Accumulation of organic compounds in paddy soils after biochar application is controlled by iron hydroxides

Soil acidity is one of the vital factors that influence organic matter transformation and accumulation. Long-term studies on the mechanisms of biochar's effects on soil organic matter (SOM) accumulation dependent on pH values are lacking. A four-year column experiment was conducted without and with biochar application (11.3 Mg ha^-1 crop^-1) in acid (pH = 5.24) and alkaline (pH = 8.22) soils under paddy rice/wheat annual rotation. To explore organic matter accumulation mechanisms, SOM pools were extracted (physical-chemical fractionation) and their chemical structures were analyzed using advanced solid-state ¹³C nuclear magnetic resonance (¹³C NMR) techniques. Biochar increased the proportion of aromatic carbon (C) in all SOM pools, which led to an increased C content in two soils. The elevated pH after biochar application (∆pH = 1.03) increased Fe (III) oxidation and precipitation, and therefore, stimulated amorphous Fe content in 53-μm pool in the acid soil. This change increased the interaction between organic compounds and Fe (hydr)oxide, which impeded bacteria access to substrates, and in turn, promoted SOM accumulation in the acid soil. Conversely, low Fe (hydr)oxide availability resulted in the decomposition of the labile substrates (di-O-alkyl C, NCH, and OCH) in mobile humic acids via microbial respiration, thereby lowering the effect of SOM sequestration in the alkaline soil. Our study revealed that organic matter accumulation after biochar amendment is not solely dependent on the chemical recalcitrance of biochar, but also is controlled by the transformation of Fe (hydr)oxide in SOM pools.