Macroscopic and structural changes at the incommensurate-normal phase transition in melilites

Summary The temperature-dependent structural and physical properties of melilites and their changes at the incommensurate-normal phase transition all are consistent with a model relating the formation of the incommensurately modulated (IC) structure to structural strain. This strain originates from an interplay between the size of the interlayer cation, its thermal vibration, and the size and deformation of the tetrahedral sheet. Consequently, the IC structure changes its properties continuously towards those of the high-temperature normal (N) phase as the IC-N phase transition is approached. Far below the transition temperature the modulation is rectangular and the structure can eventually be described by a static microdomain model. Besides chemical effects (essentially cation size), structural defects play a key role in the behaviour of the incommensurately modulated phase.

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Makroskopische und strukturelle Änderungen am inkommensurabel-normal Phasenübergang in Meliliten

Zusammenfassung Die temperaturabängigen strukturellen und physikalischen Eigenschaften der Melilite und ihre Änderungen am Phasenübergang von der inkommensurablen (IC) zur Normal(N)-Struktur sind konsistent mit einem Modell, das die Bildung der IC-Struktur durch strukturelle Verspannung erklärt. Die Verspannung entsteht durch die Wechselbeziehung zwischen der Größe des Zwischenschicht-Kations, seiner thermischen Schwingung und der Abmessung und Deformation der Tetraederschicht. Dementsprechend ändern sich die Eigenschaften der IC-Struktur bei Annäherung an den IC-N-Phasenübergang kontinuierlich in Richtung auf die Hochtemperatur-Normal-Struktur. Weit unterhalb der Übergangstemperatur ist die Modulation rechteckig und die Struktur kann durch ein statisches Mikrodomänen-Modell beschrieben werden. Neben chemischen Einflüssen (vor allem Radien der Kationen) spielen auch strukturelle Defekte eine Schlüsselrolle im Verhalten der IC-Phase.

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With 8 Figures     

Seismostratigraphy and structural framework of the SW Baltic Sea

The SW part of the Baltic Sea between Scania, Rügen, Bornholm and Mön constitutes a complex crustal transition between the Baltic Shield and the accreted Phanerozoic provinces of the West European Platform. An integrated interpretation of marine reflection seismic data sets from the BABEL AC line and two commercial surveys offshore NE Germany and S Sweden have resulted in a complete view of the structural framework in the area. The general seismic picture can best be detected by two characteristic sets of reflection phases. The lower set is dominated by slightly dipping and vertically displaced prominent reflectors corresponding to downfaulted Lower Palaeozoic strata on top of the Precambrian basement. The upper set represents Mesozoic and Cenozoic coherent reflection phases including a thick Upper Cretaceous unit. The Caledonian deformation front is identified in the southern part of the investigated area as the border against which basement rocks have been affected by Caledonian metamorphism and deformation. Major structural elements also include the N–S trending Agricola–Svedala Fault and North Rügen-Skurup Fault. Several NW–SE trending faults are also identified including the Nordadler–Kamien Fault, Jutland–Mön Fault, Carlsberg Fault, Romeleåsen Fault Zone and the Fyledalen Fault Zone. The sedimentary record from NE German offshore wells and Scanian boreholes is compared with the seismic data. The Cambro-Silurian strata are composed mainly of quartzitic sandstones, shales and biomicritic limestones. The Silurian is dominated by grey, micaceous shale and micaceous siltstone deposited in a marginal basin. Upper Palaeozoic strata are merely encountered in the southernmost part of the investigated area. These include Zechstein strata. The Mesozoic deposits are dominated by a thick Cretaceous sequence of mainly limestones with interbedded sandstones.     

Relict nebkhas (pimple mounds) record prolonged late Holocene drought in the forested region of south-central United States

The origin and significance of pimple mounds (low, elliptical to circular dune-like features found across much of the south-central United States) have been debated for nearly two centuries. We cored pimple mounds at four sites spanning the Ozark Plateau, Arkansas River Valley, and Gulf of Mexico Coastal Plain and found that these mounds have a regionally consistent textural asymmetry such that there is a significant excess of coarse-grained sediment within their northwest flanks. We interpret this asymmetry as evidence of an eolian depositional origin of these mounds and conclude they are relict nebkhas (coppice dunes) deposited during protracted middle to late Holocene droughts. These four mounds yield optically stimulated luminescence ages between 2400 and 700 yr that correlate with well-documented periods of eolian activity and droughts on the southern Great Plains, including the Medieval Climate Anomaly. We conclude vegetation loss during extended droughts led to local eolian deflation and pimple mound deposition. These mounds reflect landscape response to multi-decadal droughts for the south-central U.S. The spatial extent of pimple mounds across this region further underscores the severity and duration of late Holocene droughts, which were significantly greater than historic droughts.     

Formation of Al-rich titanite (CaTiSiO4O–CaAlSiO4OH) reaction rims on ilmenite in metamorphic rocks as a function of fH2O and fO2

Reaction rims of titanite on ilmenite are described in samples from four terranes of amphibolite-facies metapelites and amphibolites namely the Tamil Nadu area, southern India; the Val Strona area of the Ivrea-Verbano Zone, northern Italy, the Bamble Sector, southern Norway, and the northwestern Austroalpine Ötztal Complex. The titanite rims, and hence the stability of titanite (CaTiSiO₄O) and Al–OH titanite, i.e. vuaganatite (hypothetical end-member CaAlSiO₄OH), are discussed in the light of fH₂O- and fO₂-buffered equilibria involving clinopyroxene, amphibole, biotite, ilmenite, magnetite, and quartz in the systems CaO–FeO/Fe₂O₃–TiO₂–SiO₂–H₂O–O₂ (CFTSH) and CaO–FeO/Fe₂O₃–Al₂O₃–SiO₂–H₂O–O₂ (CFASH) present in each of the examples. Textural evidence suggests that titanite reaction rims on ilmenite in rocks from Tamil Nadu, Val Strona, and the Bamble Sector originated most likely due to hydration reactions such as clinopyroxene + ilmenite + quartz + H₂O = amphibole + titanite and oxidation reactions such as amphibole + ilmenite + O₂ = titanite + magnetite + quartz + H₂O during amphibolite-facies metamorphism, or, as in the case of the Ötztal Complex, during a subsequent greenschist-facies overprint. Overstepping of these reactions requires fH₂O and fO₂ to be high for titanite formation, which is also in accordance with equilibria involving Al–OH titanite. This study shows that, in addition to P, T, bulk–rock composition and composition of the coexisting fluid, fO₂ and fH₂O also play an important role in the formation of Al-bearing titanite during amphibolite- and greenschist-facies metamorphism.     

Gene Expression Analysis for Exposure to Estrogenic Substances

Zebrafish (Danio rerio) were exposed with 17β‐estradiol (E2) and nonylphenol (NP) in different concentrations. Gene expression analysis was carried out by two different approaches. First, RT‐PCR experiments were performed for the examination of expression levels of the two marker genes vitellogenin and aromatase. This approach showed a significant increase in the expression of the vitellogenin gene in exposed male fish (500 ng/L 17β‐estradiol and 250 μg/L nonylphenol). This egg yolk protein is usually not synthesized in male vertebrates. A slight decrease of expression of the aromatase gene was observed in exposed female zebrafish. Aromatase is known to catalyze the conversion of androgens to estrogens. Second, DNA microarray experiments were carried out, which allow the simultaneous examination of the expression levels of a great number of marker genes. The microarray experiments resulted in an up‐regulation of vitellogenin up to 850‐fold. In addition, several other genes were identified to be up‐regulated by estrogens, for example the high mobility group box protein ssrp1 (78‐fold) or the chaperonin containing t‐complex polypeptide 1, beta subunit cctb (22‐fold).     

Euphotic zone bacterioplankton sources major sedimentary bacteriohopanepolyols in the Holocene Black Sea

Bacteriohopanepolyols (BHPs) are lipid constituents of many bacterial groups. Geohopanoids, the diagenetic products, are therefore ubiquitous in organic matter of the geosphere. To examine the potential of BHPs as environmental markers in marine sediments, we investigated a Holocene sediment core from the Black Sea. The concentrations of BHPs mirror the environmental shift from a well-mixed lake to a stratified marine environment by a strong and gradual increase from low values (∼30 μg g⁻¹ TOC) in the oldest sediments to ∼170 μg g⁻¹ TOC in sediments representing the onset of a permanently anoxic water body at about 7500 years before present (BP). This increase in BHP concentrations was most likely caused by a strong increase in bacterioplanktonic paleoproductivity brought about by several ingressions of Mediterranean Sea waters at the end of the lacustrine stage (∼9500 years BP). δ¹⁵N values coevally decreasing with increasing BHP concentrations may indicate a shift from a phosphorus- to a nitrogen-limited setting supporting growth of N₂-fixing, BHP-producing bacteria. In sediments of the last ∼3000 years BHP concentrations have remained relatively stable at about 50 μg g⁻¹ TOC.The distributions of major BHPs did not change significantly during the shift from lacustrine (or oligohaline) to marine conditions. Tetrafunctionalized BHPs prevailed throughout the entire sediment core, with the common bacteriohopanetetrol and 35-aminobacteriohopanetriol and the rare 35-aminobacteriohopenetriol, so far only known from a purple non-sulfur α-proteobacterium, being the main components. Other BHPs specific to cyanobacteria and pelagic methanotrophic bacteria were also found but only in much smaller amounts.Our results demonstrate that BHPs from microorganisms living in deeper biogeochemical zones of marine water columns are underrepresented or even absent in the sediment compared to the BHPs of bacteria present in the euphotic zone. Obviously, the assemblage of molecular fossils in the sediments does not represent an integrated image of the entire community living in the water column. Remnants of organisms living in zones where effective transport mechanisms - such as the fecal pellet express - exist are accumulated while those of others are underrepresented. Our work shows a high stability of BHPs over geological time scales. Largely uniform distributions and only minor changes in structures like an increasing prevalence of saturated over unsaturated BHPs with time were observed. Consequently, sedimentary BHP distributions are less suitable as markers for in situ living bacteria but are useful for paleoreconstructions of bacterioplanktonic communities and productivity changes.     

Petrology and geochemistry of the shoshonite-hosted Skouries porphyry Cu–Au deposit, Chalkidiki, Greece

The Skouries porphyry Cu-Au deposit, containing an indicated reserve of 206 Mt at 0.54% Cu and 0.80 g/t Au, is hosted by at least four hypabyssal monzonite-porphyry phases. In decreasing age, they are: (1) pink monzonite, (2) main monzonite, (3) intra-mineral monzonite, and (4) late-stage porphyry. High-grade ore is directly associated with the main and intra-mineral monzonite phases. All intrusive phases are cut by late-stage monzonite dykes that are barren. The monzonites have porphyritic textures with phenocrysts of plagioclase, alkali feldspar and amphibole as well as apatite and titanite microphenocrysts in a fine-grained feldspar-dominated groundmass. Mineralized samples are affected to varying degrees by potassic alteration, ranging from weak biotite-magnetite disseminations, through cross-cutting veinlets of hydrothermal orthoclase, to zones with pervasive orthoclase flooding. The high halogen contents of the Skouries intrusions are reflected in the high Cl and F concentrations of mica phases (up to 0.19 and 2.48 wt% respectively). The presence of magmatic magnetite in all intrusive phases implies high oxygen fugacities of the parental melts. All four monzonite phases have relatively evolved compositions, as reflected by their high SiO₂, low MgO and low mg#, and variable but low contents of mantle-compatible elements such as V, Ni and Co. However, their mg# suggests increasing degrees of fractionation of the parental melts with decreasing age. Their high K₂O (up to 5.8 wt%) and K₂O/Na₂O ratios (>1), as well as their high Ce/Yb and Th/Yb ratios (>34 and >21 respectively), which are believed to have been unaffected by alteration processes, are typical of alkaline rocks of the shoshonite association. Importantly, the Skouries intrusions are characterized by very high U and Th contents (up to 18.9 ppm and 62 ppm, respectively) that are consistent with accessory thorite and rare allanite in several samples. The high initial ⁸⁷Sr/⁸⁶Sr ratios (0.7082) for the Skouries intrusions suggest crustal contamination during emplacement. The use of geochemical discrimination diagrams assigns the rocks to a continental arc setting in accord with the interpretation of previous workers.     

Constraining a SHRIMP U-Pb age: micro-scale characterization of zircons from Saxonian Rotliegend rhyolites

We present results of a detailed investigation of zircons from two rhyolites from St. Egidien and Chemnitz, Saxony, using a combination of microprobe techniques (SHRIMP ion probe, Raman microprobe, SEM: SE, BSE, and CL imaging). These rhyolites belong to the so-called “lower volcanics”, which is the older of two series of Late Variscan volcanic rocks occurring in the Saxonian Sub-Erzgebirge basin (Germany). The purpose of the present contribution is to demonstrate that detailed characterization of zircons, as provided by the different micro-techniques, facilitates soundest interpretation of geochronological data. The zircons (at most 40 to 80 m in size) show oscillatory growth zoning, with reversely correlated CL and BSE signal intensities. These zircons are interpreted to have grown during crystallization of the rhyolite because, apart from some cracking, they do not appear to have experienced any alteration since the time of their growth: The shapes of the zircons and their internal structures revealed by CL and BSE imaging appear to be magmatic, and neither annealing of the accumulated alpha-decay damage nor disturbance of the U-Pb system is observed. The SHRIMP ion probe measurements on the zircons gave a Permian ²⁰⁶Pb/²³⁸U age of 278 ± 5 Ma (95% confidence). The concordance of this age is supported by the correlation between the low degrees of metamictization (estimated from Raman parameters) and the accumulated alpha fluxes (calculated from SHRIMP data). The 278 Ma zircon age is interpreted to represent the age of the “lower rhyolites” series and, with that, the age of postkinematic Late Variscan volcanism in the Sub-Erzgebirge basin, which has been related to anorogenic extension and uplift as a result of intracontinental rifting. Because of genetic association of rhyolites in the Sub-Erzgebirge basin and Li-F granites and lamprophyres in the neighbouring Erzgebirge, the rhyolite age also indirectly contributes to the understanding of the geological history of the Erzgebirge. The 278 Ma age is the first absolute dating result for rhyolites from the Saxonian Sub-Erzgebirge basin. Received: 16 December 1997 / Accepted: 4 May 1998