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.

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.

Mitigation of N2O emissions via enhanced denitrification in a biological landfill leachate treatment using external carbon from fermented sludge.

The effects of an external carbon source (C-source) on the mitigation of N2O gas (N2O(g)) emissions from landfill leachate were investigated via enhanced denitrification using anaerobically fermented sewage sludge. Anaerobic fermentation of sewage sludge was conducted under thermophilic conditions with progressively increasing organic loading rates (OLR). Optimal conditions for fermentation were determined based on the efficiency of hydrolysis and the concentrations of sCOD and volatile fatty acids (VFAs) as follows: at an OLR of 40.48 ± 0.77 g COD/L·d with 1.5 days of solid retention time (SRT), 14.68 ± 0.59% of efficiency of hydrolysis, 14.42 ± 0.30 g sCOD/L and 7.85 ± 0.18 g COD/L of VFAs. Analysis of the microbial community in the anaerobic fermentation reactor revealed that degradation of sewage sludge might be potentially affected by proteolytic microorganisms producing VFAs from proteinaceous materials. Sludge-fermentate (SF) retrieved from the anaerobic fermentation reactor was used as the external C-source for denitrification testing. The specific nitrate removal rate (KNR) of the SF-added condition was 7.54 mg NO3-N/g VSS·hr, which was 5.42 and 2.43 times higher than that of raw landfill leachate (LL) and a methanol-added condition, respectively. In the N2O(g) emission test, the liquid phase N2O (N2O-N(l)) of 20.15 mg N/L was emitted as N2O(g) of 19.64 ppmv under only LL-added condition. On the other hand, SF led to the specific N2O(l) reduction rate (KN2O) of 6.70 mg N/g VSS hr, resulting in mitigation of 1.72 times the N2O(g) emission compared to under the only-LL-added condition. The present study revealed that N2O(g) emissions from biological landfill leachate treatment plants can be attenuated by simultaneous reduction of NO3-N and N2O(l) during enhanced denitrification via a stable supply of an external C-source retrieved from anaerobically fermented organic waste.

Biomass formation and organic carbon migration potential of microplastics from a PET recycling plant: Implication of biostability.

The growth of the polyethylene terephthalate (PET) mechanical recycling industry has resulted in the challenge of generating microplastics (MPs). However, little attention has been given to investigating the release of organic carbon from these MPs and their roles in promoting bacterial growth in aquatic environments. In this study, a comprehensive method is proposed to access the potential of organic carbon migration and biomass formation of MPs generated from a PET recycling plant, and to understand its impact on the biological systems of freshwater habitats. Various MPs sizes from a PET recycling plant were selected to conduct a series of tests, including the organic carbon migration test, biomass formation potential test, and microbial community analysis. The MPs smaller than 100 µm, which are difficult to remove from the wastewater, exhibited greater biomass in the observed samples (1.05 × 1011 bacteria per gram MPs). Moreover, PET MPs altered the microbial diversity, with Burkholderiaceae becoming the most abundant, while Rhodobacteraceae was eliminated after being incubated with MPs. This study partly revealed that organic matter adsorbed on the surface of MPs was a significant nutrient source that increased biomass formation. PET MPs acted not only as carriers for microorganisms but also for organic matter. As a result, it is crucial to develop and refine recycling methods in order to decrease the production of PET MPs and minimize their adverse effects on the environment.

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.

In vitro bioanalytical assessment of the occurrence and removal of bioactive chemicals in municipal wastewater treatment plants in Korea.

Effluents of wastewater treatment plants (WWTPs) contain various organic micropollutants, some of which can exert negative effects on the quality of receiving waters or drinking water sources. This study monitored two full-scale WWTPs in Korea for the occurrence and removal of bioactive chemicals for a one-year period using a battery of in vitro bioassays as a complementary approach to chemical analysis. Bioassays covering different endpoints were employed, such as hormone receptor activation (AR and ERα), xenobiotic metabolism (PAH and PXR), oxidative stress response (Nrf2), and cytotoxicity. The WWTP influents showed AR, ERα, and PAH activities at ng/L - µg/L and PXR and Nrf2 activities at µg/L - mg/L as bioanalytical equivalent concentrations of a reference compound for each bioassay. These bioactivities decreased along with the WWTP treatment train, with significant removals achieved by the secondary biological treatment processes. Cytotoxicity was observed only for some municipal wastewater (M-WWTP) influents but was below the limit of quantification for most cases. The influent and effluent bioactivities observed in this study were mostly comparable to those reported in other WWTPs in the literature. Comparison of the bioactivities with the effect-based trigger (EBT) values indicates that the impact of WWTP effluents on receiving water quality was low for most endpoints. For Nrf2, however, further investigation is required to evaluate the observed high bioactivities compared with the current EBT. The observed ERα activity could partly be explained by the presence of some steroid estrogens. Overall, our results contribute to an important database for the concentrations and removal efficiencies of bioactive chemicals in WWTPs and demonstrate bioassays as a useful tool for urban water quality monitoring.

Elimination efficiency of synthetic musks during the treatment of drinking water with ozonation and UV-based advanced oxidation processes.

This study investigated the reaction kinetics and elimination efficiency of eleven synthetic musks during ozonation and UV254nm-based, advanced oxidation processes. The synthetic musks containing olefin moieties with electron-donating alkyl substituents such as octahydro tetramethyl naphthalenyl ethanone (OTNE) and ambrettolide (AMBT) showed high reactivity toward ozone (k ≥ 3.7 × 105 M-1 s-1) and free available chlorine (FAC) (k = 9.2 - 88 M-1 s-1), while all other synthetic musks were less ozone reactive (k = 0.3 - 560 M-1 s-1) and FAC-refractory. All synthetic musks showed high •OH reactivity (k > 5 × 109 M-1 s-1), except musk ketone (MK) (k = 2.3 × 109 M-1 s-1). In concordance with the kinetic information, OTNE and AMBT were efficiently eliminated (>97%) in simulated ozone treatments of drinking water at a specific ozone dose of 0.5 gO3/gDOC. The elimination levels of the other synthetic musks were below 50% at 0.5 gO3/gDOC. The fluence-based UV photolysis rate constant of the synthetic musks was determined to be (0.2 - 2.7) × 10-3 cm2/mJ. The elimination levels of synthetic musks during UV alone treatment ranged from 7 to 81% at a UV fluence of 500 mJ/cm2. The addition of 10 mg/L H2O2 (UV/H2O2) significantly enhanced the elimination of most synthetic musks (achieving >90% elimination at 500 mJ/cm2), indicating that the •OH reaction was mainly responsible for their elimination. The addition of 10 mg/L FAC (UV/FAC) also significantly enhanced the elimination of olefinic and aromatic synthetic musks (>90%), for which the reaction with ClO• was mainly responsible. For MK and two alkyl synthetic musks, their elimination during UV/FAC treatment was still limited (28 - 64%) and was mainly achieved by UV photolysis or reaction with •OH. In summary, this study substantiates the chemical kinetics approach as a helpful tool for predicting or interpreting the elimination of micropollutants during oxidative water treatment.

Hierarchical deep learning model to simulate phytoplankton at phylum/class and genus levels and zooplankton at the genus level.

Harmful algal blooms (HABs) have become a global issue, affecting public health and water industries in numerous countries. Because funds for monitoring HABs are limited, model development may be an alternative approach for understanding and managing HABs. Continuous monitoring based on grab sampling is time-consuming, costly, and labor-intensive. However, improving simulation performance remains a major challenge in modeling, and current methods are limited to simulating phytoplankton (e.g., Microcystis sp., Anabaena sp., Aulacoseira sp., Cyclotella sp., Pediastrum sp., and Eudorina sp.) and zooplankton (e.g., Cyclotella sp., Pediastrum sp., and Eudorina sp.) at the genus level. The traditional modeling approach is limited for evaluating the interactions between phytoplankton and zooplankton. Recently, deep learning (DL) models have been proposed for solving modeling problems because of their large data handling capabilities and model structure flexibilities. In this study, we evaluated the applicability of DL for simulating phytoplankton at the phylum/class and genus levels and zooplankton at the genus level. Our work was an explicit representation of the taxonomic and ecological hierarchy of the DL model structure. The prerequisite for this model design was the data collection at two taxonomic and hierarchical levels. Our model consisted of hierarchical DL with classification transformer (TF) and regression TF models. These DL models were hierarchically connected; the output of the phylum/class level model was transferred to the genus level simulation model, and the output of the genus level model was fed into the zooplankton simulation model. The classification TF model determined the phytoplankton occurrence initiation date, whereas the regression TF model quantified the cell concentration of plankton. The hierarchical DL showed potential to simulate phytoplankton at the phylum/class and genus levels by producing average R2, and root mean standard error values of 0.42 and 0.83 [log(cells mL-1)], respectively. All simulated plankton results closely matched the measured concentrations. Particularly, the simulated cyanobacteria showed good agreement with the measured cell concentration, with an R2 value of 0.72. In addition, our simulated result showed good agreement in peak concentration compared to observations. However, a limitation remained in following the temporal variation of Tintinnopsis sp. and Bosmia sp. Using an importance map from the TF model, water temperature, total phosphorus, and total nitrogen were identified as significant variables influencing phytoplankton and zooplankton blooms. Overall, our study demonstrated that DL can be used for modeling HABs at the phylum/class and genus levels.

Spatial and temporal effects of fish feed on antibiotic resistance in coastal aquaculture farms.

For the first time, both spatial and temporal effects of fish feed on changes in abundance of antibiotic resistance genes (ARGs) were investigated in South Korea via quantifying ARGs and analyzing physicochemical parameters in the influent (IN) and effluent before (BF) and 30 min after (AF) the fish feeding time of sixteen flow-through fish farms. The absolute abundance of ARGs in AF samples was 5 times higher than in BF and 12 times higher than in IN samples. Values of physicochemical parameters such as ammonia, total nitrogen, suspended solids and turbidity in the effluent significantly increased by 21.6, 4.2, 2.6 and 1.65 times, respectively, after fish feeding. Spatially, the fish farms on Jeju Island exhibited higher relative abundance (3.02 × 10-4 - 6.1 × 10-2) of ARGs compared to the farms in nearby Jeollanam-do (3.4 × 10-5 - 8.3 × 10-3). Seasonally, samples in summer and autumn showed a higher abundance of ARGs than in winter and spring. To assess risk to the food chain as well as public health, further studies are warranted to explore the pathogenic potential of these ARGs.

Identification of factors affecting removal of antibiotic resistance genes in full-scale anaerobic digesters treating organic solid wastes.

Efficiencies of removing antibiotic resistance genes (ARGs) and intI1 were explored using eight full-scale anaerobic digesters. The digesters demonstrated different characteristics on the basis of substrate types (food waste, manure or sludge); configuration (single or two-stage); temperature (psychrophilic, mesophilic or thermophilic); hydraulic retention time (HRT) (9.7-44 days); and operation mode (continuous stirred tank reactor or plug flow reactor). Digesters' configuration or operating parameters showed a greater effect on abundance of ARGs than the type of input substrate. Redundancy analysis (RDA) accounted for 85.2% of the total variances and digesters with the same configuration and operational conditions showed similar performance for removal of ARGs. The highest efficiencies of removing ARGs (99.99%) were observed in two-stage thermophilic digesters with relatively long HRTs (32 days). The lowest removal efficiency (97.93%) was observed in single-stage mesophilic with relatively short HRTs (9.7 days), likely due to vertical and horizontal gene transfer.

Activation of persulfate by humic substances: Stoichiometry and changes in the optical properties of the humic substances.

Persulfate activation through electron transfer from humic substances (HS) was investigated. Persulfate consumption in the presence of standard HS and HS model compounds linearly correlated with the phenol contents of the HS. Redox-active carbonyl groups such as aromatic ketones and quinone also contributed to persulfate consumption by donating electrons while being reduced. Phenols activated persulfate through direct electron transfer from the phenolate forms but reduced ketones activated persulfate through reactions between their organic radicals and persulfate. Persulfate was activated more by terrestrially derived aquatic HS containing large numbers of phenol groups than by other species, and this caused more benzene oxidation to occur in the presence of terrestrially derived aquatic HS than in the presence of other species. Larger amounts of sulfate radicals were scavenged by soil-derived HS than other types of HS because soil-derived HS were composed of larger molecules than other types of HS. The fluorescence regional integration volume for HS reacted with persulfate linearly correlated with persulfate consumption. Decreases in the fluorescence regional integration value could be used to predict persulfate activation through electron transfer from HS to persulfate if the electron-donating capacity cannot be determined. Persulfate activation by HS is expected to be stoichiometrically more advantageous than conventional persulfate-Fe2+ processes when treating an aquifer containing large amounts of electron-rich HS.

Reaction kinetics and degradation efficiency of halogenated methylparabens during ozonation and UV/H2O2 treatment of drinking water and wastewater effluent.

This study investigated the reaction kinetics and degradation efficiency of methylparaben and its halogenated products (Cl-, Br-, Cl,Cl-, Br,Cl-, and Br,Br-methylparabens) during ozonation and UV254/H2O2 treatment. Second-order rate constants for reactions of the parabens with ozone and •OH were [Formula: see text] = 107 - 108 M-1 s-1 and [Formula: see text] = (2.3 - 4.3)× 109 M-1 s-1 at pH 7. Species-specific [Formula: see text] values of the protonated and deprotonated parabens were closely related to phenol ring substituent effects via quantitative structure-activity relationships with other substituted phenols. The UV photolysis rate of the parabens [kUV = (2.4 - 7.2)× 10-4 cm2 mJ-1] depended on the halogenation state of the paraben and solution pH, from which species-specific quantum yields were also determined. In simulated treatments of drinking water and wastewater effluent, the parabens were efficiently eliminated during ozonation, requiring a specific ozone dose of > 0.26 gO3/gDOC for > 97% degradation. During UV/H2O2 treatment with 10 mg L-1 H2O2, the degradation levels were > 90% at a UV fluence of 2000 mJ cm-2, except for Cl,Cl-methylparaben. Kinetic models based on the obtained reaction kinetic parameters could successfully predict the degradation levels of the parabens. Overall, ozonation and UV/H2O2 were effective in controlling parabens and their halogenated products during advanced water treatment.

Removal efficiency of organic micropollutants in successive wastewater treatment steps in a full-scale wastewater treatment plant: Bench-scale application of tertiary treatment processes to improve removal of organic micropollutants persisting after secondary treatment.

The goal of this study was to investigate the occurrence and removal of 52 organic micropollutants (OMPs) during each wastewater treatment step in a full-scale wastewater treatment plant (WWTP). Pharmaceuticals such as metformin, acetaminophen, caffeine, ibuprofen, cimetidine and naproxen were found with high average concentrations in the influent. Most OMPs were not affected by the primary treatment (removal <10%), while secondary biological treatment contributed the most to overall removal of the OMPs. Among the three lanes of the secondary treatment of the WWTP, a combined anaerobic-anoxic-oxic process followed by a membrane bioreactor (A2O-MBR) process effectively facilitated removal of the OMPs (96%) using a different redox: a conventional activated sludge (CAS) process exhibited removal of approximately 85% of total concentrations of the OMPs, while a Modified Ludzack-Ettinger (MLE) process achieved approximately 92.1% removal. Removal of more than 50% of the concentrations of 13 targeted OMPs was observed in the secondary effluent (except for metformin showing only 3.8% removal) via adsorption with powdered activated carbon (PAC) as additional tertiary treatment. Metformin, inadequately removed by additional tertiary treatments, was effectively removed by a biological activated carbon (BAC) process, reaching a removal efficiency of 90.5%. To increase the removal of the amounts and types of OMPs with various physico-chemical properties, hybrid processes through a combination of diverse advanced treatment should be tailored to WWTPs.

Occurrence and transformation of gabapentin in urban water quality engineering: Rapid formation of nitrile from amine during drinking water chlorination.

The occurrence and fate of the popular pharmaceutical gabapentin (GBP) in the urban water cycle were investigated with a focus on its transformation during water chlorination. GBP was detected in all samples with average concentrations of 1285 ng/L (n = 24) for wastewater effluent, 304 ng/L for river water (n = 22), and 180 ng/L for drinking water treatment plant (DWTP) influent (n = 4). The monitoring sites were located in the Nakdong River watershed, Korea. GBP was rapidly (within 20 min) transformed into 1-cyanocyclohexylacetic acid (GBP-nitrile) under typical chlorination conditions (1.4 mgCl2/L). When there was a molar excess of chlorine to GBP, the primary amine of GBP was double-chlorinated to form N-Cl2 GBP with a second-order rate constant of >103 M-1 s-1. Decomposition of N-Cl2 GBP had a first-order rate constant of (0.5-1.0) × 10-2 s-1 and produced GBP-nitrile with a yield of 87%-100%. We propose that N-Cl2 GBP is transformed into N-Cl GBP imine and then to GBP-nitrile via two consecutive dehydrochlorinations with the former as the rate-limiting step. N-Cl2 GBP had a much higher decomposition rate than N-Cl2 produced from other simple aliphatic amines, which could be related to the structural features of GBP such as its carboxyl group and quaternary ß-carbon. The wastewater effluent samples did not contain GBP-nitrile even in the chlorinated effluent because of the relatively low chlorine dose or high ammonia level. In a full-scale DWTP employing a pre-chlorination unit, GBP present in the influent river water was fully transformed into GBP-nitrile. The formed GBP-nitrile was degraded in subsequent ozonation (•OH oxidation) and biological activated carbon filtration (biodegradation) processes. The toxicity of GBP-nitrile is thought to be low but further studies are warranted to assess the toxicological relevance of nitrile formation during water chlorination.

Effects of phosphate and hydrogen peroxide on the performance of a biological activated carbon filter for enhanced biofiltration.

Biofilm formation on biofilters can influence their hydraulic performance, thereby leading to head loss and an increase in energy use and costs for water utilities. The effects of a range of factors, including hydrogen peroxide and phosphate, on the performance of biological activated carbon (BAC) and biofilm formation were investigated using laboratory-scale columns. Head loss, total carbohydrates, and proteins were reduced in the nutrient-enhanced, oxidant-enhanced, and nutrient + oxidant-enhanced BAC filters. However, there were no changes in the removal of dissolved organic matter, trihalomethane formation potential, or selected trace organic contaminants. The biofilm formation on polyvinyl chloride and stainless steel coupons using the laboratory biofilm reactor system was lower when the effluent from a nutrient-enhanced column was used, which indicated that there was less biofilm formation in the distribution systems. This may have been because the effluent from the nutrient-enhanced column was more biologically stable. Therefore, enhanced biofiltration could be used not only to reduce head loss in biofilters, but also to delay biofilm formation in distribution systems.

Transformation of an Amine Moiety of Atenolol during Water Treatment with Chlorine/UV: Reaction Kinetics, Products, and Mechanisms.

Transformation of atenolol (ATN), a micropollutant containing a secondary (2°) amine moiety, can be significantly enhanced in water treatment with sequential and combined use of chlorine and UV (chlorine/UV) through photolysis of the N-Cl bond. This study investigated the transformation kinetics, products, and mechanisms of the amine moiety of ATN in chlorine/UV (254 nm). The fluence-based, photolysis rate constant for N-Cl ATN was 2.0 × 10-3 cm2/mJ. Transformation products (TPs) with primary (1°) amines were mainly produced, but TPs with 2° and 3° amines were also formed, on the basis of liquid chromatography (LC)/quadrupole-time-of-flight/mass spectrometry and LC/UV analyses. The amine-containing TPs could be further transformed in chlorine/UV (with residual chlorine in post UV) via formation and photolysis of new N-Cl bonds. Photolysis of N-Cl 1° amine TPs produced ammonia as a major product. These data could be explained by a reaction mechanism in which the N-Cl bond was cleaved by UV, forming aminyl radicals that were transformed via 1,2-hydrogen shift, ß-scission, intramolecular addition, and 1,2-alkyl shift. Among these, the 1,2-alkyl shift is newly discovered in this study. Despite enhanced transformation, only partial mineralization of the ATN's amine moiety was expected, even under chlorine/UV advanced oxidation process conditions. Overall, the kinetic and mechanistic information from this study can be useful for predicting the transformation of amine moieties by chlorine/UV water treatment.

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.

Formation characteristics of carbonaceous and nitrogenous disinfection by-products depending on residual organic compounds by CGS and DAF.

Allogenic organic matter (AOM) composed of extracellular and intracellular organic matter (EOM and IOM) is a major precursor of halogenated carbonaceous and nitrogenous disinfection by-products (C-DBPs and N-DBPs) upon chlorination. The EOM and IOM extracted from Microcystis aeruginosa were analyzed based on bulk parameters and organic fractions with different molecular weight by liquid chromatography with organic carbon detection (LC-OCD). It investigated the efficiency of a conventional gravity system (CGS) and dissolved air flotation (DAF) in the removal of organic precursors, together with measurement of the formation of four major trihalomethanes (THMs) and haloacetonitriles (HANs) in treated water upon chlorination. The results showed that EOM accounted for 59% of building blocks and humic substances, whereas for IOM, 54% were low molecular weight (LMW) neutrals. Both CGS and DAF showed 57-59% removal of dissolved organic carbon (DOC) from EOM and IOM. Regarding DON removal, DAF was found to be more effective, i.e., 8% higher than CGS for EOM. Moreover, the removal of LMW acids and neutrals (not easy to remove and are major precursors of DBPs) from EOM and IOM by DAF was higher than from CGS. The amounts of DBPs measured in all the samples treated for interchlorination were much lower than in the samples for prechlorination. Although the precursors of EOM had a higher concentration than in IOM, THMs and HANs were detected for IOM at a higher concentration, which might be attributed to higher amounts of aromatic, aliphatic moisture and protein compounds in the IOM. Comparatively, DAF showed lower THM and HAN values than CGS water, particularly for IOM. Also, DAF showed a sharp decrease in THMs and an insignificant increase in HANs according to time.

Transformation of methylparaben during water chlorination: Effects of bromide and dissolved organic matter on reaction kinetics and transformation pathways.

The reaction kinetics, products, and pathways of methylparaben (MeP) during water chlorination with and without bromide (Br-) were investigated to better understand the fate of parabens in chlorinated waters. During the chlorination of MeP-spiked waters without Br-, MeP was transformed into mono-Cl-MeP and di-Cl-MeP with apparent second-order rate constants (kapp) of 64M-1s-1 and 243M-1s-1 at pH7, respectively, while further chlorination of di-Cl-MeP was relatively slower (kapp=1.3M-1s-1 at pH7). With increasing Br- concentration, brominated MePs, such as mono-Br-MeP, Br-Cl-MeP, and di-Br-MeP, became major transformation products. The di-halogenated MePs (di-Cl-MeP, Br,Cl-MeP, and di-Br-MeP) showed relatively low reactivity to chlorine at pH7 (kapp=1.3-4.6M-1s-1) and bromine (kapp=32-71M-1s-1), which explains the observed high stability of di-halogenated MePs in chlorinated waters. With increasing pH from 7 to 8.5, the transformation of di-halogenated MePs was further slowed due to the decreasing reactivity of di-MePs to chlorine. The formation of the di-halogenated MePs and their further transformation become considerably faster at Br- concentrations higher than 0.5µM (40µg/L). Nonetheless, the accelerating effect of Br- diminishes in the presence of dissolved organic matter (DOM) extract (Suwannee River humic acid (SRHA)) due to a more rapid consumption of bromine by DOM than chlorine. The effect of Br- on the fate of MeP was less in the tested real water matrices, possibly due to a more rapid bromine consumption by the real water DOM compared to SRHA. A kinetic model was developed based on the determined species-specific second-order rate constants for chlorination/bromination of MeP and its chlorinated and brominated MePs and the transformation pathway information, which could reasonably simulate the transformation of MePs during the chlorination of water in the presence of Br- and selected DOM.

Nitrosamine occurrence at Korean surface water using an analytical method based on GC/LRMS.

The survey of nitrosamine occurrence at Korean surface water of Nakdong river is conducted in this study. For this purpose, the nitrosamine analytical method based on more affordable GC/LRMS (low resolution mass spectrometry) has been developed. According to the study results, six nitrosamine compounds (NDEA as N-nitrosomethylethylamine, NDPA as N-nitrosodi-n-propylamine, NDMA as N-nitrosodimethylamine, NMEA as N-nitrosomethylethylamine, NDBA as N-nitrosodi-n-butylamine, and NDPHA as N-nitrosodiphenylamine) were detected at the Nakdong river. Among these, NDEA and NDPA are the most important compounds in terms of the nitrosamine contamination of the Nakdong river. The detected concentration of NDEA exceeded the CDHCS (California Department of Health Care Services) response level of 100 ng/L at several sites. The detected concentration of NDPA approached the response level (500 ng/L) at a few sites. When all nitrosamine concentrations were summed up, the maximum concentration of 735.7 ng/L was detected at the Nakdong river. An equation describing a decrease in total nitrosamine concentration along downstream sampling sites was proposed in this study. The equation can be used to predict the downstream nitrosamine contamination at the Nakdong river. Among various water quality parameters, T-N showed a good correlation with total nitrosamine concentration.