Enhanced triallyl isocyanurate (TAIC) degradation through application of an O3/UV process: Performance optimization and degradation pathways

• UV/O₃ process had higher TAIC mineralization rate than O₃ process. • Four possible degradation pathways were proposed during TAIC degradation. • pH impacted oxidation processes with pH of 9 achieving maximum efficiency. • CO₃^2– negatively impacted TAIC degradation while HCO₃^– not. • Cl^– can be radicals scavenger only at high concentration (over 500 mg/L Cl^–). Triallyl isocyanurate (TAIC, C₁₂H₁₅N₃O₃) has featured in wastewater treatment as a refractory organic compound due to the significant production capability and negative environmental impact. TAIC degradation was enhanced when an ozone(O₃)/ultraviolet(UV) process was applied compared with the application of an independent O₃ process. Although 99% of TAIC could be degraded in 5 min during both processes, the O₃/UV process had a 70%mineralization rate that was much higher than that of the independent O₃ process (9%) in 30 min. Four possible degradation pathways were proposed based on the organic compounds of intermediate products identified during TAIC degradation through the application of independent O₃ and O₃/UV processes. pH impacted both the direct and indirect oxidation processes. Acidic and alkaline conditions preferred direct and indirect reactions respectively, with a pH of 9 achieving maximum Total Organic Carbon (TOC) removal. Both CO₃^2– and HCO₃^– decreased TOC removal, however only CO₃^2– negatively impacted TAIC degradation. Effects of Cl^– as a radical scavenger became more marked only at high concentrations (over 500 mg/L Cl^–). Particulate and suspended matter could hinder the transmission of ultraviolet light and reduce the production of HO· accordingly.     

土壤及地下水有机污染的化学与生物修复

现阶段,工业的生产任务越来越繁重,因此在其进行生产的时候,制造的污染物也会越来越多。在这个对于环保极度关注的时代,本文对于被污染的土壤还有地下水实施修复展开讨论。     

Hierarchical pre-positioning of emergency resources for a chemical industrial parks concentrated area

Accidents in chemical industrial parks always cause fateful damage which can be reduced greatly by providing emergency resources sufficiently and timely. One effective way to enhance the emergency response capacity and agility is by pre-positioning of emergency resources for the potential accidents. The Yangtze River Delta of China is a large region where a large number of chemical industrial parks are concentrated. According to the distributing characteristics of demand points in this region, a mathematical model of hierarchical pre-positioning of emergency resources is proposed to ensure that accidents in all chemical industrial parks in this region can be responded timely and effectively. Considering accident domino effect and minimizing the total cost, the model gives optimal decisions of pre-positioning emergency resources, including the location and inventory of depots. The innovative hierarchical pre-positioning method greatly reduces the total cost in the premise of sufficient preparation for supplying emergency resources. Finally, in a visual graph of the Yangtze River Delta, the model is applied and the result shows its applicability.     

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     

Fluoride removal by a continuous flow electrocoagulation reactor

Long-term consumption of water containing excessive fluoride can lead to fluorosis of the teeth and bones. Electrocoagulation (EC) is an electrochemical technique, in which a variety of unwanted dissolved particles and suspended matter can be effectively removed from an aqueous solution by electrolysis. Continuous flow experiments with monopolar aluminium electrodes for fluoride removal were undertaken to investigate the effects of the different parameters such as: current density (12.5-50A/m(2)), flow rate (150-400 mL/min), initial pH (4-8), and initial fluoride concentration (5-25mg/L). The highest treatment efficiency was obtained for the largest current and the removal efficiency was found to be dependent on the current density, the flow rate and the initial fluoride concentration when the final pH ranged between 6 and 8. The composition of the sludge produced was analysed using the X-ray diffraction (XRD) spectrum. The strong presence of the aluminium hydroxide [Al(OH)(3)] in the above pH range, which maximizes the formation of aluminium fluoride hydroxide complex [Al(n)F(m)(OH)(3n-m)], is the main reason for defluoridation by electrocoagulation. The results obtained showed that the continuous flow electrocoagulation technology is an effective process for defluoridation of potable water supplies and could also be utilized for the defluoridation of industrial wastewater.     

Elimination of diclofenac from water using irradiation technology

The effluents of wastewater treatment plants, usually directly emitted to the environment, often contain the anti-inflammatory drug diclofenac (DCF). The paper investigates DCF elimination using irradiation technology. Hydroxyl radical and hydrated electron reactive intermediates resulting from water radiolysis effectively degrade DCF and strongly reduce the toxicity of the solutions. OH attaches to one of the rings of DCF, and hydroxylated molecules, 2,6-dichloroaniline and quinoid type compounds are the products. Hydrated electron adds to the chlorine atom containing ring, in the reaction quinoid type compounds and 4-chloroacridine form. At a 0.1 mM DCF concentration, a ∼1 kGy absorbed dose is needed for the degradation of DCF molecules, but for mineralization of the products (in presence of O₂) an order of magnitude higher dose is required.For irradiation of wastewater after biological treatment a ∼1 kGy dose is suggested. At this dose DCF and other drugs or metabolites present at μg L⁻¹ level are eliminated together with microorganism deactivation.     

春季生物作用对山地岩溶池水地球化学特征的影响

岩溶水文系统对外界环境变化敏感,使得岩溶区水质存在昼夜、小时甚至分钟等尺度的变化.许多地表水体都会经历p H值、溶解性气体、微量元素以及其他水化学指标的昼夜变化.重庆金佛山水房泉及受其补给的水池地处海拔2 050 m的山地岩溶区,具有温带气候特征.通过对水房泉泉水(以下简称泉水)及水池进行为期3 d的昼夜监测,以期探究春季生物作用对岩溶池水地球化学的影响.研究发现,在昼夜时间尺度上,泉水地球化学指标基本稳定,未表现出昼夜变化,池水地球化学指标化学表现出了昼夜波动,但水温、溶解氧、p H值、电导率等物理化学指标昼夜变化幅度较小.在不同的天气条件下,水温、溶解氧、Cl-等昼夜变化幅度存在差别;池水二氧化碳分压(p CO2)、Ca2+、DIC白天降低、晚上升高,方解石饱和指数(SIc)相反;这些指标的变化受控于温度、碳酸盐岩矿物的溶解与沉淀、水生植物光合作用与呼吸作用;通过亨利常数的计算,发现水温变化对p CO2变化的影响仅占0.79%~10.01%,水温、碳酸盐岩沉淀等物理因素对DIC损失量的贡献率为39%,水生植物光合作用的贡献率为61%.     

基于质谱技术的在线大气颗粒物来源与污染过程解析研究——以江苏省淮安市为例

通过大气细颗粒物实时在线源解析技术(质谱直接测量法)采集录入淮安市市区部分特征污染源排放成分谱,对淮安市大气细颗粒物进行在线源解析,获取高时间分辨的颗粒物源解析结果,分析颗粒物来源、季度变化和重污染天气的污染过程,评估形成重污染过程的污染影响因子和影响程度,为区域大气污染综合整治提供重要目标指向,同时也为淮安环境空气PM2.5重度污染实时预警与监控、大气污染源减排方案评估、污染事件监控等提供有效的在线监测技术平台.     

小飞扬草(Euphorbia thymifolia L.)中镉的亚细胞分布及化学形态

采用差速离心法和逐步提取法,分析Cd超积累植物小飞扬草根、茎、叶中Cd的亚细胞分布和化学形态.培养液中Cd浓度5mg/L和10 mg/L条件下,在小飞扬草根、茎、叶中,细胞壁和细胞膜是Cd主要的结合场所,含量分别占总量的47.1％～49.0％、39.7％～41.4％、42.9％～56.2％,其次是胞液组分,含量分别占37.5％～41.4％、28.2％～40.7％、35.2％～46.8％,细胞器组分中Cd含量较少.Cd在小飞扬草根、茎、叶中均以氯化钠提取态为主,含量分别占70.5％～84.8％、72.4％～83.0％、50.0％～74.8％.根部各提取态含量依次为CNaCl＞CHAC＞CEtOH＞CHCl＞CW＞CR,茎、叶中各提取态含量依次为CNaCl＞CHCI＞CHAC＞CEtOH＞CW＞CR.在小飞扬草中,Cd与细胞壁和细胞膜中的果胶酸和蛋白质等物质结合固定,而进入细胞的Cd大部分与有机酸络合而隔离于液泡内,这可能是小飞扬草忍耐并超积累Cd的机制.     

化工企业突发性环境污染事故的应急监测

化工企业突发性环境污染事故,具有污染毒性大,危害性强,后果严重等特性,及时有效地开展应急监测,可为应急处置和救援提供有力的保障。该文从前期准备、现场监测、数据上报等方面,探讨了如何做好应急监测工作。