Organic geochemistry of the Boltysh impact crater, Ukraine

The Boltysh crater has been know for several decades and was originally drilled in the 1960s - 1980s in a study of economic oil shale deposits. Unfortunately, the cores were not curated and have been lost. However we have recently re-drilled the impact crater and have recovered a near continuous record of ~400m of organic rich sediments deposited in a deep isolated lake which overly the basement rocks spanning a period ~10 Ma. The Boltysh impact crater, centred at 48°54–N and 32°15–E is a complex impact structure formed on the basement rocks of the Ukrainian shield. The age of the impact is 65.17±0.64 Ma [1]. At 24km diameter, the impact is unlikely to have contributed substantially to the worldwide devastation at the end of the Cretaceous. However, the precise age of the Boltysh impact relative to the Chicxulub impact and its location on a stable low lying coastal plain which allowed formation of the postimpact crater lake make it a particularly important locality. After the impact, the crater quickly filled with water, and the crater lake received sediment input from the surrounding land surface for a period >10 Ma [2]. These strata contain a valuable record of Paleogene environmental change in central Europe, and one of very few terrestrial records of the KT event. This preeminent record of the Paleogene of central Europe can help us to answer several related scientific questions. What is the relative age of Boltysh compared with Chicxulub? How long was the hydrothermal system active for after the impact event? How did the devastated area surrounding the crater recover, and how rapid was the recovery? The first sediments to be deposited in the crater lake were a series of relatively thin turbidites, the sediments then become organic rich shales and oil shales. Within the core there is ~400 m of organic rich shales/oil shales spanning a period of ~10 Ma some of which contain macrofossils such as ostracods, fish and plant fossils. Preliminary palynological studies suggest initial sedimentation was slow after the impact followed by more rapid sedimentation through the Late Paleocene. Hydrocarbons extracted from these samples are commonly dominated by terrestrial n-alkanes (Fig 1), Hopanes (including 3-methylhopanes) and steranes are also abundant and indicate the immaturity of the samples. The immaturity of samples is also evident from the abundance of hopenes, sterenes and oleanenes especially in the upper section of the core. In some of the oil shales the hopenes and sterenes are the most abundant hydrocarbons present. There is variation in the distribution of hydrocarbons/biomarkers and palynology throughout the core caused by changing inputs and environmental conditions

Potential of short wavelength laser ablation of organic materials

Although the literature contains several articles on UV laser ablation of synthetic polymers [1] and human tissue for surgical applications, to our knowledge there is no published record on organic geochemical applications for UV laser pyrolysis–gas chromatography–mass spectrometry (LA-GC-MS). In this study we have demonstrated the use of a 213 nm UV laser beam for ablating kerogens and organic rich rocks to liberate and analyse hydrocarbon signatures and compared the results against IR laser pyrolysis and traditional Py-GC-MS. It is possible to equate laser wavelength to electron volts where 1064 nm (IR) = 1.2 eV and 213 nm (UV) = 5.8 eV. Most chemical bonds have an energy between 2-4 eV and C-C bonds are ~3.6 eV. Organic materials can absorb radiation from a UV laser and chemical bonds can be cleaved cleanly by complex photochemical pathways by a single photon [2]. Ablation occurs with almost no heating of the sample and hence the term laser ablation instead of pyrolysis. Visible or IR lasers have insufficient energy to break bonds with a single photon this results in the heating of sample by the absobtion of energy into the vibrational modes of the molecule which can then result in pyrolysis. A solvent-extracted kerogen consisting mainly of higher plant material (Brownie Butte, Montanna, ~ 70 Ma) was used for initial experiments. A number of other samples have also been analysed. Laser ablation work was performed off-line in a static helium cell followed by solvent extraction of the laser cell. Separate analysis of the same samples using a more traditional flash pyrolysis approach was performed with a CDS pyroprobe and IR laser pyrolysis [3] for comparative purposes. As can be seen in Fig 1 UV laser ablation is able to liberate relatively high molecular weight fragments with no alkenes or other pyrolysis artefacts detected. SEM images of ablation pits indicate there is no obvious thermal alteration of the sample. The results of the pyrolysis techniques (on-line and IR laser pyrolysis) are similar and display a number of artefacts related to the pyrolysis process. Laser ablation of a number of samples has also shown that the distributions of biomarkers are comparable with the solvent extracts. Product yields although not quantified appear to be much higher than traditional pyrolysis technique

Is UV laser ablation a suitable tool for geochemical analysis of organic rich source materials?

Abstract not available

Rapid assembly of highly-functionalised difluorinated cyclooctenones via ring-closing metathesis

Building block methodology from trifluoroethanol and ringclosing metathesis using a Fürstner modification of Grubbs’ conditions allows the rapid synthesis of novel difluorinated cyclooctenones

Molecular, isotopic and <i>in situ</i> analytical approaches to the study of meteoritic organic material

Organic materials isolated from carbonaceous meteorites provide us with a record of pre-biotic chemistry in the early Solar System. Molecular, isotopic and in situ studies of these materials suggest that a number of extraterrestrial environments have contributed to the inventory of organic matter in the early Solar System including interstellar space, the Solar nebula and meteorite parent bodies. There are several difficulties that have to be overcome in the study of the organic constituents of meteorites. Contamination by terrestrial biogenic organic matter is an ever-present concern and a wide variety of contaminant molecules have been isolated and identified including essential plant oils, derived from either biological sources or common cleaning products, and aliphatic hydrocarbons, most probably derived from petroleum-derived pollutants. Only 25% of the organic matter in carbonaceous chondrites is amenable to extraction with organic solvents; the remainder is present as a complex macromolecular aromatic network that has required the development of analytical approaches that can yield structural and isotopic information on this highly complex material. Stable isotopic studies have been of paramount importance in understanding the origins of meteoritic organic matter and have provided evidence for the incorporation of interstellar molecules within meteoritic material. Extending isotopic studies to the molecular level is yielding new insights into both the sources of meteoritic organic matter and the processes that have modified it. Organic matter in meteorites is intimately associated with silicate minerals and the in situ examination of the relationships between organic and inorganic components is crucial to our understanding of the role of asteroidal processes in the modification of organic matter and, in particular, the role of water as both a solvent and a reactant on meteorite parent bodies

Thermochemolysis of the Murchison meteorite: identification of oxygen bound and occluded units in the organic macromolecule

An organic macromolecular residue, prepared from the Murchison meteorite by treatment with hydrofluoric and hydrochloric acids, was subjected to online thermochemolysis with tetramethylammonium hydroxide (TMAH). The most abundant compound released by thermochemolysis was benzoic acid. Other abundant compounds include methyl and dimethyl benzoic acids as well as methoxy benzoic acids. Short chain dicarboxylic acids (C4–8) were also released from the organic macromolecule. Within the C1 and C2 benzoic acids all possible structural isomers are present reflecting the abiotic origin of these units. The most abundant isomers include 3,4-dimethylbenzoic acid (DMBA), 3,5-DMBA, 2,6-DMBA and phenylacetic acid. Thermochemolysis also liberates hydrocarbons that are not observed during thermal desorption; these compounds include naphthalene, methylnaphthalenes, biphenyl, methylbiphenyls, acenaphthylene, acenaphthene, phenanthrene, anthracene, fluoranthene and pyrene. The lack of oxygen containing functional groups in these hydrocarbons indicates that they represent non-covalently bound, occluded molecules within the organic framework. This data provides a valuable insight into oxygen bound and physically occluded moieties in the Murchison organic macromolecule and implies a relative order of synthesis or agglomeration for the detected organic constituents