Geology topics

E.J. Essene

Publications and source records attributed to E.J. Essene.

8 recordsLinked to original sources

USGS1993

Experimental investigation and application of the equilibrium rutile + orthopyroxene = quartz + ilmenite

Equilibria in the Sirf (Silica-Ilmenite-Rutile-Ferrosilite) system: {Mathematical expression} have been calibrated in the range 800-1100?? C and 12-26 kbar using a piston-cylinder apparatus to assess the potential of the equilibria for geobarometry in granulite facies assemblages that lack garnet. Thermodynamic calculations indicate that the two end-member equilibria involving quartz + geikielite = rutile + enstatite, and quartz + ilmenite = rutile + ferrosilite, are metastable. We therefore reversed equilibria over the compositional range Fs40-70, using Ag80Pd20 capsules with {Mathematical expression} buffered at or near iron-wu??stite. Ilmenite compositions coexisting with orthopyroxene are {Mathematical expression} of 0.06 to 0.15 and {Mathematical expression} of 0.00 to 0.01, corresponding to KD values of 13.3, 10.2, 9.0 and 8.0 (??0.5) at 800, 900, 1000 and 1100?? C, respectively, where KD=(XMg/XFe)Opx/(XMg/XFe)Ilm. Pressures have been calculated using equilibria in the Sirf system for granulites from the Grenville Province of Ontario and for granulite facies xenoliths from central Mexico. Pressures are consistent with other well-calibrated geobarometers for orthopyroxeneilmenite pairs from two Mexican samples in which oxide textures appear to represent equilibrium. Geologically unreasonable pressures are obtained, however, where oxide textures are complex. Application of data from this study on the equilibrium distribution of iron and magnesium between ilmenite and orthopyroxene suggests that some ilmenite in deep crustal xenoliths is not equilibrated with coexisting pyroxene, while assemblages from exposed granulite terranes have reequilibrated during retrogression. The Sirf equilibria are sensitive to small changes in composition and may be used for determination of activity/composition (a/X) relations of orthopyroxene if an ilmenite model is specified. A symmetric regular solution model has been used for orthopyroxene in conjunction with activity models for ilmenite available from the literature to calculate a/X relations in orthopyroxene of intermediate composition. Data from this study indicate that FeSiO3-MgSiO3 orthopyroxene exhibits small, positive deviations from ideality over the range 800-1100??C. ?? 1993 Springer-Verlag.

Contributions to Mineralogy and Petrology↗

USGS1993

Heat capacity and phase equilibria of almandine, Fe3Al2Si3O12

The heat capacity of a synthetic almandine, Fe 3 Al 2 Si 3 O 12 , was measured from 6 to 350 K using equilibrium, intermittent-heating quasi-adiabatic calorimetry and from 420 to 1000 K using differential scanning calorimetry. These measurements yield Cp 298 = 342.80 ± 1.4 J/mol · K and S 298 o = 342.60 J/mol · K. Mössbauer characterizations show the almandine to contain less than 2 ± 1% of the total iron as Fe 3+ . X-ray diffraction studies of this synthetic almandine yield a = 11.521 ± 0.001 Å and V 298 o = 115.11 +- 0.01 cm 3 /mol, somewhat smaller than previously reported. The low-temperature Cp data indicate a lambda transition at 8.7 K related to an antiferromagnetic-paramagnetic transition with T N = 7.5 K . Modeling of the lattice contribution to the total entropy suggests the presence of entropy in excess of that attributable to the effects of lattice vibrations and the magnetic transition. This probably arises from a low-temperature electronic transition (Schottky contribution). Combination of the Cp data with existing thermodynamic and phase equilibrium data on almandine yields ΔG f ,298 o = −4938.3 kJ/mol and ΔH f ,298 o = —5261.3 kJ/mol for almandine when calculated from the elements. The equilibrium almandine = hercynite + fayalite + quartz limits the upper T P "> TP for almandine and is metastably located at ca. 570°C at P = 1 bar, with a dP dT "> dPdT of +17 bars/°C. This agrees well with reversed experiments on almandine stability when they are corrected for magnetite and hercynite solid-solutions. In ‖ O 2- T space, almandine oxidizes near QFM by the reactions almandine + O 2 = magnetite + sillimanite + quartz and almandine + 02 = hercynite + magnetite + quartz . With suitable correction for reduced activities of solid phases, these equilibria provide useful oxygen barometers for medium- to high-grade metamorphic rocks.

Geochimica et Cosmochimica Acta↗

USGS1992

Differential unroofing within the central metasedimentary Belt of the Grenville Orogen: constraints from 40Ar/39Ar thermochronology

An 40Ar/39Ar thermochronological investigation of upper greenschist to granulite facies gneiss, amphibolite and marble was conducted in the Central Metasedimentary Belt (CMB), Ontario, to constrain its cooling history. Incremental 40Ar/39Ar release spectra indicate that substantial differential unroofing occurred in the CMB between ??? 1000 and ??? 600 Ma. A consistent pattern of significantly older hornblende and phlogopite 40Ar/3Ar cooling ages on the southeast sides of major northeast striking shear zones is interpreted to reflect late displacement due to extensional deformation. Variations in hornblende 40Ar/39Ar age plateaus exceeding 200 Ma occur over distances less than 50 km with major age discontinuities occurring across the Robertson Lake shear zone and the Sharbot Lake mylonite zone which separate the Sharbot Lake terrane from the Elzevir and Frontenac terranes. Extensional displacements of up to 14 km are inferred between the Frontenac and Elzevir terranes of the CMB. No evidence for significant post argon-closure vertical displacement is indicated in the vicinity of the Perth Road mylonite within the Frontenac terrane. Variations of nearly 100 Ma in phlogopite 40Ar/39Ar plateau ages occur in undeformed marble on either side of the Bancroft Shear Zone. Phlogopites from sheared and mylonitized marble within the shear zone yield 40Ar/39Ar diffusional loss profiles, but have older geologically meaningless ages thought to reflect incorporation of excess argon. By ??? 900 Ma, southeast directed extension was occurring throughout the CMB, possibly initiated along previous zones of compressional shearing. An easterly migration of active zones of extension is inferred, possibly related to an earlier, overall easterly migration of active zones of regional thrusting and easterly migration of an ancient subduction zone. The duration of extensional shearing is not well constrained, but must have ceased before ??? 600 Ma as required by the deposition of overlying undeformed Cambrian and/or Ordovician sedimentary rocks. ?? 1992 Springer-Verlag.

Contributions to Mineralogy and Petrology↗

USGS1990

Metamorphism in the Adirondacks: II. The role of fluids

Quantitative estimates of metamorphic fluid speciation, stable isotopic analyses, and studies of fluid inclusions all document the local complexity of fluids in the deep crustal rocks exposed in the Adirondack Mountains, NY. Estimates of the activity of H 2 O in the granulite facies are substantially lower than in the amphibolite facies gneisses. The onset of low water activities in semi-pelitic gneisses generally correlates with migmatitic textures in the uppermost amphibolite facies, suggesting that partial melts absorbed H 2 O at the peak of metamorphism. In granulite facies marbles and calc-silicates, conditions varied from extremely undersaturated in H 2 O-CO 2 fluid to fluid saturated, and α H2O and α CO2 show sharp gradients within single outcrops. Low values of f O2 and f H2O , or of f CO2 , and f H2O indicate fluid-absent conditions for some orthogneisses and marbles, which are inferred to have been ‘dry’ rocks before and during granulite facies recrystallization. Wollastonite is preserved from early contact metamorphism and serves as an index mineral for fluid-absent conditions in granulites where α H2O is low. Values of f O2 range from near the hematite + magnetite buffer in metamorphosed iron formation to substantially below the quartz + magnetite + fayalite buffer in some orthogneisses. The anorthosite suite is more oxidized than some associated granitic gneisses. Halogens (F and Cl) substitute extensively for OH in micas and amphiboles, extending their stability, although F 2 , Cl 2 , HCl, and HF are minor components in any fluid. Oxybiotite-type exchanges involving O for OH are also important, extending the stability of biotite. Stable isotopic ratios of O and C demonstrate that premetamorphic whole-rock compositions are commonly preserved whereas mineral compositions generally reflect equilibration at the peak of metamorphism. The Marcy Anorthosite Massif was intruded as a high δ 18 O magma. The combination of mineral equilibria, stable isotope data, and fluid inclusions is used to identify and to distinguish among pre-orogenic contact metamorphic/hydrothermal events, peak metamorphic events, and retrograde/postmetamorphic events. Polymetamorphism is documented at skarn zones adjacent to anorthosite, where large volumes of hydrothermal fluid were channeled during early, shallow contact metamorphism and where conditions were fluid poor during subsequent regional metamorphism. Peak metamorphic events are inferred to have been caused primarily by magmatic processes of intrusion and anatexis. Partial melting has caused low values of α H2O in many rocks, but in other cases low values of α H2O are recorded in orthogneisses derived from H 2 O-poor magmas. Isotopic studies show that maximum fluid/rock ratios were <0·l and possibly 0·0 for infiltrating fluids at the peak of metamorphism in many localities. No evidence of pervasive, regional infiltration by a fluid at the peak of metamorphism has been substantiated in the Adirondacks. Fluid inclusions containing high-density CO 2 or CO 2 + H 2 O represent conditions from after the peak of metamorphism and document isobaric cooling, in agreement with estimates from garnet zoning. Fine-scale retrograde veins are common and are associated with high-density CO 2 -rich fluid inclusions.

New York↗

USGS1988

Oxygen isotope variations in granulite-grade iron formations: constraints on oxygen diffusion and retrograde isotopic exchange

The oxygen isotope ratios of various minerals were measured in a granulite-grade iron formation in the Wind River Range, Wyoming. Estimates of temperature and pressure for the terrane using well calibrated geothermometers and geobarometers are 730??50?? C and 5.5??0.5 kbar. The mineral constraints on fluid compositions in the iron formation during retrogression require either very CO2-rich fluids or no fluid at all. In the iron formation, isotopic temperature estimates from quartz-magnetite fractionations are controlled by the proximity to the enclosing granitic gneiss, and range from 500?? C (??qz - mt=10.0???) within 2-3 meters of the orthogneiss contact to 600?? C (??qz - mt=8.0???) farther from the contact. Temperature estimates from other isotopic thermometers are in good agreement with those derived from the quartz-magnetite fractionations. During prograde metamorphism, the isotopic composition of the iron formation was lowered by the infiltration of an external fluid. Equilibrium was achieved over tens of meters. Closed-system retrograde exchange is consistent with the nearly constant whole-rock ??18Owr value of 8.0??0.6???. The greater ??qz-mt values in the iron formation near the orthogneiss contact are most likely due to a lower oxygen blocking temperature related to greater exchange-ability of deformed minerals at the contact. Cooling rates required to preserve the quartz-magnetite fractionations in the central portion of the iron formation are unreasonably high (???800?? C/Ma). In order to preserve the 600?? C isotopic temperature, the diffusion coefficient D (for ??-quartz) should be two orders of magnitude lower than the experimentally determined value of 2.5??10-16 cm2/s at 833 K. There are no values for the activation energy (Q) and pre-exponential diffusion coefficient (D0), consistent with the experimentally determined values, that will result in reasonable cooling rates for the Wind River iron formation. The discrepancy between the diffusion coefficient inferred from the Wind River terrane and that measured experimentally is almost certainly due to the enhancement of exchange by the presence of water in the laboratory experiments. Cooling rate estimates were also determined for iron formation retrograded under water-rich conditions. Application of the experimentally determined data to these rocks results in a reasonable cooling rate estimate, supporting the conclusion that the presence of water greatly enhances oxygen diffusion. ?? 1988 Springer-Verlag.

Contributions to Mineralogy and Petrology↗

USGS1987

Heat capacity measurements for cryolite (Na3AlF6) and reactions in the system NaFeAlSiOF

The heat capacity of cryolite (Na 3 AlF 6 ) has been measured from 7 to 1000 K by low-temperature adiabatic and high-temperature differential scanning calorimetry. Low-temperature data were obtained on material from the same hand specimen in the calorimetric laboratories of the University of Michigan and U.S. Geological Survey. The results obtained are in good agreement, and yield average values for the entropy of cryolite of: S 0 298 = 238.5 J / mol K "> S 0 298 = 238.5J/mol K S 0 T − S 0 298 = 145.114 ln T+ 193.009∗10 −3 T− 10.366∗ 10 5 T 2 − 872.89 J / mol K (273−836.5 K ) "> S 0 T −S 0 298 = 145.114lnT+ 193.009∗10 −3 T−10.366∗ 10 5 T 2 − 872.89J/mol K(273−836.5K) Δ S Trans = 9.9 J / mol K "> ΔS Trans = 9.9J/mol K S 0 T − S 0 298 =198.414 ln T+73.203∗ 10 −3 T−63.814∗ 10 5 T 2 −1113.11 J / mol K (836.5−1153 K ) "> S 0 T −S 0 298 =198.414 ln T+73.203∗ 10 −3 T−63.814∗10 5 T 2 −1113.11J/mol K(836.5−1153K) with the transition temperature between α- and β-cryolite taken at 836.5 K. These data have been combined with data in the literature to calculate phase equilibria for the system Na Fe Al Si O F. The resultant phase diagrams allow constraints to be placed on the f O 2 , f F 2 , a SiO 2 and T conditions of formation for assemblages in alkalic rocks. A sample application suggests that log f O 2 is approximately −19.2, log f F 2 is −31.9 to −33.2, and a SiO 2 is −1.06 at assumed P T "> PT conditions of 1000 K, 1 bar for the villiaumite-bearing Ilimaussaq intrusion in southwestern Greenland.

Geochimica et Cosmochimica Acta↗

USGS1986

The heat capacity of a natural monticellite and phase equilibria in the system CaO-MgO-SiO2-CO2

The heat capacity of a natural monticellite (Ca 1.00 Mg .09 Fe .91 Mn .01 Si 0.99 O 3.99 ) measured between 9.6 and 343 K using intermittent-heating, adiabatic calorimetry yields C p 0 (298) and S 298 0 of 123.64 ± 0.18 and 109.44 ± 0.16 J · mol −1 K −1 respectively. Extrapolation of this entropy value to end-member monticellite results in an S 0 298 = 108.1 ± 0.2 J · mol −1 K −1 . High-temperature heat-capacity data were measured between 340–1000 K with a differential scanning calorimeter. The high-temperature data were combined with the 290–350 K adiabatic values, extrapolated to 1700 K, and integrated to yield the following entropy equation for end-member monticellite (298–1700 K): S T 0 ( J · mol −1 K −1 ) = S 298 0 + 164.79 In T + 15.337 · 10 −3 T + 22.791 · 10 5 T −2 − 968.94. Phase equilibria in the CaO-MgO-SiO 2 system were calculated from 973 to 1673 K and 0 to 12 kbar with these new data combined with existing data for akermanite ( Ak ), diopside ( Di ), forsterite ( Fo ), merwinite ( Me ) and wollastonite ( Wo ). The location of the calculated reactions involving the phases Mo and Fo is affected by their mutual solid solution. A best fit of the thermodynamically generated curves to all experiments is made when the S 0 298 of Me is 250.2 J · mol −1 K −1 less than the measured value of 253.2 J · mol −1 K −1 . A best fit to the reversals for the solid-solid and decarbonation reactions in the CaO-MgO-SiO 2 -CO 2 system was obtained with the ΔG 0 298 ( kJ · mole −1 ) for the phases Ak (−3667), Di (−3025), Fo (−2051), Me (−4317) and Mo (−2133). The two invariant points − Wo and − Fo for the solid-solid reactions are located at 1008 ± 5 K and 6.3 ± 0.1 kbar, and 1361 ± 10 K and 10.2 ± 0.2 kbar respectively. The location of the thermodynamically generated curves is in excellent agreement with most experimental data on decarbonation equilibria involving these phases.

Geochimica et Cosmochimica Acta↗

USGS1985

The heat-capacity of ilmenite and phase equilibria in the system Fe-T-O

Low temperature adiabatic calorimetry and high temperature differential scanning calorimetry have been used to measure the heat-capacity of ilmenite (FeTiO 3 ) from 5 to 1000 K. These measurements yield S 298 0 = 108.9 J /( mol · K ). Calculations from published experimental data on the reduction of ilmenite yield Δ 298 0 ( I 1) = −1153.9 kJ /( mol · K ). These new data, combined with available experimental and thermodynamic data for other phases, have been used to calculate phase equilibria in the system Fe-Ti-O. Calculations for the subsystem Ti-O show that extremely low values of ƒO 2 ">ƒ ƒO2 are necessary to stabilize TiO, the mineral hongquiite reported from the Tao district in China. This mineral may not be TiO, and it should be re-examined for substitution of other elements such as N or C. Consideration of solid-solution models for phases in the system Fe-Ti-O allows derivation of a new thermometer/oxybarometer for assemblages of ferropseudobrookite-pseudobrookite ss and hematite-ilmenite ss . Preliminary application of this new thermometer/oxybarometer to lunar and terrestrial lavas gives reasonable estimates of oxygen fugacities, but generally yields subsolidus temperatures, suggesting re-equilibration of one or more phases during cooling.

Geochimica et Cosmochimica Acta↗