纳米Fe3C/炭纤维非均相电芬顿降解二甲基砷的研究

针对结构稳定且难以靠常规方法去除的二甲基砷,制备新型负载Fe_3C纳米粒子的炭纤维催化剂,并对其非均相电芬顿降解二甲基砷进行了研究.结果表明,纳米Fe_3C/CF与阴极产生的H2O2发生电芬顿催化反应产生羟基自由基将二甲基砷降解为一甲基砷和As(V),As(V)可被同步吸附在Fe_3C/CF催化剂表面.通过考察电催化过程中初始p H、反应物初始浓度、电流强度和催化剂投加量等因素对催化氧化DMA效果的影响,表明在初始p H为3,二甲基砷初始浓度为5 mg·L~(-1),Fe_3C/CF投量为500 mg·L~(-1)的最佳条件下,经非均相电芬顿反应360 min后,二甲基砷去除率高达96%.     

硫自养反硝化耦合厌氧氨氧化脱氮条件控制研究

采用全混式厌氧搅拌罐,研究自养条件下,厌氧氨氧化与硫自养反硝化共同存在时,前者对系统中硫酸盐的产生和碱度消耗的影响.投加单质硫颗粒50 g·L~(-1),接种厌氧氨氧化颗粒污泥100 g·L~(-1)(湿重),控制温度35℃±0.5℃,搅拌强度120r·min-1,p H为8.0~8.4.启动硫自养反硝化阶段,进水硝酸盐浓度为200 mg·L~(-1),水力停留时间为5.3 h,反应器硝态氮负荷达0.56~0.71 kg·(m~3·d)~(-1).硫自养反硝化耦合厌氧氨氧化反应过程中,添加60 mg·L~(-1)氨氮后,硝态氮负荷仍维持在0.66~0.88kg·(m~3·d)~(-1),氨氮负荷为0.27 kg·(m~3·d)~(-1).反应体系内单位硝酸盐转化产生的硫酸盐Δn(SO~(2-)_4)∶Δn(NO~-_3)由1.21±0.06降低至1.01±0.10,Δ(IC)∶Δ(NO~-_3-N)由0.72±0.1降低至0.51±0.11,出水p H值由6.5上升至7.2.序批试实验优化反应条件:在搅拌强度G_T值为22~64 s~(-1),p H值为8.08时,耦合反应Δn(NH~+_4)∶Δn(NO~-_3)最高达到0.43,硝酸盐转化速率提升60%,过高搅拌强度(搅拌速度G_T值64 s~(-1))、不适宜的p H值(最适p H值为8.02)环境都会起同步转化效率的降低.     

过硫酸盐-石灰苏打处理印染反渗透浓水研究

本文通过热活化过硫酸盐(PS)氧化印染反渗透浓水(ROC)中的难降解有机物,并辅以石灰苏打软水技术降低其硬度,以期实现印染ROC的回用.PS氧化研究表明,酸性条件相对于中性和碱性条件更有利于反应的进行,适宜的初始PS浓度为1000 mg·L~(-1),经济有效的活化温度为75℃.PS氧化降解ROC中难降解有机物的过程符合一级降解动力学模型.经PS氧化处理后,ROC中SO2-4浓度由9600 mg·L~(-1)上升到10350 mg·L~(-1),节省了回用时印染助剂的投加;TOC浓度1.0 mg·L~(-1),表明ROC中难降解有机物已基本矿化.石灰苏打脱除印染ROC中硬度的研究表明,150 mg·L~(-1)的石灰和800 mg·L~(-1)的苏打投加量是降低硬度的最为适宜的药剂组合方式.PS-石灰苏打处理印染ROC可稳定实现出水COD21.5 mg·L~(-1),硬度17.5 mg·L~(-1),满足印染废水回用要求.     

VUV/HPW/BMMs体系对全氟辛酸（PFOA）的脱氟研究

采用真空紫外灯(VUV)和双模型介孔材料(BMMs)负载磷钨酸(HPW)催化剂构建光催化体系,探究该体系对水中全氟辛酸(PFOA)的脱氟效果.研究了PFOA初始浓度、HPW/BMMs投加量、初始p H值对体系脱氟的影响,并采用响应曲面法(Response Surface Method,RSM)分析了最佳边界反应条件.结果表明,体系对PFOA具有明显的脱氟效果:脱氟效率随PFOA初始浓度的增大而减小;催化剂投加量为0.2 g·L~(-1),脱氟效率最高达50.2%;体系p H为3~4时,体系脱氟效果显著.基于Box-Behnken响应曲面法,各影响因子对脱氟效率的显著性排序为:p HPFOA初始浓度HPW/BMMs投加量.p H值与HPW/BMMs投加量及初始PFOA浓度交互作用显著,模型回归性良好,最佳运行条件为:p H=3.82,HPW/BMMs投加量为0.3 g·L~(-1),PFOA初始浓度为20 mg·L~(-1),反应4 h的脱氟率达到52.6%,与预测值相比偏差为1.2%.本研究为高效降解全氟化合物提供了新思路.     

臭氧氧化饮用水过程中可同化有机碳生成的影响因素

研究臭氧化过程中,臭氧投加量、p H值和离子强度对可同化有机碳(assimilable organic carbon,AOC)生成量的影响.结果表明,臭氧投加量在1~5 mg·L~(-1)范围,AOC的生成量随着投加量的增加而增加,但过高的臭氧投加量(9 mg·L~(-1))反而导致AOC生成量下降.p H越高(6~9),AOC的生成量也越高.AOC的生成量随着离子强度的升高而下降.臭氧氧化强疏组分AOC的生成量最高,其次为弱疏,而极亲和中亲最低.研究发现,AOC的生成量与小分子有机物的SUVA有密切的关系,较低的SUVA产生较多的AOC.     

富里酸-膨润土复合体对氟的吸附特性

采用共沉淀法制备了富里酸-膨润土复合体(FA-BENT),研究了FA-BENT的基本性质及其在不同环境条件下对氟的吸附特性.XRD分析显示,FA-BENT中蒙脱石的(001)面衍射峰强度有所减弱,但其层间距没有明显变化,表明FA-BENT中富里酸主要包被在膨润土外表面.FTIR结果表明,FA-BENT膨润土的矿物组分主要与富里酸表面C=O、—OH等官能团结合,配位体交换、表面络合作用是其主要作用机制.低p H范围内,升高反应体系的初始p H有利于FA-BENT对氟的吸附;当初始p H上升至4.50以后,吸附量随p H升高而降低;FA-BENT对氟的吸附也受离子强度的影响,其主要原因可能是"极性"效应;FA-BENT对氟的动力学吸附过程遵循拟二级动力学机制,受化学过程控制(R~2=0.999 2);与Freundlich模型相比,Langmuir模型对氟在FA-BENT上的吸附数据具有较高的拟合优度(R~20.994 9).热力学参数表明,FA-BENT对氟的吸附属于熵驱动的自发吸热反应过程[ΔH为32.57 k J·mol~(-1),ΔS为112.31 J·(mol·K)~(-1),ΔG为-0.65~-1.76 k J·mol~(-1)].     

臭氧-混凝交互作用对水体有机物的影响

研究臭氧在纯水和混凝剂[Al_2(SO_4)_3]溶液中残余浓度的变化;采用差异吸收分析(differential absorbance,DA)、三维荧光(three dimensional fluorescence excitation-emission matrix spectroscopy,3D-EEM)和气相色谱(gas chromatograph,GC)、总有机碳分析(total organic carbon analyser,TOC)等研究水体有机物(富里酸)光谱特征、有机物和消毒副产物(DBPs)生成量在预臭氧、预臭氧-混凝(POC)以及臭氧-混凝联用(OC)后的差异;研究臭氧和混凝联合作用对有机物氧化程度及其对DBPs生成的影响.结果表明POC与OC作用存在明显差别,臭氧与混凝剂Al_2(SO_4)_3存在交互作用.交互作用主要体现在:(1)臭氧-混凝联用时臭氧降解速率加快;且臭氧降解中自由基产量相对增加.当臭氧投量2 mg·L~(-1),Al3+含量为1 mg·L~(-1)、3 mg·L~(-1)时,自由基捕获量比单独臭氧分别高15.2%和23.9%.(2)联用和预臭氧-混凝对有机物反应的差异,体现在OC有机物去除率低于POC,二者对有机物的反应途径不同;进而导致有机物与消毒剂反应的差异以及DBPs生成的差异.联用对DOC的去除能力明显强于单独臭氧和单独混凝,但弱于预氧化-混凝.当O3浓度为1 mg·L~(-1)、Al3+1 mg·L~(-1)时POC处理后二氯乙酸生成势(DCAAFP)和三氯乙酸生成势(TCAAFP)分别为47μg·L~(-1)和20.5μg·L~(-1),三氯甲烷生成势(CFFP)为97.8μg·L~(-1),较原水分别降低51%、64.6%和41.5%;而相应臭氧-混凝处理后DCAAFP和TCAAFP分别为48.4μg·L~(-1)和21.4μg·L~(-1),CFFP为117.3μg·L~(-1);较原水分别降低49.6%、63%和29.5%.同等臭氧投量下,增加混凝剂的剂量,POC和OC处理效果的差异进一步扩大.为保证用水安全和处理效率,臭氧和混凝联用时对臭氧的浓度、投加位置、混凝剂的种类等都需要进一步的研究论证,慎重选择.     

羟基自由基氧化降解水中土臭素的效率与机制

土臭素(Geosmin,GSM)是一种由蓝绿藻及放线菌产生,具有令人讨厌土霉味的化合物.地表水中存在土臭素,尽管量少,但因传统水处理工艺难以去除,大大降低了饮用水的感官质量.本文采用大气压强电场电离放电结合水力射流空化方式制备的羟基自由基(Hydroxyl radicals,·OH)对水中GSM进行氧化降解,研究了氧化剂投加剂量、接触时间因素的影响,并根据气相色谱-质谱(GC-MS)全扫描获取的中间产物探讨了·OH氧化降解GSM的机制.实验结果表明:当氧化剂投加剂量为0.8 mg·L~(-1),管路中接触反应6 s,可把初始浓度100 ng·L~(-1)的GSM降解到10 ng·L~(-1)以下;提高氧化剂投加量至2.6 mg·L~(-1),接触反应180 s,可氧化降解500 ng·L~(-1)的GSM至10 ng·L~(-1)以下,达到我国《生活饮用水卫生标准》(GB5749—2006).在GSM水样中加入叔丁醇(Tertiary butyl alcohol,TBA)·OH淬灭剂,GSM氧化降解效果明显降低,间接证明了降解GSM的主要物质为·OH.对氧化降解GSM的中间产物分析表明·OH可以破坏GSM双环结构并最终将其矿化成CO_2和H_2O.     

臭氧降解高浓度腐殖酸动力学

采用臭氧氧化法降解高浓度腐殖酸废水,并研究了臭氧对腐殖酸的降解动力学,考察了臭氧投量、初始腐殖酸浓度、初始pH和反应温度对臭氧降解高浓度腐殖酸废水的影响.结果表明,在臭氧投量为3.46 g.h-1,初始腐殖酸浓度为1 000mg.L-1,初始pH=8.0,反应温度为303 K,反应30 min的条件下,腐殖酸的去除率达到89.04%.在臭氧投量为1.52～6.01g.h-1,初始腐殖酸浓度为250～1 000 mg.L-1,初始pH为2.0～10.0,反应温度在283～323 K的范围内,臭氧降解腐殖酸符合拟一级动力学模型,通过对实验数据拟合,得到反应动力学方程,反应活化能较低(Ea=1.30×104J.mol-1),并且模型计算数值与实际数据吻合良好(平均相对误差为7.62%).     

钴活化过一硫酸盐氧化过程中卤代副产物的生成

活化过硫酸盐产生的硫酸根自由基(SO~(·-)_4)可以降解大多数有机污染物,被广泛用于地下水、土壤修复等领域.本研究发现在钴活化过一硫酸盐(PMS)高级氧化过程中,溴离子会被SO~(·-)_4氧化生成自由溴,继而和苯酚反应生成溴代苯酚,最终生成三溴甲烷和二溴乙酸等副产物.当反应液中苯酚初始浓度为0.05 mmol·L~(-1)、Br~-浓度0.2 mmol·L~(-1)、Co~(2+)浓度5μmol·L~(-1)、PMS浓度1 mmol·L~(-1)、p H为6.0时,三溴甲烷和二溴乙酸的生成随反应的进行先增加后降低,在8 h达到最大,分别为10.3μmol·L~(-1)和14.6μmol·L~(-1).卤代副产物的生成随p H的升高而降低.当卤离子总量保持不变,随着溶液中Cl~-/Br~-比例的增加,卤代副产物的生成总量逐渐降低,而含氯副产物的产量逐渐增加.本研究为全面评价过硫酸盐高级氧化工艺在污染控制方面的应用可行性提供了依据.     

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.     

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.     

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.