Challenges and opportunities for on-line monitoring of chlorine-produced oxidants in seawater using portable membrane-introduction Fourier transform-ion cyclotron resonance mass spectrometry

Adrien Roumiguières; Stéphane Bouchonnet; Said Kinani

doi:10.1007/s00216-020-03043-3

Challenges and opportunities for on-line monitoring of chlorine-produced oxidants in seawater using portable membrane-introduction Fourier transform-ion cyclotron resonance mass spectrometry

Anal Bioanal Chem. 2021 Jan;413(3):885-900. doi: 10.1007/s00216-020-03043-3. Epub 2020 Nov 19.

Authors

Adrien Roumiguières^{1

2}, Stéphane Bouchonnet², Said Kinani³

Affiliations

¹ Laboratoire National d'Hydraulique et Environnement (LNHE), Division Recherche et Développement, Electricité de France (EDF), 6 Quai Watier, 78401, Chatou Cedex 01, France.
² Laboratoire de Chimie Moléculaire, CNRS, Institut polytechnique de Paris, Route de Saclay, 91128, Palaiseau, France.
³ Laboratoire National d'Hydraulique et Environnement (LNHE), Division Recherche et Développement, Electricité de France (EDF), 6 Quai Watier, 78401, Chatou Cedex 01, France. said.kinani@edf.fr.

PMID: 33211126
DOI: 10.1007/s00216-020-03043-3

Abstract

The present study reports the first evaluation of a MIMS device equipped with a high-resolution Fourier transform-ion cyclotron resonance mass spectrometer (FT-ICR MS) for comprehensive speciation of chlorine-produced oxidants (CPO) in seawater. A total of 40 model compounds were studied: 4 inorganic haloamines (mono-, di-, and trichloramine and monobromamine), 22 organic N-haloamines, 12 N-haloamino acids, and 2 free oxidants (HOCl/ClO^- and HOBr/BrO^-). The main key factors influencing the analytes' introduction and their detection were optimized. Under optimized conditions, the rise and fall times of the MIMS signal ranged from 8 to 79 min and from 7 to 73 min, respectively, depending on the compound. Free oxidants and N-haloamino acids, which are ionic or too polar at seawater pH, hardly crossed the membrane, and MIMS analysis was thus unsuitable. Nevertheless, better enrichment and therefore better sensitivity were achieved with organic N-haloamines than with inorganic haloamines. The observed detection limits ranged from tens of μM to sub-μM levels. Oxidant decomposition occurred inside the MIMS device, at a higher rate for N-bromamines than for chlorinated analogues.Graphical abstract.

Keywords: Chlorine-produced oxidants; Fourier transform-ion cyclotron resonance; Membrane-introduction mass spectrometry; Proton transfer reaction; Seawater.