Solution mechanisms of H2O in depolymerized peralkaline melts

Solubility mechanisms of water in depolymerized silicate melts quenched from high temperature (1000°-1300°C) at high pressure (0.8-2.0 GPa) have been examined in peralkaline melts in the system Na₂O-SiO₂-H₂O with Raman and NMR spectroscopy. The Na/Si ratio of the melts ranged from 0.25 to 1. Water contents were varied from ∼3 mol% and ∼40 mol% (based on O = 1). Solution of water results in melt depolymerization where the rate of depolymerization with water content, ∂(NBO/Si)/∂X_H2O, decreases with increasing total water content. At low water contents, the influence of H₂O on the melt structure resembles that of adding alkali oxide. In water-rich melts, alkali oxides are more efficient melt depolymerizers than water. In highly polymerized melts, Si-OH bonds are formed by water reacting with bridging oxygen in Q⁴-species to form Q³ and Q² species. In less polymerized melts, Si-OH bonds are formed when bridging oxygen in Q³-species react with water to form Q²-species. In addition, the presence of Na-OH complexes is inferred. Their importance appears to increase with Na/Si. This apparent increase in importance of Na-OH complexes with increasing Na/Si (which causes increasing degree of depolymerization of the anhydrous silicate melt) suggests that water is a less efficient depolymerizer of silicate melts, the more depolymerized the melt. This conclusion is consistent with recently published ¹H and ²⁹Si MAS NMR and ¹H-²⁹Si cross polarization NMR data.     

Speciation of reduced C-O-H volatiles in coexisting fluids and silicate melts determined in-situ to ∼1.4 GPa and 800 °C

The structure of silicate melts in the system Na₂O·4SiO₂ saturated with reduced C-O-H volatile components and of coexisting silicate-saturated C-O-H solutions has been determined in a hydrothermal diamond anvil cell (HDAC) by using confocal microRaman and FTIR spectroscopy as structural probes. The experiments were conducted in-situ with the melt and fluid at high temperature (up to 800 °C) and pressure (up to 1435 MPa). Redox conditions in the HDAC were controlled with the reaction, Mo + H₂O = MoO₂ + H₂, which is slightly more reducing than the Fe + H₂O = FeO + H₂ buffer at 800 °C and less.The dominant species in the fluid are CH₄ + H₂O together with minor amounts of molecular H₂ and an undersaturated hydrocarbon species. In coexisting melt, CH₃ - groups linked to the silicate melt structure via Si-O-CH₃ bonding may dominate and possibly coexists with molecular CH₄. The abundance ratio of CH₃ - groups in melts relative to CH₄ in fluids increases from 0.01 to 0.07 between 500 and 800 °C. Carbon-bearing species in melts were not detected at temperatures and pressures below 400 °C and 730 MPa, respectively. A schematic solution mechanism is, Si-O-Si + CH₄?Si-O-CH₃+H-O-Si. This mechanism causes depolymerization of silicate melts. Solution of reduced (C-O-H) components will, therefore, affect melt properties in a manner resembling dissolved H₂O.     

Acidification of Lower St. Lawrence Estuary Bottom Waters

Accumulation of metabolic CO₂ can acidify marine waters above and beyond the ongoing acidification of the ocean by anthropogenic CO₂. The impact of respiration on carbonate chemistry and pH is most acute in hypoxic and anoxic basins, where metabolic CO₂ accumulates to high concentrations. The bottom waters of the Lower St. Lawrence Estuary (LSLE), where persistently severe hypoxia has developed over the last 80 years, is one such case. We have reconstructed the evolution of pH in the bottom waters from historical and recent data, and from first principles relating the stoichiometry of CO₂ produced to oxygen consumed during microbial degradation of organic matter. Based on the value of the atmospheric partial pressure of CO₂ that best reproduces the preformed dissolved inorganic carbon concentration in the bottom waters, we estimate the average ventilation age of the bottom waters to be 16?±?3 years. The pH of the bottom waters has decreased by 0.2 to 0.3 over the last 75 years, which is four to six times greater than can be attributed to the uptake of anthropogenic CO₂. The pH decrease is accompanied by a decline in the saturation state with respect to both calcite and aragonite. As of 2007, bottom waters in the LSLE are slightly supersaturated with respect to calcite (Ω_c?≈?1.06?±?0.04) but are strongly undersaturated with respect to aragonite (Ω_a?≈?0.67?±?0.03).

     

Application of Dynamic Subgrid-scale Models for Large-eddy Simulation of the Daytime Convective Boundary Layer over Heterogeneous Surfaces

The sensitivity of large-eddy simulation (LES) to the representation of subgrid-scale (SGS) processes is explored for the case of the convective boundary layer (CBL) developing over surfaces with varying degrees of spatial heterogeneity. Three representations of SGS processes are explored: the traditional constant Smagorinsky–Lilly model and two other dynamic models with Lagrangian averaging approaches to calculate the Smagorinsky coefficient (C _S ) and SGS Prandtl number (Pr). With initial data based roughly on the observed meteorology, simulations of daytime CBL growth are performed over surfaces with characteristics (i.e. fluxes and roughness) ranging from homogeneous, to striped heterogeneity, to a realistic representation of heterogeneity as derived from a recent field study. In both idealized tests and the realistic case, SGS sensitivities are mostly manifest near the surface and entrainment zone. However, unlike simulations over complex domains or under neutral or stable conditions, these differences for the CBL simulation, where large eddies dominate, are not significant enough to distinguish the performance of the different SGS models, irrespective of surface heterogeneity.