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 δ ¹³C 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 δ ¹³C 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 δ ¹³C values. Bulk SOC content was twice as high in the CaCO₃-bearing profiles, which also had lower bulk δ ¹³C 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 δ ¹³C 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 δ ¹³C values.

Supplementary information

The online version of this article (10.1007/s10533-021-00779-7) contains supplementary material, which is available to authorized users.

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.

Grasslands are one of the most common land-cover types, providing important ecosystem services globally, yet few studies have examined grassland critical-zone functioning throughout hillslopes. This study characterised a coastal grassland over a small hillslope at Point Reyes National Seashore, California, using multidisciplinary techniques, combining remotely-sensed, geophysical, plant, and soil measurements. Clustering techniques delineated the study area into four landscape zones, up-, mid-, and down-slope, and a bordering riparian ecotone, which had distinct environmental properties that varied spatially across the site, with depth, and time. Soil moisture increased with depth and down slope towards a bordering riparian zone, and co-varied with soil CO2 flux rates both spatially and temporally. This highlighted three distinct controls of soil moisture on soil respiration: CO2 fluxes were inhibited by high moisture content in the down-slope during the wet winter months, and converged across landscape positions in the dry summer months, while also displaying post-rain pulses. The normalised difference vegetation index (NDVI) ranged from 0.32 (September)–0.80 (April) and correlated positively with soil moisture and aboveground biomass, moving down slope. Yet, NDVI, aboveground biomass, and soil moisture were not correlated to soil organic carbon (SOC) content (0.4%–4.5%), which was highest in the mid-slope. The SOC content may instead be linked to shifts in dominant grassland species and their rhizosphere properties with landscape position. This multidisciplinary characterisation highlighted significant heterogeneity in grassland properties with landscape position, and demonstrated an approach that could be used to characterise other critical-zone environments on hillslopes.