UV降解水溶液中文拉法辛的影响因素及机制
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摘要
采用UV工艺处理水体中的抗抑郁药物文拉法辛,分别考察了初始浓度、pH值、水质等因素对文拉法辛降解的影响.结果表明,文拉法辛的降解过程符合伪一级动力学模型,其降解速率常数随着药物浓度的降低而增加. pH为10时,文拉法辛降解速率最快.其降解过程包括直接光解、·OH和~1O_2参与的自敏化反应,其中直接光解贡献较大.水体中常见无机阴离子Br~-、Cl~-、NO_3~-和NO_2~-均抑制文拉法辛降解,其中NO_2~-的抑制作用最强.天然有机物腐殖酸和富里酸也会影响文拉法辛的降解.相比超纯水,文拉法辛在二级出水中的降解速率明显降低.经超高效液相色谱质谱联用仪(UPLC-MS/MS)对文拉法辛降解产物的全扫描分析,推测出5种主要的转化途径:①芳香环的顺序羟基化;②去甲基化;③去胺基化;④环己烷的断链;⑤小分子有机酸的转化.此外,文拉法辛中87%的N元素转化成无机离子(NH_4~+和NO_3~-).
As a member of antidepressants,venlafaxine degradation by UV was investigated in this study. The influence of initial concentration of venlafaxine,p H value,and water quality on venlafaxine removal were studied. The results showed that venlafaxine degradation fitted the pseudo-first-order kinetics model. The reaction rate increased with the decrease of venlafaxine concentration. It was found that the highest removal rate of venlafaxine occurred at p H 10. The degradation of venlafaxine involves direct photolysis and self-sensitized photolysis caused by hydroxyl radical( ·OH) and singlet oxygen(~1O_2). Moreover,the direct photolysis played a dominant role in the venlafaxine removal. Water matrix also affected venlafaxine degradation. The results indicated that the degradation rate of venlafaxine in the secondary effluent was lower than that in the ultrapure water. Inorganic anions( Br~-,Cl~-,NO_3~-,and NO_2~-)impacted venlafaxine removal,and the inhibition of NO_2~- was stronger than others'. Both humic acid and fulvic acid also inhibited venlafaxine decomposition. UPLC-MS/MS was used to perform full scan to identify intermediates of venlafaxine degradation. Five degradation pathways were proposed: ①demethylation; ②deamination; ③sequential hydroxylation of aromatic rings; ④ring opening of cyclohexane; ⑤low-molecular-weight acid transformation. In addition,87% of the N element in the molecules were transformed into inorganic ions( ammonium ions and nitrate ions).
As a member of antidepressants,venlafaxine degradation by UV was investigated in this study. The influence of initial concentration of venlafaxine,p H value,and water quality on venlafaxine removal were studied. The results showed that venlafaxine degradation fitted the pseudo-first-order kinetics model. The reaction rate increased with the decrease of venlafaxine concentration. It was found that the highest removal rate of venlafaxine occurred at p H 10. The degradation of venlafaxine involves direct photolysis and self-sensitized photolysis caused by hydroxyl radical( ·OH) and singlet oxygen(~1O_2). Moreover,the direct photolysis played a dominant role in the venlafaxine removal. Water matrix also affected venlafaxine degradation. The results indicated that the degradation rate of venlafaxine in the secondary effluent was lower than that in the ultrapure water. Inorganic anions( Br~-,Cl~-,NO_3~-,and NO_2~-)impacted venlafaxine removal,and the inhibition of NO_2~- was stronger than others'. Both humic acid and fulvic acid also inhibited venlafaxine decomposition. UPLC-MS/MS was used to perform full scan to identify intermediates of venlafaxine degradation. Five degradation pathways were proposed: ①demethylation; ②deamination; ③sequential hydroxylation of aromatic rings; ④ring opening of cyclohexane; ⑤low-molecular-weight acid transformation. In addition,87% of the N element in the molecules were transformed into inorganic ions( ammonium ions and nitrate ions).
引文
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[12]Fong P P,Molnar N.Antidepressants cause foot detachment from substrate in five species of marine snail[J].Marine Environmental Research,2013,84:24-30.
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[16]魏红,孙博成,杨小雨,等.超声、紫外增强H2O2/KI降解磺胺甲基嘧啶[J].环境科学,2017,38(6):2393-2399.Wei H,Sun B C,Yang X Y,et al.Enhancement of sulfamerazine degradation under H2O2/KI system by ultrasound and UVA irradiation[J].Environmental Science,2017,38(6):2393-2399.
[17]罗从伟,马军,江近,等.UV/H2O2降解2,4,6-三氯苯甲醚动力学及产物研究[J].中国环境科学,2017,37(5):1831-1837.
[18]Pereira V J,Weinberg H S,Linden K G,et al.UV degradation kinetics and modeling of pharmaceutical compounds in laboratory grade and surface water via direct and indirect photolysis at 254nm[J].Environmental Science&Technology,2007,41(5):1682-1688.
[19]Chu W H,Gao N Y,Li C,et al.Photochemical degradation of typical halogenated herbicide 2,4-D in drinking water with UV/H2O2/micro-aeration[J].Science in China Series B:Chemistry,2009,52(12):2351.
[20]Zhang N,Liu G,Liu H,et al.Diclofenac photodegradation under simulated sunlight:Effect of different forms of nitrogen and kinetics[J].Journal of Hazardous Materials,2011,192(1):411.
[21]马杜娟,刘国光,吕文英,等.水中萘普生的紫外光降解机制及其产物毒性研究[J].环境科学,2013,34(5):1782-1789.Ma D J,Liu G G,LüW Y,et al.Photodegradation of naproxen in aqueous systems by UV irradiation:mechanism and toxicity of photolysis products[J].Environmental Science,2013,34(34):1782-1789.
[22]彭娜,王开峰,刘国光,等.水中普萘洛尔的紫外光降解机制及其产物毒性[J].环境科学,2014,35(10):3794-3799.Peng N,Wang K F,Liu G G,et al.UV photolysis of propranolol in aqueous solution:mechanism and toxicity of photoproducts[J].Environmental Science,2014,35(10):3794-3799.
[23]Chen Y,Li H,Wang Z P,et al.Photodegradation of selectedβ-blockers in aqueous fulvic acid solutions:kinetics,mechanism,and product analysis[J].Water Research,2012,46(9):2965-2972.
[24]胡继业,张文吉,李建中,等.2-烯丙基苯酚在液相中的光化学降解研究[J].环境科学学报,2004,24(5):815-821.Hu J Y,Zhang W J,Li J Z,et al.Photo-degradation of 2-allylphenol in the aqueous phase[J].Acta Scientiae Circumstantiae,2004,24(5):815-821.
[25]Cogan S,Has Y.Self-sensitized photo-oxidation of paraindenylidene-dihydropyridine derivatives[J].Journal of Photochemistry and Photobiology A:Chemistry,2008,193(1):25-32.
[26]Xu H M,Cooper W J,Jung J Y,et al.Photosensitized degradation of amoxicillin in natural organic matter isolate solutions[J].Water Research,2011,45(2):632-638.
[27]Buxton G V,Greenstock C L,Phillip Helman W,et al.Critical review of rate constants for reactions of hydrated electrons,hydrogen atoms and hydroxyl radicals(·OH/·O-)in aqueous solution[J].Journal of Physical and Chemical Reference Data,1988,17(2):513-886.
[28]Gan Z W,Sun H W,Wang R N,et al.Transformation of acesulfame in water under natural sunlight:joint effect of photolysis and biodegradation[J].Water Research,2014,64:113-122.
[29]Ma J S,Lv W Y,Chen P,et al.Photodegradation of gemfibrozil in aqueous solution under UV irradiation:kinetics,mechanism,toxicity,and degradation pathways[J].Environmental Science and Pollution Research International,2016,23(14):14294-14306.
[30]Bai Q,Yang L H,Li R J,et al.Accelerating quinoline biodegradation and oxidation with endogenous electron donors[J].Environmental Science&Technology,2015,49(19):11536-11542.
[31]岳玲,张晓宏,吴世康.卤素离子对联有吖啶基三元共聚物薄膜的荧光猝灭[J].影像科学与光化学,2003,21(1):53-60.
[32]朱燕,郁志勇,孙震,等.过氧化氢和卤离子对亚甲基蓝光化学降解的影响[J].安徽大学学报(自然科学版),2004,28(3):75-78.Zhu Y,Yu Z Y,Su Z,et al.Effects of hydrogen peroxide and Cl-/Br-/I-on the photochemical degradation of methylene blue[J].Journal of Anhui University Natural Sciences,2004,28(3):75-78.
[33]Arakaki T,Miyake T,Hirakawa T,et al.pH dependent photoformation of hydroxyl radical and absorbance of aqueousphase N(Ⅲ)(HNO2and NO-2)[J].Environmental Science&Technology,1999,33(15):2561-2565.
[34]S9rensen M,Tanner U,Sagawe G,et al.Photochemical degradation of hydrophilic xenobiotics in the UV/H2O2-process.Influence of humic matter on the degradation rate of 2-amino-1-naphthalenesulfonate and ethylenediaminetetraacetate[J].CLEAN Soil Air Water,1996,24(3):132-136.
[35]Chen Y,Hu C,Hu X X,et al.Indirect photodegradation of amine drugs in aqueous solution under simulated sunlight[J].Environmental Science&Technology,2009,43(8):2760-2765.
[36]García-Galán M J,Anfruns A,Gonzalez-Olmos R,et al.UV/H2O2degradation of the antidepressants venlafaxine and O-desmethylvenlafaxine:elucidation of their transformation pathway and environmental fate[J].Journal of Hazardous Materials,2016,311:70-80.
[37]Santoke H,Song W H,Cooper W J,et al.Advanced oxidation treatment and photochemical fate of selected antidepressant pharmaceuticals in solutions of Suwannee River humic acid[J].Journal of Hazardous Materials,2012,217-218:382-390.
[38]安娜.水中溶解性有机质对四种典型抗抑郁药物光降解行为的影响[D].大连:大连理工大学,2012.
[2]Andrews J M,Ninan P T,Nemeroff C B.Venlafaxine:a novel antidepressant that has a dual mechanism of action[J].Depression,1996,4(2):48-56.
[3]Stadler L B,Su L J,Moline C J,et al.Effect of redox conditions on pharmaceutical loss during biological wastewater treatment using sequencing batch reactors[J].Journal of Hazardous Materials,2015,282:106-115.
[4]Schultz M M,Furlong E T.Trace analysis of antidepressant pharmaceuticals and their select degradates in aquatic matrixes by LC/ESI/MS/MS[J].Analytical Chemistry,2008,80(5):1756-1662.
[5]Fatta-Kassinos D,Vasquez M I,Kümmerer K.Transformation products of pharmaceuticals in surface waters and wastewater formed during photolysis and advanced oxidation processesdegradation,elucidation of byproducts and assessment of their biological potency[J].Chemosphere,2011,85(5):693-709.
[6]Gros M,Rodríguez-Mozaz S,BarcelóD.Fast and comprehensive multi-residue analysis of a broad range of human and veterinary pharmaceuticals and some of their metabolites in surface and treated waters by ultra-high-performance liquid chromatography coupled to quadrupole-linear ion trap tandem mass spectrometry[J].Journal of Chromatography A,2012,1248:104-121.
[7]Beel R,Lütke Eversloh C,Ternes T A.Biotransformation of the UV-filter sulisobenzone:challenges for the identification of transformation products[J].Environmental Science&Technology,2013,47(13):6819-6828.
[8]Silva L J G,Meisel L M,Lino C M,et al.Profiling serotonin reuptake inhibitors(SSRIs)in the environment:trends in analytical methodologies[J].Critical Reviews in Analytical Chemistry,2014,44(1):41-67.
[9]Papageorgiou M,Kosma C,Lambropoulou D.Seasonal occurrence,removal,mass loading and environmental risk assessment of 55 pharmaceuticals and personal care products in a municipal wastewater treatment plant in Central Greece[J].Science of the Total Environment,2016,543:547-569.
[10]Valcárcel Y,González Alonso S,Rodríguez-Gil J L,et al.Detection of pharmaceutically active compounds in the rivers and tap water of the Madrid Region(Spain)and potential ecotoxicological risk[J].Chemosphere,2011,84(10):1336-1348.
[11]Bisesi Jr J H,Bridges W,Klaine S J.Effects of the antidepressant venlafaxine on fish brain serotonin and predation behavior[J].Aquatic Toxicology,2014,148:130-138.
[12]Fong P P,Molnar N.Antidepressants cause foot detachment from substrate in five species of marine snail[J].Marine Environmental Research,2013,84:24-30.
[13]Gros M,Petrovic'M,Ginebreda A,et al.Removal of pharmaceuticals during wastewater treatment and environmental risk assessment using hazard indexes[J].Environment International,2010,36(1):15-26.
[14]Juretic D,Puric J,Kusic H,et al.Structural influence on photooxidative degradation of halogenated phenols[J].Water,Air,&Soil Pollution,2014,225:2143.
[15]冯欣欣,杜尔登,郭迎庆,等.UV/H2O2降解羟苯甲酮反应动力学及影响因素[J].环境科学,2015,36(6):2129-2137.Feng X X,Du E D,Guo Y Q,et al.Degradation of organic sunscreens 2-hydroxy-4-methoxybenzophenone by UV/H2O2process:kinetics and factors[J].Environmental Science,2015,36(6):2129-2137.
[16]魏红,孙博成,杨小雨,等.超声、紫外增强H2O2/KI降解磺胺甲基嘧啶[J].环境科学,2017,38(6):2393-2399.Wei H,Sun B C,Yang X Y,et al.Enhancement of sulfamerazine degradation under H2O2/KI system by ultrasound and UVA irradiation[J].Environmental Science,2017,38(6):2393-2399.
[17]罗从伟,马军,江近,等.UV/H2O2降解2,4,6-三氯苯甲醚动力学及产物研究[J].中国环境科学,2017,37(5):1831-1837.
[18]Pereira V J,Weinberg H S,Linden K G,et al.UV degradation kinetics and modeling of pharmaceutical compounds in laboratory grade and surface water via direct and indirect photolysis at 254nm[J].Environmental Science&Technology,2007,41(5):1682-1688.
[19]Chu W H,Gao N Y,Li C,et al.Photochemical degradation of typical halogenated herbicide 2,4-D in drinking water with UV/H2O2/micro-aeration[J].Science in China Series B:Chemistry,2009,52(12):2351.
[20]Zhang N,Liu G,Liu H,et al.Diclofenac photodegradation under simulated sunlight:Effect of different forms of nitrogen and kinetics[J].Journal of Hazardous Materials,2011,192(1):411.
[21]马杜娟,刘国光,吕文英,等.水中萘普生的紫外光降解机制及其产物毒性研究[J].环境科学,2013,34(5):1782-1789.Ma D J,Liu G G,LüW Y,et al.Photodegradation of naproxen in aqueous systems by UV irradiation:mechanism and toxicity of photolysis products[J].Environmental Science,2013,34(34):1782-1789.
[22]彭娜,王开峰,刘国光,等.水中普萘洛尔的紫外光降解机制及其产物毒性[J].环境科学,2014,35(10):3794-3799.Peng N,Wang K F,Liu G G,et al.UV photolysis of propranolol in aqueous solution:mechanism and toxicity of photoproducts[J].Environmental Science,2014,35(10):3794-3799.
[23]Chen Y,Li H,Wang Z P,et al.Photodegradation of selectedβ-blockers in aqueous fulvic acid solutions:kinetics,mechanism,and product analysis[J].Water Research,2012,46(9):2965-2972.
[24]胡继业,张文吉,李建中,等.2-烯丙基苯酚在液相中的光化学降解研究[J].环境科学学报,2004,24(5):815-821.Hu J Y,Zhang W J,Li J Z,et al.Photo-degradation of 2-allylphenol in the aqueous phase[J].Acta Scientiae Circumstantiae,2004,24(5):815-821.
[25]Cogan S,Has Y.Self-sensitized photo-oxidation of paraindenylidene-dihydropyridine derivatives[J].Journal of Photochemistry and Photobiology A:Chemistry,2008,193(1):25-32.
[26]Xu H M,Cooper W J,Jung J Y,et al.Photosensitized degradation of amoxicillin in natural organic matter isolate solutions[J].Water Research,2011,45(2):632-638.
[27]Buxton G V,Greenstock C L,Phillip Helman W,et al.Critical review of rate constants for reactions of hydrated electrons,hydrogen atoms and hydroxyl radicals(·OH/·O-)in aqueous solution[J].Journal of Physical and Chemical Reference Data,1988,17(2):513-886.
[28]Gan Z W,Sun H W,Wang R N,et al.Transformation of acesulfame in water under natural sunlight:joint effect of photolysis and biodegradation[J].Water Research,2014,64:113-122.
[29]Ma J S,Lv W Y,Chen P,et al.Photodegradation of gemfibrozil in aqueous solution under UV irradiation:kinetics,mechanism,toxicity,and degradation pathways[J].Environmental Science and Pollution Research International,2016,23(14):14294-14306.
[30]Bai Q,Yang L H,Li R J,et al.Accelerating quinoline biodegradation and oxidation with endogenous electron donors[J].Environmental Science&Technology,2015,49(19):11536-11542.
[31]岳玲,张晓宏,吴世康.卤素离子对联有吖啶基三元共聚物薄膜的荧光猝灭[J].影像科学与光化学,2003,21(1):53-60.
[32]朱燕,郁志勇,孙震,等.过氧化氢和卤离子对亚甲基蓝光化学降解的影响[J].安徽大学学报(自然科学版),2004,28(3):75-78.Zhu Y,Yu Z Y,Su Z,et al.Effects of hydrogen peroxide and Cl-/Br-/I-on the photochemical degradation of methylene blue[J].Journal of Anhui University Natural Sciences,2004,28(3):75-78.
[33]Arakaki T,Miyake T,Hirakawa T,et al.pH dependent photoformation of hydroxyl radical and absorbance of aqueousphase N(Ⅲ)(HNO2and NO-2)[J].Environmental Science&Technology,1999,33(15):2561-2565.
[34]S9rensen M,Tanner U,Sagawe G,et al.Photochemical degradation of hydrophilic xenobiotics in the UV/H2O2-process.Influence of humic matter on the degradation rate of 2-amino-1-naphthalenesulfonate and ethylenediaminetetraacetate[J].CLEAN Soil Air Water,1996,24(3):132-136.
[35]Chen Y,Hu C,Hu X X,et al.Indirect photodegradation of amine drugs in aqueous solution under simulated sunlight[J].Environmental Science&Technology,2009,43(8):2760-2765.
[36]García-Galán M J,Anfruns A,Gonzalez-Olmos R,et al.UV/H2O2degradation of the antidepressants venlafaxine and O-desmethylvenlafaxine:elucidation of their transformation pathway and environmental fate[J].Journal of Hazardous Materials,2016,311:70-80.
[37]Santoke H,Song W H,Cooper W J,et al.Advanced oxidation treatment and photochemical fate of selected antidepressant pharmaceuticals in solutions of Suwannee River humic acid[J].Journal of Hazardous Materials,2012,217-218:382-390.
[38]安娜.水中溶解性有机质对四种典型抗抑郁药物光降解行为的影响[D].大连:大连理工大学,2012.
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