The effect of CO2 and oxidation rate on the formation of goethite versus lepidocrocite from an Fe(II) system at pH 6 and 7

Abstract

AbstractTo investigate the influence of carbonate on the formation of goethite and lepidocrocite, ∼200 samples were synthesized by oxidizing FeCl2 solutions with air/CO2 gas mixtures at ambient temperature and pH 6 and 7. The proportion of lepidocrocite in the lepidocrocite/goethite mixtures (Lp/(Lp + Gt)) decreased from 100 to 0% with increasing in solution and with decreasing average oxidation rate (AOR). These two parameters explained 81% of the variation of Lp/(Lp + Gt)). At a given , more goethite was formed at pH 6 than at pH 7. The Lp + Gt mixtures contained 0–8 mg g−1 carbon (Ct) which could not be removed by washing. Ct reached apparent saturation at a equilibrium concentration of ∼6–8 and 60–80 mmol l−1 at pH 6 and pH 7, respectively. In a plot of Ct vs. Lp/(Lp + Gt) all data fell on the same line irrespective of oxidation parameters (pH, AOR). IR spectra showed two broad bands at ∼1300 and 1500 cm−1 which can be assigned to distorted carbonate adsorbed at the goethite surface. Identical bands were also found in a young, poorly crystalline goethite formed from coal mine drainage in Ohio. It is suggested that carbonate anions direct the polymerization of the double bands of FeO3(OH)3 octahedra common to both minerals toward a corner sharing arrangement, and thereby to goethite, whereas chloride permits edge-sharing as in lepidocrocite.