矿区污染土壤Pb、Cd、Cu和Zn的形态分布及其生物活性的研究

调查湘南某铅锌矿区周围的菜园土和水稻土Pb、Cd、Cu和Zn的形态分布及其生物活性和迁移性。结果表明:两种土壤中Pb、Cd、Cu和Zn的总量分别超过国家土壤环境质量相应的标准。运用Tessier连续提取法研究发现,土壤中Pb、Cd、Cu和Zn的各形态含量之和与其总量非常的接近,其中菜园土Pb的提取率为96.3%,Cd的为94.1%,Cu的为93.4%和Zn的为91.7%;水稻土Pb的为97.6%,Cd的为92.0%,Cu的为92.1%和Zn的为91.7%,表明该形态分析方法的结果是合理的。土壤中Pb、Cd、Cu和Zn各形态的分布存在很大的差别,残渣态是主要形态,其中Pb的含量占60.7%~58.2%,Cd的是50.4%~59.2%,Cu的是37.3%~53.4%,Zn的是54.9%~46.9%,而交换态所占的比例最小。菜园土重金属的生物活性系数的大小是:Cd>Cu>Pb>Zn,迁移能力的顺序是Cd>Cu>Zn>Pb;水稻土重金属的活性大小和迁移能力的顺序都是:Cd>Pb>Zn>Cu。菜园土重金属的生物活性和迁移性较水稻土的大,其中Cd的生物活性和迁移性的最大。研究结果将为评估矿区污染土壤中重金属的危害提供科学依据。     

大气PM2.5中重金属的化学形态分布

运用多级连续提取法,对广州市不同季节不同采样高度大气PM2.5中重金属的化学形态和生物有效性进行分析。研究表明,PM2.5中各重金属元素之间的化学形态分布差异较大,Zn、Cd、As、Mn主要分布在F1(可溶态与可交换态)和F2(碳酸盐态、可氧化态与可还原态),绝大部分的Pb以F2存在,Ni和Mo主要分布在F1和F3(有机质、氧化物与硫化物结合态),Cu主要以F2和F3存在,Cr主要分布在F3和F4(残渣态),Co则4种形态平均分布。采样高度对重金属的化学形态分布影响不大,同一采样期内楼顶与地面样品中同一元素的化学形态分布结果比较一致。两个采样季节重金属的形态百分比存在不同程度的变化,2007年春重金属的不稳定态(F1)比例比2006年秋普遍增加,次稳定态(F2、F3)比例减少。在10种重金属中,Cd、Zn、Pb和As的生物有效性系数高(>0.7),属于生物可利用性元素,在环境中的活动性要明显高于其它元素;Mn、Cu、Mo、Co、Ni和Cr元素的生物有效性系数值在0.2～0.6之间,属于潜在生物有效性元素,在环境中比较稳定。     

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.     

大气PM_（2.5）中重金属的化学形态分布

运用多级连续提取法,对广州市不同季节不同采样高度大气PM2.5中重金属的化学形态和生物有效性进行分析。研究表明,PM2.5中各重金属元素之间的化学形态分布差异较大,Zn、Cd、As、Mn主要分布在F1（可溶态与可交换态）和F2（碳酸盐态、可氧化态与可还原态）,绝大部分的Pb以F2存在,Ni和Mo主要分布在F1和F3（有机质、氧化物与硫化物结合态）,Cu主要以F2和F3存在,Cr主要分布在F3和F4（残渣态）,Co则4种形态平均分布。采样高度对重金属的化学形态分布影响不大,同一采样期内楼顶与地面样品中同一元素的化学形态分布结果比较一致。两个采样季节重金属的形态百分比存在不同程度的变化,2007年春重金属的不稳定态（F1）比例比2006年秋普遍增加,次稳定态（F2、F3）比例减少。在10种重金属中,Cd、Zn、Pb和As的生物有效性系数高（〉0.7）,属于生物可利用性元素,在环境中的活动性要明显高于其它元素;Mn、Cu、Mo、Co、Ni和Cr元素的生物有效性系数值在0.2～0.6之间,属于潜在生物有效性元素,在环境中比较稳定。     

大气PM_(2.5)中重金属的化学形态分布

运用多级连续提取法,对广州市不同季节不同采样高度大气PM2.5中重金属的化学形态和生物有效性进行分析。研究表明,PM2.5中各重金属元素之间的化学形态分布差异较大,Zn、Cd、As、Mn主要分布在F1(可溶态与可交换态)和F2(碳酸盐态、可氧化态与可还原态),绝大部分的Pb以F2存在,Ni和Mo主要分布在F1和F3(有机质、氧化物与硫化物结合态),Cu主要以F2和F3存在,Cr主要分布在F3和F4(残渣态),Co则4种形态平均分布。采样高度对重金属的化学形态分布影响不大,同一采样期内楼顶与地面样品中同一元素的化学形态分布结果比较一致。两个采样季节重金属的形态百分比存在不同程度的变化,2007年春重金属的不稳定态(F1)比例比2006年秋普遍增加,次稳定态(F2、F3)比例减少。在10种重金属中,Cd、Zn、Pb和As的生物有效性系数高(>0.7),属于生物可利用性元素,在环境中的活动性要明显高于其它元素;Mn、Cu、Mo、Co、Ni和Cr元素的生物有效性系数值在0.2～0.6之间,属于潜在生物有效性元素,在环境中比较稳定。     

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.     

子牙新河下游湿地土壤重金属垂直分布及形态特征

2014年秋季在子牙新河下游湿地采集柱状土壤样品,分析了Cd、Zn、Cu、Pb的垂向分布特征,利用Tessier连续浸提法,分析了典型湿地N1、N3、B3的重金属形态.研究结果表明,Cd、Zn、Cu、Pb含量垂向分布差异性比较大,波动幅度比较大,多数点位Cd、Cu、Zn在11—19 cm深度处出现峰值,可能与过去金属的输入和周期性淹水有关.Zn、Cu、Pb形态分布为残渣态铁锰氧化物结合态有机物结合态可交换态碳酸盐结合态,Cd形态分布为铁锰氧化物结合态可交换态残渣态有机物结合态碳酸盐结合态,Cd的生物有效性较高.湿地淹水条件影响到湿地重金属Cd的交换态和铁锰氧化物结合态的垂直分布.Cd主要以铁锰氧化物结合态的形式存在于湿地土壤中,其百分含量占53.2%,而重金属Zn、Cu、Pb主要以残渣态的形式存在于湿地土壤中,其百分含量均高于60%.根据风险评价编码法(RAC)对重金属的化学形态进行风险评价,风险顺序为:CdZnCuPb,因此重金属Cd应引起足够的重视.     

PM10中重金属的提取方法及生物可利用性研究

分别运用模拟生物提取法与化学连续提取法对PM10标准参考样品城市源（NIST-1648A）和工业源（BCR-038）中6种重金属（Cd、Co、Cu、Mn、Ni、Pb）质量分数及赋存形态进行分析。其目标是验证2种提取大气固体颗粒物中重金属方法的有效性,并比较2种方法的优缺点,为将来提取PM10中重金属的方法选取提供依据。模拟生物提取法中,使用Gamble溶液模拟人体肺液对 PM10样品进行溶解,实验方法操作较为简单快捷;化学连续提取法中,不同溶解步骤则可确定重金属的不同赋存形态。在需要快速确定 PM10中某种重金属总量时,应优先使用模拟生物提取法。化学连续提取结果表明,城市源PM10中重金属赋存形态分布没有统一规律,工业源PM10中重金属多以残渣态存在。通过对2种来源的PM10样品中重金属生物可利用性分析,城市源的大气颗粒物对人体的毒性更大,其中标准参考样品城市源 PM10中生物可利用性较高的是重金属Cd（BIBio为61.65%±3.45%;BISE为69.02%±3.82%）和Cu,最低的是重金属Co和Pb;标准参考样品工业源PM10中重金属的生物可利用性最高的是Cd（BIBio为27.66%±1.52%;BISE为15.05%±2.13%）,而Ni、Co和Pb的生物可利用性较低。     

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。     

泉州湾洛阳江河口潮滩表层沉积物中重金属赋存形态分析

对比3种重金属形态提取方法,其中稀HCl法提取率比EDTA法高,改进的BCR四步提取法提取率最高.用改进的BCR法分析泉州湾洛阳江河口潮间带沉积物中重金属的4种形态(弱酸溶态、可还原态、可氧化态和残渣态)的含量.结果表明,大部分金属元素(V、Cr、Co、Ni、Zn、Fe和Cd)主要以残渣态存在,Mn主要以弱酸溶态存在,Pb和Cu则以可还原态存在.各形态与其总量间的相关性分析结果表明,Fe受人类活动的影响相对较小,而Cr、Co、Ni、Pb、Cd和Cu的前三态与其总量之间呈现极显著的正相关,说明它们主要污染源来自人类活动.     

Evaluation of tests to assess the quality of mine-contaminated soils

An acid metal-contaminated soil from the Aljustrel mining area (a pyrite mine located in SW Portugal in the Iberian Pyrite Belt) was subjected to chemical characterisation and total metal quantification (Cd, Cr, Cu, Ni, Pb and Zn). Water-soluble metals were determined and a sequential extraction procedure was used to investigate metal speciation. Two bioavailable metal fractions were determined: a mobile fraction and a mobilisable fraction. Soil ecotoxicity was studied using a battery of bioassays: plant growth test and seed germination with cress (Lepidium sativum L.), earthworm (Eisenia fetida) mortality, E. fetida avoidance behaviour, luminescent inhibition of Vibrio fischeri and Daphnia magna immobilisation. Although the total content of Cu, Zn and Pb in the soil was large (362, 245 and 1,250 mg/kg dry matter, respectively), these metals were mostly structurally bound (87% for Cu, 81% for Zn and 89% for Pb) and, therefore, scarcely bioavailable. Nonetheless, the D. magna immobilization test using soil leachate showed an EC₅₀ (48 h) of 36.3% (v/v), and the luminescent inhibition of V. fischeri presented an EC₂₀ (15 min) of 45.2% and an EC₂₀ (30 min) of 10.7% (v/v), suggesting a considerable toxic effect. In the direct exposure bioassays, E. fetida avoided the mine soil at the highest concentrations (50%, 75% and 100% v/v). At the same soil concentrations, cress showed negligible growth. The results suggest the need to use a battery of toxicity tests, in conjunction with chemical methods, in order to assess the quality of mine-contaminated soils correctly.     

Speciation of heavy metals in sediments from the Scheldt estuary,Belgium

A simple three-step sequential extraction procedure was applied to study the speciation of heavy metals in sediment from Scheldt estuary, and their relationship to sediment grain size and organic matter content. The sedimentary metal content was fractionated into carbonate and exchangeable, metals bound to organic matter and residual fractions. Sedimentary total metal content was also determined using an industrial microwave (ETHOS 900) HF/HNO₃ extraction method. The extracts were analysed for metals using inductively coupled plasma atomic emission spectrometry. The bioavailable fraction (exchangeable and metals bound to organic matter) comprised less than the other forms. Residue metals were the dominant form of metals in almost all studied sites. The average total metal content for the studied sites decreased in the order Fe>Cr>Cu>Co>Zn>Pb>Cd. Based on average values for the studied sites, the highest bioavailable metals in sediments were Cd (38%) from Westkapelle, Zn (17%) from Yerseke, Co (12%) from Domburg, Cr (9%) from Vlissingen, Fe and Pb each (2%) from Yerseke, and Cu (1%) from Domburg. Metal recovery was good, with<10% difference between the total metal recovered through the extractant steps and the total metal determined using HF/HNO₃ extract.     

Rieselfelder

Soils of the large sewage farm area south of Berlin are contaminated with heavy metals such as Cd, Cr, Cu, Hg, Ni, Pb, Zn. Based on earlier studies the total amount and the bioavailable proportions of heavy metals in soil samples were analysed. In some samples very high levels of total heavy metal concentrations were detected. For Pb, Cd, Cu and Hg the maximum values were 1360, 29.7, 817 and 40.8 mg/kg soil dry matter, respectively. The biovailable fractions of heavy metals which were found primarily in the acetate and EDTA fractions and to a lesser degree in the water extract account for about 50 % (Pb, Ni), 70 % (Cd) or 90% (Zn) of their total amount and may therefore pose a considerable environmental risk.     

Chemical speciation and potential ecological risk assessment of heavy metals in volcanic rocks of Southern Qinghai,China

ABSTRACT

Seven volcanic rocks samples were collected from Southern Qinghai to analyze chemical speciation and migration behavior of heavy metals by sequential chemical extraction procedure and column leaching test. The geo-accumulation index, ecological risk index and the risk assessment code were applied to assess the heavy metal pollution and potential environmental effects in this area. Results revealed that the total concentrations of heavy metals did not exceed the background values in soil of this area. Most of the samples produced acid rock drainage. The order of heavy metal migration and transformation sequence in the volcanic rocks of Zhiduo region was Cd?>?Pb?>?As?=?Cu?=?Zn?=?Mn based on the geo-accumulation index and Cd caused heavy pollution, which was also confirmed by the leaching test. Moderate potential ecological risk posed by heavy metals occurred in the study area based on the potential ecological risk index. Cd contributed to most of ecological risk while the remaining heavy metals (except As) exerted medium to high risks to the environment according to the risk assessment code evaluation results. In summary, volcanic rocks possessed potential risks to the surroundings due to potential release of heavy metals. Cd that caused the pollution should be paid special attention.     

外源铅铜镉在长三角和珠三角农业土壤中的转化

选择了我国经济发达地区的长江三角洲和珠江三角洲10个代表性农业土壤，采用室内培养和化学分级方法研究了加入外源铅、铜、镉在土壤中的动态变化及转化趋势，探讨了碳酸钙、粉煤灰、猪粪和钢渣等土壤改良剂对土壤重金属形态的影响。结果表明，随着土壤重金属负荷的提高，土壤中交换态重金属的比例增大，残余态比例下降，有效性提高，对环境威胁增大。当重金属加入最较低时，重金属优先向氧化物结合态、有机质结合态转化；而当加入最较高时，向交换态和碳酸盐结合态转化的比例明皿增加。pH和土壤组分对重金属在土壤中的转化有显著的影响，土壤pH下降可使交换态Cd、Cu、Pb的比例递增。加入碳酸钙、粉煤灰、猪粪和钢渣等改良剂可显著地降低土壤中交换态重金属比例，增加其它形态的重金属比例。     

Speciation study of trace elements in surface sediment of Winam Gulf,Lake Victoria,by sequential extraction,aqua-regia acid digestion,and ICP-OES

The speciation of trace metals in surface sediment in Kisumu Carwash area of Winam Gulf, was studied and results compared with those found at Usoma beach which was found to be several orders of magnitude less polluted. High proportions of the metals were bioavailable (fractions 1–6) with BA% ranging from 21.7% (Al) to 94.5% (Pb) at Carwash and 19.6% (Al) to ～100% (for Cd and Pb) at Usoma beach. The readily mobilizable fraction (fractions 1–4) decreased in the order: Pb > Mn > Sn > Cu > Co > Zn > Mg > Cd > Mo > Ni > Cr > Fe > Al at Carwash and Mn > Mo > Sn > Pb > Cd > Mg > Cu > Zn > Co > Ni > Fe > Cr > Al at Usoma beach. The total Zn, Cd, Cr, and Cu sediment concentrations at Carwash were higher than the threshold effect concentrations (TECs), although their bioavailable concentrations were lower than these limits. Both the total and bioavailable concentrations of Pb in surface sediment at Kisumu Carwash area were higher than the TEC threshold limit indicating significant contamination from this heavy metal. Although there was a general good agreement on data obtained by sequential extraction as compared with those obtained by direct aqua-regia digestion, there were large discrepancies for some specific metal analytes which could be accounted for in terms of analytical variations and lack of uniformity in physical and chemical composition of the sediment samples analyzed.     

Effects of salinity on the transformation of heavy metals in tropical estuary wetland soil

Tropical estuary wetlands are important for aquaculture and wildlife. However, many of them receive large amounts of anthropogenic heavy metals annually. Here, the transformation of spiked heavy metals, namely, Cd, Cr, Cu, Ni, Pb, and Zn, and the effects of salinity on their transformation in wetland soils after an eight-month-long incubation under moisture-saturation conditions were studied in the Pearl River estuary in China. Cd exhibited high mobility and bioavailability, with 12.2% to 25% Cd existing in the exchangeable fraction. Other heavy metals primarily existed in the reducible and oxidisable forms, and less than 2% were bound to the exchangeable fraction. Compared with the controls, contents of none of the metals associated with residual forms were significantly altered. These results imply that most exchangeable metals, except for Cd, transformed into other stable fractions through an eight-month-long ageing process, but not into the residual fraction. Thus, transformation from non-residual to residual forms was very slow in the tropical estuary wetland environment. Addition of NaCl increased the exchangeable fractions of Cd, Pb, and Zn, suggesting that increased soil salinity induced by flood tides during the dry season may enhance their mobility.     

Relationship between total concentration and dilute HCl extraction of heavy metals in sediments of harbors and coastal areas in Korea

Total concentrations of Cr, Ni, Cu, Zn, Cd and Pb in surface sediments were determined to investigate the regional trends of heavy metal contamination in 11 coastal areas in Korea. Enrichment factor (EF) of heavy metals was calculated by comparing the level of their regional background. The averages of EF values in study areas were 0.99 for Cr, 1.05 for Ni, 4.23 for Cu, 1.80 for Zn, 3.92 for Cd and 1.54 for Pb, respectively. Dilute HCl extractions were useful to deduce the anthropogenic sources of heavy metals and the 1 M HCl extractable fractions of each metal varied from 0.3 to 37.3% for Cr, 1.9 to 66.3% for Ni, 4.2 to 92.9% for Cu, 7.1 to 99.7% for Zn, 10.9 to 98.9% for Cd and 15.0 to 99.1% for Pb. Comparing 1 M HCl extractable fraction to total concentration, large portions of Cu, Zn, Cd and Pb were present as potentially bioavailable fractions from anthropogenic input and were significantly correlated with their EF values showing r > 0.68.