Radioiodine is one of the long-lived fission products and also an important radionuclide released during nuclear accidents, which generates interest in its environmental fate. Its sorption has been studied in a wide range of materials, but no equivalent study exists for microplastics, an emerging environmental vector. Weathering and biofilm formation on microplastics can enhance radioiodine sorption. For the first time, we're reporting how radioiodine interacts with different types of polyethylene derived microplastics (pristine, irradiated, and biofilm developed microplastics). This study revealed that exposure to radiation and the marine environment significantly alters the physico-chemical properties of microplastics. In particular, in marine-exposed samples, a signature of biofilm development was detected. Speciation study indicates that iodine exists in the iodide form in the studied marine environment. The study revealed that, iodide ions attach to biofilm-developed microplastics via electrostatic, ion-dipole, pore filling, and van der Waals interactions. Pore filling, ion-dipole, and van der Waals interactions may cause iodide binding to irradiated microplastics, whereas pore-filling and van der Waals interactions cause iodide binding to pristine microplastics. The distribution coefficient (Kd) of iodine on microplastics is positively correlated with biofilm biomass, which signifies the role of biofilm in radioiodine uptake. The Kd indicates microplastics are potential iodide accumulators and could be a possible vector in the marine system.

Recently, hetero junction materials (p-n-p and n-p-n) have been developed for uplifting the visible light activity to destroy the harmful pollutants in wastewater. This manuscript presents a vivid description of novel n-p-n junction materials namely CeO₂-PPy-ZnO. This novel n-p-n junction was applied as the photocatalyst in drifting the mobility of charge carriers and hence obtaining the better photocatalytic activity when compared with p-n and pure system. Such catalyst's syntheses were successful via the copolymerization method. The structural, morphological and optical characterization techniques were applied to identify the physio-chemical properties of the prepared materials. Additionally, the superior performance of this n-p-n nanostructured material was demonstrated in the destruction of micro organic (chlorophenol) toxic wastes under visible light. The accomplished ability of the prepared catalysts (up to 92% degradation of chlorophenol after 180 min of irradiation) and their profound degradation mechanism was explained in detail.

Catalytic pyrolysis is a promising chemical recycling technology to supplement mechanical recycling since plastics can be broken down into monomers or converted to the required fuels and chemicals. In this study, a microwave (MW) -responsive SiC foam@zeoltie core-shell structured catalyst was proposed for the catalytic pyrolysis of polyolefins. Under microwave irradiation, the SiC foam core works as both microwave adsorber and catalyst support, thus concentrating the generated heat energy on the ZSM-5 zeolite shell, where the catalytic reaction takes place. SiC foam with an open cellular structure can also improve the global transport of mass and heat during plastics pyrolysis. In this work, the effects of the SiO₂/Al₂O₃ ratio and alkaline treatment of ZSM-5 zeolite coated SiC foam under MW irradiation on the variations in product distribution from low-density polyethylene (LDPE) pyrolysis were investigated at 450 °C. The results indicated that the appropriate acidity and pore structure were crucial to upgrading gas and liquid products. Particularly, the creation of a mesoporous structure in ZSM-5 zeolite via alkaline treatment could improve the diffusion of large molecules and products, thus significantly increasing the selectivity of high-valued light olefins and aromatics while inhibiting the formation of unwanted alkanes, which are expected in the chemical industry. Concretely, the concentration of olefins in gas increased to 51.0 vol% for ZSM-5(50)-0.25AT, and 65.6 vol% for ZSM-5 (50)-0.50AT, compared with 45.2 vol% for the parent ZSM-5(50). The relative concentration of aromatics in liquid decreased from 96.6% for ZSM-5(50) to 75.9% for ZSM-5(50)-0.25AT, and 71.1% for ZSM-5(50)-0.50AT. Given the respective yield of gas and liquid, the total selectivity of C2–C4 olefins and aromatics for mesoporous ZSM-5 zeolites could reach 58.6–64.9% during LDPE pyrolysis, which were higher than that for the parent ZSM-5 zeolite.

As an emerging brominated flame retardant (BFR), tetrabromobisphenol S (TBBPS) has been frequently detected in the environmental media and organisms. Knowledges on the transformation and fate of TBBPS in both environment and engineering systems are essential to its ecological risk assessment. Herein, we reported the photochemical decomposition of TBBPS in aqueous solution upon 254 nm ultraviolet irradiation (UV₂₅₄). Results show that TBBPS was highly photoreactive, most likely due to the presence of four ortho-bromine substituents. The molar absorption coefficient and quantum yield of TBBPS were found to be pH-dependent, with the monoanionic form being most photoreactive. A series of photoproducts were identified by solid phase extraction (SPE) combined with liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI(+)-MS/MS. The photolysis of TBBPS likely proceeded through photonucleophilic substitution, photoreductive debromination, and β-scission reactions. A ketocarbene, possibly derived from the lower lying excited triplet state, was proposed to be involved in the photolysis of TBBPS. Ion chromatography analysis revealed that debromination occurred quickly, and the yield of bromide (Br⁻) approached 100% after 90 min irradiation. The presence of SRNOM and MRNOM inhibited the photodegradation rate of TBBPS, which is likely due to the light-screening and physical quenching effects of natural organic matter (NOM). Our results reveal that photolysis is an important process for the attenuation of TBBPS in aquatic system; however, naturally occurring species such as NOM can appreciably retard the decay of TBBPS.

Fabric and foam samples from popular children car seats marketed in the United States during 2018 were tested for fluorine content by particle-included gamma ray emission spectroscopy (PIGE, n = 93) and X-ray photoelectron spectroscopy (XPS, n = 36), as well as for per- and polyfluoroalkyl substances (PFAS) by liquid and gas chromatography mass spectrometry (LC/MS and GC/MS, n = 36). PFAS were detected in 97% of the car seat samples analyzed with MS, with total concentrations of 43 PFAS (∑PFAS) up to 268 ng/g. Fabric samples generally had greater ∑PFAS levels than foam and laminated composites of foam and fabric. The three fabric samples with the highest total fluorine content as represented by the highest PIGE signal were also subjected to ultraviolet (UV) irradiation and the total oxidizable precursor (TOP) assay. Results from these treatments, as well as the much higher organofluorine levels measured by PIGE compared to LC/MS and GC/MS, suggested the presence of side-chain fluorotelomer-based polymers (FTPs), which have the potential to readily degrade into perfluoroalkyl acids (PFAAs) under UV light. Furthermore, fluorotelomer (meth)acrylates were found to be indicators for the presence of (meth)acrylate-linked FTPs in consumer products, and thus confirmed that at least half of the tested car seats had FTP-treated fabrics. Finally, extraction of selected samples with synthetic sweat showed that ionic PFAS, particularly those with fluorinated carbons ≤8, can migrate from fabric to sweat, suggesting a potential dermal route of exposure.

In this study, heterojunction photocatalysts, XAg@C-TCZ, based on MOF-derived C–TiO₂ and Cd₀.₅Zn₀.₅S decorated with Ag nanoparticles (Ag NPs) were successfully synthesized through hydrothermal and calcination methods. The catalytic effectiveness of XAg@C-TCZ was evaluated by simultaneous photocatalytic degradation of rhodamine B (RhB) and reduction of Cr(VI) under simulated sunlight irradiation. The presence of the Z-scheme heterojunction was demonstrated through trapping experiments, X-ray photoelectron spectroscopy (XPS), time-resolved photoluminescence (PL) investigations, and electron spin resonance (ESR) spectroscopy. With an initial RhB and Cr(VI) concentration of 7 mg L⁻¹ and 5 mg L⁻¹, the catalyst 10Ag@C-TCZ achieved a simultaneous removal of 95.2% and 95.5% within 120 min, respectively. With the same catalyst, the degradation rate of RhB was 2.75 times higher and the reduction rate of Cr(VI) was 9.3 times higher compared to pure Cd₀.₅Zn₀.₅S. Total organic carbon (TOC) analysis confirmed the extent of mineralization of RhB, while the reduction of Cr(VI) was corroborated by XPS. Compared to pure RhB and Cr(VI) solutions, the reaction rates are smaller in the solution containing both contaminants, which is attributed to the competition for ·O₂⁻. 10Ag@C-TCZ also exhibited a stable catalytic performance in tap water and lake water. This work provides a new perspective on the construction of heterojunctions with doped MOF derivatives for the purification of complex pollutant systems.

The most promising technique for directly converting solar energy into clean fuels and environmental remediation by organic dye degradation is photoelectrochemical (PEC) process. We introduced Sn⁴⁺/Ti⁴⁺ doped α-Fe₂O₃@CuₓO heterojunction photoanode with complete optimization for PEC hydrogen (H₂) generation and organic dye degradation. Improvement of photocurrent photo and reducing overpotentials under optimized conditions lead to enhancing PEC performances, degradation efficiency of organic compounds, and H₂ generation generation rate. The optimized heterojunction photoanode (5TiFe@CuₓO-D) showed IPCE exceeding 42% compared with pristine hematite (Fe₀.₀₁–800₆ₕ) nanostructures (28%). Additionally, all the optimized photoanodes showed higher PEC stability for 10 h. Time-resolved PL spectra confirm the improved average lifetime for heterojunction photoanodes, supporting the enhanced PEC performance. Optimized 5TiFe@CuₓO-D material achieved PEC H₂ generation of ∼300 μL h⁻¹.cm⁻² which is two times higher than pristine hematite’s activity (150 μL h⁻¹.cm⁻²) and almost 99% degradation efficiency within 120 min of irradiation time. Therefore, a state-of-the-art study has been explored for hematite-based heterojunction photoanodes reflecting the superior PEC performance and hydrogen, methyl orange (MO) dye degradation activities. The improved results were reported because of stable morphology and better crystallinity acquired through systematic investigation of thermal effects and hydrothermal duration, improved electrical properties by Sn/Ti doping into the lattice of α-Fe₂O₃ and optimization of CuₓO deposition methods. The formation of well-defined heterojunction minimizes the recombination of the charge carrier and leads to effective transportation of excited electrons for the enhanced PEC performance.

In this work, we prepared nanocomposites of nickel-decorated manganese oxynitride on graphene nanosheets and demonstrated them as photocatalysts for degradation of acetylsalicylic acid (ASA). The catalyst exhibited a high degradation efficiency over ASA under visible light irradiation and an excellent structural stability after multiple uses. Compared to manganese oxide (MnO) and manganese oxynitride (MnON) nanoparticles, larger specific surface area and smaller band gap were observed for the nanocomposite accounting for the enhanced photocatalytic efficiency. Besides the compositional effect of the catalyst, we also examined the influence of various experimental parameters on the degradation of ASA such as initial concentration, catalyst dose, initial pH and additives. The best performance was obtained for the nanocomposite when the catalyst dose was 10 mg/mL and the initial pH 3. Detection of intermediates during photocatalysis showed that ASA undergoes hydroxylation, demethylation, aromatization, ring opening, and finally complete mineralization into CO₂ and H₂O by reactive species. For practical applications as a photocatalyst, cytotoxicity of the nanocomposite was also evaluated, which revealed its insignificant impact on the cell viability. These results suggest the nanocomposite of nickel-decorated manganese oxynitride on graphene nanosheets as a promising photocatalyst for the remediation of ASA-contaminated water.

Disastrous oil spills cause severe environmental issues. The shortcomings of current cleaning methods for remediating oil have prompted the latest research drive to create intelligent nanoparticles that absorb oil. We, therefore, synthesized 197 ± 50 nm floatable photoreactive hybrid nanoparticles with Ag–TiO₂ plasmonic photocatalyst (Eg = 3.08 eV) content to eliminate interfacial water pollutants, especially toluene-based artificial oil spill. We found that the composite particles have non-wetting properties in the aqueous media and float easily on the surface of the water due to the moderate hydrophobic nature (Θ = 113°) of the matrix of polystyrene, and these properties lead to elevated absorption of the interfacial organic pollutants (e.g., mineral oil). We showed that (28.5 mol%) divinylbenzene cross-linker content was required for adequate swelling capacity (2.15 g/g), whereas incorporated 15.8% Ag–TiO₂ content in the swollen particles was enough for efficient photodegradation of the artificial oil spill under 150 min LED light (λₘₐₓ = 405 nm) irradiation. The swollen polymer particles with embedded 32 ± 7 nm Ag–TiO₂ content increase the efficiency of photooxidation by increased the direct contact between both the photocatalysts and the artificial oil spill. Finally, it was also presented that the composite particles destroy themselves: after approximately one and a half months of continuous LED light irradiation, the organic polymer component of the composite was almost completely (88.5%) photodegraded by the incorporated inorganic photocatalyst particles.

Phosphorus (P) plays a critical role in eutrophication and algal growth; therefore, improving our understanding of the impact of P is essential to control harmful algal blooms. In this study, Microcystis aeruginosa was treated with 5-h ambient irradiation in the medium with different dissolved inorganic P (DIP) concentrations, DIP-free, moderate-DIP, and high-DIP, to explore its growth and other physiological responses. Compared to photosynthetically active radiation (PAR), UV-A (320–400 nm) and UV-B (280–320 nm) radiation had inhibitive effects on the photosynthesis and growth of M. aeruginosa, while high P availability could alleviate or eliminate the negative effects of UV radiation. The photosynthetic parameters had a minimum reduction and quickly recovered after re-inoculation under high-DIP conditions. Confirmed by SEM, photosynthetic pigments, the generation of reactive oxygen species (ROS), superoxide dismutase (SOD) activity and other methods, ambient UV radiation exerted oxidative stresses rather than direct lethal effects on M. aeruginosa. Photosynthetic parameters indicated that algal UV-adaptation processes could include decreasing photo-induced damages and increasing self-repair efficiency. The P acquired by M. aeruginosa cells can have two function, which included alleviating UV-induced negative effects and sustaining algal growth. Consequently, UV-adaptation processes of M. aeruginosa resulted in an elevated demand for DIP, which resulted to increased P uptake rates and cellular P quota under moderate and high-DIP conditions. Therefore, the production of carotenoid and phycocyanin, and SOD activity increased under UV stress, leading to a better adaptation capability of M. aeruginosa and decreased negative effects of UV radiation on its growth. Overall, our findings demonstrated the significant interactive effects of P enrichment and irradiation on typical cyanobacteria, and the strong adaptation capability of M. aeruginosa in the eutrophic UV-radiated waters.