敏感区域目标污染物空间溯源分析

基于SPARROW模型,利用新安江流域2009~2010年60个监测站点的TN浓度数据,以及相关污染源及空间属性数据对流域水质进行模拟分析,结果表明,流域内69%的河段TN模拟浓度可以达到III类及以上水质标准.对跨省界评估断面——街口断面进行TN污染源溯源分析,发现上游各子流域的工业源污染对断面污染总量的贡献比例为7.41%,农业源污染贡献比例为57.52%,生活源污染贡献比例为35.07%,且分别具有不同的空间分布特征,可以考虑使用该方法为以跨界断面污染物浓度控制为目标的相关削减措施的提出提供技术支持.     

海河流域氮磷面源污染空间特征遥感解析

以MODIS遥感数据为驱动,采用以遥感像元为基本模拟单元的DPeRS（Diffuse pollution estimation with remote semsing）面源污染负荷估算模型,分析了2016年海河流域氮磷面源污染空间分布特征,并对“十三五”《重点流域水污染防治规划》中划定的海河流域172个控制单元进行面源污染优先控制单元分析.结果表明,2016年海河流域总氮（TN）排放量为13.62万t,入河量为2.53万t;总磷（TP）排放量为8152t,入河量为1597t;空间分布上,海河流域中部和南部地区氮磷面源污染较重,其中河北省片区氮磷面源污染物排放量及入河量最大;农田径流型是海河流域氮磷面源污染的主要类型,其次城镇径流影响也较大;筛选出海河流域TN和TP面源污染优先控制单元分别为127和131个,面积占比分别为84.2%和87.0%.     

SWAT模型下“十三五”中期污染减排措施及气象条件对岷江流域水环境改善贡献

基于SWAT构建了岷江流域分布式水文和污染负荷模型,模拟水文变化过程的效率系数超过0.6,模拟污染物浓度的效率系数超过0.5,能够有效模拟岷江流域2015-2018年的水文、污染浓度和通量变化过程。通过模型计算分析了岷江流域主要污染物排放量变化、《水污染防治行动计划》不同减排措施及气象驱动条件对岷江流域水环境改善贡献。结果表明:岷江流域11个国考断面COD、NH₃-N、TP排放量分别下降8%、13%和12%,其中8个考核断面废水排放量上升,主要污染物排放量降低,其中点源强度下降,密度上升;岷江流域中段排放强度高、减排量同样凸显,成都市对岷江出境断面污染物排放及减排贡献均高于眉山市;各项减排措施中,城镇生活污染治理对污染物减排及通量降低占主导作用,对COD_Mn、NH₃-N、TP通量减排分别贡献53%、71%、81%;生活源减排贡献大于工业源减排,点源减排贡献率大于面源污染减排;污染减排措施对凉姜沟断面COD_Mn、NH₃-N和TP浓度变化的贡献率分别为20.7%、26.8%和34.4%。     

基于流域水环境模型评估重金属面源污染负荷

为定量评估重金属面源污染负荷,以分布式流域水环境模型SWAT模型为基础,借鉴输出系数模型,考虑溶出率影响,发展了一个重金属面源污染模型—SWAT-MT模型. SWAT-MT模型模拟重金属在流域内的大气沉降、地表径流冲刷、土壤和河道中的运移过程,结构较为简单,兼具机理模型和输出系数模型的优点. 本文应用SWAT-MT模型评估了湘江株洲段一个子流域的铅面源负荷,并通过敏感性分析和蒙特卡洛模拟识别了铅面源模拟的敏感参数,量化了模型输出中的不确定性. 结果表明:①研究区铅的面源侵蚀量为2.09 t/a,侵蚀强度为5.27 kg/(km2·a). 铅侵蚀强度时空差异明显,汛期(4—7月)雨水集中,铅的侵蚀量大. 侵蚀强度高的地方集中在流域下游,城镇用地的侵蚀强度约为流域平均水平的2倍. ②流域出口的铅负荷为0.79 t/a,约60%的铅侵蚀量滞留在河道,说明沉降是河道运移的主要过程. ③蒙特卡洛模拟结果显示,模型输出存在显著的不确定性, 95%置信区间下,铅的面源侵蚀量为1.62～2.59 t/a,流域出口负荷为0.50～1.16 t/a;为降低模拟不确定性并提高模型可靠性,应重点关注城市地表积尘的铅浓度、铅溶出率和河道铅沉降速率等敏感参数的取值. 研究显示,通过合理的参数赋值,SWAT-MT模型能够提供较为可靠的重金属面源负荷估算结果,为重金属污染综合防治工作提供科学工具.      

SWAT模型在洱海流域面源污染评价中的应用

重点污染区域和污染因子的识别是面源污染控制的基础. 通过将物理过程模拟及排污系数法计算进行整合,建立了SWAT模型,以描述农业生产活动与污染入湖量之间的关联关系,并以云南洱海流域总氮污染为例,使用验证后的SWAT模型模拟计算不同空间单元和不同农业生产活动对入湖TN的污染贡献系数,定量分析流域内各区域的农业面源污染源结构,识别洱海流域重点农业污染源和农业污染村镇. 结果表明,奶牛养殖、生猪养殖和大蒜种植是目前洱海流域内入湖TN污染的最重要农业污染源,占流域总污染负荷的66.12%. 对入湖TN污染贡献最大的6个村镇为江尾、右所、三营、玉湖、凤仪和喜洲,占流域总污染负荷的63.41%.      

基于SWAT与DNDC模型对比研究亚热带流域氮淋溶与输出过程

本研究通过对亚热带香溪河小流域的氮输出进行长期监测,并通过DNDC与SWAT模型对流域氮素流失进行对比模拟研究,以期为合理建立适合亚热带流域氮循环模型提供科学依据.结果表明:(1)影响DNDC模型模拟小流域内氮素流失的关键参数包括降水、坡度以及氮肥施用量,而影响SWAT模型模拟的关键参数包括地下水滞后系数、最大冠层截留量、基流系数和土壤蒸发补偿系数;(2)DNDC模型模拟小流域内2014年的径流量、TN和NO-3-N排放量与实测值的偏差分别为5.19%、8.10%和71.70%,SWAT模型模拟小流域内2014年的TN、NO_3~--N和NH_4~+-N的排放量与实测值的偏差分别为2.04%、14.29%和8.89%;(3)通过对SWAT与DNDC模拟结果对比分析香溪小流域氮素流失时空分布特征,进一步耦合了DNDC和SWAT模型,有助于提高亚热带流域氮素流失模拟精确度.     

降雨时间分辨率对SWAT水文模拟的影响

分别基于13个雨量站的日降雨量和小时降雨量,在率水流域建立SWAT（Soil and Water Assessment Tool）水文模型,对基于不同降雨时间分辨率的SWAT模型进行独立的参数率定和验证,在此基础上分析降雨时间分辨率对率水流域SWAT模拟性能的影响.结果表明,降雨输入的时间分辨率对率水流域SWAT模型的水文模拟性能有显著影响.小时降雨输入SWAT模型的纳什系数（NSE）和决定系数（R²）在率定期分别为0.89、0.90,在验证期分别为0.86、0.88,均显著高于日降雨输入SWAT模型对应的模型评价统计量值.究其原因,小时降雨输入SWAT模型对于峰值流量的模拟要明显优于日降雨输入SWAT模型.建议应在不同气候与自然环境条件的流域内开展类似的降雨时间分辨率对水文模型模拟性能的影响研究.     

降雨时间分辨率对SWAT水文模拟的影响

分别基于13个雨量站的日降雨量和小时降雨量,在率水流域建立SWAT（Soil and Water Assessment Tool）水文模型,对基于不同降雨时间分辨率的SWAT模型进行独立的参数率定和验证,在此基础上分析降雨时间分辨率对率水流域SWAT模拟性能的影响.结果表明,降雨输入的时间分辨率对率水流域SWAT模型的水文模拟性能有显著影响.小时降雨输入SWAT模型的纳什系数（NSE）和决定系数（R²）在率定期分别为0.89、0.90,在验证期分别为0.86、0.88,均显著高于日降雨输入SWAT模型对应的模型评价统计量值.究其原因,小时降雨输入SWAT模型对于峰值流量的模拟要明显优于日降雨输入SWAT模型.建议应在不同气候与自然环境条件的流域内开展类似的降雨时间分辨率对水文模型模拟性能的影响研究.     

考虑面源污染的农业开发流域生态安全评价研究

随着农业开发的进程,流域生态安全会发生相应变化,在考虑面源污染的基础上,以挠力河为例开展该研究.该流域14年来的土地利用类型发生较大变迁,耕作方式改变,破坏了流域的生态安全,同时大量农药化肥的使用,使得大量氮、磷为主的营养污染物引发农业面源污染,面源污染将成为生态安全评价的一项重要指标.为了对农业面源污染进行量化,对生境质量进行直观评价,考虑面源污染做出流域生态安全的变化评估,选取SWAT模型和InVEST模型（生态系统服务和交易的综合评估模型）,同时考虑面源污染及生境质量,对比挠力河流域2000年、2006年、2014年三个年份的生态安全变化.根据输出结果,分析时空变化模式,得到氮磷负荷、生态环境质量对时空变化的响应,讨论提出有效的防控建议.     

SWAT模型在我国流域水环境模拟应用中的评估验证过程评价

模型评估验证是模型开发和应用过程中的重要环节,是管控模型应用于管理决策风险的重要手段.近年来,以SWAT模型为代表的流域水环境模型在我国流域水环境管理中得到广泛应用,但模型评估验证过程尚缺乏规范性指导.结合SWAT模型建模过程和模型评估验证的基本步骤,梳理总结SWAT模型评估验证过程的评价方法,针对确定研究或决策目标、获取输入数据、构建模型、模型率定验证、展示模型结果等5个阶段分别设计评价指标.筛选中国知网收录的2015—2017年发表的以SWAT模型为主题的428篇学术论文作为研究对象,评价现有研究的模型评估验证过程,分析我国SWAT模型评估验证的现状以及存在的问题和不足.评价结果表明,我国现有的SWAT模型应用研究总体比较重视模型评估验证过程,能够清晰定义研究区域、建模目标和期望产出,说明输入数据来源和质量以及模型概化、参数灵敏度分析、参数识别、不确定性分析的方法和结果,模型模拟效果较好.但是,针对SWAT模型评估验证方法的研究较少,在模型参数识别方面还存在参数选取未考虑研究区域特征、参数识别结果不合理等问题.建议在SWAT模型应用研究中关注参数灵敏度分析和参数识别,结合研究区域特征建立本地化应用数据库,加强模型评估验证方法研究.当模型应用于流域水环境管理决策时,应完整地开展模型评估验证,并分析模型不确定性对决策的影响.      

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.     

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.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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