碱渣对海洋水环境中PO4^3—的吸附动力学特征

本文作为碱渣倾倒对海洋水环境影响现场调查的先期研究，从理论上推导了固－液体系的二级吸附动力学模型。在室内试验的基础上，利用该模型对碱渣－海水混合体系的吸附试验数据进行了理论分析，认为碱渣对海水中磷酸盐的吸附是二级动力学过程。     

天然水体中生物膜对磷的吸附动力学特征

天然水体生物膜对水环境中的磷具有很强的吸附作用,因此,本文进行了生物膜对水中磷的吸附动力学特征研究.从几个典型天然水体中获取生物膜,捣碎、振荡、称重后,取2g湿重的生物膜在恒定温度下吸附配制好的250mL、浓度在0.6～2.0mg·L-1之间的正磷酸盐溶液.在生物膜吸附磷的不同时间内,采用钼酸铵分光光度法测定溶液的磷浓度,并计算生物膜的吸附量,研究了吸附过程的动力学特征,分析了环境因素对吸附过程的影响.结果表明,生物膜对磷具有很强的吸附活性,吸附量可达100～2000mg·kg-1,吸附动力学特征符合准二级、准一级动力学模型.温度对生物膜吸附磷的速率和平衡吸附量影响较大,最佳吸附温度为25～30℃,溶液pH值对生物膜吸附活性没有太大影响.     

SDBS对重油在胶州湾沉积物上吸附行为的影响

采用批量定时取样法和批量平衡振荡法研究了人工海水介质中阴离子表面活性剂十二烷基苯磺酸钠（SDBS）存在时,重油在胶州湾沉积物上的吸附行为.结果表明,重油在胶州湾沉积物上的吸附速率和吸附量均随SDBS初始浓度的增加而增大,吸附速率方程可以用伪二级动力学模型进行较好地描述,吸附等温线较好地符合Freundlich吸附模型,...     

天然沸石吸附氨氮和磷的研究

选用浙江缙云产颗粒状天然沸石为材料对氨氮和磷进行吸附动力学和吸附等温试验,考察初始浓度、振荡时间对吸附量、去除率的影响。试验结果表明：沸石对氨氮和磷吸附显示出＂快速吸附,缓慢平衡＂的特点;吸附动力学过程符合准二级动力学模型;吸附等温线更符合Freundlich方程;氨氮初始浓度小于7 mg/L、振荡时间在1h内和磷初始浓度小于30 mg/L、振荡时间在15 min内,吸附量、去除率随初始浓度、振荡时间增加而增加,当超过此阶段后,吸附量增加缓慢、去除率下降。     

共聚苯胺/邻氨基苯酚介孔硅复合材料对Hg(Ⅱ)的吸附动力学研究

利用共聚苯胺邻氨基酚与介孔硅SBA-15的复合材料进行了汞离子的吸附性能试验研究,发现该复合材料对Hg(Ⅱ)具有较优异的吸附去除效果,对几种不同初始浓度的汞离子的去除率均可达到95%以上;对初始浓度为100mg/L的汞溶液的吸附动力学分别进行了一级和二级动力学模型拟合,结果表明该吸附材料对汞的吸附符合准二级动力学模型。     

沸石、钢渣组合填料对氨氮和磷的定量去除研究

试验研究基于沸石和钢渣分别对城市二级出水中残留氨氮和正磷酸盐的吸附效能,构建混合配比填料装置,实现对城市二级出水中氨氮和磷的深度、定量去除。研究表明,Freundlich和Langmuir模型均能较好地拟合沸石和钢渣分别对氨氮、磷的吸附,沸石和钢渣分别对氨氮和磷的吸附具有相似的动力学特征。钢渣和沸石分别对一定浓度的磷和氨氮的吸附速率趋于定值,在由此构建的混合配比填料装置的试验周期内,出水N/P控制在一定范围内,故表明混合一定配比的氨氮和磷的吸附功能性填料,可达到深度、定量去除城市二级出水中氨氮和磷的目的。     

聚乙烯及聚丙烯对抗生素的吸附行为研究

该研究选取微塑料聚丙烯(PP)和聚乙烯(PE)以及抗生素磺胺嘧啶(SDZ)和环丙沙星(CIP)为研究对象,探讨了在海水和纯水中的抗生素在微塑料上的吸附行为。研究结果表明:在不同背景溶液下微塑料对抗生素的吸附能力从大到小依次为:PP-纯水PE-纯水PP-海水PE-海水;抗生素吸附能力从大到小依次为:CIP-纯水SDZ-纯水SDZ-海水CIP-海水。除在海水体系中,PE对SDZ的吸附过程使用准一级动力学模型拟合效果较好外,其他吸附均符合准二级动力学模型,起始阶段吸附较快,随后吸附变慢,最终达到动态平衡。Freundlich模型对等温吸附过程拟合效果较好,表明吸附为非均匀的多层吸附,存在多个吸附位点。使用傅里叶红外光谱仪分析发现在吸附过程中没有产生新的基团,即没有化学吸附。不同微塑料对SDZ和CIP的吸附存在差异,且不同的水环境因素影响较为明显,微塑料在海水中的吸附能力低于纯水。这些结果可为了解微塑料作为载体协同迁移抗生素提供理论依据。     

碳纳米管-羟磷灰石对铅的吸附特性研究

采用多壁碳纳米管-羟磷灰石(MWCNT-HAP)复合材料,通过间歇试验研究了MWCNT-HAP对Pb(Ⅱ)的吸附特性.主要探讨了固液比、p H、离子强度、反应时间、Pb(Ⅱ)的初始质量浓度及温度等因素对吸附的影响.结果表明,固液比、p H与温度对于去除Pb(Ⅱ)的影响较大,离子强度影响较小.当温度为20℃,固液比为0.08 g·L-1,p H0为5.5,Pb(Ⅱ)的初始质量浓度为100 mg·L-1时,吸附量为716.13 mg·g-1.动力学试验结果表明,MWCNT-HAP吸附Pb(Ⅱ)为快速反应过程,在30 min时,吸附量可达最大吸附量的90%,60 min即可达平衡.伪二级动力学模型可较好地拟合动力学试验数据,可采用该模型描述MWCNT-HAP对Pb(Ⅱ)吸附的动力学过程.热力学试验结果表明,在不同温度下的自由能变均为负值,表明MWCNT-HAP对Pb(Ⅱ)的吸附为自发反应,升温有利于反应进行.Langmuir模型拟合不同温度下的等温试验结果得到可决定系数(R2为0.999 8~1.000 0),可采用该模型模拟MWCNT-HAP对Pb(Ⅱ)的等温吸附过程.MWCNT-HAP去除Pb(Ⅱ)的主要机制为MWCNT-HAP表面含氧官能团与Pb2+间的络合反应、HAP的分解-沉淀、Pb2+与Ca2+离子交换等.     

板栗壳吸附Cu2+的平衡与动力学研究及工艺设计

研究了板栗壳吸附Cu2+的平衡、动力学和热力学特征并对吸附工艺进行设计.采用Langmuir和Freundlich等温线对静态吸附平衡数据进行了拟合,同时采用准一级动力学和准二级动力学模型对静态吸附动力学数据进行了拟合,并计算了吸附过程的热力学参数自由能变（ΔGo）、焓变（ΔHo）和熵变（ΔSo）.结果表明,平衡实验数据符合Langmuir等温吸附模型,分离因子RL值在0~1之间,为有利吸附;动力学实验数据符合准二级动力学方程,平衡吸附量随Cu2+起始浓度增大而增大;ΔHo和ΔSo分别为12.206kJ·mol-1和21.534J·mol-1·K-1,ΔGo为负值,表明板栗壳吸附Cu2+为放热过程,可以自发进行,吸附过程增加了固液界面的混乱度.基于Langmuir等温吸附模型推导出的板栗壳用量计算公式可用于预测将一定体积一定起始浓度Cu2+溶液经过吸附降至所需浓度的板栗壳用量.     

铈基水热纤维素微球对水体中磷酸盐的吸附效应

通过浸渍-焙烧-浸渍处理方法制备了铈基水热纤维素微球(CHM),并研究CHM对水体磷酸盐的吸附性能以及吸附机制。结果表明:CHM对磷酸盐吸附在8 h达到平衡。准二级动力学吸附方程以及Langmuir等温线能更好地描述CHM对磷酸盐的吸附过程。CHM的饱和吸附量Qm为29.8591 mg/g,是未负载铈基的纤维素微球的4.56倍。p H对CHM吸附磷酸盐影响明显,p H越高,越不利于CHM对磷酸盐的吸附。     

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.     

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.     

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.     

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.     

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.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.