The relationship between soil organic matter (SOM) content and organic molecular assemblages (n‐alkane/alkenes pairs and n‐fatty acids) with soil water repellency (WR) in different sieve fractions (1–2, 0·25–1, 0·05–0·5 and <0·05 mm) was studied in sandy soils from the Doñana National Park (SW Spain) under four vegetation species: Quercus suber (QS), Pteridium aquilinum (PA), Pinus pinea (PP) and Halimium halimifolium (HH). The severity of soil WR [assessed according to the water drop penetration time (WDPT) test] was ordered according to the sequence QS > PA > PP > HH. A positive correlation was found between soil WR from each sieve fraction and SOM content. Most severe soil WR was detected in QS for all sieve fractions, followed by the finer fractions (<0·05 mm) from PA, PP and HH samples. The finer fraction had the highest SOM content, ranging between 20·9% (PP) and 46·9% (QS). Coarser PA, PP and HH soil fractions (1–2 mm) showed the highest long‐chain‐even C numbered fatty acids in the order PP > PA > HH. A significant correlation was observed between SOM content and the severity of soil WR in QS samples and finer fractions of soil under other vegetation (PA, PP and HH). Coarser fractions (1–2 mm) from PP, PA and HH 1–2 mm sieve fractions showed high severity of WR and relatively low SOM contents that could be explained by a low degree of evolution of the organic residues as seen by analytical pyrolysis, that is, higher alkane/alkene carbon preference index values and the presence of a higher diversity of fatty acid structures. Copyright © 2014 John Wiley & Sons, Ltd.

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Pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) of humic acids (HAs) from 30 agricultural soils from a volcanic island (Tenerife, Spain) was used to discern the molecular characteristics of soil organic matter (SOM) associated to resilience. For faster perceptual identification of the results, the yields of the pyrolysis products in the form of surface density plots were compared in an update of the Van Krevelen graphical statistical method. This approach, with respect to data reduction and visualization, was also used to collectively represent statistical indices that were obtained after simple and partial least squares (PLS) regression. The resulting plots illustrate different SOM structural domains (for example, carbohydrate- and lignin-derived and condensed lipid). The content of SOM and total mineralization coefficient (TMC) values can be well estimated from the relative abundance of 57 major pyrolysis compounds: SOM content and composition parallels the accumulation of lignin- and carbohydrate-derived structures (lignocellulosic material) and the depletion of condensed polyalkyl structures. In other words, in the volcanic ash soils that were studied, we found that the higher the amount of SOM, the lower its quality in terms of resilience. Although no cause-and-effect is inferred from this fact, it is evident that the resistance to biodegradation of the SOM is related to its molecular composition.

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