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。     

污染场地原位化学药剂注射修复要点分析

原位修复技术被越来越多的应用于污染场地修复工程的实践,原位化学氧化、原位化学还原、原位生物修复以及原位稳定化等污染场地原位修复技术均需采用原位化学药剂注射这一修复施工工法。对实验室小试、修复设计、现场中试、注射系统构建与运行以及注射后监测等几个原位化学药剂注射修复的重点环节进行了实施要点的分析,以指导相关污染场地原位修复技术的顺利开展。     

铬污染场地修复技术进展

土壤中六价铬污染主要来源于铬化工、电镀和制革等行业。简述了我国涉铬行业概况,铬污染土壤的来源及铬特性,重点综述了国内外铬污染场地修复技术研究与应用进展,分析了各种修复方法的优缺点,并列举分析了国内外的修复工程案例。我国是铬盐生产大国,铬化工场地污染尤为严重且复杂。电镀类铬污染场地呈现铬、镍、铜、锌多重金属复合污染特点。制革类铬污染场地具有铬有机物复合污染特征。目前铬污染土壤的修复技术主要是基于六价铬的还原稳定化原理,具体包括化学还原、化学淋洗、电动力学修复以及生物修复技术等。考虑到技术适用性和经济性,目前铬污染土壤修复工程绝大部分采用化学还原的修复技术。开发经济、环境友好型修复材料,探讨其修复机理和长期安全性是未来铬污染场地修复技术的发展方向。     

几种稳定化药剂修复铬污染土壤的研究

采用FeSO_4、K_2HPO_4、EDTA二钠、Na_2S、膨润土、粉煤灰、Ca(OH)_2和水泥8种药剂分别对铬污染土壤进行修复,考察这8种药剂对不同养护时期(7,15,28d)铬污染土壤浸出液中总铬和六价铬的稳定效果,以及对土壤pH值的影响。结果表明,FeSO_4对铬污染的稳定化具有很好的效果,浸出液中总铬和六价铬含量分别降低到2.21,0.76mg/L以下;硫化钠可以使浸出液中总铬和六价铬含量降低50%左右;EDTA二钠对于六价铬有明显的去除作用,但对总铬去除作用不明显。其余几种药剂中,氢氧化钙效果稍微好,其他药剂稳定效果较差。硫酸亚铁和硫化钠对铬土pH影响较大,经过28d修复后也未恢复到原土pH值水平。经过EDTA二钠、氢氧化钙和水泥作用的铬土在第28天的pH值接近原污染铬土壤。其他药剂对土壤pH影响不大。     

污染场地水平修复井技术的研究进展及应用实践

常用的污染场地原位修复技术主要通过竖直井实现,但竖直井修复技术存在单井接触范围小、精准度低、难以在地表设施较多的场地实施等问题。污染场地水平修复井技术通过水平定向钻进手段协同化学氧化/还原、气相抽提、地下水抽出处理等修复方式靶向去除场地土壤/地下水污染区域的污染物,克服了竖直井修复技术的不足,适用于在产设施和构筑物下方的土壤/地下水修复。针对该技术的应用原理、技术优势及局限性、国内外研究进展等方面进行探讨。该技术在J省N市某石油烃污染场地进行了工程示范,并结合软件模拟论证,采用水平修复井技术协同碱活化的过硫酸钠药剂注入。结果表明：该技术的实施不受修复区域地表市政设施的限制,对场地及周边环境扰动小,单井接触范围大,修复精度更高,工期100 d内石油烃浓度降低了96.47%,达到修复目标值。该技术的成功示范可为我国原位修复技术的发展提供切实可行参考,其推广和使用前景广阔。     

原位还原稳定化—高压旋喷注射技术修复铬污染场地中试研究

根据场地土壤条件(如pH、渗透性、地下水位等)、污染程度和前期小试效果,选用高压旋喷注射技术,将硫化物和矿物质组成的还原型药剂注入污染土壤中,还原Cr~(6+)为Cr~(3+),从而降低土壤中Cr~(6+)含量和毒性。中试结果表明,在注射压力为10 MPa,影响半径为0.5 m,提升速率为10 cm/min,药剂投加比为3%时,修复后的土壤Cr~(6+)含量0.5 mg/kg,低于修复目标值0.75 mg/kg,达标率为100%。另外,六价铬和总铬的浸出毒性均低于《GB8978-1996污水综合排放标准》中的第一类污染物最高允许排放浓度,达到了预期的修复目标值,且药剂的加入不会对土壤pH造成较大影响。原位还原稳定化—高压旋喷注射修复技术成功应用于某铬盐厂中试,修复效果明显,适应于类似污染场地的浅层土壤修复。     

某焦化厂旧址氰化物污染地下水修复工程实例分析

介绍了某焦化厂旧址氰化物污染地下水原位注入修复工程。前期场地调查及风险评估,确定场地污染现状、修复目标及修复工程量。通过修复技术比选,确定适合项目的修复技术路线。小试试验确定适宜的氧化药剂(二氧化氯)及药剂添加范围。现场中试试验,确定单井注入影响半径、注入压力及药剂的最佳投加比。修复施工完成后,由第三方检测机构对修复工程进行采样、检测,根据检测结果评估修复效果。该项修复工程的成功实施能够为其他类似污染场地土壤修复项目提供参考。     

铬污染场地修复技术研究及应用

综述了国内外铬污染场地修复技术的研究动态,探讨了铬污染修复技术研发的需求,重点讨论了铬污染土壤的主要修复技术如:土壤清洗技术、化学解毒技术、电动修复技术和稳定化技术等。并针对这些技术存在的不足,开发了化学解毒与稳定化联合技术,对山西某铬渣堆存场地中受污染土壤进行修复。结果表明:运用化学解毒与稳定化联合技术可以降低污染土壤中总铬和六价铬的浸出浓度,稳定效果好且能在工程实际中高效应用。     

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。     

美国污染场地修复技术对我国修复行业发展的启示

随着我国工业化进程的发展,暴露出来的土壤污染问题越来越严重。对我国2005—2019年以来455个污染场地修复项目进行了统计分析,发现我国污染场地修复项目数量逐年递增,修复方式以异位修复为主,占比为63%,修复技术以阻隔/填埋（29%）、固化/稳定化（18%）为主。相比之下,2005—2014年,美国污染场地修复方式实现了从异位修复到原位修复的转换,原位修复技术占比达到54%,其中土壤气相抽提技术、物理分离、固化/稳定化技术、化学修复和生物修复技术应用居多,地下水抽提-处理技术的应用逐年下降。基于美国修复技术发展趋势,我国未来修复技术路线应以原位修复为主。     

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.