A method for the analysis of 11 haloacetic acids in water samples has been developed. It involves enrichment of the target analytes from water samples by solid-phase extraction, derivatization to methyl esters, and gas chromatography coupled with tandem mass spectrometry determination. Gas chromatography conditions were optimized for a good separation of all haloacetic acids in a short runtime. Data were acquired in the multiple reaction monitoring mode. Six solid-phase extraction sorbents among the most widely used in environmental analysis were tested. Bakerbond SDB was retained because it has been shown to provide the best results for a large class of targeted haloacetic acids. The performances of the developed method have been assessed according to the French Standard NF T 90-210. The calibration curves for all the studied haloacetic acids had consistent slopes with r² values > 0.99. Quantification limits between 0.01 and 0.50 µg l⁻¹ were achieved. Satisfactory repeatability (relative standard deviation ≤ 14.3%) and intermediate precision (relative standard deviation ≤ 15.7%) were obtained. Applied to the analysis of 15 untreated water samples collected from three rivers, the method allowed the detection of five haloacetic acids including monochloroacetic acid (in 100% of the samples, <0.5–1.85 µg l⁻¹), dichloroacetic acid (87%, <0.05–0.22 µg l⁻¹), trichloroacetic acid (93%, <0.05–0.52 µg l⁻¹), dibromoacetic acid (53%, <0.01–0.40 µg l⁻¹), tribromoacetic acid (20%, <0.05–0.14 µg l⁻¹), and bromodichloroacetic acid (6%, < 0.05 µg l⁻¹).

Seawater chlorination has three main industrial uses: disinfection of water and installations, control of biofouling, and preventing the transport of aquatic invasive species. Once in contact with seawater, chlorine reacts rapidly with water constituents (e.g. bromide ions, ammonia, and nitrogen-containing compounds) to form a range of oxidative species (e.g. bromine and N-haloamines), termed “chlorine-produced oxidants” (CPOs) or “total residual oxidants” (TRO). The chemical nature of CPOs and their concentration are a function of two categories of parameters related to treatment modality (e.g. chlorine dose) and water quality (e.g. temperature, pH, ammonia concentration, and organic constituents). The chlorination process may result in continuous or intermittent releases of CPOs in seawater. The reactivity and potential ecotoxicity of CPO species largely depend on their physical and chemical properties. Therefore, evaluation of the biocidal effectiveness of chlorination and its potential impacts requires not only determining the sum of CPOs (via a bulk parameter), but also their chemical speciation. The aim of this article – which is the first of a trilogy dedicated to the chemical speciation of CPOs in seawater – is to provide an overview of current knowledge about chlorine chemistry in seawater and to discuss the biocidal efficacy and the environmental fate of resulting CPOs. The 2nd and 3rd articles delineate a comprehensive and critical review of analytical methods and approaches for the determination of CPOs in seawater.

Membrane-introduction mass spectrometry (MIMS) has been presented as one of the promising approaches for online and real-time analysis of monochloramine (NH₂Cl) in diverse matrices such as air, human breath, and aqueous matrices. Selective pervaporation of NH₂Cl through the introduction membrane overcomes the need for sample preparation steps. However, both the selectivity and sensitivity of MIMS can be affected by isobaric interferences, as reported by several researchers. High-resolution mass spectrometry helps to overcome those interferences. Recent miniaturization of Fourier transform—ion cyclotron resonance—mass spectrometry (FT-ICR MS) technology coupled to the membrane-introduction system provides a potent tool for in field analysis of monochloramine in environmental matrices. Monochloramine analysis by MIMS based FT-ICR MS system demonstrated decomposition into ammonia. To further clarify the origin of this decomposition, headspace analyses after bypassing the membrane were undertaken and showed that monochloramine decomposition was not exclusively related to interactions within the membrane. Adsorption inside the MIMS device, followed by surface-catalyzed decomposition, was suggested as a plausible additional mechanism of monochloramine decomposition to ammonia.