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.

Cr-Doped FeC2O4 Microrods Formed Directly on AISI 420 Stainless Steel to Enhance Electrochemical NO3- Reduction to N2 at Circumneutral pH.

We synthesized low-cost cathodes for use in the electrochemical NO3- reduction reaction (NO3RR) via the simple reconstruction of AISI 420 stainless steel (SS). Thermochemical treatment of the SS in oxalic acid generated iron oxalate (FeC2O4) microrods (BL-SS), with further anodization affording Cr-doped Fe2O3 (R-SS) or FeC2O4 (G-SS). G-SS displayed supreme N2 selectivity during galvanostatic electrolysis at circumneutral pH. Electroanalysis and descriptor/scavenger analysis indicated that Fe sites were the primary active sites of NO3- adsorption, with C2O42- as the H-binding sites. The C2O42- ligands and Cr dopants altered the electronic structures of the Fe sites. A parametric study of the current density, pH, [NO3-]0, and [Cl-]0 indicated an Eley-Rideal N2 generation mechanism, with NO2- as an intermediate. Cl- elevated the N2 selectivity but reduced the NO3RR efficiency. To demonstrate the practical applicability of G-SS with a proposed regeneration strategy, its durability was examined in synthetic and real wastewater matrices. Compared with that in synthetic wastewater, G-SS displayed more stable performance in real wastewater owing to the natural buffering capacity at the cathode, which reduced the corrosion rate. Cr-doped FeC2O4 is viable for use in the low-cost, efficient electrochemical treatment of wastewater containing NO3-.

Limonin, a Component of Immature Citrus Fruits, Activates Anagen Signaling in Dermal Papilla Cells.

Hair loss remains a significant problem that is difficult to treat; therefore, there is a need to identify safe natural materials that can help patients with hair loss. We evaluated the hair anagen activation effects of limonin, which is abundant in immature citrus fruits. Limonin increased the proliferation of rat dermal papilla cells (rDPC) by changing the levels of cyclin D1 and p27, and increasing the number of BrdU-positive cells. Limonin increased autophagy by decreasing phosphorylated mammalian target of rapamycin levels and increasing the phospho-Raptor, ATG7 and LC3B. Limonin also activated the Wnt/ß-catenin pathway by increasing phospho-ß-catenin levels. XAV939, a Wnt/ß-catenin inhibitor, inhibited these limonin-induced changes, including induced autophagy, BrdU-positive cells, and cell proliferation. Limonin increased the phosphorylated AKT levels in both two-dimensional cultured rDPC and three-dimensional spheroids. Treatment with the PI3K inhibitor wortmannin inhibited limonin-induced proliferation, and disrupted other limonin-mediated changes, including decreased p27, increased BrdU-positive cells, induced autophagy, and increased ATG7 and LC3B levels. Wortmannin also inhibited limonin-induced cyclin D1 and LC3 expression in spheroids. Collectively, these results indicate that limonin can enhance anagen signaling by activating autophagy via targeting the Wnt/ß-catenin and/or PI3K/AKT pathways in rDPC, highlighting a candidate nutrient for hair loss treatment.

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.

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.

In vitro and in vivo toxicological evaluation of transition metal-doped titanium dioxide nanoparticles: Nickel and platinum.

Transition metal-doped titanium dioxide nanoparticles (M-TiO2 NPs) have been studied to enhance the activity of TiO2 NPs in biomedical applications. In this study, in vitro and in vivo toxicological aspects of M-TiO2 NPs were reported to assess the safety of these materials. M-TiO2 NPs were synthesized via a photo-deposition technique. Nickel (Ni) and platinum (Pt) were used as dopants. Physicochemical properties, cytotoxicity, phototoxicity, gene ontology (GO) and dermal toxicity of M-TiO2 NPs were investigated. Ni-TiO2 (Ni, 1.02%) and Pt-TiO2 (Pt, 0.26%) NPs were sphere shape crystals with nanoscale size. ARPE-19 cells were more susceptible to Pt-TiO2 NPs (EC50, 0.796 mg/mL) than Ni-TiO2 NPs (EC50, 2.945 mg/mL). M-TiO2 NPs were rated as probably phototoxic to phototoxic. GO suggested binding function and metabolic processes as a risk mechanism of M-TiO2 NPs. In vivo toxicological effects of Ni-TiO2 NPs were not observed on body weight, serum aspartate transaminase/alanine transaminase levels, and skin histology at 61.5-6150 mg/kg. Specifically, skin thickness was not significantly modified (max. 33.2 ± 8.7 µm) and inflammation grade was less than level 2 (max. 1.2 ± 0.4). From these results, Ni-TiO2 and Pt-TiO2 NPs show promise as enhanced photocatalysts for safe and sustainable usage.

Differential Microbicidal Effects of Bimetallic Iron-Copper Nanoparticles on Escherichia coli and MS2 Coliphage.

Bimetallic iron-copper nanoparticles (Fe/Cu-NPs) were synthesized by a single-pot surfactant-free method in aqueous solution [via the reduction of ferrous ion to zerovalent iron nanoparticles (Fe-NPs) and the subsequent copper-coating by metal ion exchange]. The produced Fe/Cu-NPs formed aggregates of spherical nanoparticles (approximately 30-70 nm) of Fe-Cu core-shell structures with 11 wt % copper content. The microbicidal effects of Fe/Cu-NPs were explored on Escherichia coli and MS2 coliphage, surrogates for bacterial and viral pathogens, respectively. Fe/Cu-NPs exhibited synergistically enhanced activity for the inactivation of E. coli and MS2, compared to single-metal nanoparticles (i.e., Fe-NPs and Cu-NPs). Various experiments (microbial inactivation tests under different conditions, fluorescence staining assays, experiments using ELISA and qRT-PCR, etc.) suggested that Fe/Cu-NPs inactivate E. coli and MS2 via dual microbicidal mechanisms. Two biocidal copper species [Cu(I) and Cu(III)] can be generated by different redox reactions of Fe/Cu-NPs. It is suggested that E. coli is strongly influenced by the cytotoxicity of Cu(I), while MS2 is inactivated mainly due to the oxidative damages of protein capsid and RNA by Cu(III).

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.

Sub-lethal pharmaceutical hazard tracking in adult zebrafish using untargeted LC-MS environmental metabolomics.

Antibiotics in the aquatic environment are dispersed through anthropogenic activities at low concentrations. Despite their sub lethal concentration, these biologically active compounds may still have adverse effects to non-target species. This study examined the response of adult zebrafish to 0.1mg/L concentration of clarithromycin, florfenicol, sulfamethazine, and their mixture using environmental metabolomics. Embryo and larvae of the fish were also used to assess fish embryo acute toxicity and behavior tests respectively. The fish embryo toxicity test did not show any inhibition of growth and development of the embryos after 96h of exposure to the antibiotics. Changes in swimming activity were seen in 5-dpf larvae which is believed to be correlated with the length of exposure to the compounds. Meanwhile, environmental metabolomics revealed diverse metabolites and pathways that were affected after 72h of exposure of the adult fish to sub-lethal concentration of the compounds. We found that even at low concentration of the antibiotics, behavioral and metabolic effects were still observed despite the lack of visible morphological changes. Further studies involving other aquatic organisms and bioactive compounds are encouraged to strengthen the findings presented in this novel research.

Polyphosphate-enhanced production of reactive oxidants by nanoparticulate zero-valent iron and ferrous ion in the presence of oxygen: Yield and nature of oxidants.

The production of reactive oxidants from nanoparticulate zero-valent iron (nZVI) and ferrous ion (Fe(II)) in the presence of oxygen was greatly enhanced by the addition of tetrapolyphosphate (TPP) as an iron-chelating agent. Compared to other ligands, TPP exhibited superior activity in improving the oxidant yields. The nZVI/TPP/O2 and the Fe(II)/TPP/O2 systems showed similar oxidant yields with respect to the iron consumed, indicating that nZVI only serves as a source of Fe(II). The degradation efficacies of selected organic compounds were also similar in the two systems. It appeared that both hydroxyl radical (OH) and ferryl ion (Fe(IV)) are produced, and OH dominates at acidic pH. However, at pH > 6, little occurrence of hydroxylated oxidation products suggests that Fe(IV) is a dominant oxidant. The degradation rates of selected organic compounds by the Fe(II)/TPP/O2 system had two optimum points at pH 6 and 9, and these pH-dependent trends are likely attributed to the speciation of Fe(IV) with different reactivities.

Titanium dioxide nanofibers integrated stainless steel filter for photocatalytic degradation of pharmaceutical compounds.

A photocatalytically active stainless steel filter (P-SSF) was prepared by integrating electrospun TiO2 nanofibers on SSF surface through a hot-press process where a poly(vinylidene fluoride) (PVDF) nanofibers interlayer acted as a binder. By quantifying the photocatalytic oxidation of cimetidine under ultraviolet radiation and assessing the stability of TiO2 nanofibers integrated on the P-SSF against sonication, the optimum thickness of the TiO2 and PVDF layer was found to be 29 and 42 µm, respectively. At 10L/m(2)h flux, 40-90% of cimetidine was oxidized when the thickness of TiO2 layer increased from 10 to 29 µm; however, no further increase of cimetidine oxidation was observed as its thickness increased to 84 µm, maybe due to limited light penetration. At flux conditions of 10, 20, and 50 L/m(2) h, the oxidation efficiencies for cimetidine were found to be 89, 64, and 47%, respectively. This was attributed to reduced contact time of cimetidine within the TiO2 layer. Further, the degradation efficacy of cimetidine was stably maintained for 72 h at a flux of 10 L/m(2) h and a trans-filter pressure of 0.1-0.2 kPa. Overall, our results showed that it can potentially be employed in the treatment of effluents containing organic micropollutants.

Photocatalytic pre-treatment with food-grade TiO(2) increases the bioavailability and bioremediation potential of weathered oil from the Deepwater Horizon oil spill in the Gulf of Mexico.

Using the 2010 Deepwater Horizon oil spill in the Gulf of Mexico as an impetus, we explored the potential for TiO(2)-mediated photocatalytic reactive oxygen species (ROS) generation to increase the bioavailability (solubility) and biodegradability of weathered oil after a spill. Food grade TiO(2), which is FDA approved for use as food additive in the United States, was tested as a photocatalyst for this novel application. Photocatalytic pre-treatment (0.05 wt.% TiO(2), UV irradiation 18 W m(-2), 350-400 nm) for 24 h in a bench top photoreactor increased the soluble organic carbon content of weathered oil by 60%, and enhanced its subsequent biodegradation (measured as O(2) consumption in a respirometer) by 37%. Photocatalytic pre-treatment was also tested outdoors under sunlight illumination, but no significant increase in solubility or biodegradation was observed after 11 d of exposure. Although sunlight irradiation of food-grade TiO(2) generated ROS (assessed by the degradation of 4-chlorophenol as a probe compound), the efficacy of weathered oil pre-treatment was apparently hindered by sinking of the photocatalysts under quiescent conditions and illumination occlusion by the oil. Overall, results indicate that photocatalytic pre-treatment to stimulate bioremediation of weathered oil deserves further consideration, but controlling the buoyancy and surface hydrophobicity of the photocatalysts will be important for future efforts to enable ROS generation in proximity to the target compounds.