High-pressure deformation of calcite marble and its transformation to aragonite under non-hydrostatic conditions

doi:10.1016/0191-8141(93)90164-6

Journal of Structural Geology

Volume 15, Issues 9–10, September–October 1993, Pages 1207-1222

https://doi.org/10.1016/0191-8141(93)90164-6 Get rights and content

Abstract

We conducted deformation experiments on Carrara marble in the aragonite and calcite stability fields to observe the synkinematic transformation of calcite to aragonite, and to identify any relationships between transformation and deformation or sample strength. Deformation-induced microstructures in calcite crystals varied most significantly with temperature, ranging from limited slip and twinning at 400°C, limited recrystallization at 500°C, widespread recrystallization at 600 and 700°C, to grain growth at 800–900°C. Variations in confining pressure from 0.3 to 2.0 GPa have no apparent effect on calcite deformation microstructures. Aragonite grew in 10⁻⁶-10⁻⁷ s⁻¹strain rate tests conducted for 18–524 h at confining pressures of 1.7–2.0 GPa and temperatures of 500–600°C. As in our previously reported hydrostatic experiments on this same transformation, the aragonite nucleated on calcite grain boundaries. The extent of transformation varied from a few percent conversion near pistons at 400°C, 2.0 GPa and 10⁻⁴ s⁻¹ strain rate in a 0.8 h long experiment, to 98% transformation in a 21-day test at a strain rate of 10⁻⁷ s⁻⁷, a temperature of 600°C and a pressure of 2.0 GPa. At 500°C, porphyroblastic 100–200 μm aragonite crystals grew at a rate faster than 8 × 10⁻¹m s⁻¹. At 600°C, the growth of aragonite neoblasts was slower, ≈6 × 10⁻¹ m s ⁻¹, and formed ‘glove-and-finger’ cellularprecipitation-like textures identical to those observed in hydrostatic experiments. The transformation to aragonite is not accompanied by a shear instability or anisotropic aragonite growth, consistent with its relatively small volume change and latent heat in comparison with compounds that do display those features.

References (45)

J.W Cahn
The kinetics of grain-boundary nucleated reactions
Acta metall.
(1956)
K.J Rowe et al.
Paleostress estimation using calcite twinning: experimental calibration and application to nature
J. Struct. Geol.
(1990)
E.H Rutter
The influence of interstitial water on the rheological behaviour of calcite rocks
Tectonophysics
(1972)
E.H Rutter
The influence of temperature, strain rate, and interstitial water in the experimental deformation of calcite rocks
Tectonophysics
(1974)
S.M Schmid et al.
Superplastic flow in finegrained limestone
Tectonophysics
(1977)
S.M Schmid et al.
High temperature flow and dynamic recrystallization in Carrara marble
Tectonophysics
(1980)
P.J Vaughan et al.
Anisotropic growth in the olivine-spinet phase transformation of Mg₂GeO₄ under nonhydrostatic stress
Tectonophysics
(1984)
H.R Wenk
Carbonates
F.D Adams et al.
An experimental investigation into the flow of marble
Phil. Trans. R. Soc. Lond.
(1901)
N.S Brat et al.
Effects of pressure, temperature, and grain size on the kinetics of the calcite→aragonite transformation
Can. J. Earth Sci.
(1979)

P.C Burnley et al.

Faulting associated with the olivine to spinel transformation in Mg₂GeO₄and its implications for deep-focus earthquakes

J. geophys. Res.

(1991)

P.C Burnley et al.

Pressure-induced embrittlement of polycrystalline tremolite Ca₂Mg₅Si₈O₂₂(OH,F)₂

Eos

(1982)

W.D Carlson et al.

Optical determination of topotactic aragonite-calcite growth kinetics: metamorphic implications

J. Geol.

(1981)

M Casey et al.

Texture development in experimentally deformed calcite rocks

W.B Durham et al.

Experimental deformation of polycrystalline H₂O ice at high pressure and low temperature; preliminary results

J. geophys. Res.

(1983)

M.P Ferreira et al.

Microscopic structure and fabric of Yule marble experimentally deformed at different strain rates

J. Geol.

(1964)

M Friedman et al.

Calcite fabrics in experimental shear zones

P Gillet et al.

The calcite-aragonite transition: mechanism and microstructures induced by the transformation stress and strain

Bull. Mineral.

(1987)

J.J Gilman

Direct measurements of the surface energies of crystals

J. appl. Phys.

(1960)

H.W Green et al.

A new self-organizing, mechanism for deep-focus earthquakes

Nature

(1989)

D.T Griggs

Hydrolytic weakening of quartz and other silicates

Geophys. J. R. astr. Soc.

(1967)

D.T Griggs

The sinking lithosphere and the focal mechanism of deep earthquakes

Cited by (27)

Calcite pseudomorphs after aragonite: A tool to unravel the structural history of high-pressure marbles (Evia Island, Greece)
2021, Journal of Structural Geology
Citation Excerpt :
Ιf static conditions follow the deformation, aragonite may rapidly grow parallel to its c-axis, resulting in columnar crystals oriented almost normal to the foliation (e.g., Brady et al., 2004). In addition, calcite deformed experimentally in HP conditions may also result in aragonite columnar crystals that grow parallel to the compression direction (normal to the foliation plane) (Hacker and Kirby, 1993; Whitney et al., 2014). The shape and crystallography of the former aragonite may be inherited by calcite that replaces aragonite at lower pressure conditions.
Calcite pseudomorphs after aragonite were recorded throughout the high-pressure marbles of the Basal Unit (Evia Island, Greece). The pseudomorphs form a columnar microstructure oriented normal to the foliation, which developed at peak metamorphic conditions within the stability field of aragonite. Modification of the columnar microstructure by bending of the long axis of the calcite pseudomorph and dynamic recrystallization, was mainly dependent on the intensity of subsequent, exhumation-related deformation. We used the degree of preservation or modification of the columnar microstructure observed in shear zones, to distinguish between the subduction- and exhumation-related nature of the studied shear zones. The degree of modification of the columnar microstructure was also used as a tool to investigate variations in strain intensity, recrystallization mechanism and kinematics during the exhumation of the high-pressure marbles. Combined field and microstructural data suggest that subduction-related ductile deformation preceded the growth of the columnar microstructure and was associated with internal imbrication by SE-directed thrusting. The ductile stage of the exhumation was characterized by strain localization at the middle and upper structural levels of the Basal Unit, and E-directed thrusting (i.e., northeast in pre-Neogene configuration). Final exhumation of the Basal Unit was achieved by top-to-the-E ductile to brittle thrusting, which was accompanied by syn-orogenic extension at the upper crustal levels.
Multispectral imaging of mineral samples by infrared quantum dot focal plane array sensors
2020, Measurement: Journal of the International Measurement Confederation
Citation Excerpt :
The limestone is forced to change by the application of heat and pressure and is then altered to form coarse grained calcite in the recrystallization process. After that, with the application of appropriate temperature, pressure, and hydrostatic conditions, the calcite crystal in marble can transform into aragonite, which is another crystal structure of CaCO3 [20]. Furthermore, the different colors in marble come from the different structure of the CaCO3 crystal because the morphology of compounds with impurities is different in the recrystallization phase, which leads to different infrared spectra between calcite and aragonite.
Infrared (IR) spectral imaging is a powerful tool for component analysis and identification in the geological field. In this report, we originally use quantum dot infrared photodetector (QDIP) focal plane arrays (FPAs) with different peak-responsivity wavelengths to analyze the mineral composition of rock samples by IR spectral imaging and show the QDIP’s potential as a solution for some geological problems. After clarifying fundamental characteristics such as the blackbody responsivity, current noise density, and spectral responsivity of QDIPs, we present qualitative and quantitative analyses of mineral samples including conglomerate, sandstone, marble, and dolomite. In the qualitative analysis, we distinguish two different compositions in each rock. In the quantitative analysis, we measure the emittance of dolomite and show the emittance errors. Finally, we discuss which experimental factor determines the quantitative precision most dominantly.
Campaign-style titanite U-Pb dating by laser-ablation ICP: Implications for crustal flow, phase transformations and titanite closure
2013, Chemical Geology
Citation Excerpt :
Large-scale Earth dynamics is driven by buoyancy contrasts (Anderson, 2007). Understanding buoyancy—in particular, “chemical buoyancy” related to mineralogy and phase transformations—relies on quantifying how the rates of phase transformations depend on intensive parameters (e.g., stress and temperature) and material properties (Rubie and Thompson, 1985; Hacker and Kirby, 1993). Geodynamic models that include phase transformation are forced to make general assumptions about rates (e.g., Sung and Burns, 1976; Behn et al., 2011) or to extrapolate experimental data (e.g., Mosenfelder et al., 2001)—which, in spite of our best efforts, remain uncertain because of an inability to quantify nucleation rates with sufficient precision (e.g., Rubie et al., 1990; Hacker et al., 2005).
U–Pb dates of titanite from > 150 samples of chiefly quartzofeldspathic gneiss and leucosomes were measured across the Western Gneiss Region of Norway to understand deformation and metamorphism of typical crustal rocks during ultrahigh-pressure (UHP) subduction and exhumation. Titanite is unstable at these high temperatures and pressures, and, indeed, most of the titanite yielded post-UHP dates. A modest number of titanites sampled across large areas, however, have pre-UHP U–Pb dates, indicating that they survived their excursion to and return from mantle depths metastably. This has three important implications. 1. Titanite grains can remain closed to complete Pb loss during regional metamorphism at temperatures as high as 750 °C and pressures as high as 3 GPa. 2. Phase transformations in quartzofeldspathic rocks can be inhibited at the same conditions. 3. Quartz-bearing rocks can remain undeformed even at high temperature and pressure. Both of the latter were previously recognized; the present study simply presents a new method for evaluating both using titanite U–Pb dates.
Aragonite pseudomorphs in high-pressure marbles of Syros, Greece
2004, Journal of Structural Geology
Numerous rod-shaped calcite crystals occur in the blueschist to eclogite facies marbles of Syros, Greece. The rods show a shape-preferred orientation, and the long axes of the rods are oriented at a large angle to foliation. The crystals also have a crystallographic-preferred orientation: calcite c-axes are oriented parallel to the long axes of the rods. Based on their chemical composition, shape, and occurrence in high-pressure marbles, these calcite crystals are interpreted as topotactic pseudomorphs after aragonite that developed a crystallographic-preferred orientation during peak metamorphism. This interpretation is consistent with deformation of aragonite by dislocation creep, which has been observed in laboratory experiments but has not been previously reported on the basis of field evidence. Subsequent to the high-pressure deformation of the aragonite marbles, the aragonite recrystallized statically into coarse rod-shaped crystals, maintaining the crystallographic orientation developed during deformation. During later exhumation, aragonite reverted to calcite, and the marbles experienced little further deformation, at least in the pseudomorph-rich layers. Some shearing of pseudomorph-bearing marble layers did occur and is indicated by twinning of calcite and by a variable inclination of the pseudomorphs relative to foliation.
Seismic-frequency laboratory measurements of shear mode viscoelasticity in crustal rocks I: Competition between cracking and plastic flow in thermally cycled Carrara marble
1996, Physics of the Earth and Planetary Interiors
In the first phase of a seismic-frequency study of the viscoelasticity of cracked and fluid-saturated crustal rocks, forced torsional oscillation experiments have been conducted on specimens of Carrara marble subjected to multiple thermal cycles up to 560°C, under confining pressure of 50 MPa. The experimental results showed distinctly different behaviour of both the shear modulus and internal friction between the first and subsequent thermal cycles. A pronounced reduction in shear modulus (G) observed during the first series of thermal cycles at temperature T < 300°C is attributed to thermal cracking. This large modulus deficit is recovered at higher temperatures, presumably through crack closure by plastic deformation processes that are also reflected in time dependence (over hours) of the shear modulus at temperatures above 300°C. Following the first excursion to 500°C, the shear modulus varies reproducibly with thermal cycling with a monotonic temperature dependence dominated by intrinsic (anharmonic) effects. It is inferred that thermal cracking in Carrara marble is suppressed by plastic flow following the first cycle to 500°C. The experimental results suggest that thermal history has strong effects on mechanical properties of calcite rock (Carrara marble) measured at relatively low temperatures. Internal friction or attenuation of Carrara marble is generally low and temperature-insensitive at low temperatures (< 400°C), but increases dramatically at 400–500°C. The frequency-dependence of internal friction at high temperatures (> 400°C), presumably due to dislocation relaxation, contrasts with frequency-independent $Q$ ⁻¹ at lower temperatures. The relatively sudden onset of markedly frequency-dependence seismic wave attenuation might prove to be a useful diagnostic of temperature under crustal conditions.
Experimental dynamic metamorphism of mineral single crystals
1993, Journal of Structural Geology
This paper is a review of some of the rich and varied interactions between non-hydrostatic stress and phase transformations or mineral reactions, drawn mainly from results of experiments done on mineral single crystals in our laboratory or our co-authors. The state of stress and inelastic deformation can enter explicitly into the equilibrium phase relations and kinetics of mineral reactions. Alternatively, phase transformations can have prominent effects on theology and on the nature of inelastic deformation. Our examples represent five types of structural phase changes, each of which is distinguished by particular mechanical effects. In increasing structural complexity, these include: (1) displacive phase transformations involving no bond-breaking, which may produce anomalous brittle behavior. A primary example is the a-β quartz transition which shows anomalously low fracture strength and tertiary creep behavior near the transition temperature; (2) martensitic-like transformations involving transformation strains dominated by shear deformation. Examples include the orthoenstatite → clinoenstatite and $w u ̈ rtzite → sphalerite$ transformations; (3) coherent exsolution or precipitation of a mineral solute from a supersaturated solid-solution, with anisotropy of precipitation and creep rates produced under nonhydrostatic stress. Examples include exsolution of corundum from MgO · nAl₂O₃ spinels and Ca-clinopyroxene from orthopyroxene; (4) order-disorder transformations that are believed to cause anomalous plastic yield strengthening, such as MgO - nAl₂O₃ spinels; and (5) near-surface devolatilization of hydrous silicate single-crystals that produces a fundamental brittleness thought to be connected with dehydration at microcracks at temperatures well below nominal macroscopic dehydration temperatures.
As none of these interactions between single-crystal phase transformations and non-hydrostatic stress is understood in detail, this paper serves as a challenge to field structural geologists to test whether interactions of these types occur in nature, and to theoreticians to reach a deeper understanding of the complex relations between phase transformations, the local state of stress and associated deformation and deformation rates.

View all citing articles on Scopus

View full text

High-pressure deformation of calcite marble and its transformation to aragonite under non-hydrostatic conditions

Abstract

Acta metall.

J. Struct. Geol.

Tectonophysics

Tectonophysics

Tectonophysics

Tectonophysics

Tectonophysics

An experimental investigation into the flow of marble

Phil. Trans. R. Soc. Lond.

Effects of pressure, temperature, and grain size on the kinetics of the calcite→aragonite transformation

Can. J. Earth Sci.

Faulting associated with the olivine to spinel transformation in Mg2GeO4and its implications for deep-focus earthquakes

J. geophys. Res.

Pressure-induced embrittlement of polycrystalline tremolite Ca2Mg5Si8O22(OH,F)2

Eos

Optical determination of topotactic aragonite-calcite growth kinetics: metamorphic implications

J. Geol.

Texture development in experimentally deformed calcite rocks

Experimental deformation of polycrystalline H2O ice at high pressure and low temperature; preliminary results

J. geophys. Res.

Microscopic structure and fabric of Yule marble experimentally deformed at different strain rates

J. Geol.

Calcite fabrics in experimental shear zones

The calcite-aragonite transition: mechanism and microstructures induced by the transformation stress and strain

Bull. Mineral.

Direct measurements of the surface energies of crystals

J. appl. Phys.

A new self-organizing, mechanism for deep-focus earthquakes

Nature

Hydrolytic weakening of quartz and other silicates

Geophys. J. R. astr. Soc.

The sinking lithosphere and the focal mechanism of deep earthquakes

Faulting associated with the olivine to spinel transformation in Mg₂GeO₄and its implications for deep-focus earthquakes

Pressure-induced embrittlement of polycrystalline tremolite Ca₂Mg₅Si₈O₂₂(OH,F)₂

Experimental deformation of polycrystalline H₂O ice at high pressure and low temperature; preliminary results