Summary Measuring the specific surface area (SSA) of soils that contain much organic matter (OM) is problematic. The adsorption of p‐nitrophenol (pNP) from xylene at room temperature yielded realistic values for the SSA of a wide range of clays, oxides and subsoils. Here we have extended the same measurement to some topsoils with varied OM content, texture and clay mineral composition. Specifically, we have compared the surface areas measured by adsorption of N2, and, applying the BET equation, with the values obtained by adsorption of pNP, before and after treatment of the samples with hydrogen peroxide. In all instances, the removal by H2O2 of organic matter – albeit in part only – led to a marked increase in the SSAs measured by nitrogen because of the exposure of micropores previously blocked or covered by OM. The surface areas measured by pNP were appreciably larger than those obtained by the standard BET equation, and showed little change after removal of organic matter. However, the surface area of two smectite‐rich samples measured by pNP increased substantially after peroxidation, presumably because smectite crystals decomposed during treatment with H2O2. The results suggest that, under the experimental conditions used, pNP could diffuse without hindrance into and through organic matter, enabling it to adsorb on to micropore surfaces within clay aggregates (domains). In keeping with this suggestion, the relation between the surface areas measured by pNP and the corresponding values calculated from the clay and OM contents, and clay mineral composition, of the soils was close to 1:1. An even stronger relation was observed between the measured and calculated values for cation exchange capacity.

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The shallow soils of Pianosa-a small calcareous island in the Mediterranean Sea, facing Tuscany, central Italy-developed under the same pedogenic factors with the exception of vegetation and, in the last two centuries, human impact. Originally, they were covered by ''macchia,'' a tangled mix of bushy species, or, in a few more fertile sites, by Quercus ilex L. Currently there are six land uses on the island: (1) pristine macchia, (2) groves of Olea europaea L. totally reinvaded by macchia, (3) degraded residual thickets of Q. ilex, (4) cropland, (5) recently abandoned pastures, and (6) stands of Pinus halepensis Mill. The related soils were analysed by solid-state cross polarisation/magic angle spinning 13 C-nuclear magnetic resonance (NMR) to compare the spectroscopic properties of their organic pool. The prevalence of O-alkyl C over other C forms is evident in all cases, while there is large variability with respect to the alkyl C to aromatic C ratio between both the different soils, and the horizons of a same soil. On the whole, the results show that on Pianosa Island, human impact has profoundly altered not only the amount but also the quality of soil organic matter (SOM). The SOM residual of the dichromate oxidation in the Walkley-Black method-a widely used method to measure soil organic C-was also analysed by NMR. It comprised almost exclusively alkyl C and aromatic C, as a result of the removal of carbonyl and O-alkyl C. Most of the aromatic C seems to belong to charcoal.

Detailed maps of soil C are needed to guide sustainable soil uses and management decisions. The quality of soil C maps of Italian Mediterranean areas may be improved and the sampling density reduced using secondary data related to the nature of the ecosystem. The current study was conducted to determine: (i) the improvements obtainable in mapping soil C over a Mediterranean island by using ecosystem features and (ii) the effect of different sampling densities on the map accuracy. This work relied on field sampling (n=164) of soil properties measured over the island of Pianosa (Central Italy). Statistical analysis assessing the relationship between soil properties and ecosystem features revealed that the conceptual model of ecosystems defined on the basis of environmental features such as vegetation cover, land use, and soil type was mainly related to the variation of soil organic carbon (OC) content and to the type of Mediterranean environment. The distribution of ecosystems was used to improve the accuracy of soil OC maps obtainable by a simple interpolation approach (ordinary kriging). Substantial improvement was obtained by: (i) stratification into ecosystem types and (ii) applying locally calibrated regressions to satellite imagery that introduced both inter-ecosystem and intra-ecosystem information linked to vegetation features. This study showed that interpolation methods using information on ecosystem distribution can produce accurate maps of soil OC in Mediterranean environments, mostly because of the linkage between soil OC and vegetation types, which are spatially fragmented and heterogeneous.