以膜分离为主的物化法对城市污水中污染因子的去除特性分析

利用高效液相色谱法、三维荧光光谱法分析,考察以膜分离为主的物化处理方式对城市污水中各污染因子的去除特性,尤其对溶解性有机物的富集特性.结果表明,经以膜分离为主的物化方式处理后的城市生活污水属于低碳氮比废水;微絮凝过滤主要富集的是原水中非溶解性有机物和相对分子质量大于30000的芳香类蛋白物质,富集程度在60.93%,尤其是类酪氨酸和类色氨酸;0.45μm和0.22μm醋酸纤维膜能将相对分子质量大于30000的溶解性有机物全部富集,但是微滤膜对有机物的富集没有选择性;钠滤主要对城市污水中的富里酸类物质和腐殖酸类物质有很好富集效果,富集程度分别为52.01%和53.57%,溶解性有机物的总体富集程度在42%左右.     

白塔堡河不同粒级有机物的三维荧光特征解析

利用三维荧光扫描(3DEEM)和体积积分法(FRI),分析了辽河流域白塔堡河在春汛期水中溶解性有机物(DOM)、小粒径有机物(0.22~0.7μm)和大粒径有机物(>0.7μm)的分布。结果显示:白塔堡河中有机物以芳香类蛋白质和溶解性微生物代谢产物为主,腐植酸类物质含量极少;5类组分在不同粒径有机物中分布相似,在0.22μm以下的DOM中分布最多;溯源分析显示,DOM来源较单一,表现出较强的内源生物降解特性,而颗粒状有机物则表现出内源和陆源的双重特性;多元统计分析显示,白塔堡河点位有机物分布基本上呈现区域性分布特征。     

基于2D-COS分析的难凝聚有机物臭氧化特性研究

基于二维相关光谱分析,对污水厂二级出水难凝聚有机物的臭氧化特性进行了研究.结果表明,混凝很难去除污水厂二级出水中的溶解性有机物,污水厂二级出水溶解性有机物大部分属于难凝聚有机物,以腐殖酸类物质为主.臭氧氧化可以降低二级出水混凝后上清液的色度及UV₂₅₄,去除率分别可达到70%和40%以上,但是对难凝聚有机物的去除率较低,去除率在10%以下,只是与难凝聚有机物进行了反应,改变其性质.同时,臭氧可以降低二级出水中难凝聚有机物的荧光强度,其中腐殖酸类物质的荧光强度降低较为明显.基于不同臭氧投加量下难凝聚有机物的同步荧光分析,可以得到二级出水难凝聚有机物的二维相关光谱,结果表明,腐殖酸类物质对臭氧氧化最为敏感,腐殖酸类物质与富里酸类物质相比会优先和臭氧反应.     

污水管网中无机氮类营养盐迁变规律

以一套长1 200 m的城市污水模拟管网为对象,采用人工配水方式,研究了管网中含氮化合物的变化情况,分析评价了沿程氮类营养盐的迁变转化特性.结果表明,以氯化铵为氮源基质,管网微生物将其同化合成生命所需的物质以进行细胞增殖.游离氨基酸、结合氨基酸、核酸是代谢产生的主要含氮有机化合物,其中氨基酸占溶解性有机氮(DON)的绝大多数.同时利用三维荧光光谱、尺寸排阻色谱技术对水中有机物的荧光特性及相对分子质量分布的表征结果显示,污水中有机物的特征荧光峰有所增多,主要以类蛋白、类微生物代谢产物为主,且荧光强度随管网沿程逐渐增强;水中的小分子营养盐在微生物的同化作用下转化为复杂的大分子有机物.     

污水中溶解性有机物组分特性及其氯消毒副产物生成潜能

以城市污水厂二级出水为研究对象,采用大孔吸附树脂将污水中溶解性有机物分离成亲水性物质、疏水酸性物质、疏水中性物质和疏水碱性物质4个组分,分析了各组分的有机物特性、三维荧光光谱特征和氯消毒副产物生成潜能.结果表明,亲水性物质和疏水酸性物质分别占水样中溶解性有机碳的33%和30%,其中亲水性物质相对含有较多的生物源腐殖质类物质,疏水酸性物质相对含有更多的芳香族蛋白质和溶解性微生物代谢产物类物质.氯消毒后,亲水性物质的三卤甲烷生成潜能分别为630.4μg.L-1,占污水三卤甲烷生成潜能的73.7%.亲水性物质和疏水酸性物质的卤乙酸生成潜能分别为644.6μg.L-1和123.2μg.L-1,是污水氯消毒副产物的主要前体物.     

热、热碱处理对污泥溶胞和溶解性有机物的影响

污泥有机物的水解是厌氧消化过程中的限速步骤,预处理可以有效地将污泥固体有机物转化为溶解态有机物,从而提高有机物降解速率和甲烷转化速率.本文研究了热、热碱处理(两种常用的预处理方法)对污泥溶胞释放溶解性有机物的组成、相对分子质量分布和结构的影响.结果表明,热、热碱处理均能大量释放溶解性有机物,相比对照组污泥,溶解性化学需氧量可分别增加21.9倍(热处理)和47.8倍(热碱处理).两种预处理会改变溶解性有机物相对分子质量分布,且含量最多的有机物相对分子质量减小.两种预处理均对污泥溶解性有机物中的主要组分(蛋白质)有水解作用,且热碱处理效果更显著.三维荧光光谱分析表明溶出的有机物中溶解性微生物副产物类物质和胡敏酸类物质难以被两种预处理进一步水解.另外,两种预处理不仅使污泥溶解性物质中出现新的有机结构,还会使原有的有机结构发生变化,甚至消失.     

水中藻类溶解性有机物特性研究

试验从分子量分布、三维荧光光谱和亲疏水特性3个方面研究了水中藻类(鱼腥藻、小球藻和小环藻)溶解性有机物(AOM)的特性。结果表明,3种AOM有机物在分子量分布上大分子和中小分子有机物各占一定比例。鱼腥藻AOM和小球藻AOM均表现出大分子和小分子有机物所占比例较大,中等分子有机物所占比例较小;小环藻AOM所含大分子有机物的比例相对较小,中小分子有机物是小环藻AOM的主要组成部分。荧光光谱分析得出,鱼腥藻AOM的大分子有机物主要是大分子蛋白类和腐植酸类有机物,中小分子有机物主要是小分子糖类和大分子疏水性腐殖类有机物的分解产物。小球藻AOM大分子有机物以大分子蛋白质类为主,中小分子有机物含有较多的蛋白类和腐殖酸类物质。而小环藻AOM大分子有机物主要以大分子腐殖酸类为主,中小分子有机物腐殖酸类物质含量也较多。亲疏水性分析表明,藻类AOM呈现较强的亲水特性,其SUVA值较低,主要是由亲水性的多糖和蛋白类有机物组成,疏水性腐殖类有机物质的含量相对较少。     

藻类有机物的特性以及对超滤膜的污染

采用凝胶色谱、亲疏水性、荧光色谱等方法研究铜绿微囊藻类有机物的特性.结果表明,铜绿微囊藻类有机物(AOM)主要由亲水性组分构成,占78%,比紫外吸光度仅为1.1 L/(mg.m).超滤膜法测定结果表明,藻类有机物中相对分子质量30 000的有机物占40%以上,并且主要由中性亲水性组分构成.荧光色谱分析表明,AOM中含有蛋白质类和腐殖质类物质.膜过滤试验表明,藻类有机物对超滤膜造成严重的通量下降,这可归结为大分子的中性亲水性组分堵塞膜孔的缘故.     

腈纶废水溶解性有机物的分级解析及可生化性

采用超滤膜法将腈纶废水中溶解性有机物分离为6个不同相对分子质量组分,分析不同组分的溶解性有机碳、UV₂₅₄、SUVA含量和分布情况,应用紫外吸收光谱、傅里叶变换红外光谱等光谱学分析方法对各组分物质结构进行定性分析,评价各组分的可生化性.结果表明废水中以相对分子质量< 3kDa的有机物为主,占比为（56.75±1.38）%;相对分子质量为3k~10kDa的有机物占比为（25.76±1.40）%;相对分子质量> 10kDa的有机物占比为（17.49±0.98）%,且该组分有机物的芳香度高.不同相对分子质量组分的紫外光谱和红外光谱均呈现相似吸收峰,均存在酰基、羧基、羰基及芳香族化合物和不饱和双键类有机物.各组分可生化性结果表明,废水中相对分子质量> 10kDa有机物是腈纶废水低可生化性的主要原因,可能是造成腈纶废水难以达标排放的根源.研究结果可为该废水处理工艺的开发与优化提供重要的指导.     

污水厂二级出水中THMs前体物卤代活性荧光光谱分析

通过分析城市污水处理厂二级出水中溶解性有机物(DOM)及其XAD树脂分级组分的荧光光谱,研究了DOM的结构特性以及DOM中的THMs前体物在加氯消毒过程中的反应特性与荧光强度之间的相关性.三维荧光光谱显示DOM分级组分中均存在富里酸类、腐殖酸类、芳香性蛋白质类及微生物沥出物类荧光特征峰, 且以芳香性蛋白质类和富里酸类荧光物质为主.荧光光谱区域积分法(FRI)定量分析结果表明,4类荧光物质在DOM各分级组分中的累计荧光强度(ΦT,n)分布与其在二级出水中的分布趋势较相似,总体上呈现疏水性有机酸(HPO–A) >过渡亲水性有机酸 (TPI-A)>过渡性亲水性中性物质(TPI-N)>疏水性有机中性物质(HPO-N)>亲水性物质(HPI).此外,ΦT,n与单位浓度DOC在紫外254nm处的吸光度值(SUVA)及三氯甲烷生成活性(STHMFP)有较好的相关性,但与DOC相关性较差.同步荧光光谱结果表明,在单位DOC条件下,总DOM中稠环类芳香性物质的含量高于DOM各分级组分,而DOM各分级组分中稠环类芳香性物质的含量少于腐殖酸类物质的含量.     

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.