Thermal Stability and Resistance to Biodegradation of Humic Acid Adsorbed on Clay Minerals

This article studies sorption regularities and evaluates thermal stability and resistance to microbial degradation of humic acid during three sorption cycles on bentonite clay, kaolinite, and muscovite using TGA/DSC, XRD, hydrophobic chromatography, light and electron microscopy, etc. The experiment revealed that kaolinite sorbed more humic acids (HAs) in terms of unit surface area (1.03 × 10−3 C, g/m2) compared to bentonite (0.35 × 10−3 C, g/m 10−3 g/m2). Sorption at pH 4.5 showed HA fractionation in amphiphilicity and chemical composition. HA was sorbed on the surface of all sorbents, mainly via hydrophobic components. No intercalation of HA into the interlayer spaces of montmorillonite was observed during sorption. Sorption via hydrophilic interactions was mostly performed on muscovite and bentonite rather than on kaolinite. Sorption of HA resulted in changes in its chemical composition and decreased C/N compared to free HA, which demonstrated selective sorption of nitrogen-containing compounds more typical of muscovite. All minerals adsorbed only a relatively thermolabile HA fraction, while its thermal stability increased compared to that before the experiment. The thermal stability and ratio of the Exo2/Exo1 peak areas on the DSC curves of sorbed HA increased with each subsequent sorption cycle. We revealed the following relationship between thermal stability and resistance to microbial oxidation of the sorbed HA: The higher the thermal stability, the less available the sorbed HA becomes for utilization by microorganisms.