Recent laboratory and field studies show the need to consider the formation of aqueous Mn(III)-siderophore complexes in manganese (Mn) and iron (Fe) geochemical cycling, a shift from the historical view that aqueous Mn(III) species are unstable and thus unimportant. In this study, we quantified Mn and Fe mobilization by desferrioxamine B (DFOB), a terrestrial bacterial siderophore, in single (Mn or Fe) and mixed (Mn and Fe) mineral systems. We selected manganite (γ-MnOOH), δ-MnO2, lepidocrocite (γ-FeOOH), and 2-line ferrihydrite (Fe2O3·0.5H2O) as relevant mineral phases. We found that DFOB mobilized Mn(III) as Mn(III)-DFOB complexes to varying extents from both Mn(III,IV) oxyhydroxides but reduction of Mn(IV) to Mn(III) was required for the mobilization of Mn(III) from δ-MnO2. The initial rates of Mn(III)-DFOB mobilization from manganite and δ-MnO2 were not affected by the presence of lepidocrocite but decreased by a factor of 5 and 10 for manganite and δ-MnO2, respectively, in the presence of 2-line ferrihydrite. Additionally, the decomposition of Mn(III)-DFOB complexes through Mn-for-Fe ligand exchange and/or ligand oxidation led to Mn(II) mobilization and Mn(III) precipitation in the mixed-mineral systems (∼10% (mol Mn/mol Fe)). As a result, the concentration of Fe(III) mobilized as Fe(III)-DFOB decreased by up to 50% and 80% in the presence of manganite and δ-MnO2, respectively, compared to the single mineral systems. Our results demonstrate that siderophores, through their complexation of Mn(III), reduction of Mn(III,IV), and mobilization of Mn(II), can redistribute Mn to other soil minerals and limit the bioavailability of Fe in natural systems.

Organo-mineral and organo-metal associations play an important role in the retention and accumulation of soil organic carbon (SOC). Recent studies have demonstrated a positive correlation between calcium (Ca) and SOC content in a range of soil types. However, most of these studies have focused on soils that contain calcium carbonate (pH > 6). To assess the importance of Ca-SOC associations in lower pH soils, we investigated their physical and chemical interaction in the grassland soils of Point Reyes National Seashore (CA, USA) at a range of spatial scales. Multivariate analyses of our bulk soil characterisation dataset showed a strong correlation between exchangeable Ca (Ca_Exch; 5-8.3 c.mol_c kg^-1) and SOC (0.6-4%) content. Additionally, linear combination fitting (LCF) of bulk Ca K-edge X-ray absorption near-edge structure (XANES) spectra revealed that Ca was predominantly associated with organic carbon across all samples. Scanning transmission X-ray microscopy near-edge X-ray absorption fine structure spectroscopy (STXM C/Ca NEXAFS) showed that Ca had a strong spatial correlation with C at the microscale. The STXM C NEXAFS K-edge spectra indicated that SOC had a higher abundance of aromatic/olefinic and phenolic C functional groups when associated with Ca, relative to C associated with Fe. In regions of high Ca-C association, the STXM C NEXAFS spectra were similar to the spectrum from lignin, with moderate changes in peak intensities and positions that are consistent with oxidative C transformation. Through this association, Ca thus seems to be preferentially associated with plant-like organic matter that has undergone some oxidative transformation, at depth in acidic grassland soils of California. Our study highlights the importance of Ca-SOC complexation in acidic grassland soils and provides a conceptual model of its contribution to SOC preservation, a research area that has previously been unexplored.

Supplementary information

The online version contains supplementary material available at 10.1007/s10533-023-01059-2.