Unlocking high-efficiency decontamination by building a novel heterogeneous catalytic reduction system of thiourea dioxide/biochar.

Herein, we reported a new contaminant purification paradigm, which enabled highly efficient reductive denitration and dechlorination using a green, stable reducing agent thiourea dioxide (TDO) coupled with biochar (BC) over a wide pH range under anoxic conditions. Specifically, BC acted as both activators and electron shuttles for TDO decomposition to achieve complete anoxic degradation of p-nitrophenol (PNP), p-nitroaniline, 4-chlorophenol and 2,4-dichlorophenol within 2 h. During this process, multiple strongly reducing species (i.e., SO22-, SO2•- and e-/H•) were generated in BC/TDO systems, accounting for 13.3%, 9.7% and 75.5% of PNP removal, respectively. While electron transfer between TDO and H+ or contaminants mediated by BC led to H• generation and contaminant reduction. These processes depended on the electron-accepting capacity and electron-conducting domains of biochar. Significantly, the BC/TDO systems were highly efficient at a pH of 2.0-8.0, especially under acidic conditions, which performed robustly in common natural water constituents.

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.

A state-of-art review on the redox activity of persistent free radicals in biochar.

Biochar-bound persistent free radicals (biochar-PFRs) attract much attention because they can directly or indirectly mediate the transformation of contaminants in large-scale wastewater treatment processes. Despite this, a comprehensive top-down understanding of the redox activity of biochar-PFRs, particularly consumption and regeneration mechanisms, as well as challenges in redox activity assessment, is still lacking. To tackle this challenge, this review outlines the identification and determination methods of biochar-PFRs, which serve as a prerequisite for assessing the redox activity of biochar-PFRs. Recent developments concerning biochar-PFRs are discussed, with a main emphasis on the reaction mechanisms (both non-free radical and free radical pathways) and their effectiveness in removing contaminants. Importantly, the review delves into the mechanism of biochar-PFRs regeneration, triggered by metal cations, reactive oxygen species, and ultraviolet radiations. Furthermore, this review thoroughly explores the dilemma in appraising the redox activity of biochar-PFRs. Components with unpaired electrons (particular defects and metal ions) interfere with biochar-PFRs signals in electron paramagnetic resonance spectra. Scavengers and extractants of biochar-PFRs also inevitably modify the active ingredients of biochar. Based on these analyses, a practical strategy is proposed to precisely determine the redox activity of biochar-PFRs. Finally, the review concludes by presenting current gaps in knowledge and offering suggestions for future research. This comprehensive examination aims to provide new and significant insights into the redox activity of biochar-PFRs.

Arsenite adsorption and oxidation affected by soil humin: The significant role of persistent free radicals and reactive oxygen species.

Humin (HM), as the main component of soil organic matter, carries various reactive groups and plays a crucial regulatory role in the transformation of arsenic (As). However, current research on the redox pathway of As and its interactions with HM is relatively limited. This study aimed to explore the impact of different HM samples on the redox characteristics of As. The results showed that HM can not only adsorb arsenite [As(III)] but also oxidize As(III) into arsenate [As(V)]. However, once As(III) is adsorbed on the HM, it cannot undergo further oxidation. HMNM (extracted from peat soil) exhibited the highest adsorption capacity of As(III), with a maximum amount of 1.95 mg/kg. The functional groups of HM involved in As complexation were primarily phenolic hydroxyl and carboxyl groups. The adsorption capacity of HM samples for As(III) was consistent with their carboxyl group contents. The oxygen-containing functional groups and environmentally persistent free radicals (EPFRs) on HM can directly oxidize As(Ⅲ) through electron transfer, or indirectly induce the production of reactive oxygen species (ROS), such as hydroxyl radicals, to further oxidize As(Ⅲ). This study provides new insight into the transport and transformation process of As mediated by soil HM, and establishes a theoretical basis for As remediation.

Biodegradable plastics fragments induce positive effects on the decomposition of soil organic matter.

The escalating accumulation of plastic waste in ecosystems poses a significant health concern to soil environment, yet the environmental effects of plastics remains largely unexplored. Biodegradable plastics could offer a viable alternative to conventional persistent plastics, but our understanding of their potential benefits or detrimental effects on the decomposition of plant debris by soil biomass is limited. In this study, we conducted a year-long field experiment to examine the environmental response and impact on plant debris decomposition in the presence of varying quantities of persistent versus biodegradable plastics. Our findings indicate that the decomposition rate decreased by 2.8-4.9% for persistent plastics, while it increased by 1.3-4.2% for biodegradable plastics. Persistent plastics primarily induced adverse effects, including a reduction in soil nutrients, microbial diversity, bioturbation, enzyme activity, easily decomposable carbon, and microbial biomass carbon in plant debris. In contrast, biodegradable plastics resulted in beneficial effects such as an increase in enzyme activity, microbial biomass carbon, and easily decomposable carbon. We also observed that the decomposition rate of plant residues and nutrient release are closely associated with changes in the organic carbon chemical structure induced by different plastic film fragments. A significant shift in alkoxy carbon content facilitated the release of nutrients and soluble carbon, while modifications in carboxyl and aromatic carbon content hindered their release. Overall, our study reveals over one year that biodegradable plastics primarily induce positive effects on the decomposition of soil organic matter.

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.

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.

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.

Molecular insights into microbial transformation of bioaerosol-derived dissolved organic matter discharged from wastewater treatment plant.

Wastewater treatment plants (WWTP) are important sources of aerosol-derived dissolved organic matter (ADOM) which may threaten human health via the respiratory system. In this study, aerosols were sampled from a typical WWTP to explore the chemical molecular diversity, molecular ecological network, and potential toxicities of the ADOM in the aerosols. The high fluorescence index (>1.9) and biological index (0.66-1.17) indicated the strong autogenous microbial source characteristics of the ADOM in the WWTP. DOM and microbes in the wastewater were aerosolized due to strong agitation and bubbling in the treatment processes, and contributed to 74 % and 75 %, respectively, of the ADOM and microbes in the aerosols. The ADOM was mainly composed of CHO and CHOS accounting for 35 % and 29 % of the total number of molecules, respectively, with lignin-like (69 %) as the major constituent. 49 % of the ADOM transformations were thermodynamically limited, and intragroup transformations were easier than intergroup transformations. Bacteria in the aerosols involved in ADOM transformations exhibited both cooperative and divergent behaviors and tended to transform carbohydrate-like and amino sugar/protein-like into recalcitrant lignin-like. The microbial compositions were affected by atmosphere temperature and humidity indirectly by modulating the properties of ADOM. Tannin-like, lignin-like, and unsaturated hydrocarbon-like molecules in the ADOM were primary toxicity contributors, facilitating the expression of inflammatory factors IL-ß (2.2-5.4 folds), TNF-α (3.5-7.0 folds), and IL-6 (3.5-11.2 folds), respectively.

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.

Earthworm activity effectively mitigated the negative impact of microplastics on maize growth.

Microplastic pollution can have detrimental effects on soil environments and inhibit crop growth. Earthworms, known as soil engineers, promote crop growth, but their role and impact on the amelioration of microplastic-polluted soil is not yet clear. In this study, we investigated the impact and pathways of earthworm activity on microplastic-contaminated soil by introducing varying densities (without earthworm:0, low-density: 1, medium-density: 2, high-density: 5 ind column-1) of earthworms (epi-endogeic) into soil contaminated with two types of microplastics: polyethylene and polyvinyl chloride. Our results showed that earthworms all survived in soil polluted with two types of microplastics. Meanwhile, earthworm activity increased nutrient content and enzyme activity by 0.2-36.1% and 2.9-34.3%, respectively, and significantly increased soil microbial biomass and community diversity index. Earthworm activity also decreased antioxidant enzyme activity and promoted maize plant growth, including agronomic traits such as plant height, biomass, root length, and root surface area. Furthermore, the nutrient content of maize organs increased by 1.1-29.7%. Partial least squares models confirmed that earthworm activity alleviated the stress effect of microplastic pollution on plant growth by improving soil structure, fertility, and microbial abundance and diversity. The greatest effect on maize growth was observed with the improvement of soil physical-chemical properties. Our results suggest that medium densities of earthworms have the greatest soil improvement effect and provide an important basis for bioremediation of farmland contaminated by microplastics and promoting green and efficient development in agriculture.

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.

Multi-scale modeling of natural organic matter-heavy metal cations interactions: Aggregation and stabilization mechanisms.

Interaction between natural organic matters (NOM) and heavy metal cations in aqueous environment are of great significance for maintaining stability of organic carbon and restraining transport of heavy metal contaminants in (bio)geochemical processes. We systematically explore the aggregation process and complexation between NOM and heavy metal cations (Ag+, Cd2+, Pb2+, Zn2+, Eu3+) under different pH condition by molecular dynamics (MD) simulations, umbrella sampling method, and quantum chemistry calculations. The character of molecular structures NOM-heavy metal complexes and association are quantified. In acidic pH condition, aggregation proceeds via H-bonding and π-π interactions between NOM fragments. In neutral condition, Ag+, Cd2+, Pb2+, and Eu3+ can form inner-sphere complexes with the surface carboxylic groups and therefore reduce intermolecular charge repulsion, eventually leading to NOM aggregation, and it shows that even without direct binding, the outer-sphere adsorbed Zn2+ can also result in the formation of NOM assemble through H-bonding. Consequently, these heavy metals are capable of promoting NOM aggregation regardless of the complexing ways. Complexing free energy calculations characterized the dynamic processes of cations binding to the carboxylic groups of NOM fragment and the related energy landscape. This study provides quantitative insights for understanding the environmental processes of heavy metals and cycle of C in aquatic ecosystem, and contributes to developing environment-friendly strategies for controlling heavy metal contaminants.

Using soil enzyme Vmax as an indicator to evaluate the ecotoxicity of lower-ring polycyclic aromatic hydrocarbons in soil: Evidence from fluorescein diacetate hydrolase kinetics.

Fluorescein diacetate hydrolase (FDA hydrolase) is a reliable biochemical biomarker of changes in soil microbial activity and quality. However, the effect and mechanism of lower-ring polycyclic aromatic hydrocarbons (PAHs) on soil FDA hydrolase are still unclear. In this work, we investigated the effects of two typical lower-ring PAHs, naphthalene (Nap) and anthracene (Ant), on the activity and kinetic characteristics of FDA hydrolases in six soils differing in their properties. Results demonstrated that the two PAHs severely inhibited the activities of the FDA hydrolase. The values of Vmax and Km dropped by 28.72-81.24 % and 35.84-74.47 % at the highest dose of Nap, respectively, indicating an uncompetitive inhibitory mechanism. Under Ant stress, the values of Vmax decreased by 38.25-84.99 %, and the Km exhibited two forms, unchanged and decreased (74.00-91.61 %), indicating uncompetitive and noncompetitive inhibition. The inhibition constant (Ki) of the Nap and Ant ranged from 0.192 to 1.051 and 0.018 to 0.087 mM, respectively. The lower Ki of Ant compared to Nap indicated a higher affinity for enzyme-substrate complex, resulting in higher toxicity of Ant than Nap to soil FDA hydrolase. The inhibitory effect of Nap and Ant on soil FDA hydrolase was mainly affected by soil organic matter (SOM). SOM influenced the affinity of PAHs with enzyme-substrate complex, which resulted in a difference in PAHs toxicity to soil FDA hydrolase. The enzyme kinetic Vmax was a more sensitive indicator than enzyme activity to evaluate the ecological risk of PAHs. This research offers a strong theoretical foundation for quality control and risk evaluation of PAH-contaminated soils through a soil enzyme-based approach.

P-doped biochar regulates nZVI nanocracks formation for superefficient persulfate activation.

In this study, a novel P-doped biochar loaded with nano zero-valent iron (nZVI) composite (nZVI@P-BC), with abundant nanocracks from inside to outside in nZVI particles, was designed for ultra-efficient persulfate (PS) activation and gamma-hexachlorocyclohexane (γ-HCH) degradation. Results showed that P-doping treatment significantly enhanced specific surface area, hydrophobicity and adsorption capacity of biochar. Systematic characterizations revealed that the additional electrostatic stress and continuously generated multiple new nucleation sites of P-doped biochar were the main mechanism for the formation of nanocracked structure. nZVI@P-BC with KH2PO4 as P precursor showed superefficient PS activation and γ-HCH degradation, by which 92.6 % of 10 mg/L γ-HCH was removed within 10 min using 1.25 g/L catalyst and 4 mM PS, being 10.5-fold greater than that of without P-doping. Electron spin resonance and radical quenching test showed that •OH and 1O2 were the dominant active species, and further revealed that the unique nanocracked nZVI, high adsorption capacity and abundant P sites in nZVI@P-BC enhanced their generation and mediated extra direct surface electron transfer. nZVI@P-BC also exhibited high tolerance to different anions, humic acid and wide pH conditions. This work provides a new strategy and mechanism insight for the rational design of nZVI and diversified application of biochar.

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.

Formation of emerging disinfection byproducts from agricultural biomass-derived DOM: Overlooked health risk source.

Carbon-derived dissolved organic matter (CDOM) are inevitably released to surface water during returning agricultural biomass carbon to farmland, which are potential precursors of disinfection byproducts (DBPs). In this study, CDOM was extracted from aerobic incineration ("OX") and anoxic pyrolysis ("PY") of three kinds of straw (wheat, corn, and rice), and the emerging DBPs from them were deciphered. The CDOM with molecular weight < 1 kDa in the OX and PY groups accounted for 53-87%, and it was higher in the PY group. A total 1343-2107 of CHO and 641-1761 of CHNO formulas were detected in the CDOM derived from the OX group, among which 74%-83% contained aromatic structures rich in oxygen containing groups. 1919-3289 of CHO and 785-1954 of CHNO formulas were observed in the PY group, and 77%-86% of them were lignins/CRAM-like compounds. Surprisingly, 765-2158 and 895-1648 of emerging DBPs were identified in the OX and PY groups, and the proportions of N-DBPs were 20.3-54.8% and 2.8-4.8%, respectively. Based on HOCl addition and Cl substitution mechanisms, the H/C ratios of the DBP precursors in the OX and PY groups were in the range of 0.2-1.5 and 0.6-2.0, respectively. The DBPs derived from the OX group exhibited higher cytotoxicity and genotoxicity due to the higher aromaticity and more N-DBPs. Thus, returning agricultural biomass carbon, particularly that produced by direct combustion, to farmland brought potential threat to drinking water safety.

Formation of halogenated macromolecular organics induced by Br- and I- during plasma oxidation/chlorination of DOM: Highlighting competitive mechanisms.

Understanding the effects of halogens on the production of macromolecular disinfection byproducts (DBPs) is critical for drinking water safety. The effects of Br- and I- on the chemical diversity of dissolved organic matter (DOM) during plasma preoxidation and the subsequent formation of macromolecular halogenated DBPs after chlorination were deciphered. Plasma preoxidation changed DOM diversity from aromatic component-oriented to lignin and tannin component-oriented, resulting in 62.0% and 21.2% decreases in N-DBPs (CkHnOmNzClx formulas) and C-DBPs (CkHnOmClx formulas) after chlorination, respectively. Br- could induce the formation of organobromine compounds (OBrCs) during plasma oxidation; however, the intensities of OBrCs decreased by 56.3% (CHO formulas) and 75.2% (CHON formulas) after further chlorination. OBrCs still accounted for 79.8% of the total organohalogen compounds (OXCs, X=Cl or Br) due to the higher substitutability of bromine. I-promoted OIC production in the DOM preoxidation process, and OICs acted as intermediates to form OClCs during chlorination. When Br-and I-coexisted, Br- promoted OIC production in the DOM preoxidation process; therefore, more OBrCs and OClCs were generated due to intermediates of OICs in subsequent chlorination. Connections between OXCs and their precursors were established using network computation. The precursors of OClCs were located in the aromatic structure region (0.2 < H/C ≤ 0.7; O/C ≤ 0.67); those of OBrCs and OICs were located in the lignin (0.7 < H/C ≤ 1.5; 0.1 < O/C < 0.67) and tannin (0.6 ≤ H/C ≤ 1.5, 0.67 < O/C < 1.0) regions with relatively greater H/C and O/C ratios, respectively.