Apparent Reactivity of Bromine in Bromochloramine Depends on Synthesis Method: Implicating Bromine Chloride and Molecular Bromine as Important Bromine Species
Publication: Journal of Environmental Engineering
Volume 148, Issue 12
Abstract
The chloramination of bromide containing waters results in the formation of bromine containing haloamines: monobromamine (), dibromamine (), and bromochloramine (NHBrCl). Many studies have directly shown that bromamines are more reactive than chloramines in oxidation and substitution reactions with organic water constituents because the bromine atom in oxidants is more labile than the chlorine atom. However, similar studies have not been performed with NHBrCl. It has been assumed that NHBrCl has similar reactivity as bromamines with organic constituents in both oxidation and substitution reactions because NHBrCl, like bromamines, rapidly oxidizes N,N-diethyl-p-phenylenediamine. In this study, we examined the reactivity of NHBrCl with phenol red to determine if NHBrCl reacts as readily as bromamines in an isolated substitution reaction. NHBrCl was synthesized two ways to assess whether NHBrCl or the highly reactive intermediates, bromine chloride (BrCl) and molecular bromine (), were responsible for bromine substitution of phenol red. NHBrCl was found to be much less reactive than bromamines with phenol red and that BrCl and appeared to be the true brominating agents in solutions where NHBrCl is formed. This work highlights the need to reexamine what the true brominating agents are in chloraminated waters containing bromide.
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Data Availability Statement
All data, models, and code generated or used during the study appear in the published article.
Acknowledgments
This work was supported by the National Science Foundation under Grant 1953206.
Disclaimer
The research presented was not performed or funded by EPA and was not subject to EPA’s quality system requirements. The views expressed in this article are those of the author(s) and do not necessarily represent the views or the policies of the US Environmental Protection Agency. Any mention of trade names, manufacturers, or products does not imply an endorsement by the United States Government or the US Environmental Protection Agency. The EPA and its employees do not endorse any commercial products, services, or enterprises.
References
Allard, S., K. Cadee, R. Tung, and J. P. Croué. 2018a. “Impact of brominated amines on monochloramine stability during in-line and pre-formed chloramination assessed by kinetic modelling.” Sci. Total Environ. 618 (Mar): 1431–1439. https://doi.org/10.1016/j.scitotenv.2017.09.281.
Allard, S., W. Hu, J. B. Le Menn, K. Cadee, H. Gallard, and J. P. Croué. 2018b. “Method development for quantification of bromochloramine using membrane introduction mass spectrometry.” Environ. Sci. Technol. 52 (14): 7805–7812. https://doi.org/10.1021/acs.est.8b00889.
Alsulaili, A. 2009. Impact of bromide, NOM, and prechlorination on haloamine formation, speciation, and decay during chloramination. Austin, TX: Univ. of Texas at Austin.
American Water Works Association. 2018. 2017 water utility disinfection survey report. Denver: American Water Works Association.
Amy, G., and AWWA Research Foundation, Metropolitan Water District of Southern California. 1994. Survey of bromide in drinking water and impacts on DBP formation. Denver: American Water Works Research Foundation Report.
Broadwater, M. A., T. L. Swanson, and J. D. Sivey. 2018. “Emerging investigators series: Comparing the inherent reactivity of often-overlooked aqueous chlorinating and brominating agents toward salicylic acid.” Environ. Sci. Water Res. Technol. 4 (3): 369–384. https://doi.org/10.1039/C7EW00491E.
Brodfuehrer, S. H., D. G. Wahman, A. Alsulaili, G. E. Speitel Jr., and L. E. Katz. 2020. “Role of carbonate species on general acid catalysis of bromide oxidation by hypochlorous acid (HOCl) and oxidation by molecular chlorine (Cl2).” Environ. Sci. Technol. 54 (24): 16186–16194. https://doi.org/10.1021/acs.est.0c04563.
Diehl, A. C., G. E. Speitel Jr., J. M. Symons, S. W. Krasner, C. J. Hwang, and S. E. Barrett. 2000. “DBP Formation during chloramination.” Am. Water Works Assoc. 92 (6): 76–90. https://doi.org/10.1002/j.1551-8833.2000.tb08961.x.
Furman, C. S., and D. W. Margerum. 1998. “Mechanism of chlorine dioxide and chlorate ion formation from the reaction of hypobromous acid and chlorite ion.” Inorg. Chem. 37 (17): 4321–4327. https://doi.org/10.1021/ic980262q.
Gazda, M. 1994. “Non-metal redox reactions of chloramines with bromide ion and with bromine and the development and testing of a mixing cell for a new pulsed-accelerated-flow spectrophotometer with position-resolved observation.” Ph.D. dissertation, Dept. of Chemistry, Purdue Univ.
Gazda, M., L. E. Dejarme, T. K. Choudhury, R. G. Cooks, and D. W. Margerum. 1993. “Mass spectrometric evidence for the formation of bromochloramine and N-Bromo-N-chloromethylamine in aqueous solution.” Environ. Sci. Technol. 27 (3): 557–561. https://doi.org/10.1021/es00040a015.
Gazda, M., and D. W. Margerum. 1994. “Reactions of monochloramine with Br2, Br3-, HOBr, OBr-: Formation of bromochloramines.” Inorg. Chem. 33 (1): 118–123. https://doi.org/10.1021/ic00079a022.
Guo, G., and F. Lin. 2009. “The bromination kinetics of phenolic compounds in aqueous solution.” J. Hazard. Mater. 170 (2–3): 645–651. https://doi.org/10.1016/j.jhazmat.2009.05.017.
Hach Company. 2018. Method 10070, chlorine, free and total, high range. USEPA DPD Method, 0.1 to 10 mg Cl2/L. Loveland, CO: Hach Company.
Hand, V. C., and D. W. Margerum. 1983. “Kinetics and mechanisms of the decomposition of dichloramine in aqueous solution.” Inorg. Chem. 22 (10): 1449–1456. https://doi.org/10.1021/ic00152a007.
Heeb, M. B., J. Criquet, S. G. Zimmermann-Steffens, and U. von Gunten. 2014. “Oxidative treatment of bromide-containing waters: Formation of bromine and its reactions with inorganic and organic compounds—A critical review.” Water Res. 48 (Oct): 15–42. https://doi.org/10.1016/j.watres.2013.08.030.
Heeb, M. B., I. Kristiana, D. Trogolo, J. S. Arey, and U. Von Gunten. 2017. “Formation and reactivity of inorganic and organic chloramines and bromamines during oxidative water treatment.” Water Res. 110 (Mar): 91–101. https://doi.org/10.1016/j.watres.2016.11.065.
Hu, W., F. R. Lauritsen, and S. Allard. 2021. “Identification and quantification of chloramines, bromamines and bromochloramine by membrane introduction mass spectrometry (MIMS).” Sci. Total Environ. 751 (Jan): 142303. https://doi.org/10.1016/j.scitotenv.2020.142303.
Hua, G., and D. A. Reckhow. 2007. “Comparison of disinfection byproduct formation from chlorine and alternative disinfectants.” Water Res. 41 (8): 1667–1678. https://doi.org/10.1016/j.watres.2007.01.032.
Huwaldt, J. A., and S. Steinhorst. 2020. “Plot digitizer 3.1.4. PlotDigitizer-software.” Accessed May 20, 2022. https://plotdigitizer.com.
Kristiana, I., H. Gallard, C. Joll, and J. P. Croué. 2009. “The formation of halogen-specific TOX from chlorination and chloramination of natural organic matter isolates.” Water Res. 43 (17): 4177–4186. https://doi.org/10.1016/j.watres.2009.06.044.
Kumar, K., R. A. Day, and D. W. Margerum. 1986. “Atom-transfer Redox kinetics: General-acid-assisted oxidation of iodide by chloramines and hypochlorite.” Inorg. Chem. 25 (24): 4344–4350. https://doi.org/10.1021/ic00244a012.
Kumar, K., and D. W. Margerum. 1987. “Kinetics and mechanism of general-acid-assisted oxidation of bromide by hypochlorite and hypochlorous acid.” Inorg. Chem. 26 (16): 2706–2711. https://doi.org/10.1021/ic00263a030.
Luh, J., and B. J. Mariñas. 2012. “Bromide ion effect on N -Nitrosodimethylamine formation by monochloramine.” Environ. Sci. Technol. 46 (9): 5085–5092. https://doi.org/10.1021/es300077x.
Luh, J., and B. J. Mariñas. 2014. “Kinetics of bromochloramine formation and decomposition.” Environ. Sci. Technol. 48 (5): 2843–2852. https://doi.org/10.1021/es4036754.
Pope, P. G., and G. E. Speitel. 2008. “Reactivity of bromine-substituted haloamines in forming haloacetic acids.” Disinfection by-products in drinking water: Occurrence, formation, health effects, and control. ACS symp. ser. 995, 182–197. Washington, DC: American Chemical Society.
Sivey, J. D., J. Samuel Arey, P. R. Tentscher, and A. Lynn Roberts. 2013. “Reactivity of BrCl, Br2, BrOCl, Br2O and HOBr toward dimethenamid in solutions of bromide + aqueous free chlorine.” Environ. Sci. Technol. 47 (15): 8990. https://doi.org/10.1021/es302730h.
Sollo, F. W., T. E. Larson, and F. F. McGurk. 1971. “Colorimetric methods for bromine.” Environ. Sci. Technol. 5 (3): 240–246. https://doi.org/10.1021/es60050a009.
Trofe, T. W., G. W. Inman, and J. Donald Johnson. 1980. “Kinetics of monochloramine decomposition in the presence of bromide.” Environ. Sci. Technol. 14 (5): 544–549. https://doi.org/10.1021/es60165a008.
Troy, R. C., and D. W. Margerum. 1991. “Non-metal Redox kinetics: Hypobromite and hypobromous acid reactions with iodide and with sulfite and the hydrolysis of bromosulfate.” Inorg. Chem. 30 (18): 3538–3543. https://doi.org/10.1021/ic00018a028.
Valentine, R. L. 1982. “The disappearance of chloramines in the presence of bromide and nitrite.” Ph.D. dissertation, Dept. of Civil Engineering, Univ. of California.
Valentine, R. L. 1986. “Bromochloramine oxidation of N,N-diethyl-p-phenylenediamine in the presence of monochloramine.” Environ. Sci. Technol. 20 (2): 166–170. https://doi.org/10.1021/es00144a009.
Wajon, J. E., and J. C. Morris. 1982. “Rates of formation of N-bromo amines in aqueous solution.” Inorg. Chem. 21 (12): 4258–4263. https://doi.org/10.1021/ic00142a030.
Yang, Y., Y. Komaki, S. Y. Kimura, H. Y. Hu, E. D. Wagner, B. J. Mariñas, and M. J. Plewa. 2014. “Toxic impact of bromide and iodide on drinking water disinfected with chlorine or chloramines.” Environ. Sci. Technol. 48 (20): 12362–12369. https://doi.org/10.1021/es503621e.
Zhai, H., X. Zhang, X. Zhu, J. Liu, and M. Ji. 2014. “Formation of brominated disinfection byproducts during chloramination of drinking water: New polar species and overall kinetics.” Environ. Sci. Technol. 48 (5): 2579–2588. https://doi.org/10.1021/es4034765.
Zhu, X., and X. Zhang. 2016. “Modeling the formation of TOCl, TOBr and TOI during chlor(am)ination of drinking water.” Water Res. 96 (Jun): 166–176. https://doi.org/10.1016/j.watres.2016.03.051.
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© 2022 American Society of Civil Engineers.
History
Received: Feb 17, 2022
Accepted: Jul 11, 2022
Published online: Sep 19, 2022
Published in print: Dec 1, 2022
Discussion open until: Feb 19, 2023
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