Thermal Stability of Goethite-Bound Natural Organic Matter Is Impacted by Carbon Loading

Dissolved natural organic matter (NOM) sorption at mineral surfaces can significantly affect the persistence of organic carbon in soils and sediments. Consequently, determining the mechanisms that stabilize sorbed NOM is crucial for predicting the persistence of carbon in nature. This study determined the effects of loadings and pH on the thermal stability of NOM associated with synthetic goethite (α-FeOOH) particle surfaces, as a proxy for NOM-mineral interactions taking place in nature. NOM thermal stability was investigated using temperature-programmed desorption (TPD) in the 30-700 °C range to collect vibration spectra of thermally decomposing goethite-NOM assemblages, and to concomitantly analyze evolved gases using mass spectrometry. Results showed that NOM thermal stability, indicated by the range of temperatures in which CO2 evolved during thermal decomposition, was greatest in unbound NOM and lowest when NOM was bound to goethite. NOM thermal stability was also loading dependent. It decreased when loadings were in increased the 0.01 to 0.42 mg C m(-2) range, where the upper value corresponds to a Langmuirian adsorption maximum. Concomitant Fourier transform infrared (FTIR) spectroscopy measurement showed that these lowered stabilities could be ascribed to direct NOM-goethite interactions that dominated the NOM binding environment. Mineral surface interactions at larger loadings involved, on the contrary, a smaller fraction of the sorbed NOM, thus increasing thermal stability toward that of its unbound counterpart. This study thus identifies a sorption threshold below which NOM sorption to goethite decreases NOM thermal stability, and above which no strong effects are manifested. This should likely influence the fate of organic carbon exposed to thermal gradients in natural environments.