A photoautotrophic source for lycopane in marine water columns

Suspended particulate matter and recent sediments from diverse oceanic sites have been investigated for their contents of lycopane. Lycopane was present in all samples, including both oxic and anoxic water column and sediments. The highest concentrations in the water column were found in surface waters of the central Pacific gyre (1.5 ng/L) and in the anoxic waters of the Cariaco Trench (1.1 ng/L) and the Black Sea (0.3 ng/L). Vertical concentration profiles suggest that lycopane is probably algal in origin. Moreover, biogeochemical conditions in anoxic zones apparently result in a secondary production of lycopane from an as yet unidentified precursor. Compound-specific carbon isotopic analyses have been carried out on lycopane from water column and sediment samples. Isotopic compositions of lycopane range between -23.6% and -32.9% and are consistent with a photoautotrophic origin. We postulate that some lycopane is produced in surface waters of the ocean, while additional lycopane is produced in anoxic zones by anaerobic microbial action on an algal precursor.     

Carbon and nitrogen isotopic compositions of alkyl porphyrins from the Triassic Serpiano oil shale

The carbon and nitrogen isotopic compositions of seven of the most abundant alkylporphyrins from the Serpiano oil shale (marine, Triassic) were determined. For the C31 and C32 butanoporphyrins, values of delta 13CPDB and delta 15NAIR averaged -24.0% and -3.1%. In contrast, the C31 and C32 methylpropanoporphyrins, DPEP, and a C30 13-nor etioporphyrin had delta 13C and delta 15N values averaging -27.5 and -3.3%, respectively. Carbon and nitrogen isotopic values for kerogen averaged -30.8 and -0.9, whereas those for total extract averaged -31.6, and -4.0%. The butanoporphyrins apparently derive from a biological source different from that giving rise to the other porphyrins, their 13C enrichment not being related to carbon isotopic fractionation accompanying diagenetic reactions. The delta 15N values for all the porphyrins indicate that the depletion of 15N observed in the kerogen is of primary origin. Consistent with the very high abundance of hopanoids and methyl hopanoids in the aliphatic hydrocarbon fraction, it is suggested that cyanobacterial fixation of N2 may have been the main cause of 15N depletion.     

Photoelectric photometry of the stars HD 29647 and HDE 283809 in the Taurus dark cloud

Photoelectric Vilnius photometry of the B-type stars HD 29 647 and HDE 283 809 in the direction of the Taurus molecular cloud indicates their brightness and energy distribution to be constant within 1–2%. The interstellar extinction law is determined for the star HDE 283 809 from the photometry data in the Vilnius andUBVRJHKL systems, which yield the ratioR=A _V/E_B-V=3.5 and grain sizes exceeding the average by approximately 10%. The interstellar extinction law for the two stars is found to be the same in the infrared, however, it is very different in the near ultraviolet. The new spectra of HDE 283 809 confirm the earlier classification and indicate an absence of emission in the hydrogen lines. The interstellar band at 443 nm is observed but its intensity is a half of what is expected forE _B-V=1.61. The observed peculiarities of the energy distribution in the spectrum of HDE 283 809 apparently originate in interstellar or circumstellar dust, not in the star itself.Operated by the Association of Universities for Research in Astronomy, Inc., under contract with the National Science Foundation.     

An isotopic biogeochemical study of Neoproterozoic and Early Cambrian sediments from the Centralian Superbasin, Australia

Organic matter from Neoproterozoic and Early Cambrian sediments of the Amadeus and Officer basins of the Centralian Superbasin, Australia, has been studied for biomarker distributions and the carbon isotopic compositions of kerogen and individual hydrocarbons. These sediments represent both shallow and deep water marine facies in the older sections and marine and saline lacustrine carbonate deposits in the Cambrian. Hydrocarbon biomarker patterns were found to be quite consistent with the known sedimentary environments and provide valuable insights into the biogeochemical changes which accompanied the transition from a microbially-dominated ocean to the early stages of metazoan radiation. In particular, carbon isotopic data for n-alkyl and isoprenoid lipids presented here, and in earlier studies, showed a reversal in carbon isotopic ordering between the Proterozoic and Phanerozoic. By comparison with the delta 13C of kerogen, n-alkyl lipids from deep-water Proterozoic sediments were enriched in 13C and appear to be derived mainly from heterotrophs whilst open marine Phanerozoic counterparts are 13C depleted and evidently derived mainly from autotrophs. Data from the samples studied here are consistent with a model invoking a change in the redox structure of the ocean, possibly aided by the innovation of faecal pellets.     

Evidence for gammacerane as an indicator of water column stratification

A new route for the formation of gammacerane from tetrahymanol is proposed; in addition to dehydration and hydrogenation, sulphurisation and early C-S cleavage are shown to be important in the pathway of formation, especially in marine sediments. Evidence is twofold. First, relatively large amounts of the gammacerane skeleton are sequestered in S-rich macromolecular aggregates formed by natural sulphurisation of functionalised lipids. Selective cleavage of polysulphide linkages with MeLi/MeI led to formation of 3-methylthiogammacerane, indicating that the gammacerane skeleton is primarily bound via sulphur at position 3, consistent with the idea that tetrahymanol (or the corresponding ketone) is the precursor for gammacerane. Second, upon mild artificial maturation of two sediments using hydrous pyrolysis, gammacerane is released from S-rich macromolecular aggregates by cleavage of the relatively weak C-S bonds. The stable carbon isotopic compositions of gammacerane and lipids derived from primary producers and green sulphur bacteria in both the Miocene Gessoso-solfifera and Upper Jurassic Allgau Formations indicate that gammacerane is derived from bacterivorous ciliates which were partially feeding on green sulphur bacteria. This demonstrates that anaerobic ciliates living at or below the chemocline are important sources for gammacerane, consistent with the fact that ciliates only biosynthesize tetrahymanol if their diet is deprived of sterols. This leads to the conclusion that gammacerane is an indicator for water column stratification, which solves two current enigmas in gammacerane geochemistry. Firstly, it explains why gammacerane is often found in sediments deposited under hypersaline conditions but is not necessarily restricted to this type of deposits. Secondly, it explains why lacustrine deposits may contain abundant gammacerane since most lakes in the temperate climatic zones are stratified during summer.     

A molecular and carbon isotopic study towards the origin and diagenetic fate of diaromatic carotenoids

Pyrolysates of high-molecular-weight sedimentary fractions of the Duvernay Formation (Western Canada Basin) are dominated by 1,2,3,4- and 1,2,3,5-tetramethylbenzene, which, generated via beta-cleavage, indicate the presence of diaromatic carotenoids in the macromolecular aggregates. This was substantiated by desulphurization of sulphur-rich aggregates of the polar fraction, which released (partly) hydrogenated carotenoids. Furthermore, these components were important constituents of the aromatic hydrocarbon fractions and related oils. Apart from renieratane and isorenieratane, 1H NMR analysis established the aromatic substitution pattern of the most abundant component present, which was identified as a diaromatic compound with an unprecedented 2,3,6-/3,4,5-trimethyl aromatic substitution pattern. Molecular and isotopic analyses of both soluble and insoluble fractions of organic matter revealed relationships between diagenetically-derived carotenoids found in bitumen and related oils and their precursors incorporated into high-molecular-weight fractions. Aryl isoprenoids, important components in extracts and oils, were apparently derived from thermal cracking of bound diaromatic carotenoids rather than cleavage of free carotenoids as previously suggested. Furthermore, products derived from diaromatic carotenoids were substantially enriched in 13C relative to n-alkanes of algal origin. Together with the characteristic carotenoids, this isotopic enrichment provides evidence of significant contributions from photosynthetic green sulphur bacteria (Chlorobiaceae), which fix carbon via the reversed tricarboxylic acid (TCA) cycle. In spite of the prominence of these molecular signals, the overall isotopic composition of the organic matter indicated that only a very small portion of the preserved organic carbon was derived from the biomass of photosynthetic green sulphur bacteria.     

Predictive isotopic biogeochemistry: hydrocarbons from anoxic marine basins

Carbon isotopic compositions were determined for individual hydrocarbons in water column and sediment samples from the Cariaco Trench and Black Sea. In order to identify hydrocarbons derived from phytoplankton, the isotopic compositions expected for biomass of autotrophic organisms living in surface waters of both localities were calculated based on the concentrations of CO2(aq) and the isotopic compositions of dissolved inorganic carbon. These calculated values are compared to measured delta values for particulate organic carbon and for individual hydrocarbon compounds. Specifically, we find that lycopane is probably derived from phytoplankton and that diploptene is derived from the lipids of chemoautotrophs living above the oxic/anoxic boundary. Three acyclic isoprenoids that have been considered markers for methanogens, pentamethyleicosane and two hydrogenated squalenes, have different delta values and apparently do not derive from a common source. Based on the concentration profiles and isotopic compositions, the C31 and C33 n-alkanes and n-alkenes have a similar source, and both may have a planktonic origin. If so, previously assigned terrestrial origins of organic matter in some Black Sea sediments may be erroneous.     

The combined application of organic sulphur and isotope geochemistry to assess multiple sources of palaeobiochemicals with identical carbon skeletons

Five immature sediments from a Messinian evaporitic basin, representing one evaporitic cycle, were studied using molecular organic sulphur and isotope geochemistry. It is shown that a specific carbon skeleton which is present in different "modes of occurrence" ("free" hydrocarbon, alkylthiophene, alkylthiolane, alkyldithiane, alkylthiane, and sulphur-bound in macromolecules) may have different biosynthetic precursors which are possibly derived from different biota. It is demonstrated that the mode of occurrence and the carbon isotopic composition of a sedimentary lipid can be used to "reconstruct" its biochemical precursor. This novel approach of recognition of the suite of palaeobiochemicals present during the time of deposition allows for identification of the biological sources with an unprecedented specificity.     

An isotopic biogeochemical study of the Green River oil shale

Thirty-five different samples from three different sulfur cycles were examined in this stratigraphically oriented study of the Shell 22x-l well (U.S.G.S. C177 core) in the Piceance Basin, Colorado. Carbon isotopic compositions of constituents of Green River bitumens indicate mixing of three main components: products of primary photoautotrophs and their immediate consumers (delta approximately -30% vs PDB), products of methanotrophic bacteria (delta approximately -85%), and products of unknown bacteria (delta approximately -40%). For individual compounds synthesized by primary producers, delta-values ranged from -28 to -32%. 13C contents of individual primary products (beta-carotane, steranes, acyclic isoprenoids, tricyclic triterpenoids) were not closely correlated, suggesting diverse origins for these materials. 13C contents of numerous hopanoids were inversely related to sulfur abundance, indicating that they derived both from methanotrophs and from other bacteria, with abundances of methanotrophs depressed when sulfur was plentiful in the paleoenvironment. gamma-Cerane coeluted with 3 beta(CH3),17 alpha(H),21 beta(H)-hopane, but delta-values could be determined after deconvolution. gamma-Cerane (delta approximately -25%) probably derives from a eukaryotic heterotroph grazing on primary materials, the latter compound (delta approximately -90%) must derive from methanotrophic organisms. 13C contents of n-alkanes in bitumen differed markedly from those of paraffins generated pyrolytically. Isotopic and quantitative relationships suggest that alkanes released by pyrolysis derived from a resistant biopolymer of eukaryotic origin and that this was a dominant constituent of total organic carbon.