Molecular characteristics of permanganate- and dichromate-oxidation-resistant soil organic matter from a black-C-rich colluvial soil

Abstract

Samples from a colluvial soil rich in pyrogenic material (black C, BC) in north-west Spain were subjected to K2Cr2O7 and KMnO4 oxidation and the residual soil organic matter (SOM) was NaOH-extracted and analysed using analytical pyrolysis–gas chromatography–mass spectroscopy (Py-GC/MS) and solid-state 13C cross-polarisation magic angle spinning–nuclear magnetic resonance (13C CP MAS-NMR) in order to study the susceptibility of different SOM fractions (fresh, degraded/microbial, BC and aliphatic) towards these oxidising agents. Untreated samples that were NaOH-extracted were also analysed. The Py-GC/MS and 13C NMR indicated that KMnO4 promotes the oxidation of carbohydrate products, mostly from degraded/microbial SOM and lignocellulose, causing a relative enrichment of aliphatic and aromatic structures. Residual SOM after K2Cr2O7 oxidation contained BC, N-containing BC and aliphatic structures. This was corroborated by a relatively intense resonance of aromatic C and some signal of alkyl C in 13C NMR spectra. These results confirm that dichromate oxidation residues contain a non-pyrogenic fraction mainly consisting of aliphatic structures.