Controlled experimental soil organic matter modification for study of organic pollutant interactions in soil

Abstract

Interactions of organic pollutants with soil organic matter can be studied by adsorption of the pollutants on well-characterized soil samples with constant mineralogy but different organic matter compositions. Therefore, the objectives of the current study are establishing a set of different, well-characterized soil samples by systematic modifications of their organic matter content and molecular composition and prove these modifications by advanced complementary analytical techniques. Modifications were done by off-line pyrolysis and removal/addition of hot-water extracted organic fraction (HWE) from/to the original soil sample. Both pyrolysis-field ionization mass spectrometry (Py-FIMS) and synchrotron-based C- and N- X-ray absorption near-edge structure spectroscopy (XANES) were applied to investigate the composition of the soil organic matter. These complementary analytical methods in addition to elemental analysis agreed in showing the following order of organic matter contents: pyrolyzed soil<soil residue<original soil<soil+3 HWE<soil+6 HWE<HWE. The addition of HWE to the soil sample increases the relative proportions of carbohydrates, N-containing heterocyclic compounds and peptides, and decreases the relative proportions of phenols, lignin monomers and dimers, and lipids. The most abundant organic compound classes in the pyrolyzed sample are aromatics, aliphatic nitriles, aldehydes, five- and six-membered N-containing heterocyclic compounds, and aliphatic carboxylic acids. It can be expected that removal or addition of HWE, that mimic biomass inputs to soil or soil amendments, change the binding capacity for organic pollutants less intensively than heat impact, e.g. from vegetation burning. It will be possible to interpret kinetic data on the pollutants adsorption by these original and modified soil samples on the basis of the bond- and element-specific speciation data through C-XANES and N-XANES and the molecular-level characterization through Py-FIMS. Finally, this combination of analytical techniques can be recommended for similar problems that require characterizing the bulk, non-extracted SOM instead of pre-selected compounds or compound classes.