Photocatalytic degradation is an attractive strategy to purify waste water contaminated by macromolecular organics. Compared with the single-component photocatalysts, heterostructures of different semiconductors have been widely used to improve the photocatalytic performance. In this work, we fabricate a hetero-structured photocatalyst consisting of two-dimensional graphitic carbon nitride (g-C3N4) nanosheets and commercial MoO3 microparticles through a simple mixing and annealing process. The photocatalytic performance was evaluated in various dye degradation reactions, especially Rhodamine (RhB) degradation. The MoO3/g-C3N4 composite shown a significant improvement compared with individual MoO3 or g-C3N4 as well as their physical mixture. By applying electron spin resonance (ESR) spin-trap spectra, radical scavenge experiments and electrochemical analysis, we find that a direct Z-scheme charge transfer between MoO3 and g-C3N4 not only causes an accumulation of electrons in g-C3N4 and holes in MoO3, but also boosts the formation of superoxide radical and hydroxyl radical. The superoxide radical and hole dominate the photocatalytic degradation, while the hydroxyl radical plays a negligible role and its production can be suppressed by lowering the pH value.

The cobalt ferrite-reduced oxidized graphene (CoFe2O4/rGO) catalyst was synthesized by hydrothermal method and characterized by Powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Scanning electron microscope (SEM), Brunauere Emmette Teller (BET) and Hysteresis loop. For developing a new method of removing elemental mercury (Hg0) from flue gas, the effects of catalyst dosage, PMS concentration, solution pH and reaction temperature on the removal efficiency were investigated experimentally by using peroxymonosulfate (PMS) catalyzed by CoFe2O4/rGO at a self-made bubbling reactor. The average removal efficiency of Hg0 in a 30-min period reached 95.56%, when CoFe2O4/rGO dosage was 0.288 g/L, PMS concentration was 3.5 mmol/L, solution pH was 5.5 and reaction temperature was 55 °C. Meanwhile, based on the free radical quenching experiments, in which, ethyl alcohol and tert butyl alcohol were used as quenchers to prove indirectly the presence of •OH and SO4•−, the characterizations of catalysts and reaction products, and the existing results from other scholars. The reaction mechanism was proposed.

Alternative transportation fuels (ATFs) can reduce air pollution. However, the influence of conventional fuels—diesel and gasoline, and particularly ATFs on photochemical air pollution is not well-characterized, limiting assessments of ATFs and air quality. This is mainly due to frequent use of lumped chemical mechanisms by related atmospheric modeling. Here we hypothesized that applying a chemical mechanism that is specifically developed according to both emission fractions and photochemical ozone creation potential of volatile organic compounds (VOCs) is key to gaining reliable insights into the impact of transportation fuels on photochemistry. We used a heterogeneous chemical mechanism with 927 reactions and relatively detailed emission inventories to specifically meet the requirements for reliable simulation of the effect of exhaust emissions from vehicles fueled by selected model fuels—diesel, gasoline, and mixtures of 15% gasoline with 85% ethanol (E85) or 85% methanol (M85)—on photochemistry. These dispersion-box model simulations revealed a strong influence of atmospheric background balance between VOCs and nitrogen oxides (NOX = [NO] + [NO2]) on the impact of exhaust emissions on photochemistry, with higher tendency toward ozone (O3) formation or destruction for more VOC-limited or NOX-limited conditions, respectively. Accordingly, higher [NOX]/[VOC] exhaust emission, such as from diesel and M85, resulted in lower O3, not only locally but also downwind of the emission. This offers a new perspective and measure for transportation fuel assessment. Rapid conversion of O3 to hydroxyl and hydroperoxyl radicals downwind of the exhaust emission indicates the importance of simulating the impact of road transportation on photochemistry at high spatial and temporal resolution. Peroxyacetyl nitrate formation was more sensitive to VOC emission under VOC-limited conditions than to NOX emission under NOX-limited conditions. Secondary formaldehyde dominated over primary emitted formaldehyde several minutes after emission. These findings should be verified using a 3D modeling study under varying meteorological conditions.

Reduced graphene oxide (rGO) is one of the most widely used carbon nanomaterials. When it is released into the environment, rGO can markedly affect the transformation of many pollutants, and change their fate and risk. In this work, the synergetic effects of rGO and Cu(II) on the oxidation of 2-naphthol were examined in water in the dark. It was found that the coexistence of rGO and Cu(II) significantly promoted the oxidation of 2-naphthol. Corresponding products were identified as the coupling oligomers of 2-naphthol (dimer, trimer and tetramer) and hydroxylated compounds (OH-2-naphthol, OH-dimer, di–OH–dimer and naphthoquinone derivatives). In the oxidation reaction, rGO played dual roles, i.e. adsorbent and electron-transfer mediator. rGO firstly adsorbed Cu(II) and 2-naphthol on its surface, and then transferred electrons from 2-naphthol to Cu(II) to yield 2-naphthol radicals and Cu(I). 2-Naphthol radicals coupled to each other to form different oligomers of 2-naphthol. Cu(I) was re-oxidized back to Cu(II) by dissolved oxygen, which sustained the continuous oxidation of 2-naphthol. During the autoxidation of Cu(I), reactive oxygen species were generated, which further reacted with 2-naphthol to form hydroxylated products. These findings provide new insights into the risk assessment of rGO and 2-naphthol in aquatic environments.

Environmentally persistent free radicals (EPFRs) are defined as organic free radicals stabilized on or inside particles. They are persistent because of the protection by the particles and show significant toxicity to organisms. Increasing research interests have been attracted to study the potential environmental implications of EPFRs. Because of their different physical forms from conventional contaminants, it is not applicable to use the commonly used technique and strategy to predict and assess the behavior and risks of EPFRs. Current studies on EPFRs are scattered and not systematic enough to draw clear conclusions. Therefore, this review is organized to critically discuss the current research progress on EPFRs, highlighting their occurrence and transport, generation mechanisms, as well as their environmental implications (including both toxicity and reactivity). EPFR formation and stabilization as affected by the precursors and environmental factors are useful breakthrough to understand their formation mechanisms. To better understand the major differences between EPFRs and common contaminants, we identified the unique processes and/or mechanisms related to EPFRs. The knowledge gaps will be also addressed to highlight the future research while summarizing the research progress. Quantitative analysis of the interactions between organic contaminants and EPFRs will greatly improve the predictive accuracy of the multimedia environmental fate models. In addition, the health risks will be better evaluated when considering the toxicity contributed by EFPRs.

Environmentally persistent free radicals (EPFRs) are a new class of environmental risk substances that can stably exist in atmospheric particles and pose a potential threat to human health. In this study, electron paramagnetic resonance (EPR) spectroscopy was used to study the concentration levels, species characteristics, and sources of EPFRs in PM₂.₅ in Xi'an in 2017. The results showed that the concentrations of EPFRs in PM₂.₅ in Xi'an in 2017 ranged from 9.8 × 10¹¹ to 6.9 × 10¹⁴ spins/m³. The highest concentration of EPFRs occurred in winter when the average concentration was 2.1 × 10¹⁴ spins/m³. The lowest concentration of EPFRs occurred in autumn when the average concentration was 7.0 × 10¹³ spins/m³. According to the annual average atmospheric concentration of EPFRs, the amount of EPFRs inhaled by people in Xi'an is equivalent to approximately 5 cigarettes per person per day and approximately 23 cigarettes per person per day in winter when haze occurs. The results of the study on the EPFR characteristics show that the EPFRs in PM₂.₅ in Xi'an are mainly C-center organic radicals that are primarily non-decaying types, accounting for approximately 75% and 85% of total concentration of EPFRs in autumn and winter, respectively. Finally, a correlation analysis was used to explore the origins of EPFRs in PM₂.₅. Significant positive correlations were found between EPFRs and SO₂, NO₂ and the thermally derived OC3 and OC4 carbonaceous components. The results suggested that coal-fired and traffic may be important sources of EPFRs in PM₂.₅ in Xi'an. In addition, EPFRs are significantly positively correlated with O₃ in summer, suggesting that some EPFRs may also originate from secondary processes. This study provides important basic data and evidence for further assessments of the potential health risks of EPFRs in PM₂.₅ and the development of effective air pollution control measures.

The application of biochar in remediation and recovery of heavy metals and/or organic contaminants in water and soil is increasing. However, the adverse effect of biochar to aquatic organisms has not received enough attention. In this study, we conducted a study on the biotoxicity of biochar pyrolyzed from pine needle under oxygen-limited conditions. The toxicity of biochar was expressed with the following endpoints: cell growth, chlorophyll-a (Chl-a), reactive oxygen species (ROS), superoxide dismutase (SOD) content of Scenedesmus obliquus (S. obliquus) and the luminescence of Photobacterium phosphoreum (P. phosphoreum). Here, the effect of free radicals (FRs) contained in biochar was stressed. Our results show that the toxicity of biochar is significantly correlated with the concentration of FRs in biochar particles. Meanwhile, we found the FRs-containing biochar could induce the production of acellular ROS (such as ·OH) in water, which would also induce the production of interior cellular ROS in aquatic organisms. Our findings provide a new insight into the mechanism of toxicity aroused by biochar applications and aid in understanding its potential ecological risk.

Muzzle emissions from firing an M4 carbine rifle in a semi-enclosed chamber were characterized for an array of compounds to provide quantitative data for future studies on potential inhalation exposure and rangeland contamination. Air emissions were characterized for particulate matter (PM) size distribution, composition, and morphology; carbon monoxide (CO); carbon dioxide (CO₂); energetics; metals; polycyclic aromatic hydrocarbons; and methane. Three types of ammunition were used: a “Legacy” (Vietnam-era) round, the common M855 round (no longer fielded), and its variant, an M855 round with added potassium (K)-based salts to reduce muzzle flash. Average CO concentrations up to 1500 ppm significantly exceeded CO₂ concentrations. Emitted particles were in the respirable size range with mass median diameters between 0.33 and 0.58 μm. PM emissions were highest from the M855 salt-added ammunition, likely due to incomplete secondary combustion in the muzzle blast caused by scavenging of combustion radicals by the K salt. Copper (Cu) had the highest emitted metal concentration for all three round formulations, likely originating from the Cu jacket on the bullet. Based on a mass balance analysis of each round's formulation, lead (Pb) was completely emitted for all three round types. This work demonstrated methods for characterizing emissions from gun firing which can distinguish between round-specific effects and can be used to initiate studies of inhalation risk and environmental deposition.

Growth of textile industries led to production of enormous dye varieties. These textile dyes are largely used, chemically stable and easy to synthesize. But they are recalcitrant and persist as less biodegradable pollutants when discharged into waterbodies. Potential use of enzyme-linked bioremediation of textile dyes will control their toxicity in waterbodies. Bioinformatics and Molecular docking tool provides an insight into remediation mechanism by predicting susceptibility of dye degradation using oxidoreductive enzymes. In this study, six dyes, Reactive Red F3B, Remazol Red RGB, Joyfix Red RB, Joyfix Yellow MR, Remazol Blue RGB and Turquoise CL-5B of azo, anthraquinone and phthalocyanine molecular class were identified as potential targets for degradation by laccase and azoreductase of Aeromonas hydrophila in addition to Lysinibacillus sphaericus through in silico docking tool BioSolveIT-FlexX. Azoreductase breaks azo bonds by ping-pong mechanism whereas laccase decolorizes dyes by free radical mechanism which is not specific in nature. Results were analyzed based on parameters like stability, catalytic action and selectivity for enzyme-dye interactions. Amino acids of enzymes interacted with several dyes substantiating variations in active site for enzyme-ligand binding affinity. This suggests the role of enzymes in decolorizing an extensive variety of textile dyes, thereby, aiding in understanding the enzyme mechanisms in Bioremediation.

Short chain chlorinated paraffins (SCCPs) have attracted worldwide attention in recent years, due to their high production volume, persistent, bioaccumulative and toxic properties. In this study, 1-chlorodecane (CD) was selected as a model of SCCPs to explore its photochemical degradation behavior under UV irradiation. The results found that CD could be completely photochemical degradation within 120 min, and the •OH was found to be the main reactive species from both quenching experiments and electron paramagnetic resonance (EPR) results. However, the contribution of triple excited state of CD (³CD*) was still nonnegligible from the results with the absorption peak at 480 nm obtained by laser flash photolysis. Based on the identified intermediates as well as the data from theoretical chemical calculation, the detailed photochemical degradation mechanism of CD was tentatively proposed that CD firstly was excited and photo-ionized under UV irradiation, and the released Cl• in water could result in generating •OH. Then •OH initiates CD degradation mainly through the H-abstraction pathway, leading to the generation of several dehydrogenation radicals, which further generated alcohols or long chain intermediates through radical-radical reactions. The results will provide a comprehensive understanding of the degradation mechanism and environmental fates of SCCPs in water under UV irradiation.