Timescales of carbon turnover in soils with mixed crystalline mineralogies

Abstract

Organic matter–mineral associations stabilize much of the carbon (C) stored globally in soils. Metastable short-range-order (SRO) minerals such as allophane and ferrihydrite provide one mechanism for long-term stabilization of organic matter in young soil. However, in soils with few SRO minerals and a predominance of crystalline aluminosilicate or Fe (and Al) oxyhydroxide, C turnover should be governed by chemisorption with those minerals. Here, we correlate mineral composition from soils containing small amounts of SRO minerals with mean turnover time (TT) of C estimated from radiocarbon (¹⁴C) in bulk soil, free light fraction and mineral-associated organic matter. We varied the mineral amount and composition by sampling ancient soils formed on different lithologies in arid to subhumid climates in Kruger National Park (KNP), South Africa. Mineral contents in bulk soils were assessed using chemical extractions to quantify Fe oxyhydroxides and SRO minerals. Because of our interest in the role of silicate clay mineralogy, particularly smectite (2 : 1) and kaolinite (1 : 1), we separately quantified the mineralogy of the clay-sized fraction using X-ray diffraction (XRD) and measured ¹⁴C on the same fraction. <br><br> Density separation demonstrated that mineral associated C accounted for 40–70 % of bulk soil organic C in A and B1 horizons for granite, nephelinite and arid-zone gabbro soils, and &gt; 80 % in other soils. Organic matter strongly associated with the isolated clay-sized fraction represented only 9–47 % of the bulk soil C. The mean TT of C strongly associated with the clay-sized fraction increased with the amount of smectite (2 : 1 clays); in samples with &gt; 40 % smectite it averaged 1020 ± 460 years. The C not strongly associated with clay-sized minerals, including a combination of low-density C, the C associated with minerals of sizes between 2 µm and 2 cm (including Fe oxyhydroxides as coatings), and C removed from clay-sized material by 2 % hydrogen peroxide had TTs averaging 190 ± 190 years in surface horizons. Summed over the bulk soil profile, we found that smectite content correlated with the mean TT of bulk soil C across varied lithologies. The SRO mineral content in KNP soils was generally very low, except for the soils developed on gabbros under more humid climate that also had very high Fe and C contents with a surprisingly short, mean C TTs. In younger landscapes, SRO minerals are metastable and sequester C for long timescales. We hypothesize that in the KNP, SRO minerals represent a transient stage of mineral evolution and therefore lock up C for a shorter time. <br><br> Overall, we found crystalline Fe-oxyhydroxides (determined as the difference between Fe in dithionate citrate and oxalate extractions) to be the strongest predictor for soil C content, while the mean TT of soil C was best predicted from the amount of smectite, which was also related to more easily measured bulk properties such as cation exchange capacity or pH. Combined with previous research on C turnover times in 2 : 1 vs. 1 : 1 clays, our results hold promise for predicting C inventory and persistence based on intrinsic timescales of specific carbon–mineral interactions