Effect of long-term straw return on organic matter transformation by hydroxyl radical during paddy soil oxygenation

Abstract

The generation of hydroxyl radicals (OH) mediated by Fe(II) has drawn increasing amounts of attention due to its significant role in the transformation of soil organic carbon (SOM) during redox fluctuations in paddy soil. This study further examined the effect of long-term (since 1984) straw return on Fe(II) on driving OH formation and SOM transformation upon paddy soils oxygenation. We found that long-term straw return could inhibit the OH and CO2 production in abiotic processes. The OH production decreased from 190.4 to 133.4 µM as the straw return amount increased from 0 to 19.16 t·hm−2·year−1. Moreover, 14.7–38.6 % of the CO2 production was associated with OH during oxygenation. By combining radical quenching and OM extraction, we determined that straw return could increase O2 reduction to H2O2 through a two-electron transfer pathway. Based on chemical extraction, Mössbauer spectra and multilinear regression model, we demonstrated that straw return resulted in more active Fe(II) species that controls the OH production. The results of 3DEEMs and FT-ICR MS showed that oxidative transformation can be accomplished by the introduction of OH to aromatic structures or olefins through ring opening and hydroxylation mechanisms. And OM at high straw return concentrations was likely oxidized by OH into bioavailable aliphatic compounds. Therefore, this study highlights the underappreciating effects of long-term straw return on Fe(II) oxidation in driving OH generation and SOM transformation in paddy soil redox fluctuation events.