4种NAPLs污染物在二维砂箱中的指进锋面形态特征研究

为明确介质和流体性质等因素对非水相液体(NAPLs)在多孔介质中入渗迁移的影响,利用数码图像分析技术对甲苯、柴油、1,2-二氯乙烷和四氯乙烯这4种NAPLs在4种不同粒径多孔介质中的非饱和入渗特性进行了实验研究.结果表明,数码图像分析技术能够动态、全过程记录NAPLs的迁移锋面;NAPLs在驱替气体过程中会出现指进形式的不稳定流;指进生长过程中出现分叉、合并和屏蔽等现象;NAPLs的迁移特性受介质性质和流体特性的共同影响,入渗过程中垂向上的迁移速率和污染面积增长率与介质粒径大小呈正相关,与流体密度呈正相关(甲苯除外),入渗过程中形成的指进与介质和流体本身性质也密切相关.相同时间内,DNAPL相较于LNAPL入渗的距离更深,造成的污染面积更大,其环境风险明显大于LNAPL.     

人工注气及生物产气对孔隙介质中DNAPL运移影响

重非水相液体(DNAPLs)的污染和治理问题是国内外研究热点,由地下水曝气技术注入的人工气体或生物作用等产生的气体必然对DNAPL在地下水系统中的运移及修复产生影响.采用CCD实时监测系统,以TCE为目标污染物,通过3个二维砂箱试验,以饱水条件下DNAPL的运移为对照,研究了人工注气及生物产气对DNAPL在孔隙介质中运移的影响.结果表明:(1)基于CCD相机的透射光监测系统是一种研究二维孔隙介质中多相流迁移规律的有效非侵入式监测方法,应用于实时监测水/NAPL,水/气,水/NAPL/气多相系统中流体渗流过程.(2)人工注气和生物产气两种条件下,气体在多孔介质中的分布特征有差异,前一条件下气体连续分布,后一条件下则以非连续分布的气泡为主.(3)在水/气两相系统中,气体的存在使得DNAPL污染羽的整体形状更加不规则;同时缩短了TCE污染羽前缘整体平均垂向下迁距离;也导致迁移路径上孔隙中TCE的截留量变小.DNAPL的入渗过程受重力影响以垂向渗流为主,垂向渗流时易于驱替孔隙中的水分,然而水平渗流时优先驱替孔隙中的空气.     

浅水富营养化湖泊蓝藻垂向分布特征及其动力机制研究——以太湖为例

蓝藻垂向运动的表征对于理解浅水富营养化湖泊中蓝藻水华的形成过程至关重要.本研究以太湖为研究区,通过野外实验观测,分析蓝藻生物量及颗粒物粒径分布的垂向变化特征,结合一维蓝藻平流运动模型,研究在不同扰动强度和群体粒径下的蓝藻垂向运动规律.结果表明,在低风速条件下(风速小于3 m·s^-1),太湖水体中蓝藻生物量在垂向上分布不均匀,其垂直分布剖线在水表或水柱某一深度形成峰值.当水华发生时,直径> 75μm的蓝藻群体主要聚集在水表,其剖线在水下形成不明显的峰值;在水华未发生时,75～175μm直径范围内的蓝藻群体主要聚集在水深1.2 m处,175～250μm直径范围内的大粒径蓝藻群体仍聚集在水表.垂向运动模拟表明,直径> 100μm的蓝藻群体随光照变化在水柱中进行周期性上浮下沉运动,直径<100μm的蓝藻群体,由于垂向迁移速度较小,在弱扰动条件下聚集在真光层深度附近.不同粒径蓝藻群体的垂向运动规律不同,导致蓝藻生物量垂直剖线在水表和水下形成两类特征峰.     

垂向环流作用下湖泊沉积物磷迁移行为

以巢湖十五里河入湖河口原位底泥为研究对象,通过室内模型实验,模拟了垂向环流的动水条件下,溶解态无机磷（DIP）在泥水界面的释放-吸附过程,探讨了不同强度环流对河口底泥DIP迁移的影响行为.结果表明：垂向环流扰动会引起上覆水中溶解氧（DO）和悬浮颗粒物（SPM）含量明显上升,且其平衡浓度与扰动强度均呈正相关,但悬浮物中值粒径（D₅₀）则随扰动强度的增大而降低;垂向环流作用下沉积物DIP的释放量随时间呈“Λ”型分布,显著区别于其他动水扰动情形,释放峰值与环流强度成显著正相关（P=0.047<0.05）,但平衡值则与之呈显著负相关（P=0.034<0.05）;环流扰动的增强促进了DIP在沉积物上的吸附,并构建了耦合天然水动力效应的沉积物DIP Freundlich等温吸附经验公式：lgQ_e=2.7074e^1.3487τ+0.9463e^-1.4830τlgC_e.     

底栖动物扰动对河床渗透性的影响研究

河床渗透性是影响地表水与地下水相互交换的重要因素,为探究底栖动物扰动对河床渗透性的影响,以渭河干流上5个研究点为例,通过对河床沉积物垂向渗透系数和沉积物粒度进行分析,再结合底栖动物的种类和密度,研究垂向渗透系数与底栖动物之间的相关性,以及底栖动物扰动对河床渗透性的影响.结果表明,沉积物成分分布以沙和砾石为主的草滩,渗透系数达到18.479 m·d-1,底栖动物的生物密度为139 ind·m-2;沉积物成分中粉沙和黏土占很大比重的眉县,渗透系数为2.807 m·d-1,底栖动物的生物密度为2 742 ind·m-2;沉积物粒度分布基本相同的眉县、咸阳、临潼和华县等4个渗透性较差研究点中底栖动物的生物密度和垂向渗透系数均差别较大,但是生物密度和垂向渗透系数呈显著相关性,其两者之间皮尔森相关系数r=0.987.不同研究点影响沉积物渗透性的主要决定因素不同,渗透性较强研究点主要为沉积物颗粒大小,渗透性较差研究点主要为底栖动物扰动;不同研究点内生物密度差别较大,不同生物种类差别也较大;底栖动物的生物扰动能够缓解细小沉积物的阻塞,以使弱渗透性河床沉积物的渗透性增强.     

离子强度对蒙脱石胶体在饱和多孔介质中运移与释放的影响

胶体在介质中的沉积和释放过程直接影响污染物的迁移和固定能力,本文以蒙脱石胶体作为主要实验材料,通过室内模拟实验,研究了不同离子强度条件下,蒙脱石胶体在多孔介质中的迁移和释放规律.结果表明:溶液离子强度的变化,会强烈影响蒙脱石胶体的运移及释放过程,随着溶液离子强度的增加,胶体在多孔介质中的沉积量增大,而当降低溶液的离子强度,又会使沉积在多孔介质中的胶体得以释放,并且离子强度改变次数越多,胶体的释放总量越大.     

典型抗生素在多孔介质中迁移特性的对比研究

为系统探究抗生素在饱和多孔介质中的迁移行为,选取两类典型抗生素—磺胺类（Sulfonamides, SAs）和氟喹诺酮类抗生素（Fluoroquinolones, FQs）,通过室内砂柱迁移实验,重点对比研究了水化学条件及介质粒径对两类抗生素迁移的影响.结果表明,不同种类抗生素在饱和石英砂多孔介质中的迁移特性不同.在实验pH（5.6~9.5）条件下,低解离常数使得SAs多以带负电形态出现,因静电斥力导致SAs在石英砂介质中具有强迁移能力,流出液中SAs回收率>97%;pH、离子强度（NaCl、CaCl₂）及介质粒径对抗生素的迁移无显著影响.FQs多呈阳离子形态及两性形态,受静电引力控制,FQs迁移能力相对较弱,但移动性随溶液pH升高而增大,NaCl和介质粒径对FQs迁移影响不显著,竞争吸附导致高浓度CaCl₂促进FQs迁移能力.本研究结果阐明了SAs和FQs在多孔介质中不同水化学条件（pH、NaCl及CaCl₂离子强度）下及不同介质粒径中的迁移过程,可为抗生素环境风险的预测和评估及污染修复提供指导.     

粤港澳大湾区典型潮间带环境多介质中Cd形态空间分布特征及其影响因素

在粤港澳大湾区典型潮间带开展了 14个站位同步采样和观测,分析各采样点表水、孔隙水、悬浮物和沉积物中Cd形态的空间分布特征,并结合环境因子采用统计分析方法探讨不同介质中Cd形态分布差异的影响因素.结果表明,各潮间带环境表水、孔隙水、悬浮物和沉积物中Cd含量范围分别为0.41～15.03 μg·L-1、0.41～27.5...     

铜陵矿区河流沉积物重金属的迁移及环境效应

测定铜陵矿区的新桥至顺安河沉积物中5种重金属的全量和形态,并结合环境条件分析它们的迁移变化特征,以阐明不同重金属对河流沉积物环境影响的程度.结果表明,该区域沉积物重金属除Cr外,Cu、Zn、Pb、Cd的均值皆远超长江下游沉积物背景值,其中以Cu和Cd最显著.重金属横向迁移结果显示,矿山重金属会随着沉积物的距离增加而显著降低,新桥河沉积物的迁移变化显著高于顺安河沉积物.重金属Cu、Zn、Pb、Cr皆以残渣态为优势,Cd则以酸提取态为主;迁移过程中Cu、Zn、Cr残渣态逐步增加,毒性减弱;Pb、Cd的活性态比例增大,仍有较高的释放风险.重金属的纵向迁移结果表明,离矿山的位置远近对沉积柱金属的总量和形态起决定作用;新桥河沉积物金属总量高、活性组分多且垂向变化幅度相对较小,说明尾矿堆积速度较快且释放风险较高;顺安河金属总量较低但垂向变化幅度较大,且多种元素的变化趋势不同,说明矿区下游河流沉积物既受尾矿的影响,也受河流流域物质本身的影响.     

渭河陕西段潜流带沉积物重金属变化初步分析

为厘清潜流带沉积物重金属时空变化及与水量交换、沉积物颗粒结构间的关系,于2013年春夏两季对渭河陕西段5个研究断面66个测试点位沉积物的野外原位渗透系数、颗粒粒径、重金属含量进行分析.结果表明:影响渭河沉积物渗透系数的主要因素是沉积物粒径,同时沉积物垂向分层、排列组合也影响其渗透性能;沉积物重金属Cu、Zn、Pb、Cd质量分数在垂向上不同深度其含量大小不同,在时间上总体呈现春季夏季,富集系数(EF指数)分析结果显示春季Cu、Zn(除华县)、Pb(除眉县)、Cd富集严重且主要受人为输入源影响,夏季除Cd元素外,Cu、Zn、Pb的EF值均1.5,说明其含量主要来源于地壳和岩石圈的自然风化过程;Pearson相关分析发现粘土与粉砂(粒径0.075 mm)百分比与沉积物重金属质量分数呈弱相关,重金属粒径效应不显著,粒径不是控制重金属含量的主要环境影子;对单一重金属垂向不同深度含量进行相关性研究发现除Cd外,其余3种重金属在垂向上的相关系数均0.5(p0.01),说明单一重金属在垂向上具有同源性且存在相互迁移与转化.     

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.     

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.