Karst morphology and groundwater vulnerability of high alpine karst plateaus

High alpine karst plateaus are recharge areas for major drinking water resources in the Alps and many other regions. Well-established methods for the vulnerability mapping of groundwater to contamination have not been applied to such areas yet. The paper characterises this karst type and shows that two common vulnerability assessment methods (COP and PI) classify most of the areas with high vulnerability classes. In the test site on the Hochschwab plateau (Northern Calcareous Alps, Austria), overlying layers are mostly absent, not protective or even enhance point recharge, where they have aquiclude character. The COP method classifies 82% of the area as highly or extremely vulnerable. The resulting maps are reasonable, but do not differentiate vulnerabilities to the extent that the results can be used for protective measures. An extension for the upper end of the vulnerability scale is presented that allows identifying ultra vulnerable areas. The proposed enhancement of the conventional approach points out that infiltration conditions are of key importance for vulnerability. The method accounts for karst genetical and hydrologic processes using qualitative and quantitative properties of karst depressions and sinking streams including parameters calculated from digital elevations models. The method is tested on the Hochschwab plateau where 1.7% of the area is delineated as ultra vulnerable. This differentiation could not be reached by the COP and PI methods. The resulting vulnerability map highlights spots of maximum vulnerability and the combination with a hazard map enables protective measures for a manageable area and number of sites.     

Quartz Reference Materials for Oxygen Isotope Analysis by SIMS

Two quartz samples of igneous origin, UNIL‐Q1 (Torres del Paine Intrusion, Chile) and BGI‐Q1 (Shandong province, China), were calibrated for their oxygen isotope composition for SIMS measurements. UNIL‐Q1 and BGI‐Q1 were evaluated for homogeneity using SIMS. Their reference δ¹⁸O values were determined by CO₂ laser fluorination. The average δ¹⁸O value found for UNIL‐Q1 is 9.8 ± 0.06‰ and that for BGI‐Q1 is 7.7 ± 0.11‰ (1s). The intermediate measurement precision of SIMS oxygen isotope measurements was 0.32–0.41‰ (2s; UNIL‐Q1) and 0.40–0.48‰ (2s; BGI‐Q1), respectively. While less homogeneous in its oxygen isotope composition, BGI‐Q1 is also suitable for SIMS trace element measurements.     

The polarization of decimetric pulsations

A sample of 10 decimetric broadband pulsations were observed in 1980–1983 and analyzed in polarization. Half of the data set was 85–100% circularly polarized, the other half showed a mild polarization of 15–55%. The polarization is constant in time and frequency for the strongly polarized group. All the mildly polarized bursts originate from near the limb; the lower degree of circular polarization is likely to be caused by depolarization due to propagation effects. The degree of polarization is constant throughout the event, but varies in frequency for the mild polarized group. Following the leading spot hypothesis, the magneto-ionic mode of the emission was found to be extraordinary. The high circular polarization of the pulsations was interpreted to be determined by the emission mechanism itself, not by propagation effects or cut-offs (contrary to the metric type I noise storms). Implications for pulsation models are discussed.Proceedings of the Workshop on Radio Continua during Solar Flares, held at Duino (Trieste), Italy, 27–31 May, 1985.     

A Comparative Analysis of Favorability Mappings by Weights of Evidence,Probabilistic Neural Networks,Discriminant Analysis,and Logistic Regression

This study compares the performance of favorability mappings by weights of evidence (WOE), probabilistic neural networks (PNN), logistic regression (LR), and discriminant analysis (DA). Comparisons are made by an objective measure of performance that is based on statistical decision theory. The study further emphasizes out-of-sample inference, and quantifies the extent to which outcome is influenced by optimum variable discretization with classification and regression trees (CARTS).Favorability mapping methodologies are evaluated systematically across three case studies with contrasting scale and geologic information:

Eine Uranerzlagerstätte in permotriadischen Sedimenten Tirols

Zusammenfassung Im Zuge lagerstättenkundlicher Untersuchungen in der Nördlichen Grauwackenzone Tirols konnten im nördlich vorgelagerten und primär mit dem Paläozoikum im Zusammenhang stehenden permotriadischen Sedimentstreifen lokal lagerstättenbildende Uran-Thorium-Anreicherungen festgestellt werden. Im Gebiet südlich von Fieberbrunn-Hochfilzen enthalten, dem Bundsandstein zugehörige, feinkörnige graue Quarzpsammite und quarzsandige Serizitpsammopelite an Pflanzenreste gebundene Pechblende, häufig begleitet von Pyrit, Markasit und Kupferkies. Die Erzminerale treten imprägnationsähnlich in den permoskytischen Sedimenten auf und werden als authigene Bildungen durch syndiagenetische chemische Anlagerung gedeutet. Im Nebengestein treten lagenweise auch syndiagenetische Magnesitbildungen auf.Erzminerale sowie detritische und authigene Gesteinskomponenten wurden alpidisch durchbewegt und reagierten unterschiedlich, nämlich durch Formung im Feinbau oder durch Kataklase. Postdeformative Neubildungen, zum Teil verbunden mit lokalen Stoffwanderungen und Rekristallisationen, sind an Gesteins- und Erzmineralen festzustellen.Herkunftsgebiete des Urans sind in den heute aufgeschlossenen Arealen bisher nicht bekannt. Für die Kupfererze jedoch ergeben sich wahrscheinliche Beziehungen zu voralpidischen, paläozoischen Kupfermineralisationen, die innerhalb der Grauwackenzone mit zahlreichen Lagerstätten vertreten sind.An sekundären Mineralien finden sich Goethit, Lepidokrokit, Digenit, Covellin, Cuprit, gediegen Kupfer, Malachit sowie Zippeit als Uranabkömmling.Die Verbreitung der in einigen Schichtbänken des Sandsteinhorizontes auftretenden U-Th-Anreicherung ist bisher auf 10 km streichende Distanz bekannt. Wenn auch über die stratigraphische Lagekonstanz und über Schwankungen der Radioaktivität infolge spärlicher Geländeaufschlüsse vorläufig noch keine wirtschaftlich brauchbaren Aussagen gemacht werden können, kann immerhin von der ersten in Österreich nachgewiesenen Uranlagerstätte gesprochen werden, in der punktförmige lokale U-Anreicherungen von 1% (=10.000 ppm), in einem Einzelfall 2% U, nachgewiesen sind.

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A uranium deposit in permotriassic sediments in the province of Tyrol, Austria

Summary During an investigation of the mineral deposits in the Northern Grauwackenzone of the Tyrol, zones of uranium-thorium enrichment were detected in the Permotriassic sediments unconformably overlying the Paleozoic sequence. In the area south of Fieberbrunn-Hochfilzen pitchblende (parapitchblende) associated with plant remains was found in fine-grained grey sandstones and sericitic sandy shales. The pitchblende frequently occurs together with pyrite, marcasite and chalcopyrite. All these minerals are found in Permoskytic sediments in a form similar to impregnation. They are regarded as being authigenic having formed by syndiagenetic chemical deposition. Nearby country rock contains beds of syndiagenetic magnesite.During the Alpine orogenesis the ore minerals as well as the detrital and authigenic rock components underwent deformation of the lattice structure or cataclastic processes. Post-tectonic processes resulted in mobilization and recrystallization of the rock and ore minerals.The source areas of the uranium are not yet known. The copper ores may be related to Pre-alpidian Paleozoic copper mineralizations. Numerous deposits containing such copper mineralizations are found in the Grauwackenzone.Goethite, lepidocrocite, digenite, covellite, cuprite, copper, malachite, and zippeite were found as secondary minerals.The distribution of the U-Th enrichment is observed in some beds of the sandstone horizon over a distance of 10 km along strike. At the present time no economic conclusions can be drawn as to the stratigraphic extent and fluctuations of radioactivity; however, this occurrence can be described as the first uranium deposit in Austria where very local U-concentrations of 1% (=10.000 ppm), in a single case 2% U, have been measured.

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pH changes in peralkaline late-magmatic fluids

The 1.15-Ga-old Ilimaussaq intrusive complex in South Greenland shows an extensive fractionation trend from alkaline augite syenite to various varieties of strongly peralkaline, agpaitic nepheline syenites. The peralkaline nepheline-bearing syenites crystallized between ca. 900 and 450 °C at 1 kbar and they are cut by late-magmatic hydrothermal veins with nepheline-absent assemblages of albite + aegirine + analcime - sodalite - Na-Be-silicates (tugtupite, chkalovite, sørensenite) - ussingite (NaAlSi₃O₈*NaOH). Based on fluid inclusions and phase equilibria, these veins crystallized between 300 and 500 °C at 1 kbar. Textures indicate that the hydrothermal veins at least partly replaced earlier Ilimaussaq rocks. The occurrence of ussingite and tugtupite suggests that the late-magmatic fluids had strongly basic pH values. Speciation calculations show that the pH in fluids of the system Na-Al-Si-O-H-Cl mainly depends on the Na/Cl ratio and, to a lesser degree, on salinity and temperature. If the Na/Cl ratio is greater than 1, pH (at 400 °C and 1 kbar, where neutrality is about at pH 5) lies between 7 and 12. Because Na/Cl tends to decrease in the final stages of magmatism and during crystallization of the vein assemblage, pH of late-magmatic fluids generally should become more acidic, and only two processes can increase Na/Cl and, thus, pH: dissolution of a Cl-poor or Cl-free Na silicate or unmixing of an HCl-enriched vapour phase. Field observations and microtextures suggest that replacement reactions are responsible for the change to basic pH at least in some alteration assemblages. While replacement of 1 mol nepheline by 1 mol analcime would not alter the pH, the volume-conserving reaction 1.85  Ne + 2.3  H₂ O + 0.19  H₄ SiO₄ = 1.02  Anl + 0.83   Na⁺ + 0.83  Al(OH)₄^-1.85\;{\rm Ne} + 2.3\;{\rm H}_{\rm 2} {\rm O} + 0.19\;{\rm H}_{\rm 4} {\rm SiO}_4 = 1.02\;{\rm Anl} + 0.83\,\;{\rm Na}^ + + 0.83\;{\rm Al(OH)}_4^ - can be used to model the replacement process quantitatively, provided it occurred in a more or less closed system. Progress of this reaction leads to successively increasing pH of the fluid during fluid-rock interaction and stabilizes minerals such as ussingite and tugtupite. Transferring the two processes to a larger scale, it is proposed that the extreme 'hyper-agpaitic' assemblages at Ilimaussaq or at the Kola peninsula, which include copious amounts of very basic, water-soluble minerals such as trona, villiaumite or thermonatrite, are formed either in this way by autometasomatic reactions of late-magmatic fluids or melts (or supercritical fluid-melt-mixtures) with earlier crystallized rocks of the same plutonic complex or by large-scale vapour unmixing in the very final stages of magmatism.     

Solubility of the assemblage albite+K-feldspar+andalusite+quartz in supercritical aqueous chloride solutions at 650 °C and 2 kbar

The solubility of the high grade pelite assemblage albite+K-feldspar+andalusite+quartz at 650 °C and 2 kbar was determined in aqueous solutions over a total chloride range of 0.01–3 m_Cl^tot using rapid-quench hydrothermal technique. The concentration of Na, K, Si, and Al was determined in the fluid phase after quench. The K/Na ratio was determined by approaching the equilibrium from below and above. It is 0.34 at low chloride concentrations and decreases slightly to 0.31 with increasing total chloride. Silica and aluminum concentrations were determined only from undersaturation. The silica solubility is found to be independent of chloride concentration and is 0.13 molal. Aluminum is nearly independent of chloride concentration decreasing only slightly from 0.0015 to 0.0007 molal. Comparison of the experimental data with thermodynamic model calculations demonstrates that the silica concentrations are well predicted, while significant differences exist between individual databases for Al speciation and its total concentration. Al concentrations are underestimated by up to 10 to 15 orders of magnitude using the SUPCRT92 database. Predicted K/Na ratios are underestimated by up to 30%. The best predictions achieved for this simplified high-grade pelite assemblage are those using the SUPCRT92 database with revised thermodynamic data for feldspars and K- and Na-species (J. Phys. Chem. Ref. Data 24 (1995) 1401) and additional Al-species (Am. J. Sci. 295 (1995) 1255; Geochim. Cosmochim. Acta 61 (1997) 2175). The use of ideal mixing for neutral complexes in combination with the extended Debye–Hückel activity model for the charged species yields the most compatible speciation model.     

Factors controlling carbonate dissolution rates quantified in a field test in the Austrian alps

Carbonate dissolution rates were investigated by measuring the mass difference of carbonate tablets exposed to natural dissolution for 1 year. 70 tablets were distributed over 13 test sites on the north slope of the Hochschwab Massif in the Austrian Alps. The influences of altitude, subsoil vs. sub-aerial exposure, vegetation, karst morphology, soil humidity, sample lithology, and sample surface morphology were investigated. The observed dissolution rates varied between 13 and 40 μm/a for subcutaneous samples and about 11 μm/a for sub-aerial exposure. Outstandingly high rates of 48 μm/a were observed in a doline and nearly zero rates were measured at a site influenced by seeping spring water.A mass balance, using high-resolution hydrological data, was calculated for the Kläffer Spring, which has an average outflow of 4.8 m³/s. It indicated a loss of 21×10⁶ kg of carbonate rock per year which gives an average dissolution rate of 95 μm/a for the catchment area of 83 km². The dissolution rates of 10 μm/a from the sub-aerially exposed samples are comparable to values from limestone pedestals, which were protected from dissolution by glacial erratics for the past 15 ka.     

Drought 2002 in Colorado: An Unprecedented Drought or a Routine Drought?

The 2002 drought in Colorado was reported by the media and by public figures, and even by a national drought-monitoring agency, as an exceptionally severe drought. In this paper we examine evidence for this claim. Our study shows that, while the impacts of water shortages were exceptional everywhere, the observed precipitation deficit was less than extreme over a good fraction of the state. A likely explanation of this discrepancy is the imbalance between water supply and water demand over time. For a given level of water supply, water shortages become intensified as water demands increase over time. The sobering conclusion is that Colorado is more vulnerable to drought today than under similar precipitation deficits in the past.     

The large-scale context for the TOGA Coupled Ocean-Atmosphere Response Experiment

Summary The TOGA Coupled Ocean-Atmosphere Response Experiment (COARE) concentrated a variety of observational systems in the warm pool of the western equatorial Pacific for an Intensive Observation Period (IOP) November 1992 through February 1993. In this paper, aspects of the largescale variations of the tropical atmosphere and Pacific Ocean surrounding the observations of air-sea interaction in the Intensive Flux Array (IFA) during the IOP are described, with the objective of providing a context for the future analyses of these observations.The evolution of the 1991–1992 El Niño/Southern Oscillation event was unusual: Warm SST anomalies in the equatorial cold tongue region switched to colder than climatology in the last half of 1992, but waters warmer than 30°C remained displaced eastward just west of the dateline, coninuing to fuel anomalous convection there during the IOP. Fortunately, SST in the IFA remained warmer than 29°C during most of the IOP, and convective activity was observed over the IFA. The Southern Oscillation Index, which had relaxed to near zero prior to the experiment, decreased during the IOP, reflecting sea level presure changes associated with renewed westerly wind activity. In response to these westerly wind events, the warm pool migrated back into the central equatorial Pacific, leading to a reintensification of the ENSO warm SST anomalies east of the dateline.With 10 Figures