Phosphate and glyphosate adsorption by hematite and ferrihydrite and comparison with other variable-charge minerals

Abstract

AbstractAdsorption by synthetic 2-line ferrihydrite and hematite of glyphosate and phosphate, separately and together, was compared with adsorption results for goethite, gibbsite and two kaolinites in order to determine adsorption differences and similarities, in particular competition and phosphate preference, of these variable-charge minerals. Hematite rapidly adsorbed both compounds, while adsorption by ferrihydrite was slow, in particular of glyphosate, probably because of very slow diffusion of the bulky glyphosate molecules into interior sites in ferrihydrite particles. Accordingly, the Langmuir adsorption capacity of glyphosate (GAC) was considerably smaller (1.85 µmol m−2)than GAC for hematite (2.61 µmol m−2). The phosphate adsorption capacities (PAC) for ferrihydrite and hematite were more alike, 2.91 µmol m−2 and 2.85 µmol m−2, respectively. Differences between surface coordination (mono- or bidentate) may also contribute to the observed differences but conflicting information about the nature of the surface complexes makes this a difficult contributary factor to assess. The minerals were found to exhibit great variation in extent of competition and phosphate preference. Little competition and phosphate preference characterized hematite adsorption, while phosphate almost completely outcompeted glyphosate on goethite; ferrihydrite adsorption fell between these extremes. These differences may be attributed to different numbers of common (competitive) and specific (selective) adsorption sites on the three Fe oxides with a decreasing number of common sites in the order: goethite>>ferrihydrite>hematite, i.e. almost all goethite sites are common but with strong phosphate preference, while most hematite sites are specific for either glyphosate or phosphate. Alternatively, the result may be explained by adsorption in more planes, e.g. glyphosate adsorption onto the inner-Helmholtz-plane-adsorbed phosphate. For all six minerals compared, desorption of glyphosate following phosphate addition was found to be significantly correlated with the difference between the amounts of phosphate and glyphosate adsorbed indicating that this difference may be used as a competition index for predicting the influence of phosphate on glyphosate adsorption.