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Chlorination of parabens: reaction kinetics and transformation product identification

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Abstract

The reactivity and fate of parabens during chlorination were investigated in this work. Chlorination kinetics of methylparaben (MeP), ethylparaben (EtP), propylparaben (PrP), and butylparaben (BuP) were studied in the pH range of 4.0 to 11.0 at 25 ± 1 °C. Apparent rate constants (k app) of 9.65 × 10−3 M-0.614·s−1, 1.77 × 10−2 M-1.019·s−1, 2.98 × 10−2 M-0.851·s−1, and 1.76 × 10−2 M-0.860·s−1 for MeP, EtP, PrP, and BuP, respectively, were obtained at pH 7.0. The rate constants depended on the solution pH, temperature, and NH4 + concentration. The maximum k app was obtained at pH 8.0, and the minimum value was obtained at pH 11.0. The reaction rate constants increased with increasing temperature. When NH4 + was added to the solution, the reaction of parabens was inhibited due to the rapid formation of chloramines. Two main transformation products, 3-chloro-parabens and 3,5-dichloro-parabens, were identified by GC-MS and LCMS-IT-TOF, and a reaction pathway was proposed. Dichlorinated parabens accumulated in solution, which is a threat to human health and the aqueous environment.

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Acknowledgments

This research was partly supported by the National Natural Science Foundation of China (51578205, 51108149), the Fundamental Research Funds for the Central Universities (JZ2016HGTB0722), and the Open Topic of State Key Laboratory of Pollution Control and Resource Reuse (PCRRF11014).

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Correspondence to Shoujun Yuan.

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Responsible Editor: Roland Kallenborn

Highlights

The exact rate orders of four parabens were calculated.

The effect of parameters such as pH, temperature, NH4 + and water quality on the reaction of chlorine with parabens was investigated.

The dichlorinated parabens were accumulated in solution with the presence of chlorine in a long time.

Novelty statement

Parabens have been widely used as antimicrobial preservatives in cosmetics, foodstuffs, paper, and pharmaceuticals. Parabens have estrogenic activity and may have a potential relationship with breast cancer. However, the fate of parabens during chlorine disinfection process is unclear; complete kinetic study has not been reported. In this study, the exact rate order and apparent rate constants for the reaction of chlorine with four parabens were determined, and the effect of pH, temperature, NH4 +, and water quality on the reaction were investigated. Moreover, the possible transformation pathway was proposed, and the stability of transformation products in the long time was studied.

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Mao, Q., Ji, F., Wang, W. et al. Chlorination of parabens: reaction kinetics and transformation product identification. Environ Sci Pollut Res 23, 23081–23091 (2016). https://doi.org/10.1007/s11356-016-7499-y

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