title: Effect of replacing a hydroxyl group with a methyl group on arsenic (V) species adsorption on goethite (alpha-FeOOH).
abstract: Arsenate and methylated arsenicals, such as dimethylarsinate (DMA) and monomethylarsonate (MMA), are being found with increasing frequency in natural water systems. The mobility and bioavailability of these arsenic species in the environment are strongly influenced by their interactions with mineral surface, especially iron and aluminum oxides. Goethite (alpha-FeOOH), one of the most abundant ferric (hydr)oxides in natural systems, has a high retention capacity for arsenic species. Unfortunately, the sorption mechanism for the species is not completely understood, which limits our ability to model their behavior in natural systems. The purpose of this study is to investigate the effect of replacing a hydroxyl group with a methyl group on the adsorption behaviors of arsenic (V) species using adsorption edges, the influence of the background electrolyte on arsenic adsorption, and their effect on the zeta potential of goethite. The affinity of the three species to the goethite surface decreases in the order of AsO4=MMA>DMA. The uptake of DMA and MMA is independent of the concentration of background electrolyte, indicating that both species form inner-sphere complexes on the goethite surface and the most charge of adsorbed DMA and MMA locates at the surface plane. Arsenate uptake increases with increasing concentrations of background electrolyte at pH above 4, possibly due to that the charge of adsorbed arsenate is distributed between the surface plane and another electrostatic plane. DMA and lower concentrations of MMA have small effect on the zeta potential, whereas the zeta potential of goethite decreases in the presence of arsenate. The small effect on zeta potential of DMA or MMA adsorption suggests that the sorption sites for the anions is not important in controlling the surface charge. This observation is inconsistent with most adsorption models that postulate a singly coordinated hydroxyls contributing to both the adsorption and the surface charge, but supports the thesis that the charge on the goethite surface comes primarily from protonation of the triply bound oxygen atoms on the surface.
authors.affiliation: Department of Chemical & Biomolecular Engineering, National University of Singapore, 10 Kent Ridge Crescent, 119260 Singapore.
authors.forename: J S
authors.initials: JS
authors.lastname: Zhang
authors.forename: R S
authors.initials: RS
authors.lastname: Stanforth
authors.forename: S O
authors.initials: SO
authors.lastname: Pehkonen
mesh_terms: D000327:Adsorption; D001152:Arsenicals / Q000493:pharmacokinetics*; D002101:Cacodylic Acid / Q000493:pharmacokinetics*; D058085:Iron Compounds; D008903:Minerals; D013329:Structure-Activity Relationship
chemical_list: D001152:Arsenicals; D058085:Iron Compounds; D008903:Minerals; C094886:goethite; D002101:Cacodylic Acid; C020300:monomethylarsonic acid