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Thermodynamic Model for Tourmaline /

Roozen, Stan,

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Thermodynamic Model for Tourmaline /

Record Type:	Electronic resources : Monograph/item
Title/Author:	Thermodynamic Model for Tourmaline // Stan Roozen.
Author:	Roozen, Stan,
Description:	1 electronic resource (688 pages)
Notes:	Source: Dissertations Abstracts International, Volume: 87-04, Section: B.
Contained By:	Dissertations Abstracts International87-04B.
Subject:	Solid solutions. -
Online resource:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=32261842
ISBN:	9798291532720

Thermodynamic Model for Tourmaline /
Roozen, Stan,

Thermodynamic Model for Tourmaline /Stan Roozen. - 1 electronic resource (688 pages)

Source: Dissertations Abstracts International, Volume: 87-04, Section: B.

Tourmaline, XY₃Z₆T₆O₁₈(BO₃)₃V₃W, is a common borosilicate in crustal settings, recording phase relationships with minerals, fluids, and melts across tectonic environments. Its diverse sites enable elemental incorporation, while stability and low diffusivity preserve zoning, which is crucial for reconstructing P-T-X histories. Accurate interpretation requires a thermodynamic model, which this thesis develops through crystal-chemical and calorimetric measurements.A tourmaline set of ~50 natural and synthetic samples was assembled within the Na-Ca-B-Fe²⁺-Fe³⁺-Mg-Al-Si-Ti-O-H-F system. Natural samples capture real-world variability, while synthetic samples reduce multicollinearity. Tourmalines were characterised by EMPA (main elements), LA-ICP-MS (trace), Karl-Fischer titration (H2O) and Mössbauer spectroscopy (Fe²⁺/³⁺). Single-crystal XRD provided structural constraints for formula optimisation using composition, site electrons, bond valence sums, and crystal-chemical assumptions. A uniform methodology including uncertainty assessment ensured internal consistency.Two models were developed: 1. The bulk model, X(YZ)₉SixAl(1-x)(VW)₄, defines a polytope with 9 independent endmembers and applies when only bulk composition is available; 2. The speciation model, XY₃Z₆T₆V₃W, uses 14 independent endmembers and requires site assignments. For both models, entropy (S), molar volume (VM), and heat capacity (CP) were measured and regressed to endmembers, while enthalpy (∆H) was determined only for the bulk model due to data scarcity.Molar volume was calculated from SC-XRD data. Given tourmaline's complexity, 50 samples were insufficient to assign endmember VM conclusively, so 21 methods, including OLS, errors-in-variables, and robust regression, were compared to find best estimates. Robust regression minimised outlier effects for the bulk model, while EIV regression worked best for the speciation model, mitigating multicollinearity. Hierarchical subset selection identified interaction parameters, but test validation showed insignificance.Heat capacity was measured from 2 to 774 K and integrated to entropy using linear interpolation (to 298 K) and a Berman fit for high-T data. S₀ is dominated by a low-T spin-glass transition. Enthalpy was measured for 15 samples in lead-borate drop-calorimetry at 700°C under O₂ flushing and converted to ∆Hfox through a thermodynamic cycle of oxidation, devolatilization, and reference oxide formation. Major uncertainty sources included Fe²⁺/Fe³⁺ ratios, reference oxides, and mineral normalization. Bulk model H exhibited multicollinearity due to data scarcity. No excess S or ∆H was found. Configurational S was modelled using Bragg-Williams long-range order or molecular short-range order models. The SRO model with limited dimensions provides the simplest Sconf description but leads to fixed element correlations from missing polytope dimensions.The model enables forward modelling of net-transfer and exchange equilibria, allowing tourmaline to be used in thermobarometry, provenance studies, mineral exploration, and fluid and magma reconstructions.

English

ISBN: 9798291532720Subjects--Topical Terms:

3566211
Solid solutions.
Subjects--Index Terms:

Tectonic environments

Thermodynamic Model for Tourmaline /
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500 $a Advisors: van Hinsberg, Vincent Johan.
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520 $a Tourmaline, XY₃Z₆T₆O₁₈(BO₃)₃V₃W, is a common borosilicate in crustal settings, recording phase relationships with minerals, fluids, and melts across tectonic environments. Its diverse sites enable elemental incorporation, while stability and low diffusivity preserve zoning, which is crucial for reconstructing P-T-X histories. Accurate interpretation requires a thermodynamic model, which this thesis develops through crystal-chemical and calorimetric measurements.A tourmaline set of ~50 natural and synthetic samples was assembled within the Na-Ca-B-Fe²⁺-Fe³⁺-Mg-Al-Si-Ti-O-H-F system. Natural samples capture real-world variability, while synthetic samples reduce multicollinearity. Tourmalines were characterised by EMPA (main elements), LA-ICP-MS (trace), Karl-Fischer titration (H2O) and Mössbauer spectroscopy (Fe²⁺/³⁺). Single-crystal XRD provided structural constraints for formula optimisation using composition, site electrons, bond valence sums, and crystal-chemical assumptions. A uniform methodology including uncertainty assessment ensured internal consistency.Two models were developed: 1. The bulk model, X(YZ)₉SixAl(1-x)(VW)₄, defines a polytope with 9 independent endmembers and applies when only bulk composition is available; 2. The speciation model, XY₃Z₆T₆V₃W, uses 14 independent endmembers and requires site assignments. For both models, entropy (S), molar volume (VM), and heat capacity (CP) were measured and regressed to endmembers, while enthalpy (∆H) was determined only for the bulk model due to data scarcity.Molar volume was calculated from SC-XRD data. Given tourmaline's complexity, 50 samples were insufficient to assign endmember VM conclusively, so 21 methods, including OLS, errors-in-variables, and robust regression, were compared to find best estimates. Robust regression minimised outlier effects for the bulk model, while EIV regression worked best for the speciation model, mitigating multicollinearity. Hierarchical subset selection identified interaction parameters, but test validation showed insignificance.Heat capacity was measured from 2 to 774 K and integrated to entropy using linear interpolation (to 298 K) and a Berman fit for high-T data. S₀ is dominated by a low-T spin-glass transition. Enthalpy was measured for 15 samples in lead-borate drop-calorimetry at 700°C under O₂ flushing and converted to ∆Hfox through a thermodynamic cycle of oxidation, devolatilization, and reference oxide formation. Major uncertainty sources included Fe²⁺/Fe³⁺ ratios, reference oxides, and mineral normalization. Bulk model H exhibited multicollinearity due to data scarcity. No excess S or ∆H was found. Configurational S was modelled using Bragg-Williams long-range order or molecular short-range order models. The SRO model with limited dimensions provides the simplest Sconf description but leads to fixed element correlations from missing polytope dimensions.The model enables forward modelling of net-transfer and exchange equilibria, allowing tourmaline to be used in thermobarometry, provenance studies, mineral exploration, and fluid and magma reconstructions.
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650 4 $a Temperature effects. $3 3560297
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650 4 $a Mineralogy. $3 516743
650 4 $a Heat. $3 573595
650 4 $a Entropy. $3 546219
650 4 $a Provenance. $3 3687788
650 4 $a Geology. $3 516570
650 4 $a Environmental science. $3 677245
653 $a Tectonic environments
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710 2 $a McGill University (Canada). $e degree granting institution. $3 3759190
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