Rejuvenation of iron oxides enhances carbon sequestration by the ‘iron gate’ and ‘enzyme latch’ mechanisms in a rice-wheat cropping system

The 'enzyme latch' theory believes that oxygen constraints on phenol oxidase can restrain the activity of hydrolytic enzymes responsible for decomposition, while the 'iron (Fe) gate' theory suggests that Fe oxidation can decrease phenol oxidase activity and enhance Fe-lignin complexation under oxygen exposure. The objective of this study was to explore the roles of the 'enzyme latch' and 'Fe gate' mechanisms in regulating soil organic carbon (SOC) sequestration in a rice-wheat cropping system subjected to six fertilization treatments: control (CT), chemical fertilizer (CF), CF plus manure (CFM), CF plus straw (CFS), CF plus manure and straw (CFMS), and CF plus organic-inorganic compound fertilizer (OICF). Soil samples were collected after the rice and wheat harvests and wet sieved into large macroaggregates, small macroaggregates, microaggregates, and silt and clay particles. Variations in amorphous and free Fe oxides, Fe-bound organic carbon and phenol oxidase activity were examined. After nine years, compared with the initial soil, the activation degree of free Fe oxides increased by 1.3- to 1.6-fold and the topsoil SOC stock increased by 13-61% across all treatments. Amorphous Fe oxide content, phenol oxidase activity and aggregate mean-weight diameter were higher after the wheat harvest than after the rice harvest. Amorphous Fe oxide content was positively correlated with Fe-bound organic carbon content (P < 0.001) but negatively correlated with phenol oxidase activity (P < 0.001). Therefore, seasonal alternation of wetting and drying can progressively drive the rejuvenation of Fe oxides and simultaneously affect the activity of phenol oxidase. Oxidative precipitation of amorphous Fe oxides promoted the formation of organo-Fe complexes and macroaggregates, while flooding of the paddies decreased the activity of phenol oxidase, thereby resulting in year-round hindered decomposition. Organic fertilization strengthened the roles of the 'Fe gate' and 'enzyme latch' mechanisms, and thus accelerated SOC sequestration in the rice-wheat cropping system.