Oceanic intraplate explosive eruptions fed directly from the mantle.

Constraining the volatile content of magmas is critical to our understanding of eruptive processes and their deep Earth cycling essential to planetary habitability [R. Dasgupta, M. M. Hirschmann, Earth Planet. Sci. Lett. 298, 1 (2010)]. Yet, much of the work thus far on magmatic volatiles has been dedicated to understanding their cycling through subduction zones. Further, studies of intraplate mafic volcanism have disproportionately focused on Hawaii [P. E. Wieser et al., Geochem. Geophys. Geosyst. 22, e2020GC009364 (2021)], making assessments of the overall role of intraplate volcanoes in the global volatile cycles a challenge. Additionally, while mafic volcanoes are the most common landform on Earth and the Solar System [C. A. Wood, J. Volcanol. Geotherm. Res. 7, 387-413 (1980)], they tend to be overlooked in favor of silicic volcanoes when it comes to their potential for explosivity. Here, we report primitive (olivine-hosted, with host Magnesium number - Mg# 78 to 88%) melt inclusion (MI) data from Fogo volcano, Cabo Verde, that suggest that oceanic intraplate silica-undersaturated explosive eruptions sample volatile-rich sources. Primitive MI (melt Mg# 70 to 71%) data suggest that these melts are oxidized (NiNiO to NiNiO+1) and very high in volatiles (up to 2 wt% CO2, 2.8 wt% H2O, 6,000 ppm S, 1,900 ppm F, and 1,100 ppm Cl) making Fogo a global endmember. Storage depths calculated from these high volatile contents also imply that magma storage at Fogo occurs at mantle depths (~20 to 30 km) and that these eruptions are fed from the mantle. Our results suggest that oceanic intraplate mafic eruptions are sustained from the mantle by high volatile concentrations inherited from their source and that deep CO2 exsolution (here up to ~800 MPa) drives their ascent and explosivity.

Speciation and Structural Properties of Hydrothermal Solutions of Sodium and Potassium Sulfate Studied by Molecular Dynamics Simulations.

Aqueous solutions of salts at elevated pressures and temperatures play a key role in geochemical processes and in applications of supercritical water in waste and biomass treatment, for which salt management is crucial for performance. A major question in predicting salt behavior in such processes is how different salts affect the phase equilibria. Herein, molecular dynamics (MD) simulations are used to investigate molecular-scale structures of solutions of sodium and/or potassium sulfate, which show contrasting macroscopic behavior. Solutions of Na-SO4 exhibit a tendency towards forming large ionic clusters with increasing temperature, whereas solutions of K-SO4 show significantly less clustering under equivalent conditions. In mixed systems (Nax K2-x SO4 ), cluster formation is dramatically reduced with decreasing Na/(K+Na) ratio; this indicates a structure-breaking role of K. MD results allow these phenomena to be related to the characteristics of electrostatic interactions between K(+) and SO4 (2-) , compared with the analogous Na(+) -SO4 (2-) interactions. The results suggest a mechanism underlying the experimentally observed increasing solubility in ternary mixtures of solutions of Na-K-SO4 . Specifically, the propensity of sodium to associate with sulfate, versus that of potassium to break up the sodium-sulfate clusters, may affect the contrasting behavior of these salts. Thus, mutual salting-in in ternary hydrothermal solutions of Na-K-SO4 reflects the opposing, but complementary, natures of Na-SO4 versus K-SO4 interactions. The results also provide clues towards the reported liquid immiscibility in this ternary system.

Dense hydrated Mg-silicates in diamond: Implications for transport of H2O into the mantle.

Water in Earth's upper mantle is a minor and yet critically important component that dictates mantle properties such as strength and melting behavior. Minerals with stoichiometric water, such as those of the humite group, are important yet poorly characterized potential reservoirs for volatiles in the upper mantle. Here, we report observation of hydroxyl members of the humite group as inclusions in mantle-derived diamond. Hydroxylchondrodite and hydroxylclinohumite were found coexisting with olivine, magnesiochromite, Mg-bearing calcite, dolomite, quartz, mica, and a djerfisherite-group mineral in a diamond from Brazil. The olivine is highly forsteritic (Mg# 97), with non-mantle-like oxygen isotope composition (δ18O +6.2‰), and is associated with fluid inclusions and hydrous minerals-features that could be inherited from a serpentinite protolith. Our results constitute direct evidence for the presence of deserpentinized peridotitic protoliths in subcratonic mantle keels, placing important constraints on the stability of hydrous phases in the mantle and the origin of diamond-forming fluids.

Volumetrics of CO2 storage in deep saline formations.

Concern about the role of greenhouse gases in global climate change has generated interest in sequestering CO(2) from fossil-fuel combustion in deep saline formations. Pore space in these formations is initially filled with brine, and space to accommodate injected CO(2) must be generated by displacing brine, and to a lesser extent by compression of brine and rock. The formation volume required to store a given mass of CO(2) depends on the storage mechanism. We compare the equilibrium volumetric requirements of three end-member processes: CO(2) stored as a supercritical fluid (structural or stratigraphic trapping); CO(2) dissolved in pre-existing brine (solubility trapping); and CO(2) solubility enhanced by dissolution of calcite. For typical storage conditions, storing CO(2) by solubility trapping reduces the volume required to store the same amount of CO(2) by structural or stratigraphic trapping by about 50%. Accessibility of CO(2) to brine determines which storage mechanism (structural/stratigraphic versus solubility) dominates at a given time, which is a critical factor in evaluating CO(2) volumetric requirements and long-term storage security.

Magmatic immiscibility and the origin of magnetite-(apatite) iron deposits.

The origin of magnetite-(apatite) iron deposits (MtAp) is one of the most contentious issues in ore geology with competing models that range from hydrothermal to magmatic processes. Here we report melt inclusions trapped in plagioclase phenocrysts in andesite hosting the MtAp mineralization at El Laco, Chile. The results of our study reveal that individual melt inclusions preserve evidence of complex processes involved in melt immiscibility, including separation of Si- and Fe-rich melts, the latter hosting Cu sulfide-rich, phosphate-rich, and residual C-O-HFSE-rich melts, with their melting temperature at 1145 °C. This association is consistent with the assemblages observed in the ore, and provides a link between silicate and Fe-P-rich melts that subsequently produced the magnetite-rich magmas that extruded on the flanks of the volcano. These results strongly suggest that the El Laco mineralization was derived from crystallization of Fe-P-rich melts, thus providing insight into the formation of similar deposits elsewhere.

Vibrational mode frequencies of silica species in SiO2-H2O liquids and glasses from ab initio molecular dynamics.

Vibrational spectroscopy techniques are commonly used to probe the atomic-scale structure of silica species in aqueous solution and hydrous silica glasses. However, unequivocal assignment of individual spectroscopic features to specific vibrational modes is challenging. In this contribution, we establish a connection between experimentally observed vibrational bands and ab initio molecular dynamics (MD) of silica species in solution and in hydrous silica glass. Using the mode-projection approach, we decompose the vibrations of silica species into subspectra resulting from several fundamental structural subunits: The SiO(4) tetrahedron of symmetry T(d), the bridging oxygen (BO) Si-O-Si of symmetry C(2v), the geminal oxygen O-Si-O of symmetry C(2v), the individual Si-OH stretching, and the specific ethane-like symmetric stretching contribution of the H(6)Si(2)O(7) dimer. This allows us to study relevant vibrations of these subunits in any degree of polymerization, from the Q(0) monomer up to the fully polymerized Q(4) tetrahedra. Demonstrating the potential of this approach for supplementing the interpretation of experimental spectra, we compare the calculated frequencies to those extracted from experimental Raman spectra of hydrous silica glasses and silica species in aqueous solution. We discuss observed features such as the double-peaked contribution of the Q(2) tetrahedral symmetric stretch, the individual Si-OH stretching vibrations, the origin of the experimentally observed band at 970 cm(-1) and the ethane-like vibrational contribution of the H(6)Si(2)O(7) dimer at 870 cm(-1).

Vibrational mode frequencies of H4SiO4, D4SiO4, H6Si2O7, and H6Si3O9 in aqueous environment, obtained from ab initio molecular dynamics.

We report the vibrational properties of H(4)SiO(4), D(4)SiO(4), H(6)Si(2)O(7), and H(6)Si(3)O(9) in aqueous solution at 300 K and 1000 K, obtained from the combination of ab initio molecular dynamics (MD) and a mode-decomposition approach. This combination yields vibrational subspectra for selected vibrational modes at finite temperatures. We also performed normal-mode analysis (NMA) on numerous configurations from the same MD run to sample the effect of the variable molecular environment. We found good agreement between both approaches. The strongest effect of temperature is on the SiOH bending mode δSiOH, which is at about 1145 cm(-1) in solution at 300 K, opposed to about 930 cm(-1) in solution at 1000 K. The frequency of the δSiOH vibration also depends on environment, shifting from 1145 cm(-1) in solution to about 845 cm(-1) in the gas-phase. We found both in the mode-decomposition approach and in multiple-configuration NMA that the H(6)Si(2)O(7) dimer shows a vibrational mode at about 790 cm(-1), which we consider to be responsible for a hitherto unexplained shoulder of the monomer Raman band at 770 cm(-1) in dilute silica solutions. Our results demonstrate the importance of temperature and solvation environment in calculations that aim to support the interpretation of experimental Raman spectra of dissolved silica.

Ion Association in Hydrothermal Sodium Sulfate Solutions Studied by Modulated FT-IR-Raman Spectroscopy and Molecular Dynamics.

Saline aqueous solutions at elevated pressures and temperatures play an important role in processes such as supercritical water oxidation (SCWO) and supercritical water gasification (SCWG), as well as in natural geochemical processes in Earth and planetary interiors. Some solutions exhibit a negative temperature coefficient of solubility at high temperatures, thereby leading to salt precipitation with increasing temperature. Using modulated FT-IR Raman spectroscopy and classical molecular dynamics simulations (MD), we studied the solute speciation in solutions of 10 wt % Na2SO4, at conditions close to the saturation limit. Our experiments reveal that ion pairing and cluster formation are favored as solid saturation is approached, and ionic clusters form prior to the precipitation of solid sulfate. The proportion of such clusters increases as the phase boundary is approached either by decreasing pressure or by increasing temperature in the vicinity of the three-phase (vapor-liquid-solid) curve.