As an important component of soil organic matter (SOM), the transformation of pyrogenic carbon plays a critical role in the biogeochemical cycles of carbon and other redox-active elements such as iron (Fe). Herein, we studied the influences of wheat straw-derived biochars on the microbial reduction of 100 mM of hematite by the dissimilatory metal reducing bacteria Shewanella oneidensis MR-1 under anoxic conditions. The long-term microbial reduction extent and initial reduction rate of hematite were accelerated by more than 2-fold in the presence of 10 mg L(-1) biochar. Soluble leachate from 10 mg L(-1) biochar enhanced Fe(III) reduction to a similar degree. Microbially prereduced biochar leachate abiotically reduced hematite, consistent with the apparent electron shuttling capacity of biochar leachate. Electron paramagnetic resonance (EPR) analysis suggested that biochar leachate-associated semiquinone functional groups were likely involved in the redox reactions. In addition to electron shuttling effects, biochar particles sorbed 0.5-1.5 mM biogenic Fe(II) and thereby increased the long-term extent of hematite reduction by 1.4-1.7 fold. Our results suggest that Fe redox cycling may be strongly impacted by pyrogenic carbon in soils with relatively high content of indigenous pyrogenic carbon or substantial application of biochar.

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Organo-mineral associations of organic carbon (OC) with iron (Fe) oxides play a major role in environmental OC sequestration, a process crucial to mitigating climate change. Calcium has been found to have high coassociation with OC in soils containing high Fe content, increase OC sorption extent to poorly crystalline Fe oxides, and has long been suspected to form bridging complexes with Fe and OC. Due to the growing realization that Ca may be an important component of C cycling, we launched a scanning transmission X-ray microscopy (STXM) investigation, paired with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, in order to spatially resolve Fe, Ca, and OC relationships and probe the effect of Ca on sorbed OC speciation. We performed STXM-NEXAFS analysis on 2-line ferrihydrite reacted with leaf litter-extractable dissolved OC and citric acid in the absence and presence of Ca. Organic carbon was found to highly associate with Ca ( R = 0.91). Carboxylic acid moieties were dominantly sequestered; however, Ca facilitated the additional sequestration of aromatic and phenolic moieties. Also, C NEXAFS revealed polyvalent metal ion complexation. Our results provide evidence for the presence of Fe-Ca-OC ternary complexation, which has the potential to significantly impact how organo-mineral associations are modeled.

Stabilization of organic matter in soil is important for natural ecosystem to sequestrate carbon and mitigate greenhouse gas emission. It is largely unknown what factors govern the preservation of organic carbon in soil, casting shadow on predicting the response of soil to climate change. Iron oxide was suggested as an important mineral preserving soil organic carbon. However, ferric minerals are subject to reduction, potentially releasing iron and decreasing the stability of iron-bound organic carbon. Information about the stability of iron-bound organic carbon in the redox reaction is limited. Herein, we investigated the sorptive interactions of organic matter with hematite and reductive release of hematite-bound organic matter. Impacts of organic matter composition and conformation on its sorption by hematite and release during the reduction reaction were analyzed. We found that hematite-bound aliphatic carbon was more resistant to reduction release, although hematite preferred to sorb more aromatic carbon. Resistance to reductive release represents a new mechanism that aliphatic soil organic matter was stabilized by association with iron oxide. Selective stabilization of aliphatic over aromatic carbon can greatly contribute to the widely observed accumulation of aliphatic carbon in soil, which cannot be explained by sorptive interactions between minerals and organic matter.

Degradation of three kinds of bioplastics and their effects on microbial biomass and microbial diversity in soil environment were analyzed. The degradation rate of bioplastic in soil was closely related to the main components in the bioplastics. Poly (butylene succinate)-starch (PBS-starch) and poly (butylene succinate) (PBS) were degraded by 1% to 7% after 28 days in a soil with an initial bacterial biomass of 1.4 × 10 9 cells/g-soil, however poly lactic acid (PLA) was not degraded in the soil after 28 days. When the powdered-bioplastics were examined for the degradation in the soil, PBS-starch also showed the highest degradability (24.4% degradation after 28 days), and the similar results were obtained in the case of long-term degradation experiment (2 years). To investigate the effect of bacterial biomass in soil on biodegradability of bioplastics, PBS-starch was buried in three kinds of soils differing in bacterial biomass (7.5 × 10 6 , 7.5 × 10 7 , and 7.5 × 10 8 cells/gsoil). The rate of bioplastic degradation was enhanced accompanied with an increase of the bacterial biomass in soil. 16S rDNA PCR-DGGE analysis indicated that the bacterial diversity in the soil was not affected by the degradation of bioplastics. Moreover, the degradation of bioplastic did not affect the nitrogen circulation activity in the soil.