Mg tracer diffusion in synthetic forsterite and San Carlos olivine as a function of P,T and fO2

We present new experimental data on Mg tracer diffusion in oriented single crystals of forsterite (Fo₁₀₀) and San Carlos olivine (Fo₉₂) between 1000–1300° C. The activation energies of diffusion are found to be 400 (±60) kJ/mol (96 kcal/mol) and 275 (±25) kJ/mol (65 kcal/ mol) in forsterite and San Carlos olivine, respectively, along [001] at a fO₂ of 10^–12 bars. There is no change in activation energy of Mg tracer diffusion within this temperature range. Mg tracer diffusion in a nominally pure forsterite is found to be anisotropic (D_c > D_a > D _b) and a function of fO₂. This fO₂ dependence is different from that in olivine containing Fe as a major element, which suggests that the diffusion mechanism of Mg in forsterite is different from that in Fe-bearing olivine at least over some range of fO₂. The diffusion mechanism in nominally pure forsterites may involve impurities present below the limits of detection or alternately, Si or Fe³⁺ interstitial defects, Fe being present as impurity (ppm level) in forsterite. Pressure dependence of Mg tracer diffusivity in forsterite measured to 10 GPa in a multianvil apparatus yields an activation volume of approximately 1–3.5 cm³/ mol. It is found that presence of small amounts of hydrogen bearing species in the atmosphere during diffusion anneal (f_H2 0.2 bars, f_H20 0.24 bars) do not affect Mg tracer diffusion in forsterite within the resolution of our measurement at a total pressure of 1 bar. The observed diffusion process is shown to be extrinsic; hence extrapolation of the diffusion data to lower temperatures should not be plagued by uncertainties related to change of diffusion mechanism from intrinsic to extrinsic.     

Grain boundary diffusion of oxygen,potassium and calcium in natural and hot-pressed feldspar aggregates

 Grain boundary diffusion rates of oxygen, potassium and calcium in fine-grained feldspar aggregates were determined experimentally. The starting materials were a natural albite rock from the Tanco pegmatite and aggregates hot-pressed from fragments of Amelia albite or Ab, Or and An composition glasses. The technique employed isotopic tracers (¹⁸O, ⁴¹K, ⁴²Ca) either evaporated onto the surface or in an aqueous solution surrounding the sample, and depth profiling using an ion microprobe (SIMS). From the depth profiles, the product of the grain boundary diffusion coefficient (D′) and effective boundary width (δ) was calculated using numerical solutions to the appropriate diffusion equation. The experimental reproducibility of D′δ is a factor of 3. A separate determination of D′ independent of δ yields an effective grain boundary width of ∼3 nm, consistent with high resolution TEM observations of a physical grain boundary width <5 nm. Oxygen (as molecular water) grain boundary diffusion rates were determined in the Ab and Or aggregates at 450°–800° C and 100 MPa (hydrothermal), potassium rates in Or aggregates at 450°–700° C both at 0.1 MPa (in air) and at 100 MPa (hydrothermal), and calcium rates in An aggregates at 700°–1100° C and 0.1 MPa (in air). Oxygen grain boundary diffusion rates are similar in all three of the Ab aggregates and in the Or aggregate. Potassium and oxygen depth profiles measured in the same samples yield different D′δ values, confirming a diffusional transport mechanism. Potassium diffusion in the Or aggregate has a greater activation energy (216 vs 78 kJ/mol) than oxygen, and the Arrhenius relations cross at ∼625° C. Potassium D′δ values in Or aggregates are about a factor of five greater in hydrothermal experiments at 100 MPa than in experiments at 0.1 MPa in air. Calcium grain boundary diffusion rates in An aggregates are 4 to 5 orders of magnitude slower than potassium in Or and have a greater (291 kJ/mol) activation energy. This suggests that differences in formal charge and/or size of diffusing species may play an important role in their relative grain boundary diffusion rates. Received: 24 December 1993 / Accepted: 16 June 1994     

Volume and grain boundary diffusion of calcium in natural and hot-pressed calcite aggregates

 Calcium self-diffusion rates in natural calcite single crystals were experimentally determined at 700 to 900° C and 0.1 MPa in a stream of CO₂. Diffusion coefficients (D) were determined from ⁴²Ca concentration profiles measured with an ion microprobe. The Arrhenius parameters yield an activation energy (Q)=382±37 kJ/mol and pre-exponential factor (D₀)=0.13 m²/s, and there is no measurable anisotropy. Calcium grain boundary diffusion rates were experimentally determined in natural (Solnhofen) limestone and hot-pressed calcite aggregates at 650° to 850° C and 0.1 to 100 MPa pressure. The Solnhofen limestone was first pre-annealed for 24 h at 700° C and 100 MPa confining pressure under anhydrous conditions to produce an equilibrium microstructure for the diffusion experiments. Values for the product of the grain boundary diffusion coefficient (D′) and the effective grain boundary diffusion width (δ) were determined from ⁴²Ca concentration profiles measured with an ion microprobe. The results show that there is no measurable difference between D′δ values obtained for pre-annealed Solnhofen samples at 0.1 and 100 MPa or between hot-pressed calcite aggregates and pre-annealed Solnhofen samples. The temperature dependence for calcium grain boundary diffusion in Solnhofen samples annealed at 0.1 MPa is described by the Arrhenius parameters D^′ ₀δ=1.5×10⁻⁹ m³/s and Q=267±47 kJ/mol. Comparison of the results of this study with previously published data show that calcium is the slowest volume diffusing species in calcite. The calcium diffusivities measured in this study place constraints on several geological processes that involve diffusive mass transfer including diffusion-accommodated mechanisms in the deformation of calcite rocks. Received: 19 December 1994/Accepted: 30 June 1995     

Oxygen diffusion in amphiboles

The kinetics of oxygen isotope self-diffusion in natural samples of hornblende, tremolite, and richterite have been measured. Samples were run under hydrothermal conditions using ¹⁸O enriched water. Profiles of ${}^{18}\text{O}\text{(}{}^{16}\text{O +}{}^{18}\text{O)}$vs depth into the crystal were obtained using an ion microprobe; the depths of sputtered holes were measured using an optical interferometer. At 1000 bars (100 MPa) water pressure, the activation energies (Q) and pre-exponential factors (D₀) for diffusion parallel to c are: D₀(cm²/sec) Q (kcal/gm-atom) T (°C) Hornblende 1⁺²⁰_?1 × 10^?741 ± 6 650–800 Tremolite 2⁺³⁰_?2× 10^?8 39 ± 5 650–800 Richterite 3⁺⁵_?2 × 10^?4 57 ± 2 650–800The diffusion coefficient (D) for hornblende at 800°C and 1000 bars water pressure measured parallel to the c crystallographic direction is at least ten times greater than that parallel to the a or b directions. An increase in water pressure from 200 to 2000 bars increases D by a factor of 2.7 for diffusion parallel to c at 800°C. The D value for hornblende at 800°C is about 0.01 that for quartz and 0.001 that for anorthite. As a result, closure temperatures for oxygen exchange in natural primary amphiboles are significantly higher than for quartz or feldspars. It is unlikely that amphiboles will exchange oxygen isotopes by diffusion under most crustal conditions.     

Oxygen bulk diffusion measurements and TEM characterization of a natural ultramylonite: implications for fluid transport in mica-bearing rocks

Oxygen bulk diffusion rates were experimentally determined in a natural ultramylonite sample ( c . 5   μ m grain size; 15–20% biotite, 20% quartz, 60–65% feldspars, and minor Fe-oxides) from the Gerrish Island shear zone, SE Maine, USA. The diffusion experiments were performed at 250–550  °C and 100  MPa water pressure. Oxygen bulk diffusion rates were determined both parallel and perpendicular to the strong foliation of the sample. The Arrhenius parameters for transport parallel to the foliation are: D _bulk0=2.0×10⁻¹¹ m² s⁻¹ and Q =30±6 kJ mol⁻¹. The bulk diffusivity perpendicular to the foliation is about a factor of 3.5 less than that parallel to the foliation with the same activation energy. The values of bulk diffusivity and activation energy obtained are consistent with ionic diffusion through a static aqueous fluid, suggesting that an interconnected fluid exists in the ultramylonite even under hydrostatic conditions. The microstructure of the ultramylonite was characterized using transmission electron microscopy (TEM). The nature and distribution of the interconnected fluid cannot be completely resolved from the TEM analysis; however, the low percentage of three-grain channels and open grain/interphase boundaries suggests that the fluid resides as a thin film on the grain surfaces. The results of this study have direct applications in many important geological settings and provide valuable insights into the observed rapid diffusion rates, strong lithological control and pervasive nature of fluid transport in mica-bearing rocks.     

Patterns and processes of oxygen isotope exchange in a fossil meteoric hydrothermal system,Cuillins Gabbro Complex,Isle of Skye,Scotland

Oxygen isotope compositions of whole rock specimens and mineral separates from the Cuillins Gabbro Complex, Isle of Skye, Scotland, are employed to determine the patterns and processes of¹⁸O depletion in the Outer Unlayered Gabbro (OUG) and associated dikes. Whole rock ¹⁸O values range from +4.8 to –1.1 (SMOW) and dike ¹⁸O values range from +4.7 to –2.8 Mineral separates from three OUG samples yield ¹⁸O values from +5.3 to +4.8 for augite and +4.1 to +0.8 for plagioclase. An early, small-scale hydrothermal circulation system was initiated by the OUG prior to the large-scale hydrothermal convection established by the later Layered Cuillins Complex (LCC). Dikes were emplaced in the OUG after intrusion of the LCC and had only a minor effect on hydrothermal circulation in the OUG. There is evidence of enhanced fluid flow along dike/gabbro contacts. Isotopic compositions of augite separates demonstrate a normal ¹⁸O value for the OUG magma with all¹⁸O depletion in the OUG due to subsolidus exchange processes including diffusion and surface reaction. The mineral separates yield a pattern of¹⁸O depletion consistent with a diffusion mechanism, the bulk of the exchange having occurred in the plagioclase. Secondary mineral formation played a subordinate role in the¹⁸O depletion of the OUG. The calculated water to rock mass ratio necessary to effect the observed¹⁸O depletion in the OUG is on the order of 0.2, although a much greater amount of water circulation probably occurred. The cooling duration required to explain the measured¹⁸O depletion in the OUG by diffusion is very short (140 years at 750° C, 2400 years at 550° C) compared to the duration necessary for pure conductive cooling (10⁵ to 10⁶ years). Rapid local cooling rates in the OUG due to meteoric water convection are consistent with the observed¹⁸O depletion in OUG samples.