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Abstract

We present in situ secondary ion mass spectrometry (SIMS) and electron microprobe analyses of coexisting garnet, omphacite, phengite, amphibole, and apatite, combined with pyrohydrolysis bulk-rock analyses to constrain the distribution, abundance, and behavior of halogens (F and Cl) in six MORB-like eclogites from the Raspas Complex (Southern Ecuador). In all cases concerning lattice-hosted halogens, F compatibility decreases from apatite (1.47–3.25 wt%), to amphibole (563–4727 μg/g), phengite (610–1822 μg/g), omphacite (6.5–54.1 μg/g), and garnet (1.7–8.9 μg/g). The relative compatibility of Cl in the assemblage is greatest for apatite (192–515 μg/g), followed by amphibole (0.64–82.7 μg/g), phengite (1.2–2.1 μg/g), omphacite (<0.05–1.0 μg/g), and garnet (<0.05 μg/g). Congruence between SIMS-reconstructed F bulk abundances and yield-corrected bulk pyrohydrolysis analyses indicates that F is primarily hosted within the crystal lattice of eclogitic minerals. However, SIMS-reconstructed Cl abundances are a factor of five lower, on average, than pyrohydrolysis-derived bulk concentrations. This discrepancy results from the contribution of fluid inclusions, which may host at least 80% of the bulk rock Cl. The combination of SIMS and pyrohydrolysis is highly complementary. Whereas SIMS is well suited to determine bulk F abundances, pyrohydrolysis better quantifies bulk Cl concentrations, which include the contribution of fluid inclusion-hosted Cl. Raspas eclogites contain 145–258 μg/g F and at least 7–11 μg/g Cl. We estimate that ~95% of F is retained in the slab through eclogitization and returned to the upper mantle during subduction, whereas at least 95% of subducted Cl is removed from the rock by the time the slab equilibrates at eclogite facies conditions. Our calculations provide further evidence for the fractionation of F from Cl during high-pressure metamorphism in subduction zones. Although the HIMU (high U/Pb) mantle source (dehydrated oceanic crust) is often associated with enrichments in Cl/K and F/Nd, Raspas eclogites show relatively low halogen ratios identical within uncertainty to depleted MORB mantle (DMM). Thus, the observed halogen enrichments in HIMU ocean island basalts require either further fractionation during mantle processing or recycling of a halogen-enriched carrier lithology such as serpentinite into the mantle.

Abstract

Diopside is one of the most important end-members of clinopyroxene, which is an abundant mineral in upper-mantle petrologic models. The amount of clinopyroxene in upper-mantle pyrolite can be ∼15 vol%, while pyroxenite can contain as high as ∼60 vol% clinopyroxene. Knowing the elastic properties of the upper-mantle diopside at high pressure-temperature conditions is essential for constraining the chemical composition and interpreting seismic observations of region. Here we have measured the single-crystal elasticity of Fe-enriched diopside (Di80Hd20, Di-diopside, and Hd-hedenbergite; also called Fe-enriched clinopyroxene) at high-pressure conditions up to 18.5 GPa by using in situ Brillouin light-scattering spectroscopy (BLS) and synchrotron X-ray diffraction in a diamond-anvil cell. Our experimental results were used in evaluating the effects of pressure and Fe substitution on the full single-crystal elastic moduli across the Di-Hd solid-solution series to better understand the seismic velocity profiles of the upper mantle. Using the third- or fourth-order Eulerian finite-strain equations of state to model the elasticity data, the derived aggregate adiabatic bulk and shear moduli (K S0, G 0) at ambient conditions were determined to be 117(2) and 70(1) GPa, respectively. The first- and second-pressure derivatives of bulk and shear moduli at 300 K were (∂KS/P)T = 5.0(2), (∂2 KS/P 2)T = –0.12(4) GPa−1 and (∂G/P)T = 1.72(9), (∂2 G/P 2)T = –0.05(2) GPa−1, respectively. A comparison of our results with previous studies on end-member diopside and hedenbergite in the literatures shows systematic linear correlations between the Fe composition and single-crystal elastic moduli. An addition of 20 mol% Fe in diopside increases K S0 by ∼1.7% (∼2 GPa) and reduces G 0 by ∼4.1% (∼3 GPa), but has a negligible effect on the pressure derivatives of the bulk and shear moduli within experimental uncertainties. In addition, our modeling results show that substitution of 20 mol% Fe in diopside can reduce V P and V S by ∼1.8% and ∼3.5%, respectively, along both an expected normal mantle geotherm and a representative cold subducted slab geotherm. Furthermore, the modeling results show that the V P and V S profiles of Fe-enriched pyroxenite along the cold subducted slab geotherm are ∼3.2% and ∼2.5% lower than AK135 model at 400 km depth, respectively. Finally, we propose that the presence of Fe-enriched pyroxenite (including Fe-enriched clinopyroxene, Fe-enriched orthopyroxene, and Feenriched olivine), can be an effective mechanism to cause low-velocity anomalies in the upper mantle regions atop the 410 km discontinuity at cold subudcted slab conditions.

Abstract

Experimental studies and measurements of inclusions in diamonds show that ferric iron components are increasingly stabilized with depth in the mantle. To determine the thermodynamic stability of such components, their concentration needs to be measured at known oxygen fugacities. The metal-oxide pair Ru and RuO2 are ideal as an internal oxygen fugacity buffer in high-pressure experiments. Both phases remain solid to high temperatures and react minimally with silicates, only exchanging oxygen. To calculate oxygen fugacities at high pressure and temperature, however, requires information on the phase relations and equation of state properties of the solid phases.

We have made in situ synchrotron X‑ray diffraction measurements in a multi-anvil press on mixtures of Ru and RuO2 to 19.4 GPa and 1473 K with which we have determined phase relations of the RuO2 phases and derived thermal equations of state (EoS) parameters for both Ru and RuO2. Rutile-structured RuO2 was found to undergo two phase transformations, first at ~7 GPa to an orthorhombic structure and then above 12 GPa to a cubic structure. The phase boundary of the cubic phase was constrained for the first time at high pressure and temperature. We have derived a continuous Gibbs free energy expression for the tetragonal and orthorhombic phases of RuO2 by fitting the second-order phase transition boundary and P-V-T data for both phases, using a model based on Landau theory. The transition between the orthorhombic and cubic phases was then used along with EoS terms derived for both phases to determine a Gibbs free energy expression for the cubic phase. We have used these data to calculate the oxygen fugacity of the Ru + O2 = RuO2 equilibrium, which we have parameterized as a single polynomial across the stability fields of all three phases of RuO2. The expression is log10 f O2(Ru – RuO2) = (7.782 – 0.00996P + 0.001932P 2 – 3.76 × 10–5 P 3) + (–13 763 + 592P – 3.955P 2)/T + (–1.05 × 106 – 4622P)/T2, which should be valid from room pressure up to 25 GPa and 773–2500 K, with an estimated uncertainty of 0.2 log units. Our calculated f O2 is shown to be up to 1 log unit lower than estimates that use previous expressions or ignore EoS terms.

Abstract

The stability relations of Pt and Pd antimonides and bismuthinides in the Sb- and Bi-bearing Fe-Ni-Cu sulfide systems have been experimentally determined at temperatures between 1100 and 700 °C in evacuated silica tubes. Both PtSb and PdSb are stable as immiscible liquids at temperatures above 1100 and 1000 °C, respectively. The Fe-Ni-Cu-sulfide melt that coexists with the immiscible antimonide melt can dissolve up to 3.8 wt% Sb at 1100 °C, whereas monosulfide solid solution (mss) dissolves very low amounts of Sb over the entire 1100–700 °C temperature range. The liquidus of Pt-antimonides and Pd-antimonides are above 980 and 750 °C, respectively. Bismuth does not form immiscible melt at 1100 °C but may partially partition into a vapor phase at 1050 °C. The Pt- and Pd-bismuthinides crystallize directly from immiscible bismuthinide melt only after crystallization of the sulfide melt into intermediate solid solution (iss). Insizwaite (PtBi2) and froodite (PdBi2) are stable at 780 and 700 °C, respectively. At the last stage of evolution of Sb-bearing magmatic Fe-Ni-Cu sulfide melts, Sb will form immiscible antimonide melt that will extract Pt and Pd from the sulfide melt. During cooling, Pt and Pd-antimonides will crystallize directly from the immiscible antimonide melt, and Pt-phases will form at higher temperatures relative to Pd-phases. Bismuth will partition into vapor phase and concentrate into a low-temperature melt in hydrothermal and porphyry systems that scavenge precious metals. The Sb and Bi (like Te) will be highly incompatible at moderate degrees of mantle partial melting.

Abstract

Volatile elements (e.g., H, C, N) have a strong influence on the physical and chemical evolution of planets and are essential for the development of habitable conditions. Measurement of the volatile and incompatible heavy halogens, Cl, Br, and I, can provide insight into volatile distribution and transport processes, due to their hydrophilic nature. However, information on the bulk halogen composition of martian meteorites is limited, particularly for Br and I, largely due to the difficulty in measuring ppb-level Br and I abundances in small samples. In this study, we address this challenge by using the neutron irradiation noble gas mass spectrometry (NI-NGMS) method to measure the heavy halogen composition of five olivine-phyric shergottite meteorites, including the enriched (Larkman Nunatak LAR 06319 and LAR 12011) and depleted (LAR 12095, LAR 12240, and Tissint) compositional end-members. Distinct differences in the absolute abundances and halogen ratios exist between enriched (74 to136 ppm Cl, 1303 to 3061 ppb Br, and 4 to 1423 ppb I) and depleted (10 to 26 ppm Cl, 46 to 136 ppb Br, and 3 to 329 ppb I) samples. All halogen measurements are within the ranges previously reported for martian shergottite, nakhlite, and chassignite (SNC) meteorites. Enriched shergottites show variable and generally high Br and I absolute abundances. Halogen ratios (Br/Cl and I/Cl) are in proportions that exceed those of both carbonaceous chondrites and the martian surface. This may be linked to a volatile-rich martian mantle source, be related to shock processes or could represent a small degree of heavy halogen contamination (a feature of some Antarctic meteorites, for example). The differences observed in halogen abundances and ratios between enriched and depleted compositions, however, are consistent with previous suggestions of a heterogeneous distribution of volatiles in the martian mantle. Depleted shergottites have lower halogen abundances and Br and Cl in similar proportions to bulk silicate Earth and carbonaceous chondrites. Tissint in particular, as an uncontaminated fall, allows an estimate of the depleted shergottite mantle source composition to be made: 1.2 ppm Cl, 7.0 ppb Br, and 0.2 ppb I. The resultant bulk silicate Mars (BSM) estimate (22 ppm Cl, 74 ppb Br, and 6 ppb I), including the martian crust and depleted shergottite mantle, is similar to estimates of the bulk silicate earth (BSE) halogen composition.

Abstract

The primary aim of this study was the accurate determination of unit-cell parameters and description of disorder in chlorites with semi-random stacking using common X‑ray diffraction (XRD) data for bulk powder samples. In the case of ordered chlorite structures, comprehensive crystallographic information can be obtained based on powder XRD data. Problems arise for samples with semi-random stacking, where due to strong broadening of hkl peaks with k3n, the determination of unit-cell parameters is demanding. In this study a complete set of information about the stacking sequences in chlorite structures was determined based on XRD pattern simulation, which included determining a fraction of layers shifted by ±1/3b, interstratification with different polytypes and 2:1 layer rotations.

A carefully selected series of pure Mg-Fe tri-trioctahedral chlorites with iron content in the range from 0.1 to 3.9 atoms per half formula unit cell was used in the study. In addition, powder XRD patterns were carefully investigated for the broadening of the odd-number basal reflections to determine interstratification of 14 and 7 Å layers. These type of interstratifications were finally not found in any of the samples. This result was also confirmed by the XRD pattern simulations, assuming interstratification with R0 ordering.

Based on h0l XRD reflections, all the studied chlorites were found to be the IIbb polytype with a monoclinic-shaped unit cell (β ≈ 97°). For three samples, the hkl reflections with k3n were partially resolvable; therefore, a conventional indexing procedure was applied. Two of the chlorites were found to have a monoclinic cell (with α, γ = 90°). Nevertheless, among all the samples, the more general triclinic (pseudomonoclinic) crystal system with symmetry C1 was assumed, to calculate unit-cell parameters using Le Bail fitting.

A detailed study of semi-random stacking sequences shows that simple consideration of the proportion of IIb-2 and IIb-4/6 polytypes, assuming equal content of IIb-4 and IIb-6, is not sufficient to fully model the stacking structure in chlorites. Several, more general, possible models were therefore considered. In the first approach, a parameter describing a shift into one of the ±1/3b directions (thus, the proportion of IIb-4 and IIb-6 polytypes) was refined. In the second approach, for samples with slightly distinguishable hkl reflections with k3n, some kind of segregation of individual polytypes (IIb-2/4/6) was considered. In the third approach, a model with rotations of 2:1 layers about 0°, 120°, 240° was shown to have the lowest number of parameters to be optimized and therefore give the most reliable fits. In all of the studied samples, interstratification of different polytypes was revealed with the fraction of polytypes being different than IIbb ranging from 5 to 19%, as confirmed by fitting of h0l XRD reflections.

Abstract

Negevite, ideally NiP2, is a new phosphide mineral from pyrometamorphic complex of the Hatrurim Formation (the Mottled Zone), Southern Levant. It is found in phosphide assemblages of the Hatrurim Basin, south Negev Desert, Israel, and Daba-Siwaqa complex, Jordan. The mineral occurs as tiny isometric grains reaching 15 μm in size and forms intimate intergrowths with other phosphides related to the Fe-Ni-P system. In reflected light, negevite is white with yellowish tint and isotropic. Reflectance values for COM recommended wavelengths [R (%), λ (nm)] are as follows: 54.6 (470), 55.0 (546), 55.3 (589), 55.6 (650). Chemical composition of the holotype specimen (electron micro-probe, wt%): Ni 42.57, Co 3.40, Fe 2.87, P 42.93, S 8.33, total 100.10, corresponding to the empirical formula (Ni0.88Co0.07Fe0.06)S1.01(P1.68S0.31)S1.99. The crystal structure of negevite was solved and refined to R 1 = 1.73% based on 52 independent observed [I >2σ(I)] reflections. The mineral is cubic, space group Pa3̅, a = 5.4816(5) Å, V = 164.71(3) Å3, and Z = 4. D x = 4.881(1) g/cm3 calculated on the basis of the empirical formula. Negevite is a first natural phosphide belonging to the pyrite structure type. It is a chemical and structural analog of vaesite, NiS2, krutovite, NiAs2, and penroseite, NiSe2. The well-explored catalytic and photocatalytic properties of a synthetic counterpart of negevite could provide new insights into the possible role of higher phosphides as a source of low-valent phosphorus in prebiotic phosphorylation processes.

Abstract

The pressure dependence of Si diffusion in γ-Fe was investigated at pressures of 5–15 GPa and temperatures of 1473–1673 K using the Kawai-type multi-anvil apparatus to estimate the rate of mass transportation for the chemical homogenization of the Earth’s inner core and those of small terrestrial planets and large satellites. The obtained diffusion coefficients D were fitted to the equation D = D 0 exp[–(E* + PV*)/(RT)], where D 0 is a constant, E * is the activation energy, P is the pressure, V* is the activation volume, R is the gas constant, and T is the absolute temperature. The least-squares analysis yielded D 0 = 10-1.17±0.54 m2/s, E* = 336 ± 16 kJ/mol, and V* = 4.3 ± 0.2 cm3/mol. Moreover, the pressure and temperature dependences of diffusion coefficients of Si in γ-Fe can also be expressed well using homologous temperature scaling, which is expressed as D = D 0exp{–g[T m(P)]/T}, where g is a constant, T m(P) is the melting temperature at pressure P, and D 0 and g are 10-1.0±0.3 m2/s and 22.0 ± 0.7, respectively. The present study indicates that even for 1 billion years, the maximum diffusion length of Si under conditions in planetary and satellite cores is less than ~1.2 km. Additionally, the estimated strain of plastic deformation in the Earth’s inner core, caused by the Harper–Dorn creep, reaches more than 103 at a stress level of 103–104 Pa, although the inner core might be slightly deformed by other mechanisms. The chemical heterogeneity of the inner core can be reduced only via plastic deformation by the Harper–Dorn creep.

Abstract

Carbonates play an important role in the transport and storage of carbon in the Earth’s mantle. However, the abundance of carbon and carbonates in subduction zones is still an unknown quantity. To determine the most abundant accessory phases and how they influence the dynamical processes that operate within the Earth, investigations on the vibrational, elastic, and thermodynamic properties of these phases are crucial for interpreting seismological observations. Recently, the nuclear inelastic scattering (NIS) method has proved to be a useful tool to access information on the lattice dynamics, as well as to determine Debye sound velocities of Fe-bearing materials. Here we derive the acoustic velocities from two carbonate compositions in the FeCO3-MgCO3 binary system up to ~70 GPa using the NIS method. We conclude that more Mg-rich samples, in this case (Fe0.26Mg0.74)CO3, have ~19% higher sound velocities than the pure end-member Fe composition. In addition, we observed a significant velocity increase after the Fe2+ spin transition was complete. After laser heating of FeCO3 at lower mantle conditions, we observed a dramatic velocity drop, which is probably associated with thermal decomposition to another phase. Parallel to our NIS experiments, we conducted a single-crystal X‑ray diffraction (SCXRD) study to derive the equation of states of FeCO3 and (Fe0.26Mg0.74)CO3. The combined information from NIS (i.e., Debye velocities) and SCXRD (i.e., densities and bulk moduli) experiments enabled us to derive the primary and shear wave velocities of our samples. Our results are consistent with results obtained by other methods in previous studies, including Brillouin spectroscopy, inelastic X‑ray scattering, and DFT calculations, supporting NIS as a reliable alternative method for studying the elastic properties of Fe-bearing systems at high pressures and temperatures. Finally, we discuss the seismic detectability of carbonates. We determine that nearly 22 wt% CO2 must be present in the subduction slab to detect a 1% shear wave velocity decrease compared to non-carbonated lithologies at the transition zone to lower mantle boundary depths.