Fulvic acid sorption on muscovite mica as a function of pH and time using in situ X-ray reflectivity

Interfacial structures of the basal surface of muscovite mica in 100 mg kg(-1) Elliott Soil Fulvic Acid II solutions were investigated using in Situ X-ray reflectivity. Molecular-scale variations in the thickness and internal structure of the fulvic acid (FA) film were observed and quantified as a function of pH (2-12) and reaction time (3-500 h at pH 3.7). At pH <= 6, the electron-density profile of the FA layer sorbed on the muscovite surface was composed of one near-surface peak followed by a broad peak that diminished in electron density with distance from the surface. The presence of the near-surface peak is attributed to condensation of FA molecules during sorption. The apparent thickness of the FA layer decreased from 12.3 to 7.2 to 6.4 angstrom as pH increased from 2 to 3.7 to 6, respectively. At pH >= 8.5, a distinct interfacial structure was observed, consisting of sharper peaks similar to those previously observed for muscovite in the absence of FA. These peaks are most likely composed of smaller aqueous species, such as H2O molecules, metal ion impurities from FA, and Na+ from NaOH. The FA sorbed on the muscovite Surface at pH 3.7 maintained a relatively constant thickness after 3 hours. However, the electron density of the near-surface FA peak increased by about 24% from 3 to 12 hours, and remained relatively constant from 12 to 500 hours. The electron density of the more distant part of the sorbed FA layer increased slightly after 12-50 hours of reaction but then decreased, and the broad peak flattened by 500 hours. Internal structural changes are possibly due to the slow sorption rate of FA molecules, or a fractionation effect, i.e., continuous substitution of smaller FA molecules by larger FA molecules.