紫外光降解黑索金(RDX)的研究

本课题对模拟废水中RDX在紫外光和氧化剂等作用下的光化学降解情况进行了研究.运用正交设计法来安排实验,获得了废水的酸碱度、过氧化氢与亚铁离子的投加量、紫外光照射的时间等RDX降解的最佳条件.自行设计了光化学降解装置.在最佳条件下对RDX模拟废水进行光化学处理,并利用721分光光度计以及TOC-500测试仪对实验结果进行鉴定,取得了较为满意的结果.     

萘在选择性催化还原脱硝系统内的转化机制

萘是燃煤烟气中多环芳烃(PAHs)的主要成分,在经过选择性催化还原(SCR)脱硝系统时能被部分降解,但在脱硝烟气组分影响下难以彻底降解为CO_x.不仅如此,部分萘会聚合生成高毒性PAHs.基于此,本文研究了脱硝烟气组分对V₂O₅-WO₃/TiO₂催化萘降解性能的影响.结果表明：不含烟气组分时,萘经过1,4-萘醌、邻苯二甲酸酐和马来酸酐等中间产物降解为CO_x,其中酸酐(邻苯二甲酸酐和马来酸酐)是CO_x生成的重要中间体.除此之外,酸酐生成过程中不可避免的会生成乙炔基,该物质与萘结合生成更高分子量的菲和蒽,导致PAHs总选择性较高(0.24%).而在烟气(NO+NH₃)条件下,NH3会与萘作用生成含N副产物,极大抑制酸酐生成,使CO_x选择性从38.9%下降至22.5%.同时,伴随酸酐生成的乙炔基大幅降低,使PAHs总选择性从0.24%下降至0.03%.因此同步实现酸酐和乙炔基的彻底降解是萘高效去除的...     

几种光化学体系中自由基的产生和测定

在人工光源照射下，以水杨酸为探针性物质，探讨了过氧化氢，二氧化钛，亚硝酸钠，硝酸钠和杂多酸盐等５种光化学体系中羟自由基的产生，并测定了羟自由基的稳态浓度。     

土壤中多环芳烃微生物降解能力模拟

为了揭示微生物菌种(组合)对土壤中PAHs(多环芳烃)降解率的影响以及不同类型PAHs抗微生物降解能力的差异,分析了北京市6个不同环境功能区土壤中微生物种类及其分布特征,从中筛选出部分微生物菌种对典型PAHs和原油进行降解模拟试验,对比分析微生物对不同PAHs降解能力的差异.结果表明:① 不同菌种组合对PAHs的降解能力存在明显差异,与假单胞菌属、无色杆菌、短稳杆菌混合菌相比,假单胞菌属、无色杆菌、短稳杆菌和微杆菌混合菌对PAHs的降解率高0.6%~4.5%;② 在相同降解条件下,不同PAHs的降解率存在明显差异,在单体培养基中,LMW PAHs(低环数PAHs)的降解率在25.3%以上,而HMW PAHs(高环数PAHs)的降解率都小于20.1%;③ 在单体培养基与混合培养基中PAHs的降解能力也存在一定差别,单体培养基中PAHs的降解率较混合培养基中高4.2%~26.6%;④ 无论在单体培养基中,还是混合培养基中这些化合物的降解率均存在随着降解时间的增加而增大的现象;⑤ 在原油培养基中不同PAHs的降解率更为复杂,并且出现了中低分子量PAHs降解率随降解时间增加反而降低的假象,这可能是由于随着时间增加,微生物对PAHs的降解能力加强,原油中含烷基的PAHs基团降解或HMW PAHs被微生物降解产生LMW PAHs中间产物造成.研究显示,假单胞菌属、无色杆菌、短稳杆菌和微杆菌对HMW PAHs和LMW PAHs均有明显的降解效果,但不同PAHs的降解率存在明显的差异,即使是同一单体化合物,在单体培养基、混合培养基和原油培养基三种不同的降解条件下,其降解率也具有不同程度的差别.      

硫酸盐还原条件下多环芳烃在土壤中的迁移转化

为研究硫酸盐还原条件下多环芳烃(Polycyclic Aromatic Hydrocarbons,PAHs)类有机污染物在土壤中的污染分布规律和迁移转化过程,设计了室内土柱淋溶试验,选择菲、蒽和芘作为PAHs的代表,模拟硫酸盐还原条件下PAHs在土壤中的迁移转化过程.监测土壤中PAHs的垂直分布、淋出液中ρ(PAHs)和ρ(SO₄2-)、淋出液的氧化还原电位(E_h)和总体积,并通过质量平衡计算出PAHs的降解率.结果表明:①菲和蒽的相对淋出率总体都不超过2%.120 d后菲和蒽在土壤中的残留率分别为51.87%和51.21%,而芘有90%以上吸附在土壤中,在淋出液中未检出.②随着淋溶时间的延长,土壤中的氧气逐渐被消耗,淋出液中ρ(SO₄2-)和E_h逐渐降低,并趋于稳定,硫酸盐还原作用发生.③3种PAHs在硫酸盐还原条件下都存在一定程度的降解.菲和蒽的降解率相差不大且随淋溶时间的延长逐渐增大,120 d后菲和蒽的降解率分别为47.41%和48.10%,而4环的芘降解速率非常低,120 d后降解率仅为3.61%.      

底泥中多环芳烃的微生物降解与原位修复技术

水体底泥是多环芳烃(PAHs)重要的环境载体之一,PAHs通过多种途径进入各种水体,经过复杂的过程沉积富集于水体底泥中。PAHs在环境中的迁移转化有多种途径,其中微生物降解是去除环境中PAHs的最主要途径。PAHs可以作为微生物的唯一碳源或通过共代谢而被降解。影响微生物降解PAHs的因素有:PAHs的生物可利用性、温度、pH值、供氧条件、营养条件以及其它的环境因素。受PAHs污染底泥的微生物原位修复技术通过导入高效微生物,提供电子受体、营养盐和表面活性剂等来降解底泥中的PAHs。该技术被认为是去除底泥中PAHs污染物的重要手段,但还存在着多方面的缺点而使其应用存在着很大的局限性,需要从高分子量的PAHs的降解机理、生物降解过程中基因调控机制、环境因子与微生物降解PAHs的相互作用关系以及受PAHs污染底泥的微生物原位修复过程的监测、风险评估和效果评估等多个方面进行深入的研究。     

生物表面活性剂-微生物强化紫花苜蓿修复多环芳烃污染土壤

在温室盆栽条件下,通过单独或联合添加生物表面活性剂鼠李糖脂(RH)和接种多环芳烃专性降解菌(DB),研究了利用生物表面活性剂-微生物强化紫花苜蓿(Medicago sativa L.)修复多环芳烃(PAHs)长期污染土壤的效果.结果表明,添加鼠李糖脂和接种PAHs专性降解菌能促进紫花苜蓿的生长和土壤中PAHs的降解.培养90d后,RH、DB处理的PAHs的降解率分别为30.0%和49.6%,均高于对照处理(CK)(21.7%).RH+DB处理PAHs的降解率最高达53.9%,说明鼠李糖脂和PAHs专性降解菌协同作用显著.另外,随着PAHs苯环数的增加,其平均降解率逐渐降低,但是接种PAHs专性降解菌能够提高4环和5环PAHs的降解率.同时也发现土壤中脱氢酶活性和PAHs降解菌数量越高的处理,土壤PAHs的降解率也越高.所以添加鼠李糖脂和接种PAHs专性降解菌能够有效促进土壤多环芳烃降解.     

通风及营养元素对多环芳烃污染土壤修复影响

文章在无外源接种体的条件下,评估了强制通风(通风量为1.51 L/min)与营养元素对土壤中多环芳烃(PAHs)降解的交互作用。结果表明:仅靠合适的营养液配方和长时间通风可以刺激污染土壤中的土著微生物生长,并影响微生物菌群的形成。通风同时添加营养液有利于好氧菌生长、加快PAHs的降解;与通风相比,添加营养元素是影响PAHs降解的主要因素。通风和添加营养元素对3环PAHs降解影响不显著,但可促进4环、5环和6环PAHs污染物降解。60 d内,仅通风、仅添加营养元素、同时通风和添加营养元素处理的PAHs分别降解了52%、59%、67%。     

表面活性剂对白腐真菌降解多环芳烃的影响

研究了4种表面活性剂吐温80(Tween80)、曲拉通100(Trition X-100)、十二烷基苯磺酸钠(LAS)、十二烷基硫酸钠(SDS)对白腐真菌降解水溶液和土水系统中多环芳烃(PAHs)的影响.结果表明,表面活性剂的类型、浓度、PAHs的赋存状态以及体系pH值、温度等均影响着PAHs的降解.在水溶液中(无土),加入4种表面活性剂均降低溶液中PAHs的降解.在土水系统中,Trition X-100和SDS抑制PAHs降解,而Tween80和LAS对PAHs的影响则受到浓度的影响.低浓度Tween80和LAS对土壤中PAHs的降解没有促进作用,甚至有微弱的抑制作用,但适当浓度的Tween80和LAS促进PAHs降解,并且对土壤中PAHs降解的促进作用随着浓度的增大而逐渐增大,但过高浓度的Tween80和LAS没有表现出对PAHs降解更大的促进作用.     

生物强化和生物刺激对土壤中PAHs降解的影响

采用生物强化(农田土中添加PAHs污染土或污泥)和生物刺激(PAHs污染土中添加(NH4)2HPO4)2种措施,研究了土壤中13种PAHs的降解及CO2的释放量.结果显示,农田土壤中的微生物对2~5环的PAHs都有较强的降解能力,添加污染土显著增强了对5环PAHs的降解,表明污染土中的微生物对高环PAHs的降解能力更强;添加污泥对促进PAHs降解的作用不明显,可能是好氧培养条件不适合厌氧菌的生长.添加N、P营养盐可显著提高污染土中3~4环PAHs的降解,但5环PAHs在添加和未添加N、P中的降解率始终较低,均小于10%.CO2的释放呈现先增加再降低,再略微增加直至平稳的过程,且与PAHs的降解高度响应,说明PAHs的降解与微生物活性密切相关.     

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.     

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.     

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

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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.     

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.     

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.