Oxygen isotopic distribution in an amoeboid olivine aggregate from the Allende CV chondrite: Primary and secondary processes

The oxygen isotopic distribution in an amoeboid olivine aggregate (AOA), TTA1-02, from the Allende CV3 chondrite has been determined by secondary ion mass spectrometry. The irregular shaped TTA1- 02 (5×3mm) consists mostly of olivine grains of ca. 5μm in diameter. Olivine grains of Mg-rich (Fo₉₅) and Fe-rich (Fo₆₀) composition are in direct contact with each other, with a sharp compositional boundary. Oxygen isotopic compositions of Fe-rich olivine grains are ¹⁶O-poor (Δ¹⁷O ≅ −5‰), whereas Mg-rich olivine is ¹⁶O-rich (Δ¹⁷O ≅ −25‰). Several Al-rich inclusions (<ca. 500 μm in diameter) are enclosed by olivine grains in the AOA. Oxygen isotopic compositions of spinel and fassaite in Al-rich inclusions are ¹⁶O-rich (Δ¹⁷O ≅ −20‰), whereas those of anorthite, nepheline and phyllosilicate are ¹⁶O-poor (Δ¹⁷O ≅ −5‰). We propose the following sequence of events during the formation of AOAs in the Allende meteorite: 1) Formation of Al-rich inclusions with ¹⁶O-rich oxygen isotopic composition; 2) Accretion of Mg-rich olivine grains with ¹⁶O-rich oxygen isotopic composition around Al-rich inclusions; 3) Accretion into parent body; and 4) Aqueous alteration in the parent body, which led to crystallization of ¹⁶O-poor minerals, Fe-rich olivine, anorthite, nepheline, and phyllosilicate. This is reflecting reactions among primary ¹⁶O-rich AOA minerals and aqueous fluid having ¹⁶O-poor oxygen isotopic composition. Fe-rich olivine grains precipitated from aqueous fluids, which partially dissolved pre-existing Mg-rich olivine grains. Sintering and Mg-Fe diffusion occurred during thermal metamorphism. Anorthite, nepheline and phyllosilicate in Al-rich inclusions replaced primary anorthite or melilite during the aqueous alteration stage.     

Experimental determination of the diffusion coefficient for calcium in olivine between 900°C and 1500°C

Experiments have been carried out to determine the temperature, oxygen fugacity (fO₂) and compositional dependence of the tracer diffusion coefficient (D) of calcium in olivine. These data constrain the diffusion coefficient over the temperature range 900 to 1500°C for the three principal crystallographic axes. Well constrained linear relationships between the reciprocal of the absolute temperature and log(D) exist at any given oxygen fugacity. There is a strong dependence of the diffusion coefficient on oxygen fugacity with D ∝ fO₂^(1/3). This makes a knowledge of the T-fO₂ path followed by geological samples a prerequisite for modelling Ca diffusion in olivine. The best fitting preexponential factor (Do) and activation energy (E) to the Arrhenius equation log (D) = log [Do exp(−E/RT)] + 0.31Δ log fO₂ for Ca diffusion in olivine at a given oxygen fugacity (fO₂*) are given by:diffusion along [100]: log [Do (m²/s)] = −10.78 ± 0.43; E = 193 ± 11 kJ/moldiffusion along [010]: log [Do (m²/s)] = −10.46 ± 0.37; E = 201 ± 10 kJ/moldiffusion along [001]: log [Do (m²/s)] = −10.02 ± 0.29; E = 207 ± 8 kJ/molwhere Δ log fO₂ = log[fO₂*] − log[10⁻¹²] with fO₂* in units of bars. There is no measurable compositional dependence of the diffusion coefficient between Fo₈₃ and Fo₉₂. Diffusion in Fo₁₀₀ has a much higher activation energy than in Fe-bearing olivine and has a weaker fO₂ dependence.     

Application of the cBΩ model to the calculation of diffusion parameters of He in olivine

The validity of the thermodynamic cBΩ model is tested in terms of the experimentally determined diffusion coefficients of He in a natural Fe-bearing olivine (Fo₉₀) and a synthetic end-member forsterite (Mg₂SiO₄) over a broad temperature range (250–950 °C), as reported recently by Cherniak and Watson (Geochem Cosmochim Acta 84:269–279, 2012). The calculated activation enthalpies for each of the three crystallographic axes were found to be (134 ± 5), (137 ± 13) and (158 ± 4) kJ mol^?1 for the [100], [010] and [001] directions in forsterite, and (141 ± 9) kJ mol^?1 for the [010] direction in olivine, exhibiting a deviation of <1 % with the corresponding reported experimental values. Additional point defect parameters such as activation volume, activation entropy and activation Gibbs free energy were calculated as a function of temperature. The estimated activation volumes (3.2–3.9 ± 0.3 cm³ mol^?1) of He diffusion in olivine are comparable with other reported results for hydrogen and tracer diffusion of Mg cations in olivine. The pressure dependence of He diffusion coefficients was also determined, based on single experimental diffusion measurements at 2.6 and 2.7 GPa along the [001] direction in forsterite at 400 and 650 °C.     

Partitioning of Ni between olivine and silicate melt: The ‘Henry's Law problem’ reexamined

The partitioning of Ni between olivine and silicate melt has been investigated experimentally at atmospheric pressure in air. Beta track autoradiography using ⁶³Ni and direct microprobe analysis of polished run products were employed. At constant temperature and bulk composition, the $\text{olivine}\text{liquid}$ partition coefficient for Ni in the system Di₇₀Fo₂₅Qtz₅ remains independent of concentration from approximately 10 ppm to 40,000 ppm Ni in olivine. Similar experiments by Mysen (1979) in the system Jd₈₀Fo₂₀ utilizing beta track autoradiography alone indicated that Henry's Law was followed only in the concentration interval of approx. 10–1000 ppm Ni in olivine. Above 1000 ppm, olivine/liquid partition coefficients decreased monotonically to about half of the value observed below 1000 ppm. We have performed experiments in the system Jd₈₀Fo₂₀, but are unable to replicate Mysen's results. While in agreement with Mysen below 1000 ppm Ni in olivine, we do not observe the decrease in partition coefficient value at higher concentrations. We conclude from our reversed experiments that, at constant temperature and bulk composition, the $\text{olivine}\text{liquid}$ partition coefficient for Ni in the system Jd₈₀Fo₂₀ remains independent of concentration from approx. 10–60,000 ppm Ni in olivine. Attempts to resolve these differing conclusions by changing experimental techniques have been unsuccessful.     

Cr-spinel/olivine and Cr-spinel/liquid nickel partition coefficients from natural samples

The Nernst partition coefficient of nickel (D^Ni) between Cr-spinel and silicate melt in natural systems has been investigated using mid-ocean ridge basalts (MORB) and other volcanic rocks. The Cr-spinel/olivine D^Ni values in volcanic rocks are between 1.2 and 0.3, indicating that the Cr-spinel/liquid D^Ni values vary from slightly higher to significantly lower than the olivine/liquid D^Ni values in natural systems. The Cr-spinel/liquid D^Ni values from the MORB samples vary between 6 and 11, slightly higher than those from the S-bearing experiments of Satari et al. [Satari P., Brenan J. M., Horn I. and McDonough W. F. (2002) Experimental constraints on the sulfide- and chromite-silicate melt partitioning behavior of rhenium and platinum-group elements. Economic Geology97, 385-398]. The results of the MORB samples and the experiments of Satari et al. (2002) indicate a negative correlation between the Cr-spinel/liquid D^Ni and the X_Cr values in Cr-spinels (Cr cation number on the basis of 3 total cations in the spinel structure). Variations of Cr-spinel/liquid D^Ni values with Cr-spinel compositions can be estimated from an empirical equation based on the results of the MORB samples and the experiments by Satari et al. (2002). The choice of Cr-spinel/liquid D^Ni = 10 for numerical modeling by Righter et al. [Righter K., Leeman W. P. and Hervig R. L. (2006) Partitioning of Ni, Co, and V between spinel-structured oxides and silicate melts: importance of spinel composition. Chemical Geology227, 1-25] is reasonable for basaltic systems. For picritic and komatiitic systems a lower value of ∼5 is more appropriate.     

Base metal mineral segregation and Fe-Mg exchange inducing extreme compositions of olivine and chromite from the Xiadong Alaskan-type complex in the southern part of the Central Asian Orogenic Belt

The Xiadong Alaskan-type complex shares much in common with typical Alaskan-type complexes worldwide, while showing some unique features in terms of mineral compositions. Olivine from the Xiadong dunites is characterized by extremely high Fo component of 91.7–96.7 and anomalously negative correlation of Fo with NiO, while chromite is featured by high 100 × Fe³⁺/(Fe³⁺ + Cr + Al) (>70), high 100 × Fe²⁺/(Fe²⁺ + Mg) (>70), high 100 × Cr/(Cr + Al) (>90), low MnO (<0.6 wt%) and TiO₂ contents (<0.5 wt%). To investigate these particular features, we conducted petrographic observation and mineral composition analyses for the Xiadong dunite. A number of Fe and/or Ni sulfides and alloys occurring as inclusions in olivine and chromite indicate that base metal mineral segregation took place prior to crystallization of olivine and chromite and probably induced Fe and Ni depletions in olivine. The FeO and MgO variations in profile analyses from chromite to adjacent olivine are compatible with Fe-Mg exchange. The diffusion mechanism of Fe from olivine to chromite and Mg from chromite to olivine may have elevated both Fo of olivine and 100 × Fe²⁺/(Mg + Fe²⁺) ratio of chromite and further enhanced the decoupling of Fo and NiO in olivine. We thus suggest that base metal mineral segregation and Fe-Mg exchange play important roles in the extreme compositions of the Xiadong dunite. The Ni depletion of olivine and degree of Fe-Mg exchange between olivine and chromite may be used as indicators of mineralization in mafic-ultramafic intrusions.     

Diffusion of trace elements in FeNi metal: Application to zoned metal grains in chondrites

We have measured diffusion coefficients for P, Cr, Co, Ni, Cu, Ga, Ge, Ru, Pd, Ir, and Au in Fe metal from 1150 to 1400°C and at 1 bar and 10 kbar. Diffusion couples were prepared from high-purity Fe metal and metal from the IIA iron meteorite Coahuila (single crystal kamacite) or the pallasite Springwater (polycrystalline kamacite) and held at run conditions for 3.5 to 123 h. Diffusion profiles were measured using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) or the electron microprobe. Many elements were measured from the same experimental runs so interelemental comparisons are improved over other data sets in which data for different elements come from different experiments. Some literature diffusion coefficients (D) for Ni and Co in taenite can be up to a factor of 3 higher for Ni than Co, yet our results show no difference (e.g., D_Ni and D_Co ∼ 2.2 × 10^-15 m²/s at 1150°C). Thus, diffusion of Ni and Co in single crystal taenite will not measurably fractionate the Ni/Co ratio. On the other hand, the large difference in D_Ni and D_Ir (D_Ir is ∼5 times lower) and the similarity of D_Ni and D_Ru at all temperatures investigated indicates that Ni/Ir and Ni/Ru ratios in zoned metal grains will be useful discriminators of processes controlled by diffusion vs. volatility. In zoned metal grains in primitive chondrites, deviations of the Ni/Ru and Ni/Ir ratios from a condensation curve are opposite to a diffusion-controlled process, but consistent with a volatility-controlled process. The new multielement diffusion coefficients will also be useful in evaluating a variety of other processes in planetary science.     

Development of orthopyroxene-Fe/Mg ferrite symplectites by continuous olivine oxidation

The development of orthopyroxene-Fe/Mg ferrite symplectites associated with olivine is discussed with respect to the chemical reactions by which they form. Previously proposed reactions are presented graphically and the differences between them are reviewed. With the exception of exsolution, these are all discontinuous reactions in the sense that olivine is replaced by the two-phase symplectite assemblage.Olivine-hosted symplectites developed in the margins of lherzolite xenoliths from Kauai, Hawaii, demonstrate a reaction mechanism which has not been previously documented from natural samples. Original Fo₉₀ olivine in these samples oxidized to a new assemblage consisting of orthopyroxene (En_92–95)-Fe/Mg ferrite (Mf_35–50) symplectites developed within more magnesian olivine (Fo_92–96) hosts. Thus, by this mechanism, olivine of a different composition persists as part of a final three-phase assemblage. As oxidation advanced, the compositions of all three product phases became continuously more magnesian and the stoichiometric coefficients of the orthopyroxene and Fe/Mg ferrite continuously increased, whereas those of the product olivine decreased in the mass-balance equations. These characteristics demonstrate that the reaction was controlled by oxygen diffusion into the xenoliths from the highly oxidized alkali picrite melt in which they were entrained. Thermodynamic calculations suggest that a gradient in oxygen fugacity of 10^0.9 bars existed across the xenolith rims and resulted in compositional gradients of 4 mol% fayalite and ferrosilite and 15 mol% magnetite.     

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.     

Tracer diffusion of Mg, Ca, Sr, and Ba in Na-aluminosilicate melts

We employed the thin source technique to investigate tracer diffusion of Mg, Ca, Sr, and Ba in glasses and supercooled melts of albite (NaAlSi₃O₈) and jadeite (NaAlSi₂O₆) compositions. The experiments were conducted at 1 bar and at temperatures between 645 and 1025°C. Typical run durations ranged between 30 min and 35 days. The analysis of the diffusion profiles was performed with the electron microprobe. Diffusivities of Ca, Sr, and Ba were found to be independent of either duration t of the experiment or tracer concentration M, initially introduced into the sample. Mg exhibits a diffusivity depending on run time and concentration and tracer diffusivity is derived by extrapolation to M/√t = 0. Temperature dependence of the diffusivity D can be represented by an Arrhenius equation D = D_o exp(−E_a/RT), yielding the following least-squares fit parameters (with D in m²/s and E_a in kJ/mol): D_Mg = 1.8 · 10⁻⁵ exp(−234 ± 20/RT), D_Ca = 3.5 · 10⁻⁶ exp(−159 ± 6/RT), D_Sr = 3.6 · 10⁻⁶ exp(−160 ± 6/RT), and D_Ba = 6.0 · 10⁻⁶ exp(−188 ± 12/RT) for albite; and D_Mg = 8.3 · 10⁻⁶ exp(−207 ± 18/RT), D_Ca = 3.8 · 10⁻⁶ exp(−153 ± 4/RT), D_Sr = 2.3 · 10⁻⁶ exp(−150 ± 4/RT), and D_Ba = 3.7 · 10⁻⁵ exp(−198 ± 4/RT) for jadeite composition. Ca and Sr diffusivities agree within error in both compositions and exhibit the fastest diffusivities, whereas Mg reveals the lowest diffusivity. The relationship between activation energy and radius shows a minimum at Ca and Sr for albite and jadeite compositions extending the relationship already observed elsewhere for alkalies. With increasing substitution of Si by (Na + Al), diffusivities increase, whereas activation energies decrease. Furthermore, a simple model modified from that of Anderson and Stuart (Anderson O. L. and Stuart D. A., “Calculation of activation energy of ionic conductivity in silica glasses by classical methods,” J. Am. Ceram. Soc.37, 573-580, 1954) is discussed for calculating the activation energies.     

Platinum group element geochemistry of komatiites from the Alexo and Pyke Hill areas, Ontario, Canada

Thirty-three whole-rock drill core samples and thirteen olivine, chromite, and sulfide separates from three differentiated komatiite lava flows at Alexo and Pyke Hill, Canada, were analyzed for PGEs using the Carius tube digestion ID-ICP-MS technique. The emplaced lavas are Al-undepleted komatiites with ∼27% MgO derived by ∼50% partial melting of LILE-depleted Archean mantle. Major and minor element variations during and after emplacement were controlled by 30 to 50% fractionation of olivine Fo_93-94. The emplaced lavas are characterized by (Pd/Ir)_N = 4.0 to 4.6, (Os/Ir)_N = 1.07, and Os abundances of ∼2.3 ppb. Variations in PGE abundances within individual flows indicate that Os and Ir were compatible (bulk D_Os,Ir = 2.4-7.1) and that Pt and Pd were incompatible (bulk D_Pt,Pd < 0.2) during lava differentiation, whereas bulk D_Ru was close to unity. Analyses of cumulus olivine separates indicate that PGEs were incompatible in olivine (D_PGEs^Ol-Liq = 0.04-0.7). The bulk fractionation trends cannot be accounted for by fractionation of olivine alone, and require an unidentified Os-Ir-rich phase. The composition of the mantle source (Os = 3.9 ppb, Ir = 3.6 ppb, Ru = 5.4 ppb, Pt and Pd = 5.7 ppb) was constrained empirically for Ru, Pt, and Pd; the Os/Ir ratio was taken to be identical to that in the emplaced melt, and the Ru/Ir ratio was taken to be chondritic, so that the absolute IPGE abundances of the source were determined by Ru. This is the first estimate of the PGE composition of a mantle source derived from analyses of erupted lavas. The suprachondritic Pd/Ir and Os/Ir of the inferred Abitibi komatiite mantle source are similar to those in off-craton spinel lherzolites, orogenic massif lherzolites, and enstatite chondrites, and are considered to be an intrinsic mantle feature. Bulk partition coefficients for use in komatiite melting models derived from the source and emplaced melt compositions are: D_Os,Ir = 2.3, D_Ru = 1.0, D_Pt,Pd = 0.07. Ruthenium abundances are good indicators of absolute IPGE abundances in the mantle sources of komatiite melts with 26 to 29% MgO, as Ru fractionates very little during both high degrees of partial melting and lava differentiation.     

Diffusion compensation in natural silicates

The temperature dependence of diffusion is usually found to follow the Arrhenius law: D = D₀e^?E/RT Winchell (1969) showed that there is commonly an inter-dependence between D₀ and E (for diffusion in silicate glasses), such that diffusion of different species show a positive correlation on a log D₀ vs E plot. A similar effect was noted by Hofmann (1980) for cation diffusion in basalt. This implies that diffusion rates of different species tend to converge at a particular temperature; this effect is known as the ‘compensation effect’. I will show that this effect is also present for diffusion in feldspars and olivines. The equations for the compensation lines (with E given in kcal/mol) are: basalt—E = 50 + 7.5 log D₀ feldspar—E = 50.7 + 3.4 log D₀ olivine—E = 78.0 + 7.5 log D₀ The convergence, or crossover, temperatures for diffusion in various materials are: obsidian—3400°C basalt—1370°C olivine—1360°C feldspar—460°C Compensation plots are useful for evaluating and comparing experimental diffusion data (though of limited usefulness in a predictive sense) and for understanding ‘closure temperatures’ for diffusion in petrogenetic processes (since closure temperature, the temperature at which natural diffusion processes are frozen in, is dependent on E, log d₀, and cooling rate). I show that most diffusing species in feldspar have a closure-temperature close to the crossover or convergence temperature, implying that all species in feldspars can be expected to ‘freeze-in’ simultaneously at temperatures in the range 400–600°C (for cooling rates in the range 10¹–10⁵°C/myr). Closure temperatures of various species in olivine, on the other hand, span a much larger range (800°C) for a similar range in cooling rates, implying that different elements in olivine will record different time-temperature stages in petrogenetic processes.     

Co2+ and Ni2+ diffusion in olivine determined by secondary ion mass spectrometry

Diffusion coefficients of Co²⁺ and Ni²⁺ in synthetic single crystal forsterite along the c-axis were determined in the temperature ranges, 700–1200?°C and 800–1300?°C, respectively. The synthesized forsterite specimens were coated with thin evaporated films of CoO and NiO on the c-surface and annealed for diffusion experiments. The short penetration distance of diffusing ions in forsterite was measured by secondary ion mass spectrometry using the depth profile method. The diffusion coefficients of Co (700–1200?°C) and Ni (800–1300?°C) are given by: and The observed diffusion coefficient values show good linear relationships in Arrhenius plots and the activation energy values obtained agree well with the previous values, although the diffusion coefficient values observed at the high temperature end of the experimental range deviate from the previous values. These results indicate that Co and Ni diffuse in olivine with a single mechanism within the temperature range observed, possibly with an extrinsic in nature as in the case of Mg tracer diffusion observed by Chakraborty et?al. 1994 and of Fe-Mg interdiffusion by Chakraborty.     

Fe–Mg interdiffusion rates in clinopyroxene: experimental data and implications for Fe–Mg exchange geothermometers

Chemical interdiffusion of Fe–Mg along the c-axis [001] in natural diopside crystals (X _Di = 0.93) was experimentally studied at ambient pressure, at temperatures ranging from 800 to 1,200 °C and oxygen fugacities from 10^?11 to 10^?17 bar. Diffusion couples were prepared by ablating an olivine (X _Fo = 0.3) target to deposit a thin film (20–100 nm) onto a polished surface of a natural, oriented diopside crystal using the pulsed laser deposition technique. After diffusion anneals, compositional depth profiles at the near surface region (~400 nm) were measured using Rutherford backscattering spectroscopy. In the experimental temperature and compositional range, no strong dependence of D ^Fe–Mg on composition of clinopyroxene (Fe/Mg ratio between Di₉₃–Di₆₅) or oxygen fugacity could be detected within the resolution of the study. The lack of fO₂-dependence may be related to the relatively high Al content of the crystals used in this study. Diffusion coefficients, D ^Fe–Mg, can be described by a single Arrhenius relation with $$D^{{{\text{Fe}} - {\text{Mg}}}} = 2. 7 7\pm 4. 2 7\times 10^{ - 7} {\text{exp(}}-3 20. 7\pm 1 6.0{\text{ kJ}}/{\text{mol}}/{\text{RT)m}}^{ 2} /{\text{s}}.$$ D ^Fe–Mg in clinopyroxene appears to be faster than diffusion involving Ca-species (e.g., D ^Ca–Mg) while it is slower than D ^Fe–Mg in other common mafic minerals (spinel, olivine, garnet, and orthopyroxene). As a consequence, diffusion in clinopyroxene may be the rate-limiting process for the freezing of many geothermometers, and compositional zoning in clinopyroxene may preserve records of a higher (compared to that preserved in other coexisting mafic minerals) temperature segment of the thermal history of a rock. In the absence of pervasive recrystallization, clinopyroxene grains will retain compositions from peak temperatures at their cores in most geological and planetary settings where peak temperatures did not exceed ~1,100 °C (e.g., resetting may be expected in slowly cooled mantle rocks, many plutonic mafic rocks, or ultra-high temperature metamorphic rocks).     

Effects of fO2, fS2, temperature, and melt composition on Fe-Ni exchange between olivine and sulfide liquid: implications for natural olivine-sulfide assemblages

The apparent equilibrium constant for the exchange of Fe and Ni between coexisting olivine and sulfide liquid (K_D = (X_NiS/X_FeS)_liquid/(X_NiSi12O2/X_FeSi12O2)_olivine; X_i = mole fraction) has been measured at controlled oxygen and sulfur fugacities (fO₂ = 10^−8.1 to 10⁻¹⁰ and fS₂ = 10^−0.9 to 10^−1.7) over the temperature range 1200 to 1385°C, with 5 to 37 wt% Ni and 7 to 18 wt% Cu in the sulfide liquid. At log fO₂ of −8.7 ± 0.1, and log fS₂ of −0.9 to −1.7, K_D is relatively insensitive to sulfur fugacity, but comparison with previous results shows that K_D increases at very low sulfur fugacities. K_D values show an increase with the nickel content of the sulfide liquid, but this effect is more complex than found previously, and is greatest at log fO₂ of −8.1, lessens with decreasing fO₂, and K_D becomes independent of melt Ni content at log fO₂ ≤ −9.5. The origin of this variation in K_D with fO₂ and fS₂ is most likely the result of nonideal mixing of Fe and Ni species in the sulfide liquid. Such behavior causes activity coefficients to change with either melt oxygen content or metal/sulfur ratio, effects that are well documented for metal-rich sulfide melts.Application of these experimental results to natural samples shows that the relatively large dispersion that exists in K_D values from different olivine + sulfide-saturated rock suites can be interpreted as arising from variations in fO₂, fS₂, and the nickel content of the sulfide liquid. Estimates of fO₂ based on K_D and sulfide melt composition in natural samples yields a range from fayalite-magnetite-quartz (FMQ)-1 to FMQ-2 or lower, which is in good agreement with previous values determined for oceanic basalts that use glass ferric/ferrous ratios. Anomalously high K_D values recorded in some suites, such as Disko Island, probably reflect low fS₂ during sulfide saturation, which is consistent with indications of low fO₂ for those samples. It is concluded that the variation in K_D values from natural samples reflects olivine-sulfide melt equilibrium at conditions within the T-fO₂-fS₂ range of terrestrial mafic magmas.     

Evidence for heterogeneous enriched shergottite mantle sources in Mars from olivine-hosted melt inclusions in Larkman Nunatak 06319

Larkman Nunatak (LAR) 06319 is an olivine-phyric shergottite whose olivine crystals contain abundant crystallized melt inclusions. In this study, three types of melt inclusion were distinguished, based on their occurrence and the composition of their olivine host: Type-I inclusions occur in phenocryst cores (Fo_77-73); Type-II inclusions occur in phenocryst mantles (Fo_71-66); Type-III inclusions occur in phenocryst rims (Fo_61-51) and within groundmass olivine. The sizes of the melt inclusions decrease significantly from Type-I (∼150-250 μm diameter) to Type-II (∼100 μm diameter) to Type-III (∼25-75 μm diameter). Present bulk compositions (PBC) of the crystallized melt inclusions were calculated for each of the three melt inclusion types based on average modal abundances and analyzed compositions of constituent phases. Primary trapped liquid compositions were then reconstructed by addition of olivine and adjustment of the Fe/Mg ratio to equilibrium with the host olivine (to account for crystallization of wall olivine and the effects of Fe/Mg re-equilibration). The present bulk composition of Type-I inclusions (PBC1) plots on a tie-line that passes through olivine and the LAR 06319 whole-rock composition. The parent magma composition can be reconstructed by addition of 29 mol% olivine to PBC1, and adjustment of Fe/Mg for equilibrium with olivine of Fo₇₇ composition. The resulting parent magma composition has a predicted crystallization sequence that is consistent with that determined from petrographic observations, and differs significantly from the whole-rock only in an accumulated olivine component (∼10 wt%). This is consistent with a calculation indicating that ∼10 wt% magnesian (Fo_77-73) olivine must be subtracted from the whole-rock to yield a melt in equilibrium with Fo₇₇. Thus, two independent estimates indicate that LAR 06319 contains ∼10 wt% cumulate olivine.The rare earth element (REE) patterns of Type-I melt inclusions are similar to that of the LAR 06319 whole-rock. The REE patterns of Type-II and Type-III melt inclusions are also broadly parallel to that of the whole-rock, but at higher absolute abundances. These results are consistent with an LAR 06319 parent magma that crystallized as a closed-system, with its incompatible-element enrichment being inherited from its mantle source region. However, fractional crystallization of the reconstructed LAR 06319 parent magma cannot reproduce the major and trace element characteristics of all enriched basaltic shergottites, indicating local-to-large scale major- and trace-element variations in the mantle source of enriched shergottites. Therefore, LAR 06319 cannot be parental to the enriched basaltic shergottites.     

Diffusion kinetics of Fe and Mg in aluminous spinel: experimental determination and applications

The diffusion coefficients of Fe²⁺ and Mg in aluminous spinel at ∼20 kb, 950 to 1325°C, and at 30 kb, 1125°C have been determined via diffusion couple experiments and numerical modeling of the induced diffusion profiles. The oxygen fugacity, fO₂, was constrained by graphite encapsulating materials. The retrieved self-diffusion coefficients of Fe²⁺ and Mg at ∼20 kb, 950 to 1325°C, fit well the Arrhenian relation, D = D₀exp(−Q/RT), where Q is the activation energy, with D₀(Fe) = 1.8 (±2.8) × 10⁻⁵, D₀(Mg) = 1.9 (±1.4) × 10⁻⁵ cm²/s, Q(Fe) = 198 ± 19, and Q(Mg) = 202 ± 8 kJ/mol. Comparison with the data at 30 kb suggests an activation volume of ∼5 cm³/mol. From analysis of compositional zoning in natural olivine-spinel assemblages in ultramafic rocks, previous reports concluded that D(Fe-Mg) in spinel with Cr/(Cr + Al) ≤0.5 is ∼10 times that in olivine. The diffusion data in spinel and olivine have been applied to the problems of preservation of Mg isotopic inhomogeneity in spinel within the plagioclase-olivine inclusions in Allende meteorite and cooling rates of terrestrial ultramafic rocks.     

Interdiffusion of Mg–Fe in olivine at 1,400–1,600 °C and 1 atm total pressure

The interdiffusion coefficient of Mg–Fe in olivine (D _Mg–Fe) was obtained at 1,400–1,600 °C at the atmospheric pressure with the oxygen fugacity of 10^?3.5–10^?2 Pa using a diffusion couple technique. The D _Mg–Fe shows the anisotropy (largest along the [001] direction and smallest along the [100] direction), and its activation energy (280–320 kJ/mol) is ~80–120 kJ/mol higher than that estimated at lower temperatures. The D _Mg–Fe at temperatures of >1,400 °C can be explained by the cation-vacancy chemistry determined both by the Fe³⁺/Fe²⁺ equilibrium and by the intrinsic point defect formation with the formation enthalpy of 220–270 kJ/mol depending on the thermodynamical model for the Fe³⁺/Fe²⁺ equilibrium in olivine. The formation enthalpy of 220–270 kJ/mol for the point defect (cation vacancy) in olivine is consistent with that estimated from the Mg self-diffusion in Fe-free forsterite. The increase in the activation energy of D _Mg–Fe at >1,400 °C is thus interpreted as the result of the transition of diffusion mechanism from the transition metal extrinsic domain to the intrinsic domain at the atmospheric pressure.     

Mechanisms of hydrogen incorporation and diffusion in iron-bearing olivine

The incorporation and diffusion of hydrogen in San Carlos olivine (Fo₉₀) single crystals were studied by performing experiments under hydrothermal conditions. The experiments were carried out either at 1.5 GPa, 1,000°C for 1.5 h in a piston cylinder apparatus or at 0.2 GPa, 900°C for 1 or 20 h in a cold-seal vessel. The oxygen fugacity was buffered using Ni–NiO, and the silica activity was buffered by adding San Carlos orthopyroxene powders. Polarized Fourier transform infrared (FTIR) spectroscopy was utilized to quantify the hydroxyl distributions in the samples after the experiments. The resulting infrared spectra reproduce the features of FTIR spectra that are observed in olivine from common mantle peridotite xenoliths. The hydrogen concentration at the edges of the hydrogenated olivine crystals corresponds to concentration levels calculated from published water solubility laws. Hydrogen diffusivities were determined for the three crystallographic axes from profiles of water content as a function of position. The chemical diffusion coefficients are comparable to those previously reported for natural iron-bearing olivine. At high temperature, hydrogenation is dominated by coupled diffusion of protons and octahedrally coordinated metal vacancies where the vacancy diffusion rate limits the process. From the experimental data, we determined the following diffusion laws (diffusivity in m² s⁻¹, activation energies in kJ mol⁻¹): for diffusion along [100] and [010]; for diffusion along [001]. These diffusion rates are fast enough to modify significantly water contents within olivine grains in xenoliths ascending from the mantle.