500 days of swimmers: the chemical water quality of swimming pool waters from the beginning.

Many studies of disinfection by-products (DBPs) in pools have focused on haloacetic acids, trihalomethanes, and chloramines, with less studies investigating the occurrence of other DBPs, such as haloketones, haloacetaldehydes, haloacetonitriles, halonitromethanes, and haloacetamides. Furthermore, while many studies have achieved a broadscreen analysis across several pools, fewer studies have followed the water quality of pools over time, with information regarding the production and fate of DBPs in pools over extended periods (e.g. > 1 year) being limited. This study reports the occurrence of 39 DBPs and several general water quality parameters in two newly built and filled swimming pools over 15 months, where investigations began prior to opening. DBP concentrations measured in this study were generally similar to or higher than those previously reported in chlorinated pools, with concentrations of chloroacetic acid, dichloroacetic acid, trichloroacetic acid, and chloral hydrate (trichloroacetaldehyde) in some samples being higher than previously reported maximum concentrations. Considering both pools, lower concentrations of DBPs were measured in the pool where a steady state non-purgeable organic carbon concentration was achieved, highlighting the importance of the establishment of a steady state balance of mineralisation versus addition of organic carbon to reduce precursors for DBP formation in pools. Pools were found to exhibit significantly higher estimated cytotoxicity than their filling water, which reflects the significantly higher concentrations of DBPs measured in the pools in comparison to the filling water. Chloral hydrate accounted for up to 99% the total estimated cytotoxicity and was found to be correlated to the number of pool entries, suggesting that swimmers may be a potential source of chloral hydrate precursors in pools. The presence and subsequent peak of non-purgeable organic carbon and DBPs prior to, and soon after, opening suggest that the building process and/or new pool infrastructure may have had a significant impact on the chemical water quality, particularly on DBP formation. This study includes the first quantification of bromochloroacetaldehyde, bromodichloroacetaldehyde, bromochloronitromethane, and dichloronitromethane in chlorinated swimming pools, and provides important new knowledge on the long-term trends of DBPs in pools.

An analytical method for the analysis of trihalomethanes in ambient air using solid-phase microextraction gas chromatography-mass spectrometry: An application to indoor swimming pool complexes.

A simple method for the collection and analysis of the four brominated and chlorinated trihalomethanes (THMs) in air samples is described. Ambient air samples were collected in pre-prepared glass vials, with THM analysis performed using solid-phase microextraction gas chromatography-mass spectrometry, where the need for chemical reagents is minimized. Analytical parameters, including oven temperature program, solvent volume, incubation time, vial agitation, extraction time and temperature, as well as desorption time and temperature, were evaluated to ensure optimal method performance. The developed method allows for point-in-time quantification (compared to an average concentration measured over extended periods of time), with detection limits between 0.7 to 2.6 µg/m3 . Excellent linearity (r2  > 0.99), repeatability (3% to 11% RSD), and reproducibility (3% to 16% RSD) were demonstrated over a concentration range from 2 to 5000 µg/m3 . The method was validated for the analysis of THMs in indoor swimming pool air and was used to investigate the occurrence of THMs in the air above 15 indoor swimming pools. This is the first study to report the occurrence of THMs in swimming pool air in Australia, and concentrations higher than those previously reported in other countries were measured.

Occurrence of disinfection by-products in swimming pools and the estimated resulting cytotoxicity.

Swimming pools are disinfected to protect against the risk of microbial disease, however, the formation of disinfection by-products (DBPs) is an unwanted consequence. While many studies have reported the occurrence of commonly investigated DBPs (trihalomethanes and haloacetic acids) in pools, few studies have investigated emerging DBP classes, such as the haloketones or haloacetaldehydes, and the nitrogenous haloacetamides, halonitromethanes, haloacetonitriles and N-nitrosamines. This study investigated the occurrence of sixty four DBPs from the eight aforementioned DBP classes in pools employing different treatment methods. Approximately 70% of the DBPs were detected in at least one of the pools, with most concentrations being equal to or greater than those previously reported. Chloral hydrate (trichloroacetaldehyde) was one of many DBPs detected in all chlorinated waters (202 to 1313 µg/L), and, on a molar basis, was the predominant DBP. Several other DBPs, namely chloroacetic acid, dichloroacetic acid, trichloroacetic acid, dichloroacetamide, dibromoacetamide, dibromochloroacetamide and trichloroacetamide, and many of the N-nitrosamines, were measured at concentrations greater than previously reported: up to 200 to 479 µg/L for the haloacetic acids, 56 to 736 µg/L for the haloacetamides and up to 1093 ng/L for some N-nitrosamines. The higher disinfectant residuals required to be employed in Australian pools, and poor pool management (e.g. of chlorine residual and pH) are likely factors contributing to these relatively high DBP concentrations. Where possible, the cytotoxicity values of the investigated DBPs were evaluated, with chloral hydrate representing over 90% of the total chronic cytotoxicity despite only representing up to 64% of the total molar DBP concentration. This study is the first report of bromodichloroacetaldehyde and bromochloroacetaldehyde in pools and is the first investigation of N-nitrosamines in a brominated pool. Furthermore, this work aids in understanding DBPs in both chlorine and bromine treated pools, the latter being the subject of only limited previous studies.

Simultaneous analysis of haloacetonitriles, haloacetamides and halonitromethanes in chlorinated waters by gas chromatography-mass spectrometry.

Nitrogenous classes of disinfection by-products (DBPs), such as haloacetamides (HAAms), haloacetonitriles (HANs) and halonitromethanes (HNMs), while generally present at lower concentrations in disinfected waters than carbonaceous DBPs, such as trihalomethanes or haloacetic acids, have been shown to be more detrimental to human health. While several methods have been shown to be suitable for the analysis of some nitrogenous DBPs (N-DBPs) in disinfected waters, many are unable to quantify HAAms, the most detrimental to health of these three N-DBP classes. Here, we report the first method for the simultaneous analysis of twenty-five N-DBPs (nine HANs, nine HNMs and seven HAAms) in disinfected waters using liquid-liquid extraction followed by gas chromatography-mass spectrometry. The use of a programmable temperature vaporiser injector minimises degradation of the thermally labile HNMs, while avoiding the concomitant decreases in HANs and HAAms which occur when using lower injector temperatures. Extraction parameters, including sample pH, solvent volume, salt addition and sample pre-concentration, were investigated to determine the optimal conditions across all target N-DBPs. Good detection limits were achieved for all analytes (0.8-1.7 µg L-1) and both laboratory and instrumental runtimes were significantly reduced compared to previous methods. The method was validated for the analysis of N-DBPs in drinking, swimming pool and spa waters, and concentrations of up to 41 µg L-1 of some N-DBPs were measured in some pools.

Occurrence and formation of disinfection by-products in the swimming pool environment: A critical review.

Disinfection of water for human use is essential to protect against microbial disease; however, disinfection also leads to formation of disinfection by-products (DBPs), some of which are of health concern. From a chemical perspective, swimming pools are a complex matrix, with continual addition of a wide range of natural and anthropogenic chemicals via filling waters, disinfectant addition, pharmaceuticals and personal care products and human body excretions. Natural organic matter, trace amounts of DBPs and chlorine or chloramines may be introduced by the filling water, which is commonly disinfected distributed drinking water. Chlorine and/or bromine is continually introduced via the addition of chemical disinfectants to the pool. Human body excretions (sweat, urine and saliva) and pharmaceuticals and personal care products (sunscreens, cosmetics, hair products and lotions) are introduced by swimmers. High addition of disinfectant leads to a high formation of DBPs from reaction of some of the chemicals with the disinfectant. Swimming pool air is also of concern as volatile DBPs partition into the air above the pool. The presence of bromine leads to the formation of a wide range of bromo- and bromo/chloro-DBPs, and Br-DBPs are more toxic than their chlorinated analogues. This is particularly important for seawater-filled pools or pools using a bromine-based disinfectant. This review summarises chemical contaminants and DBPs in swimming pool waters, as well as in the air above pools. Factors that have been found to affect DBP formation in pools are discussed. The impact of the swimming pool environment on human health is reviewed.