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.     

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.     

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.     

Changes in palaeoenvironmental conditions during deposition of the Permian Kupferschiefer (Lower Rhine Basin, northwest Germany) inferred from molecular and isotopic compositions of biomarker components

Biomarker distributions based on GC and GC-MS data supplemented by stable carbon isotopic compositions based on irm (isotope ratio monitoring) GC-MS data have been used to investigate changes in depositional conditions in a number of samples from a 2 m core (Rheinberger Heide) covering the entire deposition of the Permian Kupferschiefer (Lower Rhine Basin, northwest Germany). Compound classes investigated are aliphatic and aromatic hydrocarbons and maleimides (1H-pyrrole-2,5-diones). The core has been previously divided into four sections: TI, TIIA, TIIB and TIII based on lithology. The biomarker distributions and the δ¹³C values of components indicate contributions from cyanobacteria, algae, green sulphur bacteria and higher plants (minor) throughout Kupferschiefer deposition. All of the phytoplanktonic components show ¹³C enrichment in the lowest section, suggesting a greater productivity. The occurrence of components derived from green sulphur bacteria (Chlorobiaceae) indicates that the entire deposition was characterised by periods of photic zone anoxia. Such conditions were rapidly established after the initial transgression of the Zechstein Sea and may have been productivity-driven, but were less prevalent during deposition of the upper core sections.     

Molecular and bulk isotopic analyses of organic matter in marls of the Mulhouse Basin (Tertiary, Alsace, France)

Contents of 13C in kerogens and carbonates in 21 samples from a core of the MAX borehole, Mulhouse Evaporite Basin, range from -27.3 to -23.5 and -3.7 to -1.8% vs PDB, respectively. Organic nitrogen in the same samples is enriched in 15N relative to atmospheric N2 by 12.2-15.7%. Hydrogen indices and delta values for kerogens vary systematically with facies, averaging 493 mg HC/g Corg and -25.7% in the most saline facies (dominated by inputs from aquatic sources) and 267 mg HC/g Corg and -23.7% in the least saline facies (50/50 aquatic/terrigenous). Values of delta were measured for individual aliphatic hydrocarbons from three samples representing three different organic facies. For all samples, terrigenous inputs were unusually rich in 13C, the estimated delta value for bulk terrigenous debris, apparently derived partly from CAM plants, being -22.5%. In the most saline facies, isotopic evidence indicates the mixing of 13C-depleted products of photosynthetic bacteria with 13C-enriched products of halotolerant eukaryotic algae. At lower salinities, a change in the producer community is marked by a decrease in the 13C content of algal lipids. The content of 13C in algal lipids increases in the least saline facies, due either to succession of different organisms or to decreased concentrations of dissolved CO2.     

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.     

贵州瓮安陡山沱组磷块岩生物标志物特征及对沉积环境的指示

贵州瓮安新元古界陡山沱组磷块岩中发现的瓮安生物群主要包括多细胞藻类、蓝菌、疑源类、后生动物休眠卵及胚胎、管状后生动物和两侧对称的后生动物等化石类型。对瓮安陡山沱组磷块岩的有机地球化学分析表明,烃类有机组分包括正构烷烃、萜类、甾类和类异戊二烯烃。正构烷烃主峰为C21,碳数分布范围宽;OEP值为1．03,接近1。Pr／Ph比值为0．95,植烷略显优势。规则甾烷呈不对称的“V”字形分布,表现为C27〉C29〉C28的分布特征。C27占优势可能是由大量的带刺疑源类昕致。生物标志物特征指示瓮安陡山沱组磷块岩中的有机物来源于藻类和细菌,显示还原性、较高盐度的成磷沉积环境。     

Lipid biogeochemistry of Phormidium and Microcoleus mats

A study on the predominant sources of organic matter and the main diagenetic processes in two different cyanobacterial mats from evaporite-controlled environments was performed. Fatty acids, hydrocarbons, alcohols, ketones and aldehydes were anlyzed in selected millimetre and submillimetre core sections. The changes in lipid composition were evaluated by comparison with the vertical distributions of the populations observed by optic microscopy and with the lipid patterns of enrichment cultures of species such as cyanobacteria, diatoms, purple bacteria, sulphate-reducers and methanogens obtained from the mats.The cyanobacteria Phormidium valderianum and Microcoleus chthonoplastes are the predominant primary producers, and occur almost as monocultures in the respective top layers. However, these mat-forming organisms only leave minor features in the solvent-extractable lipid sedimentary record. The predominant fatty acid distributions parallel the composition observed in the enrichment cultures of purple bacteria and appear mixed with acids characteristic of heterotrophic eubacteria such as sulphate-reducers. The concentrations of these lipids are, however, 5–10 times lower than the cyanobacterial acids from the top layer. De novo heterotrophic eubacterial synthesis is also observed in cases such as the highly branched isoprenoid eicosenes, the major hydrocarbon in the deep layers (>2 mm) of the Phormidium mat. Other major diagenetic changes involve dehydration and hydrogenation. These two processes take place concurrently under anoxic conditions and have been observed among the sterols and the isoprenoid alcohols. Significant amounts of 5ß(H)-stanols were observed in the more reducing sections where molecular indicators of methanogenic bacteria were also found.     

Hydrogen-isotopic variability in fatty acids from Yellowstone National Park hot spring microbial communities

We report the abundances and hydrogen-isotopic compositions (D/H ratios) of fatty acids extracted from hot-spring microbial mats in Yellowstone National Park. The terrestrial hydrothermal environment provides a useful system for studying D/H fractionations because the numerous microbial communities in and around the springs are visually distinct, separable, and less complex than those in many other aquatic environments. D/H fractionations between lipids and water ranged from −374‰ to +41‰ and showed systematic variations between different types of microbial communities. Lipids produced by chemoautotrophic hyperthermophilic bacteria, such as icosenoic acid (20:1), generally exhibited the largest and most variable fractionations from water (−374‰ to −165‰). This was in contrast to lipids characteristic of heterotrophs, such as branched, odd chain-length fatty acids, which had the smallest fractionations (−163‰ to +41‰). Mats dominated by photoautotrophs exhibited intermediate fractionations similar in magnitude to those expressed by higher plants. These data support the hypothesis that variations in lipid D/H are strongly influenced by central metabolic pathways. Shifts in the isotopic compositions of individual fatty acids across known ecological boundaries show that the isotopic signature of specific metabolisms can be recognized in modern environmental samples, and potentially recorded in ancient ones. Considering all sampled springs, the total range in D/H ratios is similar to that observed in marine sediments, suggesting that the trends observed here are not exclusive to the hydrothermal environment.     

川西坳陷南段天然气来源与碳同位素地球化学研究

川西坳陷南段是四川盆地主要的天然气产区之一。前人对该区天然气的来源有多种见解。为了更清楚地认识此地区天然气的来源与运移，本文分析了平落坝、大兴西和白马庙气田16件天然气样品的C1-C4烃及CO2组份的碳同位素组成。所获得的同位素数据结合化学成份和地质资料表明，3个气田的烃类完全是热解成因的，都来源于气田下面的上三叠统烃源岩。这些气田的甲、乙烷碳同位素组成随深度呈不同规律的变化，这些变化归因于烃源岩生烃的热解过程和烃类运移的动力学过程。平落坝气田中侏罗统气藏的烃类大部份形成于烃源岩低成熟和成熟的早期阶段并受到晚期成熟气体的不断补给。平落坝和大兴西气田多数气藏的烃类被认为是从源区垂直向上运移通过上伏地层而进入气藏的，白马庙气田的烃类被认为是沿断裂通道向上侏罗统气藏聚集的。平落坝和大兴西气田的δ^13Cco2值有很宽的分布范围(-10.7‰～-0.7‰)，这表明气田的CO2由来自基底的海洋碳酸盐岩无机碳成份和沉积地层的有机碳成份混合而成。这些气田的[He／CH4]-[N2／CH4]值之间和δ^13Cco2-δ^13Cc1值之间的相关性表明，非烃气体在进入气藏前已同烃类很好地混合，并被CH4为主流相的气流携带着向气藏运移。     

Carbon isotopic fractionation in lipids from methanotrophic bacteria: relevance for interpretation of the geochemical record of biomarkers

Experiments with cultured aerobic methane oxidising bacteria confirm that their biomarker lipids will be significantly depleted in 13C compared to the substrate. The methanotrophic bacteria Methylococcus capsulatus and Methylomonas methanica, grown on methane and using the RuMP cycle for carbon assimilation, show maximum 13C fractionation of approximately 30% in the resultant biomass. In M. capsulatus, the maximum fractionation is observed in the earliest part of the exponential growth stage and decreases to approximately 16% as cells approach stationary phase. This change may be associated with a shift from the particulate form to the soluble form of the methane monooxygenase enzyme. Less than maximum fractionation is observed when cells are grown with reduced methane availability. Biomass of M. capsulatus grown on methanol was depleted by 9% compared to the substrate. Additional strong 13C fractionation takes place during polyisoprenoid biosynthesis in methanotrophs. The delta 13C values of individual hopanoid and steroid biomarkers produced by these organisms were as much as l0% more negative than total biomass. In individual cultures, squalene was 13C-enriched by as much as 14% compared to the triterpane skeleton of bacteriohopaneaminopentol. Much of the isotopic dispersion in lipid metabolites could be attributed to shifts in their relative abundances, combined with an overall reduction in fractionation during the growth cycle. In cells grown on methanol, where there was no apparent effect of growth stage on overall fractionation there were still significant isotopic differences between closely related lipids including a 5.3% difference between the hopane and 3 beta-methylhopane skeletons. Hopane and sterane polyisoprenoids were also 13C-depleted compared to fatty acids. These observations have significant implications for the interpretation of specific compound isotopic signatures now being measured for hydrocarbons and other lipids present in sediments and petroleum. In particular, biomarker lipids produced by a single organism do not necessarily have the same carbon isotopic composition.     

Sulphur cycling in organic-rich marine sediments from a Scottish fjord

In this study, the biogeochemical transformations of sulphur in organic‐rich marine sediments in a Scottish fjord are investigated by a combination of pore water and sediment geochemistry with sulphide diffusive gradient thin‐film probes and sulphate isotopic data (δ³⁴S and δ¹⁸O). Particular attention is paid to sulphur cycling in the upper sediment profile where sulphate reduction occurs but free sulphide is below the detection limits of conventional pore water geochemical analysis but quantifiable by sulphide diffusive gradient thin film. In the uppermost part of the sediment core, δ¹⁸O sulphate decreased from near‐sea water values to +7‰, indicating that anoxic sulphide oxidation dominated during this interval. Sulphate δ³⁴S remained unchanged as there was no net sulphate reduction (i.e. reduction was balanced by re‐oxidation). Below 4 cm depth, there was a slight increase in sulphate δ³⁴S from 20‰ to 23‰ associated with minor accumulation of iron sulphide. The δ¹⁸O of the sulphate also increased, to around +10‰ at 10 cm depth, as a result of the isotopic exchange of sulphate–oxygen with pore water and/or sulphur disproportionation reactions mediated during sulphur cycling. These processes continued to increase the δ¹⁸O of the sulphate to 14‰ at 20 cm depth with no further change in the δ³⁴S of the sulphate. Below 20 cm depth, free sulphide is detectable in pore waters and both the δ³⁴S of the sulphate and sulphide increase with depth with an offset controlled by kinetic fractionation during bacterial sulphate reduction. The δ³⁴S of the sedimentary organic fraction shifted towards lower, more bacteriogenic, values with depth in the profile, without any increase in the size of this sulphur pool. Thus, the organic sulphur fraction was open to interaction with bacteriogenic sulphide without the occurrence of net addition. Therefore, caution should be exercised when using sulphur isotopic compositions to infer simple net addition of bacteriogenic sulphide to the organic sulphur fraction.     

Contrasting lipid biomarkers in mountain rivers in the Nepal Himalayas:Organic matter characteristics and contribution to the fluvial carbon pool

The Nepal Himalayas is the source of many glacial and spring-fed river systems crisscrossing the moun-tainous terrain.There is an increasing recognition of small mountain rivers(SMRs)to have a significant combined export of dissolved and particulate organic carbon to the global carbon flux.We analyzed flu-vial sediments from two SMRs and compared the results with two large mountain rivers(LMRs)in Nepal.We investigated the organic matter(OM),its compositional variability,and seasonal export using a suite of lipid biomarkers,namely n-alkanes,n-alkanoic acids,n-alkanols,and sterols.The SMRs indicated a similarity in lipid distribution and were affected by a strong seasonal variability.The LMRs showed a dis-tinct contrast in the distribution of lipids in suspended sediments.Bedload sediments in SMRs were derived from diverse sources with weak terrigenous dominance all-year-round compared to the sus-pended load.Functional lipids(n-alkanoic acids and n-alkanols)were the major constituents in SMR sed-iments,indicating better preservation.In contrast,n-alkane concentration dominated over other fractions in suspended sediments retrieved from LMRs.The biomarker trends differentiate SMRs from LMRs with lower transformed/degraded OM in SMRs.A common observation was the strong presence of even carbon compounds in short-chain n-alkanes in SMR bedload sediments and their predominance in suspended sediments in LMRs.Such an unusual trend is attributed to specific biomarker sources from the catchment and ongoing processes in fluvial systems.Topsoil colonized by fungal species under moist acidic condi-tions and autochthonous bacteria contributes to the organic matter pool in shallow SMRs.In LMRs,the contribution from thermally mature sedimentary hydrocarbons and the diagenetic reduction of n-alkanoic acids to n-alkanes are additional contributors to the allochthonous carbon pool.The differences in lipid concentrations,their distribution,seasonality,and the size of rivers suggest differential preserva-tion/degradation of the organic matter pool and their importance in contributing to the carbon budget.     

Partial resolution of sources of n-alkanes in the saline portion of the Parachute Creek Member, Green River Formation (Piceance Creek Basin, Colorado)

Systematic variations in the 13C contents of individual extractable n-alkanes (C16-C29) can be modelled quantitatively and interpreted as indicating contributions from at least five distinct sources. These appear to be cyanobacterial (C16-C18, delta 13C = -37% vs PDB), phytoplanktonic (C16-C23, delta = -32%), chemoautotrophic bacterial (C20-C29, delta = -38%), phytoplanktonic or heterotrophic bacterial (C20-C29, delta = -30%), and vascular plants (C23-C29, delta = -29%). Hydrous pyrolysis of related kerogens yields large quantities of additional n-alkanes with different and much more uniform delta values. The latter materials are apparently derived from the thermolysis of aliphatic biopolymers whose presence in the Green River Oil Shale has been recognized visually.     

The carbon isotopic response of algae, (cyano)bacteria, archaea and higher plants to the late Cenomanian perturbation of the global carbon cycle: Insights from biomarkers in black shales from the Cape Verde Basin (DSDP Site 367)

The stable carbon isotopic compositions of free and sulfur (S)-bound biomarkers derived from algae, (cyano)bacteria, archaea and higher plants and total organic carbon (TOC) during the first phase of the late Cenomanian/Turonian oceanic anoxic event (OAE) were measured in black shales deposited in the southern proto-Atlantic Ocean in the Cape Verde basin (DSDP Site 367) to determine the response of these organisms to this major perturbation of the global carbon cycle resulting from widespread burial of marine organic matter. The average positive isotope excursions of TOC and biomarkers varied from 5.1‰ to 8.3‰. The δ¹³C values were cross correlated to infer potential common sources of biomarkers. This revealed common sources for C₃₁ and C₃₂ hopanes but no 1:1 relationship for pristane and phytane. The correlation of δ¹³C_TOC with the δ¹³C value of sulfur (S)-bound phytane is the strongest. This is because S-bound phytane is derived from phytol that originates from all marine primary producers (algae and cyanobacteria) and thus represents a weighted average of their carbon isotopic compositions. The δ¹³C values of S-bound phytane and C₃₅ hopane were also used to estimate pCO₂ levels. Before the OAE burial event, pCO₂ levels are estimated to be ca. 1300 ppmv using both biomarkers and the independent maximum Rubisco fractionation factors. At times of maximum organic carbon burial rates during the OAE, reconstructed pCO₂ levels are estimated to be ca. 700 ppmv. However, compared to other C/T OAE sections the positive isotope excursion of S-bound phytane is also affected by an increased production during the OAE. When we compensate for this, we arrive at pCO₂ levels around 1000 ppmv, a reduction of ca. 25%. This indicates that burial of organic matter can have a large effect on atmospheric CO₂ levels.     

Carbon isotopic fractionation in lipids from methanotrophic bacteria II: the effects of physiology and environmental parameters on the biosynthesis and isotopic signatures of biomarkers

Controls on the carbon isotopic signatures of methanotroph biomarkers have been further explored using cultured organisms. Growth under conditions which select for the membrane-bound particulate form of the methane monooxygenase enzyme (pMMO) leads to a significantly higher isotopic fractionation than does growth based on the soluble isozyme in both RuMP and serine pathway methanotrophs; in an RuMP type the delta delta 13Cbiomass equaled -23.9% for pMMO and -12.6% for sMMO. The distribution of biomarker lipids does not appear to be significantly affected by the dominance of one or the other MMO type and their isotopic compositions generally track those of the parent biomass. The 13C fractionation behaviour of serine pathway methanotrophs is very complex, reflecting the assimilation of both methane and carbon dioxide and concomitant dissimilation of methane-derived carbon. A limitation in CH4 availability leads to the production of biomass which is 13C-enriched with respect to both carbon substrates and this occurs irrespective of MMO type. This startling result indicates that there must be an additional fractionation step downstream from the MMO reaction which leads to incorporation of 13C-enriched carbon at the expense of dissimilation of 13C-depleted CO2. In these organisms, polyisoprenoid lipids are 13C-enriched compared to polymethylenic lipid which is the reverse of that found in the RuMP types. Serine cycle hopanoids, for example, can vary anywhere from 12% depleted to 10% enriched with respect to the CH4 substrate depending on its concentration. Decrease in growth temperature caused an overall increase in isotopic fractionation. In the total biomass, this effect tended to be masked by physiological factors associated with the type of organism and variation in the bulk composition. The effect was, however, clearly evident when monitoring the 13C signature of total lipid and individual biomarkers. Our results demonstrate that extreme carbon isotopic depletion in field samples and fossil biomarker lipids can be indicative of methanotrophy but the converse is not always true. For example, the hopanoids of a serine cycle methanotroph may be isotopically enriched by more than 10% compared to the substrate methane when the latter is limiting. In other words, hopanoids from some methanotrophs such as M. trichosporium would be indistinguishable from those of cyanobacteria or heterotrophic bacteria on the basis of either chemical structure or carbon isotopic signature.     

Inverse relationship between D/H fractionation in cyanobacterial lipids and salinity in Christmas Island saline ponds

Sediments from 28 saline and hypersaline (salinity 13.6-149.2) ponds on Christmas Island (Kiritimati), in the Central tropical Pacific Ocean, were investigated for the effect of salinity on the D/H ratios of lipid biomarkers. Hydrogen isotope ratios (expressed as δD values) of total lipid extracts, and individual hydrocarbons heptadecane, heptadecene, octadecane, octadecene, diploptene, and phytene from cyanobacteria, became increasingly enriched in deuterium as salinity increased, spanning a range of 100‰, while lake water δD values spanned a range of just 12‰. Net D/H fractionation between lipids and source water thus decreased as salinity increased. Isotope fractionation factors (α_lipid-water) were strongly correlated with salinity, and increased in all compound classes studied by up to 0.0967 over a salinity range of 136. Differences in the hydrogen isotopic composition of lipids derived from three biosynthetic pathways (acetogenic, mevalonate, and non-mevalonate) remained similar irrespective of the salinity. This suggests that the mechanism responsible for the observed α_lipid-water-salinity relationship originates prior to the last common biosynthetic branching point, the Calvin Cycle. We propose that a decrease in the exchange of intra- and extra-cellular (ambient) water resulting from down-regulation or closure of water channels (aquaporins) within cyanobacterial cell membranes, and subsequent isotopic enrichment of the intracellular water, likely resulting from metabolic reactions. These findings imply that caution must be exercised when attempting to reconstruct source water δD values using lipid δD values from environments that may have experienced salinity variations. On the other, hand our results can be used to establish a paleo-salinity proxy based on lipid δD, if additional constraints on source water δD values can be made.     

Okenane, a biomarker for purple sulfur bacteria (Chromatiaceae), and other new carotenoid derivatives from the 1640 Ma Barney Creek Formation

Carbonates of the 1640 million years (Ma) old Barney Creek Formation (BCF), McArthur Basin, Australia, contain more than 22 different C₄₀ carotenoid derivatives including lycopane, γ-carotane, β-carotane, chlorobactane, isorenieratane, β-isorenieratane, renieratane, β-renierapurpurane, renierapurpurane and the monoaromatic carotenoid okenane. These biomarkers extend the geological record of carotenoid derivatives by more than 1000 million years. Okenane is potentially derived from the red-colored aromatic carotenoid okenone. Based on a detailed review of the ecology and physiology of all extant species that are known to contain okenone, we interpret fossil okenane as a biomarker for planktonic purple sulfur bacteria of the family Chromatiaceae. Okenane is strictly a biomarker for anoxic and sulfidic conditions in the presence of light (photic zone euxinia) and indicates an anoxic/oxic transition (temporarily) located at less than 25 m depth and, with a high probability, less than 12 m depth.For the BCF, we also interpret renierapurpurane, renieratane and β-renierapurpurane as biomarkers for Chromatiaceae with a possible contribution of cyanobacterial synechoxanthin to the renierapurpurane pool. Although isorenieratane may, in principle, be derived from actinobacteria, in the BCF these biomarkers almost certainly derive from sulfide-oxidizing phototrophic green sulfur bacteria (Chlorobiaceae). Biological precursors of γ-carotane, β-carotane and lycopane are found among numerous autotrophic and almost all phototrophic organisms in the three domains of life. In the BCF, a paucity of diagnostic eukaryotic steroids suggests that algae were rare and, therefore, that cyanobacterial carotenoids such as β-carotene, echinenone, canthaxanthin and zeaxanthin are the most likely source of observed β-carotane. γ-Carotane may be derived from cyanobacteria, Chlorobiaceae and green non-sulfur bacteria (Chloroflexi), while the most likely biological sources for lycopane in the BCF are carotenoids of the lycopene, rhodopin and spirilloxanthin series abundant in purple sulfur bacteria.     

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.     

Hydrocarbons in Mississippi Fan and intraslope basin sediments

Aliphatic and aromatic hydrocarbons in sediments of the middle and lower Mississippi Fan and two intraslope basins in the Gulf of Mexico are derived from terrestrial organic matter and thermogenic, mature hydrocarbons. The terrestrial hydrocarbon component consists primarily of terrigenous, plant biowaxes (n-alkanes with 21 to 33 carbons). The occurrence of thermogenic hydrocarbons in immature near-surface sediments, their molecular distributions and concentration variations with depth suggest that the majority of these mature hydrocarbons have migrated from a source much deeper in the sediment column. A portion of the thermogenic hydrocarbons may be derived from recycled material and includes phenanthrene, methyl phenanthrenes, chrysene and benzopyrenes. The migrated, thermogenic hydrocarbons include normal and isoprenoid alkanes with less than 21 carbons, naphthalene, methyl naphthalenes, ethyl naphthalenes and other aromatics of similar volatility (i.e., biphenyl, acenaphthene and fluorene). Triterpane, sterane and aromatized sterane distributions suggest that the thermogenic hydrocarbons at both sites have a common source and are overprinted with immature sediment hydrocarbons. The biomarker distributions and carbon isotopic compositions of the thermogenic hydrocarbons are atypical for petroleum produced in the Gulf of Mexico. Molecular distributions of the hydrocarbons are constant, regardless of the present depth of occurrence, suggesting that they have migrated in a separate phase. The upward migration of hydrocarbons from deeper sources is a wide-spread phenomenon in the Gulf of Mexico with several documented cases of massive seepage (visible oil) as well as the more diffuse permeation of Pleistocene sediments of the Mississippi Fan and two intraslopes reported here.