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1. An experimentally validated numerical model for bubble growth in magma.

   https://doi.org/10.1016/j.jvolgeores.2020.107002  

   Coumans, J. ; Llewellin, E. ; Wadsworth, F. ; Humphreys, M. ; Mathias, S.A. ; Yelverton, B. ; Gardner, J. ( January 2020 , Journal of volcanology and geothermal research)

   null (Ed.)

   The di!usion of water through silicate melts is a key process in volcanic systems. Di!usion controls the growth of the bub- bles that drive volcanic eruptions and determines the evolution of the spatial distribution of dissolved water during and after magma mingling, crystal growth, fracturing and fragmentation, and welding of pyroclasts. Accurate models for water di!u- sion are therefore essential for forward modelling of eruptive behaviour, and for inverse modelling to reconstruct eruptive and post-eruptive history from the spatial distribution of water in eruptive products. Existing models do not include the kinetics of the homogeneous species reaction that interconverts molecular (H2Om) and hydroxyl (OH) water; reaction kinetics are impor- tant because final species distribution depends on cooling history. Here we develop a flexible 1D numerical model for di!usion and speciation of water in silicate melts. We validate the model against FTIR transects of the spatial distribution of molecular, hydroxyl, and total water across di!usion-couple experiments of haplogranite composition, run at 800–1200 C and 5 kbar. We adopt a stepwise approach to analysing and modelling the data. First, we use the analytical Sauer-Freise method to deter- mine the e!ective di!usivity of total water DH2Ot as a function of dissolved water concentration CH2Ot and temperature T for each experiment and find that the dependence of DH2 Ot on CH2 Ot is linear for CH2 Ot K 1:8 wt.% and exponential for CH2 Ot J 1:8 wt.%. Second, we develop a 1D numerical forward model, using the method of lines, to determine a piece-wise function for DH2 Ot !CH2 Ot ; T " that is globally-minimized against the entire experimental dataset. Third, we extend this numerical model to account for speciation of water and determine globally-minimized functions for di!usivity of molecular water DH2 Om !CH2 Ot ; T " and the equilibrium constant K for the speciation reaction. Our approach includes three key novelties: (1) functions for dif- fusivities of H2Ot and H2Om, and the speciation reaction, are minimized simultaneously against a large experimental dataset, covering a wide range of water concentration (0:25 CH2 Ot 7 wt.%) and temperature (800  C T 1200  C), such that the resulting functions are both mutually-consistent and broadly applicable; (2) the minimization allows rigorous and robust analysis of uncertainties such that the accuracy of the functions is quantified; (3) the model can be straightforwardly used to determine functions for di!usivity and speciation for other melt compositions pending suitable di!usion-couple experiments. The modelling approach is suitable for both forward and inverse modelling of di!usion processes in silicate melts; the model is available as a MATLAB script from the electronic supplementary material. 

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2. Nonlinear effects of hydration on high-pressure sound velocities of rhyolitic glasses

   https://doi.org/10.2138/am-2021-7597  

   Gu, Jesse T. ; Fu, Suyu ; Gardner, James E. ; Yamashita, Shigeru ; Okuchi, Takuo ; Lin, Jung-Fu ( July 2021 , American Mineralogist)

   Abstract Acoustic compressional and shear wave velocities (VP, VS) of anhydrous (AHRG) and hydrous rhyolitic glasses (HRG) containing 3.28 wt% (HRG-3) and 5.90 wt% (HRG-6) total water concentration (H2Ot) have been measured using Brillouin light scattering (BLS) spectroscopy up to 3 GPa in a diamond-anvil cell at ambient temperature. In addition, Fourier-transform infrared (FTIR) spectroscopy was used to measure the speciation of H2O in the glasses up to 3 GPa. At ambient pressure, HRG-3 contains 1.58 (6) wt% hydroxyl groups (OH–) and 1.70 (7) wt% molecular water (H2Om) while HRG-6 contains 1.67 (10) wt% OH– and 4.23 (17) wt% H2Om where the numbers in parentheses are ±1σ. With increasing pressure, very little H2Om, if any, converts to OH– within uncertainties in hydrous rhyolitic glasses such that HRG-6 contains much more H2Om than HRG-3 at all experimental pressures. We observe a nonlinear relationship between high-pressure sound velocities and H2Ot, which is attributed to the distinct effects of each water species on acoustic velocities and elastic moduli of hydrous glasses. Near ambient pressure, depolymerization due to OH– reduces VS and G more than VP and KS. VP and KS in both anhydrous and hydrous glasses decrease with increasing pressure up to ~1–2 GPa before increasing with pressure. Above ~1–2 GPa, VP and KS in both hydrous glasses converge with those in AHRG. In particular, VP in HRG-6 crosses over and becomes higher than VP in AHRG. HRG-6 displays lower VS and G than HRG-3 near ambient pressure, but VS and G in these glasses converge above ~2 GPa. Our results show that hydrous rhyolitic glasses with ~2–4 wt% H2Om can be as incompressible as their anhydrous counterpart above ~1.5 GPa. The nonlinear effects of hydration on high-pressure acoustic velocities and elastic moduli of rhyolitic glasses observed here may provide some insight into the behavior of hydrous silicate melts in felsic magma chambers at depth. 

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3. Non-linear Effects of Hydration on Sound Velocities of Rhyolitic Glasses up to 3 GPa.

   Gu, J. ; Fu, S. ; Gardner, J. E. ; Yamashira, S. ; Okuchi, T. ; Lin, J. F. ( January 2021 , The American mineralogist)

   null (Ed.)

   Acoustic compressional and shear wave velocities (VP, VS) of anhydrous (AHRG) and hydrous rhyolitic glasses (HRG) containing 3.28 wt% (HRG-3) and 5.90 wt% (HRG-6) total water concentra- tion (H2Ot) have been measured using Brillouin light scattering (BLS) spectroscopy up to 3 GPa in a diamond-anvil cell at ambient temperature. In addition, Fourier-transform infrared (FTIR) spectroscopy was used to measure the speciation of H2O in the glasses up to 3 GPa. At ambient pressure, HRG-3 contains 1.58 (6) wt% hydroxyl groups (OH–) and 1.70 (7) wt% molecular water (H2Om) while HRG-6 contains 1.67 (10) wt% OH– and 4.23 (17) wt% H2Om where the numbers in parentheses are ±1σ. With increasing pressure, very little H2Om, if any, converts to OH– within uncertainties in hydrous rhyolitic glasses such that HRG-6 contains much more H2Om than HRG-3 at all experimental pressures. We observe a nonlinear relationship between high-pressure sound velocities and H2Ot, which is attributed to the distinct effects of each water species on acoustic velocities and elastic moduli of hydrous glasses. Near ambient pressure, depolymerization due to OH– reduces VS and G more than VP and KS. VP and KS in both anhydrous and hydrous glasses decrease with increasing pressure up to ~1–2 GPa before increasing with pressure. Above ~1–2 GPa, VP and KS in both hydrous glasses converge with those in AHRG. In particular, VP in HRG-6 crosses over and becomes higher than VP in AHRG. HRG-6 displays lower VS and G than HRG-3 near ambient pressure, but VS and G in these glasses converge above ~2 GPa. Our results show that hydrous rhyolitic glasses with ~2–4 wt% H2Om can be as incompressible as their anhydrous counterpart above ~1.5 GPa. The nonlinear effects of hydration on high-pressure acoustic velocities and elastic moduli of rhyolitic glasses observed here may provide some insight into the behavior of hydrous silicate melts in felsic magma chambers at depth. 

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4. Nitrogen partitioning between silicate phases and aqueous fluid depends on concentration

   https://doi.org/10.1016/j.gca.2023.05.017  

   Jackson, Colin R.M. ; Cottrell, Elizabeth ( August 2023 , Geochimica et Cosmochimica Acta)

   The distribution of nitrogen in geologic systems is modulated by its partitioning between silicate (mineral and melt) and fluid phases. Under geologically applicable oxygen fugacity, pressure, and temperatures, nitrogen can be multiply-speciated, with N2 coexisting with reduced nitride (N􀀀 3) species. Non-polar, neutral species, including N2, tend to concentrate in fluids, while charged nitride species have a greater propensity to concentrate in silicate phases. The stoichiometry of converting N2 to single N atom nitride species implies that nitrogen speciation may depend on its concentration, and this leads to the hypothesis that the partitioning of nitrogen between silicate and fluid phases also depends on concentration, potentially biasing prior experimental work in doped systems and influencing the behavior of nitrogen in geologic systems. To test this hypothesis, we have completed a series high pressure (~1.75 GPa, 800 ◦C) experiments that react minerals, melts, and fluids with variable nitrogen concentrations (3.1–17.1 wt% N). Our results imply order-of-magnitude-scale increases in mineral/melt and melt/fluid partitioning as nitrogen concentrations decrease within natural ranges. For example, decreasing the N concentration from 2500 to 2 ppm increases predicted DN melt/fluid values by over an order of magnitude at constant PT conditions. This means that loss of nitrogen from a degassing magma or dehydrating slab is a self-limiting process that becomes increasingly inefficient as nitrogen concentration falls. Despite this, nitrogen remains highly concentrated in the atmosphere, which receives N from fluids exsolved from slabs and magmas. To maintain a nitrogen-rich atmosphere we therefore suggest that warm and oxidizing conditions have prevailed over subduction zones because warm slabs dehydrate under lower pressures where nitrogen is more easily partitioned into fluids, and oxidizing conditions also promote nitrogen partitioning into fluids. Concentration-dependent partitioning of nitrogen will also serve to moderate any initial variations of N/K in slab materials upon dehydration, and this may help to explain the relatively uniform N/K ratio of MORB mantle. We supplement our nitrogen concentration experiments with a temperature series (1.5–2 GPa, 750–950 ◦C). Our temperature series data reveal that at high temperature nitrogen favors melts over fluids, while temperature has no resolvable effect of biotite-fluid partitioning. 

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5. The potential for aqueous fluid-rock and silicate melt-rock interactions to re-equilibrate hydrogen in peridotite nominally anhydrous minerals

   https://doi.org/10.2138/am-2020-7435  

   Lynn, Kendra J ; Warren, Jessica M ( January 2021 , The American mineralogist)

   Hydrogen is a rapidly diffusing monovalent cation in nominally anhydrous minerals (NAMs, such as olivine, orthopyroxene, and clinopyroxene), which is potentially re-equilibrated during silicate melt-rock and aqueous fluid-rock interactions in massif and abyssal peridotites. We apply a 3D numerical diffusion modeling technique to provide first-order timescales of complete hydrogen re-equilibration in olivine, clinopyroxene, and orthopyroxene over the temperature range 600-1200°C. Model crystals are 1-3 mm along the c-axis and utilize H+ diffusion coefficients appropriate for Fe-bearing systems. Two sets of models were run with different boundary compositions: 1) “low-H models” are constrained by mineral-melt equilibrium partitioning with a basaltic melt that has 0.75 wt% H2O and 2) “high-H models,” which utilize the upper end of the estimated range of mantle water solubility for each phase. Both sets of models yield re-equilibration timescales that are identical and are fast for all phases at a given temperature. These timescales have strong log-linear trends as a function of temperature (R2 from 0.97 to 0.99) that can be used to calculate expected re-equilibration time at a given temperature and grain size. At the high end of the model temperatures (1000-1200°C), H+ completely re-equilibrates in olivine, orthopyroxene, and clinopyroxene within minutes to hours, consistent with previous studies. These short timescales indicate that xenolith NAM mantle water contents are likely to be overprinted prior to eruption. The models also resolve the decoupled water-trace element relationship in Southwest Indian Ridge peridotites, in which peridotite REE abundances are reproduced by partial melting models whereas the relatively high NAM H2O contents require later re-equilibration with melt. At temperatures of 600-800°C, which correspond to conditions of hydrothermal alteration of pyroxene to amphibole and talc, H+ re-equilibration typically occurs over a range of timescales spanning days to years. These durations are well within existing estimates for the duration of fluid flow in oceanic hydrothermal systems, suggesting that peridotite NAM water contents are susceptible to diffusive overprinting during higher temperature hydrothermal alteration. Thus, diffusion during aqueous fluid-rock interactions may also explain NAM H2O contents that are too high to reflect residues of melting. These relatively short timescales at low temperatures suggest that the origin of water contents measured in peridotite NAMs requires additional constraints on sample petrogenesis, including petrographic and trace element analyses. Our 3D model results also hint that H+ may diffuse appreciably during peridotite serpentinization, but diffusion coefficients at low temperature are unconstrained and additional experimental investigations are needed. 

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