Molecular mechanisms and biomineralization processes of ferromanganese nodule formation: Insights its effect on nutrient imbalance and heavy metal immobilization in native soil profiles

Abstract

Ferromanganese nodules (FMNs), simultaneously termed as manganese nodules, are metallic concretions typically found in the B horizon of iron and manganese-rich soils. These nodules are primarily formed through the biomineralization process driven by favorable redox reactions and microbial activity. The formation of FMNs in the soil is governed by complex geochemical interactions and influenced by both biotic and abiotic factors, such as temperature, pH, organic matter, redox potential (Eh), wet/dry cycles, and nucleation sites. FMNs typically vary in size, ranging from a few microns to several centimeters, and exhibit diverse shapes, from spherical to irregular. These nodules play a crucial role in nutrient cycling and the adsorption of heavy metals, including phosphorus, lead, copper, zinc, cobalt, and nickel, thereby improving soil quality and preventing metal leaching into aquatic environments. The ion exchange during redox reactions, complexation, occlusion, and adsorption are the key mechanisms through which heavy metals can become immobilized in soil FMNs. The formation of FMNs involves Mn-oxidizing bacteria, such as Bacillus, Pedomicrobium, Erythrobacter, Pseudomonas putida, Geobacter, and Leptothrix discophora, which use specific functional genes such as mnxG, moxA, mopA, CumA, ombB, omaB, OmcB, and mofA to facilitate manganese oxidation. This process reacts with geological material, resulting in the precipitation of metal leachates and the development of metal oxide coatings that serve as nucleation sites for FMNs. Such microbial activities are not only essential for FMNs formation but also for trapping heavy metals in soil, highlighting their importance in soil biogeochemical cycling and ecological functions. However, further research is needed to unravel the complex biogeochemical interactions that influence FMNs growth and composition, as well as to understand the stabilization and release dynamics of nutrients and heavy metals, and the roles of microbial communities and functional genes involved in these processes, particularly in relation to soil fertility and plant nutrition.