Exposure to airborne disinfection by-products, especially trichloramine (TCA), could cause various occupational health effects in indoor swimming pools. However, TCA concentration measurements involve specialized analysis conducted in specific laboratories, which can result in significant costs and time constraints. As an alternative, modeling techniques for estimating exposures are promising in addressing these challenges. This study aims to predict airborne TCA concentrations in indoor swimming pools using a mathematical model, the well-mixed box model, found in the IHMOD tool, freely available on the American Industrial Hygiene Association website. The model\'s predictions are compared with TCA concentrations measured during various bather load scenarios. The research involved conducting 2-hr successive workplace measurements over 16- to 18-hr periods in four indoor swimming pools in Quebec, Canada. TCA concentrations were estimated using the well-mixed box model, assuming a homogeneous mixing of air within the swimming pool environment. A novel approach was developed to estimate the TCA generation rate from swimming pool water, incorporating the number of swimmers in the model. Average measured concentrations of TCA were 0.24, 0.26, 0.14, and 0.34 mg/m3 for swimming pools 1, 2, 3, and 4, respectively. The ratio of these measured average concentrations to their corresponding predicted values ranged from 0.51 to 1.30, 0.67 to 1.04, 0.57 to 1.14, and 0.68 to 1.49 for the respective swimming pools. In a worst-case scenario simulating the swimming pool at full capacity (maximum bathers allowed), TCA concentrations were estimated as 0.23, 0.36, 0.14, and 0.37 mg/m3 for swimming pools 1, 2, 3, and 4. Recalculated concentrations by adjusting the number of swimmers so as not to exceed the recommended occupational limit concentration of 0.35 mg/m3 gives a maximum number of swimmers of 63 and 335 instead of currently 80 and 424 for swimming pools 2 and 4, respectively. Similarly, for swimming pools 1 and 3, the maximum number of swimmers could be 173 and 398 (instead of the current 160 and 225, respectively). These results demonstrated that the model could be used to estimate and anticipate airborne TCA levels in indoor swimming pools across various scenarios.

BACKGROUND: Trihalomethanes (THM), a major class of disinfection by-products, are widespread and are associated with adverse health effects. We conducted a global evaluation of current THM regulations and concentrations in drinking water.
METHODS: We included 120 countries (∼7000 million inhabitants in 2016), representing 94% of the world population. We searched for country regulations and THM routine monitoring data using a questionnaire addressed to referent contacts. Scientific and gray literature was reviewed where contacts were not identified or declined participation. We obtained or estimated annual average THM concentrations, weighted to the population served when possible.
RESULTS: Drinking water regulations were ascertained for 116/120 (97%) countries, with 89/116 (77%) including THM regulations. Routine monitoring was implemented in 47/89 (53%) of countries with THM regulations. THM data with a varying population coverage was obtained for 69/120 (58%) countries consisting of ∼5600 million inhabitants (76% of world\'s population in 2016). Population coverage was ≥90% in 14 countries, mostly in the Global North, 50-89% in 19 countries, 11-49% among 21 countries, and ≤10% in 14 countries including India, China, Russian Federation and Nigeria (40% of world\'s population).
CONCLUSIONS: An enormous gap exists in THM regulatory status, routine monitoring practice, reporting and data availability among countries, especially between high- vs. low- and middle-income countries (LMICs). More efforts are warranted to regulate and systematically assess chemical quality of drinking water, centralize, harmonize, and openly report data, particularly in LMICs.

Artificial sweeteners have raised emerging concern due to their potential threats to human health, which were frequently detected in aquatic environment with median concentrations. Although current researches have widely reported that ultraviolet light-activated persulfate process (UV/PS) was superior to UV/H2O2 process for the degradation of refractory organic contaminants, UV/H2O2 process presented a more satisfactory saccharin (SAC) removal efficiency than UV/PS process, completely degraded 20 mg/L SAC within 45 min. Hence, quenching and probe experiments were employed to investigate the difference between hydroxyl radical (OH)- and sulfate radical (SO4-)-mediated oxidation mechanisms, which revealed the higher reactivity of OH (1.37-1.56 × 109 M-1 s-1) toward SAC than SO4- (3.84-4.13 × 108 M-1 s-1). A combination of density functional theory calculation and transformation products identification disclosed that OH preferred to attack the benzene ring of SAC via hydrogen atom transfer pathway, whereas SO4- oxidation was conducive to the cleavage of -C-NH2 bond. Increasing oxidant concentration significantly accelerated SAC degradation in both processes, while UV/H2O2 process consumed lower electrical energy with respect to UV/PS process. Additionally, UV/H2O2 system presented excellent adaptability and stability under various water matrices parameters (e.g. pH, anions and humic acid). While both UV/H2O2 and UV/PS processes promoted the generation of disinfection by-products (DBPs) during subsequent chlorination, and prolonging pretreatment time posed positive effect on reducing the formation of DBPs. Overall, the results clearly demonstrate the high efficiency, economy and practicality of UV/H2O2 process in the remediation of SAC-contaminated water.

The potential toxicity of haloacetic acids (HAAs), common disinfection by products (DBPs), has been widely studied; but their combined effects on freshwater green algae remain poorly understood. The present study was conducted to investigate the toxicological interactions of HAA mixtures in the green alga Raphidocelis subcapitata and predict the DBP mixture toxicities based on concentration addition, independent action, and quantitative structure-activity relationship (QSAR) models. The acute toxicities of 6 HAAs (iodoacetic acid [IAA], bromoacetic acid [BAA], chloroacetic acid [CAA], dichloroacetic acid [DCAA], trichloroacetic acid [TCAA], and tribromoacetic acid [TBAA]) and their 68 binary mixtures to the green algae were analyzed in 96-well microplates. Results reveal that the rank order of the toxicity of individual HAAs is CAA > IAA ≈ BAA > TCAA > DCAA > TBAA. With concentration addition as the reference additive model, the mixture effects are synergetic in 47.1% and antagonistic in 25%, whereas the additive effects are only observed in 27.9% of the experiments. The main components that induce synergism are DCAA, IAA, and BAA; and CAA is the main component that causes antagonism. Prediction by concentration addition and independent action indicates that the 2 models fail to accurately predict 72% mixture toxicity at an effective concentration level of 50%. Modeling the mixtures by QSAR was established by statistically analyzing descriptors for the determination of the relationship between their chemical structures and the negative logarithm of the 50% effective concentration. The additive mixture toxicities are accurately predicted by the QSAR model based on 2 parameters, the octanol-water partition coefficient and the acid dissociation constant (pKa ). The toxicities of synergetic mixtures can be interpreted with the total energy (ET ) and pKa of the mixtures. Dipole moment and ET are the quantum descriptors that influence the antagonistic mixture toxicity. Therefore, in silico modeling may be a useful tool in predicting disinfection by-product mixture toxicities. Environ Toxicol Chem 2021;40:1431-1442. © 2021 SETAC.

Acetaminophen (ACT) and phenacetin (PNT) removal during light-emitting diode (LED)-UV photolysis of persulfate (PS) was evaluated with a typical wavelength of 365 nm. Decay of PNT and ACT in pH ranges of 5.5-8.5 followed pseudo-first order kinetics. Maximum pseudo-first order rate constants (kobs) of ACT and PNT decomposition of 1.8 × 10-1 and 1.2 × 10-1 min-1, respectively, were obtained at pH 8.5. Hydroxyl radicals (·OH), sulfate radicals (SO4·-), superoxide radicals (O2-·), and singlet oxygen (1O2) were determined in-situ electron paramagnetic resonance (EPR) and alcohol scavenging tests. The average contributions of ·OH and SO4·- were 23.5% and 53.0% for PNT removal, and 15.9% and 53.0% for ACT removal at pH ranges of 5.5-8.5. In samples subjected to chlorination after LED-UV365/PS pre-oxidation, a relatively small total concentration of five halogenated disinfection by-products (DBPs) was obtained of 90.9 μg L-1 (pH 5.5) and 126.7 μg L-1 (pH 7.0), which is 58.5% and 30.2% lower than that in system without LED-UV365/PS pre-oxidation. Meanwhile, a higher maximum value of total DBP concentration was obtained at pH 8.5 (445.6 μg L-1) following LED-UV365/PS pre-oxidation. The results of economy evaluation showed that UV365 was more cost-effective in application for organic contaminant removal compared with UV254.

The effect of the UV-C/free chlorine (FC) process on the removal of contaminants of emerging concern (CECs) from real urban wastewater as well as the effect of UV-C radiation on the formation of trihalomethanes (THMs) compared to FC process alone was investigated. Unlike of FC process, UV-C/FC was really effective in the degradation of the target CECs (carbamazepine (CBZ), diclofenac, sulfamethoxazole and imidacloprid) in real wastewater (87% degradation of total CECs within 60 min, QUVC = 1.33 kJ L-1), being CBZ the most refractory one (49.5%, after 60 min). The UV-C radiation significantly affected the formation of THMs. THMs concentration (mainly chloroform) was lower in UV-C/FC process after 30 min treatment (<1 μgL-1 = limit of quantification (LOQ)) than in FC process in dark (2.3 μgL-1). Noteworthy, while in FC treated wastewater chloroform concentration increased after treatment, UV-C/FC process resulted in a significant decrease (residual concentrations below the LOQ), even after 24 h and 48 h post-treatment incubation. The formation of radicals due to UV-C/FC process can reduce THMs compared to chlorination process, because part of FC reacts with UV-C radiation to form radicals and it is no longer available to form THMs. These results are encouraging in terms of possible use of UV-C/FC process as advanced treatment of urban wastewater even for possible effluent reuse.

Nitrosamines (NAs) as a group of emerging nitrogenous disinfection byproducts were present in drinking water at ng/L levels. Accurate measurements of NAs at such a trace level in samples is a challenging task. Solid phase extraction (SPE), which is used in the sample pretreatment, plays a critical role in the analysis of NAs in water. In this study, a highly selective and sensitive method for the determination of five less polar NAs, namely nitrosodiethylamine nitrosopiperidine, nitrosodi-n-propylamine, nitrosodibutylamine and nitrosodiphenylamine, in water and beverage samples was developed. A new molecularly imprinted polymer (MIP) was synthesized and used as sorbents in SPE for the sample preparation. Prepared samples were analyzed using high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Satisfactory recoveries were obtained at three different concentrations (5, 20, and 50 ng/L, n = 3) in the range of 93-107% with relative standard deviations of 3.1-9.8%. Limit of detection and limit of quantitation for the five NAs were in the range of 0.2-0.7 ng/L and 0.6-2.1 ng/L, respectively. Method precisions ranged from 4.9% to 10.5%. This novel method of MIP-SPE coupled with HPLC-MS/MS was successfully applied to the determination of these five NAs in different types of water and beverages samples.

In this study, the molecularly imprinted polymers (MIPs) with high specific surface area and extraction efficiency of N-Nitrosodiphenylamine (NDPhA) were successfully prepared and a highly sensitive and selective method was developed for determination of NDPhA in water samples using MIPs solid-phase extraction (SPE) coupled with gas chromatography mass spectrometry (GC-MS) detection. The MIPs were successfully prepared using the method of precipitation polymerization and using methacrylic acid as the functional monomer, ethylene glycol dimethacrylate as the cross-linker, and N, N-Diphenylformamide as the template molecule. The newly synthesized MIPs were characterized and used as SPE sorbents. Under the optimized conditions, the average recoveries of NDPhA spiked in ultrapure water were higher than 94% ± 2.9% at three different concentrations and the limit of detection and limit of quantitation were 0.8 ng L-1 and 2.4 ng L-1, respectively. Moreover, the high selectivity of MIPs was attained and the satisfactory recoveries of NDPhA which were spiked in to real samples were achieved in the range of 92-107% with relative standard deviations (RSDs) within 0.3-7.9%. The low levels of NDPhA were detected in the two of twelve wastewater samples with concentrations of 5.6 ng L-1 and 3.6 ng L-1 with RSDs of 5.6% and 2.8%, respectively. The developed MIP-SPE method was proved to be practically feasible for selective extraction and enrichment of NDPhA in real water samples.

A cohort-friendly biomonitoring protocol has been developed for measuring biomarkers of exposure to disinfection by-products (trihalomethanes, THM) in urine using small initial volume (3mL) and short analysis time (∼10min) that facilitates the throughput of a large number of samples. The objective of this study was to optimise a cohort-friendly biomonitoring protocol for the determination of four THM analytes in human urine using gas chromatography coupled with triple quadrupole mass spectrometry (GC-QqQ-MS/MS). The proposed methodology will facilitate the inclusion of such urinary THM measurements into large population health studies.

Exopolymeric substances (EPS) as an external matrix of biofilm could react with disinfectants in drinking water networks forming disinfection by-products (DBP). Based on an experimental setup using two chlorine conditions-biofilm 1 (2.6 ± 0.8 mgCl/L) and biofilm 2 (0.7 ± 0.2 mg Cl/L)-samples of biofilms were recovered during 9 campaigns and EPS were extracted. Analyses of SUVA, fluorescence and amino acid (AA) content were carried out on the EPS to observe variation over time and correlations with DBP formation potential (DBPfp) after chlorination. SUVA values were under 2 L/mgC*m showing that both EPS were hydrophilic. Slightly higher SUVA in biofilm 2 with low variation over time was observed. Fluorescence showed that aromatic proteins and fulvic like substances were the principal components and increased in biofilm 1 over time. AA decreased with time, and higher values of alanine, threonine, proline and isoleucine were observed in biofilm 2. Based on general associations, the SUVA of biofilm 2 correlated well with chloroform (CF) (r = 0.80). Generally, in both biofilms, tryptophan-like substances were negatively correlated with DBP while humic acid-like substances correlated positively, but with low indexes (r = 0.3-0.6). Correlations of data from individual sampling increased the indices (r over 0.8), suggesting a temporal influence of other factors on DBPfp such as inorganics, filtered water and the structural composition of EPS. In biofilm 1, Br-haloacetic acids (Br-HAA), dibromoacetonitrile and bromochloro acetonitrile were inversely associated with arginine and valine, as were di and trichloropropanone to arginine. On the contrary, in biofilm 2, the following amino acids correlated positively with DBP: alanine with Br-HAA, alanine with CF, alanine with N-DBP (chloropicrin, di and tri-chloro acetonitrile), and valine with CF. As this is the first report about the relation between temporal variation of EPS and DBPfp of biofilms in two different chlorinated conditions, it provides new evidence about the function of these complex substances in drinking water systems.