Organo-mineral interactions and soil carbon mineralizability with variable saturation cycle frequency

The response of mineral-stabilized soil organic carbon (SOC) to environmental change is a source of uncertainty in the understanding of SOC cycling. Fluctuating wet-dry cycles and associated redox changes in otherwise well-drained soils may drive mineral dissolution, organic carbon (OC) mobilization, and subsequent OC mineralization. However, the extent to which rapid fluctuations between water-saturated and unsaturated conditions (i.e., flashy conditions) result in long-term changes in mineral composition and organo-mineral interactions is not well understood. In this study, the effect of variable saturation frequency on soil mineral composition, mineral-associated OC, and OC mineralizability was tested using selective dissolution, bulk spectroscopy, microscale imaging, and aerobic-anaerobic incubation experiments. Previous water table fluctuation measurements and diagnostic profile characteristics at Hubbard Brook Experimental Forest (NH) were used to identify soils with high, medium, and low saturation frequency regimes (defined by historical water table cycling frequency; i.e., water table presence and recession in the upper B horizon). We found the amount of OC released during extractions targeting non-crystalline minerals was of similar magnitude as extracted iron (Fe) in lower saturation frequency soils. However, the magnitude of extracted OC was 2.5 times greater than Fe but more similar to extractable aluminum (Al) in higher saturation frequency soils. Bulk soil Fe was spatially more strongly correlated to soil organic matter (SOM) in lower saturation frequency soils (Spearman Rank r(s) = 0.62, p < 0.005), whereas strong correlations between Al and SOM were observed in higher saturation frequency soils (r(s) = 0.88, p < 0.005) using nanoscale secondary ion mass spectrometry (NanoSIMS) imaging. Characterization of bulk soil Fe with X-ray absorption spectroscopy showed 1.2-fold greater Fe(II) and 1-fold lower contribution of Fe-organic bonding in soils with high saturation frequency. Fe(III) interactions with carboxylic and aromatic C were identified with C-13 nuclear magnetic resonance (NMR) spectroscopy Fe(III) interference experiments. Additionally, carboxylic acid enrichment in high saturation frequency soils quantified by C K-edge X-ray absorption spectroscopy point towards the role of carboxylic functional groups in Al-organic in addition to Fe-organic interactions. In our incubation experiments, a doubling in short-term CO2 evolution (per unit total soil C) was detected for high relative to low saturation frequency soils. Further, an order of magnitude increase in CO2 evolution (per unit water-extractable OC) following anaerobic incubation was only detected in high saturation frequency soils. The observed shift towards Al-dominated SOC interactions and higher OC mineralizability highlights the need to describe C stabilization in soils with flashy wet-dry cycling separately from soils with low saturation frequency or persistent saturation.