时,随着土壤含盐量的上升,土壤Cd和Pb的可交换态比例逐步增大.     

Metal binding capacity of soft acid,organic‐rich waters

Organic carbon from one stream and two ponds in South Carolina was fractionated into five nominal molecular diameter fractions by ultrafiltration. The concentrations associated with and binding capacity for Ca, Cd, Cu and Pb were determined for each fraction. The distribution of organic carbon among ultrafilter fractions varied from water to water, with the largest percentage occurring in the smaller fractions. Calcium was associated with each of the fractions isolated from each of the three waters, indicating Ca is bound to organics in all fractions, however, more than 99% of the Ca which passed the smallest ultrafilter was removed by cationic exchange resin. Each fraction bound more Ca than Cd, Cu or Pb except in a few cases where Pb binding was greater. All of the organic fractions had their Ca++ binding sites saturated. Calcium was not an effective competitive ion against Cd, Cu or Pb for organic binding sites. The total Cu binding capacity was less than that of Ca or Pb but similar to that of Cd. Naturally occurring organics bound more Pb than Cd or Cu but less than Ca. Saturation of Cu binding sites was less than 20% in most ultrafilter fractions except that with a nominal molecular weight of between 10,000 and 300,000 where the percent of saturation was as much as 60%. Approximately 50% of the Cu was removed onto anionic exchange resin in two waters while more than 90% was removed from water with a high organic content. Percent saturation of Cd and Pb binding sites ranged from 0.091% to 5.4% and 0.059% to 1.5%, respectively. All ions tested effectively competed with Cd, Cu or Pb for some but not all binding sites, indicating that organic binding sites were heterogeneous. A generalized order of metal‐organic stabilities based on competition for binding sites is Al>Cd>Pb>Cu>Ni = Mg=Zn = Mn>Ca. Both Cd+2 and Al+3 effectively out competed Pb++ and Cd and Pb out competed Cu for most organic binding sites.     

水稻不同生育期土壤砷形态分布特征及其生物有效性研究

采用田间原位试验和Tessier连续提取方法,在水稻（Oryza sativa L.）不同生育期研究了重金属复合污染高、中、低3个水平下的土壤砷的形态分布特征及其生物有效性。结果表明：在水稻不同生育期中,土壤各种形态的砷质量分数均表现为高污染水平土壤〉中等污染水平土壤〉低污染水平土壤;土壤中砷在水稻整个生育期均以残留态为主,占90%以上,交换态砷所占比例最低,不到0.5%;不同形态砷之间大都显著正相关,但是两种有效性较高的砷形态（交换态和碳酸盐结合态）与有机态砷之间的相关性较差;土壤砷的生物有效性表现为高污染水平土壤〉中等污染水平土壤〉低污染水平土壤,且随着水稻生育期的延长,土壤砷的生物有效性逐渐升高。     

外源Cd~(2+)在土壤各级微团聚体中的含量和形态分布

采用室内培养和室内分析相结合的方法,研究了外源Cd~(2+)进入土壤30 d后,在土壤各级微团聚体中的含量富集和形态赋存情况.研究结果表明:外源水溶性镉进入土壤30 d后,100%转化成了颗粒态,其中58.5%转化为了可交换态,0.98%转化成了碳酸盐结合态,1.26%转化成了铁锰氧化物结合态,7.68%转化成了有机结合态,31.5%转化成了残渣态,这基本与其中各粒级微团聚体中的赋存形态的情况一致.在土壤中赋存的镉主要分布在各级微团聚体中,在各粒级微团聚体中的含量分布顺序为<10μm微团聚体>10～50μm微团聚体>50～250 μm微团聚体;外源镉向小粒级微团聚体的富集倾向明显高于向大粒级微团聚体的富集倾向,其中在<10μm微团聚体中富集系数为1.43,在50～250μm微团聚体中的富集系数只有0.60.     

马缨丹对镉的生长响应及其富集、转运和亚细胞分布特点研究

镉是植物非必需且生物毒性最强的重金属元素之一，然而镉富集植物能通过一定的响应机制来减少镉对自身产生的毒害，且不同植物之间镉的解毒机制存在差异。马缨丹（Lantana camara L.）是四川汉源铅锌矿区镉污染土壤的修复植物，但是关于其镉的分布特征和解毒机制并不明确。因此本文采用盆栽模拟试验，分别设置0（对照，不添加镉）、30、90、150、210 mg·kg-1镉5个处理，研究马缨丹对镉的富集、转运及其亚细胞分布特点，探讨马缨丹对镉的耐性和解毒机制，以期为植物耐镉的生理和分子生物学机制提供一定的理论依据。结果表明：镉质量分数低于90 mg·kg-1时对马缨丹生长没有影响，而镉质量分数高于150 mg·kg-1时对马缨丹生长有显著的抑制作用；随着镉质量分数的增加，马缨丹各器官中镉的质量分数逐渐增加，表现为根＞茎＞叶，且其转运系数小于1，表明马缨丹对镉有较强的根部滞留能力，可限制过量的镉向地上部器官的转运，减少镉对地上部的毒害，这可能是马缨丹耐受镉胁迫的机制之一；随着镉质量分数的增加，马缨丹地下部和地上部的镉富集量总体上均呈增加趋势，在210 mg·kg-1镉处理时，均达到最大值，分别为142.8和1031.6μg·plant-1，不同质量分数镉处理下，马缨丹地上部的镉富集量较大，占全株镉富集量的94.0%~88.3%；镉在马缨丹根和叶细胞可溶性组分中的分配比例最高，分别占62.1%~54.2%和59.8%~52.6%，其次在细胞壁中，分别占23.8%~34.4%和28.7%~39.5%，在细胞器和细胞膜中的较低，表明可溶性组分和细胞壁是镉在马缨丹根和叶细胞中的主要分布位点，液泡区隔化和细胞壁固持可能是马缨丹对镉的重要解毒和耐性机制之一。     

Heavy-metal fractionation and distribution in soil profiles short-term-irrigated with sewage wastewater

Six soil profiles irrigated and non-irrigated with sewage wastewater were investigated for soil pH, electrical conductivity (EC), organic matter (OM), and CaCO₃. The distributions and chemical fractions of Cu, Zn, Cd, and Pb, and their lability were also studied. The results indicated that pH, EC, OM, and CaCO₃, as well as metal fractionation in soil profiles were affected by wastewater irrigation, especially in the surface layer. The surface layer (0-15 cm) irrigated with wastewater exhibited a 0.6 unit decrease in soil pH, a 40.6% decrease in CaCO₃, and a 200% increase in EC as compared with that of the non-irrigated soil. The soil OM increased from 0.04% to 0.35% in the surface layer. The irrigation of soil with wastewater resulted in transformation of metals from the carbonate fraction (CARB) towards the exchangeable (EXCH), Fe-Mn oxide (ERO), and organic (OM) fraction for Zn, towards the EXCH, the OM, and residual fraction for Cu, and towards the exchangeable (EXCH) fraction for Cd. It was concluded that the use of sewage wastewater led to salt accumulation and an increase in the readily labile fraction of Zn, Cu, and Cd in the surface layer. Therefore, this reason may limit the use of wastewater under arid and semi-arid conditions.     

Polypropylene microplastics alter the cadmium adsorption capacity on different soil solid fractions

• PP-MPs reduced the adsorption capacity of the bulk soil for Cd in aqueous medium. • The responses of the POM, OMC and mineral fractions to PP-MPs were different. • PP-MPs reduced the adsorption of POM and OMC fractions to Cd. • PP-MPs increased the adsorption of mineral fraction to Cd. • Effect of MPs on soil may be controlled by proportion of POM, OMC and mineral fractions. Microplastics (MPs) are widely present in a variety of environmental media and have attracted more and more attention worldwide. However, the effect of MPs on the the interaction between heavy metals and soil, especially in soil fraction level, is not well understood. In this study, batch experiments were performed to investigate the adsorption characteristics of Cd in bulk soil and three soil fractions (i.e. particulate organic matter (POM), organic-mineral compounds (OMC), and mineral) with or without polypropylene (PP) MPs. The results showed that the addition of PP-MPs reduced the Cd adsorption capacity of the bulk soil in aqueous solution, and the effects varied with PP-MPs dose and aging degree. Whereas, the responses of the three fractions to PP-MPs were different. In presence of PP-MPs, the POM and OMC fractions showed negative adsorption effects, while the mineral fraction showed positive adsorption. For the bulk soil, POM and OMC fractions, the adsorption isotherm fitted to the Langmuir model better than the Freundlich model, whereas, the Freundlich isotherm model is more fitted for the mineral fraction. Combined with the comprehensive analysis of the partitioning coefficients, XRD and FTIR results, it was found that OMC fraction extremely likely play a leading role in the bulk soil adsorption of Cd in this study. Overall, the effect of MPs on adsorption capacity of the bulk soil for Cd may be determined by the proportion of POM, OMC, and mineral fractions in the soil, but further confirmation is needed.     

耕地土壤铜、镉、锌形态及生物有效性研究

土壤重金属总量常被用来评估土壤质量安全,但是大量事实说明单纯用土壤重金属总量并不能完全说明土壤重金属的生物有效性及其环境风险。相对于国内外常用的Tessier的五态方法,欧共体标准物质局提出的三步提取法(BCR法),中国地质调查局地质连续提取法的七态标准少见报道。本研究选取河南平原耕地样品,采用中国地质调查局地质连续提取法(DD2005-03)进行耕地中重金属元素(Cu、Cd、Zn)的形态分布,结果表明:Cu、Zn主要以残渣态存在,其残渣态分别占全量的55.80%和67.35%。Cd以离子交换态为主,占全量的27.30%。Cu、Cd、Zn各态含量占全量比例的顺序是,Cu:残渣态弱有机结合交换态铁锰氧化态碳酸盐结合态强有机结合态水溶态离子交换态。Cd:离子交换态弱有机结合交换态强有机结合态残渣态碳酸盐结合态铁锰氧化态水溶态。Zn:残渣态铁锰氧化态弱有机盐结合态离子交换态强有机结合态碳酸盐态水溶态。从生物可利用性系数k来看,Cd主要以活动性较大的状态存在,很容易被作物吸收。     

典型城市污染水体底泥中重金属形态分布和相关性

采用Tessier五步连续提取法,研究了南京市莫愁湖、玄武湖、秦淮河13个底泥样品中的重金属的形态分布情况,分析了重金属浸出量与各形态间的相关性及有机质与有机结合态的相关性,并通过红外谱图分析了有机质与重金属结合的机理.结果表明:底泥中Pb,cu,zh,Ni,Cr主要以有机结合态和残渣态俘在,两种形态的含量占总量70%以上,Zn和Cd的可交换态和碳酸盐结合态含量相列较高,Zn约占20%,Cd约占30%;Zn,Cu,Cd,Ni,Cr的浸出量均与可交换离子态呈现显著的相关性,因此可通过减小可交换离子态含量控制底泥重金属污染的风险性;研究还表明,有机质与有机结合态呈现显著的正相关,因此增加底泥中有机质含量有助于重金属向有_棚结合态转化,有机质与重金属的结合主要是由于其中-些官能团和重金属形成稳定的络合物.     

Compost and sulfur affect the mobilization and phyto-availability of Cd and Ni to sorghum and barnyard grass in a spiked fluvial soil

Soil reclamation via additives can cause contradictory effects on the mobilization of toxic elements in soils under dry and wet conditions. Therefore, our aim was to investigate the impact of compost and sulfur in two rates (1.25 and 2.5%) on fractionation, mobilization, and phyto-availability of cadmium (Cd) and nickel (Ni) to sorghum (dry soil) and barnyard grass (wet soil) in a fluvial soil spiked with 25 mg Cd or 200 mg Ni/kg soil. Compost decreased the solubility and mobilization of Cd (especially in dry soil) and Ni (in both soils). Sulfur increased the solubility of Cd (31% in dry soil—49% in wet soil) and Ni (4.6% in wet soil—8.7% in dry soil). Sulfur altered the carbonate fraction of Cd to the soluble fraction and the residual fraction of Cd and Ni to the non-residual fraction. Compost decreased Cd and increased Ni in sorghum, but enhanced Cd and degraded Ni in grass. Sulfur increased Cd and Ni in both plants, and the increasing rate of Cd was higher in grass than in sorghum, while Ni was higher in sorghum than in grass. These results suggest that compost can be used as an immobilizing agent for Cd in the dry soil and Ni in the wet soil; however, it might be used as mobilizing agent for Cd in the wet soil and Ni in the dry soil. Sulfur (with rate 2.5%) can be used for enhancing the phyto-extraction of Cd and Ni (especially Cd) from contaminated alkaline soils.     

Effects of dissolved organic matter on the desorption of Cd in freeze–thaw treated Cd-contaminated soils

Lab-scale experiments were conducted to investigate the effects of dissolved organic matter (DOM) on the desorption of Cd in freeze–thaw treated Cd-contaminated soils. The results indicated that DOM significantly facilitated the desorption of Cd from freeze–thaw treated soils when comparing with that of non-frozen soils. Effects of DOM on the Cd desorption were highly dependent on the soil type and contamination concentration. The maximum desorption ratios of Cd by DOM generated from straw and sludge were 15.6% and 13.65%, respectively, in brown soils, and the maximum desorption ratios reached 14.7% and 9.3%, respectively, when using black soils through the same treatment. The higher the Cd contamination concentration in soils, the higher the ratio of Cd desorption by DOM. This was because of the integrated effects of the soil properties changed by the freeze–thaw treatment and the species transformation of Cd. The characteristics of DOM, such as its concentration and properties, had shown obvious impacts on the Cd desorption by DOM. The desorption was promoted with the increased DOM concentration and the hydrophilic fraction, and lowered pH and the low-molecular-weight of DOM.