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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°C) than similar stratigraphic horizons in the north. The irregular downhole variation of illite crystallinity values provides further information on 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 at 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 ∼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 east of the Termite 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 (δ18O = 3.5-9.7‰ V-SMOW; δD = -94 to -36‰ V-SMOW). The extent of the 18O 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 an extensive ferroan carbonate alteration halo. Modeling suggests that the ore siderite formed at temperatures of 120° to 150°C, whereas siderite and ankerite in the alteration halo formed at temperatures of 150° to 180°C. The calculated isotopic compositions of the fluids are consistent with 18O-rich basinal brines and mixed inorganic and organic carbon sources (δ18O = 3-10‰ V-SMOW; δ18C = -7 to -3‰ 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 18O and 13C depleted relative to the sedimentary carbonates. The good agreement between temperature estimates from illite crystallinity and organic reflectance (160°-270°C) and inverse correlation with carbonate δ18O values indicates that organic maturation and carbonate precipitation in the northeast Lawn Hill platform resulted from interaction with the 1250 to 1150 Ma fluids.… [ABSTRACT FROM AUTHOR]

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) > 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. δ13C and δ2H data support a gas mixing hypothesis with δ13C-CH4 increasing from secondary biogenic values to thermogenic values at depth (δ13C −62.2‰ to −46.3‰), whereas correlated methane and carbon dioxide carbon isotope compositions, Δ13C(CO2–CH4) values and δ13CDIC/alkalinity trends are largely consistent with microbial CO2 reduction. In addition, below 200 m, the majority of δ13C-CO2 values are positive (δ13C: −1.2‰ to 7.1‰) and δ13CDIC 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. [ABSTRACT FROM AUTHOR]

Abstract: The Late Permian coal measures of the Bowen Basin, Australia express both environmental and climatic changes that occurred prior to the Permian Triassic (P–T) boundary. In order to decouple the influence of environmental factors (salinity, pH, base level and temperature) from depositional and climatic factors (atmospheric CO2) in organic δ13C, a high resolution study was performed on 24 coal seams (total 24.6m) in the Late Permian stratigraphy in the northern Bowen Basin. The Late Permian stratigraphy of the Bowen Basin records a transition from deltaic and lacustrine conditions within the Tinowan Formation and Black Alley Shale Formation, to fluvial deposition in the Kaloola and Bandanna Formations. Intermittent volcanism is recorded by tuff layers during periods of peat accumulation. Variations of coal lithotypes were recorded and formed the basis of sampling for petrography and isotope analysis. Coal samples were etched to expose cellular anatomy, and systematically identified to recognise palaeoflora assemblages. When observed within seam, δ13C of the coal varied cyclically (13C enriched-depleted-enriched) as a response to environmental changes expressed in palaeoflora communities. The total range of δ13C was −26.6‰ to −21.9‰. The overall trend of δ13C progresses to increasing 13C enrichment, corresponding with dull lithotypes (rich in inertinite) which indicate fluctuations in base level. The 13C enrichment peaks at −22.5‰ within the Kaloola Member and shifting rapidly toward a depletion (maximum −26.6‰) of 13C in the upper Bandanna Formation, prior to the P–T boundary. These changes are expressed in palaeoflora communities where ecosystems shifted from dominant Glossopteris flora, to climax community flora including Palaeosmunda, Cycadales and Ginkgo, suited to temperate, early Mesozoic climates. The results of this study represent an insight into the effects of environmental variables on 13C uptake of plants. The identification of flora within coal gives an insight into palaeowetland evolution, and can be partnered with classic petrographical techniques for integrated analysis in coals. Both the geochemistry and the anatomical aspects of coal represent an important tool for future palaeowetland research. [Copyright &y& Elsevier]

Abstract: 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 ∼85Ma and ∼95Ma. 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. [Copyright &y& Elsevier]

A new, fast, continuous flow technique is described for the simultaneous determination of delta33S and delta34S using SO masses 48, 49 and 50. Analysis time is approximately 5 min/sample with measurement precision and accuracy better than +/-0.3 per thousand. This technique, which has been set up using IAEA Ag2S standards S-1, S-2 and S-3, allows for the fast determination of mass-dependent or mass-independent fractionation (MIF) effects in sulfide, organic sulfur samples and possibly sulfate. Small sample sizes can be analysed directly, without chemical pre-treatment. Robustness of the technique for natural versus artificial standards was demonstrated by analysis of a Canon Diablo troilite, which gave a delta33S of 0.04 per thousand and a delta34S of -0.06 per thousand compared to the values obtained for S-1 of 0.07 per thousand and -0.20 per thousand, respectively. Two pyrite samples from a banded-iron formation from the 3710 Ma Isua Greenstone Belt were analysed using this technique and yielded MIF (Delta33S of 2.45 and 3.31 per thousand) comparable to pyrite previously analysed by secondary ion probe., (Copyright (c) 2004 John Wiley & Sons, Ltd.)