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.     

Arsenic residue in residential area after cleanup of pesticide illegal dumping sources in Thanh Hoa province,Central Vietnam

In Vietnam, Nicotex's site is perhaps the most infamous case of illegal disposal of toxic pesticides near residential areas. In 2013, affected villagers discovered illegal burials of around 1,000 tons of expired pesticides in the Nicotex factory. Organic pesticides were detected in illegal burial areas (IBAs) around 60 times greater than acceptable levels, but no attention was paid to contamination of metals, metalloids, and other classes of organic contaminants, which could be co-contaminants in pesticide formulation. This study assessed the contaminants remaining in the IBAs and surrounding residential areas two years after the source removal conducted in 2014. Additionally, a preliminary health risk assessment from residual contaminants was performed. Nine classes of chemicals including parental pesticides, inorganic and organic degradation byproducts, and metals and metalloids, comprising 123 chemicals were quantified in soil, sediment, and water samples from Nicotex and surrounding residential areas. Although concentrations of organic pesticides were below acceptable levels, arsenic contamination in the soil in a Nicotex IBA named NCT5 and Nap village (NV) exceeded the acceptable level. The enrichment factor and log-probability plot indicate that arsenic enrichment at NV is not from natural sources but is associated with arsenic contamination in NCT5. Arsenic may be a co-contaminant in pesticide manufacturing or an arsenical pesticide, such as monosodium methanearsonate. Arsenic found in NV was toxic arsenate for which the preliminary risk assessment yielded an unacceptable excess carcinogenic risk (1 × 10^?4). While all attention was paid to investigate and treat contamination of organic pesticides, it turns out that arsenic is the major existing threat which poses an unacceptable cancer risk in good agreement with the high cancer rate claimed by villagers near Nicotex. This justifies the need for further investigation of the extent of the arsenic contamination and restoration of the contaminated land.     

内循环活性炭生物流化床处理农药生产废水的试验研究

采用内循环活性炭生物流化床反应器处理某农药厂生产废水,通过试验研究了该反应器在室温条件下处理农药生产废水的性能.结果表明:当进水pH值控制在7.0～7.5、水力停留时间为6h、曝气量控制在使活性炭处于流化状态时,CODcr的去除率为50％,总氮的去除率为32.33％,同时可生化性明显提高,生物毒性有所降低.     

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。     

停留时间对滴滴涕农药热处理特性的影响研究

利用高温管式炉研究停留时间对滴滴涕农药热处理特性的影响。结果表明,600℃时ηDDT在15 min内迅速增长,在15 min后稳定在85%上下;900℃时,当停留时间≥15 min,ηDDT≥99%;1 200℃时,各时段的ηDDT≥99.9%。在滴滴涕农药残渣中,DDTs在600℃和900℃时的配比随停留时间的增加变化甚微,在1 200℃时,p,p’-DDD、DDT和o,p’-DDT分别占DDTs总量的比例随时间增加明显降低,p,p’-DDE则大幅增加。在尾气中,DDTs在600℃时的配比随停留时间的增加无明显变化,DDT为主要尾气残留物质,900℃时DDTs在尾气中配比变化混乱,1 200℃时,p,p’-DDE的比例随停留时间的增长迅速增加,并成为尾气中的主要DDTs残留物质。     

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.     

Identification of rice cultivars with low brown rice mixed cadmium and lead contents and their interactions with the micronutrients iron, zinc, nickel and manganese

Paddy fields in mining areas are usually co-contaminated by a cocktail of mixed toxic heavy metals (e.g., Cd and Pb in Pb/Zn mines). However, previous studies on rice cultivars screened for effective metal exclusion have mostly focused on individual metals, and have been conducted under pot-trial or hydroponic solution conditions. This study identified rice cultivars with both low Cd and Pb accumulation under Cd-and Pb-contaminated field conditions, and the interactions of the toxic elements Cd and Pb with the micronutrient elements Fe, Zn, Mn and Ni were also studied. Among 32 rice cultivars tested, there were significant differences in Cd (0.06-0.59 mg/kg) and Pb (0.25-3.15 mg/kg) levels in their brown rice, and similar results were also found for the micronutrient elements. Significant decreases in concentrations of Fe and Mn were detected with increasing Cd concentrations and a significant elevation in Fe, Mn and Ni with increasing Pb concentrations. A similar result was also shown by Cd and Ni. Three cultivars were identified with a combination of low brown rice Cd and Pb, high micronutrient and grain yield (Wufengyou 2168, Tianyou 196 and Guinongzhan). Present results suggest that it is possible to breed rice cultivars with low mixed toxic element (Cd, Pb) and high micronutrient contents along with high grain yields, thus ensuring food safety and quality.     

红松阔叶混交林林隙极端地面温度的地统计学分析

以小兴安岭原始红松阔叶混交林林隙为研究对象,采用网格法布点,通过对生长季内林隙各样点极端地面温度的连续观测,利用经典统计学和地统计学的方法分析并揭示了林隙极端地面温度的时空分布格局。研究结果表明:林隙极端地面温度不同空间样点之间存在异质性,而且异质性的强度、 尺度和空间结构组成随时间而改变,各月平均极端地面温度斑块形状复杂,最高地面温度大小顺序均为6月>7月>8月>9月,最低地面温度大小顺序为7月>8月>6月>9月,月平均地温的最大值和最小值分布位置不固定,同一月份地面最高温度的大小顺序是空旷地>林隙>郁闭林分,地面最低温度大小顺序是郁闭林分>林隙>空旷地。研究旨在为红松阔叶混交林的可持续经营提供基础数据和理论参考。