Environmentally Persistent Free Radicals Concentrations Research Articles

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.

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.

Formation and biotoxicity of environmentally persistent free radicals in steelworks soil under thermal treatment

Thermal treatment are commonly used to address organic contaminated soils. In particular, the pyrolysis of organic substances can result in the creation of environmentally persistent free radicals (EPFRs). We investigated a steelworks site in Chongqing (China) to observe changes in EPFRs before and after thermal treatment. Our findings revealed that the EPFRs were carbon-centered radicals with a g-factor < 2.0030 and a spin density ranging from n.d.–5.23 × 1015 spins/mg. The formation of EPFRs was driving by polycyclic aromatic hydrocarbons (PAHs), Mn, Cu, and total organic carbon (TOC). Following the thermal treatment, the spin densities of EPFRs increased by a factor of 0.25 to 1.81, with maximum levels reached at 300 °C. High molecular weight PAHs exhibited high heat capacity, enabling the generation of more EPFRs. The thermal decay of EPFRs occurred in two stages, with the shortest 1/e lifetime lasting up to 16.8 h. Raising the temperature or prolonging time can significantly reduce EPFRs levels. Thermal treatment increased the generation of EPFRs, hydroxyl radicals (•OH) and superoxide radical (•O2–), leading to a decrease in bacterial luminescence. Specifically, •OH contributed to approximately 73% of the B. brilliantus inhibition. Our results highlight that the thermal treatment significantly enhance EPFRs concentrations, and the treated soil remained ecologically risky. The knowledge of the formation of EPFRs and their biotoxicity is shedding new light on the thermal treatment risk management.

Investigating environmentally persistent free radicals (EPFRs) emissions of 3D printing process

In recent years, the emission of particles and gaseous pollutants from 3D printing has attracted much attention due to potential health risks. This study investigated the generation of environmentally persistent free radicals (EPFRs, organic free radicals stabilized on or inside particles) in total particulate matter (TPM) released during the 3D printing process. Commercially available 3D printer filaments, made of acrylonitrile–butadiene–styrene (ABS) in two different colors and metal content, ABS-blue (19.66 µg/g Cu) and ABS-black (3.69 µg/g Fe), were used for printing. We hypothesized that the metal content/composition of the filaments contributes not only to the type and number of EPFRs in TPM emissions, but also impacts the overall yield of TPM emissions. TPM emissions during printing with ABS-blue (11.28 µg/g of printed material) were higher than with ABS-black (7.29 µg/g). Electron paramagnetic resonance (EPR) spectroscopy, employed to measure EPFRs in TPM emissions of both filaments, revealed higher EPFR concentrations in ABS-blue TPM (6.23 × 1017 spins/g) than in ABS-black TPM (9.72 × 1016 spins/g). The presence of copper in the ABS-blue contributed to the formation of mostly oxygen-centered EPFR species with a g-factor of ∼2.0041 and a lifetime of 98 days. The ABS-black EPFR signal had a lower g-factor of ∼2.0011, reflecting the formation of superoxide radicals during the printing process, which were shown to have an “estimated tentative” lifetime of 26 days. Both radical species (EPFRs and superoxides) translate to a potential health risk through inhalation of emitted particles.

Effects of excess sludge composting process, environmentally persistent free radicals, and microplastics on antibiotics degradation efficiency of aging biochar

Simulation of microbial aging biochar in compost is an important index for evaluating the biochar degradation efficiency of antibiotics. In this study, biochar was prepared by adding microplastics (MPs) to sludge, and the degradation effect of biochar/(peroxymonosulfate, PMS) on antibiotics was evaluated during the compost aging process of biochar. After the compost aging of biochars, the antibiotic degradation efficiency of HPBC500, HPBC500 + polystyrene (PS), HPBC900/PMS, and HPBC900 + PS/PMS decreased by 6.47, 15.2, 10.16, and 10.33 %, respectively. Environmentally persistent free radicals (EPFRs) and defect structure were the main contributors to the activation of PMS. EPFRs produced through PS pyrolysis of biochar exhibited strong reactivity but poor stability during the degradation of antibiotics. Biochar enhanced the growth of microorganisms in compost but reduced its specific surface area. The antibiotic degradation efficiency of the biochar was positively correlated with the concentration of EPFRs. This study elucidated the durability of different biochar toward antibiotic degradation.

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.

Evolution and prediction model of environmentally-persistent free radicals in biomass three-component pyrolytic carbon with pyrolysis temperature

To clarify the evolution mechanism of environmentally-persistent free radicals (EPFRs) in biochar as a function of pyrolysis temperature, three-component pyrolytic carbon was characterized by electron paramagnetic resonance (EPR) spectroscopy. Four types of EPFRs were distinguished by using the peak splitting method. The EPFRs in three-component pyrolytic carbon obtained at a pyrolysis temperature of 300 °C were mainly oxygen-containing free radicals (57.31–83.63 %). Upon increasing the pyrolysis temperature, simple aromatic ring radicals were formed by the dehydrogenation of biomass, and then the polymeric aromatic radicals formed, accompanied by π-electron delocalization to form phenyl-π radicals. Biomass pyrolysis was simulated by mechanically mixing the three components in different proportions. A comparison of the experimental and theoretical values indicated that interactions between the three components did not obviously affect the EPFR concentration in the range of 450–550 °C, with a maximum relative error of 12.78 %. A prediction model for the EPFRs concentration in multi-component pyrolytic carbon was proposed. This study also clarified the generation and transformation mechanisms of EPFRs in three-component pyrolytic carbon, thus providing guidance for generating and regulating biochar EPFRs.

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.

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.

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.

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.

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.

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.

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.

Particle-size distributions of environmentally persistent free radicals and oxidative potential of soils from a former gasworks site

The formation of toxic by-products, such as environmentally persistent free radicals (EPFRs), is one of the causes for concern by polycyclic aromatic hydrocarbons (PAHs) in soils. However, the distribution of EPFRs in different soil fractions and their relative contribution to the oxidation potential (OP) have not been investigated. In the present paper, contaminated samples were obtained from the former gasworks sites and were fractionated into different size particles, which were analyzed for EPFRs, reactive oxygen species (ROS), and OP-assayed by dithiothreitol (DTT) (OPDTT). The results showed the highest concentration of EPFRs in the soil particle size with diameters <0.15 mm due to co-existence of PAHs and transition metals. ROS generation is in accordance with the size-specific distribution of EPFRs. Using the DTT assays, the redox activity of various size soil particles was examined, and found it was approximately 4- to 8-folds higher than that of un-contaminated samples and strongly associated with EPFRs, ROS, and PAHs. The obtained results advanced our knowledge on the EPFRs distribution in soil fractions at former MGP sites and emphasized the significance of PAH-EPFRs as a class of compounds to be considered in risk assessment of contaminated sites.

Removal mechanism of tetracycline-Cr(Ⅵ) combined pollutants by different S-doped sludge biochars: Role of environmentally persistent free radicals

In this work, by using sodium thiosulfate as the S source, S-doped biochars were prepared to remove tetracycline/hexavalent chromium (TC-Cr (Ⅵ)) combined pollutants in aqueous solutions. The concentration of environmentally persistent free radicals (EPFRs) was used to directly determine the degradation of TC and the reduction of Cr (Ⅵ). The concentration of EPFRs in S-doped hydrothermal + pyrocarbon (S-HPBC) (3.64 × 1019 spins/g) was greater than that of S-doped hydrochar (S-HBC) (5.64 × 1018 spins/g) and S-doped pyrocarbon (S-PBC) (6.53 × 1018 spins/g). The increase in EPFRs concentration after S doping was positively correlated with the number of defect structures. In the TC-Cr (Ⅵ) system, the reduction efficiency of Cr (Ⅵ) decreased due to competition for electrons, while the TC degradation efficiency remained high. This was likely because Cr (Ⅵ) reduction promoted the degradation of TC. In addition, de-complexation was the primary factor for the removal of TC-Cr (Ⅵ), and some ROS were consumed during this process. The thiophene groups (-C-S-C-) that formed after S-doping of biochar were the main functional groups involved in the catalytic degradation of TC. In the radical pathway, SO4•- and •OH provided the greatest contribution to the degradation of TC, while 1O2 contributed the most to TC degradation via a non-radical pathway. The regeneration experiment confirmed that S-doped biochar could be reused and maintained a high pollutant removal efficiency. S-HPBC is a promising modified biochar material for removing mixed pollutants.

Formation and regulation of environmentally persistent free radicals in biochar and removal of diethyl-phthalate in water

Biochar contains environmentally persistent free radicals (EPFRs), a class of pollutants whose regulation and influencing factors need to be studied. In this study, electron paramagnetic resonance (EPR) signals were observed for biochar samples obtained by the pyrolysis of wheat straw, corn straw, peanut shell, and cotton stalk. The effects of pyrolysis temperature, residence time, and alkali/alkaline earth metals (AAEMs) on EPFRs in biochar were investigated. The adsorption effect of diethyl phthalate (DEP) on biochar obtained from the pyrolysis of wheat straw impregnated with K, Na, Ca, and Mg was also studied. The concentration of EPFRs increased first and then decreased upon increasing the pyrolysis temperature within the rage of 300–700 ℃, conforming to a Gaussian fit. Residence time experiments showed that the concentration of EPFRs was the highest at a residence time of 10 min. The effect of AAEMs on the EPFRs concentration followed the order Mg > K > Ca > Na due to the catalysis of a secondary reaction. Because of hole-filling and electrostatic attraction, biochar obtained by pyrolysis of wheat straw impregnated with MgCl2 (WSMg) had the highest DEP removal rate of 95.969%. DEP removal efficiency of the five adsorbents followed the order WSMg > WSCa (88.701%) > WS (68.867%) > WSNa (53.852%) > WSK (50.845%). Hydroxyl radicals (•OH) signals were detected in these five adsorption systems, showing that EPFRs could activated H2O2 to produce •OH. However, the five •OH signals had similar intensities, indicating that AAEMs had not significantly effects on the process of activation of H2O2 to produce •OH by EPFRs. The results of this study are of great significance for understanding the formation and regulation of EPFRs and the utilization of biochar.

Effects of Nitrogen Oxides on the Production of Reactive Oxygen Species and Environmentally Persistent Free Radicals from α-Pinene and Naphthalene Secondary Organic Aerosols.

Reactive oxygen species (ROS) and environmentally persistent free radicals (EPFR) play an important role in chemical transformation of atmospheric aerosols and adverse aerosol health effects. This study investigated the effects of nitrogen oxides (NOx) during photooxidation of α-pinene and naphthalene on the EPFR content and ROS formation from secondary organic aerosols (SOA). Electron paramagnetic resonance (EPR) spectroscopy was applied to quantify EPFR content and ROS formation. While no EPFR were detected in α-pinene SOA, we found that naphthalene SOA contained about 0.7 pmol μg–1 of EPFR, and NOx has little influence on EPFR concentrations and oxidative potential. α-Pinene and naphthalene SOA generated under low NOx conditions form OH radicals and superoxide in the aqueous phase, which was lowered substantially by 50–80% for SOA generated under high NOx conditions. High-resolution mass spectrometry analysis showed the substantial formation of nitroaromatics and organic nitrates in a high NOx environment. The modeling results using the GECKO-A model that simulates explicit gas-phase chemistry and the radical 2D-VBS model that treats autoxidation predicted reduced formation of hydroperoxides and enhanced formation of organic nitrates under high NOx due to the reactions of peroxy radicals with NOx instead of their reactions with HO2. Consistently, the presence of NOx resulted in the decrease of peroxide contents and oxidative potential of α-pinene SOA.

Medium-Low Temperature Conditions Induce the Formation of Environmentally Persistent Free Radicals in Microplastics with Conjugated Aromatic-Ring Structures during Sewage Sludge Pyrolysis.

Medium-low temperature pyrolysis is an effective method of retaining active components in sludge char. However, we found that incomplete cracking reactions resulted in residues of microplastics (MPs) remaining in the char; moreover, high levels of environmentally persistent free radicals (EPFRs) were detected in these MPs. Here, we investigated the temperature-dependent variations in the char-volatile products derived from sludge and MPs under different pyrolysis scenarios using multiple in situ probe coupling techniques and electron paramagnetic resonance spectroscopy, thereby identifying the sources of EPFRs and elucidating the corresponding formation-conversion mechanisms. The temperature was the key factor in the formation of EPFRs; in particular, in the 350-450 °C range, the abundance of EPFRs increased exponentially. Reactive EPFR readily formed in MPs with conjugated aromatic-ring structures (polyethylene terephthalate and polystyrene) at a temperature above 350 °C; EPFR concentrations were 5-17 times higher than those found in other types of polymers, and these radicals exhibited half-lives of more than 90 days. The EPFR formation mechanism could be summarized as solid-solid/solid-gas interfacial interactions between the polymers and the intermediate products from sludge pyrolysis (at 160-350 °C) and the homolytic cleavage-proton transfer occurring in the polymers themselves under the dual action of thermal induction and acid sites (at 350-450 °C). Based on the understanding of the evolution of EPFRs, temperature regulation and sludge components conditioning may be effective approaches to inhibit the formation of EPFRs in MPs, constituting reliable strategies to diminish the environmental risk associated with the byproducts of sludge pyrolysis.