Identifying low-temperature hydrothermal karst and palaeowaters using stable isotopes: a case study from an alpine cave,Entrische Kirche,Austria

The area south of the prominent east–west trending Salzach Valley at the northern rim of the Central Alps of Austria has long been known to host anomalously warm springs emerging from a highly deformed calcite marble (Klammkalk). This unit also hosts cavities whose shapes suggest a hydrothermal karst origin and which are lined by calcite spar. We report here petrographic and isotopic evidence suggesting that dissolution by ascending low-temperature thermal waters also played an important role in the origin of a large cave in this region, Entrische Kirche. A paleo cave wall, preserved behind a thick flowstone in the interior of this cave, revealed a brownish bleaching zone which contrasts to the medium grey colour of the unaltered marble beneath. Across this zone the C and O isotope values gradually decrease by 3 and 11‰, respectively. These compositions are very different from those of the speleothem above but are similar to phreatic calcite spar from hydrothermal karst cavities in other outcrops in the area, where the absence of two-phase fluid inclusions suggests a low-temperature (less than ca. 50°C) hydrothermal origin. U/Th dating of the flowstone capping the alteration zone yielded a minimum age of the thermal water invasion in Entrische Kirche of ca. 240 kyr. There is no evidence in Entrische Kirche that these palaeowaters reached the point of calcite precipitation, but it is physically conceivable that higher and as yet unexplored parts of this deep (ca. 900 m) cave contain cavities lined by phreatic cave spar.     

Complex zoning and resorption in Breunnerite from hall in Tyrol,Austria: Evidence from back-scattered electron microscopy

Summary Back-scattered electron imagery (BSE) coupled with energy-dispersive X-ray elemental analysis was applied to petrographic investigations of recrystallized, anchimetamorphic breunnerites (ferroan magnesites). Analyses of polished thin sections allowed the recognition of a complex zoning pattern, invisible by transmitted or reflected light microscopy. Breunnerite precipitation and replacement started with (Mg_0.90Fe_0.07Ca_0.01Mn_0.02) CO₃ and proceeded towards (Mg_0.73Fe_0.22Ca_0.00Mn_0.05)CO₃. This precipitation sequence was interrupted by at least two major events of reverse zoning (i.e. Fe-rich zones followed by Fe-poor ones). Resorption surfaces in Fe-poor zones are common and prove that short-term fluctuations occurred in the paleobrine composition and/or paleotemperature.

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Nachweis komplexer zonierung und resorption im breunnerit mittels Rückstreuelektronenbilder

Zusammenfassung Breunnerit-Proben von der Typlokalität evaporitischer Magnesitlagerstätten (ehemaliger Salzbergbau Hall in Tirol/Österreich) wurden an Hand von Rückstreuelektronen(BSE)-Bildern und energiedispersiven Röntgenanalysen (EDS) untersucht. Während Durch- und Auflichtmikroskopie lediglich eine zweiphasige Kristallisationsgeschichte erkennen ließen, konnte mittels BSE-Bildern eine detaillierte Rekonstruktion der spätdiagenetischen bzw. anchimetamorphen Breunneritbildung durchgeführt werden. Ein genereller Trend zu Fe-reicheren, häufig oszillierend-zonierter Mischkristalle der Reihe Magnesit-Siderit konnte erkannt werden, der jedoch von mindestens zwei invers zonierten Phasen unterbrochen wurde. Resorptionserscheinungen in den Fe-ärmeren Zonen sind verbreitet und belegen kurzfristige Fluktuationen in der Paläofluid-Zusammensetzung und/oder dessen Paläotemperatur.

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With 5 Figures     

探测冰盖和多年冻土层的融冰探头研发

The exploration of ice sheets by melting vertical holes into the ground has some tradition in terrestrial glaciology. Such probes have been used since the 1960's to investigate the vertical structure of the ice in Greenland and Antarctica and in alpine glaciers. In this paper we look into the possibility to develop similar devices for use on extraterrestrial icy bodies, like e.g. the polar areas on Mars or the icy satellites of the outer solar system. We report on some basic experiments performed in the cryo-vacuum laboratory of the Space Research Institute of the Austrian Academy of Sciences, Graz. In these experiments the penetration of a simple melting probe into compact and porous water ice (with a snow-like texture) was monitored, both under vacuum conditions and under air pressure. The observed penetration speeds for a given power supply are compared with a simple mathematical model. We conclude that a miniature melting probe with small overall dimensions and a reasonable power demand could well be part of the payload of a future planetary mission, for example to the poles of Mars. Such missions are currently under discussion in several space agencies. Moreover such probes could also e? ectively be used in terrestrial environments. A possible design is presented at the end of the paper.     

The thermodynamic properties of H2O in magnesium and iron cordierite

 The equilibrium water content of cordierite has been measured for 31 samples synthesized at pressures of 1000 and 2000 bars and temperatures from 600 to 750° C using the cold-seal hydrothermal technique. Ten data points are presented for pure magnesian cordierite, 11 data points for intermediate iron/magnesium ratios from 0.25 to 0.65 and 10 data points for pure iron cordierite. By representing the contribution of H₂O to the heat capacity of cordierite as steam at the same temperature and pressure, it is possible to calculate a standard enthalpy and entropy of reaction at 298.18° K and 1 bar for, (Mg,Fe)₂Al₄Si₅O₁₈+H₂O ⇄ (Fe,Mg)₂Al₄Si₅O₁₈.H₂O Combining the 31 new data points with 89 previously published experimental measurements gives: ΔH ^° _r =–37141±3520 J and ΔS ^° _r =–99.2±4 J/degree. This enthalpy of reaction is within experimental uncertainty of calorimetric data. The enthalpy and entropy of hydration derived separately for magnesian cordierite (–34400±3016 J, –96.5±3.4 J/degree) and iron cordierite (–39613±2475, –99.5±2.5 J/degree) cannot be distinguished within the present experimental uncertainty. The water content as a function of temperature, T(K), and water fugacity, f(bars), is given by n _H2O=1/[1+1/(K ⋅ f _H2O)] where the equilibrium constant for the hydration reaction as written above is, ln K=4466.4/T–11.906 with the standard state for H₂O as the gas at 1 bar and T, and for cordierite components, the hydrous and anhydrous endmembers at P and T. Received: 2 August 1994/Accepted: 7 February 1996     

Hydrothermal alteration and zeolitization of the Fohberg phonolite,Kaiserstuhl Volcanic Complex,Germany

The subvolcanic Fohberg phonolite (Kaiserstuhl Volcanic Complex, Germany) is an economic zeolite deposit, formed by hydrothermal alteration of primary magmatic minerals. It is mined due to the high (>40 wt%) zeolite content, which accounts for the remarkable zeolitic physicochemical properties of the ground rock. New mineralogical and geochemical studies are carried out (a) to evaluate the manifestation of hydrothermal alteration, and (b) to constrain the physical and chemical properties of the fluids, which promoted hydrothermal replacement. The alkaline intrusion is characterized by the primary mineralogy: feldspathoid minerals, K-feldspar, aegirine–augite, wollastonite, and andradite. The rare-earth elements-phase götzenite is formed during the late-stage magmatic crystallization. Fluid-induced re-equilibration of feldspathoid minerals and wollastonite caused breakdown to a set of secondary phases. Feldspathoid minerals are totally replaced by various zeolite species, calcite, and barite. Wollastonite breakdown results in the formation of various zeolites, calcite, pectolite, sepiolite, and quartz. Zeolites are formed during subsolidus hydrothermal alteration (<150 °C) under alkaline conditions. A sequence of Ca–Na-dominated zeolite species (gonnardite, thomsonite, mesolite) is followed by natrolite. The sequence reflects an increase in \(\log [(a_{{{\text{Na}}^{ + } }} )/(a_{{{\text{H}}^{ + } }} )]\) and decrease in \(\log [(a_{{{\text{Ca}}^{2 + } }} )/(a_{{{\text{H}}^{ + } }}^{2} )]\) of the precipitating fluid. Low radiogenic ⁸⁷Sr/⁸⁶Sr values indicate a local origin of the elements necessary for secondary mineral formation from primary igneous phases. In addition, fractures cut the intrusive body, which contain zeolites, followed by calcite and a variety of other silicates, carbonates, and sulfates as younger generations. Stable isotope analysis of late-fracture calcite indicates very late circulation of meteoric fluids and mobilization of organic matter from surrounding sedimentary units.     

Mica-feldspar equilibria in supercritical alkali chloride solutions

The equilibrium position of the reaction $$\begin{gathered} 1.5 KAlSi_3 O_8 + HCl = 0.5 KAl_3 Si_3 O_{10} (OH)_2 \hfill \\ + 3SiO_2 + KCl \hfill \\ \end{gathered} $$ has been located at 1 and 2 kb pressure and temperatures between 600° and 670° C using the Ag-AgCl buffer. These data can be combined with information on the dissociation of KC1, HC1 and H₂O to determine species abundances in supercritical aqueous fluids in equilibrium with muscovite — K-feldspar — quartz assemblages. Chloride species become increasingly associated with increasingT, increasing total molality, (m _tot or \(m_{Cl_{tot} } \) ), and decreasing \(P_{H_2 O} \) . Master variable diagrams indicate that the pH of the solutions may vary from near neutral to quite acid. Published data on the paragonite-albite-quartz reaction and exchange reactions involving feldspars and micas were included to calculate speciation in mica-feldspar-NaCl-KCl-HCl-H₂O fluids at 2kb pressure and temperatures between 300° and 600° C. The data are not accurate enough to distinguish different feldspar structural states. Concentration gradients were calculated for individual species between K-feldspar+quartz, muscovite+quartz and andalusite+quartz assemblages at 500° C, 2 kb. Assuming that the proton diffuses most rapidly and that there are no [H⁺] gradients, the molality of the solution must vary 30-fold, with feldspar+quartz at the more concentrated side. The data on mica-feldspar-chloride equilibria are used to interpret the spacial distribution of micas, feldspar and quartz in microfolds. This distribution can be accounted for by pressure solution, due to the fact that non-hydrostatic pressure affects congruently dissolving minerals, auch as quartz, differently from minerals which dissolve incongruently, such as micas and feldspars. We postulate, that during folding at constant \(P_{H_2 O} \) ,T and \(m_{Cl - } \) , gradients in KC1 and SiO₂ are created by stress differences between hinge and limb of a microfold, such that both migrate to the hinge area where quartz precipitates and muscovite is converted to K-felspar, thus accounting for the observed mineral distribution.     

Lithospheric thickness beneath the southern Kenya Rift: implications from basalt geochemistry

Geochemical data are reported for samples from the flanks and floor of the southern Kenya Rift Valley in the Lake Magadi area, and from two central volcanoes located within the rift valley. Rift lavas include samples of Singaraini and Ol Tepesi basalts on the eastern flank, Kirikiti basalts from the western flank, and plateau trachytes from the rift valley floor. Central volcano samples are from Ol Esayeiti and Lenderut located on the eastern flank. The rift basalts are mildly ne-normative, moderately evolved (Mg#=0.39-0.62) alkali basalts and show an overall range in differentiation. Incompatible trace element abundances are moderately elevated (Nb=17-51; Zr=93-274; La=17-55 ppm) and show strongly coherent variations and constant inter-element ratios (e.g. Zr/Nb=4.2-5.5; Nb/Ta=17.5ǂ.4; (La/Sm)_n=7.3ǃ.1); isotope ratios are restricted in range (⁸⁷Sr/⁸⁶Sr=0.70393-0.70436; ¹⁴³Nd/¹⁴⁴Nd=0.51272-0.51280; ²⁰⁶Pb/²⁰⁴Pb=19.87-19.92; ²⁰⁷Pb/²⁰⁴Pb=15.68-15.70; ²⁰⁸Pb/²⁰⁴Pb=39.56-39.71). Central volcano lavas are more alkaline in character and include basanite (Ol Esayeiti; Mg# >60) and hawaiite to benmoreite (Lenderut; Mg#=0.48-0.38). Incompatible element ratio are similar to those of the rift basalts, although the chondrite normalised REE patterns are steeper (La/Sm)_n=17.4ǃ.2). ⁸⁷Sr/⁸⁶Sr (0.70358, 0.70391), ¹⁴³Nd/¹⁴⁴Nd (0.51280, 0.51267), ²⁰⁶Pb/²⁰⁴Pb (19.96,20.17), ²⁰⁷Pb/²⁰⁴Pb (15.66,15.76) and ²⁰⁸Pb/²⁰⁴Pb (39.80,40.00) ratios of Ol Esayeiti basanites are similar to the rift basalts, whereas the Lenderut lavas have unusually low¹⁴³Nd/¹⁴⁴Nd (0.512388-0.512453) ratios for their ⁸⁷Sr/⁸⁶Sr (0.70370-0.70481) ratios, and distinctly less radiogenic and variable Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb=17.93-19.01; ²⁰⁷Pb/²⁰⁴Pb=15.43-15.58; ²⁰⁸Pb/²⁰⁴Pb=37.91-39.14). An integrated model is developed in which the geochemical signature of the lavas is attributed to variable degrees of melting to depths within the garnet stability field, and in the presence of residual amphibole. The stability fields of these phases in P-T space indicates that the lavas must have formed within the sub-continental lithosphere rather than within the underlying ambient asthenosphere or a rising mantle plume. The subcontinental lithospheric mantle must therefore extend to a depth of at least 75 km beneath the Lake Magadi area, which contrasts with recent gravity models for the area, which infer that lithospheric mantle is absent beneath this section of the southern Kenya Rift.     

A Comparison of Global and Regional GRACE Models for Land Hydrology

When using GRACE as a tool for hydrology, many different gravity field model products are now available to the end user. The traditional spherical harmonics solutions produced from GRACE are typically obtained through an optimization of the gravity field data at the global scale, and are generated by a number of processing centers around the world. Alternatives to this global approach include so-called regional techniques, for which many variants exist, but whose common trait is that they only use the gravity data collected over the area of interest to generate the solution. To determine whether these regional solutions hold any advantage over the global techniques in terms of overall accuracy, a range of comparisons were made using some of the more widely used regional and global methods currently available. The regional techniques tested made use of either spherical radial basis functions or single layer densities (i.e., mascons), with the global solutions having been obtained from the various major processing centers. The solutions were evaluated using a range of computed statistics over a selection of major river basins, which were globally distributed and ranged in size from 1 to 6 million km². For one of the basins tested, the Zambezi, additional validation tests were conducted through comparisons against a custom designed regional hydrology model of the region. We could not prove that current regional models perform better than global ones. Monthly mean water storage variations agree at the level of 0.02 m equivalent water height. The differences in terms of monthly mean water storage variations between regional and global solutions are comparable with the differences among only global or regional solutions. Typically they reach values of 0.02 m equivalent water heights, which seems to be the level of accuracy of current GRACE solutions for river basins above 1 million km². The amplitudes of the seasonal mass variations agree at the sub-centimetre level. Evident from all of the comparisons shown is the importance that the choice of regularization, or spatial filtering, can have on the solution quality. This was found to be true for global as well as regional techniques.