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.     

微波-Fenton对沼液中抗生素和激素的高级氧化

采用微波强化Fenton氧化处理系统,研究H2O2浓度、Fe2+浓度、初始pH、微波辐射时间和微波辐射功率对沼液中喹乙醇、土霉素、四环素及金霉素降解效果的影响.结果发现,采用微波强化Fenton氧化降解沼液中抗生素与激素的最优条件是:H2O2浓度为40 mg/L、Fe2+浓度为12 mg/L、初始pH为4、微波辐射时间为2 min、微波辐射功率为中火(445W),沼液中喹乙醇、土霉素、四环素、金霉素和COD的去除率分别达到67％、93％、91％、88％和46％.在水浴条件下,与单独微波辐射和单独Fenton相比,微波强化Fenton氧化有明显的优越性.     

微波热解城市污水污泥的H2S释放影响因素研究

利用微波热解城市污水污泥是实现污泥无害化、减量化和资源化的有效出路之一,但热解过程中产生的恶臭气体(如H2S等)也会对大气环境造成严重的影响.以微波热解城市污水污泥10 min所收集的气体为研究对象,研究了热解终温、污泥含水率、升温速率及矿物催化剂种类4个因素对热解过程中H2S产量的影响.结果表明,随着热解终温的升高,城市污水污泥微波热解过程中的H2S产量逐渐上升,800℃时H2S产量为5.86 mg/g(以干污泥计,下同);含水率在50％～80％时,随着含水率的增加,城市污水污泥微波热解过程中的H2S产量逐渐上升,当含水率增至90％时,污泥出现了泥水分层现象,致使后续热解反应无法进行,故没有H2S产生;升温速率越快,热解反应的活化能越高,反应不易进行,H2S产量降低;添加矿物催化剂能有效固硫,且雷尼镍基催化剂的效果更好,热解终温为800℃时的H2S产量为4.15 mg/g,较不添加矿物催化剂时降低约30％;可通过铜铁吸收法和活性炭吸附两步工艺对热解产生的H2S加以吸收处理,处理后的H2S排放浓度满足《恶臭污染物排放标准》(GB 14554-93)中的厂界一级标准限值.     

Microwave/SPME method to quantify pesticide residues in tomato fruits

A new analytical method using focused microwave-assisted extraction (FMAE), coupled with solid phase micro-extraction (SPME), has been elaborated to determine 25 pesticides used in tomato cultivation. Microwave energy was used for a fast and controlled heating of solvent to selectively extract compounds. Calibration curves were plotted from blank tomato samples spiked at different concentrations with standards. A linear response was obtained between 10 and 1000 μ g/Kg for pyrethroids and between 0.1 and 5000 μ g/Kg for other compounds. For all studied substances, the resulting correlation coefficient (r²) was greater than 0.99. Limits of detection (LOD) and quantification (LOQ) were measured lower than 8 and 25 μ g/Kg, respectively. The relative standard deviation (RSD) was determined below 15% for all pesticides. Field incurred tomato samples were used to validate the new FMAE/SPME method. Observed analysis results by using this technique were in good agreement compared to those obtained by two accredited trading laboratories using traditional methods. Four tomato samples, bought in a local market, were also tested with the FMAE/SPME method.     

微波活化煤矸石反应活性及胶凝性能

研究了微波辐照对煤矸石反应活性及胶凝性能影响,通过XRD、IR等表征手段,分析了微波辐照煤矸石和煤矸石水泥的微观结构,结果表明,煤矸石经微波辐照可脱去煤矸石中的自由水和其矿物的结构水,并破坏了煤矸石矿物中牢固的Si—O和Al—O键结构,提高了SiO2、Al2O3的可溶性,提高煤矸石的反应活性和胶凝性能.煤矸石微波辐照的时间在8 min较为适宜,以30％煤矸石替代水泥时,经8 min微波辐照煤矸石的水泥净浆体28 d抗压强度为47.6 MPa,比原煤矸石的水泥净浆体高23.2 MPa.     

微波辅助Fe-H2O2联合处理罗丹明B废水

对微波辅助Fe-H2O2联合处理罗丹明B废水进行了研究,分别考察了废水pH、H2O2加入量、铁粉加入量、初始罗丹明B质量浓度以及反应时间等因素对罗丹明B去除率的影响。实验结果表明,对于100mg/L的罗丹明B废水,当加入50mg/L铁粉、10.0mL/LH2O2,反应12min后,罗丹明B去除率达到98.7%,并且拓宽了反应的pH范围。     

微波辐照技术修复氯丹污染土壤

采用微波辐照技术修复氯丹污染土壤。以α-氯丹和γ-氯丹的去除率为评价指标,采用正交实验设计确定土壤中氯丹去除的最佳微波辐照条件。实验结果表明,当微波辐照强度为5.83W/g、微波辐照时间为20min、土壤含水率为15%时,土壤中氯丹的去除效果最好,去除率达到85%以上。微波辐照技术简单高效,易于控制,且无二次污染,具有可行性,可作为修复氯丹污染土壤的新方法。     

城市污泥微波干化工艺及干化特性研究

采用微波和烘箱结合及全程烘箱2种方式对城市污泥干化进行对比研究,考察了不同粒径、微波干化预处理、预处理时间及烘箱温度对污泥干燥特性的影响。结果表明,同一温度条件下,微波预处理时间越长,污泥干化速率越快。最优条件下,全程烘箱污泥达到最大干化速率的含水率为77%。微波干燥污泥具有时间短、干燥速率大的特点,微波和烘箱结合对比全程烘箱干化速率高且能耗低。     

磷酸微波活化多孔生物质炭对亚甲基蓝的吸附特性简

以甘蔗渣为原料,采用微波辅助H₃PO₄活化法制备富含含氧酸官能团的中孔生物质炭。通过扫描电子显微镜SEM、傅立叶变换红外光谱FT-IR等技术对生物质炭物理化学性质进行表征,并通过静态实验法,探讨炭样对亚甲基蓝的吸附行为及热力学性质。结果表明,H₃PO₄活化制备蔗渣生物质炭的适宜条件为浸渍比1：1,烘干时间10 h,活化功率900 W,活化时间22 min,在此条件下制得的生物质炭得率为39.2%,碘值为817 mg/g,亚甲基蓝值为229 mg/g,为国家一级品标准的1.7倍。红外光谱分析表明,炭样表面以羟基、羰基、羧基等酸性官能团为主。静态吸附实验表明,Freundlich方程与Redlich-Peterson方程能较好地描述等温吸附行为,表现为优惠吸附。热力学研究表明,吸附吉布斯自由能（ΔG⁰）<0,说明吸附反应是自发过程,而吸附标准焓变（ΔH⁰）>70 KJ/mol,表明亚甲基蓝在制备炭样上的吸附是吸热反应,升温有利于吸附,且化学反应在吸附过程中发挥了重要作用。     

酸性条件下微波改性活性碳纤维对Pb(Ⅱ)的吸附

采用微波辐照的方法,在混酸条件下对活性碳纤维(ACF)进行改性,制备得到一种改性活性碳纤维(M-ACF).通过小试吸附实验考察了微波功率、溶液pH值对M-ACF吸附Pb(Ⅱ)的影响.通过扫描电子显微镜(SEM)、红外光谱(FTIR)、电子能谱(EDX)等技术对ACF和M-ACF进行表征.结果表明,M-ACF表面的羧基等酸性含氧官能团增多,纤维长度变短且表面粗糙化.当M-ACF的投加量为10 mg、含铅溶液初始浓度为50 mg/L、pH为6、吸附时间为24 h、吸附温度为308 K时,M-ACF对Pb(Ⅱ)的吸附量高达248.5 mg/g.吸附过程符合准二级动力学模型和Langmuir等温吸附模型;热力学参数表明吸附为吸热、自发的过程.