The use of nanovermiculite catalyst in the study of removal of the organic load and degradation of atrazine via ozone process in RPB reactor

Abstract

The main objective of this study is the degradation of a synthetic solution of atrazine by a modified vermiculite catalyzed ozonation, in a rotating packed bed (RPB) reactor. A 0.5?L RPB reactor was used to perform the experiments, using a Central Composite Design (CCD) response surface to construct the quadratic model based on the factors: pH, catalyst concentration and reactor rotation frequency. The response variable was the removal of the organic load measured in terms of Chemical Oxygen Demand (COD). After the complete quadratic model was constructed through the response surface, the COD degradation process had an optimal removal of 41% under the following conditions: pH 8.0, rotation of 1150?rpm and catalyst concentration 0.66?g L^?1.     

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.     

计算毒理学在内分泌干扰物筛选上的应用和展望

内分泌干扰物通过干扰内分泌系统导致多种疾病,如生殖疾病、肥胖症甚至癌症。然而,面对环境中大量潜在的内分泌干扰物,传统的体外、体内评估方法由于成本高、耗时长等问题,难以实现内分泌干扰物的高通量筛查。计算毒理学逐渐发展成为被美国环保局(Environmental Protection Agency,EPA)、经济合作与发展组织(Organization for Economic Co-operation and Development,OECD)等机构所推荐的内分泌干扰物筛选与预测方法。本文综述了计算毒理学在内分泌干扰物筛选上的进展,主要包括分子对接和分子动力学模拟的应用,并对有害结局路径(adverse outcome pathway,AOP)的方法进行介绍和展望。     

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.     

光电化学法处理水体中腐殖酸的初步研究

结合９０年代欧美学者提出了高级化学氧化过程（Ａｄｖａｎｃｅｄｃｈｅｍｉｃａｌｏｘｉｄａｔｉｏｎｐｒｏｃｅｓｓ，ＡＯＰ）原理，提出了并建立了一套光电化学联用的新用于处理难以生物降解的腐殖酸废水，实验表明，在通电１ｈ加光条件下（Ｉ＝０．２Ａ）总有碳（ＴＯＣ）去除率达到９０％，色度去除率达到９５％。     

Heterogeneous water phase catalysis as an environmental application: a review

Catalytic water phase processes as an environmental application is a relatively novel subject with tremendous potential in the near future. This review of 120 references presents the wide scale of heterogeneous water phase applications studied mainly within past five years. Both oxidation and hydrogenation processes are included as well as TiO₂ assisted photocatalysis. According to the references, heterogeneous catalysis is developing rapidly. New bimetallic catalysts and supports with higher surface area have improved catalytic efficiency in both oxidation and hydrogenation processes. It also seems that study on use of some waste materials such as red mud as catalyst is a very progressive field. On the whole, the chemical aspects are pretty well known, but the catalyst durability, and in many cases activity as well, has to be improved.     

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     

基于生物导向的水生态健康监测及评估概述

环境监测是水生态健康监测与评估的重要环节,基于物理、化学监测的传统水质监测通常仅能提供独立的数据信息,不能全面、直观地反映水环境状况。基于生物等生命体导向的水生态监测通过生物对环境的响应,能够直接反应复杂水体状况,在水环境健康监测与评估中占据重要地位。基于病原微生物、指示生物介绍了生物监测中的常规生物指标,总结了包括藻类、无脊椎动物和鱼类在内的常见指示生物在不同类型污染水体中的环境指示作用。从生物毒性效应出发介绍了常用的毒性效应测试方法、分析了污染物在不同生物学水平的响应,从而指明生物毒性效应在水环境健康评估中的发展优势。再从生态完整性角度阐述了生态完整性评价的一般方法和新兴分子生物学技术在水生态健康评估中的应用。重点指出环境毒理学和分子生物学在水环境监测的优势,以期为更加科学精确地进行水生态健康监测预警提供支撑。     

羟基自由基检测技术方法概述

高级氧化技术（ AOP）是一种新兴的氧化处理技术，而羟基自由基（·OH）是高级氧化技术中一种重要的中间体，具有很强的氧化能力，是一种高效环保的氧化剂，近年将其用于烟气中有害气体氧化脱除的技术方法多有研究。列举了羟基自由基的检测方法，包括：电子自旋捕集法（ ESR）、高效液相色谱法（ HPLC）、分光光度法、荧光光度法（ FD）等方法，这些方法对科研工作者检测羟基自由基提供了一定的技术支持，并对今后的研究方向起到一定的指导作用。     

O3/UV降解水中的乙酸和硝基苯

利用O3 /UV和O3/H2O2降解了水中的乙酸,结果表明,在相同条件下处理60min后,O3/UV对乙酸的去除率仅比单独臭氧化处理提高了3%,而O3/H2O2在此条件下完全降解乙酸.O3/UV在处理硝基苯过程中却显示较好的氧化降解能力,通过分析表明,硝基苯降解过程中所产生的副产物H2O2对有机物的去除具有很重要的作用.因此,O3/UV氧化降解能力的提高可能有2方面的原因,紫外光对有机物的活化作用;中间产物H2O2催化臭氧分解产生了高活性的羟基自由基. 单独紫外光催化臭氧分解产生羟基自由基的效率极低.