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Simultaneous time-resolved inorganic haloamine measurements enable analysis of disinfectant degradation kinetics and by-product formation

Nature Water (2024)Cite this article

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Abstract

We demonstrate the application of proton transfer time-of-flight mass spectrometry (PTR-TOF-MS) in monitoring the kinetics of disinfectant decay in water with a sensitivity one to three orders of magnitude greater than other analytical methods. Chemical disinfection inactivates pathogens during water treatment and prevents regrowth as water is conveyed in distribution system pipes, but it also causes formation of toxic disinfection by-products. Analytical limits have hindered kinetic models, which aid in ensuring water quality and protecting public health by predicting disinfection by-products formation. PTR-TOF-MS, designed for measuring gas phase concentrations of organic compounds, was able to simultaneously monitor aqueous concentrations of five inorganic haloamines relevant to chloramine disinfection under drinking water relevant concentrations. This novel application to aqueous analytes opens a new range of applications for PTR-TOF-MS.

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Fig. 1: Representative PTR-TOF-MS mass spectra for each haloamine.
Fig. 2: PTR-TOF-MS signal counts per second NH2Cl of seven replicate 2 µM standards.
Fig. 3: Interference from dihaloamines on monohaloamines.
Fig. 4: Measured concentrations of total haloamines and monochloramine.
Fig. 5: Comparison of model to measured haloamine concentrations during the kinetic experiment using PTR-TOF-MS.

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Data availability

All data supporting the finding of this study are available within this article and its Supplementary Information. The data that support the findings of this study are available via figshare at https://doi.org/10.6084/m9.figshare.25302220 (ref. 49).

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Acknowledgements

This work was supported by the National Science Foundation under grant 1953206. 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. EPA and its employees do not endorse any commercial products, services or enterprises.

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Author notes

  1. These authors contributed equally: Samuel H. Brodfuehrer, Daniel C. Blomdahl.

Authors and Affiliations

  1. Maseeh Department of Civil, Architectural and Environmental Engineering, University of Texas at Austin, Austin, TX, USA

    Samuel H. Brodfuehrer, Daniel C. Blomdahl, Gerald E. Speitel Jr., Pawel K. Misztal & Lynn E. Katz

  2. Office of Research and Development, United States Environmental Protection Agency, Cincinnati, OH, USA

    David G. Wahman

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Contributions

P.K.M. and L.E.K. conceived the research. S.H.B., D.C.B., P.K.M. and L.E.K. designed the research. S.H.B. and D.C.B. performed the experimental work. S.H.B., D.C.B., D.G.W., G.E.S., P.K.M. and L.E.K. contributed to interpreting the data. S.H.B. and D.C.B. wrote the original draft. S.H.B., D.C.B., D.G.W., G.E.S., P.K.M. and L.E.K. contributed to reviewing and editing the manuscript.

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Correspondence to Lynn E. Katz.

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The authors declare no competing interests.

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Peer review information

Nature Water thanks Said Kinani and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Discussion, Figs. 1–6 and Tables 1–4.

Supplementary Data 1

Mass spectrum of ambient lab air.

Supplementary Data 2

Haloamine standard curves.

Supplementary Data 3

Haloamine specific kinetic experiments.

Supplementary Data 4

Example kinetic data from experiments performed by Luh and Marinas.

Supplementary Data 5

Kinetic experiment with NOM.

Source data

Source Data Fig. 1

Individual haloamine mass spectra.

Source Data Fig. 2

PTR-TOF-MS response following sample introduction.

Source Data Fig. 3

Dihaloamine interferences.

Source Data Fig. 4

Colorimetric methods used during kinetic experiments.

Source Data Fig. 5

Haloamine specific kinetic experiments.

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Brodfuehrer, S.H., Blomdahl, D.C., Wahman, D.G. et al. Simultaneous time-resolved inorganic haloamine measurements enable analysis of disinfectant degradation kinetics and by-product formation. Nat Water (2024). https://doi.org/10.1038/s44221-024-00227-4

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