Novel Chemical Routes for Carbon Dioxide and Methane Production from Lignin Photodegradation: The Role of Environmental Free Radicals.

Sunlight irradiation significantly mediates plant litter's carbon dynamics and volatile carbon release in semi-arid and arid ecosystems. In this process, carbon loss is controlled by lignin, but the mechanisms of production of CO2 and CH4 during lignin photolysis are ambiguous. In this study, the photomineralization of plant litter and the lignocellulosic component collectively indicate that lignin is a major source of CO2 and CH4 emissions. Characterization and free radical analysis reveal that the production of CO2 is due to the oxidation and ring-opening reaction of the coniferyl alcohol unit, with the subsequent decarboxylation of carboxylic acid as an oxidation product. This reaction involves o-quinone formation by the reactions between O2, superoxide radical (O2·-), and persistent free radicals (PFRs)-bearing lignin. Of this, O2·- contributes to 43.2% of the photogenerated CO2, as a new pathway, derived from the electron transfer from PFRs to O2. Interestingly, photoinduced demethylation of the dimethoxybenzene-type compounds as the photolysis products of lignin results in a never-before-reported CH4 formation chemical route independent of that of O2. This mechanistic insight into the role of lignin in volatile carbon production from the irradiative plant litter will contribute to a deeper understanding of carbon balance in water-limited ecosystems.

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.

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.

Toxic effects and primary source of the aged micro-sized artificial turf fragments and rubber particles: Comparative studies on laboratory photoaging and actual field sampling.

Numerous micro-sized artificial turf fragments (MATF) and rubber particles (MRP) are generated and accumulated during the use of the artificial playing field. However, attention has rarely been paid to the potential toxic effects of MATF and MRP on sportsmen. In this study, the active components and chemical composition of aged MATF and MRP derived from laboratory photoaging and actual field sampling were detected, and their effects on cytotoxicity were examined correspondingly. Laboratory photoaging significantly increased environmental persistent free radicals (EPFRs), reactive oxygen species (ROS) abundances and oxidative potential (OP) levels on MATF and MRP, but they have limited cytotoxicity. Unfortunately, in the actual field, aged MATF and MRP with higher heavy metals and polycyclic aromatic hydrocarbons (PAHs) contents exhibited markedly higher cytotoxicity with the survival rate of cells of 78 % and 26 % (p < 0.05), although they had lower EPFRs and ROS yields. Correlation analysis revealed that the cell viability was closely linked to heavy metals of MATF (p < 0.05), and to organic hydroperoxide (OHP), PAHs and heavy metals of MRP (p < 0.05). By systematically considering the above results, heavy metals and PAHs enriched on MATF and MRP from the surrounding environment played the important role in the cytotoxicity, which was different from conventional perspectives. Our findings demonstrate that MATF and MRP associated with an artificial turf field contain potent mixtures of pollutants and can, therefore, be relevant yet underestimated factors contributing to the health risks.

Distribution of persistent free radicals in different molecular weight fractions from peat humic acids and their impact in reducing goethite.

Humic substances, the most abundant component of soil organic matter, play vital roles in the biogeochemical cycles and pollutant redox reactions. However, the knowledge regarding the distribution of persistent free radicals (PFRs) and redox capacity in different molecular weight fractions (MWF) of humic acid (HA) and their impact on the transformation of iron oxide minerals remains unknown. In this study, we separated bulk HA into various MWF using dialysis methods and systematically investigated their PFRs properties, redox capacity, and the impact in reducing goethite. The results showed that the PFRs in the low MWF (<3500, <7000, and <14,000 Da) can be assigned to oxygen-centered organic radicals while those in the bulk and high MWF (14000-retentate) were assigned to carbon-centered organic radicals. The PFRs concentrations of low MWF were 0.20-0.45 × 1016 spins/g, far less than those of bulk HA (3.04 × 1016 spins/g) and 14000-retentate (1.30 × 1016 spins/g). The total concentrations of reactive oxygen species (ROS) induced by PFRs in HA fractions ranged from 8.04 × 1016 (in 14000-retentate) to 32.35 × 1016 spins/g (in bulk HA). Compared with the low MWF, the 14000-retentate fractions had the higher reducing capacity, which was positively related to the content of PFRs and phenolic hydroxyl in HA. The results obtained provide valuable insight into the geochemistry processes of Fe-containing minerals during their interaction with HA in the natural environment. Overall, the results obtained provide valuable insight into the geochemical behaviors of HA-associated PFRs under natural conditions.

Emergent dynamics of coordinated cells with time delays in a tissue.

In this article, we investigate the emergence of tissue dynamics with time delays of diffusion. Such emergent dynamics, describing the tissue homeostasis, usually correspond to particular tissue functions, which are attracting a tremendous amount of attention from both communities of mathematical modeling and systems biology. Specifically, in addition to the within-cell genome dynamics and the diffusion among the cells, we consider several types of time delays of diffusion present in the coordinated cells. We establish several generalized versions of the "monotonicity condition" (MC), whose traditional version [I. Rajapakse and S. Smale, Proc. Natl. Acad. Sci. U.S.A. 114, 1462-1467 (2017)] guaranteed the stability of the equilibrium in a system of coordinated cells without time delay. Indeed, we find that one generalized MC we establish still guarantees the stability of the time-delayed system's equilibrium, which corresponds to a formation of tissue functions depending primarily on individual genome dynamics but less on interacting structures and time delays of diffusion. We also find that, when the generalized MC is further relaxed, the system is able to sustain periodic oscillations, whose periods are verified to have delicate dependence with the selected time delays. These produced oscillations usually represent realistic behaviors of "alive" cells. We use several representative examples to demonstrate the usefulness of the established analytical conditions to the understanding of the emergent dynamics observed in computational models and in real systems as well.