Kinetics and mechanism of the hydrolysis of thiamethoxam

The degradation of thiamethoxam [(EZ)-3-(2-chloro-1,3-thiazol-5-yl-methyl)-5-methyl-1,3,5-oxadiazinan-4-ylidene (nitro) amine] insecticide in buffers at different pH and temperature levels was investigated in laboratory studies. Acidic hydrolysis under conventional heating conditions and alkaline hydrolysis under both conventional heating and microwave conditions were carried out. Different hydrolysis products were found to form under alkaline and acidic conditions. Hydrolysis of thiamethoxam in acidic, neutral and alkaline buffers followed first-order reaction rate kinetics at pH 4, 7 and 9.2, respectively. Thiamethoxam readily hydrolyzed in alkaline buffer but was comparatively stable in neutral buffer solution. The main products formed under different conditions were characterized on the basis of infrared (IR), ¹H-NMR and Mass spectroscopy. The possible mechanisms for the formation of these hydrolysis products have also been proposed.     

Modelling the dissipation kinetics of six commonly used pesticides in two contrasting soils of New Zealand

We used three non-linear bi-phasic models, bi-exponential (BEXP), first-order double exponential decay (FODED), and first-order two-compartment (FOTC), to fit the measured degradation data for six commonly used pesticides (atrazine, terbuthylazine, bromacil, diazinon, hexazinone and procymidone) in two New Zealand soils. Corresponding DT₅₀ and DT₉₀ values for each compound were numerically obtained and compared against those estimated by simple first-order kinetic (SFOK) model. All 3 non-linear models gave good fit of the measured data under both soil depths and were well supported by the values obtained for the respective statistical indices (RMSE, CRM and r ²). The FOTC model gave by far the best fit for most compounds, followed by the FODED and BEXP models. Overall, DT₅₀ values derived by non-linear models for the six compounds in soils from both sites were lower than the values obtained by the SFOK model. Differences in the SFOK and the three non-linear models derived DT₉₀were, however, an order of magnitude higher for some compounds, while for others differences were very small. Although all three non-linear models described most data by giving excellent fits, in a few instances > 5–10% asymptotes hindered the estimation of DT₉₀ values. This work shows that when degradation deviates from first-order kinetic, application of non-linear decay models to describe the kinetics of degradation becomes important in order to derive the true end-points for pesticides in soil.     

Mg/Al/Fe型类水滑石焙烧产物吸附去除水中硫酸根离子

通过共沉淀法制备了Mg/AUFe型类水滑石(MgAlFe-HTLCs)并在500℃下焙烧得焙烧产物(HTLCs-500),利用HTLCs-500吸附去除水中的硫酸根离子,并用X射线衍射对MgAlFe-HTLCs及HTLCs-500吸附硫酸根离子前后的结构进行了表征,研究了环境中其他因素对HTLCs-500吸附硫酸根离子的影响.结果表明,实验数据对准二级动力学模型的拟合结果最好;吸附过程符合Langmuir吸附等温模型,通过实验得到HTLCs-500对硫酸根离子的最大吸附量为157.73 mg/g,和Langmuir等温线得到的理论最大吸附量161.29 mg/g相差不大,对硫酸根离子具有良好的吸附性能;硫酸根溶液的初始pH值对HTLCs-500吸附硫酸根离子的性能影响不大,最佳pH值为3;X射线衍射结果表明,HTLCs-500吸附去除硫酸根离子的机理之一为HTLCs-500通过吸附硫酸根离子来恢复层状结构.     

转盘液膜光电催化法处理罗丹明B的反应动力学

采用幂指数方程法建立了转盘液膜光电催化法降解罗丹明B(RhB)废水的动力学方程.结果表明,该反应动力学符合表观一级动力学.在考察的影响因素中,外加偏压对反应速率的影响最大,催化剂用量次之,其次是RhB初始浓度,转盘转速和光强度的影响相对较小.     

改性玉米秸秆吸附Cu^2＋的动力学和热力学

本研究用ZnCl2作为活化剂,使用功率640W的微波照射4min的方法制备改性玉米秸秆。考察投加量、pH、吸附时间对吸附性能的影响,并对等温吸附特征、吸附动力学和热力学进行了系统研究。结果表明：投加量为0．2g,pH为6,改性玉米秸秆对Cu^2＋具有很好的吸附效果,吸附在8h后达到平衡。该吸附过程符合Langmuir及Freundlich等温吸附模型和准二级动力学方程,其反应的吉布斯自由能△G〈0,为自发反应过程。     

Adsorption of Pb and Cd on the natural surface coatings (NSCs) in the presence of organochlorine pesticides: a preliminary investigation

Adsorption of Pb and Cd in the presence and absence of organochlorine pesticides (OCPs) on natural surface coatings (NSCs), which were collected in the Nanhu Lake in Changchun, China, was measured in order to investigate the effect of the OCPs on the adsorption of heavy metals on the NSCs. Adsorption of Pb/Cd was carried out under controlled laboratory conditions (mineral salt solution with defined species, ionic strength 0.05 mol/l, 25 degrees C and pH 6.0) with initial Pb and Cd concentrations ranging from 0.2 to 2.5 mol/l. The classical Langmuir adsorption isotherm was applied to estimate the equilibrium coefficients of the adsorption of Pb and Cd on the NSCs. Adsorption interference between Pb/Cd and the OCPs on the NSCs indicated that the adsorption of Pb/Cd on the NSCs was influenced by the OCPs, and competitive adsorption between Pb and the OCPs was observed while adsorption of Cd was enhanced by addition of the OCPs. Adsorption data fit the Langmuir isotherm well for the NSCs treated with the OCPs at different equilibrium concentrations. The results showed that the amount of adsorbed Pb decreased by more than 40% while the amount of adsorbed Cd increased by over 60% with an increase in the initial concentrations of the OCPs ranging from 0 to 5.0 microg/l and that adsorption of Pb/Cd on the NSCs was strongly affected by the OCPs. This preliminary study highlights the importance of the OCPs on the NSCs in controlling the transport, fate, biogeochemistry, bioavailability and toxicity of trace metals in aquatic environments.     

Degradation of anionic surfactants during drying of UASBR sludges on sand drying beds

Anionic surfactant (AS) concentrations in wet up-flow anaerobic sludge blanket reactor (UASBR) sludges from five sewage treatment plants (STPs) were found to range from 4480 to 9233mgkg(-1)drywt. (average 7347mgkg(-1)drywt.) over a period of 18 months. After drying on sand drying beds (SDBs), AS in dried-stabilized sludges averaged 1452mgkg(-1)drywt., a reduction of around 80%. The kinetics of drying followed simple first-order reduction of moisture with value of drying constant (k(d))=0.051d(-1). Reduction of AS also followed first-order kinetics. AS degradation rate constant (k(AS)) was found to be 0.034d(-1) and half-life of AS as 20 days. The order of rates of removal observed was k(d)>k(AS)>k(COD)>k(OM) (drying >AS degradation>COD reduction>organic matter reduction). For the three applications of dried-stabilized sludges (soil, agricultural soil, grassland), values of risk quotient (RQ) were found to be <1, indicating no risk.     

天然沸石对溶液中氨氮吸附特性的研究

为了探讨天然沸石对NH4 的吸附规律,以浙江缙云出产的粒径为2~3.2mm的天然斜发沸石为实验材料,进行吸附等温线实验和吸附动力学实验。结果表明,实验沸石对NH4 的吸附等温线符合Langmuir公式,且对氨氮吸附量的极限值为1.624mol·kg-1;实验沸石对NH4 的吸附反应符合一级动力学方程,反应速率常数为0.1882h-1。通过监测溶液中各阳离子浓度的变化,可确定沸石晶体内与NH4 进行交换的主要离子为Ca2 和Na ,二者占交换总量的96%以上;在交换反应初期,出现了由于沸石晶体中的离子在固液两相中的再分配所造成的离子交换的不等量现象。     

酸性条件下H+ - Cu2+在红壤表面反应的能量特征

研究了酸性条件下H -Cu2 在红壤表面反应动力学的能量特征,结果表明:酸性条件下Cu2 的吸附分为快反应和慢反应两个阶段.用一级动力学方程拟合,Cu2 的最大吸附量随酸度的增加而显著下降,随温度的升高提前达到平衡.用双常数方程描述Cu2 在吸附点位能量分布的不均匀性,用扩散速率常数b计算,活化能(Eb*)随酸度的增加而增加,Cu2 扩散需要克服的能障变大;ΔH*值为正,温度升高可促进Cu2 的扩散;ΔS*均为负值,表明吸附反应使体系的有序度增加.原液pH值为3.8和3.3时,流出液的pH值高于原液,这是由于土壤的缓冲作用、土壤表面质子化和硫酸根专性吸附释放的羟基中和;反应初期H 消耗是快反应过程,反应后期H 对矿物的溶蚀为速率控制步骤.