工业发达城市土壤重金属时空变异与源解析

采集了宁波市区2003和2013年两期共1130个土壤样品,测定了8种典型重金属元素的含量,运用污染指数评价法土壤重金属污染程度进行了评价,运用地统计学方法剖析了污染的时空变异特征,并分别运用主成分分析和UNMIX受体模型解析了重金属的污染来源。结果表明:(1)除了As,两期重金属元素的含量均值都超过了浙江省土壤背景值和国家土壤背景值,说明土壤普遍存在重金属污染;从2003~2013年,所有元素的含量均值都不同程度地增大,说明10年间重金属污染普遍加剧;(2)单因子污染指数的评价结果表明,Hg为重度污染,Cd、Cu、Pb为中度污染,Zn、Cr、Ni为轻度污染,As为非污染状态;所有采样点的内梅罗综合污染指数都超过了警戒值,10年间综合污染指数3、呈重度污染的样本显著增加。(3)同种元素不同时期的污染空间格局相近,不同元素则呈现一定差异,Pb和Hg,Cr、As、Cu、Zn和Ni的空间分布特征具有相似性,高值区主要集中在污染企业分布密集和人类活动频繁的海曙、江北、江东、镇海四区;○4研究区重金属污染源主要包括两类,即以Ni、As、Cr、Zn、Cd为主要成分的工业污染源,以Pb和Hg为主要成分的生活污染源,前者源自工业废水、废弃和废渣的排放,后者源自于生活垃圾、汽车尾气及道路磨损造成的颗粒物和粉尘污染。     

滇黔桂岩溶区河漫滩土壤重金属含量、来源及潜在生态风险

利用全国地球化学基准计划在滇黔桂岩溶区35个点位采集的70件河漫滩表、深层土壤样品,分析了As、Cd、Cr、Cu、Hg、Ni、Pb和Zn 8种重金属元素含量特征,探究了重金属来源、污染状况及潜在生态风险.结果表明,8种重金属元素含量大部分均高于全国土壤背景值,在滇东南地区含量最高,桂西北地区最低.表层土壤Cd、Hg明显富集,As、Cr、Cu、Ni与深层土壤含量相当;As、Cd、Hg、Pb、Zn在农田、菜地中明显高于深层土壤,Cr、Cu和Ni在各类土地中与深层土壤相当.因子分析结果显示,表层土壤中Cd、Cr、Cu、Ni受地质背景控制,As、Pb、Zn既与地质背景有关,也受人为活动影响,Hg受人为活动影响较严重;深层土壤中Cd、Cr、Cu、Ni、Cr、Zn继承了区域母岩特征,As、Hg和Pb受地质背景和人为活动双重影响.地累积指数法和富集因子法污染评价结果表明,研究区河漫滩表层土壤中Cd、Hg污染较重,As、Cr、Cu、Ni、Pb、Zn大部分为轻度污染或无污染.各重金属潜在生态风险指数高低顺序依次为Hg > Cd > As > Cu > Ni > Pb > Cr > Zn,Cd和Hg的生态风险指数之和占综合指数的82.43%,生态风险最高;滇东南地区重金属潜在风险综合指数最高,具重度生态风险.     

基于特定源-风险评估模型的兰州黄河风情线绿地土壤重金属污染优先控制源分析

为甄别城市滨河公园景区绿地土壤重金属污染优先控制因子和污染源,以兰州市黄河风情线大景区为研究区,采集并测定64个绿地土壤样品重金属As、Cd、Cr、Cu、Hg、Ni、Pb和Zn的含量;采用单因子污染指数法和污染负荷指数法量化重金属污染程度,利用绝对因子得分-多元线性回归（APCS-MLR）模型对绿地土壤重金属进行源解析.并运用APCS-MLR模型与综合生态风险指数和人体健康风险评价模型相耦合方法,解析各污染源对生态风险和人体健康风险的贡献率.结果表明,除Cr和Ni之外,As、Cd、Cu、Hg、Pb和Zn的含量均值高于兰州市土壤元素背景值,但所有元素含量均低于《土壤环境质量建设用地土壤污染风险管控标准》（GB 36600-2018）的筛选值.单因子污染指数结果显示,As、Cd、Cr、Cu、Ni、Pb和Zn为无污染至轻微污染水平,而Hg属于轻度污染.污染负荷指数评价结果显示,绿地土壤总体上属于轻度污染水平.源解析表明,绿地土壤重金属源自于交通源、自然-农业源和自然-工业源,贡献率分别为34.79%、23.12%和18.49%.特定源-综合生态风险指数结果表明,Cd和Hg为生态风险优先控制元素,自然-工业源为优先控制污染源;特定源-健康风险评价模型分析结果表明,As和Ni为人体健康优先控制元素,自然-农业源为优先控制污染源.     

广西百色不同功能区土壤重金属污染与来源

以百色城区及周边县城土壤为研究对象,测定不同功能区(清洁区、矿区、工业区和城市中心区)土壤Co、Cr、Cu、Ni、Pb、Zn、Cd、As和Hg含量,采用地质累积指数法评价重金属污染水平。结果表明,百色地区土壤重金属含量差异很大,除Cu以外,工矿区土壤重金属污染达到中度污染水平以上,其中Cd达到强污染水平;清洁区和城市中心区土壤大部分重金属元素则处于无污染水平。采用主因子分析法分析了矿区和工业区土壤重金属可能的污染源,结果显示工矿区土壤重金属可能有三个来源:工业源的Co、Ni、Pb、As、Hg,混合源的Cd、Cr、As、Zn,自然源的Cu、Zn。     

张家口市万全区某种植区土壤重金属污染评价与来源分析

以张家口市万全区某蔬菜种植区土壤为研究对象,采集132件表层和80件深层土壤样品,测试分析As、 Cd、 Cr、 Hg、 Cu、 Ni、 Pb和Zn等8种重金属元素含量以及Cr和Ni赋存形态.综合应用地统计学分析和PMF受体模型,并结合3种重金属污染评价方法,摸清了研究区土壤重金属空间分布特征、重金属污染程度和垂向上Cr和Ni赋存形态的分布情况,探析了土壤重金属污染源和贡献率.结果表明,表层土壤重金属Cd和Pb含量平均值均高于河北省土壤背景值,表层土壤Cr、 Ni、 Cu, Cd、 Pb和Zn空间分布特征存在相似性.地累积指数法表明研究区以无污染为主,分布少量轻污染点位,以Cd污染点居多;富集因子法表明研究区主要以无-弱污染为主,各元素均存在中污染情况,背景区显著污染元素为As、 Pb和Hg,重点区中显著污染元素为Cd;潜在生态风险指数法表明研究区以轻污染为主,局部分布“中”和“强”风险点,背景区Hg存在“很强”风险点,重点区Cd存在“很强”风险点.这3种评价结果表明背景区以Cd和Hg污染为主,而重点区则以Cd污染为主.垂向土壤赋存形态研究表明Cr以残渣态(F4)为主,可氧化态(F3)...     

西南某铅锌矿区农田土壤重金属空间主成分分析及生态风险评价

以西南某铅锌矿区周边农田土壤作为研究对象,采集土壤表层(0~20 cm)149个土壤样品,分析测定了As、Cd、Cr、Cu、Hg、Ni、Pb、Zn共8种重金属含量.采用多元统计分析,揭示了研究区农田土壤重金属污染的主要来源及各元素之间的相关性;并应用Hakanson潜在生态风险指数法,对农田土壤生态风险进行评价.结果表明,研究区农田土壤重金属Cd、Pb、Zn含量相对处于极高水平,均值分别为15.56、419.4、933.4 mg·kg~(-1),污染十分严重;Hg和As的均值分别为0.13 mg·kg~(-1)和37.3 mg·kg~(-1),属于中度污染;Cu、Ni、Cr的均值分别为26.1、14.3、33.4 mg·kg~(-1),未超过云南省土壤环境背景值;多元统计分析结果显示Cd、Pb、Zn、Hg、As这5种元素来源相似,主要来源于矿山开采和工业活动;Cu、Ni、Cr这3种元素来源相似,主要是自然来源;研究区综合潜在生态风险指数RI的均值为2 294.8,整体上处于极高生态风险水平.矿区开采和工业活动对农田土壤造成了严重的重金属污染.     

石家庄市大气降尘重金属元素来源分析

在石家庄市采集了51件大气降尘样品,对其重金属来源进行了解析。主要针对样品所含有的As、Cd、Cr、Cu、Hg、Ni、Pb、Zn等8种重金属元素,进行相关性、富集因子及主成分分析。通过分析表明Pb与Cr、As、Hg、Ni相关性明显,Cr元素主要来源于土壤颗粒,As、Zn、Pb、Ni、Cu元素可能叠加工业污染,Hg、Cd污染严重,Pb元素主要受到燃煤和交通污染。重金属元素的空间分布表明市区含量低,二环外含量高,受交通和废气污染较重。     

阳新县复垦工矿废弃地土壤重金属污染及潜在生态风险评价

为探究湖北省阳新县复垦工矿废弃地土壤重金属污染状况及其潜在生态风险,对研究区采集的69个复垦工矿废弃地表层土壤样品中As、Cd、Cr、Cu、Hg、Ni、Pb和Zn 8种重金属元素的含量进行了测定,在此基础上分别采用内梅罗综合污染指数法和潜在生态风险指数法对复垦土壤中重金属污染程度和潜在生态风险进行了评价。结果表明:研究区复垦土壤中重金属元素Cd、Cu、Hg、Pb和Zn的含量均值高于湖北省土壤元素背景值,存在一定程度的富集,部分复垦土壤中重金属元素As、Cd、Cu和Ni的含量超过《土壤环境质量农用地土壤污染风险管控标准(试行)》(GB 15618—2018)中的土壤污染风险筛选值,超标率分别为8.7%、4.3%、10.1%和1.4%;复垦土壤中无清洁级别,预警、轻度污染、中度污染和重度污染土壤分别占1.48%、69.57%、18.84%和10.14%,各类型复垦土壤中重金属污染程度依次为金属矿采选废弃地其他工矿废弃地砂石场废弃地煤矿采选废弃地,复垦土壤中各重金属单因子污染指数依次为CdCuHgPbZnNiAsCr;复垦土壤中重金属元素As、Cr、Cu、Ni、Pb和Zn的单项潜在生态风险均处于低生态风险级别,而Cd和Hg最高分别达到较高和极高生态风险级别,复垦土壤重金属综合生态风险中,低生态风险、中等生态风险和高生态风险级别的土壤分别占66.67%、30.43%和2.90%,无极高生态风险级别的土壤。总体而言,研究区复垦土壤中重金属元素Cd和Cu的污染较突出,但考虑到毒性响应,复垦土壤中重金属Hg和Cd的污染更应引起警惕。     

鄂西北某农田保护区土壤重金属分布特征及生态风险评价

为了解鄂西北农田土壤重金属污染状况,采集了湖北省某农田保护区89份表层土壤样品,运用多元统计分析法和潜在生态危害指数法研究了土壤重金属分布特征和生态风险。结果显示:研究区Ni、Cd、Cu、Zn、As和Hg具有不同程度的累积效应,Cd均值含量超过了不同p H条件下农用地土壤污染风险筛选值;多元统计分析结果显示:化肥、农药的不合理施用是Ni、Cd、Cu、Zn和As的主要来源,Cr、Pb来源于自然源,Hg主要来源于锅炉燃煤等人为污染源;单因子指数、综合污染指数和生态风险指数结果均表明,研究区具有较强的Cd污染风险,Cd是主要的污染因子。     

典型高原城市绿地土壤重金属特征评价及分析

绿地重金属污染因严重危害生态环境和人体健康而备受关注。文章为了解典型高原城市（拉萨）绿地土壤环境状况,对绿地105个表层土壤重金属（Cu、Cr、Ni、Zn、Pb、Cd、As及Hg）的分布特征及污染状况进行分析评价,应用绝对主成分得分-多元线性回归模型对重金属来源进行解析。结果表明,研究区绿地中Cu、Cr、Ni、Zn、Pb、Cd、As及Hg含量分别为31.00、43.00、18.00、70.00、33.70、0.15、18.00和0.079 mg/kg,是城市背景值的1.41、1.02、0.86、1.08、1.09、1.25、0.90和0.87倍,但远低于《绿化种植土壤》（CJ/T 340-2016）限值。元素Cu、Zn、Pb和Cd在道路绿地含量最高,元素Cr、Ni与As在各个类型绿地中含量无显著差异,元素Hg在公园绿地含量最高且变异系数大。研究区内梅罗综合污染指数值为1.96,为轻度污染;8种重金属地积累指数均值均小于0,未受到污染;综合潜在生态风险指数为140.13,生态风险低,绿地环境质量良好。交通源对Cu、Zn、Pb和Cd元素的贡献率分别为36.78%、73.55%、82.24%...     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

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.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

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.     

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.     

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.