Volume 105, Issue 12

The structures of the silica polymorphs α-quartz and stishovite have been geometry optimized at highly simulated isotropic pressure within the framework of Density Functional Theory. The atoms of the high-pressure polymorph stishovite are virtually incompressible with the bonded radii for Si and O atoms decreasing by only 0.04 and 0.08 Å, respectively, at 100 GPa. In compensating for the increase in the effective interatomic potential associated with the compression of the Si-O bonded interactions, the electron density at the bond critical point between the bonded pair increases from 0.69 to 0.89 e/ Å 3 . The bonded radii of the Si and O atoms for α-quartz decrease by 0.006 and 0.008 Å, respectively, between 1 bar and 26.4 GPa. The impact of simulated, isotropic pressure on the bonded radii of the atoms for three perovskites YAlO 3 , LaAlO 3 , and CaSnO 3 was also examined at high pressure. For the YAlO 3 perovskite, the bonded radii for Y and Al decrease by 0.06 and 0.05 Å, respectively, at 80 GPa, while the electron density between the bonded atoms increases by 0.12 and 0.15 e/Å 3 , on average. The calculations also show that the coordination number of the Y atom increases from 9 to 10 while the coordination number of the O1 atom increases concomitantly in the structure from 5 to 6 at 20 GPa. Hence pressure not only promotes an increase in the coordination number of the metal atoms but also a necessary concomitant increase in the coordination number of the O atoms. The bonded radii, determined at a lower pressure between 0.0 and 15 GPa for LaAlO 3 and CaSnO 3 , decrease a smaller amount with the radii for the La and Ca atoms decreasing by 0.03 and 0.04 Å, respectively, while the radii for the smaller Al and Sn atoms decrease by 0.01 and 0.02 Å, respectively. In general, O atoms are more compressible than the metal atoms, but overall the calculations demonstrate that the bonded radii for the atoms in crystals are virtually incompressible when subjected to high pressure. The reason that the bonded radii change little when subjected to high pressure is ascribed to the changes in the effective interatomic potentials that result in increased repulsion when the atoms are squeezed together.

Constraining the accommodation, distribution, and circulation of hydrogen in the Earth’s interior is vital to our broader understanding of the deep Earth due to the significant influence of hydrogen on the material and rheological properties of minerals. Recently, a great deal of attention has been paid to the high-pressure polymorphs of FeOOH (space groups P 2 1 nm and Pnnm ). These structures potentially form a hydrogen-bearing solid solution with AlOOH and phase H (MgSiO 4 H 2 ) that may transport water (OH – ) deep into the Earth’s lower mantle. Additionally, the pyrite-type polymorph (space group Pa 3 of FeOOH), and its potential dehydration have been linked to phenomena as diverse as the introduction of hydrogen into the outer core (Nishi et al. 2017), the formation of ultralow-velocity zones (ULVZs) (Liu et al. 2017), and the Great Oxidation Event (Hu et al. 2016). In this study, the high-pressure evolution of FeOOH was re-evaluated up to ~75 GPa using a combination of synchrotron-based X‑ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and optical absorption spectroscopy. Based on these measurements, we report three principal findings: (1) pressure-induced changes in hydrogen bonding (proton disordering or hydrogen bond symmetrization) occur at substantially lower pressures in Ɛ-FeOOH than previously reported and are unlikely to be linked to the high-spin to low-spin transition; (2) Ɛ-FeOOH undergoes a 10% volume collapse coincident with an isostructural Pnnm → Pnnm transition at approximately 45 GPa; and (3) a pressure-induced band gap reduction is observed in FeOOH at pressures consistent with the previously reported spin transition (40 to 50 GPa).

Ophiolite pulses, which are periods of enhanced ophiolite generation and emplacement, are thought to have a relevance to highly active superplumes (superplume model). However, the Cambrian-Ordovician pulse has two critical geological features that cannot be explained by such a superplume model: predominance of subduction-related ophiolites and scarcity of plume-related magma activities. We addressed this issue by estimating the mechanism and condition of magma generation, including mantle potential temperature (MPT), from a ~500 Ma subduction-related ophiolite, the Hayachine-Miyamori ophiolite. We developed a novel method to overcome difficulties in global MPT estimation from an arc environment by using porphyritic ultramafic dikes showing flow differentiation, which have records of the chemical composition of the primitive magma, including its water content, because of their high pressure (~0.6 GPa) intrusion and rapid solidification. The solidus conditions for the primary magmas are estimated to be ~1450 °C, ~5.3 GPa. Geochemical data of the dikes show passive upwelling of a depleted mantle source in the garnet stability field without a strong influence of slab-derived fluids. These results, combined with the extensive fluxed melting of the mantle wedge prior to the dike formation, indicate sudden changes of the melting environment, its mechanism, and the mantle source from extensive fluxed melting of the mantle wedge to decompressional melting of the sub-slab mantle, which has been most plausibly triggered by a slab breakoff. The estimated MPT of the sub-slab mantle is ~1350 °C, which is very close to that of the current upper mantle and may reflect the global value of the upper mantle at ~500 Ma if small-scale convection maintained the shallow sub-slab mantle at a steady thermal state. We, therefore, conclude that the Cambrian-Ordovician ophiolite pulse is not attributable to the high temperature of the upper mantle. Frequent occurrence of slab breakoff, which is suggested by our geochemical compilation of Cambrian-Ordovician ophiolites, and subduction termination, which is probably related to the assembly of the Gondwana supercontinent, may be responsible for the ophiolite pulse.

Praseodymium is capable of existing as Pr 3+ and Pr 4+ . Although the former is dominant across almost all geological conditions, the observation of Pr 4+ by XANES and Pr anomalies (both positive and negative) in multiple light rare earth element minerals from Nolans Bore, Australia, and Stetind, Norway, indicates that quadrivalent Pr can occur under oxidizing hydrothermal and supergene conditions. High-temperature REE partitioning experiments at oxygen fugacities up to more than 12 log units more oxidizing than the fayalite-magnetite-quartz buffer show negligible evidence for Pr 4+ in zircon, indicating that Pr likely remains as Pr 3+ under all magmatic conditions. Synthetic Pr 4+ -bearing zircons in the pigment industry form under unique conditions, which are not attained in natural systems. Quadrivalent Pr in solutions has an extremely short lifetime, but may be sufficient to cause anomalous Pr in solids. Because the same conditions that favor Pr 4+ also stabilize Ce 4+ to a greater extent, these two cations have similar ionic radii, and Ce is more than six times as abundant as Pr, it seems that Pr-dominant minerals must be exceptionally rare if they occur at all. We identify cold, alkaline, and oxidizing environments such as oxyhalide-rich regions at the Atacama Desert or on Mars as candidates for the existence of Pr-dominant minerals.

Fe oxidation/reduction reactions play a fundamental role in a wide variety of geological processes. In natural materials, Fe redox state commonly varies across small spatial scales at reaction interfaces, yet the approaches available for quantitatively mapping the Fe redox state at the microscale are limited. We have designed an optimized synchrotron-based X‑ray spectroscopic approach that allows microscale quantitative mapping of Fe valence state by extending the Fe XANES pre-edge technique. An area of interest is mapped at nine energies between 7109–7118 eV and at 7200 eV, allowing reconstruction, baseline subtraction, and integration of the pre-edge feature to determine Fe(III)/ΣFe with 2 μm spatial resolution. By combining the Fe redox mapping approach with hyperspectral Raman mineralogy mapping, the Fe oxidation state distributions of the major mineral phases are revealed. In this work, the method is applied to a partially serpentinized peridotite with various Fe-bearing secondary mineral phases to trace the Fe transformations and redox changes that occurred during its alteration. Analysis with the Fe redox mapping technique revealed that the peridotite contained relict olivine with abundant Fe(II), while serpentine, pyroaurite, and another hydroxide phase are secondary mineral reservoirs of Fe(III). Although serpentine is not Fe-rich, it contained approximately 74% ± 14% Fe(III)/ΣFe. These analytical results are integral to interpreting the sequence of alteration reactions; serpentinization of primary olivine formed Fe(II)-rich brucite and oxidized serpentine, which could have contributed to H 2 production during serpentinization. Subsequent weathering by oxidizing, CO 2 -bearing fluids led to the partial carbonation and oxidation of brucite, forming pyroaurite and a hydroxide phase containing dominantly Fe(III). This Fe redox imaging approach is applicable to standard petrographic thin sections or grain mounts and can be applied to various geologic and biogeochemical systems.

Initial excess protactinium ( 231 Pa) is a frequently suspected source of discordance in baddeleyite (ZrO 2 ) geochronology, which limits accurate U/Pb dating, but such excesses have never been directly demonstrated. In this study, Pa incorporation in late Holocene baddeleyite from Somma-Vesuvius (Campanian Volcanic Province, central Italy) and Laacher See (East Eifel Volcanic Field, western Germany) was quantified by U-Th-Pa measurements using a large-geometry ion microprobe. Bad-deleyite crystals isolated from subvolcanic syenites have average U concentrations of ~200 ppm and are largely stoichiometric with minor abundances of Nb, Hf, Ti, and Fe up to a few weight percent. Measured ( 231 Pa)/( 235 U) activity ratios are significantly above the secular equilibrium value of unity and range from 3.4(8) to 14.9(2.6) in Vesuvius baddeleyite and from 3.6(9) to 8.9(1.4) in Laacher See baddeleyite (values within parentheses represent uncertainties in the last significant figures reported as 1σ throughout the text). Crystallization ages of 5.12(56) ka (Vesuvius; MSWD = 0.96, n = 12) and 15.6(2.0) ka (Laacher See; MSWD = 0.91, n = 10) were obtained from ( 230 Th)/( 238 U) disequilibria for the same crystals, which are close to the respective eruption ages. Applying a corresponding age correction indicates average initial ( 231 Pa)/( 235 U) 0 of 8.8(1.0) (Vesuvius) and 7.9(5) (Laacher See). For reasonable melt activities, model baddeleyite-melt distribution coefficients of D Pa / D U = 5.8(2) and 4.1(2) are obtained for Vesuvius and Laacher See, respectively. Speciation-dependent (Pa 4+ vs. Pa 5+ ) partitioning coefficients ( D values) from crystal lattice strain models for tetra- and pentavalent proxy ions significantly exceed D Pa / D U inferred from direct analysis of 231 Pa for Pa 5+ . This is consistent with predominantly reduced Pa 4+ in the melt, for which D values similar to U 4+ are expected. Contrary to common assumptions, baddeleyite-crystallizing melts from Vesuvius and Laacher See appear to be dominated by Pa 4+ rather than Pa 5+ . An initial disequilibrium correction for baddeleyite geochronology using D Pa / D U = 5 ± 1 is recommended for oxidized phonolitic melt compositions.

Oxygen fugacities (fO2)$\left( {{f}_{{{\text{O}}_{2}}}} \right)$of mantle-derived mafic magmas have important controls on the sulfur status and solubility of the magmas, which are key factors to the formation of magmatic Ni-Cu sulfide deposits, particularly those in convergent margin settings. To investigate the fO2${{f}_{{{\text{O}}_{2}}}}$of mafic magmas related to Ni-Cu sulfide deposits in convergent margin settings, we obtained the magma fO2${{f}_{{{\text{O}}_{2}}}}$of several Ni-Cu sulfide-bearing mafic-ultramafic intrusions in the Central Asian Orogenic Belt (CAOB), North China, based on the olivine-spinel oxygen barometer and the modeling of V partitioning between olivine and melt. We also calculated the mantle fO2${{f}_{{{\text{O}}_{2}}}}$on the basis of V/ Sc ratios of primary magmas of these intrusions. Ni-Cu sulfide-bearing mafic-ultramafic intrusions in the CAOB include arc-related Silurian-Carboniferous ones and post-collisional Permian-Triassic ones. Arc-related intrusions formed before the closure of the paleo-Asian ocean and include the Jinbulake, Heishan, Kuwei, and Erbutu intrusions. Post-collisional intrusions were emplaced in extensional settings after the closure of the paleo-Asian ocean and include the Kalatongke, Baixintan, Huangshandong, Huangshan, Poyi, Poshi, Tulaergen, and Hongqiling No. 7 intrusions. It is clear that the magma fO2${{f}_{{{\text{O}}_{2}}}}$values of all these intrusions in both settings range mostly from FMQ+0.5 (FMQ means fayalite-magnetite-quartz oxygen buffer) to FMQ+3 and are generally elevated with the fractionation of magmas, much higher than that of MORBs (FMQ-1 to FMQ+0.5). However, the mantle fO2${{f}_{{{\text{O}}_{2}}}}$values of these intrusions vary from ~FMQ to ~FMQ+1.0, just slightly higher than that of mid-ocean ridge basalts (MORBs) (≤FMQ). This slight difference is interpreted as the intrusions in the CAOB may have been derived from the metasomatized mantle wedges where only minor slab-derived, oxidized components were involved. Therefore, the high-magma f O 2 values of most Ni-Cu sulfide-bearing mafic-ultramafic intrusions in the CAOB were attributed to the fractionation of magmas derived from the slightly oxidized metasomatized mantle. In addition, the intrusions that host economic Ni-Cu sulfide deposits in the CAOB usually have magma f O 2 of >FMQ+1.0 and sulfides with mantle-like δ 34 S values (–1.0 to +1.1‰), indicating that the oxidized mafic magmas may be able to dissolve enough mantle-derived sulfur to form economic Ni-Cu sulfide deposits. Oxidized mafic magmas derived from metasomatized mantle sources may be an important feature of major orogenic belts.

Olivine is the most abundant mineral in the Earth’s upper mantle and subducting slabs. Studying the structural evolution and equation of state of olivine at high-pressure is of fundamental importance in constraining the composition and structure of these regions. Hydrogen can be incorporated into olivine and significantly influence its physical and chemical properties. Previous infrared and Raman spectroscopic studies indicated that local structural changes occur in Mg-rich hydrous olivine (Fo ≥ 95; 4883–9000 ppmw water) at high-pressure. Since water contents of natural olivine are commonly <1000 ppmw, it is inevitable to investigate the effects of such water contents on the equation of state (EoS) and structure of olivine at high-pressure. Here we synthesized a low water content hydrous olivine (Fo 95 ; 1538 ppmw water) at low SiO 2 activity and identified that the incorporated hydrogens are predominantly associated with the Si sites. We performed high-pressure single-crystal X‑ray diffraction experiments on this olivine to 29.9 GPa. A third-order Birch-Murnaghan equation of state (BM3 EoS) was fit to the pressure-volume data, yielding the following EoS parameters: V T0 = 290.182(1) Å 3 , K T0 = 130.8(9) GPa, and KT0′ =4.16(8).$K_{\mathrm{T} 0}^{\prime}=4.16(8).$The K T0 is consistent with those of anhydrous Mg-rich olivine, which indicates that such low water content has negligible effects on the bulk modulus of olivine. Furthermore, we carried out the structural refinement of this hydrous olivine as a function of pressure to 29.9 GPa. The results indicate that, similar to the anhydrous olivine, the compression of the M1-O and M2-O bonds are comparable, which are larger than that of the Si-O bonds. The compression of M1-O and M2-O bonds of this hydrous olivine are comparable with those of anhydrous olivine, while the Si-O1 and Si-O2 bonds in the hydrous olivine are more compressible than those in the anhydrous olivine. Therefore, this study suggests that low water content has negligible effects on the EoS of olivine, though the incorporation of water softens the Si-O1 and Si-O2 bond.

The oxidation state of iron in upper mantle minerals is widely used to constrain the Earth mantle’s oxidation state. Previous studies showed high levels of ferric iron in high-pressure majoritic garnets and pyroxenes despite reducing conditions. To disentangle the effects of pressure and increasing oxygen fugacity on the Fe 3+ /ΣFe ratios of garnet and clinopyroxene, we performed high-pressure experiments at a pressure of 10 GPa in a 1000-ton Walker-type multi-anvil apparatus at the University of Münster. We synthesized majoritic garnets and clinopyroxenes with a total iron content close to natural mantle values at different oxygen fugacities, ranging from IW+4.7 to metal saturation at IW+0.9. We analyzed the iron oxidation state in garnets with the electron microprobe “flank method.” Furthermore, we investigated the oxidation state of iron in garnets and clinopyroxenes with transmission electron microscopy (TEM) electron energy loss spectroscopy (EELS). Although the flank method measurements are systematically lower than the EELS measurements, Fe 3+ /ΣFe obtained with both methods agree well within 2σ errors. The “flank method” has the advantage of being much faster and more easily to set up, whereas TEM-EELS has a much higher spatial resolution and can be applied to various non-cubic minerals such as orthopyroxenes and clinopyroxenes. We used our experimental results to compare two geobarometers that contain a term for ferric iron in garnet (Beyer and Frost 2017; Tao et al. 2018) with two geobarometers that do not account for ferric iron (Collerson et al. 2010; Wijbrans et al. 2016). We found that for garnets with low total Fe and Fe 3+ (like many natural garnets), the pressures can be calculated without including the ferric iron content.

Titanium oxide minerals along the P2 fault in the eastern Athabasca Basin are characterized to constrain their origin and the geological history of the area. Two types of rutile are recognized in the basement rocks. Early rutile is disseminated in graphitic metapelite and quartzite, and it formed during regional metamorphism and post-metamorphic hydrothermal activity. Late rutile occurs as a needle-like alteration product of mica and likely formed during retrogression of the basement. In graphitic metapelite, early rutile commonly occurs with an assemblage of oxy-dravite, quartz, graphite, zircon, pyrite, biotite, and muscovite. In quartzite, rutile occurs with quartz, sillimanite, muscovite, and zircon. Metamorphic rutile is characterized by high Nb/ Ta ratios (up to 47) with high concentrations of U (up to 126 ppm) and V 4+ (up to 1.44 wt%; V valance calculated from EPMA data). Hydrothermal rutile contains distinctly low Nb/Ta (as low as 4.80) with high Ta (≤3050 ppm), and relatively low V (as V 3+ ; as low as 0.02 wt%) and U (as low as 9.06 ppm), reflecting fluids in reduced oxidation conditions. Anatase forms small anhedral (rarely coarse and euhedral) grains in the basal sandstones and altered basement rocks. In sandstones, anatase occurs with the late diagenetic mineral assemblage, whereas in basement rocks it commonly occurs with the clay-sized minerals related to uranium mineralization. In both rocks, anatase likely formed through the dissolution of rutile and/or other Ti-bearing minerals. Anatase is characterized by variably high Fe (up to 0.99 wt%; possibly contributed by hematite micro-or nanoinclusions) and U (up to 180 ppm). The mineral assemblages and composition of anatase suggest its protracted crystallization from relatively low temperature, oxidizing, acidic, uraniferous fluids of the sandstones during late diagenesis and hydrothermal activity. Therefore, the occurrence of anatase records the incursion of basin fluids into the basement, and the interaction of basement rocks with fluids responsible for the formation of the McArthur River uranium deposit. The results of this study confirm that Ti-oxides are useful in unraveling the geological history of an area that underwent prolonged hydrothermal activity.

Evidence of immiscibility between arsenide and sulfide melts has been observed both in experimental studies and natural samples from several localities worldwide (e.g., Ronda, Spain; Beni Bousera, Morocco; Dundonald Beach South, Canada). Platinum-group elements (PGE) have shown to have a strong affinity for arsenide melts, but little is known about their partitioning behavior between arsenide and sulfide melts. In this study, we experimentally determine the partition coefficients of PGE (Pt, Pd, Ir, Ru, and Os) between both types of melt in As-saturated sulfide systems doped with trace amounts of PGE. Results show that all PGE display a strong preference to the arsenide melt with DPGEAs/sulf melts $D_{\text{PGE}}^{\text{As}/\text{sulf}\text{ melts }}$ranging from 20 to 2700, with Ir and Pt showing a marked preference for arsenide melts. These partition coefficients values are similar to estimates made from natural samples and demonstrate that the separation of arsenide melts from sulfide magmas can be an efficient mechanism to scavenge PGE from magmas and to fractionate Os, Ru, and Pd from Pt and Ir.

Melt inclusions record the depth of magmatic processes, magma degassing paths, and volatile budgets of magmas. Extracting this information is a major challenge. It requires determining melt volatile contents at the time of entrapment when working with melt inclusions that have suffered post-entrapment modifications. Several processes decrease internal melt inclusion pressure, resulting in nucleation and growth of a vapor bubble and, time permitting, diffusion of volatiles (especially CO 2 ) into the vapor bubble. Previous studies have shown how this process may lead to most of the CO 2 in the bulk melt inclusion being lost to the bubble. Without reconstruction, most of the melt inclusion data in the literature vastly underestimate the CO 2 concentrations of magmas by measuring the glass phase only. Methods exist that attempt to reconstruct the entrapped CO 2 contents, but they can be difficult to apply and do not always yield consistent results. Here, we explore bubble growth, evaluate CO 2 reconstruction approaches, and develop improved experimental and computational approaches. Piston-cylinder experiments were conducted on olivine-hosted melt inclusions from Seguam (Alaska, U.S.A.) and Fuego (Guatemala) volcanoes at the following conditions: 500–800 MPa, 1140–1200 °C for Seguam and 1110–1140 °C for Fuego, 4–8 wt% H 2 O in the KBr brine filling the experimental capsules, and run durations of 10–120 min. Heated melt inclusions form well-defined S-CO 2 trends consistent with degassing models. CO 2 contents are enriched by a factor of ~2.5, on average, relative to those of the glasses in unheated melt inclusions, whereas S contents of heated and unheated melt inclusion glasses overlap, indicating that insignificant amounts of S partition into the vapor bubble. For naturally quenched melt inclusions, relatively low closure temperatures for CO 2 diffusion enables some CO 2 to enter vapor bubbles during quench, whereas higher closure temperatures for S diffusion limits its loss to vapor bubbles. We evaluate the timescales of post-entrapment processes and use the results to develop a new computational model to restore entrapped CO 2 contents: melt inclusion modification corrections (MIMiC). Heated melt inclusion data are used as a benchmark to evaluate the results from MIMiC and other published methods of CO 2 reconstruction. The methods perform variably well. Key advantages to our experimental technique are accurate measurements of CO 2 contents and efficient rehomogenization of large quantities of melt inclusions. Our new computational model produces more accurate results than other computational methods, has similar accuracy to the Raman method of CO 2 reconstruction in cases where Raman can be applied (i.e., no C-bearing phases in the bubble), and can be applied to the vast body of published melt inclusion data. To obtain the most robust data on bubble-bearing melt inclusions, we recommend taking both experimental- and MIMiC-based approaches.

In this issue This New Mineral Names has entries for 13 new species, including falottaite, meieranite and high-pressure minerals found in meteorites, terrestrial impact rocks, and as inclusions in diamonds: hemleyite, hiroseite, ice-VII, kaitianite, maohokite, proxidecagonite, riesite, rubinite, uakitite, wangdaodeite, and zagamiite.