典型冶炼行业场地土壤重金属空间分布特征及来源解析

以韶关某冶炼厂为冶炼行业典型工业区,对冶炼厂区内土壤中的Cd、Pb、Hg、Sb、As、Zn、Cu、Cr和Ni等9种重金属元素的总量和有效态含量进行了测定,利用ArcGIS 10.2进行了冶炼厂地土壤中重金属空间分布的插值分析,采用的污染状况评价方法有单因子污染指数法、富集因子法和潜在生态危害指数法,重金属来源分析方法有相关性分析法和主成分分析法.对研究区土壤的重金属污染状况及来源进行分析.结果表明,Cd和As的单因子指数为1.50和2.13,分别属于轻微污染和轻度污染;Pb的单因子指数为5.58,属于重度污染.As、Hg和Zn的富集因子为3.73、10.4和22.4,分别属于中度污染、重度污染和严重污染;Cd、Pb的富集因子超过40,属于极重污染,受人为污染程度明显.Pb和Cd的有效态占总量的质量分数较高,分别在0.57％～46.0％和0.87％～69.2％之间.其次为Zn和Cu,而Hg、Sb、Ni、As和Cr的有效态质量分数均在5％以下.研究区重金属潜在生态风险指数的空间分布由西向东整体呈由低到高再降低的变化趋势,其中北部点位的指数显著高于其他点位,可能存在局部泄漏.Hg和Sb的空间分布与其他元素不同,呈现中部区域较高、东西部区域较低的特点.相关性和主成分分析结果表明,Cu、Zn、As、Cd和Pb元素之间的相关性显著,主要来源为工业生产活动的输入;Hg和Sb元素之间具有显著的正相关性,但与其他元素无相关性;Ni的主要来源更符合自然输入的规律.     

煤中微量有害元素的挥发性

利用3 种热解反应装置(密闭模拟下落床、流动气氛模拟下落床和固定床)研究了 6种煤中 As、Pb、Cr、Cd 和 Mn等微量有害元素的挥发性随温度(300～1000℃)的变化规律,同时考察了热解装置的影响.结果表明,这 5 种元素的挥发性均随热解温度的升高而升高;6 种煤中 As、Pb、Cd均表现出与Cr 和 Mn相比具有较强的挥发性,但它们的挥发温度不同,其中 As 的挥发主要发生在 300～700℃,Cd 主要在 500℃以上挥发,Pb 主要在 800℃以上挥发.热解过程中,微量元素在半焦孔道内扩散时产生的反应是影响元素析出的重要因素之一.     

煤矸石中重金属的淋滤特征研究

以内蒙古某矿区的煤矸石为研究对象,采用试验模拟法对煤矸石中的重金属的淋滤特征进行研究.结果表明:经过8 d的淋滤试验,重金属淋滤强度达到稳定,各个样品中各元素的最大淋出率平均值为:Cd＞Cr＞Pb＞Cu＞Hg＞As;Hg,Cr,Cd元素的最大淋出率与样品中元素背景值负相关;淋滤液中的As来源于硫化物的风化;煤矸石中重金属对环境的影响主要发生在淋滤初期,且重金属在自然条件下的淋滤过程对环境的影响较小,只有Cr和Cd的浓度超过了国家地表水Ⅲ类水质标准.     

焚烧飞灰高温过程中重金属的挥发及其氯转化特征

研究了垃圾与污泥掺烧后的焚烧飞灰在900℃、1 000℃高温处置过程中重金属(Cu、Zn、Pb、Cd)随不同停留时间的挥发特性,并研究了添加剂氯化物(CaCl2、MgCl2、NaCl、FeCl3、AlCl3)对重金属转化与挥发特性的影响.结果表明,没有添加氯化剂情况下,污泥焚烧飞灰中不同重金属的挥发特性有较大的差别,其中Pb的挥发率超过80%,而Cu的挥发率<30%,重金属的挥发性大小依次为:Pb>Cd>Zn>Cu.热处置过程中重金属的挥发率受温度的影响较大,而停留时间的延长对重金属挥发促进效果较小,并且易挥发元素Pb和Cd表现尤为明显.飞灰中添加氯化剂后,重金属的挥发性有显著的改变,并且难挥发元素Cu和Zn的挥发性增加较Pb和Cd显著.随着Cl含量的增加,重金属挥发率有增加的趋势,但不同种类的氯化物对重金属氯转化差异较大,其中NaCl对重金属Cd、Zn和Cu挥发特性的促进效果小于其它氯化剂.研究结果为飞灰最大限度无害化处理及资源化回收利用提供理论依据.     

长江口沉积物重金属的分布、来源及潜在生态风险评价

为了解长江口潮滩沉积物中重金属的污染特征,采用电感耦合等离子体发射光谱法(ICP-AES)分析了长江口北支、南支和杭州湾27个表层沉积物中Cu、Pb、Ni、Ag、As、Cd、Zn、Sn、Sb和Hg 10种重金属的含量,并对其分布、来源及生态风险进行了评价.结果表明,沉积物中10种重金属的含量和介于102.9 ～ 326.4 mg· kg-1之间,北支、南支和杭州湾的平均值分别为180.9、244.7和155.6 mg·kg-1.方差分析结果表明,南支与北支、杭州湾平均含量之间均存在显著性差异(p＜0.01),南支因受沿岸工业污水和生活污水的影响污染加重.来源分析表明,沉积物中大多数重金属的来源具有一定的相似性,主要来源于各种工农业废水、船舶运输、农药和化肥污染,而Ag和Hg具有不同的来源.地积累指数评价结果表明,10种重金属的平均污染程度由高到低依次为:Cd＞ Hg＞ Sb＞ Ag＞ As＞ Cu ＞Zn＞ Ni＞ Sn＞ Pb,Hg和Cd在多数采样点分别为中度污染和偏重污染,南支Cd和Ag的污染程度高于北支和杭州湾,而在杭州湾Hg的污染程度高于北支和南支.潜在生态风险系数评价结果表明,长江口沉积物7种重金属潜在生态风险系数从高到低依次为:Cd＞Hg＞As＞Cu ＞Ni＞Pb ＞Zn,长江口沉积物的潜在生态风险主要由Cd和Hg引起,两者的贡献分别为62.6％和34.0％,各采样点7种重金属的潜在生态风险指数(RI)介于565.9～1601之间,均达到极强生态风险.     

海南小海沉积物中的重金属分布特征及潜在生态风险评价

对小海沉积物进行采集,测定了沉积物中的Cu、Pb、Cd、Zn、Hg、As重金属的含量,用单因子指数法和Hakanson生态风险指数法评价了沉积物中重金属综合污染效应.研究结果表明:小海湾内沉积物中Cu、Pb、Cd、Zn、Hg、As的平均含量分别为0.20 mg/kg、0.18 mg/kg、0.30 mg/kg、0.22 mg/kg、0.44 mg/kg、0.23 mg/kg.沉积物所监测的重金属中,Hg金属的空间波动程度最高,其他重金属的空间波动程度较低.沉积物质量评价结果表明:小海沉积物中主要的重金属污染因子是As,其重金属影响因子的顺序为As＞Hg＞Pb＞Cr＞Zn＞Cu＞Cd;各种重金属的潜在生态危害系数大小顺序为Hg＞As＞Cd＞Pb＞Cu＞Cr＞Zn;潜在生态风险指数 RI平均值为37.06,属于轻微潜在生态风险.     

火电厂粉煤灰中重金属元素的分布和富集特性

将取自火电厂的2种燃煤燃烧后不同电场捕获到的粉煤灰依次过筛,分选为不同粒径组份,并检测分析各粒径组分中重金属元素含量,研究了火电厂褐煤和烟煤粉煤灰中As、Hg、Cu、Pb、Zn、Cd 6种元素在不同粒径组分中的分布与富集特性。烟煤和褐煤燃烧产生的粉煤灰粒径组份有差异。As、Cu、Pb、Zn、Cd随粉煤灰粒径的增大而含量降低。Hg元素由于挥发性较高,其分布与粒径大小无相关性。褐煤粉煤灰中各重金属元素富集程度从大到小依次为CdPbZnAsCu;烟煤粉煤灰中各重金属元素富集程度从大到小依次为AsCdZnPbCu。静电除尘器对褐煤燃烧产生的粉煤灰中Cd元素有较好的去除率,对于烟煤粉煤灰中的As和Cd元素排放有较好的去除率。相对于褐煤,燃烧烟煤可以更好的控制As排放,建议火电厂优先使用烟煤。     

广东红海湾海域表层水环境中重金属含量特征及污染评价

为了研究红海湾海域水体中重金属的污染水平,2015年5月和11月在研究海域设48个采样站位进行了表层水样分析,分析了Cu、Pb、Zn、Cd、Cr、Hg和As共7种重金属的含量及污染特征,采用单因子污染指数评价法和综合污染评价法对研究海域的水质污染情况进行评价分析,利用变异系数法来分析了各调查站位之间污染物在空间尺度上离散程度,使用相关性分析和PCA方法分析重金属污染物的主要来源。结果表明,该海域表层海水中Cu、Pb、Zn、Cd、Cr、Hg和As含量的平均值均满足《海水水质标准》二类水质要求,单因子污染指数法评价结果显示7种重金属平均含量的污染程度大体排序为:Zn＞Pb＞Cu＞As＞Cd＞Cr＞Hg。综合污染评价法显示评价海域表层海水中7种重金属综合污染指数的平均值均小于1,且综合污染指数整体相差不大,研究海域属于清洁海域。变异系数结果表明各站位间水体中重金属含量在调查海域空间离散度较大,研究海域的重金属污染物来自不同的污染源。相关性分析和PCA方法分析表明,重金属元素Cu、Pb、Zn、Cd、Cr、Hg和As之间的相关系数较小,且前三个主分中的研究重金属元素正载荷较低,因此重金属元素相互之间都不具有相似的污染水平或共同的污染来源,元素之间具有共同来源的概率较低。     

典型流域农田土壤重金属污染特征及生态风险评价

采用野外采样和室内分析相结合的方法,以原有工业污染较严重的某流域农田表层土壤为研究对象,分析了土壤中重金属Hg,Cr,Cd,As,Pb,Cu,Zn和Mn的含量及污染特征,并采用地累积指数法和潜在生态危害指数法对农田土壤重金属污染进行了生态风险评价. 结果表明:研究区农田土壤中各元素的含量均高于背景值,仍存在一定程度的污染,其污染程度由强至弱依次为Cd＞As＞Zn＞Cu＞Pb＞Cr＞Hg＞Mn;研究区农田土壤存在较高的潜在生态风险,在8种重金属中镉的风险指数最高. 表明流域内历史工业污染对农田土壤环境仍具有一定的生态危害性.      

成都市PM2.5中有毒重金属污染特征及健康风险评价

2009年4月至2010年1月在成都市城区采集PM2.5样品.采用X射线荧光光谱法分析20种元素,并重点分析As、Cd、Cr、Mn、Ni、Pb和Sb 7种有毒重金属元素.采用富集因子法、地累积指数法、相关性分析法和美国环保局暴露模型分别讨论了有毒重金属的污染特征、来源和健康风险.结果表明:成都市PM2.5中有毒重金属浓度处于较高水平,分别是:As(40.5±30.3),Cd(9.5±13.2),Cr(17.9±10.5)、Mn(137.6±84.3),Ni(5.1±4.1),Pb(320.5±186.0)和Sb(11.0±16.0)ng/m3.As严重超标,Cd和Pb也有超标现象.多数元素均在冬季达到最大值,夏季达到最小值.Cr、Mn、Ni污染程度较低,属于轻微污染,As、Cd、Pb、Sb的污染程度极高.PM2.5中有毒重金属主要来源于土壤尘及其扬尘,机动车排放和煤燃烧,冶金及机械制造和刹车磨损.Mn对儿童、成人均产生较严重的非致癌健康风险,分别为6.01、2.59、2.46,As、Cd、Cr、Ni、Pb、Sb的非致癌风险值均小于1,健康影响较小.As、Cr对人体有致癌健康风险.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.