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Shale oil and gas is of recent interest in Australia, and the Roseneath, Epsilon and Murteree (REM) shales of the Cooper Basin, Australia, are unconventional gas targets. Shales have a high proport...

The end of the Late Palaeozoic Ice Age (LPIA) ushered in a period of significant change in Earth’s carbon cycle, demonstrated by the widespread occurrence of coals worldwide. In this study, we present stratigraphically constrained organic stable carbon isotope (δ13Corg) data for Early Permian coals (312 vitrain samples) from the Moatize Basin, Mozambique, which record the transition from global icehouse to greenhouse conditions. These coals exhibit a three-stage evolution in atmospheric δ13C from the Artinskian to the Kungurian. Early Kungurian coals effectively record the presence of the short-lived Kungurian Carbon Isotopic Excursion (KCIE), associated with the proposed rapid release of methane clathrates during deglaciation at the terminus of the Late Palaeozoic Ice Age (LPIA), with no observed disruption to peat-forming and terrestrial plant communities. δ13Corg variations in coals from the Moatize Basin are cyclic in nature on the order of 103–105 years and reflect changes in δ13Corg of ~±1‰ during periods of stable peat accumulation, supporting observations from Palaeozoic coals elsewhere. These cyclic variations express palaeoenvironmental factors constraining peat growth and deposition, associated with changes in base level. This study also demonstrates the effectiveness of vitrain in coal as a geochemical tool for recording global atmospheric change during the Late Palaeozoic.

Strontium isotopes, water chemistry and whole rock chemistry have been used to investigate the evolution of water from its surface meteoric composition into methane-rich groundwater. Previous studies established that co-produced Surat Basin coal seam gas waters from the Walloon Subgroup (Queensland, Australia) are meteoric in origin and are distinct across the main production regions but the dominant hydrochemical processes have yet to be determined. In this study, strontium isotope ratios (87Sr/86Sr) were measured on production waters from 36 coal seam gas wells, 14 sequentially leached host rock samples and 6 whole rock samples to improve understanding of the water-rock reactions that control spatial variability in solute and isotope chemistry. Strontium isotope ratios of Walloon Subgroup production waters across all production areas are uniformly low in value, ranging from 0.70338 to 0.70456. The majority of values are significantly lower than shallow Walloon formation waters in the recharge zone and extend the lower range of 87Sr/86Sr ratios recorded for Surat Basin groundwaters. These very low 87Sr/86Sr ratios (0.70338) are reached early along the flow paths, within 10 km of the shallow recharge area waters, before then undergoing a gradual increase with flow distance. Mineralogical and geochemical analyses of whole rock samples representing each of the main lithologies across the Walloon Subgroup has identified that the low 87Sr/86Sr ratios are not derived from any one interval but rather the combination of the same few minerals that are present in every unit. The rapid accumulation of relatively non-radiogenic strontium early in the flow path across all three gas producing regions has been attributed to a combination of fluid-rock interactions occurring within the Walloon Subgroup itself. Initial surface 87Sr/86Sr ratio values are quickly dominated through a combination of processes whereby recharge waters with low Sr concentrations are absorbed onto montmorillonite clays via cation exchange and this combined with weathering of plagioclase causes a re-equilibration of the groundwater to lower 87Sr/86Sr ratios. Strontium ratios then start to slowly increase again with flow distance through silicate weathering of K-feldspars and muscovites, which are present at low levels across the basin. Local geological features such as the Hutton-Wallumbilla fault and the Kogan and Undulla anticlines appear to influence flow paths and consequently water and gas composition.

The Precipice Sandstone in the Surat Basin is being appraised for CO2 geological storage owing to its high porosity and permeability and expected high injectivity. Generally it is quartz rich with variable kaolinite, however detailed characterisation of core shows that it contains minor to trace amounts of potentially reactive minerals including carbonates, plagioclase, chlorite, and muscovite, increasing towards the overlying Evergreen Formation top seal. The Evergreen Formation is more variable, with interbedded low porosity and permeability mudstones, fine-grained sandstones, and calcite cemented zones. Injected CO2 dissolves into formation water forming carbonic acid. The geochemical reactivity of drill core samples affects the predicted pH and the dissolution or precipitation of minerals which could permanently trap CO2 as carbonates such as siderite, or dynamically change porosity and permeability altering CO2 migration. Comparative kinetic geochemical modelling of the CO2 reactivity of four representative mineralogies from drill core samples from deeper parts of the central basin indicates that the Evergreen Formation is potentially more reactive to CO2 than the Precipice Sandstone, especially for calcite or siderite containing zones. In the Precipice Sandstone small amounts of albite and siderite dissolved with traces of siderite and kaolinite precipitated. Dissolution of calcite and siderite in the Evergreen Formation favourably buffered acidity, with predicted precipitated minerals including siderite, kaolinite, ankerite, and smectites. The geochemical models indicate overall changes to porosity are however minor. Recent data from capture technologies has reported that CO2 from coal combustion may retain NOx impurities in the form of NO. Simulations with the addition of 30-100 ppm NO in the CO2 stream indicated the generated pH in the quartz rich Precipice Sandstone is similar to that on injection of pure CO2 after 30 years. The precipitation of Fe-rich smectite clays was additionally predicted.

This study was carried out to document the source and stable isotopic characteristics of coal bed gas and associated coal bed water samples of the Raniganj Basin, West Bengal, India. The Raniganj Basin is one of the largest coal bed gas-producing sites in India. However, the gas isotopic composition of this basin was not well investigated until now. The exploration has been focused on mature coals with a high content of assumed thermogenic methane. Interestingly, the present study has revealed that although the gas is thermogenic, there is a significant effect of microbial activities in gas generation. The gas explored from this Basin contains almost 98–99% methane (CH4) in general with very little portions of other hydrocarbons and thus, this gas can be considered as “dry gas”. It is consistent also with late-stage microbial alteration of thermogenic gases. The δ13C and δD values of CH4 range from −47.4 to −49.7‰ and −207 to −211‰ respectively across the three wells as well as from −48.8 to −50.1‰ and −209 to −211‰ respectively in the gas samples collected from gas gathering station. The Whiticar style cross plot of these two parameters reveals that the gas samples have mixed thermogenic and biogenic sources and the microbial gas was generated through the CO2 reduction pathway rather than the acetate fermentation pathway. The difference in δD values of water and methane samples [δD (H2O-CH4)], that varies from 173 to 175‰, may also exhibit that the biogenic methane was produced through reduction of CO2. The stable hydrogen and oxygen isotopic signatures of formation water samples (δD and δ18O-H2O) stand with the mixed origin of the gas. The cross-plot of these two parameters reveals that the water samples lie almost along the Global Meteoric Water Line (GMWL), which may suggest the combined effect of methanogenesis due to mixing of coal seam formation water with modern meteoric water. In summary, the produced coal bed gas from the Raniganj Basin, although being largely thermogenic in origin, has been influenced by secondary microbial alteration.

Coal bed methane (CBM) has recently been produced from sub-bituminous to high volatile bituminous low rank coals (vitrinite reflectance 0.39 to 0.53%) from the Paleocene Cuervos Formation in the Cesar Sub-basin, Colombia. Understanding CBM gas origin is vital for designing exploration and production strategies, in order to target either shallow economic accumulations of microbial gas or deeper and thermally mature coal seams. In this context, this study aims to determine whether thermogenic gas, biogenic gas, or a mixture of both gas types have contributed to gas yield in the Cesar Sub-basin; it also discusses the relationship between gas origin and tectonics. For the first time, co-produced waters and gas samples from CBM multi-seam production wells and shallow aquifer water-wells were collected in the Boqueron compartment (Cesar Sub-basin) and were analysed via stable isotope composition and molecular geochemistry. Structural compartmentalisation in the Sub-basin as a result of interplate shortening during the Mid-Paleogene has resulted in slightly different coal ranks, saturation, and gas contents between compartments of the Paleocene Cuervos Formation. This event could have interrupted early thermogenesis and allowed the introduction of meteoric waters carrying bacteria consortia responsible for biogenesis. The produced waters from the CBM wells were HCO3 > Na+ > Cl− type, and ranged in TDS (Total dissolved solids) from 2268 to 6602 mg/L (avg. 3887 mg/L). Recently revised genetic diagrams of δ13C-CH4 versus δ2H-CH4 and additional parameters, such as gas dryness ratio and water chemistry, corroborated biogenesis as the main gas origin. Carbon isotopic differences between carbon dioxide and methane (Δ13CH2O–CH4), as well as those of hydrogen isotopes in water and methane (Δ2HH2O–CH4), also indicated a typical microbial CO2 reduction pathway. The positive carbon isotope composition of dissolved inorganic carbon (δ13C-DIC) not only showed a clear differentiation between waters from CBM wells and those from shallow aquifers, but also confirmed the occurrence of methanogenesis when paired with high alkalinity. In addition, the water quality analysis showed increasing sodium and bicarbonate concentrations with depth, which is typical of CBM production basins. Although biogenic gas was identified, tectonic settings do not seem to explain gas origin occurrence, since secondary biogenesis was expected in an uplifted basin such as Cesar Rancheria. Isotopic data was not decisive in differentiating primary versus secondary biogenesis, since the gas isotope compositions plot close to the boundary between the primary and secondary biogenic gas fields. Further studies on isotopic chemistry are required to refine this interpretation and confirm gas generation in the other two compartments.

Hydrochemical data responds at a much slower rate to changes in groundwater conditions than does the propagation of hydraulic pressure, and therefore may provide more insight to groundwater flow paths. In low rank coal measures, where gas is biogenic, it is important to understand the fluid-rock and microbial interactions that affect the spatial and temporal distribution of groundwater composition. Pressure data may not reflect true groundwater conditions pre-anthropogenic influence, nor does it provide information on the main drivers of groundwater composition, actual aquifer behaviour or even prove groundwater flow. This study uses a process-based approach to interpret a combination of tracer (Cl, C, Sr/Sr, O/O) and hydrochemical data obtained from coal seam gas production wells to identify the main geochemical processes and thus controls on the groundwater composition in different coal seam producing areas of the Walloon Subgroup, Surat Basin, Australia. This is arguably one of the largest coal seam gas producing regions in the world. Tracer data measured in this study show that the Walloon Subgroup behaves as a stagnant aquitard, as indicated by the almost total loss of cosmogenic tracers over relatively short groundwater flow distances (~15 km), suggestive of very low ground water flow velocities. The range of Cl is 9.0 to 23.8 (x 10) while the Cl values across the Undulla anticline in the eastern edge of the basin, are essentially the same (12.2–14.7) within analytical error. It is argued that these isotopic values represent secular equilibrium for the Walloon Subgroup. Radiometric carbon (C) levels across all three production areas (Roma, Undulla Nose, Kogan Nose) are also too low (range = 0.12–1.95 pMC) for viable field interpretation largely owing to the long residence time of the groundwater and the local activity of methanogens. Groundwater flow velocity was estimated to be

This paper uses hydrochemical and multi-isotope analysis to investigate geological controls on coal seam gas (CSG) saturation domains and gas well production performance in a high-rank (vitrinite reflectance (Rv) &gt, 1.1) CSG field in the north-western Bowen Basin, Australia. New hydrochemical and stable isotope data were combined with existing geochemical datasets to refine hypotheses on the distribution and origins of CSG in two highly compartmentalized Permian coal seams. Stable isotopic results suggest that geographic variations in gas content, saturation and production reflect the extent of secondary microbial gas generation and retention as a function of hydrodynamics. &delta, 13C and &delta, 2H data support a gas mixing hypothesis with &delta, 13C-CH4 increasing from secondary biogenic values to thermogenic values at depth (&delta, 13C &minus, 62.2&permil, to &minus, 46.3&permil, ), whereas correlated methane and carbon dioxide carbon isotope compositions, &Delta, 13C(CO2&ndash, CH4) values and &delta, 13CDIC/alkalinity trends are largely consistent with microbial CO2 reduction. In addition, below 200 m, the majority of &delta, 13C-CO2 values are positive (&delta, 13C: &minus, 1.2&permil, to 7.1&permil, ) and &delta, 13CDIC shows an erratic increase with depth for both seams that is characteristic of evolution via microbial activity. The progression of carbon isotope values along the CO2 reduction fractionation line suggests progressive depletion of the CO2 reservoir with increasing depth. Faults clearly segment coal seams into areas having significantly different production, with results of geochemical analysis suggesting that pooling of biogenic gas and waters and enhanced methanogenesis occur north of a faulted hinge zone.

Illitic clay is ubiquitous in clastic hydrocarbon reservoirs, and the host for several radiometric isotopes such as the potassium-argon (K-Ar) and rubidium-strontium (Rb-Sr) systems. This study applied the isotope-dilution thermal ionization mass spectrometry technique for small samples (3–4 mg) to conduct illite Rb-Sr isotope dating of five illitic clay samples from the Silurian bituminous sandstone (SBS) intersected by five drillholes in the Tarim Basin, NW China. The 87Rb/86Sr ratio of clays is fractionated mainly by the addition of Rb during the illitization of mixed-layer illite/smectite (I/S), which is the dominant clay species in the Tarim Basin samples. The subsample-scale Rb/Sr isotope values suggest that each subsample may contain I/S particles of slightly variable degrees of illitization. Three of the analyzed samples (H6, KQ1 and TZ67) generated Rb-Sr isochron ages of 141 ± 61 Ma, 332 ± 32 Ma and 235 ± 8 Ma (errors quoted at 2σ), respectively. These results are similar to the corresponding K-Ar ages (125 Ma, 389 Ma and 234 Ma). The isotopic ages are consistent with the timing of hydrocarbon charge which varies in different drillholes as constrained by basin modelling, indicating that a closed-system behavior is attained by the hydrocarbon charge that inhibits the illitization of I/S. The Rb-Sr isotope analyses of the other two samples (YM35-1 and Q1) that did not yield isochron ages suggest the conditions for producing isochrons were not satisfied, which may be caused by disturbance of the isotope system by a post-charge hydrothermal event. The outcomes of this study show the robust potential of Rb-Sr clay subsample geochronology for cross-checking isotopic ages yielded by other systems (e.g. K-Ar system) and constraining the timing of hydrocarbon charge.

Apatite may be a common accessory mineral in coal seams, but interpretation of its origins can vary from syndepositional mineral detritus, early precipitation during diagenesis, and post coalification precipitation and replacement from hydrothermal or other fluids. It is hypothesised that paragenesis is reflected in the modes of occurrence in different stratigraphic units of the Late Permian in the Bowen Basin. From samples analysed in this study, apatite in the youngest unit, the Rangal Coal Measures, most commonly occurs as pore-apatites (i.e. apatites infilling preserved plant cell cavities of fusinite and semifusinite macerals and commonly associated with kaolinite) and less commonly as fracture-apatites (i.e. apatites infilling micro-fractures) and detrital-apatites intermixed with the organic coal layers (Detrital-B). In the tuffaceous Fort Cooper Coal Measures and equivalents, apatite occurs more commonly as detrital-apatites intermixed with the lithic layers (Detrital-A) (Detrital. Within the basal unit, the Moranbah Coal Measures and its equivalents, the mode is commonly encrusting-apatites (i.e. small apatite crystallites encrusting silicate minerals). Almost all apatites in the coal samples tested by electron microprobe microanalysis (EPMA), regardless of stratigraphic location and mode, are fluorapatite. Although there are some locality-driven enrichments, the minor and trace-element chemistry vary more so by mode of occurrence. For comparison, apatites from dykes intersecting the coal measures and from tuffs were also added to the study. These had lower fluorine (F) but measurable chlorine (Cl) contents and are enriched in light rare earth elements (LREE), similar to the Durango apatite that is of magmatic origins. Most of the detrital-A apatites are also enriched in LREE similar to the tuff-apatites, but with variable enrichment in the rare earth and yttrium elements. Detrital-B apatites have minimal Cl but also show the magmatic LREE trend. The pore- and fracture-apatites exhibited two trends. In the samples from tuffaceous coals (e.g., Fort Cooper Coal Measures), the pore- and fracture apatites tended to follow the magmatic LREE trend. In the Rangal Coal Measures, the pore- and fracture-apatites have elevated F contents, minimal Cl contents and depleted LREE contents (or Middle REE enrichment). Depletion of LREE could occur through leaching in an acidic environment, which is suggested by the abundance of kaolinite. Apatite precipitates under more neutral conditions although pore-apatites are commonly considered “early” and fracture-apatites “late” or post coalification. Their geochemical similarity suggests they have similar fluid origins and/or timing, with geothermal fluids moving through the porosity afforded by the structured inertinite group macerals and fractures. Verification of that geothermal source still requires further work and a technique that can analyse the isotopic composition—e.g., carbon (13C/12C), oxygen (18O/16O) and strontium (87Sr/86Sr)—of micron-sized crystals in situ.

Reservoir and cap-rock core samples with variable lithology's representative of siliciclastic reservoirs used for CO2 storage have been characterized and reacted at reservoir conditions with an impure CO2 stream and low salinity brine. Cores from a target CO2 storage site in Queensland, Australia were tested. Mineralogical controls on the resulting changes to porosity and water chemistry have been identified. The tested siliciclastic reservoir core samples can be grouped generally into three responses to impure CO2-brine reaction, dependent on mineralogy. The mineralogically clean quartzose reservoir cores had high porosities, with negligible change after reaction, in resolvable porosity or mineralogy, calculated using X-ray micro computed tomography and QEMSCAN. However, strong brine acidification and a high concentration of dissolved sulphate were generated in experiments owing to minimal mineral buffering. Also, the movement of kaolin has the potential to block pore throats and reduce permeability. The reaction of the impure CO2-brine with calcite-cemented cap-rock core samples caused the largest porosity changes after reaction through calcite dissolution; to the extent that one sample developed a connection of open pores that extended into the core sub-plug. This has the potential to both favor injectivity but also affect CO2 migration. The dissolution of calcite caused the buffering of acidity resulting in no significant observable silicate dissolution. Clay-rich cap-rock core samples with minor amounts of carbonate minerals had only small changes after reaction. Created porosity appeared mainly disconnected. Changes were instead associated with decreases in density from Fe-leaching of chlorite or dissolution of minor amounts of carbonates and plagioclase. The interbedded sandstone and shale core also developed increased porosity parallel to bedding through dissolution of carbonates and reactive silicates in the sandy layers. Tight interbedded cap-rocks could be expected to act as baffles to fluids preventing vertical fluid migration. Concentrations of dissolved elements including Ca, Fe, Mn, and Ni increased during reactions of several core samples, with Mn, Mg, Co, and Zn correlated with Ca from cap-rock cores. Precipitation of gypsum, Fe-oxides and clays on seal core samples sequestered dissolved elements including Fe through co-precipitation or adsorption. A conceptual model of impure CO2-water-rock interactions for a siliciclastic reservoir is discussed.

An integrated analysis of megascopic lithotype, microscopic maceral and mineral composition, stable carbon isotope and interburden sedimentology from a single well was used to interpret the response of the Late Permian Fort Cooper Coal Measures (FCCM) to regional and global environmental influences. The FCCM are differentiated from underlying, relatively high vitrinite Moranbah Coal Measures, and overlying higher inertinite Rangal Coal Measures in the Bowen Basin by their intercalation with abundant tuff and siliciclastic partings and interbeds. Besides this, there is little described about the variation in the organic composition of the FCCM and its causes. The FCCM can be subdivided into a lower aggradational Fair Hill Formation, transgressed by the shallow marine-derived Black Alley Shale that interfinger with/is overlain by the progradational Middle Main Seams and Burngrove Formation coal measures. The coals are dominantly dull with minor bright bands that are more abundant in the Burngrove Formation representing a change in plant composition. The maceral analysis shows that the coals in the Fair Hill Formation and Middle Main Seams are vitrinite-rich (80–90% mmf) albeit with high mineral matter suggesting the formation of precursory peat under rising water levels and with high sediment (tuff) influx and preservation. The coals in the Burngrove Formation have an increased inertinite content (30% mmf) but are also high in mineral matter suggesting a shift to increased decomposition arising from a fluctuating water table, possibly increased aridity and/or microbial activity. Tuffs occur throughout, and although their frequency is higher in the lower Fair Hill Formation, the preservation of thicker tuffs in the upper Burngrove Formation indicates increased intensity of volcanism that could have modified the environment. Variation in carbon isotope compositions show a parabolic trend, from around − 24.1‰ in the Fair Hill Formation to more variable values in the Middle Main Seams with an overall 13 C-enrichment upwards in the Burngrove Formation, prior to the δ 13 C values becoming negative (depleted between − 1 to − 4% from the average − 24.1‰) in the top seams and into the overlying Rangal Coal Measures. The 13 C-depletion trend in the upper part of the section is unexpected in view of corresponding increase in inertinite content of the coals indicating that the δ 13 C values/plant composition and inertinite content are decoupled, unless the inertinite origin is from intense microbial decay. Similar stable carbon isotope depletion trends have been observed elsewhere in an equivalent stratigraphic interval of the Bowen Basin suggesting that the carbon isotope values are responding to global conditions that cause negative excursions in carbon isotopes before the P-T boundary. Overall, the basin was continuously subsiding and peats accumulated with constant interruptions from excessive sedimentation and volcanic eruptions. The low proportion of visible thick bright bands coupled with high telovitrinite (mmf) content suggests a marsh to fen environment, with an open canopy and ponding able to preserve volcanic ash falls.

The Late Jurassic Walloon Subgroup (recently dated as Oxfordian) is a productive, subbituminous coal seam gas source in the Surat Basin and can be subdivided from bottom to top into the Taroom Coal Measures, the Tangalooma Sandstone, the Lower and Upper Juandah Coal Measures, which have different coal character. The lower Taroom coals are commonly thick, associated with sandstones and interpreted to form as base level is rising, creating sodden anoxic conditions for peat accumulation. The middle Tangalooma to Lower Juandah contains fewer and thinner coals, and transitions upwards from a sandstone to siltstone dominated sequence responding to inundation with the development of floodplain lakes. The strata then coarsen upward in both grain size and coal thickness in the Upper Juandah Coal Measures, which may be eroded by an overlying unit, the Springbok Sandstone. This unconformable surface is basin wide and depending on age, can be tied into global changes in climate and base level. Existing models for peat growth under changing base level and the variability in terms of the conditions of peat formation through time, as well as throughout the basin, are tested. Environment of peat deposition and changes therein, are investigated by petrographic analysis of the Walloon coals, coupled with high resolution lithotype logging of core and organic stable carbon isotope analysis. Fine microlayering and abundance of root suberinite, telo- and detrovitrinite indicate precursory peat formation in a mostly herbaceous marsh to fen environment, in which bigger trees are either infrequent or absent, except for the lower seams of the Taroom Coal Measures and the upper seams of the Lower Juandah Coal Measures, where bright bands are thicker (≥ 10 mm) and more frequent. No extended periods of dehydration-oxidation ( Stable carbon isotopes of coal show a distinct positive shift in the Lower Juandah Coal Measures that sets in well before the increased inertinite content in the Upper Juandah Coal Measures. The enrichment in 13 C could be linked to a change in climate during the high stand depositional cycle, marking the onset of late stage falling, where base level begins to drop, later creating exposures and water stress. A shift to a less humid climate in the Upper Juandah Coal Measures could have favoured the conditions for desiccation, mouldering and bush fires, which is reflected in the coal's maceral composition. The Surat Basin δ 13 C isotope trend follows the global trend found in marine carbonate samples from the same age interval that corroborates increasing enrichment towards the top of the coal measures (approximately middle Oxfordian), followed by a shift to more negative compositions, which corresponds to the onset of the Springbok Sandstone deposition on an unconformable surface.

An injected CO2 or greenhouse gas (GHG) stream will dissolve into formation water forming carbonic acid, especially in the case of low salinity reservoir storage. Industrial GHG streams from coal combustion, cement or streel production may contain accessory gases including N2, Ar, SOx, NOx, or O2, several including SOx and NOx form stronger acids. The dissolved GHG stream will have reactivity to some rock forming minerals, potentially modifying porosity or water chemistry, or mineral trapping CO2. The Precipice Sandstone in the Surat Basin, Australia, is a low salinity target reservoir for CO2 storage. The Surat CCS project proposes to a demonstration-scale injection test of 60,000 t per year of a GHG stream captured from black coal PCC into the quartz rich Lower Precipice Sandstone. The dissolved GHG stream is expected to interact with the Lower and Upper Precipice Sandstone and sink to interact with the underlying Moolayember Formation of the Bowen Basin. However little was known about the lithologies of the Moolayember Formation which unconformably underlies the projects proposed injection site. Drill cores from the Moolayember Formation were sampled and characterized: indicating a high proportion of carbonate cements, potentially reactive clays, feldspars, and trace amounts of sulphides and coal. Complex carbonate assemblages and secondary textures indicate this may already be a valuable example of a natural analogue of CO2 alteration. Kinetic geochemical modelling was performed to predict the CO2 or CO2-SO2-NO reactivity of several lithologies. This indicted that after 30 years, low concentrations of SOx and NO (100 ppm) had minimal effect on the pH which was buffered to similar values relative to pure CO2 for these reactive mineralogies. The pH was instead controlled by the carbonate mineral content, which buffered acidity. Reaction of clay and feldspar rich lithologies resulted in dissolution of K-feldspar, chlorite, and plagioclase to form kaolinite, smectite, and additionally siderite mineral trapping CO2. SO2 was predicted to be mineral trapped as pyrite or alunite. The net predicted mineral volumes or porosities however did not change significantly. Experiments at reservoir conditions and further characterization are planned to validate and improve model predictions.

An understanding of the long-term reactivity of different rock types to injected CO2 is needed for sequestration site assessment. Relative to saline aquifer studies, the long term reactivity of CO2 in low salinity aquifers has received little attention. Currently in Australia, the Surat Basin is being appraised for its large-scale CO2 storage potential within low salinity aquifers. Sixteen core samples from the Precipice Sandstone and Evergreen Formation – the notional target reservoir and seal complex – were characterized for mineral content; helium, mercury-injection and micro CT porosities; air permeability; and, imaged with SEM-EDS. Samples consisted of quartz rich reservoir sandstones, feldspar and clay rich or calcite cemented sandstones (secondary reservoir), mudstones (sealing complex), and oolitic ironstones (sealing complex) derived from braided river, fluvial-deltaic, and restricted marine shoal depositional environments, respectively. The reservoir sandstone samples characterized here had measured total porosity that ranged from 11 to 23% with pore throats mainly between 90 and 100 μm, and core air permeability from 558 to 3397 mD. In the Precipice Sandstone reservoir sample μCT plugs, 98% of the pore space was connected with calculated vertical permeability 145–4611 mD and horizontal 4291–8200 mD. Feldspar and clay rich sandstone and mudstone samples from the overlying Evergreen Formation had porosity that ranged between 0.2 and 22.9%, with a wide range of pore throat sizes from ~0.005 to 30 μm, and permeability from 0.2 to 28.1 mD, respectively. Ironstone and mudstone samples from the Westgrove Ironstone Member (Evergreen Formation) had porosity from 0.7 to 9.7% and a low permeability of 0.04 mD. Kinetic geochemical CO2 reactivity models made predictions over two time-scales: 30 or 1000 years. Selected models also accounted for the potential presence of 10 ppm SO2 gas. The Precipice Sandstone quartz-rich reservoir sandstones had consistently small amounts of reactive minerals and mineral trapping or scaling of the reservoir was not predicted over 30 years, with the pH approximately 4.5 after 30 years. Samples from the Evergreen Formation included feldspar and clay rich sandstones and mudstones, several contained variable amounts of carbonate cement. Their response to CO2 was more influenced by mineral content than rock type. Plagioclase feldspars and Fe-rich chlorite were the main silicate minerals that reacted to produce siderite and ankerite mineral trapping up to 2.57 kg/m3 CO2. In the very unlikely event that CO2 rich fluids migrated upwards as far as the Westgrove Ironstone Member, chlorite is predicted to alter to siderite. This study indicates that the Precipice Sandstone reservoir in the study region has a low likelihood of mineral scaling which is favorable to avoid CO2 injectivity issues. Mineral trapping as ankerite and siderite could be expected to trap CO2 in the chlorite and plagioclase rich Evergreen Formation seal lithologies. Further work is suggested on validating long term predictions with observation data from natural analogue studies.

The Walloon Subgroup coal seam gas (CSG) play in the Surat Basin, Queensland, is Australia's pre-eminent onshore gas field. Concerted multi-disciplinary research is underway investigating the distribution, origin and composition of waters and gases in this dominantly microbial CSG reservoir, to guide both continued production and potential microbially enhanced coal bed methane (MECoM) applications. However, prior to the present research, a detailed study of co-produced waters and gases from across the Surat Basin was not available in the public domain. This study tested whether co-produced water compositional and stable isotopic data show relationships with production gas stable isotope compositions, to elucidate further evidence for microbial CO2 reduction and explore the down-dip geochemical evolution of Walloon coal bed waters and gases. A total of 41 wells were sampled with 50 water and 25 gas samples spanning the 3 major production areas of the Surat Basin. Detailed isotopic and hydrochemical analysis of these samples revealed distinct spatial trends between the different production locales. Water compositions were distinct for each of the production regions reflecting the different lithologies of adjacent recharge zones, differing fluid–rock interactions, likely different microbial consortia, and the extent of methanogenesis. On the western side of the basin near Roma, waters were the ‘freshest’ with the lowest median values for alkalinity (861 mg/L), and Cl− (588 mg/L) and a δ13CDIC of 14.2‰. On the eastern side of the basin, the Kogan Nose waters were the most saline with the highest median values for Na+ (1955 mg/L), Cl− (2280 mg/L) and δ13CDIC (20.0‰). Also in the east, in the present gas fairway, the Undulla Nose waters had the highest median alkalinity (1841 mg/L) and were found to have a Na+ excess (median = 1050 mg/L) and a lower than expected median δ13CDIC (14.0‰). Co-mingled, produced methane carbon isotope values (δ13C − 57.0‰ to − 44.5‰) from both the upper (Juandah) and lower (Taroom) coal measures plot within the mixed ‘thermogenic/microbial’ genetic field. By contrast, deuterium isotopic difference [Δ2H(H2O–CH4)] values and cross-plots of δ2H–H2O and δ18O–H2O suggest that microbially mediated CO2 reduction is the dominant methane generation process in situ. At a given depth, the Undulla Nose waters in the east are more depleted in 2H and 18O than elsewhere in the Surat Basin, which may suggest these samples have been more heavily impacted by water–rock–microbial reactions. 14C values from the 3 production regions (0.115 to 1.769 pmC; age: 32,400 to > 50,000 years before present (B.P.)) suggest that Walloon coals likely recharged in the last ~ 50,000 years (limit of radiocarbon dating). Consistent with these dates, δ2H–H2O and δ18O–H2O values for the Surat Basin (δ2H − 32‰ to − 56‰, δ18O − 5.9‰ to − 9.0‰) echo the stable isotopic composition of meteoric waters during the initial part of the last glacial period in southeast Queensland. Based on a strong correlation between δ2H–CH4 and δ2H–H2O, we suggest that methane was generated since the Late Pleistocene. PCA analysis showed a degree of positive correlation between total alkalinity and both the δ13CDIC (median 14.2‰) and δ13C–CH4 (median − 52.1‰) vectors that is consistent with finite reservoir effects. The results inform ongoing studies of gas distribution and origins and MECoM potential in the Surat Basin, and underpin a broader study examining aquifer interactions.

Some industrial CO2 streams stored geologically may contain impurities including SO2, O2, and NOX. The impacts of these reactive gases in CO2–water–rock interactions have received limited attention relative to pure CO2 studies. An experimental and geochemical modelling study of reservoir and cap-rock core samples from a potential CO2 storage site in the Surat Basin, Queensland, Australia is described. Reservoir and cap-rock samples were reacted with low salinity fluid saturated with an impure CO2 stream containing 0.16% SO2 at reservoir simulated in situ conditions. This study is relevant to the storage of impure CO2 streams from industrial sources in sandstone reservoirs. Experimentally, dissolution of SO2 from the supercritical gas phase into the aqueous phase showed a kinetic control. The acidification from sulphuric acid generation, and the resulting silicate and carbonate dissolution were generally observed in all experiments. Significant dissolved cation concentrations in solution (up to ~ 843 mg/kg) indicated a higher potential for CO2 trapping, especially from mineralogically reactive core samples. The extent of mineral dissolution was dependent on the rock mineralogy. Precipice Sandstone samples showed the lowest reactivity indicating its suitability as a reservoir unit. However this study indicates the potential for localised changes to water quality in the near wellbore region that necessitate further investigation. Corrosion of the carbonates calcite, siderite and ankerite, and silicates including iron-rich chlorite, plagioclase, and K-feldspar was observed on rock surfaces in potential seal rocks. Calcite cement partially dissolved and acicular gypsum precipitated on the surface of a sandstone formation that could act as a potential secondary sealing unit. The formation of dense sulphates may self-seal some cap-rock. Simulations showed a good history match with the experiments, with the main predicted reactive phases including calcite, ankerite, siderite and chlorite +/− Fe oxides on the time scale of the experiments. Redox potential of the system was important; where oxidised iron was present SO2 oxidation to sulphuric acid was predicted to dominate in the simulations; otherwise pyrite and elemental S formation were also predicted (as observed experimentally). The findings of this study are generally applicable to understanding likely impacts to water quality from impure CO2 injection in CCS sites in Australia and internationally. Data has been provided which may be used to improve longer term modelling predictions.

The Pretty Hill Formation of the Otway Basin (Australia) has been studied as a natural analogue for geological storage of anthropogenic CO2 in order to examine the effects that CO2 concentration and reservoir heterogeneity have on CO2-related reactions. New petrographic data are presented, which validate the use of Hylogger™ as a tool to investigate high-resolution vertical changes in reservoir mineralogy. The integrated data set confirms earlier interpretations, showing that chlorite has been altered to kaolinite and siderite/ankerite in reservoir facies exposed to moderate and high CO2 concentrations, while chlorite remains the dominant clay mineral in all parts of the formation where CO2 content is low. Differences have been observed in the degree of CO2-related reaction relative to CO2 concentration and reservoir heterogeneity. Where CO2 content is very high (c. 98 mol%) and associated with high water saturations, both chlorite and detrital feldspars have undergone complete reaction in the reservoir facies, resulting in quartzose sandstones with a kaolinite matrix, and with siderite as the dominant carbonate precipitate. Conversely, where CO2 content is moderate (c. 29–57 mol%) and within the gas leg of the reservoir, chlorite has undergone significant reaction, but much of the original feldspar is preserved, suggesting relatively minor reaction. Carbonate cements from the moderate CO2 gas-leg comprise calcite, siderite and ankerite, occurring as cemented zones associated with rock heterogeneities and the present-day gas–water contact. Heterogeneities within the gas-leg are likely to have associated pore fluid contacts, whereby relatively high water saturations will be present in the fine-grained baffles and seals. The most advanced feldspar reaction occurs locally at the contact between baffles and reservoir rock, while reactions have been significantly impeded in the finer grained units due to their low permeabilities. Stable isotope data presented for carbonate cements analysed from wells with low and moderate CO2 levels show no clear distinction. Relatively early formed calcite has δ13C values that require an organic carbon source, suggesting precipitation unrelated to the reservoir CO2 in the Otway Basin. In contrast, diagenetically late calcite and siderite samples display two distinct δ13C groups (dependent on carbonate type), where the calculated fluid carbon isotope compositions are similar to documented magmatic CO2 reservoired in the nearby Caroline Field. This suggests that magma-derived CO2 may have been more prevalent through the Pretty Hill Formation than previously thought. Although the CO2 has not been contained over the long term in the low CO2 sites, it may have caused the local dissolution of carbonate and laumontite cement, and also contributed a source of carbon for late-stage calcite cements. These studies illustrate the importance of understanding both the reservoir composition and vertical heterogeneity of potential storage systems. Fluid–mineral reactions are likely to be advanced within stacked reservoir facies and impeded within siltstone layers, while the distribution of carbonate cement may increase the reservoir heterogeneity by the formation of cemented siltstone/sandstone layers, thereby creating impermeable barriers or baffles to CO2.

The interactions between CO2, water and rock in low-salinity host formations remain largely unexplored for conditions relevant to CO2 injection and storage. Core samples and sub-plugs from five Jurassic-aged Surat Basin sandstones and siltstones of varying mineralogy have been experimentally reacted in low-salinity water with supercritical CO2 at simulated in situ reservoir conditions (P=12MPa and T=60°C) for 16days (384h), with a view to characterising potential CO2-water-rock interactions in fresh or low-salinity potential siliclastic CO2 storage targets located in Queensland, Australia. CO2-water-rock reactions were coupled with detailed mineral and porosity characterisation, obtained prior to and following reaction, to identify changes in the mineralogy and porosity of selected reservoir and seal rocks during simulated CO2 injection. Aqueous element concentrations were measured from fluid extracts obtained periodically throughout the experiments to infer fluid-rock reactions over time. Fluid analyses show an evolution of dissolved concentration over time, with most major (e.g. Ca, Fe, Si, Mg, Mn) and minor (e.g. S, Sr, Ba, Zn) components increasing in concentration during reaction with CO2. Similar trends between elements reflect shared sources and/or similar release mechanisms, such as dissolution and desorption with decreasing pH. Small decreases in concentration of selected elements were observed towards the end of some experiments; however, no precipitation of minerals was directly observed in petrography. Sample characterisation on a fine scale allowed direct scrutiny of mineralogical and porosity changes by comparing pre- and post-reaction observations. Scanning electron microscopy and registered 3D images from micro-computed tomography (micro-CT) indicate dissolution of minerals, including carbonates, chlorite, biotite members, and, to a lesser extent, feldspars. Quantitative mineral mapping of sub-plugs identified dissolution of calcite from carbonate cemented core, with a decrease in calcite content from 17vol.% to 15vol.% following reaction, and a subsequent increase in porosity of 1.1vol.%. Kinetic geochemical modelling of the CO2-water-rock experiments successfully reproduced the general trends observed in aqueous geochemistry for the investigated major elements. After coupling experimental geochemistry with detailed sample characterisation and numerical modelling, expected initial reactions in the near-well region include partial dissolution and desorption of calcite, mixed carbonates, chloritic clays and annite due to pH decrease, followed in the longer-term by dissolution of additional silicates, such as feldspars. Dissolution of carbonates is predicted to improve injectivity in the near-well environment and contribute to the eventual re-precipitation of carbonates in the far field.

The Warburton–Cooper–Eromanga basins of central–eastern Australia contain a number of reactivated fracture–fault networks that relate to a complex and poorly understood thermal and tectonic evolution. Authigenic illite was sampled from two prominent features of the Warburton–Cooper basins: the Gidgealpa–Merrimelia–Innamincka Ridge, composed of anticlinal imbricate thrust fault blocks, and the synclinal Nappamerri Trough. These sample sets were investigated using a combination of clay mineralogical, trace element and stable isotope analyses to deduce the palaeofluid chemistry associated with past tectonothermal perturbations. The Nappamerri Trough hosts the highly radiogenic Big Lake Suite granite and part of one of Australia’s larger on-shore oil and gas reserves. Calculated fluid stable isotope values from the trough, in conjunction with calculated palaeotemperatures, indicate an influx of evolved high-latitudinal meteoric waters under an extremely high geothermal gradient (∼100 °C km −1 ) and high water/rock ratios consistent with an extensional environment. Such high water/rock ratios resulted in intense alteration of the granite during which it underwent substantial enrichment in the heat-producing elements (HPE), particularly Th. This hydrothermal system is interpreted to result from continent-wide transmission of tensional stress originating from episodic rifting of the eastern Australian margin in the mid Cretaceous, as dated by Sm–Nd, Rb–Sr and Ar–Ar. The Gidgealpa–Merrimelia–Innamincka Ridge, by contrast, is marked by a lower, but still elevated, palaeogeothermal gradient (∼42 °C km −1 ) and calculated fluid isotopic values compatible with evolved basinal fluids of meteoric origin under low water/rock ratio conditions. Distinct trace element compositions of residue and leachate aliquots further indicate two periods of fluid flow with unique chemical compositions. In light of previous geochronology, these events are interpreted as westward extensions of widespread crustal tensional stress that affected much of central and eastern Queensland in the Carboniferous and Late Triassic. Integrated analyses of authigenic illite provide evidence for three periods of fluid flow and elevated thermal regime associated with regional tectonism during the Carboniferous, Late Triassic and Cretaceous. Our data further show that due to the extremely high geothermal gradient and water/rock ratios, Cretaceous fluid flow had profound effects on the surrounding geology, which may have formed/enhanced two of Australia’s most significant energy resources.

The sustainable in situ regeneration of microbial (biogenic) methane or microbially enhanced coal bed methane (‘MECoM’) is an emerging concept being investigated globally. Promising results and recommendations of a preliminary culture study of Walloon Subgroup co-produced coal seam gas (CSG) waters from the Surat Basin, Queensland established the presence of viable methanogens and suggested that in situ methanogenesis could be stimulated using physical and chemical reservoir treatments. This paper represents the culmination of a stepwise basin analysis project ultimately aimed at siting potential in situ bioreactor locations in the eastern Surat Basin. The integration of stratigraphically located data on the molecular and isotopic composition of desorbed gases, host coal properties and spatially associated waters through the core production zone has allowed the spatial variability and relative influence of hydro-geological factors on methanogenesis to be evaluated in detail for the first time. Higher gas contents and systematically enriched CH 4 and CO 2 carbon isotopic compositions in the stratigraphically central coal seams (oldest-youngest: in the upper Taroom Coal Measures, Tangalooma Sandstone lower Juandah Coal Measures) are best explained by increased rates of microbial CO 2 reduction and substrate depletion. There is a building case to trial MECoM in the central coal seams in a depleted/underperforming well in an area of high permeability. Integrated microbiological, chemical engineering, hydro-chemical and geological studies are ongoing to further enhance understanding of Walloon Subgroup CSG and the bioreactor potential of the Surat Basin.

Coupling carbon and nitrogen isotopes and petrography of coals and related intra-seam carbonaceous mudstone partings from basins in northern China provides insight into regional palaeoenvironments and palaeoclimate during the late Carboniferous–early Permian. The carbon isotopic composition (δ13Ccoal, VPDB) of coal samples from the Taiyuan and Shanxi formations of Qinshui and North China-Bohaiwan basins ranges from −25.3‰ to −22.7‰, with an average of −23.7‰. The average δ13Ccoal value is −23.6‰ in the late Carboniferous, −23.4‰ in the early Permian and −23.5‰ in the mid–early Permian. By contrast, equivalent early Permian coals in the southern North China-Bohaiwan Basin to the east were found to be significantly more negative at −25.2‰, likely as a function of regional aridity changes. Related δ15N in coal seams ranges from +2.3‰ to +4.7‰, with an average of +3.7‰. Within the thick, economically important #15coal seam of the Qinshui Basin, δ15Ncoal is significantly more negative than δ15N in mudstone partings (avg. +7.1‰), implying that the coals underwent a stronger degree of microbial degradation during peat formation. δ15N of mudstone partings varies stratigraphically, with significantly more positive δ15N (+8.1‰, +8.3‰) for the lower partings and lower δ15N (+4.8‰) for the upper parting. This may reflect varying degrees of microbial activity, but could reflect higher thermal maturity in the upper part of the seam as indicated in the coal rank profile. δ13Ccoal in this region was used to calculate the carbon isotopic composition of atmospheric CO2(δ13Ca). Calculated δ13Ca ranges from −6.0‰ to −3.4‰, with an average of −4.5‰, which is more positive than the δ13Ca of modern atmospheric CO2(−8.5‰, Graven et al., 2017). Two δ13Ca excursions are noted: a positive one (magnitude 3.7‰) in the late Carboniferous and a tentative negative excursion (magnitude 6.0‰) in the mid–early Permian. The positive shift coincided with a sea-level transgression in the Qinshui Basin. The rise in sea level may have led to the burial of more terrestrial plant debris that decreased photosynthesis and enriched atmospheric CO2in 13C. More data are needed to understand mid-early Permian variation in δ13C, as this could reflect a regional aridity or humidity effect rather than a global signal.

Lead and multiple sulphur isotope compositions were measured in-situ by SIMS on sulphide minerals from phoscorites and carbonatites of the ca. 2.06 Ga Phalaborwa Complex in South Africa. Additionally, sulphide mineral separates and bulk-rock samples were analyzed with IRMS methods to confirm SIMS data. Lead isotope ratios define a trend stretching from unradiogenic to highly radiogenic ratios corresponding to a Pb–Pb regression date of 2054 ± 99 Ma. This apparent date is consistent with the timing of emplacement and thus provides an age estimate for the sulphide mineralization. The least radiogenic Pb isotope compositions overlap, and the regression line intersects, a hypothetical mixing line between MORB mantle and an upper crustal reservoir at ca. 2.1 Ga, suggesting that either a significant quantity of crustal Pb contributed to sulphide mineralization, or that sulphidic xenomelts were derived from an isotopically enriched mantle source. Sulphur isotope ratios of individual sulphide minerals obtained by SIMS are highly variable ( δ 34 S: −15 to +15‰ V-CDT) and, importantly, reveal the contribution of pre-Great Oxidation Event (GOE) atmospheric sulphur with mass-independent isotope fractionation ( Δ 33 S = δ 33 S–[(1 + δ 34 S)0.515-1]×1000 ≠0.0‰). Mass-independent sulphur isotope fractionation is also revealed by sulphur isotope ratios measured on sulphide mineral separates ( Δ 33 S: 0.2 to 0.7‰) and bulk rock samples ( Δ 33 S: 0.2 to 0.4‰). Generally, the range of sulphur isotope ratios obtained with SIMS is much larger than that observed in non-SIMS data, possibly reflecting isotopic variability at the μm scale, resolvable only with microbeam measurements. Various sources and mechanisms by which supracrustal material may have been incorporated into mantle-derived carbonatite-phoscorite magmas are assessed, taking into account that geological evidence for the presence of sedimentary material available for assimilation during shallow-level magma emplacement is lacking. Given the variability in S and Pb isotopic compositions, it is inferred that pre-GOE surficial Pb and S were not derived from asthenospheric mantle contaminated with supracrustal materials. Instead, whole rock trace element compositions, in concert with published geochemical and petrological evidence, are consistent with interaction of asthenospheric, plume-derived melt with compositionally heterogeneous lithospheric mantle that was metasomatically modified by fluids and melts released from a subducting slab. Despite geochemical and geochronological similarities with the 2055 Ma Busvheld Complex, lead and sulphur isotope data for both complexes are resolvably different, pointing to distinct lithospheric mantle sources involved in sulphide mineralization.

The Warburton-Cooper basins, central Australia, include a multitude of reactivated fracture-fault networks related to a complex, and poorly understood, tectonic evolution. We investigated authigenic illites from a granitic intrusion and sedimentary rocks associated with prominent structural features (Gidgealpa-Merrimelia-Innamincka Ridge and the Nappamerri Trough). These were analysed by 40Ar-39Ar, 87Rb-87Sr and 147Sm-143Nd geochronology to explore the thermal and tectonic histories of central Australian basins. The combined age data provide evidence for three major periods of fault reactivation throughout the Phanerozoic. While Carboniferous (323.3 ± 9.4 Ma) and Late Triassic ages (201.7 ± 9.3 Ma) derive from basin-wide hydrothermal circulation, Cretaceous ages (~128 to ~86 Ma) reflect episodic fluid flow events restricted to the synclinal Nappamerri Trough. Such events result from regional extensional tectonism derived from the transferral of far-field stresses to mechanically and thermally weakened regions of the Australian continent. Specifically, Cretaceous ages reflect continent-wide transmission of tensional stress from a > 2500 km long rifting event on the Eastern (and southern) Australian margin associated with break-up of Gondwana and opening of the Tasman Sea. By integrating 40Ar-39Ar, 87Rb-87Sr and 147Sm-143Nd dating, this study highlights the use of authigenic illite in temporally constraining the tectonic evolution of intracontinental basins that would otherwise remain unknown. Furthermore, combining Sr- and Ar-isotopic systems enables more accurate dating of authigenesis whilst significantly reducing geochemical pitfalls commonly associated with these radioisotopic dating methods.

This paper reviews various coal seam gas (CSG) models that have been developed for the Sydney Basin, and provides an alternative interpretation for gas composition layering and deep-seated CO2 origins. Open file CSG wells, supplemented by mine-scale information, were used to examine trends in gas content and composition at locations from the margin to the centre of the basin. Regionally available hydrochemistry data and interpretations of hydrodynamics were incorporated with conventional petroleum well data on porosity and permeability. The synthesised gas and groundwater model presented in this paper suggests that meteoric water flow under hydrostatic pressure transports methanogenic consortia into the subsurface and that water chemistry evolves during migration from calcium-rich freshwaters in inland recharge areas towards sodium-rich brackish water down-gradient and with depth. Groundwater chemistry changes result in the dissolution and precipitation of minerals as well as affecting the behaviour of di...

This study used compositional and stable isotopic analysis to test hypotheses on the distribution and origins of Walloon Subgroup coal seam gas (CSG) in the eastern Surat Basin, Queensland, Australia. The Middle Jurassic Walloon Subgroup play differs from many other low-rank CSG plays-particularly in methane carbon isotopic signature, i.e., the CSG is not as 'microbial' as could be expected. The carbon isotope compositions of desorbed methane from three cored appraisal wells fall within the generally accepted range for thermogenic or mixed gas (δ13C -58.5‰ to -45.3‰). The δ13C-CH4 values from stratigraphically placed coal core samples increased (became more 'thermogenic') from the top of the upper (Juandah) coal measures to the base of the Tangalooma Sandstone. Below the Tangalooma Sandstone, in the lower (Taroom) coal measures, the δ13C-CH4 values decreased with increasing depth. These positively parabolic δ13C profiles tracked total measured gas content in two out of the three wells studied. The third well displayed lower variance of δ13C-CH4 and gas content increased uniformly with depth.A genetic classification based on methane stable carbon isotopes alone might interpret this pattern as a transition from microbially- to thermogenically-sourced methane in the central coal seams. However, a δ13C-CO2 profile for one well tracks total gas content and δ13C-CH4, and exhibits an inverse relationship with δD-CH4. These results, together with the mostly dry nature of the gas samples [(C1/(C2+C3)) ratios up to ~10,000] and relatively uniform δD-CH4 values (δD -238‰ to -202‰), suggest that microbial CO2 reduction is the primary source of Walloon Subgroup methane. As such, stratigraphic variations in gas content mainly reflect the extent of microbial methanogenesis. We suggest that peak microbial utilisation of H2-CO2 occurred at the Tangalooma Sandstone level, enriching the residual CO2 pool and derived methane in 13C. Carbon [δ13C(CO2-CH4)] and deuterium isotopic differences [δD(H2O-CH4)], and cross-plots of δD-H2O and δ18O-H2O are also consistent with kinetic isotope fractionation during microbial-mediated carbonate reduction. The results are relevant for applying microbially enhanced coal bed methane (MECoM) in the Surat Basin.

Copper deposits occur in rocks of all ages and are formed as a result of geological processes that concentrated copper initially dispersed through large volumes of magma or rock. The majority of copper deposits were created by hydrothermal processes when metal sulfides were precipitated from hot waters in fractures and permeable rocks in the subsurface and at seafloor hydrothermal vents. Copper minerals can also crystallise in magma chambers or form as a result of secondary enrichment processes when primary copper deposits are weathered. Porphyry copper and associated skarn, vein and replacement deposits are the most important type of copper deposits accounting for some 60% of current world copper production. Sediment-hosted stratiform copper deposits in sedimentary basins account for some 20% of historic world copper production and were some of the earliest copper ores mined. Volcanic-hosted massive sulfide deposits occur in submarine volcanic rocks and are observed forming today at seafloor hydrothermal vents. Magmatic nickel-copper sulfide deposits in igneous rocks have a very different origin than the hydrothermal copper deposits that dominate current and historic world copper production. This type of deposit forms when mafic and ultramafic magmas separate a metal-sulfide magma that sinks to the bottom of the magma chamber or flow conduit.

High-CO2-containing coal seams in the Oaky Creek area of the Bowen Basin, eastern Australia provide natural analogues of the processes likely to occur as a result of CO2 injection and storage in coal systems. We conducted mineralogical, stable and radiogenic isotope and major element analyses of mudstones and sandstones adjacent to the coal seams and stable isotope and compositional studies of coal seam gas desorbed from the coals to establish the impact of the high CO2 levels and the mechanisms that keep the CO2 naturally sequestered. Siderite is the earliest carbonate phase present and occurs with kaolinite in mudstones and sandstones. It is interpreted to have formed under low-temperature, reducing conditions where methanogenesis has produced residual 13C-enriched CO2. Enhanced kaolinite concentrations adjacent to a low-CO2-containing coal seam reflect interaction with acidic fluids produced during the coalification of organic matter. Stable isotope data for carbonates and Rb–Sr isochron ages for illit...

The metaluminous Soultz-sous-Forets monzogranite, France, is highly evolved and contains elevated concentrations of rare-earth elements (REE), Y and particularly Th. Primary accessory minerals include fluorapatite, allanite-(Ce) and Th-rich titanite. Primary titanite has been altered to anatase + calcite + quartz + synchysite-(Ce) ± bastnaesite-(Ce) or anatase + calcite + quartz + monazite-(Ce) + xenotime-(Y) ± thorite. Fluorocarbonate-bearing assemblages are restricted to those samples exhibiting minor selective alteration, whereas those containing phosphate-rich assemblages formed in pervasively altered samples that have experienced high fluid/rock ratios. Comparative electron-microprobe analysis of primary and hydrothermally-derived accessory phases found middle REE, Y and Th concentrations depleted in synchysite-(Ce) relative to primary titanite. Such depletions are not seen in phosphate-rich samples containing monazite-(Ce) and xenotime-(Y). Variability in elemental concentrations may be attributed to distinct fluid chemistries and hence, lead to differential mobility during alteration. Following previous experimental work and mineralogical observations, the ingress of CO2-rich solutions was integral for titanite breakdown and the resultant metasomatic assemblage. The influx of CO2-rich fluids concomitantly with chloritisation of biotite produced fluids enriched in FCO3−. We, therefore, hypothesise that after the alteration of titanite, remnant HCO3− or FCO3−-rich fluids were able to mobilise significant proportions of MREE, Y and Th not accommodated into the synchysite-(Ce) structure. Conversely, those samples rich in monazite-(Ce) and xenotime-(Y) retained their REE, Y and Th concentrations due to the presence of aqueous HPO42− derived from apatite dissolution.

International audience; Direct dating of brittle fault activity is of fundamental impor- tance to tectonic reconstructions and paleoseismic studies. One way to address this issue is by constraining the timing of fault striations, but this requires a better understanding of the striation formation mechanism and associated mineralization. We present results from a microstructural, geochemical, and geochronological study of cal- cite precipitates associated with striated fault planes from the Dead Sea fault zone in northern Israel. We recognize four types of coexist- ing calcite precipitates, including calcite cement in dilation breccia, calcite in striated groove morphology, calcite gouge associated with hydraulic fracturing and pressure solution, and calcite coating of the fault surface. Carbon-oxygen isotopes, 87Sr/86Sr ratios, and rare earth element and yttrium (REY) patterns indicate various precipi- tation mechanisms associated with formation of syntectonic (calcite cement and striations), coseismic (calcite gouge), and interseismic (calcite coating) precipitates in the fault zone. Using U-Th dating of samples from three adjacent fault planes, we delineate four well- defined deformation ages in the period from 220 to 60 ka. We con- clude that these ages constrain the timing of activity along the Dead Sea fault zone in northern Israel, and argue that a similar meth- odological approach could potentially shed light on the timing of deformation in other brittle fault zones.

Late Permian age samples of black coal from the coeval Bandanna Formation and Baralaba Coal Measures of Queensland's Bowen Basin, as well as Carboniferous coal from Germany's Ruhr Basin, were investigated. This paper presents scanning electron microscope (SEM) analysis of the mode of occurrence of minerals within these coals, and characterisation of the natural fractures present within the samples. The coal samples located proximal to orogenic fronts in both basins are structurally complex, with multiple generations of mineralisation evident. Stable isotope analyses of carbonates from selected samples indicate that methanogenesis-related CO2 reduction has occurred at two of the Bowen Basin sampling locations. Ankerite precipitated from a magmatic fluid or basinal brine is associated with significant sulphide mineralisation within brecciated Ruhr coal proximal to major fault intersections with anticlines, and has been meteorically altered to ferroan calcite and sulphates in coal from immediately below the Carboniferous/Cretaceous unconformity. Similar alteration has occurred within a Bowen Basin coal sample close to the present day land surface. Variation of mineralisation within both the cleats and the coal matrix occurs on a fine scale, with crystals of multiple mineral species often being present within micrometres of each other.

The emplacement of calcite-filled veins perpendicular to the Dead Sea Fault Zone in northern Israel reflects strain partitioning during transpression. We present structural, geochemical, and U–Th geochronological data that constrain the mechanism, conditions and timing of vein formation. Vein walls are strongly brecciated and commonly cemented with coarsely crystalline calcite, whereas calcite-filled veins are composed of wall-parallel bands of calcite crystals. Elongated blocky and fibrous calcite crystals grew perpendicular to the vein walls and are characterised by a truncate sealing-hiatus morphology, indicating episodes of partial or complete sealing of the fractures during calcite precipitation. Stable isotope and rare-earth element and yttrium (REY) analyses indicate that calcite-filled veins precipitated by karst processes, involving meteoric water and limited fluid-rock interactions. U–Th dating results show a prolonged history of vein growth. While some veins initiated prior to 500 ka, the majority of the veins were active between 358 and 17 ka. Age constraints on vein activity correspond to an ∼E–W regional shortening phase in this sector of the Dead Sea Fault Zone, associated with an increased component of convergence during the late-Pleistocene.

Intensive carbonate and clay mineral authigenesis took place throughout the Late Permian Bowen-Gunnedah-Sydney basin system in eastern Australia. We conducted isotopic and trace element analyses of carbonate and clay minerals from clastic sedimentary rocks of the Gunnedah Basin and the Denison Trough in the Bowen Basin. Rb-Sr isochron age data of the illitic clays are consistent with episodic hydrothermal fluid flow events that occurred in association with Gondwana rifting accompanied by alkaline magmatism at similar to 85 Ma and similar to 95 Ma. Stable isotope data of carbonate and clay minerals from the Gunnedah Basin are indicative of meteoric waters from a high-latitude environment as the main fluid source, whereas trace element, Sr and Nd isotope data highlight mixing of meteoric fluids with magmatic and/or crustal components, with a possible input from marine carbonates for some samples. Trace metals, oxygen and strontium isotopes of dawsonites from the Denison Trough are interpreted to have been mobilised by fluids that interacted with evolved clastic sedimentary and marine carbonate end members. According to the carbon isotope data, CO2 for calcite and ankerite precipitation was sourced mainly from thermal degradation of organic matter and magmatism, whereas the CO2 used for dawsonite formation is inferred to have been derived from magmatic and marine sources. In the low permeability environments (particularly in coal seams), the increasing accumulation and oversaturation of CO2 particularly promote the precipitation of dawsonite. (C) 2011 Elsevier Ltd. All rights reserved.

Southwest Turkey is seismically active as a result of the Hellenic subduction process in the Eastern Mediterranean. We conducted high-resolution micro-sampling, high-precision U-series dating and microchemical analysis on an extensional vein system in a tectonically active but non-hydrothermal area. U/Th age data and microscopic observations provide evidence of repeated fracturing of a previously sealed crack system followed by a new increment of veining. Repeated injection of veinlets suggests that the vein system was formed by the crack-seal mechanism. Four major U/Th age groups for the emplacement of the vein system fall between 23.9 +/- 0.2 ka and 23.2 +/- 0.4 ka, 21.7 +/- 0.4 ka and 19.2 +/- 0.2 ka, 17.3 +/- 0.1 ka and 16.2 +/- 0.3 ka, and at 11.8 +/- 0.2 ka. Stable and Sr isotope geochemistry of the calcite vein samples indicates that surface water interacting with the soil cover was the major component of the groundwater system from which the extensional veins precipitated. Trace element and 0 isotope data of the vein system are interpreted to reflect carbonate precipitation associated with seismic cycles involving fluids with different trace element compositions and CO2 contents. Initial carbonate precipitation during a single seismic cycle occurred from CO2-dominated fluids that were degassed from the original CO2 water mixture. This was followed consecutively by carbonate precipitation from the remaining water, which was relatively impure with higher trace element contents. Millimetre to submillimetre-scale U-series dating in conjunction with geochemistry of carbonate veins related to active tectonism offers an innovative means of constraining the absolute timing of late Quaternary seismic and inter-seismic events. (C) 2010 Elsevier B.V. All rights reserved.

Fault-related calcite precipitates taken from different segments along the East Anatolian (SE Turkey) and Dead Sea (Israel) fault zones were investigated structurally, geochemically and geochronologically. The results indicate major differences in the nature of calcite precipitates and temporal relationship to faulting. In the Du¨zic¸i Fault, calcite-filled veins and hydraulic fractures precipitated co-seismically during three consecutive faulting events. Calcite precipitated in veins at the Har Zefiyya Fault was controlled by near-surface karst processes. Initial opening of the veins occurred prior to about 500 ka and may represent the onset of an east–west contractional deformation. In the Carmel Fault Zone the calcite coating the fault plane precipitated by karst processes, with no evidence of subsequent deformation. Calcite fault gouge from the same site are a mix of host-rock gouge and newly formed authigenic calcite, and their overall geochemistry suggests pervasive fluid–rock interaction in the fault zone. In the Baraq Fault Zone the precipitation of calcite within syntectonic tension gashes and veins occurred prior to 540 ka by the pervasive infiltration of meteoric water into the fault zone. The results demonstrate that geochemical and structural analyses, combined with U–Th geochronology, can shed light on co-seismic and interseismic fault activity, and can potentially provide precise age constraints on the timing of brittle deformation.

Coal bed methane (CBM) is a significant growing industry in Queensland's energy sector. It is, however, a relatively new industry with little local water quality data and stable isotope compositions of production waters and gases available in the public domain. This study aims to determine whether water quality and stable isotope data can be correlated with gas and groundwater production and flow pathways, and identify zones of recharge and water mixing. Stable isotope analysis and accessory water quality tests were conducted on CBM production gas and water samples collected from two CBM producing bituminous coal seams within a single field in the Bowen Basin. In the production field, the reservoir seams are gently folded with eastwardly dipping fold axes, and compartmentalised by an ENE normal fault on the flank of a broad central anticline that contains minor faults. For one seam, splitting and a change in coal quality parallels the fault and fold axes. Although virgin reservoir conditions were similar, differing production performance north and south of the main fault suggests it acts as a barrier to water and gas flow along strike. The stable isotope analysis on the production water showed that waters with more positive δD and δ18O compositions were associated with areas of higher water production and shallower depths, whereas more negative δD and δ18O compositions were associated with lower water production and high gas production. The gas isotope analysis showed that production gases had both biogenic and thermogenic origins and that secondary biogenic gas generated through CO2 reduction comprises a significant portion of the CBM produced from this field. More negative CH4 δ13C values characterize the zones of meteoric recharge in shallow, up-dip areas. Gas production data and CO2 δ13C values suggest that this may result from 13CH4 stripping by the recharge waters and/or increased biogenic activity in this area. Smaller CO2–CH4 carbon isotopic fractionation values characterized zones of meteoric recharge, whereas higher isotopic fractionation values characterized the high gas production domain.

Natural CO2 discharges are abundant in Turkey as evident from ongoing deposition of recent terrace-mound travertines and emplacement of significant travertine vein and breccia deposits in fractured damage zones of active fault systems. We report high-precision U-series age data for the vein carbonates combined with important field observations and geochemical data to evaluate the travertine veining and CO2 degassing history in seismically active areas. Field evidence suggests that travertine-filled veins and associated breccias represent hydrothermal eruption products, which probably formed by hydraulic fracturing in response to overpressure Of CO2-rich fluids. Stable isotope and REE data support the field observations and indicate that travertine veins formed as thermogene deposits from rapidly ascending CO2-rich fluids. Travertine veins from the Kirsehir geothermal field give U-series ages in a range from 10.6 +/- 0.3 ka to 86.16 +/- 1.24 ka, with a majority of ages failing between 10.6 +/- 0.3 and 11.3 +/- 0.2 ka. Vein samples from the Pamukkale geothermal field yield U-series ages between 21.1 +/- 0.1 ka and 73.6 +/- 0.6 ka. Two major age groups are evident in Pamukkale that cluster coherently around 21 ka and 25 ka. A large number of travertine veins we dated by high-precision U-series technique coincide with times of cold/dry climate events. This is different from surface sinter deposits in geothermal fields, which more frequently form during warm and wet periods. We propose that a significant reduction in surface discharge Of CO2 by spring or geothermal waters during dry climate periods may promote oversaturation of CO2 in deep reservoirs. Host rock fracturing in response to seismic shaking and fluid overpressure results in rapid exsolution and expansion of the dissolved gas and may lead to hydrothermal eruptions. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

The sulfur isotope record in late Archean and early Paleoproterozoic rocks is of considerable importance because it provides evidence for changes in early Earth atmospheric oxygen levels and potentially constrains the origin and relative impact of various microbial metabolisms during the transition from an anoxic to oxic atmosphere. Mass independently fractionated (MIF) sulfur isotopes reveal late Archean and early Paleoproterozoic sulfur sources in different pyrite morphologies in Western Australia's Hamersley Basin. Multiple sulfur isotope values in late Archean pyrite vary according to morphology. Fine grained pyrite has positive sulfur MIF, indicating a reduced elemental sulfur source, whereas pyrite nodules have negative sulfur MIF, potentially derived from soluble sulfate via microbial sulfate reduction. The Hamersley Basin δ 34 S–Δ 33 S record suggests that the extent of oxygenation of the surface ocean fluctuated through the Late Archean from at least 2.6 Ga, more than 150 million yr before the Great Oxidation Event. In the early Paleoproterozoic, there is less distinction between pyrite morphologies with respect to sulfur isotope fractionation, and pyrite from the Brockman Iron Formation trends toward modern sulfur isotope values. An important exception to this is the strong negative MIF recorded in layer parallel pyrite in Paleoproterozoic carbonate facies iron formation. This may suggest that deeper water hydrothermal environments remained anoxic while shallower water environments became more oxidised by the early Paleoproterozoic. The results of the current study indicate that sulfide paragenesis is highly significant when investigating Archean and early Paleoproterozoic multiple sulfur isotope compositions and sulfur sources.

Application of multiple chronometers (including U–Pb and 40Ar/39Ar geochronology and zircon and apatite (U–Th)/He thermochronology) to porphyry intrusions at the Bajo de la Alumbrera porphyry copper–gold deposit, Argentina, reveals a complex history of reheating that spans millions of years. Previous U–Pb geochronology, combined with our new 40Ar/39Ar data, shows that the multiple porphyritic intrusions at Bajo de la Alumbrera were emplaced during two episodes, the first at about 8.0 Ma (P2 and associated porphyries) and the second about a million years later (Early and Late P3 porphyries). Complex overprinting alteration events have obscured the earliest hydrothermal history of the deposit. By contrast, 40Ar/39Ar data reveal the close temporal relationship of ore-bearing potassic alteration assemblages (7.12 ± 0.13 Ma; biotite) to the emplacement of the P3 intrusions. Consistent with low closure temperatures, younger ages have been determined for associated hydrothermal alkali feldspar (6.82 ± 0.05 Ma and 6.64 ± 0.09 Ma). The temperature-sensitive Ar data also record an unexpected prolonged cooling history (to below 200°C) extending to 5.9 Ma. Our data suggest that the Bajo de la Alumbrera system underwent protracted cooling, after the collapse of the main hydrothermal system, or that one or more low-temperature (~100–200°C) reheating events occurred after emplacement of the porphyritic intrusions at Bajo de la Alumbrera. These have been constrained in part by our new 40Ar/39Ar data (including multidomain diffusion modeling) and (U–Th)/He ages. Single-grain (U–Th)/He ages (n = 5) for phenocrystic zircon from P2 and P3 intrusive phases bracket these thermal events to between 6.9 (youngest crystallization of intrusion) and 5.1 Ma. Multidomain modeling of alkali feldspar data (from both igneous and hydrothermal crystals) is consistent with the deposit cooling rapidly from magmatic temperatures to below about 300°C, with a more protracted history down to 150°C. We conclude that the late-stage low-temperature (150 to 200°C) thermal anomaly localized at Bajo de la Alumbrera resulted from radiation of heat and/or fluids sourced from deeper-seated magma bodies, emplaced beneath the deposit. To produce the observed thermal longevity of the porphyry system, magma bodies underlying the Bajo de la Alumbrera deposit must have been repeatedly replenished by new magma batches. Without replenishment, crystallization of the source magma will occur, and heat release will stop, leading to rapid cooling (in less than ten thousand years). The influx of deep-seated magma may have caused the development of late low-temperature hydrothermal alteration assemblages at Bajo de la Alumbrera, at the same time that mineralization formed at Agua Rica, some 25 km away. All available chronologic data for the Bajo de la Alumbrera deposit suggest that the hydrothermal system was active episodically over at least a three-million and possibly up to a four-million-year period.

We present a method to constrain the timing of fissure generation related to late Quaternary seismic events using the uranium-series technique. Dated samples were from travertine deposits precipitated in co-seismic extensional fissures along major active faults in Western Turkey. Stable isotope and REE data indicate that the precipitation of the fissure travertines was not controlled by the hydrologic regime that is responsible for the speolethem deposition in the same region. Moreover, the REE composition and concentration of the water from which the fissure travertine precipitated were significantly different from those of the current geothermal waters in the study area. The carbonate generation in the co-seismic fissures is interpreted to be the product of rapid precipitation from deeply infiltrated and CO2-enriched surface water during seismic strain cycles. Results show that U-series dating of fracture-filling travertine deposits from seismically active areas provide important temporal information relevant to establishing recurrence intervals of late Quaternary and prehistoric major earthquake events. Precise dating of prehistoric earthquakes may be of great value for seismic hazard studies and earthquake forecasting research, for which accurate estimates of recurrence intervals are critical. (c) 2007 Elsevier B.V. All rights reserved.

A fluid inclusion investigation of the polymetallic mineralization at Yinshan from the Le-De metallogenic belt in Jiangxi Province of China has been carried out using petrographic and microthermometric techniques. The data obtained here indicate that three major types of fluids were involved during the formation of the deposit. They are type I vapor-rich, type II liquid-rich and type III halite-bearing inclusions within the H2O-NaCl system. The high salinity fluids represented by type III inclusions, being unusual to the distal part of an intrusion-centered ore-forming system such as Yinshan, have been interpreted as the product of direct exsolution of a crystallizing magma, rather than a result of fluid immiscibility from a low salinity fluid. Evidence used to support such an interpretation includes the mode of homogenization of type III inclusions exclusively via halite dissolution, spatial separation of type I and type III inclusions on microscopic scale, the consistent phase ratios within the inclusions concerned, and considerable deviation in homogenization temperature for both type I and type III inclusions. Trapping conditions for type I inclusions were estimated to be around 440 degrees C and 260 bars, while type III inclusions were constrained to be trapped at least above 900 bars and > 500 degrees C. The formation temperatures for type II inclusions range from 270 to 390 degrees C if a lithostatic pressure of 260 bars is assumed. Pressure fluctuation determined by this fluid inclusion study coupled with decreases in salinity and temperature as result of the potential fluid mixing are supposed to have played an important role in triggering the precipitation of ore minerals from the hydrothermal solution. (c) 2006 Elsevier B.V All rights reserved.

Late Permian coals and coal measures in the Bowen Basin, Australia, are extensively mineralised with carbonates as cleat fillings and veins. The calcites in coal samples exhibit large variations in rare-earth element (REE) patterns and Sm-Nd ratios with some superchondritic values. Samples enriched in heavy REE (HREE) relative to light REE (LREE) define an Sm-Nd isochron corresponding to an age of 235 +/- 15 Ma, which is consistent with the timing of final contractional phase of the Hunter-Bowen orogeny. The corresponding initial epsilon Nd is + 1.2 combined with HREE-enriched patterns suggests significant fluid interaction with primitive source rocks, which are consistent with arc-related volcanogenic sediments in the basin. Calcites characterised by HREE depletion relative to LREE are not in Sm-Nd isotopic equilibrium with the former samples that is interpreted to be due to the effect of a later hydrothermal event during the Late Triassic-Early Jurassic. Vein calcites in mudrocks from the coal measures display more pronounced HREE depletion and significant positive EuCN anomalies, which is related to the later hydrothermal event. REE distributions, together with the basin burial history, suggest that physico-chemical environments of fluid-flow events during the two separate major tectonic regimes were significantly different. This study shows that a combined application of Sm-Nd dating and REE geochemical tracing of authigenic carbonate minerals is very useful to constrain the evolution of multiple fluid-flow events in a sedimentary basin with a complex history. (c) 2006 Elsevier B.V All rights reserved.

Isa Superbasin strata in the Lawn Hill Platform host major base metal sulfide mineralization including the giant Century Zn-Pb deposit. Mineral paragenesis, organic maturation, K-Ar dating and stable isotope studies demonstrate that long-lived structures such as the Termite Range Fault acted as hot fluid conduits several times during the Paleoproterozoic and Mesoproterozoic. K-Ar dating of illites, in combination with other datasets, may identify three thermal events in the Lawn Hill Platform at 1500, 1440-1400 and 1250-1150 Ma. 1500 Ma is a Late Isan Orogeny age recorded only in the south that may reflect exhumation of a provenance region. The 1440-1300 Ma ages are related to fault reactivation and a thermal/?fluid pulse at ~1440-1400 Ma, with subsequent enhanced cooling. The youngest thermal/fluid flow event at 1250-1150 Ma is recorded mainly in the northeast and is probably related to the assembly of Rodinia. An extensive carbonate alteration halo in the footwall of the circa 1575 Ma Century Zn-Pb deposit extends some 15 km along strike. Calculations of fluid oxygen and carbon isotope composition based on model temperatures of 120°C for the ore zone siderites and 180°C for siderites and ankerites in the regional carbonate alteration halo indicate similar ore and alteration fluid compositions (d18O = 3 to 10 per mil; d13C = -7 to -3 per mil). This fluid isotope composition is consistent with highly evolved basinal brines and mixed inorganic and organic carbon sources. The good agreement between maximum temperature estimates from illite crystallinity and organic reflectance and inverse correlation with carbonate oxygen isotopes in northeast Lawn Hill platform boreholes indicate thermal maturation and carbonate formation resulted from interaction with the 1250-1150 Ma fluids. The calculated fluid isotope compositions are consistent with an evolved basinal brine (d18O = 5.1 to 9.4 per mil V- SMOW; d13C = -13.2 to -3.7 per mil V-PDB) that contained a significant organic carbon component. Differences in carbon and oxygen isotope systematics of alteration carbonate are significant to their use with lithogeochemical vectors in mineral exploration in the northern Australian basins.

Dating of shallow faults is crucial to understanding of the mechanism of earthquake generation and future seismic risk. However, radiometric dating of low temperature authigenic minerals in shallow fault zones has been a major challenge because of the contamination of fault rocks by older mineral phases and the overprinting of the syn-tectonic isotopic signature by post-tectonic re-crystallisation events. We present a technique for a reliable dating of fault movements using a combined application of low temperature geochronology, mineralogy and isotope-trace element geochemistry. Such combined studies further allow constraining the origin and migration of seismically mobilised fluids along active fault zones. We investigated illitic clay minerals from fault gouges and late Quaternary carbonate deposits in co-seismic fissures along currently active fault zones in Turkey. Our results indicate that the North Anatolian Fault Zone has been active since the Late Paleocene ? Early Eocene that followed immediately the continental collision related to the closure of the Neotethys Ocean. Fault movement is considered to have driven deeply sourced fluids, with metamorphic fluids being supplied by the compression along the Neotethyan orogenic suture zone. Precise dating of the late Quaternary carbonate deposits by U-series geochronology provide important constraints on the late Quaternary fissure generation related to the neotectonic processes and active faulting. Isotopic and trace element data indicate that the fissure carbonate deposits precipitated from deeply hydrothermal fluids. Mobilisation of deep fluids and their surface effusion is attributed to tectonic processes such as seismic pumping. K-Ar and U-series dating of clay and carbonate minerals respectively in seismically active areas is very promising for further studies for dating of major earthquake events and their recurrent intervals, with significant implications for the Australian active fault systems.

The ca. 1575 Ma Century Zn-Pb deposit and the 47 near-by discordant Zn-Pb lode deposits of the Burketown Mineral Field, northern Australia host ore and gangue minerals that have not been overprinted by deformation associated with the the 1610?1520 Ma Isan Orogeny (Page and Bell, 1986; Blake, 1987), which obliterated many of the primary textural features at the Mt Isa, Hilton and George Fisher deposits. The Burketown Mineral Field deposits, which are hosted in shales and siltstones belonging to the Isa Superbasin, comprise sphalerite, pyrite, carbonate, quartz, galena, chalcopyrite and minor illite that lend themselves to isotopic and fluid inclusion studies that cannot be performed on the deposits to the south. For instance, there are no published O-H isotopic data from any of the known Zn-Pb deposits in the Mt Isa Basin and very limited, pre-Isan 40Ar/39Ar and fluid inclusion data (Rohrlach et al., 1998). A paragenetic and isotopic study of Century and 14 of the discordant lode deposits combined with published Pb/Pb model ages reveal that multiple fluid events spanning a period lasting ca. 400 million years since the initial formation of the Century deposit are preserved in this area.

Mudrocks and carbonates of the Isa superbasin in the Lawn Hill platform in northern Australia host major base metal sulfide mineralization, including the giant strata-bound Century Zn-Pb deposit. Mineral paragenesis, stable isotope, and K-Ar dating studies demonstrate that long-lived structures such as the Termite Range fault acted as hot fluid conduits several times during the Paleoproterozoic and Mesoproterozoic in response to major tectonic events. Illite and chlorite crystallinity studies suggest the southern part of the platform has experienced higher temperatures (up to 300 degrees C) than similar stratigraphic horizons in the north. The irregular downhole variation of illite crystallinity values provides further information oil the thermal regime in the basin and shows that clay formation was controlled not only by temperature increase with depth but also by high water/rock ratios along relatively permeable zones. K-Ar dating of illite, in combination with other data, may indicate three major thermal events in the central and northern Lawn Hill platform Lit 1500, 1440 to 1400, and 1250 to 1150 Ma. This study did not detect the earlier Century base metal mineralizing event at 1575 Ma. 1500 Ma ages are recorded only in the south and correspond to the age of the Late Isan orogeny and deposition of the Lower Roper superbasin. They may reflect exhumation of a provenance region. The 1440 to 1300 Ma ages are related to fault reactivation and a thermal pulse at similar to 1440 to 1400 Ma possibly accompanied by fluid flow, with subsequent enhanced cooling possibly due to thermal relaxation or further crustal exhumation. The youngest thermal and/or fluid-flow event at 1250 to 1150 Ma is recorded mainly to the cast of the Tern-lite Range fault and may be related to the assembly of the Rodinian supercontinent. Fluids in equilibrium with illite that formed over a range of temperatures, at different times in different parts of the platform. have relatively uniform oxygen isotope compositions and more variable hydrogen isotope compositions (delta O-18 = 3.5-9.7 parts per thousand V-SMOW; delta D = -94 to -36 parts per thousand V-SMOW). The extent of the 180 enrichment and the variably depleted hydrogen isotope compositions suggest the illite interacted with deep-basin hypersaline brines that were composed of evaporated seawater and/or highly evolved meteoric water. Siderite is the most abundant iron-rich gangue phase in the Century Zn-Pb deposit, which is surrounded by all extensive ferroan carbonate alteration halo. Modeling suggests that the ore siderite formed at temperatures of 120 degrees to 150 degrees C, whereas siderite and ankerite in the alteration halo formed at temperatures of 150 degrees to 180 degrees C. The calculated isotopic compositions of the fluids are consistent with O-18-rich basinal brines and mixed inorganic and organic carbon Sources (6180 = 3-10 parts per thousand V-SMOW, delta C-13 = -7 to -3 parts per thousand V-PDB). in the northeast Lawn Hill platform carbonate-rich rocks preserve marine to early diagenetic carbon and oxygen isotope compositions, whereas ferroan carbonate cements in siltstones and shales in the Desert Creek borehole are O-18 and C-13 depleted relative to the sedimentary carbonates. The good agreement between temperature estimates from illite crystallinity and organic reflectance (160 degrees-270 degrees C) and inverse correlation with carbonate delta O-18 values indicates that organic maturation and carbonate precipitation in the northeast Lawn Hill platform resulted from interaction with the 1250 to 1150 Ma fluids. The calculated isotopic compositions of the fluid are consistent with evolved basinal brine (delta O-18 = 5.1-9.4 parts per thousand V-SMOW; delta C-13 = -13.2 to -3.7 parts per thousand V-PDB) that contained a variable organic carbon component from the oxidation and/or hydrolysis of organic matter in the host sequence. The occurrence of extensive O-18- and C-13-depleted ankerite and siderite alteration in Desert Creek is related to the high temperature of the 1250 to 1150 Ma fluid-flow event in the northeast Lawn Hill platform, in contrast to the lower temperature fluids associated with the earlier Century Zn-Pb deposit in the central Lawn Hill platform.

Hydrocarbon migration pathways and organic mineral matter associations were used to identify brine pathways in Paleoproterozic to early Mesoproterozoic rocks from the Lawn Hill platform, Mount Isa. Several types of organic matter are identified, and their thermal imprints are used to reconstruct the thermal history of the northern to central parts of the Isa superbasin. Three major thermal hydrothermal episodes are recognized from the organic maturation studies. Isotherm plots on a 175-km-long structural-sedimentological north-south section of the Isa superbasin highlight specific fault systems that acted as hot fluid conduits during the geologic history of the basin. Some of these systems indicate continuing activity into the south Nicholson basin, supported by the presence of low reflectance (type B) bitumen. This bitumen has not been overprinted by later hydrothermal episodes and therefore represents the latest thermal event. Along the north-south profile a general southward increase in temperature is evident. The lowest temperatures are recorded in proximity to the basin margin on the southern flank of the Murphy inlier. Thermal processes and their sequence of events in the basin are recorded by organic maturation, subsequent hydrocarbon generation, its migration and destruction coincident with transport and precipitation of minerals. As some timing and trapping mechanisms for minerals may have analogues with hydrocarbon entrapment, relative timing of processes leading to organic maturation, hydrocarbon generation and migration are utilized in this study to enhance understanding of ore-grade mineralization. In the Proterozoic successions of the Mount Isa basin multiple hydrocarbon generation events are recognized. These events record the transient passage of potential metal-bearing fluids rather than background conductive heat flow from the basement. Such hydrothermal fluids are responsible for inverse maturation profiles in the vicinity of the Termite Range fault and extreme maturation (reflectance values) up to 6 percent Ro at the Grevillea prospect. At Century, intermediate Ro values of

Paleoproterozoic rocks of northern Australia host one of the world’s largest base metal repositories and are the world’s most important zinc repository. The McArthur-Mount Isa-Cloncurry mineral belt contains several world-class Zn-Pb-Ag, U, Cu, and Cu-Au deposits (Ewers and Fergusson, 1980; Williams, 1998; Betts et al., 2003; Large et al., 2005; Fig. 1⇓). The province has the potential to host additional base metal and uranium reserves. Advances in exploration techniques in the 1980s led to the discovery of several major new Zn and Cu-Au deposits, including Cannington, Century, Ernest Henry, and Osborne. However, recent exploration results have been disappointing and new exploration strategies are required if the region is to further its growth potential and if new resources are to be realized beneath shallow cover. Fig. 1. Map of northeastern Australia, showing the principal tectonostratigraphic subdivisions for the region. The map highlights the areas of study covered by the thematic papers in this volume and the location of the principal Zn-Pb-Ag, Cu, and Cu-Au deposits. The locations of profiles P1 and P2, the Comalco seismic grid, and deep boreholes including Desert Creek 1 are shown in the inset map (bottom left). Between 1975 to 1995 geoscientists from Geoscience Australia, the Geological Survey of Queensland, and the Northern Territory Geological Survey mapped the Paleoproterozoic outcrop belt of northern Australia at a scale of 1:100,000. Subsequently, researchers at Monash University undertook detailed studies of the deformation history of the Mount Isa block, placing the ore deposits within a tectonic context (e.g., O’Dea et al., 1997; Betts et al., 1998, 2003; Betts and Lister, 2002). Researchers at James Cook University carried out structural, metamorphic and mineralization studies across the Mount Isa block, with their principal focus concentrating on the deposits and their immediate environs (Bell et al., 1988 …

The stratiform Century Zn-Pb deposit and the discordant Zn-Pb lode deposits of the Burketown mineral field, northern Australia, host ore and gangue minerals with primary fluid inclusions that have not been affected by the Isan orogeny, thus providing a unique opportunity to investigate the nature of the ore-forming brines. All of the deposits are hosted in shales and siltstones belonging to the Isa superbasin and comprise sphalerite, pyrite, carbonate, quartz, galena, minor chalcopyrite, and minor illite. According to Pb model ages, the main ore stage of mineralization at Century formed at 1575 Ma, some 20 m.y. after deposition of the host shale sequence. Microthermometry on undeformed, primary fluid inclusions hosted in porous sphalerite shows that the Zn at Century was transported to the deposit by a homogeneous, Ca 2+ - and Na + -bearing brine with a salinity of 21.6 wt percent NaCl equiv. δD fluid of the fluid inclusion water ranges from −89 to −83 per mil, consistent with a basinal brine that evolved from meteoric water. Fluid inclusion homogenization temperatures range between 74° and 125°C, which are lower than the 120° to 160°C range calculated from vitrinite reflectance and illite crystallinity data from the deposit. This discrepancy indicates that mineralization likely formed at 50 to 85 Mpa, corresponding to a depth of 1,900 to 3,100 m. Transgressive galena-sphalerite veins that cut stratiform mineralization at Century and breccia-filled quartz-dolomite-sphalerite-galena veins in the discordant Zn-Pb lodes have Pb model ages between 1575 and 1485 Ma. Raman spectroscopy and microthermometry reveal that the primary fluid inclusions in these veins contain Ca 2+ , Na + , but they have lower salinities between 23 and 10 wt percent NaCl equiv and higher δD fluid values ranging from −89 to −61 per mil than fluid inclusions in porous sphalerite from Century. Fluid inclusion water from sphalerite in one of the lode deposits has δ 18 O fluid values of 1.6 and 2.4 per mil, indistinguishable from δ 18 O fluid values between −0.3 to +7.4 per mil calculated from the isotopic composition of co-existing quartz, dolomite, and illite. The trend toward lower salinities and higher δD fluid values relative to the earlier mineralizing fluids is attributed to mixing between the fluid that formed Century and a seawater-derived fluid from a different source. Based on seismic data from the Lawn Hill platform and paragenetic and geochemical results from the Leichhardt River fault trough to the south, diagenetic aquifers in the underlying Calvert superbasin appear to have been the most likely sources for the fluids that formed Century and the discordant lode deposits. Paragenetically late sphalerite and calcite cut sphalerite, quartz, and dolomite in the lode deposits and contain Na + -dominated fluid inclusions with much lower salinities than their older counterparts. The isotopic composition of calcite also indicates δ 18 O fluid from 3.3 to 10.7 per mil, which is larger than the range obtained from synmineralization minerals, supporting the idea that a unique fluid source was involved. The absolute timing of this event is unclear, but a plethora of Pb model, K-Ar, and 40 Ar/ 39 Ar ages between 1440 and 1300 Ma indicate that a significant volume of fluid was mobilized at this time. The deposition of the Roper superbasin from ca. 1492 ± 4 Ma suggests that these late veins formed from fluids that may have been derived from aquifers in overlying sediments of the Roper superbasin. Clear, buck, and drusy quartz in veins unrelated to any form of Pb-Zn mineralization record the last major fluid event in the Burketown mineral field and form distinct outcrops and ridges in the district. Fluid inclusions in these veins indicate formation from a low-salinity, 300° ± 80°C fluid. Temperatures approaching 300°C recorded in organic matter adjacent to faults and at sequence boundaries correspond to K-Ar ages spanning 1300 to 1100 Ma, which coincides with regional hydrothermal activity in the northern Lawn Hill platform and the emplacement of the Lakeview Dolerite at the time of assemblage of the Rodinia supercontinent.

This study presents the first attempt to constrain the evolution of the North Anatolian Fault Zone (NAFZ) by age dating and isotope tracing of clay minerals formed during near-surface faulting. Extensive illitic clay mineralisation occurred along the NAFZ related to hydrothermal alteration of the fault gouges and pseudotachylytes. Samples representing the pre-fault protoliths outside the fault zone do not contain authigenic illitic clay minerals indicating that hydrothermal processes were confined to the areas within the fault zone. K-Ar age data indicate that the hydrothermal system and the associated illite authigenesis initiated at similar to 57 Ma. This process is interpreted to reflect the onset of significant strike-slip or transtensional faulting immediately after the continental collision related to the closure of the Neotethys Ocean. Following the initiation of the fault movements in the latest Paleocene-Early Eocene, displacements along the NAFZ have continued, with probably intensified fault activities at similar to 26 Ma and later than similar to 8 Ma. Oxygen isotope compositions of the illitic clays from different locations along the NAFZ are similar, with narrow ranges in delta O-18 values indicating clay precipitation from fluids with similar oxygen isotope compositions and crystallisation temperatures. The delta O-18 and delta D values of the calculated fluid isotopic composition (delta O-18=5.9 parts per thousand to 11.2 parts per thousand, delta D=-59 parts per thousand to -73 parts per thousand) are consistent with metamorphic and magmatic origin of fluids mobilised during active tectonism. The interpretation of the fluid flow history of the NAFZ is in agreement with that reported previously for some well-known large-scale high-angle fault zones, which similarly developed along collisional-type orogenic belts and are commonly associated with significant mesothermal ore mineralisation. (c) 2005 Elsevier B.V. All rights reserved.