Abstract
The isotopic composition of sulfur, carbon and oxygen was determined in 106 samples mainly from profiles of “Kupferschiefer” occurences in N.W. Germany and N. Holland. From the bulk samples pyrite, non-pyritic sulfides and gypsum have been concentrated for isotopical analysis. C13/C12-ratios were measured in carbonates and in organic carbon and O18/O16-ratios in carbonates and in sulfates. Analytical data on CO2, C, S in all samples and on Fe, Cu, Zn and Pb in a part of the profile samples are presented.
Primary sulfates can be distinguished from sulfates formed from oxydized sulfides by their sulfur and oxygen isotopic composition. The abundance of light carbon and sulfur as well as the correlation between the δS- and δC-values are strong indications for bacterial sulfate reduction. Highly S32-enriched metal sulfides (δS34 averages −30 to −35‰) have fixed the H2S from bacterial production at its starting conditions. A large variation of the sulfide-δS-values (−4 to −44‰) and the occurence of S34-enriched “residue”-sulfates from closed systems (+11 to +26‰) support the above mentioned theory. A systematic fractionation of sulfur between the sulfur minerals as observed in hydrothermal deposits (increasing S34 in the sequence: pyrite>sphalerite>chalcopyrite>galena) has not been detected. In our case the regular difference in δS34 between the sulfides is consistent with the idea of a successive precipitation of the metals due to their different solubility with increasing bacterial H2S production. In such a sequence the increase of S34 is due to the consumption of light sulfate by bacterial reduction after the transition from an open to a closed system.
It is alternately discussed, whether bacterial reduction and metal precipitation took place in bodies of stagnant sea water above or within the sediment. Presuming a precipitation of metals in a closed water-reservoir observations of other authors concerning the vertical sequence of metals and of the present author regarding the accumulation of S34 in the sequence of precipitated sulfides can be easily explained.
Evidence from isotope fractionation in sediment sequences favours the assumption of a precipitation of metals in the sediment: light carbon above the zone rich in carbonates (with a “marine” carbon composition) and metals. This characteristic change in the C13/C12-ratio is due to the increasing influence of light carbon dioxide of biogenic origin. Assuming the production of H2S as restricted to the sediment, the transition from the open to the closed system as a result of growing thickness of the sediment (with lowered permeability for sulfate- and metalbearing water) controls the sequence of carbon composition. The restriction of metal precipitation in the sediment causes difficulties in interpreting regular zoning of metals and the metal supply. Especially the numerous exchanges of pore water required for the supply of sulfate and metals in the bituminous sediment with very low permeability cannot be explained.
The assumption of a syngenetic sulfide precipitation is confirmed by the results of the carbon isotope analysis. The trend to heavy carbonates in the sequence of the profiles can be interpreted as due to rising marine influence with time in the early Zechstein basin. This trend is only interrupted several times in the “Kupferschiefer”-sediment by the occurence of light carbonates of biogenic origin above zones of sulfide accumulation. A model of epigenetic metal supply forming this regular pattern of correlated sulfur and carbon distribution and composition cannot be constructed. The evidence from our data favours the assumption of concurring processes of carbon fixation in carbonates and in organic substances and sulfur precipitation as sulfides during the formation of the sediment.
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Herrn Prof. Dr. K. H. Wedepohl danke ich für die Stellung des Themas, Überlassung des Probenmaterials und für sein reges Interesse am Fortgang der Arbeit. Meinen Dank möchte ich auch allen Mitarbeitern der mineralogischen Anstalten und des Zentrallabors aussprechen, die mich durch vielerlei Anregungen und Diskussionsbereitschaft unterstützt haben. Die massenspektrometrischen Untersuchungen wurden von der Deutschen Forschungsgemeinschaft durch die Einrichtung des Zentrallabors für Geochemie der Isotope an der Universität Göttingen ermöglicht.
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Marowsky, G. Schwefel-, Kohlenstoff- und Sauerstoff-Isotopenuntersuchungen am Kupferschiefer als Beitrag zur genetischen Deutung. Contr. Mineral. and Petrol. 22, 290–334 (1969). https://doi.org/10.1007/BF00400127
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DOI: https://doi.org/10.1007/BF00400127