大连市海产品中短链氯化石蜡的含量与分布研究

在大连市金石滩采集海产品,使用GC/ECNI-LRMS技术对样品中短链氯化石蜡(SCCPs)的累积和分布特征进行了研究.结果表明,ΣSCCPs在香螺样品中含量最低,毛蚶样品中含量最高,干重浓度分别为77 ng·g-1和8 250 ng·g-1.ΣSCCPs在鱼类、虾蟹和贝类中的干重浓度分别为100~3 510、394~5 440和77~8 250 ng·g-1.总体上看,海产品中SCCPs碳原子同族体以C10和C11为主,约占总量的61.1%,ΣSCCPs含量越高的海产品倾向于累积更高比重的C12和C13.Cl7、Cl8和Cl6为主要的氯原子同族体,约占总量的87.6%.除了Cl5与Cl10,样品中SCCPs各碳(氯)同族体之间均存在显著相关性,这表明它们可能有着相同的来源和相似的生物蓄积以及迁移转化过程.     

电子废物拆解区农业土壤中多氯联苯的污染特征

用GC-μECD分析法测定了路桥表层土壤中144种多氯联苯同类物的含量.目的是了解该地区表层土壤中PCBs的污染水平、空间分布特征和来源.结果表明,样品中ΣPCBs为0.779～937 ng.g-1,均值为75.7 ng.g-1,研究区域中南部污染水平较高.同族体组成特征表明,38个样品组成以penta-CBs、hexa-CBs和tetra-CBs为主,含量范围分别为13.0%～61.1%、4.59%～48.8%和10.1%～31.5%;另外3个样品组成以di-CBs为主,范围为47.1%～75.2%.聚类分析表明,大多数样品主要受到Ar1254工业品的污染,少数样品的污染与Ar1221工业品有关.ΣPCBs与TOC显著相关,表明土壤中TOC的含量是影响PCBs在土壤中蓄积的重要因素之一;各PCBs同族体(除di-CBs与nona-CBs之间外)显著相关,表明各PCBs同族体有相似的输入途径.与国内外其它研究相比,研究区域表层土壤PCBs污染处于中高水平.     

上海市崇明岛农田土壤中多环芳烃分布和生态风险评价

为研究崇明岛农田土壤中PAHs浓度分布和生态风险,于2008年采集崇明岛农田表层土壤33个.使用加速溶剂萃取仪（ASE300）进行萃取,经净化后,使用气相色谱-质谱联用仪（GC-MS）测定.结果表明,在采集的土壤样品中,PAHs的含量范围为24.92～1 014.61 ng·g-1（干重）,均值为192.83 ng·g-1（干重）.16种美国EPA优控的多环芳烃,只有茚并（1,2,3-cd）芘（IcdP）和二苯并（a,h）蒽（DahA）未全部检出.PAHs主要以2～4环为主,其中2环和3环多环芳烃所占比例为42.6%;4环多环芳烃的比例为42.2%;5～6环多环芳烃的比例为15.7%.使用浓度比值法判定,主要来源为石油源以及煤和木材的燃烧;崇明岛生活燃烧和汽车等尾气排放可能是农田土壤中PAHs的重要来源之一.生态效应区间法评价显示,崇明岛农田土壤中PAHs生态风险较小.     

天津滨海工业区土壤中多环芳烃的污染特征及来源分析

采集天津滨海工业区38个表层土壤样品,利用GC/MS分析技术,研究了土壤中16种优控多环芳烃的含量和组分特征,运用主成分因子载荷方法分析了其污染来源,并初步评价了其风险水平.结果表明,该区域内94.7%土壤已被污染,其中重污染土壤占39.5%,最高污染样点PAHs含量高达5991.7 ng·g-1,平均含量为1148.1 ng·g-1,且城区土壤残留水平明显高于乡村土壤;PAHs的组分特征为以毒性水平较高的高环化合物为主;其污染来源主要是煤、天然气和汽油燃烧组成的混合源.     

基于被动采样技术的垃圾焚烧厂及周边大气中PAHs分布研究

垃圾焚烧是大气PAHs污染的重要来源,为监测垃圾焚烧过程产生的PAHs,利用被动采样技术对垃圾焚烧厂及周边大气中的多环芳烃(PAHs)进行了定量分析.结果表明,PAHs总量为146.29～396.30 ng·d-1,其中气相中PAHs为128.03～377.05 ng·d-1,颗粒相中PAHs为10.698～19.251 ng·d-1.气相中PAHs组成以菲、荧蒽、芴等低环化合物为主,菲的含量高达55.1%.选定松针作为被动植物样品,测得松针中PAHs的浓度为651.88～1 044.43 ng·g-1;考察土壤中PAHs的分布特征,测得土壤中PAHs浓度为35.04～998.89 ng·g-1.被动采样和松针、土壤中所含的PAHs分布特征相似,说明被动采样能反映PAHs在环境中的真实积累情况.此外,通过比较主动采样与被动采样结果,表明两者对大气中PAHs的富集能达到基本一致的效果.     

岩溶地下河流域表层土壤多环芳烃污染特征及来源分析

采集重庆南山老龙洞地下河流域农田土壤(0～20 cm),利用气相色谱-质谱联用仪(GC/MC)测定了土壤样品中16种优控多环芳烃(polycyclic aromatic hydrocarbons,PAHs)含量,分析其含量和组成,污染水平及污染来源.结果表明,流域内不同地点表层土壤16种PAHs总量变化范围为277～3301 ng·g-1,平均值为752.6 ng·g-1±635.5 ng·g-1,所有样品均遭受污染,其中57%为轻污染,29%为污染土壤,而14%为重污染.多环芳烃的组成以2～3环为主,占总量的28.72%～72.68%,平均值为48.20%;4环和5～6环含量分别为7.77%和34.03%.土壤PAHs含量与有机质(SOM)含量显著相关,而与pH值相关性不强.比值法和主成分分析(PCA)表明,流域内土壤主要来自交通排放与煤炭、石油及生物质燃烧的混合源以及石油源.     

中国东北主要河流沉积物中多溴二苯醚的含量状况及生态风险分析

为揭示多溴二苯醚(PBDEs)在东北主要河流流域内的污染现状,通过采集该地区流域内表层沉积物样品,采用GC-NCIMS技术对沉积物中41种PBDEs同类物进行分析.结果发现沉积物中BDE209含量低于检出限,其它40种PBDEs同类物总含量(不包含BDE209)范围(干重)为0.91~17.67 ng·g-1.其中第二松花江吉林市上游和下游沉积物样品中PBDEs的检出含量最高,分别为15.86 ng·g-1、17.67 ng·g-1,以BDE207和BDE47为主,分别占PBDEs总量的86.5%和76.6%;其它河流沉积物中各同族体含量差异并不明显.实验结果与国内外最近的文献报道值相比较,再结合生态风险分析显示,东北主要河流沉积物中PBDEs的含量处于低污染水平,目前不存在生态风险.     

电子废物拆解区农业土壤中PCNs的污染水平、分布特征与来源解析

用GC-NCI-MS法测定了路桥农业表层土壤中46种多氯萘(PCNs)的含量.目的是了解该地区表层土壤中PCNs的污染水平、空间分布特征和来源.结果表明,所有表层土壤样品中ΣPCNs的含量为0.062～2.92 ng.g-1,平均值为0.630 ng.g-1.多数样品中tetra-CNs和penta-CNs是最主要的同族体,分别占18.4%～88.8%(平均值为46.7%)和8.40%～53.1%(平均值为30.7%),其次是tri-CNs,范围为0～47.3%,平均值为10.6%.聚类分析和燃烧指示物分析表明,采样点主要受Halowax1014和Halowax 1013工业品污染,PCBs工业品和电子废物燃烧也可能对污染有贡献.与国内外其它研究相比,研究区域内土壤中PCNs污染处于中等水平.     

舟山青浜岛不同环境介质中PAHs的分布特征

于2013年7月在青浜岛上采集11个土壤样品、3个大气被动采样样品以及周边3个海水样品,分析了样品中16种多环芳烃(PAHs)的含量,并对其分布特征、来源、生态风险进行了讨论.结果表明,土壤、海水和大气中Σ16PAHs的含量范围分别为60.30~123.34 ng·g-1(平均值为105.49 ng·g-1)、45.96~101.08 ng·L-1(平均值为66.45 ng·L-1)和5.09~5.41ng·d-1(平均值为5.35 ng·d-1).分布特征为:潮汐带土壤中PAHs含量低于非潮汐带;3个海水样中,以靠近水文条件复杂的海域内样品中的PAHs含量最高;岛上大气中PAHs分布均匀.土壤、海水和大气中PAHs主要以2~4环的PAHs为主;通过比值法和因子分析得出,青浜岛土壤中的PAHs来源于煤、木炭等生物质燃烧以及柴油、汽油的燃烧,海水和大气中的PAHs来源于混合源.生态风险评价结果表明青浜岛土壤和周边海水中PAHs生态风险较低.     

深圳市表层土壤多环芳烃污染及空间分异研究

以深圳为研究区域,选择土壤为研究对象,以多环芳烃(polycyclic aromatic hydrocarbons,PAHs)为目标物,采集表层土壤样品188个,调查样品中PAHs的赋存状态,以此为基础,分析土壤PAHs污染水平与城市化进程的关系,并初步评估深圳土壤中PAHs的生态风险.结果表明,表层土壤中的28种PAHs(Σ28PAHs)、16种美国环保署优控PAHs(Σ16PAHs)和7种致癌PAHs(Σ7CarPAHs)的含量范围分别为5~7 939 ng·g-1、2~6 745 ng·g-1和未检出~3 786 ng·g-1.8种土地利用类型中Σ16PAHs平均含量由高到低依次为:交通用地、商业用地、工业用地、农业用地、居住用地、城市绿地、果园和林地.来源分析表明,化石燃料的燃烧是建设用地和非建设用地样品Σ16PAHs的主要来源,贡献率分别为75.1%和68.2%.研究还发现高分子量PAHs浓度和城市化水平呈显著正相关关系,深圳市土壤中PAHs生态风险总体处于较低水平.     

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.     

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.