The present study investigated the impact of solar UV radiation on ZnO nanoparticle toxicity through photocatalytic ROS generation and photo-induced dissolution. Toxicity of ZnO nanoparticles to Daphnia magna was examined under laboratory light versus simulated solar UV radiation (SSR). Photocatalytic ROS generation and particle dissolution were measured on a time-course basis. Two toxicity mitigation assays using CaCl2 and N-acetylcysteine were performed to differentiate the relative importance of these two modes of action. Enhanced ZnO nanoparticle toxicity under SSR was in parallel with photocatalytic ROS generation and enhanced particle dissolution. Toxicity mitigation by CaCl2 to a less extent under SSR than under lab light demonstrates the role of ROS generation in ZnO toxicity. Toxicity mitigation by N-acetylcysteine under both irradiation conditions confirms the role of particle dissolution and ROS generation. These findings demonstrate the importance of considering environmental solar UV radiation when assessing ZnO nanoparticle toxicity and risk in aquatic systems.

Microcystin-LR (MC-LR), one of the most common cyanotoxins, is produced by harmful cyanobacteria. The current study focuses on the photosensitized transformation of MC-LR in dissolved organic matter (DOM) enriched solutions under solar simulated irradiation. It appears that the direct energy transfer of triplet excited state DOM with MC-LR plays a key role and leads to photosensitized isomerization of Adda side chain. Furthermore a micro-heterogeneous mechanism has been proposed. Size exclude chromatograph (SEC) has been applied to explore the adsorption of MC-LR on the DOM. The adsorption phenomenon supported the fact that the pseudo first-order photodegradation rates showed positive correlation with the adsorption. The photo-transformation rate of MC-LR increases as pH decreases which is also the result of the adsorptive interaction of MC-LR with DOM. Finally two bulk water parameters (TOC and UV350 nm) have been applied to predict the photodegradation rates of MC-LR in the varied water matrixes.

To advance the knowledge of environmental fate of nanomaterials, we systematically investigated the dissolution of polymer-coated CdSe/ZnS quantum dots (QDs) under UV (254 nm) irradiation. The environmental effects (i.e., irradiation intensity, dissolved oxygen, temperature, and humic acid), as well as the coating effects on dissolution kinetics of QDs were investigated. Our results showed that higher irradiation intensity and temperature increased ion release rates (Cd²⁺, SeO₄ ²⁻, and Zn²⁺), whereas the different polymer coatings varied the dissolution rates. The absence of dissolved oxygen inhibited the dissolution of QDs, and we further demonstrated that the dissolution was a photo-oxidative process involved superoxide radical formation. Humic acid had a twofold effect on dissolution due to its photosensitization and photoabsorption for UV irradiation. Finally, an empirical kinetic law was proposed to interpret the above environmental effects. This study lays groundwork to better understand the environmental fate of QDs.

It is estimated that over 700,000 tons of synthetic dyes are produced annually, 15% of which are emitted as effluents. These highly stable dyes enter the world water ecosystems and stay in the environment, and eventually cause adverse impacts to the environment. Current wastewater treatment methods, such as filtration, coagulation, and chemical oxidation, have sideeffects, including toxic residue formation, membrane fouling, bioaccumulation, and secondary pollutant formation. Given the issues mentioned, it is necessary to study how to improve the degradation of synthetic dye with a cost-effective and ecofriendly approach. Natural oxidation provides a greener option. Recently, Deuteromycetes fungus Myrothecium verrucaria G-1 (M. verrucaria G-1) has shown great potential in producing high level of dye oxidase. This study aims to generate a dye oxidase hyperproducer, 3H6 from M. verrucaria G-1 by using atmospheric and room temperature plasma (ARTP) coupled with ultraviolet (UV) irradiation. This method increases oxidase production by nearly 106.15%. After a simple precipitation and dialysis, this mutant oxidase increases by 1.97-fold in a specific activity with dye degradation rates at 70% for Mmethylene blue (MB) and 85% for Congo red (CR). It is found that the genetic stability of 3H6 remains active for ten generations. The size of oxidase is 65 kDa, and optimum temperature for reaction is 30 °C with 4.5 pH. This study presents that the first combined mutagenesis approach by ARPT-UV on fungus species generates an impressive increment of acid dye oxidases production. As such, this method presents a cost-effective alternative to mitigate hazardous dye pollution.

Deca-brominated diphenyl ether (BDE-209) is shown to be persistent in soil and it's urgent to find an effective method to remove BDE-209 from contaminated soil. In this study, the investigation of BDE-209 degradation in three different rice-vegetable rotation soils induced by electron beam (E-beam) irradiation under flooded and non-flooded conditions was conducted. The reductive efficiency of ¹⁴C-BDE209 reached the highest level at 50 kGy and the values in flooded soils of rice-eggplant rotation soil (RES), rice-peanut soil (RPS), and rice-chili pepper soil (RCS) were 93.5%, 87.2%, and 73.8%, respectively. The reductive efficiencies in non-flooded soils of RES, RPS, and RCS were 73.4%, 81.0%, and 78%, respectively. The D₀.₅ values (dose required for reducing 50% BDE-209) of BDE-209 in non-flooded soils were lower than those in flooded soils, suggesting greater degradation efficiency of BDE-209 in non-flooded soils than in flooded soils. The BDE-209 was degraded into higher-brominated PBDEs and lower-brominated PBDEs by E-beam irradiation. The results demonstrate that BDE-209 in the soil can be degraded by E-beam irradiation, non-flooded condition is better than flooded condition for the removal of BDE-209, and the main degradation mechanism of BDE-209 by E-beam irradiation is debromination. This study provides a rapid and effective method for degrading BDE-209 that is persistent in soils, and has important implications for the remediation of soil contaminated by PBDEs in and around E-waste dismantling areas.

Herein, an efficient visible-light-driven BiFeO₃/AgVO₃ nanocomposite was effectively fabricated via a facile co-precipitation procedure. The physicochemical properties of BiFeO₃/AgVO₃ nanocomposites were investigated via Fourier transform-infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL), UV visible diffuse reflectance spectroscopy (DRS) and photoelectrochemical studies (PEC). The photocatalytic activity (PCA) of BiFeO₃/AgVO₃ nanocomposites was assessed with regard to the photocatalytic degradation of Rhodamine-B (RhB) when subjected to visible light irradiation (VLI). Upon 90 min of illumination, the optimal 3%-BiFeO₃/AgVO₃ nanocomposite showed a greater photocatalytic degradation, which was ∼3 times higher than the bare AgVO₃. The lower PL intensity of 3%-BiFeO₃/AgVO₃ nanocomposite exposed the low recombination rate, which improved the photo-excited charge carriers separation efficiency. The experimental outcomes showed that the BiFeO₃/AgVO₃ nanocomposite might be an encouraging material for treatment of industrial and metropolitan wastewater. Moreover, a plausible RhB degradation mechanism was proposed proving the participation of the generated OH and O₂– radicals in the degradation over BiFeO₃/AgVO₃ nanocomposite.

Nitrous acid (HONO) production from the heterogeneous photochemical reaction of NO₂ on several Chinese soils was performed in a cylindrical reactor at atmospheric pressure. The NO₂ uptake coefficient (γ) and HONO yield (YHONO) on different soils were (0.42–5.16) × 10⁻⁵ and 6.3%–69.6%, respectively. Although the photo-enhanced uptake of NO₂ on different soils was observed, light could either enhance or inhibit the conversion efficiency of NO₂ to HONO, depending on the properties of the soils. Soils with lower pH generally had larger γ and YHONO. Soil organics played a key role in HONO formation through the photochemical uptake of NO₂ on soil surfaces. The γ showed a positive correlation with irradiation and temperature, while it exhibited a negative relationship with relative humidity (RH). YHONO inversely depended on the soil mass (0.32–3.25 mg cm⁻²), and it positively relied on the irradiance and RH (7%–22%). There was a maximum value for YHONO at 298 K. Based on the experimental results, HONO source strengths from heterogeneous photochemical reaction of NO₂ on the soil surfaces were estimated to be 0.2–2.7 ppb h⁻¹ for a mixing layer height of 100 m, which could account for the missing daytime HONO sources in most areas.

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 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.

A novel Z-scheme photocatalyst consisting of acidified graphitic carbon nitrogen (ag-C₃N₄)/carbon quantum dots/CdIn₂S₄ (CN/CQDs/CIS) was successfully synthesized via a one-step hydrothermal method. The optimized CN-2/CQDs-3/CIS exhibited significantly improved photocatalytic performance in the degradation of ibuprofen under visible-light irradiation. Based on a series of characterizations, the ag-C₃N₄ and CQDs were distributed uniformly on the surface of the cubic spinel structure of CIS, with intimate contact among the materials. This intimate heterogeneous interface facilitated the migration of photogenerated carriers, further leading to enhanced photocatalytic performance. These results also indicated that the CQDs not only connect ag-C₃N₄ with CIS through covalent bonds but also enhance the visible-light adsorption. According to the analysis of the UV–vis diffuse reflectance spectra (DRS) and Mott-Schottky curves, the mechanism of the Z-scheme heterojunction is proposed. The CQDs serve as electron mediators and transfer the electrons in the conduction band (CB) of ag-C₃N₄ to recombine with the holes in the valence band (VB) of CIS in the Z-scheme, leading to the enhanced separation efficiency of the photogenerated electrons in the CB of ag-C₃N₄ and the holes in the VB of CIS. The pollutant IBU was degraded by h⁺, ·O₂⁻ and ·OH, as determined by electron paramagnetic resonance (EPR) analysis.