ALBERT

Description: We performed decompression experiments on sulfur-bearing hydrous rhyolite magma at a temperature of 800 °C to investigate redox evolution during magma decompression. The magma was continuously decompressed from 100 MPa to 10–50 MPa at rates of 10 and 100 MPa h–1. The evolution of the ferric to total iron ratio (Fe3+/Fetotal) during decompression was investigated using XANES, and redox evolution was determined based on a thermodynamic calculation and measured Fe3+/Fetotal. Before decompression, the sample was buffered from NNO to NNO+1, and the pre-exsolved fluid phase and sulfide crystal coexisted. Sulfide crystals were found in all decompressed samples, and Fe3+/Fetotal showed a slight decrease with decompression. It was confirmed that the sample in a gold capsule was not influenced by the change in redox conditions outside of the capsule for the timescale of the decompression experiments; thus, the decompressed sample reflected the redox evolution in magma during decompression. Our experiments indicated that magma decompression causes a slight reduction when it includes water and sulfur. This evolution is qualitatively explained by sulfur degassing and fluid-melt redox equilibria. During the fluid-melt redox equilibria, magma is reduced if the existence of a pre-exsolved fluid phase is assumed, while the model calculation shows that magma is oxidized when it contains only water or no pre-exsolved fluid phases. This is because sulfur buffers the oxidation of magma through a reaction with oxygen in the fluid phase. Therefore, we inferred that the redox condition of magma is not oxidized during explosive volcanism with a pre-exsolved fluid phase and closed-system degassing. In contrast, if magma experiences open-system degassing, it may be oxidized, resulting in the breakdown of sulfide crystals as observed in some pyroclasts and lavas.

Description: Olivine is a major rock-forming mineral in various magmatic and metamorphic rocks and the upper mantle. In this paper, we present the first high-precision analyses of olivine from 15 samples of magnesian skarns and silicate marbles (MSSM) from the collection of the Fersman Mineralogical Museum (Moscow, Russia). Mg# [Mg/(Mg+Fe2+)·100, mol%] of olivine from the samples studied varies from 86 to nearly 100. The main distinctive features of the olivine are anomalously low contents of Co (

Description: Thermometry of high-grade metamorphic rocks is difficult due to fast cationic diffusion during slow cooling, but the titanium content of calcium amphibole (Ti-Amp) can retrieve amphibole-forming temperature as high as ~1000 °C. Based on pseudosection modeling and past research survey, we find that Ti-Amp is controlled by temperature under the conditions of oxygen fugacity

Description: Dark blue lazurite from the Malo-Bystrinskoe lazurite deposit, Baikal Lake area, Eastern Siberian region, Russia, was analyzed by electron microprobe and revealed an unusually high content of total sulfur corresponding to 8.3 wt% S. The relative content of sulfur in sulfate and sulfur in sulfide form was determined by wet chemical analysis. The H2O content was measured by means of differential thermal analysis in combination with mass spectrometry and infrared (IR) spectroscopy. The charge-balanced empirical formula of lazurite calculated on the basis of 12 (Al+Si) atoms per formula unit was (Na6.97Ca0.88K0.10)Σ7.96[(Al5.96Si6.04)Σ12O24](SO4)1.092−(S3−)0.55S0.052− Cl0.04·0.72H2O. The presence of H2O molecules and (S3)– and (SO4)2– groups was confirmed by the combination of IR, Raman, electron paramagnetic resonance (EPR), and X-ray photoelectron spectroscopy (XPS) methods. The idealized formula of lazurite is Na7Ca[Al6Si6O24](SO4)2–(S3)–·H2O, and it is believed that extra-framework cations and anions are grouped into clusters of [Na3Ca·SO4]3+ and [Na4(S3)–]3+. The types of isomorphous substitutions in nosean and haüyne are discussed. Lazurite is a clathrate-type mineral, which may be an effective (S3)– sensor due to the stability of the trisulfur radical anion in isolated cages of the crystal structure. This specific feature makes it possible to study the behavior of this ubiquitous radical anion over larger T and P ranges as compared to free species. This kind of lazurite, with oxidized and reduced sulfur species, seems to be appropriate for the estimation of the fugacity of SO2 and O2 in metasomatic systems forming lazurite-containing rocks. The systematic presence of incommensurate modulations is a unique structural feature of Baikal lazurite and may be an important marker indicating provenance of the mineral.

Description: An olivine-melt thermometer based on the partitioning of Ni (DNiOl/liq) was hypothesized by Pu et al. (2017) to have a negligible dependence on dissolved water in the melt (and pressure variations from 0–1 GPa), in marked contrast to thermometers based on DMgOl/liq. In this study, 15 olivine-melt equilibrium experiments were conducted on a basaltic glass starting material (9.6 wt% MgO; 353 ppm Ni) to test this hypothesis by comparing the effect of dissolved H2O in the melt on DMgOl/liq and DNiOl/liq on the same set of experiments. Results are presented for six anhydrous experiments at 1 bar, two anhydrous experiments at 0.5 GPa, and seven hydrous experiments at 0.5 GPa. Analyzed olivine and glass compositions in the quenched run products were used to calculate DMgOl/liq and DNiOl/liq values for each experiment, which in turn permit temperature to be calculated with the Mg- and Ni-thermometers calibrated in Pu et al. (2017) on anhydrous, 1-bar experiments from the literature. The Ni-thermometer recovers the temperatures of all 15 experiments from this study with an average deviation of –3 °C, including those with up to 4.3 wt% H2O dissolved in the melt. In contrast, the Mg-thermometer recovers the anhydrous, 1-bar experimental temperatures within +14 °C on average, but overestimates the hydrous experimental temperatures by +49 to +127 °C, with an average of +83 °C. When the Mg-thermometer of Putirka et al. (2007) is applied, which includes a correction for analyzed H2O (≤4.3 wt%) in the quenched melts of the run products, all experimental temperatures are recovered with an average (±1σ) deviation of +7 °C. The combined results show that DNiOl/liq has a negligible dependence on dissolved water in the melt (≤4.3 wt% H2O), which is in marked contrast to the strong dependence of DMgOl/liq on water in the melt. An understanding of why DNiOl/liq is insensitive to dissolved water, unlike DMgOl/liq, is obtained from spectroscopic evidence in the literature, which shows that Ni2+ (transition metal) and Mg2+ (alkaline earth metal) have distinctly different average coordination numbers (predominantly fourfold and sixfold, respectively) in silicate melts and that fourfold-coordinated Ni2+ is unaffected by the presence of dissolved water in the melt. This difference in coordination number explains why DNiOl/liq and DMgOl/liq each have a different dependence on pressure, anhydrous melt composition, and melt water content. Application of the Ni-thermometer of Pu et al. (2017) to five natural samples from the Mexican arc, for which H2O contents (3.6–6.7 wt%) in olivine-hosted melt inclusions are reported in the literature, leads to temperatures that match those obtained from the Putirka et al. (2007) Mg-thermometer that corrects for analyzed H2O contents. This study demonstrates that a thermometer based on DNiOl/liq can be applied to hydrous basalts at crustal depths without the need to correct for dissolved water content or pressure.

Description: Tourmaline is a common mineral in granites and metamorphic rocks in collisional orogens. This paper describes graphite-bearing, metasomatic tourmalinites in sillimanite-zone schists of the Proterozoic Black Hills Orogen, South Dakota. The tourmalinites bound quartz veins and beyond about 1 m grade into schists with disseminated tourmaline, and ultimately tourmaline becomes only a trace, intrinsic phase in the schists. Next to the quartz veins, tourmaline has almost completely replaced schist minerals, including biotite, muscovite, and plagioclase. The tourmaline is generally anhedral and follows the original foliation direction of the schist. However, tourmaline is euhedral in quartz veinlets cutting through the tourmalinites. Tourmaline is compositionally zoned from having about 22 to 2% of apparent Al occupancy on the Y sites. There are very good negative correlations of Y(Fe2++Mg2+), XCa2+, and YTi4+ with YAl3+, and a very good positive correlation of X-site vacancies with YAl3+. Mg# [molar Mg2+/(Mg2++Fe2+)] is fairly invariant at approximately 0.5, which is somewhat higher than that in the precursor biotite. This is in contrast to tourmaline in the neighboring peraluminous Harney Peak leucogranite where the range of Y site occupancy of Al is small at about 20%, but the Mg# ranges from 0.12 to 0.5. The compositional trends in the metasomatic tourmaline are dominated by the exchange X☐ + 4 YAl3+ = XCa2+ + 3 Y(Fe2++Mg2+) + YTi4+. Mass-balance calculations suggest the metasomatizing fluid brought in H+ and B(OH)3 and removed K+, SiO2, and some Fe2+ during tourmalinization. Other elements in the tourmaline largely reflect the bulk composition of the replaced schist. The calculations show that silica in the quartz veins was locally derived, not brought in by the metasomatizing fluid. Interstitial graphite in the tourmalinites shows precipitation of carbon from the methane-bearing fluid. The study demonstrates an important effect of boron transfer by fluids during metamorphism and magmatism in the Earth's crust.

Description: Micrometer- to submicrometer-scale indium-rich domains are preserved within sphalerite included in hornfels-hosted pyrrhotite from the Dulong polymetallic skarn, Yunnan, China. The nano-mineralogy of the ZnS-bearing blebs was investigated using scanning transmission electron microscopy on thinned foils extracted in situ from pyrrhotite. Indium incorporation in sphalerite occurs via the coupled substitution 2Zn2+ ↔ Cu+ + In3+; the results thus allow insights into phase relationships in the system ZnS-CuInS2 in which solubility limits are debated with respect to a cubic to tetragonal phase transition. The highest concentrations of In are measured in basket-weave domains from the smallest ZnS blebs or from un-patterned areas in coarser, irregular ZnS inclusions in pyrrhotite. Indium-rich domains contain 17–49 mol% CuInS2, whereas In-poor sphalerite contains

Description: Crowningshieldite is the natural analog of the synthetic compound α-NiS. It has a NiAs-type structure and is the high-temperature polymorph relative to millerite (β-NiS), with an inversion temperature of 379 °C. Crowningshieldite is hexagonal, space group P63/mmc, with a = 3.44(1) Å, c = 5.36(1) Å, V = 55.0(2) Å3, and Z = 2. It has an empirical formula (Ni0.90Fe0.10)S and dcalc = 5.47(1) g/cm3. The five strongest lines in the powder X-ray diffraction data are [dmeas in angstroms (I) (hkl)]: 1.992 (100) (102), 1.718 (55) (110), 2.978 (53) (100), 2.608 (35) (101), and 1.304 (17) (202). Crowningshieldite was found as part of a multiphase inclusion in a gem-quality, colorless, type IIa (containing less than ~5 ppm N) diamond from the Letseng mine, Lesotho. The inclusion contains crowningshieldite along with magnetite-magnesioferrite, hematite, and graphite. A fracture was observed that extended from the inclusion to the diamond exterior, meaning that fluids, possibly kimberlite-related, could have penetrated into this fracture and altered the inclusion. Originally, the inclusion might have been a more reduced, metallic Fe-Ni-C-S mixture made up of cohenite, Fe-Ni alloy, and pyrrhotite, akin to the other fracture-free, pristine inclusions within the same diamond. Such metallic Fe-Ni-C-S primary inclusions are a notable recurring feature of similar type IIa diamonds from Letseng and elsewhere that have been shown to originate from the sublithospheric mantle. The discovery of crowningshieldite confirms that the α-NiS polymorph occurs in nature. In this case, the reason for its preservation is unclear, but the relatively iron-rich composition [Fe/(Fe+Ni) = 0.1] or the confining pressure of the diamond host are potential factors impeding its transformation to millerite. The new mineral name honors G. Robert Crowningshield (1919–2006) (IMA2018-072).

Description: It is not known if the thermodynamic behavior of some minerals and their synthetic analogues are quantitatively the same. Olivine is an important rock-forming substitutional solid solution consisting of the two end-members forsterite, Mg2SiO4, and fayalite, Fe2SiO4. We undertook the first heat capacity, CP, measurements on two natural olivines between 2 and 300 K; nearly end-member fayalite and a forsterite-rich crystal Fo0.904Fa0.096. Their CP(T) behavior is compared to that of synthetic crystals of similar composition, as found in the literature. The two natural olivines are characterized by X-ray powder diffraction and 57Fe Mössbauer spectroscopy. The X-ray results show that the crystals are well crystalline. The Mössbauer hyperfine parameters, obtained from a fit with two Fe2+ quadrupole split doublets, are similar to published values measured on synthetic olivines. There are slight differences in the absorption line widths (i.e., FWHM) between the natural and synthetic crystals. CP (2 to 300 K) is measured by relaxation calorimetry. The CP results of the natural nearly end-member fayalite and published values for two different synthetic Fa100 samples are in excellent agreement. Even CP resulting from a Schottky anomaly and a paramagnetic-antiferromagnetic phase transition with both arising from Fe2+ are similar. There are slight differences in the Néel temperature between the natural 63 K and synthetic ~65 K fayalites. This is probably related to the presence of certain minor elements (e.g., Mn2+) in the natural crystal. The third-law entropy, S°, value is 151.6 ± 1.1 J/(mol·K). CP behavior of the natural forsterite, Fo0.904Fa0.096, and a synthetic olivine, Fo90Fa10, are in excellent agreement between about 7 and 300 K. The only difference lies at T 〈 7 K, as the former does not show Debye T3 behavior, but, instead, a plateauing of CP values. The S° value for the natural forsterite is 99.1 ± 0.7 J/(mol·K).

Description: A multi-methodical characterization of a sauconite (Zn-bearing trioctahedral smectite) specimen from the Skorpion ore deposit (Namibia) was performed by combining X-ray powder diffraction (XRPD), cation exchange capacity (CEC) analysis, differential thermal analysis (DTA), thermo-gravimetry (TG), Fourier transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM-HRTEM-AEM). The X-ray diffraction pattern exhibits the typical features of turbostratic stacking disorder with symmetrical basal 00l reflections and long-tailed hk bands, as confirmed by TEM observations. Besides sauconite, the sample contains minor amounts of kaolinite, dioctahedral smectite, and quartz. CEC analysis provides a total of Ca (~69%), Mg (~26%), Na (~4%), and K (0.7%) exchangeable cations. Therefore, Zn is located exclusively within the octahedral site of sauconite. TG analysis of the sample yields a total mass loss of about 17%. Three endothermic peaks can be observed in the DTA curve, associated with dehydration and dehydroxylation of the material. An exothermic peak at 820 °C is also present as a consequence of decomposition and recrystallization. The infrared spectrum shows the typical Zn3OH stretching signature at 3648 cm–1, whereas, in the OH/H2O stretching region two bands at 3585 and 3440 cm–1 can be attributed to stretching vibrations of the inner hydration sphere of the interlayer cations and to absorbed H2O stretching vibration, respectively. Diagnostic bands of kaolinite impurity at ~3698 and 3620 cm–1 are also found, whereas 2:1 dioctahedral layer silicates may contribute to the 3585 and 3620 cm–1 bands. Finally, using the one-layer supercell approach implemented in the BGMN software, a satisfactory XRPD profile fitting model for the Skorpion sauconite was obtained. These findings have implications not only for economic geology/recovery of critical metals but also, more generally, in the field of environmental sciences.

Description: For four decades fairbankite was reported to have the formula Pb2+(Te4+O3), but repeated attempts to isolate fairbankite crystals for structural determination found only the visually similar cerussite and, more rarely, anglesite. The crystal-structure determination of fairbankite using single-crystal X-ray diffraction, supported by electron microprobe analysis and X-ray powder diffraction on the type specimen, has shown that fairbankite contains essential S, along with Pb, Te, and O. The chemical formula of fairbankite has been revised to Pb122+(Te4+O3)11(SO4). This change has been accepted by the IMA–CNMNC, Proposal 19-I. The crystal structure of fairbankite [space group P1 (no. 1); revised cell: a = 7.0205(3) Å, b = 10.6828(6) Å, c = 14.4916(8) Å, a = 75.161(5)°, b = 81.571(4)°, g = 83.744(4)°, V = 1036.35(9) Å3, and Z = 1] is the first atomic arrangement known to contain a Te34+O96− non-cyclic, finite building unit. Fairbankite has an average structure, formed from a 3D framework of Pb2+On polyhedra, Te4+On polyhedra, and SO4 tetrahedra in a 12:11:1 ratio. The stereoactive lone pairs of the Pb2+ and Te4+ cations are oriented into void space within the structure. Fairbankite contains two mixed sites statistically occupied by Te4+ and S6+ in approximately 4:1 and 1:4 ratios. These two sites possess Te4+ in trigonal-pyramidal environment and S6+ in tetrahedral environment (with an additional O site to create tetrahedral SO4 shape for the S-dominant site). Six of the 10 fully occupied Te4+ sites have Te4+ in trigonal-pyramidal environment, while four have Te4+ at the center of highly distorted Te4+O4 disphenoids. The disphenoids allow for the creation of two dimeric Te24+O64− units in addition to the Te34+O96− trimeric unit, which contains two disphenoids. All linkage between disphenoids and trigonal pyramids is via corner-linking. Secondary connectivity is via long Te–O and Pb–O bonds.

Description: Jasonsmithite (IMA2019-121), Mn42+ZnAl(PO4)4(OH)(H2O)7·3.5H2O, is a pegmatite-phosphate mineral from the Foote Lithium Company mine, Kings Mountain district, Cleveland County, North Carolina, U.S.A. It is interpreted as having formed by late-stage, low-temperature hydrothermal alteration. Crystals are colorless to light brown, slightly flattened prisms to about 1 mm in length with wedge-shaped terminations. The mineral is transparent with vitreous luster, white streak, Mohs hardness 2, brittle tenacity, irregular fracture, and perfect {001} cleavage. The density is 2.63(2) g/cm3. Jasonsmithite is biaxial (–), with α = 1.561(2), β = 1.580(2), γ = 1.581(2), measured in white light. The 2V is 25(5)° and dispersion is r 〈 ν moderate. The optical orientation is Y = b, X ^ c = 18° in obtuse β. The Raman spectrum is dominated by vibrational modes of PO4 and ZnO4 tetrahedra, AlO6 and MnO6 octahedra, and OH groups. Electron microprobe analyses gave the empirical formula (Mn3.09Fe0.87)Σ3.96Zn1.05Al0.98(PO4)4(OH)(H2O)7·3.5H2O. The mineral is monoclinic, P21/c, a = 8.5822(3), b = 13.1770(6), c = 20.3040(14) Å, β = 98.485(7)°, V = 2271.0(2) Å3, and Z = 4. The structure (R1 = 0.0443 for 3685 I〉2σI reflections) contains zigzag chains of edge-sharing MnO6 octahedra that corner-link to adjacent chains and to PO4 tetrahedra to form sheets, which are decorated by ZnO4 tetrahedra. The sheets are linked to one another via dimers of AlO6 octahedra, forming a framework with large channels containing H2O groups. With H2O groups removed, the framework has a void space of 70.2% per unit cell, and a framework density of 14.5 polyhedral atoms/1000 Å3, which would place jasonsmithite among the most porous minerals.

Description: American Mineralogist greatly values the time and effort of the 2020 reviewers, especially in such an unprecedented year. The Journal thrives due to the commitment of many people. It could not do so without the support of these crucial volunteers.

Description: Two Cenozoic prominent features are spatio-temporally associated in central Mongolia, i.e., the continental basalts and regional uplift, but their genesis and relationship remain unclear. This study presents major- and trace-element compositions for olivine phenocrysts and xenocrysts, as well as data of bulk-rock geochemistry and Sr-Nd-Hf isotopes for the host basalts. The studied basalts mostly have trachybasalt compositions with high total alkali (Na2O + K2O = 5.1–8.2 wt%) contents and all display OIB-like trace element patterns (e.g., spikes of Ba, Nb, and Ta and troughs of Th and U) and EM1-like Sr-Nd-Hf isotopic compositions. Compared to the partial melting products of mantle peridotite, these basaltic samples have higher FeO/MnO, Zn/Mn, and Zn/Fe ratios. Meanwhile, phenocrystic olivines are characterized by lower Ca, Mn, Mn/Zn, and Mn/Fe but higher Ni than their counterparts in the peridotitic melts, indicating a pyroxenite-rich mantle source. The above geochemical data suggest that the source of the studied basalts was mainly made up of secondary pyroxenite produced by the reaction of recycled oceanic crust with its ambient mantle peridotite. The calculated magma oxygen fugacities (ΔFMQ-0.26 to +0.42) and mantle melting temperatures (1343–1430 °C) do not support a genetic link with the stagnant Pacific slab or with a deep mantle plume. Instead, the far-field effect of India-Eurasia convergence possibly tapped the upper asthenospheric mantle, subsequent melting of which gave rise to the dispersive Cenozoic basalts. On the other hand, the xenocrystic olivines exhibit zoned textures with high-Fo (up to 92) cores and low-Fo (down to 76) rims, reflecting the melt-rock interaction. Preservation of zoned olivine xenocrysts indicates rapid magma ascent and widespread melt-rock reaction in the mantle lithosphere, which may modify the rheology and accelerate the mechanical erosion of mantle lithosphere. Consequently, mass deficit in the lithosphere could have caused isostatic uplift of central Mongolia in the Cenozoic.

Description: In the present study, the competitive adsorption geometries for arsenate and phosphate on magnetite surfaces over a pH range of 4–9 were investigated using in situ attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR) and two-dimensional correlation analysis (2D-COS). The adsorption energies and infrared vibrational frequencies of these surface complexes were also calculated by first-principles simulations. Arsenate and phosphate have different preferences for the magnetite surface in the presence of aqueous solvent at both acid and alkaline pH. For the adsorption of phosphate, mono-protonated monodentate mononuclear (MMM) complexes dominated at acid pH, while non-protonated bidentate binuclear (NBB) complexes were dominant at alkaline pH. Arsenate mainly formed bidentate binuclear (BB) complexes with some outer-sphere species, both of which were more prevalent at acid pH. The pre-absorbed inner-sphere arsenate species were scarcely affected by the introduction of phosphate. However, the pre-absorbed phosphate oxyanions, especially the MMM complexes, were significantly substituted by BB arsenate at the magnetite surfaces. The adsorption affinity of phosphate and arsenate species for magnetite surface was found to increase in the following order: MMM phosphate complex 〈 NBB phosphate complex 〈 BB arsenate complex, which was consistent with the calculated adsorption energies. The simulated infrared vibrational frequencies for the most favorable adsorption modes of each oxyanion display distinctive patterns, and their trends are in excellent agreement with experimental data. The effects of pH, adsorption sequence, and mineral species on the competitive adsorption between arsenate and phosphate oxyanions are also discussed, and their different competing ability and stability on the magnetite surfaces can be ascribed to the variations in adsorption geometry and strength of binding. To the best of our knowledge, this is the first study aiming to distinguish the stability of the different phosphate and arsenate complexes on magnetite by employing a combined approach of in situ spectroscopy and DFT simulations. Our results provide molecular-level insight into the geometries and relative stabilities of the adsorption of phosphate and arsenate on magnetite surfaces, which is useful for interpretation of the mobility and bioavailability of these anions.

Description: The source of fluids and their mechanism of metal precipitation in sediment-hosted, disseminated orogenic gold deposits are ambiguous. Pyrite texture, trace element, S, Pb, and He-Ar isotope compositions of sulfides and C-O isotope data of calcite from Chang'an orogenic gold deposit in the Ailaoshan orogenic belt, southwest (SW) China, were studied to provide a new genetic model for the sediment-hosted orogenic gold deposit, furthering knowledge of the source of fluids and their mechanism of metal precipitation. Orebodies at Chang'an are mainly hosted by Ordovician turbidite with a few in Oligocene syenite. Two stages of mineralization have been identified in the deposit: stage I disseminated quartz-arsenopyrite-pyrite and stage II veined quartz-calcite-polymetallic sulfides. Five generations of pyrite have been identified in turbidite: pre-ore syn-sedimentary pyrite, pyI-1, and pyI-2 in stage I, and pyII-1 and pyII-2 in stage II, and an unzoned pyrite population developed in syenite. PyI-1 commonly overgrows syn-sedimentary pyrite with irregular boundaries and contains arsenopyrite, galena, chalcopyrite, and electrum inclusions along the boundaries. PyI-1 is overgrown by thin and inclusion-free pyI-2, and crosscut by pyII-1, which is rimmed by pyII-2.The syn-sedimentary pyrite is distributed parallel to the sedimentary bedding and contains As (620.8 ppm), Pb (61.6 ppm), Ni (59.8 ppm), Mo (54.4 ppm), Co (23.4 ppm), and Cu (13.0 ppm) with low-Au content of 0.06 ppm. This pyrite has δ34S values of −18.1 to +30.4‰ and high-radiogenic Pb isotope ratios (average 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb of 19.05, 15.86, and 39.87, respectively). PyI-1 and coexisting arsenopyrite are enriched in invisible Au (up to 227.1 and 353.3 ppm, respectively), As, Ni, Cu, and Pb, while pyI-2 contain much lower trace element abundances relative to pyI-1 and arsenopyrite. Partial replacement of syn-sedimentary pyrite by pyI-1 plus arsenopyrite, galena, chalcopyrite, and electrum, and similar Pb isotope ratios between syn-sedimentary pyrite and pyI-1 indicate that reaction of external deep Au-rich fluids with syn-sedimentary pyrite is responsible for gold precipitation in stage I. PyI-1, arsenopyrite, and pyI-2 show a narrower δ34S range of −3.2 to 7.1‰ relative to syn-sedimentary pyrite, demonstrating that the fluid-pyrite interaction has homogenized the sulfur. The unzoned pyrite in syenite has similar mineral inclusions (arsenopyrite, galena, etc.), δ34S values (+0.6 to 6.3‰) and Pb isotope ratios to pyI-1, but much lower trace element abundances relative to pyI-1. It may be attributed to different reactions of similar fluids with different wall-rocks. PyII-1 and pyII-2 in stage II contain elevated As, Pb, Cu, Sb, Zn, and Ag with low mean Au content (3.3 ppm) and have δ34S ranges of −2.8 to +1.2‰ and −6.2 and −0.8‰, respectively. Galena in stage II has lower radiogenic Pb isotope ratios than stage I pyrites, indicative of a different Pb source or fluid evolution. The gases released from a mixture of pyII-1-pyII-2 have R/Ra of 0.38 to 0.98 and 40Ar*/4He of 0.50 to 1.34, falling between the fields of mantle-derived and crustal fluids. Late ore calcites have δ13CPDB of −8.7 to 2.7‰ and δ18OSMOW of 8.05 to 25.58‰, also plotting between sedimentary carbonate and mantle fields. These signatures indicate that ore fluids in stage II are base metal-rich fluids with a small amount of contribution from the mantle. Different ore assemblages, trace element composition and isotope data between stages I and II at Chang'an suggest that the deposit experienced an evolution from early Au-rich fluids to late base metal-rich ones. This study highlights that ore metals in sediment-hosted disseminated orogenic gold deposits may be sourced from both deep fluids and local wall-rock, and that fluid-rock interaction behaved as a key control on ore precipitation.

Description: Detailed knowledge of the structural evolution of diverse aluminum (oxy)hydroxides with varying temperatures up to ~300 °C provides insights into the dehydration processes involving transitions among metastable phases on Earth's surface and in the crust. Here, we report the high-resolution solid-state 27Al NMR spectra for three different types of aluminum (oxy)hydroxides (i.e., boehmite, bayerite, and gibbsite) with varying annealing temperatures up to 300 °C, revealing the effect of distinct precursor minerals on the stability of metastable alumina. 27Al MAS NMR results allow us to obtain the quantitative fractions and NMR parameters for each phase during transformation. The results demonstrate that each aluminum (oxy)hydroxide phase follows a unique transformation path to metastable alumina. The 27Al MAS and 3QMAS NMR spectra of boehmite show that a minor but observable [4]Al signal (~2%) is detected at ~50 °C, and the [4]Al fraction gradually increases up to 300 °C (~16%), indicating that the phase transformation from boehmite to γ-/η-Al2O3 occurs at a temperature as low as ~50 °C, significantly lower than earlier estimations based on XRD. Together with the [4]Al fraction, the [5]Al fraction increases from 150 °C). Furthermore, the phase transformation from boehmite to γ-/η-Al2O3 occurs gradually within broad temperature ranges from ~50 °C. This is due to their configurational disorder as evidenced by the presence of [5]Al. The observed structural evolution in aluminum (oxy)hydroxides in the low-temperature range facilitates our understanding of the nature of phase transformation and dehydration of oxides and hydroxides in the Earth's surface environments.

Description: Knowledge of the stability of carbonate minerals at high pressure is essential to better understand the carbon cycle deep inside the Earth. The evolution of Raman modes of carbonates with increasing pressure can straightforwardly illustrate lattice softening and stiffening. Here, we report Raman modes of natural magnesite MgCO3 up to 75 GPa at room temperature using helium as a pressure-transmitting medium (PTM). Our Raman spectra of MgCO3 show the splitting of T and ν4 modes initiated at approximate 30 and 50 GPa, respectively, which may be associated with its lattice distortions. The MgCO3 structure was referred to as MgCO3-Ib at 30–50 GPa and as MgCO3-Ic at 50–75 GPa. Intriguingly, at 75.4 GPa some new vibrational signatures appeared around 250–350 and ~800 cm–1. The emergence of these Raman bands in MgCO3 under relatively hydrostatic conditions is consistent with the onset pressure of structural transition to MgCO3-II revealed by theoretical predictions and high-pressure and high-temperature experiments. This study suggests that hydrostatic conditions may significantly affect the structural evolution of MgCO3 with increasing pressure, which shall be considered for modeling the carbon cycle in the Earth's lower mantle.

Description: Iron isotope fractionation in hydrothermal systems is a useful diagnostic tool for tracing ore-forming processes. Here, we report on the Fe isotopic compositions of a suite of hydrothermal minerals from ores (pyrite, pyrrhotite, and quartz) from the Wulong gold deposit, Liaodong Peninsula, East China. Pyrites from quartz sulfide ores show a δ56Fe (56Fe/54Fe in the sample relative to IRMM-14) range from +0.11 ± 0.03‰ to +0.78 ± 0.03‰ (2SD), and pyrrhotites from the same vein are isotopically lighter than the pyrites, varying between −0.85 ± 0.01‰ and −0.07 ± 0.00‰. This result is consistent with theoretical predictions of equilibrium fractionation and published mineral compositions. For the first time, to our knowledge, we report the Fe isotopes of hydrothermal quartz that records the isotopic compositions of the ore-forming fluids. Two quartz separates in the quartz-sulfide vein yield δ56Fe values of −0.02 ± 0.02‰ and +0.07 ± 0.07‰. Our Fe isotope fractionation calculations show that pyrrhotite with light Fe isotopes crystallized first from the ore-forming fluids, which indicates a relatively reduced condition for the initial ore-forming fluids. Then the remaining fluids with heavy Fe isotopes precipitated pyrites with positive δ56Fe values, and their mineral crystallization sequence records an increase of oxygen fugacity during mineralization. Gold deposits in Wulong and Jiaodong share many similar geological characteristics. The pyrites from the Wulong deposit have higher δ34S values (+0.5 to +4.1‰) than the pyrrhotites (–1.2 to +1.2‰). Pyrites from the Jiaodong gold deposits show a wide range of both positive and negative δ56Fe values as well as high δ34S values, whereas those from the Wulong deposit have a relatively narrow range of positive δ56Fe values and near-zero δ34S values. The differences in Fe isotopes may be due to early precipitation of pyrrhotite with light Fe isotopes under a relatively low oxygen fugacity environment in the Wulong deposit, resulting in pyrite precipitated from the remaining fluids with heavy isotopes. The sulfur isotope variations between Wulong and Jiaodong gold deposits reflect differences in their source regions rather than oxygen fugacities. In addition, we have compiled Fe isotopic compositions of pyrites and pyrrhotites from different types of ore deposits to investigate their Fe isotopic behavior in magmatic-hydrothermal systems. Pyrite grains show a wide range of δ56Fe values. Positive pyrite δ 56Fe values reflect an equilibrium isotope effect, whereas negative pyrite δ56Fe values may be due to kinetic isotope effects or to a mixture of sedimentary host rocks. Pyrrhotite grains show similar negative δ56Fe values, and they have a strong influence on the Fe isotope systematics in magmatic and hydrothermal systems. Our data show that Fe isotopes can be used to trace precipitation orders of pyrite and pyrrhotite and oxygen fugacity evolution in relatively reduced hydrothermal deposits.

Description: Tungsten deposits are usually associated with granitic intrusions that record a long and complex evolution of the magmatic-hydrothermal system. However, the genetic link between magmatic-hydrothermal evolution and tungsten mineralization remains unclear. The Xihuashan tungsten deposit in South China, an important vein-type wolframite deposit, is closely associated with greisen and multi-phase intrusive activity that produced biotite granite, two-mica granite, and muscovite granite. From the biotite granite to the two-mica granite to the muscovite granite, micas vary from siderophyllite to lithian siderophyllite, with decreasing K/Rb and Nb/Ta ratios and increasing Rb and Cs contents. The zoned micas in the muscovite granite and greisen display fluorine-depleted rims, reflecting subsolidus replacement by external aqueous fluids. The presence of siderite indicates a Fe-, Mn-, and CO2-rich fluid under reducing conditions. The micas in the greisen have higher-F contents and lower Fe3+/Fe2+ ratios than those in the muscovite granite, suggesting that the fluids contributing to greisen formation had a relatively high-fluorine content and were reduced. The increase of CO2 in the fluid enhanced its ability to unlock W from melts/rocks into fluids. The reducing environment also facilitated the tungsten mineralization. During greisenization, the pH value of the fluid increased, which destabilized the polymeric tungstates to form WO42–. The mixture of W-rich solution and Fe-, Mn-rich external fluid eventually precipitated as vein-type wolframite in favorable locations. An empirical equation (Li2O = 0.0748 × F2 + 0.0893 × F) was introduced for estimating the Li2O contents of hydrothermal micas using the F contents determined by EPMA.

Description: Information-rich attributes of minerals reveal their physical, chemical, and biological modes of origin in the context of planetary evolution, and thus they provide the basis for an evolutionary system of mineralogy. Part III of this system considers the formation of 43 different primary crystalline and amorphous phases in chondrules, which are diverse igneous droplets that formed in environments with high dust/gas ratios during an interval of planetesimal accretion and differentiation between 4566 and 4561 Ma. Chondrule mineralogy is complex, with several generations of initial droplet formation via various proposed heating mechanisms, followed in many instances by multiple episodes of reheating and partial melting. Primary chondrule mineralogy thus reflects a dynamic stage of mineral evolution, when the diversity and distribution of natural condensed solids expanded significantly.

Description: Raman spectra were collected for an extensive set of well-characterized layer-structure Mn oxide mineral species (phyllomanganates) employing a range of data collection conditions. We show that the application of various laser wavelengths, such as 785, 633, and 532 nm, at low power levels (30–500 μW) in conjunction with the comprehensive database of standard spectra presented here, makes it possible to distinguish and identify the various phyllomanganate minerals. The Raman mode relative intensities can vary significantly as a function of crystal orientation relative to the incident laser light polarization direction as well as incident laser light wavelength. Consequently, phase identification success is enhanced when using a standards database that includes multiple spectra collected for different crystal orientations and with different laser light wavelengths. The position of the highest frequency Raman mode near 630–665 cm–1 shows a strong linear correlation with the fraction of Mn3+ in the octahedral Mn sites. With the comprehensive Raman database of well-characterized Mn oxide standards provided here (and available online as Online Material1), and use of appropriate data collection conditions, micro-Raman is a powerful tool for identification and characterization of biotic and abiotic Mn oxide phases from diverse natural settings, including on other planets, as well as for laboratory and industrial materials.

Description: We determined for the first time the crystal structures of high-pressure K-cymrite (KAlSi3O8⋅H2O) and its dehydrated form kokchetavite (KAlSi3O8) using single-crystal X-ray diffraction. The K-cymrite structure has been successfully refined in the hexagonal space group P6/mmm [a = 5.3361(3) Å, c = 7.7081(7) Å, V = 190.08(3) Å3, R1 = 0.036 for 127 unique observed reflections], which is in agreement with previous models from powder X-ray diffraction. In contrast, kokchetavite shows superstructural reflections, suggesting a different unit cell and a space group of P6/mcc [a = 10.5757(3) Å, c = 15.6404(6) Å, V = 1514.94(10) Å3, R1 = 0.068 for 1455 unique observed reflections]. Upon dehydration, single-crystal grains of K-cymrite transform into single-crystal grains of kokchetavite. The latter questions a previous interpretation of kokchetavite crystals in mineral inclusions as a product of direct crystallization from fluid/melt. The Raman spectrum of K-cymrite shows a strong polarization dependence, which is important in identification of the mineral inclusions.

Description: Modeling of ionic diffusion in natural crystals has been developed over the last three decades to calculate timescales of geological processes. As the number of studies and the size of data sets have expanded, improvements in the precision of the general technique are needed to resolve temporal patterns that would otherwise be masked by large uncertainties. This contribution examines fundamental aspects of timescale calculation uncertainty using Mg-Fe zonation in olivine crystals from a Piton de la Fournaise oceanite erupted in 2002 CE. First, we quantitatively consider the role of geometric uncertainty in data sets from the perspectives of sectioning angle, crystal shape, and crystal agglomeration. Second, we assess how crystal growth and changing boundary conditions during diffusion pose problems for simplistic, 1D, diffusion-only modeling. An initial database of 104 timescales (7–45 days) was generated using typical, 1D, isothermal diffusion-only methods for profiles taken from 30 compositionally and texturally zoned crystals of olivine. This simplistic modeling yields poor model fits and imprecise timescales; prior to this work, we would have rejected 〉60% of these data. Universal-stage measurements of crystal boundary angles and three-dimensional (3D) X-ray microcomputed tomography observations of crystal shape address geometric uncertainties. U-stage measurements show that, contrary to expectations of random sectioning, most boundaries modeled initially were close to the ideal sectioning plane. Assessment of crystal morphology from 2D thin sections suggests olivine crystals are dominantly euhedral; however, 3D imaging reveals that they are significantly subhedral and often exist as agglomerates, an observation that underscores both the potential for diverse crystal interactions through time in the magma (Wieser et al. 2019) and out-of-plane effects capable of influencing calculations of diffusion profiles. Refinements to timescale determination can be made using a dynamic 1D modeling code to resolve growth and changing boundary effects simultaneous with diffusion. We incorporated temperature-dependent crystal growth rates (both linear growth and quadratically increasing, with a peak growth rate ~1.9 ×10–11 ms–1) and temperature-dependent boundary conditions (controlled using a cooling rate of −0.5 ± 0.1 °C/h) to remodel 13 timescales, resulting in significantly improved fits of the diffusion model to the initial data, better agreement between different faces of the same crystal, and less scatter within the whole data set. The use of 3D imaging and the inclusion of changing boundary conditions and crystal growth for diffusion calculations will enable more robust conclusions to be drawn from similar data in the future. Accurately retrieving timescale information from these crystals expands the pool of data available and reduces sampling bias toward “well-behaved” crystals.

Description: Since granitic rocks in high-grade terranes commonly undergo amphibolite-granulite facies meta-morphic overprint, recovering magmatic records from the metamorphic modification remains a major challenge. Here, we report an early Paleozoic, garnet-bearing Yunlu charnockite that outcropped in the Yunkai terrane of the Cathaysia block from South China and underwent amphibole-grade metamorphic overprint in the late Devonian. Field observation, micro-texture, and mineral geochemistry combined with diffusion modeling constrain that the metamorphic overprint with an extremely short duration of ~0.2–0.5 Ma only influences a narrow rim of 900 °C, and an initial H2O content of ~4.0 wt% with rare CO2 components. The orthopyroxene-garnet, biotite-garnet, and biotite-orthopyroxene thermometers yield a consistent temperature range of 770–820 ± 60 °C, which is significantly higher than the H2O-saturated solidus temperature of ~630 °C estimated from experimental results and two-feldspar thermometry. These results indicate that the early crystallized minerals (e.g., garnet, orthopyroxene, and some euhedral biotite) of the Yunlu charnockite equilibrate at higher temperatures with crystallinities of ~30–45%, rather than the H2O-saturated solidus conditions. We thus propose a hypothesis of melt extraction at 780–820 °C in a deep-seated, slowly cooling, partially crystalline magma reservoir. The melt extraction physically segregates the early crystallized minerals from residual interstitial melts, which inhibits element diffusion equilibration between these minerals and interstitial melts. Granite thermometry commonly yields a large range of temperature estimations, which may be related to melt extraction events. Our study shows that melt extraction recorded in granites can be identified by combining micro-texture, mineral thermometry and rhyolite-MELTS modeling, which further provides quantitative insights into the fractionation process of silicic magmas.

Description: Two generations of garnet are recognized in a granite and a pegmatite from the Gangdese orogen in southeastern Tibet on the basis of a combined study of petrography, major and trace element profiles, and garnet O isotopes. Zircon U-Pb dating and Hf-O isotope compositions also help constrain the origin of both granite and pegmatite. The first generation of garnet (Grt-I) occurs as residues in the center of garnet grains, and it represents an early stage of nucleation related to magmatic-hydrothermal fluids. Grt-I is dark in backscattered electron (BSE) images, rich in spessartine, and poor in almandine and grossular. Its chondrite-normalized rare earth element (REE) patterns show obvious negative Eu anomalies and depletion in heavy REE (HREE) relative to middle REE (MREE). The second generation of pegmatite garnet (Grt-II) occurs as rims of euhedral garnets or as patches in Grt-I domains of the pegmatite, and it crystallized after dissolution of the preexisting pegmatite garnet (Grt-I domains) in the presence of the granitic magma. Compared with Grt-I, Grt-II is bright in BSE images, poor in spessartine, and rich in almandine and grossular contents. Its chondrite-normalized REE patterns exhibit obvious negative Eu anomalies but enrichment in HREE relative to MREE. The elevation of grossular and HREE contents for Grt-II relative to Grt-I domains indicate that the granitic magma had higher contents of Ca than the magmatic-hydrothermal fluids. The garnets in the granite, from core to rim, display homogenous profiles in their spessartine, almandine, and pyrope contents but increasing grossular and decreasing REE contents. They are typical of magmatic garnets that crystallized from the granitic magma. Ti-in-zircon temperatures demonstrate that the granite and pegmatite may share the similar temperatures for their crystallization. Grt-II domains in the pegmatite garnet have the same major and trace element compositions as the granite garnet, suggesting that the pegmatite Grt-II domains crystallized from the same granitic magma. Therefore, the pegmatite crystallized at first from early magmatic-hydrothermal fluids, producing small amounts of Grt-I, and the fluids then mixed with the surrounding granitic magma. The U-Pb dating and Hf-O isotope analyses of zircons from the granite and pegmatite yield almost the same U-Pb ages of 77–79 Ma, positive eHf(t) values of 5.6 to 11.9, and d18O values of 5.2 to 7.1‰. These data indicate that the granite and pegmatite were both derived from reworking of the juvenile crust in the newly accreted continental margin prior to the continental collision in the Cenozoic.

Description: To clarify the effect of water on carbonate-silicate liquid immiscibility in the diamond stability field, we performed experiments in the system KAlSi3O8-CaMgSi2O6-NaAlSi2O6-CaMg(CO3)2 under nominally dry and hydrous conditions by adding 1.5 wt% H2O at a pressure of 6 GPa and temperatures of 1000 to 1500 °C. Both systems start to melt at 1050–1100 °C. Under anhydrous condition the melting occurs via the following reaction: 6KAlSi3O8 (K-feldspar) + 6CaMg(CO3)2 (dolomite) = 2(Can,Mg1-n)3Al2Si3O12 (garnet) + Al2SiO5 (kyanite) + 11SiO2 (coesite) + 3 K2(Ca1-n, Mgn)2(CO3)3 (carbonatitic melt) + 3CO2 (fluid and/or liquid), whereñ 0.3–0.4. The carbonatitic melt has the following composition 38(K0.92Na0.08)2CO3⋅62Ca0.62Mg0.38CO3. A second immiscible silicic melt containing (in wt%, volatile free) SiO2 = 68.8, Al2O3 = 12.6, CaO = 3.7, MgO = 2.4, Na2O = 1.1, and K2O = 11.3 appears at 1250 °C. Both melts remain stable up to 1500 °C and coexist with the clinopyroxene ± garnet ± coesite residue. In the presence of water stored away in phengite, the melting begins with silicic melt, which contains (in wt%, volatile free) SiO2 = 61.4, Al2O3 = 15.3, CaO = 4.8, MgO = 3.0, Na2O = 2.2, and K2O = 13.3, and coexists with phengite, dolomite, clinopyroxene, and coesite. The phengite + dolomite assemblage remains to 1100 °C and disappears at 1200 °C producing two immiscible melts carbonatitic with approximate composition, 19(K0.89Na0.11)2CO3⋅81Ca0.57Mg0.43CO3, and silicic containing (in wt%, volatile free) SiO2 = 63.3, Al2O3 = 15.6, CaO = 4.5, MgO = 3.0, Na2O = 2.0, K2O = 11.6. The present results imply that partial melting of continental material subducted to a depth of 200 km can yield simultaneous formation of two immiscible melts, K-dolomitic and K-aluminosilicate. Under dry conditions, carbonatitic melt appears earlier (at a lower temperature). Given the low density and high mobility of this melt, it must rapidly percolate upward, leaving a refractory eclogite-like residue and leaving no chance for the formation of a second aluminosilicate melt. However, under hydrous conditions silicate melt appears earlier than carbonatitic melt, leaving a phengite- and dolomite-bearing residue, which finally yields the formation of two immiscible silicic and carbonatitic melts. The compositions of these melts fall in the compositional range of carbonatitic and silicic high-density fluids (HDFs) in diamonds worldwide. Thus, we suggest that the presence of water is a necessary requirement for the formation of immiscible HDFs inclusions in diamonds, and this suggestion is strongly supported by natural data from HDFs.

Description: Trace/minor element variation in pyrite is a feature that has proved invaluable for reconstructing a wide range of geological processes. Routine reflectance observations commonly fail to constrain this variation due to the typically subtle and barely perceptible change in reflectance brought about by deviation from ideal stoichiometry. Such differences may be difficult or impossible to observe in conventional polished sections using standard optical microscopes, at least without oil immersion. Chemical etching and staining, although widely used, are destructive, hazardous, or both, and the etching process is not completely reproducible. Here we use the g correction method to enhance optical digital signal differences obtained in reflected light to constrain compositional heterogeneity in pyrite from a representative hydrothermal ore deposit in eastern China. The g-enhanced images show significant reflectance variation caused by compositional heterogeneity, confirmed by quantitative electron microprobe analysis and qualitative imaging. Higher reflectance domains in g-enhanced images correspond to increases in the effective number of free electrons, whereas darker domains are attributed to the decrease of these free electrons by trace/minor element substitution in pyrite (e.g., As). Gamma correction provides a rapid, effective, non-destructive method to constrain compositional heterogeneity of pyrite through enhancement of reflectance variation. Used alone, this method is unable to determine the chemical composition due to simultaneous substitutions, causing a disparate increase or decrease of reflectance, in most ore minerals. Nevertheless, γ correction may be sufficient to predict the substitution of trace/minor elements under the optical microscope prior to scanning electron microscope imaging and quantitative investigation of mineral composition and may help constrain links between textures and compositions of pyrite in evolving ore systems, which could also be applied to other ore minerals with negligible bireflectance.

Description: Carbonate minerals play a dominant role in the deep carbon cycle. Determining the high-pressure and high-temperature vibrational properties of carbonates is essential to understand their anharmonicity and their thermodynamic properties under crustal and upper mantle conditions. Building on our previous study on aragonite, calcite (both CaCO3 polymorphs), dolomite [CaMg(CO3)2], magnesite (MgCO3), rhodochrosite (MnCO3), and siderite (FeCO3) (Farsang et al. 2018), we have measured the pressure- and temperature-induced frequency shifts of Raman-active vibrational modes up to 6 GPa and 500 °C for all naturally occurring aragonite- and calcite-group carbonate minerals, including cerussite (PbCO3), strontianite (SrCO3), witherite (BaCO3), gaspeite (NiCO3), otavite (CdCO3), smithsonite (ZnCO3), and spherocobaltite (CoCO3). Our Raman and XRD measurements show that cerussite decomposes to a mixture of Pb2O3 and tetragonal PbO between 225 and 250 °C, smithsonite breaks down to hexagonal ZnO between 325 and 400 °C, and gaspeite to NiO between 375 and 400 °C. Spherocobaltite breaks down between 425 and 450 °C and otavite between 375 and 400 °C. Due to their thermal stability, carbonates may serve as potential reservoirs for several metals (e.g., Co, Ni, Zn, Cd) in a range of crustal and upper mantle environments (e.g., subduction zones). We have determined the isobaric and isothermal equivalents of the mode Grüneisen parameter and the anharmonic parameter for each Raman mode and compare trends in vibrational properties as a function of pressure, temperature, and chemical composition with concomitant changes in structural properties. Finally, we use the anharmonic parameter to calculate the thermal contribution to the internal energy and entropy, as well as the isochoric and isobaric heat capacity of certain carbonates.

Description: Controversies on the origin of zircon, corundum, titanomagnetite, and quartz megacrysts in alkali basalts mostly reflect the lack of direct evidence of a “melt reservoir” required for their formation. Various mineral megacrysts are carried up by Cenozoic (mostly younger than 25 Ma) alkali basalts that extend more than 4000 km along eastern China. Here we report unusual inclusions in corundum megacrysts from Changle, and we attribute their origin to the existence of a FeO*-SiO2-Al2O3-ZrO2-rich melt. The inclusions, analyzed using electron microprobe and Raman microscopy, may be divided into two types. Type I inclusions are dominated by glassy materials, may exhibit a dark part in backscattered eletron (BSE) images composed of quartz, corundum, and an amorphous substance (AS-1), and a bright part in BSE images composed of baddeleyite and a second distinct amorphous substance (AS-2). Compared with AS-1, AS-2 has higher concentrations of ZrO2 and FeO* but lower concentrations of Al2O3 and SiO2. We argue that the formation temperature of Type I inclusions is ~1200 °C, and the generation of their bright and dark parts in BSE images may be attributed to the coexistence of immiscible melts. Type II inclusions are composed of zircon, quartz, and an amorphous substance (AS-3). Both types of inclusions might be derived from a similar parent melt, which is FeO*-SiO2-Al2O3-ZrO2-rich. New secondary ion mass spectroscopy (SIMS) in situ U-Pb ages of 18 Ma and 13–14 Ma for zircon inclusions suggest that the corundum megacrysts, occurring in basaltic host rocks distributed along the middle segment of the north and south-trending Tanlu fault zone, formed from precursor residual magmas related to underplating basalts stalled at the crust-mantle boundary, and were brought to the surface by entrainment in later basalts. This study provides new insights into the genesis of the corundum-related megacryst suite.

Description: High concentrations of vanadium cause very unusual coloration in hibonite (purple) and grossite (light violet) crystals in an exotic mineral assemblage from Sierra de Comechingones (Argentina). In the hibonite (CaAl12O19) structure vanadium ions, in various valence states (divalent, trivalent, and tetravalent), may be distributed over five crystallographic sites with coordinations corresponding to different polyhedra, namely, three unequal octahedra [M1 (D3d), M4 (C3ν), and M5 (Cs)], one M3 tetrahedron (C3ν), and one unusual fivefold-coordinated trigonal bipyramid M2 (D3h). Possible locations of vanadium ions in grossite (CaAl4O7) are limited to two crystallographically distinct sites (T1 and T2, both C1) in tetrahedral coordination. The combination of single-crystal X-ray diffraction and absorption spectroscopy techniques aided by chemical analyses has yielded details on the nature of the vanadium-induced color in both hibonite and grossite crystals. In hibonite, both M4 face-sharing octahedral and M2 trigonal bipyramid sites of the R-block are partially occupied by V3+. Strongly polarized bands recorded at relatively low energies in optical absorption spectra indicate that V2+ is located at the M4 octahedral site of the hibonite R-block. Chemical analyses coupled with an accurate determination of the electron densities at structural sites in hibonite suggest that the vanadium ions occupy about 10 and 5% of the M4 and M2 sites, respectively. For grossite, polarized optical absorption spectra reveal no indications of V2+; all observed absorption bands can be assigned to V3+ in tetrahedral coordination. Although not evident by the observed electron densities at the T sites of grossite (due to the low-V content), longer bond distances, and a higher degree of polyhedral distortion suggest that V3+ is located at the T2 site.

Description: Parent body thermal metamorphism is an important process that alters the structure of organic matter in the parent asteroid of meteorites. Increasing and progressing thermal metamorphism results in carbonization and graphitization of carbonaceous matter in the parent body. Such modifications in the carbon structures can be studied by Raman microspectroscopy, thanks to its high sensitivity to structure and bonding within carbonaceous molecules. We have characterized polyaromatic carbonaceous matter in a total of 24 Antarctic CV3 and CO3 chondrites using micro-Raman imaging spectroscopy in an effort to better understand parent body thermal metamorphism and assess its effects on the carbon structures. Raman spectral parameters of the first-order carbon peaks (D and G) were extracted from at least 200 spectra for each meteorite and were compared to deduce relationships that yield information regarding the thermal metamorphism conditions. We also show, for the first time, spectral trends and relations of the second-order carbon peaks (2D and D+G) within the 2500–3200 cm−1 with thermal metamorphic history. The second-order peaks appear to contain information that is lacking in the first-order peaks. Based on the second-order carbon peak parameters, we tentatively classify four CV3 chondrites into subtypes, and reclassify another. Peak metamorphic temperatures of the investigated meteorites have been estimated based on the width of the D band as well as the calculated Raman spectral curvature. Estimated temperatures appear to correlate well with the assigned petrologic types. We have calculated higher peak metamorphic temperatures for the CV3 chondrites than for the considered CO3 chondrites and further showed that the peak metamorphic temperatures of CV3oxA chondrites are higher than those of CV3oxB, indicating possibly different metamorphic conditions for the two oxidized subtypes. We observe that there is a relatively larger temperature increase going from CO3.2 to CO3.4 (150 °C increase) compared to CO3.4–CO3.6 (20 °C), which may indicate that the graphitization and structural ordering of carbon reach a critical temperature regime around petrologic type CO3.3.

Description: Many rhyolites contain quartz crystals with relatively Ti-rich rims and Ti-poor cores, with a sharp interface between zones, attributed to partial dissolution followed by overgrowth following a heating event due to mafic recharge of the system. Quartz crystals in the compositionally zoned, high-silica rhyolite Tshirege Member of the Bandelier Tuff erupted at 1.26 Ma from the Valles caldera, New Mexico, show a range in zoning styles with Ti-rich rims becoming more abundant upward in the ignimbrite sheet among progressively less evolved magma compositions. Here we compare times between quartz overgrowth and eruption obtained by applying Ti diffusion coefficients to Ti concentration profiles in Tshirege Member quartz crystals with those from cathodoluminescence (CL) brightness profiles and show that panchromatic CL provides only a crude proxy for Ti in quartz in this unit. Titanium concentrations are measured to detection limits of ~1.2 ppm with small analytical errors (

Description: In this paper, we discuss information on crystal structure and morphology available from nuclear magnetic resonance (NMR) spectroscopy of 207Pb for the mineral family [Pb(4f)]2[Pb(6h)]3(AO4)3Cl with A = V (vanadinite), P (pyromorphite), and As (mimetite). The isotropic chemical shift of the 207Pb atoms at Wyckoff positions 4f and 6h was (re-)determined from either static single-crystal or magic angle spinning NMR experiments. This isotropic shift can be linearly correlated to the unit-cell volume within the mineral family, and in the wider context of lead-bearing minerals, to the shortest Pb-O distance for position 4f, in which 207Pb is solely coordinated by oxygen. By evaluating the number of resonances and their respective line widths in the 207Pb-NMR spectra of these three naturally grown minerals, it could be established that vanadinite forms single-domain macroscopic crystals with very small mosaicity, whereas pyromorphite crystals show NMR characteristics, which can be interpreted as being caused by significant mosaicity. In some instances, this mosaic spread could be quantitatively approximated by a Gaussian distribution with a standard deviation angle of σ = 5°. In contrast, our mimetite specimen was composed of multiple sub-crystals with a very high variability of orientations, going beyond mere mosaicity effects. By extending the NMR methodology presented here to other minerals, it may be possible to gain new insights about structure-property relationships and the morphology of natural grown minerals.

Description: The high-pressure CaCO3 phase diagram has been the most extensively studied within the carbonates group. However, both the diverse mineralogy of carbonates and the abundance of solid solutions in natural samples require the investigation of multi-component systems at high pressures (P) and temperatures (T). Here we studied a member of the CaCO3–SrCO3 solid-solution series and revealed the effect of cationic substitution on the pressure-induced phase transitions in calcium carbonate. A synthetic solid solution Ca0.82Sr0.18CO3 was studied in situ by Raman spectroscopy in a diamond-anvil cell (DAC) up to 55 GPa and 800 K. The results of this work show significant differences in the high-pressure structural and vibrational behavior of the (Ca,Sr)CO3 solid solution compared to that of pure CaCO3. The monoclinic CaCO3-II-type structure (Sr-calcite-II) was observed already at ambient conditions instead of the “expected” rhombohedral calcite. The stress-induced phase transition to a new high-pressure modification, termed here as Sr-calcite-IIIc, was detected at 7 GPa. Sr-calcite-VII formed already at 16 GPa and room T, which is 14 GPa lower compared to CaCO3-VII. Finally, crystallization of Sr-aragonite was detected at 540 K and 9 GPa, at 200 K lower T than pure aragonite. Our results indicate that substitution of Ca2+ by bigger cations, such as Sr2+, in CaCO3 structures can stabilize phases with larger cation coordination sites (e.g., aragonite, CaCO3-VII, and post-aragonite) at lower P-T conditions compared to pure CaCO3. The present study shows that the role of cationic composition in the phase behavior of carbonates at high pressures should be carefully considered when modeling the deep carbon cycle and mantle processes involving carbonates, such as metasomatism, deep mantle melting, and diamond formation.

Description: The study of nominally anhydrous minerals with vibrational spectroscopy, despite its sensitivity, tends to produce large uncertainties (in absorbance or intensity) if the observed dispersion of the values arising from the anisotropy of interaction with light in non-cubic minerals is not assessed. In this study, we focused on Raman spectroscopy, which allows the measurement of crystals down to a few micrometers in size in backscattered geometry, and with any water content, down to 200 ppm by weight of water. Using synthetic hydrous single-crystals of olivine and wadsleyite, we demonstrate that under ideal conditions of measurement and sampling, the data dispersion reaches ±30% of the average (at 1s) for olivine and ±32% for wadsleyite, mostly because of their natural anisotropy. As this anisotropy is linked to physical properties of the mineral, it should not be completely considered as an error without treatment. By simulating a large number of measurements with a 3D model of the OH/Si spectral intensity ratio for olivine and wadsleyite as a function of orientation, we observe that although dispersion increases when increasing the number of measured points in the sample, analytical error decreases, and the contribution of anisotropy to this error decreases. With a sufficient number of points (five to ten, depending on the measurement method), the greatest contribution to the error on the measured intensities is related to the instrument's biases and reaches 12 to 15% in ideal cases, indicating that laser and power drift corrections have to be carefully performed. We finally applied this knowledge on error sources (to translate data dispersion into analytical error) on olivine and wadsleyite standards with known water contents to build calibration lines for each mineral to convert the intensity ratio of the water bands over the structural bands (OH/Si) to water content. The conversion factors from OH/Si to parts per million by weight of water (H2O) are 93 108 ± 24 005 for olivine, 250 868 ± 53 827 for iron-bearing wadsleyite, and 57 862 ± 12 487 for iron-free wadsleyite, showing the strong effect of iron on the spectral intensities.

Description: The behavior of nitrogen during magmatic degassing and the potential kinetic fractionation between N and other volatile species (H, C, O, noble gases) are poorly known due to the paucity of N diffusion data in silicate melts. To better constrain N mobility during magmatic processes, we investigated N diffusion in silicate melts under reducing conditions. We developed uniaxial diffusion experiments at 1 atm, 1425 °C, and under nominally anhydrous reducing conditions (fO2 ≤ IW-5.1, where IW is oxygen fugacity, fO2, reported in log units relative to the iron-wüstite buffer), in which N was chemically dissolved in silicate melts as nitride (N3–). Although several experimental designs were tested (platinum, amorphous graphite, and compacted graphite crucibles), only N diffusion experiments at IW-8 in compacted graphite crucibles for simplified basaltic andesite melts were successful. Measured N diffusivity (DN) is on the order of 5.3 ± 1.5 × 10−12 m2 s−1, two orders of magnitude lower than N chemical diffusion in soda-lime silicate melts (Frischat et al. 1978). This difference suggests that nitride diffusivity increases with an increasing degree of melt depolymerization. The dependence of N 3– diffusion on melt composition is greater than that of Ar. Furthermore, N3– diffusion in basalticandesitic melts is significantly slower than that of Ar in similarly polymerized andesitic-tholeiitic melts at magmatic temperatures (1400–1450 °C; Nowak et al. 2004). This implies that N/Ar ratios can be fractionated during reducing magmatic processes, such as during early Earth's magma ocean stages.

Description: Rutile is a common mineral in many types of ore deposits and can carry chemical or isotopic information about the ore formation. For closer understanding of this information, the mechanisms of incorporation of minor elements should be known. In this work, we have investigated natural rutile crystals with elevated concentrations of WO3 (up to 17.7 wt%), Cr2O3,tot (7.5), V2O3,tot (4.1), FeOtot (7.3), and other metals. X-ray absorption spectroscopy (XAS) of rutile at the Fe K, Cr K, V K, and W L1 and L3 edges shows that all cations are coordinated octahedrally. The average oxidation state of V is +3.8, and that of Cr is near +4. Shell-by-shell fitting of the W L3 EXAFS data shows that W resides in the rutile structure. Raman spectroscopy excludes the possibility of hydrogen as a charge-compensating species. High-resolution TEM and electron diffraction confirm this conclusion as the entire inspected area consists of rutile single crystal with variable amounts of metals other than Ti. Our results show that rutile or its precursors can be efficient vehicles for tungsten in sedimentary rocks, leading to their enrichment in W and possibly later fertility with respect to igneous ore deposits. Leucoxene, a nanocrystalline mixture of Ti and Fe oxides, is an especially suitable candidate for such a vehicle.

Description: Nanophase materials including silicates, aluminosilicates, and iron oxides are widespread on Mars. These minerals are important because they likely represent a solid-phase record of ancient climatic conditions on the martian surface. Identification and characterization of nanophase compounds is technically challenging due to the small size and poorly ordered nature of these materials, particularly because their chemical compositions can vary widely. This study presents spectra of several synthetic allophane and imogolite samples with a range of chemical compositions that are typical of the natural variability of allophanic materials. These samples were formed under controlled conditions and have been thoroughly characterized in terms of chemical composition and short-range structure. Analyses confirmed that the synthetic materials were allophane and imogolite and were structurally similar to previously studied natural and synthetic examples of these phases. NMR and XAFS data indicated that high-Al proto-imogolite allophanes were similar in structure to imogolite but were less well ordered, and supported the proposed nanoball structures based on rolled octahedral Al sheets. Increasing Si content in allophane produced increasing tetrahedral Al substitution as well as polymerized Si chain structures at Al-Si mole ratios of 1:1, and sheets and possible framework structures at Al-Si mole ratios of 1:2. Fe in allophanes and imogolites substituted exclusively for octahedral Al. Reflectance spectra of the synthetic allophanes and imogolites were comparable to previously analyzed samples. Variations in Fe content of allophane and imogolite resulted in some observable changes in visible/near-infrared (VNIR) reflectance spectra, but these changes were not detectable in emission spectra. Emission spectra of the samples suggest that variations in Al-Si ratio of allophanes should be detectable using remotely sensed data. Because allophanes with different Al-Si ratios typically form in very different environments, this could be significant for interpretation of formation conditions on Mars, with high-Al compositions suggesting possible tephra weathering and high-Si compositions indicating possible formation from thermal waters.

Description: The new mineral vasilseverginite, ideally Cu9O4(AsO4)2(SO4)2, was found in the Arsenatnaya fumarole at the second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with tenorite, lammerite, stranskiite, lammerite-β, langbeinite, dolerophanite, sanidine, hematite, and gahnite. Vasilseverginite occurs as prismatic crystals up to 0.02 × 0.02 × 0.06 mm3 combined in groups or interrupted crusts up to 1 × 2 cm2 in area and up to 0.1 mm thick. It is transparent, bright green, with vitreous luster. Dcalc is 4.41 g·cm−3. Vasilseverginite is optically biaxial (–), α 1.816(5), β 1.870(5), γ 1.897(5), estimated 2V is 30(15)°. Chemical composition (wt%, electron-microprobe) is: CuO 64.03, ZnO 0.79, Fe2O3 0.25, P2O5 0.05, As2O5 20.83, SO3 14.92, total 100.87. The empirical formula calculated on O = 20 apfu is (Cu8.78Zn0.11Fe0.033+)Σ8.92As1.98P0.01S2.03O20. Vasilseverginite is monoclinic, P21/n, a = 8.1131(4), b = 9.9182(4), c = 11.0225(5) Å, β = 110.855(2)°, V = 828.84(6) Å3, and Z = 2. The strongest reflections in the powder XRD pattern [d,Å(I)(hkl)] are: 7.13(41)(101), 5.99(70)(110, 111), 5.260(100)(101), 4.642(46)(111), 3.140(31)(031), 2.821(35)(023), 2.784(38)(132, 032), 2.597(35)(204), and 2.556(50) (231, 212). The crystal structure, solved using single-crystal X-ray diffraction data, R1 = 0.025, is based upon complex [O4Cu9]10+ layers parallel to (101) that are composed of edge- and corner-sharing (OCu4) tetrahedra. The topology is unprecedented in inorganic structural chemistry. The crystal structure can be considered a hybrid of the structures of popovite Cu5O2(AsO4)2 and dolerophanite Cu2O(SO4) according to the scheme Cu9O4(AsO4)2(SO4)2 = Cu5O2(AsO4)2 + 2Cu2O(SO4). The chemical hybridization does not result in a significant increase in chemical complexity of vasilseverginite compared to the sum of those of popovite and dolerophanite, whereas the structural hybridization leads to the doubling of structural information per unit cell. The mineral is named in memory of the outstanding Russian mineralogist, geologist, and chemist Vasiliy Mikhailovich Severgin (1765–1826).

Description: A continuously increasing number of research groups are adopting elastic geobarometry for retrieving pressures and temperatures of entrapment of inclusions into a host from both natural and experimental samples. However, a few misconceptions of some of the general concepts underlying elastic geobarometry are still widespread. One is the difference between various approaches to retrieve the residual pressures and residual strains from Raman measurements of inclusions. In this paper, the estimation of uncertainties and the validity of some general assumptions behind these methods are discussed in detail, and we provide general guidelines on how to deal with inclusion strain, measurements, inclusion pressure, and their uncertainties.

Description: The model of Fe3+ distribution between octahedra and tetrahedra in dioctahedral smectites by Decarreau and Petit (2014) used data from infrared analysis. From their own and other general evidence, the resulting data are likely to be affected by significant uncertainty. This aside, their model has limited application because it is based on synthetic smectites containing only Si, Al, and Fe3+.

Description: Cuadros et al. (2019) used a wide range of data from dioctahedral and trioctahedral Fe3+-bearing, 2:1 phyllosilicates to propose a model describing how tetrahedral occupancy by Fe3+ takes place in both dioctahedral and trioctahedral 2:1 phyllosilicates. The partition coefficient approach (Decarreau and Petit 2014) focusing on the distribution of Al3+ and Fe3+ between octahedral and tetrahedral sites of dioctahedral smectites has been disregarded in the study of Cuadros et al. (2019). This approach was applied here on the set of data from Cuadros et al. (2019). The partition coefficient value linked to the distribution of Al3+ and Fe3+ between octahedral and tetrahedral sites determined from natural and synthetic dioctahedral smectites applies well to trioctahedral phyllosilicates too. Data from synthetic iron-rich 2:1 smectites also fit well with both Cuadros et al. (2019) and Decarreau and Petit (2014) models.

Description: In this issue This New Mineral Names has entries for 11 new species, including bohuslavite, fanfaniite, ferrierite-NH4, feynmanite, hjalmarite, kenngottite, potassic-richterite, rockbridgeite-group minerals (ferrirockbridgeite and ferrorockbridgeite), rudabányaite, and strontioperloffite.

Description: Zoned plagioclase crystals are often interpreted as proxies for magmatic history because the mineral is present in most silicic magmas and has compositional sensitivity to magmatic conditions (pressure, temperature, and composition) with slow internal diffusion that preserves compositional zones. Changes in growth rates and crystal dissolution present challenges to quantitatively relating time to particular zoning patterns. The numerical model SNGPlag uses Rhyolite MELTS to determine the equilibrium phase assemblage and compositions for a user-defined magma composition experimentally determined instantaneous nucleation and growth rates, and reasonable dissolution rates to examine plagioclase crystallization and population dynamics through time. The model tracks the numbers, sizes, morphologies, and compositional zoning of plagioclase crystals through time in response to changes in pressure, temperature, and volume or mass inputs. Model results show that significant fractions of time are functionally missing from the crystal record because of effectively zero growth rates or erased from the record through dissolution; in some instances, those processes can together remove ≫50% of time from the crystal record. The results show that temperature- (or pressure-) cycling alone will not produce substantial compositional zoning but that the addition of new magma is required to grow complexly zoned phenocrysts. Comparison of the input pressure-temperature-time series with compositional transects shows that the crystal record is biased toward more recent intervals and periods of decreasing temperature (i.e., neither the peak temperatures nor intervals of prolonged, cool storage are favored). Crystallization (or dissolution during heating) acts to return magmas to near-equilibrium crystal fractions within hundreds of days.

Description: Xenocrysts and xenoliths in Upper Cretaceous pyroclastics on Mount Carmel (northern Israel) represent a series of similar magma-fluid systems at different stages of their evolution, recording a continuous decrease in oxygen fugacity (fO2) as crystallization proceeded. Corundum coexisting with Fe-Mg-Cr-Al spinels, other Fe-Mg-Al-Na oxides, and Fe-Ni alloys in apparent cumulates crystallized at fO2 values near the iron-wüstite (IW) buffer (fO2 = IW±1) and is zoned from high-Cr cores to lower-Cr rims, consistent with fractional crystallization trends. The reconstructed parental melts of the cumulates are Al-Cr-Fe-Mg oxides with ca. 2 wt% SiO2. Corundum in other possible cumulates that contain Cr-Fe (Fe 45 wt%) alloys has low-Cr cores and still lower-Cr rims. Corundum coexisting with Cr0 (fO2 = IW-5) in some possible cumulates has low-Cr cores, but high-Cr rims (to 〉30% Cr2O3). These changes in zoning patterns reflect the strong decrease in the melting point of Cr2O3, relative to Al2O3, with decreasing fO2. The electron energy loss spectroscopy (EELS) analyses show that all Cr in corundum that coexists with Cr0 is present as Cr3+. This suggests that late in the evolution of these reduced melts, Cr2+ has disproportionated via the reaction 3Cr2+(melt) → 2Cr3+(Crn) + Cr0. The most Cr-rich corundum crystallized together with β-alumina phases including NaAl11O17 (diaoyudaoite) and KAl11O17 (kahlenbergite) and β″-alumina phases; residual melts crystallized a range of (K,Mg)2(Al,Cr)10O17 phases with the kahlenbergite structure. The parental melts of these assemblages appear to have been Al-Cr-K-Na-Mg oxides, which may be related to the Al-Cr-Fe-Mg oxide melts mentioned above, through fractional crystallization or liquid immiscibility. These samples are less reduced (fO2 from IW to IW-5) than the assemblages of the trapped silicate melts in the more abundant xenoliths of corundum aggregates (fO2 = IW-6 to IW-10). They could be considered to represent an earlier stage in the fO2 evolution of an “ideal” Mt. Carmel magmatic system, in which mafic or syenitic magmas were fluxed by mantle-derived CH4+H2 fluids. This is a newly recognized step in the evolution of the Mt. Carmel assemblages and helps to understand element partitioning under highly reducing conditions.

Description: We present 〉500 zircon δ18O and Lu-Hf isotope analyses on previously dated zircons to explore the interplay between spatial and temporal magmatic signals in Zealandia Cordillera. Our data cover ~8500 km2 of middle and lower crust in the Median Batholith (Fiordland segment of Zealandia Cordillera) where Mesozoic arc magmatism along the paleo-Pacific margin of Gondwana was focused along an ~100 km wide, arc-parallel zone. Our data reveal three spatially distinct isotope domains that we term the eastern, central, and western isotope domains. These domains parallel the Mesozoic arc-axis, and their boundaries are defined by major crustal-scale faults that were reactivated as ductile shear zones during the Early Cretaceous. The western isotope domain has homogenous, mantle-like δ 18O (Zrn) values of 5.8 ± 0.3‰ (2 St.dev.) and initial εHf (Zrn) values of +4.2 ± 1.0 (2 St.dev.). The eastern isotope domain is defined by isotopically low and homogenous δ18O (Zrn) values of 3.9 ± 0.2‰ and initial εHf values of +7.8 ± 0.6. The central isotope domain is characterized by transitional isotope values that display a strong E-W gradient with δ18O (Zrn) values rising from 4.6 to 5.9‰ and initial εHf values decreasing from +5.5 to +3.7. We find that the isotope architecture of the Median Batholith was in place before the initiation of Mesozoic arc magmatism and pre-dates Early Cretaceous contractional deformation and transpression. Our data show that Mesozoic pluton chemistry was controlled in part by long-lived, spatially distinct isotope domains that extend from the crust through to the upper mantle. Isotope differences between these domains are the result of the crustal architecture (an underthrusted low-δ18O source terrane) and a transient event beginning at ca. 129 Ma that primarily involved a depleted-mantle component contaminated by recycled trench sediments (10–20%). When data showing the temporal and spatial patterns of magmatism are integrated, we observe a pattern of decreasing crustal recycling of the low-δ18O source over time, which ultimately culminated in a mantle-controlled flare-up. Our data demonstrate that spatial and temporal signals are intimately linked, and when evaluated together they provide important insights into the crustal architecture and the role of both stable and transient arc magmatic trends in Cordilleran batholiths.

Description: Studies of the new growth and re-distribution of Cu-rich phases in chondrites of different petrologic subtypes can potentially provide insights into post-accretionary parent-body processes. We present a systematic study of the distribution of Cu-rich phases and metallic Cu in Ornans-like carbonaceous chondrites (CO3) that underwent little aqueous alteration or shock (most with shock stages of S1) but exhibit a range of thermal metamorphism (subtype 3.0–3.7). A comparison to ordinary chondrites (OCs), which have undergone a larger range of shock levels, allows us to constrain the relative roles of radiogenic and shock heating in the origin of Cu distribution in chondrites. We found that the Cu content of Ni-rich metal and calculated bulk Cu content of CO3 chondrites (based on mass-balance calculations) show an increase from CO3.0 to CO3.2 chondrites. We speculate that some unidentified phases in the matrix account for a significant portion (nearly ~100 ppm) of the Cu budget in bulk samples of CO3.0 chondrites, while Ni-rich metal is the main Cu-carrier for CO3.2–3.7 chondrites. Within CO3.2–3.7 chondrites, Cu and Ni contents of Ni-rich metal are positively correlated, showing a systematic decrease from lower to higher subtype (~0.41 wt% Cu and ~45.0 wt% Ni in CO3.2 Kainsaz; ~0.28 wt% Cu and ~38.8 wt% Ni in CO3.7 Isna). Metallic Cu grains were found in every sample of CO3.2–3.7 chondrites, but not in any CO3.0–3.1 chondrites. Metallic Cu is: (1) present at metallic-Fe-Ni-pyrrhotite interfaces; (2) associated with fine irregular pyrrhotite grains in Ni-rich-metal-pyrrhotite nodules; (3) associated with fizzed pyrrhotite (fine-grained mixtures of irregularly shaped metal grains surrounded by pyrrhotite); (4) present at the edges of metallic Fe-Ni grains; and (5) present as isolated grains. In some metallic-Cu-bearing mineral assemblages, pyrrhotite has higher Cu concentrations than adjacent Ni-rich metal and shows a drop in Cu concentration at the interface between metallic Cu and Cu-rich pyrrhotite. This implies that the precipitation of metallic Cu grains could be related to the local Cu enrichment of pyrrhotite. We consider that radiogenic heating is mainly responsible for the formation of opaque phases in CO chondrites based on the relatively slow metallographic cooling rate (~0.1–5 °C/Ma), the increasing uniformity of Ni contents in Ni-rich metal with increasing CO subtype (44.3 ± 17.3 wt% in CO3.00 to 38.8 ± 3.4 wt% in CO3.7 chondrite), and the relatively narrow range of pyrrhotite metal/sulfur ratios (~0.976–0.999). Metal/sulfur ratios of pyrrhotite grains in most CO3.2–3.7 chondrites (mean = ~0.986–0.997; except Lancé) are slightly higher than those in CO3.0–3.1 chondrites (mean = ~0.981–0.987; except Y-81020), possibly indicative of a release and re-mobilization of sulfur during progressive heating as previously reported for type-3 chondrites. In this regard, we suggest most metallic Cu grains in CO3 chondrites may have precipitated from Cu-rich pyrrhotite due to sulfidation of Fe-Ni metal during parent-body thermal metamorphism. Locally, a few metallic Cu grains associated with fizzed pyrrhotite could have formed during transient shock-heating. Both thermal and shock metamorphism could be responsible for the formation of metallic Cu. Although the systematic decrease in the Ni contents of Ni-rich metal from subtype-3.2 to subtype-3.8 also occurs in OCs, the average Cu contents of Ni-rich metal grains are indistinguishable among type-3 OCs of different subtypes. The paucity of metallic Cu in weakly shocked type-3 OCs could be related to: (1) the relatively low-bulk Cu contents of OCs, and/or (2) the relatively rapid metallographic cooling rates at

Description: Antigorite, a high-pressure polymorph of serpentine, is considered to be the most abundant hydrous mineral in subduction zones. Although antigorite dehydration is presumed as one of the origins of intermediate-depth earthquakes in the subduction zone, the amount of antigorite is uncertain because the amount of water infiltrated into the oceanic lithosphere is still debated. To investigate whether antigorite can be formed even with limited water availability, we conducted the axial deformation experiments of magnesium germanate at 1.2 GPa and T = 500–800 °C using a Griggs-type deformation apparatus. Magnesium germanate is an analog material of magnesium silicate, and the starting material was dried prior to experimentation. Nevertheless, the samples had initially high porosity, and hence a small amount of water (about 200 ppm wt H2O) was retained in the samples. In the samples deformed at 600 °C, stable slip occurred, and TEM analysis revealed that fine-grained platelets of germanate antigorite existed along the faults. A sharp absorption band assigned to the OH-stretching vibration of antigorite in Fourier transform infrared spectroscopic (FTIR) analysis also implies that antigorite was formed in the samples deformed at a temperature lower than 600 °C. Our results indicate that strain-induced hydration of germanate olivine results in antigorite formation even with only a small amount of water present. Thus, partial serpentinization in the oceanic lithosphere can occur under slight water infiltration due to the high strain accumulated by subduction.

Description: Gold (Au) deposits have formed in orogenic belts throughout Earth’s history. However, the upper temperature limits of orogenic Au vein formation are difficult to constrain because measurements made on fluid inclusions focus on intermediate to late-stage minerals (e.g., quartz and calcite) or are based on P-T estimates for the metamorphic mineral assemblages of the host rocks. We conducted a study of TiO2 polymorphs that are among the earliest minerals that grew in Au-bearing veins of the Dongyuan deposit, Jiangnan orogenic Au belt, South China. Based on Raman analyzes, we identified TiO2 polymorphs of anatase (with Raman peaks at 396, 515, and 638 cm−1), rutile (with Raman peaks at 235, 447, and 613 cm−1), and anatase–rutile intergrowths. Transmission electron microscope (TEM) confirmed the polymorphs identifying the [111] zone axis of anatase, [110] zone axis of rutile, and [111] and [111] zone axes of rutile–anatase intergrowths. The TiO2 polymorphs in the Dongyuan Au veins constrain a temperature range for early mineral precipitation in the veins of 450–550 °C. The results show that ore-forming fluids for this orogenic Au deposit emplaced in the shallow crust originated from deeper and hotter crustal levels (e.g., high-grade metamorphic rocks in the middle to lower crust).

Description: The transport of calcium carbonate (CaCO3) into the Earth’s interior through subduction is one of the key processes in the global cycling of carbon. To develop a better understanding of the CaCO3 structural stability during subduction processes, the phase transitions among CaCO3-I (calcite), CaCO3-II, -III/IIIb, and aragonite under pressure-temperature (P-T) conditions up to 2.5 GPa and 600 °C, in hydrous and anhydrous environments, were investigated using a hydrothermal diamond-anvil cell. One displacive and two reconstructive processes during the phase transitions among CaCO3 polymorphs were confirmed from the results obtained from in situ observations and Raman spectroscopic measurements. Meanwhile, the effect of Ca-substitutional metal cations (e.g., Mg2+) in CaCO3 and the presence of an aqueous fluid on the phase transition processes have been determined. Specifically, the CaCO3-I ↔ -II phase transition is a displacive process, occurring instantly at pressures varying from 1.6 GPa at room temperature to 1.5 GPa at 500 °C with the phase equilibrium boundary having a minimum P-T point at ~1.4 GPa at 300 °C, and is completely reversible upon cooling and decompression. The CaCO3-II → -III phase transition is a reconstructive process, observed at P-T conditions from 2.0 GPa at room temperature to 2.5 GPa at 150 °C, and is accomplished by solid recrystallization starting from CaCO3-II, transitioning through an intermediate CaCO3-IIIb, and ending at the CaCO3-III structure. The phase transition between CaCO3-I or -II and aragonite, which is also a reconstructive process, was found to occur by progressive solid recrystallization under high P-T hydrous and anhydrous conditions, or alternatively, via dissolution-precipitation under low-P-T hydrous conditions, depending on the presence of aqueous fluids and the heating rate of the system. The substitution for Ca2+ by other metal cations (e.g., Mg2+, Mn2+, Fe2+) in CaCO3 results in a significant increase in the pressures for the displacive and solid recrystallization reconstructive phase transitions, but has no detectable influence on the CaCO3-I/II ↔ aragonite transformation via a dissolution-precipitation process under hydrous conditions. Our results show that the presence of Ca-substitutional metal cations in CaCO3 is a key factor controlling the phase stability of CaCO3 under high P-T conditions, and suggest that aragonite should be the predominant phase in the upper mantle in subduction zones where the heating rate is very low and slab dehydration is prevalent.

Description: The Mogok metamorphic belt (MMB), Myanmar, is one of the most well-known gemological belts on Earth. Previously, 40Ar/39Ar, K-Ar, and U-Pb dating have yielded Jurassic-Miocene magmatic and metamorphic ages of the MMB and adjacent areas; however, no reported age data are closely related to the sapphire and moonstone deposits. Secondary ion mass spectrometry (SIMS) U-Pb dating of acicular rutile inclusions in sapphire and furnace step-heating 40Ar/39Ar dating of moonstone (antiperthite) in syenites from the MMB yield ages of 13.43 ± 0.92 and 13.55 ± 0.08 Ma, respectively, indicating both Myanmar sapphire and moonstone formed at the same time, and the ages are the youngest published in the region. The ages provide insight into the complex histories and processes of magmatism and metamorphism of the MMB, the formation of gemstone species in this belt, and the collision between India and Asia. In addition, our high field strength element data for the oriented rutile inclusions suggest an origin by co-precipitation rather than exsolution. In situ age determination of this nature is particularly significant since rutile inclusions in other gemstones, such as rubies, can be used to help constrain the geological history of their host rocks elsewhere.

Description: X-ray computed microtomography (CT) of impact rock varieties from the Kara astrobleme is used to test the method’s ability to identify the morphology and distribution of the rock components. Three types of suevitic breccias, clast-poor melt rock, and a melt clast from a suevite were studied with a spatial resolution of 24 µm to assess CT data values of 3D structure and components of the impactites. The purpose is first to reconstruct pore space, morphology, and distribution of all distinguishable crystallized melt, clastic components, and carbon products of impact metamorphism, including the impact glasses, after-coal diamonds, and other carbon phases. Second, the data are applied to analyze the morphology and distribution of aluminosilicate and sulfide components in the melt and suevitic breccias. The technical limitations of the CT measurements applied to the Kara impactites are discussed. Because of the similar chemical composition of the aluminosilicate matrix, glasses, and some lithic and crystal clasts, these components are hard to distinguish in tomograms. The carbonaceous matter has absorption characteristics close to air, so the pores and carbonaceous inclusions appear similar. However, X-ray microtomography could be used to prove the differences between the studied types of suevites from the Kara astrobleme using structural-textural features of the whole rock, porosity, and the distributions of carbonates and sulfides.

Description: Fibrous amphibole and clay mineral inclusions that form striking trapiche-like star patterns within quartz crystals from Inner Mongolia, China, present a challenge to uncover how these crystals grow and incorporate inclusions in a geological context. We propose that the patterns formed as a result of protogenic clay (ferrosaponite or nontronite) inclusions that were preferentially trapped on rough surfaces during quartz crystal growth. The rough surface texture of these crystals is the result of multiple growth centers during 2D nucleation and spread and split crystal formation. Observations via optical microscopy, cathodoluminescence, and three-dimensional micro-CT scanning highlight how the exterior surface textures on the termination of a complete quartz crystal mimic its interior inclusion patterns. Cathodoluminescence images, as well as varying aluminum concentrations along a core-to-exterior transect in a quartz crystal slice, suggest that the formation fluid underwent a heterogeneous chemical history. Measurements of Ti and observations of fluid inclusions suggest the quartz formed at a temperature of under 348 °C. This study presents the details surrounding split crystal growth in quartz in a natural geological setting, which has implications for inspiring new materials and may serve as an indicator for turbid and highly supersaturated formation fluid conditions in geological formations.

Description: The concentration of sulfur that can be dissolved in a silicate liquid is of fundamental importance because it is closely associated with several major Earth-related processes. Considerable effort has been made to understand the interplay between the effects of silicate melt composition and its capacity to retain sulfur, but the dependence on pressure and temperature is mostly based on experiments performed at pressures and temperatures below 6 GPa and 2073 K. Here we present a study of the effects of pressure and temperature on sulfur content at sulfide saturation of a peridotitic liquid. We performed 14 multi-anvil experiments using a peridotitic starting composition, and we produced 25 new measurements at conditions ranging from 7 to 23 GPa and 2173 to 2623 K. We analyzed the recovered samples using both electron microprobe and laser ablation ICP-MS. We compiled our data together with previously published data that were obtained at lower P-T conditions and with various silicate melt compositions. We present a new model based on this combined data set that encompasses the entire range of upper mantle pressure-temperature conditions, along with the effect of a wide range of silicate melt compositions. Our findings are consistent with earlier work based on extrapolation from lower-pressure and lower-temperature experiments and show a decrease of sulfur content at sulfide saturation (SCSS) with increasing pressure and an increase of SCSS with increasing temperature. We have extrapolated our results to pressure-temperature conditions of the Earth’s primitive magma ocean, and show that FeS will exsolve from the molten silicate and can effectively be extracted to the core by a process that has been termed the “Hadean Matte.” We also discuss briefly the implications of our results for the lunar magma ocean.

Description: A new mineral of the beryl group, johnkoivulaite, Cs(Be2B)Mg2Si6O18, was recovered from the gem gravels in the Pein Pyit area of the Mogok region in Myanmar. Thus far, only a single crystal has been identified. It has dimensions of about 5.8 × 5.7 × 5.5 mm. This specimen has an irregular shape but still has discernible crystal form with geometric growth patterns observed on the crystal faces. The crystal of johnkoivulaite is grayish-violet in color and strongly pleochroic, going from nearly colorless with E┴c to dark bluish-violet with E||c. Johnkoivulaite has a Mohs hardness of about 7½ and a measured density of 3.01(10) g/cm3. It is uniaxial (–) with ω = 1.607(1) and ε = 1.605(1) (white light). Electron microprobe analyses gave the empirical formula of (Cs0.85K0.10Na0.01)(Be1.88B1.12)(Mg1.66Fe0.27Mn0.01Al0.05) (Si5.98)O18 with Be calculated by stoichiometry and confirmed by LA-ICP-MS measurements. Johnkoivulaite is hexagonal, P6/mmc (no. 192) with a = 9.469(2), c = 9.033(2) Å, V = 701.5(3) Å3, and Z = 2. Johnkoivulaite is isostructural with beryl and exhibits partial substitution of B for Be at the distorted tetrahedral site, Mg for Al at the octahedral site, and Cs in the channel sites within the stacked Si6O18 rings. This substitution can be written as (CsMg2B)(☐Al2Be)–1. Johnkoivulaite, the seventh member of the beryl group, is named in honor of gemologist John Koivula in recognition of his contributions to mineralogy and gemology.

Description: In this paper, we report a first-principles Molecular Dynamics (FPMD) study of interfacial structures and acidity constants of goethite. The pKa values of the groups on (010), (110), and (021) surfaces (space group Pbnm) are derived with the FPMD based vertical energy gap technique. The results indicate that major reactive groups include ≡Fe2OH2 and ≡FeOH2 on (010), ≡FeOH2, ≡Fe3OLH, and ≡Fe3OUH on (110), and ≡FeOhH2 and ≡Fe2OH on (021). The interfacial structures were characterized in detail with a focus on the hydrogen bonding environment. With the calculated pKa values, the point of zero charges (PZCs) of the three surfaces are derived and the overall PZC range of goethite is found to be consistent with the experiment. We further discuss the potential applications of these results in future studies toward understanding the environmental processes of goethite.

Description: The mobility of Ti, a member of high field strength elements, in metamorphic fluids is crucial to understand the recycling of commonly perceived nominally soluble elements and for mass-flux calculations during crustal processes. In this study, we present evidence for large-scale Ti mobility from a suite of clinohumite±spinel-bearing dolomitic marbles from the Makrohar area in central India. The studied rocks mostly contain dolomite and calcite (in subequal proportions) and a subordinate amount of forsterite. It commonly develops 1–5 cm thick, laterally continuous, mostly parallel, sometimes anastomosing, brown-colored clinohumite rich bands with variable spinel. Clinohumite has moderate Ti and F (TiO2 = 0.55–2.88 wt%; F = 0.94–1.88 wt%; n = 32). Textural and phase equilibria modeling indicate that clinohumite grew at the expense of forsterite + dolomite under static conditions due to infiltration of F- and Ti-bearing extremely H2O-rich fluids (XCO2 〈 0.03), at ~5–6 kbar pressure and ~650–700 °C temperature. The Ti and F were most likely supplied by highly channelized aqueous fluids restricted within the centimeter-thick bands. The negative volume change of the reactions further facilitated fluid ingress. The lateral continuity of the bands over several meters across multiple out-crops indicates that Ti was mobile at the meter to kilometer scale. The results are in accordance with experimental studies that solubility of Ti increases in the presence of halides and imply that Ti may be much more mobile in metamorphic fluids during regional metamorphism than previously anticipated.

Description: δ-AlOOH has emerged as a promising candidate for water storage in the lower mantle and could have delivered water into the bottom of the mantle. To date, it still remains unclear how the presence of iron affects its elastic, rheological, vibrational, and transport properties, especially across the spin crossover. Here, we conducted high-pressure X-ray emission spectroscopy experiments on a δ-(Al0.85Fe0.15) OOH sample up to 53 GPa using silicone oil as the pressure transmitting medium in a diamond-anvil cell. We also carried out laser Raman measurements on δ-(Al0.85Fe0.15)OOH and δ-(Al0.52Fe0.48)OOH up to 57 and 62 GPa, respectively, using neon as the pressure-transmitting medium. Evolution of Raman spectra of δ-(Al0.85Fe0.15)OOH with pressure shows two new bands at 226 and 632 cm−1 at 6.0 GPa, in agreement with the transition from an ordered (P21nm) to a disordered hydrogen bonding structure (Pnnm) for δ-AlOOH. Similarly, the two new Raman bands at 155 and 539 cm−1 appear in δ-(Al0.52Fe0.48)OOH between 8.5 and 15.8 GPa, indicating that the incorporation of 48 mol% FeOOH could postpone the order-disorder transition upon compression. On the other hand, the satellite peak (Kβ′) intensity of δ-(Al0.85Fe0.15)OOH starts to decrease at ~30 GPa and it disappears completely at 42 GPa. That is, δ-(Al0.85Fe0.15)OOH undergoes a gradual electronic spin-pairing transition at 30–42 GPa. Furthermore, the pressure dependence of Raman shifts of δ-(Al0.85Fe0.15)OOH discontinuously decreases at 32–37 GPa, suggesting that the improved hydrostaticity by the use of neon pressure medium could lead to a relatively narrow spin crossover. Notably, the pressure dependence of Raman shifts and optical color of δ-(Al0.52Fe0.48)OOH dramatically change at 41–45 GPa, suggesting that it probably undergoes a relatively sharp spin transition in the neon pressure medium. Together with literature data on the solid solutions between δ-AlOOH and ε-FeOOH, we found that the onset pressure of the spin transition in δ-(Al,Fe)OOH increases with increasing FeOOH content. These results shed new insights into the effects of iron on the structural evolution and vibrational properties of δ-AlOOH. The presence of FeOOH in δ-AlOOH can substantially influence its high-pressure behavior and stability at the deep mantle conditions and play an important role in the deep-water cycle.

Description: While much progress has been made in electron-probe microanalysis (EPMA) to improve the accuracy of point analysis, the same level of attention has not always been applied to the quantification of wavelength-dispersive spectrometry (WDS) X-ray intensity maps at the individual pixel level. We demonstrate that the same level of rigor applied in traditional point analysis can also be applied to the quantification of pixels in X-ray intensity maps, along with additional acquisition and quantitative processing procedures to further improve accuracy, precision, and mapping throughput. Accordingly, X-ray map quantification should include pixel-level corrections for WDS detector deadtime, corrections for changes in beam current (beam drift), changes in standard intensities (standard drift), high-accuracy removal of background intensities, quantitative matrix corrections, quantitative correction of spectral interferences, and, if required, time-dependent corrections (for beam and/or contamination sensitive materials). The purpose of quantification at the pixel level is to eliminate misinterpretation of intensity artifacts, inherent in raw X-ray intensity signals, that distort the apparent abundance of an element. Major and minor element X-ray signals can contain significant artifacts due to absorption and fluorescence effects. Trace element X-ray signals can contain significant artifacts where phases with different average atomic numbers produce different X-ray continuum (bremsstrahlung) intensities, or where a spectral interference, even an apparently minor one, can produce a false-positive intensity signal. The methods we propose for rigorous pixel quantification require calibration of X-ray intensities on the instrument using standard reference materials, as we already do for point analysis that is then used to quantify multiple X-ray maps, and thus the relative time overhead associated with such pixel-by-pixel quantification is small. Moreover, the absolute time overhead associated with this method is usually less than that required for quantification using manual calibration curve methods while resulting in significantly better accuracy. Applications to geological, synthetic, or engineering materials are numerous as quantitative maps not only show compositional 2D variation of fine-grained or finely zoned structures but also provide very accurate quantitative analysis, with precision approaching that of a single point analysis, when multiple-pixel averaging in compositionally homogeneous domains is utilized.

Description: Carletonmooreite (IMA 2018-68), Ni3Si, is a new nickel silicide mineral that occurs in metal nodules from the Norton County aubrite meteorite. These nodules are dominated by low-Ni iron (kamacite), with accessory schreibersite, nickelphosphide, perryite, and minor daubréelite, tetrataenite, taenite, and graphite. The chemical composition of the holotype carletonmooreite determined by wavelength-dispersive electron-microprobe analysis is (wt%) Ni 82.8 ± 0.4, Fe 4.92 ± 0.09, and Si 13.08 ± 0.08 (n = 6, total = 100.81) giving an empirical formula of (Ni2.87Fe0.18)Σ3.05Si0.95, with an end-member formula of Ni3Si. Further grains discovered in the specimen after the new mineral submission extend the composition, i.e., (wt%) Ni 81.44 ± 0.82, Fe 5.92 ± 0.93, Cu 0.13 ± 0.02, and Si 13.01 ± 0.1 (n = 11, total = 100.51 ± 0.41), giving an empirical formula (Ni2.83Fe0.22Cu0.004)Σ3.05Si0.95. The backscat tered electron-diffraction patterns were indexed by the Pm3m auricupride (AuCu3)-type structure and give a best fit to synthetic Ni3Si, with a = 3.51(1) Å, V = 43.2(4) Å3, Z = 1, and calculated density of 7.89 g/cm3. Carletonmooreite is silver colored with an orange tinge, isotropic, with a metallic luster and occurs as euhedral to subhedral crystals 1 × 5 µm to 5 × 14 µm growing on tetrataenite into kamacite. The dominant silicide in the Norton County aubrite metal nodules is perryite (Ni,Fe)8(Si,P)3, with carletonmooreite restricted to localized growth on rare plessite fields. The isolated nature of small euhedral carletonmooreite single crystals suggests low-temperature growth via solid-state diffusion from the surrounding kamacite and epitaxial growth on the tetrataenite. This new mineral is named in honor of Carleton B. Moore, chemist and geologist, and founding director of the Center for Meteorite Studies at Arizona State University, for his many contributions to cosmochemistry and meteoritics.

Description: Spectral features of hydrogen defects in natural mantle minerals derive from physico-chemical conditions of the lithosphere. Although hydrogen defects in synthetic orthopyroxene have been well investigated, their complex spectral features in natural orthopyroxenes are still difficult to decipher. To clarify this issue, it is indispensable to reveal what happens to hydrogen defects during high-temperature processes, thereby fingerprinting the origins of hydrogen defects observed in natural orthopyroxene. Here, we carry out Fourier transform infrared spectroscopic studies on hydrogen defects of three natural orthopyroxenes at elevated temperatures to 1000 °C. Hydrogen defects display reversible disordering at temperatures above 700 °C, which is different from those at ambient conditions. Moreover, hydrogen diffusivities are significantly different between the orthopyroxene samples from different tectonic settings despite their similar iron contents. Even for the same crystal, different hydrogen defects display different diffusion behaviors. Hydrogen defects corresponding to the 3420 cm−1 band have the fastest diffusivity relative to the other hydrogen defects. Most importantly, hydrogen defects can redistribute in the crystal, with new hydrogen defects produced at the cost of the initial hydrogen defects rather than involving a reaction with an external hydrogen source. Combining these findings with previously reported hydrogen defects in natural olivine and clinopyroxene at high temperatures, we propose that: (1) to correctly relate hydrogen defects features to geological processes, it is imperative to understand their behavior and origin, and (2) hydrogen disordering should be taken into account when predicting and extrapolating data on physical properties of the mantle from room-temperature measurements.

Description: Sound velocities of iron and iron-based alloys at high pressure and high temperature are crucial for understanding the composition and structure of Earth’s and other telluric planetary cores. In this study, we performed ultrasonic interferometric measurements of both compressional (νP) and shear (νS) velocities on a polycrystalline body-centered-cubic (bcc)-Fe90Ni10 up to 8 GPa and 773 K. The elastic moduli and their pressure and temperature derivatives are derived from least-square fits to third-order finite strain equations, yielding KS0 = 154.2(8) GPa, G0 = 73.2(2) GPa, KS0′ = 4.6(2), G0′ = 1.5(1), ∂KS/∂T = –0.028(1) GPa/K, and ∂G/∂T = –0.023(1) GPa/K. A comparison with literature data on bcc-Fe suggests that nickel not only decreases both P and S wave velocities but also weakens the temperature effects on the elastic moduli of Fe-Ni alloys.

Description: In this issue This New Mineral Names has entries for 21 new minerals, including alexkhomyakovite, andreadiniite, arsenmedaite, barwoodite, bodieite, ciriottiite, clino-oscarkempffite, ferrovorontsovite, ilirneyite, kannanite, magnesiohornblende, merelaniite, oyonite, pararaisaite, petříčekite, quijarroite, staročeskéite, tantalowodginite, topsøeite, tsygankoite, and vorontsovite.

Description: In this issue This New Mineral Names has entries for 16 new minerals, including, ariegilatite, aurihydrargyrumite, carmeltazite, cerromojonite, dargaite, ewingite, fiemmeite horákite, nöggerathite-(Ce), paddlewheelite, parafiniukite, sharyginite, thalhammerite, thermaerogenite, tiberiobardiite, and verneite.

Description: A major unsolved problem of the Proterozoic is the genesis and tectonic evolution of the massif type anorthosites. The idea of large-scale floating of plagioclase crystals in a basaltic magma chamber eventually generating massif type anorthosite diapirs from the floatation cumulates is not supported by observations of the major layered basic complexes of Proterozoic to Eocene age. In this paper, we test and propose a new genetic process of anorthosite diapirism through Rayleigh-Taylor instability. We have carried out a numerical modeling study of parallel, horizontal, multiple layers of norite and anorthosite, in a model layered basic complex, behaving like Newtonian or non-Newtonian power law fluids in a jelly sandwich model of the continental lithosphere. We have shown that in this pressure-temperature-rheology configuration the model lithosphere generates Rayleigh-Taylor instability, which triggers diapirism of the anorthosite. In our model, the anorthosite diapirs buoyantly rise through stages of simple, symmetrical upwelling and pronounced bulbous growth to a full-blown mushroom-like form. This is the growth path of diapirs in nearly all analog and numerical previous studies on diapirism. Our anorthosite diapirs fully conform to this path. Furthermore, we demonstrate that the progressive diapirism brings in striking internal changes within the diapir itself. In the process, the lowermost anorthosite layer rises displacing the upper norite and anorthosite layers as progressively stretched and isolated segments driven to the margin of the rising diapir—a feature commonly seen in natural anorthosite massifs. We propose that a large plume-generated basaltic magma chamber may be ponded at the viscous lower crust or ductile-plastic upper mantle or further down in the weaker mantle of the jelly sandwich type continental lithosphere. The magma may cool and crystallize very slowly and resolve into a thick-layered basic complex with anorthosite layers. Rheologically behaving like Newtonian or non-Newtonian power law fluids, the layers of the basic complex with built-in density inversions would generate RT (Rayleigh-Taylor) instability. The RT instability would trigger a buoyant rise of the unstable anorthosite from the layered complex. The upward driven anorthosite, accumulated as anorthosite plutons, would gradually ascend across the lower and middle crust as anorthosite diapirs.

Description: The nominally anhydrous, calcium-silicate garnets, grossular (Ca3Al2Si3O12), andradite (Ca3Fe23+Si3O12), schorlomite (Ca3Ti24+[Si,Fe23+]O12), and their solid solutions can incorporate structural OH-, often termed “water.” The IR single-crystal spectra of several calcium silicate garnets were recorded between 3000 and 4000 cm–1. Spectroscopic results are also taken from the literature. All spectra show various OH- stretching modes between 3500 and 3700 cm–1 and they are analyzed. Following the conclusions of Part I of this study, the garnets appear to contain local microscopic- and nano-size Ca3Al2H12O12- and Ca3Fe23+H12O12-like domains and/or clusters dispersed throughout an anhydrous “matrix.” The substitution mechanism is the hydrogarnet one, where (H4O4)4– ↔ (SiO4)4–, and various local configurations containing different numbers of (H4O4)4– groups define the cluster type. A single (H4O4) group is roughly 3 Å across and most (H4O4)-clusters are between this and 15 Å in size. This model can explain the IR spectra and also other experimental results. Various hypothetical “defect” and cation substitutional mechanisms are not needed to account for OH- incorporation and behavior in garnet. New understanding at the atomic level into published dehydration and H-species diffusion results, as well as H2O-concentration and IR absorption-coefficient determinations, is now possible for the first time. End-member synthetic and natural grossular crystals can show similar OH- “band patterns,” as can different natural garnets, indicating that chemical equilibrium could have operated during their crystallization. Under this assumption, the hydrogarnet-cluster types and their concentrations can potentially be used to decipher petrologic (i.e., P-T-X) conditions under which a garnet crystal, and the rock in which it occurs, formed. Schorlomites from phonolites contain no or very minor amounts of H2O (0.0 to 0.02 wt%), whereas Ti-bearing andradites from chlorite schists can contain more H2O (∼0.3 wt%). Different hydrogarnet clusters and concentrations can occur in metamorphic grossulars from Asbestos, Quebec, Canada. IR absorption coefficients for H2O held in hydrogrossularand hydroandradite-like clusters should be different in magnitude and this work lays out how they can be best determined. Hydrogen diffusion behavior in garnet crystals at high temperatures is primarily governed by the thermal stability of the different local hydrogarnet clusters at 1 atm.

Description: The origin of banding patterns in malachite [Cu2CO3(OH)2] is an enduring problem in geology. While the bright green, vivid colors of this mineral have been attributed to the presence of Cu, no specific process has been proposed that can explain the perfect circularly concentric banding and geometrical shapes in botryoidal malachite. These patterns of concentric equidistant laminations are comparable to those arising from chemically oscillating experiments using the classical reactants of the Belousov-Zhabotinsky (B-Z) reaction. Through optical microscopy and micro-Raman imaging, this contribution documents that the geometric centers of the self-similar geometric patterns are often composed of organic matter. Carbon isotopes and trace elements further suggest that non-biological decarboxylation reactions of biological organic matter took place during diagenesis. Hence, the morphological and chemical characteristics of chemically oscillating reactions offer a plausible explanation for the formation of botryoidal malachite and abiotic environmental decarboxylation reactions.

Description: My geologic research began at Carleton College. I studied heavy minerals in some midcontinent orthoquartzites, publishing my very first paper in American Mineralogist in 1954. As a master's candidate at the University of Minnesota, I investigated igneous differentiation in a diabase-granophyre sill of the Duluth Gabbro Complex. Later, in a Ph.D. program at Johns Hopkins University, I became Joe Boyd's apprentice at the Geophysical Laboratory (GL), and for a time was phase-equilibrium god of the Na-amphiboles. Doctoral research earned me an offer of a UCLA assistant professorship as a mineralogist in 1960. There, I continued pursuing amphibole P-T stability relations in lab and field. My glaucophane phase equilibrium research would later be found to have instead crystallized Na-magnesiorichterite. However, amphibole research led me to map field occurrences of HP-LT (high P-low T) blueschists of the Franciscan Complex. Thus, when plate tectonics emerged in the late 1960s, I was deep in the subduction zone. My recent studies focused on the petrology and geochemistry of oceanic crustal rocks, Californian calc-alkaline arcs, and coesite ± microdiamond-bearing crustal margin rocks in various parts of Eurasia. Other works treated global mineral resources and population, mineralogy and human health, and early Earth petrotectonic evolution. I tried to work on important problems, but mainly studied topics that fired my interest. For the future, I see the existential challenge facing humanity and the biosphere as the imperative to stop our overdrafting of mineral resources. This will require reaching a dynamic equilibrium between the use and replenishment of near-surface resources (i.e., nutrients) essential for life. Earth scientists are planetary stewards, so we must lead the way forward in life-supporting mineral usage, recycling, substitution, and dematerialization. In any event, sustainable development will soon return to the Earth's Critical Zone of life because Mother Nature—the ruling terrestrial economist—abhors long-term overdrafting of resources1.

Description: The Miocene Cuonadong leucogranites in the easternmost section of the Tethyan Himalaya, Southern Tibet, are characterized by two types of tourmaline. Tourmaline occurs as needle-like crystals in the two-mica ± tourmaline granites (Tur G) and large patches in the pegmatites (Tur P). Both the granite and the pegmatites yield Miocene ages (ca. 20 Ma) based on monazite U(-Th)-Pb dating, whereas 40Ar/39Ar geochronology of the coarse-grained tourmalines (Tur P) crosscut by pegmatite veins yielded an Eocene mini-plateau age of 43 ± 6 Ma. Major element concentrations of tourmaline indicate that both Tur P and Tur G belong to the schorl group with a magmatic origin, but trace elements such as V indicate that they are not cogenetic. Boron isotopes suggest that Tur P (average –9.76‰) was derived from typical crustal sources, whereas Tur G (average –7.65‰) contains relatively more mafic input. The capture of Eocene tourmaline by the Miocene leucogranites at Cuonadong suggests that the crustally derived Eocene magmatism may have occurred in the southern Tethyan Himalaya. Identification of the inherited magmatic tourmaline (Tur P), although not common, challenges the current application of tourmaline chemistry to the investigation of magmatic-hydrothermal systems.

Description: To understand the effects of H2O on the mineral phases forming under the pressure-temperature conditions of the lower mantle, we have conducted laser-heated diamond-anvil cell experiments on hydrous ringwoodite (Mg2SiO4 with 1.1 wt% H2O) at pressures between 29 and 59 GPa and temperatures between 1200 and 2400 K. Our results show that hydrous ringwoodite (hRw) converts to crystalline dense hydrous silica, stishovite (Stv) or CaCl2-type SiO2 (mStv), containing 1 wt% H2O together with Brd and MgO at the pressure-temperature conditions expected for shallow lower-mantle depths between approximately 660 to 1600 km. Considering the lack of sign for melting in our experiments, our preferred interpretation of the observation is that Brd partially breaks down to dense hydrous silica and periclase (Pc), forming the phase assembly Brd + Pc + Stv. The results may provide an explanation for the enigmatic coexistence of Stv and Fp inclusions in lower-mantle diamonds.

Description: The crystal structure of a new high-pressure hydrous phase, Si-rich Mg-sursassite, of ideal composition Mg4Al5Si7O23(OH)5, that was produced by sub-solidus reaction at 24 GPa and 1400 °C in an experiment using a model sedimentary bulk composition, has been determined by single-crystal X-ray diffraction. The phase was found to be topologically identical to Mg-sursassite, Mg5Al5Si6O21(OH)7, and has space group P21/m and lattice parameters a = 8.4222(7), b = 5.5812(3), c = 9.4055(9) Å, b = 106.793(8)°, V = 423.26(6) Å3, and Z = 1. The empirical formula determined by electron microprobe analysis of the same crystal as was used in the X-ray experiment is [Mg3.93(3)Fe0.03(1)]Σ3.96[Al4.98(3)Cr0.04(1)]S5.02 Si7.02(4)O23(OH)5, with hydroxyl content implied by the crystal-structure analysis. The most significant aspect of the structure of Si-rich Mg-sursassite is the presence of octahedrally coordinated Si. Its structural formula is M1,VIIMg2M2,VIMg22+M3,VI(Al0.5Si0.5)2M4,VIAl2M5,VIAl2T1,IVSi2T2,IVSi2T3,IVSi2 O23(OH)5. Si-rich Mg-sursassite joins the group of hydrous ultrahigh-pressure phases with octahedrally coordinated Si that have been discovered by experiment, and that may play a significant role in the distribution and hosting of water in the deep mantle at subduction zones. The reactions defining the stability of Si-rich Mg-sursassite are unknown, but are likely to be fundamentally different from those of Mg-sursassite, and involve other ultrahigh-pressure dense structures such as phase D, rather than phase A.

Description: We performed a multi-scale characterization of aqueous alteration of Mars analog basaltic rock from a Mauna Kea drill core using high-resolution visible and short-wave infrared (VIS-SWIR) spectral imaging, scanning electron microscopy, X-ray diffraction, and point VIS-SWIR spectra. Several types of smectites, zeolites, and primary minerals were identified. Mineral classes were mapped in cut sections extracted from the drill core and used to represent the range of alteration products seen in field data collected over 1000 m depth (Calvin et al. 2020). Ten distinct spectral end-members identified in the cut sections were used to map the field point spectra. Trioctahedral Fe- and Mg-rich smectites were present toward the top of the zone of analysis (972 m below the surface) and increased in abundance toward the bottom of the drill core (1763 m depth). The mineralogy demonstrates a general trend of discontinuous alteration that increases in intensity with depth, with less pervasive phyllosilicate alteration at the top, several zones of different mixtures of zeolites toward the center, followed by more abundant phyllosilicates in the lowest sections. Distinctly absent are Fe-Mg phyllosilicates other than smectites, as well as carbonates, sulfates, and Al phyllosilicates such as kaolinite or illite. Furthermore, hematite was only detected in two of 24 samples. The suite of assemblages points to aqueous alteration at low-to-moderate temperatures at neutral to basic pH in low-oxygen conditions, with little evidence of extensive surface interaction, presenting a possible analog for an early Mars subsurface environment. We also present a library of VIS-SWIR spectra of the analyzed cut sections, including both spatial averages (i.e., unweighted linear mixtures) of spectral images of each cut section and single point spectra of the cut sections. This will allow for consideration of nonlinear mixing effects in point spectra of these assemblages from natural surfaces in future terrestrial or planetary work.

Description: The calcium-silicate garnets, grossular (Ca3Al2Si3O12), andradite (Ca3Fe23+Si3O12), and their solid solutions [Ca3(Alx,Fe1−x3+)2Si3O12], can incorporate various amounts of structural OH–. This has important mineralogical, petrological, rheological, and geochemical consequences and extensive experimental investigations have focused on the nature of “water” in these phases. However, it was not fully understood how OH- was incorporated and this has seriously hampered the interpretation of different research results. IR single-crystal spectra of several nominally anhydrous calcium silicate garnets, both “end-member” and solid-solution compositions, were recorded at room temperature and 80 K between 3000 and 4000 cm–1. Five synthetic hydrogarnets in the system Ca3Al2(SiO4)3-Ca3Al2(H4O4)3-Ca3Fe23+(SiO4)3-Ca3Fe23+(H4O4)3 were also measured via IR ATR powder methods. The various spectra are rich in complexity and show several OH- stretching modes at wavenumbers between 3500 and 3700 cm–1. The data, together with published results, were analyzed and modes assigned by introducing atomic-vibrational and crystal-chemical models to explain the energy of the OH- dipole and the structural incorporation mechanism of OH-, respectively. It is argued that OH- is located in various local microscopic- and nano-size Ca3Al2H12O12- and Ca3Fe23+H12O12-like clusters. The basic substitution mechanism is the hydrogarnet one, where (H4O4)4– ↔ (SiO4)4–, and various local configurations containing different numbers of (H4O4)4– groups define the cluster type. Some spectra also possibly indicate the presence of tiny hydrous inclusion phases, as revealed by OH- modes above about 3670 cm–1. They were not recognized in earlier studies. Published proposals invoking different hypothetical “defects” and coupled-substitution mechanisms involving H+ are not needed to interpret the IR spectra, at least for OH- modes above about 3560 cm–1. Significant mineralogical, petrological, and geochemical consequences result from the analysis and are discussed in the accompanying Part II (this issue) of the investigation.

Description: Hydrogenation reactions are a major route of electron and proton flow on Earth. Interfacing geology and organic chemistry, hydrogenations occupy pivotal points in the Earth’s global geochemical cycles. Some examples of hydrogenation reactions on Earth today include the production and consumption of methane in both abiotic and biotic reactions, the reduction of protons in hydrothermal settings, and the biological synthesis and degradation of fatty acids. Hydrogenation reactions were likely important for prebiotic chemistry on the early Earth, and today serve as one of the fundamental reaction classes that enable cellular life to construct biomolecules. An understanding and awareness of hydrogenation reactions is helpful for comprehending the larger web of molecular and material inter-conversions on our planet. In this brief review we detail some important hydrogenation and dehydrogenation reactions as they relate to geology, biology, industry, and atmospheric chemistry. Such reactions have implications ranging from the suite of reactions on early Earth to industrial applications like the production of hydrocarbon fuel.

Description: The alteration of magmatic monazite and its consequences for monazite geochronology are explored in granitoids from the western part of the Ryoke belt (Iwakuni-Yanai area, SW Japan). Biotite-granite samples were collected in two plutons emplaced slightly before the main tectono-metamorphic event: the first one, a massive granite (Shimokuhara) adjoins schistose rocks affected by greenschist facies metamorphism; and the second, a gneissose granite (Namera) adjoins migmatitic gneiss that experienced upper-amphibolite facies conditions. Despite contrasting textures, the granite samples have similar mineral modes and compositions. Monazite in the massive granite is dominated by primary domains with limited secondary recrystallization along cracks and veinlets. It is variably replaced by allanite+apatite±xenotime±Th-U-rich phases. The outermost rims of primary domains yield a weighted average 206Pb/238U date of 102 ± 2 Ma while the Th-U phases show Th-U-Pb dates of 58 ± 5 and 15 to 14 ± 2–3 Ma. Monazite in the gneissose granite preserves sector- or oscillatory-zoned primary domains cross-cut by secondary domains enriched in Ca, Y, U, P, and containing numerous inclusions. The secondary domains preserve concordant 206Pb/238U dates spreading from 102 ± 3 to 91 ± 2 Ma while primary domain analyses are commonly discordant and range from 116 to 101 Ma. Monazite alteration textures in the two granites chiefly reflect differences in their post-magmatic histories. In the massive granite, monazite replacement occurred via a nearly stoichiometrically balanced reaction reflecting interaction with an aqueous fluid enriched in Ca+Al+Si±F during hydrothermal alteration of the granitic assemblage, likely below 500 °C. In the gneissose granite, a small amount of anatectic melt, probably derived from the neighboring metasedimentary rocks, was responsible for pseudomorphic recrystallization of monazite by dissolution-reprecipitation above 600 °C. Regardless of whether monazite underwent replacement or recrystallization, primary monazite domains preserve the age of magmatic crystallization for both plutons (102 ± 2 and 106 ± 5 Ma). Conversely, the age of monazite alteration is not easily resolved. Monazite replacement in the massive granite might be constrained using the Th-U-rich alteration products; with due caution and despite probable radiogenic Pb loss, the oldest date of 58 ± 5 Ma could be ascribed to chloritization during final exhumation of the granite. The spread in apparently concordant 206Pb/238U dates for secondary domains in the gneissose granite is attributed to incomplete isotopic resetting during dissolution-reprecipitation, and the youngest date of 91 ± 2 Ma is considered as the age of monazite recrystallization during a suprasolidus metamorphic event. These results reveal a diachronous, ca. 10 Ma-long high-temperature (HT) history and an overall duration of about 15 Ma for the metamorphic evolution of the western part of the Ryoke belt.