Catalytic and biocatalytic degradation of microplastics.

In recent years, there has been a surge in annual plastic production, which has contributed to growing environmental challenges, particularly in the form of microplastics. Effective management of plastic and microplastic waste has become a critical concern, necessitating innovative strategies to address its impact on ecosystems and human health. In this context, catalytic degradation of microplastics emerges as a pivotal approach that holds significant promise for mitigating the persistent effects of plastic pollution. In this article, we critically explored the current state of catalytic degradation of microplastics and discussed the definition of degradation, characterization methods for degradation products, and the criteria for standard sample preparation. Moreover, the significance and effectiveness of various catalytic entities, including enzymes, transition metal ions (for the Fenton reaction), nanozymes, and microorganisms are summarized. Finally, a few key issues and future perspectives regarding the catalytic degradation of microplastics are proposed.

Urban Stormwater Phosphorus Export Control: Comparing Traditional and Low-impact Development Best Management Practices.

Data from the International Stormwater Best Management Practices (BMP) Database were used to compare the phosphorus (P) control performance of six categories of stormwater BMPs representing traditional systems (stormwater pond, wetland basin, and detention basin) and low-impact development (LID) systems (bioretention cell, grass swale, and grass strip). Machine learning (ML) models were trained to predict the reduction or enrichment factors of surface runoff concentrations and loadings of total P (TP) and soluble reactive P (SRP) for the different categories of BMP systems. Relative to traditional BMPs, LIDs generally enriched TP and SRP concentrations in stormwater surface outflow and yielded poorer P runoff load control. The SRP concentration reduction and enrichment factors of LIDs also tended to be more sensitive to variations in climate and watershed characteristics. That is, LIDs were more likely to enrich surface runoff SRP concentrations in drier climates, when inflow SRP concentrations were low, and for watersheds exhibiting high impervious land cover. Overall, our results imply that stormwater BMPs do not universally attenuate urban P export and that preferentially implementing LIDs over traditional BMPs may increase TP and SRP export to receiving freshwater bodies, hence magnifying eutrophication risks.

Mollisol Erosion-Driven Efflux of Energetic Organic Carbon and Microflora Increases Greenhouse Gas Emissions from Cold-Region Rivers.

Massive soil erosion occurs in the world's Mollisol regions due to land use change and climate warming. The migration of Mollisol organic matter to river systems and subsequent changes in carbon biogeochemical flow and greenhouse gas fluxes are of global importance but little understood. By employing comparative mesocosm experiments simulating varying erosion intensity in Mollisol regions of northeastern China, this research highlights that erosion-driven export and biomineralization of terrestrial organic matter facilitates CO2 and CH4 emission from receiving rivers. Stronger Mollisol erosion, as represented by a higher soil-to-water ratio in suspensions, increased CO2 efflux, particularly for the paddy Mollisols. This is mechanistically attributable to increased bioavailability of soluble organic carbon in river water that is sourced back to destabilized organic matter, especially from the cultivated Mollisols. Concurrent changes in microbial community structure have enhanced both aerobic and anaerobic processes as reflected by the coemission of CO2 and CH4. Higher greenhouse gas effluxes from paddy Mollisol suspensions suggest that agricultural land use by supplying more nitrogen-containing, higher-free-energy organic components may have enhanced microbial respiration. These new findings highlight that Mollisol erosion is a hidden significant contributor to greenhouse gas emissions from river water, given that the world's four major Mollisol belts are all experiencing intensive cultivation.

Soil respiration induces co-emission of greenhouse gases and methylated selenium from cold-region Mollisols: Significance for selenium deficiency.

Mollisols rich in natural organic matter are a significant sink of carbon (C) and selenium (Se). Climate warming and agricultural expansion to the cold Mollisol regions may enhance soil respiration and biogeochemical cycles, posing a growing risk of soil C and Se loss. Through field-mimicking incubation experiments with uncultivated and cultivated soils from the Mollisol regions of northeastern China, this research shows that soil respiration remained significant even during cold seasons and caused co-emission of greenhouse gases (CO2 and CH4) and methylated Se. Such stimulus effects were generally stronger in the cultivated soils, with maximum emission rates of 7.45 g/m2/d C and 1.42 µg/m2/d Se. For all soil types, the greatest co-emission of CO2 and dimethyl selenide occurred at 25 % soil moisture, whereas measurable CH4 emission was observed at 40 % soil moisture with higher percentages of dimethyl diselenide volatilization. Molecular characterization with three-dimensional fluorescence and ultra-high resolution mass spectrometry suggests that CO2 emission is sensitive to the availability of microbial protein-like substances and free energy from organic carbon biodegradation under variable moisture conditions. Predominant Se binding to biodegradable organic matter resulted in high dependence of Se volatilization on rates of greenhouse gas emissions. These findings together highlight the importance of dynamic organic carbon quality for soil respiration and consequent Mollisol Se loss risk, with implications for science-based management of C and Se resources in agricultural lands to combat with Se deficiency.

Co-precipitation of iron and silicon: Reaction kinetics, elemental ratios and the influence of phosphorus.

A sufficient supply of dissolved silicon (DSi) relative to dissolved phosphorus (DP) may decrease the likelihood of harmful algal blooms in eutrophic waters. Oxidative precipitation of Fe(II) at oxic-anoxic interfaces may contribute to the immobilization of DSi, thereby exerting control over the DSi availability in the overlying water. Nevertheless, the efficacy of DSi immobilization in this context remains to be precisely determined. To investigate the behavior of DSi during Fe(II) oxidation, anoxic solutions containing mixtures of aqueous Fe(II), DSi, and dissolved phosphorus (DP) were exposed to dissolved oxygen (DO) in the batch system. The experimental data, combined with kinetic reaction modeling, indicate that DSi removal during Fe(II) oxidation occurs via two pathways. At the beginning of the experiments, the oxidation of Fe(II)-DSi complexes induces the fast removal of DSi. Upon complete oxidation of Fe(II), further DSi removal is due to adsorption to surface sites of the Fe(III) oxyhydroxides. The presence of DP effectively competes with DSi via both of these pathways during the initial and later stages of the experiments, with as a result more limited removal of DSi during Fe(II) oxidation. Overall, we conclude that at near neutral pH the oxidation of Fe(II) has considerable capacity to immobilize DSi, where the rapid homogeneous oxidation of Fe(II)-DSi results in greater DSi removal compared to surface adsorption. Elevated DP concentration, however, effectively outcompetes DSi in co-precipitation interactions, potentially contributing to enhanced DSi availability within aquatic systems.

Effects of riboflavin and desferrioxamine B on Fe(II) oxidation by O2.

Flavins and siderophores secreted by various plants, fungi and bacteria under iron (Fe) deficient conditions play important roles in the biogeochemical cycling of Fe in the environment. Although the mechanisms of flavin and siderophore mediated Fe(III) reduction and dissolution under anoxic conditions have been widely studied, the influence of these compounds on Fe(II) oxidation under oxic conditions is still unclear. In this study, we investigated the kinetics of aqueous Fe(II) (17.8 µM) oxidation by O2 at pH 5‒7 in the presence of riboflavin (oxidized (RBF) and reduced (RBFH2)) and desferrioxamine B (DFOB) as representative flavins and siderophores, respectively. Results showed that the addition of RBF/RBFH2 or DFOB markedly accelerates the oxidation of aqueous Fe(II) by O2. For instance, at pH 6, the rate of Fe(II) oxidation was enhanced 20‒70 times when 10 µM RBFH2 was added. The mechanisms responsible for the accelerated Fe(II) oxidation are related to the redox reactivity and complexation ability of RBFH2, RBF and DFOB. While RBFH2 does not readily complex Fe(II)/Fe(III), it can activate O2 and generate reactive oxygen species, which then rapidly oxidize Fe(II). In contrast, both RBF and DFOB do not reduce O2 but react with Fe(II) to form RBF/DFOB-complexed Fe(II), which in turn accelerates Fe(II) oxidation. Furthermore, the lower standard reduction potential of the Fe(II)-DFOB complex, compared to the Fe(II)-RBF complex, correlates with a higher oxidation rate constant for the Fe(II)-DFOB complex. Our study reveals an overlooked catalytic role of flavins and siderophores that may contribute to Fe(II)/Fe(III) cycling at oxic-anoxic interfaces.