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.     

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.     

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。     

北京某环路两侧土壤重金属污染风险评价

为了解北京市某环路两侧土壤重金属污染现状,对其22处采样截面的44个样品中的Cr、Ni、Cu、Zn、Cd和Pb总量进行测定,并用改进的BCR法对重金属形态进行分步提取和测定.结果表明,Cr、Pb和Cd的总量分别是北京地区土壤背景值的7.48、6.65和5.13倍;从提取形态来看,6种重金属主要以活性较低的还原态、氧化态和残渣态存在.采用4种评价方法从不同角度对研究区域土壤中重金属的污染风险进行了评价.基于总量的地累积评价结果显示,Cr、Pb和Cd污染级别最高,Ni、Cu和Zn次之;潜在生态风险指数法评价结果为Cd>Pb>Ni>Cr>Cu>Zn;基于形态学的评价方法 RAC风险评价法得到生物可利用性顺序为Zn>Cd>Ni>Cu>Pb>Cr;而次生相与原生相比值法的结论是生物潜在可利用性依次为Zn>Pb>Cd>Cu>Ni>Cr.     

北京市西城区雨水管道沉积物中重金属特征

在对北京市西城区部分排水管道调研的基础上,对几个典型雨水检查井连接雨水管道沉积物中赋存的主要重金属污染物污染水平及形态分布进行了研究,分析了沉积物粒径及有机质含量对重金属污染物赋存水平的影响.结果表明,排水管道沉积物中:Cr主要以残渣态存在;Cu和Zn以具有活性潜力的铁锰氧化物形态及碳酸盐结合态两种形态为主;Pb的残渣态含量平均值达到了56.4%;Ni的可交换态和碳酸盐结合态含量相对较大;可交换态Cd占其总量的比例最高值达22.4%,而残渣态的Cd含量极小.     

准好氧填埋场垃圾中重金属化学形态分布特征

通过模拟准好氧填埋场中试试验,对垃圾原样和经准好氧填埋消化8个月后不同空间位置固体样中重金属含量、化学形态分布和迁移性进行研究.结果表明,垃圾原样中Pb,Ni,Cr,Cu和Fe的含量分别为88 mg·kg-1,52 mg·kg-1,304.667 mg·kg-1,29 mg·kg-1 和1632.67 mg·kg-1.垃圾原样中Ni和Cu以残渣态所占比例最高,分别为60.26%和60.92%,Pb以有机物结合态所占比例最高,为54.92%,Cr以铁锰氧化物结合态所占比例最高,为57.44%,而Fe以铁锰氧化物结合态、有机物结合态、残渣态为主,所占比例相近,为31%-34%左右.垃圾经准好氧填埋消化8个月后,Pb,Ni的有机物结合态所占比例降低,可交换态、碳酸盐结合态或铁锰氧化物结合态所占比例增加;Cu,Fe残渣态所占比例降低,可交换态、碳酸盐结合态或有机物结合态所占比例增加;Cr铁锰氧化物结合态所占比例降低,碳酸盐态或残渣态所占比例增加,金属活性增大.垃圾中Fe,Ni,Pb的迁移能力较强,迁移能力依次为Fe＞Ni＞Pb＞Cr＞Cu.     

中国三个不同富营养化湖泊沉积物中Cu、Zn赋存特征及其与营养盐的相关性分析

对太湖、南四湖、白洋淀三个不同富营养化湖泊沉积物进行采样,采用Tessier连续提取法,测定了3个湖泊表层沉积物中Cu、Zn两种重金属的赋存形态,并初步探讨了重金属各形态与沉积物及上覆水中营养盐的相关关系。结果表明,沉积物中重金属总量以白洋淀最高,太湖最低,但重金属污染程度为太湖＆gt;南四湖＆gt;白洋淀,太湖Cu污染指数为1.34~1.6,白洋淀Cu污染指数仅为0.79~1.17。沉积物中重金属赋存形态Cu主要以残渣态和有机质结合态为主（二者之和占73%以上）, Zn则以残渣态和Fe-Mn氧化态占优（二者之和比例达83%以上）,含量最少的均为可交换态。不同湖泊沉积物重金属赋存形态差异较大,太湖残渣态重金属占总量的比例最小（Cu为43%~56%,Zn为49%~63%）,南四湖残渣态占的比例最大（Cu为59%~82%、Zn为64%~77%）;可交换态比重在太湖中最高（Cu占3.2%~5.6%,Zn为1.3%~1.5%）,在南四湖中最低（Cu为1.1%~2.9%,Zn未检出）。从“非稳定态”重金属（除残渣态外的四种形态之和）所占比例看,相较其它两个湖泊,太湖沉积物中重金属污染人为输入的活性态占较大比重,具有较高的二次释放风险。相关性分析得出,重金属Cu的可交换态与上覆水中总氮及总磷之间存在着极显著的正相关关系,碳酸盐结合态Cu与沉积物中营养盐呈现出显著的负相关性,说明水体的富营养化程度加剧可能会增强沉积物中Cu向水体释放的风险。     

成都市部分区域淡水混养池塘水体与沉积物中重金属风险评价及分配特征

为探讨成都市部分区域淡水混养池塘环境中重金属的生态风险和分配特征,对成都市10个淡水混养池塘水体和沉积物中Cu、Zn、Cd、Pb、Cr、Ni这6种重金属进行检测,采用BCR连续提取法分析沉积物中6种重金属的赋存形态,并评价其潜在生态风险。结果表明,除S8和S10样点Zn年均浓度超出GB 11607—1989《渔业水质标准》外,其余元素均未超标,重金属浓度总体呈现出春、夏季高于秋、冬季的特征。沉积物除S3、S4和S8样点Cu年均含量超出生物低影响阈值(ERL)外,其余元素均未超标,Cd为研究区域沉积物中主要生态风险因子,沉积物中重金属无明显季节变化规律。沉积物中Cd的弱酸提取态比例高于其余元素,为22. 91%～64. 51%,Pb和Cu可还原态比例较大,Zn以残渣态为主,同时存在较大比例的弱酸提取态和还原态,Cr和Ni主要以残渣态和可氧化态存在。水体-沉积物中重金属分配系数由高到低依次为Ni、Pb、Cr、Cu、Cd和Zn。因此,应加强成都市淡水混养池塘Cd元素的污染防控。     

湛江湾红树林湿地表层沉积物重金属形态特征、生态风险评价及来源分析

随着工业化与城市化进程加快,湛江湾重金属污染物入海量逐年增加,沿岸红树林湿地承受着愈来愈大的环境压力。为了解湛江湾红树林表层(0-15 cm)沉积物重金属污染状况,对湾内沉积物中8种重金属元素(As、Cd、Cr、Cu、Hg、Ni、Pb、Zn)的质量分数、赋存形态特征及潜在生态风险进行了研究。采用改进BCR提取法分析重金属形态特征,运用基于总质量分数的潜在生态风险指数法和基于形态学的次生相与原生相分布比值法与风险评估编码法进行风险评价,并结合多元统计方法对重金属来源进行解析。结果表明,(1)沉积物中除Cr、Pb外,其余6种重金属的质量分数平均值均超过雷州半岛土壤环境背景值;8种重金属空间分布差异明显,变异系数在37.24%-108.19%之间。(2)As、Hg以残渣态为主要赋存形态,Cd、Zn以酸提取态为主要赋存形态,Cu、Ni、Pb以可还原态为主要赋存形态,Cr、Ni以可氧化态为主要赋存形态。(3)8种重金属元素非残渣态所占比例排序依次为CdCuNiZnPbCrAsHg,其中Cd、Cu、Ni、Zn、Pb、Cr的非残渣态所占比例均超过70%,说明重金属元素具有极强的迁移性和生物有效性,再次释放风险较大;非残渣态质量分数高值区出现在NHD和GHCL站位,说明这两个区域红树林沉积物重金属活性较高,重金属污染问题应引起重视。(4)湛江湾红树林表层沉积物中重金属RI均值为273.076,为中等潜在生态风险;而总体RSP值为5.79,表现为重度污染。从空间分布看,各站位重金属元素为中度至重度污染;其中NHD站位重金属污染程度最高,RSP值为11.97,与非残渣态空间分布特征一致。(5)多元统计结果表明,湾内红树林表层沉积物中重金属来源主要与生活排污、养殖排污和工业排污有关,其次为自然风化产物的输入。     

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.     

贵阳市冬季PM_(2.5)中典型重金属元素的化学形态分析与健康风险评价

为了更准确地研究重金属的生物有效性和对环境与人体的潜在生态危害,采用改进BCR法分析了贵阳市冬季PM_(2.5)中Cu、Mn、Co、Cd、Pb这5种重金属元素的化学形态,并评价了它们的生物有效性和健康风险。结果表明:不同重金属元素形态分布存在差异,Cu主要是弱酸溶态,其次是可氧化态;Mn主要是弱酸溶态,其次是残渣态;Co没有检测出可还原态,而在其他3种形态分布比较平均;Pb和Cd绝大部分都是弱酸溶态。生物有效性系数(K)分析结果表明:重金属生物有效性强弱顺序为CdPbMnCuCo,其中Cd和Pb的K0.8,属于生物可利用性元素;Mn、Cu、Co的K值在0.4~0.7之间,属于潜在生物可利用性元素。健康风险评价表明:成人的致癌风险比儿童大,尤其Cd对成年人存在潜在的致癌风险,且成年男性高于成年女性;Mn存在潜在非致癌风险,且对儿童的风险最大。     

Effect of acid rain on the fractionation of heavy metals and major elements in contaminated soils

Acid rain is a serious environmental problem worldwide. In the present study, we investigated the effect of acid rain (1:1 equivalent basis H₂SO₄:HNO₃) at pH values of 2.0, 4.0 and 7.0 on the fractionation of heavy metals (Cd, Cu, Fe, Mn, Ni, Pb and Zn) and major elements (K, Na, Ca, and Mg) in contaminated calcareous soils over a 2084 h period. Heavy metals and major elements in soil samples were fractionated before and after 2084 h kinetic release using a sequential extraction procedure. Before kinetic studies the predominant fractions of K, Na, Ca, Mg, Cd and Ni were mainly associated with carbonate fraction (CARB), whereas Fe, Mn and Zn were associated with the Fe–Mn oxide fraction (Fe–Mn oxide). The highest percentage of Pb and Cu were found in the exchangeable (EXC) and organic matter (OM) fractions, respectively. After kinetic study using different simulated acid rain solutions, the major fractions of heavy metals (expect of Cu) and Na was the same as before release. Upon the application of different acid rain solutions, K and Mg were found dominantly in Fe–Mn oxide fraction, whereas Ca was in the EXC fraction. The results provide valuable information regarding metal mobility and indicated that speciation of metals (Cu and Zn) and major elements in contaminated calcareous soils can be affected by acid rain.     

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。     

Effect of lime on speciation of heavy metals during composting of water hyacinth

Composting is attractive and inexpensive method for treatment and biomass disposal of water hyacinth. However, the major disadvantage of water hyacinth composting is the high content of heavy metals in the final compost. Addition of lime sludge significantly reduced most bioavailable fractions (exchangeable and carbonate) of heavy metals. Studies were carried on composting of water hyacinth (Eichhornia crassipes) with cattle manure and sawdust (6:3:1 ratio) and effects of addition of lime (1%, 2% and 3%) on heavy metal speciation were evaluated during 30 days of composting period. The Tessier sequential extraction method was employed to investigate the changes in speciation of heavy metals such as Zinc (Zn), Copper (Cu), Manganese (Mn), Iron (Fe), Lead (Pb), Nickel (Ni), Cadmium (Cd) and Chromium (Cr) during water hyacinth composting. Effects of physicochemical parameters such as temperature, pH and organic matter on speciation of heavy metals were also studied during the process. Results showed that, the total metal content was increased during the composting process. The higher reduction in bioavailability factor (BF) of Cu, Fe, Ni, Cd and Cr was observed in lime 2 treatment about 62.1%, 64.4%, 71.9%, 62.1% and 58.9% respectively; however higher reduction in BF of Zn and Pb was observed in lime 1 treatment during the composting process. Reducible and oxidizable fractions of Ni, Pb and Cd were not observed during the process. Addition of lime was very effective for reduction of bioavailability of heavy metals during composting of water hyacinth with cattle manure and sawdust.     

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。     

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.     

Distribution and speciation of heavy metals in Apulian coastal sediments

In the framework of the Interreg II Project Italy–Greece, distribution and speciation of trace metals in surface coastal sediments of Apulian regions were studied. A sequential extraction technique was used to determine the chemical association of heavy metals (Zn, Pb, Ni, Fe, Cr, Mn, Cu and Cd) with major sedimentary phases (acid soluble phases, easily reducible fraction and oxidizable matter). The relationship between the metals' content and the grain-size composition of the sediments was also considered: generally the elements resulted associated with the fine fraction, even if in some cases (Cu in the oxidizable phase) the opposite behaviour was observed. The studied area is not particularly polluted, except for some defined zones, as for example Brindisi's harbour. Speciation analysis revealed that the major part of the heavy metals are not easily mobilizable and bioavailable. Even in this case, there are some exceptions to the general behaviour: Cu and Pb in several samples are largely present in the oxidizable phase, which even if not immediately available can become a source of associated elements when redox conditions change.     

Distribution and mobility of metals in agricultural soils near a copper smelter in South China

The distribution and mobility of heavy metals in the paddy soils surrounding a copper smelting plant in south China was investigated. We assessed the degree of metal contamination using an index of geoaccumulation. The metals were divided into two groups: (1) Cu, Zn, Pb and Cd, whose concentrations were heavily affected by anthropogenic inputs, and (2) Ni, Co and Cr, which were mainly of geochemical origin. Concentrations of Cu, Cd, Zn, and Pb in the polluted soils were higher than the Chinese soil quality criteria. The chemical partitioning patterns of Pb, Zn and Cu indicated that Pb was largely associated with the residual and NH₂OH HCl extractable fractions. In contrast, Cd was predominantly associated with the MgCl₂ extractable fraction. A large proportion of Cu was bound to the acidic H₂O₂ extractable fractions, while Zn was predominantly found in the residual phase. The fraction of mobile species, which potentially is the most harmful to the environment, was found to be elevated compared to unpolluted soils in which heavy metals are more strongly bound to the matrix. The mobility of the metals was studied by water extraction using a modification of Tessier’s procedure, and the order of mobility was Zn > Cd > Cu  > Pb.     

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.     

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。