Analytical solutions of one‐dimensional infiltration before and after ponding

This paper is a continuation of previous research, which obtained a convenient solution for arbitrary surface fluxes before ponding. By means of Fourier Transformation this has been extended to derive analytical solutions of a linearized Richards' equation for arbitrary input fluxes after surface saturation. Copyright © 2003 John Wiley & Sons, Ltd.     

Peak metamorphic temperatures in type 6 ordinary chondrites: An evaluation of pyroxene and plagioclase geothermometry

Abstract— Quantifying the peak temperatures achieved during metamorphism is critical for understanding the thermal histories of ordinary chondrite parent bodies. Various geothermometers have been used to estimate equilibration temperatures for chondrites of the highest metamorphic grade (type 6), but results are inconsistent and span hundreds of degrees. Because different geothermometers and calibration models were used with different meteorites, it is unclear whether variations in peak temperatures represent actual ranges of metamorphic conditions within type 6 chondrites or differences in model calibrations. We addressed this problem by performing twopyroxene geothermometry, using QUILF95, on the same type 6 chondrites for which peak temperatures were estimated using the plagioclase geothermometer (Nakamuta and Motomura 1999). We also calculated temperatures for published pyroxene analyses from other type 6 H, L, and LL chondrites to determine the most representative peak metamorphic temperatures for ordinary chondrites. Pyroxenes record a narrow, overlapping range of temperatures in H6 (865–926 °C), L6 (812–934 °C), and LL6 (874–945 °C) chondrites. Plagioclase temperature estimates are 96–179 °C lower than pyroxenes in the same type 6 meteorites. Plagioclase estimates may not reflect peak metamorphic temperatures because chondrule glass probably recrystallized to plagioclase prior to reaching the metamorphic peak. The average temperature for H, L, and LL chondrites (～900 °C), which agrees with previously published oxygen isotope geothermometry, is at least 50 °C lower than the peak temperatures used in current asteroid thermal evolution models. This difference may require minor adjustments to thermal model calculations.     

Palaeoenvironmental significance of Late Permian palaeosols in the South‐Eastern Iberian Ranges,Spain

The Late Permian (Wuchiapingian) Alcotas Formation in the SE Iberian Ranges consists of one red alluvial succession where abundant soil profiles developed. Detailed petrographical and sedimentological studies in seven sections of the Alcotas Formation allow six different types of palaeosols, with distinctive characteristics and different palaeogeographical distribution, to be distinguished throughout the South‐eastern Iberian Basin. These characteristics are, in turn, related to topographic, climatic and tectonic controls. The vertical distribution of the palaeosols is used to differentiate the formation in three parts from bottom to top showing both drastic and gradual vertical upwards palaeoenvironmental changes in the sections. Reconstruction of palaeoenvironmental conditions based on palaeosols provides evidence for understanding the events that occurred during the Late Permian, some few millions of years before the well‐known Permian‐Triassic global crisis.     

Methane‐related microbial gypsum calcitization in stromatolites of a marine evaporative setting (Münder Formation,Upper Jurassic,Hils Syncline,north Germany)

Fossil stromatolites may reveal information about their hydrochemical palaeoenvironment, provided that assignment to a specific microbial community and a corresponding biogeochemical mechanism of formation can be made. Tithonian stromatolites of the Münder Formation at Thüste, north Germany, have traditionally been considered as formed by intertidal cyanobacterial communities. However, thin sections of the stromatolites show elongated angular traces of former gypsum crystals in a dense arrangement, but no algal or cyanobacterial filament traces. Moreover, high Fe²⁺ and Mn²⁺ contents, oxygen‐isotope and sulphur‐isotope ratios of carbonate‐bound sulphates, and sulphurized hydrocarbon biomarkers of the stromatolitic carbonate indicate that CaCO₃ precipitation occurred near the oxic–anoxic interface as a result of intensive bacterial sulphur cycling rather than photosynthetic activity. Furthermore, anaerobic oxidation of methane by Archaea may have driven CaCO₃ precipitation in deeper parts of the biofilm community, as reflected by high concentrations of squalane with a strongly negative δ¹³C in conjunction with evaporite pseudomorphs showing extremely low δ¹³C_Carb ratios. Consequently, the Thüste stromatolites are now interpreted as having initially formed by gypsum impregnation of biofilms. Subsequently, early Mg‐calcitic calcitization within the biofilms occurred because of combined bacterial iron, manganese and sulphate reduction, with an increasing contribution of anaerobic oxidation of methane with depth. This model plausibly explains the prominent preservation of signals derived from oxygen‐independent metabolic pathways, whereas virtually no geochemical record exists for an aerobic community that may, nevertheless, have prevailed at the stromatolite surface. Photic‐zone stromatolites with a prominent signal of anaerobic oxidation of methane may be common in, and indicative of, oxygen‐depleted sulphate‐bearing environments with high rates of methane production, conditions that possibly were fulfilled at the Archaean to Proterozoic transition.     

Diagenesis, palaeoclimate and tectono-sedimentary influences on clay mineralogy and stable isotopes from Upper Cretaceous marine successions of the Basque-Cantabrian Basin (N Spain)

Clay mineralogy and whole-rock stable isotopes (δ¹⁸O and δ¹³C) of Upper Cretaceous marly sediments on the Basque-Cantabrian Basin have been integrated to determine the main effects of diagenesis, palaeoclimate and tectono-sedimentary factors in sections belonging to deep- (Barrika) and platform-marine (Isla de Castro, Villamartín and Olazagutía) settings.The mean values for the clay assemblages and δ¹⁸O exhibit notable differences among the sections, partially explainable by the influence of diagenesis. The Barrika sediments, with more diagenetically advanced illite-smectite (I-S) mixed-layer (R1, 70% illite), authigenic chlorite, and low δ¹⁸O (−4.05‰ PDB), experienced higher diagenetic grade than Isla de Castro and Olazagutía, which have R0 I-S (20% illite) and heavier δ¹⁸O. Villamartín was also affected by higher diagenesis than Isla de Castro and Olazagutía, given the occurrence of R1 I-S (60% illite) and low δ¹⁸O (−4.11‰ PDB). However, the absence of other clays in Villamartín (e.g. authigenic chlorite) is indicative of less diagenetic grade than Barrika. These results show the useful integration of clay mineralogy and stable isotopes to detect different diagenetic grades in distinct marine successions of the same basin.Despite being influenced by diagenesis, the clay mineralogy partially preserves its inherited signature. This allows detection of major contents of I-S and mica, and minor kaolinite, interpreted as indicative of warm palaeoclimatic conditions. High kaolinite content in Villamartín and absence of kaolinite in Isla de Castro, though, are considered to be a product of neither diagenesis nor palaeoclimatic influences. Instead, tectono-sedimentary causes, related to unsuitable conditions for clay formation and transport from the local source areas, contributed to original clay differences. The inferred effects of diagenesis, palaeoclimate and tectono-sedimentary factors make this work important to show the potentially great variety of controls on the clay mineralogy of marine sections, which are often uncritically treated in studies concerning the Late Cretaceous.     

Origins of high pH mineral waters from ultramafic rocks, Central Portugal

This paper reviews the geochemical, isotopic (²H, ¹⁸O, ¹³C, ³H and ¹⁴C) and numerical modelling approaches to evaluate possible geological sources of the high pH (11.5)/Na–Cl/Ca–OH mineral waters from the Cabeço de Vide region (Central-Portugal). Water–rock interaction studies have greatly contributed to a conceptual hydrogeological circulation model of the Cabeço de Vide mineral waters, which was corroborated by numerical modelling approaches. The local shallow groundwaters belong to the Mg–HCO₃ type, and are derived by interaction with the local serpentinized rocks. At depth, these type waters evolve into the high pH/Na–Cl/Ca–OH mineral waters of Cabeço de Vide spas, issuing from the intrusive contact between mafic/ultramafic rocks and an older carbonate sequence. The Cabeço de Vide mineral waters are supersaturated with respect to serpentine indicating that they may cause serpentinization. Magnesium silicate phases (brucite and serpentine) seem to control Mg concentrations in Cabeço de Vide mineral waters. Similar δ²H and δ¹⁸O suggest a common meteoric origin and that the Mg–HCO₃ type waters have evolved towards Cabeço de Vide mineral waters. The reaction path simulations show that the progressive evolution of the Ca–HCO₃ to Mg–HCO₃ waters can be attributed to the interaction of meteoric waters with serpentinites. The sequential dissolution at CO₂ (g) closed system conditions leads to the precipitation of calcite, magnesite, amorphous silica, chrysotile and brucite, indicating that the waters would be responsible for the serpentinization of fresh ultramafic rocks (dunites) present at depth. The apparent age of Cabeço de Vide mineral waters was determined as 2790 ± 40 a BP, on the basis of ¹⁴C and ¹³C values, which is in agreement with the ³H concentrations being below the detection limit.     

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.     

The spatial implications of the functional proximity deriving from air passenger flows between European metropolitan urban regions

Until recently the traditional spatial configuration of the European geography was based upon the core-periphery model. The ‘pentagon’, broadly defined as lying between London, Paris, Milan, Munich and Hamburg, was seen as the core area characterised by having the highest concentration of economic development in the European Union (EU), with the remainder of the European territory viewed as peripheral, albeit to varying degrees. In a number of cases such peripheral areas equated with clear regional disparities. The elaboration of the European Spatial Development Perspective (ESDP) (CEC, European spatial development perspective, towards balanced and sustainable development in the territory of the European Union, 1999) challenged this core-periphery model. European spatial planning policies, aimed at encouraging social and economic, and with ever increasing importance, territorial cohesion, seek amongst other aspects to encourage the development of a balanced and polycentric urban system. This paper adopts a network analysis approach to the analysis of air passenger flows between some 28 principal European metropolitan urban regions. The evaluation of these flows contributes to an enhanced comprehension of the spatial dynamics of the European metropolitan territory which goes beyond that deriving from the more standard analyses of the individual components of the urban system. Several indicators are used, deriving from gravitational modelling techniques, to analyse the complexity of the air passenger flows. A multidimensional scaling (MDS) technique is introduced in order to interpret and visualise the resulting spatial configuration and positioning of the different metropolitan centres within the conceptual European ‘space of air passenger flows’, thereby contrasting with the more traditional map-based geographical image of Europe, based upon Cartesian coordinates.

Numerical estimation of REV and permeability tensor for fractured rock masses by composite element method

The Monte Carlo method is used to generate parent stochastic discrete fracture network, from which a series of fractured rock samples of different sizes and orientations are extracted. The fracture network combined with a regular grid forms composite element mesh of the fractured rock sample, in which each composite element is composed of sub‐elements incised by fracture segments. The composite element method (CEM) for the seepage is implemented to obtain the nodal hydraulic potential as well as the seepage flow rates through the fractured rock samples. The application of CEM enables a large quantity of stochastic tests for the fractured rock samples because the pre‐process is facilitated greatly. By changing the sizes and orientations of the samples, the analysis of the seepage characteristics is realized to evaluate the variation of the permeability components, the existence of the permeability tensor and the representative element volume. The feasibility and effectiveness are illustrated in a numerical example. Copyright © 2008 John Wiley & Sons, Ltd.