Amorphous iron oxides protect aggregate-associated organic carbon from microbial utilization and decomposition evidenced from the natural abundance of 13C

Iron oxides play a critical role in promoting organic carbon sequestration through adsorption or co-precipitation. However, the effects of iron oxide types on the stabilization of aggregate-associated organic carbon are still poorly understood. We investigated the distribution of crystalline iron oxides (Fec), amorphous iron oxides (Feo), δ13C and Fe-bound OC in soil aggregate fractions of red earth (Ferrisol). The results showed that the δ13C values in microaggregate and silt+clay fractions were significantly lower than macro- and mesoaggregate (p < 0.05). The contents of Feo and Fe-bound OC in the microaggregate and silt+clay fractions were significantly higher than macro- and masoaggregate fractions (p < 0.05), while the content of Fec increased with the increase of aggregate size. The OC: Fe molar ratio of Feo was higher than Fec in all aggregate fractions. The FTIR spectroscopy analyses showed that polysaccharides had the highest proportion of all OC functional groups and increased with the increase of aggregate size. Likewise, the ratio of aromatic-C/aliphatic-C increased with the increase of aggregate size. Both Feo and Fe-bound OC had a significant negative correlation with δ13C values in microaggregate and silt+clay fractions, while Fec had no significant correlation with δ13C values in all aggregate fractions. Furthermore, the Fe-bound OC and fFe-bound OC were positively correlated with Feo and negatively correlated with Fec in all aggregate fractions. This study highlighted the importance of Feo in the sequestration of aggregate-associated organic carbon and confirmed the hypothesis that the SOC in microaggregates and silt+clay underwent less cycles of microbial utilization due to the protection of Feo, thereby limiting the molecular structure complexity and aromaticity of SOM.