Occurrence, removal, and prioritization of organic micropollutants in four full-scale wastewater treatment plants in Korea.

This study investigated the occurrence, removal rate, and potential risks of 43 organic micropollutants (OMPs) in four municipal wastewater treatment plants (WWTPs) in Korea. Results from two-year intensive monitoring confirmed the presence of various OMPs in the influents, including pharmaceuticals such as acetaminophen (pain relief), caffeine (stimulants), cimetidine (H2-blockers), ibuprofen (non-steroidal anti-inflammatory drugs- NSAIDs), metformin (antidiabetics), and naproxen (NSAIDs) with median concentrations of >1 µg/L. Some pharmaceuticals (carbamazepine-anticonvulsants, diclofenac-NSAIDs, propranolol-ß-blockers), corrosion inhibitors (1H-benzotriazole-BTR, 4-methyl-1H-benzotriazole-4-TTR), and perfluorinated compounds (PFCs) were negligibly removed during WWTP treatment. The OMP concentrations in the influents and effluents were mostly lower in August than those of other months (p-value <0.05) possibly due to wastewater dilution by high precipitation or enhanced biodegradation under high-temperature conditions. The anaerobic-anoxic-oxic process (A2O) with a membrane bioreactor exhibited higher OMP removal than other processes, such as A2O with sedimentation or the conventional activated sludge process (p-value <0.05). Pesticides (DEET and atrazine), corrosion inhibitors (4-TTR and BTR), and metformin were selected as priority OMPs in toxicity-driven prioritization, whereas PFCs were determined as priority OMPs given their persistence and bioaccumulation properties. Overall, our results contribute to an important database on the occurrence, removal, and potential risks of OMPs in Korean WWTPs.

Effects of Low-Load, High-Repetition Resistance Training on Maximum Muscle Strength and Muscle Damage in Elite Weightlifters: A Preliminary Study.

This study aimed to assess the impact of different resistance training (RT) loads and repetition on muscle damage, intramuscular anabolic signaling, and maximal muscle strength (MMS) in weightlifters. Eighteen male weightlifters were randomly assigned to 8 weeks of supervised RT regimes: high-load, low-repetition (HL), low-load, high-repetition (LH), and combination of HL and LH (COMBI). All groups exhibited a significant increase in skeletal muscle mass (SMM) and growth hormone levels, which ultimately contributed to improvement in MMS as indicated by 1-repetition maximum in the back squat and back muscle strength. Notably, while there were no significant changes in the mTOR protein, the phosphorylation of phosphorylation of p70 ribosomal protein S6 kinase 1 (p70S6K1), eukaryotic initiation factor 4E-binding protein 1 (4E-BP1), and eukaryotic elongation factor 2 (eEF2), which are involved in muscle cell growth, was significantly affected by the different training regimens. More importantly, LH-RT led to a significant reduction in muscle damage markers, creatine kinase (CK) and lactate dehydrogenase (LDH), suggesting reduced recovery time and fatigue. Our results demonstrated that the LH-RT paradigm could be a viable alternative for weightlifters to enhance MMS and muscle hypertrophy similar to HL-RT, while reducing RT-induced muscle damage, ultimately contributing to the enhancement of exercise performance.

Predicting micropollutant fate during wastewater treatment using refined classical kinetic model based on quantitative monitoring in multi-metropolitan regions of South Korea.

This study aimed to implement an extensive prediction model for the fate of micropollutants (MPs) in wastewater treatment plants (WWTPs). Five WWTPs equipped with seven different biological treatment processes were monitored from 2020 to 2022 with three to four sampling events in each year, and 27 datasets for 20 MPs were collected. Among these datasets, 12 were used to investigate the behavior and fate of MPs in WWTPs in South Korea. Metformin, acetaminophen, caffeine, naproxen, and ibuprofen were the MPs with the highest influent concentrations (ranging from 3,933.3-187,637.0 ng L-1) at all WWTPs. More than 90% of MPs were removed by biological treatment processes in all WWTPs. The Kruskal-Wallis test verified that their efficacy did not differ statistically (p-value > 0.05). Meanwhile, to refine the performance of the prediction model, this study optimized the biodegradation rate constants (kbio) of each MP according to the variation of seasonal water temperature. As a result, compared to the original prediction model, the mean difference between the actual data and predicted results (MEAN) decreased by 6.77%, while the Nash-Sutcliffe efficiency (NSE) increased by 0.226. The final MEAN and NSE for the refined prediction model were calculated to be 5.09% and 0.964, respectively. The prediction model made accurate predictions, even for MPs exhibiting behaviors different from other cases, such as estriol and atrazine. Consequently, the optimization strategy proposed in this study was determined to be effective because the overall removal efficiencies of MPs were successfully predicted even with limited reference datasets.

Efficiency of ozonation and O3/H2O2 as enhanced wastewater treatment processes for micropollutant abatement and disinfection with minimized byproduct formation.

Ozonation, a viable option for improving wastewater effluent quality, requires process optimization to ensure the organic micropollutants (OMPs) elimination and disinfection under minimized byproduct formation. This study assessed and compared the efficiencies of ozonation (O3) and ozone with hydrogen peroxide (O3/H2O2) for 70 OMPs elimination, inactivation of three bacteria and three viruses, and formation of bromate and biodegradable organics during the bench-scale O3 and O3/H2O2 treatment of municipal wastewater effluent. 39 OMPs were fully eliminated, and 22 OMPs were considerably eliminated (54 ± 14%) at an ozone dosage of 0.5 gO3/gDOC for their high reactivity to ozone or •OH. The chemical kinetics approach accurately predicted the OMP elimination levels based on the rate constants and exposures of ozone and •OH, where the quantum chemical calculation and group contribution method successfully predicted the ozone and •OH rate constants, respectively. Microbial inactivation levels increased with increasing ozone dosage up to ∼3.1 (bacteria) and ∼2.6 (virus) log10 reductions at 0.7 gO3/gDOC. O3/H2O2 minimized bromate formation but significantly decreased bacteria/virus inactivation, whereas its impact on OMP elimination was insignificant. Ozonation produced biodegradable organics that were removed by a post-biodegradation treatment, achieving up to 24% DOM mineralization. These results can be useful for optimizing O3 and O3/H2O2 processes for enhanced wastewater treatment.

Nitriles as main products from the oxidation of primary amines by ferrate(VI): Kinetics, mechanisms and toxicological implications for nitrogenous disinfection byproduct control.

Ferrate (Fe(VI)), a promising water treatment oxidant, can be used for micropollutant abatement or disinfection byproduct mitigation. However, knowledge gaps remain concerning the interaction between Fe(VI) and dissolved organic matter structures, notably primary amines. This study investigated degradation kinetics and products of several aliphatic primary amines by Fe(VI). Primary amines showed appreciable reactivity toward Fe(VI) (2.7-68 M-1s-1 at pH 7-9), ranking as follows: benzylamine > phenethylamine > phenylpropylamine > methylamine ≈ propylamine. Nitriles were the main oxidation products of the primary amines, with molar yields of 61-103%. Minor products included aldehydes, carboxylic acids, nitroalkanes, nitrite, nitrate, and ammonia. The buffering conditions were important. Compared to phosphate, borate enhanced the reactivity of the amines and shifted the products from nitriles to carbonyls. An evaluation of the effect potency of some cyano-compounds by an in vitro bioassay for oxidative stress response and cytotoxicity suggested that non-halogenated nitriles are unlikely to pose a significant threat because they were only toxic at high concentrations, acted as baseline toxicants and did not cause oxidative stress, unlike halonitroalkanes or halonitriles. The formation of non-halogenated nitriles is preferable to the formation of nitroalkanes arising from the ozonation of primary amines (other than amino acid N-terminals) because, during chlorination, nitriles remain unreactive while nitroalkanes lead to potent halonitroalkanes.

Elimination efficiency of organic UV filters during ozonation and UV/H2O2 treatment of drinking water and wastewater effluent.

The efficiency of elimination of organic UV filters by ozonation and UV254nm/H2O2 processes was assessed and predicted in simulated treatments of sewage-impaired drinking water and wastewater effluent in bench-scale experiments. Second-order rate constants (k) for the reactions of the eight UV filters with ozone and OH were determined by quantum chemical calculations and competition kinetics methods, respectively. The UV filters containing phenolic (ethylhexyl-salicylate, homosalate, and benzophenone-3) and olefinic moieties (4-methylbenzylidene-camphor, benzyl-cinnamate, and 2-ethylhexyl-4-methoxycinnamate) showed high ozone reactivity (k ≥ 8 × 104 M-1s-1 at pH 7), while those without such electron-rich moieties (isoamyl-benzoate and benzophenone) were ozone-refractory. All the UV filters showed high OH reactivity (k ≥ 6.2 × 109 M-1s-1). In concordance with the rate constant information, the phenolic and olefinic UV filters were efficiently eliminated by ozone treatment, requiring specific ozone doses of <0.5 mgO3/mgDOC for ∼100% elimination. The UV filters were eliminated by ≤ 38% at a UV fluence of 1500 mJ/cm2 in the UV254nm-only treatment. Rapid photoisomerisation between the E and Z geometric isomers was observed for the olefinic UV filter, benzyl-cinnamate. The addition of H2O2 (10 mg/L) greatly enhanced the elimination of all UV filters, indicating that OH was the main contributor to their elimination in the UV254nm/H2O2 treatment. A chemical kinetics approach developed previously for ozonation and UV/H2O2 processes was shown to predict the elimination of the UV filters in the tested water matrices reasonably well, demonstrating that the chemical kinetics method can be used for a priori prediction of micropollutant elimination in oxidative treatment processes for potable reuse of municipal wastewater effluents.

N-nitrosodimethylamine (NDMA) formation during ozonation of N,N-dimethylhydrazine compounds: Reaction kinetics, mechanisms, and implications for NDMA formation control.

Compounds with N,N-dimethylhydrazine moieties ((CH3)2N-N-) form N-nitrosodimethylamine (NDMA) during ozonation, but the relevant reaction chemistry is hitherto poorly understood. This study investigated the reaction kinetics and mechanisms of NDMA formation during ozonation of unsymmetrical dimethylhydrazine (UDMH) and daminozide (DMZ) as structural model N,N-dimethylhydrazine compounds. The reaction of ozone with these NDMA precursor compounds was fast, and kO3 at pH 7 was 2 × 106 M-1 s-1 for UDMH and 5 × 105 M-1 s-1 for DMZ. Molar NDMA yields (i.e., Δ[NDMA]/Δ[precursor] × 100) were 84% and 100% for UDMH and DMZ, respectively, determined at molar ozone dose ratio ([O3]0/[precursor]0) of ≥4 in the presence of tert-butanol as hydroxyl radical (OH) scavenger. The molar NDMA yields decreased significantly in the absence of tert-butanol, indicating OH formation and its subsequent reaction with the parent precursors forming negligible NDMA. The kOH at pH 7 was 4.9 × 109 M-1 s-1 and 3.4 × 109 M-1 s-1 for UDMH and DMZ, respectively. Reaction mechanisms are proposed in which an ozone adduct is formed at the nitrogen next to N,N-dimethylamine which decomposes via homolytic and heterolytic cleavages of the -N+-O-O-O- bond, forming NDMA as a final product. The heterolytic cleavage pathway explains the significant OH formation via radical intermediates. Overall, significant NDMA formation was found to be unavoidable during ozonation or even O3/H2O2 treatment of waters containing N,N-dimethylhydrazine compounds due to their rapid reaction with ozone forming NDMA with high yield. Thus, source control or pre-treatment of N,N-dimethylhydrazine precursors and post-treatment of NDMA are proposed as the mitigation options.