The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals     

降低循环冷却水水耗的生产措施

为了有效降低循环冷却水系统补充水量、排污量,节约水处理剂的消耗、降低冷却水处理成本,关键在于提高循环水的浓缩倍数。本文对影响循环水浓缩倍数的因素进行了分析,总结了哈尔滨石化公司循环水场存在的问题。同时本文给出了提高循环水浓缩倍数的方法,上述方法能取得显著的环境效益和经济效益。     

Profile of Methane Concentrations in Soil and Atmosphere in Alpine Steppe Ecosystem on Tibetan Plateau

The methane concentration profile from -1.5m depth in soil to 32m height in air was measured in alpine steppe located in the permafrost area. Methane concentrations showed widely variations both in air and in soil during the study period. The mean concentrations in atmosphere were all higher than those in soil, and the highest methane concentration was found in air at the height of 16m with the lowest concentration occurring at the depth of 1.5m in soil. The variations of atmospheric methane concentrations did not show any clear pattern both temporally and spatially, although they exhibited a more steadystable state than those in soil. During the seasonal variations, the methane concentrations at different depths in soil were significantly correlated （R^2〉0.6） with each other comparing to the weak correlations （R^2〈0.2） between the atmospheric concentra- tions at different heights. Mean methane concentrations in soil significantly decreased with depth. This was the compositive influence of the decreasing production rates and the increasing methane oxidation rates, which was caused by the descent soil moisture with depth. Although the methane concentrations at all depths varied widely during the growing season, they showed very distinct temporal variations in the non-growing season. It was indicated from the literatures that methane oxidation rates were positively correlated with soil temperature. The higher methane concentrations in soil during the winter were determined by the lower methane oxidation rates with decreasing soil temperatures, whereas methane production rates had no reaction to the lower temperature. Relations between methane contribution and other environmental factors were not discussed in this paper for lacking of data, which impulse us to carry out further and more detailed studies in this unique area.     

NaCl和KCl对厌氧污泥抑制的动力学研究

在厌氧颗粒污泥和厌氧絮状污泥系统中,进行盐质量浓度(NaCl或KCl质量浓度,下同)对厌氧污泥抑制动力学的研究,得到不同拟合的COD降解动力学方程及参数.实验结果表明:当盐质量浓度为10～30 g/L时,KCl对厌氧污泥的COD比降解速率的抑制程度大于NaCl;当盐质量浓度由0 g/L增至10 g/L时,半速率常数逐渐增加;当盐质量浓度由10 g/L增至30 g/L时,半速率常数逐渐减小;在厌氧污泥系统中,NaCl抑制作用下的盐抑制常数高于KCl,且颗粒污泥的盐抑制常数高于絮状污泥.     

固态排渣煤粉炉NOx产生浓度影响因素偏相关分析

利用第一次全国污染源普查“火力发电行业产排污系数核算”工作中现场监测得到的数据,首次采用偏相关分析的方法,对固态排渣煤粉炉中机组规模、空气过剩系数、煤中挥发分和发电负荷率等因素对NOx产生浓度的影响进行定性分析,结论：NOx产生浓度与前三种因素存在显著的相关。而与发电负荷率的关系受锅炉是否采用低氮燃烧技术的影响。空气过剩系数越大,煤的挥发分越高,NOx产生浓度越低;采用低氮燃烧装置的锅炉中,机组规模越大,产生的NOx越少,且对于同一锅炉来说,NOx产生浓度随着发电负荷率的升高而增大;未采用燃烧控制的锅炉中,机组规模越大,NOx产生浓度越高,且与发电负荷率不相关。根据分析结果,提出了控制燃煤电厂固态排渣煤粉炉NOx排放的优化措施和建议。     

农药混配制剂环境风险评估现状与展望

本文综述了欧洲和美国农药混配制剂的环境风险评估方法。详细介绍了欧洲食品安全局(EFSA)评估体系中的2种方法,即,基础的"整体测试法"和近年来提倡的"基于组分的方法"。"基于组分的方法"的特点是以浓度加和模型(CA模型)作为默认假设进行初级评估,以独立作用模型(IA模型)等作为高级评估手段的农药混配制剂环境风险评估方法。此外,本文还介绍了模型偏差率(MDR)、毒性相似度及毒力单元(TU)等概念以及混配制剂风险评估流程。本文的目的旨在为建立我国农药混配制剂的环境风险评估方法体系提供参考。     

自动化前处理-气相色谱串联质谱法测定淡水鱼体中的有机磷阻燃剂

应用自动化前处理设备和气相色谱串联四级杆质谱仪建立了淡水鱼体中10种有机磷阻燃剂的检测方法。该方法先采用自动索氏提取仪进行样品的提取,再应用凝胶渗透色谱净化仪和florisil柱对提取液进行两级净化,最后用气相色谱串联四级杆质谱法(多反应监测模式)对样品中的有机磷阻燃剂(OPFRs)定性定量。实验表明,凝胶渗透色谱净化系统在以乙酸乙酯∶环己烷(1∶1,V/V)为流动相,流速为5.0 m L·min-1的条件下,收集OPFRs的最佳时间为900~1 680 s;方法的检出限为0.002~0.192 ng·g~(-1)湿重,加标水平为5.000 ng·g~(-1)湿重时,平均加标回收率为48.7%~122%,相对偏差除磷酸三乙酯(TEP)(17.7%)和磷酸三(1,3-二氯异丙基)酯(TDCP)(11.9%)外均小于10%。应用该方法测定采集于东江某污水处理厂入河排污口的鱼类样品时,回收率指示物(d27-TBP)的回收率为82.4%~114%,鱼类样品中∑OPFRs的浓度范围为nd~6.41 ng·g~(-1)湿重。     

Corynebacterium glutamicum as an indicator for environmental cobalt and silver stress–A proteome analysis

Cobalt and silver are toxic for cells, but mechanisms of this toxicity are largely unknown. Analysis of Corynebacterium glutamicum proteome from cells grown in control and cobalt or silver enriched media was performed by two dimensional gel electrophoresis (2DE) followed by mass spectrometry. Our results indicate that the cell adapted to cobalt stress by inducing five defense mechanisms: Scavenging of free radicals, promotion of the generation of energy, reparation of DNA, reparation and biogenesis of Fe-S cluster proteins and supporting and reparation of cell wall. In response to the detoxification of Ag⁺ many proteins were up-regulated, which involved reparation of damaged DNA, minimizing the toxic effect of reactive oxygen species (ROS) and energy generation. Overexpression of proteins involved in cell wall biosynthesis (1,4-alpha-glucan branching enzyme and nucleoside-diphosphate-sugar epimerase) upon cobalt stress and induction of proteins involved in energy metabolism (2-methylcitrate dehydratase and 1, 2-methylcitrate synthase) upon silver demonstrate the potential of these enzymes as biomarkers of sub-lethal Ag⁺ and Co toxicity.     

陶瓷膜污染过程分析与膜清洗方法优化

采用膜孔径为50 nm的陶瓷膜错流过滤方式,对碱性高浓度有机洗涤废水进行9个周期的膜通量衰减及反向脉冲清洗再生实验研究.通过设计膜污染阻力构成实验,测算膜污染总阻力及其构成比例.实验结果表明,膜固有阻力比例较低,浓差极化污染较弱,Rt和Rc+Rirt污染阻力稳定性较高,膜堵塞形式兼有孔内堵塞和滤饼过滤;选择质量分数0.1％的稀盐酸和0.2％的草酸溶液膜清洗效果均较好,清洗时间为3 min,脉冲时间和频率为3 s/5 s.