Sorptive stabilization of organic matter by microporous goethite: sorption into small pores vs. surface complexation

Stabilization of organic matter (OM) by sorption to minerals is thought to be due to (i) sorption into small pores (O < 50 nm) that prevents hydrolytic enzymes approaching and decomposing the organic substrate or (ii) reduced availability of organic molecules after formation of strong multiple bonds by complexation of organic ligands at mineral surfaces. We tested these two potential mechanisms by studying the binding of dissolved OM to microporous goethite (alpha-FeOOH). The size of organic molecules dissolved prior to and after equilibration with goethite was determined using atomic force microscopy (AFM). The goethite-OM complexes were analysed for bulk and surface elemental composition (by X-ray photoelectron spectroscopy, XPS), specific surface area (SSA) and mesopore and micropore volumes (by N-2 adsorption/desorption), by scanning electron microscopy (SEM), and by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. The absolute density of goethite-OM complexes was determined by gas pycnometry and the sorbed OM's apparent density was calculated by assuming no major changes in the volumes of the goethite upon sorption of OM. The stability of the OM-mineral interactions was tested in desorption experiments and by treatment with NaOCl. Surface accumulation of OM by sorption decreased the N-2-accessible SSA of the goethite, mostly because micropores (O < 2 nm) were rendered inaccessible to N-2. The decrease in accessibility of micropores was most pronounced at small surface OM concentrations. The majority of dissolved organic molecules detected with AFM prior to interaction with goethite were globular with a diameter of 4-10 nm, the rest were mainly linear, 20-100 nm long and 4-8 nm thick. After contact with goethite, the latter type of molecules dominated, which suggests preferential sorption of globular molecules. Their size exceeded or equalled the size of micropores and small mesopores (O < 10 nm) and so sorption therein is unlikely. Also, the changes in volumes of pores with a size of 2-50 nm were smaller than the estimated volume of the OM sorbed. The apparent density of sorbed OM always exceeded that of the freeze-dried OM and was largest at small surface concentrations. DRIFT spectroscopy showed that most carboxyl groups at the goethite surface were in their complexed form. The proportion of complexed carboxyl groups dropped at larger surface concentrations, parallel to the decrease in micropore volume. Thus, micropores seem to favour the formation of multiple complex bonds per molecule. Scanning electron microscopy showed that at small surface concentrations, OM coated the goethite crystals and crystallites tightly, while at larger surface concentrations bulky accumulations of OM were more abundant. Even strongly desorbing reagents such as NaOH and Na pyrophosphate released only part of the sorbed OM. Treatment with NaOCl removed mainly bulky accumulations of OM; the OM tightly bound to goethite crystals was hardly affected by NaOCl. We conclude that molecules tightly bound via multiple complex bonds, probably at the mouths of small pores, are barely desorbable and resist the attack of chemical reagents and probably also of enzymes.