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Specific surface area can be a strong predictor of organic carbon (SOC) contents in soils. Specific surface area can be estimated reliably and cost‐effectively from water adsorption by air‐dry soil samples, but SOC itself can also adsorb water. For estimating the mineral component of specific surface area, it is, therefore, necessary to exclude water‐adsorption by SOC. Here, we refer to “apparent specific surface area” for measurements that include water adsorption by both mineral soil and SOC. We used a mathematical approach to estimate water adsorption by SOC so that this component can be subtracted from measurements of apparent specific surface area. We used a dataset of apparent specific surface area and soil carbon at seven depths from 50 soil cores collected from a research farm in the Manawatu region in New Zealand. Both apparent specific surface area and SOC content decreased with soil depth with very high correlation (r² = 0.98). We estimated the SOC contribution to apparent specific surface area from the slope of the relationship between changes in apparent specific surface area and SOC content. For our soils, the SOC contribution to apparent specific surface area was estimated as 0.43 ± 0.02 m² mgC⁻¹. This parameter allows apparent specific surface area measurements to be corrected for the water adsorption by SOC to calculate the functionally relevant mineral specific surface area. HIGHLIGHTS: Soil surface area can be estimated from the H₂O content of air‐dry soil but SOC also adsorbs H₂O. We developed a mathematical approach to estimate water adsorption by SOC. We estimated the contribution of SOC to apparent specific surface area as 0.43 ± 0.02 m² mgC⁻¹. Mineral specific surface area can be inferred by subtracting SOC‐based H₂O adsorption.

In principle, greenhouse gas emissions can be offset by increasing soil carbon stocks. Full utilisation of that potential, however, requires a good understanding of the controls on carbon stocks to identify factors that can be modified through management changes and distinguish those from factors that are inherent soil properties that cannot be modified. Here, we present a conceptual model of protected (or stabilised) carbon stocks in soils based on observations from two farms in New Zealand, and from a combined soils data set from observations from throughout New Zealand. These data showed that 1) When other factors, such as climate, plant cover and pasture management, were identical, soil carbon stocks were highly, and linearly correlated with the soil's specific surface area estimated from soil water adsorption. 2) The slopes of these relationships decreased with soil depth. 3) Extrapolation of the relationships to zero specific surface area resulted in relatively small intercepts on the soil carbon axis. These intercepts decreased with soil depth. 4) The intercepts were considered to correspond to unprotected labile carbon, with highest contents near the soils surface where most carbon inputs are received by soils. 5) Together, these observations implied that virtually all protected carbon in the analysed soils was protected by the soil matrix rather than biochemically, and that mineral surface area was the functionally relevant key attribute that defined the soils' protective capacity. 6) It implied that protected organic carbon, C p , in a soil can be described as: C p = k C i n A m / f ( T , W , pH , A l , … ) , where k is a simple constant, C i n is the total carbon inflow rate into the soil, A m is specific surface area, and f(T, W, pH, Al, …) is a specific turn-over rate of protected carbon as a function of temperature, soil water, pH, aluminium concentration, or any other factors apart from soil texture that may affect soil-carbon turn-over rates. These observations improve our understanding of the important carbon-protection mechanisms in the soil, with significant implications for the optimal manipulation of carbon input rates into different soils to maximise overall soil carbon storage. They imply that overall carbon storage of soils could be enhanced by physically transferring any available carbon from soils with low to soils with high specific surface areas.

Subsoil carbon is generally older and decomposes more slowly than topsoil carbon. It has, therefore, been suggested that carbon stocks could be increased by burying carbon-rich topsoil at depth to slow its decomposition. This has been supported by recent experiments that showed that buried topsoil carbon indeed decomposed more slowly, but the mechanisms causing the reduction have not yet been identified. We investigated three theoretical mechanisms that may explain reduced decomposition rates at depth: (1) lower soil-temperature variability, (2) lower oxygen concentrations/redox potential and (3) less priming (biological synergy). Temperature variability decreases with soil depth. As decomposition rates vary non-linearly with temperature, reduced temperature variability should, therefore, reduce annual decomposition rates. However, detailed simulations showed that it changed annual decomposition rates by only a few percent. Maximal decomposition rates also require adequate oxygen, but our simulations showed that oxygen diffusion rates would need to be reduced 1000 to 10 000-fold compared to the topsoil for it to protect buried soil carbon. Oxygen limitation is, therefore, likely to be confined to soils that are water-logged for extended periods. Priming (or biological synergy) is assumed to be the stimulation of decomposition rates by the availability of labile organic carbon. Our simulations showed that lower labile carbon inputs could reduce priming and potentially preserve up to half of buried carbon for centuries. If experimental work can further substantiate the role of this mechanism, carbon burial at depth could become a practical and useful climate-change mitigation option.

Conversion of soils supporting native vegetation to agricultural production has led to a loss of soil carbon stocks. Replacing a portion of the lost stocks will sequester atmospheric carbon with the concurrent benefit of enhancing soil sustainability. The ability of the fine fraction of soils (≤50-µm fraction) to adsorb organic carbon (OC) is considered a key mechanism capable of stabilising soil OC against loss. The difference between the current and maximum concentrations of OC in the soil fine fraction (FFC) has been termed the ‘saturation deficit’ (SatDef) and used to define the potential for a soil to sequester carbon. For New Zealand surface 0–15 cm soil layers, pedotransfer functions have been derived to quantify the soil carbon SatDef. The ability of combining infrared spectroscopy (IR) with partial least squares regression (PLSR) to derive predictive algorithms for soil properties included in these pedotransfer functions, the capacity of the soil fine fraction to stabilise carbon and the SatDef of the soil fine fraction were assessed in this study. A total of 168 air-dried and finely ground New Zealand surface soils representative of the major soil orders used for agricultural production were included. Principal components analysis of IR spectra showed a grouping by soil order that was related to mineralogy. Predictive IR/PLSR algorithms were derived for specific surface area, pyrophosphate-extractable aluminium, the FFC content, the 90th quantile regression of FFC and the SatDef of the fine fraction (R2 values ≥0.85; ratio of performance to interquartile range values ≥2.9). The results indicate that IR/PLSR provides a rapid and cost-effective mechanism for deriving information related to the amount of FFC in soils and the SatDef of the fine fraction. The IR/PLSR approach could be used to define the potential of soils to sequester carbon and identify the soil types to target for carbon sequestration technologies. The approach would also generate valuable data for soil carbon in national inventories or national soil condition monitoring programs.

In New Zealand, pastoral soils have substantial organic carbon (OC) stocks, which may be vulnerable to loss from disturbance and environmental perturbations. We assessed OC vulnerability using two approaches. For the first approach, we postulated that the OC deficit of continuously cropped soils relative to nearby pastoral soils would provide a measure of the quantity of potentially vulnerable OC in pastures. As a test, soils were sampled to a depth of 15 cm at 149 sites and the total organic carbon (TOC) and particulate organic carbon (POC) contents were measured. The second approach involved measurement of OC mineralisation in a laboratory assay (98 day aerobic incubation at 25°C). For the pastoral soils, the mean TOC and POC was about twice that of the cropped soils. On average, 89% more OC was mineralised from the pastoral soils compared with the cropped counterparts. However, the quantity of OC mineralised in pasture soils was small relative to the potential for OC loss inferred from the difference in TOC between pastoral and cropped soils. Carbon mineralisation was explained using a two-pool exponential model with rate constants of the ‘fast’ and ‘slow’ pools equating to 0.36 ± 0.155 and 0.007 ± 0.003 day–1 respectively. The larger, slow OC pool correlated strongly with hot water extractable OC whereas the fast pool was related to OC extracted using cold water. Our results suggest that water extraction (using cold and hot water) can provide a rapid estimate of the quantity of mineralisable OC across a wide range of New Zealand soils.