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.     

水溶性有机物对菲的表观溶解度和正辛醇/水分配系数的影响

以农业上常用有机物料绿肥、猪粪和污泥作为水溶性有机物(DOM)的提取材料,以菲(Phe)作为多环芳烃(PAHs)的代表,通过摇瓶法研究了不同来源的DOM对菲在水中的表观溶解度和正辛醇/水分配系数的影响.结果表明,菲在超纯水中的溶解近似一级反应动力学过程.超纯水体系中添加了DOM后,菲溶解的平衡时间相对滞后,但却明显增加了菲的表观溶解度.当DOM浓度为150 mg·L-1(以DOC计)时,在含Tween-80、猪粪DOM、污泥DOM和绿肥DOM的体系中菲的表观溶解度分别是纯水体系的20.39、2.082、1.838和1.549倍.菲的表观溶解度随着外加DOM浓度的增加而增大,它们之间存在着明显的线性关系.回归直线的斜率可以用来表征DOM对菲的增溶效果,本试验4种体系中DOM的增溶效果大小依次为表面活性剂Tween-80＞猪粪DOM＞污泥DOM＞绿肥DOM.同时,DOM可降低菲的正辛醇/水溶液分配系数,各体系中logKow值的高低顺序与增溶效果的顺序恰好相反.研究结果显示,DOM的存在可明显地改变PAHs在水相中的溶解度和正辛醇/水溶液分配系数.     

绿脓杆菌S6产表面活性剂对PAHs增溶效果研究

文章以超声取-高效液相色谱法研究铜绿似单细胞S6菌产生物表面活性剂在浓度、pH值、温度及时间下对萘、蒽.芘、苯并蒽的增溶效果,结果表明:一定浓度范围内,表面活性剂浓度越高,萘、蒽、芘、苯并蒽的溶解度越大;固定生物表面活性剂浓度下,在对萘、蒽、苯并蒽及芘进行增溶时,pH值应控制在6～8之间,最好设置pH值为8;在对萘、蒽...     

新型螯合型表面活性剂增溶菲的热力学和动力学研究

采用批平衡试验法,研究了新型螯合型表面活性剂N-十二酰基乙二胺三乙酸钠(N-LED3A)增溶菲的性能,并探讨了其增溶热力学和动力学特征.结果表明:N-LED3A可有效增溶菲,菲的表观溶解度S*w及其在表面活性剂单体和胶束相的分配系数Kmn和Kmc均随温度升高而增大;N-LED3A的临界胶束浓度(CMC)随温度的升高(15、25、35、45℃)呈现先减小后增大的趋势;菲在N-LED3A单体/水、胶束/水的表观摩尔分配焓变ΔH*mm、ΔH*mc分别为18.30、13.12 kJ·mol-1,菲在水、N-LED3A单体和胶束中的表观摩尔溶解热分别为18.87、37.17和31.99 kJ·mol-1,均为吸热过程,故温度升高有利于菲在N-LED3A单体和胶束中的分配作用,菲在水、N-LED3A单体和胶束中的溶解量随温度升高而增大。动力学方程拟合结果表明,一级动力学方程最适合描述N-LED3A对菲的增溶过程.     

生物源表面活性剂对焦化土壤中多环芳烃增溶效能研究

考察了单一生物源表面活性剂鼠李糖脂、黄腐酸、槐糖脂、烷基糖苷、无患子皂苷及鼠李糖脂与各非离子生物源表面活性剂复配体系对萘和菲的增溶效能,并将优选的淋洗剂体系应用于焦化场地土壤多环芳烃（PAHs）的去除.结果表明：相较其他生物源表面活性剂,鼠李糖脂和黄腐酸对萘的增溶效果更好;对于菲的增溶,槐糖脂的增溶效果更好,这与其较低的临界胶束浓度和多环芳烃的性质有关.生物源表面活性剂复配体系的增溶能力较单一表面活性剂明显增强,以3∶1复配时增溶效果最佳.60 mmol·L^-1的鼠李糖脂-黄腐酸复配体系（3∶1）对土壤中萘的去除率可达96.64%,分别是单一鼠李糖脂和黄腐酸的1.09倍和2.21倍;而对土壤中蒽、苯并（a）蒽和苯并（k）荧蒽的去除率远低于萘,分别为63.31%、42.51%和39.10%,这是由于PAHs与鼠李糖脂-黄腐酸复配体系的相互作用随苯环数的增加而减弱.本研究可为生物源表面活性剂及其复配体系高效修复PAHs污染土壤提供科学依据.     

双子表面活性剂CG_(12-3-12)、鼠李糖脂与TX-100对多环芳烃增溶作用的比较研究

对新季铵盐型Gemini阳离子表面活性剂CG12-3-12、生物表面活性剂鼠李糖脂Rhamnolipid、普通非离子表面活性剂TX-100以及它们的混合体系对多环芳烃菲和芘的增溶效果进行了比较研究.通过计算与比较临界胶束浓度(CMC)、摩尔增溶率(MSR)和增溶的标准自由能ΔG0s,评价了3种不同类型表面活性剂及它们的混合体系对菲和芘的增溶能力.3种表面活性剂对菲和芘的增溶性大小顺序为:CG12-3-12RhamnolipidTX-100.TX-100/CG12-3-12与TX-100/Rhamnolipid混合表面活性剂都较相对应的单一表面活性剂有更好的增溶能力,在降低表面张力效率方面都能够产生协同效应.但是两种混合溶液都不符合理想溶液的性质.TX-100/CG12-3-12系统的CMCexp相对于CMCmi有更大的负偏差.由两混合体系的吉布斯自由能ΔG0m可以看出,TX-100与鼠李糖脂比与CG12-3-12更容易形成混合胶束.TX-100/CG12-3-12与TX-100/Rhamnolipid表现出协同作用.TX-100/Rhamnolipid混合体系对菲和芘的增溶能力的提高大于TX-100/CG12-3-12混合体系.本实验研究结果可为疏水性有机物污染环境修复效果的强化提供科学依据.     

同步荧光法研究HPCD存在下溶解态芘的生物降解

利用同步荧光法研究了羟丙基-(-环糊精对微生物降解矿物盐水溶液中溶解态芘的影响。结果表明,加入一定量的HPCD,体系的荧光强度大大增加;芘的表观溶解度增大。所建方法在降解过程中对芘的检测限为0.017 ng/mL。相对标准偏差小于0.4％(n=7)。降解实验结果表明,HPCD的存在增加了芘的生物有效性,从而加快了微生物(Alcaligenes xylosoxi-dants,Ax)降解芘的速率。     

铜绿假单胞菌S6分泌的生物表面活性剂特性

研究了1株铜绿假单胞菌S6(Pseudomonas aeruginosa S6)分泌的生物表面活性剂的理化性质.该生物表面活性剂的临界胶束浓度为50mg·L-1,此时其表面张力为29.3mN·m-1.pH值对S6产表面活性剂有一定影响,在中性及弱碱性条件下,S6长势较好且表面活性剂表面张力较低.该生物表面活性剂对菲具有非常明显的增溶效应,使水中菲的溶解度增加了约23倍.原油的加入有利于S6产表面活性物质.与原油的相互作用说明该生物表面活性剂能够乳化原油且维持乳化液稳定性于80%以上;原油浓度为6%～8%时,能达到最佳乳化效果.HPLC-ESI-MS分析检出该生物表面活性剂含有13种鼠李糖脂同系物.     

Tween80对植物吸收菲和芘的影响

以水培体系模拟研究了非离子表面活性剂Tween80对黑麦草吸收菲和芘的影响.结果表明,当培养液中菲和芘的起始浓度分别为1 00mg·L-1和0 12mg·L-1时,0～105 6mg·L-1范围内,低浓度Tween80可促进根和茎叶吸收菲和芘,Tween80浓度为6 6mg·L-1时促进作用最为明显,根和茎叶中菲和芘含量、富集系数为无表面活性剂对照处理的116%～216%;而高浓度则有抑制作用.当培养液中菲和芘的起始浓度为相应Tween80浓度下的表观溶解度时,根和茎叶中菲和芘含量随Tween80浓度上升明显增大,Tween80的增溶作用有利于根和茎叶对菲和芘的吸收.     

植物CytP450和抗氧化酶对土壤菲、芘暴露的生态毒理响应

以玉米(Zea mays L.)为供试植物,草甸棕壤为供试土壤,以微粒体细胞色素P450含量、超氧化物歧化酶(SOD)、过氧化氢酶(CAT)和过氧化物酶(POD)活性为指标,进行了土壤菲、芘暴露的生态毒理响应研究.结果表明,菲、芘暴露均能引起植物代谢解毒和抗氧化防御系统的胁迫响应,不同程度引发植物代谢解毒及抗氧化能力的改变.P450酶活性与低浓度菲、芘单-暴露浓度具有相关性(r=0.834,P<0.01),与菲、芘复合暴露浓度负相关,说明菲、芘复合暴露导致代谢解毒能力下降,对植物的代谢解毒具有协同毒性效应;SOD酶活性与菲、芘单一暴露浓度负相关,CAT酶活性与菲、芘单-暴露浓度正相关,POD酶活性与菲的水溶解度正相关,而与芘的总浓度负相关.SOD、CAT和POD酶活性与菲、芘复合暴露浓度均呈正相关,说明菲、芘复合暴露导致氧化损伤程度减弱,对植物的氧化损伤具有拮抗作用.     

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.     

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.     

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.     

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.     

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.     

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.