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- Lützenkirchen, Johannes, et al.
(författare)
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Limitations of the potentiometric titration technique in determining the proton active site density of goethite surfaces
- 2002
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Ingår i: Geochimica et Cosmochimica Acta: Volume 66, Issue 19, 1 October 2002, Pages. ; 66:19, s. 3389-96
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Tidskriftsartikel (refereegranskat)abstract
- Density of proton active surface sites at mineral surfaces is a property of fundamental importance in equilibrium modeling of surface complexation reactions. In this article, methods for an experimental determination of these sites at the surface of α-FeOOH (goethite) are explored. It is shown that previously obtained saturation data of goethite with respect to protons do not yield a site density that can be considered as an intrinsic sorbent property: the results are below crystallographically expected values and values for different ionic media in terms of composition and concentration yield different numbers—for example, chloride would yield higher values than nitrate at the same concentration, and higher electrolyte concentration would favor higher apparent maxima. Although site saturation might be explained by electrostatic repulsion, which is more efficient at high electrolyte concentration or for certain ions, further independent experimental results show that no saturation occurs on goethite down to ph ≡ −log[H+] = 2.2 and possibly to PH = 1.0 in 0.6 M NaCl. For those very low pH values, the experimental charging curve was obtained by coulometric back titration (using the Gran plot) or titrations with tris (hydroxymethyl)-aminomethane of the supernatant of acidified goethite suspension. These experimental data are to our knowledge the first high quality data at such low pHs. However, small errors in the determination of proton concentrations (1%) are shown to strongly affect the shape of the charging curve for ph < 2. Furthermore, goethite dissolution (proton consumption and iron reduction in coulometric titrations) and liquid junction effects interfere at low ph, hampering the straightforward application of coulometric Gran titrations over the whole pH range. From these experiments, it can nonetheless be ascertained that a minimum of 2.5 protons/nm2 can be adsorbed at the goethite surface from the point of zero charge (ph 9.4) to pH 0.9. Although these studies are restricted to goethite, those studies in which titrations with excess acid and base have been used for the determination of proton active site concentrations of sorbents should be reconsidered.
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- Ramstedt, Madeleine, et al.
(författare)
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Characterization of hydrous manganite (-MnOOH) surfaces - an XPS study
- 2002
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Ingår i: Surface and Interface Analysis. - : Wiley. - 0142-2421. ; 34:1, s. 632-6
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Tidskriftsartikel (refereegranskat)abstract
- Crystalline manganite (-MnOOH) has been synthesized and characterized using x-ray diffraction and high-resolution transmission electron microscopy techniques. The surface composition was studied with XPS between pH 0.4 and 11. Special pre-cooling procedures were developed to keep the manganite/water interface intact before and during XPS measurements. The O/OH group ratio differs between pH 6 and 11, in agreement with the acid/base characteristics of the surface. Below pH 6, on the other hand, drastic changes can be seen in the O 1s spectra due to dissolution of manganite. Possibly the interaction of OH groups with H+ in acidic suspensions is a first step leading to dissolution. The surface charge arising at high and low pH is compensated by the counter-ions Na+ and Cl-, respectively. The XPS spectra are presented and discussed in terms of the mechanisms for surface complexation and dissolution processes.
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- Sheals, Julia, et al.
(författare)
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Adsorption of Glyphosate on Goethite: Molecular Characterization of Surface Complexes
- 2002
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Ingår i: Environmental Science & Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 36:14, s. 3090-5
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Tidskriftsartikel (refereegranskat)abstract
- As a component of herbicides, the fate of glyphosate (PMG) in the environment is of significant interest. The nature of PMG adsorption on mineral surfaces plays a significant role in the degradation of PMG. The adsorption of PMG on goethite (-FeOOH) has been studied as a function of pH and PMG concentration. Adsorption was investigated with batch experiments, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), and X-ray photoelectron spectroscopy (XPS). The N 1s line in XPS spectra showed deprotonation of the amine group of PMG (NH2+) with increasing pH. IR analyses showed no evidence for the interaction of PMG's carboxylate group with the goethite surface, while the phosphonate group formed inner-sphere complexes. There is evidence for intramolecular hydrogen bonding between NH2+ and both the carboxylate and the phosphonate groups at low pH. Intramolecular hydrogen bonding is lost when the amine group is deprotonated, and the trend in intramolecular hydrogen bonding between NH2+ and phosphonate shows that PMG adsorbs via predominantly monodentate complexation. A minor quantity of bidentate complexes is thought to form both at near-neutral pH and when the surface concentration of PMG is low. While the phosphonate group of PMG binds directly, the carboxylate group remains relatively "free" from complexation with goethite, leaving it subject to degradation and/or complexation with metal ions present in the environment.
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