Evaluation of photolysis and hydrolysis of pyraclostrobin in aqueous solutions and its degradation products in paddy water

This study evaluated the hydrolysis and photolysis kinetics of pyraclostrobin in an aqueous solution using ultra-high-performance liquid chromatography–photodiode array detection and identified the resulting metabolites of pyraclostrobin by hydrolysis and photolysis in paddy water using high-resolution mass spectrometry coupled with liquid chromatography. The effect of solution pH, metal ions and surfactants on the hydrolysis of pyraclostrobin was explored. The hydrolysis half-lives of pyraclostrobin were 23.1–115.5?days and were stable in buffer solution at pH 5.0. The degradation rate of pyraclostrobin in an aqueous solution under sunlight was slower than that under UV photolysis reaction. The half-lives of pyraclostrobin in a buffer solution at pH 5.0, 7.0, 9.0 and in paddy water were less than 12?h under the two light irradiation types. The metabolites of the two processes were identified and compared to further understand the mechanisms underlying hydrolysis and photolysis of pyraclostrobin in natural water. The extracted ions obtained from paddy water were automatically annotated by Compound Discoverer software with manual confirmation of their fragments. Two metabolites were detected and identified in the pyraclostrobin hydrolysis, whereas three metabolites were detected and identified in the photolysis in paddy water.     

Determination of the residue dynamics and dietary risk of thiamethoxam and its metabolite clothianidin in citrus and soil by LC-MS/MS

A modified quick, easy, cheap, effective, rugged and safe (QuEChERS) method was developed for the determination of thiamethoxam and its metabolite clothianidin in citrus (including the whole citrus, peel and pulp) and soil samples by liquid chromatography-tandem mass spectrometry. The sample was extracted with acetonitrile and purified with octadecylsilane. The detection limits of both compounds were 0.0001–0.0002?mg kg^–1, while the limit of quantification of thiamethoxam was 0.002?mg kg^–1 and the limit of quantitation of metabolites was 0.001?mg kg^–1. The recovery was 70.37%–109.76%, with inter-day relative standard deviations (RSD) (n?=?15) values ≤9.46% for the two compounds in the four matrices. The degradation curve of thiamethoxam in whole citrus and soil was plotted using the first-order kinetic model. The half-life of the whole citrus was 1.9–6.2?days, and the half-life of the soil was 3.9–4.2?days. The terminal residue of thiamethoxam (the sum of thiamethoxam and clothianidin, expressed as thiamethoxam) was found to be concentrated on the peel. The final residual amount of thiamethoxam in the edible portion (pulp) was less than 0.061?mg kg^–1. The risk quotient values were all below 1, indicating that thiamethoxam as a citrus insecticide does not pose a health risk to humans at the recommended dosage.     

页岩气加砂压裂高压管汇失效爆裂风险 控制措施研究与实践

随着页岩气平台井工厂化压裂施工启动,在大排量、高压力、长时间施工条件下,高压管汇失效爆裂大幅增加。为减少高压管汇在压裂过程中失效爆裂风险,运用故障假设、因果分析法从人的因素、物的因素、技术工艺、生产管理、工作环境5个方面分析事故的原因,提出了提升采购产品质量、修订完善高压管汇使用技术规范和管理制度、实施专业化管理、应用大数据管理高压管汇、优化现场地面高压管汇流程分配布局设计与联接工艺等高压管汇失效爆裂风险预防控制措施和失效后应急安全防护措施,建立了生命周期全过程、专业化的高压管汇失效爆裂防控与应急防护体系,实现风险可防受控。为页岩气压裂作业的安全提供了参考。     

不同级配垃圾焚烧底渣固化市政污泥工程特性分析

开展了（炉排炉和流化床炉）两种垃圾焚烧底渣与固化剂共同作用下固化市政污泥的工程特性研究。分析了两种底渣化学成份及物理级配上的差异,重点考察了在密封养护情况下,测定了不同底渣固化体的含水率、pH值、无侧限抗压强度及28d渗透系数等工程特性指标。研究结果表明：相同含量的两种底渣固化体含水率及pH相同,且含水率随底渣含量增加而降低,而pH值随底渣含量增加而增加;随着底渣含量增加,级配良好的炉排炉底渣固化体强度比级配不良的流化床底渣固化体强度从高8 kPa增加到30 kPa;受底渣级配的影响,炉排炉底渣固化体渗透系数随底渣含量增加而增大,而流化床底渣固化体渗透系数基本不变。级配良好的炉排炉底渣固化体工程特性优于级配不良的流化床底渣固化体,具有更强的骨架作用。研究成果为污泥及垃圾焚烧底渣填埋处置提供了科学借鉴。     

生物炭基固定化菌剂对石油类污染物的高效降解

以生物炭为载体,采用吸附法制备固定化菌剂,通过分析不同材料生物炭的结构差异,探讨了不同生物炭的结构在固定化中的影响机制。SEM和EDS分析表明,降解菌主要固定在生物炭表面。生物炭内含有C、N和P成分,能为降解菌提供营养物质。生物炭的多孔结构能促进石油污染物的降解。结果表明,经玉米芯和秸秆生物炭固定化后F-3、R-7及其混合菌的除油率显著提高,分别为41.7%和29.5%、52.5%和42.8%、63.8%和53.2%。玉米芯生物炭固定化菌剂的除油率比秸秆生物炭固定化菌剂高10.6%。玉米芯生物炭表面比秸秆生物炭粗糙,其固定的微生物量为4.2×1010 cfu·g-1,固定效率达71.2%;秸秆生物炭固定的微生物量为2.5×1010 cfu·g-1,固定效率为57.6%。固定化菌剂的最佳制备条件为：选择500℃下热解3 h的玉米芯生物炭为载体,微生物接种量为10%,载体投加量为10 g·L-1,置于35℃、130 r·min-1摇床中固定18 h。     

微波活化对Ca(OH)2孔隙结构及脱氯性能的影响

采用微波炉对一定质量的氢氧化钙样品进行活化，利用压汞仪考察了不同微波活化时间及脱氯反应前后的Ca(OH)2总比孔表面积、分段比表面积和孔径分布的变化，并在脱氯实验台上对脱氯效率进行实际测试。结果表明，微波活化存在一个最佳时间，在此时间内样品比孔表面积增大50%左右，而超过这一时间样品比表面积回复性减小；微波活化主要通过增加3～20 nm孔径段的微孔为样品提供更大比表面积；这些新增加的微孔在脱氯反应过程中被完全利用或消耗； 最佳活化时间下的微波活化使Ca(OH)₂在较低Ca/Cl摩尔比下获得更大脱氯效率，Ca/Cl摩尔比=4.1时，脱氯效率增加了20%。     

压力环境下活性污泥的耐盐驯化过程

通过逐步提高盐浓度的梯度盐度方法驯化耐盐活性污泥,采用加压-常压对比实验,探讨活性污泥耐盐驯化过程中,0.3 MPa的压力环境对有机物降解规律、污泥脱氢酶活性及胞外聚合物（EPS）含量的影响。结果表明,经耐盐驯化的活性污泥在5%的高盐度环境下仍可达到75%以上的有机物去除率;当驯化盐度达3.5%及以上,加压耐盐活性污泥有机物去除率及污泥脱氢酶活性均高于常压,其优势更为突出。耐盐驯化过程中活性污泥胞外聚合物（EPS）含量较稳定,加压系统EPS含量低于常压,这可能是加压活性污泥法可以实现原位污泥减量的重要原因之一。     

Influence of metal oxides on PCDD/Fs formation from pentachlorophenol

Chlorophenols (ClPhs) are considered as important precursors for PCDD/Fs formation. The influences of series of metal oxides including MgO, Al2O3, CaO, BaO, TiO2, V2O5, MnO2, Fe2O3, Co3O4, CuO, Ag2O, ZnO, HgO, SnO, PbO, La2O3, CeO2, and Eu2O3 on PCDD/Fs formation from pentachlorophenol (PCP) were investigated in a laboratory-scale reactor. The results indicated that most of the above metal oxides have obvious suppressing effects on the total amount of PCDD/Fs formation from precursor PCP except for CuO, ZnO, MnO2, TiO2 and Co3O4 with promotion effects at 280 degrees C for 2 h. Although MgO, Al2O3, Fe2O3, PbO, La2O3 and Eu2O3 could reduce the amount of octachlorinated dibenzo-p-dioxin (OCDD), they promote the formation of more toxic 1,2,3,4,6,7,8-HpCDD at the same time. The total suppressing efficiencies of several metal oxides including CaO, BaO, PbO, Ag2O, HgO and SnO which have lower Z/r (charge to radius ratio) <2 are all over 90%. The theories of generalized acid-base and atomic parameter (Z/r) were used to speculate the effecting mechanisms. The factors including time and temperature on suppressing efficiencies of CaO, BaO and PbO have also been studied in the present paper. The results showed that the total suppressing efficiencies of CaO, BaO and PbO increase with the increase of heated time and temperature.     

几种印染助剂对壳聚糖稳定纳米铁去除酸性品红的影响

以氯化铁为铁源,硼氢化钠为还原剂,壳聚糖为稳定剂,采用液相还原法制备壳聚糖稳定纳米铁（CS-nZⅥ）;研究了印染废水中常见助剂NaNO₃、Na₂SO₄、NaH₂PO₄、K₂Cr₂O₇、EDTA二钠盐存在下,超声波辅助CS-nZⅥ对酸性品红（AF）降解的影响。结果表明,反应15 min,0.01 g CS-nZⅥ对25 mL、100 mg/L AF的去除率高达99.9%;各种助剂的存在使得纳米铁表面不同程度失活,阻碍反应的进行,使得AF的去除率下降。NaNO₃、K₂Cr₂O₇、EDTA二钠盐与纳米铁发生反应,与AF存在明显的竞争作用。重复利用实验表明,CS-nZⅥ重复利用7次仍具有一定的反应活性。此外,CS-nZⅥ对加标（50 mg/L）实际废水中AF的去除率达到99%以上,表明CS-nZⅥ是一种潜在的环境修复材料。     

城市固体废物好氧生物反应器填埋方式的实验研究

MSW（城市固体废物）生物反应器型填埋是一种较新颖的方法.在系统分析现有填埋方法优缺点的基础上,对其加以改进,将强制通风好氧和渗滤液循环2种方式有机地结合在一起,构建了MSW好氧生物反应器.考察了NH3、CH4、CO2、pH和温度等因素,并监测分析了渗滤液中的COD、BOD5、Zn^2＋、NH4^＋和NO3^-等指标,旨在研究其中垃圾的降解及渗滤液中COD、BOD5、Zn^2＋、NH4^＋和NO3^-的去除情况,探讨该生物反应器对垃圾和渗滤液相关参数的作用机理.结果表明,该反应器对渗滤液中COD、BOD5、NO3^-的去除率分别达到96.34%、94.58%和99.9%,对其中的Zn^2＋也有较好的脱除效果.