Correlation between hydrogen isotope ratios of lipid biomarkers and sediment maturity

We investigated the influence of thermal maturity on the hydrogen isotope ratios of sedimentary hydrocarbons to prove that the isotope ratio of hydrocarbons mirrors paleoclimate signatures. δD values from n-alkanes and acyclic isoprenoids of two sediment sections (Kupferschiefer [KS], 258 Ma, and Posidonienschiefer [PS], 184 Ma) with different maturation history were investigated. Both covered thermal maturity from 0.48 to 1.3 R_c (vitrinite reflectance and reflectance calculated from MPI1). Sediment burial up to 4500 m caused thermal maturation of organic matter in the KS horizon from the Early Zechstein basin of Poland, whereas contact metamorphic thermal maturation originated in the Early Toarcian PS (Posidonienschiefer) of the North German Vlotho Massif. The δD values of the extracted n-alkanes positively correlate with thermal maturity in the KS (y = 56‰ × MPI1[x] − 160‰ [VSMOW]) and in the PS (y = 104‰ × MPI1[x] − 200‰ [VSMOW]). The δD values of isoprenoids (i.e., pristane, phytane) were even more enriched with increasing maturity (y = 179‰ × MPI1[x] − 341‰ [VSMOW] in the KS; y = 300‰ × MPI1[x] − 415‰ [VSMOW] in PS).These results explain why isotope ratios of n-alkanes and isoprenoids in mature sediments are generally enriched in D and do not have the expected isotopic difference between n-alkanes and isoprenoids of ∼190‰. Moreover, the correlation between sediment maturity parameters and δD values suggests that after correction the δD values of n-alkanes can be used to reconstruct climate and environment in the geological past.     

The birth of the Paratethys during the Early Oligocene: From Tethys to an ancient Black Sea analogue?

Deeper water black shales, overlain by coccolith-bearing marlstones representing the incipient Paratethys (example: Early Oligocene; Austrian Molasse Basin), have sedimentary characteristics similar to those of the Holocene Black Sea since 7500 years bp. Framboid pyrite size, biomarker and C–N-isotope data additionally indicate that isolation of the Paratethys resulted in Black Sea-type characteristics during nannoplankton zone NP 23.In contrast to the estuarine circulation across the Bosphorus since 7500 years bp, marine conditions prevailed in the incipient Paratethys during NP 21/22. Nitrogen was fixed and low organic carbon accumulation rates prevailed. In both settings a vertical density water-column stratification was accompanied by photic zone anoxia, and by anaerobic methane oxidation in the Paratethys. In the Paratethys increased run off, starting in NP 22, led to estuarine circulation during NP 23. During this period cyclic blooms of calcareous nannoplankton resulted in high calcite accumulation rates which diluted the coeval clay sedimentation. Similar sedimentary features in the Black Sea and the Paratethys during the earliest Oligocene are result from opposite paleoceanographic developments, both leading to estuarine circulation patterns. In the Black Sea, permanent photic zone anoxic conditions were established 7500 years bp in response to the first invasion of saline Mediterranean waters into the former freshwater lake. In contrast, brackish surface water in the Paratethys resulted from nutrient-rich freshwater diluting the marine water body.     

Biogeochemistry of particulate organic matter from lakes of different trophic levels in Switzerland

Biomarker compositions of particulate organic matter (POM) from the oligotrophic Lake Brienz and the eutrophic Lake Lugano (both Switzerland) are compared, in order to obtain information about organic matter (OM) production and transformation processes in relation to water column stratification. Eutrophic conditions in Lake Lugano are reflected by enhanced alkalinity, elevated total organic carbon (TOC) and chlorin contents compared with Lake Brienz. Lower δ¹³C values of dissolved inorganic carbon (DIC) in Lake Lugano reflect enhanced OM respiration in the water column.Differences in OM dynamics between both lakes, as well as seasonal variations, are evidenced by TOC-normalised concentration profiles of total fatty acids (FAs) and total neutrals. In Lake Brienz, the results reflect the relative contributions of primary productivity and refractory, allochthonous OM to POM, governed by particle load and interflows due to density stratification. The depth trends at Lake Lugano are a result of high primary productivity, water column stratification and associated particle load in the upper layers, as well as microbially induced degradation close to the chemocline and greater preservation under anoxic conditions. Minor differences exist with regard to the OM composition. In both lakes, FA distributions and the composition of n-alkanols indicate a predominant autochthonous OM source (algae, zooplankton, bacteria). Inputs of OM from diatoms are reflected in highly-branched isoprenoid (HBI) alkenes, 16:1 n-FAs and 24-methylcholesta-5,22-dien-3β-ol (either epibrassicasterol or brassicasterol). Differences in relative proportions of n-C₁₆ vs. n-C₁₈ FAs and alkanols, respectively, as well as in the percentages of C₂₇, C₂₈ and C₂₉ sterols relative to the sum of sterols are related to differences in the abundances of chrysophytes, diatoms and green algae within the euphotic zone of both lakes as well as in bacterial activity and soil in-wash. High relative proportions of cholesterol in the autumn samples, most pronounced at Lake Lugano, were attributed to an increased input from zooplankton grazing in the water column.Differences in OM degradation processes are reflected in slightly higher chlorin index values and higher relative proportions of saturated vs. unsaturated n-FAs in Lake Lugano. Higher contents of branched chain FAs, 16:1ω7 n-FA, and enhanced 18:1ω7/18:1ω9 n-FA ratios suggest enhanced bacterial biomass in the water column of Lake Lugano close to the chemocline. Increasing proportions of saturated n-FAs and n-alkanols with increasing water depth, most distinct in the autumn for both lakes, argue for intensified bacterial activity and degradation of OM during autumn. High relative contents of sterols and low n-alkanol concentrations in POM close to the chemocline at Lake Lugano during spring are interpreted to reflect higher primary productivity in the photic zone, OM export to the deeper parts and enhanced degradation rates of more labile constituents (i.e. C₁₃–C₂₀ n-alkanols), as compared to Lake Brienz.     

Composition and origin of organic matter in surface sediments of Lake Sarbsko: A highly eutrophic and shallow coastal lake (northern Poland)

We present an organic geochemical study of surface sediments of Lake Sarbsko, a shallow coastal lake on the middle Polish Baltic coast. The aim was to provide evidence concerning the origin of the organic matter (OM) and its compositional diversity in surface deposits of this very productive, highly dynamic water body. The content and composition of the OM in the bottom sediments were investigated at 11 sampling stations throughout the lake basin. OM sources were assigned on the basis of bulk indicators [total organic carbon (TOC), total nitrogen (TN), δ¹³C_TOC and δ¹⁵N and extractable OM yield], biomarker composition of extractable OM and compound-specific C isotope signatures. The source characterization of autochthonous compounds was verified via phytoplankton analysis. The distribution of gaseous hydrocarbons in the sediments, as well as temporal changes in lake water pH, the concentration of DIC (dissolved inorganic carbon) and δ¹³C_DIC were used to trace OM decomposition.The sedimentary OM is composed mainly of well preserved phytoplankton compounds and shows minor spatial variability in composition. However, the presence of CH₄ and CO₂ in the bottom deposits provides evidence for microbial degradation of sedimentary OM. The transformation of organic compounds in surface, bottom and pore waters via oxidative processes influences carbonate equilibrium in the lake and seasonally favours precipitation or dissolution of CaCO₃.The data enhance our understanding of the relationships between the composition of sedimentary OM and environmental conditions within coastal ecosystems and shed light on the reliability of OM proxies for environmental reconstruction of coastal lakes.     

Geochemical and isotopic composition of organic matter in the Kupferschiefer of the Polish Zechstein basin: relation to maturity and base metal mineralization

max vs the present depth of the Kupferschiefer, soluble organic matter (SOM) yields, and relative proportions of saturated and aromatic hydrocarbons of the SOM provide evidence for an oxidative alteration of organic matter in highly mineralized Kupferschiefer samples near the Rote F?ule zones. This is confirmed by differences in the composition of the saturated and aromatic hydrocarbon fractions of the soluble organic matter: Saturated hydrocarbons from Rote F?ule samples are dominated by short-chain n-alkanes and higher abundances of pristane and phytane relative to heptadecane (n-C17) and octadecane (n-C18), respectively, compared with samples more distant to the Rote F?ule zone. Compositional changes of the aromatic hydrocarbon fractions with decreasing distance to that zone are characterized by the occurrence of polycyclic aromatic hydrocarbons and elevated ratios of phenanthrene to methylphenanthrenes that are attributed to demethylation reactions and resulted in a decrease of the methylphenanthrene index (MPI 1). Kupferschiefer samples from the barren zone of the Polish Basin do not show these alteration patterns. The observed variations in organic matter composition with burial depth are consistent with changes due to increasing thermal maturation. Maturity assessment is achieved from MPI 1 and the methyldibenzothiophene ratio (MDR). From the relationship between the maturity of organic matter in terms of vitrinite reflectance values and depth of the Kupferschiefer strata, a continuous increase in reflectance of vitrinite is obtained within the Polish Basin. The alteration pattern of organic matter related to base metal mineralization of the Kupferschiefer corresponds to changes in the isotopic composition of organic carbon and calcite. Kerogen within, or close to, Rote F?ule zone is enriched in ¹³C caused by the preferential release of isotopically light organic compounds through progressive degradation of organic matter. The opposite tendency towards lower δ ¹³C and δ ¹⁸O values of calcite provides evidence for isotopic exchange between carbonate and the oxidizing, ore-bearing solutions and for organic matter remineralization. In contrast, organic matter and calcite from the Kupferschiefer do not show regular trends in δ ¹³C with increasing thermal maturation. Received: 25 June 1999 / Accepted: 1 December 1999     

Origin of ore fluids in the Muruntau gold system: Constraints from noble gas, carbon isotope and halogen data

Hydrothermal vein minerals directly associated with native gold mineralization in the Muruntau vein system (Uzbekistan) have been studied for noble gas, carbon isotope and halogen chemistry of the trapped ore-related fluids. Helium trapped in early arsenopyrite 1, which has preserved the original fluid signature better than associated scheelite and quartz, indicates a small input from a mantle source (?5% of total He). However, the overwhelming majority of the He in the fluid (∼95%) is from crustal sources. The noble gases Ne, Kr and Xe in the sample fluids are dominated by gases of atmospheric origin. The carbon isotope (δ¹³C: −2.1‰ to −5.3‰) and halogen characteristics of the fluids (log Br/Cl: −2.64 to −3.23) lend further support for the activity of juvenile fluids during the main ore stage. The high proportion of crustal components in the ore-forming fluids may be explained by intense fluid-rock interaction and is also supported by previous Nd and Sr isotope studies. The involvement of a juvenile fluid component during the main stage of hydrothermal activity at Muruntau (∼275 Ma) can be linked to the emplacement of lamprophyric dikes at Muruntau, due to apparently overlapping ages for high-temperature alteration, related ore vein formation and intrusion of the dikes. The input of mantle-derived fluids, possibly related to the Hercynian collisional event in the western Tien Shan, stimulated intense fluid-rock interaction in the crust. In this context, the mantle-derived fluid should be considered as one possible carrier of metals. Significant amounts of external meteoric fluids circulating in fracture systems are interpreted to have modified the noble gas signature of fluid in quartz, mostly during late, low temperature fluid circulation.     

Depositional environment and hydrocarbon source potential of the Oligocene Ruslar Formation (Kamchia Depression; Western Black Sea)

The Oligocene Ruslar Formation is a hydrocarbon source rock in the Kamchia Depression, located in the Western Black Sea area. Depositional environment and source potential of the predominantly pelitic rocks were investigated using core and cuttings samples from four offshore wells. In these wells the Ruslar Formation is up to 500 m thick. Based on lithology and well logs, the Ruslar Formation is subdivided from base to top into units I–VI. Dysoxic to anoxic conditions and mesohaline to euhaline salinities prevailed during deposition of the Ruslar Formation. Relatively high oxygen contents occurred during early Solenovian times (lower part of unit II), when brackish surface water favoured nannoplankton blooms and the deposition of bright marls (“Solenovian event”). Anoxic conditions with photic zone anoxia were established during late Oligocene times (units III and IV) and, probably, reflect a basin-wide anoxic event in the Eastern Paratethys during Kalmykian times. Organic carbon content in the Ruslar Formation is up to 3%. Autochthonous aquatic and allochthonous terrigenous biomass contribute to the organic matter. Relatively high amounts of aquatic organic matter occur in the lower part of the Ruslar Formation (units I and II) and in its upper part (unit VI). Diatoms are especially abundant in the lower part of unit VI. The kerogen is of type III and II with HI values ranging from 50 to 400 mgHC/gTOC. Units I and II (Pshekian, lower Solenovian) are characterized by a fair (to good) potential to produce gas and oil, but potential sources for gas and oil also occur in the Upper Oligocene units IV–VI.     

Oxygen isotope fractionation between oxygen of different sites in illite minerals: a potential single-mineral thermometer

The experimental results of Hamza and Epstein mark internal oxygen isotope fractionations of hydrosilicates as potential single-mineral thermometers. In this study methodical investigations were made to determine the oxygen isotope ratios of hydroxyl groups in silicate minerals. As a reference material a commercial kaolinite was examined by vacuum extraction and by use of a modified partial fluorination technique first deseribed by Hamza and Epstein. The concordance of the results argue against oxygen isotope fractionation during dehydroxylation. Consequently, vacuum extraction can be used to determine the internal fractionation of minerals, which contain no ferrous iron. For calibration of the internal oxygen isotope fractionation, hydrothermally formed illites from the Lone Gull uranium deposit in Canada and from the Leuggern exploration drill site in Switzerland were investigated. Formation temperatures of the hydrothermal mineralization were estimated by mineral paragenesis, illite crystallinity and by oxygen isotope fractionations on coexisting mineral phases. the oxygen isotope fractionation between oxygen of different sites in several selected illites from both regions has been analysed. The results indicate a linear correlation between the illite-OH oxygen isotope fractionation and temperature. The fractionation can be expressed by the following equation:

Bacterial methane in the Atzbach-Schwanenstadt gas field (Upper Austrian Molasse Basin), Part I: Geology

Bacterial methane gas accumulations occur in Upper Oligocene to Early Miocene clastic deepwater sediments in the Austrian Molasse Basin. Methane gas is produced from the Upper Puchkirchen Fm. (Aquitanian) in the Atzbach-Schwanenstadt gas field which is one of the largest gas fields in this basin.