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- Estmark Kalinowski, Birgitta
(författare)
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Dissolution Kinetics and Alteration Products of Micas and Epidote in Acidic Solutions at Room Temperature
- 1997
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The reaction kinetics of the weathering of several phyllosilicates and one sorosilicate were stud ied experimentally. The alteration products were characterised by various methods in clud ing XRD, HRTEM, SEM, FTIR, NMR and Mössbauer spectroscopy. Weathering of silicates is of particular concern to our knowledge of several areas in low temperature geochemistry, such as el e ment cy cling, ground water chemistry and soil formation. The importance of these processes ex tends to the long-term nutrient supply to forest ecosystems and control of soil and water acidity, es pe cial ly in Scandinavia.Several soil models designed to predict the impact of acid rain on the soil chemistry rely on kinetic data of mineral weathering. The reaction kinetics for minerals are used in such models to predict chang es in soil chem is try. This enables calculation of the effect of acid rain (i. e. critical load) in a 100-year per spec tive. For some minerals relatively little knowledge is available for the reaction kinetics. There fore the dissolution kinetics of muscovite, biotite, phlogopite, vermiculite and epi dote were studied over the pH range 1 to 6.5 at room temperature using flow-through reactors.Silica release rates based on specific surface area are about the same for as divers silicates as epidote (sorosilicate), K-feldspar (tectosilicate) and phlogopite (phyllosilicate). At pH 3 log R = -15.41, -15.5 and -15.46 respectively for these min er als. However, the framework of Si and Al is likely to determine with what ease cations positioned in between the conformation of Si and Al tetrahedra are re leased. For example, K in micas have transportation channels due to the layer struc ture and ought there fore to be released easier than in K-feldspar. In most cases Si is the most slowly released element in silicates, but in epidote, Si and Ca are the fastest released elements from the structure, while Al and Fe are retained. Leaching of inter framework cations creates strain and charge im bal ance in the silicate structure, causing Si to be more readily released in base cation containing silicates than in quartz. Released Si may repolymerise directly at the surface of silicates or interlayers. Amor phous silica gel has been detected, as a weathering product between packages of 2:1 layers in bi otite, using AEM. Iron(hydr)oxides have been found as the end-product of biotite weathering. Re sid u al layer calculations based on the solution composition show that Al and Fe form an enriched layer with a thickness of 1-2 nm at the surface of epidote.Biotite and phlogopite probably alter to trioctahedral vermiculite from the edges and inwards. Mössbauer spectroscopy shows that weathering of biotite as well as ver micu lite is accompanied by oxidation. Al-hydroxy polymers are introduced in the in ter lay er during weathering of phlogopite and vermiculite, which is supported by both XRD and 27Al MAS-NMR analyses. Additions of KCl and AlCl3 to the reactant solutions show that release rates, exfoliation and oxidation processes decrease with increased concentrations for both biotite and phlogopite. Leaching of interlayer cat i ons seems thus to initiate oxidation of ferrous iron.
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