开放系统下方解石对邻苯二甲酸的吸附

通过批量平衡法,研究开放系统条件下方解石对邻苯二甲酸的吸附特性.结果表明:1邻苯二甲酸在方解石上的吸附3 h后渐趋平衡,一级动力学方程与二级动力学方程都能较好拟合吸附过程;2当p H从7.7增加到9.7时,邻苯二甲酸的吸附率逐渐降低,溶液中HCO-3和CO2-3的竞争效应及方解石表面的静电效应是其主导因素;3邻苯二甲酸的吸附率随离子强度升高而减少,这是由于电解质的"盐效应"作用增大了竞争离子HCO-3和CO2-3的浓度;4与间、对苯二甲酸相比,邻苯二甲酸的吸附率明显较高,可能是由于邻苯二甲酸的两个羧基距离较近,容易在方解石表面形成环状的络合物结构.通过研究邻苯二甲酸在方解石上的吸附特性,有助于了解二者的相互作用机制,为利用方解石去除环境中的邻苯二甲酸提供理论支持.     

不同铁锰浓度的低温铁锰氨地下水净化中氨氮去除途径

在某地下水除铁锰氨氮水厂,以中试滤柱开展了低温(5～6℃)、铁锰氨[Fe(Ⅱ) 0～19.26 mg·L~(-1)、Mn(Ⅱ) 0.52～2.05 mg·L~(-1)和NH~+_4-N 0.37～2.59 mg·L~(-1)]净化工艺实验研究,探究了不同铁锰浓度时氨氮的去除途径.结果表明,当保持进水锰浓度约为0.6 mg·L~(-1),提高进水亚铁浓度时,随着滤层中铁氧化物的增加,通过铁氧化物吸附去除的氨氮比例会升高,通过硝化作用去除的氨氮比例会降低,且吸附作用先于硝化作用.当保持进水亚铁浓度分别约为8 mg·L~(-1)和11 mg·L~(-1),提高进水锰浓度时,通过吸附去除的氨氮比例并没有随着锰氧化物的增加而增加,即氨氮的去除途径几乎未发生改变.其原因是,在滤层前20 cm形成的锰氧化物较少,对此范围内吸附的氨氮影响较小,锰氧化物的生成区域集中在滤层的20 cm以下,而绝大部分氨氮在该区域之前已经通过吸附和硝化作用去除,该区域中的锰氧化物并没有吸附氨氮.     

选择性吸附法处理含表面活性剂和多环芳烃的土壤淋洗液研究

比较研究了H103树脂、活性炭、沸石、硅藻土和膨润土等5种吸附剂对土壤淋洗液中TX-100与PAHs的吸附性能.批实验结果表明,H103树脂、活性炭、沸石、硅藻土和膨润土吸附后,淋洗液中T-PAHs及TX-100浓度分别为0.03和0 mg·L~(-1)、0.16和3623 mg·L~(-1)、15.21和6175 mg·L~(-1)、15.98和6555 mg·L~(-1)、9.49和4332 mg·L~(-1),选择性吸附系数排序依次为活性炭膨润土沸石硅藻土H103树脂.其中,活性炭能够去除淋洗液中99%的PAHs,同时保留51.33%的TX-100回收再利用,选择吸附系数达到109.5.活性炭固定床实验中,由淋洗液溶质的穿透曲线计算出物质的吸附容量.当空隙体积为2.5-7PV时,活性炭能够去除淋洗液中72%的PAHs,同时保留81%的TX-100,平均选择吸附系数为10.08.由此可见,活性炭固定床可有效处理含表面活性剂土壤淋洗液中的多环芳烃,同时实现表面活性剂的回收再利用.     

纳米TiO2吸附HgCl2水溶液中Hg(Ⅱ)

通过室内模拟实验研究了3种不同粒径TiO_2添加量、溶液pH、吸附时间及初始Hg~(2+)浓度等因素对模拟废水中Hg(Ⅱ)吸附效果的影响.由单因素研究可知最优条件为:5 nm TiO_2和100 nm TiO_2添加量分别为7.5 g·L~(-1)和2.0 g·L~(-1),其它条件相同,溶液pH为8.0,初始Hg~(2+)浓度均为15 mg·L~(-1),吸附5 min,汞的去除率分别为99.5%和99.3%;25 nm TiO_2添加量为10 g·L~(-1),溶液pH为8.0,初始Hg~(2+)浓度为15 mg·L~(-1),吸附60 min时,汞的去除率为62.8%.3种粒径TiO_2吸附Hg(Ⅱ)强弱顺序为:100 nm TiO_25 nm TiO_225 nm TiO_2.分两次量吸附结果表明,5nm TiO_2分量吸附效果明显优于单独吸附效果;100 nm TiO_2的分量吸附与单独吸附差异不大.正交试验结果表明,影响Hg(Ⅱ)去除率的因素排序为:溶液pH初始Hg~(2+)浓度吸附时间TiO_2添加量.最优实验方案为:溶液pH=8.0,100 nm TiO_2添加量为2.0 g·L~(-1),初始Hg~(2+)浓度为25 mg·L~(-1),吸附10 min.在此实验条件下,Hg(Ⅱ)去除率为99.9%,吸附后溶液中Hg(Ⅱ)平衡浓度为0.033 mg·L~(-1)0.05mg·L~(-1),低于目前企业规定的水污染物中汞的排放限值,Hg(Ⅱ)的最大吸附量为26.95 mg·g~(-1).吸附等温线符合Langmuir等温方程,说明100 nm TiO_2对Hg(Ⅱ)的吸附是典型的单分子层吸附.     

纳米铁去除废水中硫离子的研究

研究了实验室自制的纳米铁对人工配制的含硫废水中S2-吸附的影响因素、吸附等温线、吸附动力学.并对纳米铁去除S2-的机制进行了初探.结果表明.增加纳米铁的投加量能增大S2-的去除率;增加初始S2-浓度,去除率下降,<100 mg·L-1的初始S2-浓度能被10 g·L-1纳米铁完全去除;纳米铁对S2-的吸附能力随pH值的升高而下降.且变化较大,pH为2、7、13时的去除率分别为87.34%、65.80%和44.61%;25℃时纳米铁对S2-的吸附能力最强,平衡吸附量为19.17 mg·g-1;温度升高或降低,吸附能力均下降,但变化不大;纳米铁对S2-的吸附等温线符合Langmuir和Freundlich方程;纳米铁吸附S2-的过程符合拟二级动力学方程,初始时刻的吸附速率h在25℃最大,为1.575 3 mg·(g·mg)-1,而吸附速率常数随温度的升高而增大;吸附反应的活化能E.为8.22 kJ·mol-1;纳米铁对S2-的去除主要是通过形成表面络合物、硫氢基氧化铁和硫化铁(FeS、FeS2、FeSn)沉淀吸附在纳米铁表面来去除.     

二氧化钛光催化氧化阿散酸

阿散酸(p-arsanilic acid,ASA)是一种重要的有机砷化合物,较无机砷更加难以去除,目前关于去除水中ASA研究少有报道.本研究主要评价了TiO_2光催化剂(P25)对ASA的去除效果,考察了P25投量、pH和光照强度对其光催化氧化ASA的影响,探究了ASA光降解产物和主要机制.结果表明,在P25催化作用下,模拟自然光可氧化降解ASA为As(V),最终通过P25对As(V)的吸附作用将水中砷有效去除.当ASA初始浓度为2 mg·L~(-1),P25投量为1 g·L~(-1)时,光催化氧化-吸附0.5 h后,水中剩余砷的浓度约为0.34 mg·L~(-1).酸性条件下ASA的去除率远远高于碱性条件,最佳光照强度为68.5 mW·cm~(-2).P25光催化氧化ASA过程中羟基自由基起到了主要作用.     

机械活化蛇纹石吸附除磷性能及机理研究

为实现废水中磷的绿色高效去除,采用机械活化法制备活性蛇纹石吸附材料,探讨了该材料对废水中30 mg·L^-1正磷酸盐的吸附性能、关键影响因素及吸附去除机理.结果表明,活性蛇纹石对磷的理论最大吸附量(以P计)为126.58 mg·g^-1,当初始pH为7.0、温度为20℃、投加量为0.5 g·L^-1、吸附时间为240 min时,材料对磷的去除率为89.73%.磷的去除率随活化时间、吸附时间和投加量的增加而增大,随pH和温度的增加而降低.利用激光粒度仪、XRD、FTIR和SEM等现代分析测试手段研究了活性蛇纹石对磷的吸附机理.结果表明,机械活化致使蛇纹石颗粒的中值粒径从41.32μm迅速降低到12.00μm,之后粒径不再发生明显变化,进一步的机械力作用使蛇纹石晶体结构受到破坏,导致Mg—OH键能减弱,增强了颗粒表面的Mg吸附位点的活性,并使颗粒表面呈碱性,最终使磷能够以磷酸镁(Mg₃(PO₄)₂·22H₂O)的形式固定在材料表面.等温吸附和吸...     

微藻固定化条件优化及其污水氨氮去除潜力分析

微藻污水处理被视为新概念引领下极具潜力的一项绿色技术,然而,微藻分离与采收一直是限制其大规模应用的瓶颈.本研究立足于固定化技术,以斜生栅藻(Scenedesmus obliquus)为研究对象,采用响应曲面法(RSM)耦合Box-Behnken设计,以固定剂浓度、交联剂浓度和交联时间为自变量,以藻球的机械强度、传质速率和生长速率为响应值,对固定化的过程参数进行优化,制备性能最优的固定化藻球;并探索和分析藻球对氨氮(NH4+-N)去除的最佳条件及其潜力.结果表明,固定剂浓度、交联剂浓度和交联时间分别为5%、2%和16 h为制备固定化藻球的最优条件,且包埋密度为1×106cells·m L~(-1),有机物(COD)浓度为300 mg·L~(-1)时,藻球混合培养去除NH4+-N的能力最强;此外,固定藻对高浓度NH4+-N的去除潜力显著优于自由藻,当初始浓度约为50和70 mg·L~(-1)时,固定藻混合培养5 d后NH4+-N去除率分别为(96. 6±0. 1)%和(65. 2±4. 5)%,而初始浓度约为30 mg·L~(-1)时,自由藻优势明显,3 d后NH4+-N去除率高达(97. 8±0. 6)%;但异养条件下固定藻对NH4+-N的去除率整体偏低且随浓度增加而降低,当初始浓度约为30 mg·L~(-1)时,去除率仅为(49. 0±3. 1)%.本研究为污水可持续处理提供了新思路,为资源回收提供了新途径,更为该技术推广应用奠定了较好的理论基础.     

改性海绵铁深度除磷及其再生磷回收方法

为了从污染水体中去除磷并有效回收磷资源,本文研究了海绵铁改性前后吸附除磷特性,并构建海绵铁除磷渗滤床,考察了其连续流除磷特性及再生活化方法,并探究再生废液中磷回收生成鸟粪石的工艺条件.结果表明:硫酸改性后的海绵铁对磷的最大理论吸附容量从改性前4.17 mg·g~(-1)提升至18.18 mg·g~(-1).吸附饱和的改性海绵铁,采用1 mol·L~(-1)氢氧化钠解吸和6%硫酸再活化后,能够达到98%的活化率.海绵铁除磷渗滤床在长达约200 d的连续流运行实验中表现出良好的除磷能力,在进水TP=10 mg·L~(-1),HRT=1 h条件下,磷综合去除率达30%～89%,累积单位容积磷吸附量达到6.95 kg·m~(-3).海绵铁碱再生后的废液可以用于回收鸟粪石,其最佳生成条件为:pH=10,n(Mg~(2+))∶n(PO_4~(3-))∶n(NH~+_4)=1.3∶1∶1.1.在最优条件下,磷回收率可以达到97.8%.本研究提供的方法对于污染水体中磷营养元素的去除及回收利用具有理论与实践意义.     

开放系统中碳酸盐矿物(方解石)对四环素的吸附

通过批量平衡法,研究开放系统条件下方解石对四环素(TC)的吸附特性。结果表明:(1)四环素在方解石上的吸附很快,3 h后便渐趋平衡;(2)当pH从7.7增加到9.7时,四环素的吸附率先上升然后下降,在pH(8.3~8.7)范围内存在最大吸附率,由此现象推测,四环素通过其形态(TCH_2~0、TCH~-)与方解石表面形成内层络合物结构;(3)离子强度对四环素的吸附影响甚微,该现象也暗示四环素与方解石表面吸附点位形成内层络合物;(4)四环素在方解石上的等温吸附曲线可以很好地用Freundlich模型来拟合,四环素在25℃时的吸附量大于其15℃时的吸附量,推测其吸附过程为吸热过程。     

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.