Soils play an essential role in the global cycling of carbon and understanding the stabilisation mechanisms behind the preservation of soil organic carbon (SOC) pools is of globally recognised significance. Until recently, research into SOC stabilisation has predominantly focused on acidic soil environments and the interactions between SOC and aluminium (Al) or iron (Fe). The interactions between SOC and calcium (Ca) have typically received less attention, with fewer studies conducted in alkaline soils. Although it has widely been established that exchangeable Ca (Ca Exch ) positively correlates with SOC concentration and its resistance to oxidation, the exact mechanisms behind this relationship remain largely unidentified. This synthesis paper critically assesses available evidence on the potential role of Ca in the stabilisation of SOC and identifies research topics that warrant further investigation. Contrary to the common view of the chemistry of base cations in soils, chemical modelling indicates that Ca 2? can readily exchange its hydration shell and create inner sphere complexes with organic functional groups. This review therefore argues that both inner-and outer-sphere bridging by Ca 2? can play an active role in the stabilisation of SOC. Calcium carbonate (CaCO 3 ) can influence occluded SOC stability through its role in the stabilisation of aggregates; however, it could also play an unaccounted role in the direct sorption and inclusion of SOC. Finally, this review highlights the importance of pH as a potential predictor of SOC stabilisation mechanisms mediated by Al-or Fe-to Ca, and their respective effects on SOC dynamics.

The largest terrestrial carbon sink on earth is soil carbon stocks. As the climate changes, the rate at which the Earth’s climate warms depends in part on the persistence of soil organic carbon. Microbial turnover forms the backbone of soil organic matter (SOM) formation and it has been recently proposed that SOM molecular complexity is a key driver of stability. Despite this, the links between microbial diversity, chemical complexity and biogeochemical nature of SOM remain missing. Here we tested the hypotheses that distinct microbial communities shape the composition of SOM, and microbial-derived SOM has distinct decomposition potential depending on its community of origin. We inoculated microbial communities of varying diversities into a model soil matrix amended with simple carbon (cellobiose) and measured the thermal stability of the resultant SOM. Using a Rock-Eval® ramped thermal analysis, we found that microbial community composition drives the chemical fingerprint of soil carbon. While diversity was not a driver of SOM composition, bacteria-only communities lead to more thermally labile soil C pools than communities with bacteria and fungi. Our results provide direct evidence for a link between microbial community structure, SOM composition, and thermal stability. This evidence demonstrates the relevance of soil microorganisms in building persistent SOM stocks.

Geochemical indicators are emerging as important predictors of soil organic carbon (SOC) dynamics, but evidence concerning the role of calcium (Ca) is scarce. This study investigates the role of Ca prevalence in SOC accumulation by comparing otherwise similar sites with (CaCO3-bearing) or without carbonates (CaCO3-free). We measured the SOC content and indicators of organic matter quality (C stable isotope composition, expressed as δ13C values, and thermal stability) in bulk soil samples. We then used sequential sonication and density fractionation (DF) to separate two occluded pools from free and mineral-associated SOC. The SOC content, mass, and δ13C values were determined in all the fractions. X-ray photoelectron spectroscopy was used to investigate the surface chemistry of selected fractions. Our hypothesis was that occlusion would be more prevalent at the CaCO3-bearing site due to the influence of Ca on aggregation, inhibiting oxidative transformation, and preserving lower δ13C values. Bulk SOC content was twice as high in the CaCO3-bearing profiles, which also had lower bulk δ13C values, and more occluded SOC. Yet, contrary to our hypothesis, occlusion only accounted for a small proportion of total SOC (< 10%). Instead, it was the heavy fraction (HF), containing mineral-associated organic C, which accounted for the majority of total SOC and for the lower bulk δ13C values. Overall, an increased Ca prevalence was associated with a near-doubling of mineral-associated SOC content. Future investigations should now aim to isolate Ca-mediated complexation processes that increase organo-mineral association and preserve organic matter with lower δ13C values.

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