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.

The geological debate about whether, and to what extent, humic coals have sourced oil is likely to continue for some time, despite some important advances in our knowledge of the processes involved. Both liptinites and perhydrous vitrinites have the potential to generate oil; the key problem is whether this oil can be expelled. Expulsion of hydrocarbons is best explained by activated diffusion of molecules to maceral boundaries and ultimately by cleats and fractures to coal seam boundaries. The relative timing of release of generated CO2 and CH4 could have considerable importance in promoting the expulsion of liquid hydrocarbons. The main reason for poor expulsion from coal is the adsorption of oil on the organic macromolecule, which may be overcome (1) if coals are thin and interbedded with clastic sediments, or (2) if the coals are very hydrogen rich and generate large quantities of oil. Review of the distribution of oil-prone coals in time and space reveals that most are Jurassic-Tertiary, with key examples from Australia, New Zealand and Indonesia. Regarding establishing oil-coal correlations, a complication is that the molecular geochemistry of coals is often very similar to that of the enclosing, fine-grained rocks containing terrestrial organic matter. One potential solution to this problem is the use of carbon and hydrogen isotopes of n-alkanes, which have recently been shown to be powerful discriminators of mudstone and coal sources in the Turpan Basin (China). There is a continuum from carbonaceous shales to pure coals, but the question as to which of these are effective oil sources is an extremely important issue, because volumetric calculations hinge on the result. Unambiguous evidence of expulsion from coals is limited. Bitumen-filled microfractures in sandstones interbedded with coals in offshore mid-Norway and in Scotland have been interpreted to be the migration routes of hydrocarbons from the coal seams towards the sandstones. In the San Juan Basin, USA, direct evidence for the primary migration of oil within coal is provided by the sub-economic quantities (10s to 100s of barrels per well) of light oil produced directly from coal beds of the Upper Cretaceous Fruitland Formation. The Gippsland Basin (Australia) is commonly cited as the outstanding example of a province dominated by oil from coal, but there is no literature that explicitly demonstrates that generation and expulsion has been from the coal seams and not the intervening carbonaceous mudstones. The best evidence for coals as source for oil in the Gippsland appears to be volumetric modelling, which indicates that it would have been impossible to generate the volume of oil discovered to date from the organic-rich shales alone. However, early reports that mid-Jurassic coals in mid-Norway were a major source of the reservoired oils, also based to a large extent on oil generation and expulsion modelling, have now been shown to be inaccurate by detailed biomarker, isotope, whole oil and pyrolysis studies. The most convincing commercial oil discoveries that can be correlated to coals are: (1) Taranaki Basin oils in New Zealand, where Late Cretaceous and Tertiary coals, shaly coals and carbonaceous mudstones are likely to have sourced oils in approximate proportion to their volumes and organic contents, and (2) the oils and condensates in the Harald, Amalie and Lulita oilfields (Danish North Sea) which are likely to have been sourced are least partially from mid-Jurassic coals. New oil-source correlation studies based on diterpane, triterpane and sterane distributions in the Bass Basin (Australia), which lies adjacent to the Gippsland Basin and contains sub-economic reserves of oil and gas, has shown that the Tertiary coals and not the associated shales are best correlated with the oils.

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.

APPEA 2000 joint paper to arrive at a better understanding of the petroleum systems active in the Northern Bonaparte Basin, geochemical data from oils and source rock-extracts were compiled and interpreted from over 20 wells in the area.

We have demonstrated for the first time the application of a small angle neutron scattering (SANS) technique for the precise determination of the onset of hydrocarbon transport (primary migration) in shaly source rocks. We used a sequence of rocks pyrolysed in the laboratory under nitrogen at temperatures in the range 310-370°C. These rocks contained several percent of dispersed marine Type II organic matter. Geochemical analysis indicated a peak of the hydrocarbon generation in the middle of the temperature range (at 340°C). We observed a sharp decrease of SANS intensity in a narrow maturity range within the geochemically determined region of the onset of hydrocarbon generation. This decrease was a direct consequence of the SANS contrast variation caused by the invasion of the pore space by bitumen during the primary migration of hydrocarbons. A similar phenomenon was observed for a natural maturity sequence of source rocks originating from the same location.

Organic geochemists are increasingly involved in multi-disciplinary collaborative studies but not often in the initial sample collection phase, so understanding the origin and source of contaminants derived from sample handling and containers is of vital importance as standard laboratory blanks cannot assess this contamination. A variety of organic contaminants was detected in different sediments collected during Geoscience Australia marine survey S282. These include fatty acid amides, chemical antioxidants such as butylated hydroxytoluene and octadecyl-3, 5-di-tert-butyl-4-hydroxyhydrocinnamate (Irganox 1076), plus the UV absorbers octabenzone and octyl methoxycinnamate. These compounds were introduced during sampling on board the research vessel or during subsequent handling. Solvent extraction of potential contamination sources identified two brands of plastic sampling bags as the main source for the fatty acid amides, butylated hydroxytoluene and Irganox 1076. Direct contact of samples with hands covered with sunscreen appears to have caused contamination by octabenzone and octyl methoxycinnamate. As the primary aim of the survey was to detect evidence for hydrocarbon seepage in the Arafura Sea, care was also taken to identify potential sources of hydrocarbons that might have been introduced during sampling and storage. Detailed examination of solvent extracts from plastic bags revealed the occurrence of several homologous series of branched alkanes with quaternary carbon atoms (BAQCs), as well as distributions of alkyl cyclohexanes and alkyl cyclopentanes with strong even over odd carbon predominance. These compounds were also found in sediment samples collected during the survey. Other potential sources of contamination used on board the ship, such as PVC core liners and lubricants, yielded hydrocarbons that could easily be mistaken for evidence of naturally occurring petroleum if care is not taken during interpretation.

An inverted phase (polar to non-polar) column set has been compared with a non-polar to polar column set for the GC-GC separation of petroleum hydrocarbons crude oil. This is shown to provide greatly enhanced resolution for less polar compounds and makes greater use of the two-dimensional separation space. This column configuration improves resolution of a greater number of components within one analysis and offers new possibilities for crude oil fingerprinting.

abstract

Methane is present in all coals, but a number of geological factors influence the potential economic concentration of gas. The key factors are (1) depositional environment, (2) tectonic and structural setting, (3) rank and gas generation, (4) gas content, (5) permeability, and (6) hydrogeology. Commercial coal seam gas production in Queensland has been entirely from the Permian coals of the Bowen Basin, but the Jurassic coals of the Surat and Clarence-Moreton basins are poised to deliver commercial gas volumes. Depositional environments range from fluvial to delta plain to paralic and marginal marine coals in the Bowen Basin are laterally more continuous than those in the Surat and Clarence-Moreton basins. The tectonic and structural settings are important as they control the coal characteristics both in terms of deposition and burial history. The important coal seam gas seams were deposited in a foreland setting in the Bowen Basin and an intracratonic setting in the Surat and Clarence-Moreton basins. Both of these settings resulted in widespread coal deposition. The complex burial history of the Bowen Basin has resulted in a wide range of coal ranks and properties. Rank in the Bowen Basin coal seam gas fields varies from vitrinite reflectane of 0.55% to >1.1% Rv and from Rv 0.35-0.6% in the Surat and Clarence-Moreton basins in Queensland. High vitrinite coals provide optimal gas generation and cleat formation. The commercial gas fields and the prospective ones contain coals with >60% vitrinite. Gas generation in the Queensland basins is complex with isotopic studies indicating that biogenic gas, thermogenic gas and mixed gases are present. Biogenic processes occur at depths of up to a kilometre. Gas content is important, but lower gas contents can be economic if deliverability is good. Free gas is also present. Drilling and production techniques play an important role in making lower gas content coals viable. Since the Bowen and Surat basins are in a compressive regime, permeability becomes a defining parameter. Areas where the compression is offset by tensional forces provide the best chances for commercial coal seam gas production. Tensional setting such as anticline or structural hinges are important plays. Hydrodynamics control the production rate though water quality varies between the fields.

The molecular composition of fluid inclusion (FI) oils from Leander Reef-1, Houtman 1 and Gage Roads-2 provide evidence of the origin of palaeo-oil accumulations in the offshore Perth Basin. These data are complemented by compound specific isotope (CSI) profiles of n-alkanes for the Leander Reef-1 and Houtman-1 samples, which were acquired on purified n-alkane fractions gained by micro-fractionation of lean FI oil samples, showing the technical feasibility of this technique. The Leander Reef-1 FI oil from the top Carynginia Formation shares many biomarker similarities with oils from the Dongara and Yardarino oilfields, which have been correlated with the Early Triassic Kockatea Shale. However, the heavier isotopic values for the C15-C25 n-alkanes in the Leander Reef-1 FI oil indicate that it is a mixture, and suggest that the main part of this oil (~90%) was sourced from the more terrestrial and isotopically heavier Early Permian Carynginia Formation or Irwin River Coal Measures. This insight would have been precluded when looking at molecular evidence alone. The Houtman-1 FI oil from the top Cattamarra Coal Measures (Middle Jurassic) was sourced from a clay-rich, low sulphur source rock with a significant input of terrestrial organic matter, deposited under oxic to suboxic conditions. Biomarkers suggest sourcing from a more prokaryotic-dominated facies than for the other FI oils, possibly a saline lagoon. The Houtman-1 FI oil ?13C CSI data are similar to data acquired on the Walyering-2 oil. Possible lacustrine sources include the Early Jurassic Eneabba Formation or the Late Jurassic Yarragadee Formation. The low maturity Gage Roads-2 FI oil from the Carnac Formation (Early Cretaceous) was derived from a strongly terrestrial, non-marine source rock containing a high proportion of Araucariacean-type conifer organic matter. It has some geochemical differences to the presently reservoired oil in Gage Roads-1, and was probably sourced from the Early Cretaceous Parmelia Formation.