δ13C of aromatic compounds in sediments, oils and atmospheric emissions: A review

This review discusses major applications of stable carbon isotopic measurements of aromatic compounds, along with some specific technical aspects including purification of aromatic fractions for baseline separation. d13C measurements of organic matter (OM) in sediments and oils are routine in all fields of organic geochemistry, but they are predominantly done on saturated compounds. Aromatic compounds are important contributors to sedimentary organic matter, and provide indication of diagenetic processes, OM source, and thermal maturity. Studies have found evidence for a small13C-enrichment during diagenetic aromatisation of approximately 1–2‰, but the formation of polycyclic aromatic hydrocarbons (PAHs) from combustion and hydrothermal processes seems to produce no effect. Likewise, maturation and biodegradation also produce only small isotopic effects. An early application of d13C of aromatic compounds was in the classification of oil families by source. Bulk measurements have had some success in differentiating marine and terrigenous oils, but were not accurate in all settings. Compound-specific analyses measure certain aromatics with strong links to source, therefore allowing more accurate source identification. d13C measurements of individual aromatic compounds also allow identification of higher plant input in ancient sediments, even after severe diagenetic alteration or combustion to PAHs. Perylene, a PAH with a historically contentious origin, was assigned a source from wood-degrading fungi on the basis of its isotopic composition. Stable carbon isotopic measurements are also important in the analysis of organic matter from Chlorobiaceae, which is an important indicator of photic zone euxinic conditions in ancient sediments. A large range of aromatic products are formed from the carotenoid pigments of Chlorobiaceae, with an enriched carbon isotopic composition characteristic of the reverse tricarboxylic acid photosynthetic pathway employed by this family of organisms. In future, site-specific isotope analysis using techniques such as nuclear magnetic resonance spectrometry and high-resolution isotope ratio mass spectrometry may reveal more information about isotopic effects associated with aromatisation processes and maturation

Novel 1H-Pyrrole-2,5-dione (maleimide) proxies for the assessment of photic zone euxinia

1H-Pyrrole-2,5-diones (maleimides) and 1-alkyl-2,3,6-trimethylbenzenes (aryl isoprenoids), degradation products of tetrapyrrole pigments and carotenoids respectively, were analysed and compared with pristane/phytane (Pr/Ph) ratios to reconstruct past redox conditions in three geologic sections. One section comes from the Middle–Late Devonian and was deposited before the Frasnian–Famennian boundary mass extinction. The two other sections span the Late Permian to the Early Triassic as well as the Late Triassic to the Early Jurassic, and recorded the Permian–Triassic (P/T) and Triassic–Jurassic (T/J) extinction events respectively. The 2-methyl-3-isobutyl-maleimide (Me,i-Bu maleimide) to 2-methyl-3-ethyl-maleimide (Me,Et maleimide) and 2-methyl-3-npropyl- maleimide (Me,n-Pr maleimide) to Me,Et maleimide ratios (Me,i-Bu/Me,Et and Me,n-Pr/Me,Et ratios) in the studied sections revealed amoderate to strong negative correlation to the aryl isoprenoid ratio (AIR), defined as (C13–C17 1-alkyl-2,3,6-trimethylbenzenes)/(C18–C22 1-alkyl-2,3,6-trimethylbenzenes), indicating that these maleimide ratios can be used as robust, specific indicators of photic zone euxinia (PZE). These results agreed with Pr/Ph ratios, which were used as diagnostic indicators to differentiate between oxic and anoxic conditions. In agreement with previous studies, the novel maleimide proxies suggest that all three mass extinctions werelargely characterised by PZE depositional conditions

Australasian asphaltite strandings revisited: Their origin and the effects of weathering and biodegradation on their biomarker and isotopic profiles

Reports of bitumen strandings on the coastlines of South Australia, Victoria, Tasmania and Western Australia date from the early 19th Century (Sprigg and Woolley, 1963; Currie et al., 1992; Volkman et al., 1992; McKirdy et al., 1994; Padley, 1995; Edwards et al., 1998 and references therein). The locations of these strandings along Australia’s southern margin (Fig. 1), and their greater frequency in southeastern South Australia, western Victoria and southern Tasmania, fuelled early petroleum exploration in the region on the assumption that they were sourced from local submarine seepages (Sprigg, 1986; Volkman et al., 1992; McKirdy et al., 1994). Accounts describe a variety of oily substances that can be assigned to three categories, each with a different origin: oils (crude and refined), waxy bitumens and asphaltites (McKirdy et al., 1986, 1994; Padley, 1995; Edwards et al., 1998)

Bitumen II from the Paleoproterozoic Here’s Your Chance Pb/Zn/Ag deposit: Implications for the analysis of depositional environment and thermal maturity of hydrothermally-altered sediments

The formation of sedimentary exhalative (SEDEX) Pb/Zn deposits is linked to ocean euxinia, but recent evidence suggests that ferruginous conditions may have dominated the deep ocean during the Middle Proterozoic, a maximum period for SEDEX distribution. Biomarkers of sulfate-reducing and sulfide-oxidising bacteria are valuable indicators of euxinic conditions in such settings. Organic matter (OM) from SEDEX deposits is often affected by alteration and/or migration, but OM entrapped within the kerogen/mineral matrix (Bitumen II) may be less affected than the freely-extractable OM (Bitumen I). We analysed Bitumen II from the Paleoproterozoic Here’s Your Chance (HYC) Pb/Zn/Ag deposit to find evidence of euxinic conditions in the depositional environment. n-Alkane distributions in Bitumen II are markedly distinct from previously reported Bitumen I. Bitumen II contains long-chain n-alkanes (up to C36 or C38) and a strong even-over-odd distribution in a number of samples, which are 4& to 7& depleted in 13C compared to n-alkanes in Bitumen I and verified as indigenous by comparison with d13C of isolated kerogen.These features are interpreted as evidence of sulfate-reducing and sulfide-oxidising bacteria, confirming that HYC was deposited under euxinic conditions. Bitumen II has the potential to reveal information from OM that is degraded and/or overprinted in Bitumen I. Commonly-used methylphenanthrene maturity ratios give conflicting information as to the relative maturity of Bitumens I and II. Bitumen I contains a far higher proportion of methylated phenanthrenes than Bitumen II. As Bitumen II is sequestered within the kerogen/mineral matrix it may have restricted access to the ‘methyl pool’ of organic compounds that can donate methyl groups to aromatic hydrocarbons. Parameters that include both phenanthrene and methylphenanthrenes do not appear suitable to compare the maturity of Bitumens I and II; hence there is no clear evidence that Bitumen II is of lower thermal maturity than Bitumen I

Biomarker and isotopic trends in a Permian-Triassic sedimentary section at Kap Stosch, Greenland

We report a geochemical study of a composite sedimentary section that captures the Permian-Triassic (PT) transition at Kap Stosch, East Greenland. The samples were from the original paleontological collection of early PT researchers. The rocks, which include samples from four proximal outcrop localities, were deposited during the Late Permian and Early Triassic at the margin of the Boreal Sea with a depositional hiatus and erosional event of unknown duration. Bulk geochemical measurements for most of the samples show good correlation between S2 and TOC% which, combined with low Tmax values, indicate that the organic matter (OM) that formed contemporaneously with sediment deposition is of relatively low maturity. Significant changes through the PT transition include a pronounced switch in the δ13C of TOC from high values near -24% to lower values averaging 32%, that is matched by a significant increase in the hydrogen index (HI) of the kerogen. The Permian samples containing 13C enriched OM also have low Rock-Eval HI values and anomalous pyrograms, indicating that the kerogen is heterogeneous in terms of source and maturity, as confirmed by microscopic analysis of the kerogen concentrates.Samples from the Permian section contain an abundance of black angular fragments of woody tissue in addition to gymnosperm pollen and spinose acritarchs of the Vittatina-Association (Balme, B., 1979. Palynology of Permian-Triassic boundary beds at Kap Stosch. Meddeleleser om Gronland 200, 1-36). In contrast, black woody tissue is rare in samples from the Early Triassic section with well preserved gymnosperm and lycopod pollen and spores of the Protohaploxypinus and Taeniaesporites associations. Biomarkers indicate moderate maturity for Permian samples, with the C27 sterane 20S/(20S + 20R), C31 homohopane 22S/(22S + 22R) ratio and Ts/(Ts + Tm) values all being higher than those for Triassic sediments. The marked switch in maturity indicators across the PT transition suggests an unconformity consistent with palynological observations. The pristane/phytane values are low and the homohopane index values high, indicating that anoxic conditions prevailed throughout deposition of the sediments.Additionally, markers of photic zone euxinia (i.e. isorenieratane, crocetane and 2,3,6-aryl isoprenoids) were present in all samples and all show maximum abundance closest to the PT transition. The C33 n-alkyl cyclohexane, a potential event marker for the onset of the biotic crisis in the Late Permian, was found in samples at, and immediately following, the paleontological PT transition. Despite the distinct change in lithology across the PT transition, the redox and Chlorobi-derived biomarkers indicate that photic zone euxinic conditions prevailed throughout the deposition of the Kap Stosch sedimentary sequence

An organic record of terrestrial ecosystem collapse and recovery at the Triassic–Jurassic boundary in East Greenland

Terrestrial ecosystem collapse at the end of the Triassic Period coincided with a major mass extinction in the marine realm and has been linked to increasing atmospheric carbon dioxide, global warming, and fire activity. Extractable hydrocarbons in samples from the fluvial Triassic–Jurassic boundary section at Astartekløft, East Greenland were analyzed to investigate the molecular and isotopic organic record of biotic and environmental change during this event. Carbon isotopic compositions of individual plant wax lipids show a >4‰ negative excursion coinciding with peak extinction and a further decrease of 2‰ coinciding with peak pCO2 as estimated from the stomatal indices of fossil Gingkoales. An increase of ∼30‰ in the hydrogen isotopic compositions of the same plant wax lipids coincides with ecosystem collapse, suggesting that the biotic crisis was accompanied by strong hydrologic change. Concentrations of polycyclic aromatic hydrocarbons related to combustion also increase together with abrupt plant diversity loss and peak with fossil charcoal abundance and maximum plant turnover, supporting the role of fire in terrestrial extinctions. Anomalously high concentrations of a monoaromatic diterpenoid related to gymnosperm resin derivatives (and similar to dehydroabietane) occur uniquely in samples from the boundary bed, indicating that environmental stress factors leading to peak plant extinction stimulated increased resin production, and that plant resin derivatives may be effective biomarkers of terrestrial ecosystem stress

Comparison of GC–MS, GC–MRM-MS, and GC GC to characterise higher plant biomarkers in Tertiary oils and rock extracts

Higher plant biomarkers occur in various compound classes with an array of isomers that are challenging to separate and identify. Traditional one-dimensional (1D) gas chromatographic (GC) techniques achieved impressive results in the past, but have reached limitations in many cases. Comprehensive two-dimensional gas chromatography (GC × GC) either coupled to a flame ionization detector (GC × GC–FID) or time-of-flight mass spectrometer (GC × GC–TOFMS) is a powerful tool to overcome the challenges of 1D GC, such as the resolution of unresolved complex mixture (UCM). We studied a number of Tertiary, terrigenous oils, and source rocks from the Arctic and Southeast Asia, with special focus on angiosperm biomarkers, such as oleanoids and lupanoids. Different chromatographic separation and detection techniques such as traditional 1D GC–MS, metastable reaction monitoring (GC–MRM-MS), GC × GC–FID, and GC × GC–TOFMS are compared and applied to evaluate the differences and advantages in their performance for biomarker identification. The measured 22S/(22S + 22R) homohopane ratios for all applied techniques were determined and compare exceptionally well (generally between 2% and 10%). Furthermore, we resolved a variety of angiosperm-derived compounds that co-eluted using 1D GC techniques, demonstrating the superior separation power of GC × GC for these biomarkers, which indicate terrigenous source input and Cretaceous or younger ages. Samples of varying thermal maturity and biodegradation contain higher plant biomarkers from various stages of diagenesis and catagenesis, which can be directly assessed in a GC × GC chromatogram.The analysis of whole crude oils and rock extracts without loss in resolution enables the separation of unstable compounds that are prone to rearrangement (e.g. unsaturated triterpenoids such as taraxer-14-ene) when exposed to fractionation techniques like molecular sieving. GC × GC–TOFMS is particularly valuable for the successful separation of co-eluting components having identical molecular masses and similar fragmentation patterns. Such components co-elute when analysed by 1D GC and cannot be resolved by single-ion-monitoring, which prevents accurate mass spectral assessment for identification or quantification

Rapid offline isotopic characterisation of hydrocarbon gases generated by micro scale sealed vessel pyrolysis

The method of offline coupling of micro scale sealed vessel pyrolysis (MSSV-Py) and gas chromatography-isotopic ratio mass spectrometry (GC-IRMS) was developed using a purpose built gas sampling device. The sampling device allows multiple GC and GC-IRMS injections to quantify the molecular composition and isotopic evolution of hydrocarbon gases (n-C1 to n-C5) generated by artificial maturation of sedimentary organic matter. Individual MSSV tubes were introduced into the gas sampling device, which was then evacuated to remove air and filled with helium at atmospheric pressure. The tube was crushed using a plunger after which the device was heated at 120 °C for 1 min to thermally mobilize and equilibrate the generated gas products. Aliquots of the gas phase were sampled using a gas tight syringe and analysed via GC-FID and GC-IRMS. Hydrocarbon gas yields using this technique have been calculated and compared with those obtained previously by online MSSV pyrolysis of the same samples under the same conditions. The major objective of this study was to investigate the potential isotopic fractionation of generated gaseous hydrocarbons within the gas sampling device as a function of time and temperature. For this purpose several tests using a standard gas mixture have been performed on the GC-IRMS. The analyses showed no isotopic fractionation of C1–5 hydrocarbons within 1 hour, minor δ13C enrichment after 5 hours, and significant enrichment after 22 hours for all the compounds at a temperature of 120 °C

Metagenomics of pigmented and cholesterol gallstones: the putative role of bacteria

There is growing evidence for bacteria playing a role in the pathogenesis and formation of pigmented gallstones from humans. These studies mainly involved cultivation of gallstone-associated bacteria and 16S rRNA profiling, providing an indirect link between processes involved in gallstone formation by the bacteria in-situ. Here, we provide functional metagenomic evidence of a range of genes involved in bile stress response, biofilm formation, and anaerobic energy metabolism by Gram-negative Klebsiella in pigmented gallstones from a 76-year-old male patient. Klebsiella was also present in one cholesterol-type stone in a 30-year-old female patient who had additional cholesterol gallstones characterised by Gram-positive bacteria. Pigmented stones further revealed a predominance of genes involved in carbohydrate metabolism, whilst cholesterol stones indicated a profile dominanted by protein metabolism possibly reflecting known chemical differences between Gram-negative and Gram-positive biofilm matrices. Archaeal genes were not detected. Complementary carbon and hydrogen isotopic analyses of cholesterol within the patients' stones revealed homogeneity, suggesting a common diet or cholesterol biosynthesis pathway that has little influence on microbial composition. This pilot study provides a framework to study microbial processes that play a potential role in gallstone formation across markedly different types of stones and patient backgrounds