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OH-initiated oxidation mechanism and kinetics of organic sunscreen benzophenone-3: A theoretical study

  • Ming-Guo Peng , Hua-Jie Li , Er-Deng Du EMAIL logo , Hong-Qi Feng , Juan-Lin Wang , Dong-Dong Li and Jing Zhou
Published/Copyright: February 2, 2016
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Chemical Papers
From the journal Chemical Papers Volume 70 Issue 6

Abstract

Benzophenone-3 (BP-3), as an important organic UV filter, is widely used in the sunscreen, cosmetic, and personal care products. The chemical reaction mechanism and kinetics of BP-3 degradation initiated by hydroxyl (OH) radical was investigated in the atmosphere based on the density functional theory (DFT). The results showed that the OH radical is more easily added to the C3 position of the aromatic ring (pathway 3), while the H atom abstraction from the OH group on the aromatic ring (pathway 23) is an energetically favorable reaction pathway. At ambient temperature, 298 K, the overall rate constant for the primary reaction is about 1.50 × 10−10 cm3 mol −1 s−1 with the lifetime of 1.92 h. OH addition reactions play the key role in the OH-initiated reaction of BP-3. The study is helpful for better understanding of the removal, transformation, and fate of BP-3 in the atmosphere.

Keywords: OH radical; benzophenone-3 (BP-3); mechanism and kinetics; organic sunscreen; quantum calculation

Acknowledgements

This work was supported by the Key Special Program on S&T for the Pollution Control and Treatment of Water Bodies (No. 2012ZX07301-001), National Natural Science Foundation of China (No. 51308078), Natural Science Foundation of the Jiangsu Province, China (No. BK20130252). Chemical calculations and software services were also provided by the Supercomputing Center of the Chinese Academy of Science, and the High Performance Computing Cluster System of the Changzhou University.

References

Azofra, L. M., Alkorta, I., Elguero, J., & Toro-Labbé, A. (2012). Mechanisms of formation of hemiacetals: Intrinsic reactivity analysis. The Journal of Physical Chemistry A, 116, 8250–8259. DOI: 10.1021/jp304495f.10.1021/jp304495fSearch in Google Scholar

Bai, J., Sun, X., Zhang, C., Gong, C., Hu, J., & Zhang, J. (2014). Mechanism and kinetics study on the ozonolysis reaction of 2,3,7,8-TCDD in the atmosphere. Journal of Environmental Sciences, 26, 181–188. DOI: 10.1016/s1001-0742(13)60396-4.10.1016/s1001-0742(13)60396-4Search in Google Scholar

Brausch, J. M., & Rand, G. M. (2011). A review of personal care products in the aquatic environment: Environmental concentrations and toxicity. Chemosphere, 82, 1518–1532. DOI: 10.1016/j.chemosphere.2010.11.018.10.1016/j.chemosphere.2010.11.018Search in Google Scholar PubMed

Burnett, M. E., & Wang, S. Q. (2011). Current sunscreen controversies: a critical review. Photodermatology, Photoimmunology & Photomedicine, 27, 58–67. DOI: 10.1111/j.1600-0781.2011.00557.x.10.1111/j.1600-0781.2011.00557.xSearch in Google Scholar PubMed

Caliman, F. A., & Gavrilescu, M. (2009). Pharmaceuticals, personal care products and endocrine disrupting agents in the environment –a review. CLEAN - Soil, Air, Water, 37, 277–303. DOI: 10.1002/clen.200900038.10.1002/clen.200900038Search in Google Scholar

Canneaux, S., Bohr, F., & Henon, E. (2014). KiSThelP: A program to predict thermodynamic properties and rate constants from quantum chemistry results. Journal of Computational Chemistry, 35, 82–93. DOI: 10.1002/jcc.23470.10.1002/jcc.23470Search in Google Scholar PubMed

Cao, H., He, M., Han, D., Sun, Y., Zhao, S., Ma, H., & Yao, S. (2012). Mechanistic and kinetic study on the reaction of 2;4-dibrominated diphenyl ether (BDE-7) with OH radicals. Computational and Theoretical Chemistry, 983, 31–37. DOI: 10.1016/j.comptc.2011.12.017.10.1016/j.comptc.2011.12.017Search in Google Scholar

Cao, H., He, M., Han, D., Li, J., Li, M., Wang, W., & Yao, S. (2013). OH-initiated oxidation mechanisms and kinetics of 2,4,4′-tribrominated diphenyl ether. Environmental Science & Technology, 47, 8238–8247. DOI: 10.1021/es400088v.10.1021/es400088vSearch in Google Scholar PubMed

Chan, B., & Radom, L. (2012). Approaches for obtaining accurate rate constants for hydrogen abstraction by a chlorine atom. The Journal of Physical Chemistry A, 116, 3745–3752. DOI: 10.1021/jp3007409.10.1021/jp3007409Search in Google Scholar PubMed

Dang, J., Shi, X., Zhang, Q., Hu, J., & Wang, W. (2015). Mechanism and kinetic properties for the OH-initiated atmospheric oxidation degradation of 9,10-dichlorophenanthrene. Science of the Total Environment, 505, 787–794. DOI: 10.1016/j.scitotenv.2014.10.081.10.1016/j.scitotenv.2014.10.081Search in Google Scholar PubMed

Duirk, S. E., Bridenstine, D. R., & Leslie, D. C. (2013). Reaction of benzophenone UV filters in the presence of aqueous chlorine: Kinetics and chloroform formation. Water Research, 47, 579–587. DOI: 10.1016/j.watres.2012.10.021.10.1016/j.watres.2012.10.021Search in Google Scholar PubMed

Fent, K., Zenker, A., & Rapp, M. (2010). Widespread occurrence of estrogenic UV-filters in aquatic ecosystems in Switzerland. Environmental Pollution, 158, 1817–1824. DOI: 10.1016/j.envpol.2009.11.005.10.1016/j.envpol.2009.11.005Search in Google Scholar PubMed

Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G. A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H. P., Izmaylov, A. F., Bloino, J., Zheng, G., Sonnenberg, J. L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J. A., Jr., Peralta, J. E., Ogliaro, F., Bearpark, M., Heyd, J. J., Brothers, E., Kudin, K. N., Staroverov, V. N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J. C., Iyengar, S. S., Tomasi, J., Cossi, M., Rega, N., Millam, N. J., Klene, M., Knox, J. E., Cross, J. B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R. E., Yazyev, O., Austin, A. J., Cammi, R., Pomelli, C., Ochterski, J. W., Martin, R. L., Morokuma, K., Zakrzewski, V. G., Voth, G. A., Salvador, P., Dannenberg, J. J., Dapprich, S., Daniels, A. D., Farkas, Ö. Foresman, J. B., Ortiz, J. V., Cioslowski, J., & Fox, D. J. (2009). Gaussian 09, Revision A.1 [computer software]. Wallingford, CT, USA: Gaussian, Inc.Search in Google Scholar

Gago-Ferrero, P., Díaz-Cruz, M. S., & Barceló, D. (2012). An overview of UV-absorbing compounds (organic UV filters) in aquatic biota. Analytical and Bioanalytical Chemistry, 404, 2597–2610. DOI: 10.1007/s00216-012-6067-7.10.1007/s00216-012-6067-7Search in Google Scholar PubMed

Gago-Ferrero, P., Demeestere, K., Díaz-Cruz, M. S., & Barceló, D. (2013). Ozonation and peroxone oxidation of benzophenone-3 in water: Effect of operational parameters and identification of intermediate products. Science of the Total Environment, 443, 209–217. DOI: 10.1016/j.scitotenv.2012.10.006.10.1016/j.scitotenv.2012.10.006Search in Google Scholar PubMed

Kaiser, D., Sieratowicz, A., Zielke, H., Oetken, M., Hollert, H., & Oehlmann, J. (2012a). Ecotoxicological effect characterisation of widely used organic UV filters. Environmental Pollution, 163, 84–90. DOI: 10.1016/j.envpol.2011.12.014.10.1016/j.envpol.2011.12.014Search in Google Scholar PubMed

Kaiser, D., Wappelhorst, O., Oetken, M., & Oehlmann, J. (2012b). Occurrence of widely used organic UV filters in lake and river sediments. Environmental Chemistry, 9, 139–147. DOI: 10.1071/en11076.10.1071/en11076Search in Google Scholar

Kim, S., & Choi, K. (2014). Occurrences, toxicities, and ecological risks of benzophenone-3, a common component of organic sunscreen products: A mini-review. Environment International, 70, 143–157. DOI: 10.1016/j.envint.2014.05.015.10.1016/j.envint.2014.05.015Search in Google Scholar PubMed

Li, C., Xie, H. B., Chen, J., Yang, X., Zhang, Y., & Qiao, X. (2014a). Predicting gaseous reaction rates of short chain chlorinated paraffins with OH: Overcoming the difficulty in experimental determination. Environmental Science & Technology, 48, 13808–13816. DOI: 10.1021/es504339r.10.1021/es504339rSearch in Google Scholar PubMed

Li, P., Niu, W., Gao, T., & Wang, H. (2014b). Gas-phase water activation by Th atom: Reaction mechanisms and topological analysis. International Journal of Quantum Chemistry, 114, 760–768. DOI: 10.1002/qua.24651.10.1002/qua.24651Search in Google Scholar

Liu, Y. S., Ying, G. G., Shareef, A., & Kookana, R. S. (2011). Photostability of the UV filter benzophenone-3 and its effect on the photodegradation of benzotriazole in water. Environmental Chemistry, 8, 581–588. DOI: 10.1071/en11068.10.1071/en11068Search in Google Scholar

Liu, Y. S., Ying, G. G., Shareef, A., & Kookana, R. S. (2012). Biodegradation of the ultraviolet filter benzophenone-3 under different redox conditions. Environmental Toxicology and Chemistry, 31, 289–295. DOI: 10.1002/etc.749.10.1002/etc.749Search in Google Scholar PubMed

Lu, T., & Chen, F. (2012). Multiwfn: A multifunctional wave-function analyzer. Journal of Computational Chemistry, 33, 580–592. DOI: 10.1002/jcc.22885.10.1002/jcc.22885Search in Google Scholar PubMed

Manová, E., von Goetz, N., Hauri, U., Bogdal, C., & Hungerbühler, K. (2013). Organic UV filters in personal care products in Switzerland: A survey of occurrence and concentrations. International Journal of Hygiene and Environmental Health, 216, 508–514. DOI: 10.1016/j.ijheh.2012.08.003.10.1016/j.ijheh.2012.08.003Search in Google Scholar PubMed

Rodil, R., Quintana, J. B., Concha-Gra´na, E., López-Mahía, P., Muniategui-Lorenzo, S., & Prada-Rodríguez, D. (2012). Emerging pollutants in sewage, surface and drinking water in Galicia (NW Spain). Chemosphere, 86, 1040–1049. DOI: 10.1016/j.chemosphere.2011.11.053.10.1016/j.chemosphere.2011.11.053Search in Google Scholar PubMed

Tsui, M. M. P., Leung, H. W., Lam, P. K. S., & Murphy, M. B. (2014a). Seasonal occurrence, removal efficiencies and preliminary risk assessment of multiple classes of organic UV filters in wastewater treatment plants. Water Research, 53, 58–67. DOI: 10.1016/j.watres.2014.01.014.10.1016/j.watres.2014.01.014Search in Google Scholar PubMed

Tsui, M. M. P., Leung, H. W., Wai, T. C., Yamashita, N., Taniyasu, S., Liu, W., Lam, P. K. S., & Murphy, M. B. (2014b). Occurrence, distribution and ecological risk assessment of multiple classes of UV filters in surface waters from different countries. Water Research, 67, 55–65. DOI: 10.1016/j.watres.2014.09.013.10.1016/j.watres.2014.09.013Search in Google Scholar PubMed

US EPA (2012). Estimation programs interface suite for Microsoft Windows, Version 4.11 [computer software]. Washington, DC, USA: United States Environmental Protection Agency.Search in Google Scholar

Wang, L., & Kannan, K. (2013). Characteristic profiles of benzonphenone-3 and its derivatives in urine of children and adults from the United States and China. Environmental Science & Technology, 47, 12532–12538. DOI: 10.1021/es4032908.10.1021/es4032908Search in Google Scholar PubMed

Wang, S., Hao, C., Gao, Z., Chen, J., & Qiu, J. (2014). Theoretical investigations on direct photolysis mechanisms of polychlorinated diphenyl ethers. Chemosphere, 111, 7–12. DOI: 10.1016/j.chemosphere.2014.03.040.10.1016/j.chemosphere.2014.03.040Search in Google Scholar PubMed

Wei, X., Chen, J., Xie, Q., Zhang, S., Ge, L., & Qiao, X. (2013). Distinct photolytic mechanisms and products for different dissociation species of ciprofloxacin. Environmental Science & Technology, 47, 4284–4290. DOI: 10.1021/es400425b.10.1021/es400425bSearch in Google Scholar PubMed

Wu, P. Z., Li, J., Li, S. J., & Tao, F. M. (2012). Theoretical study of mechanism and kinetics for the addition of hydroxyl radical to phenol. Science China-Chemistry, 55, 270–276. DOI: 10.1007/s11426-011-4380-1.10.1007/s11426-011-4380-1Search in Google Scholar

Xie, H. B., Li, C., He, N., Wang, C., Zhang, S., & Chen, J. (2014). Atmospheric chemical reactions of monoethanolamine initiated by OH radical: Mechanistic and kinetic study. Environmental Science & Technology, 48, 1700–1706. DOI: 10.1021/es405110t.10.1021/es405110tSearch in Google Scholar PubMed

Yang, B., & Ying, G. G. (2013). Oxidation of benzophenone-3 during water treatment with ferrate(VI). Water Research, 47, 2458–2466. DOI: 10.1016/j.watres.2013.02.018.10.1016/j.watres.2013.02.018Search in Google Scholar PubMed

Zhang, C., Yang, W., Bai, J., Zhao, Y., Gong, C., Sun, X., Zhang, Q., & Wang, W. (2012a). Mechanism and kinetic study on the gas-phase reactions of OH radical with carbamate insecticide isoprocarb. Atmospheric Environment, 60, 460–466. DOI: 10.1016/j.atmosenv.2012.07.015.10.1016/j.atmosenv.2012.07.015Search in Google Scholar

Zhang, C., Zhao, Y., Bai, J., Gong, C., & Sun, X. (2012b). Mechanism and kinetic study on the OH-initiated degradation of 2,3,7,8-tetrachlorinated dibenzofuran in atmosphere. Science of the Total Environment, 435–436, 53–60. DOI: 10.1016/j.scitotenv.2012.07.007.10.1016/j.scitotenv.2012.07.007Search in Google Scholar PubMed

Zhang, H., Xie, H., Chen, J., & Zhang, S. (2015). Prediction of hydrolysis pathways and kinetics for antibiotics under environmental pH conditions: A Quantum chemical study on cephradine. Environmental Science & Technology, 49, 1552–1558. DOI: 10.1021/es505383b.10.1021/es505383bSearch in Google Scholar PubMed

Zhou, J., Chen, J., Liang, C. H., Xie, Q., Wang, Y. N., Zhang, S., Qiao, X., & Li, X. (2011). Quantum chemical investigation on the mechanism and kinetics of PBDE photooxidation by OH: A case study for BDE-15. Environmental Science & Technology, 45, 4839–4845. DOI: 10.1021/es200087w.10.1021/es200087wSearch in Google Scholar PubMed

Received: 2015-6-17
Revised: 2015-9-13
Accepted: 2015-10-29
Published Online: 2016-2-2
Published in Print: 2016-6-1

© 2016 Institute of Chemistry, Slovak Academy of Sciences

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https://doi.org/10.1515/chempap-2016-0003
Keywords for this article
OH radical; benzophenone-3 (BP-3); mechanism and kinetics; organic sunscreen; quantum calculation

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