Environmentally Persistent Free Radicals Research Articles

Environmentally persistent free radicals on photoaged nanopolystyrene induce neurotoxicity by affecting dopamine, glutamate, serotonin and GABA in Caenorhabditis elegans

Microplastics are widely detected in the environment and induce toxic effects in various organisms. However, the properties and toxicity associated with environmentally persistent free radicals (EPFRs) in photoaged nanopolystyrene (NPS) remain largely unknown. We investigated the generation of EPFRs on photoaged NPS and their neurotoxicity and underlying mechanism in Caenorhabditis elegans. The results suggested that photoaging induces the generation of EPFRs and reactive oxygen species (O2•−, •OH, and 1O2), which altered the physicochemical properties (morphology, crystallinity, and functional groups) of NPS. Acute exposure to 1 μg/L of NPS-60 (NPS with light irradiation time of 60 d) significantly decreased locomotion behaviors and neurotransmitter contents (e.g., glutamate, serotonin, dopamine, and γ-aminobutyric acid). Treatment with N-acetyl-L-cysteine (NAC) by radical quenching test significantly reduced EPFRs levels on the aged NPS, and the toxicity of NAC-quenching NPS was decreased in nematodes compared to those in photoaged NPS. EPFRs also caused dysfunction of neurotransmission-related gene expression in C. elegans. Thus, EPFRs generated on photoaged NPS contributed to neurotoxicity by affecting dopamine, glutamate, serotonin, and γ-aminobutyric acid neurotransmission. The study highlights the potential risks of photoaged NPS and the contributions of EPFRs to toxicity.

Differential cytotoxicity to human cells in vitro of tire wear particles emitted from typical road friction patterns: The dominant role of environmental persistent free radicals

Tire wear particles (TWPs) have been recognized as one of the major sources of microplastics (MPs), however, effects of initial properties and photochemical behavior of TWPs on cytotoxicity to human cells in vitro have not been reported. Therefore, here, three TWPs generated from typical wear of tires and pavements (i.e., rolling friction (R-TWPs) and sliding friction (S-TWPs)) and cryogenically milled tire tread (C-TWPs), respectively, and their photoaging counterparts were used to study the reasons for their differential cytotoxicity to 16HBE cells in vitro. Results showed in addition to changes of surface structure and morphology, different preparation methods could also induce formation of different concentration levels of environmental persistent free radicals (EPFRs) (from 1.24 to 3.06 × 1017 spins/g with g-factors ranging 2.00307–2.00310) on surfaces of TWPs, which contained 7.3%–65.8% of reactive EPFRs (r-EPFRs). Meanwhile, photoaging for 90 d could strengthen formation of EPFRs (from 4.03 to 4.61 × 1017 spins/g) with containing 74.7%–78.1% r-EPFRs on surfaces of TWPs and improve their g-factor indexes (ranging 2.00309–2.00313). At 100 μg mL−1 level, compared to C-TWPs, both R-TWPs and S-TWPs (whether photoaging or not) carried higher intensity EPFRs could significantly inhibit 16HBE cells proliferation activity, cause more cells oxidative stress and induce more cell apoptosis/necrosis and secretion of inflammatory factor (P < 0.05). However, regardless of how TWPs were prepared, photoaged or not, exposure at a concentration of 1 μg mL−1 appeared to be non-acute cytotoxic. Correlation analysis suggested dominant toxicity of TWPs was attributed to the formation of r-EPFRs on their surfaces, which could promote accumulation of excess reactive oxygen species in cells and the massive deposition of intracellular particles. This study provides direct evidence of TWPs cytotoxicity, and underlining the need for a better understanding of the influences of initial properties and photochemical characteristics on risk assessment of TWPs released into the environment.

Biochar-activated persulfate oxidation of arsenic(III): Nonnegligible roles of environmentally persistent free radicals

The water ecosystem and public health are often threatened by Arsenic (As). The primary type of As in paddy field and ground water is As(III), which is more toxic and mobile than As(V). In this research, biochar prepared from sewage sludge (SBC) through hydrothermal technique was used to activate persulfate (PS) to oxidate As(III), making it less toxic As(V). The developed SBC/PS system could oxidate As(III) effectively in the wide pH values (2−10). Excluding the influence of specific surface area and functional groups, the concentration of environmental persistent free radicals (EPFRs) had a good linear relationship with the oxidation of As(III), reaching above 0.96. According to a mechanism analysis, EPFRs on SBC could transfer electrons to directly activate PS to produce SO4−·, ·OH, O2−·, and 1O2 to improve the oxidation of As(III). These results not only indicated that the biochar/PS system’s application scope can be successfully increased by adjusting the preparation conditions, but also revealed the invaluable role of EPFRs in As(III) oxidation process.

Toxic effects of environmentally persistent free radicals (EPFRs) on the surface of tire wear particles on freshwater biofilms: The alleviating role after sewage-incubation-aging

The aquatic ecological risks posed by the surface-active components of tire wear particles (TWPs) are not fully understood. This study aimed to determine the acute (24 h exposure) aquatic toxicity effects of TWPs on freshwater biofilms in terms of total organic carbon (TOC), chlorophyll-a (Chl-a) abundance, quantum yield (ФM), and adenosine triphosphate (ATP). Three types of TWP were tested: TWPs produced via the typical wear of tires and roads (i.e., rolling friction (R-TWPs) and sliding friction (S-TWPs)) and cryogenically milled tire treads (C-TWPs). The results showed that the surface structural properties of the three TWPs differed significantly in morphology, bare composition, functional groups, and surface-active components (environmental persistent free radicals). The exposure of biofilms to the TWPs increased TOC and ATP at low concentrations (1 mg L−1) but inhibited them at high concentrations (50 mg L−1). All TWP types inhibited biofilm photosynthesis (reduced Chl-a and ФM) and altered the community structure of algae to varying degrees; in addition, the toxicity mechanisms of the TWPs contributed to the accumulation of reactive oxygen species and cell membrane (or cell-wall) fragmentation, leading to lactate dehydrogenase release. S-TWPs were the most toxic because their surface carried the highest environmental persistent free radicals. R-TWPs were the second most toxic, which was attributed to their smaller particle size. The toxicity of all TWPs was tested after sewage incubation aging. The results showed that the toxicity of all TWPs reduced as the sewage covered their surface components and active sites. This process also reduced the differences in toxicity among the TWPs. This study filled a research gap in our understanding of aquatic toxicity caused by the surface structural properties of tire microplastics and has implications for the study of microplastic biotoxicity mechanisms.

Contamination profiles and potential health risks of environmentally persistent free radicals in PM2.5 over typical central Chinese megacity

As one of the most important transportation hubs and industrial bases in China, Zhengzhou has suffered from serious PM2.5 pollution for a long time. However, the investigation of contamination status and possible exposure risks of environmentally persistent free radicals (EPFRs) in PM2.5 from Zhengzhou is rare. In this work, a comprehensive study of pollution levels, seasonal variations, sources, and potential health risks of PM2.5-bound EPFRs in Zhengzhou was conducted for the first time. The atmospheric concentrations of EPFRs in PM2.5 from Zhengzhou ranged from 1.732 × 1012 spin m−3 to 7.182 × 1014 spin m−3 between 2019 and 2020. Relatively serious contamination was noticed in winter and spring. Primary fossil fuel combustion and Fe-mediated secondary formation were apportioned as possible sources of PM2.5-bound EPFRs in Zhengzhou. Moreover, to avert the bias of the toxicity assessment induced by utilization of incompletely extracted EPFRs from sample filter, simulatively generated EPFRs were applied to toxicological evaluations (cell viability and reactive oxygen species assays). Corresponding experimental dosages were based on the estimated adults’ annual exposure amounts of EPFRs in real PM2.5 samples. The results elucidated that EPFRs might cause growth inhibition and oxidative stress of human lung cells, suggesting the possible exposure-induced health concerns for local people in Zhengzhou. This study provides practical information of real contamination status of PM2.5-bound EPFRs in Zhengzhou, which is favorable to local air pollution control and reduction of exposure risks on public health in central China.

Oxidation 1-methyl naphthalene based on the synergy of environmentally persistent free radicals (EPFRs) and PAHs in particulate matter (PM) surface

Studies of the environmental fate through the interactions of particle-associated polycyclic aromatic hydrocarbons (PAHs) with environmentally persistent free radicals (EPFRs) are presented. The formation of PAHs and EPFRs typically occurs side by side during combustion-processes. The laboratory simulation studies of the model PAH molecule 1-Methylnaphthalene (1-MN) interaction with model EPFRs indicate a transformational synergy between these two pollutants due to mutual and matrix interactions. EPFRs, thorough its redox cycle result in the oxidation of PAHs into oxy-/hydroxy-PAHs. EPFRs have been shown before to produce OH radical during its redox cycle in aqueous media and this study has shown that produced OH radical can transform other PM constituents resulting in alteration of PM chemistry.In model PM, EPFRs driven oxidation process of 1-MN produced 1,4-naphthoquinone, 1-naphthaldehyde, 4-hydroxy-4-methylnaphthalen-1-one, and various isomers of (hydroxymethyl) naphthalene. Differences were observed in oxidation product yields, depending on whether EPFRs and PAHs were cohabiting the same PM or present on separate PM. This effect is attributed to the OH radical concentration gradient as a factor in the oxidation process, further strengthening the hypothesis of EPFRs’ role in the PAH oxidation process.This finding is revealing new environmental role of EPFRs in a natural degradation process of PAHs. Additionally, it points to implications of such PM surface chemistry in the changing mobility of PAHs into an aqueous medium, thus increasing their bioavailability.

Size-resolved environmentally persistent free radicals in urban road dust and association with transition metals.

Environmental persistent free radicals (EPFRs) are receiving growing concerns owing to their potentially adverse impacts on human health. Road dust is one important source of air pollution in most cities and may pose significant health risks. Characteristics of EPFRs in urban road dusts and its formation mechanism(s) are still rarely studied. Here, we evaluated occurrenceand size distributions of EPFRs in road dusts from different functional areas of an urban city, and assessed relationship between EPFRs and some transition metals.Strong electron paramagnetic resonance signals of 6.01 × 1016 - 1.3 × 1019 spins/g with the mean g value of 2.0029 ± 0.0019 were observed, indicating that EPFRs consisted of a mixture of C-centered radicals, and C-centered radicals with an adjacent oxygen atom in the urban road dust. Much more EPFRs enriched in finer dust particles. EPFRs significantly correlated with the total Fe, but not water-soluble Fe, suggesting different impacts of water-soluble and insoluble metals in the formation of EFPRs. Health risk assessment results indicated high risk potentials via the ingestion and dermal exposure to EPFRs in road dusts. Future studies are calling to look into formation mechanisms of EPFRs in urban road dusts and to quantitatively evaluate its potential risks on human health.

First-principles study on the heterogeneous formation of environmentally persistent free radicals (EPFRs) over α-Fe2O3(0001) surface: Effect of oxygen vacancy

Metal oxides with oxygen vacancies have a significant impact on catalytic activity for the transformation of organic pollutants in waste-to-energy (WtE) incineration processes. This study aims to investigate the influence of hematite surface oxygen point defects on the formation of environmentally persistent free radicals (EPFRs) from phenolic compounds based on the first-principles calculations. Two oxygen-deficient conditions were considered: oxygen vacancies at the top surface and on the subsurface. Our simulations indicate that the adsorption strength of phenol on the α-Fe2O3(0001) surface is enhanced by the presence of oxygen vacancies. However, the presence of oxygen vacancies has a negative impact on the dissociation of the phenol molecule, particularly for the surface with a defective point at the top layer. Thermo-kinetic parameters were established over a temperature range of 300–1000 K, and lower reaction rate constants were observed for the scission of phenolic O-H bonds over the oxygen-deficient surfaces compared to the pristine surface. The negative effects caused by the oxygen-deficient conditions could be attributed to the local reduction of FeIII to FeII, which lower the oxidizing ability of surface reaction sites. The findings of this study provide us a promising approach to regulate the formation of EPFRs.

Environmentally persistent free radicals: Methods for combustion generation, whole-body inhalation and assessing cardiopulmonary consequences

Particulate matter (PM) containing environmentally persistent free radicals (EPFRs) results from the incomplete combustion of organic wastes which chemisorb to transition metals. This process generates a particle-pollutant complex that continuously redox cycles to produce reactive oxygen species. EPFRs are well characterized, but their cardiopulmonary effects remain unknown. This publication provides a detailed approach to evaluating these effects and demonstrates the impact that EPFRs have on the lungs and vasculature. Combustion-derived EPFRs were generated (EPFR lo: 2.1e−16 radical/g, EPFR hi: 5.5e−17 radical/g), characterized, and verified as representative of those found in urban areas. Dry particle aerosolization and whole-body inhalation were established for rodent exposures. To verify that these particles and exposures recapitulate findings relevant to known PM-induced cardiopulmonary effects, male C57BL6 mice were exposed to filtered air, ∼280 μg/m3 EPFR lo or EPFR hi for 4 h/d for 5 consecutive days. Compared to filtered air, pulmonary resistance was increased in mice exposed to EPFR hi. Mice exposed to EPFR hi also exhibited increased plasma endothelin-1 (44.6 vs 30.6 pg/mL) and reduced nitric oxide (137 nM vs 236 nM), suggesting vascular dysfunction. Assessment of vascular response demonstrated an impairment in endothelium-dependent vasorelaxation, with maximum relaxation decreased from 80% to 62% in filtered air vs EPFR hi exposed mice. Gene expression analysis highlighted fold changes in aryl hydrocarbon receptor (AhR) and antioxidant response genes including increases in lung Cyp1a1 (8.7 fold), Cyp1b1 (9 fold), Aldh3a1 (1.7 fold) and Nqo1 (2.4 fold) and Gclc (1.3 fold), and in aortic Cyp1a1 (5.3 fold) in mice exposed to EPFR hi vs filtered air. We then determined that lung AT2 cells were the predominate locus for AhR activation. Together, these data suggest the lung and vasculature as particular targets for the health impacts of EPFRs and demonstrate the importance of additional studies investigating the cardiopulmonary effects of EPFRs.

Measurement report: Atmospheric aging of combustion-derived particles – impact on stable free radical concentration and its ability to produce reactive oxygen species in aqueous media

Abstract. Environmentally persistent free radicals (EPFRs) are a pollutant found on fine atmospheric particulate matter (PM2.5), particularly on PM2.5 formed from combustion processes. EPFRs are organic radicals that can endure in the environment for days to years. Interest in the toxicity of EPFRs has increased significantly in recent years, as it has been shown to have substantial ability to form reactive oxygen species (ROS), but little is known about how its characteristics change as PM2.5 ages in the atmosphere. Here, we exposed newly produced hexane-generated soot to simulated sunlight for 24 h. Changes to the EPFR characteristics of the particles were measured by electron paramagnetic resonance (EPR) spectroscopy. The soot was then added to water, and a second exposure to light was used to measure hydroxyl radical (OH) formation from both photoaged and dark-aged soot. There were no changes to EPFR characteristics (spin concentration, g factor, peak width, or lineshape) due to the exposure to simulated sunlight; however, the soot's ability to form OH was greatly reduced by photoaging. Photoaged soot resulted in an almost 60 % reduction in OH formation over soot which had been aged in the dark for the same amount of time.

Mechanisms of biochar-mediated promotion of acidogenic fermentation in waste activated sludge and propionic acid production pathways

The conversion of organic matter in waste activated sludge (WAS) into high value-added chemicals of volatile fatty acids (VFAs) has become a focus of attention worldwide. However, the conversion of WAS to a certain acid among VFAs is difficult. Herein, for the first time, biochar was used to promote sludge solubilization, hydrolysis and acidogenic fermentation for the production of propionic acid. The results illustrated that biochar (prepared at 450 °C, containing environmental persistent free radicals (EPFRs) of 15.91 × 1015 spins/g) stimulated sludge solubilization, hydrolysis and VFAs production, enhancing sludge cell lysis rate, VFAs production, propionic acid ratio, protease, α-glucosidase and nicotinamide adenine dinucleotide hydrogen (NADH)/nicotinamide adenine dinucleotide (NAD+) ratio by 10.53 %, 107.42 %, 17.52 %, 68 %, 32 % and 76.10 % respectively, compared with those observed in the control group without biochar addition. And once the EPFRs were shielded, they decreased. The signal of EPFRs decreased from 15.91 × 1015 spins/g to 15.20 × 1015 spins/g on day 2 and 8.50 × 1015 spins/g on day 4. The EPFRs contained in the biochar played an important role in the intermediary function and interfered with the bacterial metabolic pathways. Metagenomics sequencing also revealed that biochar EPFRs promoted the sludge acidogenic fermentation to produce propionic acid ([EC:7.1.1.2]) and partly inhibited acetic acid production ([EC:1.2.1.3]). This study reveals that biochar could promote sludge solubilization, hydrolysis and promote propionic acid production, which could be used as a new strategy for acid production in the future.

Occurrence and formation of environmentally persistent free radicals in incineration and their impact on soil and water

Incineration is a thermal waste treatment technique that can be understood as a controlled combustion process with the primary objective of volume reduction of waste mass. Combustible waste including gaseous, aqueous, muddy, molten, and solid waste is typically deal with incineration at temperature ranges from 750 to 1200 °C. End products of incineration include a considerable amount of particulate matter (PM) and pollutants. Particulate matter released from the incineration process plays an important role in forming environmentally persistent free radicals (EPFRs) which are the most toxic and stable substance emitted from the incinerator. Other major compounds released during the incineration process are dioxins, polychlorinated biphenyls, polychlorinated naphthalene, chlorinated benzenes, and polycyclic aromatic hydrocarbons (PAH). Although incineration is significantly used to control the waste crisis but emissions of toxic substances from an incinerator have various health impacts on the environment and humans. Long exposures to these hazardous compounds lead to respiratory and cardiovascular diseases. These toxic compounds participate in various redox activities as well as metal complexation events and deteriorate the physiochemical parameter of soil and water. The aim of the present study is to summarize the existing knowledge regarding the formation of harmful compounds released during waste incineration and major environmental challenges associated with them.

Formation of Environmentally Persistent Free Radicals from the Irradiation of Polycyclic Aromatic Hydrocarbons.

Polycyclic aromatic hydrocarbons (PAHs) provide a complex matrix for environmentally persistent free radicals (EPFRs) to stabilize in particulate matter, allowing them to be transported over long distances in the atmosphere while participating in light-driven reactions and causing various cardiopulmonary diseases. In this study, four PAHs ranging from three to five rings (anthracene, phenanthrene, pyrene, and benzo[e]pyrene) were investigated for EPFR formation upon photochemical and aqueous-phase aging. Through electron paramagnetic resonance (EPR) spectroscopy, it was found that approximately 1015 to 1016 spins g-1 of EPFRs were formed from the PAH upon aging. EPR analysis also revealed that carbon-centered and monooxygen-centered radicals were predominantly formed by irradiation. However, oxidation and fused-ring matrices have added complexity to the chemical environment of these carbon-centered radicals, as observed by their g-values. This study showed that atmospheric aging results not only in the transformation of PAH-derived EPFR but also in an increase in EPFR concentrations of up to 1017 spins g-1. Therefore, because of their stability and photosensitivity, PAH-derived EPFRs have a major impact on the environment.

Outdoor Health Risk of Atmospheric Particulate Matter at Night in Xi'an, Northwestern China.

The deterioration of air quality via anthropogenic activities during the night period has been deemed a serious concern among the scientific community. Thereby, we explored the outdoor particulate matter (PM) concentration and the contributions from various sources during the day and night in winter and spring 2021 in a megacity, northwestern China. The results revealed that the changes in chemical compositions of PM and sources (motor vehicles, industrial emissions, coal combustion) at night lead to substantial PM toxicity, oxidative potential (OP), and OP/PM per unit mass, indicating high oxidative toxicity and exposure risk at nighttime. Furthermore, higher environmentally persistent free radical (EPFR) concentration and its significant correlation with OP were observed, suggesting that EPFRs cause reactive oxygen species (ROS) formation. Moreover, the noncarcinogenic and carcinogenic risks were systematically explained and spatialized to children and adults, highlighting intensified hotspots to epidemiological researchers. This better understanding of day-night-based PM formation pathways and their hazardous impact will assist to guide measures to diminish the toxicity of PM and reduce the disease led by air pollution.

Structural properties of alumina surfaces and their roles in the synthesis of environmentally persistent free radicals (EPFRs)

Abstract Alumina oxides have been widely utilised as independent catalysts or as support materials for other catalysts. From an environmental perspective, alumina nanoclusters dispersed on surfaces of particulate matter PM12, generated from various combustion processes, play a critical role in the synthesis of environmentally persistent free radicals (EPFRs). Of particular importance are phenoxy-type EPFRs that often act as building blocks for the formation of notorious pollutants. Herein, we present a systematic review of the literature pertinent to structural features of alumina surfaces at the nano-scale and their well-established role in the synthesis of EPFRs. Central to the capacity of alumina surfaces in mediating the formation of EPFRs are their active Lewis acid–base sites. The nature of these sites is very sensitive to hydration scenarios. As evident in electroparamagnetic resonance measurements, more than one category of EPFR forms on alumina surfaces. This generally entails the co-existence of various surface terminations, varying degrees of hydrations, and distinct underlying reaction pathways. The mechanisms for the formation of EPFRs over alumina surfaces involve interactions with terminal OH groups followed by creating genuine chemical bonds with Al3+ sites. Higher concentrations of EPFRs were often detected on alumina surfaces, in reference to other transition metal oxides. We envisage that future studies may focus on the generation of EPFRs from potential precursors other than phenols and catechol, such as brominated species and substituted thiophenols.

Assessing the Effects and Environmental Implications of Biochar Amendment in Agricultural Soils

In recent years, the production and use of biochar have been increasing rapidly, and the biochar market is projected to continue growing between 2019 and 2025. Given that biochar has a long residence time in the environment (soil), a systematic review was conducted to assess the major environmental impacts of its application in agricultural soils. The results were largely consistent in indicating the positive effects of biochar on soil fertility, moisture content, and microbial communities. Moreover, biochar has been shown to improve soil physical properties and provide habitats for soil microorganisms. Biochar application in soil has the potential to mitigate climate change and reduce human health risks. However, the oxidation and ageing process of biochar has the potential to lead to the absorption, accumulation, and release of environmental pollutants such as heavy metals, polycyclic aromatic hydrocarbons (PAHs), dioxins, environmentally persistent free radicals (EPFRs), perfluorochemicals (PFCs), and volatile organic compounds (VOCs) depending on the type of biomass used. Therefore, when considering biochar application in soil for agricultural purposes, it is important to consider the biomass type and investigate the potential negative secondary environmental consequences.

Pollution characteristics and light-driven evolution of environmentally persistent free radicals in PM2.5 in two typical northern cities of China

Environmentally persistent free radicals (EPFRs) in PM2.5 can pose significant health risks by generating reactive oxygen species (ROS). In this study, Beijing and Yuncheng were chosen as two representative northern cities of China that mainly relied on natural gas and coal respectively as the energy source for domestic heating in winter. The pollution characteristics and exposure risks of EPFRs in PM2.5 around the heating season of 2020 were investigated and compared between the two cities. Through laboratory simulation experiments, the decay kinetics and secondary formation of EPFRs in PM2.5 collected in both cities were also studied. EPFRs in PM2.5 collected in Yuncheng in the heating period showed longer lifetime and lower reactivity, suggesting that EPFRs originated from coal combustion were more stable in the atmosphere. However, the generation rate of hydroxyl radical (·OH) by the newly formed EPFRs in PM2.5 in Beijing under ambient conditions was 4.4 times of that in Yuncheng, suggesting higher oxidative potential of EPFRs from the atmospheric secondary processes. Accordingly, the control strategies of EPFRs and their health risks were raised for the two cities, which would also have direct implication for the control of EPFRs in other areas of similar atmospheric emission and reaction patterns.

Decontamination of Cr(VI) from water using sewage sludge-derived biochar: Role of environmentally persistent free radicals

Biochar is a well-known material for pollutant removal owing to its low cost and rich surface functionality. A kind of highly active substance, called environmentally persistent free radicals (EPFRs), can be produced in the preparation process of biochar, playing an important role in the removal of pollutants. In this study, sludge-derived biochars (SBC120 and SBC270) were prepared by the hydrothermal carbonization under two temperatures (120 °C and 270 °C) to investigate their removal abilities of Cr(VI). The maximum removal amounts of Cr(VI) by SBC120 and SBC270 were 16.58 and 22.93 mg·g-1, respectively. It further revealed that the appearance of Cr(III), as a result of EPFRs on sludge-derived biochar (SBC) transferred electrons to Cr(VI) in neutral solutions. That is to say, oxygen-centered (O-centered) EPFRs on SBC120 and carbon-centered (C-centered) EPFRs on SBC270 all could be used as electron donors to Cr(VI) to make it become Cr(III). This study not only provides a theoretical basis for the mechanism of pollutants removal by sludge-derived biochar, but also offers a new perspective on the direct effect of EPFRs on pollutants.

Comparative 6+studies of environmentally persistent free radicals on nano-sized coal dusts

Coal dust is the major hazardous pollutant in the coal mining environment. Recently environmentally persistent free radicals (EPFRs) were identified as one of the key characteristics which could impart toxicity to the particulates released into the environment. The present study used Electron Paramagnetic Resonance (EPR) spectroscopy to analyze the characteristics of EPFRs present in different types of nano-size coal dust. Further, it analyzed the stability of the free radicals in the respirable nano-size coal dust and compared their characteristics in terms of EPR parameters (spin counts and g-values). It was found that free radicals in coal are remarkably stable (can remain intact for several months). Also, Most of the EPFRs in the coal dust particles are either oxygenated carbon centered or a mixture of carbon and oxygen-centered free radicals. EPFRs concentration in the coal dust was found to be proportional to the carbon content of coal. The characteristic g-values were found to be inversely related to the carbon content of coal dust. The spin concentrations in the lignite coal dust were between 3.819 and 7.089 μmol/g, whereas the g-values ranged from 2.00352 to 2.00363. The spin concentrations in the bituminous coal dust were between 11.614 and 25.562 μmol/g, whereas the g-values ranged from 2.00295 to 2.00319. The characteristics of EPFRs present in coal dust identified by this study are similar to the EPFRs, which were found in other environmental pollutants such as combustion-generated particulates, PM2.5, indoor dust, wildfires, biochar, haze etc., in some of the previous studies. Considering the toxicity analysis of environmental particulates containing EPFRs similar to those identified in the present study, it can be confidently hypothesized that the EPFRs in the coal dust might play a major role in modulating the coal dust toxicity. Hence, it is recommended that future studies should analyze the role of EPFR-loaded coal dust in mediating the inhalation toxicity of coal dust.

Enhanced Formation of 6PPD-Q during the Aging of Tire Wear Particles in Anaerobic Flooded Soils: The Role of Iron Reduction and Environmentally Persistent Free Radicals.

Rapid urbanization drives increased emission of tire wear particles (TWPs) and the contamination of a transformation product derived from tire antioxidant, termed as N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone (6PPD-Q), with adverse implications for terrestrial ecosystems and human health. However, whether and how 6PPD-Q could be formed during the aging of TWPs in soils remains poorly understood. Here, we examine the accumulation and formation mechanisms of 6PPD-Q during the aging of TWPs in soils. Our results showed that biodegradation predominated the fate of 6PPD-Q in soils, whereas anaerobic flooded conditions were conducive to the 6PPD-Q formation and thus resulted in a ∼3.8-fold higher accumulation of 6PPD-Q in flooded soils than wet soils after aging of 60 days. The 6PPD-Q formation in flooded soils was enhanced by Fe reduction-coupled 6PPD oxidation in the first 30 days, while the transformation of TWP-harbored environmentally persistent free radicals (EPFRs) to superoxide radicals (O2•-) under anaerobic flooded conditions further dominated the formation of 6PPD-Q in the next 30 days. This study provides significant insight into understanding the aging behavior of TWPs and highlights an urgent need to assess the ecological risk of 6PPD-Q in soils.