Determination of 27 pharmaceuticals and personal care products (PPCPs) in water: The benefit of isotope dilution

• Isotope dilution method was developed for the determination of 27 PPCPs in water. • The established method was successfully applied to different types of water samples. • The correction effect of corresponding 27 ILSs over 70 d was investigated. • Benefit of isotopic dilution method was illustrated for three examples. Pharmaceuticals and personal care products (PPCPs) are a unique group of emerging and non-persistent contaminants. In this study, 27 PPCPs in various water samples were extracted by solid phase extraction (SPE), and determined by isotope dilution method using liquid chromatography coupled to tandem triple quadruple mass spectrometer (LC-MS/MS). A total of 27 isotopically labeled standards (ILSs) were applied to correct the concentration of PPCPs in spiked ultrapure water, drinking water, river, effluent and influent sewage. The corrected recoveries were 73%–122% with the relative standard deviation (RSD)<16%, except for acetaminophen. The matrix effect for all kinds of water samples was<22% and the method quantitation limits (MQLs) were 0.45–8.6 ng/L. The developed method was successfully applied on environmental water samples. The SPE extracts of spiked ultrapure water, drinking water, river and wastewater effluent were stored for 70 days, and the ILSs-corrected recoveries of 27 PPCPs were obtained to evaluate the correction ability of ILSs in the presence of variety interferences. The recoveries of 27 PPCPs over 70 days were within the scope of 72%–140% with the recovery variation<37% in all cases. The isotope dilution method seems to be of benefit when the extract has to be stored for long time before the instrument analysis.     

Research on the degradation mechanism of pyridine in drinking water by dielectric barrier discharge

Pyridine, an important chemical raw material, is widely used in industry, for example in textiles,leather, printing, dyeing, etc. In this research, a dielectric barrier discharge(DBD) system was developed to remove pyridine, as a representative type of nitrogen heterocyclic compound in drinking water. First, the influence of the active species inhibitors tertiary butanol alcohol(TBA),HCO_3~-, and CO_3~(2-)on the degradation rate of pyridine was investigated to verify the existence of active species produced by the strong ionization discharge in the system. The intermediate and final products generated in the degradation process of pyridine were confirmed and analyzed through a series of analytical techniques, including liquid chromatography–mass spectrometry(LC–MS), high performance liquid chromatography(HPLC), ion chromatography(IC), total organic carbon(TOC) analysis, ultraviolet(UV) spectroscopy, etc. The results showed that the degradation of pyridine was mainly due to the strong oxidizing power of ozone and hydroxyl radical produced by the DBD system. Several intermediate products including 3-hydroxyl pyridine, fumaric acid, 2, 3-dihydroxypyridine, and oxalic acid were detected. Nitrogen was removed from the pyridine molecule to form nitrate. Through analysis of the degradation mechanism of pyridine, the oxidation pathway was deduced. The study provided a theoretical and experimental basis for the application of DBD strong ionization discharge in treatment of nitrogen heterocyclic compounds in drinking water.     

单光子/光电子在线质谱实时分析聚氯乙烯热分解/燃烧产物

实验室研制了低能光电子磁场增强电离(MEPEI)和单光子电离(SPI)复合电离源,该电离源具有电离化合物范围宽、碎片离子少、质谱图简单等优点,结合飞行时间质谱(TOF-MS)实现了聚氯乙烯(PVC)热分解/燃烧产物的在线分析.针对不同的目标化合物,MEPEI/SPI复合电离源通过调节电离区电场强度,可以快速在SPI和SPI-MEPEI之间切换.PVC热分解/燃烧产物中电离能大于光子能量(10.60 eV)的HCl和CO2(12.74 eV、13.77 eV)利用MEPEI模式电离;而烯烃、二氯乙烯、苯系物、氯苯、苯乙烯、茚满及萘系物等可通过SPI-MEPEI复合模式电离.通过实时监测PVC主要燃烧产物的信号强度随温度的变化趋势可推断出,PVC燃烧产物主要是通过两种机制生成:①250～370℃时,PVC发生脱氯及分子内环化反应,产生大量的HCl、苯和萘;②380～510℃时,PVC发生分子间交联反应,生成烷基芳烃,如甲苯和二甲苯/乙苯等.实验结果表明,SPI/SPI-MEPEI复合离子源TOF-MS分析速度快,应用范围广,在在线分析中具有广泛的应用前景.     

基于生命周期的产品碳足迹评价与核算分析

近年来,越来越多的企业对其产品进行碳足迹评价,评价方法主要采用产品碳足迹评价标准提供的碳计量方程,如GHG Protocol、ISO14064、PAS 2050、TS Q 0010等。在介绍相关评价标准的基础上,分析了产品碳足迹的评价步骤,最后利用河北盛华化工有限公司生产的PVC产品为例,给出了基于生命周期的B2B模式的产品碳足迹评价的案例。为企业及相关机构开展碳足迹评价提供借鉴作用。     

水产品中甲氰菊酯残留的ELISA快速检测

为快速检测水产品中甲氰菊酯的残留,应用水溶性碳化二亚胺(EDC)法将甲氰菊酸与牛血清白蛋白(BSA)和卵清蛋白(OVA)偶联,合成了甲氰菊酯的人工免疫抗原和包被抗原.免疫抗原经紫外扫描和聚丙烯酰胺电泳验证构建成功,用此抗原免疫试验兔子,获得了甲氰菊酯的多克隆抗体.经检测,抗体对甲氰菊酯具有较好的特异性和灵敏性.在此基础上建立了水产品中甲氰菊酯残留的间接ELISA检测法.理想的甲氰菊酯-OVA包被抗原质量浓度为1.6 mg/L,酶标二抗(羊抗兔IgG-HRP)的稀释度为1∶1000,多抗的稀释度为1∶3 200,最适检测范围为20～200 μg/kg,在实际样品检测时的最低检出限为20 μg/kg,接近或达到气相色谱法的测定水平,但检测速度大大提高,可在3 h内完成近百个样品的分析,适合甲氰菊酯的快速检测.     

廊坊市环保产业发展现状与市场需求分析

针对目前廊坊市环保产业发展现状及存在的问题,以及今后一段时间内环保产品市场的需求进行了分析,并提出了一些建议。     

Formation pathways of brominated products from benzophenone-4 chlorination in the presence of bromide ions

The brominated products, formed in chlorination treatment of benzophenone-4 in the presence of bromide ions, were identified, and the formation pathways were proposed.Under disinfection conditions, benzophenone-4 would undertake electrophilic substitution generating mono- or di-halogenated products, which would be oxidized to esters and further hydrolyzed to phenol derivatives. The generated catechol intermediate would be transformed into furan-like heterocyclic product. The product species were p H-dependent,while benzophenone-4 elimination was chlorine dose-dependent. When the chlorination treatment was performed on ambient water spiked with benzophenone-4 and bromide ions, most of brominated byproducts could be detected, and the acute toxicity significantly increased as well.     

煤气负压管道裂纹的修补

介绍了河南天宏焦化公司采用可赛新金属修补系列产品,对煤气负压管道裂纹进行修补,取得了良好效果,避免了煤气负压管道普通焊补作业的危险性和停机检修对生产造成的诸多不利因素,实现了煤气负压管道补漏作业的安全高效.同时,对可赛新金属修补系列产品的技术性能作了介绍.     

豆制品加工废水处理工程设计分析

豆制品加工废水有机物和悬浮物浓度较高,水量及水质波动大,且容易发酸发臭。浙江某豆制品生产企业采用化学沉淀+SBR生化工艺对废水进行处理,出水水质达到《污水综合排放标准》GB8978-1996三级标准。该工艺操作简便,运行稳定,处理效率高,适合中小规模豆制品企业废水的处理。     

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.