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.     

异戊醇低压热解的同步辐射真空紫外光电离质谱研究

作为新兴生物燃料,大分子醇类燃料在低压下的火灾安全基础迫切需要得到深入研究。热解过程作为火灾过程的初始阶段直接控制着火过程,火灾中碳烟颗粒的产生也依赖于热解反应,因此可燃物的低压热解研究在其低压火灾基础研究中具有重要意义。利用同步辐射真空紫外光电离质谱方法研究了异戊醇在0.2atm下的流动反应器热解,探测到了20余种热解产物,包括烯丙基自由基和C_4H_8O、C_5H_8、C_6H_6等同分异构体,并测量了其摩尔分数。基于实验结果,对燃料分解路径和主要产物的生成及消耗路径进行了探讨。与本组之前正戊醇热解实验的对比表明,由于存在支链结构,异戊醇在热解中比正戊醇更容易产生戊烯、丁烯和丙烯,但更少地产生乙烯。此外,异戊醇在热解中能够生成更多的丙炔和丙二烯等环状化合物前驱体,令其苯和1,3-环戊二烯的生成量更高,表明异戊醇比正戊醇更易于生成多环芳烃和碳烟。     

A product analysis-based study on the mechanism of inflammable gas explosion suppression

To study the mechanism of the suppressing effect of Expanded Aluminium (EA) on the premixed gas explosion, premixed methane-air and propane-air gases were undergone explosion reaction in the presence of EA in a self-designed closed pipeline with the overpressures and the compositions, rates and sensitivities of products analyzed. The results showed that the 9.5% methane-air and 5% propane-air explosions produced peak pressures decreased by 79.3% and 65.6%, and residual methane and propane contents increased by 270% and 560% respectively than without EA. In addition, the results revealed that the explosions of propane in the presence of EA produced less methane and carbon oxides contents, but more ethylene and propylene contents. The simulation showed that H, O, and OH are the key factors affecting the rate of products. The product compositions, together with other parameters, suggested that EA decreased temperature, inhibited chain initiation and propagation reaction, but facilitated chain termination reaction by advancing and accelerating the gas phase and wall destruction reaction of radicals, especially collisions and concentration of key free radicals. This new research method based on the analysis of explosion products can be used for in-depth research into gas explosion features and shed light on the suppressing mechanism of EA in flammable gas explosion.     

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。     

Efficiency and degradation products elucidation of the photodegradation of mefenpyrdiethyl in water interface using TiO2 P-25 and Hombikat UV100

The photodegradation of mefenpyrdiethyl (MFD), an herbicide safener, was investigated in aqueous suspensions by using Degussa P-25 and Hombikat UV100 titanium oxide under simulated sunlight irradiation. The effects of initial concentration of the herbicide, pH, catalysts and hydrogen peroxide doses as well as their combinations were studied and optimized. Accordingly, the kinetic parameters were determined and the effectiveness of the processes was assessed by calculating the rate constants. A pseudo first-order kinetics was observed. Under experimental conditions, the degradation rate constants were strongly influenced using P-25 and no noticeable effect was observed for Hombikat UV100. DFT calculations with B3LYP/6-311+G(2d,p)//B3LYP/6-31+G(d,p) level of theory were performed to check whether significant conformational changes occur when the charge state of the MFD substrate changes and whether these changes could play a role in the dependency of photodegradation rate constant on the studied pH. High resolution mass spectrometry (FT-ICR/MS) was implemented to identify the main degradation products.     

O3/H2O2降解水中扑灭通效能研究

利用拟一级降解速率常数表征O3/H2O2对扑灭通(Prometon)的氧化效能,探讨了n(H2O2)/n(O3)、pH值、水质和碳酸氢根离子对去除的影响,对有机氧化产物进行了气相和液相质谱分析,以离子色谱法测定了反应过程中产生的NO3-,在此基础上对扑灭通降解途径进行了研究.结果表明,扑灭通初始浓度2 mg.L-1,反应温度25℃,O3投量13 mg.L-1时,最佳反应条件为n(H2O2)/n(O3)=0.7,体系pH为7～8;扑灭通在自来水中的去除效果好于纯水;HCO3-浓度>50 mg.L-1时,对扑灭通的氧化有明显的抑制作用.液质和气质的分析结果表明扑灭通并未开环,氧化过程中扑灭通三嗪环支链上的2个异丙基首先被氧化脱去,离子色谱检测到的NO3-是三嗪环支链胺基氧化的产物.     

杂质对废塑料裂解产物及污染物排放的影响

从垃圾中分选出的废塑料混有大量杂质,杂质对现有废塑料裂解工艺有直接的影响.针对这一问题,对混有厨余、纸、织物和渣土等杂质的废塑料裂解产物和污染物排放进行了研究.同时检测和分析了厨余、纸、织物和沙土等常见杂质所含N、Cl、S元素向裂解油、裂解气中的迁移规律.研究表明,厨余的混入将对裂解油的产物产生严重不利影响,如热值降低至27 MJ/kg,油品的含水率高达25%以及多环芳烃含量大大提高,因而应在分选过程中除去.厨余、织物和纸张等杂质的混入导致裂解气体中污染物浓度的显著上升.渣土的混入对气体产物有有利影响,对油品无明显不利影响.     

絮凝沉降处理乳业废水的研究

用硫酸铝PAM混合絮凝剂净化乳制品行业废水,寻找一种最佳的处理方案。通过多组实验显示：硫酸铝投入量280mg／L,pH值为6—7,水温20℃,搅拌速度为40～70r／min时,经处理的废水外观清晰、透明度高,COD去除率均在80％左右,对保障乳品行业的可持续发展起到科学的借鉴作用。     

温度对膜生物反应器运行特性及膜污染的影响

温度对膜生物反应器（MBR）污染物去除效果和膜污染速率都有很大的影响。采用两套相同的MBR蓑置在冬季运行,其中一套维持20℃的恒温,另一套水温与周围环境相同。对两套装置处理效果及膜污染速率进行对比,并通过反应器中溶解性微生物产物（SMF）、胞外聚合物（EPS）含量、污泥粒径分布扣膜面污染物的比较,分析温度对MBR运行的影响。研究结果表明膜对污染物的截留能有效补偿低温时微生物作用的不足,因此低温对出水水质并没有显著的影响。此外,低温时虽然SMP和EPS的释放增加,但并没有引起膜污来的加剧。相反地,低温时污泥粒径较高温时小,而粒径较大的颗粒更易沉积于膜表面,因此低温时膜面固体物质含量较低,膜污染速率反而比高温时低。     

O3/H2O2降解Atrazine效能研究

利用O3/H2O2降解莠去津,对氧化产物进行了色谱分析,以评价该体系降解莠去津效能.莠去津初始浓度2 mg/L,7.5mg/L的O3单独氧化去除率为27.2%;相同O3投量下,H2O2/O3摩尔比0.75时,5 min莠去津的去除率最高可达96.5%,表明H2O2/O3体系对莠去津的去除效果良好,降解速度快.以离子色谱对产物的离子进行分析,莠去津浓度下降的同时,硝酸根和氯离子浓度增高.GC-MS检测的产物和对LC-MS谱图的分析表明,有机产物中存在脱乙基、脱异丙基和脱氯莠去津,说明H2O2/O3并不能彻底氧化莠去津,因此工程中作为主要去除单元或突发性污染事件的应急手段可能还需要与活性炭等单元联用.