典型山区燃煤型电厂周边土壤重金属形态特征及污染评价

为了揭示毕节金沙电厂周边土壤重金属（Hg、As、Cd、Cr、Cu、Pb和Zn）污染状况,在电厂周围采集了32个土壤表层样品,采用改进的BCR连续提取法进行形态分析,并以Hakanson潜在生态危害指数法、改性灰色聚类法及风险评估编码法（RAC）进行生态风险评估.结果表明：重金属含量变化具有一定的空间变异结构和空间分布特征,除了Cd和Cr的含量平均值低于贵州省土壤平均背景值外,其余重金属含量的平均值均大于该背景值.土壤中的大部分重金属主要以残渣态形式存在,而Cd主要以酸可提取态和可还原态存在,具有很强的环境危害.相关性分析结果显示,Hg与As、Cd表现为极显著相关,而Zn与其余重金属元素相关性都较弱.生态风险评价得出7种重金属的生态风险大小顺序为Cd > Hg > As > Cu > Pb > Zn > Cr,综合潜在生态风险指数（RI）平均值为129.72,处于中等生态风险.通过改性灰色聚类法对土壤重金属污染进行分析评价,表明电厂西面污染明显高于东面,且Hg和Cd为主要污染物;由风险评估编码法得出元素Cd有效态占18.17%,对环境构成中等风险等级,元素Cr和Zn对环境的危害处于低风险状态,元素Hg、Pb、As和Cu处于无风险状态.综合以上研究结果,金沙电厂土壤受到不同程度的重金属污染,应特别重视Hg和Cd这两种重金属污染的治理.     

Assessment of metal contamination in soil banks of the Rhumel wadi (Northeast Algeria)

Levels of six trace metals were assessed in bank soils of the Rhumel wadi (Northeast Algeria) and their association with soil properties was investigated. Samples were collected at 10 sites. The soils are neutral to moderately alkaline, have high contents of carbonate, and are low in organic carbon and clay. Mean metal concentrations are 1.1 (Cd), 63 (Cr), 20 (Cu), 26 (Ni), 31 (Pb), and 98 (Zn) mg kg^?1. The Cd, Cu, Pb, and Zn contents in soil from sites closest to Constantine City were higher than in uncontaminated soils worldwide, indicating accumulation due to human activities (residential, industrial, and agricultural). Statistical analyses (correlation and principal component analysis) demonstrated that Cd, Pb, and Zn are of anthropogenic origin in the urban areas, whereas Cr and Cu enrichment in some situations is caused by industrial activities, while Ni was geogenic.     

Genotoxicity biomarkers in the amphipod Gammarus elvirae exposed in vivo to mercury and lead,and basal levels of DNA damage in two cell types

The present work deals with the application of genotoxicity biomarkers by means of the Comet assay in haemocytes and spermatozoa of the crustacean Gammarus elvirae exposed in vivo to heavy metals. Furthermore, a basal levels (BLs) study of DNA damage in the two cell types considered for two different gammarids species, G. elvirae and Echinogammarus veneris, was carried out. It is important to identify factors that influence the outcome of the assay in order to obtain reliable and reproducible results usable for risk assessment purposes. Our results highlight that the Italian legal limits for Hg and Pb, respectively, 0.5 and 50?µg/L, are inadequate for establishing safety thresholds in the aquatic environment. Furthermore, the freshwater invertebrate G. elvirae, used for the first time to measure the effect of genotoxicants, is a good candidate for evaluating the genotoxicity damage induced by heavy metals. Our results concerning spermatozoa show excessively variable responses and high BLs.     

丙烯腈-丁二烯-苯乙烯塑料、四溴双酚A混合物的热解实验:含溴二噁英生成研究

模拟电子垃圾热回收处理过程,将丙烯腈-丁二烯-苯乙烯塑料(ABS)、四溴双酚A(TBBPA)分别与4种金属(Cu、Fe、Zn和Ni)进行混合,在自制的加热装置内开展了不同气氛、不同温度条件下热解实验研究。对产物溴代二噁英(PBDD/Fs)检测显示,2,3,7,8-TBDF、2,3,7,8-TBDD及1,2,3,4,7,8-与1,2,3,6,7,8-Hx BDD为主要产物,其中2,3,7,8-TBDF含量最高,约占总PBDD/Fs的12%~90%。反应生成的8种2,3,7,8-PBDD/Fs浓度范围为0.05~2 082 ng·g-1。在同等实验条件下,温度升高有利于ABS塑料混合物中PBDD/Fs的生成。Cu、Fe、Zn和Ni四种金属都具有催化效应。空气、氮气气氛下热解实验显示,空气气氛下PBDD/Fs的生成量大,2种条件下生成的二噁英总量比值在0.8~99.6之间变化。无金属催化条件下此比值变化范围较小,为0.8~1.5;在金属参与条件下,此比值变化范围加大,为1.2~99.6;其中,在Cu和Fe参与下,此比值较高。各种热解条件下形成的PBDD/Fs都具有PBDFsPBDDs的特征。研究结果说明,虽然无金属参与条件下含TBBPA的ABS热解生成溴代二噁英浓度较低,但金属(如Cu等)存在时,此类污染物的浓度显著增加。     

云南山区野生牛肝菌中重金属汞和镉来源分析及食用安全评估

分析重金属在"环境-牛肝菌-人体"系统中的迁移、富集规律,为牛肝菌重金属污染防治及食用安全评价提供依据。采用ICP-AES法测定云南野生牛肝菌及其生长土壤中Cd和Hg含量,分析牛肝菌对重金属的富集特征及牛肝菌的重金属含量与土壤的联系,推测云南野生牛肝菌中重金属Cd和Hg的来源;根据FAO/WHO规定的每周Cd或Hg的允许摄入量(provisional tolerable weekly intake,PTWI)评估牛肝菌的重金属暴露风险。结果显示,(1)不同种类、产地牛肝菌中Hg和Cd含量具有差异,菌盖中Hg、Cd的含量分别在0.92~16.00 mg·kg~(-1)dw,4.97~24.07 mg·kg~(-1)dw之间,菌柄的Hg、Cd含量分别介于0.46~8.2mg·kg~(-1)dw和2.11~22.08 mg·kg~(-1)dw之间。同一种牛肝菌菌盖中Hg或Cd的含量均高于菌柄(Q(C/S)1),表明牛肝菌菌盖对Hg和Cd的富集能力强于菌柄。(2)牛肝菌菌盖和菌柄对Hg的富集系数(bioaccumulation factor,BCF)分别在1.72~19.12和1.30~6.40之间,菌盖、菌柄的Hg含量均高于相应生长土壤的含量,其中采自楚雄永仁县的铜色牛肝菌菌盖的Hg含量是土壤的19.12倍,表明牛肝菌中的Hg不仅来自土壤,根据山地"Hg诱捕效应"及云南大气Hg升高的相关报道,可以推测云南野生牛肝菌中的Hg主要来源于大气沉降。(3)牛肝菌菌盖、菌柄对Cd的富集系数分别在0.16~1.82和0.07~1.67之间,多数牛肝菌的Cd含量低于土壤含量,表明牛肝菌中的Cd主要来自生长土壤。(4)假设成年人(60 kg)毎周食用300 g新鲜牛肝菌则多数牛肝菌菌盖、菌柄的Hg摄入量低于PTWI(Hg)标准,Hg的暴露风险较低(假设未通过其他途径摄入Hg);食用300 g黑粉孢牛肝菌菌盖或菌柄摄入的Cd达到0.722 mg和0.662 mg,超过PTWI(Cd)标准,食用有Cd暴露风险。     

基于PBPK模型的大鼠体内镉分布的比较:联合暴露及单独暴露

环境中同时存在着多种重金属元素,联合暴露与单独暴露时,重金属在体内的蓄积分布情况也可能有所差异。为探究重金属元素(汞、铬、砷、铅)对镉(Cd)在体内分布的影响,建立了大鼠在Cd暴露下的药代动力学(PBPK)模型,并进行了包括Cd在内5种重金属的联合毒性实验,比较了Cd单独给药与重金属混合物给药2种方式下大鼠肝脏、肾脏中的Cd浓度水平。结果表明,联合暴露高(Hg Cl23.67 mg·kg~(-1),NaAsO_2 3.67 mg·kg~(-1),CdCl_2 10.55 mg·kg~(-1),K_2Cr_2O_7 6.40 mg·kg~(-1),Pb(OOCCH_3)_2·3H_2O 133.33 mg·kg~(-1))、中(HgCl_20.367 mg·kg~(-1),NaAsO_2 0.367 mg·kg~(-1),CdCl_2 1.055 mg·kg~(-1),K2Cr2O70.640 mg·kg~(-1),Pb(OOCCH_3)_2·3H_2O 13.333 mg·kg~(-1))、低(HgCl_2 0.0367 mg·kg~(-1),Na As O20.0367 mg·kg~(-1),Cd Cl20.1055 mg·kg~(-1),K_2Cr_2O_7 0.0640 mg·kg~(-1),Pb(OOCCH3)2·3H2O 1.3333 mg·kg~(-1))剂量组大鼠肝脏中Cd浓度分别为13.37、0.78和0.06μg·g~(-1);肾脏中Cd浓度分别为14.41、1.64和0.15μg·g~(-1)。与对照组相比,暴露组中Cd浓度有显著升高,且不同剂量组之间均有显著性差异。同剂量Cd单独暴露的PBPK模拟结果显示,肝脏及肾脏中的Cd浓度水平落在联合毒性实验结果的浓度范围内,初步推断其他4种重金属的联合暴露并没有影响Cd在大鼠肾脏和肝脏中的浓度分布。     

纹缟虾虎鱼对Cu~(2+)、Cd~(2+)和氨氮的毒性响应和敏感性分析

以纹缟虾虎鱼为受试生物,分别进行了Cu~(2+)、Cd~(2+)和氨氮为环境因子的急性毒性实验和氨氮慢性暴露实验,结合文献数据分析纹缟虾虎鱼对3种污染物的敏感性。结果表明,Cu~(2+)、Cd~(2+)和氨氮对纹缟虾虎鱼的EC50分别为4.527、40.408和63.182mg·L~(-1)。组织切片结果显示,氨氮暴露能够引起纹缟虾虎鱼肝组织结构退化,组织细胞畸变,其损伤程度随着氨氮浓度的升高而加剧。氨氮暴露对肠管未见明显影响。敏感性分析结果表明,纹缟虾虎鱼对Cu~(2+)、Cd~(2+)和氨氮的累积概率分别为83.33%、96.27%和90.48%,均表现为不敏感。在Cu~(2+)、Cd~(2+)和氨氮对海洋生物的敏感性排名中,纹缟虾虎鱼分别在第31/35、32/32和19/20位。在8~12种海洋鱼类中,纹缟虾虎鱼对上述3种污染物的敏感性都处在较低水平。     

重金属污染下龟壳攀鲈组织中ACP和AKP的活力比较

龟壳攀鲈是一种在极端污染水域中具备生存优势的鱼类,收集重污染区和轻污染区的龟壳攀鲈,并通过比较其体内各组织中的酸性磷酸酶(ACP)及碱性磷酸酶(AKP)活性来揭示其耐污能力。贵屿作为重污染区有4个采样点:大陇村、市上村、联堤村和北林村;潮州作为轻污染区有2个采样点:卧石村和洗马桥。水质结果表明,贵屿采样地水中的Pb、Cd、Cr、As、Hg含量分别是潮州采样点的27.6倍、3.9倍、5.8倍、3.9倍和3.5倍,说明贵屿采样地的污染远高于潮州的。酶活结果表明,在龟壳攀鲈所有组织中,内脏组织(胃肠、性腺、肝脏、脾脏、肾脏)中的ACP和AKP活力均高于外周组织(肌肉、鳞片、鳃);重金属污染均能提高攀鲈体内所有组织的ACP和AKP活力;AKP活性更容易受到重金属的影响,各组织的AKP活力增幅普遍超过ACP活力增幅;其中,受重金属影响最大的组织是脾脏,ACP和AKP活力可增长到2.37倍和6.21倍。这些结果说明了龟壳攀鲈可以通过显著升高内脏组织(如肠胃、肝脏、肾脏等)中ACP和AKP活性,以便更好地应对高污染环境;其中AKP更容易受到重金属的影响,适合用于作为评估污染的指标。     

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.     

Effects of sepiolite on stabilization remediation of heavy metal-contaminated soil and its ecological evaluation

Stabilization in the remediation of heavy metal contaminated soils has been gaining prominence because of its cost-effectiveness and rapid implementation. In this study, microbial properties such as microbial community and enzyme activities, chemical properties such as soil pH and metal fraction, and heavy metal accumulation in spinach (Spinacia oleracea) were considered in assessing stabilization remediation effectiveness using sepiolite. Results showed that soil pH values increased with rising sepiolite concentration. Sequential extraction results indicated that the addition of sepiolite converted significant amounts of exchangeable fraction of Cd and Pb into residual form. Treatments of sepiolite were observed to reduce Cd and Pb translocation from the soil to the roots and shoots of spinach. Concentrations of Cd and Pb exhibited 12.6%–51.0% and 11.5%–46.0% reduction for the roots, respectively, and 0.9%–46.2% and 43.0%–65.8% reduction for the shoots, respectively, compared with the control group. Increase in fungi and actinomycete counts, as well as in catalase activities, indicated that soil metabolic recovery occurred after sepiolite treatments.