二氧化氯对典型磺胺类抗生素的降解机制
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摘要
磺胺类药物(sulfonamides,SAs)是十分常见且应用广泛的一类抗生素,由其引起的生态环境风险备受关注.本文研究了典型磺胺类药物磺胺醋酰(sulfacetamide,SFA)及磺胺噻唑(sulfathiazole,STZ)与二氧化氯(ClO_2)的反应机制及影响因素.结果表明,SFA及STZ与ClO_2的反应符合二级动力学模型,在pH 5.0和25℃条件下,反应二级速率常数分别为505.35 L·(mol·s)-1及1382.85 L·(mol·s)~(-1).温度、pH及水质条件等因素均对反应过程存在影响.SFA及STZ与ClO_2的反应机制受ClO_2投加量影响,在ClO_2过量时([ClO_2]∶[SAs]≥5),SAs得到一定程度的矿化,SFA及STZ与ClO_2的反应产物主要为乳酸、草酸及富马酸等有机酸;在ClO_2浓度较低时([ClO_2]∶[SAs]≤3),SAs与ClO_2发生亲电取代反应,生成毒性较强的氯代产物.
Sulfonamides( SAs) is a common and widely used class of antibiotics,which have received increasing attention due to their ecological and environmental risks. This study investigated the degradation mechanisms and influencing factors of the reaction of two sulfonamides( sulfonamide sfa,sulfathiazole STZ) with chlorine dioxide( ClO_2).The results showed that the reaction of SFA and STZ with chlorine dioxide conformed to the second-order kinetics model,and the reaction rate constants were 505.35 L·( mol·s)-1and 1382.85 L·( mol·s)-1,respectively,under the condition of pH 5.0 and 25 ℃. Temperature,p H,humic acid and water quality influenced the reaction rates.The transformation mechanisms of SFA and STZ were dependent on the dosage of ClO_2.With excess of ClO_2( [ClO_2]∶[SAs]≥5),SAs had a certain degree of mineralization,and the transformation products of SFA and STZ were mainly organic acids such as lactic acid,oxalic acid and fumaric acid. While at lower concentrations of ClO_2( [ClO_2]∶[SAs] ≤ 3),electrophilic substitution reaction occurred,which resulted in the generation of toxic chlorinated products in the solution.
Sulfonamides( SAs) is a common and widely used class of antibiotics,which have received increasing attention due to their ecological and environmental risks. This study investigated the degradation mechanisms and influencing factors of the reaction of two sulfonamides( sulfonamide sfa,sulfathiazole STZ) with chlorine dioxide( ClO_2).The results showed that the reaction of SFA and STZ with chlorine dioxide conformed to the second-order kinetics model,and the reaction rate constants were 505.35 L·( mol·s)-1and 1382.85 L·( mol·s)-1,respectively,under the condition of pH 5.0 and 25 ℃. Temperature,p H,humic acid and water quality influenced the reaction rates.The transformation mechanisms of SFA and STZ were dependent on the dosage of ClO_2.With excess of ClO_2( [ClO_2]∶[SAs]≥5),SAs had a certain degree of mineralization,and the transformation products of SFA and STZ were mainly organic acids such as lactic acid,oxalic acid and fumaric acid. While at lower concentrations of ClO_2( [ClO_2]∶[SAs] ≤ 3),electrophilic substitution reaction occurred,which resulted in the generation of toxic chlorinated products in the solution.
引文
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[18] APHA. Standard methods for the examination of water and wastewater[M]. Washington:American Public Health Association(APHA),1995,481-486.
[19] WANG P,HE Y L,HUANG C H. Reactions of tetracycline antibiotics with chlorine dioxide and free chlorine[J]. Water Research,2011,45(4):1838-1846.
[20]范志云,黄君礼,王鹏,等.二氧化氯氧化水中苯胺的反应动力学及机理研究[J].环境科学,2004,25(1):95-98.FAN Z Y,HUANG J L,WANG P,et al. Kinetics and mechanism of Aniline oxidation with chlorine dioxide in water[J]. Environmental Science,2004,25(1):95-98(in Chinese).
[21]黄君礼.水消毒剂和处理剂:二氧化氯[M].北京:化学工业出版社,2010.HUANG J L. Water disinfectant and treatment agent:Chlorine dioxide[M]. Beijing:Chemical Industry Press,2010(in Chniese).
[22] WANG Y,LIU H,LIU G,et al. Kinetics for diclofenac degradation by chlorine dioxide in aqueous media:Influences of natural organic matter additives[J]. Journal of the Taiwan Institute of Chemical Engineers,2015,56:131-137.
[23]周舒月,张玉先,杨建强,等.二氧化氯预氧化处理微污染水源水及影响因素研究[J].给水排水,2008,34(5):150-153.ZHOU S Y,ZHANG Y X,YANG J Q,et al. Study on the treatment of micro polluted source water by preoxidation with chlorine dioxide and its influencing factors[J].China Water and Wastewater,2008,34(5):150-153(in Chinese).
[2] HIRSCH R,TERNES T,HABERER K,et al. Occurrence of antibiotics in the aquatic environment[J]. Science of the Total Environment,1999,225(1-2):109-118.
[3] KARTHIKEYAN K G,MEYER M T. Occurrence of antibiotics in wastewater treatment facilities in Wisconsin,USA[J]. Science of the Total Environment,2006,361(1-3):196-207.
[4] BROWN K D,KULIS J,THOMSON B,et al. Occurrence of antibiotics in hospital,residential,and dairy effluent,municipal wastewater,and the Rio Grande in New Mexico[J]. Science of the Total Environment,2006,366(2-3):772-783.
[5] SARMAH A K,MEYER M T,BOXALL A B. A global perspective on the use,sales,exposure pathways,occurrence,fate and effects of veterinary antibiotics(VAs)in the environment[J]. Chemosphere,2006,65(5):725-759.
[6] NAVALON S,ALVARO M,GARCIA H. Reaction of chlorine dioxide with emergent water pollutants:Product study of the reaction of threeβ-lactam antibiotics with ClO2[J]. Water Research,2008,42(8-9):1935-1942.
[7] WANG P,HE Y L,HUANG C H. Oxidation of fluoroquinolone antibiotics and structurally related amines by chlorine dioxide:Reaction kinetics,product and pathway evaluation[J]. Water Research,2010,44(20):5989-5998.
[8]崔崇威,黄君礼.二氧化氯与苯酚的单电子转移反应机理[J].环境化学,2003,22(6):560-563.CUI C W,HUANG J L. Mechanism of the single electron transfer between ClO2and phenol[J]. Environmental Chemistry,2003,22(6):560-563(in Chinese).
[9]叶必雄,王五一,杨林生,等.二氧化氯与氯联合消毒对饮用水中消毒副产物的影响[J].环境化学,2011,30(7):1236-1240.YE B X,WANG W Y,YANG L S,et al. Effect of combined disinfection with chlorine and chlorine dioxide on the fomation of disinfection by-products in drinking water[J]. Environmental Chemistry,2011,30(7):1236-1240(in Chinese).
[10]陈汝硕,沙净,苏喆,等.二氧化氯预氧化控制卤代消毒副产物研究[J].供水技术,2016,10(2):20-23.CHEN R S,SHA J,SU Z,et al.Research on preoxidation by chlorine dioxide to control chlorination disinfection by-products[J]. Water Technology,2016,10(2):20-23(in Chinese).
[11] LIM M Y,KIM J M,KO G. Disinfection kinetics of murine norovirus using chlorine and chlorine dioxide[J]. Water Research,2010,44(10):3243-3251.
[12]张金松,卢小艳.饮用水消毒工艺及副产物控制技术发展[J].给水排水,2016,42(9):1-3.ZHANG J S,LU X Y. The development of drinking water disinfection and by-product control technology[J]. Water&Wasterwater Engineering,2016,42(9):1-3(in Chinese).
[13]梁锡念,黄隽,何伦发,等. 2013-2016年某市市政供水出厂水消毒副产物监测结果分析[J].环境卫生学杂志,2017,7(4):284-290.LIANG X N,HUANG J,HE L F,et al. Analysis on levels of disinfection byproducts in municipal water supplies of a city in 2013-2016[J]. Journal of Enviromental Hygiene,2017,7(4):284-290(in Chinese).
[14] CHAMBERLAIN E,ADAMS C. Oxidation of sulfonamides,macrolides,and carbadox with free chlorine and monochloramine[J]. Water Research,2006,40(13):2517-2526.
[15] GAFFNEY V J,CARDOSO V V,BENOLIEL M J,et al. Chlorination and oxidation of sulfonamides by free chlorine:Identification and behaviour of reaction products by UPLC-MS/MS[J]. Journal of Environmental Management,2016,166:466-477.
[16] DODD M C,HUANG C H. Transformation of the antibacterial agent sulfamethoxazole in reactions with chlorine:Kinetics,mechanisms,and pathways[J]. Environmental Science&Technology,2004,38(21):5607-5615.
[17] HUBER M M,KORHONEN S,TERNES T A,et al. Oxidation of pharmaceuticals during water treatment with chlorine dioxide[J]. Water Research,2005,39(15):3607-3617.
[18] APHA. Standard methods for the examination of water and wastewater[M]. Washington:American Public Health Association(APHA),1995,481-486.
[19] WANG P,HE Y L,HUANG C H. Reactions of tetracycline antibiotics with chlorine dioxide and free chlorine[J]. Water Research,2011,45(4):1838-1846.
[20]范志云,黄君礼,王鹏,等.二氧化氯氧化水中苯胺的反应动力学及机理研究[J].环境科学,2004,25(1):95-98.FAN Z Y,HUANG J L,WANG P,et al. Kinetics and mechanism of Aniline oxidation with chlorine dioxide in water[J]. Environmental Science,2004,25(1):95-98(in Chinese).
[21]黄君礼.水消毒剂和处理剂:二氧化氯[M].北京:化学工业出版社,2010.HUANG J L. Water disinfectant and treatment agent:Chlorine dioxide[M]. Beijing:Chemical Industry Press,2010(in Chniese).
[22] WANG Y,LIU H,LIU G,et al. Kinetics for diclofenac degradation by chlorine dioxide in aqueous media:Influences of natural organic matter additives[J]. Journal of the Taiwan Institute of Chemical Engineers,2015,56:131-137.
[23]周舒月,张玉先,杨建强,等.二氧化氯预氧化处理微污染水源水及影响因素研究[J].给水排水,2008,34(5):150-153.ZHOU S Y,ZHANG Y X,YANG J Q,et al. Study on the treatment of micro polluted source water by preoxidation with chlorine dioxide and its influencing factors[J].China Water and Wastewater,2008,34(5):150-153(in Chinese).