The capacity of soil as a carbon (C) sink is mediated by interactions between organic matter and mineral phases. However, previously proposed layered accumulation of organic matter within aggregate organo–mineral microstructures has not yet been confirmed by direct visualization at the necessary nanometer-scale spatial resolution. Here, we identify disordered micrometer-size organic phases rather than previously reported ordered gradients in C functional groups. Using cryo-electron microscopy with electron energy loss spectroscopy (EELS), we show organo–organic interfaces in contrast to exclusively organo–mineral interfaces. Single-digit nanometer-size layers of C forms were detected at the organo–organic interface, showing alkyl C and nitrogen (N) enrichment (by 4 and 7%, respectively). At the organo–mineral interface, 88% (72–92%) and 33% (16–53%) enrichment of N and oxidized C, respectively, indicate different stabilization processes than at organo–organic interfaces. However, N enrichment at both interface types points towards the importance of N-rich residues for greater C sequestration.

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Variation in soil organic C (%OC) concentration has been associated with the concentration of reactive Fe-and Al-oxyhydroxide phases and exchangeable Ca, with the relative importance of these two stabilizing components shifting as soil pH moves from acid to alkaline. However, it is currently unknown if this pattern is similar or different with regard to measures of soil C persistence. We sampled soils from 3 horizons (uppermost A, uppermost B, C or lowest B horizons) across a pH gradient of 11 grass-dominated and 13 deciduous/mixed forest-dominated NEON sites to examine similarities and differences in the drivers of C concentration and persistence. Variation in C concentrations in all soils could be linked to abundances of Fe, Al and Ca, but were not significantly linked to variation in soil C persistence. Though pH was related to variation in D 14 OC, higher persistence was associated with more alkaline pH values. In forested soils, depth explained 75% of the variation in D 14 OC (p \ 0.0001), with no significant additional correlations with extractable metal phases. In grasslands, soil organic C persistence was not associated with exchangeable Ca concentrations, but instead was explained by depth and inorganic C concentrations (R 2 = 0.76, p \ 0.0001), implying stabilization of organic C through association with carbonate

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 welldrained 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 Feorganic bonding in soils with high saturation frequency. Fe(III) interactions with carboxylic and aromatic C were identified with 13 C 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 Feorganic interactions. In our incubation experiments, a doubling in short-term CO 2 evolution (per unit total soil C) was detected for high relative to low saturation frequency soils. Further, an order of magnitude increase in CO 2 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.

The rarity of rapid campaigns to characterize soils across scales limits opportunities to investigate variation in soil carbon stocks (SOC) storage simultaneously at large and small scales, with and without site-level replication. We used data from two complementary campaigns at 40 sites in the United States across the National Ecological Observatory Network (NEON), in which one campaign sampled profiles from closely co-located intensive plots and physically composited similar horizons, and the other sampled dozens of pedons across the landscape at each site. We demonstrate some consistencies between these distinct designs, while also revealing that within-site replication reveals patterns and predictors of SOC stocks not detectable with non-replicated designs. Both designs demonstrate that SOC stocks of whole soil profiles vary across continental-scale climate gradients. However, broad climate patterns may mask the importance of localized variation in soil physicochemical properties, as captured by within-site sampling, especially for SOC stocks of discrete genetic horizons. Within-site replication also reveals examples in which expectations based on readily explained continental-scale patterns do not hold. For example, even wide-ranging drainage class sequences within landscapes do not duplicate the clear differences in profile SOC stocks across drainage classes at the continental scale, and physicochemical factors associated with increasing B horizon SOC stocks at continental scales frequently do not follow the same patterns within landscapes. Because inferences from SOC studies are a product of their context (where, when, how), this study provides context—in terms of SOC stocks and the factors that influence them—for others assessing soils and the C cycle at NEON sites.

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Mineral stabilization of soil organic matter is an important regulator of the global carbon (C) cycle. However, the vulnerability of mineral-stabilized organic matter (OM) to climate change is currently unknown. We examined soil profiles from 34 sites across the conterminous USA to investigate how the abundance and persistence of mineral-associated organic C varied with climate at the continental scale. Using a novel combination of radiocarbon and molecular composition measurements, we show that the relationship between the abundance and persistence of mineral-associated organic matter (MAOM) appears to be driven by moisture availability. In wetter climates where precipitation exceeds evapotranspiration, excess moisture leads to deeper and more prolonged periods of wetness, creating conditions which favor greater root abundance and also allow for greater diffusion and interaction of inputs with MAOM. In these humid soils, mineral-associated soil organic C concentration and persistence are strongly linked, whereas this relationship is absent in drier climates. In arid soils, root abundance is lower, and interaction of inputs with mineral surfaces is limited by shallower and briefer periods of moisture, resulting in a disconnect between concentration and persistence. Data suggest a tipping point in the cycling of mineral-associated C at a climate threshold where precipitation equals evaporation. As climate patterns shift, our findings emphasize that divergence in the mechanisms of OM persistence associated with historical climate legacies need to be considered in process-based models.

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