Coupled effects of Fenton-like systems with different concentrations of H2O2/Biochar on diethyl phthalate removal: Dominant role of environmental persistent free radicals (EPFRs).

To investigate the impact of different H2O2 concentrations on the Fenton-like systems of H2O2/biochar, this study examined the mechanism of the physical structure and environmental persistent free radicals (EPFRs) of biochar during diethyl phthalate (DEP) removal by the Fenton-like system. The peak-splitting method was utilized to differentiate EPFRs types in cotton stalk biochar produced at different temperatures. High-temperature environments promote π-electron delocalization, which facilitates phenyl π free radicals and σ-π oxygen-containing free radicals. By analyzing relationships between the removal rate K1 and removal constant Kobs of DEP with the structural properties of biochar, it was discovered that EPFRs concentrations in biochar had a significant positive correlation with K1 (r = 0.92) and Kobs (r = 0.97). Different H2O2 concentrations added to the biochar removal system resulted in varied DEP removal efficiency. Among them, CS500, CS550, and CS600 exhibited superior DEP removal efficiency when H2O2 concentration was 5 mM.

Generation and persistency of combustion-derived environmentally persistent free radicals from phenolic compounds over a Fe2O3/SiO2 surface.

Combustion of organic solid wastes releases phenolic compounds which can act as precursors in the formation of environmentally persistent free radicals (EPFRs) in the post-flame, cooling zone of waste combustion. The study investigated the generation mechanism of EPFRs from phenolic compounds catalyzed by transition metals in air atmosphere under simulated combustion conditions. Representative combustion-derived phenolic compounds were used, and SiO2 particulates containing different mass ratio of Fe2O3 were synthesized as carriers. EPFRs formed had g-factors between 1.9998 and 2.0066, indicating phenoxyl-, cyclopentadienyl-, and semiquinone-type radicals, along with paramagnetic F-centers. The promotion effect of phenolic compounds on EPFR formation during heating decreased as catechol > hydroquinone > phenol > p-cresol. This trend is related to hydroxyl groups and activation energy. In particular, catechol chemically adsorbed on Fe2O3 at 600 K led to the formation of EPFRs with relatively high spin concentrations (up to 1.28 × 1017 spin/g). Higher Fe2O3 concentrations promoted the transformation of phenoxyl-type radicals into cyclopentadienyl-type and paramagnetic F-centers. However, as the Fe2O3 loading increased from 1.25% to 5%, the density of EPFRs decreased. The findings related to the influence of various precursors and Fe2O3 concentration on EPFR formation provide valuable insights for estimating EPFR generation and associated risk during combustion processes.

Seasonal variations and sources of atmospheric EPFRs in a megacity in severe cold region: Implications for the influence of strong coal and biomass combustion.

Environmentally persistent free radicals (EPFRs) can pose exposure risks by inducing the generation of reactive oxygen species. As a new class of pollutants, EPFRs have been frequently detected in atmospheric particulate matters. In this study, the seasonal variations and sources of EPFRs in a severe cold region in Northeastern China were comprehensively investigated, especially for the high pollution events. The geomean concentration of EPFRs in the total suspended particle was 6.58 × 1013 spins/m3 and the mean level in winter was one order of magnitude higher than summer and autumn. The correlation network analysis showed that EPFRs had significantly positive correlation with carbon component, K+ and PAHs, indicating that EPFRs were primarily emitted from combustion and pyrolysis process. The source appointment by the Positive Matrix Factorization (PMF) model indicated that the dominant sources in the heating season were coal combustion (48.4%), vehicle emission (23.1%) and biomass burning (19.4%), while the top three sources in the non-heating season were others (41.4%), coal combustion (23.7%) and vehicle emissions (21.2%). It was found that the high EPFRs in cold season can be ascribed to the extensive use of fossil fuel for heating demand; while the high EPFRs occurred in early spring were caused by the large-scale opening combustion of biomass. In summary, this study provided important basic information for better understanding the pollution characteristics of EPFRs, which suggested that the implementation of energy transformation and straw utilization was benefit for the control of EPFRs in severe cold region.

Airborne environmentally persistent free radicals (EPFRs) in PM2.5 from combustion sources: Abundance, cytotoxicity and potential exposure risks.

As an emerging atmospheric pollutant, airborne environmentally persistent free radicals (EPFRs) are formed during many combustion processes and pose various adverse health effects. In health-oriented air pollution control, it is vital to evaluate the health effects of atmospheric fine particulate matter (PM2.5) from different emission sources. In this study, various types of combustion-derived PM2.5 were collected on filters in a partial-flow dilution tunnel sampling system from three typical emission sources: coal combustion, biomass burning, and automobile exhaust. Substantial concentrations of EPFRs were determined in PM2.5 samples and associated with significant potential exposure risks. Results from in vitro cytotoxicity and oxidative potential assays suggest that EPFRs may cause substantial generation of reactive oxygen species (ROS) upon inhalation exposure to PM2.5 from anthropogenic combustion sources, especially from automobile exhaust. This study provides important evidence for the source- and concentration-dependent health effects of EPFRs in PM2.5 and motivates further assessments to advance public health-oriented PM2.5 emission control.

Generation of environmentally persistent free radicals on photoaged tire wear particles and their neurotoxic effects on neurotransmission in Caenorhabditis elegans.

Tire wear particles (TWP) are a prevalent form of microplastics (MPs) extensively distributed in the environment, raising concerns about their environmental behaviors and risks. However, knowledge regarding the properties and toxicity of these particles at environmentally relevant concentrations, specifically regarding the role of environmentally persistent free radicals (EPFRs) generated during TWP photoaging, remains limited. In this study, the evolution of EPFRs on TWP under different photoaging times and their adverse effects on Caenorhabditis elegans were systematically investigated. The photoaging process primarily resulted in the formation of EPFRs and reactive oxygen species (O2•-, ⋅OH, and 1O2), altering the physicochemical properties of TWP. The exposure of nematodes to 100 µg/L of TWP-50 (TWP with a photoaging time of 50 d) led to a significant decrease in locomotory behaviors (e.g., head thrashes, body bends, and wavelength) and neurotransmitter contents (e.g., dopamine, glutamate, and serotonin). Similarly, the expression of neurotransmission-related genes was reduced in nematodes exposed to TWP-50. Furthermore, the addition of free-radical inhibitors significantly suppressed TWP-induced neurotoxicity. Notably, correlation analysis revealed a significantly negative correlation between EPFRs levels and the locomotory behaviors and neurotransmitter contents of nematodes. Thus, it was concluded that EPFRs on photoaged TWP induce neurotoxicity by affecting neurotransmission. These findings elucidate the toxicity effects and mechanisms of EPFRs, emphasizing the importance of considering their contributions when evaluating the environmental risks associated with TWP.

Can the concentration of environmentally persistent free radicals describe its toxicity to Caenorhabditis elegans? Evidence provided by neurotoxicity and oxidative stress.

Environmentally persistent free radicals (EPFRs) are emerging pollutants stabilized on or inside particles. Although the toxicity of EPFR-containing particles has been confirmed, the conclusions are always ambiguous because of the presence of various compositions. A clear dose-response relationship was always challenged by the fact that the concentrations of these coexisted components simultaneously changed with EPFR concentrations. Without these solid dose-response pieces of evidence, we could not confidently conclude the toxicity of EPFRs and the description of potential EPFR risks. In this study, we established a particle system with a fixed catechol concentration but different reaction times to obtain particles with different EPFR concentrations. Caenorhabditis elegans (C. elegans) in response to different EPFR concentrations was systematically investigated at multiple biological levels, including behavior observations and biochemical and transcriptome analyses. Our results showed that exposure to EPFRs disrupted the development and locomotion of C. elegans. EPFRs cause concentration-dependent neurotoxicity and oxidative damage to C. elegans, which could be attributed to reactive oxygen species (ROS) promoted by EPFRs. Furthermore, the expression of key genes related to neurons was downregulated, whereas antioxidative genes were upregulated. Overall, our results confirmed the toxicity from EPFRs and EPFR concentration as a rational parameter to describe the extent of toxicity.

Ecotoxicity of three typical tire wear particles to periphytic biofilms: The potentiating role after natural water-incubation-aging.

Tire wear particles (TWPs), abundant in the aquatic environment, pose potential ecological risks, yet their implications have not been extensively studied. Rolling friction TWPs, sliding friction TWPs (S-TWPs) and cryogenically milled tire treads were used as research objects to study the ecotoxicity and difference of the above materials before and after aging in natural water (AS-TWPs) to the periphytic biofilm. The results showed that there were significant differences in the microstructure, surface elements, size, functional groups and environmentally persistent free radicals (EPFRs) of the three TWPs. After aging in natural water, the properties of the three TWPs mentioned above showed homogenization, but the EPFRs and reactive oxygen species (ROS) yield were different. After exposure to TWPs (10 mg L-1), total organic carbon and adenosine triphosphate decreased significantly (p < 0.05), and the production of extracellular polymeric substances (EPS) in the periphytic biofilm increased, in which the content of humic-like substance and proteins (tryptophan protein and humic acid-like substances) increased obviously. The increment of TB-EPS was higher than that of LB-EPS, and S-TWPs and AS-TWPs had the strongest promoting effect on EPS secretion. In addition, 10 mg L-1 TWPs caused massive cell death in the periphytic biofilm, which was more obvious in the S-TWPs and AS-TWPs exposure group. The toxic mechanism of TWPs promotes intracellular ROS accumulation and leads to the release of lactate dehydrogenase, which was attributed to the formation of EPFRs on the surface of TWPs and an increase in EPFRs intensity after aging in natural water. TWPs at environmentally relevant concentrations (0.1 mg L-1) had no biological toxicity to periphytic biofilms. This study fills the gap in the study of the surface structure characteristics of TWPs on the toxicity of periphytic biofilms, and is of great significance to the study of the aquatic toxicity mechanism of TWPs.

Oxidative potential, environmentally persistent free radicals and reactive oxygen species of size-resolved ambient particles near highways.

Particulate matter (PM) is a group of atmospheric pollutants with an uncertain toxicity, particularly when collected near highways. This study examined the oxidative potential (OP) of, as well as the environmentally persistent free radicals (EPFRs) and reactive oxygen species (ROS) present in PM samples collected near highways in Xiamen, China. Our findings revealed that PM had a relatively high OP, ranging from 3.8 to 18.5 nmol/min/µg, surpassing values reported in previous research. The oxidative potential of the water-insoluble fraction (OPWIS), which accounted for 68% of the total oxidative potential (OPTotal), demonstrated rapid toxicity, whereas the oxidative potential of the water-soluble fraction (OPWS) displayed a steadier toxicity release pattern. The primary free radicals detected in PM were oxygen-centered. The measured concentration of EPFRs was 6.073 × 1014 spins/m3, which is lower than that reported in previous studies, possibly because of the high relative humidity of the road environment in Xiamen. We also investigated the interaction between PM and water near highways and observed the generation of R and OH radicals. Additionally, we analysed the sample composition and evaluated the contributions of the different components to OPTotal. Transition metals (Fe, Cu, and Zn) were identified as the major contributors, accounting for 33.2% of the OPTotal. The positive correlation observed between EPFRs and ROS suggests that EPFRs may be involved in ROS generation. The correlation analysis indicated that the oxidative potential measured using the DTT method (OPDTT) could serve as an indicator of ROS generation. Finally, based on the relationship between OPDTT, EPFRs, and ROS, we propose that reducing the emission of transition metals, particularly Fe, represents an effective control measure for mitigating PM toxicity near highways.

Adjuvant effect of inhaled particulate matter containing free radicals following house-dust mite induction of asthma in mice.

INTRODUCTION: Exposures to particulate matter (PM) from combustion sources can exacerbate preexisting asthma. However, the cellular and molecular mechanisms by which PM promotes the exacerbation of asthma remain elusive. We used a house dust mite (HDM)-induced mouse model of asthma to test the hypothesis that inhaled DCB230, which are PM containing environmentally persistent free radicals (EPFRs), will aggravate asthmatic responses. METHODS: Groups of 8-10-week-old C57BL/6 male mice were exposed to either air or DCB230 aerosols at a concentration of 1.5 mg/m3 4 h/day for 10 days with or without prior HDM-induction of asthma. RESULTS: Aerosolized DCB230 particles formed small aggregates (30-150 nm). Mice exposed to DCB230 alone showed significantly reduced lung tidal volume, overexpression of the Muc5ac gene, and dysregulation of 4 inflammation related genes, Ccl11, Ccl24, Il-10, and Tpsb2. This suggests DCB230 particles interacted with the lung epithelium inducing mucous hypersecretion and restricting lung volume. In addition to reduced lung tidal volume, compared to respective controls, the HDM + DCB230-exposed group exhibited significantly increased lung tissue damping and up-regulated expression of Muc5ac, indicating that in this model, mucous hypersecretion may be central to pulmonary dysfunction. This group also showed augmented lung eosinophilic inflammation accompanied by an up-regulation of 36 asthma related genes. Twelve of these genes are part of IL-17 signaling, suggesting that this pathway is critical for DCB230 induced toxicity and adjuvant effects in lungs previously exposed to HDM. CONCLUSION: Our data indicate that inhaled DCB230 can act as an adjuvant, exacerbating asthma through IL-17-mediated responses in a HDM mouse model.

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.

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 occurrence and 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.

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.

Applications, impacts, and management of biochar persistent free radicals: A review.

Biochar is a promising environmental contaminant remediation agent because of its adsorptive and catalytic properties. However, the environmental effects of persistent free radicals (PFRs) produced by biomass pyrolysis (biochar production) are still poorly understood, though they have received increasing research attention in recent years. Although PFRs both directly and indirectly mediate biochar's removal of environmental pollutants, they also have the potential to cause ecological damage. In order to support and sustain biochar applications, effective strategies are needed to control the negative effects of biochar PFRs. Yet, there has been no systematic evaluation of the environmental behavior, risks, or management techniques of biochar PFRs. Thus, this review: 1) outlines the formation mechanisms and types of biochar PFRs, 2) evaluates their environmental applications and potential risks, 3) summarizes their environmental migration and transformation, and 4) explores effective management strategies for biochar PFRs during both production and application phases. Finally, future research directions are recommended.

Formation of environmentally persistent free radicals on microplastics under UV irradiations.

Microplastics (MPs) are widely distributed in the environment due to breakdown of widespread plastic wastes through physicochemical and biological processes. Environmentally persistent free radicals (EPFRs) might be generated as intermediates when MPs are further fragmented and decomposed under ultraviolet (UV) radiation. Formation of EPFRs is highly depended upon the radiation energy level. This study was designed to establish the correlation between EPFRs concentrations and UV energy. Polystyrene (PS) and polyethylene (PE) were employed to investigate the generation of EPFRs under the irradiation of three ultraviolet light sources (long-wave UVA, medium-wave UVB and short-wave UVC). Electron paramagnetic resonance (EPR) spectroscopy revealed that free radical signals were detected on PS irradiated by UVC and UVB and PE irradiated by UVC, which may be due to the difference in the MPs structure and UV energy. The g-factor and ΔHp-p of EPR suggested that three different types of EPFRs may be formed on PS while two types of EPFR may be formed on PE. Meanwhile, EPFRs were detected within shorter time under UVC radiation than UVB and UVA, indicating that UVC radiation could lead to faster generation of free radicals. Results of Fourier transform infrared spectroscopy (FTIR) and two-dimensional correlation spectroscopy revealed that tertiary alkyl radicals, peroxy radicals and tertiary alkoxy radicals were dominant in PS whereas alkoxy radicals and keto radicals for PE. The study provides insight to the mechanisms for EPFRs formation on ubiquitously found microplastic particles. Our finding is of great significance as EPFRs may not only play important roles in decomposition of MPs and abiotic reactions of MPs-bound pollutants, but also affect physicochemical properties of MPs and MPs toxicity to aquatic organisms, hence possessing broad impacts on MPs fate and transport in aquatic environmental systems.

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.

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.

The generation of environmentally persistent free radicals on photoaged microbeads from cosmetics enhances the toxicity via oxidative stress.

Microbeads used in personal care products have been one of the important sources of microplastics (MPs), and little has been reported on their environmental behaviors and health risks. The characteristics of environmentally persistent free radicals (EPFRs) and the toxicity assessment of MPs (environmentally relevant concentrations) from cosmetics during photoaging remains largely unknown. In this study, the formation of EPFRs on polyethylene (PE) microbeads from facial scrubs under light irradiation and their toxicity were investigated using C. elegans as a model organism. The results suggested that light irradiation induced the generation of EPFRs, which accelerates the aging process and alters the physicochemical properties of PE microbeads. Acute exposure to PE (1 mg/L) at photoaged times of 45-60 d significantly decreased the physiological indicators (e.g., head thrashes, body bends, and brood size). The oxidative stress response and stress-related gene expression were also enhanced in nematodes. The addition of N-acetyl-l-cysteine induced significant inhibition of toxicity and oxidative stress in nematodes exposed to 45-60 d of photoaged PE. The Pearson correlation results showed that the concentration of EPFRs was significantly correlated with physiological indicators, oxidative stress, and related-genes expression in nematodes. The data confirmed that the generation of EPFRs combined with heavy metals and organics contributed to toxicity induced by photoaged PE, and oxidative stress might be involved in regulating adverse effects in C. elegans. The study provides new insight into the potential risks of microbeads released into the environment during photoaging. The findings also highlight the necessity for considering the role of EPFRs formation in evaluating the impacts of microbeads.

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.

Distribution of environmentally persistent free radicals in size-segregated PMs emitted from residential biomass fuel combustion.

Environmentally persistent free radicals (EPFRs) are considered as an emerging pollutant due to their potential environmental risks, but the distribution characteristics of particulate matters (PMs)-EPFRs from residential combustion source are poorly understood. In this study, biomass (corn straw, rice straw, pine and jujube wood) combustion was studied in lab-controlled experiments. More than 80% of PM-EPFRs were distributed in PMs with aerodynamic diameter (dae) ≤ 2.1 µm, and their concentration in fine PMs was about 10 times that in coarse PM (2.1 µm ≤ dae ≤ 10 µm). The detected EPFRs were carbon-centered free radicals adjacent to oxygen atoms or a mixture of oxygen- and carbon-centered radicals. The concentrations of EPFRs in coarse and fine PMs were positively correlated with char-EC, but the EPFRs in fine PMs exhibited a negative correlation with soot-EC (p < 0.05). The increase of PM-EPFRs signals with the increased dilution ratio during pine wood combustion was more significant than that from rice straw, which may be resulted from the interactions between the condensable volatiles and the transition metals. Our study provides useful information for better understanding the formation of combustion-derived PM-EPFRs, and will be instructive for its purposeful emissions control.

Characteristics and Risk Assessment of Environmentally Persistent Free Radicals (EPFRs) of PM2.5 in Lahore, Pakistan.

Environmentally persistent free radicals (EPFRs) are an emerging pollutant and source of oxidative stress. Samples of PM2.5 were collected at the urban sites of Lahore in both winter and summertime of 2019. The chemical composition of PM2.5, EPRF concentration, OH radical generation, and risk assessment of EPFRs in PM2.5 were evaluated. The average concentration of PM2.5 in wintertime and summertime in Lahore is 15 and 4.6 times higher than the national environmental quality standards (NEQS) of Pakistan and WHO. The dominant components of PM2.5 are carbonaceous species. The concentration of EPFRs and reactive oxygen species (ROS), such as OH radicals, is higher in the winter than in the summertime. The secondary inorganic ions do not contribute to the generation of OH radicals, although the contribution of SO42+, NO3-, and NH4+ to the mass concentration of PM2.5 is greater in summertime. The atmospheric EPFRs are used to evaluate the exposure risk. The EPFRs in PM2.5 and cigarette smoke have shown similar toxicity to humans. In winter and summer, the residents of Lahore inhaled the amount of EPFRs equivalent to 4.0 and 0.6 cigarettes per person per day, respectively. Compared to Joaquin County, USA, the residents of Lahore are 1.8 to 14.5 times more exposed to EPFRs in summer and wintertime. The correlation analysis of atmospheric EPFRs (spin/m3) and carbonaceous species of PM2.5 indicates that coal combustion, biomass burning, and vehicle emissions are the possible sources of EPFRs in the winter and summertime. In both winter and summertime, metallic and carbonaceous species correlated well with OH radical generation, suggesting that vehicular emissions, coal combustion, and industrial emissions contributed to the OH radical generation. The study's findings provide valuable information and data for evaluating the potential health effects of EPFRs in South Asia and implementing effective air pollution control strategies.