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- Nelson, Hanna, 1976-, et al.
(författare)
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Surface complexation modelling of arsenate and copper adsorbed at the goethite/water interface
- 2013
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Ingår i: Applied Geochemistry. - Oxford : Elsevier. - 0883-2927 .- 1872-9134. ; 35, s. 64-74
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Tidskriftsartikel (refereegranskat)abstract
- The co-adsorption of Cu(II) and arsenate onto the surface of goethite has been studied by performing adsorption experiments and potentiometric titrations, and a surface complexation model has been developed to describe the experimental results. Models for the binary systems, Cu-goethite and arsenate-goethite, were acquired separately and the model parameters were then included in the ternary system, together with the solubility products of solid Cu(II) arsenates reported in the literature. The adsorption of Cu(II) was described applying a model in which Cu(II) forms bidentate bridging mono- and binuclear surface complexes. According to recent interpretations of ATR-FTIR and EXAFS data the arsenate ions are assumed to be coordinated in a monodentate fashion to singly coordinated hydroxyl groups at the surface, and hydrogen-bonded to neighbouring triply coordinated surface oxide sites. In the case of co-adsorption of Cu(II) and arsenate, the adsorption could not be predicted by applying the combined model from the two binary systems. Two ternary Cu(II)-arsenate-goethite surface complexes must be included, one complex in which an arsenate ion is coordinating to surface Fe(III) (≡FeOAsO3Cu0.5-) and one complex in which arsenate is bound to the surface by coordinating to an adsorbed Cu(II) ion (≡(Fe3OFeOH)Cu2(OH)2HAsO41-). No solid Cu (II) arsenate phases were formed under the experimental conditions in the present study. From constructed predominance area diagrams, the significance of adsorption and precipitation processes are discussed. Furthermore, calculated solubility of Cu(II) and As(V) is used to indicate optimum conditions for the cleaning of contaminated natural waters.
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| 2. |
- Nelson, Hanna, 1976-
(författare)
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Modelling precipitation and surface complexation reactions in systems with Goethite, Cu(II) and Oxyanions Containing As(V) or P(V)
- 2012
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The aqueous solubility of oxyanion (e.g. phosphates and arsenates), and thereby their mobility, bioavailability (phosphates) and toxicity (arsenates), in soils and sediments is dependent upon their chemical speciation. In complex, multicomponent systems, equilibrium modelling can be a useful tool to predict chemical speciation. When establishing a model, it is essential to understand the interactions between all the components not only in solution but also on mineral surfaces at a molecular level. By applying surface complexation models processes at mineral surfaces can be accounted for. This thesis is a summary of four papers and focuses on surface complexation of the oxyanions arsenate, phosphate and monomethyl phosphate adsorbed onto the surface of goethite (α-FeOOH). Furthermore, adsorption and precipitation of copper(II) arsenates from aqueous solutions has been studied. Solid copper(II) arsenates obtained in precipitation experiments were characterised and five different solid phases with different Cu(II) to As(V) ratio, as well as proton and Na +content, were identified; Cu5Na(HAsO4)(AsO4)3(s), Cu5Na2(AsO4)4(s), Cu3(AsO4)2(s), Cu3(AsO4)(OH)3(s) and Cu2(AsO4)(OH)(s). The adsorption of arsenate and copper(II) to the goethite surface, could not be predicted by only applying the combined model from the two binary systems, arsenate-goethite and copper(II)-goethite. Instead, two ternary copper-arsenate-goethite surface complexes were added. In one of the surface complexes arsenate is bound to goethite surface via a copper(II) ion coordinating to surface hydroxyl groups and in the other surface complex, copper(II) is coordinating arsenate bound to the goethite surface. Surface complexation models, in agreement with macroscopic data and detailed spectroscopic results, were designed for monomethyl phosphate, phosphate and arsenate adsorbed to goethite. The models contain monodentate inner sphere surface complexes stabilized by hydrogen bonding to neighbouring surface sites. The charge distribution of the complexes was assigned according to Pauling’s valence bond theory. The monomethyl phosphate model consists of three singly protonated surface isomers, only differentiated by the location of the proton . In the case of phosphate and arsenate, six surface complexes, including two pair-wise surface isomers, are suggested to form; ≡FeOAsO 32.5-; (≡FeOAsO3; ≡Fe3OH)2-;(≡FeOAsO3H; ≡Fe3O)2-; (≡FeOAsO3H; ≡Fe3OH)1-; (≡FeOAsO3H2; ≡Fe3O)1- and ≡FeOAsO3H20.5-. A combination of structural information from spectroscopic measurements and quantitative data from spectroscopy, potentiometry and adsorption experiments provides a better understanding of the complexity of the coordination chemistry of particle surfaces and forms the basis for equilibrium models with high physical/chemical relevance.
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| 3. |
- Persson, Per, et al.
(författare)
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Surface complexes of monomethyl phosphate stabilized by hydrogen bonding on goethite (α-FeOOH) nanoparticles
- 2012
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Ingår i: Journal of Colloid and Interface Science. - : Elsevier. - 0021-9797 .- 1095-7103. ; 386:1, s. 350-358
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Tidskriftsartikel (refereegranskat)abstract
- Typically, a significant fraction of phosphorus in soils is composed of organic phosphates, and this fraction thus plays an important role in the global phosphorus cycle. Here we have studied adsorption of monomethyl phosphate (MMP) to goethite (α-FeOOH) as a model system in order to better understand the mechanisms behind adsorption of organic phosphates to soil minerals, and how adsorption affects the stability of these molecules. The adsorption reactions and stability of MMP on goethite were studied at room temperature as a function of pH, time and total concentration of MMP by means of quantitative batch experiments, potentiometry and infrared spectroscopy. MMP was found to be stable at the water-goethite interface within the pH region 3-9 and over extended periods of time, as well as in solution. The infrared spectra indicated that MMP formed three predominating pH-dependent surface complexes on goethite, and that these interacted monodentately with surface Fe. The complexes differed in hydrogen bonding interactions via the auxiliary oxygens of the phosphate group. The presented surface complexation model was based on the collective spectroscopic and macroscopic results, using the Basic Stern approach to describe the interfacial region. The model consisted of three monodentate inner sphere surface complexes where the MMP complexes were stabilized by hydrogen bonding to a neighboring surface site. The three complexes, which had equal proton content and thus could be defined as surface isomers, were distinguished by the distribution of charge over the 0-plane and β-plane. In the high pH-range, MMP acted as a hydrogen bond acceptor whereas it was a hydrogen bond donor at low pH.
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| 4. |
- Nelson, Hanna, et al.
(författare)
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Composition and solubility of precipitated copper(II) arsenates
- 2011
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Ingår i: Applied Geochemistry. - : Elsevier. - 0883-2927 .- 1872-9134. ; 26:5, s. 696-704
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Tidskriftsartikel (refereegranskat)abstract
- Equilibrium reactions involving Cu(II) and As(V) have been studied with respect to formation of complexes in aqueous solutions as well as formation of solid phases. Potentiometric titrations performed at 25 °C (I = 0.1 M Na(Cl)) and at different Cu to As ratios gave no evidence for the existence of Cu(II) arsenate complexes in solution below the pH of the precipitation boundaries (pH ≈ 4), irrespective of the Cu to As ratio and pH. Mixing of solutions of Cu(II) and As(V) at different proportions and adjusting pH to values ranging from 4 to 9 resulted in precipitation of five different solid phases. The elemental composition of the solids was determined using X-ray Photoelectron Spectroscopy, and Environmental Scanning Microscopy–Field Emission Gun equipped with an energy dispersive spectroscopy detector. The average Cu/As ratio was determined by dissolving the solids. Total soluble concentrations of the components Cu(II) and As(V), as well as the basicity of the solid phases were determined by analysis of aqueous solutions. Based upon these experimental data the stoichiometric composition of the solid phases and their stability were determined. The resulting equilibrium model includes the solid phases Cu3(AsO4)2, Cu3(AsO4)(OH)3, Cu2(AsO4)(OH), Cu5Na(HAsO4)(AsO4)3 and Cu5Na2AsO4)4, where Cu5Na(HAsO4)(AsO4)3 and Cu5Na2(AsO4)4 have not been reported previously. In 0.1 M Na(Cl), Na+ was found to be a significant component in two of the solid phases. The Cu5Na2(AsO4)4 was formed in weakly alkaline conditions with pNa < 2.5. Stability constants for all solid phases have been determined. Distribution diagrams as well as predominance area (pNa–pH) diagrams are presented to illustrate stability fields of the different solid phases.
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