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Bromide measurements and mass balances in the catchments of major Swiss rivers revealed that chemical industry and municipal waste incinerators are the most important bromide sources and account for similar to 50% and similar to 20%, respectively, of the similar to 2000 tons of bromide discharged in the Rhine river in 2014 in Switzerland. About 100 wastewater treatment plants (WWTPs) will upgrade their treatment for micropollutant abatement in the future to comply with Swiss regulations. An upgrade with ozonation may lead to unintended bromate formation in bromide containing wastewaters. Measured bromide concentrations were

Trichloramine is a hazardous disinfection by-product, which is present in chlorinated swimming pools. Although it is primarily taken up by inhalation, the concentration in pool water is important to monitor pool water quality and to assess trichloramine mitigation strategies. To date, scarce data is available on trichloramine concentration in pool water due to the lack of a suitable and easily applicable analytical method. This study presents a novel low cost, colorimetric method which is easy to operate and suitable for on-site measurements of trichloramine concentrations ≥0.05 μM (≥0.01 mg L−1 as Cl2). The analytical method (termed “extraction-based ABTS method”) consists of, (i) trichloramine stripping from pool water samples, (ii) passing it through a solid phase filter, composed of silica gel impregnated with sulfamic acid to eliminate interferences and (iii) trichloramine reaction with the indicator 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) to produce the coloured ABTS•− radical, which is measured at λ = 405 nm to determine the trichloramine concentration in the pool water sample. A comparison of the extraction-based ABTS method with membrane introduction mass spectrometry (MIMS) for 28 pool samples revealed a good correlation of the two methods. The trichloramine concentration in pool samples is correlated to HOCl, which is the most important factor for its formation. Other parameters such as combined chlorine and pH play a minor role while no correlation between trichloramine and the urea or the TOC concentration was observed. On-site measurements with MIMS in a wading pool over 6 days with a time resolution of 1 h confirmed that trichloramine concentrations strongly responded to changes in free chlorine concentrations. A diurnal measurement of trichloramine with a time resolution of 20 min revealed that trichloramine concentrations reacted quickly and sensitively to the bather load and that urea is probably not the main precursor for its formation.

Despite their potential carcinogenicity and probable formation during water disinfection processes, little is known about the occurrence of other nitro(so) compounds than a few specific N-nitroso compounds such as N-nitrosodimethylamine (NDMA). An analytical method was developed to monitor various nitro(so) compounds including N-nitrosamines based on the Griess colorimetric determination of nitrite generated by UV-254 nm photolysis of nitro(so) compounds after separation by HPLC (HPLC-Post Column UV-photolysis/Griess reaction (HPLC-PCUV)). To differentiate N-nitro(so) compounds (i.e. UV-labile) from other nitro(so) and N-containing compounds (i.e. UV-resistant), a pretreatment was established by photolyzing solid-phase extracted samples at 254 nm (1000 mJ/cm(2)) and thus removing N-nitro(so) compounds selectively. Considering a 1000-fold concentration factor and extraction efficiencies (57-83%) during solid phase extraction, the method detection limits ranged from 4 to 28 ng/L for dimethylnitramine and eight N-nitrosamines (EPA 8270 nine nitrosamines mixture except for N-nitrosodiphenylamine). For four pool waters, the UV-resistant groups accounted for more than 78% of the estimated total concentration of nitro(so) and other N-containing compounds (6.1-48.6 nM). Only one unknown UV-labile compound was detected in one pool water (2.0-7.9 nM). NDMA was most frequently detected and N-nitrosodipropylamine (NDPA) and N-nitrosodibutylamine (NDBA) were additionally detected in one pool water. Chloramination of a secondary wastewater effluent with NDMA (0.2 nM) and UV-resistant compounds (7.9 nM) from a pilot-scale municipal wastewater treatment plant led to a significant formation of not only unidentified UV-resistant compounds (67.8 nM) and UV-labile compounds (14.6 nM), but also identified nitrosamines such as NDMA (4.3 nM), N-nitrosopiperidine (1.8 nM), NDPA (0.5 nM), and NDBA (0.5 nM). Overall, the novel HPLC-PCUV system is a powerful screening tool for the detection of (un)known N-nitro(so) as well as other nitro(so) and UV-induced nitrite-producing compounds. (C) 2013 Published by Elsevier Ltd.

Wastewater treatment plants (WWTPs) are important point sources for micropollutants, which are harmful to freshwater organisms. Ozonation of wastewater is a powerful option to abate micropollutants, but may result in the formation of the potentially toxic oxidation by-product bromate in bromide containing wastewaters. This study investigates options to reduce bromate formation during wastewater ozonation by (i) reducing the bromide concentration of the wastewater, (ii) lowering the ozone dose during wastewater treatment and (iii) adding hydrogen peroxide to limit the lifetime of ozone and quench the intermediates of the bromate formation pathway. Two examples demonstrate that a high share of bromide in wastewater can originate from single point sources (e.g., municipal waste incinerators or landfills). The identification of major point sources requires laborious sampling campaigns, but may facilitate the reduction of the bromide load significantly. To reduce the bromate formation by lowering the ozone dose interferes with the aim to abate micropollutants. Therefore, an additional treatment is necessary to ensure the elimination of micropollutants. Experiments at a pilot-plant illustrate that a combined treatment (ozone/powdered activated carbon) allows to eliminate micropollutants with low bromate yields. Furthermore, the addition of hydrogen peroxide was investigated at bench scale. The bromate yields could be reduced by similar to 50% and 65% for a hydrogen peroxide dose of 5 and 10 mg L-1, respectively. In conclusion, there are options to reduce the bromate formation during wastewater ozonation, however, they are not simple with sometimes limited efficiency. (C) 2017 Elsevier Ltd. All rights reserved.

N-Nitrosamines, in particular N-nitrosodimethylamine (NDMA), are carcinogens, which occur as chlorine disinfection by-products (DBPs) in swimming pools and hot tubs. UV treatment is a commonly used technique in swimming pools for disinfection and DBP attenuation. UV irradiation is known to efficiently degrade N-nitrosamines. However, UV irradiation (at lambda = 254 nm) of chlorinated dimethylamine (CDMA) and monochloramine, two NDMA precursors present in swimming pool water, resulted in a substantial UV-induced NDMA formation (similar to 1-2% molar yield based on initial CDMA concentration) simultaneously to NDMA photolysis. Maximum NDMA concentrations were found at UV doses in the range used for advanced oxidation (350-850 mJ cm(-2)). Very similar behaviour was found for other chlorinated secondary amines, namely diethylamine and morpholine. Effectiveness of UV irradiation for N-nitrosamine abatement depends on initial N-nitrosamine and precursor concentrations and the applied UV dose. N-Nitrosamine formation is hypothesized to occur via the reaction of nitric oxide or peroxynitrite with the secondary aminyl radical, which are products from the photolysis of monochloramine and chlorinated secondary amines, respectively. Experiments with pool water showed that similar trends were observed under pool water conditions. UV treatment (UV dose: similar to 360 mJ cm(-2)) slightly increased NDMA concentration in pool water instead of the anticipated 50% abatement in the absence of NDMA precursors. (C) 2012 Elsevier Ltd. All rights reserved.