Volume 106, Issue 5

Characterization of terrestrial analog sites is critical for detection and determination of clay mineralogy in remote sensing studies of Mars aimed at geological, hydrological, and potentially biological investigations. In this study, we investigate a suite of hydrothermally altered early Archean rocks from the Barberton greenstone belt (BGB) of South Africa as potential petrological, mineralogical, and spectral analogs to hydrothermally altered metabasalts and mafic-ultramafic intrusions in the martian subsurface and impact craters. We present the first spectral imaging measurements on exceptionally well-preserved early Archean mafic-ultramafic rocks from the BGB, with the aim of studying their clay mineralogy and spectral signatures. Multiple spectral analyses were conducted on different sample textures (rock powders, crushed rocks, and rock slabs) appropriate for Mars rover and remote sensing exploration. Visible/near-infrared (VNIR) and mid-IR reflectance spectra were acquired on particulate samples, while VNIR spectral imaging data were collected on rock slabs. Mid-IR emission spectra were measured for the rock slabs and grains. Spectral features are compared from these different spectral techniques to identify the minerals present in the samples and compare macroscale vs. microscale detections. The measured spectra reveal absorption bands that correspond to clay mineralogy of the serpentine and chlorite mineral groups, consistent with petrographic observations, as well as magnetite, olivine, quartz, feldspar, and Al-phyllosilicate. The spectral data acquired in this study expand the reference spectra data set for remote sensing studies. The implications of this study are that rocks from early Archean greenstone belts, such as those of the BGB, serve as potential clay-bearing petrological analogs for hydrothermal environments on Mars.

Silicate melt inclusions (SMI) containing several daughter minerals, residual glass, and a CO 2 bubble were analyzed to constrain the composition and evolution of the metasomatic melt present in the upper mantle beneath the Nógrád-Gömör Volcanic Field (NGVF), northern Hungary to southern Slovakia. The SMI were analyzed with a combination of Raman spectroscopy, FIB-SEM, and LA-ICP-MS to identify phases and obtain their volume proportions and major- and trace-element geochemistry. Slicing through the entire volume of the inclusions and collecting geochemical information at each slice with FIB-SEM allowed us to model the 3D appearance of the phases within the SMI and to use this information to calculate bulk major-element compositions. The partially crystallized SMI are hosted in clinopyroxene in a lherzolite xenolith that shows evidence of a metasomatic event that altered the lherzolites to produce wehrlites. Based on bulk compositions, the SMI trapped the metasomatic melt linked to wehrlite formation in the NGVF. The melt is enriched in Fe and has an OIB-like trace-element pattern, which suggests an intraplate mafic melt similar to the host basalt, but with slightly different chemistry. Pre-entrapment evolution and reaction with the lherzolite wall rock produced an intermediate melt composition. Petrogenetic modeling indicates that the melt was generated as a result of a very small degree of partial melting of a garnet lherzolite source. Following entrapment, a volatile bubble exsolved from the residual melt during ascent to shallow depths as suggested by consistent densities of CO 2 in vapor bubbles. Small crystals, including sulfates and mica, that formed at the boundary of the bubble and the glass indicate that the exsolved fluid originally contained S and H 2 O, in addition to CO 2 .

Hydrogen is a rapidly diffusing monovalent cation in nominally anhydrous minerals (NAMs, such as olivine, orthopyroxene, and clinopyroxene), which is potentially re-equilibrated during silicate melt-rock and aqueous fluid-rock interactions in massif and abyssal peridotites. We apply a 3D numerical diffusion modeling technique to provide first-order timescales of complete hydrogen re-equilibration in olivine, clinopyroxene, and orthopyroxene over the temperature range 600–1200 °C. Model crystals are 1–3 mm along the c -axis and utilize H + diffusion coefficients appropriate for Fe-bearing systems. Two sets of models were run with different boundary compositions: (1) “low-H models” are constrained by mineral-melt equilibrium partitioning with a basaltic melt that has 0.75 wt% H 2 O, and (2) “high-H models,” which utilize the upper end of the estimated range of mantle water solubility for each phase. Both sets of models yield re-equilibration timescales that are identical and are fast for all phases at a given temperature. These timescales have strong log-linear trends as a function of temperature (R 2 from 0.97 to 0.99) that can be used to calculate the expected re-equilibration time at a given temperature and grain size. At the high end of the model temperatures (1000–1200 °C), H + completely re-equilibrates in olivine, orthopyroxene, and clinopyroxene within minutes to hours, consistent with previous studies. These short timescales indicate that xenolith NAM mantle water contents are likely to be overprinted prior to eruption. The models also resolve the decoupled water-trace element relationship in Southwest Indian Ridge peridotites, in which peridotite REE abundances are reproduced by partial melting models whereas the relatively high NAM H 2 O contents require later re-equilibration with melt. At temperatures of 600–800 °C, which correspond to conditions of hydrothermal alteration of pyroxene to amphibole and talc, H + re-equilibration typically occurs over a range of timescales spanning days to years. These durations are well within existing estimates for the duration of fluid flow in oceanic hydrothermal systems, suggesting that peridotite NAM water contents are susceptible to diffusive overprinting during higher temperature hydrothermal alteration. Thus, diffusion during aqueous fluid-rock interactions may also explain NAM H 2 O contents that are too high to reflect residues of melting. These relatively short timescales at low temperatures suggest that the origin of water contents measured in peridotite NAMs requires additional constraints on sample petrogenesis, including petrographic and trace element analyses. Our 3D model results also hint that H + may diffuse appreciably during peridotite serpentinization, but diffusion coefficients at low temperature are unconstrained and additional experimental investigations are needed.

The 119 Ma Dinkey Dome pluton in the central Sierra Nevada Batholith is a peraluminous granite and contains magmatic garnet and zircon that are complexly zoned with respect to oxygen isotope ratios. Intracrystalline SIMS analysis tests the relative importance of magmatic differentiation processes vs. partial melting of metasedimentary rocks. Whereas δ 18 O values of bulk zircon concentrates are uniform across the entire pluton (7.7‰ VSMOW), zircon crystals are zoned in δ 18 O by up to 1.8‰, and when compared to late garnet, show evidence of changing magma chemistry during multiple interactions of the magma with wall rock during crustal transit. The evolution from an early high-δ 18 O magma [δ 18 O(WR) = 9.8‰] toward lower values is shown by high-δ 18 O zircon cores (7.8‰) and lower δ 18 O rims (6.8‰). Garnets from the northwest side of the pluton show a final increase in δ 18 O with rims reaching 8.1‰. In situ REE measurements show zircon is magmatic and grew before garnets. Additionally, δ 18 O in garnets from the western side of the pluton are consistently higher (avg = 7.3‰) relative to the west (avg = 5.9‰). These δ 18 O variations in zircon and garnet record different stages of assimilation and fractional crystallization whereby an initially high-δ 18 O magma partially melted low-δ 18 O wallrock and was subsequently contaminated near the current level of emplacement by higher δ 18 O melts. Collectively, the comparison of δ 18 O zoning in garnet and zircon shows how a peraluminous pluton can be constructed from multiple batches of variably contaminated melts, especially in early stages of arc magmatism where magmas encounter significant heterogeneity of wall-rock assemblages. Collectively, peraluminous magmas in the Sierran arc are limited to small <100 km 2 plutons that are intimately associated with metasedimentary wall rocks and often surrounded by later and larger metaluminous tonalite and granodiorite plutons. The general associations suggest that early-stage arc magmas sample crustal heterogeneities in small melt batches, but that with progressive invigoration of the arc, such compositions are more effectively blended with mantle melts in source regions. Thus, peraluminous magmas provide important details of the nascent Sierran arc and pre-batholithic crustal structure.

The fourth installment of the evolutionary system of mineralogy considers two stages of planetesimal mineralogy that occurred early in the history of the solar nebula, commencing by 4.566 Ga and lasting for at least 5 million years: (1) primary igneous minerals derived from planetesimal melting and differentiation into core, mantle, and basaltic components and (2) impact mineralization resulting in shock-induced deformation, brecciation, melting, and high-pressure phase transformations. We tabulate 90 igneous differentiated asteroidal minerals, including the earliest known occurrences of minerals with Ba, Cl, Cu, F, and V as essential elements, as well as the first appearances of numerous phosphates, quartz, zircon, and amphibole group minerals. We also record 40 minerals formed through high-pressure impact alteration, commencing with the period of asteroid accretion and differentiation. These stages of mineral evolution thus mark the first time that high pressures, both static and dynamic, played a significant role in mineral paragenesis.

The solubility of CO 2 in hydrous basaltic andesite was examined in f O 2 -controlled experiments at a temperature of 1125 °C and pressures between 310–1200 MPa. Concentrations of dissolved H 2 O and CO 2 in experimental glasses were determined by ion microprobe calibrated on a subset of run glasses analyzed by high-temperature vacuum manometry. Assuming that the solubility of H 2 O in mafic melt is relatively well known, estimates ofXH2Ofluid and  PH2Ofluid$X_{{{\text{H}}_{2}}\text{O}}^{\text{fluid}}\ \text{and}\,\,\text{P}_{{{\text{H}}_{2}}\text{O}}^{\text{fluid}}$ in the saturating fluid were modeled, and by difference, values for XCO2fluid and  PCO2fluid$X_{\text{C}{{\text{O}}_{2}}}^{\text{fluid}}\ \text{and}\,\,\text{P}_{\text{C}{{\text{O}}_{2}}}^{\text{fluid}}$were obtained ( X CO 2 ~0.5–0.9); f CO 2 could be then calculated from the fluid composition, temperature, and pressure. Dissolved H 2 O over a range of 2.3–5.5 wt% had no unequivocal influence on the dissolution of CO 2 at the pressures and fluid compositions examined. For these H 2 O concentrations, dissolved CO 2 increases with f CO 2 following an empirical power-law relation: dissolved CO 2 (ppmw) = 14.9− 3.5+4.5fCO2 $14.9_{-3.5}^{+4.5}\left[f_{\mathrm{CO}_{2}}\right.$(MPa)] 0.7±0.03 . The highest-pressure results plot farthest from this equation but are within its 1 standard-error uncertainty envelope. We compare our experimental data with three recent CO 2 -H 2 O solubility models: Papale et al. (2006); Iacono-Marziano et al. (2012); and Ghiorso and Gualda (2015). The Papale et al. (2006) and Iacono-Marizano et al. (2012) models give similar results, both over-predicting the solubility of CO 2 in a melt of the Pavlof basaltic andesite composition across the f CO 2 range, whereas the Ghiorso and Gualda (2015) model under-predicts CO 2 solubility. All three solubility models would indicate a strong enhancement of CO 2 solubility with increasing dissolved H 2 O not apparent in our results. We also examine our results in the context of previous high-pressure CO 2 solubility experiments on basaltic melts. Dissolved CO 2 correlates positively with mole fraction (Na+K+Ca)/Al across a compositional spectrum of trachybasalt-alkali basalt-tholeiite-icelandite-basaltic andesite. Shortcomings of current solubility models for a widespread arc magma type indicate that our understanding of degassing in the deep crust and uppermost mantle remains semi-quantitative. Experimental studies systematically varying concentrations of melt components (Mg, Ca, Na, K, Al, Si) may be necessary to identify solubility reactions, quantify their equilibrium constants, and thereby build an accurate and generally applicable solubility model.

Electrical conductivities of diaspore (α-AlOOH), δ-AlOOH, and ε-FeOOH were measured by impedance spectroscopy with a frequency range from 10 –1 to 10 6 Hz at pressures from 8 to 20 GPa and temperatures from 500 to 1200 K, well below the dehydration temperatures of these phases at the relevant pressures. For diaspore, the relationship between electrical conductivity and reciprocal temperature can be well fitted by the Arrhenius formula: σ =σ 0exp− (Δ E+PΔ V)kT,$$ \begin{equation} \sigma=\sigma_{0} \exp \left[\frac{-(\Delta E+P \Delta V)}{k T}\right], \end{equation}$$ where σ 0 is the pre-exponential factor, Δ E is the activation energy, and Δ V is activation volume of 56.0 ± 1.2 S/m, 0.55 ± 0.02 eV, and 1.68 ± 0.12 cm 3 /mol, respectively. The electrical conductivity of diaspore decreases with increasing pressure ranging from 8 to 12 GPa by a half order of magnitude, whereas the conductivity becomes almost constant in a pressure range above 12 GPa. δ-AlOOH and ε-FeOOH show one and two orders of magnitude higher electrical conductivity than diaspore. Electrical conductivities of δ-AlOOH and ε-FeOOH, which have isostructural CaCl 2 -type hydroxide structure, show the nearly identical activation enthalpies (0.38 ± 0.01, 0.33 ± 0.05 eV), which are relatively lower than that of diaspore. The dominant conduction mechanism of AlOOH phases can be regarded as proton conduction. The conductivity difference between diaspore and δ-AlOOH attributes to result in the different O 1 H bond lengths of each phase. The reduction of O 1 H bond length with increasing pressure could enhance the proton migration by reducing the potential barrier, thereby raising the electrical conductivity. Small polaron conduction may contribute to the conductivity of ε-FeOOH to generate higher conductivity than δ-AlOOH. Furthermore, hydrogen bond symmetrization will also play an important role in the conductivity discrepancy of these hydrous minerals with CaCl 2 -type hydroxide structure. For subducted sedimentary rocks, polymorphs of AlOOH and FeOOH are representative hydrous phases. Al-rich sediments show conductivity reduction with increasing depth until phase transformation occurs because diaspore represents negative pressure dependence of conductivity. After transformation to δ-AlOOH, the conductivity will jump up around 18 GPa. If ε-FeOOH is stable above 5 GPa in an iron-rich lithology, such as banded iron formation (BIF), a high conductivity zone with positive pressure dependence could be observed to the deep lower mantle.

The amphibole-plagioclase NaSi-CaAl exchange thermometer by Holland and Blundy (1994) (expression B) has been extensively applied to calcic amphibole-bearing assemblages from metamorphic and igneous rocks, whereas the more recent calibrations of the amphibole-only thermometer by Ridolfi and Renzulli (2012) (expression 2) and Putirka (2016) (expressions 5 and 6) are employed for determining amphibole-saturation temperatures in hydrous magmas. However, a test of these expressions performed on experimental data compiled from the literature reveals significant inaccuracies, tending expression B to underestimate temperatures in high-Mg amphibole, and the amphibole-only expressions to overestimate temperatures in amphibole with either low Mg or high Al VI occupancies. Amphibole Na M4 and Fe 3+ occupancies can also affect significantly the accuracy of expression B. In this work, we present three new accurate calibrations (expressions A1, A2, and B2) of the amphibole-plagioclase NaSi-CaAl exchange thermometer calculated by robust regression methods based on multiple maximum-likelihood estimators (MM-estimators; Yohai 1987), considering various calibration and test data subsets to evaluate the robustness of the derived parameters in the thermodynamic models, and the accuracy and precision of the expressions. Non-ideality in plagioclase was corrected using the ternary feldspar solution model of Elkins and Grove (1990) in expressions A1 and A2, whereas the simplified version of the Darken’s Quadratic Formalism (DQF) approach of Holland and Powell (1992) was used in expression B2. The formulation of the multisite macroscopic solution model of Powell and Holland (1993) was used for deriving the mixing parameters of amphibole in the three calibrations. Expression B2 is strictly pressure-independent, while the two others show a negligible dependence on pressure for plagioclase with low orthoclase component (<11 mol%). The three calibrations yield an overall precision close to those reported for the tested amphibole-based thermometers but are significantly more accurate, a requisite for an unambiguous interpretation of precision. The new expressions can be used in a wide range of igneous and high-grade metamorphic rocks that bear subcalcic to calcic amphibole and oligoclase or more calcic plagioclase. However, they must be applied only to amphibole-plagioclase pairs whose compositions lie in the optimal region of use prescribed in the work.

The crystal structures of 19 samples from the nepheline (NaAlSiO 4 ; Ne)–kalsilite (KAlSiO 4 ; Ks) series, previously prepared via ion-exchange, were examined using synchrotron high-resolution powder X‑ray diffraction (HRPXRD) data and Rietveld structure refinements. Parent materials for the three series include a natural Monte Somma nepheline (series-1), synthetic Na nepheline (series-2), and high-Si synthetic nepheline (series-3), having excess Si mole percentages of 5.2, 1.7, and 12.5%, respectively. Three different structure-types were found to occur among the samples examined: nepheline ( P 63), tetrakalsilite ( P 63), and kalsilite (both P 6 3 and P 31 c intergrowth). Trikalsilite was not observed in this study. Vacancies (◻) at the K site as well as Ca and K atoms at the Na1 site play an important role in the crystal-chemical behavior of nepheline solid solutions. Vacancies cause an elongation in the average <K-O>[9] distance in nepheline. When K atoms enter the Na1 site in nepheline, the average <(Na,K)-O>[7] distance increases linearly and is parallel to the average <(Na,K)-O>[9] distance in kalsilite and the grand mean of such distances in trikalsilite and tetrakalsilite. Before K atoms enter the Na1 site, the average <(Na,K)-O>[7] distance is constant because of the full occupancy of the Na1 site with Na atoms. Ca atoms at the Na1 site in the Monte Somma sample-1 cause a contraction in the <(Na,K)-O>[7] distance. In Na-rich nepheline samples, Na atoms in the large channels occupy a Na(K) site that is off the 6 3 axis and close to the usual K site. In natural nepheline samples, the K site in most cases contains K atoms and ◻, and the Na1 site is filled mainly with Na, minor Ca, and K atoms in K-rich samples. Nepheline from Monte Somma (sample-1) contains weak satellite reflections that are also present in some other kalsilite samples. Average < T -O> distances indicate a high degree of Al-Si disorder in nepheline but increasing Al-Si order in tetrakalsilite and kalsilite. Increasing the amount of K atoms beyond the ideal composition of K 0.25 Na 0.75 [AlSiO 4 ] causes expansion in multiple structural parameters because of the larger size of K + relative to Na + .

Overstepping of porphyroblast-forming reactions has been shown to occur in regional, contact, and subduction zone metamorphism, calling into question the paradigm that metamorphic mineral reactions occur at or very close to thermodynamic equilibrium. These overstepped reactions result from the fact that nucleation and growth of new phases requires a thermodynamic driving force or a “departure” from equilibrium. We use phase equilibria modeling to elucidate the energetic consequences of overstepped garnet nucleation and growth by comparing the chemical potentials of garnet-forming oxide components (MnO, CaO, FeO, MgO, Al 2 O 3 ) in two sets of calculations: one in which Gibbs free energy is minimized and one in which the minimization proceeds under identical conditions but in the forced absence of garnet. We focus on 12 examples from the literature that have previously described garnet nucleation as minimally overstepped (garnet nucleation at the P-T of initial garnet stability) or garnet nucleation as more substantially overstepped (garnet nucleation at P-T conditions greater than initial garnet stability). For a small P-T interval above nominal garnet-in reactions, differences in the chemical potentials between the two calculations are commonly minimal. In all tested examples calculated using two versions of the THERMOCALC thermodynamic data set, the chemical potential of Al 2 O 3 (μ Al 2 O 3 ) diverges between garnet-bearing and garnet-absent calculations at greater P-T conditions than that of MnO, CaO, FeO, and MgO. The P-T interval between thermodynamic garnet-in and the point at which μ Al 2 O 3 differs substantially between the two sets of calculations appears to be a function of bulk-rock MnO content, reemphasizing the role that small quantities of MnO play in the apparent stability of garnet in calculated phase equilibria. These results highlight the importance of considering multiple thermodynamic data sets, the location of the garnet-in curve, and the abundance of mineral phases in the discussion of overstepped metamorphic reactions. The results have implications for determining kinetic barriers to crystal nucleation and growth and considering the most appropriate way of defining “garnet-in” for samples that have experienced overstepping.

EntraPT is a web-based application for elastic geobarometry freely accessible at the “Fiorenzo Mazzi” experimental mineralogy lab website (http://www.mineralogylab.com/software/). It provides an easy-to-use tool to calculate the entrapment conditions of inclusions, with error propagation, from the residual strain measured in mineral inclusions. EntraPT establishes a method and a workflow to import and analyze the measured residual strains, correctly calculates the mean stress in the inclusions, computes the entrapment isomekes with uncertainty estimation, and visualizes all the results in relevant graphs. It enables the user to avoid the many possible errors that can arise from manual handling of the data and from the numerous steps required in geobarometry calculations. All of the data, parameters, and settings are stored in a consistent format and can be exported as project files and spreadsheets, and imported back to EntraPT for further analysis. This allows researchers to store and/or share their data easily, making the checking and the comparison of data and results reliable. EntraPT is an online tool that does not require any download and/or installation, and it will be updated in the future with new functionalities made available from advances in the development of elastic geobarometry.

The presence of metal Na nanoparticles causes the bright, thermally unstable colors of villiaumite (NaF) and halite (NaCl). These nanoparticles have been suspected for a long time to be caused by external irradiation. Metal nanoparticles, often referred to as metal colloids, cause surface plasmon resonance effects, characterized by a single Lorentzian-shaped absorption band. The color of these minerals is due to metal Na nanoparticles of 2.5–3 nm. A key point is that the resonance wavelength, which corresponds to the maximum of the absorption band, is inversely related to the value of the refractive index of the embedding mineral. This causes the position of the main absorption band to be offset downward by 140 nm in halite relative to villiaumite. As a consequence, the optical transmission window is shifted from the long to the short wavelength domain, explaining the color of blue halite and red villiaumite, respectively. Similar refractive index dependence may explain the purple color of fluorite caused by metallic Ca nanoparticles. Finally, the origin of the villiaumite irradiation may be the presence of Th-rich (about 8.8 wt% ThO 2 ) nano-inclusions, about 500 nm large, illustrating the specific geochemistry of peralkaline rocks where villiaumite is found.