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     

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.     

Statistical characteristics of the vertical ozone distribution in mid-latitudes

Summary The correlation matrix for the vertical ozone distribution and the temperature-ozone cross-correlation matrix, which was calculated from ozone soundings made over Berlin between 1967 and 1970, the statistical structure of the vertical ozone profile (correlation coefficients, average profiles, average standard deviation, relative variability) was derived for the three ozone seasons. The partial ozone pressure does not at all heights follow a normal distribution (e. g. at tropopause level). Generally, the correlation between tropospheric and stratospheric ozone is rather poor. In some layers the highest correlation coefficients, i.e. –0.3 and +0.4, occur in autumn (October to December) and in winter and spring (January to April). The correlation between the ozone amounts of various stratospheric layers is distinct in autumn, less distinct in summer (May to September) and entirely missing from January to April. Conspicuous cross-correlations between temperature and ozone have been found for all three seasons. a) With a negative correlation between tropospheric temperature and middle tropospheric to middle stratospheric ozone (maximum up to –0.8); b) with a rather strong positive correlation between the ozone amount and the temperature in the lower stratosphere (maximum up to +0.84); c) with a positive correlation between the ozone amount of the middle stratosphere and the temperature of the middle stratosphere (maximum up to +0.8). The highest correlation coefficients occur in autumn.     

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.     

Chronology building using objective identification of annual signals in trace element profiles of stalagmites

Determination of annual lamination provides important additional constraints to radiometric dates on speleothems, both for dating the duration of specific growth intervals and optimizing growth models. In the absence of visible laminae, however, speleothem age models are reliant upon curve fitting through discretely dated points and are therefore inherently more uncertain than annual chronologies from laminae. Given that the impact of seasonality on speleothems is expected to be strong enough to generate an annual pulse in trace element chemistry regardless of whether or not visible or fluorescent growth laminae are visible, we demonstrate the potential for deriving high-resolution stalagmite chronologies from non-laminated samples using annual chemical variations in stalagmites from two Alpine caves (Obir, Austria and Ernesto, NE Italy). Trace element data were obtained by ion microprobe analyses for H, P, Mg, Na, Sr and Ba and the annual signal was sought using spectral and wavelet analysis. An automated chemical peak-counting software tool was developed in MATLAB^©. It counts significant annual peaks using criteria of minimum amplitude in relation to the local standard deviation of signal variation and minimum separation between peaks determined by the thickness of the preceding layers. Verification of the tool using visibly laminated samples suggests the software is a reliable and accurate method of chronology building, with hit ratios greater than 0.93 and less than 0.75% false alarm occurrences. Used in conjunction with other dating methods such as radiocarbon, U–Th and sulphur peak dating, the automated chemical laminae chronology-building approach provides a more meaningful alternative to simple age-depth curve fitting for non-laminated samples.     

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.     

The significance of chemical,isotopic, and detrital components in three coeval stalagmites from the superhumid southernmost Andes (53°S) as high-resolution palaeo-climate proxies

Stalagmites are important palaeo-climatic archives since their chemical and isotopic signatures have the potential to record high-resolution changes in temperature and precipitation over thousands of years. We present three U/Th-dated records of stalagmites (MA1–MA3) in the superhumid southern Andes, Chile (53°S). They grew simultaneously during the last five thousand years (ka BP) in a cave that developed in schist and granodiorite. Major and trace elements as well as the C and O isotope compositions of the stalagmites were analysed at high spatial and temporal resolution as proxies for palaeo-temperature and palaeo-precipitation. Calibrations are based on data from five years of monitoring the climate and hydrology inside and outside the cave and on data from 100 years of regional weather station records.Water-insoluble elements such as Y and HREE in the stalagmites indicate the amount of incorporated siliciclastic detritus. Monitoring shows that the quantity of detritus is controlled by the drip water rate once a threshold level has been exceeded. In general, drip rate variations of the stalagmites depend on the amount of rainfall. However, different drip-water pathways above each drip location gave rise to individual drip rate levels. Only one of the three stalagmites (MA1) had sufficiently high drip rates to record detrital proxies over its complete length. Carbonate-compatible element contents (e.g. U, Sr, Mg), which were measured up to sub-annual resolution, document changes in meteoric precipitation and related drip-water dilution. In addition, these soluble elements are controlled by leaching during weathering of the host rock and soils depending on the pH of acidic pore waters in the peaty soils of the cave’s catchment area. In general, higher rainfall resulted in a lower concentration of these elements and vice versa. The Mg/Ca record of stalagmite MA1 was calibrated against meteoric precipitation records for the last 100 years from two regional weather stations. Carbonate-compatible soluble elements show similar patterns in the three stalagmites with generally high values when drip rates and detrital tracers were low and vice versa. δ¹³C and δ¹⁸O values are highly correlated in each stalagmite suggesting a predominantly drip rate dependent kinetic control by evaporation and/or outgassing. Only C and O isotopes from stalagmite MA1 that received the highest drip rates show a good correlation between detrital proxy elements and carbonate-compatible elements. A temperature-related change in rainwater isotope values modified the MA1 record during the Little Ice Age (～0.7–0.1 ka BP) that was ～1.5 °C colder than today. The isotopic composition of the stalagmites MA2 and MA3 that formed at lower drip rates shows a poor correlation with stalagmite MA1 and all other chemical proxies of MA1. ‘Hendy tests’ indicate that the degassing-controlled isotope fractionation of MA2 and MA3 had already started at the cave roof, especially when drip rates were low. Changing pathways and residence times of the seepage water caused a non-climatically controlled isotope fractionation, which may be generally important in ventilated caves during phases of low drip rates. Our proxies indicate that the Neoglacial cold phases from ～3.5 to 2.5 and from ～0.7 to 0.1 ka BP were characterised by 30% lower precipitation compared with the Medieval Warm Period from 1.2 to 0.8 ka BP, which was extremely humid in this region.     

Chronology of the Last Glacial Maximum in the Salzach palaeoglacier area (Eastern Alps)

A chronostratigraphy based on luminescence data was established at a key loess profile (Duttendorf) in the northern alpine foreland of Austria. The data help to constrain the timing and duration of the Last Glacial Maximum (LGM) in the area of one of the largest east Alpine piedmont glaciers, the Salzach palaeoglacier. Climate deterioration and maximum advance of this glacier were coeval with the beginning of the main loess accumulation phase in the glacier forefield at ～29–30 ka. A late LGM‐outwash gravel layer deposited on top of the loess profile marks the end of the LGM glacier activity at ～20 ka. The geomorphological setting around the loess profile provides evidence of a major glacier oscillation during the course of the LGM, a phenomenon qualitatively known from other alpine palaeoglaciers but never interpreted in terms of palaeoclimate. A LGM glacier oscillation similar to that of the Salzach palaeoglacier was reported recently from the south Alpine Tagliamento palaeoglacier, suggesting a common forcing. The onset of loess deposition at Duttendorf and the tentatively contemporal advance of the Salzach palaeoglacier reflect, as do other data, the drastic cooling in Europe as a result of Heinrich event 3. The first glacier maximum is not well constrained in the study area but a correlation with the better dated Tagliamento amphitheatre suggests a possible response to Heinrich 2. The second re‐advance occurred synchronously (within dating uncertainties) in both palaeoglaciers forefields (at ～21 ka) but the forcing mechanism remains unknown. Copyright © 2011 John Wiley & Sons, Ltd.