An evaporitic facies in Neoproterozoic post-glacial carbonates: The Gifberg Group, South Africa

A geological study of the hitherto poorly described Neoproterozoic Gifberg Group, with emphasis on lithogeochemistry and O, C and Sr isotopic composition of the carbonate-dominated Widouw Formation (Vredendal Outlier, westernmost South Africa) revealed that the entire group is an equivalent of the relatively well constrained Port Nolloth Group in the external, paraautochthonous part of the Pan-African Gariep Belt further north. Thus, the Vredendal Outlier can be regarded as the southern extension of the Port Nolloth Zone. Two diamictite units are recognised in the Vredendal Outlier, which can be correlated respectively with the c. 750 Ma Kaigas Formation diamictite and the 583 Ma, syn-Gaskiers Numees Formation diamictite in the Gariep Belt proper. The dominating carbonate unit in the studied area is post-glacial with respect to the older of the two diamictite units. The combined textural, structural and geochemical evidence suggests that parts of the variably dolomitised limestone succession represent former evaporite beds. Sedimentation in a restricted, very shallow and proximal basin led to a wide range in C isotope ratios (δ¹³C_PDB from − 4.2 to + 4.8‰), very high Sr concentrations (derived from original anhydrite) and initial ⁸⁷Sr/⁸⁶Sr ratios that are significantly higher (0.70785) than those of coeval seawater. As C and Sr isotopes are commonly used for chemostratigraphic correlation, and high Sr concentrations in Neoproterozic carbonates are often interpreted as evidence of former aragonite, the findings of this study should be used as warning against uncritical use of geochemical and isotopic parameters for describing ancient seawater composition. Thus C and Sr isotope ratios alone in Neoproterozoic carbonates may be less powerful proxies of ancient seawater composition, and high Sr contents are not necessarily indicative of an “aragonite sea”, as previously inferred.     

Oxygen and carbon isotopic study on the genesis of the Steirischer Erzberg siderite deposit (Austria)

The carbon and oxygen isotopic composition of Fe-carbonate ore and its calcitic to dolomitic Devonian host rocks at the Steirischer Erzberg siderite deposit (Greywacke zone, Upper Austroalpine Unit) were determined in order to constrain the source and nature of the Fe-rich mineralizing fluid. The ¹⁸O-values obtained for various Fe-carbonate generations and the carbonate host lie within a similar range between + 14.6 and + 21.6 (V-SMOW). No good correlation exists between the relative ages of the carbonate phases and their O isotopic composition. The variation in ¹⁸O-values is due to metamorphic recrystallization with locally variable fluid/rock ratios. The average ¹³C-value of the carbonate host is +0.5 ± 1.2 (PDB) which corresponds well to worldwide Phanerozoic marine carbonate values. The first Fecarbonate generation has slightly lower ¹³C-values, on average -1.4 ± 0.8 (PDB). Recrystallization of both the carbonate host minerals and the ankerite/siderite led to significantly lower ¹³C-values of -4.2 ± 0.6 and-4.7 ± 0.7, respectively. Within the basal breccia of the post-Hercynian transgression series matrix calcite/ dolomite shows an average ¹³C-value of -2.9 ± 0.7, and matrix siderite/ankerite an average value of-4.1 ± 0.4. These data, together with Sr isotope data published previously, strongly support a late-diagenetic or epigenetic first Fe-mineralization from convecting formation waters. They ascended along extension faults and were driven by an increased heat flow caused by crustal thinning during a Devonian rifting phase that initiated the separation of the Noric terrane from Africa. A potential source of the Fe could have been the underlying Ordovician acid volcanics. Regional metamorphism related to collision tectonics in the Late Carboniferous (Hercynian) and later during the Alpine orogeny, caused intensive recrystallization and partial mobilization of the various carbonate phases.     

Witwatersrand iron-formations and their significance for gold genesis and the composition limits of orthoamphibole

Summary In the West Rand Group of the 3.07–2.71 Ga old Witwatersrand Supergroup, South Africa, a series of banded iron-formations occur. They are of chemical origin and were deposited in an offshore shelf environment. The coarser-grained, in places pyrite-bearing, and partly auriferous metasedimentary rocks forming the bulk of the Witwatersrand Supergroup are regressive. The iron-formations, however, were deposited during transgression. The presence of allogenic pyrite in the fluviatile metaconglomerates and that of magnetite and, in places, haematite in the marine iron-formations suggests a lower pH and higher sulfur activity for the Archaean meteoric environment than for recent hydrothermal fluids on the ocean floor. Post-depositional alteration of the Witwatersrand rocks includes burial metamorphism at temperatures between 300 and 350 °C and pressures around 2.5 kbar, and multiple hydrothermal inflitration events at slightly lower temperatures, coeval with the brittle deformation of the basin fill during the deposition of the Transvaal Supergroup and the Bushveld Vredefort events.Additional thermal metamorphic overprint of the iron-formations around the Vredefort Dome caused the growth of orthoamphiboles. They show a wide range of compositions between ferro-anthophyllite and ferrous alumino-gedrite, suggesting that the crest of the solvus curve for Fe-rich orthoamphiboles is below 500 °C.Chlorite and amphibole compositions, and the presence of Fe-oxide-bearing horizons between pyrite-bearing ones indicate that the fluid composition during post-depositional alteration was largely controlled by the bulk rock composition of the infiltrated stratigraphic horizons and not by some external source.

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Zusammenfassung Die West Rand Group innerhalb der 3.07–2.71 Milliarden Jahre alten Witwatersrand Supergroup, Südafrika, führt eine Reihe von Magnetit- und Hämatit-haltigen Eisenformationen. Diese sind chemischen Ursprungs und wurden in einem flachmarinen Schelfmilieu abgelagert. Der überwiegende Teil der Witwatersrand Abfolge, bestehend aus klastischen, verschiedentlich Pyrit-führenden und teilweise goldhaltigen Metasedimentgesteinen, kann regressiven Phasen zugeschrieben werden. Die Eisenformationen wurden hingegen während transgressiven Phasen abgelagert. Aufgrund des Auftretens allogener Pyrite in den fluviatilen Konglomeratlagen und von Magnetit und Hämatit in den marinen Eisenformationen lassen sich für den meteorischen Bereich im Archaikum niedrigere pH-Werte und höhere Schwefelfugazität ableiten als für rezente submarine hydrothermale Fluide. Post-diagenetische Alterationsprozesse sind der Versenkungsmetamorphose mit Temperaturen zwischen 300 und 350 °C und Drucken um 2.5 kbar sowie etwas niedriger temperierten hydrothermalen Fluiden zuzuschreiben, die als Folge der inkompetenten Deformation der Beckenfüllung in diese während mehrer Stadien infiltrierten. Infiltration hydrothermaler Fluide während der Ablagerung der Transvaal Supergroup (2.55 Ga) und während des Bildung der Vredefort Struktur (2.0 Ga) sind durch Altersdaten belegt.Zusätzliche thermische Metamorphose der Fe-reichen Pelite und Eisenformationen im Bereich der Vredefort Struktur führte zur Bildung von Orthoamphibolen, deren Zusammensetzung von Anthophyllit bis zu Fe-reichem Alumino-Gedrit reicht. Dies läßt darauf schließen, daß die Solvuskurve für Fe-reiche Orthoamphibole unterhalb von 500 °C liegt.Die Zusammensetzung der Chlorite und Amphibole sowie das Auftreten von Fe-Oxid-führenden Horizonten in den generall Pyrit-reichen Metasedimentgesteinen gestatten die Annahme, daß die post-diagenetische Fluidzusammensetzung hauptsächlich durch die jeweilige Zusammensetzung der infiltrierten Gesteinshorizonte und nicht durch eine externe Quelle bestimmt wurde.

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With 8 Figures     

Metamorphic evolution of the Maud Belt: P–T–t path for high-grade gneisses in Gjelsvikfjella, Dronning Maud Land, East Antarctica

A metamorphic petrological study, in conjunction with recent precise geochronometric data, revealed a complex P–T–t path for high-grade gneisses in a hitherto poorly understood sector of the Mesoproterozoic Maud Belt in East Antarctica. The Maud Belt is an extensive high-grade, polydeformed, metamorphic belt, which records two significant tectono-thermal episodes, once towards the end of the Mesoproterozoic and again towards the late Neoproterozoic/Cambrian. In contrast to previous models, most of the metamorphic mineral assemblages are related to a Pan-African tectono-thermal overprint, with only very few relics of late Mesoproterozoic granulite-facies mineral assemblages (M₁) left in strain-protected domains. Petrological and mineral chemical evidence indicates a clockwise P–T–t path for the Pan-African orogeny. Peak metamorphic (M_2b) conditions recorded by most rocks in the area (T = 709–785 °C and P = 7.0–9.5 kbar) during the Pan-African orogeny were attained subsequent to decompression from probably eclogite-facies metamorphic conditions (M_2a).The new data acquired in this study, together with recent geochronological and geochemical data, permit the development of a geodynamic model for the Maud Belt that involves volcanic arc formation during the late Mesoproterozoic followed by extension at 1100 Ma and subsequent high-grade tectono-thermal reworking once during continent–continent collision at the end of the Mesoproterozoic (M₁; 1090–1030 Ma) and again during the Pan-African orogeny (M_2a, M_2b) between 565 and 530 Ma. Post-peak metamorphic K-metasomatism under amphibolite-facies conditions (M_2c) followed and is ascribed to post-orogenic bimodal magmatism between 500 and 480 Ma.     

Geochronology,stratigraphy and geochemistry of Cambro-Ordovician,Silurian and Devonian volcanic rocks of the Saxothuringian Zone in NE Bavaria (Germany)—new constraints for Gondwana break up and ocean–island magmatism

International Journal of Earth Sciences - Stratigraphically well-defined volcanic rocks in Palaeozoic volcano-sedimentary units of the Frankenwald area (Saxothuringian Zone, Variscan Orogen) were...     

Beeinflussung der Enzymaktivität einer Protease durch Huminstoffe Influence of Humic Substances on the Activity of a Protease

This paper deals with the influence of different humic substances (HS) on the enzyme activity (EA) of the proteolytic enzyme pronase E. The EA was determined by analyzing the concentration of the amino acid valine hydrolyzed from caseine. For amino acid analysis, a flourescence detector was used after precolumn derivatization and HPLC-separation of the hydrolysis products. The data show that the presence of HS has no adverse effects on amino acid analysis. Based on this result, a decrease of EA was observed in the presence of HS acting as enzyme inhibitors. Clear inhibition effects could be seen for different fulvic acids (HO3 FA, FBR FA and FBR 1.0 FA) at concentrations of 150 mg/L. In case of FBI-2 FA, higher concentrations were necessary to decrease the EA significantly. At an inhibitor concentration of 1500 mg/L the EA was mostly found to be less than 50%. The standard deviations of the results don't allow a differentiation between the HS of different origin and treatment. Specifying HS according to their influence on EA has to remain uncertain. As shown in a kinetic study of the hydrolysis of L-Leucine-2-naphthylamide-hydrochloride, the inhibitor HO3 FA decreases the maximum velocity of the reaction but has no effect on the Michaelis constant. These results indicate that this HS acts as a noncompetitive inhibitor.     

Anwendung einer enzymatischen Methode zur Charakterisierung von Huminstoffen Enzymatic Characterization of Humic Substances

A method is described for the specific hydrolysis of amino acids from humic substances by using the proteolytic enzyme “Pronase E”. The amino acids are analyzed by a fluorescence detector after precolumn derivatization and HPLC-separation. The pattern and the concentration of amino acids after the enzymatic hydrolysis are set up for humic substances of different origin. Due to the results the enzymatic hydrolysis is suitable for the characterization of humic substances with a nitrogen content higher than 3%. As shown in a kinetic study of the hydrolysis of a fulvic acid the influence of humic substances on the enzyme activity increases in case of lower nitrogen content. Due to the specificity of the proteolytic enzyme the operationally defined method is limited as shown by a protein of a known amino acid content. The amino acids leucine, valine, tyrosine and histidine are released to the highest extent. The determined total extent for the hydrolysis of Insulin B is 26.34% and for Casein 38.37%. By comparison of the enzymatic hydrolysis with the classic acid hydrolysis the advantages of the biochemical method are the simple experimental handling and the mild reaction conditions. Amino acids which are very unstable like glutamine and asparagine can only be analyzed by the enzymatic hydrolysis.