Photochlorination of aniline in Fe3+-containing saline water under simulated solar light irradiation
Lei Wu A B and Xuefeng Hu A C
+ Author Affiliations
- Author Affiliations
A Key Laboratory of Coastal Environmental Processes, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003, P. R. China.
B University of Chinese Academy of Sciences, Beijing 100049, P. R. China.
C Corresponding author. Email: xfhu@yic.ac.cn
Environmental Chemistry 9(6) 558-563 https://doi.org/10.1071/EN12143
Submitted: 21 September 2012 Accepted: 19 November 2012 Published: 20 December 2012
Environmental context. Aromatic amines are widely used chemicals, which show enhanced toxicity and longer environmental persistence when halogenated. We investigated the chlorination of aniline in seawater and in natural aqueous solutions containing Fe3+ and Cl–, under simulated sunlight irradiation. The results increase our understanding of the transformation pathway of typical nitrogen-containing aromatic contaminants in the environment.
Abstract. Photochlorination of aniline was observed in aqueous solutions containing dissolved FeIII and chloride ions under simulated solar light irradiation. Effects of O2, Cl–, Fe3+ and pH on the formation of chloroanilines (CAs) were investigated. para-chloroaniline (4CA) was identified as the main chlorinated product. The formation of 4CA is enhanced with increased concentrations of Cl– or Fe3+, and decreased pH, whereas oxygen plays a negligible role in the process. The results indicate that, Cl• is formed mainly by the photodissociation of FeCl2+–FeCl2+ complexes, and reacts with Cl– to produce Cl2•–. Aniline is then oxidised by Cl2•– into an anilino radical cation, which further reacts with Cl2•– to generate CAs. The photochlorination of aniline in natural seawater was also observed. Other phototransformation products of aniline were detected and a transformation pathway was proposed. This work provides evidence for the photochemical chlorination path of aniline-based aromatic amines in aqueous solutions.
Additional keywords: chloroanilines.
References
[1] M. L. Canle, J. A. Santaballa, E. Vulliet, On the mechanism of TiO2-photocatalyed degradation of aniline derivatives. J. Photochem. Photobiol. A 2005, 175, 192.| On the mechanism of TiO2-photocatalyed degradation of aniline derivatives.Crossref | GoogleScholarGoogle Scholar |
[2] S. P. Kamble, S. B. Sawant, J. C. Schouten, V. G. Pangarkar, Photocatalytic and photochemical degradation of aniline using concentrated solar radiation. J. Chem. Technol. Biotechnol. 2003, 78, 865.
| Photocatalytic and photochemical degradation of aniline using concentrated solar radiation.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXmtVyqu74%3D&md5=e9a0502a31c861bc27d71f85a8174944CAS |
[3] E. Brillas, E. Mur, R. Sauleda, L. Sànchez, J. Peral, X. Domènech, J. Casado, Aniline mineralization by AOP’s: anodic oxidation, photocatalysis, electro-Fenton and photoelectron-Fenton processes. Appl. Catal. B 1998, 16, 31.
| Aniline mineralization by AOP’s: anodic oxidation, photocatalysis, electro-Fenton and photoelectron-Fenton processes.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXhvVyhtb4%3D&md5=801d556327a592dbe623334617132a5bCAS |
[4] R. Sauleda, E. Brillas, Mineralization of aniline and 4-chlorophenol in acidic solution by ozaonation catalyzed with Fe2+ and UVA light. Appl. Catal. B 2001, 29, 135.
| Mineralization of aniline and 4-chlorophenol in acidic solution by ozaonation catalyzed with Fe2+ and UVA light.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXot1Ons7g%3D&md5=38b77db0891592e5d78eb112358b8a5bCAS |
[5] J. Anotai, M.-C. Lu, P. Chewpreecha, Kinetics of aniline degradation by Fenton and electro-Fenton prcesses. Water Res. 2006, 40, 1841.
| Kinetics of aniline degradation by Fenton and electro-Fenton prcesses.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XjslOmsbk%3D&md5=5e564e3a38bbf562140463def07b1059CAS |
[6] P. Piccinini, C. Minero, M. Vincenti, E. Pelizzetti, Photocatalytic interconvertion of nitrogen-containing benzene derivatives. J. Chem. Soc., Faraday Trans. 1997, 93, 1993.
| Photocatalytic interconvertion of nitrogen-containing benzene derivatives.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2sXjvVOgu78%3D&md5=59d90d0d070cbbd2bd9d56da233b34eaCAS |
[7] L. Oliviero, J. Barbier, J. D. Duprez, Wet air oxidation of nitrogen-containing organic compounds and ammonia in aqueous media. Appl. Catal. B 2003, 40, 163.
| Wet air oxidation of nitrogen-containing organic compounds and ammonia in aqueous media.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXptFCjsg%3D%3D&md5=33f18371a279d70effcbf81029aaea25CAS |
[8] T. C. An, L. Sun, G. Y. Li, Y. P. Gao, G. G. Ying, Photocatalytic degradation and detoxification of o-chloroaniline in the gas phase: mechanistic consideration and mutagenicity assessment of its decomposed gaseous intermediate mixture. Appl. Catal. B 2011, 102, 140.
| Photocatalytic degradation and detoxification of o-chloroaniline in the gas phase: mechanistic consideration and mutagenicity assessment of its decomposed gaseous intermediate mixture.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXnvVansA%3D%3D&md5=891c1475a81ec63f8986bc99e6167cffCAS |
[9] P. Hongsawat, A. S. Vangnai, Biodegradation pathways of chloroanilines by Acinetobacter baylyi strain GFJ2. J. Hazard. Mater. 2011, 186, 1300.
| Biodegradation pathways of chloroanilines by Acinetobacter baylyi strain GFJ2.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhvVajtb0%3D&md5=3a5b4cfbeb434ac02d89b2875588ab49CAS |
[10] V. A. Nadtochenko, J. Kiwi, Photolysis of FeOH2+ and FeCl2+ in aqueous solution. Photodissociation kinetics and quantum yields. Inorg. Chem. 1998, 37, 5233.
| Photolysis of FeOH2+ and FeCl2+ in aqueous solution. Photodissociation kinetics and quantum yields.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXlslOmur8%3D&md5=774fa1a64fb74c9a28113a9480c65420CAS |
[11] K. Hasegawa, P. Neta, Rate constants and mechanisms of reaction of Cl2– radicals. J. Phys. Chem. 1978, 82, 854.
| Rate constants and mechanisms of reaction of Cl2– radicals.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE1cXhsVahtro%3D&md5=778f1b8a7999bc2bed770bc07f9c2818CAS |
[12] M. L. Alegre, M. Geronés, J. A. Rosso, S. G. Bertolotti, A. M. Braun, D. O. Mártire, M. C. Gonzalez, Kinetic study of the reactions of chlorine atoms and Cl2•– radical anions in aqueous solutions. 1. Reaction with benzene. J. Phys. Chem. A 2000, 104, 3117.
| Kinetic study of the reactions of chlorine atoms and Cl2•– radical anions in aqueous solutions. 1. Reaction with benzene.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXhsl2lsbg%3D&md5=f96c146ba175fa790076f9a9d895c293CAS |
[13] M. Jonsson, J. Lind, T. E. Eriksen, G. Merényl, Redox and acidity properties of 4-substituted aniline radical cations in water. J. Am. Chem. Soc. 1994, 116, 1423.
| Redox and acidity properties of 4-substituted aniline radical cations in water.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2cXhvFSquro%3D&md5=eaeb41a287d28cf47e69a5ea38f792ceCAS |
[14] K. Junker, G. Zandomeneghi, Z. W. Guo, R. Kissner, T. Ishikawa, J. Kohlbrechere, P. Walde, Mechanistic aspects of the horseradish peroxidase-catalysed polymerization of aniline in the presence of AOT vesicles as templates. RSC Adv. 2012, 2, 6478.
| Mechanistic aspects of the horseradish peroxidase-catalysed polymerization of aniline in the presence of AOT vesicles as templates.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XhtVeis7fN&md5=f31911e3eb2ac8ef09c02cade3f0fa28CAS |
[15] K. Othmen, P. Boule, B. Szczepanik, K. Rotkiewicz, G. Grabner, Photochemistry of 4-chloroaniline in solution. Formation and kinetic properties of a new carbine, 4-iminocyclohexa-2,5-dienylidene. J. Phys. Chem. A 2000, 104, 9525.
| Photochemistry of 4-chloroaniline in solution. Formation and kinetic properties of a new carbine, 4-iminocyclohexa-2,5-dienylidene.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXmvFOnsbs%3D&md5=3ecd13ea11737fd105cfe5814294c5ecCAS |
[16] K. Othmen, P. Boule, C. Richard, Mechanism of 3-halogenoaniline photolysis in methanol. New J. Chem. 1999, 23, 857.
| Mechanism of 3-halogenoaniline photolysis in methanol.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXks1Oksb4%3D&md5=83051957e49f4d1aa9794fc436c2ed6fCAS |
[17] C. D. Cook, R. C. Woodworth, Oxidation of hindered phenols. II. The 2,4,6-tri-t-butylphenoxy radical. J. Am. Chem. Soc. 1953, 75, 6242.
| Oxidation of hindered phenols. II. The 2,4,6-tri-t-butylphenoxy radical.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaG2MXotVOr&md5=9e6506106c9e16477d75c2819cbf62f7CAS |
[18] D. Vione, V. Maurino, C. Minero, P. Calza, E. Pellizzetti, Phenol chlorination and photochlorination in the presence of chloride ions in homogeneous aqueous solution. Environ. Sci. Technol. 2005, 39, 5066.
| Phenol chlorination and photochlorination in the presence of chloride ions in homogeneous aqueous solution.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXksVersL4%3D&md5=6dd262181f2fa4eb5e6e1b0633bd045dCAS |
[19] J. Kiwi, A. Lopez, V. Nadtochenko, Mechanism and kinetics of the OH-radical intervention during Fenton oxidation in the presence of a significant amount of radical scavenger (Cl–). Environ. Sci. Technol. 2000, 34, 2162.
| Mechanism and kinetics of the OH-radical intervention during Fenton oxidation in the presence of a significant amount of radical scavenger (Cl–).Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXisVOqu7s%3D&md5=1b437415306a263ccbb2f79296f843a3CAS |
[20] H. Liu, H. M. Zhao, X. Quan, Y. Zhang, S. Chen, Formation of chlorinated intermediate from bisphenol A in surface saline water under simulated solar light irradiation. Environ. Sci. Technol. 2009, 43, 7712.
| Formation of chlorinated intermediate from bisphenol A in surface saline water under simulated solar light irradiation.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXhtFWqu73I&md5=1ce13b6980493489f9798d8e9c8e9e30CAS |
[21] H. Liu, H. M. Zhao, S. Chen, X. Quan, Y. B. Zhang, Photochlorination of bisphenol A by UV-Vis light irradiation in saline solution: effects of iron, nitrate and citric acid. Environ. Chem. 2010, 7, 548.
| Photochlorination of bisphenol A by UV-Vis light irradiation in saline solution: effects of iron, nitrate and citric acid.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhtFGrtg%3D%3D&md5=94fd608901ff69a3c31b86dabff8b9ddCAS |
[22] T. S. Singh, S. P. Gejji, B. S. M. Rao, H. Mohan, J. P. Mittal, Radiation chemical oxidation of aniline derivatives. J. Chem. Soc., Perkin. Trans. 2 2001, 2, 1205.
| Radiation chemical oxidation of aniline derivatives.Crossref | GoogleScholarGoogle Scholar |
[23] F. Wu, N. S. Deng, Photochemistry of hydrolytic iron(III) species and photoinduced degradation of organic compounds. A mini-review. Chemosphere 2000, 41, 1137.
| Photochemistry of hydrolytic iron(III) species and photoinduced degradation of organic compounds. A mini-review.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXksF2ntr4%3D&md5=27b285cafcd2e5c36a928fb8f8b6eef9CAS |
[24] F. Gosetti, M. Bottaro, V. Gianotti, E. Mazzucco, P. Frascarolo, D. Zampieri, C. Oliveri, A. Viarengo, M. C. Gennaro, Sun light degradation of 4-chloroaniline in waters and its effect on toxicity. A high performance liquid chromatography-diode array-tandem mass spectrometry study. Environ. Pollut. 2010, 158, 592.
| Sun light degradation of 4-chloroaniline in waters and its effect on toxicity. A high performance liquid chromatography-diode array-tandem mass spectrometry study.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXhsFyksLzK&md5=06f249a672d6bfa4de1a5551e6251ac6CAS |
[25] G. Mailhot, L. Hykrdová, J. Jirkovský, K. Lemr, G. Grabner, M. Bolte, Iron(III)-photoinduced degradation of 4-chloroaniline in aqueous solution. Appl. Catal. B 2004, 50, 25.
| Iron(III)-photoinduced degradation of 4-chloroaniline in aqueous solution.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXjt1aru74%3D&md5=86dabd5e1b98d603bf5aadfc57d2b129CAS |
[26] E. T. Denisov, I. V. Khudyakov, Mechanisms of action and reactivities of the free radicals of inhibitors. Chem. Rev. 1987, 87, 1313.
| Mechanisms of action and reactivities of the free radicals of inhibitors.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL2sXlvFOitrs%3D&md5=3d95f9ba97000ce9967f35b661b406fdCAS |
