开关表面活性剂对土壤及地下水中多环芳烃污染的增效修复研究进展

开关表面活性剂在环境中主要应用于处理土壤及地下水系统中疏水性有机污染物,污染物多环芳烃(PAHs)是目前其应用研究的热点. 本文详细阐述了开关表面活性剂对土壤及地下水中PAHs污染的可逆增效机理,增效机理基于开关表面活性剂胶束形态的改变;汇总了常用于土壤及地下水PAHs污染修复的三类开关型表面活性剂,通过比较光开关型、CO₂/N₂开关型和氧化还原开关型在开关前后的表面活性理化指标来解释其微观调控特征,认为微观调控基于其响应基团发生化学反应;重点总结了这三类开关表面活性剂在改变表面张力的可逆性与对PAHs增溶的可逆性上具备的优缺点;阐述了开关表面活性剂在实际应用中可能受很多外界因素的影响,并重点关注温度、pH、无机离子和土壤矿物对其的影响. 今后需通过一定规模的野外场地试验,探究多种环境因素动态耦合对开关表面活性剂增溶PAHs的影响机制,厘清在环境因素动态耦合下不同调控方式与分离效率之间的关系,为筛选适合不同环境的开关表面活性剂提供理论数据支撑.      

生物表面活性剂强化植物修复重金属污染土壤的可行性

利用有机配体强化植物修复重金属污染土壤是提高植物修复效果的常用措施．但大部分有机配体会引起二次污染而限制了其在土壤重金属修复中的应用。如果能将生物表面活性剂强化植物修复不仅会弥补这一不足．而且还能降低费用。生物表面活性剂在重金属污染土壤修复中的应用以及生物表面活性剂去除重金属的机理表明,将其强化植物修复是完全可行的,并且可以增加植物细胞膜透性,更好地促进植物对重金属的吸收。     

生物表面活性剂清洗土壤有机污染物的研究与展望

重点阐述了生物表面活性剂清洗土壤有机污染物的机理及影响因素.根据国内外最新文献,对使用生物表面活性剂溶液修复有机物污染土壤的研究进展进行了综述.并展望了生物表面活性剂在清洗土壤有机污染物中的研究前景.     

表面活性剂对受污染环境修复作用研究进展

综述了９０年代后国外利用表面活性剂对受有机物污染有地下水和土壤进行修复的最新研究进展，介绍了表面活性剂对憎水性有机物污染物增溶作用的规律，表面活性剂－增强修复技术的原理，以及表面活性剂存在时对污染物降解作用的影响。     

有机污染物界面行为调控技术及其应用

污染物的多介质/多界面行为影响其赋存状态、迁移转化及生物生态效应.阐明污染物界面行为及其调控技术原理,是准确认识污染物源汇机制、预测其生物有效性、发展污染控制新材料与新技术的重要基础.本文介绍了典型有机污染物的多介质界面行为及其微观机制,表面活性剂调控有机污染物固-液界面分配行为及生物有效性的基本原理,重点阐述了污染物界面行为调控技术在难降解有机废水吸附处理、土壤有机污染缓解与修复中的应用.     

电动力修复重金属复合污染土壤关键因素研究进展

基于电动力修复重金属复合污染土壤的核心机理和关键问题分析,介绍了现有实验模型的特点,详细分析了电动力修复复合污染土壤中主要影响因素,包括土壤理化性质、pH、修复液种类、污染物类型与形态、修复运行时间、电极材料等,提出了不同影响因素下电动力修复复合污染土壤实施的解决措施。     

石油污染土壤的植物修复研究进展

石油的开采、加工、输送及使用过程中,对大气、土壤、水体带来了严重污染,对土壤环境的危害尤为严重。植物修复以其处理成本低、吸收污染物的生物量大等优点已成为人们普遍能接受的去除污染物的首选技术。植物主要通过三种途径去除土壤中有机污染物,即植物直接吸收有机污染物;释放分泌物和酶,刺激根区微生物活性和生物转化作用;增强根区的矿化作用。植物修复石油烃污染土壤的影响因素有:环境条件、污染物的浓度和滞留时间、营养元素、表面活性剂、根系分布等。通过植物-微生物联合修复、机械-微生物-植物多技术联用等措施,可提高石油烃的降解率。     

有机污染场地原位化学氧化高压旋喷修复试验

原位化学氧化高压旋喷修复技术在有机污染场地修复工程中具有广阔的应用前景。以某复合有机污染场地修复工程为依托,通过现场影响半径试验确定了该场地的高压旋喷最佳施工参数,经过室内小试研究了氧化药剂投加比与污染物初始浓度对修复效果的影响,并通过中试规模工程应用确定了该场地氧化药剂的最佳投加比。结果表明：该场地的高压旋喷最佳施工参数为旋转速度15 r/min,喷嘴直径2.5 mm,注药压力25 MPa,提升速度15 cm/min; NaOH活化过硫酸钠的复配型氧化药剂的修复效果良好,氧化药剂投加比越低,污染物初始浓度越高,则污染物去除率越高;当氧化药剂投加比增加到5%时,中试规模工程应用区域内的各有机污染物浓度均可降至修复目标值。研究结果可为相关工程实践提供新思路。     

微米炭介导下4-硝基氯苯的还原-氧化耦合修复

针对土壤和地下水中难以去除的污染物4-硝基氯苯(4CNB),本文提出了微米级活性炭(MAC)介导的先还原后氧化的耦合修复工艺.通过序批实验、密度泛函分析、电子顺磁共振分析等手段研究了MAC表面性质、温度对强化硫化物还原4CNB的影响,探究了4CNB还原-氧化反应机理.结果表明在MAC介导下,4CNB可能发生了热力学有利的双电子还原过程,并且MAC对污染物的吸附富集作用减轻硫化物对过硫酸盐氧化过程的影响,高效去除了难以被硫化物还原和过硫酸盐氧化的4CNB.MAC强化下,4CNB还原速率相比单独硫化物作还原剂时提高8～82倍,35℃以上反应4h其降解率超99%.当4CNB还原为4-氯苯胺(CAN)后在炭表面经自由基氧化和过硫酸盐直接氧化去除.本研究提出了一种新的微米炭介导的4CNB还原-氧化耦合修复路线,为利用热处理工艺余热,实现低能耗、低成本修复4CNB污染土壤和地下水提供了新的思路.     

电动力修复土霉素污染土壤的效果及机理研究

由抗生素引起的细菌耐药性问题日益严峻。为了建立一种高效去除土壤中抗生素和耐药菌污染的方法,文章以土霉素为特征污染物,开展了电动力修复污染土壤的实验研究。经过7 d的电动力修复处理,土壤中土霉素平均去除率达40.8%,这主要源自电场的直接和间接作用、土壤中土著微生物的作用以及水解等过程。经电动力处理后,土壤中的细菌总数(2.42×10~6CFU/g)与空白土壤(2.45×10~6CFU/g)的差异不大,而抗土霉素菌数由空白土壤中的3.73×10~6CFU/g降低到2.24×10~6CFU/g(p0.05),抗土霉素菌的平均抑制率为15.3%。电动力修复系统中,四环素的降解主要归因于土壤微生物、电场作用下的直接氧化和电极反应产生活性物质的间接氧化以及土壤中的水解等作用。门水平和纲水平的细菌分类研究结果表明,电动力处理前后土壤中的优势菌群发生了改变。综上,电动力修复技术是治理土壤抗生素和耐药菌污染的有效手段。     

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.     

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.     

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.     

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.     

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.