title: Silicic acid competes for dimethylarsinic acid (DMA) immobilization by the iron hydroxide plaque mineral goethite.
abstract: A surface complexation modeling approach was used to extend the knowledge about processes that affect the availability of dimethylarsinic acid (DMA) in the soil rhizosphere in presence of a strong sorbent, e.g., Fe plaques on rice roots. Published spectroscopic and molecular modeling information suggest for the organoarsenical agent to form bidentate-binuclear inner-sphere surface complexes with Fe hydroxides similar to the inorganic As oxyanions. However, since also the ubiquitous silicic acid oxyanion form the same bidentate binuclear surface complexes, our hypothesis was that it may have an effect on the adsorption of DMA by Fe hydroxides in soil. Our experimental batch equilibrium data show that DMA is strongly adsorbed in the acidic pH range, with a steep adsorption edge in the circumneutral pH region between the DMA acidity constant (pKa=6.3) and the point of zero charge value of the goethite adsorbent (pHpzc=8.6). A 1-pK CD-MUSIC surface complexation model was chosen to fit the experimental adsorption vs. pH data. The same was done for silicic acid batch equilibrium data with our goethite adsorbent. Both model parameters for individual DMA and silicic acid adsorption were then merged into one CD-MUSIC model to predict the binary DMA+Si adsorption behavior. Silicic acid (500 μM) was thus predicted by the model to strongly compete for DMA with up to 60% mobilization of the latter at a pH6. This model result could be verified subsequently by experimental batch equilibrium data with zero adjustable parameters. The thus quantified antagonistic relation between DMA and silicic acid is discussed as one of factors to explain the increase of the DMA proportion in rice grains as observed upon silica fertilization of rice fields.
authors.affiliation: Geosciences Institute, Johannes Gutenberg-University, Mainz 55099, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Kersten
authors.affiliation: UFZ - Helmholtz Centre for Environmental Research, Department of Analytical Chemistry, Permoserstrasse 15, 04318 Leipzig, Germany.
authors.forename: Birgit
authors.initials: B
authors.lastname: Daus
mesh_terms: D000327:Adsorption; D002101:Cacodylic Acid / Q000737:chemistry*; D058085:Iron Compounds / Q000737:chemistry*; D008903:Minerals / Q000737:chemistry*; D008958:Models, Molecular; D012824:Silicic Acid / Q000737:chemistry*; D013499:Surface Properties
chemical_list: D058085:Iron Compounds; D008903:Minerals; C094886:goethite; D012824:Silicic Acid; D002101:Cacodylic Acid
keywords: Adsorption; Arsenic; CD-MUSIC; DMA; Goethite; Paddy soil; Plaques; Rice