| 1. |
- Wang, Xiaoming, et al.
(författare)
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Phosphate Sorption Speciation and Precipitation Mechanisms on Amorphous Aluminum Hydroxide
- 2019
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Ingår i: Soil Systems. - : MDPI. - 2571-8789. ; 3:1
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Tidskriftsartikel (refereegranskat)abstract
- Aluminum (Al) oxides are important adsorbents for phosphate in soils and sediments, and significantly limit Phosphate (P) mobility and bioavailability, but the speciation of surface-adsorbed phosphate on Al oxides remains poorly understood. Here, phosphate sorption speciation on amorphous Al hydroxide (AAH) was determined under pH 3-8 and P concentration of 0.03 mM-15 mM using various spectroscopic approaches, and phosphate precipitation mechanisms were discussed as well. AAH exhibits an extremely high phosphate sorption capacity, increasing from 3.80 mmol/g at pH 7 to 4.63 mmol/g at pH 3. Regardless of reaction pH, with increasing P sorption loading, the sorption mechanism transits from bidentate binuclear (BB) surface complexation with d(P-Al) of 3.12 angstrom to surface precipitation of analogous amorphous AlPO4 (AAP), possibly with ternary complexes, such as (equivalent to Al-O)(2)-PO2-Al, as intermediate products. Additionally, the percentage of precipitated phosphate occurring in AAP linearly and positively correlates with P sorption loading. Compared to phosphate reaction with ferrihydrite, phosphate adsorbs and precipitates more readily on AAH due to the higher solubility product (K-sp) of AAH. The formation of AAP particles involves Al-III release, which is promoted by phosphate adsorption, and its subsequent precipitation with phosphate at AAH surfaces or in the bulk solution.
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| 2. |
- Djodjic, Faruk, et al.
(författare)
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Soils potentially vulnerable to phosphorus losses : speciation of inorganic and organic phosphorus and estimation of leaching losses
- 2023
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Ingår i: Nutrient Cycling in Agroecosystems. - : Springer. - 1385-1314 .- 1573-0867. ; 127, s. 225-245
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Tidskriftsartikel (refereegranskat)abstract
- Eutrophication is an important threat to aquatic ecosystems world-wide, and reliable identification of areas vulnerable to phosphorus (P) losses from diffuse sources is essential for high efficiency of mitigation measures. In this three-step study we investigated (i) relationships between the agronomic (Olsen-P and P-AL) and environmental soil P tests (P-CaCl2) with molecular techniques (P-31 NMR and XANES) followed by (ii) rainfall simulation experiment on topsoil lysimeters and (iii) comparison to long-term field measurements of water quality. Soil samples were collected from seven sites indicated to be vulnerable to nutrient losses due to underlying geology. High P release correlated to standard agronomic P tests (Olsen P, r = 0.67; and P-AL, r = 0.74) and low P sorption capacity (r = - 0.5). High content of iron-bound P compounds indicated more labile P and higher release of dissolved P (r = 0.67). The leaching experiment showed that three out of four soils with high initial soil P status had both higher P leaching concentrations before fertilization (0.83-7.7 mg P l(-1)) compared to soil with low initial soil P status (0.007-0.23 mg P l(-1)), and higher increase in P concentrations after fertilization. Higher soil P sorption capacity reduced P leaching losses. Finally, long-term monitoring data show no significant trends in P losses in a field with low initial P content and moderate P fertilization rates whereas high and over time increasing P losses were recorded in a field with high initial soil P content and repetitively high P fertilization rates.
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| 3. |
- Gebauer, Denis, et al.
(författare)
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Proto-Calcite and Proto-Vaterite in Amorphous Calcium Carbonates
- 2010
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Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 49:47, s. 8889-8891
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Tidskriftsartikel (refereegranskat)abstract
- Amorphous order: Amorphous calcium carbonates (ACC) have an intrinsic structure relating to the crystalline polymorphs of calcite and vaterite. The proto-crystalline structures of calcite and vaterite (pc-ACC and pv-ACC) are analyzed by NMR (see picture), IR, and EXAFS spectroscopy, which shows that the structuring of ACC relates to the underlying pH-dependent equilibria.
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| 4. |
- Wang, Xiaoming, et al.
(författare)
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Binding geometries of silicate species on ferrihydrite surfaces
- 2018
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Ingår i: ACS Earth and Space Chemistry. - : AMER CHEMICAL SOC. - 2472-3452. ; 2:2, s. 125-134
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Tidskriftsartikel (refereegranskat)abstract
- Silicate sorption on ferrihydrite surfaces, as monomers, oligomers, and polymers, strongly affects ferrihydrite crystallinity, thermodynamic stability, and surface reactivity. How these silicate species bind on ferrihydrite surfaces is, however, not well understood. We have determined silicate binding geometries using a combination of X-ray absorption spectroscopy (XAS), differential atomic pair distribution function (d-PDF) analysis, and density functional theory (DFT) calculations. Silicon K-edge absorption pre edges and DFT-predicted energies indicate that silicate forms monomeric monodentate mononuclear (MM) complexes at low silicate sorption loadings. With increasing silicate loading, the pre-edge peak shifts to higher energies, suggesting changes in the silicate binding geometry toward multidentate complexation. The d-PDF analysis determines the Si Fe interatomic distance to be 3.25 A for the high-loading samples. The DFT calculations indicate that such distance corresponds to an oligomer in the bidentate binuclear (BB) binding geometry. The transition of the silicate sorption geometry accompanied by polymerization can affect stability of ferrihydrite and its adsorption and redox reactivity and increase the degree of Si isotopic fractionation upon silicate sorption on Fe oxides. MM monomeric complexes and BB oligomeric complexes should be used for surface complexation models predicting silicate sorption on Fe oxide surfaces.
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