GaMin’11 – an International Inter-laboratory Comparison for Geochemical CO2 - Saline Fluid - Mineral Interaction Experiments

Due to the strong interest in geochemical CO2-fluid-rock interaction in the context of geological storage of CO2 a growing number of research groups have used a variety of different experimental ways to identify important geochemical dissolution or precipitation reactions and – if possible – quantify the rates and extent of mineral or rock alteration. In this inter-laboratory comparison the gas-fluid-mineral reactions of three samples of rock-forming minerals have been investigated by 11 experimental labs. The reported results point to robust identification of the major processes in the experiments by most groups. The dissolution rates derived from the changes in composition of the aqueous phase are consistent overall, but the variation could be reduced by using similar corrections for changing parameters in the reaction cells over time. The comparison of experimental setups and procedures as well as of data corrections identified potential improvements for future gas-fluid-rock studies

Glass–water interaction: Effect of high-valence cations on glass structure and chemical durability

International audienceBorosilicate glass is a durable solid, but it dissolves when in contact with aqueous fluids. The dissolution mechanism, which involves a variety of sequential reactions that occur at the solid–fluid interface, has important implications for the corrosion resistance of industrial and nuclear waste glasses. In this study, spectroscopic measurements, dissolution experiments, and Monte Carlo simulations were performed to investigate the effect of high-valence cations (HVC) on the mechanisms of glass dissolution under dilute and near-saturated conditions. Raman and NMR spectroscopy were used to determine the structural changes that occur in glass, specifically network formers (e.g., Al, Si, and B), with the addition of the HVC element hafnium in the Na 2 O–Al 2 O 3 –B 2 O 3 –HfO 2 –SiO 2 system (e.g., Na/[Al + B] = 1.0 and HfO 2 /SiO 2 from 0.0 to 0.42). Spectroscopic measurements revealed that increasing hafnium content decreases N 4 (tetrahedral boron/total boron) and increases the amount of Si–O–Hf moieties in the glass. Results from flow-through experiments conducted under dilute and near-saturated conditions show a decrease of approximately 100Â or more in the dissolution rate over the series from 0 to 20 mol% HfO 2. Comparing the average steady-state rates obtained under dilute conditions to the rates obtained for near-saturated conditions reveals a divergence in the magnitude between the average steady state rates measured in these different conditions. The reason for this divergence was investigated more thoroughly using Monte Carlo simulations. Simulations indicate that the divergence in glass dissolution behavior under dilute and near-saturated conditions result from the stronger binding of Si sites that deposit on the surface from the influent when Hf is present in the glass. As a result, the residence time at the glass surface of these newly-formed Si sites is longer in the presence of Hf, which increases the density of anchor sites from which altered layers with highe