观测数据权重对地下水有机污染物生物降解模型参数估计的影响

地下水多组分反应运移模型是刻画解释微生物降解地下水有机污染物的水文地质、生物地球化学耦合过程并对各组分分布特征进行预测的重要工具.反应运移模型往往包含多个参数,并含有多种不同生物化学组分的观测数据,高维参数和观测数据类型的多样性给模型参数的反演带来了极大的困难.因此,本文以反应运移软件PHT3D模拟某污染场地地下水中有机污染物生物降解的理想正问题为例,对比讨论了不同观测数据权重对反应运移模型参数估计的影响.结果表明:未考虑观测数据权重时参数估计结果与真实值相差较大,而采用反映观测误差的权重时参数估计值与真实值更接近.敏感性分析表明,参数对于不同观测组数据的敏感度有明显差异.对于本例,生物降解模型中的降解反应参数最敏感,其次是溶解速率迁移常数,多相溶解度摩尔分数敏感度较小.     

甲苯在渗流区的生物通风去除模拟

建立了数学模型来描述生物通风过程中渗流区土壤中甲苯的运移和生物降解过程,模型考虑了对流通量、扩散通量、相间传质和生物降解项,模型中的生物降解参数由独立间歇实验用Levenberg Marquardt方法确定.在实验室中用土柱实验来模拟生物通风过程,结果显示,实验数据与模型比较吻合,经过50h后,约有98%的甲苯已被去除.利用土柱尾气中甲苯实验数据和质量衡算式计算可得:挥发去除的甲苯占初始加入甲苯的53 78%,生物降解去除的甲苯为42 92%,土壤中残余甲苯浓度为2 56mg·kg-1.     

人工神经网络及分子拓扑参数在酚类有机物QSBR研究中的应用

利用分子拓扑参数作为输入参数,探索了人工神经网络对２７种酚类有机物的定量结构－生物降解性能关系（ＱＳＢＲ）。结果表明,将人工神经网络运用于有机物的生物降解性能建模是可行的。所建模型预测结果和文献数据十分接近,预测能力优于已有文献报道,且能够较好区分同分异构体。     

地下水曝气修复过程的三维数值模拟

地下水曝气法是去除挥发性有机污染物的重要原位修复方法之一,目前已得到广泛应用,但其现场设计主要依据经验,缺乏系统的设计标准.为深入了解曝气去除污染物过程,并为现场设计提供重要参考依据,针对地下水曝气过程开展了数值模拟研究.水气两相渗流数值模型以水压力和气压力作为基本未知量,利用达西定律和质量守恒原理可以建立水气两相渗流过程的控制方程.利用Van Genuchten(VG)模型及Mualem公式,建立渗透系数-饱和度-基质吸力(K-S-P)三者之间的关系.污染物的去除过程则是在水气两相渗流的基础上,引入污染物的溶质运移、相间交换及生物降解模型.采用开发的有限元数值模型,对地下水曝气过程及污染物去除过程进行三维数值模拟,并将三维数值模拟的结果与二维数值模拟的结果进行对比.结果表明,三维模型的曝气影响区域偏小,在曝气口附近,水有效饱和度最小;在曝气口上方,水饱和度先增大后减小.考虑气体所受的浮力作用或不考虑气体可压缩性均会使计算得到的曝气影响区域偏小.污染物去除边界与曝气影响区域的边界基本一致,在曝气区域内,溶质交换过程大大促进了污染物的去除速率;在曝气区域外,污染物的去除主要通过生物降解作用,去除较慢.结果表明实际工程地下水曝气修复系统设计时,应使得曝气影响区域覆盖污染区域以得到较好的修复效果.研究结果表明,两相渗流模型结合污染物迁移转化模型的三维有限元数值模拟可以较好地模拟地下水曝气法去除污染物的全过程,对地下水曝气的设计、应用与效果评价具有重要指导意义.     

水平潜流人工湿地有机物去除模型研究

以总有机碳(TOC)做为模型参数,建立了1个水平潜流人工湿地有机物去除机理模型.通过对试验数据的拟合得到模型中的未知参数,再对模型进行验证.结果表明,模型预测值与实测值的吻合较好.种植花叶芦竹的水平潜流人工湿地和空白湿地对生活污水中总有机碳的去除率分别为92%和91%,去除的主要途径为生物降解作用,生物降解量占进水总有机碳的84%.植物对总有机碳去除有促进作用,但影响不大.     

Bayes理论在河流水质模型参数识别中的应用

参数识别是水环境数学模型建模的重要步骤.在实际模拟过程中,往往难以获得理想的数据进行模型参数识别.充分利用研究者已有的经验,可在一定程度上减少模拟过程的风险.Bayes理论为把研究者的经验或前验信息纳入到水质模拟提供了一个定量手段.采用离散Bayes理论的基本方法,以国内某河段实际监测数据为基础,完成了模型的参数识别过程,并对识别结果进行了分析.验证结果表明,采用Bayes理论获得的参数识别结果能够达到模型验证的要求.     

基于MCMC方法的SWMM模型参数不确定性分析

基于贝叶斯理论,采用马尔科夫链蒙特卡罗法的差分演化自适应Metropolis算法,即MCMC-DREAM算法,对SWMM模型水量参数及输出的不确定性进行了系统分析。研究结果表明:在模型模拟过程中,不透水区面积比率和管道曼宁系数对模型的模拟结果具有较大的影响,不确定性较小,而其他参数不确定性较大,是水量模拟参数不确定性的主要来源。参数不确定性是造成模型输出不确定的主因。径流峰值模拟最容易产生偏差,是模型输出不确定性的主要来源,提高峰值的模拟精度将有效地提高模型整体的模拟效果。     

SCS-CN模型中土壤参数的作用机制研究

土壤参数是地表径流模型中的关键参数,对径流过程模拟有重要影响,因此有必要明确土壤参数的作用机制。论文结合SWAT (Soil and Water Assessment Tool) 模型,以广泛应用的径流曲线数模型(SCS-CN) 为例,对土壤参数在SCS-CN模型中的作用进行了理论推导、分析和实例研究。分析表明,土壤饱和含水量参数与田间持水量参数的比值,是影响不同土壤湿度下地表产流能力的重要因素,两者比值越大,土壤含水量对地表产流能力的调节越弱,导致基于不同土壤模拟的地表径流量随土壤湿度的波动而上下反转。以实际流域为例,发现不同土壤数据模拟地表径流间差别的显著季节性特征;阐明该差别季节性变化的内在机制,验证了理论分析结论。为深入理解产流过程、合理选择土壤数据、模型参数优化及模拟结果解释提供了参考。     

紫外辐射与生物膜同步耦合降解喹啉

紫外辐射光解与生物降解同步耦合的气升式内循环反应器用于喹啉的降解.实验过程中分别采用单独紫外光解、单独生物降解和紫外光解与生物降解同步耦合的方法对喹啉进行降解.结果表明,喹啉在紫外光解与生物降解同步耦合的作用下,其降解速率明显提高.喹啉降解动力学分析结果表明,喹啉的生物降解可以用有抑制性的Haldane模型描述.相比生物降解过程,单独紫外光解对喹啉的降解速率可以忽略,但将紫外辐射与生物降解耦合在一起后,可以提高喹啉的最大降解速率近1倍并减小抑制常数36%,同时还可以提高喹啉的矿化程度.     

基于SWAT模型的挠力河流域地表径流数值模拟与不确定性分析

为探究水文模型参数敏感性及模型不确定性对径流模拟的影响,运用SWAT模型对挠力河流域地表径流过程进行了数值模拟,利用SUFI-2方法评价模型参数敏感性及不确定性对模拟结果的影响,选取决定系数（R2）与Nash-Sutcliffe效率系数（E_NS）对模型精度进行评价。敏感性分析结果表明:对挠力河流域径流模拟影响最大的4个参数是CN2（SCS径流曲线数）、SLSUBBSN （平均坡长）、SOL_BD （土壤湿密度）和SOL_K （土壤饱和导水率）,表明SCS径流曲线数、土壤与地形地貌是影响挠力河流域地表径流最重要的因素。月径流模拟过程与实测水文过程拟合较好,率定期和验证期R2与E_NS分别为0.68、0.67和0.76、0.44,均达到令人满意的结果。不确定性分析结果表明:p因子为0.78,r因子为0.94,模型不确定性较小,进一步验证了模型的适用性。研究结果可为其他相似流域SWAT模型的应用及参数的率定提供参考。     

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.     

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.     

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.