Surface Charge Concentrations on Silica in Different 1.0 M Metal-Chloride Background Electrolytes and Implications for Dissolution Rates

The empirical rate laws formulated to describe the dissolution rates of oxide minerals include the surface charge concentration that results from the protonation and deprotonation of surface functional groups. Previous experiments on quartz and silica have shown that dissolution rates vary as a function of different background electrolyte solutions, however, such experiments are often conducted at elevated temperatures where it is difficult to estimate surface charge along with the dissolution rates. In the present study we measuresurface charge concentrations for silica in different electrolyte solutions at 298 K in order to quantify the extent to which the different counterions could affect the dissolution rates through their influence on the surface charge concentrations. The experimental solutions in the electrolyte series: LiCl, NaCl, KCl, RbCl, CaCl₂, SrCl₂ and BaCl₂ were prepared to maintain a constant metal concentration of 1.0 M. For the alkali-metal chlorides, the surface charge concentrations correlate with the size of the hydrated alkali metal, consistent with the idea that these counterions affect charge via outer-sphere coordination that shield proton surface complexes from one another. The reactivity trend for alkaline-earth cations is less clear, but the data demonstrate distinct differences in the acid-base propertiesof the silica surface in these different electrolytes. We then discuss how these trends are manifested in the rate equations used to interpret dissolution experiments.     

A model for underpressure development in a glacial valley,an example from Adventdalen,Svalbard

The underpressure observed in the glacial valley Adventdalen at Svalbard is studied numerically with a basin model and analytically with a compartment model. The pressure equation used in the basin model, which accounts for underpressure generation, is derived from mass conservation of pore fluid and solid, in addition to constitutive equations. The compartment model is derived as a similar pressure equation, which is based on a simplified representation of the basin geometry. It is used to derive analytical expressions for the underpressure (overpressure) from a series of unloading (loading) intervals. The compartment model gives a characteristic time for underpressure generation of each interval, which tells when the pressure state is transient or stationary. The transient pressure is linear in time for short‐time spans compared to the characteristic time, and then it is proportional to the weight removed from the surface. We compare different contributions to the underpressure generation and find that porosity rebound from unloading is more important than the decompression of the pore fluid during unloading and the thermal contraction of the pore fluid during cooling of the subsurface. Our modelling shows that the unloading from the last deglaciation can explain the present day underpressure. The basin model simulates the subsurface pressure resulting from erosion and unloading in addition to the fluid flow driven by the topography. Basin modelling indicates that the mountains surrounding the valley are more important for the topographic‐driven flow in the aquifer than the recharging in the neighbour valley. The compartment model turns out to be useful to estimate the orders of magnitude for system properties like seal and aquifer permeabilities and decompaction coefficients, despite its geometric simplicity. We estimate that the DeGeerdalen aquifer cannot have a permeability that is higher than 1 · 10^?18 m², as otherwise, the fluid flow in the aquifer becomes dominated by topographic‐driven flow. The upper value for the seal permeability is estimated to be 1 · 10^?20 m², as higher values preclude the generation and preservation of underpressure. The porosity rebound is estimated to be <0.1% during the last deglaciation using a decompaction coefficient α_r = 1 · 10^?9 Pa^?1.     

Value of information analysis in rock engineering: a case study of a tunnel project in Äspö Hard Rock Laboratory

Geoengineering prognoses are often based on data from a limited number of investigations of soil and rock mass. There is generally a desire to reduce the uncertainty in the prognoses while minimising the investigation costs. Value of Information Analysis (VOIA) is a support for decisions regarding investigation strategies and the aim of this paper is to present methodology for VOIA that takes into account four decision alternatives where the input data could be provided by experts. The methodology will be applied in a case study where the value of information related to an investigation borehole will be calculated. The results indicate that the value of information of the borehole is low compared with the realisation costs of the investigation. It was found that models for VOIA in underground construction projects are complex but that the analysis can be simplified with extensive use of expert knowledge and calculations of the value of perfect information as a benchmark for investigation strategies.     

A new formula for the total longshore sediment transport rate

A new predictive formula for the total longshore sediment transport (LST) rate was developed from principles of sediment transport physics assuming that breaking waves mobilize the sediment, which is subsequently moved by a mean current. Six high-quality data sets on hydrodynamics and sediment transport collected during both field and laboratory conditions were employed to evaluate the predictive capability of the new formula. The main parameter of the formula (a transport coefficient), which represents the efficiency of the waves in keeping sand grains in suspension, was expressed through a Dean number based on dimensional analysis. The new formula yields predictions that lie within a factor of 0.5 to 2 of the measured values for 62% of the data points, which is higher than other commonly employed formulas for the LST rate such as the CERC equation or the formulas developed by Inman–Bagnold and Kamphuis, respectively. The new formula is well suited for practical applications in coastal areas, as well as for numerical modeling of sediment transport and shoreline change in the nearshore.     

Revised ab initio models for H2-H2 collision-induced absorption at low temperatures

A revised ab initio calculation of the H₂-H₂ collision-induced absorption results in significant differences compared with the work of J. Borysow et al. [Borysow, J., Trafton, L., Frommhold, L., Birnbaum, G., 1985. Astrophys. J. 296, 644-654] for wavenumbers greater than 600 cm⁻¹ and temperatures below 120 K. The revision has significant influence on the spectra of Uranus and Neptune, and essentially removes the need for models with “super-solar” helium abundances or stratospheric hazes to explain the spectrum of Uranus.     

Coupling Between Seismic Activity and Hydrogeochemistry at the Shillong Plateau, Northeastern India

Transient hydrogeochemical anomalies were detected in a granite-hosted aquifer, which is located at a depth of 110 m, north of the Shillong Plateau, Assam, India, where groundwater chemistry is mainly buffered by feldspar alteration to kaolinite. Their onsets preceded moderate earthquakes on December 9, 2004 (M_W = 5.3) and February 15, 2005 (M_W = 5.0), respectively, 206 and 213 km from the aquifer. The ratios [Na+K]/Si, Na/K and [Na+K]/Ca, conductivity, alkalinity and chloride concentration began increasing 3–5 weeks before the M_W = 5.3 earthquake. By comparison with field, experimental and theoretical studies, we interpret a transient switchover between source aquifers, which induced an influx of groundwater from a second aquifer, where groundwater chemistry was dominantly buffered by the alteration of feldspar to smectite. This could have occurred in response to fracturing of a hydrological barrier. The ratio Ba/Sr began decreasing 3–6 days before the M_W = 5.0 earthquake. We interpret a transient switchover to anorthite dissolution caused by exposure of fresh plagioclase to groundwater interaction. This could have been induced by microfracturing, locally within the main aquifer. By comparison with experimental studies of feldspar dissolution, we interpret that hydrogeochemical recovery was facilitated by groundwater interaction and clay mineralization, which could have been coupled with fracture sealing. The coincidence in timing of these two hydrogeochemical events with the only two M_W ≥ 5 earthquakes in the study area argues in favor of cause-and-effect seismic-hydrogeochemical coupling. However, reasons for ambiguity include the lack of similar hydrogeochemical anomalies coupled with smaller seismic events near the monitoring station, the >200 km length scale of inferred seismic-hydrogeochemical coupling, and the potential for far-field effects related to the Great Sumatra–Andaman Islands Earthquake of December 26, 2004.