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).

     

Early fill of the Western Irish Namurian Basin: a complex relationship between turbidites and deltas

The Western Irish Namurian Basin developed in Early Carboniferous times as a result of extension across the Shannon Lineament which probably coincides with the lapetus Suture. During the late Dinantian, axial areas of the NE-SW elongate trough became deep, whilst shallow-water limestones were deposited on the flanks. This bathymetry persisted into the Namurian when carbonate deposition ceased. In axial areas, a relatively thick mudstone succession spans earliest Namurian to Chokierian whilst on the northwestern marginal shelf, a thin, condensed Namurian mudstone sequence, in which pre-Chokierian sediments are apparently absent, rests unconformably on the Dinantian. From late Chokierian to early Kinderscoutian, the basin was filled by sand-dominated clastic sediments. Sand deposition began in the axial area with deposition of a thick turbidite sequence, the Ross Formation, which is largely equivalent to the condensed mudstone succession on the flanks. Turbidity currents flowed mainly axially towards the north-east and deposited a sequence lacking well-defined patterns of vertical bed-thickness change. Channels and slide sheets occur towards the top of the formation. The turbidite system seems to have lacked well-defined lobes and stable distributary channels. Overlying the Ross Formation, the Gull Island Formation shows a decreasing incidence of turbidite sandstones at the expense of increasing siltstones. This formation is characterized by major slides and slumps interbedded with undisturbed strata. In the flanking areas of the basin, the formation is thinner, has only a few turbidites in the sequence above the condensed mudstones and contains only one slide sheet. Overall the formation is interpreted as the deposit of a major prograding slope, the lower part representing a ramp upon which turbidites were deposited, the upper part a highly unstable muddy slope lacking any conspicuous feeder channels through which sand might have been transferred to deeper water. Progradation of the slope appears to have been increasingly from the northwestern flank of the trough which is similar to the direction deduced for the overlying deltaic Tullig cyclothem which completes the initial basin fill. Whilst several features of the succession can be explained by envisaging the whole sequence as the product of one linked depositional system, the shifting directions of palaeocurrents and palaeoslope raise problems. The switch from axial to lateral supply casts doubt on the strict application of Walther's Law to the total sequence and seems to demand large avulsive shifts of the delta system on the shelf area to the west.