北京大气沉降样品中的PCBs

采集了4个北京大气沉降样品,包括3个总沉降与1个湿沉降样品.利用高分辨率气质联用仪(HRGC-HRMS),参照国际标准方法分析测定了其中的多氯联苯(PCBs)含量.总沉降样品的PCBs含量水平为4.47～7.08ng·g-1(平均为5.52ng·g-1)和TEQ为0.55～5.43 pg·g-1(平均为2.27 pg·g-1).湿沉降样品含量水平为15.02 ng·g-1,其TEQ为2.87 pg·g-1.首钢样品的TEQ远高于其它3个样品.根据我国大气降尘数据,粗略估计北京PCBs大气沉降通量平均值为67.9 ng·m-2·m-1和TEQ平均通量为27.9 pg·m-2·m-1.首钢样品中,IUPAC编号为77的类二(噁)英PCBs含量异常高,但TEQ仍以编号为126的PCBs所占比例最高.随着取代氯原子数的增加,同族体的含量逐渐降低.     

西安城区大气中多氯联苯季节变化及来源解析

为了解西安城区大气中多氯联苯(Polychlorinated biphenyls,PCBs)的浓度水平、季节变化特征及来源,于2012年夏季、冬季分别对西安市城区大气进行每周1次的主动采样,共获得22对大气样品(气态和颗粒态).结果表明,西安城区大气中∑64PCBs的浓度为76.21~338.77pg·m-3,平均浓度为183.85 pg·m-3,且主要存在于气态样品中.组成上主要以低氯代PCBs为主,其中,三氯和四氯代PCBs占总浓度的59.64%~91.39%.气态样品中,夏季、冬季PCBs的平均浓度分别为201.68、151.11 pg·m-3;颗粒态样品中,冬季PCBs平均浓度是夏季的6.65倍.通过主成分分析法对西安城区大气中PCBs的来源进行解析,发现主成分1的方差贡献率为36.06%,主要为来自我国生产的变压器油源;主成分2的方差贡献率为20.29%,可能来自于油漆的使用.     

小流域大气氮干湿沉降特征

大气氮沉降是陆源污染物和营养物质向水生生态系统传输的重要途径之一.在人类活动影响较大的流域,大量氮素通过大气沉降的形式输入到水体中,能够对地表水体的营养结构、水生生物的生存环境等造成严重的负面生态效应.本文以密云水库石匣小流域为例,采集并分析了研究区大气氮沉降(颗粒态干沉降与湿沉降)样品,探讨了该流域大气氮沉降通量的变化特征及其主要影响因子,进而明确了大气氮沉降对流域氮输入的贡献程度.结果表明:(1)石匣流域大气氮总沉降(颗粒态干沉降与湿沉降之和)呈现出明显的季节变化特征;对湿沉降而言,总氮、氨氮在夏季沉降通量最大,溶解性有机氮沉降通量在春季最大,而硝态氮季节变化并不明显;对颗粒态干沉降而言,总氮和氨氮的沉降通量在冬季最高;硝态氮在不同季节变化不明显,但其沉降趋势与总氮基本一致;溶解性有机氮在秋季出现最高值.(2)该流域氮沉降通量为43. 14 kg·hm-2,其中湿沉降通量占39. 85%,颗粒态干沉降通量占60. 15%.(3)降雨和风速条件是影响大气氮沉降的重要影响因子,其中雨量和雨强与氮湿沉降浓度均呈明显的负相关关系;对颗粒态干沉降而言,监测期内平均风速是影响颗粒态氨氮干沉降通量的重要因子.(4)大气氮沉降占该流域总的氮素输入量的15. 09%,是仅次于畜禽养殖和农村生活的重要污染源.本研究结果可为密云水库上游流域氮素综合管理提供科学参考.     

戴云山国家级自然保护区大气氮沉降特点

利用干湿沉降采集器,持续观测戴云山国家级自然保护区内大气氮素干、湿沉降,调查当地大气氮沉降的种类和沉降通量.结果表明,2015-03-27~2015-10-09观测期间,戴云山自然保护区大气氮干、湿沉降量分别为2.30 kg·hm~(-2)和14.79kg·hm~(-2),以湿沉降形式为主(87%).干沉降中可溶性有机氮的沉降量为1.21 kg·hm~(-2),占干沉降通量的53%;无机氮以硝态氮为主(0.71 kg·hm~(-2)),铵态氮相对较低(0.37 kg·hm~(-2)).湿沉降中无机氮和可溶性有机氮沉降量分别为9.41 kg·hm~(-2)和5.38 kg·hm~(-2),其中无机氮以铵态氮为主(6.07 kg·hm~(-2)).大气氮湿沉降量和当地降雨量显著正相关,降雨量越大,对应的湿沉降氮量也越大.戴云山国家级自然保护区大气氮素沉降量较高,可能会对当地生态环境产生较大的影响.     

北京大气颗粒物和重金属铅干沉降通量及季节变化

为了解大气颗粒物和重金属铅(Pb)干沉降通量的变化规律,采用聚氨酯泡沫膜片为代用面联合干湿沉降自动观测设备,于2013年12月~2014年11月在北京城区采集了颗粒物干沉降,利用微波消解和电感耦合等离子体质谱仪对样品中全量Pb和水溶性Pb进行了测试分析.结果表明,北京大气颗粒物和Pb干沉降通量分别为0.84 t·(hm~2·a)~(-1)和7.56mg·(m~2·a)~(-1),呈现出春季冬季秋季~夏季的特征.大气颗粒物中水溶性Pb干沉降通量为3.14 mg·(m~2·a)~(-1),占Pb干沉降总量的43%,这一比例呈现出冬春季高于夏秋季的特征.人为源排放不仅增加了大气颗粒物和Pb的干沉降通量,也改变了水溶性Pb干沉降通量的季节分布.研究结果对科学评估重金属沉降的生态影响和健康效应提供了科学基础,同时凸显了消减人为源重金属排放的重要性.     

黑龙江凉水国家级自然保护区大气氮沉降特征

为了监测黑龙江凉水国家级自然保护区的大气氮沉降水平,在2015年生长季用干湿沉降采集器连续观测了大气氮湿沉降和颗粒物干沉降量,并在非生长季用自制观测桶观测了大气混合氮沉降量.结果表明:(1)该区2015~2016年度大气氮沉降总通量(生长季湿沉降+颗粒物干沉降以及非生长季混合沉降)为12.93 kg·(hm~2·a)~(-1),其中无机氮沉降总通量为8.27kg·(hm~2·a)~(-1),NH_4~+/NO_3~-为1.3;有机氮沉降总通量为4.66 kg·(hm~2·a)~(-1),占全氮比例为36.0%.(2)生长季(湿沉降+颗粒物干沉降)和非生长季(混合沉降)氮沉降总量分别为11.42 kg·hm~(-2)和1.51 kg·hm~(-2),分别占全年氮沉降总通量的88.3%和11.7%.(3)生长季氮湿沉降总量为9.28 kg·hm~(-2),占生长季氮干湿沉降总量的81.3%,且与降水量显著正相关(R2=0.87,P0.001);生长季颗粒物干沉降总量为2.14 kg·hm~(-2),占生长季干湿沉降总量的18.7%.该区氮湿沉降量受降水量影响明显,且在全国属于中等水平,存在一定的环境风险,当地在生活生产过程中应注意环境保护与水质监测.     

北京城区大气金属元素干湿沉降特征

为研究北京市大气中金属元素的干湿沉降特征,评估不同观测方法的差异性,于2014年5月至2015年4月在北京城区同步采集了混合沉降和湿沉降样品.利用电感耦合等离子体质谱仪(ICP-MS)测定了样品中19种金属(Na、Mg、Al、K、Ca、V、Cr、Mn、Fe、Cu、Zn、As、Se、Mo、Cd、Sb、Tl、Th和U)的浓度.结果表明,混合沉降样品中各金属浓度[7 160.68μg·L~(-1)(Ca)～0.02μg·L~(-1)(Th)]普遍高于湿沉降样品[4 237.74μg·L~(-1)(Ca)～0.01μg·L~(-1)(Th)].两种样品中相同金属的富集因子差异较小,其中Cu、As、Tl、Zn、Cd、Se和Sb的富集因子均大于100,表明这些重金属主要来自人为污染源.气团轨迹分析表明,北京城区降水过程主要受偏南气团的影响,其中来自西南气团的降水样品中Ca、Mg、Fe、Al、Cu、Mo、U和Th等金属浓度较高,而来自南部的气团K、Zn、Mn、Sb、Cd和Tl等金属浓度较高.观测期间大气中金属元素的混合沉降通量变化于3 591.35 mg·(m~2·a)~(-1)(Ca)～0.01 mg·(m~2·a)~(-1)(Th),湿沉降通量变化于1 847.78 mg·(m~2·a)~(-1)(Ca)～0.01mg·(m~2·a)~(-1)(Th).混合沉降与湿沉降差减得到19种金属的干沉降通量变化于1 743.57 mg·(m~2·a)~(-1)(Ca)～0.01mg·(m~2·a)~(-1)(Th).大气颗粒物的粒径大小对金属的干湿沉降过程具有重要影响.     

夏季青岛大气气溶胶中不同形态磷的浓度、来源及沉降通量

利用2016年6~7月在青岛采集的总悬浮颗粒物(TSP)样品,分析了其中不同形态磷的浓度,讨论了夏季气溶胶中总磷(TP)、溶解态磷(DP)、溶解态无机磷(DIP)和溶解态有机磷(DOP)的分布特征及来源,并估算了大气P的沉降通量.结果表明,夏季青岛大气气溶胶中TP的浓度为(49.3±30.6)ng·m~(-3),其中DP浓度为(15.5±10.4)ng·m~(-3),对TP的贡献为30.9%±11.0%.DP中以DIP占主导,其贡献平均约为60%.气溶胶中不同形态P的来源分析结果显示,夏季青岛气溶胶中P的来源复杂,受地壳源、人为源、生物质燃烧、农业施肥等多种源的共同影响.其中TP的38%来自土壤源的贡献,农业活动源和工业源的贡献分别为20%左右;DP中DIP主要受到农业活动源及燃烧源的影响,其贡献分别为51%和24%;DOP主要来源于土壤源及农业活动源,其贡献分别为41%和27%.观测期间,大气TP的干沉降通量为(51.7±31.7)μg·(m~2·d)~(-1),其中DP对TP干沉降通量的贡献为23.2%±8.2%.DP中DOP有重要贡献,约为DP干沉降通量的40%.DP的干沉降通量可支持黄海(0.5±0.3)mg·(m~2·d)~(-1)浮游植物碳的生产,对新生产力的贡献约为1%.     

大气湿沉降对长江口水域营养盐的贡献

为研究我国长江口大气湿沉降对近海水域营养盐的贡献,2004年6月～2005年5月于长江口水域崇明岛收集31个大气湿沉降样品,采用分光光度法测定溶解性NH4 、NO3-、NO2-、PO)034-和SiO23-.结果表明,大气湿沉降中营养盐月平均浓度变化较大,NH4 和NO3-浓度较高.营养盐湿沉降通量具有明显的季节性,总无机氮(TIN)、PO34-和SiO32-的湿沉降通量分别为52.02、0.17、0.10 mmoll(m2·a).NH4 是TIN的主要贡献者,占TIN的70.9%.由于大气湿沉降中营养盐的浓度和组成比例与长江口表层海水有显著的差别,可使海水表层的营养盐结构、盐度、pH等发生改变,从而影响到浮游植物生长和种群结构,甚至会引发赤潮.     

西宁近郊大气氮干湿沉降研究

本研究在青海省西宁市城郊二十里铺莫家泉湾气象站开展了完整的2年(2014和2015年)大气无机氮干沉降和混合沉降(湿沉降加部分干沉降)监测.干沉降估算通过被动采样器采集的NH_3和NO_2浓度和Geos-Chem全球化学模式模拟的气体干沉降速率相乘获得;混合沉降的测定采用雨量器.结果表明,气态NH_3和NO_2年均浓度分别为8.8μg·m-3和19.6μg·m-3,且2015年NH_3月均浓度显著高于2014年.NH_3浓度的季节变化呈现春夏高、秋冬低的特征,而NO_2浓度季节变化幅度较小.降水中NH_4~+-N和NO-3-N年均浓度为2.2 mg·L~(-1)和1.8 mg·L~(-1),秋季降水NH_4~+-N浓度比其他季节低55%,而NO-3-N浓度在秋冬季比春夏季高约26%.气态NH_3和NO_2的干沉降量分别为9.0 kg·(hm~2·a)~(-1)和2.8 kg·(hm~2·a)~(-1),降水中NH_4~+-N和NO-3-N的混合沉降量分别为7.6 kg·(hm~2·a)~(-1)和6.2 kg·(hm~2·a)~(-1).还原态氮(NH_3和NH_4~+-N)在氮沉降中占主导地位.大气氮素总沉降(干沉降加混合沉降)量为25.6 kg·(hm~2·a)~(-1),为城郊农田提供重要的环境养分;但这一氮素输入量超过了陆地生态系统氮沉降临界负荷[10~20 kg·(hm~2·a)~(-1)],意味着研究区周边林地(如北山)和水体生态系统面临"氮饱和"的环境风险.     

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.     

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.     

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.     

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.     

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.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.