A Critical Review on Chemical Speciation of Chlorine-Produced Oxidants in Seawater. Part 3: Chromatographic- and Mass Spectrometric-Based Methodologies.

Chlorination of seawater forms a range of secondary oxidative species - collectively called "chlorine-produced oxidants" (CPOs) - having different biocidal, environmental and ecotoxicological properties. The chemical speciation of these compounds is an important step in attempts to assess the effectiveness of chlorination and the potential impacts of its releases. However, comprehensive determination of CPOs represents a significant analytical challenge for many reasons, including the following: CPO species are numerous, highly reactive, with short-lifetimes, difficult to isolate and generally present at low concentrations in a complex salt matrix.

A Critical Review on Chemical Speciation of Chlorine-Produced Oxidants (CPOs) in Seawater. Part 1: Chlorine Chemistry in Seawater and Its Consequences in Terms of Biocidal Effectiveness and Environmental Impact.

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.

A Critical Review on Chemical Speciation of Chlorine-Produced Oxidants (CPOs) in Seawater. Part 2: Sampling, Sample Preparation and Non-Chromatographic and Mass Spectrometric-Based Methods.

Chlorination of seawater forms a range of secondary oxidative species, collectively termed "chlorine-produced oxidants" (CPOs). These compounds do not have the same biocidal efficacy, the same fate and behavior in the marine environment, the same potential formation of chlorination by-products (CBPs), nor the same effects on marine organisms. Their chemical speciation is an important step toward an accurate assessment of the effectiveness of chlorination and the potential impacts of its releases, among others.

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

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.

Tracking Monochloramine Decomposition in MIMS Analysis.

Membrane-introduction mass spectrometry (MIMS) has been presented as one of the promising approaches for online and real-time analysis of monochloramine (NHCl) in diverse matrices such as air, human breath, and aqueous matrices. Selective pervaporation of NHCl 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.

Determination of monochloramine dissipation kinetics in various surface water qualities under relevant environmental conditions - Consequences regarding environmental risk assessment.

A total 190 experiments were performed to study the dissipation kinetics of monochloramine (NHCl, CAS no 10599-90-3) in surface water samples from six rivers (Loire, Rhône, Meuse, Garonne, Seine and Moselle) and an artificial reservoir (Mirgenbach), all located in France. Experiments were conducted in an open reactor, under relevant controlled environmental conditions. The impact of various parameters such as initial NHCl concentration, temperature, pH, presence of sediments, sampling site and collection period was investigated.

Development and validation of a multiclass method for the determination of organohalogen disinfectant by-products in water samples using solid phase extraction and gas chromatography-tandem mass spectrometry.

An analytical method employing solid phase extraction (SPE) and gas chromatography-tandem mass spectrometry (GC-MS/MS) has been developed for quantitative determination of twenty-six organohalogen disinfectant by-products (OXBPs) in water samples. Target analytes include four trihalomethanes (THMs), four iodohalomethanes (I-HMs), one haloacetaldehyde (HAL), six haloketones (HKs), four halonitromethanes (HNMs), and seven haloacetonitriles (HANs). The sample preparation procedure includes pretreatment with ascorbic acid to quench residual oxidants, followed by analyte enrichment using solid-phase extraction.

A sensitive and specific solid-phase extraction-gas chromatography-tandem mass spectrometry method for the determination of 11 haloacetic acids in aqueous samples.

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.