Evidence that co-existing cadmium and microplastics have an antagonistic effect on greenhouse gas emissions from paddy field soils.

Accumulation of microplastics (MPs) and cadmium (Cd) are ubiquitous in paddy soil. However, the combined effects of MPs and Cd on physiochemical and microbial mechanisms in soils and the attendant implications for greenhouse gas (GHG) emissions, remain largely unknown. Here, we evaluated the influence of polylactic acid (PLA) and polyethylene (PE) MPs on GHG emissions from Cd-contaminated paddy soil using a microcosm experiment under waterlogged and drained conditions. The results showed that PLA significantly increased CH4 and N2O emission fluxes and hence the global warming potential (GWP) of waterlogged soil. Soils treated with MPs+Cd showed significantly reduced GWP compared to those treated only with MPs suggesting that, irrespective of attendant consequences, Cd could alleviate N2O emissions in the presence of MPs. Conversely, the presence of MPs in Cd-contaminated soils tended to alleviate the bioavailability of Cd. Based on a structural equation model analysis, both the MPs-derived dissolved organic matter and the soil bioavailable Cd affected indirectly on soil GHG emissions through their direct influencing on microbial abundance (e.g., Firmicutes, Nitrospirota bacteria). These findings provide new insights into the assessment of GHG emissions and soil/cereal security in response to MPs and Cd coexistence that behaved antagonistically with respect to adverse ecological effects in paddy systems.

Tetrabromobisphenol A transformation by biochar supported post-sulfidated nanoscale zero-valent iron: Mechanistic insights from shell control and solvent kinetic isotope effects.

Post-sulfidated nanoscale zero-valent iron with a controlled FeSX shell thickness deposited on biochar (S-nZVI/BC) was synthesized to degrade tetrabromobisphenol A (TBBPA). Detailed characterizations revealed that the increasing sulfidation degree altered shell thickness/morphology, S content/speciation/distribution, hydrophobicity, and electron transfer capacity. Meanwhile, the BC improved electron transfer capacity and hydrophobicity and inhibited the surface oxidation of S-nZVI. These properties endowed S-nZVI/BC with highly reactive (∼8.9-13.2 times) and selective (∼58.4-228.9 times) over nZVI/BC in TBBPA transformation. BC modification improved the reactivity and selectivity of S-nZVI by 1.77 and 1.96 times, respectively. The difference of S-nZVI/BC in reactivity was related to hydrophobicity and electron transfer, particularly FeSX shell thickness and morphology. Optimal shell thickness of ∼32 nm allowed the maximum association between Fe0 core and exterior FeSX, resulting in superior reactivity. A thicker shell with abundant networks increased the roughness but decreased the surface area and electron transfer. The higher [S/Fe]surface and [S/Fe]particle were conducive to the selectivity, and [S/Fe]particle was more influential than [S/Fe]surface on selectivity upon similar hydrophobicity. The solvent kinetic isotope effects (SKIEs) exhibited that increasing [S/Fe]dose tuned the relative contributions of atomic H and electron in TBBPA debromination but failed to alter the dominant debromination pathway (i.e., direct electron transfer) in (S)-nZVI/BC systems. Mechanism of electron transfer rather than atomic H contributed to higher selectivity. This work demonstrated that S-nZVI/BC was a prospective material for the remediation of TBBPA-contaminated groundwater.