超临界水氧化法处理竹子溶解浆生产废水的实验研究

介绍了利用目前国内最大超临界水氧化中试反应器(2.2L+1.7L)对竹子溶解浆生产废水进行处理的试验,其反应装置处理水量可以达到900~1100L/d。分析了超临界水氧化过程中不同反应温度、时间、压力及其氧气浓度对该废水COD处理效率的影响。实验结果表明:在温度为500℃、压力为24MPa,氧化反应时间为60s时,其COD去除率达到99.2%;氧化反应时间为90s时,其COD去除率达到99.95%。处理后的排水能够达到国家规定的排放标准。同时对超临界水氧化反应过程中出现的反应机理及放热现象进行了探讨。     

超临界水氧化法处理剩余污泥的参数优化

为提高超临界水氧化法处理剩余污泥的效果,采用响应面分析法,以COD_Cr去除率为响应值,对超临界水氧化法处理剩余污泥的反应温度、反应压力、停留时间和氧化剂过氧比等参数进行优化. 结果表明:反应压力和反应温度是影响剩余污泥COD_Cr去除率的主要因素;反应压力、反应温度和停留时间存在交互作用;温度＜410 ℃,停留时间＜120 s时,压力对COD_Cr去除率的影响较大;最优化条件是反应温度为434 ℃,反应压力为29 MPa,停留时间为278 s和氧化剂过氧比为216%,此时,COD_Cr去除率试验值可达97.72%～98.32%.      

O_3/Mn_2O_3对钻井废水多相催化臭氧化试验研究

通过静态试验,探讨了Mn2O3催化剂对钻井废水催化臭氧化处理效果.分别考察了催化剂加量、pH值、反应时间、反应温度和强化剂对钻井废水COD去除率的影响,通过正交试验得到了最佳工艺条件,对钻井废水氧化过程中的产物进行了分析,并探讨了Mn2O3催化剂的稳定性能.结果表明:Mn2O3加量从25 mg·L-1增加到50 mg·L-1时,COD去除率由43.6%增加到54.3%;pH分别为5、11时,COD去除率分别为45.4%和64.3%;反应温度为20℃时,COD去除率最高达到59.1%;随着反应时间的延长,COD去除率也随之增加,反应时间为40 min时,COD去除率达到85.3%;由正交试验得知影响因素的主次关系为催化剂加量反应pH反应温度反应时间,最佳处理工艺条件为催化剂加量50mg·L-1、pH值11,反应温度25℃、反应时间35 min;在25 min时,Ca2+的引入使COD去除率增大了7.1%;钻井废水中的有机物得到降解和矿化;Mn2O3催化剂重复使用10次后,对钻井废水COD降解率影响不大,锰离子的溶出量在反应15 min后稳定在3 mg·L-1,Mn2O3催化剂稳定性能较好.     

超临界水氧化法处理垃圾渗滤液的研究

采用连续式超临界水氧化小试装置处理垃圾渗滤液,以双氧水作为氧化剂,研究了超临界水氧化反应的温度、压力、氧化剂比例K和催化剂等因素对渗滤液中污染物去除效果的影响,结果表明在不同温度、不同压力、不同K值单因素实验条件下,温度480℃,压力26 MPa,K=3.0是处理垃圾渗滤液的最佳工艺参数。试验加入催化剂能够提高COD和氨氮去除率,当Cu2+浓度为45 mg/L时,垃圾渗滤液中COD和氨氮去除率分别达到78.9%和38.8%。正交试验表明,主要的工艺参数中温度对处理效率的影响最大,其次是氧化剂比例K,压力影响最小。试验结果的氨氮去除率相对较低,这可能是由于垃圾渗滤液水质复杂,各污染物之间存在相互干扰,氨氮的去除机理还有待进一步的深入研究。     

超临界水氧化处理TNT-RDX混合炸药废水的试验

采用超临界水氧化(supercritical water oxidation,SCWO)技术对TNT-RDX混合炸药废水进行氧化处理,研究了反应温度、压力、停留时间、过氧量等因素对降解效果的影响。结果表明:采用超临界水氧化技术能够迅速将TNT-RDX废水中的有机物彻底分解为无害的CO2和N2,随反应温度的升高、压力的增大、反应时间的延长,COD去除率也随之提高。过氧量对废水有机物氧化的COD去除率的影响依赖于反应的进程。当反应温度超过550℃,反应时间>120 s时,TNT-RDX废水的COD去除率>99%,完全达到了国家火炸药水污染物排放标准的要求。     

一段式亚硝化厌氧氨氧化SMBBR处理中低浓度氨氮废水

在常温条件下,采用一段式亚硝化厌氧氨氧化SMBBR处理中低氨氮浓度废水.结果表明,在进水氨氮浓度为100 mg·L^-1,溶解氧为0.4~0.7 mg·L^-1条件下,负荷（以N计）为0.16 kg·（m³·d）^-1,去除率可达（51.58±6.80）%,实现了一段式亚硝化厌氧氨氧化的稳定运行.AOB、ANAMMOX和NOB活性分别稳定在（2253.21±502.10）、（4847.46±332.89）和（1455.17±473.83）mg·（m²·d）^-1,AOB和ANAMMOX菌之间形成了良好的协同作用.高通量结果显示,Ca.Brocadia（ANAMMOX）、Nitrosomonas（AOB）和Nitrospira（NOB）占比分别为11.57%、1.01%和0.94%.一段式部分亚硝化厌氧氨氧化工艺的稳定运行为厌氧氨氧化技术处理中低浓度氨氮废水提供了参考.     

生活污水预沉淀-SNAD颗粒污泥工艺小试

采用人工配水,在SBR反应器中启动同步短程硝化、厌氧氨氧化耦合反硝化（SNAD）颗粒污泥工艺,随后逐渐降低进水氨氮浓度,低氨氮稳定运行一段时间后通入预沉淀后生活污水,考察SNAD颗粒污泥工艺处理生活污水的脱氮性能及稳定性.结果表明,SNAD工艺启动成功后,氨氮去除率大于98%,总氮去除率在89%左右,随着进水氨氮浓度逐渐降低,亚硝酸盐氧化菌（NOB）活性升高,总氮去除率逐渐下降至75%左右.通入预沉淀生活污水（NH₄⁺-N 52~63 mg·L^-1,COD 99~123 mg·L^-1）后,平均总氮去除率为73.2%,出水COD浓度在35 mg·L^-1以下,最大出水氨氮和总氮浓度为0.7 mg·L^-1和12.8 mg·L^-1,连续30d以上出水氨氮和总氮浓度达到《城镇污水处理厂污染物排放标准》一级A排放标准,实现了生活污水碳氮同步高效去除的目的.     

催化湿式共氧化降解内分泌干扰物双酚A的研究

以NaNO2为催化剂、2,4,6-三氯苯酚(TCP)为共氧化物质对内分泌干扰物双酚A(BPA)进行了催化湿式共氧化(CWCO)降解,研究发现,在NaNO2存在的条件下,TCP的加入极大地促进了BPA的降解:在170℃、0.5MPa氧气压力条件下反应6h后,催化湿式共氧化体系中COD去除率达到了71.2%,而BPA单独氧化降解时,COD去除率仅为24.7%.在此基础上考察了反应温度、氧气压力、反应时间、TCP浓度和NaNO2浓度对BPA降解效率的影响,筛选出了最优反应条件(170℃的反应温度、0.5MPa的氧气压力、6h的反应时间、0.5mmol/L BPA、0.5mmol/L TCP和0.1mmol/L NaNO2).在优化条件下,BPA和TCP去除率分别达到了100%和96.4%,同时反应后溶液的可生化性大大提高,BOD5/COD值从反应前的0.08增加到了0.95.另外,GC-MS结果表明,BPA和TCP降解的产物主要为小分子有机酸,分别是乙酸,2-甲基戊二酸,丁二酸,3-甲基己二酸,己三酸以及1-丙烯基-1,2,3-三羧酸.该共氧化技术为污染水体中BPA和TCP的同时去除提供了一种可能性.     

稀土系列催化剂对焦化废水的催化湿式氧化

以稀土元素Ce制得催化剂系列 ,在高温高压条件下对焦化废水进行催化湿式氧化研究 ,考察载体、焙烧温度、活性组分的配比对催化剂的催化活性的影响以及反应温度、氧气分压、反应时间和催化剂用量对氧化过程的影响 ,设计正交实验确定最佳的工艺参数反应温度为 2 4 0℃、氧气分压 3 .0MPa ,催化剂用量 30 g/L ,此时废水的COD去除率达到 90 %以上。     

移动床生物膜反应器净化模拟水产养殖废水的研究

采用移动床生物膜反应器（MBBR）净化模拟水产养殖废水.结果表明,MBBR净化模拟水产养殖废水效果良好.在水力停留时间（HRT）为8 h,DO为2.0~3.0 mg·L^-1的条件下,反应器启动迅速、运行稳定,能使COD和氨氮去除率均达到80%以上,TP去除率达到50%左右;有机负荷为（0.76±0.03）kg·m^-3·d^-1时,TN及氨氮去除效果最好,去除率分别达到71.73%及98.42%.为达到良好的TN去除效果,有机负荷不宜低于0.5 kg·m^-3·d^-1;DO为（3.00±0.25）mg·L^-1时,TN去除效果最好,最有利于同步硝化反硝化;为保持较高的氨氮去除效率,并减少亚硝态氮积累,DO浓度不应低于2.0 mg·L^-1;HRT过短会使氨氮去除效率降低,且可能出现亚硝态氮积累;采用序批式进水运行方式,对TP的去除效果优于连续进水方式,但运行周期后半段会出现亚硝态氮积累,对鱼类产生危害.     

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.