KMnO_4氧化降解阻燃剂四氯双酚A的动力学、氧化产物及反应路径
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摘要
为探讨KMn O4氧化降解阻燃剂四氯双酚A(TCBPA)的动力学、氧化产物及反应路径,在不同p H条件下,研究KMn O4氧化降解TCBPA的动力学规律,利用三重四级杆液相质谱联用仪(LC-MS/MS)对KMn O4降解TCBPA的氧化产物进行检测分析,并推测反应路径.结果表明,KMn O4氧化降解TCBPA的二级反应速率常数k(40.1~981.7 L/(mol·s))随着p H的升高先增加而后降低,在接近p Ka(7.5/8.5)时最大.子找母质谱扫描方法(LC-MS/MS-PIS)测得KMn O4氧化降解TCBPA产生4个主要产物,质量数(m/z 35)分别为219/221(I)、201/203(II)、379/381/383/385(III&III')、523/525/527/529/531/533(IV).KMn O4氧化降解TCBPA的反应路径为TCBPA首先发生一电子反应形成酚氧自由基,并进一步断裂形成碳正离子中间体,然后反应形成产物4-(2-羟基异丙基)-2,6-二氯苯酚(I)、4-异丙烯-2,6-二氯苯酚(II)和两个聚合产物(III&III'和IV).
The purpose of this article was to investigate the kinetics,oxidation products and reaction pathways for the degradation of flame retardant tetrachlorobisphenol A( TCBPA) by aqueous potassium permanganate.Experiments were conducted to examine the reaction kinetics of potassium permanganate with TCBPA under the condition with potassium permanganate in excess over a wide p H range,determine the brominated oxidation products and theorize the reaction pathways of TCBPA by aqueous potassium permanganate using liquid chromatography-triple quadrupole mass spectrometry( LC-MS/MS). The results showed that the degradation of TCBPA followed the second-order kinetics and the rate constants( 40. 1-981. 7 L/( mol·s)) increased with the increase of p H and reached the maximum near the p Ka( 7. 5/8. 5) of TCBPA,after which they decreased gradually. Four chlorinated oxidation products were detected by the precursor scan approach of liquid chromatography tandem mass spectrometry( LC-MS/MS-PIS),the oxidation products of m/z 219/221( I),201/203( II),379/381/383/385( III&III'),523/525/527/529/531/533( IV),respectively. Reaction pathways mainly involves the initial one-electron oxidation of TCBPA to phenolic radical and subsequent release and further reactions of 2,6-dibromo-4-isopropylphenol carbocation intermediate,leading to the formation of 4-( 2-hydroxyisopropyl)-2,6-dibromophenol and 4-isopropylene-2,6-dibromophenol) as well as two polymeric products( III&III'and IV).
The purpose of this article was to investigate the kinetics,oxidation products and reaction pathways for the degradation of flame retardant tetrachlorobisphenol A( TCBPA) by aqueous potassium permanganate.Experiments were conducted to examine the reaction kinetics of potassium permanganate with TCBPA under the condition with potassium permanganate in excess over a wide p H range,determine the brominated oxidation products and theorize the reaction pathways of TCBPA by aqueous potassium permanganate using liquid chromatography-triple quadrupole mass spectrometry( LC-MS/MS). The results showed that the degradation of TCBPA followed the second-order kinetics and the rate constants( 40. 1-981. 7 L/( mol·s)) increased with the increase of p H and reached the maximum near the p Ka( 7. 5/8. 5) of TCBPA,after which they decreased gradually. Four chlorinated oxidation products were detected by the precursor scan approach of liquid chromatography tandem mass spectrometry( LC-MS/MS-PIS),the oxidation products of m/z 219/221( I),201/203( II),379/381/383/385( III&III'),523/525/527/529/531/533( IV),respectively. Reaction pathways mainly involves the initial one-electron oxidation of TCBPA to phenolic radical and subsequent release and further reactions of 2,6-dibromo-4-isopropylphenol carbocation intermediate,leading to the formation of 4-( 2-hydroxyisopropyl)-2,6-dibromophenol and 4-isopropylene-2,6-dibromophenol) as well as two polymeric products( III&III'and IV).
引文
[1]Environmental Health Criteria,No.172.Tetrabromobisphenol A andderivatives;International program on chemical safety[R].Geneva,Switzerland:World Health Organization,1995.http://www.inchem.org/documents/ehc/ehc/ehc172.htm(accessed August 2007).
[2]何敬言,宋晓红,于白.四氯双酚A的合成[J].化学工程师,1990(1):17-18.DOI:10.16247/j.cnki.23-1171/tq.1990.01.008.
[3]CHU S,HAFFNER G D,LETCHER R J.Simultaneous determination of tetrabromobisphenol A,tetrachlorobisphenol A,bisphenol A and other halogenated analogues in sediment and sludge by high performance liquid chromatography-electrospray tandem mass spectrometry[J].J Chromatogr A,2005,1097(1/2):25-32.
[4]HORIKOSHI S,MIURA T,KAJITANI M,et al.Photodegradation of tetrahalobisphenol-A(X=Cl,Br)flame retardants and delineation of factors affecting the process[J].Appl Catal B:Environ,2008,84:797-802.
[5]FAN Z,HU J,AN W,et al.Detection and occurrence of chlorinated byproducts of bisphenol A,nonylphenol,and estrogens in drinking water of china:comparison to the parent compounds[J].Environ Sci Technol,2013,47(19):10841-10850.DOI:10.1021/es401504a.
[6]KITAMURA S,JINNO N,OHTA S,et al.Thyroid hormonal activity of the flame retardants tetrabromobisphenol A and tetrachlorobisphenol A[J].Biochem Biophys Res Commun,2002,293(1):554-559.
[7]SUN H,SHEN O,WANG X,et al.Anti-thyroid hormone activity of bisphenol A,tetrabromobisphenol A and tetrachlorobisphenol A in an improved reporter gene assay[J].Toxicology in Vitro,2009,23(5):950-954.
[8]ERIKSSON J,RAHM S,GREEN N,et al.Photochemical transformations of tetrabromobisphenol A and related phenols in water[J].Chemosphere,2004,54:117-126.
[9]VOORDECKERS J W,FENNELL D E,JONES K,et al.Anaerobic biotransformation of tetrabromobisphenol A,tetrachlorobisphenol A,and bisphenol A in estuarine sediments[J].Environ Sci Technol,2002,36:696-701.DOI:10.1021/es011081h.
[10]PANG S Y,JIANG J,GAO Y,et al.Oxidation of flame retardant tetrabromobisphenol A by aqueous permanganate:Reaction kinetics,brominated products,and pathways[J].Environ Sci Technol,2014,48:615-623.DOI:10.1021/es4041094.
[11]LIN K,LIU W,GAN J.Reaction of tetrabromobisphenol A(TBBPA)with manganese dioxide:Kinetics,products,and pathways[J].Environ Sci Technol,2009,43:4480-4486.DOI:10.1021/es803622t.
[12]LEE Y,YOON J,VON GUNTEN U.Kinetics of the oxidation of phenols and phenolic endocrine disruptors during water treatment with ferrate(Fe(VI))[J].Environ Sci Technol,2005,39(22):8978-8984.DOI:10.1021/es051198w.
[13]庞素艳,鲁雪婷,江进,等.KMn O4氧化降解雌酮反应动力学与氧化产物[J].哈尔滨工业大学学报,2016,48(2):38-43.DOI:10.11918/j.issn.0367-6234.2016.02.007.PANG Suyan,LU Xueting,JIANG Jin,et al.Oxidation of estrone by aqueous permanganate:Reaction kinetics and oxidation products[J].Journal of Harbin Institute of Technology,2016,48(2):38-43.DOI:10.11918/j.issn.0367-6234.2016.02.007.
[14]庞素艳,王强,鲁雪婷,等.中间价态锰强化KMn O4氧化降解三氯生[J].哈尔滨工业大学学报,2015,47(2):87-91.DOI:10.11918/J.issn.0367-6234.2015.02.016.PANG Suyan,WANG Qiang,LU Xueting,et al.Oxidative removal of triclosan by potassium permanganate enhanced with manganese intermediates[J].Journal of Harbin Institute of Technology,2015,47(2):87-91.DOI:10.11918/J.issn.0367-6234.2015.02.016.
[15]ZHANG X,TALLEY J W,BOGGESS B,et al.Fast selective detection of polar brominated disinfection byproducts in drinking water using precursor ion scans[J].Environ Sci Technol,2008,42:6598-6603.DOI:10.1021/es800855b.
[16]ZHAI H,ZHANG X.Formation and decomposition of new and unknown polar brominated disinfection byproducts during chlorination[J].Environ Sci Technol,2011,45:2194-2201.DOI:10.1021/es800855b.
[17]PAN Y,ZHANG X.Four groups of new aromatic halogenated disinfection byproducts:Effect of bromide concentration on their formation and speciation in chlorinated drinking water[J].Environ Sci Technol,2013,47:1265-1273.DOI:10.1021/es303729n.
[18]XIAO F,ZHANG X,ZHAI H,et al.New halogenated disinfection byproducts in swimming pool water and their permeability across skin[J].Environ Sci Technol,2012,46:7112-7119.DOI:10.1021/es3010656.
[19]DING G,ZHANG X,YANG M,et al.Formation of new brominated disinfection byproducts during chlorination of saline sewage effluents[J].Water Res,2013,47:2710-2718.
[20]LIN K,LIU W,GAN J.Reaction oftetrabromobisphenol A(TBBPA)with manganese dioxide:Kinetics,products,and pathways[J].Environ Sci Technol,2009,43:4480-4486.DOI:10.1021/es803622t.
[21]FENG Y,COLOSI L M,GAOS,et al.Transformation and removal of tetrabromobisphenol A from water in the presence of natural organic matter via laccase-catalyzed reactions:Reaction rates,products,and pathways[J].Environ Sci Technol,2013,47:1001-1008.DOI:10.1021/es302680c.
[2]何敬言,宋晓红,于白.四氯双酚A的合成[J].化学工程师,1990(1):17-18.DOI:10.16247/j.cnki.23-1171/tq.1990.01.008.
[3]CHU S,HAFFNER G D,LETCHER R J.Simultaneous determination of tetrabromobisphenol A,tetrachlorobisphenol A,bisphenol A and other halogenated analogues in sediment and sludge by high performance liquid chromatography-electrospray tandem mass spectrometry[J].J Chromatogr A,2005,1097(1/2):25-32.
[4]HORIKOSHI S,MIURA T,KAJITANI M,et al.Photodegradation of tetrahalobisphenol-A(X=Cl,Br)flame retardants and delineation of factors affecting the process[J].Appl Catal B:Environ,2008,84:797-802.
[5]FAN Z,HU J,AN W,et al.Detection and occurrence of chlorinated byproducts of bisphenol A,nonylphenol,and estrogens in drinking water of china:comparison to the parent compounds[J].Environ Sci Technol,2013,47(19):10841-10850.DOI:10.1021/es401504a.
[6]KITAMURA S,JINNO N,OHTA S,et al.Thyroid hormonal activity of the flame retardants tetrabromobisphenol A and tetrachlorobisphenol A[J].Biochem Biophys Res Commun,2002,293(1):554-559.
[7]SUN H,SHEN O,WANG X,et al.Anti-thyroid hormone activity of bisphenol A,tetrabromobisphenol A and tetrachlorobisphenol A in an improved reporter gene assay[J].Toxicology in Vitro,2009,23(5):950-954.
[8]ERIKSSON J,RAHM S,GREEN N,et al.Photochemical transformations of tetrabromobisphenol A and related phenols in water[J].Chemosphere,2004,54:117-126.
[9]VOORDECKERS J W,FENNELL D E,JONES K,et al.Anaerobic biotransformation of tetrabromobisphenol A,tetrachlorobisphenol A,and bisphenol A in estuarine sediments[J].Environ Sci Technol,2002,36:696-701.DOI:10.1021/es011081h.
[10]PANG S Y,JIANG J,GAO Y,et al.Oxidation of flame retardant tetrabromobisphenol A by aqueous permanganate:Reaction kinetics,brominated products,and pathways[J].Environ Sci Technol,2014,48:615-623.DOI:10.1021/es4041094.
[11]LIN K,LIU W,GAN J.Reaction of tetrabromobisphenol A(TBBPA)with manganese dioxide:Kinetics,products,and pathways[J].Environ Sci Technol,2009,43:4480-4486.DOI:10.1021/es803622t.
[12]LEE Y,YOON J,VON GUNTEN U.Kinetics of the oxidation of phenols and phenolic endocrine disruptors during water treatment with ferrate(Fe(VI))[J].Environ Sci Technol,2005,39(22):8978-8984.DOI:10.1021/es051198w.
[13]庞素艳,鲁雪婷,江进,等.KMn O4氧化降解雌酮反应动力学与氧化产物[J].哈尔滨工业大学学报,2016,48(2):38-43.DOI:10.11918/j.issn.0367-6234.2016.02.007.PANG Suyan,LU Xueting,JIANG Jin,et al.Oxidation of estrone by aqueous permanganate:Reaction kinetics and oxidation products[J].Journal of Harbin Institute of Technology,2016,48(2):38-43.DOI:10.11918/j.issn.0367-6234.2016.02.007.
[14]庞素艳,王强,鲁雪婷,等.中间价态锰强化KMn O4氧化降解三氯生[J].哈尔滨工业大学学报,2015,47(2):87-91.DOI:10.11918/J.issn.0367-6234.2015.02.016.PANG Suyan,WANG Qiang,LU Xueting,et al.Oxidative removal of triclosan by potassium permanganate enhanced with manganese intermediates[J].Journal of Harbin Institute of Technology,2015,47(2):87-91.DOI:10.11918/J.issn.0367-6234.2015.02.016.
[15]ZHANG X,TALLEY J W,BOGGESS B,et al.Fast selective detection of polar brominated disinfection byproducts in drinking water using precursor ion scans[J].Environ Sci Technol,2008,42:6598-6603.DOI:10.1021/es800855b.
[16]ZHAI H,ZHANG X.Formation and decomposition of new and unknown polar brominated disinfection byproducts during chlorination[J].Environ Sci Technol,2011,45:2194-2201.DOI:10.1021/es800855b.
[17]PAN Y,ZHANG X.Four groups of new aromatic halogenated disinfection byproducts:Effect of bromide concentration on their formation and speciation in chlorinated drinking water[J].Environ Sci Technol,2013,47:1265-1273.DOI:10.1021/es303729n.
[18]XIAO F,ZHANG X,ZHAI H,et al.New halogenated disinfection byproducts in swimming pool water and their permeability across skin[J].Environ Sci Technol,2012,46:7112-7119.DOI:10.1021/es3010656.
[19]DING G,ZHANG X,YANG M,et al.Formation of new brominated disinfection byproducts during chlorination of saline sewage effluents[J].Water Res,2013,47:2710-2718.
[20]LIN K,LIU W,GAN J.Reaction oftetrabromobisphenol A(TBBPA)with manganese dioxide:Kinetics,products,and pathways[J].Environ Sci Technol,2009,43:4480-4486.DOI:10.1021/es803622t.
[21]FENG Y,COLOSI L M,GAOS,et al.Transformation and removal of tetrabromobisphenol A from water in the presence of natural organic matter via laccase-catalyzed reactions:Reaction rates,products,and pathways[J].Environ Sci Technol,2013,47:1001-1008.DOI:10.1021/es302680c.