三种不同氧化工艺条件下对乙酰氨基酚的降解过程与产物毒性变化研究
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摘要
作为一种典型的药物,对乙酰氨基酚(acetaminophen,ACE)由于其广泛存在和潜在毒性引起重要关注.本研究比较了氯化、紫外/过氧化氢(UV/H2O2)和紫外/氯(UV/Cl)三种工艺对ACE的降解情况.结果表明,3种工艺中,UV/Cl和UV/H2O2工艺均能完全降解ACE,其中UV/Cl工艺的降解速率更快. UV/H2O2和UV/Cl工艺降解能用准一级动力学模型很好地拟合,它们的反应动力学常数(kobs,ACE)分别为0.1343 min-1和0.0657 min-1(293K,p H=7).通过p H实验发现,酸性条件下UV/Cl工艺效果更好,而p H对UV/H2O2工艺没有显著影响.相比而言,ACE的矿化比降解困难许多,在60 min后其矿化率最高仅为5.60%(UV/Cl工艺).在UV/Cl工艺降解过程中,检测到12种主要的转化产物,其转化途径主要包括羟基化、氯取代、二聚化、脱酰化和氧化反应.通过发光菌实验对溶液毒性进行分析,3种工艺条件下ACE溶液的毒性都会有所升高,其中氯化工艺最为突出.每种工艺中不同的反应活性物质导致了ACE转化产物的不同,最终使得溶液毒性不同程度地升高.
As a typical pharmaceutical,acetaminophen( ACE) has aroused critical concerns owing to its widespread existence and potential toxicity. In this work,ACE degradation by chlorination,UV/H_2O_2 and UV/chlorine processes was inverestigated. The results showed that ACE could be degraded completely by both UV/Cl and UV/H_2O_2 processes,and the degradation rate by UV/Cl was higher among the two processes. The degradations processed by UV/H_2O_2 and UV/chlorine were well fitted by pseudo first order kinetics with the rate constant( kobs,ACE) of 0. 1343 min-1and0.0657 min-1( 293 K,pH= 7),respectively. The p H experiments indicated that,compared to other conditions,the degradation efficiencies of chlorination and UV/chlorine at acidic pH were much higher. Differently,the degradation efficiency of UV/H_2O_2 was slightly changed with pH. Themineralization of ACE was much more difficult than the degradation,and the highest mineralization efficiency was only 5. 60%( UV/Cl process) after 60 minutes. Twelve possible transformation products( TPs) were detected in UV/chlorine process,and the transformation path was mainly included hydroxylation,chlorine substitution,dimerization,deacylation and oxidation. Luminescent bacteria experiments were introduced to evaluate the toxicity of the solutions. It was found that the toxicity of the ACE solutions all increased after the three processes,in which chlorination was the most prominent. The different reactive species in each process caused ACE to transform to different TPs,ultimately leading to the different degrad of increases of the solution toxicity.
As a typical pharmaceutical,acetaminophen( ACE) has aroused critical concerns owing to its widespread existence and potential toxicity. In this work,ACE degradation by chlorination,UV/H_2O_2 and UV/chlorine processes was inverestigated. The results showed that ACE could be degraded completely by both UV/Cl and UV/H_2O_2 processes,and the degradation rate by UV/Cl was higher among the two processes. The degradations processed by UV/H_2O_2 and UV/chlorine were well fitted by pseudo first order kinetics with the rate constant( kobs,ACE) of 0. 1343 min-1and0.0657 min-1( 293 K,pH= 7),respectively. The p H experiments indicated that,compared to other conditions,the degradation efficiencies of chlorination and UV/chlorine at acidic pH were much higher. Differently,the degradation efficiency of UV/H_2O_2 was slightly changed with pH. Themineralization of ACE was much more difficult than the degradation,and the highest mineralization efficiency was only 5. 60%( UV/Cl process) after 60 minutes. Twelve possible transformation products( TPs) were detected in UV/chlorine process,and the transformation path was mainly included hydroxylation,chlorine substitution,dimerization,deacylation and oxidation. Luminescent bacteria experiments were introduced to evaluate the toxicity of the solutions. It was found that the toxicity of the ACE solutions all increased after the three processes,in which chlorination was the most prominent. The different reactive species in each process caused ACE to transform to different TPs,ultimately leading to the different degrad of increases of the solution toxicity.
引文
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[9] HUERTA-FONTELA M,GALCERAN M T,VENTURA F. Occurrence and removal of pharmaceuticals and hormones through drinking water treatment[J]. Water Research,2011,45(3):1432-1442.
[10] LIU Q,CHEN Z B,WEI D B,et al. Acute toxicity formation potential of benzophenone-type UV filters in chlorination disinfection process[J]. Journal of Environmental Sciences,2014,26(2)440-447.
[11] LEE Y,VON G U. Oxidative transformation of micropollutants during municipal wastewater treatment:comparison of kinetic aspects of selective(chlorine,chlorine dioxide,ferrate VI,and ozone)and non-selective oxidants(hydroxyl radical)[J]. Water Research,2010,44(2):555-566.
[12] KATSOYIANNIS I A,CANONICA S,VON G U. Efficiency and energy requirements for the transformation of organic micropollutants by ozone,O3/H2O2 and UV/H2O2.[J]. Water Research,2011,45(13):3811-3822.
[13] HUBER M M,CANONICA S,GUNYOUNG A,et al. Oxidation of pharmaceuticals during ozonation and advanced oxidation processes[J].Environmental Science&Technology,2003,37(5):1016-1024.
[14] YANG Y,PIGNATELLO J J,MA J,et al. Comparison of halide impacts on the efficiency of contaminant degradation by sulfate and hydroxyl radical-based advanced oxidation processes(AOPs)[J]. Environmental Science&Technology,2014,48(4):2344-2351.
[15] XIANG Y,FANG J,SHANG C. Kinetics and pathways of ibuprofen degradation by the UV/chlorine advanced oxidation process[J]. Water Research,2016,90:301-308.
[16] PENG M,DU E,LI Z,et al. Transformation and toxicity assessment of two UV filters using UV/H2O2process[J]. Science of the Total Environment,2017,s 603-604:361-369.
[17] FAIRBAIRN D J,KARPUZCU M E,ARNOLD W A,et al. Sources and transport of contaminants of emerging concern:A two-year study of occurrence and spatiotemporal variation in a mixed land use watershed[J]. Science of the Total Environment,2016,551-552(3):605-613.
[18] YANG X,SUN J,FU W,et al. PPCP degradation by UV/chlorine treatment and its impact on DBP formation potential in real waters[J].Water Research,2016,98:309-318.
[19]杨波,王社平,张林军,等.紫外线消毒技术在再生水处理中的应用[J].中国给水排水,2010,26(19):81-83.YANG B,WANG S P,ZHANG L J,et al. Application of UV disinfection technology to reclaimed wastewater treatment[J]. China Water&Wastewater,2010,26(19):81-83(in Chinese).
[20] ANDREOZZI R,CAPRIO V,INSOLA A,et al. The oxidation of metol(N-methyl-p-aminophenol)in aqueous solution by UV/H2O2,photolysis[J]. Water Research,2000,34(2):463-472.
[21] FANG J,FU Y,SHANG C. The roles of reactive species in micropollutant degradation in the UV/free chlorine system[J]. Environmental Science&Technology,2014,48(3)1859-1868.
[22] WATTS M J,LINDEN K G. Chlorine photolysis and subsequent OH radical production during UV treatment of chlorinated water[J]. Water Research,2007,41(13):2871-2878.
[23] GUO K,WU Z,SHANG C,et al. Radical Chemistry and Structural Relationships of PPCP degradation by UV/Chlorine treatment in simulated drinking water[J]. Environmental Science&Technology,2017,51(18):10431-10439.
[24] FEI C,ZHANG M,YUAN S,et al. Transformation of acetaminophen during water chlorination treatment:kinetics and transformation products identification[J]. Environmental Science&Pollution Research,2016,23(12):12303-12311.
[25] FENG S,ZHANG X,LIU Y. New insights into the primary phototransformation of acetaminophen by UV/H2O2:Photo-Fries rearrangement versus hydroxyl radical induced hydroxylation.[J]. Water Research,2015,86:35-45.
[26] LI Y,SONG W,FU W,et al. The roles of halides in the acetaminophen degradation by UV/H2O2,treatment:Kinetics,mechanisms,and products analysis[J]. Chemical Engineering Journal,2015,271:214-222.
[27] LI Y,PAN Y,LIAN L,et al. Photosensitized degradation of acetaminophen in natural organic matter solutions:The role of triplet states and oxygen.[J]. Water Research,2017,109:266-273.
[28] LAURENTIIS E D,MAURINO V,MINERO C,et al. Could triplet-sensitised transformation of phenolic compounds represent a source of fulvic-like substances in natural waters?[J]. Chemosphere,2013,90(2):881-884.
[29] LAURENTIIS E D,PRASSE C,TERNES T A,et al. Assessing the photochemical transformation pathways of acetaminophen relevant to surface waters:Transformation kinetics,intermediates,and modelling[J]. Water Research,2014,53(8):235-248.
[2] TRAN N H,LI J,HU J,et al. Occurrence and suitability of pharmaceuticals and personal care products as molecular markers for raw wastewater contamination in surface water and groundwater[J]. Environmental Science&Pollution Research International,2014,21(6):4727-4740.
[3] DAUGHTON C G,TERNES T A. Pharmaceuticals and personal care products in the environment:Agents of subtle change[J].Environmental Health Perspectives,1999,107(6):907-938.
[4]李明月,孙倩,于昌平.药品和个人护理用品在固体基底中的检测方法和分布现状[J].环境化学,2015,34(1):97-110.LIM,SUN Q,YU C. Detection and occurrence of pharmaceuticals and personal care products in the solid matrix:A review[J].Environmental Chemistry,2015,34(1):97-110(in Chinese).
[5] BRAUSCH J M,RAND G M. A review of personal care products in the aquatic environment:Environmental concentrations and toxicity.[J]. Chemosphere,2011,82(11):1518-1532.
[6]其布日,秦传玉,董军.废水中苯并噻唑类化合物的污染行为与控制原理分析[J].环境化学,2017,36(11):2498-2510.QI B,QIN C,DONG J. Occurence and mitigation of benzothiazoles in wastewater[J]. Environmental Chemistry,2017,36(11):2498-2510(in Chinese).
[7]曹飞,袁守军,张梦涛,等.臭氧氧化水溶液中对乙酰氨基酚的机制研究[J].环境科学,2014,35(11):4185-4191.CAO F,YUAN S J,ZHANG M T,et al.[Impact factors and degradation mechanism for the ozonation of acetaminophen in aqueous solution].[J]. Environmental Science,2014,35(11):4185-4191(in Chinese).
[8]刘奇,魏东斌,陈振斌,等.医药品和个人护理用品(PPCPs)类污染物氯化转化行为研究进展[J].环境化学,2012,31(3):278-286.LIU Q,WEI. A review on transformation behaviors of PPCPs in chlorination process[J]. Environmental Chemistry,2012,31(3):278-286(in Chinese).
[9] HUERTA-FONTELA M,GALCERAN M T,VENTURA F. Occurrence and removal of pharmaceuticals and hormones through drinking water treatment[J]. Water Research,2011,45(3):1432-1442.
[10] LIU Q,CHEN Z B,WEI D B,et al. Acute toxicity formation potential of benzophenone-type UV filters in chlorination disinfection process[J]. Journal of Environmental Sciences,2014,26(2)440-447.
[11] LEE Y,VON G U. Oxidative transformation of micropollutants during municipal wastewater treatment:comparison of kinetic aspects of selective(chlorine,chlorine dioxide,ferrate VI,and ozone)and non-selective oxidants(hydroxyl radical)[J]. Water Research,2010,44(2):555-566.
[12] KATSOYIANNIS I A,CANONICA S,VON G U. Efficiency and energy requirements for the transformation of organic micropollutants by ozone,O3/H2O2 and UV/H2O2.[J]. Water Research,2011,45(13):3811-3822.
[13] HUBER M M,CANONICA S,GUNYOUNG A,et al. Oxidation of pharmaceuticals during ozonation and advanced oxidation processes[J].Environmental Science&Technology,2003,37(5):1016-1024.
[14] YANG Y,PIGNATELLO J J,MA J,et al. Comparison of halide impacts on the efficiency of contaminant degradation by sulfate and hydroxyl radical-based advanced oxidation processes(AOPs)[J]. Environmental Science&Technology,2014,48(4):2344-2351.
[15] XIANG Y,FANG J,SHANG C. Kinetics and pathways of ibuprofen degradation by the UV/chlorine advanced oxidation process[J]. Water Research,2016,90:301-308.
[16] PENG M,DU E,LI Z,et al. Transformation and toxicity assessment of two UV filters using UV/H2O2process[J]. Science of the Total Environment,2017,s 603-604:361-369.
[17] FAIRBAIRN D J,KARPUZCU M E,ARNOLD W A,et al. Sources and transport of contaminants of emerging concern:A two-year study of occurrence and spatiotemporal variation in a mixed land use watershed[J]. Science of the Total Environment,2016,551-552(3):605-613.
[18] YANG X,SUN J,FU W,et al. PPCP degradation by UV/chlorine treatment and its impact on DBP formation potential in real waters[J].Water Research,2016,98:309-318.
[19]杨波,王社平,张林军,等.紫外线消毒技术在再生水处理中的应用[J].中国给水排水,2010,26(19):81-83.YANG B,WANG S P,ZHANG L J,et al. Application of UV disinfection technology to reclaimed wastewater treatment[J]. China Water&Wastewater,2010,26(19):81-83(in Chinese).
[20] ANDREOZZI R,CAPRIO V,INSOLA A,et al. The oxidation of metol(N-methyl-p-aminophenol)in aqueous solution by UV/H2O2,photolysis[J]. Water Research,2000,34(2):463-472.
[21] FANG J,FU Y,SHANG C. The roles of reactive species in micropollutant degradation in the UV/free chlorine system[J]. Environmental Science&Technology,2014,48(3)1859-1868.
[22] WATTS M J,LINDEN K G. Chlorine photolysis and subsequent OH radical production during UV treatment of chlorinated water[J]. Water Research,2007,41(13):2871-2878.
[23] GUO K,WU Z,SHANG C,et al. Radical Chemistry and Structural Relationships of PPCP degradation by UV/Chlorine treatment in simulated drinking water[J]. Environmental Science&Technology,2017,51(18):10431-10439.
[24] FEI C,ZHANG M,YUAN S,et al. Transformation of acetaminophen during water chlorination treatment:kinetics and transformation products identification[J]. Environmental Science&Pollution Research,2016,23(12):12303-12311.
[25] FENG S,ZHANG X,LIU Y. New insights into the primary phototransformation of acetaminophen by UV/H2O2:Photo-Fries rearrangement versus hydroxyl radical induced hydroxylation.[J]. Water Research,2015,86:35-45.
[26] LI Y,SONG W,FU W,et al. The roles of halides in the acetaminophen degradation by UV/H2O2,treatment:Kinetics,mechanisms,and products analysis[J]. Chemical Engineering Journal,2015,271:214-222.
[27] LI Y,PAN Y,LIAN L,et al. Photosensitized degradation of acetaminophen in natural organic matter solutions:The role of triplet states and oxygen.[J]. Water Research,2017,109:266-273.
[28] LAURENTIIS E D,MAURINO V,MINERO C,et al. Could triplet-sensitised transformation of phenolic compounds represent a source of fulvic-like substances in natural waters?[J]. Chemosphere,2013,90(2):881-884.
[29] LAURENTIIS E D,PRASSE C,TERNES T A,et al. Assessing the photochemical transformation pathways of acetaminophen relevant to surface waters:Transformation kinetics,intermediates,and modelling[J]. Water Research,2014,53(8):235-248.
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