沈抚新城不同土地利用类型多环芳烃含量、来源及人体健康风险评价

研究了处于城镇化进程中沈抚新城表层土壤多环芳烃的污染水平.从沈抚新城采集了54个土壤表层样品,包括4种不同土地利用类型(城镇用地、农村用地、林地、耕地),分析了不同土地利用类型中多环芳烃的含量,利用特征比值法与主成分分析对其进行来源分析,利用Ba P毒性当量含量及终生癌症风险增量模型(ILCR)对不同土地利用类型表层土壤内PAHs进行风险评价.城镇用地、耕地、农村用地、林地这4种土地利用类型ΣPAHs的含量分别为184~18 276、230~14 102、151~3 205、303~2 980μg·kg-1.不同土地利用类型土壤中PAHs来源相似,主要以煤燃烧源与交通源为主;风险评价表明沈抚地区存在潜在的健康风险,尤其是城镇用地风险水平最高,且最易通过皮肤接触途径暴露于土壤PAHs中.     

快速城市化区域不同用地类型土壤重金属含量分布特征及生态风险

以上海市闵行区典型快速城市化区域为例,基于36个地块595个点位土壤样品数据,分析5种不同土地利用类型中8项土壤重金属的含量分布特征,通过内梅罗综合指数法和潜在生态风险指数法进行生态风险评价.结果表明,重金属锌和镉含量的变异系数较高,受人为活动影响特征明显.涉重工业用地、非涉重工业用地的重金属赋存相对较高,住宅用地和耕地重金属含量总体不高但具有其特异性组成特征,公共管理与公共服务用地相对最低.重金属锌和镉的内梅罗综合污染指数较高,分别处于重度和中度污染水平,其余重金属均为警戒或轻度污染水平.不同土地利用类型的土壤重金属潜在生态风险水平为：涉重工业用地 > 非涉重工业用地≈住宅用地 > 耕地≈公共管理与公共服务用地,工业用地由于行业类别多、历史生产复杂和管理水平差异大等原因,具有较大的土壤重金属污染风险,住宅用地和耕地等其他用地类型也呈现出一定的重金属累积趋势.不同土地利用的土壤重金属污染源头防控和地块再开发利用的安全性及风险管控,是快速城市化区域土壤污染防治的重点和难点.     

龙口市北部平原区不同土地利用类型对土壤重金属污染距离的影响

为探究不同土地利用类型及其组成对土壤重金属污染距离的影响,以龙口市北部平原作为典型研究区域,系统采集55个表层土壤样品并对w（Pb）、w（Cd）进行了测定;通过建立基于土壤样区的梯度缓冲区,利用Pearson相关性分析,研究不同土地利用类型及其组成对土壤重金属污染距离的影响;通过热点分析和空间插值方法,探究研究区内对Pb、Cd富集贡献较大的土地利用类型.结果表明:①龙口市北部平原土壤中Pb、Cd受人类活动影响的区域差异明显,w（Pb）、w（Cd）平均值均超过了山东省土壤相应背景值,其中,w（Pb）超过背景值的样品比例达到96.36%,研究区西部富集现象明显.②土地利用类型面积占比对Pb、Cd的污染距离各异.其中,交通用地面积占比对Pb、Cd的污染距离大约在2 000、500 m处,建设用地面积占比对二者的污染距离分别在1 000、200 m处左右,而耕地及园地面积占比对二者的污染距离较小,均在50 m处左右.③w（Pb）、w（Cd）的空间分布差异明显,整体表现为西高东低.④研究区内对Pb、Cd富集贡献最大的土地利用类型是耕地,其次是交通和建设用地.研究显示,不同土地利用类型对重金属污染距离的差异性是实际存在的,因此在进行重金属污染治理时,对不同的土地利用类型要根据其对重金属污染距离的差异加以区别.      

土壤重金属累积对土地利用与景观格局的响应

土地利用/覆被既能反映重金属污染物的主要来源,亦能通过改变土壤物理、化学和生物性质从而控制重金属在土壤中的迁移性和活性,造成土壤中重金属的累积直至污染.基于2003年和2013年宁波市区土壤重金属采样点数据和土地利用数据,采用面向对象的决策树分类方法进行土地利用/覆被分类,采用单项污染指数、内梅罗综合污染指数评价土壤重金属污染状况,采用景观格局指数探索重金属不同累积程度下的土地利用变化和景观格局演变,采用冗余和偏冗余分析识别对研究区土壤重金属累积影响最为显著的景观格局因子及不同因子之间的交互作用.结果表明:①2003～2013年研究区8种土壤重金属元素均出现了不同程度的累积,其中以Hg、Ni和Cr的累积程度最高;研究区大多数区域已受到了土壤重金属的污染且重度污染区的污染程度仍在加剧.②较高的重金属累积程度并不完全出现在土地利用类型一直为建设用地的区域,或由其他类型转为建设用地的区域,有相当一部分发生在利用类型一直为耕地或者是由其他类型转为耕地的区域.③重金属污染地区都有着破碎、复杂和聚集的景观格局特征,其中耕地、住宅用地和工业用地的这种特征与土壤重金属累积的相关性最大;④建设用地的斑块聚集程度越高,大多数重金属元素的累积程度会显著增加;景观的多样性程度和农用地的形状复杂程度越高,Cu、Hg、Pb和Cd的累积程度会显著增加;距离采矿用地越近,Cd含量增加的效应越明显.     

不同海拔草地开垦对土壤重金属的影响及评价

为探究草地开垦对土壤重金属的影响,以贵州喀斯特山区不同海拔梯度下的草地和由草地开垦的耕地为研究对象,采用内梅罗综合指数法和潜在生态危害指数评估草地和耕地中Cd、Cr、Pb、Ni、Hg、As 6种重金属的污染水平和生态风险。结果表明:研究区域土壤重金属Cd、Cr、Pb、Ni、Hg、As的含量均低于贵州省背景值;不同海拔、不同土地利用/覆被对不同重金属的含量变化影响存在差异;土壤中Cr的含量与Cd和Ni的含量呈极显著正相关(P0. 01),Pb含量与Cd和Cr含量呈显著正相关,与Hg含量呈显著负相关(P0. 05);低海拔地区草地和耕地未受重金属污染;在中、高海拔地区草地重金属污染水平均为轻污染,耕地重金属污染水平均为中污染,草地开垦为耕地后污染加重,Cd是主要的重金属污染物;各海拔草地和耕地均为轻度生态风险;海拔、土地利用/覆被是影响土壤重金属含量分布的主要因素。     

城市功能对贵阳市城区土壤重金属分布的影响

将贵阳市城区土壤按照不同功能区取样分析,研究贵阳市城区多种土地利用功能下土壤重金属累积(污染)程度及分异特征。结果表明:贵阳市城区校园土壤As(21.8mg/kg)、Ni(47.1mg/kg)和Pb(139mg/kg)含量最高,工业区土壤Cd(1.48mg/kg)和Zn(314mg/kg)含量最高,垃圾中转站土壤Cu(115mg/kg)含量最高,工业区、学校、垃圾中转站和交通十字路口土壤重金属累积较重,并已达到轻度污染,住宅、公园和广场土壤重金属累积程度较轻,处于清洁水平。工业区土壤主要污染金属为Cd、Zn和Pb,学校、交通路口土壤主要污染元素是Pb和Cd,垃圾中转站土壤主要污染元素是Cd和Zn。贵阳市城区土壤Cd、Zn和Pb受人类活动影响较大,其中土地利用功能导致贵阳市城区土壤Pb的分异程度最大。     

黄河下游典型区域土壤重金属来源解析及空间分布

选取黄河下游典型区域——山东省高青县为研究区,系统采集了234个表层土壤样品(0~20 cm),测定了As、Cd、Cr、Cu、Hg、Ni、Pb和Zn等8种重金属的含量,综合运用相关分析、主成分分析和方差分析辨识了土壤重金属的来源以及与土地利用、成土母质之间的关系,并采用地统计方法分析了重金属的空间结构和分布特征.结果表明:(1)研究区8种重金属元素的平均值均超过黄河下游背景值,尤其是As、Cu、Hg的平均含量分别为各自背景值的1.23、1.20和1.29倍,存在不同程度的富集现象.(2)8种元素可辨识为两个主成分,PC1(As、Cd、Cr、Cu、Ni、Pb、Zn)主要受工农业活动和交通排放等人类活动与成土母质综合影响;PC2(Hg)主要受纺织、石油化工和塑料制造等工业活动控制.(3)不同土地利用类型和成土母质中的重金属含量差异明显.8种元素在城镇建设用地的平均含量显著高于其他地类;除了Hg以外,其余7种元素在湖积物母质发育土壤中的含量最高.(4)土壤重金属空间分布各异.As、Cd、Cr、Cu、Ni、Pb、Zn含量的高值区主要集中于中部城区和东南部,而Hg的高值区集中于西南部和东北部,说明工农业活动和交通排放加剧了当地土壤的重金属污染.     

东北老工业基地不同土地利用类型土壤重金属污染特点

以东北老工业基地北部城市群为例,对其重点区域及周边的不同土地利用类型中Hg,Pb,Cr,Zn4种元素进行测定分析,利用单因子污染评价和多因子污染评价方法进行评价。结果表明,4种元素在不同利用类型土壤中,汞和铅在土壤中的迁移能力较弱,且汞元素在土壤中积累程度不高,只是在个别区域其含量有所波动;铅在农田和工业用地土壤中都有一定的积累,但向其他利用类型土壤的迁移效果不明显;铬在个别区域的旱田,蔬菜地中的积累略高,并迁移威胁到了其周围的林地土壤;锌在某些地区的工业用地,旱田,蔬菜地的污染程度相比其他几种元素污染更为严重。     

狮子山矿区不同土地利用类型对土壤微生物群落多样性的影响

土壤微生物在生态系统功能中起着至关重要的作用,土壤微生物群落结构可由与采矿活动相关的矿山不同功能区域来反馈土壤中重金属污染现状.为研究铜陵狮子山矿区重金属污染对微生物群落结构的胁迫影响,在中国安徽狮子山矿区收集了4种不同土地利用类型(菜园、尾矿库、堆矿区和选矿区)的土壤.通过测量这4种不同土地利用类型的土壤理化性质和重金属含量,并利用Illumina MiSeq高通量测序技术,对本地土壤微生物群落丰度以及结构多样性进行了分析.结果表明,各区域理化性质差异显著,内梅罗综合污染指数依次为堆矿区(7. 28)选矿区(6. 99)尾矿库(6. 55)菜园(5. 92).微生物群落丰度及结构多样性分布表现为尾矿库选矿区菜园堆矿区.此外,PCo A、CCA和相关性分析表明,土地利用类型、土壤pH和重金属含量等相关参数对微生物群落有显著影响.优势土壤微生物群落在门(0. 01)水平上分别为Proteobacteria、Bacteroidetes、Acidobacteria和Actinobacteria,在纲水平上分别为β-Proteobacteria、α-Proteobacteria和γ-Proteobacteria,在属水平上分别为Flavobacterium、Kaistobacter和Ramlibacter.并得到对重金属较为耐受的菌群如Proteobacteria、Firmicutes、β-Proteobacteria和Kaistobacter等.这些结果加深了对重金属污染矿区土壤中微生物变化和聚集模式的认识,可为重金属矿区的生物修复提供菌种和理论依据.     

太湖流域土地利用与河流水质污染状况的相关性研究

以太湖流域为例,基于GIS空间技术分析了不同缓冲半径下土地利用类型的特征,运用Pearson相关分析及典型相关分析对6种不同土地利用类型与10种水质指标进行相关性研究。结果表明:建设用地和耕地为流域内主要土地利用类型;近岸范围内(1 km以内)建设用地为主要污染输出源,与水体水质指标呈明显的正相关,而耕地与水质指标具有较为明显的负相关性,说明耕地对污染物质具有吸附过滤作用;远岸范围内(1 km以外)耕地与TP呈显著正相关,而与DO呈显著负相关,说明耕地造成了面源污染;水域分布与NO-3-N、TP呈负相关性,而与CODMn呈正相关说明其兼具污染物质的稀释净化与汇集输送作用;林地和草地与CODMn呈明显的负相关性,说明其对污染物具有截留吸收作用。     

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.     

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.     

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.     

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.     

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.     

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.     

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.