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- Sand, K. K., et al.
(author)
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Biomineralization : long-term effectiveness of polysaccharides on the growth and dissolution of calcite
- 2014
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In: Crystal Growth & Design. - : American Chemical Society (ACS). - 1528-7483 .- 1528-7505. ; 14:11, s. 5486-5494
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Journal article (peer-reviewed)abstract
- Our results demonstrate that in addition to being used for controlling morphology during calcite growth, polysaccharide (PS) that has been designed for biomineralization is also extremely robust, influencing calcite reactions even after millions of years. We investigated calcite (CaCO3) behavior in solutions with very small concentrations of PS that was produced similar to 70 Ma ago by coccolithophorids. We used atomic force microscopy (AFM) and the constant composition method to monitor calcite growth in the presence of this ancient PS. The ancient PS is still very active and has a high affinity for calcite step edges. Adsorption, even at extremely low concentrations (0.5 mu g/mL), results in decreased growth rate and dramatic morphology changes during growth and dissolution. The experimental results are complemented with surface complexation modeling for adsorption of components of polysaccharide from a modern coccolithophorid, Emiliania huxleyi. We generated surface complexation constants for the branch components: malonate: 14.25 +/- 0.17, succinate: 11.91 +/- 0.06, tricarballylate: 14.86 +/- 0.04, and citrate: 15.25 +/- 0.04. The implication is that complex PS could hold promise for smart material engineering and for preventing scaling.
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| 2. |
- Bruggeman, C., et al.
(author)
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Redox-active phases and radionuclide equilibrium valence state in subsurface environments - New insights from 6th EC FP IP FUNMIG
- 2012
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In: Applied Geochemistry. - : Elsevier BV. - 0883-2927 .- 1872-9134. ; 27:2, s. 404-413
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Journal article (peer-reviewed)abstract
- Within the 6th EC FP Integrated Project "Fundamental Processes of Radionuclide Migration'' (FUNMIG), progress has been made to improve knowledge about the phases and reaction mechanisms involved in complex reduction processes of radionuclide contaminants in natural subsurface environments. This review paper gives an overview of the achievements made by the research groups involved in this project, and puts the scope and results of the studies in a more global context. Firstly, both thermodynamic and experimental evidence show that green rust is present and reactive in subsurface groundwater with a composition that spans the Fe(II)/Fe(III) redox boundary. Green rust has been shown to reduce Np(V), Se(VI) and Se(IV), but the pathways for the redox processes and the reaction products that result are complicated, and change as a function of the reaction parameters. Secondly, considerable evidence has emerged that Se(IV) is reduced on Fe(II)-bearing minerals which are ubiquitous in subsurface environments. The stable Se valence state in the presence of FeS(2) has been shown to be Se(0). Also, natural dissolved humic substances that contain sufficient electron donating capacity are capable of interacting with, and possibly reducing, Se(IV) to lower valence states. Thirdly, the influence of HCO(3)(-) and organic ligands on the uptake and reduction of U(VI) on Fe(II)-bearing minerals was investigated. While it appeared that HCO(3)(-) decreased the extent of U(VI) uptake by the reducing surface, the fraction of reduced U(IV) in the solid phase increased with increasing HCO(3)(-) concentration. In contrast with the observations for HCO(3)(-), organic ligands decreased both the extent of U uptake, as well as the fraction of U(IV) found in the solid phase. The studies performed within FUNMIG show that investigating reduction-oxidation mechanisms require (1) a detailed control over reaction conditions (anoxic atmosphere, purification of solid phases, initial radionuclide speciation), (2) a rigorous follow-up of reaction products (both solution chemistry and spectroscopic methods), and (3) the consideration of slow kinetics in the setting up of an experiment. These requirements make the study and assessment of redox processes one of the most demanding scientific challenges for geochemists who are asked to make predictions for radionuclide transport behaviour in the environment.
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| 4. |
- Hammer, Edith, et al.
(author)
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A mycorrhizal fungus grows on biochar and captures phosphorus from its surfaces
- 2014
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In: Soil Biology & Biochemistry. - : Elsevier BV. - 0038-0717. ; 77, s. 252-260
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Journal article (peer-reviewed)abstract
- Biochar application to soils has potential to simultaneously improve soil fertility and store carbon to aid climate change mitigation. While many studies have shown positive effects on plant yields, much less is known about the synergies between biochar and plant growth promoting microbes, such as mycorrhizal fungi. We present the first evidence that arbuscular mycorrhizal (AM) fungi can use biochar as a physical growth matrix and nutrient source. We used monoxenic cultures of the AM fungus Rhizophagus irregularis in symbiosis with carrot roots. Using scanning electron microscopy we observed that AM fungal hyphae grow on and into two contrasting types of biochar particles, strongly attaching to inner and outer surfaces. Loading a nutrient-poor biochar surface with nutrients stimulated hyphal colonization. We labeled biochar surfaces with P-33 radiotracer and found that hyphal contact to the biochar surfaces permitted uptake of P-33 and its subsequent translocation to the associated host roots. Direct access of fungal hyphae to biochar surfaces resulted in six times more P-33 translocation to the host roots than in systems where a mesh prevented hyphal contact with the biochar. We conclude that AM fungal hyphae access microsites within biochar, that are too small for most plant roots to enter (<10 mu m), and can hence mediate plant phosphorus uptake from the biochar. Thus, combined management of biochar and AM fungi could contribute to sustainable soil and climate management by providing both a carbon-stable nutrient reservoir and a symbiont that facilitates nutrient uptake from it. (C) 2014 Elsevier Ltd. All rights reserved.
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| 5. |
- Okhrimenko, Denis V., et al.
(author)
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Hydrolytic Stability of 3-Aminopropylsilane Coupling Agent on Silica and Silicate Surfaces at Elevated Temperatures
- 2017
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In: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 9:9, s. 8344-8353
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Journal article (peer-reviewed)abstract
- 3-Aminopropylsilane (APS) coupling agent is widely used in industrial, biomaterial, and medical applications to improve adhesion of polymers to inorganic materials. However, during exposure to elevated humidity and temperature, the deposited APS layers can decompose, leading to reduction in coupling efficiency, thus decreasing the product quality and the mechanical strength of the polymer–inorganic material interface. Therefore, a better understanding of the chemical state and stability of APS on inorganic surfaces is needed. In this work, we investigated APS adhesion on silica wafers and compared its properties with those on complex silicate surfaces such as those used by industry (mineral fibers and fiber melt wafers). The APS was deposited from aqueous and organic (toluene) solutions and studied with surface sensitive techniques, including X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), streaming potential, contact angle, and spectroscopic ellipsometry. APS configuration on a model silica surface at a range of coverages was simulated using density functional theory (DFT). We also studied the stability of adsorbed APS during aging at high humidity and elevated temperature. Our results demonstrated that APS layer formation depends on the choice of solvent and substrate used for deposition. On silica surfaces in toluene, APS formed unstable multilayers, while from aqueous solutions, thinner and more stable APS layers were produced. The chemical composition and substrate roughness influence the amount of deposited APS. More APS was deposited and its layers were more stable on fiber melt than on silica wafers. The changes in the amount of adsorbed APS can be successfully monitored by streaming potential. These results will aid in improving industrial- and laboratory-scale APS deposition methods and increasing adhesion and stability, thus increasing the quality and effectiveness of materials where APS is used as a coupling agent.
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