Diffusion of rare earth elements in garnets and pyroxenes: Experiment, theory and applications

Persistent Link:
http://hdl.handle.net/10150/280005
Title:
Diffusion of rare earth elements in garnets and pyroxenes: Experiment, theory and applications
Author:
Tirone, Massimiliano
Issue Date:
2002
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Abstract:
This thesis consists of three main chapters preceded by an introduction that discusses the importance of diffusion in minerals to constrain the geochemistry of various magmatic processes. The first chapter deals with the experimental technique and measurement of tracer element diffusion data in garnet and clinopyroxene. Self-diffusion coefficients of selected REE have been measured as a function of temperature (770°C-1050°) at 1 bar and oxygen fugacity (fO₂) corresponding to that defined by the iron-wustite buffer. The experimental results indicate small variations of diffusivity for REE in both garnet and clinopyroxene and an activation energy which is similar to the activation energy for diffusion of major components. In the second chapter the atomistic mechanism of Nd diffusion in garnet is investigated by molecular dynamics (MD) simulation. An optimization procedure based on genetic algorithm provides the semi-empirical coefficients that are used to reproduce the repulsive forces between atoms. Results from MD simulations at high pressure and temperature show that Schottky defect is the most favorable mechanism for vacancy formation in the intrinsic region. The preferred reaction to incorporate neodymium in the dodecahedral site involves transferring an iron atom to the octahedral site after removing the aluminum atom from the lattice site. A model of diffusion in the extrinsic region with a prescribed vacancy defect fraction in the garnet (10⁻⁴) also provides an acceptable result. The third chapter considers some of the potential applications of the REE diffusion data in garnet and clinopyroxene to magmatic processes. REE patterns obtained from the solution of a moving boundary problem shows that incompatible elements are more sensitive to disequilibration controlled by diffusion. Melt generated by disequilibrium melting is less enriched in incompatible elements than melt produced by an equilibrium melting process. Solution of a multiphase flow model, including the chemical transport equations with diffusion in a solid phase, permits a more realistic investigation of the disequilibrium melting process. During the ridge evolution the model predicts negligible effect of solid state diffusion on the geochemical evolution of the partial melt and the residual solid.
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Geochemistry.
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Graduate College; Geosciences
Degree Grantor:
University of Arizona
Advisor:
Ganguly, Jibamitra

Full metadata record

DC FieldValue Language
dc.language.isoen_USen_US
dc.titleDiffusion of rare earth elements in garnets and pyroxenes: Experiment, theory and applicationsen_US
dc.creatorTirone, Massimilianoen_US
dc.contributor.authorTirone, Massimilianoen_US
dc.date.issued2002en_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.abstractThis thesis consists of three main chapters preceded by an introduction that discusses the importance of diffusion in minerals to constrain the geochemistry of various magmatic processes. The first chapter deals with the experimental technique and measurement of tracer element diffusion data in garnet and clinopyroxene. Self-diffusion coefficients of selected REE have been measured as a function of temperature (770°C-1050°) at 1 bar and oxygen fugacity (fO₂) corresponding to that defined by the iron-wustite buffer. The experimental results indicate small variations of diffusivity for REE in both garnet and clinopyroxene and an activation energy which is similar to the activation energy for diffusion of major components. In the second chapter the atomistic mechanism of Nd diffusion in garnet is investigated by molecular dynamics (MD) simulation. An optimization procedure based on genetic algorithm provides the semi-empirical coefficients that are used to reproduce the repulsive forces between atoms. Results from MD simulations at high pressure and temperature show that Schottky defect is the most favorable mechanism for vacancy formation in the intrinsic region. The preferred reaction to incorporate neodymium in the dodecahedral site involves transferring an iron atom to the octahedral site after removing the aluminum atom from the lattice site. A model of diffusion in the extrinsic region with a prescribed vacancy defect fraction in the garnet (10⁻⁴) also provides an acceptable result. The third chapter considers some of the potential applications of the REE diffusion data in garnet and clinopyroxene to magmatic processes. REE patterns obtained from the solution of a moving boundary problem shows that incompatible elements are more sensitive to disequilibration controlled by diffusion. Melt generated by disequilibrium melting is less enriched in incompatible elements than melt produced by an equilibrium melting process. Solution of a multiphase flow model, including the chemical transport equations with diffusion in a solid phase, permits a more realistic investigation of the disequilibrium melting process. During the ridge evolution the model predicts negligible effect of solid state diffusion on the geochemical evolution of the partial melt and the residual solid.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectGeochemistry.en_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.disciplineGeosciencesen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorGanguly, Jibamitraen_US
dc.identifier.proquest3053869en_US
dc.identifier.bibrecord.b42811636en_US
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