Particles in swimming pool filters – Does pH determine the DBP formation?

The formation was investigated for different groups of disinfection byproducts (DBPs) during chlorination of filter particles from swimming pools at different pH-values and the toxicity was estimated. Specifically, the formation of the DBP group trihalomethanes (THMs), which is regulated in many countries, and the non-regulated haloacetic acids (HAAs) and haloacetonitriles (HANs) were investigated at 6.0⩽pH⩽8.0, under controlled chlorination conditions. The investigated particles were collected from a hot tub with a drum micro filter. In two series of experiments with either constant initial active or initial free chlorine concentrations the particles were chlorinated at different pH-values in the relevant range for swimming pools. THM and HAA formations were reduced by decreasing pH while HAN formation increased with decreasing pH. Based on the organic content the relative DBP formation from the particles was higher than previously reported for body fluid analogue and filling water.The genotoxicity and cytotoxicity estimated from formation of DBPs from the treated particle suspension increased with decreasing pH. Among the quantified DBP groups the HANs were responsible for the majority of the toxicity from the measured DBPs

Reactions of pyrrole, imidazole, and pyrazole with ozone:Kinetics and mechanisms

Five-membered nitrogen-containing heterocyclic compounds (azoles) belong to potential moieties in complex structures where transformations during ozonation can occur. This study focused on the azole-ozone chemistry of pyrrole, imidazole, and pyrazole as model compounds. Reaction kinetics and ozonation products were determined by kinetic and analytical methods including NMR, LC-HRMS/MS, HPLC-UV, and IC-MS. Analyses of reactive oxygen species (O-1(2), & x2d9;OH, H2O2), quantum chemical computations (Gibbs energies), and kinetic simulations were used to further support the proposed reaction mechanisms. The species-specific second-order rate constants for the reactions of ozone with pyrrole and imidazole were (1.4 +/- 1.1) x 10(6) M-1 s(-1) and (2.3 +/- 0.1) x 10(5) M-1 s(-1), respectively. Pyrazole reacted more slowly with ozone at pH 7 (k(app) = (5.6 +/- 0.9) x 10(1) M-1 s(-1)). Maleimide was an identified product of pyrrole with a 34% yield. Together with other products, formate, formamide, and glyoxal, C and N mass balances of similar to 50% were achieved. Imidazole reacted with ozone to cyanate, formamide, and formate (similar to 100% yields per transformed imidazole, respectively) with a closed mass balance. For pyrazole, a high ozone : pyrazole molar stoichiometry of 4.6 was found, suggesting that the transformation products contributed to the over-stoichiometric consumption of ozone (e.g., hydroxypyrazoles). Glyoxal and formate were the only identified transformation products (C mass balance of 65%). Overall, the identified major products are suspected to hydrolyze and/or be biodegraded and thereby abated by a biological post-treatment typically following ozonation. However, as substructures of more complex compounds (e.g., micropollutants), they might be more persistent during biological post-treatment

Degradation of Polymeric Brominated Flame Retardants: Development of an Analytical Approach Using PolyFR and UV Irradiation

Many well-established methods for studying the degradation of brominated flame retardants are not useful when working with polymeric and water insoluble species. An example for this specific class of flame retardants is PolyFR (polymeric flame retardant; CAS No 1195978–93–8), which is used as a substituent for hexabromocyclododecane. Although it has been on the market for two years now, almost no information is available about its long time behavior in the environment. Within this study, we focus on how to determine a possible degradation of both pure PolyFR as well as PolyFR in the final insulation product, expanded polystyrene foam. Therefore, we chose UV radiation followed by analyses of the total bromine content at different time points via ICP-MS and identified possible degradation products such as 2,4,6-tribromophenol through LC-MS. These results were then linked with measurements of the adsorbable organically bound bromine and total organic carbon in order to estimate their concentrations. With respect to the obtained ¹H NMR, GPC, and contact angle results, the possibility for further degradation was discussed, as UV irradiation can influence the decomposition of molecules in combination with other environmental factors like biodegradation

Direct Photolysis of Sulfamethoxazole Using Various Irradiation Sources and Wavelength RangesInsights from Degradation Product Analysis and Compound-Specific Stable Isotope Analysis

The environmental micropollutant sulfamethoxazole (SMX) is susceptible to phototransformation by sunlight and UV-C light which is used for water disinfection. Depending on the environmental pH conditions SMX may be present as neutral or anionic species. This study systematically investigates the phototransformation of these two relevant SMX species using four different irradiation scenarios, i.e., a low, medium, and high pressure Hg lamp and simulated sunlight. The observed phototransformation kinetics are complemented by data from compound-specific stable isotope and transformation product analysis using isotope-ratio and high-resolution mass spectrometry (HRMS). Observed phototransformation kinetics were faster for the neutral than for the anionic SMX species (from 3.4 (LP lamp) up to 6.6 (HP lamp) times). Furthermore, four phototransformation products (with <i>m</i>/<i>z</i> 189, 202, 242, and 260) were detected by HRMS that have not yet been described for direct photolysis of SMX. Isotopic fractionation occurred only if UV-B and UV-A wavelengths prevailed in the emitted irradiation and was most pronounced for the neutral species with simulated sunlight (ε_C = −4.8 ± 0.1 ‰). Phototransformation of SMX with UV-C light did not cause significant isotopic fractionation. Consequently, it was possible to differentiate sunlight and UV-C light induced phototransformation of SMX. Thus, CSIA might be implemented to trace back wastewater point sources or to assess natural attenuation of SMX by sunlight photolysis. In contrast to the wavelength range, pH-dependent speciation of SMX hardly impacted isotopic fractionation

Effect of pH on the formation of disinfection byproducts in swimming pool water - is less thm better?

This study investigated the formation and predicted toxicity of different groups of disinfection byproducts (DBPs) from human exudates in relation to chlorination of pool water at different pH values. Specifically, the formation of the DBP groups trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles (HANs) and trichloramine (NCl 3), resulting from the chlorination of body fluid analog, were investigated at 6.0 ≤ pH ≤ 8.0. Either the initial concentration of active chorine or free chlorine was kept constant in the tested pH range. THM formation was reduced by decreasing pH but HAN, and NCl 3 formation increased at decreasing pH whereas the formation of HAAs remained constant. Under our experimental conditions, the formation of NCl 3 (suspected asthma inducing compound) at pH = 6.0 was an order of magnitude higher than at pH = 7.5. Furthermore, the effect of the presence of bromide on DBP formation was investigated and found to follow the same pH dependency as without bromide present, with the overall DBP formation increasing, except for HAAs. Estimation of genotoxicity and cytotoxicity of the chlorinated human exudates showed that among the quantified DBP groups, HAN formation were responsible for the majority of the toxicity from the measured DBPs in both absence and presence of bromide