化学反硝化去除硝酸盐的试验研究

在间歇式完全混合反应器中,以Pd-Cu/γ-Al₂O₃为催化剂,对催化还原硝酸盐进行了实验研究.结果表明:在负载型金属催化剂作用下,硝酸盐能有效地被还原生成N₂,总氮的去除率达80%以上.催化剂的活性和对氮气的选择性受催化剂量、pH值、H₂的流量和压力、初始硝酸盐浓度等反应条件的影响,适当增加催化剂量和提高H₂的流量和压力都有利于提高催化剂的活性;而对于选择性,前者提高,后者则会导致降低,即控制反应扩散性能有利于提高催化选择性.在试验的浓度范围内,其催化还原硝酸盐的反应为一级反应.     

纳米催化剂Pd/SnO_2的制备及催化还原硝酸盐反应的调控

采用热分解法制备了SnO2载体,并用浸渍法制备了Pd/SnO2催化剂.同时,采用X射线衍射仪(XRD)、透射电镜(TEM)、扫描电镜(SEM)及BET比表面积仪等对所制载体和催化剂材料进行了分析表征.结果表明,热分解法和浸渍法都能够获得纳米材料,SnO2及Pd/SnO2的粒径均在9～10nm左右,比表面积分别达到144.99m·2g-1和147.36m·2g-1.在以甲酸为还原剂的Pd/SnO2催化还原硝酸盐体系中,在Pd与SnO2负载比为2%～7%,反应温度为20～50℃和甲酸投加量4.0～24.0mmol·L-1的条件下,催化活性为0.70～9.48mg·min-·1g-1,且催化活性随着负载比、温度和甲酸投加量的增大而增大,随着pH的升高先升后降,最佳pH为3.反应温度升高及pH降低都能够提高Pd/SnO2的选择性.甲酸-Pd/SnO2催化还原硝酸盐体系中还原反应的调控策略为:反应温度宜控制在40～50℃内,这样可同时获得较高的催化活性和选择性,温度过高对催化活性和选择性影响很小,温度过低则会同时降低催化活性和选择性;控制pH为3时,可以获得最大的催化活性及较好的选择性,pH升高会降低Pd/SnO2的催化活性和选择性,pH降低会导致催化活性迅速降低,但对选择性影响不大;甲酸与硝酸盐的物质的量比宜大于4:1,此时可以有效地抑制pH的上升,同时获得较高的催化活性和选择性,甲酸与硝酸盐的物质的量比小于4:1时,会同时降低Pd/SnO2的催化活性和选择性.     

生物碳基纳米钯铜催化剂的优化制备及脱硝研究

针对目前高效处理水体硝酸盐污染的技术瓶颈,以毛竹生物碳为载体基材,通过湿化学-浸渍还原的手段制备生物碳基纳米钯铜双金属催化剂(Nano-PdCu-BC),并以其为粒子电极,协同传统的二维电化学反应器,搭建三维粒子电催化反应体系去除水体中的硝酸盐污染物.探究了催化剂制备的前驱液浓度、初始硝酸盐氮浓度、电流强度、催化剂投加量和初始pH值对电催化还原NO₃-N的影响.结果显示,通过浸渍还原的方法可以将钯铜双金属成功负载在毛竹生物碳载体上,获得纳米钯铜双金属催化剂.在前驱液为0.60g/LPdCl₂和0.15g/LCuCl₂的溶液组合,初始硝酸盐氮(NO₃-N)浓度为100mg/L、电流强度为220mA、初始pH值为7,催化剂投加量为0.80g/L的条件下,反应180min后硝酸盐氮去除率可达99.68%,N₂选择性约为44.25%;Nano-PdCu-BC电催化还原NO₃-N的反应符合一级反应动力学,反应动力学常数k值为0.034/min;经3次循环使用后,NO...     

吸附树脂负载铁酞菁催化降解硝基苯的研究

在可见光照射下,采用吸附树脂负载铁酞菁催化过氧化氢降解硝基苯.考察了光照、催化剂投加量、双氧水投加量、温度及pH值等因素对催化效果的影响.结果表明,在功率为50W卤钨灯照射下,硝基苯溶液初始质量浓度为200 mg/L,初始pH值为3,催化剂投加量为1.5 g/L,双氧水投加量为1.0 mL/L,温度为35℃下反应10h,硝基苯去除率可达到79.9％.     

CoTPPS4催化处理敌敌畏生产废水的研究

用CoTPPS4作催化剂,Na2S2O8/H2O2为混合氧化剂处理含DDVP农药生产废水.探讨了氧化刺种类、混合氧化剂比例、催化剂投加量、农药初始浓度和pH值等因素对催化处理活性的影响,并对催化处理反应动力学进行了研究.结果表明,在pH＝9溶液中,农药初始浓度为28.93 mg/L、CoTPPS4加入量为2.4×10-...     

Pd-W-Cu/γ-Al_2O_3催化氢还原脱硝的基本性能研究

采用浸渍法制备Pd-W-Cu/γ-Al2O3催化剂,用XRD和SEM方法对该催化剂进行了表征.以氢气作为还原剂,在间歇式反应器中对催化还原地下水中硝酸盐进行了实验研究,考察了催化剂制备方法对催化还原硝酸盐性能的影响.结果表明,W的添加改善了Pd的分散性,提高了催化剂的活性和选择性.金属Pd/W/Cu质量比、浸渍顺序和焙烧温度对催化性能有较大影响.Pd/W/Cu质量比为3∶1∶1,Pd、Cu和W3种金属组分同时浸渍,焙烧温度为400℃时,催化剂的活性和选择性最高.在NO3--N初始浓度为100mg·mL-1条件下,催化反应60min后水中NO3--N和NO2--N浓度均为0mg·mL-1,NH4+-N浓度为2.5mg·mL-1.     

硝酸铁-过硫酸盐改性 GAC催化 H2 O2氧化橙黄Ⅳ

通过浸渍法在活性炭上负载硝酸铁、过硫酸盐对活性炭进行改性,以此为催化剂催化过氧化氢氧化去除有机废水橙黄Ⅳ.研究了体系pH值、催化剂投加量、反应温度、橙黄Ⅳ以及H2O2初始浓度等因素对橙黄Ⅳ去除率的影响,并对该催化剂重复使用性能进行测试.结果表明,硫的掺杂可以显著地提高硝酸铁改性活性炭的催化活性.目标物的初始浓度越低,反应速率越快,该反应遵循二级反应动力学,反应的活化能Ea为68.19 kJ.mol-1.在pH值2.4～9.1的范围内,催化剂均能有效地对橙黄Ⅳ进行催化降解.随着催化剂投量的增加,橙黄Ⅳ的去除效率明显提高,催化剂重复使用6次仍具有较好的催化活性,去除率仍可达到70%以上.自由基实验表明该氧化体系主要遵循自由基作用机制.     

对苯二酚强化多相类-Fenton过程降解活性艳红MX-5B的效能与机理

用碱沉淀法制备的硅羟基氧化铁(Si-FeOOH)作多相类-Fenton反应的催化剂,探讨了室温条件下投加还原剂对苯二酚(HQ)对其催化H2O2降解活性艳红MX-5B的影响,同时考察了pH、H2O2浓度、催化剂Si-FeOOH投量及活性艳红浓度对活性艳红MX-5B脱色率的影响,并从溶铁量方面初步探讨了Si-FeOOH/H2O2/HQ体系降解活性艳红MX-5B的机理.结果表明,对苯二酚强化以Si-FeOOH为催化剂的多相类-Fenton反应降解活性艳红的效果显著.在pH=3,活性艳红初始浓度为10mg·L-1,对苯二酚浓度为0.55mg·L-1,Si-FeOOH投量为100mg·L-1,H2O2浓度为51mg·L-1的反应条件下,活性艳红MX-5B的脱色率达94.69%.研究还发现,活性艳红脱色率与反应体系里的铁离子浓度关系密切,表明多相类-Fenton反应中除了催化剂表面吸附催化作用外,也可能存在类似均相类-Fenton的溶液催化作用.     

零价铁与过硫酸盐异相芬顿降解活性艳橙X-GN

采用零价铁(Fe~0)与过硫酸盐构建异相类芬顿体系,由Fe0腐蚀释放Fe~(2+)催化S_2 O_8~(2-)产生硫酸根自由基快速降解偶氮染料活性艳橙,考察了初始p H值、Fe~0投加量、过硫酸盐投加量和温度对降解过程的影响。结果表明,当活性艳橙初始浓度为100 mg/L、pH值为7、Fe~0投加量为0.5 g/L、过硫酸盐投加量为1 mmol/L和反应温度为30℃时,反应60 min后活性艳橙降解率达到92.6%。酸性条件和提高反应温度均有利反应的进行,而且活性艳橙的降解率在初始pH值为9时也高于90%。反应过程符合准一级动力学,表观反应速率常数k为0.0513 min~(-1)(30℃)。UV-Vis扫描显示,活性艳橙的发色基团在反应过程中被破坏。由Fe~0与S_2O_8~(2-)构成的异相Fenton体系可作为一种高效手段用于染料废水的处理。     

氢气还原海绵铁去除水体中硝酸盐的研究

利用小球烧结和氢气还原工艺制备了粒径1mm～5mm的多孔性球形海绵铁,对球形海绵铁去除水体中硝酸盐的效率及去除动力学进行了研究。结果表明:溶液初始pH值对硝酸盐去除效率的影响显著,初始pH值小于3时,硝酸盐的去除率随溶液初始pH的增加而逐渐降低;初始pH值大于3时,硝酸盐的去除率又随之升高。硝酸盐浓度低于10mgN/L时,硝酸盐去除率随着硝酸盐初始浓度的增加而增加,硝酸盐的残余量保持在0.4mgN/L左右;硝酸盐浓度高于20mgN/L时,硝酸盐的去除率随初始硝酸盐浓度的增加而略有降低。球形海绵铁去除硝酸盐为一级动力学反应,反应级数为0.970～1.378,表观反应速率常数为0.314h-1～0.536h-1。海绵铁还原硝酸盐的主要产物为氨氮,随着还原反应的进行,溶液pH值快速增加,氨氮以分子态氨的形式从水中逸出。进行归纳总结和对比,并以多环芳烃的提取为例列举了各方法的应用步骤,从而为其他环境样品其他有机物分析预处理提供参考。     

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.