Loss of micropollutants on syringe filters during sample filtration: Machine learning approach for selecting appropriate filters.

Prefiltration before chromatographic analysis is critical in the monitoring of environmental micropollutants (MPs). However, in an aqueous matrix, such monitoring often leads to out-of-specification results owing to the loss of MPs on syringe filters. Therefore, this study investigated the loss of seventy MPs on eight different syringe filters by employing Random Forest, a machine learning algorithm. The results indicate that the loss of MPs during filtration is filter specific, with glass microfiber and polytetrafluoroethylene filters being the most effective (<20%) compared with nylon (>90%) and others (regenerated-cellulose, polyethersulfone, polyvinylidene difluoride, cellulose acetate, and polypropylene). The Random Forest classifier showed outstanding performance (accuracy range 0.81-0.95) for determining whether the loss of MPs on filters exceeded 20%. Important factors in this classification were analyzed using the SHapley Additive exPlanation value and Kruskal-Wallis test. The results show that the physicochemical properties (LogKow/LogD, pKa, functional groups, and charges) of MPs are more important than the operational parameters (sample volume, filter pore size, diameter, and flow rate) in determining the loss of most MPs on syringe filters. However, other important factors such as the implications of the roles of pH for nylon and pre-rinsing for PTFE syringe filters should not be ignored. Overall, this study provides a systematic framework for understanding the behavior of various MP classes and their potential losses on syringe filters.

Insight into disparate nonradical mechanisms of peroxymonosulfate and peroxydisulfate activation by N-doped oxygen-rich biochar: Unraveling the role of active sites.

In this study, we first comprehensively studied peroxymonosulfate (PMS) and peroxydisulfate (PDS) activation mechanisms using N, O codoped sludge biochar (NOSB) to degrade organics from water. Among the catalysts, NOSB with a higher content of graphitic N, optimal edge nitrogen (pyridinic N and pyrrolic N), CO groups, sp2-hybridized C, and rich defects were demonstrated to be a superior catalyst. Therefore, by activating PDS and PMS, NOSB exhibited the highest rate of BPA degradation, which was 22-fold and 13-fold that of pristine sludge biochar, respectively. However, owing to different oxidation potentials and molecular structures, PMS and PDS show different degradation performances due to various catalytic mechanisms occurring, even with the same biochar. Due to the asymmetrical structure of PMS, electrons passed from PMS to NOSB and further generated singlet oxygen (1O2), which governs the degradation of bisphenol A with an auxiliary contribution of single electron transfer. Meanwhile, PDS is reduced at the Lewis basic sites of NOSB, forming inner-surface-bound {PDS-NOSB}, which was oxidizing around neighboring carbon and decomposed targets through transferring single and double electrons. NOSB is promising for practical applications because of its adaptation to a wide pH range, anions, high total organic carbon removal, tunable active sites, and re-usability for degrading organics via PMS/PDS activation. This study unveils knowledge about N, O codoped sludge biochar catalysts for activating PMS/PDS and advocates a great approach for organics' degradation in the environment.

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.

Real-time morphological detection of label-free submicron-sized plastics using flow-channeled differential interference contrast microscopy.

Owing to the surge in plastic waste generated during the COVID-19 pandemic, concerns regarding microplastic pollution in aqueous environments are increasing. Since microplastics (MPs) are broken down into submicron (< 1 µm) and nanoscale plastics, their real-time morphological detection in water is necessary. However, the decrease in the scattering cross-section of MPs in aqueous media precludes morphological detection by bright-field microscopy. To address this problem, we propose and demonstrate a differential interference contrast (DIC) system that incorporates a magnification-enhancing system to detect MPs in aqueous samples. To detect MPs in both the stationary and mobile phases, a microfluidic chip was designed, taking into consideration the imaging depth of focus and flow resistance. MPs of various sizes flowing in deionized, tap, and pond water at varying speeds were observed under Static and Flow conditions. Successful real-time morphological detection and quantification of polystyrene beads down to 200 nm at a constant flow rate in water were achieved. Thus, the proposed novel method can significantly reduce analysis time and improve the size-detection limit. The proposed DIC microscopy system can be coupled with Raman or infrared spectroscopy in future studies for chemical composition analysis. ENVIRONMENTAL IMPLICATION: Microplastics (MPs), particularly submicron plastics < 1-µm, can pose a risk to human health and aquatic ecosystems. Existing methods for detecting MPs in the aqueous phase have several limitations, including the use of expensive instruments and prolonged and labor-intensive procedures. Our results clearly demonstrated that a new low-cost flow-channeled differential interference contrast microscopy enables the real-time morphological detection and quantification of MPs down to 200 nm under flowing conditions without sample labeling. Consequently, our proposed rapid method for accurate quantitative measurements can serve as a valuable reference for detecting submicron plastics in water samples.

Doped and immobilized titanium dioxide photocatalysts as a potential source of nitrosamine formation.

Immobilized and visible-light-active titanium dioxide (TiO2) is widely used for water treatment. However, the accelerated generation of degradation byproducts is a potential risk of TiO2-based photocatalysis. This study aimed to investigate the structural effect of engineered TiO2 samples on the formation of major nitrosamines during photocatalysis. The nitrogen-containing impurities and leached metal ions from doped-TiO2 samples could exacerbate nitrosamine formation potential (FP) in distilled water, secondary effluent, and chloraminated water. Doped-TiO2 with 2-ethylimidazole, trimethylamine, triethylamine, and N-carbon nanotubes could leach in the range of 47-64 ng L-1 nitrosamines (including N-nitrosomethylethylamine, N-nitrosodiethylamine, N-nitrosodimethylamine, and N-nitrosopyrrolidine) even under dark conditions. Furthermore, we investigated the role of metal dopants on nitrosamine-FP during the chloramination of precursors such as dimethylamine and microcystin-LR. Metal ions such as Cu that leached from the metal-doped catalysts may catalyze the nitrosamine-FP. Therefore, pre-purification (washing) and immobilization of doped-TiO2 samples on substrates are suggested to remove a considerable amount of nitrosamines. However, during the prolonged tryout, the selection of substrates was critical. Polymeric supports, such as polyimide and polyvinylpyrrolidone, can produce up to 85 ng L-1 nitrosamine, whereas TiO2 immobilized onto steel mesh can remove nitrosamine formation during photocatalytic oxidation followed by chloramination. This study systematically screened a diverse range of dopants, supports, and solvents in engineered TiO2 photocatalysts, in 61 samples, and provided novel insights into their effect on nitrosamine formation.

Changes in levels of N-nitrosamine formed from amine-containing compounds during chloramination via photocatalytic pretreatment with immobilized TiO2: Effect of source water and pH.

We investigated the effectiveness of photocatalytic pretreatment (PCP) of precursors in minimizing the formation potentials (FPs) of carcinogenic nitrosamines, including N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA), and N-nitrosodiethanolamine (NDELA), during water chloramination. A steel mesh substrate with immobilized TiO2 was highly efficient at mitigating nitrosamine formation and removing targeted precursors such as ranitidine, nizatidine, trimebutine, triethanolamine, and metoclopramide. Compared to UVC/H2O2, PCP under UVA irradiation (intensity of 0.67 mW cm-2) was more effective for reducing nitrosamine-FPs during post-chloramination. However, the PCP efficacies varied with the water source, pretreatment pH, and irradiation time. For example, PCP of eutrophic water increased the NDMA-FPs, but produced notable reductions (up to 99%) for NDELA- and NDEA-FPs. Shorter irradiation times, up to 15 min, increased the NDELA-FP in triethanolamine, and the NDMA-FP in nizatidine and trimebutine. However, the nitrosamine-FP decreased by > 50% after PCP at a pH > 5.6, following irradiation for 120 min. Oxygen addition, N-de(m)ethylation, and N-dealkylation were responsible for decreasing nitrosamine-FPs via the destruction of key moieties; this has been elucidated by mass spectroscopy. This study suggests that PCP could be used as an alternative strategy for minimizing nitrosamine-FPs during water treatment.

Degradation of ranitidine and changes in N-nitrosodimethylamine formation potential by advanced oxidation processes: Role of oxidant speciation and water matrix.

This study investigated the effects of thirteen (photo/electro) chemical oxidation processes on the formation potential (FP) of N-nitrosodimethylamine (NDMA) during the chloramination of ranitidine in reverse osmosis (RO) permeate and brine. The NDMA-FP varied significantly depending on the pretreatment process, initial pH, and water matrix types. At higher initial pH values (> 7.0), most pretreatments did not reduce the NDMA-FP, presumably because few radical species and more chloramine-reactive byproducts were generated. At pH < 7.0, however, electrochemical oxidation assisted by chloride and Fe2+/H2O2, catalytic wet peroxide oxidation and peroxydisulfate-induced pretreatments removed up to 85% of NDMA-FP in the RO brine. Ultraviolet (UV) irradiation or prechlorination alone did not reduce the NDMA-FP effectively, but combined UV/chlorine treatment effectively reduced the NDMA-FP. In contrast, after UV irradiation (2.1 mW cm-2 for 0.5 h) in the presence of H2O2 and chloramine, NDMA formation increased substantially (up to 26%) during the post-chloramination of the RO permeate. Mass spectrometric analysis and structural elucidation of the oxidation byproducts indicated that compared with the reactive nitrogen species generated by UV/NH2Cl, sulfate radicals and (photo/electro)chemically generated reactive chlorine species were more promising for minimizing NDMA-FP. Unlike, the hemolytic •OH driven by UV/H2O2, the •OH from Fe(IV)-assisted pretreatments showed a significant synergistic effect on NDMA-FP reduction. Overall, the results suggest the need for a careful assessment of the type of radical species to be used for treating an RO water system containing amine-functionalized compounds.

Role of ranitidine in N-nitrosodimethylamine formation during chloramination of competing micropollutants.

Ranitidine (RNT) is a widely known precursor of N-nitrosodimethylamine (NDMA) as evinced by the self-catalytic formation of NDMA during chloramination. In the present study, the NDMA formation potentials (NDMA-FP) of 26 micropollutants were assessed, particularly when mixed with RNT. 11 compounds were identified as individual precursors, including trimebutine and cimetidine, which exhibited substantial NDMA-FP, with up to 10% molar yield. In addition, nitrosamines, other than NDMA, namely N-nitrosodiethylamine and N-nitrosomethylamine, were observed from diethylamine-containing precursors, such as metoclopramide. In a 1:1 mixture of RNT and a competitor, the change in NDMA-FP was mostly comparable (within 20% deviation), while antagonistic interactions were observed for competitors, such as diethylhydroxylamine. The scattered overall NDMA-FP should be considered as a product of competition among the precursors for core substrates and intermediates for NDMA formation. The co-existence of either trimebutine or metoclopramide with RNT led to an exceptionally synergetic NDMA generation. Degradation kinetics and chlorination/nitrosation experiments combined with mass spectroscopy analyses indicated that RNT would accelerate both the initial chlorination and nitrosation of trimebutine and metoclopramide, leading to N-nitroso complexes, which have well-understood NDMA formation pathways, i.e., amination with subsequent aminyl radical generation. This work demonstrates a wide array of precursors with NDMA-FP, suggesting that nitrosamine formation is potentially underestimated in field environments.

UV/sulfite chemistry to reduce N-nitrosodimethylamine formation in chlor(am)inated water.

The disinfection by-product N-nitrosodimethylamine (NDMA) is a major concern in water quality management due to its carcinogenicity. Thus, a proper pretreatment is necessary to mitigate NDMA formation upon periodic chloramination by removing precursors, such as ranitidine (RNT). This study investigated the effect of UV/sulfite pretreatment on NDMA formation from an RNT-spiked tap and chloraminated synthetic swimming pool (SSP) water. At UVC intensity of 2.1 mW cm-2 and 0.5 mM of sulfite, UV/sulfite chemistry showed complete degradation of 20 µM RNT within 30 min. It was found that SO4•- primarily reduced the NDMA formation potential (FP) of RNT, while hydrated electrons effectively mitigated the pre-formed NDMA in the SSP water. The UV/sulfite pretreatment alleviated NDMA formation during post-chloramination (24 h) by up to 82%, outperforming the commonly employed advanced oxidation processes such as UV/H2O2. However, in the presence of bromide ions, the effectiveness of UV/sulfite pretreatment was seriously deteriorated, although the bromide ion itself was found to inhibit the NDMA formation from RNT especially at pH < 8 during chloramination. Mass spectrometric analysis indicated that the NDMA-FP of RNT could be removed by UV/sulfite principally via N-methylation, dealkylation, and oxygen transfer pathways. Consequently, UV/sulfite could be used as an alternative unit process for water treatment with reduced NDMA formation.

Binder-free immobilization of TiO2 photocatalyst on steel mesh via electrospraying and hot-pressing and its application for organic micropollutant removal and disinfection.

An immobilized photocatalyst was prepared by thermally treating TiO2-coated steel mesh (TiO2-IS) in a laboratory hot-press with no binder. TiO2 coating was performed by electrospraying a 1 mg/mL methanol dispersion of Evonik P25 powder. The thermal treatment conditions at 350 °C, 100 Mpa, and 1 h were found to be the optimum conditions. Scanning electron microscopic images displayed a robust and adherent TiO2 layer on steel mesh. X-ray photoelectron spectroscopy and elemental mapping studies confirmed that the Fe3O4 interface formed during thermal treatment strongly bound the TiO2 on steel mesh. The XRD patterns of TiO2-IS indicated the preservation of crystalline structure of Evonik P25 (anatase and rutile mixture) and the existence of iron oxide interface. Under UVA irradiation, 10 µM of methylene blue was completely decolorized within 40 min using an immobilized photocatalyst with 2.120 mg of TiO2 per 2.5 × 5.0 cm2 and showed stable efficacy in 25 consecutive photocatalytic runs. Furthermore, this sample degraded the organic micropollutants (e.g., pharmaceuticals) such as carbamazepine, ranitidine, acetaminophen, and trimethoprim at the rates of 0.041, 0.165, 0.089, and 0.079 min-1, respectively. Under UVA irradiation, it exhibited high photocatalytic disinfection activity for Escherichia coli and MS2 coliphage.

Nitrite ion mitigates the formation of N-nitrosodimethylamine (NDMA) during chloramination of ranitidine.

Ranitidine (RNT) has been an important tertiary amine precursor of N-nitrosodimethylamine (NDMA) in chlorine-based water treatment, due to reaction with monochloramine (NH2Cl) with exceptionally high molar yields up to 90%. This study examined the effects of nitrite ions (NO2-) on the kinetics of NDMA formation during the chloramination of RNT under variable concentrations of dissolved oxygen (DO, 0.7-7.5mg/L), RNT (5-30µM), NH2Cl (5-20mM), NO2- or NO3- (0-2mM) and pH (5.6-8.6). In the absence of the NO2-, the ultimate molar yield of NDMA after 6h of reaction was primarily influenced by [DO] and pH, while marginally affected by initial [RNT] and [NH2Cl]. A kinetic model, prepared in accordance with the reaction sequence of NDMA formation, suggested that the rate determining step was accelerated with increasing [NH2Cl]0, [DO], and pH. A Kinetic study together with ultra-performance liquid chromatography-quadrupole-time of flight mass spectrometer (UPLC-Q-TOF MS) and gas chromatography (GC)/TOF MS analyses in parallel demonstrated that the nitrite ion inhibited the nucleophilic substitution of the terminal amine on NH2Cl, and reduced the pseudo-steady state concentration of N-peroxyl radicals, significantly decreasing the ultimate yields of NDMA.

Preparation, characterization, and application of TiO2-patterned polyimide film as a photocatalyst for oxidation of organic contaminants.

Photocatalytically active TiO2-patterned polyimide (PI) films (PI-TiO2) were fabricated using thermal transfer patterning (TTP). When subjected to hot pressing, the TiO2 nanoparticles electrosprayed on steel mesh templates were successfully transferred and formed checker plate patterns on PI film. FE-SEM studies confirmed that pressing at 350°C and 100MPa was optimum for obtaining patterns with uniform TiO2 coverage. When the quantity of TiO2 on the template increased, the amount of it immobilized on PI film also increased from 0.3245 to 1.2378mg per 25cm2. XPS studies confirmed the presence TiO2 on the patterns, and indicated the formation of carboxylic acid and amide groups on the PI surface during TTP. When tested under UVA irradiation, PI-TiO2 with 1.2378mg/25cm2 TiO2 loading exhibited the highest photocatalytic performance for methylene blue (10µM) degradation, with a rate constant of 0.0225min-1 and stable photocatalytic efficacy for 25 cycles of reuse. The PI-TiO2 was also successfully used to degrade amoxicillin, atrazine, and 4-chlorophenol. During photocatalysis, the toxicity of 4-chlorophenol against Vibrio fischeri and the antibiotic activity of amoxicillin against Escherichia coli were decreased. Overall, TTP was found to be a potentially scalable method for fabricating robust immobilized TiO2 photocatalyst.

Photocatalytic applications of paper-like poly(vinylidene fluoride)-titanium dioxide hybrids fabricated using a combination of electrospinning and electrospraying.

A paper-like photocatalyst was fabricated by electrospraying an N,N'-dimethylformamide (DMF) dispersion of titanium dioxide (TiO2) nanoparticles (NPs) on a poly(vinylidene fluoride) nanofiber (PVDF NF) mat prepared by electrospinning. Morphological studies revealed that the TiO2 NPs uniformly deposited as clusters on the surface of the PVDF NF mat. The immobilized amount of TiO2 was found to be 2.08, 2.44, 3.80, and 4.73 mg per 45 cm(2) of PVDF-TiO2 hybrids for the electrospraying of 10, 20, 40, and 60 ml of TiO2-DMF, respectively. The hybrid photocatalysts were effective in degrading bisphenol A (BPA), 4-chlorophenol (4-CP), and cimetidine (CMT), which dissolved in both deionized water and secondary wastewater effluents, with activity being proportional to the quantity of TiO2 NPs immobilized. For the highest loading amount of TiO2, BPA, 4-CP, and CMT degraded completely within 100, 100, and 40 min of UV irradiation, respectively. Stable photo-oxidation of CMT was maintained through 10 repeated cycles. During these cycles, it was confirmed that there was no loss of TiO2 NPs by inductively coupled plasma optical emission spectrometry. Our results suggest that effective and stable PVDF-TiO2 hybrid photocatalysts can be fabricated on a large scale by combining electrospinning and electrospraying techniques.