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.     

滴水湖及其水体交换区沉积物和土壤中PAHs的分布及生态风险评价

采用GC-MS联用技术分析了滴水湖及其水体交换区23个表层沉积物和土壤中16种多环芳烃(PAHs)的含量,探讨其分布特征及来源并对其生态风险进行评价.结果表明,滴水湖沉积物中16种PAHs含量范围是11.49~157.09 ng·g-1,平均含量为66.60 ng·g-1,湖区沉积物中PAHs含量比入湖区低,但比出湖区高.湖区外的沉积物和土壤中PAHs组成主要以中、高分子量PAHs(4环、5~6环)为主,而湖区内表层沉积物中PAHs组成则以低分子量PAHs(2~3环)和高分子量PAHs(5~6环)为主.通过特征化合物分子比值法、主成分分析及多元线性回归模型判源,表明湖区外沉积物和土壤中PAHs来源主要为燃烧源,而湖区内沉积物中PAHs来源为燃烧源和石油类产品泄漏的混合来源.生态风险评价显示,滴水湖及其水体交换区沉积物和土壤中PAHs生态风险较低.     

青藏高原湖泊流域土壤与牧草中多环芳烃和有机氯农药的污染特征与来源解析

2007年8月采集了青藏高原中部与北部6个典型湖泊流域的土壤与牧草样品,分析了样品中多环芳烃和有机氯农药(包括六六六和滴滴涕)的污染水平.土壤样品中Σ16PAHs、ΣHCHs和ΣDDTs的浓度范围分别为60.6~614 ng·g-1(平均194 ng·g-1)、0.06~0.74 ng·g-1(平均0.31 ng·g-1)和N.D.~0.17 ng·g-1(平均0.07 ng·g-1).牧草样品中Σ15PAHs(不包括萘)、ΣHCHs和ΣDDTs的浓度分别为262~519 ng·g-1(平均327 ng·g-1),0.55~3.92 ng·g-1(平均2.17ng·g-1)和0.20~2.19 ng·g-1(平均0.92 ng·g-1),均远低于欧洲高山中相应介质中POPs的浓度.牧草的生物浓缩效应显著,其生物浓缩因子达到4.2~19.3.POPs的浓度分布与有机质/脂肪含量、海拔均无显著相关关系.PAHs的组成以较轻组分(2、3环PAHs)为主,占总浓度的80%以上.PAHs的特征单体比值表明生物质和化石燃料的低温燃烧是青藏高原PAHs的主要来源,同时较低的α/γ-HCH比率和较高的o,p’-DDT/p,p’-DDT比率表明,林丹以及三氯杀螨醇的使用对高原介质中有机氯农药的污染有一定的贡献.根据反向气团轨迹模型,推断冬季青藏高原中部与北部的污染主要受西风带影响,夏季高原中部位点的污染物主要源自印度次大陆,而北部位点还受到中国内陆省份的影响.     

大冶湖表层沉积物-水中多环芳烃的分布、来源及风险评价

于2015年8月采集大冶湖表层沉积物8个及上覆水样8个,使用GC-MS分析16种EPA优控PAHs.结果表明在表层沉积物及水体中ΣPAHs范围分别为:35.94~2 032.73 ng·g-1和27.94~242.95 ng·L~(-1),平均值分别为940.61 ng·g-1和107.77 ng·L~(-1);表层沉积物中PAHs分布呈现湖中高于岸边趋势,水体则呈大致相反趋势,表层沉积物中以4~5环高环化合物为主要组分,在水体中主要以2环以及4环和5环PAHs为主,与国内外其他湖泊相比处于中度污染水平;来源解析表明大冶湖表层沉积物及水体中多环芳烃主要来自于高温燃烧源,沉积物中PAHs高环分子都占据绝大部分,反映出了沉积物受矿冶冶炼长期累积污染的效应;所检测沉积物中各单体PAH及ΣPAHs含量均未超过ERM以及FEL,表明大冶湖表层沉积物中PAHs无潜在生态风险;终生致癌风险评价表明大冶湖水体中PAHs通过摄入和皮肤接触风险都处于USEPA推荐的可接受水平范围之内,但都高于瑞典环保局和英国皇家协会推荐的最大可接受风险水平,需要对7种致癌PAHs污染加以防治.     

深圳大鹏湾海域表层沉积物和生物体中多环芳烃残留及其风险评价

为了研究深圳大鹏湾海域沉积物和生物体中多环芳烃的污染状况,2011年10月在大鹏湾采集表层沉积物及鱼类、虾类和贝类等生物样品,采用气相色谱-质谱法(GC-MS)分析了16种优先控制多环芳烃(PAHs)的含量.结果表明,大鹏湾海域表层沉积物和生物样品中PAHs总量范围分别为216.56~1 314.92 ng·g-1(干重,下同)和70.88~251.90 ng·g-1(湿重,下同);生物样品按平均含量计,鱼类最高(171.52 ng·g-1),贝类次之(134.75 ng·g-1),虾类最低(123.35 ng·g-1).与全球其他海域相比,大鹏湾海域表层沉积物和生物体PAHs污染处于中等水平.沉积物中PAHs的组成以4环为主,来源分析表明该海域PAHs污染主要来源于化石燃料燃烧源和石油污染源的共同输入.生物体中PAHs主要为2~3环PAHs,这与其生活习性和污染物的生物可利用性等因素有关.风险评价表明,大鹏湾表层沉积物中的PAHs在一定程度上可能会对该海域生物产生不利影响;生物样品PAHs的苯并(a)芘等效浓度值相对较高,长期食用这些水产品可能会有潜在的健康风险.     

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.     

广西大石围巨型漏斗土壤中多环芳烃与环境因素

选择典型的广西乐业大石围巨型岩溶漏斗(天坑)为研究对象,采集大石围漏斗不同部位的表层土壤,采用气象仪器观测大石围漏斗的环境因子,利用气相色谱-质谱仪(GC-MS)测定16种多环芳烃(PAHs)优先控制污染物.结果表明,大石围天坑群地表(正地形)土壤中ΣPAHs浓度范围为75.20～373.79 ng·g-1,平均值120.70 ng·g-1;地下(负地形)土壤,绝壁中ΣPAHs浓度范围为19.88～330.79 ng·g-1,平均值131.86 ng·g-1;底部中ΣPAHs浓度范围为127.48～661.62 ng·g-1,平均值395.22 ng·g-1;地下河(洞穴)中ΣPAHs浓度范围为1 132.11～1 749.95 ng·g-1,平均值为1 412.39 ng·g-1;土壤中PAHs以4～6环为主.比值法推断大石围漏斗土壤PAHs的来源主要为化石燃料燃烧源,主要污染途径为大气传输沉降.总体上,大石围漏斗土壤中PAHs浓度的空间分布随温差和相对湿度的升高呈现地面-绝壁-底部-地下河(洞穴)逐渐增加,PAHs显示"冷陷阱效应"的垂向富集与分异作用.影响PAHs分布的主要环境因素是温度,其次是湿度、风向和风速,在漏斗局部显示多环境因子共同作用.环境因子夏季影响大于冬季.监测发现,2007年比2006年大石围漏斗底部土壤中PAHs的浓度增加了3.5倍.因此,本研究提出巨型岩溶漏斗PAHs的富集和分异作用与环境因素密切相关.     

长江湖北段表层土中多环芳烃分布、来源及风险评价

应用气相质谱-色谱联用仪(GC-MS)对湖北省长江流域岸边表层土壤样品中25种多环芳烃含量进行了测定,分析了长江湖北段11个国控断面对应土壤中∑25PAHs及∑7 carcPAHs的含量分布特征,并利用同分异构体比值法及因子分析法对表层土壤中的PAHs来源进行了解析,采用苯并[a]芘的毒性当量浓度(TEQBa P)对PAHs的健康风险进行评价.结果表明,土壤中∑25PAHs的含量为34.81~2939.07 ng·g-1,均值为463.16 ng·g-1,以4~6环为主.与其他地区土壤PAHs含量相比,研究地区土壤PAHs污染处于中等水平,污染主要来源为石油、煤及草木等的不完全燃烧.根据荷兰土壤标准,采用毒性当量因子分析得出11种TEQBa P为3.02~2559.72 ng·g-1,73%的采样点大于参考值(33 ng·g-1),说明湖北地区长江流域周围土壤普遍存在潜在健康风险.     

舟山近海水体和沉积物中多环芳烃分布特征

2012年,每两个月采集1次浙江省舟山近海水样及表层沉积物样品,检测16种多环芳烃(PAHs)含量.结果表明,舟山近海水体和沉积物中PAHs均存在显著的时空差异性,水体ΣPAHs浓度范围为382.3~816.9 ng·L-1,平均值为552.5ng·L-1;沉积物ΣPAHs含量范围为1017.9~3047.1 ng·g-1,平均值为2022.4 ng·g-1.空间分布上,水体ΣPAHs最大值和最小值分别出现在小洋山和燕窝山海域,而沉积物中分别出现在小洋山和朱家尖南沙海域.时间变化上,水体ΣPAHs最大值和最小值出现在10月和6月,而沉积物中分别出现在8月和6月.PAHs污染来源主要是油类排放和木柴、煤燃烧的共同叠加作用.结合PAHs的生物阈值,利用超标系数法评价舟山近海PAHs的生态风险,结果表明,ΣPAHs存在较低几率的潜在风险,但苊单体存在较高几率的潜在风险,二氢苊和芴可能存在生态风险.对水-沉积物界面PAHs的富集研究表明,舟山近海沉积物中富集了大量PAHs,富集系数(Kd值)岱山岛大于舟山本岛,并与沉积物的PAHs含量分布一致.     

厦门杏林湾水系表层沉积物中PAHs分析与风险评估

利用ASE-GC-MS(加速溶剂萃取与气相色谱质谱仪联用)方法分析了USEPA(美国环保署)16种优控PAHs在厦门城郊杏林湾水系的19个表层沉积物样点中的含量,并对其组成、来源和风险进行了探讨.结果表明,杏林湾水系表层沉积物中PAHs含量介于413.00~2 748.81 ng·g-1,均值为949.56 ng·g-1;在检测出的13种PAHs中,强致癌性的Bk F和Bghi P检出率高达73.68%,均值分别为69.15 ng·g-1和49.86 ng·g-1;PAHs以2~4环为主,其中2+3环比例均值为61.03%,4环比例均值为23.53%;5和6环均值为15.82%.在所采集的沉积物样品中,中度污染占调查样品数的68.42%,高度污染的占31.58%.利用Ant/(Ant+Phe)和Fla/(Fla+Pyr)比值法和主成分分析方法对杏林湾流域中PAHs其来源进行分析,以及平均沉积物质量基准商(m SQG-Q)法进行生态风险评估,结果表明其PAHs的主要来源为石油源以及石油燃烧源;SQG-Q小于0.50;综合含量、组成特征以及沉积物质量基准商等评价表明,研究区域内靠近杏林工业区一侧的2、3、5和9号采样区以及13号港头采样区表层沉积物中PAHs具有较高的生态安全风险;值得进一步关注.     

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.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

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.