ALBERT

Description: We report on Precambrian microfossils from igneous rocks of the Volyn pegmatite district, associated with the Paleoproterozoic Korosten pluton, northwestern Ukraine. The fossils were recovered from meter-sized miarolitic cavities and show a well-preserved 3D morphology, mostly filamentous but with a large variety of types and also in irregular, flaky shapes reminiscent of former biofilms, as well as rare spherical objects. Based on literature data, pyrolysis experiments, and reflected light microscopy results, the organic matter (OM) is characterized as (oxy-)kerite. Further investigations with microscopic techniques, including scanning and transmission electron microscopy, and electron microprobe analysis show that fossilization likely occurred during a hydrothermal, post-pegmatitic event by silicification dominantly in the outermost 1–2 µm of the microfossils. The hydrothermal fluid, derived from the pegmatitic environment, was enriched in SiF4, Al, Ca, Na, K, Cl, and S. The OM shows O enrichment in which N and S content is low, indicating simultaneous N and S loss during anaerobic oxidation. Mineralization with Al silicates starts at the rim of the microfossils, continuing in its outer parts into identifiable encrustations and intergrowths of clay minerals, feldspar, Ca sulfate, Ca phosphate, Fe sulfide, and fluorite. Breccias, formed during collapse of some the miarolitic cavities, contain decaying OM, which released high concentrations of dissolved NH4+, responsible for the late-stage formation of tobelite-rich muscovite and buddingtonite. The age of the fossils can be restricted to the time between the pegmatite formation, at ∼1.760 Ga, and the breccia formation at ∼1.49 Ga. As the geological environment for the growth of the microorganisms and fossilization, we assume a geyser system in which the essential biological components C, N, S, and P for growth of the organisms in the miarolitic cavities were derived from microorganisms at the surface. Fossilization was induced by magmatic SiF4-rich fluids. The Volyn occurrence is a distinct and uncommon example of Precambrian fossils, and the results underline the importance of cavities in granitic rocks as a possible habitat for microorganisms preserved in the deep biosphere.

Description: Organic matter (OM) is known to be an important reductant in sediment-hosted base metal deposits like the European Kupferschiefer. However, the precise nature of interactions between OM and hydrothermal fluids are still debated as well as how the interconnected reactions develop over geological timescales. This dataset provides for the first time bulk, compositional and stable isotope data of hydrocarbons, biomarkers and organonitrogen, -sulfur and-oxygen (NSO) compounds for the mineralized Kupferschiefer Spremberg-Graustein field in Eastern Germany based on samples from two drill cores. The study aims to help to better understand the role that organic matter plays during the mineralisation and formation of the sedimentary ore deposit within the Kupferschiefer with a focus on stable hydrogen isotope compositions and NSO compositional data to especially address the origin and to assess the oxidative nature of the brines that caused the mineralization in the Spremberg-Graustein field. The data publication includes bulk, compositional and stable isotope data on inorganic metals and organic matter. The data about metal contents were generated using ICP-MS while those on the organic matter were generated using Rock-Eval pyrolysis, a microscope, a Soxhlet apparatus, medium pressure liquid chromatography (MPLC), gas chromatography with flame ionization (GC-FID) and mass spectrometric detection (GC-MS), gas chromatography isotope ratio mass spectrometry (GC-IRMS) and ultrahigh resolution mass spectrometry (Fourier Transform ion cyclotron resonance mass spectrometry, FT-ICR-MS) with Electrospray ionization (ESI) and Atmospheric pressure photoionization (APPI). The full description of samples, methods and data is given in the following sections.

Description: Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS) with negative ion electrospray ionization (ESI-N) and positive ion atmospheric pressure photoionization (APPI-P), and compound-specific carbon isotope measurements together with conventional biomarker analyses were applied on 13 crude oil samples from Cretaceous reservoirs in the Shushan, Dahab/Mireir, and Abu Gharadig basins of the northern Western Desert of Egypt to identify their origin, maturity, alteration level, and petroleum relationships. Five oil families were identified, and the FT-ICR-MS data enabled a differentiation between crude oils with terrigenous, marine, and mixed organic matter input based on polar compounds. The dominance of acidic (ESI-N) and low-polarity (APPI-P) oxygen-containing compounds in the Shushan oils reflects land plant material input and oxic depositional conditions for their source rocks. The abundance of oxygen-containing compounds gradually decreases in the NE-Abu Gharadig and Dahab/Mireir oils (source rocks: mixed Type III/II organic matter (OM)) to reach minimum values in the marine-dominated Abu Gharadig oils. Based on compound-specific carbon isotopes and hydrocarbon biomarkers, the Shushan Basin hosts two different oil families from source rocks with Type III OM that likely reveal different thermal maturities and ages. The detected APPI-P aromatic hydrocarbons together with other molecular maturity ratios suggest a higher thermal maturity for the Shushan family A and Abu Gharadig oils than for oils of Shushan family B and from the Dahab/Mireir Basins, respectively.

Description: Organosulfur compounds (OSCs) in sedimentary rocks are considered to have formed primarily by abiotic incorporation of inorganic sulfur species into biogenetic functionalized molecules during early diagenesis, thus preserving carbon skeletons of appropriate biomolecules. OSCs could be characterized at a molecular level by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) even when they are small in amounts and large in molecular weights. Herein, to reveal the palaeoecological and palaeoenvironmental information that OSCs have recorded but might not be contained in other biomarkers, OSCs’ composition in solvent extracts of rocks with different geological histories were determined utilizing FT-ICR-MS. The analyzed natural laboratories are the marine Schöneck, Dynow and Posidonia formations and the lacustrine Wealden Formation which are in the late diagenetic or early catagenetic stages. The prevailing iron-deficient sulfidic depositional settings of the marine Posidonia and Schöneck formations are reflected by abundant OSCs bearing up to three sulfur atoms. The high ratios of reduced relative to oxidized forms (Sz versus SzOx) further illustrate the restricted presence of oxidants at the oxic-anoxic interfaces. The high average oxygen numbers of S1Ox compounds and the exclusive presence of nitrogenous OSCs (SzNy and SzNyOx) found in the marine rock extracts document the high abundances of polyoxygenated compounds and proteinaceous moieties in marine organisms that can be sulfurized. In contrast, the lacustrine organisms contain abundant sulfurizable aliphatic moieties. The observed prominent enrichment of Sz and SzOx compounds containing 40, 35, 30, 25 carbon atoms are associated with the selective and efficient preservation of polyfunctionalized biomolecules via sulfurization, such as C40 carotenoids, C35 bacteriohopanepolyols, C30 unsaturated tetracyclic polyprenoid alcohols, or C25 or C30 highly branched isoprenoid (HBI) polyenes. The strong enrichment of sulfurized C35 bacteriohopanepolyols can be developed as an indicator of the low levels of oxygen exposure prior to sulfurization, which occur only in the Dynow and Schöneck formations. The prominent enrichment of sulfurized carotenoids is generally associated with high primary productivity. While the strongly enriched sulfurized HBI polyenes in the Upper Schöneck Formation is indicative for diatom blooms, the precursors of C30 pentacyclic polyprenoid organosulfur compounds are more abundant in fresh/brackish water algae.

Description: Shale gas potential of the Whitehill Formation (Permian), Karoo Basin, South Africa is strongly influenced by widespread Jurassic igneous intrusions. A high-resolution organic petrographic and geochemical study is reported here on two stratigraphic sections, the objective being to gain insights into the chemical structure and alteration of oil-prone sedimentary organic matter during contact metamorphism. One section unaffected by intrusion served as background, while the other section was intruded by two laterally continuous dolerite sills with an average thickness of 10.7 and 9.3 m, preferentially emplaced at the upper and lower contacts of the formation, respectively. Heat flow from the sills caused TOC and S2 values from programmed pyrolysis to decline over a distance of 8.7 m from 3.2 to 0.15% and 4.65 to 0.11 mg HC/g TOC, respectively, and cause the reflectance of vitrinite and solid bitumen to increase from 2.03 to 5.82% and 1.58 to 7.87%. Organic matter in the background samples is dominated by solid bitumen, a secondary thermal conversion product of oil-generative Type II kerogen. In the sill-hosting section, the thermal aureoles can be recognized by systematic changes to the optical texture and chemical structure and composition of solid bitumen. Solid bitumen particles develop anisotropy approaching the sills and become transformed into coke and pyrolytic carbon. δ13Corg values become less negative by up to 3.13‰ VPDB. These data suggest significant devolatilization of organic matter to methane and destruction of petroleum generation and retention potential in the contact aureole of the sills. The trend of these datasets, coupled with the presence of several sills and their laterally extensive nature throughout much of the study area suggests that the intrusions have been significant in increasing methane generation on a basinal scale. Together, this study indicates that the complementary application of combined light and electron microscopy (CLEM), programmed pyrolysis, and isotope ratio mass spectrometry (IRMS) is suitable for a comprehensive characterization of organic matter alteration through the maturation continuum. Results also show that contact metamorphic alteration of organic matter by intrusions produced structural and compositional changes that are distinctive from those expected from geological burial maturation where graphite is the end-product.

Description: The Southern Permian Basin in Central Europe (in Germany and Poland) hosts several sediment-hosted Cu deposits (see Borg et al., 2012). The Cu- and Zn-Pb sulfide mineralization is preserved in the coarse-grained continental siliciclastics of the uppermost Rotliegend (S1), organic matter- and carbonate-rich marine mudstones of the Kupferschiefer (T1) and dolomitic Zechstein Limestone (Ca1). In these datasets, we provide quantitative mineralogical and geochemical data of drill core samples from the Saale Basin in East Germany. The samples include the uppermost Rotliegend sandstone (S1), Kupferschiefer (T1) and lowermost Zechstein Limestone (Ca1), referred as the Kupferschiefer system, from three drill cores (Sangerhausen, Allstedt and Wallendorf). This data publication includes quantitative mineralogy (X-ray diffraction), bulk rock major, minor and trace element geochemistry (X-ray fluorescence and inductively coupled mass spectrometry) and total organic carbon (elemental analyzer).

Description: The Southern Permian basin in central Europe contains a number of important high-grade sediment-hosted Cu deposits. Laterally extensive stratabound Cu and Zn-Pb sulfide mineralized rocks are located at a major stratigraphic redox boundary, where coarse-grained continental sandstones of the uppermost Rotliegend Group are overlain by carbonaceous mudstones (T1) and limestones (Ca1) of the Zechstein Formation. This study investigates the diagenetic evolution and style of sulfide mineralization in three drill cores that intersect Cu and Zn-Pb sulfide mineralized rocks at three locations (Sangerhausen, Allstedt, and Wallendorf) in the Saale subbasin (Eastern Germany), which is located at the southern margin of the Southern Permian basin. We combine macro- to microscale petrographic data (binocular, transmitted and reflected light, and scanning electron microscopy) with quantitative X-ray diffractometry and bulk-rock geochemical analyses. Petrographic results show extensive, primary-porosity-occluding, early diagenetic calcite cementation that predates both the diagenetic alteration of detrital clasts and sulfide mineralization. The highest-grade Cu and Zn-Pb sulfides (bornite, sphalerite, and galena) replace the calcite cement, with subordinate replacement of dolomite and detrital clasts. Quantitative mineralogical and geochemical data demonstrate that the highest base metal (Cu, Zn, and Pb) concentrations are associated with carbonate-rich samples, mostly as disseminated mineralization in the middle T1. Bulk-rock geochemical results show enrichment and covariation of redox-sensitive trace elements (RSTEs, e.g., Mo) with total organic carbon content toward the lower T1, consistent with highly reducing depositional conditions. Overall, the distribution and dissolution of calcite cement across this stratigraphic redox boundary provided the main control on the lateral migration of base metal-bearing fluids and high-grade Cu and Zn-Pb sulfide mineralization in the Saale subbasin.

Description: The Kupferschiefer districts in Central Europe contain some of the world’s highest-grade sediment-hosted stratiform Cu (SSC) deposits (see Borg et al., 2012). The high-grade sulfide mineralization in the organic matter-rich marine mudstones of the Kupferschiefer (T1), and also in the underlying continental sandstones of the uppermost Rotliegend (S1) and overlying Zechstein Limestone (Ca1), in the Saale subbasin (Eastern Germany) are dominantly formed as a replacement of calcite cement (Mohammedyasin et al., 2023). We provide carbonate major element chemistry, carbon isotope composition of organic matter, and calcite carbon and oxygen isotope microanalysis datasets of drill core samples from the Saale subbasin in Eastern Germany. The samples include the uppermost Rotliegend sandstone (S1), Kupferschiefer (T1) mudstones and lowermost Zechstein Limestone (Ca1), referred as the Kupferschiefer system, from three drill cores (Sangerhausen, Allstedt and Wallendorf).

Description: The Kupferschiefer district in Central Europe contains some of the world's highest-grade sediment-hosted stratiform Cu (SSC) deposits. In the Saale subbasin (eastern Germany), high-grade sulfides formed via replacement of calcite cement in the continental sandstones of the uppermost Rotliegend (S1), the overlying organic-rich marine mudstones of the Kupferschiefer (T1) and the Zechstein Limestone (Ca1) units. The spatial distribution of the calcite cement, therefore, had a fundamental role to play in the Cu mineralizing system. In this study, we investigate the origin of the calcite cement (and crosscutting calcite veins) using detailed petrography (cathodoluminescence, CL; scanning electron microscopy, SEM), major element chemistry (electron probe microanalyzer, EPMA), and secondary ion mass spectrometry (SIMS) microanalyses of δ13C and δ18O values in drill core samples (n = 47) from the Saale subbasin. The calcite cement in the S1, T1 and Ca1 has a similar CL response and major element chemistry, suggestive of a common origin. Overlapping δ13C and δ18O values in calcite cement in samples from the S1 and T1 in the Sangerhausen and Wallendorf drill cores also suggest that the calcite cement was derived from fluids of similar composition. The low δ13C values of calcite cement in samples from the S1 (−13‰ to 4.3‰, VPDB) and T1 (−10‰ to 0.7‰) indicates carbonate alkalinity was sourced mainly from seawater-derived fluids and the oxidation of organic matter. The wide range of δ18O values in the calcite cement in the S1 (∼18‰ to 31‰, VSMOW) and T1 (∼ 22‰ to 31‰) samples suggest they are derived from pore fluids with a chemical composition influenced by early diagenetic alteration of detrital clasts, mainly dissolution of volcanic rock fragments, with minor contributions from the influx of meteoric waters and evaporated seawater. The negative δ13C values (down to −15‰) in calcite veins from the T1 and Ca1 indicate sources of carbonate alkalinity derived from organic matter degradation. Our data demonstrate that no isotopic hydrothermal alteration haloes can be inferred from the δ13C and δ18O values in calcite cement associated with the high-grade sulfide mineralization. The lack of systematic isotopic variability in the calcite cement likely indicates the mineralizing fluid flux or temperature was not sufficient to overprint the background sources of isotopic variability, which may help to explain the modest size of SSC deposits in this part of the Kupferschiefer district.

Description: The oxidation of hydrocarbons, including methane, is part of interrelated hydrogeochemical reactions affecting the carbon budget in Earth’s crust. To investigate these processes in deep siliciclastic strata, we analyzed core samples from Lower Triassic red beds in the Mahu Sag (Junggar Basin, northwest China) by coupling petrological observations with high-resolution in situ secondary ion mass spectroscopy stable carbon and oxygen isotope analyses and clumped isotopes (Δ47) of authigenic calcite. The strata contain variable oil and gas content as well as abundant high-valence Fe and/or Mn oxides. Three sequential generations of cement occur, which are characterized as (1) non-luminescent, early diagenetic calcite (MnO 〈0.3%, δ13CVPDB [Vienna Peedee belemnite] = −5.6‰ to −4.1‰); (2) bright-orange luminescent late-stage I calcite (0.75%−5.23% MnO, δ13C = −51.4‰ to −25.8‰); and (3) dull-orange late-stage II calcite (4.10%−12.93% MnO, δ13C = −91.4‰ to −30.9‰). Clumped isotopic thermometry reveals that the calcite precipitation temperature increases successively from 〈40 °C, to 81−107 °C, to finally 107−132 °C, corresponding to three precipitation time periods: before the Late Triassic, from the Early Jurassic to the Early Cretaceous, and from the Early Cretaceous to the present, respectively. δ13C values of −55.7‰ to −25.8‰ indicate that late-stage I calcite is the final product of oxidation of both methane and C2+ hydrocarbons, whereas δ13C values as low as −91‰ indicate that late-stage II calcite is mainly derived from the thermochemical oxidation of methane (δ13C = −46.8‰ to −39.3‰) induced by high-valence Mn and/or Fe oxides. For late-stage I calcite, hydrocarbon oxidation was most likely promoted by high temperatures, although microbial oxidation cannot be completely ruled out. The higher precipitation temperature of late-stage II calcite demonstrates that the oxidation of methane requires higher activation energies than oxidation of C2+ hydrocarbons. We provide reliable geochemical evidence for thermally induced sequential oxidation of hydrocarbons within deep siliciclastic strata.