Permeability and degassing of dome lavas undergoing rapid decompression: An experimental determination

The gas permeability of volcanic rocks may influence various eruptive processes. The transition from a quiescent degassing dome to rock failure (fragmentation) may, for example, be controlled by the rocks permeability, in as much as it affects the speed by which a gas overpressure in vesicles is reduced in response to decompression. Using a modified shock-tube-based fragmentation bomb (Alidibirov and Dingwell 1996a,b; Spieler et al. 2003a), we have measured unsteady-state permeability at a high initial pressure differential. Following sudden decompression above the rock cylinder, pressurized gas flows through the sample. Two pressure transducers record the pressure signals above and below the sample. A transient 1D filtration code has been developed to calculate permeability using the experimental decay curve of the lower pressure transducer. Additionally an analytical steady-state method to achieve permeability is presented as an alternative to swiftly predict the sample permeability in a sufficiently precise manner. Over 100 permeability measurements have been performed on samples covering a wide range of porosity. The results show a general positive relationship between porosity and permeability with a high data scatter. Our preferred interpretation of the results is a combination of two different, but overlapping effects. We propose that at low porosities, gas escape occurs predominantly through microcracks or elongated micropores and therefore could be described by simplified forms of Kozeny–Carman relations (Carman 1956) and fracture flow models. At higher porosities, the influence of vesicles becomes progressively stronger as they form an increasingly connected network. Therefore, a model based on the percolation theory of fully penetrable spheres is used, as a first approximation, to describe the permeability-porosity trend. In the data acquired to date it is evident, that in addition to the porosity control, the samples bubble size, shape and distribution strongly influence the permeability. This leads to a range of permeability values up to 2.5 orders of magnitude at a given porosity.     

Predicting changes in alluvial channel patterns in North-European Russia under conditions of global warming

Global climate change may have a noticeable impact on the northern environment, leading to changes in permafrost, vegetation and fluvial morphology. In this paper we compare the results from three geomorphological models and study the potential effects of changing climatic factors on the river channel types in North-European Russia. Two of the selected models by Romashin [Romashin, V.V., 1968. Variations of the river channel types under governing factors, Annals of the Hydrological Institute, vol. 155. Hydrometeoizdat, Leningrad, pp. 56–63.] and Leopold and Wolman [Leopold, L.B., Wolman, M.G., 1957. River channel pattern: braided, meandering and straight, Physiographic and hydraulic studies of rivers. USA Geological Survey Professional Paper 252, pp. 85–98.] are conventional QS-type models, which predict the existence of either multi-thread or single-tread channel types using data on discharge and channel slope. The more advanced model by Van den Berg [Van den Berg, J.H., 1995. Prediction of alluvial channel pattern of perennial rivers. Geomorphology 12, 259–270.] takes into account the size of the sediment material.We used data from 16 runoff gauges to validate the models and predict the channel types at selected locations under modern and predicted for the future climatic conditions. Two of the three models successfully replicated the currently existing channel types in all but one of the studied sites. Predictive calculations under the hypothetical scenarios of 10%, 15%, 20% and 35% runoff increase gave different results. Van den Berg's model predicted potential transformation of the channel types, from single- to multi-thread, at 4 of 16 selected locations in the next few decades, and at 5 locations by the middle of the 21st century. Each of the QS-type models predicted such transformation at one site only.Results of the study indicate that climatic warming in combination with other environmental changes may lead to transformation of the river channel types at selected locations in north-western Russia. Further efforts are needed to improve the performance of the fluvial geomorphological models and their ability to predict such changes.     

The surface chemistry of multi-oxide silicates

The surface chemistry of natural wollastonite, diopside, enstatite, forsterite, and albite in aqueous solutions was characterized using both electrokinetic techniques and surface titrations performed for 20 min in batch reactors. Titrations performed in such reactors allow determination of both proton consumption and metal release from the mineral surface as a function of pH. The compositions, based on aqueous solution analysis, of all investigated surfaces vary dramatically with solution pH. Ca and Mg are preferentially released from the surfaces of all investigated divalent metal silicates at pH less than ∼8.5-10 but preferentially retained relative to silica at higher pH. As such, the surfaces of these minerals are Si-rich and divalent metal poor except in strongly alkaline solutions. The preferential removal of divalent cations from these surfaces is coupled to proton consumption. The number of protons consumed by the preferential removal of each divalent cation is pH independent but depends on the identity of the mineral; ∼1.5 protons are consumed by the preferential removal of each Ca atom from wollastonite, ∼3 protons are consumed by the preferential removal of each Mg or Ca atom from diopside or enstatite, and ∼4 protons are consumed by the preferential removal of each Mg from forsterite. These observations are interpreted to stem from the creation of additional ‘internal’ adsorption sites by the preferential removal of divalent metal cations which can be coupled to the condensation of partially detached Si. Similarly, Na and Al are preferentially removed from the albite surface at 2 > pH > 11; mass balance calculations suggest that three protons are consumed by the preferential removal of each Al atom from this surface over this entire pH range. Electrokinetic measurements on fresh mineral powders yield an isoelectric point (pH_IEP) 2.6, 4.4, 3.0, 4.5, and <1, for wollastonite, diopside, enstatite, forsterite, and albite, respectively, consistent with the predominance of SiO₂ in the surface layer of all of these multi-oxide silicates at acidic pH. Taken together, these observations suggest fundamental differences between the surface chemistry of simple versus multi-oxide minerals including (1) a dependency of the number and identity of multi-oxide silicate surface sites on the aqueous solution composition, and (2) the dominant role of metal-proton exchange reactions on the reactivity of multi-oxide mineral surfaces including their dissolution rate variation with aqueous solution composition.     

Kinetics of brucite dissolution at 25°C in the presence of organic and inorganic ligands and divalent metals

Brucite (Mg(OH)₂) dissolution rate was measured at 25°C in a mixed-flow reactor at various pH (5 to 11) and ionic strengths (0.01 to 0.03 M) as a function of the concentration of 15 organic and 5 inorganic ligands and 8 divalent metals. At neutral and weakly alkaline pH, the dissolution is promoted by the addition of the following ligands ranked by decreasing effectiveness: EDTA ≥ H₂PO₄⁻ > catechol ≥ HCO₃⁻ > ascorbate > citrate > oxalate > acetate ∼ lactate and it is inhibited by boric acid. At pH >10.5, it decreases in the presence of PO₄³⁻, CO₃²⁻, F⁻, oxine, salicylate, lactate, acetate, 4-hydroxybenzoate, SO₄²⁻ and B(OH)₄⁻ with orthophosphate and borate being the strongest and the weakest inhibitor, respectively. Xylose (up to 0.1 M), glycine (up to 0.05 M), formate (up to 0.3 M) and fulvic and humic acids (up to 40 mg/L DOC) have no effect on brucite dissolution kinetics. Fluorine inhibits dissolution both in neutral and alkaline solutions. From F sorption experiments in batch and flow-through reactors and the analysis of reacted surfaces using X-ray Photoelectron Spectroscopy (XPS), it is shown that fluorine adsorption is followed by its incorporation in brucite lattice likely via isomorphic substitution with OH. The effect of eight divalent metals (Sr, Ba, Ca, Pb, Mn, Fe, Co and Ni) studied at pH 4.9 and 0.01 M concentration revealed brucite dissolution rates to be correlated with the water molecule exchange rates in the first hydration sphere of the corresponding cation.The effect of investigated ligands on brucite dissolution rate can be modelled within the framework of the surface coordination approach taking into account the adsorption of ligands on dissolution-active sites and the molecular structure of the surface complexes they form. The higher the value of the ligand sorption constant, the stronger will be its catalyzing or inhibiting effect. As for Fe and Al oxides, bi- or multidentate mononuclear surface complexes, that labilize Mg-O bonds and water coordination to Mg atoms at the surface, enhance brucite dissolution whereas bi- or polynuclear surface complexes tend to inhibit dissolution by bridging two or more metal centers and extending the cross-linking at the solid surface. Overall, results of this study demonstrate that very high concentrations of organic ligands (0.01-0.1 M) are necessary to enhance or inhibit brucite dissolution. As a result, the effect of extracellular organic products on the weathering rate of Mg-bearing minerals is expected to be weak.