Carbon emissions and priming effects derived from crop residues and their responses to nitrogen inputs.

Crop residue-derived carbon (C) emissions and priming effects (PE) in cropland soils can influence the global C cycle. However, their corresponding generality, driving factors, and responses to nitrogen (N) inputs are poorly understood. As a result, the total C emissions and net C balance also remain mysterious. To address the above knowledge gaps, a meta-analysis of 1123 observations, taken from 51 studies world-wide, has been completed. The results showed that within 360 days, emission ratios of crop residues C (ER) ranged from 0.22% to 61.80%, and crop residues generally induced positive PE (+71.76%). Comparatively, the contribution of crop residue-derived C emissions (52.82%) to total C emissions was generally higher than that of PE (12.08%), emphasizing the importance of reducing ER. The ER and PE differed among crop types, and both were low in the case of rice, which was attributed to its saturated water conditions. The ER and PE also varied with soil properties, as PE decreased with increasing C addition ratio in soils where soil organic carbon (SOC) was less than 10‰; in contrast, the opposite phenomenon was observed in soils with SOC exceeding 10‰. Moreover, N inputs increased ER and PE by 8.31% and 3.78%, respectively, which was predominantly attributed to (NH4 )2 SO4 . The increased PE was verified to be dominated by microbial stoichiometric decomposition. In summary, after incorporating crop residues, the total C emissions and relative net C balance in the cropland soils ranged from 0.03 to 23.47 mg C g-1 soil and 0.21 to 0.97 mg C g-1 residue-C g-1 soil, respectively, suggesting a significant impact on C cycle. These results clarify the value of incorporating crop residues into croplands to regulate global SOC dynamics and help to establish while managing site-specific crop return systems that facilitate C sequestration.

Photoaged Tire Wear Particles Leading to the Oxidative Damage on Earthworms (Eisenia fetida) by Disrupting the Antioxidant Defense System: The Definitive Role of Environmental Free Radicals.

Tire wear particles (TWPs) have caused increasing concerns due to their detrimental effects on the soil ecosystem. However, the role of weathering in altering the toxicity of TWP to soil organisms is poorly understood. In this study, the toxicity of original and photoaged TWP was compared using earthworms (Eisenia fetida) as soil model organisms. The obtained results indicated that photoaging of TWP resulted in an increase of environmentally persistent free radicals (EPFRs) from 3.69 × 1017 to 5.20 × 1017 spin/g. Meanwhile, photoaged TWP induced the changes of toxic endpoint in E. fetide, i.e., the increase of the weight loss and death ratio from 0.0425 to 0.0756 g/worm and 23.3 to 50% compared to original TWP under a 10% concentration, respectively. Analyses of transcriptomics, antioxidant enzyme activity, and histopathology demonstrated that the enhanced toxicity was mainly due to oxidative damage, which was induced by disruption in the antioxidant defense system. Free-radical quenching and correlation analysis further suggested that the excessive production of ex vivo reactive oxygen species, induced by EPFRs, led to the exhaustion of the antioxidant defense system. Overall, this work provides new insights into the potential hazard of the weathered TWP in a soil environment and has significant implications for the recycling and proper disposal of spent tire particles.

Novel Insights into the Promoted Accumulation of Nitro-Polycyclic Aromatic Hydrocarbons in the Roots of Legume Plants.

Substituted polycyclic aromatic hydrocarbons (sub-PAHs) are receiving increased attention due to their high toxicity and ubiquitous presence. However, the accumulation behaviors of sub-PAHs in crop roots remain unclear. In this study, the accumulation mechanism of sub-PAHs in crop roots was systematically disclosed by hydroponic experiments from the perspectives of utilization, uptake, and elimination. The obtained results showed an interesting phenomenon that despite not having the strongest hydrophobicity among the five sub-PAHs, nitro-PAHs (including 9-nitroanthracene and 1-nitropyrene) displayed the strongest accumulation potential in the roots of legume plants, including mung bean and soybean. The nitrogen-deficient experiments, inhibitor experiments, and transcriptomics analysis reveal that nitro-PAHs could be utilized by legumes as a nitrogen source, thus being significantly absorbed by active transport, which relies on amino acid transporters driven by H+-ATPase. Molecular docking simulation further demonstrates that the nitro group is a significant determinant of interaction with an amino acid transporter. Moreover, the depuration experiments indicate that the nitro-PAHs may enter the root cells, further slowing their elimination rates and enhancing the accumulation potential in legume roots. Our results shed light on a previously unappreciated mechanism for root accumulation of sub-PAHs, which may affect their biogeochemical processes in soils.

Seasonal and Spatial Fluctuations of Reactive Oxygen Species in Riparian Soils and Their Contributions on Organic Carbon Mineralization.

Reactive oxygen species (ROS) are ubiquitous in the natural environment and play a pivotal role in biogeochemical processes. However, the spatiotemporal distribution and production mechanisms of ROS in riparian soil remain unknown. Herein, we performed uninterrupted monitoring to investigate the variation of ROS at different soil sites of the Weihe River riparian zone throughout the year. Fluorescence imaging and quantitative analysis clearly showed the production and spatiotemporal variation of ROS in riparian soils. The concentration of superoxide (O2•-) was 300% higher in summer and autumn compared to that in other seasons, while the highest concentrations of 539.7 and 20.12 µmol kg-1 were observed in winter for hydrogen peroxide (H2O2) and hydroxyl radicals (•OH), respectively. Spatially, ROS production in riparian soils gradually decreased along with the stream. The results of the structural equation and random forest model indicated that meteorological conditions and soil physicochemical properties were primary drivers mediating the seasonal and spatial variations in ROS production, respectively. The generated •OH significantly induced the abiotic mineralization of organic carbon, contributing to 17.5-26.4% of CO2 efflux. The obtained information highlighted riparian zones as pervasive yet previously underestimated hotspots for ROS production, which may have non-negligible implications for carbon turnover and other elemental cycles in riparian soils.

Activation of persulfate for the degradation of ethyl-parathion in soil: Combined effects of microwave with biochar.

Sulfate radical (SO4•-), formed by persulfate (PS) activation during advanced oxidation process (AOPs), can be used for the remediation of organic contaminated soil. However, the role of biochar and microwave (MW) in the activation of PS is not fully understood, especially the corresponding mechanism. Herein, biochar combined with MW was used to activate PS for the remediation of ethyl-parathion (PTH)-polluted soil. The dynamic evolutions of PTH under different conditions, such as biochar content, particle size, reaction temperature, and the degradation mechanisms of PTH were also systematically investigated. Significant enhancement performance on PTH removal was observed after adding biochar, which was 88.78% within 80 min. Meanwhile, activating temperature exhibited remarkable abilities to activate PS for PTH removal. The higher content of adsorption sites in nano-biochar facilitated the removal of PTH. Furthermore, chemical probe tests coupled with quenching experiments confirmed that the decomposition of PS into active species, such as SO4•-, •OH, O2•- and 1O2, contributed to the removal of PTH in biochar combined with MW system, which could oxidize PTH into oxidative products, including paraoxon, 4-ethylphenol, and hydroquinone. The results of this study provide valuable insights into the synergistic effects of biochar and MW in the PS activation, which is helpful for the potential application of biochar materials combined with MW-activated PS in the remediation of pesticide-polluted soils.

Sulfur-Containing Persistent Free Radicals and Reactive Species on Photoaged Microplastics: Identification and the Formation Mechanism.

The elemental composition may affect the persistent free radical (PFR) and reactive species (RS) formation associated with photoaging microplastics; however, a relevant study is still lacking. This study systematically investigated the formation, evolution, and types of PFRs and RS on sulfur-containing microplastics (S-MPs) under simulated sunlight. Electron paramagnetic resonance detection and power saturation curve analysis isolated three different PFRs on each photoaging poly(phenylene sulfide) (PPS) and polysulfone (PSF). Combining the results of characterization and density functional theory calculation, these observed PFRs on the irradiated S-MPs were classified as oxygen-centered radicals with an adjacent S atom (namely, thio-oxygen radicals), oxygen-centered and sulfur-centered radicals, where the thio-oxygen radicals on PPS were benzenethiol-like radicals, and oxygen-centered radicals and sulfur-centered radicals on PSF that were identified as benzenesulfonic-like radicals and phenyl sulfonyl-like radicals, respectively. Moreover, potential precursor molecule fragments of PFRs on the photoaging S-MPs, including p-toluenesulfinic acid and benzenesulfonic acid, were detected by pyrolysis-gas chromatography/mass spectrometry and liquid chromatography-mass spectrometry. Interestingly, reactive sulfur species (SO3•-) was also observed on irradiated S-MPs in addition to reactive oxygen species, which was mainly derived from the reaction of •OH and sulfonyl radicals. These results have implications for assessing the potential risks of atmospheric S-MPs.

Biochar-Associated Free Radicals Reduce Soil Bacterial Diversity: New Insight into Ecoenzymatic Stoichiometry.

The toxicity of environmentally persistent free radicals (EPFRs), often generated during biochar production, on soil bacteria is still not truly reflected when considering the conditions in real soil. Herein, the influence of free radicals within biochar on soil bacteria was investigated from the perspectives of enzyme activity, community structure, and ecoenzymatic stoichiometry. Biochar addition enhanced the contents of EPFRs and derived hydroxyl radicals (•OH) in the soil, while it reduced bacterial alpha diversity by 5.06-35.44%. The results of redundancy analysis and inhibition experiments collectively demonstrated the key role of EPFRs and •OH in reducing the bacterial alpha diversity. Specifically, EPFRs and •OH increased the stoichiometric imbalance by promoting the release of dissolved organic carbon and ammonium N, thus aggravating the P limitation in soil. This was further confirmed by increased alkaline phosphatase activity from 702 to 874 nmol g-1 h-1. The P limitation induced by EPFRs and •OH decreased the bacterial alpha diversity, as evidenced by the negative correlation between P limitation and bacterial alpha diversity (r2 = -0.931 to -0.979, P < 0.01) and the structural equation model. The obtained results demonstrate a ubiquitous but previously overlooked mechanism for bacterial toxicity of biochar-associated free radicals, providing scientific guidance for safe utilization of biochar.

Unrecognized Role of Organic Acid in Natural Attenuation of Pollutants by Mackinawite (FeS): The Significance of Carbon-Center Free Radicals.

Organic acid is prevalent in underground environments and, against the backdrop of biogeochemical cycles on Earth, holds significant importance in the degradation of contaminants by redox-active minerals. While earlier studies on the role of organic acid in the generation of reactive oxygen species (ROS) primarily concentrated on electron shuttle or ligand effects, this study delves into the combined impacts of organic acid decomposition and Mackinawite (FeS) oxidation in contaminant transformation under dark aerobic conditions. Using bisphenol A (BPA) as a model, our findings showed that oxalic acid (OA) notably outperforms other acids in enhancing BPA removal, attaining a rate constant of 0.69 h-1. Mass spectrometry characterizations, coupled with anaerobic treatments, advocate for molecule-O2 activation as the principal mechanism behind pollutant transformation. Comprehensive results unveiled that carbon center radicals, initiated by hydroxyl radical (•OH) attack, serve as the primary agents in pollutant oxidation, accounting for at least 93.6% of the total •OH generation. This dynamic, driven by the decomposition of organic acids and the concurrent formation of carbon-centered radicals, ensures a steady supply of electrons for ROS generation. The obtained information highlights the importance of OA decomposition in the natural attenuation of pollutants and offers innovative strategies for FeS and organic acid-coupled decontamination.

Microscale Spatiotemporal Variation and Generation Mechanisms of Reactive Oxygen Species in the Rhizosphere of Ryegrass: Coupled Biotic-Abiotic Processes.

Reactive oxygen species (ROS) play key roles in soil biogeochemical processes, yet the occurrence and accumulation of ROS in the rhizosphere are poorly documented. Herein, we first developed a ROS-trapping membrane to in situ determine ROS in the ryegrass rhizosphere and then quantified the temporal and spatial variations of representative ROS (i.e., O2•─, H2O2, and •OH). Fluorescence imaging clearly visualized the production of ROS in the rhizosphere. Both O2•─ and H2O2 content increased first and then declined throughout the life cycle of ryegrass, while •OH concentration decreased continuously. Spatially, ROS contents remained at a relatively high level at 0-5 mm and then descended with increasing distance. The concentrations of ROS in different soils followed the order of black soil > latosol soil > yellow-brown soil > tier soil ∼ red soil. Analysis of soil properties suggested that both biotic factors (microbial community) and abiotic factors (Fe(II) and water-soluble phenols) played critical roles in ROS production. The combined processes, including Fe(II) and water-soluble phenol-mediated electron transfer, microbial community-driven extracellular O2•─ release, and Fe(II)/Fe(III) cycling, may be responsible for ROS production. These findings provide insights into ROS-associated rhizosphere effects and inspiration for the phytoremediation of pollutants and element cycling.

In Vitro Assessment Reveals the Effects of Environmentally Persistent Free Radicals on the Toxicity of Photoaged Tire Wear Particles.

Tire wear particles (TWP) have been identified as one of the major sources of microplastics (MPs), and few studies have focused on their environmental behaviors and impacts. However, a thorough characteristic and toxicity assessment associated with environmentally persistent free radicals (EPFRs) on the photoaged TWP is missing. In this study, we investigated EPFRs in the process of TWP photoaging and evaluated their toxicity using in vitro bioassays. Our results showed that a total of around 1.0 × 1017 spins/g EPFRs (g-factors ranging 2.00308-2.00318) was formed on TWP with 60 days of light irradiation, which contained more than 29% of reactive EPFRs (r-EPFRs). Using macrophages as model cells for bioassays, TWP-associated EPFRs trigged endpoints, including the decrease of cell viability (27 to 45%) and the increase of oxidative stress response (46-93%) and inflammatory factor secretion. The enhancement of TWP toxicity with photoaging was confirmed to be attributed to the generated EPFRs combined with other TWP's chemical compositions (e.g., various metals and organics). Most importantly, the toxicity of photoaged TWP was closely correlated with the generated r-EPFRs, which induced reactive oxidant species (ROS) generation. This study provides direct evidence of toxicity on the photoaged TWP particles, revealing the potential contributions of EPFRs to the adverse effect on human health and highlighting the need for an improved understanding of the impacts of EPFRs on the risk assessment of TWP released into the environment.

Oxygen Limitation Accelerates Regeneration of Active Sites on a MnO2 Surface: Promoting Transformation of Organic Matter and Carbon Preservation.

Birnessite (δ-MnO2) is a layered manganese oxide widely present in the environment and actively participates in the transformation of natural organic matter (NOM) in biogeochemical processes. However, the effect of oxygen on the dynamic interface processes of NOM and δ-MnO2 remains unclear. This study systematically investigated the interactions between δ-MnO2 and fulvic acid (FA) under both aerobic and anaerobic conditions. FA was transformed by δ-MnO2 via direct electron transfer and the generated reactive oxygen species (ROS). During the 32-day reaction, 79.8% of total organic carbon (TOC) in solution was removed under anaerobic conditions, unexpectedly higher than that under aerobic conditions (69.8%), suggesting that oxygen limitation was more conducive to the oxidative transformation of FA by δ-MnO2. The oxygen vacancies (OV) on the surface of δ-MnO2 were more exposed under anaerobic conditions, thus promoting the adsorption and transformation of FA as well as regeneration of the active sites. Additionally, the reaction of FA with δ-MnO2 weakened the strongly bonded lattice oxygen (Olatt), and the released Olatt was an important source of ROS. Interestingly, a part of organic carbon (OC) was preserved by forming MnCO3, which might be a novel mechanism for carbon preservation. These findings contribute to an improved understanding of the dynamic interface processes between MnO2 and NOM and provide new insights into the effects of oxygen limitation on the cycling and preservation of OC.

Insight into the Photodegradation of Microplastics Boosted by Iron (Hydr)oxides.

Iron (hydr)oxides as a kind of natural mineral actively participate in the transformation of organic pollutants, but there is a large knowledge gap in their impacts on photochemical processes of microplastics (MPs). This study is the first to examine the degradation of two ordinary plastic materials, polyethylene (PE) and polypropylene (PP), mediated by iron (hydr)oxides (goethite and hematite) under simulated solar light irradiation. Both iron (hydr)oxides significantly promoted the degradation of MPs (particularly PP) with a greater effect by goethite than hematite, related to hydroxyl radical (•OH) produced by iron (hydr)oxides. Under light irradiation, the surface Fe(II) phase catalyzed the production of H2O2 and promoted the release of Fe2+, leading to the subsequent light-driven Fenton reaction which produced a large amount of •OH. As the iron (hydr)oxides were modified with NaF at various concentrations, the activity of the surface Fe(II) as well as the release of Fe2+ were greatly reduced, and thus the •OH formation and MP degradation were depressed remarkably. It is worth noting that the surface hydroxyl groups (especially ≡FeOH) affected the reaction kinetics of •OH by regulating the activity of Fe species. These findings unveil the distinct impacts and intrinsic mechanisms of iron (hydr)oxides in influencing the photodegradation of MPs.

The First Observation of the Formation of Persistent Aminoxyl Radicals and Reactive Nitrogen Species on Photoirradiated Nitrogen-Containing Microplastics.

Nitrogen-containing microplastics (N-MPs) are widely present in the atmosphere, but their potential health risks have been overlooked. In this study, the formation of persistent aminoxyl radicals (PAORs) and reactive nitrogen species (RNSs) on the N-MPs under light irradiation was investigated. After photoaging, an anisotropic triplet with the g-factor of ∼2.0044, corresponding to PAORs, was detected on the nonaromatic polyamide (PA) rather than amino resin (AmR) by electron paramagnetic resonance and confirmed by density functional theory calculations. The generated amine oxide portions on the photoaged PA were identified using X-ray photoelectron spectroscopy and Raman spectroscopy, which were considered to be the main structural basis/precursors of a PAOR. Surprisingly, RNSs were also observed on the irradiated PA. The generated ·NO due to the aphotolysis of nitrone groups simultaneously reacted with peroxide radicals and O2·- to yield ·NO2 and peroxynitrite, respectively, which were responsible for peroxyacyl nitrates (PAN) and CO3·- formation. Besides, a significantly higher oxidative potential and reductive potential were observed for the aged PA than AmR, which is assigned to the abundant RNSs, organic hydroperoxides and PANs, and a strong ability to transfer electrons from PAOR, respectively. This work provides important information for the potential risks of airborne N-MPs and may serve as a guide for future toxicological assessments.

An Atomic-Scale Understanding of the Solution Chemistry of Antimony(V): Insights from First-Principles Molecular Dynamics Simulation.

In this study, the structure, hydrolysis, and complexation of Sb(V) in aqueous solution has been elucidated by using first-principles molecular dynamics (FPMD) simulations. The results show that both antimonic acid and its deprotonated form have an octahedral configuration, with average Sb-OH2 and Sb-OH distances of 2.25 and 2.05 Å, respectively. The computed pKa of [Sb(OH)5(OH2)] is 1.8, while [Sb(OH)6]- has an extremely high pKa. Consequently, [Sb(OH)6]- is the most dominant species of Sb(V) under common environmental conditions. A stable aqueous complex can form between [Sb(OH)6]- and common cations, and an Sb-Al bidentate complex has the largest dissociation free energy, followed by a Sb-Mg bidentate complex, indicating that they have significantly higher stabilities. For Na+ and Ca2+, their respective monodentate and bidentate complexes have similar dissociation free energies, indicating very close possibilities. These findings provide a comprehensive understanding of the solution chemistry of Sb(V) from a quantitative and microscopic perspective.

Cytotoxic Free Radicals on Air-Borne Soot Particles Generated by Burning Wood or Low-Maturity Coals.

The traditional cook stove is a major contributor to combustion-derived soot particles, which contain various chemical species that may cause a significant impact to human health and ecosystems. However, properties and toxicity associated with environmentally persistent free radicals (EPFRs) in such emissions are not well known. This paper investigated the characteristics and cytotoxicity of soot-associated EPFRs discharged from Chinese household stoves. Our results showed that the concentrations of EPFRs were related to fuel types, and they were higher in wood-burning soot (8.9-10.5 × 1016 spins/g) than in coal-burning soot (3.9-9.7 × 1016 spins/g). Meanwhile, EPFR concentrations in soot decreased with an increase of coal maturity. The soot EPFRs, especially reactive fractions, readily induced the generation of reactive oxygen species (ROS). Potential health effects of soot EPFRs were also examined using normal human bronchial epithelial cell line 16HBE as a model. Soot particles were internalized by 16HBE cells inducing cytotoxicity. The main toxicity inducers were identified to be reactive EPFR species, which generated ROS inside human cells. Our findings provided valuable insights into potential contributions of soot EPFRs associated with different types of fuel to health problems. This information will support regulations to end or limit current stove usage in numerous households.

Sorption properties of cadmium on microplastics: The common practice experiment and A two-dimensional correlation spectroscopic study.

Microplastics (MPs) that have accumulated in the environment are emerging as contaminating pollutants due to their interactions with metal ions. MPs change the migration and transformation of metal ions in the environment and afterward impact their environmental presence. Therefore, it is necessary to evaluate the interaction characteristics and mechanisms between Cd2+and MPs for assessing the ecological impacts of MPs. The traditional sequencing batch equilibrium test demonstrated that the sorption of Cd2+ onto MPs was related to the type of MPs present, the pH value of the solution, the ionic strength of the participants and the presence of humic acid. The sorption dynamics and isotherm experiment illustrated that the interactions were controlled by surface sorption and distribution effects. The specific surface area and surface charge were the main factors in managing the sorption process. FTIR spectra and a 2D-COS analysis showed that different functional groups played an important role in the sorption of Cd2+onto MPs. The results from this work afford new insights on how MPs may play an important role in the fate and transport of heavy metals and present a new analysis method for evaluating the environmental behavior of MPs and their role in transporting other contaminants.

Soil enzyme kinetics indicate ecotoxicity of long-term arsenic pollution in the soil at field scale.

Information on the kinetic characteristics of soil enzymes under long-term arsenic (As) pollution in field soils is scarce. We investigated Michaelis-Menten kinetic properties of four soil enzymes including ß-glucosidase (BG), acid phosphatase (ACP), alkaline phosphatase (ALP), and dehydrogenase (DHA) in field soils contaminated by As resulting from long-term realgar mining activity. The kinetic parameters, namely the maximum reaction velocity (Vmax), enzyme-substrate affinity (Km) and catalytic efficiency (Vmax/Km) were calculated. Results revealed that the enzyme kinetic characteristics varied in soils and were significantly influenced by total nitrogen (N) and total As, which explained 31.8% and 30.7% of the variance in enzyme kinetics respectively. Enzyme pools (Vmax) and catalytic efficiency (Vmax/Km) of BG, ACP and DHA decreased with elevated As pollution, while the enzyme affinity for substrate (Km) was less affected. Redundancy analysis and stepwise regression suggested that the adverse influence of As on enzyme kinetics may offset or weakened by soil total N and soil organic matter (SOM). Concentration-response fitting revealed that the specific kinetic parameters expressed as the absolute enzyme kinetic parameters multiplied by normalized soil total N and SOM were more relevant than the absolute ones to soil total As. The arsenic ecological dose values that cause 10% decrease (ED10) in the specific enzyme kinetics were 20-49 mg kg-1, with a mean value of 35 mg kg-1, indicating a practical range of threshold for As contamination at field level. This study concluded that soil enzymes exhibited functional adaptation to long-term As stress mainly through the reduction of enzyme pools (Vmax) or maintenance of enzyme-substrate affinity (Km). Further, this study demonstrates that the specific enzyme kinetics are the better indicators of As ecotoxicity at field-scale compared with the absolute enzyme parameters.

Formation of Environmentally Persistent Free Radicals on Microplastics under Light Irradiation.

Microplastics (MPs) are presumed to be inert during aging under ambient conditions. In this study, four types of virgin MPs, including polystyrene (PS), phenol-formaldehyde resin (PF), polyethylene (PE), and polyvinyl chloride (PVC), were aged under simulated solar light irradiation. Surprisingly, several environmentally persistent free radicals (EPFRs), which are considered to be a type of emerging contaminant, were detected on the irradiated PS and PF, rather than PE and PVC, by electron paramagnetic resonance (EPR) spectroscopy. Depending on the photoaging duration time, the characteristic g-factors of the EPFRs produced on PS and PF were 2.0044-2.0049 and 2.0043-2.0044, respectively. The generated EPFRs on PS and PF decayed rapidly at the initial stage and then slowly disappeared with the elapsed aging time. Analyses by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC) suggested that MPs might experience chemical chain scission, O2/H2O addition, and EPFR formation under the light irradiation. Accompanying with the formation of EPFRs, reactive oxygen species, such as O2•- and •OH, were also observed. The findings provide a novel insight to evaluate the potential hazards of MPs to organisms and ecosystems.

Reactive Nitrogen Species Mediated Degradation of Estrogenic Disrupting Chemicals by Biochar/Monochloramine in Buffered Water and Synthetic Hydrolyzed Urine.

There is increasing concern about the severe endocrine-related health problems because of the discharge of estrogenic disrupting chemicals (EDCs) into the natural environment. In this study, we investigated the activation of monochloramine (NH2Cl) by biochar [pyrolyzed by cotton straw at 350 °C (Cot350), wheat straw at 350 and 700 °C (WS350 and WS700), and corn straw at 350 and 700 °C (CS350 and CS700)] for the degradation of estradiol (E2) and ethinylestradiol (EE2). Approximately 95% of parent E2 and EE2 was removed by Cot350/NH2Cl in buffered solution, and 87% of E2 and 75% of EE2 were removed in urine within 24 h. Electronic paramagnetic resonance analysis and radical-quenching experiments showed that biochar activated NH2Cl and primarily generated •NO radicals for the degradation of the EDCs. The nitrogen and silicon elements of Cot350 served as primary catalytic sites for NH2Cl activation, whereas the sp2-hybridized carbon on WS700 and CS700 played a major role. The effect of major urine components (i.e., ammonia species, chloride, and bicarbonate) on the reaction pathways of biochar/NH2Cl was also elucidated. This study provides new insights into the reaction pathways of NH2Cl activation by biochar and suggests potential applications for other carbonaceous materials for NH2Cl activation.

Formation and Evolution of Solvent-Extracted and Nonextractable Environmentally Persistent Free Radicals in Fly Ash of Municipal Solid Waste Incinerators.

Environmentally persistent free radicals (EPFRs) are emerging contaminants occurring in combustion-borne particulates and atmospheric particulate matter, but information on their formation and behavior on fly ash from municipal solid waste (MSW) incinerators is scarce. Here, we have found that MSW-associated fly ash samples contain an EPFR concentration of 3-10 × 1015 spins g-1, a line width (ΔHp-p) of ∼8.6 G, and a g-factor of 2.0032-2.0038. These EPFRs are proposed to be mixtures of carbon-centered and oxygen-centered free radicals. Fractionation of the fly ash-associated EPFRs into solvent-extracted and nonextractable radicals suggests that the solvent-extracted part accounts for ∼45-73% of the total amount of EPFRs. Spin densities of solvent-extracted EPFRs correlate positively with the concentrations of Fe, Cu, Mn, Ti, and Zn, whereas similar correlations are comparatively insignificant for nonextractable EPFRs. Under natural conditions, these two types of EPFRs exhibit different stabilization that solvent-extracted EPFRs are relatively unstable, whereas the nonextractable fraction possesses a long life span. Significant correlations between concentrations of solvent-extracted EPFRs and generation of hydroxyl and superoxide radicals are found. Overall, our results suggest that the fractionated solvent-extracted and nonextractable EPFRs may experience different formation and stabilization processes and health effects.