Analyzing organic matter composition at intact biopore and crack surfaces by combining DRIFT spectroscopy and Pyrolysis‐Field Ionization Mass Spectrometry#

Abstract

AbstractIn the clay‐illuvial horizons (Bt) of Luvisols, surfaces of biopores and aggregates can be enriched in clay and organic matter (OM), relative to the bulk of the soil matrix. The OM composition of these coatings determines their bio‐physico‐chemical properties and is relevant for transport and transformation processes but is largely unknown at the molecular scale. The objective of this study was to improve the interpretation of spectra from Fourier transform infrared spectroscopy in diffuse reflectance mode (DRIFT) by using thermograms and released ion intensities obtained with pyrolysis‐field ionization mass spectrometry (Py‐FIMS) for a more detailed analysis of the mm‐scale spatial distribution of OM components at intact structural surfaces. Samples were separated from earthworm burrow walls, crack coatings, uncoated cracks, root channels, and pinhole fillings of the Bt‐horizons of Luvisols. The information from Py‐FI mass spectra enabled the assignment of OM functional groups also from spectral regions of overlapping DRIFT signal intensities to specific OM compound classes. In particular, bands from C=O and C=C bonds in the infrared range of wave numbers between 1,641 and 1,605 cm−1 were related to heterocyclic N‐compounds, benzonitrile, and naphthalene. The OM at earthworm burrow walls was composed of chemically labile aliphatic C‐rich and rather stable lignin and alkylaromatic compounds whereas the OM of thick crack coatings and pinholes was dominated by heterocyclic N and nitriles and high‐molecular compounds, likely originating from combustion residues. In combination with Py‐FIMS, DRIFT applications to intact samples seem promising for generating a more detailed mm‐scale spatial distribution of OM‐related sorption and wettability properties of crack and biopore surfaces that may serve as preferential flow paths in structured soils.