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。     

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。     

厦门市大气降尘中重金属形态分布及生物有效性

采集了2012年11月至2013年1月期间厦门市大气降尘样品,用改进的BCR四步连续提取法分析了12种重金属元素(Ba、Ti、Co、Cr、Cu、Fe、Mn、Zn、Ni、Pb、Sr、V)的含量、赋存形态和生物有效性.结果显示,重金属元素四态含量之和均值(mg·kg~(-1))顺序为:Fe(43733)Zn(4495)Ti(2728)Ba(747)Mn(723)Cu(444.4)Sr(176)Cr(171)Pb(160)Ni(40.4)V(27.6)Co(11.2);Zn和Cu含量分别为我国土壤环境质量标准第二类标准限值(250和100 mg·kg~(-1))的18倍和4.4倍;除Fe、Ti、Ba、Cr和V外,大气降尘中其他元素生物有效态含量占有相当的比例(32.2%—88.6%).Zn、Sr主要以弱酸溶态存在,Pb主要以可还原态存在,Cu主要以可氧化态存在,其余元素主要以残渣态存在.大气降尘中重金属的平均生物有效性系数顺序为:Sr(0.87)Zn(0.85)Cu(0.80)Pb(0.67)Mn(0.50)Co(0.47)Ni(0.39)Ba(0.19)≈Cr(0.19)V(0.12)Fe(0.08)Ti(0.01),Ti、Fe、V、Cr和Ba为生物不可利用元素,Ni、Co、Mn和Pb为潜在生物可利用元素,Cu、Zn和Sr为生物可利用元素.     

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.     

以设计精准修复方案为目标的土壤重金属形态分布研究

农田土壤原位钝化/稳定化修复是通过向土壤中添加化学药剂以降低重金属活性、抑制土壤重金属向农作物迁移进而降低重金属风险的一种修复技术。针对河南省某重金属污染农田土壤,为制定精准的原位稳定化修复方案,采集32个表层土壤样品测定其Cd、Pb、As、Cu、Zn、Ni、Cr 7种元素全量,并利用BCR连续提取法测定弱酸提取态、可还原态、可氧化态和残渣态4种形态含量。结果表明:土壤Cd、Pb、As、Cu、Zn、Ni和Cr含量的平均值分别为1.90、144.91、7.33、32.24、91.40、28.80和19.76 mg·kg-1,Cd和Pb含量分别超过HJ/T 332—2006《食用农产品产地环境质量评价标准》的3.17和1.81倍。BCR形态分析表明,弱酸提取态Cd含量占全量比例较高,平均值为24.06%;土壤80.35%的Pb以可还原态存在,其余5种元素主要以残渣态存在。基于不同元素的弱酸提取态含量与全量建立回归分析模型,结果显示各元素的弱酸提取态含量随全量呈线性变化且两者的正相关关系显著;根据Cd、Pb 2种元素全量与弱酸提取态含量的空间分布差异对研究区域进行分区,基于土壤全量Cd和弱酸提取态Cd含量的分区结果有一定差异,而基于弱酸提取态Cd与弱酸提取态Pb含量的分区结果大致相同,能够为设计精准的修复方案提供依据。最后,分别以重金属全量与有效态含量为出发点对研究区域重金属的污染程度与存在风险给予评价,Hakanson风险评价结果表明土壤Cd存在极强的潜在生态风险,风险评价编码法评价结果则显示Cd为中等风险,两者之间的差异提示土壤重金属修复需综合考虑不同评价方法的评价结果,这为重金属的修复评价奠定基础。     

晋江感潮河段沉积物重金属的赋存形态与生物有效性

用稀硝酸单级提取法和BCR连续提取法对晋江感潮河段沉积物中重金属生物有效性进行研究.单级提取法表明,Cu、Pb、Cr、Zn、Cd、Sb、V、Ni、Co、Fe和Mn的酸提相含量在中游河段普遍较高.除V和Fe外,表层和柱状沉积物中其他9种重金属的生物有效性均相对较高.除在个别深度外,L43柱状沉积物中多数重金属元素生物有效性变化较平稳.采用改进的BCR四步连续提取法对表层沉积物中11种重金属进行形态分析,结果表明,Mn、Ni、Pb、Cu、Cd和Cr都具有较高的生物有效性;Zn在下游河段主要分布在残渣态中,但在中上游河段弱酸溶态含量的比例普遍较高;Sb在河段下游地区非残渣态含量要明显高于中上游地区.次生相与原生相分布比值法评价结果表明,除V和Fe处于无污染水平,其他9种重金属在不同的采样点均有不同程度的污染.     

上海市居民区与工业区大气颗粒物重金属生物可给性与健康风险评估

采用具有代表性的体外模拟呼吸系统Gamble方法研究上海市两大功能区——工业区、居民区不同大气颗粒物包括PM_(10)和PM_(2.5)中重金属生物可给性和健康风险.结果表明,两大功能区大气颗粒物中均检出重金属Cu、Mn、Ni、Pb、Zn、Cr和Cd,其浓度从高到低依次为:ZnPbCuMnNi≈CrCd,工业区大气颗粒物中重金属Cu、Mn、Ni、Pb和Zn的平均浓度均高于居民区,且两大功能区PM_(10)中重金属浓度均大于PM_(2.5).居民区大气颗粒物中Cu和Ni的生物可给性低于工业区,Mn和Pb的生物可给性高于工业区,而Zn、Cr和Cd的生物可给性在两大功能区则较为接近,且PM_(2.5)中重金属生物可给性高于PM_(10).成人致癌风险高于儿童,非致癌风险低于儿童.其中Cr和Cd的致癌风险较低,Ni的致癌风险可忽略.除去Pb元素,其余重金属元素均表现为工业区非致癌风险高于或接近于居民区,不同重金属的非致癌风险值大小为:PbCdZn≈CrCuNiMn,均远小于1,可忽略.但是,Pb的人体健康风险相对其他重金属较高,Cd在大气颗粒物中的重金属浓度较低,但非致癌风险值相对较高,也应当引起重视.     

电镀企业周边大气颗粒物PM_(2.5)、PM_(10)和TSP中重金属分布特征及健康风险评价

以东莞市5个镇区为研究对象,采集电镀企业周边大气样品,分析了样品中重金属(包括As、Co、Cd、Cr、Cu、Mn、Ni、Pb、Sb、V、Zn和Hg)的含量分布,使用富集因子(enrich factor)、地累积指数(index of geoaccumulation)、Hakanson法和美国国家环境保护局(US EPA)的人体暴露健康风险评价模型,对PM_(2.5)、PM_(10)、总悬浮颗粒物(TSP)中重金属进行人体健康风险评价。结果表明,PM_(2.5)、PM_(10)和TSP中As、Cd和Cr平均浓度皆超标。Cr、Ni和V元素在3种颗粒物中非富集,主要为自然源;As、Co、Cu、Pb和Zn,可能来源于自然源和叠加的工业污染。Cd、Hg和Sb浓度受人为污染影响严重。Cd、Sb、Cu、Zn、Pb为生物可利用元素(K>0.6),在环境中的可迁移性高且易于被生物体和人体吸收。Mn元素的非致癌风险值较其他重金属要高1~4个数量级,且儿童的非致癌暴露风险值HQ均高于成人的。3种颗粒物中重金属元素通过呼吸吸入途径产生的非致癌风险HI值均高于人体可接受的上限1.0,其主要贡献来源于Mn的影响,研究区非致癌风险较为严重。除PM_(10)中Co元素和TSP中Co、Cr的成人致癌风险CR值大于10-4之外,其余大部分重金属元素通过呼吸途径产生的致癌风险CR值均在可接受范围之内,此外,3种颗粒物中的成人的致癌暴露风险值CRT均高于儿童的CRT值,并且除了PM_(2.5)中儿童的重金属致癌暴露风险CRT值(4.70E-05)低于人体可接受范围的上限(10-4),其余CRT值均高于10-4,致癌风险较为严重。     

冬季河南省若干城市室内灰尘中重金属的健康风险

大气沉降是室内灰尘的重要来源.本研究于2017年1—2月采集了河南省12个城市的室内灰尘样品共48个,并按照取样城市的空间分布探讨了重金属(Ni、Cu、Zn、Mn、Co、Cr、As、Ag、Cd、Pb)污染的南北差异(以黄河为界).运用地积累指数法对其进行污染评价.应用美国EPA人体暴露风险模型进行健康风险评价.结果表明,豫南城市室内灰尘中重金属除Pb以外平均浓度均显著高于豫北城市.豫南城市重金属平均浓度表现为Zn Mn Cr Ni Pb As Cu Co Cd Ag,浓度大小依次是306.7、249.2、223.3、116.9、55.7、41.6、30.3、7.0、1.8、1.3 mg·kg-1,而豫北城市重金属浓度表现为Zn Mn Pb Cr As Ni Cu Co Cd Ag,浓度大小依次是200.7、179.4、85.4、48.7、22.9、22.1、21.4、4.4、2.6、0.7 mg·kg-1.地累积指数结果显示Cd在豫南和豫北城市均是重污染和极重污染,而Ag在豫南城市是重污染和极重污染.豫南城市室内灰尘中4种致癌重金属的致癌风险大小依次为Cr As Ni Cd,6种非致癌重金属的非致癌风险大小依次为Zn Mn Cu Pb Co Ag;豫北城市室内灰尘中致癌重金属的致癌风险依次为Cr As Ni Cd,非致癌重金属的非致癌风险依次为ZnMn Pb Cu Co Ag.     

Characteristics,sources and health risk assessment of toxic heavy metals in PM<Subscript>2.5</Subscript> at a megacity of southwest China

Twenty trace elements in fine particulate matters (i.e., PM_2.5) at urban Chengdu, a southwest megacity of China, were determined to study the characteristics, sources and human health risk of particulate toxic heavy metals. This work mainly focused on eight toxic heavy metal elements (As, Cd, Cr, Cu, Mn, Ni, Pb and Zn). The average concentration of PM_2.5 was 165.1 ± 84.7 µg m^?3 during the study period, significantly exceeding the National Ambient Air Quality Standard (35 µg m^?3 in annual average). The particulate heavy metal pollution was very serious in which Cd and As concentrations in PM_2.5 significantly surpassed the WHO standard. The enrichment factor values of heavy metals were typically higher than 10, suggesting that they were mainly influenced by anthropogenic sources. More specifically, the Cr, Mn and Ni were slightly enriched, Cu was highly enriched, while As, Cd, Pb and Zn were severely enriched. The results of correlation analysis showed that Cd may come from metallurgy and mechanical manufacturing emissions, and the other metals were predominately influenced by traffic emissions and coal combustion. The results of health risk assessment indicated that As, Mn and Cd would pose a significant non-carcinogenic health risk to both children and adults, while Cr would cause carcinogenic risk. Other toxic heavy metals were within a safe level.     

Heavy metal speciation,leaching and toxicity status of a tropical rain-fed river Damodar,India

Speciations of metals were assessed in a tropical rain-fed river, flowing through the highly economically important part of the India. The pattern of distribution of heavy metals (Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn) were evaluated in water and sediment along with mineralogical characterization, changes with different water quality parameters and their respective health hazard to the local population along the Damodar River basin during pre-monsoon and post-monsoon seasons. The outcome of the speciation analysis using MINTEQ indicated that free metal ions, carbonate, chloride and sulfate ions were predominantly in anionic inorganic fractions, while in cationic inorganic fractions metal loads were negligible. Metals loads were higher in sediment phase than in the aqueous phase. The estimated values of I_geo in river sediment during both the seasons showed that most of the metals were found in the I_geo class 0–1 which represents unpolluted to moderately polluted sediment status. The result of partition coefficient indicated the strong retention capability of Cr, Pb, Co and Mn, while Cd, Zn, Cu and Ni have resilient mobility capacity. The mineralogical analysis of sediment samples indicated that in Damodar River, quartz, kaolinite and calcite minerals were dominantly present. The hazard index values of Cd, Co and Cr were >?1 in river water, which suggested potential health risk for the children. A combination of pragmatic, computational and statistical relationship between ionic species and fractions of metals represented a strong persuasion for identifying the alikeness among the different sites of the river.     

Speciation of Heavy Metals in Floodplain and Flood Sediments: a Reconnaissance Survey of the Aire Valley, West Yorkshire, Great Britain

A five-step sequential extraction technique was used to determine the chemical association of heavy metals (Pb, Zn, Cu and Cd), with major sedimentary phases (exchangeable, surface oxide and carbonate, Fe and Mn oxides, organic and residual metal ions), in samples from floodplain and recent flood sediments of the River Aire, West Yorkshire. Analysis indicates that metals Pb and Zn are primarily associated with the Fe and Mn oxides, Cu with the organic fraction and Cd with exchangeable and surface oxide and carbonate metal ions. Knowledge of the chemical speciation of heavy metals in river sediment, despite the procedure's inherent limitations, facilitates an understanding of their bioavailability, storage and remobilisation in floodplain and river channel environments.     

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.     

Study on particulate and metallic elements variation at daytime and nighttime period in urban atmosphere

Daily PM_2.5, PM_2.5–10 and TSP have been collected by Universal and PS‐1 sampler simultaneously at a site within Taichung between February and March 1999. The filters were analyzed by atomic absorption spectrophotometry for the elemental analysis of Ca, Fe, Mn, Pb, Cu, Zn and Cr. In general, the concentration of these metallic elements are higher in fine particles than in coarse particles. On average, PM₁₀ accounted for 67% of the TSP at daytime, while at nighttime PM₁₀ accounted for only 44% of the TSP. For PM_2.5, PM₂._5–10 and TSP concentrations, there were no significant differences between day and night period. The averaged concentrations of metallic elements in PM_2.5 at daytime were all higher than that at nighttime. Ca, Fe and Zn have large and variable PM_2.5 concentrations at both daytime and nighttime. For the daytime Zn and Pb account for the largest portion of the heavy metal elements. For the nighttime, Zn and Cr make the largest portion of the heavy metal elements. The concentrations of Mn were higher on fine particulates. The trace metals Cu and Cr in Taichung are probably due to particulates emitted by Taichung Fire Power Plants transported into the sampling area by the prevailing northwesterly wind.     

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.     

湘南某矿区菜园土中典型重金属的形态分析

分别运用Tessier连续提取法和Leleyter连续提取法研究湘南某矿区菜园土中Pb,Zn,Cu和Cd的形态分布特征.结果表明：菜园土中Pb,Zn,Cu和Cd的总浓度严重超过国家土壤环境质量标准.Pb,Zn,Cu和Cd的主要形态是残渣态,水溶态和交换态所占比例较小.重金属生物可利用性的研究表明,Pb,Zn,Cu和Cd生物可利用的含量较少;在Tessier方法中,除Cu之外,生物不可利用态是主要形态,其次是潜在生物可利用态,而在Leleyter方法中,潜在生物可利用态是主要形态,其次是生物不可利用态.