No abstract available

No abstract available

Compelling evidence is presented for the process of lipid sulfurisation in humic coal-forming environments. The production of reduced inorganic sulfides by sulfate-reducing bacteria during early diagenetic marine transgression enabled the selective sequestration of functionalised lipids in the polar and asphaltene fractions from the Eocene, marine-influenced Heartbreak Ridge lignite deposit, southeast Western Australia. Nickel boride desulfurisation experiments conducted on these fractions released small, but significant, quantities of sulfur-bound hydrocarbons. These comprised mostly higher plant triterpanes, C29 steranes and extended 17?(H),21?(H)-hopanes, linked by one sulfur atom at, or close to, sites of oxygenation in the original natural product precursors. These sulfurised lipids mostly derive from the same carbon sources as the free hydrocarbon lipids, the exception being the sulfurised extended hopanoids, which may be partially derived from a different bacterial source compared to the free hopanoids. These results indicate that the selectivity and nature of steroid and hopanoid vulcanisation in coal-forming mires is akin to that observed in other sedimentary environments. However, the diversity of sulfurised higher plant triterpanes is greater than that typically reported in immature coals. This selective preservation mechanism explains the formation of the structurally-related biomarkers in more mature sulfur-rich humic coals.

The technique of Reaction Gas Chromatography-Mass Spectrometry (R-GCMS) has been applied to the analysis of the polar extracts from a Heartbreak Ridge lignite (Bremer Basin, Western Australia; Eocene age) and a Monterey Formation shale (Naples Beach, USA; Miocene age). A catalyst, palladium black, is packed into glass liners for split vaporising injection. The liners are then placed into the injection port to catalyse the gas phase reaction of volatile polar mixtures. Hydrogen gas is used both as the reactant for hydrogenation/hydrogenolysis, and as the carrier gas for the subsequent separation. The reaction products are mostly hydrocarbons, and are swept on to the column where they are chromatographically resolved by the non-polar stationary phase. The products are then identified by mass spectrometry. The fully active catalyst is effective in hydrogenating and isomerising alkenes as well as partially hydrogenating aromatic moieties. Desulphurisation of thiols, sulphides, and thiophenes readily occurs also. Oxygenated compounds such as primary alcohols, acids, esters and ethers undergo a decarbonylation/decarboxylation, while secondary alcohols are reduced to the parent hydrocarbon. Polar fractions react to produce compound distributions that are characteristic of the organic matter source, namely angiosperm-derived triterpenoids and bacterially-derived hopanoids. The reaction of the polar fraction from the Monterey Formation shale results in the formation of high relative amounts of pristane and phytane. A suite of steroids and triterpenoids, typical of marine organic matter, is also observed. R-GCMS provides less detailed information on the exact nature of the functionalised lipids partitioned within the polar fraction compared to more conventional wet chemical analyses. However, this technique requires only a GCMS instrument fitted with a vaporising injector, which acts as a chemical reactor at the inlet of the column. The main advantages of R-GCMS are its speed, low sample requirement, and production of easily resolved and identified products.

A laboratory study has been conducted to determine the best methods for the detection of C10 to C40 hydrocarbons at naturally occurring oil seeps in marine sediments. The results indicate that a commercially available method using hexane to extract sediments and gas chromatography to screen the resulting extract is effective at recognizing the presence of migrated hydrocarbons at concentrations between 50 to 5,000 ppm. When the oil charge is unbiodegraded the level of charge is effectively tracked by the sum of n-alkanes in the gas chromatogram. However, once the charge oil becomes biodegraded, with the loss of n-alkanes and isoprenoids, the level of charge is tracked by the quantification of the Unresolved Complex Mixture (UCM). The use of GC-MS was also found to be very effective for the recognition of petroleum related hydrocarbons and results indicate that GC-MS would be a very effective tool for screening samples at concentrations below 50 ppm oil charge.

First paragraph of abstract: The importance of organic sulphur fixation in the preservation of organic matter in humic coal-forming environments is demonstrated in this thesis. The transgression of coal depositional systems by marine waters during their deposition and early diagenesis enables the production of reduced inorganic sulphur species by sulphate-reducing bacteria. The presence of these reactive sulphur species, in combination with the altered chemical and microbial regime, influences the preservation and petroleum potential of humic coal.

No abstract available

A recent Geoscience Australia sampling survey in the Bight Basin recovered hundreds of dredge samples of Early Cenomanian to Late Maastrichtian age. Given the location of these samples near the updip northern edge of the Ceduna Sub-basin, they are all immature for hydrocarbon generation with vitrinite reflectance - 0.5% RVmax, Tmax < 440oC and PI < 0.1. Excellent hydrocarbon generative potential is seen for marine, outer shelf, black shales and mudstones with TOC to 6.9% and HI up to 479 mg hydrocarbons/g TOC. These sediments are exclusively of Late Cenomanian-Early Turonian (C/T) in age. The high hydrocarbon potential of the C/T dredge samples is further supported by a dominance of the hydrogen-rich exinite maceral group (liptinite, lamalginite and telalginite macerals), where samples with the highest HI (> 200 mg hydrocarbons/g TOC) contain > 70% of the exinite maceral group. Pyrolysis-gas chromatography and pyrolysis-gas chromatography mass spectrometry of the C/T kerogens reveal moderate levels of sulphur compounds and the relative abundances of aliphatic and aromatic hydrocarbons predict the generation of a paraffinic-naphthenic-aromatic low wax oil in nature. Not enough oom for rest of Abstract

Vertical geochemical profiling of the marine Toolebuc Formation, Eromanga Basin - implications for shale gas/oil potential The regionally extensive, marine, mid-Cretaceous (Albian) Toolebuc Formation, Eromanga Basin hosts one of Australia's most prolific potential source rocks. However, its general low thermal maturity precludes pervasive petroleum generation, although regions of high heat flow and/or deeper burial may make it attractive for unconventional (shale gas and shale oil) hydrocarbon exploration. Previous studies have provided a good understanding of the geographic distribution of the marine organic matter in the Toolebuc Formation where total organic carbon (TOC) contents range to over 20% with approx. half being of labile carbon and convertible to gas and oil. This study focuses on the vertical profiling, at the decimetre to metre scale, of the organic and inorganic geochemical fingerprints within the Toolebuc Formation with a view to quantify fluctuations in the depositional environment and mode of preservation of the organic matter and how these factors influence hydrocarbon generation thresholds. The Toolebuc Formation from three wells, Julia Creek-2 and Wallimbulla-2 and -3, was sampled over an interval from 172 to 360m depth. The total core length was 27m from which 60 samples were selected. Cores from the underlying Wallumbilla Formation (11 samples over 13m) and the overlying Allaru Mudstone (3 samples) completed the sample set. Bulk geochemical analyses included %TOC, %carbonate, %total S, -15N kerogen, -13C kerogen, -13C carbonate, -18O carbonate, and major, minor and tracer elements and quantitative mineralogy. More detailed organic geochemical analyses involved molecular fossils (saturated and aromatic hydrocarbons, and metalloporphyrins), compound specific carbon isotopes of n-alkanes, pyrolysis-gas chromatography and compositional kinetics. etc.

Presentation delivered on 9 March 2012 by Marita Bradshaw.