芘污染黑土的表面活性剂洗脱修复研究

采用批量平衡振荡法研究了几种阴离子和非离子表面活性剂对黑土中芘的洗脱效果,以及不同因素对洗脱效果的影响。结果表明,非离子表面活性剂对芘的洗脱效果优于阴离子表面活性剂。将SDS和Triton X-100以不同质量配比混合后,可提高其洗脱效果,尤其在质量配比为3∶7时洗脱效果最好。不同固液比条件可影响Triton X-100对芘的洗脱,Triton X-100在低浓度时,固液比为1∶30时的洗脱效果最好;浓度大于5.0 g/L后,固液比为1∶10时的洗脱效果最好。Triton X-100对土壤中低浓度芘的洗脱效果要好于土壤中高浓度的芘。萘在土壤中的共存会降低Triton X-100对芘的洗脱率,萘浓度越高,芘的洗脱率越低。Triton X-100对不同类型土壤中芘的洗脱效果相差不大,对新疆荒漠土的洗脱效果好于哈尔滨黑土,这可能与土壤有机质含量有关。     

表面活性剂对土壤中多氯联苯的洗脱研究

采用实验室配置的PCBs污染土壤,以曲拉通X-100、吐温-80、SDS、SDBS 4种表面活性剂进行洗脱试验研究。结果表明:对于单一表面活性剂,SDS对污染土壤中多氯联苯的洗脱效果最好;采用1:20的固液比,进行2~3次洗脱,洗脱率可达50%以上;洗脱时间对洗脱效果影响不大;SDS—吐温-80混合表面活性剂对多氯联苯有协同增溶作用,且在土壤上的吸附损失较小,SDS和吐温-80的最佳质量比为5:5,在此条件下,浓度为7 000 mg/L的混合表面活性剂对多氯联苯污染土壤进行3次洗脱,洗脱率可高达97.89%。     

不同淋洗剂对土壤中多氯联苯的洗脱

应用批量平衡振荡法研究了4种化学表面活性剂〔TX-100(曲拉通X-100)、TW-80(吐温80)、SDBS(十二烷基苯磺酸钠)、CTMAB(十六烷基三甲基溴化铵)〕、2种生物表面活性剂〔Saponin(皂素)、RL(鼠李糖脂发酵液)〕和1种生物产品(β-环糊精)对污染土壤中PCBs(以Aroclor1254为例)的洗脱效果. 结果表明:在设定的质量浓度范围内,洗脱效果总体表现为TX-100≈TW-80＞SDBS＞β-环糊精＞Saponin＞RL＞CTMAB;ρ(PCBs)为10g/L时,TX-100、TW-80、SDBS、β-环糊精、Saponin、RL、CTMAB对污染土壤中PCBs的洗脱率分别为54.99%、53.12%、46.99%、25.35%、14.76%、13.70%、0%. 通过对洗脱效果、土壤吸附量、淋洗剂成本和环境友好性4个方面的综合考量,筛选出TX-100和β-环糊精2种相对较好的淋洗剂,对其洗脱时间、洗脱次数和淋洗剂pH的影响进行研究,结果表明,TX-100和β-环糊精对土壤中PCBs的洗脱率在洗脱时间为12h时出现拐点,之后洗脱率提高不大;2种淋洗剂的3次洗脱均以第1次为主,第2次和第3次洗脱对洗脱效果没有显著贡献;相同体积的淋洗剂分2次洗脱与1次洗脱效果相当;pH为4~10时,对2种淋洗剂的洗脱效果影响很小.      

非离子表面活性剂溶液中多环芳烃的溶解特性

采用3种典型非离子表面活性剂(Tween80、Tween20和Triton X-100),对4种典型多环芳烃萘(naphtha-lene)、菲(phenanthrene)、芴(fluorene)和芘(pyrene)进行了溶解特性研究.结果表明,非离子表面活性剂对多环芳烃具有较好的增溶效果,在浓度大于临界胶束浓度(CMC)时,多环芳烃的溶解度与表面活性剂浓度成正比例线性相关通过质量溶解率(WSR)的比较,确定3种非离子表面活性剂对多环芳烃的增溶效果为Triton X-100＞Tween80＞Tween20,与其HLB值呈负相关.在非离子表面活性剂溶液中,多环芳烃的正辛醇-水分配系数(K_ow)与其胶束-水分配系数(K_m)呈现良好的线性相关关系.     

硫丹及硫丹硫酸酯的土壤降解特性

在实验室条件下研究了α-硫丹、β-硫丹及硫丹硫酸酯在东北黑壤土、江苏水稻土、江西红壤土和河南二合土4种土壤中的降解特性.结果表明,硫丹及硫丹硫酸酯降解过程可用一级动力学方程描述.4种土壤中,β-硫丹的降解半衰期(DT50)分别为39、10、14和13d;α-硫丹的DT50分别为72、56、105和42d;硫丹硫酸酯的DT50分别为39、41、53和34d,因此,硫丹硫酸酯在土壤中的持久性值得关注.α-硫丹在有机质含量丰富的土壤中降解较慢,β-硫丹在碱性土壤中降解较快.用一级动力学模型模拟的硫丹(α-硫丹+β-硫丹)和总硫丹(α-硫丹+β-硫丹+硫丹硫酸酯)降解过程的计算结果表明,硫丹的DT50为18～47d,总硫丹的DT50为48～77d.试验观察到的硫丹降解产物依次为硫丹硫酸酯、硫丹二醇、硫丹醚和硫丹羟基醚.     

鼠李糖脂表面活性剂复配体系对芘的增溶特性

该研究采用Tween 80、Triton X-100、十二烷基硫酸钠(SDS)、十二烷基苯磺酸钠(SDBS)、槐糖脂(SL)、烷基糖苷(AG)6种常用的表面活性剂与鼠李糖脂(RL)进行复配,研究不同复配表面活性剂对芘增溶效率的影响.结果 发现:Triton X-l 00、Tween 80可以显著提高RL对芘的增溶效率;低浓度(＜600 mg/L) SL与RL复配也可促进芘溶解;AG与鼠李糖脂复配对芘增溶效率影响较小;加入SDS和SDBS则抑制RL对芘的增溶效率.通过Clint等模型分析发现,鼠李糖脂与Triton X-100复配后分子间产生协同效应,当两者质量比为9:1时对芘的增溶效率较高并且具有良好的pH稳定性,优于其他复配体系.该研究可为鼠李糖脂在多环芳烃增溶应用中的推广提供理论依据.     

五种表面活性剂对柴油污染土壤清洗效果的比较

研究了十二烷基硫酸钠(SDS)、十二烷基苯磺酸钠(SDBS)、皂苷(saponin)、月桂醇聚氧乙烯(23)醚(Brij35)、Triton X-100五种表面活性剂对中度柴油污染土壤的清洗效果,考察柴油和土壤混合后在不同时间段的挥发特点,认为污染时长会直接影响表面活性剂清洗修复的效果,增大清洗剂浓度可以提高对新污染土壤的洗脱率,但对老化污染土壤的效果并不明显;对不同含油量的污染土壤清洗,研究污染程度对洗脱率变化的影响,当达到一定含油量后洗脱效果产生突变。不同表面活性剂在相同CMC倍数下清洗能力存在差异,其顺序为SDS>SDBS>Triton X-100>皂苷>Brij35。     

醇类助溶剂去除砂土中多氯联苯作用机制

醇类助溶剂单一使用及复配表面活性剂使用去除砂土中多氯联苯(PCBs)的关键是增溶和降低界面张力.通过降低界面张力实验和振荡增溶实验分析了醇类助溶剂单一使用对多氯联苯界面张力的降低作用和增溶作用,以及醇类复配Triton X-100使用时醇对Triton X-100降低界面张力和增溶PCBs的影响.结果表明,醇-PCBs油的界面张力与醇浓度、醇含碳原子数均呈负相关,甲醇、乙醇、异丙醇的最佳解吸浓度分别为70%、55%、40%,最佳解吸效率达90%以上;Triton X-100-PCBs油界面张力与Triton X-100浓度呈负相关,Triton X-100浓度低于3 000 mg/L时复配10%乙醇、10%异丙醇比单一Triton X-100振荡洗脱效率低,Triton X-100浓度在3 000～7 500 mg/L时3组差异不大,Triton X-100浓度为10 000 mg/L时单一、10%乙醇、10%异丙醇TritonX-100溶液解吸效率分别为80.9%、90.36%、89.36%.表明醇类单一使用对降低界面张力与增溶均有很好的效果,但需要其体积分数达40%以上;醇类复配Triton X-100时醇的存在弱化了Triton X-100增溶和降低界面张力的作用,乙醇与异丙醇弱化作用差异性不大,当Triton X-100浓度高于3 000 mg/L时,弱化作用不显著.     

表面活性剂增溶洗脱土壤中多环芳烃的效果研究

表面活性剂增效洗脱修复技术被广泛应用于土壤修复. 本文选取11种非离子型和3种离子型表面活性剂对多环芳烃(PAHs,菲、芘、苯并[a]芘)污染土壤进行洗脱研究,筛选出洗脱效果较好的表面活性剂,并深入探索表面活性剂浓度、洗脱时间、固液比等因素以及表面活性剂的复配对土壤PAHs增效洗脱的影响,旨在比选出一种高效洗脱土壤PAHs的表面活性剂并对其洗脱方法进行优化. 结果表明:①表面活性剂浓度为10 g/L、固液比为1∶20条件下,聚氧乙烯醚-10(NSF10)的去除率最高,达到78%;其次为曲拉通X-100(TX-100)和吐温80(TW-80),去除率分别为76.7%和73.4%. ②随着表面活性剂添加浓度的增加,土壤PAHs的去除率增大,当表面活性剂浓度超过5 g/L时,PAHs去除率的增幅减缓,可见,5 g/L是相对有效且经济的表面活性剂添加浓度. ③当洗脱时间为16 h时,NSF10对PAHs的洗脱达到平衡,继续延长洗脱时间,洗脱效果并未增强. ④增加NSF10用量有利于洗脱,固液比1∶40是最优固液比,此时PAHs的去除率已达到固液比为1∶100时的85.2%. ⑤非离子表面活性剂NSF10、TX-100、TW-80与阴离子表面活性剂SDS分别以体积比9∶1进行复配时均取得了优于单一活性剂的洗脱效果,NSF10与SDS体积比为7∶3时,增溶洗脱效果最为明显,比单一表面活性剂提高了18.2%. 研究显示,NSF10是一种高效的PAHs洗脱剂,添加浓度为5 g/L、洗脱时间为16 h、固液比为1∶40是其最优参数选择,其与SDS以体积比7∶3进行复配可进一步提升增溶洗脱效果.      

Fenton试剂氧化去除土壤洗脱液中DDTs的研究

以表面活性剂Tween80对DDTs污染土壤的洗脱液为目标,研究了Fenton试剂对洗脱液中DDTs的氧化去除效果及影响因素。结果表明,对于浓度为50 mg/kg的DDTs的单一污染土壤,Tween80显示出较好的洗脱效果,2.0 g/L的Tween80对DDTs的洗脱率可达到30%以上。Fenton试剂可以有效处理DDTs污染土壤的洗脱液,Fe~(2+)浓度、H_2O_2添加量、pH值、温度以及反应时间均对DDTs的去除率产生一定的影响。综合考虑处理效率与处理成本,其最佳反应条件为:Fe~(2+)浓度为20 mmol/L,H_2O_2添加量为10 mL/L,pH值为3,温度为30℃,反应时间为30 min,该条件下单一污染土壤洗脱液中DDTs的去除率均达到70%以上;对于DDTs复合污染土壤的洗脱液,该条件下Fenton试剂对DDTs的总去除率可达到50.2%。研究结果表明利用Fenton试剂氧化处理DDTs污染土壤洗脱液是可行的。     

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.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.