The global Cretaceous-Tertiary fire: Biomass or fossil carbon

The global soot layer at the K-T boundary indicates a major fire triggered by meteorite impact. However, it is not clear whether the principal fuel was biomass or fossil carbon. Forests are favored by delta value of C-13, which is close to the average for trees, but the total amount of elemental C is approximately 10 percent of the present living carbon, and thus requires very efficient conversion to soot. The PAH was analyzed at Woodside Creek, in the hope of finding a diagnostic molecular marker. A promising candidate is 1-methyl-7-isopropyl phenanthrene (retene,), which is probably derived by low temperature degradation of abietic acid. Unlike other PAH that form by pyrosynthesis at higher temperatures, retene has retained the characteristic side chains of its parent molecule. A total of 11 PAH compounds were identified in the boundary clay. Retene is present in substantial abundance. The identification was confirmed by analysis of a retene standard. Retene is characteristic of the combustion of resinous higher plants. Its formation depends on both temperature and oxygen access, and is apparently highest in oxygen-poor fires. Such fires would also produce soot more efficiently which may explain the high soot abundance. The relatively high level of coronene is not typical of a wood combustion source, however, though it can be produced during high temperature pyrolysis of methane, and presumably other H, C-containing materials. This would require large, hot, low O2 zones, which may occur only in very large fires. The presence of retene indicates that biomass was a significant fuel source for the soot at the Cretaceous-Tertiary boundary. The total amount of elemental C produced requires a greater than 3 percent soot yield, which is higher than typically observed for wildfires. However, retene and presumably coronene imply limited access of O2 and hence high soot yield

Evidence for a single impact at the Cretaceous-Tertiary boundary from trace elements

Not only meteoritic elements (Ir, Ni, Au, Pt metals), but also some patently non-meteoritic elements (As, Sb) are enriched at the K-T boundary. Eight enriched elements at 7 K-T sites were compared and it was found that: All have fairly constant proportions to Ir and Kilauea (invoked as an example of a volcanic source of Ir by opponents of the impact theory) has too little of 7 of these 8 elements to account for the boundary enrichments. The distribution of trace elements at the K-T boundary was reexamined using data from 11 sites for which comprehensive are available. The meteoritic component can be assessed by first normalizing the data to Ir, the most obviously extraterrestrial element, and then to Cl chondrites. The double normalization reduces the concentration range from 11 decades to 5 and also facilitates the identification of meteoritic elements. At sites where trace elements were analyzed in sub-divided samples of boundary clay, namely, Caravaca (SP), Stevns Klint (DK), Flaxbourne River (NZ) and Woodside Creek (NZ), Sb, As and Zn are well correlated with Ir across the boundary implying a common deposition mechanism. Elemental carbon is also enriched by up to 10,000 x in boundary clay from 5 K-T sides and is correlated with Ir across the boundary at Woodside Creek. While biomass would appear to be the primary fuel source for this carbon a contribution from a fossil fuel source may be necessary in order to account for the observed C abundance

Nitrogen geochemistry of a Cretaceous-Tertiary boundary site in New Zealand

Nitrogen in the basal layer of the K-T boundary clay at Woodside Creek, New Zealand, has an abundance of 1100 ppm, a 20-fold enrichment over Cretaceous and Tertiary values. The enrichment parallels that for Ir and elemental carbon (soot); all decrease over the next 6 mm of the boundary clay. The C/N ratio, assuming the nitrogen to be associated with organic rather than elemental carbon, is approximately 5 for the basal layer compared to 20 to 30 for the remainder of the boundary clay. The correlation between N and Ir abundances appears to persist above the boundary, implying that the N is intimately associated with the primary fallout and remained with it during the secondary redeposition processes that kept the Ir abundance relatively high into the lowermost Tertiary. Apparently the basal layer of the boundary clay represents the accumulation of a substantial quantity of N with an isotopic composition approximately 10 percent heavier than background delta value of N-15 values. If the boundary clay represents an altered impact glass from a meteorite impact than it probably denotes a time period of less than 1 year. Therefore, the changes in nitrogen geochemistry apparently occurred over a very short period of time. The high abundance of N and the correspondingly low C/N ratio may reflect enhanced preservation of organic material as a result of the rapid sweepout and burial of plankton by impact ejecta, with little or no bacterial degradation. It is conceivable that the shift in delta value of N-15 may represent an influx of nitrogen from a different source deposited contemporaneously with the impact ejecta. An interesting possibility is that it may be derived from nitrate, produced from the combustion of atmospheric nitrogen

Organic Geochemistry of a Hydrocarbon-rich Calcarenite from the Chicxulub Scientific Drilling Program

The organic geochemistry of hydrocarbon-rich core material recovered by the CSDP is examined to establish whether hydrocarbons are associated with the migration and emplacement of organic matter by post-impact hydrothermal activity

Extraction and isotopic analysis of medium molecular weight hydrocarbons from Murchison using supercritical carbon dioxide

The large variety of organic compounds present in carbonaceous chondrites poses particular problems in their analysis not the least of which is terrestrial contamination. Conventional analytical approaches employ simple chromatographic techniques to fractionate the extractable compounds into broad classes of similar chemical structure. However, the use of organic solvents and their subsequent removal by evaporation results in the depletion or loss of semi-volatile compounds as well as requiring considerable preparative work to assure solvent purity. Supercritical fluids have been shown to provide a powerful alternative to conventional liquid organic solvents used for analytical extractions. A sample of Murchison from the Field Museum was analyzed. Two interior fragments were used; the first (2.85 g) was crushed in an agate pestel and mortar to a grain size of ca. 50-100 micron, the second (1.80 g) was broken into chips 3-8 mm in size. Each sample was loaded into a stainless steel bomb and placed in the extraction chamber of an Isco supercritical fluid extractor maintained at 35 C. High purity (99.9995 percent) carbon dioxide was used and was pressurized using an Isco syringe pump. The samples were extracted dynamically by flowing CO2 under pressure through the bomb and venting via a 50 micron fused filica capillary into 5 mls of hexane used as a collection solvent. The hexane was maintained at a temperature of 0.5 C. A series of extractions were done on each sample using CO2 of increasing density. The principal components extracted in each fraction are summarized

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

Experimental Simulation of Volatile Organic Contributions to Planetary Atmospheres and Surfaces

We present the results of a new simulation of the atmospheric entry heating experienced by extraterrestrial dust particles, quantifying their volatile loss into the early Earth atmosphere and characterising their organic volatile components

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