生物膜短程硝化系统的恢复及其转化为CANON工艺的过程

在温度为30℃±1℃条件下,以改性聚乙烯为填料,人工配置无机NH+4-N废水为进水,研究生物膜短程硝化系统的恢复过程.短程硝化首先通过过量曝气破坏,使NOB适应高浓度游离氨后,在连续曝气条件下,DO控制在0.5 mg·L~(-1)以下,FA控制在1.5 mg·L~(-1)以上,维持反应器运行83 d未实现短程硝化,84 d改连续曝气为间歇曝气,出现NO-2-N积累现象,142 d再次验证这一规律.随着反应器的运行,生物膜系统中为ANAMMOX菌提供了生存环境,厌氧氨氧化作用产生,短程硝化系统逐步转化为CANON工艺,并逐渐增加进水NH+4-N浓度和进水流量,反应器的TN去除率与TN去除负荷逐渐提高.当反应器运行至450 d,TN去除率达到64.03%,去除负荷为2.52 kg·(m~3·d)~(-1).因此,一旦NOB适应了高浓度的游离氨,生物膜系统的短程硝化恢复不易实现,但间歇曝气是一个有效的方法,随着反应器的连续运行,短程硝化工艺最终转化为CANON工艺,而且,这一转变进一步强化了短程硝化的稳定性.     

水力停留时间和溶解氧对陶粒CANON反应器的影响

以人工配制无机高氨氮废水为进水,通过接种CANON污泥,以陶粒作为填料,研究了HRT和DO对生物膜CANON反应器的影响.试验过程中,控制进水氨氮浓度基本不变,依次控制反应器的HRT为9、7、5 h,同时控制DO的范围为1.16~3.20 mg·L-1.研究发现:1当DO为1.20~1.75 mg·L-1时,尽管提高DO有利于提高AOB的活性和系统内基质的传质效果,但是CANON反应器的NH+4-N、TN去除效果依然随着HRT的缩短而下降,尤其当DO超过2.50 mg·L-1时,TN去除效果大幅度下降;2当DO为1.20~1.75 mg·L-1时,随着HRT的缩短,CANON反应器的短程硝化性能趋于稳定,而当DO超过1.75 mg·L-1时,即使缩短HRT,其短程硝化性能依然遭到严重破坏;3CANON反应器中短程硝化稳定性能和去除效果较佳的条件是HRT为7 h,且DO控制在1.20~1.75 mg·L-1之间.HRT和DO是废水生物处理的重要运行参数,直接影响到生物处理的效果和出水水质,协调控制两者的变化范围,对提高CANON工艺对高氨氮废水的处理效果非常重要.     

序批式生物膜CANON工艺的运行与温度的影响

通过序批式生物膜反应器,研究了CANON工艺的运行规律,并研究了温度对CANON工艺的影响.研究发现,通过序批式生物膜反应器反应器可以成功实现CANON工艺,TN去除率可达到88.3%,TN去除负荷达到0.52kg/(m3·d).系统中的NO2--N变化规律可以分为浓度上升期,浓度稳定期与浓度下降期.pH值先降低后升高的拐点与DO突跃的拐点均可作为反应结束的指示参数,DO拐点比pH值拐点出现要提前.在26~35℃之间,可以获得较好的硝化效果与TN去除效果,温度降低到20℃时,厌氧氨氧化性能开始受到显著影响,造成反应器中大量NO2--N积累,而硝化效果在15℃才受到显著影响.反应器中厌氧氨氧化细菌的最适温度约为30℃.     

CANON反应器运行稳定性及温度冲击的影响

为考察长期运行条件下全程自养脱氮(CANON)反应器的运行效果,以人工配置无机高氨氮废水为进水,研究了连续流CANON反应器的运行稳定性.CANON反应器在控制内部温度为35℃±1℃,pH 7.39～8.01,水力停留时间3.7～5.1 h条件下,稳定运行超过1 a,短程硝化性能与厌氧氨氧化性能均获得稳定,平均TN去除负荷达到1.8 kg.(m3.d)-1,平均TN去除率为65.09%,最大TN去除率可达81.65%.低温冲击时,虽然ANAMMOX菌与AOB都会受到低温的抑制,但由于ANAMMOX菌对低温更加敏感,受到的抑制更加严重,因此造成NO2--N严重积累.温度恢复35℃后,CANON反应器性能很快恢复正常,短暂的低温冲击不会对CANON反应器稳定性构成显著影响;当经历超过50℃以上的高温冲击时,尽管AOB可在1周内恢复正常,但ANAMMOX菌的活性被完全破坏,使CANON反应器彻底崩溃,应予以避免.     

陶粒CANON反应器的接种启动与运行

通过CANON接种污泥,以人工配制无机高氨氮废水为对象,研究以陶粒为填料的CANON反应器启动与运行情况,结果表明:①陶粒可以作为CANON反应器合适填料,温度通过水浴控制在30℃±1℃,HRT为9 h、pH控制在7.00~8.08之间,经过60 d成功启动了CANON反应器,TN的去除负荷达到0.79 kg·(m3·d)-1;②在温度30℃时,陶粒CANON反应器中临界DO范围在1.12~1.69 mg·L-1之间,CANON反应器中短程硝化和厌氧氨氧化性能可维持稳定,高于此范围时,会出现CANON反应器中短程硝化不稳定现象;③在温度25℃,控制DO在1.01~1.54 mg·L-1之间时,尽管NO-3-N变化值与TN变化值的比值(δNO-3-N/δTN)略微偏离理论值0.127,为0.150~0.204,但CANON反应器脱氮性能趋于稳定,TN去除率最高为75.56%,TN的去除负荷最高达到0.97 kg·(m3·d)-1,这意味着CANON工艺的适宜温度范围至少可以降低至25℃.     

降温过程中生物膜CANON反应器的运行特征

本文以低温高氨氮废水为着眼点,通过不断地调节运行工况,探讨降温过程中全程自养脱氮(CANON)工艺的运行特征,以探索出低温环境下进水NH_4~+-N浓度较高时,CANON工艺获得稳定短程硝化和良好脱氮效果的方法.结果表明:①相较于直接将生物膜CANON反应器的温度条件由中温转变为低温(30℃±1℃→19℃),逐步降温驯化更有利于脱氮功能菌适应低温环境,且每次降温的幅度应尽量减小,同时还应配合运行工况的调节;②温度经25 d逐步降低至19℃左右,18 d后又继续降至15℃左右,NH_4~+-N和TN去除率均能分别长期稳定在90%、70%以上,甚至当温度下降至12℃时,TN去除率与去除负荷仍能分别达到72. 52%、0. 78 kg·(m~3·d)~(-1);③降温过程中驯化生物膜CANON污泥时,应优先考虑短程硝化控制.可通过维持一定的剩余NH_4~+-N浓度并严格控制DO浓度,以抑制NOB的活性,从而获得稳定的短程硝化效果.     

好氧条件下CANON工艺的启动研究

为揭示厌氧氨氧化细菌对于DO的适应性及缩短CANON(completely autotrophic nitrogen removal over nitrite)工艺的启动时间,以海绵为填料,采用小试研究了CANON工艺直接在好氧条件下的启动启动过程中,控制温度在35％℃±1℃,pH 7.39～8.01 之司部分亚硝化在60 d得以建立,亚硝酸盐积累率(NO₂^--N/NO_x^-;-N)达到98％,并保持长期稳定;连续运行至160 d时,厌氧氨氧化作用开始逐步显现,到210 d时,TN去除负荷达到1.22 kg/(m³·d),TN去除率维持在约70％,成功地在好氧条件下启 动了CANON工艺启动过程中发现,以不含有机碳源的氨氮废水启动CANON反应器时,CANON反应器启动成功的标志为：①填料内部开始产气;②总氮损失与硝酸盐增加的比值趋于稳定,理论值为8,在本试验中,二者的比值平均为8.61     

高氨氮废水短程硝化系统影响因素研究

在SBR短程硝化系统处理高氨氮污水过程中,探讨了温度、pH和DO对短程硝化的影响。实验发现,温度升高可以促进短程硝化实现,当温度在30℃时,短程硝化系统的稳定性能良好,NH4+-N的去除率和NO2--N的积累率均达到了最佳值。适宜的pH有益于NH4+-N的去除和NO2--N的积累,当pH为8.5时,系统的NO2--N积累率较好。DO浓度会影响系统中AOB和NOB的生长平衡,当DO处于0.7~0.9mg/L时,系统内AOB的生长形成优势,NO2--N积累率最高,短程硝化效果最佳。     

ABR-MBR工艺处理生活污水实现短程硝化

采用ABR-MBR耦合工艺对MBR反应器中实现短程硝化的运行控制条件进行了研究,并为后续研究系统的反硝化除磷性能打下基础.ABR-MBR耦合工艺在不同条件下的运行研究结果表明,在ABR反应器的水力停留时间(hydraulic retention time,HRT)6 h,污泥回流比100%,硝化液回流比300%,温度30℃±2℃的条件下,通过控制好氧区溶解氧浓度(DO从0.5~1.0 mg·L~(-1)降为0.3~0.7 mg·L~(-1))以及改变MBR反应器有效容积以控制其HRT,最终在MBR反应器HRT从3 h逐步延长至5 h时短程硝化遭到破坏,亚硝酸盐积累率(nitrite accumulation rate,NAR)从60%急剧下降至15%.短程硝化影响因素的分析表明:pH值、游离氨(free ammonia,FA)和游离亚硝酸(free nitrous acid,FNA)对本试验实现短程硝化无显著影响,维持低DO浓度(0.3~0.7 mg·L~(-1))并逐步缩短HRT是本试验实现短程硝化的关键控制因素,温度和污泥停留时间(sludge retention time,SRT)可作为辅助因素与之共同调控.短程硝化期间,系统获得了高效且稳定的COD和NH_4~+-N去除效果,平均出水浓度分别低于50 mg·L~(-1)和2 mg·L~(-1),去除率均在90%以上,TN平均去除率高达72%.     

温度对反硝化过程的影响以及pH 值变化规律

以乙酸钠为碳源,采用序批式反应器(SBR)考察了不同温度对全程和短程2 种类型反硝化的影响.结果表明,在温度为10~30℃时,2 种类型反硝化均可以进行完全.相同温度下,短程反硝化的平均比反硝化速率是全程的1.312 倍.降低温度,2 种电子受体的比反硝化速率均会下降,且20~10℃的温度转变较30~20℃转变的影响显著,其中以NO2--N 的还原过程受低温影响较大.低温(10~15 ) ℃ 条件对NO3--N 向NO2--N 的还原过程有一定抑制作用.在起始电子受体浓度与pH 值相同的条件下,温度越低,反硝化过程中2 种系统pH 值增量越大,反硝化结束时的pH 值越高;温度相同条件下,短程反硝化结束时pH 值曲线上峰点的值高于全程反硝化.     

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.