高级氧化技术强化皮革废水生化处理效果初探

皮革废水中含大量难降解有机物,导致常规好氧生化处理速率低、效果差.实验考察了在Us(超声波)、UV(紫外光)、US/Fenton、UV/Fenton等高级氧化技术强化作用下的生化处理效果,结果表明,在相同水质和实验条件下,废水经Us、UV处理30min后可使后续生化反应速率显著提高,分别反应8h、24h后的COD去除率即可达到直接经微生物处理48h后达到的48%,但延长反应时间至48h对COD去除率没有明显提高;Fenton试剂强化US、UV的处理效果要高于单独Us、UV工艺,经30min预处理,随后在微生物作用下分别反应4h和8h即可达到45%和51%的COD去除率,同时延长反应时间也能使最终COD去除率明显提高,反应48h后,COD去除率可分别提高至64%和72%.     

柠檬酸盐强化UV/Fenton-生物法处理乳化油废水

以乳化油配水为对象, 研究了柠檬酸盐扩大UV/Fenton工艺的适用pH值范围与强化出水可生化性及与活性污泥法联用的效果.结果表明,柠檬酸盐可将UV/Fenton法的适用pH值范围扩大至4~8,且能提高UV/Fenton处理出水的可生化性.UV/Fenton处理后,原水BOD5/COD由0.02提高到0.32,投加1.0mmol/L柠檬酸钠后提高至0.53. UV/Fenton处理与经1.0mmol/L柠檬酸钠强化UV/Fenton处理出水经8h生物处理,COD去除率分别为78.7%,96.0%.柠檬酸钠浓度从0增加至1.0mmol/L时,经UV/Fenton处理过的出水再经生物处理出水的COD由293mg/L降低至48mg/L;继续增大时,COD基本保持不变.柠檬酸钠强化UV/Fenton处理可扩大pH值范围,改善废水的可生化性.     

絮凝沉淀-H2O2/UV体系处理发制品废水的研究

研究了发制品废水经絮凝沉淀－H2O2／UV体系处理的可行性。结果表明，废水经处理后，COD去除率可达90％以上，色度去除率达100％，探讨了投药量、反应pH、反应时间等因素对COD去除率的影响，并比较了H2O2／F^2 、H2O2／UV、H2O2／Fe^2 ／UV三种体系的处理效果。     

微电解/Fenton法预处理炼油碱渣的实验

采用铁碳微电解/Fenton试剂组合工艺对炼油碱渣废水混凝沉淀处理后出水,进行降解研究。实验结果表明:pH值为3,废水与铁碳填料的体积比为2∶1,微电解反应时间2 h,曝气的条件下,废水的处理效果最好,COD的去除率超过42.5%。Fenton试剂处理微电解反应出水的最佳操作条件是:pH值在2～3之间、反应时间2.5 h、Fe2+浓度为800 mg/L左右、H2O2浓度为0.25 mol/L,在此条件下,Fenton试剂处理微电解处理后的炼油碱渣废水COD平均去除率为63.8%以上,微电解/Fenton工艺对COD的总去除率在79.2%左右,可生化性由0.16提高到0.56。     

Fenton试剂处理活性艳红印染废水的实验研究

采用Fenton试剂对活性艳红印染废水进行了处理。通过正交实验考察了反应时间、反应温度、双氧水/硫酸亚铁摩尔比以及pH对印染废水的色度及COD去除率的影响,确定了Fenton试剂处理废水的最佳条件。结果表明,随着反应时间的延长,色度及COD去除率增大,最佳反应时间为20 min;色度及COD的去除率随着反应温度的升高而增大,最佳反应温度为50℃。色度及COD的去除率在双氧水(30%)的用量与硫酸亚铁用量之比为1:3.1时,去除效果最好;最佳pH值为4.5。出水达到排放标准。此法具有去除率高,设备简单,占地面小,操作方便,不产生二次污染等优点。     

US/O_3/TiO_2/UV氧化处理苯胺废水实验研究

实验采用US/O3/TiO2/UV氧化技术处理模拟苯胺废水,考察了各种技术组合对苯胺废水的处理效果以及技术组合的影响因素。结果表明,US单独使用对苯胺废水的处理效果较差,需要与其它技术联用;纳米TiO2/UV对苯胺废水的降解速度较慢,停留时间需保证纳米TiO2与废水污染物的充分接触,并且需要对纳米TiO2膜及技术参数进行优化以保证光催化的效果;技术组合中有O3时,COD的去除率有很大的提高;比较而言,US/O3/TiO2/UV技术组合对苯胺废水的处理效果最好。采用US/O3/TiO2/UV技术处理苯胺废水时,苯胺废水浓度的增加会导致COD去除率下降;废水pH值的增加会导致COD去除率轻微下降;随反应的进行,废水pH值会向4～6的区间靠拢;臭氧浓度要适中,过大或过小均会导致处理效率的下降;在优化条件下,该技术组合处理苯胺废水20min时的COD去除率达85%以上,60min时则达到96%。     

Fenton反应-中和-厌氧生物法处理某高盐度工业废水

实验采用Fenton反应-中和-厌氧菌法处理某高盐度工业废水,考察了各因素对COD去除率的影响。实验结果表明,Fenton反应处理该工业废水的最佳条件是:n(H2O2):n(COD)=2:1,n(H2O2):n(Fe2+)=4:1,pH=3,反应时间采用120 min。Fenton处理后废水COD由24 230 mg/L下降到13 020 mg/L,去除率达到46.26%;所得反应液用Ca(OH)2中和沉淀后COD值降低到11 060 mg/L,去除率为15.05%;最后废水经稀释后进行厌氧菌降解处理,COD为1 625 mg/L的废水经厌氧菌6天处理后降为466 mg/L,去除率为71.32%,达到GB8978-1996中规定的COD三级排放标准。     

混凝-Fenton氧化联合处理含丙烯酸化工废水

采用混凝-Fenton氧化联合技术,对可生化性差的含有丙烯酸的化工废水进行处理,考察了不同因素对COD去除率的影响。结果表明,对于COD为150000～160000mg／L的高浓度丙烯酸废水,经过混凝和Fenton氧化的联合处理,废水COD的去除率可高达80％左右,但出于实际生产运用中成本、运行难度和污泥量的考虑,选择其混凝最佳反应条件为：10％PAC投加量为5％,1‰PAM投加量为0．25％,pH为9,反应时间1h;Fenton最佳反应条件：初始pH为3,[Fe^2＋]／[H2O2]的摩尔比为0．05,H2O2与废水的体积比为2％左右,反应时间3h,沉降1h。在这个条件下,COD的去除率可达60％左右,而且可生化性比较好。     

臭氧和Fenton试剂处理石化电脱盐废水研究

利用臭氧和Fenton试剂对某石化炼油厂电脱盐废水进行了处理.结果表明:经臭氧处理后COD去除率为51.10％;用Fenton试剂处理经臭氧氧化后的电脱盐废水,效果最好,COD去除率提高到84.61％;用臭氧和Fenton试剂联合处理时,COD去除率为77.95％;这3种方法都能减轻该种废水的后续处理压力,其中第2种方法效果最好.     

抗生素化学合成生产废水可生化性改善试验研究

采用水解酸化与Fenton试剂分别处理高浓度抗生素化学合成废水的厌氧出水,并采用MBR验证其生化性的改善。试验表明:在废水ρ(COD)平均为4 084 mg/L时,水解酸化COD去除率平均为26.2%,ρ(BOD5)/ρ(COD)从0.23提高到0.31,但无法保证MBR出水ρ(COD)<120 mg/L。Fenton试剂反应条件为:ρ(H2O2)=5 000 mg/L,ρ(Fe2+)=4 000 mg/L,pH=7,反应时间1 h,COD去除率达50%。混合废水经MBR处理后,出水ρ(COD)平均为98.4 mg/L,可稳定达《制药工业水污染物排放标准》。     

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.     

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.