紫外活化过硫酸盐降解二苯甲酮-4的动力学影响及降解机理与风险评价
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摘要
活化PS(过硫酸盐)氧化工艺对于降解水中新兴微污染物具有潜在应用价值.为研究活化PS体系对BPs(二苯甲酮类)有机防晒剂的降解性能,以BP4(二苯甲酮-4)为研究对象,采用UV/PS(紫外活化过硫酸盐)工艺降解BP4,比较单一UV、单一PS和UV/PS 3种工艺对BP4的去除效果,考察各因素对UV/PS工艺去除BP4动力学的影响,同时探究BP4降解机理并进行风险评价.结果表明:BP4降解过程符合准一级反应动力学模型;最佳PS投加量为1. 0 mmol/L,反应30 min后BP4去除率可达94%,增加PS投加量或降低初始c(BP4)均可促进BP4降解,无机阴离子(HCO3-和Cl-)对BP4降解均有抑制作用,酸性条件有利于BP4降解;基于HPLC-MS/MS鉴定出8种中间产物,并提出降解路径,费氏弧菌毒性试验和ECOSAR v1. 10软件预测表明,UV/PS工艺降解BP4过程中生成的中间产物比母物质毒性更高.研究显示,UV/PS工艺可有效去除BP4,但其中间产物可能会造成潜在的生态风险,后续需进一步深入研究.
Activated persulfate( PS) oxidation process has the potential application value for the degradation of emerging micro pollutants(EMs) in water. BP4(benzophenone-4) was selected as a representative benzophenone compound. The degradation of BP4 by UV alone,PS alone and UV/PS( UV-activated persulfate) process was compared. The effects of the process parameters were further investigated. The degradation mechanisms and risk assessment of BP4 degradation were also discussed. The results showed that the pseudo-first-order kinetics model fit the BP4 degradation data well. With the optimal dose of 1. 0 mmol/L PS,the removal of BP4 reached 94% in 30 min by UV/PS process. The increasing PS dose and the decreasing initial BP4 molar concentration could accelerate the degradation of BP4. The presence of HCO3-and Cl-had an inhibition effect on BP4 degradation,while acidic conditions were favorable for BP4 degradation. Eight degradation intermediates of BP4 were identified by HPLC-MS/MS,and the degradation pathway was also proposed. Luminescent bacteria toxicity test and ECOSAR v1.10 software prediction revealed that the potential aquatic toxicity of the intermediates was significantly higher than that of the parent BP4. In summary,the UV/PS process could effectively remove BP4 in water. However,the intermediates generated during the UV/PS process may still pose potential risks,and need to be further investigated.
Activated persulfate( PS) oxidation process has the potential application value for the degradation of emerging micro pollutants(EMs) in water. BP4(benzophenone-4) was selected as a representative benzophenone compound. The degradation of BP4 by UV alone,PS alone and UV/PS( UV-activated persulfate) process was compared. The effects of the process parameters were further investigated. The degradation mechanisms and risk assessment of BP4 degradation were also discussed. The results showed that the pseudo-first-order kinetics model fit the BP4 degradation data well. With the optimal dose of 1. 0 mmol/L PS,the removal of BP4 reached 94% in 30 min by UV/PS process. The increasing PS dose and the decreasing initial BP4 molar concentration could accelerate the degradation of BP4. The presence of HCO3-and Cl-had an inhibition effect on BP4 degradation,while acidic conditions were favorable for BP4 degradation. Eight degradation intermediates of BP4 were identified by HPLC-MS/MS,and the degradation pathway was also proposed. Luminescent bacteria toxicity test and ECOSAR v1.10 software prediction revealed that the potential aquatic toxicity of the intermediates was significantly higher than that of the parent BP4. In summary,the UV/PS process could effectively remove BP4 in water. However,the intermediates generated during the UV/PS process may still pose potential risks,and need to be further investigated.
引文
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[26] LIANG Chenju,WANG Z S,MOHANTY N.Influences of carbonate and chloride ions on persulfate oxidation of trichloroethylene at20℃[J].Science of the Total Environment,2006,370(2/3):271-277.
[27] LIU Yiqing,HE Xuexiang,FU Yongsheng,et al. Kinetics and mechanism investigation on the destruction of oxytetracycline by UV-254 nm activation of persulfate[J]. Journal of Hazardous Materials,2016,305:229-239.
[28] ROMERO A,SANTOS A,VICENTE F,et al. Diuron abatement using activated persulphate:effect of p H,Fe(Ⅱ)and oxidant dosage[J].Chemical Engineering Journal,2010,162(1):257-265.
[29] PENG Mingguo,DU Erdeng,LI Zhihong,et al.Transformation and toxicity assessment of two UV filters using UV/H2O2process[J].Science of the Total Environment,2017,603/604:361-369.
[30]刘辉.典型二苯甲酮类紫外防晒剂的毒性效应与两种氧化隆解机理研究[D].南京:南京大学,2015:67-73.
[2] KUMAR A,XAGORARAKI I. Pharmaceuticals,personal care products and endocrine-disrupting chemicals in U. S. surface and finished drinking waters:a proposed ranking system[J]. Science of the Total Environment,2010,408(23):5972-5989.
[3]王樱凝,崔迪,庞长泷,等.水中PPCPs的污染现状及其控制技术研究进展[J].中国给水排水,2015,31(24):25-29.WANG Yingning,CUI Di,PANG Changlong,et al. Pollution status and control technologies of pharmaceuticals and personal care products:a review[J].China Water&Wastewater,2015,31(24):25-29.
[4] LIU Jinlin,WONG Minghung. Pharmaceuticals and personal care products(PPCPs):a review on environmental contamination in China[J].Environment International,2013,59(3):208-224.
[5] KRAUSE M,KLIT A,BLOMBERG-JENSEN M,et al.Sunscreens:are they beneficial for health? an overview of endocrine disrupting properties of UV-filters[J]. International Journal of Andrology,2012,35(3):424-436.
[6]李立平,魏东斌,李敏,等.有机紫外防晒剂内分泌干扰效应研究进展[J].环境化学,2012,31(2):150-156.LI Liping,WEI Dongbin,LI Min,et al.Review on endocrine effects of organic UV filters[J]. Environmental Chemistry,2012,31(2):150-156.
[7]刘欢,王朝英,吴立冬,等.环境中二苯甲酮类紫外稳定剂的风险评估研究进展[J].食品安全质量检测学报,2017,8(3):838-844.LIU Huan,WANG Chaoying,WU Lidong,et al. Research progress on risk assessment of benzophenone-type UV filters in environment[J].Journal of Food Safety&Quality,2017,8(3):838-844.
[8]魏东斌,赵慧敏,杜宇国.二苯甲酮类紫外防晒剂发光菌急性毒性及QSAR研究[J].生态毒理学报,2017(3):234-242.WEI Dongbin,ZHAO Huimin,DU Yuguo.Acute toxicity and QSAR studies on benzophenone-type UV filters to photobacterium[J].Asian Journal of Ecotoxicology,2017(3):234-242.
[9] WU Minghong,XIE Dengguo,XU Gang,et al. Benzophenone-type UV filters in surface waters:an assessment of profiles and ecological risks in Shanghai,China[J]. Ecotoxicology and Environmental Safety,2017,141:235-241.
[10] TSUI M M,LEUNG H W,WAI T C,et al.Occurrence,distribution and ecological risk assessment of multiple classes of UV filters in surface waters from different countries[J]. Water Research,2014,67:55-65.
[11] JURADO A,GAGO-FERRERO P,VAZQUEZ-SUNE E,et al.Urban groundwater contamination by residues of UV filters[J].Journal of Hazardous Materials,2014,271:141-149.
[12] GE Deming,ZENG Zequan,AROWO M,et al. Degradation of methyl orange by ozone in the presence of ferrous and persulfate ions in a rotating packed bed[J]. Chemosphere,2015,146:413-418.
[13] WALDEMER R H,TRATNYEK P G,JOHNSON R L,et al.Oxidation of chlorinated ethenes by heat-activated persulfate:kinetics and products[J]. Environmental Science&Technology,2007,41(3):1010-1015.
[14]李社锋,王文坦,邵雁,等.活化过硫酸盐高级氧化技术的研究进展及工程应用[J].环境工程,2016,34(9):171-174.LI Shefeng,WANG Wentan,SHAO Yan,et al.Progress in advanced oxidation technology of activated persulfate and its engineering application[J].Environmental Engineering,2016,34(9):171-174.
[15]李丽,刘占孟,聂发挥.过硫酸盐活化高级氧化技术在污水处理中的应用[J].华东交通大学学报,2014(6):114-118.LI Li,LIU Zhanmeng,NIE Fahui. Research of activating persulfate oxidation technology in sewage disposal[J]. Journal of East China Jiaotong University,2014(6):114-118.
[16]安继斌,夏春秋,陈红宇,等.UVA/Fe3O4活化过硫酸盐降解阿特拉津[J].环境科学研究,2018,31(1):130-135.AN Jibin,XIA Chunqiu,CHEN Hongyu,et al. Activation of persulfate by irradiated magnetite:implications for abatement of atrazine in aqueous solution[J]. Research of Environmental Sciences,2018,31(1):130-135.
[17] AN Dong,WESTERHOFF P,ZHENG Mengxin,et al.UV-activated persulfate oxidation and regeneration of NOM-saturated granular activated carbon[J].Water Research,2015,73:304-310.
[18] GHALY M Y,FARAH J Y,FATHY A M. Enhancement of decolorization rate and COD removal from dyes containing wastewater by the addition of hydrogen peroxide under solar photocatalytic oxidation[J].Desalination,2007,217(1):74-84.
[19] NETA P,HUIE R E,ROSS A B. Rate constants for reactions of inorganic radicals in aqueous-solution[J]. Journal of Physical and Chemical Reference Data,1988,17(3):1027-1284.
[20] XIE Pengchao,MA Jun,LIU Wei,et al. Impact of UV/persulfate pretreatment on the formation of disinfection byproducts during subsequent chlorination of natural organic matter[J]. Chemical Engineering Journal,2015,269:203-211.
[21] SAPOZHNIKOVA Y,HEDGESPETH M,WIRTH E,et al.Analysis of selected natural and synthetic hormones by LC-MS-MS using the US EPA method 1694[J]. Analytical Methods,2011,3(5):1079-1086.
[22] FERRER I,ZWEIGENBAUM J A,THURMAN E M.Analysis of 70environmental protection agency priority pharmaceuticals in water by EPA method 1694[J].Journal of Chromatography A,2010,1217(36):5674-5686.
[23] CARD M L,GOMEZ-ALVAREZ V,LEE W H,et al.History of EPI suiteTMand future perspectives on chemical property estimation in US toxic substances control act new chemical risk assessments[J].Environmental Scicece:Process&Impacts,2017,19(3):203-212.
[24] MARK G,MAN N S,SCHUCHMANN H P,et al.The photolysis of potassium peroxodisulphate in aqueous solution in the presence of tert-butanol:a simple actinometer for 254 nm radiation[J]. Journal of Photochemistry and Photobiology A:Chemistry,1990,55(2):157-168.
[25]郭佑罗,关小红,高乃云,等.紫外/过硫酸盐工艺降解水中氯贝酸的研究[J].中国环境科学,2016,36(7):2014-2019.GUO Youluo,GUAN Xiaohong,GAO Naiyun,et al. Kinetics of clofibric acid degradation by UV/persulfate system in aqueous solution[J]. China Environmental Science,2016,36(7):2014-2019.
[26] LIANG Chenju,WANG Z S,MOHANTY N.Influences of carbonate and chloride ions on persulfate oxidation of trichloroethylene at20℃[J].Science of the Total Environment,2006,370(2/3):271-277.
[27] LIU Yiqing,HE Xuexiang,FU Yongsheng,et al. Kinetics and mechanism investigation on the destruction of oxytetracycline by UV-254 nm activation of persulfate[J]. Journal of Hazardous Materials,2016,305:229-239.
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[29] PENG Mingguo,DU Erdeng,LI Zhihong,et al.Transformation and toxicity assessment of two UV filters using UV/H2O2process[J].Science of the Total Environment,2017,603/604:361-369.
[30]刘辉.典型二苯甲酮类紫外防晒剂的毒性效应与两种氧化隆解机理研究[D].南京:南京大学,2015:67-73.