Molecular composition and possible transformations of labile soil organic matter fractions in Mediterranean arable soils: Relevance and implications

Abstract

With the increased global interest in sequestering carbon in soil, it is necessary to understand the composition of different pools of soil organic matter (SOM) that cycle over suitably short timeframes. To explore in detail the chemical composition of agroecologically relevant yet distinct fractions of SOM, the light fraction of SOM (LFOM), the 53-μm particulate organic matter (POM), and the mobile humic acid (MHA) fractions were sequentially extracted from agricultural soils and characterized using both ¹³C cross polarization magic angle spinning nuclear magnetic resonance (CPMAS NMR) spectroscopy and also Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The NMR results showed a decrease in the O-alkyl C region assigned to carbohydrates (51-110 ppm) and an increase in the aromatic region (111-161 ppm) proceeding from the LFOM to the POM and then to the MHA fraction. Similarly, based on the thousands of molecular formulae assigned to the peaks detected by FT-ICR-MS, condensed hydrocarbons were dominant only in the MHA, while aliphatic formulae were abundant in the POM and LFOM fractions. The molecular formulae of the LFOM and POM were mainly grouped in the high H/C lipid-like and aliphatic space, whereas a portion of the MHA compounds showed an extremely high (17-33, average of 25) double bond equivalent (DBE) values, corresponding to low H/C values of 0.3-0.6, representative of condensed hydrocarbons. The labile components appeared most pronounced in the POM (93% of formulae have H/C ≥ 1.5) similar to the LFOM (89% of formulae have H/C ≥ 1.5) but in contrast to the MHA (74% of formulae have H/C ≥ 1.5). The presence of both labile and recalcitrant components in the MHA fraction suggests that the stability and persistence of soil organic matter is influenced by a complex interaction of physical, chemical, and biological factors in soil. Understanding the composition and distribution of different SOM fractions can provide valuable insights into the processes that govern carbon cycling in soils, which can help inform strategies for sustainable land management and climate change mitigation.

Keywords: (13)C CPMAS NMR; Condensed hydrocarbons; Double bond equivalent; ESI-FT-ICR-MS; Soil management.