Transformation of microplastics by oxidative water and wastewater treatment processes: A critical review.

Microplastics (MPs) are contaminants of emerging concern that accumulate in various environments, where they pose threats to both the ecosystem and public health. Since MPs have been detected in drinking water resources and wastewater effluents, more efficient treatment is needed at wastewater treatment plants (WWTPs) and drinking water treatment plants (DWTPs). This review discusses the potential of biological, photochemical, Fenton (-like) systems, ozonation, and other oxidation processes in the treatment of MPs in terms of their indicators of oxidation such as mass loss and surface oxidation. The oxidation processes were further analyzed in terms of limitations and environmental implications. Most previous studies examining MPs degradation using conventional treatments-such as UV disinfection, ozonation, and chlorination-employed significantly higher doses than the common doses applied in DWTPs and WWTPs. Owing to such dose gaps, the oxidative transformation of MPs observed in many previous studies are not likely to occur under practical conditions. Some novel oxidation processes showed promising MPs treatment efficiencies, while many of them have not yet been applied on a larger scale due to high costs and the lack of extensive basic research. Health and environmental impacts related to the discharge of oxidized MPs in effluents should be considered carefully in different aspects: the role as vectors of external pollutants, release of organic compounds (including organic byproducts from oxidation) and fragmentation into smaller particles as MPs circulate in the ecosystem as well as the possibility of bioaccumulation. Future research should also focus on ways to incorporate developed oxidation processes in DWTPs and WWTPs to mitigate MPs contamination.

A multi-scale framework for modeling transport of microplastics during sand filtration: Bridging from pore to continuum.

The fate and transport of microplastics (MPs) during deep bed filtration were investigated using combined laboratory experiments and numerical modeling. A series of column experiments were conducted within the designated ranges of six operating parameters (i.e., size of the MP and collector, seepage velocity, porosity, temperature, and ionic strength). A variance-based sensitivity analysis, the Fourier amplitude sensitivity test, was conducted to determine the priority in affecting both the attachment coefficient at the pore scale, and the subsequent stabilized height of the breakthrough curve at the continuum scale, which follows non-monotonic trends with singularity in the size of MP (i.e., 1 µm). Finally, Damkohler numbers were introduced to analyze the dominant mechanisms (e.g., attachment, detachment, or straining) in the coupled hydro-chemical process. The robustness of conceptual frameworks bridges the gap between pore-scale interactions and the explicit MPs removal in the continuum scale, which could support decision-making in determining the priority of parameters to retain MPs during deep bed filtration.

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.

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.

Enhanced phosphate selectivity from wastewater using copper-loaded chelating resin functionalized with polyethylenimine.

In water and wastewater, phosphate is considered a critical contaminant due to cause algae blooms and eutrophication. To meet the stringent regulation of phosphate in water, a new commercial chelating resin functionalized with polyethylenimine was tested for phosphate removal by loading Cu(2+) and Fe(2+)/Fe(3+) to enhance selectivity for phosphate. Batch and column experiments showed that CR20-Cu exhibited high selectivity for phosphate over other strong anions such as sulfate. The average binary phosphate/nitrate and phosphate/sulfate factors for CR20-Cu were calculated to be 7.3 and 4.8, respectively, which were more than 0.97 and 0.22 for a commercial anion exchanger (AMP16). The optimal pH for the phosphate removal efficiency was determined to be 7. According to the fixed-bed column test, the breakthrough sequence for multiple ions was HPO4(2-)>SO4(2-)>NO3(-)>Cl(-). Saturated CR20-Cu can be regenerated using 4% NaCl at pH 7. More than 95% of the phosphate from CR20-Cu was recovered, and the phosphate uptake capacity for CR20-Cu was not reduced after 7 regeneration cycles.

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.