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。     

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。     

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.     

不同的增强试剂对重金属污染场地土壤的电动修复影响

选择重金属污染场地土壤为修复对象,研究了添加络合剂EDTA?有机酸乳酸和柠檬酸以及无机酸硝酸对电动修复该污染土壤的影响.结果表明,增强试剂的加入,显著促进了铜?铅?镍和六价铬在电场中的迁移和去除,电动过程促进了土壤重金属向有效态(醋酸铵提取)转化.其中,在阴极加入乳酸并控制pH3.5的处理,土壤中铜的去除率最高,达78.7%.在阴?阳极都加入EDTA的处理中,土壤中重金属的去除率在30%左右,重金属在靠近阴极的部分发生聚集.在阴极加入柠檬酸的处理中,土壤中铜?镍和六价铬的去除率均较高,分别为68.5%?53.3%和52.9%.阴极加入硝酸控制pH3.5对土壤中六价铬的去除率最高,达93.3%.     

巢湖表层沉积物重金属生物有效性与生态风险评价

以巢湖表层沉积物为对象,对重金属(Cd、Cr、Cu、Zn、Ni和Pb)总量及形态进行分析并运用潜在风险指数法和风险评价编码两种方法对巢湖表层沉积物重金属的生态风险进行了评价.结果表明,巢湖表层沉积物中的重金属含量表现为西部湖区高,东部湖区低的特征,其中南淝河入湖区重金属含量是全湖的1.09~1.21倍.BCR形态分析表明,巢湖表层沉积物中Cr、Ni和Cu以残渣态为主(分别占总量82.99%、63.63%和54.25%),Cd和Zn以弱酸提取态为主(分别占总量55.96%和35.84%),Pb以可还原态和可氧化态为主(分别占总量39.66%和24.56%).潜在生态风险危害指数(RI)表明,南淝河入湖河口区域具有较大生态风险(RI值范围为351.54~381.17).风险评价编码方法(RAC) 的结果显示,Cd处于极高风险水平,Zn基本处于高风险水平,Cu 和Ni处于中低风险,Pb处于低风险水平,Cr各采样点均处于无风险.因此, 对需着重考虑对南淝河入湖湖区的Cd和Zn元素的重点治理.     

北京大气降尘中微量元素的空间变异

在北京市六环内均匀布点采集了城市核心区、城市扩展区、近郊区的大气降尘.对降尘中14种稀土元素(Y、Pm除外)以及Cr、Co、Mo、Cd、Pb等5种重金属元素的化学特征进行统计分析,并结合判别分析和Spearman相关分析方法阐释了影响各区域空间变异的主要元素.最后利用三角图解法揭示空间差异的成因.结果表明,各元素含量在空间上具有明显的阶梯变化,Cr、Mo、Cd、Pb含量沿城市核心区向近郊区方向呈递减趋势,Co与14种稀土元素含量的梯度变化特征则恰好相反,由市中心向外围郊区呈递增趋势.轻稀土富集程度表现为城市核心区>城市扩展区>近郊区,Eu亏损程度相反.Mo、Co、Pb元素可用来表征区域降尘的空间差异(68.2%).LaCeSm三角图解表明北京降尘主要来源于壳源物质.PbCoMo和CrCoMo三角图解可以很好地解释不同污染源贡献程度的差别是造成降尘中微量元素在空间尺度上的差异的原因.近郊区降尘受到土壤扬尘、燃煤的影响较大.城市核心区降尘主要受到交通排放的影响.城市扩展区处于过渡带,降尘受到交通、燃煤、土壤扬尘等的影响作用居中.     

辽东湾表层沉积物重金属生态风险及预警

为对辽东湾表层沉积物重金属的潜在生态风险进行定量评价及预警分析,根据2012—2015年每年8月的调查数据,计算了6种重金属元素（cu、PB、ZN、CD、HG和AS）的IGEO（地累积指数）、rI（综合潜在生态危害指）和IGE（生态风险预警指数）．　结果表明:2012年和2013年辽东湾表层沉积物重金属元素的IGEO由大到小顺序为AS>CU>ZN>PB>CD>HG,2014年为AS>CU>ZN>PB>CD>;2012—2014年辽东湾表层沉积物重金属污染区域主要位于北部河流入海口海域、葫芦岛周边海域．　风险分级和预警评价结果显示,各重金属元素的ＥＲＩ（单项潜在生态危害指数）平均值均小于40,rI均小于150,处于低潜在生态风险状态;辽东湾所有采样点中,2012年有5.6%的采样点处于2级生态风险等级（O　eR≤1.0）,属生态风险预警级别,94.4%的采样点处在生态风险无警级别,2013—2014年所有采样点均处于生态风险无警级别．　对辽东湾生态环境具有潜在危害的元素是CD、aS和HG,辽东湾表层沉积物中AS、ZN、CD在部分采样点已达到生态风险预警级别,应加大对该海域的环境监测力度．      

Nanosized magnetite in low cost materials for remediation of water polluted with toxic metals,azo- and antraquinonic dyes

Nanosized magnetite has emerged as an adsorbent of pollutants in water remediation. Nanoadsorbents include magnetic iron oxide and its modifiers/stabilizers, such as carbon, silica, clay, organic moieties (polymers, aminoacids, and fatty acids) and other inorganic oxides. This review is focused on the recent developments on the synthesis and use of magnetic nanoparticles and nanocomposites in the treatment of contaminated water. The emphasis is on the influence of the iron oxide modifiers on some properties of interest such as size, BET area, and magnetization. The characteristics of these nanomaterials are related to their ability to eliminate heavy metal ions and dyes from wastewater. Comparative analysis of the actual literature was performed aiming to present the magnetic material, its preparation methodology and performance in the elimination of the selected pollutants. Vast information has been properly summarized according to the materials, their properties and preferential affinity for selected contaminants. The mechanisms governing nanomaterial’s formation as well as the interactions with heavy metals and dyes have been carefully analyzed and associated to their efficiency.     

福建九龙江流域重金属分布来源及健康风险评价

为研究九龙江流域水体重金属污染水平,在其主要干流及支流采集27个表层水样,分析了Zn、Cu、As、Cr、Pb、Ni和Cd共7种重金属的含量及空间分布特征,利用因子分析方法分析重金属污染物的主要来源,并采用美国环保局推荐的健康风险评价模型对其所引起的健康风险作了初步评价.结果表明,流域水体中Zn的平均浓度最高,为154.893μg/L;As超过地表水Ⅲ类水质标准,超标率为14.81%,超标区域集中位于九龙江下游及河口区.因子分析表明,As、Cr、Cu和Ni的来源主要受各种人为活动影响,Cd、Pb和Zn的来源与成土母质、地球化学作用和农业生产活动有密切的关系.健康风险评价表明,化学致癌物对人体健康危害的个人年均风险远远超过非致癌物的年风险,儿童比成人更易于受到重金属污染的威胁.致癌物Cr和As的个人年均风险值都大于国际辐射防护委员会(ICRP)推荐的最大可接受风险水平5.0×10-5a-1,其中Cr>As;非致癌有毒化学物质通过饮水途径所引起的健康危害的个人年均风险大小为Cu>Pb>Zn>Ni,四者风险水平在10-9~10-10a-1之间,均低于ICRP标准4~5个数量级.