Determination of atmospheric hydroxyl radical by HPLC coupled with electrochemical detection

The hydroxyl radical (·OH) plays a central role in the oxidation and removal of many atmospheric compounds. Measurement of atmospheric·OH is very difficult because of its high reactivity and low atmospheric abundance. In this article, a simple and highly sensitive method, high performance liquid chromatography coupled with coulometric detection (HPLC-CD), was developed to determine·OH indirectly by determining its reaction products with salicylic acid (SAL), 2,3-dihydroxybenzoic acid (2,3-DHBA), and 2,5-dihydroxybenzoic acid (2,5-DHBA). Under the optimum conditions for its determination, 2,3-DHBA and 2,5-DHBA could be well separated and the detection limits for 2,3-DHBA were 3×10~(-10) mol/L and for 2,5-DHBA were 1.5×10~(-10) mol/L, which were lower than most previous reports. This method was also applied to measure atmospheric hydroxyl radical levels and demonstrated the feasibility in clean and polluted air.     

电-多相臭氧催化工艺深度处理焦化废水

本文采用新型电-多相臭氧催化（E-catazone）工艺深度处理焦化废水生化二级出水,开展工艺可行性研究.通过与O₃/TiO₂纳米花（TiO_2-NF）与O₃/TiO_2-NF/H₂O₂及单独电化学氧化工艺相比较,对E-catazone工艺技术优势及氧化机理进行探究.结果表明：在相同条件下（O₃浓度84mg/L）,电-多相臭氧催化获得的COD和TOC的去除率（分别为67.9%,50.0%）显著优于O₃/TiO_2-NF获得的去除率（25.8%,20.9%）,即便在O₃/TiO_2-NF体系中投加5g/L的H₂O₂以促进臭氧均相催化效果,但COD和TOC去除率也仅分别提高到63.6%,43.6%.     

Mechanism for the destruction of carbon tetrachloride and chloroform DNAPLs by modified Fenton's reagent

The destruction of a carbon tetrachloride DNAPL and a chloroform DNAPL was investigated in reactions containing 0.5 mL of DNAPL and a solution of modified Fenton's reagent (2M H2O2 and 5mM iron(III)-chelate). Carbon tetrachloride and chloroform masses were followed in the DNAPLs, the aqueous phases, and the off gasses. In addition, the rate of DNAPL destruction was compared to the rate of gas-purge dissolution. Carbon tetrachloride DNAPLs were rapidly destroyed by modified Fenton's reagent at 6.5 times the rate of gas purge dissolution, with 74% of the DNAPL destroyed within 24h. Use of reactions in which a single reactive oxygen species (hydroxyl radical, hydroperoxide anion, or superoxide radical anion) was generated showed that superoxide is the reactive species in modified Fenton's reagent responsible for carbon tetrachloride DNAPL destruction. Chloroform DNAPLs were also destroyed by modified Fenton's reagent, but at a rate slower than the rate of gas purge dissolution. Reactions generating a single reactive oxygen species demonstrated that chloroform destruction was the result of both superoxide and hydroxyl radical activity. Such a mechanism of chloroform DNAPL destruction is in agreement with the slow but relatively equal reactivity of chloroform with both superoxide and hydroxyl radical. The results of this research demonstrate that modified Fenton's reagent can rapidly and effectively destroy DNAPLs of contaminants characterized by minimal reactivity with hydroxyl radical, and should receive more consideration as a DNAPL cleanup technology.     

磁改性羊粪衍生ZVI-生物炭的制备及其活化过一硫酸盐降解AO7特性研究

以羊粪为原料，制备磁改性羊粪衍生ZVI-生物炭复合材料 （SMF₈₀₀），通过BET、SEM、XRD、N₂吸附-脱附等温线等对其表面形貌及晶体结构进行表征，并采用序批实验考查活化剂和过一硫酸盐 （PMS） 投加量、温度、溶液初始pH、无机阴离子等因素对AO7降解效率影响.结果表明，SMF₈₀₀拥有高度石墨化及多孔结构，在最佳条件下 （PMS=0.8 g·L^-1、SMF₈₀₀=0.5 g·L^-1、AO7=20 mg·L^-1、T=25 ℃），40 min内AO7能被完全降解，在弱酸条件下有利于脱色，且活化剂经过3次循环使用后仍具有良好的活化效率.猝灭实验和XPS测试结果表明，自由基 （SO4- ?、·OH、O₂^·- ） 和非自由基途径 （¹O₂） 协同作用于AO7的降解，其中以Fe⁰还原PMS产生SO4- ?的自由基途径占主导地位，以Fe⁰诱导碳电子、生物炭表面含氧官能团 （C-OH 和COOH） 激活PMS产生¹O₂为辅，而SMF₈₀₀石墨化及大量的sp²-C结构为电子转移提供良好的场所.综上，本研究设计制备了一种新型的生物炭基ZVI活化剂，以期为有机废水高效、低成本的处理方法提供新的技术支撑，同时也为粪源资源化利用提供新的途径.