The composition and crystallinity of the near-surface regions of weathered alkali feldspars

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH 1 experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost ∼9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >∼2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction.     

Sedimentary petrology and geochemistry of siliciclastic rocks from the upper Jurassic Tordillo Formation (Neuquén Basin, western Argentina): Implications for provenance and tectonic setting

The Upper Jurassic Tordillo Formation is exposed along the western edge of the Neuquén Basin (west central Argentina) and consists of fluvial strata deposited under arid/semiarid conditions. The pebble composition of conglomerates, mineralogical composition of sandstones and pelitic rocks, and major- and trace-element geochemistry of sandstones, mudstones, and primary pyroclastic deposits are evaluated to determine the provenance and tectonic setting of the sedimentary basin. Conglomerates and sandstones derived almost exclusively from volcanic sources. The stratigraphic sections to the south show a clast population of conglomerates dominated by silicic volcanic fragments and a predominance of feldspathic litharenites. This framework composition records erosion of Triassic–Jurassic synrift volcaniclastic rocks and basement rocks from the Huincul arch, which was exhumed as a result of Late Jurassic inversion. In the northwestern part of the study area, conglomerates show a large proportion of mafic and acidic volcanic rock fragments, and sandstones are characterised by a high content of mafic volcanic rock fragments and plagioclase. These data suggest that the source of the sandstones and conglomerates was primarily the Andean magmatic arc, located west of the Neuquén Basin. The clay mineral assemblage is interpreted as the result of a complex set of factors, including source rock, climate, transport, and diagenesis. Postdepositional processes produced significant variations in the original compositions, especially the fine-grained deposits. The Tordillo sediments are characterised by moderate SiO₂ contents, variable abundances of K₂O and Na₂O, and a relatively high proportion of ferromagnesian elements. The degree of chemical weathering in the source area, expressed as the chemical index of alteration, is low to moderate. The major element geochemistry and Th/Sc, K/Rb, Co/Th, La/Sc, and Cr/Th values point to a significant input of detrital volcanic material of calcalkaline felsic and intermediate composition. However, major element geochemistry is not useful for interpreting the tectonic setting. Discrimination plots based on immobile trace elements, such as Ti, Zr, La, Sc, and Th, show that most data lie in the active continental margin field. Geochemical information is not sufficiently sensitive to differentiate the two different source areas recognized by petrographic and modal analyses of conglomerates and sandstones.     

The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2

Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H₂SO₄, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L⁻¹, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe–oxyhydroxysulfates (Fe(III)–SO₄–H⁺ solutions) or Fe–oxyhydroxychlorides (Fe(III)–Cl–H⁺ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to 6–7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)–SO₄–H⁺ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)–Cl–H⁺ solutions.     

Mineralogical sources of the buffer capacity in a granite catchment determined by strontium isotopes

The role of different minerals in base cation release and thus the increase of buffering capacity of groundwater against acid deposition is controversially discussed in the literature. The ⁸⁷Sr/⁸⁶Sr ratios and base cation concentration were investigated in whole rock leachates, mineral separates, precipitation, soil solution, groundwater and stream water samples in the Lehstenbach catchment (Germany) to identify the weathering sequence of the granite bedrock. Three different approaches were followed in parallel. It was assumed that the contribution of different minerals to base cation supply of the groundwater with increasing weathering intensity would be observed by investigating (1) unweathered rock leachates, deep groundwater and shallow groundwater, (2) groundwater samples from new groundwater wells, reflecting the initial weathering of the drilled bedrock, and groundwater from wells that were drilled in 1988, (3) stream water during baseflow, dominated by deep groundwater, and stream water during high flow, being predominantly shallow groundwater. Whereas the first approach yielded consistent patterns, there was some evidence that groundwater from the new wells initially reflected contamination by the filter gravel rather than cation release in an initial stage of weathering. Time series samples of stream water and groundwater solute concentrations and isotope ratios turned out to reflect varying fractions of soil water and precipitation water at baseflow and high flow conditions rather than varying contributions of different minerals that prevail at different stages of granite weathering.     

Quantitative sinkhole hazard assessment. A case study from the Ebro Valley evaporite alluvial karst (NE Spain)

Quantitative sinkhole hazard assessments in karst areas allow calculation of the potential sinkhole risk and the performance of cost-benefit analyses. These estimations are of practical interest for planning, engineering, and insurance purposes. The sinkhole hazard assessments should include two components: the probability of occurrence of sinkholes (sinkholes/km² year) and the severity of the sinkholes, which mainly refers to the subsidence mechanisms (progressive passive bending or catastrophic collapse) and the size of the sinkholes at the time of formation; a critical engineering design parameter. This requires the compilation of an exhaustive database on recent sinkholes, including information on the: (1) location, (2) chronology (precise date or age range), (3) size, and (4) subsidence mechanisms and rate. This work presents a hazard assessment from an alluvial evaporite karst area (0.81 km²) located in the periphery of the city of Zaragoza (Ebro River valley, NE Spain). Five sinkholes and four locations with features attributable to karstic subsidence where identified in an initial investigation phase providing a preliminary probability of occurrence of 0.14 sinkholes/km² year (11.34% in annual probability). A trenching program conducted in a subsequent investigation phase allowed us to rule out the four probable sinkholes, reducing the probability of occurrence to 0.079 sinkholes/km² year (6.4% in annual probability). The information on the severity indicates that collapse sinkholes 10–15 m in diameter may occur in the area. A detailed study of the deposits and deformational structures exposed by trenching in one of the sinkholes allowed us to infer a modern collapse sinkhole approximately 12 m in diameter and with a vertical throw of 8 m. This collapse structure is superimposed on a subsidence sinkhole around 80 m across that records at least 1.7 m of synsedimentary subsidence. Trenching, in combination with dating techniques, is proposed as a useful methodology to elucidate the origin of depressions with uncertain diagnosis and to gather practical information with predictive utility about particular sinkholes in alluvial karst settings: precise location, subsidence mechanisms and magnitude, and timing and rate of the subsidence episodes.     

Stability at high-pressure,elastic behaviour and pressure-induced structural evolution of CsAlSi<Subscript>5</Subscript>O<Subscript>12</Subscript>, a potential host for nuclear waste

The elastic and structural behaviour of the synthetic zeolite CsAlSi₅O₁₂ (a = 16.753(4), b = 13.797(3) and c = 5.0235(17) Å, space group Ama2, Z = 2) were investigated up to 8.5 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase-transition occurs within the P-range investigated. Fitting the volume data with a third-order Birch–Murnaghan equation-of-state gives: V ₀ = 1,155(4) ų, K _T0 = 20(1) GPa and K′ = 6.5(7). The “axial moduli” were calculated with a third-order “linearized” BM-EoS, substituting the cube of the individual lattice parameter (a ³, b ³, c ³) for the volume. The refined axial-EoS parameters are: a ₀ = 16.701(44) Å, K _T0a = 14(2) GPa (β_a = 0.024(3) GPa^?1), K′ _a = 6.2(8) for the a-axis; b ₀ = 13.778(20) Å, K _T0b = 21(3) GPa (β_b = 0.016(2) GPa^?1), K′ _b = 10(2) for the b-axis; c ₀ = 5.018(7) Å, K _T0c = 33(3) GPa (β_c = 0.010(1) GPa^?1), K′ _c = 3.2(8) for the c-axis (K _T0a:K _T0b:K _T0c = 1:1.50:2.36). The HP-crystal structure evolution was studied on the basis of several structural refinements at different pressures: 0.0001 GPa (with crystal in DAC without any pressure medium), 1.58(3), 1.75(4), 1.94(6), 3.25(4), 4.69(5), 7.36(6), 8.45(5) and 0.0001 GPa (after decompression). The main deformation mechanisms at high-pressure are basically driven by tetrahedral tilting, the tetrahedra behaving as rigid-units. A change in the compressional mechanisms was observed at P ≤ 2 GPa. The P-induced structural rearrangement up to 8.5 GPa is completely reversible. The high thermo-elastic stability of CsAlSi₅O_12, the immobility of Cs at HT/HP-conditions, the preservation of crystallinity at least up to 8.5 GPa and 1,000°C in elastic regime and the extremely low leaching rate of Cs from CsAlSi₅O₁₂ allow to consider this open-framework silicate as functional material potentially usable for fixation and deposition of Cs radioisotopes.     

Methodology of hydrogeological characterization of deep carbonate aquifers as potential reservoirs of groundwater. Case of study: the Jurassic aquifer of <Emphasis Type="Italic">El Maestrazgo</Emphasis> (Castellón,Spain)

A methodology for the characterization of deep carbonate aquifers has been developed and applied to El Maestrazgo Jurassic aquifer in Castellón, Spain. Characterization of these aquifer formations, located at more than 300 m deep, consisted of a previous phase of compilation, analysis and synthesis of the existing information about the area, followed by a coordinated combination of different speciality studies: geology, stratigraphy, structural analysis, hydrogeology, hydrochemistry, geophysics and remote sensing. Geological studies included geological mapping, definition of stratigraphical units and facies and structural analysis. The aim of the hydrogeology study was to define aquifer formations, recharge area, aquifer points inventory and groundwater flow directions for the establishment of piezometric and water quality observation nets. Special techniques were applied, like thermal infrared aerial images and the evaluation of submarine groundwater discharge by means of natural radium isotopes. Hydrochemical techniques, including majority elements characterization and stable isotopes (¹⁸O, ²H and ³H) determination, allowed classifying hydrochemical facies and establishing a renewal pattern for water within the system. Geophysics was useful in determining the aquifer geometry, the features of the basement and the petrophysical characteristics of the geological formations. Preliminary results show an important tectonic complexity and the possibilities for groundwater uses in the area of study.     

Ermittlung der QNH-werte aus dem luftdruckfeld der synoptischen bodenkarte

Резюме Дабление воздуха, переснитанное иа уровень моря по стандартной атмосфере в Q-коде обозчачается через QNH. Давление воздуха пересчитанное на уровень моря по высотной барометрической формуле обознаеается через QFF. Для целей авиационной службы погоды должны быть известны значения QNH, однако Зе барическое поле на синоптических картах выражается через QFF. С помощью рис. 1 для соответствующей температуры воздуха на станцин и ее высоты н. у. м. можно определить разность значений QFF—QNH при давленин QFF=1000мб. Далее по табл. 2 можно определить поправку для каждого значения QFF отличного от значения QFF при ином давлении, чем 1000мб путем умножения табулированного значения ва разность QFF—1000мб и его алгебраического сложения со значением, полученным по рис. 1.      

Correlation of atmospheric occurences over the United States with some physical and chemical parameters. Part III: Frequencies of precipitation

Summary Correlation between some physical and chemical variables, measured at 28 stations of the United States Weather Bureau Network, and seasonal and annual frequencies of precipitation, has been attempted with the aim of gaining insight into the bearing of such variables, on occurrence of precipitation. — Concurrent trends of frequencies with local temperature functions, altitude parameters, precipitable water vapour increments, and some chemical species have been found.Contribution of the «Centro Nucleazione Aerosoli» of the National Research Council of Italy, Via Vettore 4 (Monte Sacro),Roma.