地下水循环井技术修复硝基苯污染含水层效果模拟

实验在二维模拟槽中进行,以曝气前后地下水水位高度变化表征地下水循环强度,分析了地下水初始水位,曝气量和地下水初始流速对循环井运行的影响,并以得到的最佳运行参数进行硝基苯污染地下水修复效果模拟.结果表明,地下水初始水位45 cm,曝气量0.7 m3·h-1,地下水初始流速低于1.0 m·d-1时,循环井可以达到良好运行状态.硝基苯在地下水中的纵向迁移距离明显大于横向,泄漏第50 d时,平均浓度达到246.97 mg·L-1.循环井修复过程中,逐渐形成一个以循环井为中心的有机物高效修复区域.该区域内有机物被优先去除,浓度持续下降.高效修复区域外,存在过渡区域,该区域内有机物的浓度受有机物吸附/解吸和迁移性共同作用影响.整个修复过程中,硝基苯的浓度经历了快速下降-缓慢下降-浓度拖尾3个阶段,累计曝气14 h后,硝基苯的平均浓度下降至71.19 mg·L-1,残留的硝基苯分布在远离循环井的区域.由此可见,地下水循环井技术能够较好地修复硝基苯污染的地下水,修复过程存在最佳运行条件及最适修复时间.     

地下水苯系物污染原位曝气修复模拟研究

通过TMVOC软件模拟了苯系物在拟定渗流区“自然”环境条件下的污染物运移行为和原位曝气修复过程中的污染物衰减过程,确定了最佳曝气流量和所需要的曝气井数量及分布,并对修复效果进行了模拟.模拟显示,泄露过程中,在重力作用下,不饱和区的苯系物以竖直迁移为主,同时在毛细作用下横向迁移;在饱和区中以顺水流方向水平迁移为主,同时会溶解进入地下水,污染羽可到达含水层底部.从含水层底部的7个曝气孔同时以12m3/h的速率将空气注入时,只需180d即可完全修复苯系物污染区域.该条件下单井有效修复半径约5m,有效修复范围优于从含水层中部和中下部进行曝气.     

确定空气注射技术影响半径的现场试验——以北京某焦化厂为例

以北京某焦化厂地下水污染场地为例,设计和建立了一套由1口注射井、3口地下水监测井和5口土壤气监测井组成的现场试验系统,并进行了现场注气压力与流量测试,地下水压力响应测试,溶解氧测试,氦气示踪测试与土壤气测试,确定了试验区域的最佳注气压力与流量和影响半径.注气压力与流量测试确定了最佳注气压力与流量为0.03MPa, 23.2m3/h.在最佳注气条件下,地下水监测井G3、G5、G8中,水位分别在10,15,15min后上升到最大值0.36,0.11,0.04m,地下水溶解氧浓度分别在60,65,75min后增加到7.35、2.47、0.74mg/L,以上结果表明,G3和G5响应较明显,G8响应不明显.土壤气监测井S2、S4、S5中氦气浓度分别在10,7,6min后达到最大值83%、13%、41%,S6中氦气无检出;S2、S3、S4、S5、S6中O2浓度分别上升到19.9%、19.6%、19.2%、19.0%、16.6%,以上结果表明,S2~S5响应较明显,S6响应不明显.综合分析以上4种测试结果,确定试验区域的影响半径为5m.     

SVE法修复污染场地所需工艺参数的确定

SVE是一种针对挥发性和某些半挥发性污染物的土壤原位修复技术。介绍了通过现场试验,来确定用SVE法修复污染场地所需的工艺参数,包括最佳真空度、抽气井有效影响半径、土壤气流量等,为类似的场地修复问题提供工程技术参考。     

地下水硝酸盐污染抽出处理优化方法模拟研究

以北京某场地生活垃圾填埋场硝酸盐污染地下水为研究对象,针对抽出处理技术,利用遗传算法(GA)和模拟退火法(SA)对地下水硝酸盐污染羽治理区中布置18口备选井方案进行优化.优化目标函数最小化治理成本,确定最佳井数及其井的位置和抽水速率,同时达到在100 d内将研究区硝酸盐浓度降低至10 mg·L-1的治理目标.GA优化结果为8号井优化抽水速率为155 m3·d-1,14号井优化抽水速率为10 m3·d-1.SA优化结果为8号井优化抽水速率为82 m3·d-1,14号井优化抽水速率为39 m3·d-1.基于GA和SA优化抽水速率,硝酸盐总量去除率分别为76.89%和84.92%.优化结果说明,最佳井的位置应位于硝酸盐污染羽中游及中下游的中轴线上,且中游抽水速率比下游要大.两种优化算法对比表明SA优化系统治理成本比GA节省6.8%,且波动性小,更收敛.     

基于保护地下水的土壤修复目标层次化制订方法

按照复杂程度将污染物从土壤经地下水迁移到下游饮水井的过程划分为3个层次,采用分层评估框架建立了基于保护地下水的土壤修复目标的制订方法,并利用该方法确定了某污染场地的土壤修复目标值. 结果表明,在污染场地下游200 m处的饮水井内水质标准不降低的前提下,随着评价层次的不断提高,需要修复的污染物由4种(苯、甲苯、乙苯、二甲苯)减至1种(苯),待修复土方量由23.1×104 m3降至4.7×104 m3,可极大地节约修复成本. 该场地污染土壤的第一层次和第二层次修复目标值与部分国家/地区的有关标准限值较为一致;第三层次修复目标值考虑的污染物迁移过程更加完整,更能反映场地的实际情况. 参数的敏感性分析表明,对土壤修复目标值计算结果影响最大的参数为土壤有机质质量分数、土壤有机碳-水分配系数和入渗速度. 在确定修复方案时,应该通过试验或补充调查获取这些参数,以降低结果的不确定性. 研究显示,将第三层次评估结果作为该污染场地的修复目标能充分保证下游饮水井内水质满足要求,并且可以避免过度修复.      

数值模拟技术在污染地下水抽出-处理运行中的应用

数值模拟技术在污染地下水修复中具有非常广泛的应用，该技术通常应用于修复设计阶段，但该阶段获取的模型参数准确性在时间、空间尺度上存在一定程度局限性，使修复效果存在较多不确定性。将数值模拟技术应用于实际修复过程更具有实际意义。结合地下水污染修复实例，考虑对流、弥散、吸附等地块特征因素，建立三维数值模型进行地下水流及溶质运移模拟，以地下水修复过程中多个监测井的水位、水质监测数据作为模型参数修正，分析随着地下水修复过程的开展，污染物在地下水环境中的变化趋势，以及时调整抽出-处理方案，指导后续地下水修复实施。结果表明：基于修复过程中监测资料进行数值模型修正的方法，能更真实地反映模拟区地下水系统特征，更有效地指导后续修复实施工作。     

原位注入地下水化学修复的MHC耦合模拟

原位注入化学修复地下水时将修复药剂通过注入井注入污染地下水,它具有典型的渗流-应力-化学（MHC）耦合特征。论文建立了耦合的平衡微分方程、渗流连续性方程和反应溶质运移方程,利用COMSOL Multiphysics软件对模型参数敏感性及某场地污染地下水原位注入化学修复过程进行了模拟分析,结果表明,渗透系数、水动力弥散系数和注入压力对污染地下水修复效果影响显著,其值越大,达到修复目标的时间越短;土体中孔隙水压力消散滞后于注入井注入压力的消失,这种滞后消散特性有助于修复药剂在地下水中进一步扩散,提高地下水修复效果;药剂注入压力使土层产生明显位移,尤其是垂直方向的位移,弹性模量对土体位移的影响显著。整个场地在80 d时可达到污染物浓度小于0.6 mg/L的修复要求。     

土壤及地下水原位注入-高压旋喷注射修复技术工程应用案例分析

南京、宁波、青海等地诸多工业污染场地修复工程项目中采用了原位注入-高压旋喷注射修复技术,以原位化学氧化/还原修复技术为代表,根据不同场地污染物的特性、污染程度、污染分布及修复场地水文地质情况,设计了原位注入-高压旋喷注射修复系统及修复工艺,通过大量工程实践获得了系统施工参数,验证了系统的修复效果。最终工程实施结果表明:所采用的原位注入-高压旋喷修复技术对主要污染物苯、氯苯、对/邻硝基氯化苯、苯胺、多环芳烃、石油烃等VOCs/SVOCs及重金属(六价铬)的修复效果显著,所修复的土壤/地下水均达到修复目标,相比现有Geoprobe水力压裂、注入井等原位修复技术,解决了注射压力不足、注射效率低、药剂扩散半径偏小、饱和层修复注射难以保证注浆量影响扩散效果等问题,且彻底解决了异位修复噪声、大气环境二次污染问题,为我国工业污染场地土壤及地下水原位修复问题解决提供了新思路,具有广阔的应用前景和工程借鉴价值。     

原位生物稳定固化技术在铬污染场地治理中的应用研究

原位生物稳定固化方法是控制铬污染场地地下水风险的有效方法,通过实地工程试验,初步验证了原位生物稳定固化法治理南方某铬污染场地的修复效果.实地工程试验的场地面积约600 m2,位于整个污染场地的上游,受高浓度铬污染,总铬含量高值为11 850 mg.kg-1,六价铬含量高值为349 mg.kg-1,污染最为严重的土层为-0.5～-2 m.通过对在试验场地范围内设置注射井注射还原剂和微生物调节剂等,并通过监测井监测分析不同时间不同深度范围内在药剂注射的作用下地下水中六价铬和总铬的浓度变化.工程试验结果表明,原位生物稳定固化技术显著改变了土壤中铬的形态,进而降低了铬的迁移性,消减了地下水污染风险.注入的药剂对注入井(有效范围)内的地下水六铬污染治理效果很好,六价铬转成三价铬并固定稳定率达到94%～99.9%,总铬固定稳定率达到83.9%～99.8%.试验结果对于浅层地下水深度较浅、土壤以粉质黏土和砂质黏土为主的污染场地修复具有重要的参考价值.     

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.     

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.     

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.     

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.     

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.     

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

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Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.