Geochemistry of Archean shales from the Pilbara Supergroup,Western Australia

Archean clastic sedimentary rocks are well exposed in the Pilbara Block of Western Australia. Shales from turbidites in the Gorge Creek Group (ca. 3.4 Ae) and shales from the Whim Creek Group (ca. 2.7 Ae) have been examined. The Gorge Creek Group samples, characterized by muscovite-quartzchlorite mineralogy, are enriched in incompatible elements (K, Th, U, LREE) by factors of about two, when compared to younger Archean shales from the Yilgarn Block. Alkali and alkaline earth elements are depleted in a systematic fashion, according to size, when compared with an estimate of Archean upper crust abundances. This depletion is less notable in the Whim Creek Group. Such a pattern indicates the source of these rocks underwent a rather severe episode of weathering. The Gorge Creek Group also has fairly high B content (85 ± 29 ppm) which may indicate normal marine conditions during deposition.Rare earth element (REE) patterns for the Pilbara samples are characterized by light REE enrichment ($\text{La}{}_{\mathrm{N}}\text{Yb}{}_{\mathrm{N}}\text{≥ 7.5}$) and no or very slight Eu depletion ($\text{Eu}\text{Eu}{}^1\text{= 0.82 – 0.99}$). A source comprised of about 80% felsic igneous rocks without large negative Eu-anomalies (felsic volcanics, tonalites, trondhjemites) and 20% mafic-ultramafic volcanics is indicated by the trace element data. Very high abundances of Cr and Ni cannot be explained by any reasonable provenance model and a secondary enrichment process is called for.     

Provincialism and correlations between some properties of vitrinites

Optical and chemical properties for hand-picked samples of vitrinite from a number of British coalfields are correlated and the correlations compared with previously published data. The form of the relationship found for the properties of British vitrinites is generally similar to that exhibited by a number of other sets of analyses, but some significant differences also exist in several of the correlations. For maximum reflectance as a function of carbon content, the present data indicate that at medium and low ranks, maximum reflectance is lower than the level suggested by most previous studies. The relationships of volatile-matter yield to reflectance and carbon content suggest that at low ranks, volatile-matter yield is strongly dependent upon the nature of the coalification history of the vitrinite. Furthermore, these correlations are likely to show provincialism, in that correlations which hold for one coalfield may not be representative of the relationship in other coalfields. Similarly, major differences in relationships involving bireflectance are associated with the tectonic setting at the time of effective coalification. The data presented here indicate that for low-rank coals at least, correlations between properties of vitrinites must take account of provincialism if they are to be sufficiently reliable to be useful. The measurement of a number of rank-sensitive variables can yield additional information about rank, as compared with the use of a single rank-sensitive variable.     

Primary fractionation of elements among iron meteorites

The primary fractionation process in iron meteorites is that responsible for the distribution of elements between the groups, most notably Ga and Ge, which show concentration ranges of 10³ and 10⁴ respectively. To investigate the cause of the primary fractionation, concentrations of 16 elements were converted to relative abundances by dividing the element/Ni ratio by the CI chondrite ratio. These abundances were plotted on logarithmic graphs with data for each group (except IB and IIICD) and each cluster of closely related anomalous irons averaged.Co, P, Au, As, Cu, Sb, Ge and Zn are positively correlated with Ga. For most groups (except IA, IC and IIAB) relative abundances of these elements tend to decrease from about 1 in approximately the order listed above. This is the expected order in which these elements will condense into Fe, Ni during equilibrium nebular condensation. Mean relative abundances of refractory elements in groups generally lie within a narrow range of 0.5–2, and are uncorrelated with Ga. Although the equilibrium model may be only a gross approximation, it suggests that most primary fractionation did occur during nebular condensation.The anomalous irons are essential for defining many of the primary fractionation trends. On several element-Ga graphs the displacements of the anomalous irons from the primary curves indicate that these irons experienced the same secondary fractionation process (probably fractional crystallization) that produced the trends within most groups. The anomalous irons appear to be samples from over 50 minor groups, which have similar histories to the 12 major groups.     

Geological and geotechnical aspects of underground coal mining methods within Australia

About one quarter of the coal produced in Australia is by underground mining methods. The most commonly used underground coal mining methods in Australia are longwall, and room and pillar. This paper provides a detailed review of the two methods, including their advantages and disadvantages, the major geotechnical and operational issues, and the factors that need to be considered regarding their choice, including the varying geological and geotechnical conditions suited to a particular method. Factors and issues such as capital cost, productivity, recovery, versatility and mine safety associated with the two methods are discussed and compared. The major advantages of the longwall mining method include its suitability for mining at greater depth, higher recovery, and higher production rate compared to room and pillar. The main disadvantages of the room and pillar method are the higher risks of roof and pillar collapse, higher capital costs incurred as well as lower recovery rate.     

Comparison of isotope pairing and N2:Ar methods for measuring sediment denitrification—Assumption, modifications, and implications

Denitrification has been measured during the last few years using two different methods in particular: isotope pairing measured on a triple-collector isotopic ratio mass spectrometer and N₂:Ar ratios measured on a membrane inlet mass spectrometer (MIMS). This study compares these two techniques in short-term batch experiments. Rates obtained using the original N₂∶Ar method were up to 3 to 4 times higher than rates obtained using the isotope pairing technique due to O₂ reacting with the N₂ during MIMS analysis. Oxygen combines with N₂ within the mass spectrometer ion source forming NO⁺ which reduces the N₂ concentration. The decrease in N₂ is least at lower O₂ concentrations and since oxygen is typically consumed during incubations of sediment cores, the result is often a pseudo-increase in N₂ concentration being interpreted as denitrification activity. The magnitude of this ocygen effect may be instrument specific. The reaction of O₂ with N₂ and the subsequent decrease in N₂ was only partly correctly using an O₂ correction curve for the relationship between N₂ and O₂ concentrations. The O₂ corrected N₂∶Ar denitrification rates were lower, but still did not match the isotope pairing rates and the variability between replicates was much higher. Using a copper reduction column heated to 600°C to remove all of the O₂ from the sample before MIMS analysis resulted in comparable rates (slightly lower), and comparable variability between replicates, to the isotope pairing technique. The N₂:Ar technique determines the net N₂ production as the difference between N₂ production by denitrification and N₂ consumption by N-fixation, while N-fixation has little effect on the isotope pairing technique which determines a rate very close to the gross N₂ production. When the two different techniques were applied on the same sediment, the small difference in rates obtained by the two methods seemed to reflect N-fixation as also supported from measurements of ethylene production in acetylene enriched sediment cores. The N₂:Ar and isotope pairing techniques may be combined to provide simultaneous measurements of denitrification and N-fixation. Both techniques have several assumptions that must be met to achieve accurate rates; a number of tests are outlined that can be applied to demonstrate that these assumptions are being meet.     

Extension of the specific interaction model to include gas solubilities in high temperature brines

A semi-empirical model for gas solubilities in high temperature brines was developed by modification of the Pitzer interaction model (Pitzer, 1973) and evaluated by least-squares fitting to available P-T-X data for carbon dioxide, hydrogen sulfide, and methane in pure water and in aqueous sodium chloride solutions. Over the range of experimental data used (25°–350°C, NaCl concentration 0–6 m, P_CO2 1–150 atm. P_CH4 1–30 atm, P_CH4 1–1700 atm), standard deviations of fit in the natural logarithm of the Henry's law ratio were 0.096 for CO₂, 0.093 for H₂S and 0.116 for CH₄.The model has several advantages. First, it has a theoretical basis which can easily be extended for the inclusion of more than one salt or gas. Second, the equations simplify to the empirically derived equation of Setschenow, in the limit of infinite dilution. Finally, the model is easily integrated into a framework of equations which can yield all of the thermodynamic properties of the system.An example in which values of the model parameters for interaction of gas with salt may be used to estimate the effect of dissolved gas or salt solubility is given.     

An infrared spectroscopic study of lawsonite to 20 GPa

The infrared spectrum of CaAl₂Si₂O₇ · H₂O-lawsonite, has been characterized to pressures of 20 GPa at 300 K. Our results constrain the response to compression of the silicate tetrahedra, hydroxyl units, and water molecules in this material. The asymmetric and symmetric stretching and bending vibrations of the Si₂O₇ groups (at zero pressure frequencies between 600 and 1000 cm⁻¹) increase in frequency with pressure at rates between 3.6 and 5.9 cm⁻¹/GPa. All silicate modes appear to shift continuously with pressure to 20 GPa, although the lowest frequency stretching vibration becomes unresolvable above 18 GPa, and a splitting of the main bending vibration is observed near this pressure. The O-H stretches of the hydroxyl units exhibit a discontinuity in their mode shifts at ∼8–9 GPa, which we interpret to be produced by a pressure-induced change in hydrogen bonding. The stretching and bending vibrations of the water molecule are relatively unaffected by compression to 20 GPa, thus demonstrating that the structural cavities in which water molecules reside are relatively rigid. Significant changes in the amplitude of the O-H stretches of the hydroxyl and water units are observed at this pressure as well; nevertheless, our results demonstrate that the dominant structural units in lawsonite persist metastably at 300 K with only modest structural modifications well beyond the known stability field of this phase. Received: 10 July 1998 / Revised, accepted: 23 October 1998     

Use of photo-based 3D photogrammetry in analysing the results of laboratory pressure grouting tests

This paper presents a non-destructive, low-cost, photo-based, 3D reconstruction technique for characterizing geo-materials with irregular shapes of a relatively large size. After being validated against two traditional volume measurement methods, namely the vernier caliper method and the fluid displacement method for regular and irregular shapes, respectively, 3D photogrammetry was used to analyse the grout bulbs formed in laboratory pressure grouting tests. The reconstructed 3D mesh model of the sample provides accurate and detailed 3D vertex data, which allowed the volume, densification efficiency and bleeding behaviour of the grout bulbs to be analysed. Comparing the bulb section views at different grouting pressures also offers an intuitive observation of the grout development and propagation process. Moreover, the 3D vertex data and surface area included in the model are of great importance in validating numerical predictions of the pressure grouting process and analysing the interface shear resistance of grouted soil nails or anchors. Compared to existing approaches, the new 3D photogrammetry method possesses several key advantages: (a) it does not require expensive, specialized equipment; (b) samples are not destroyed or modified during testing; (c) it allows to reconstruct objects of various scales and (d) the software is public domain. Therefore, the adoption of this 3D photogrammetry method will facilitate research in the pressure grouting process and can be extended to other problems in geotechnical engineering.     

Northwest Africa 773: lunar mare breccia with a shallow-formed olivine-cumulate component, inferred very-low-Ti (VLT) heritage, and a KREEP connection

Lunar meteorite Northwest Africa 773 (herein referred to as NWA773) is a breccia composed predominantly of mafic volcanic components, including a prominent igneous clast lithology. The clast lithology is an olivine-gabbro cumulate, which, on the basis of mineral and bulk compositions, is a hypabyssal igneous rock related compositionally to volcanic components in the meteorite. The olivine-gabbro lithology exhibits cumulus textures and, in our largest section of it, includes some 48% olivine (Fo₆₄ to Fo₇₀, average Fo₆₇), 27% pigeonite (En₆₀Fs₂₄Wo₁₆ to En₆₇Fs₂₇Wo₆), 11% augite (En₅₀Fs₁₇Wo₃₃ to En₄₇Fs₁₃Wo₄₀), 2% orthopyroxene (En₇₀Fs₂₆Wo₄), 11% plagioclase (An₈₀ to An₉₄), and trace barian K-feldspar, ilmenite, Cr-spinel, RE-merrillite, troilite, and Fe-Ni metal. The Mg/Fe ratios of the mafic silicates indicate equilibration of Fe and Mg; however, the silicates retain compositional variations in minor and trace elements that are consistent with intercumulus crystallization. Accessory mineralogy reflects crystallization of late-stage residual melt. Both lithologies (breccia and olivine cumulate) of the meteorite have very-low-Ti (VLT) major-element compositions, but with an unusual trace-element signature compared to most lunar VLT volcanic compositions, i.e., relative enrichment in light REE and large-ion-lithophile elements, and greater depletion in Eu than almost all other known lunar volcanic rocks. The calculated composition of the melt that was in equilibrium with pyroxene and plagioclase of the cumulate lithology exhibits a KREEP-like REE pattern, but at lower concentrations. Melt of a composition calculated to have been in equilibrium with the cumulate assemblage, plus excess olivine, yields a major-element composition that is similar to known green volcanic glasses. One volcanic glass type from Apollo 14 in particular, green glass B, type 1, has a very low Ti concentration and REE characteristics, including extremely low Eu concentration, that make it a candidate parent melt for the olivine-gabbro cumulate. We infer an origin for the parent melt of NWA773 volcanic components by assimilation of a trace-element-rich partial or residual melt by a magnesian, VLT magma deep in the lunar crust or in the mantle prior to transportation to the near-surface, accumulation of olivine and pyroxene in a shallow chamber, eruption onto a volcanic surface, and incorporation of components into local, predominantly volcanic regolith, prior to impact mixing of the volcanic terrain and related hypabyssal setting, and ejection from the surface of the Moon. Volcanic components such as these probably occur in the Oceanus Procellarum region near the site of origin of the green volcanic glasses found in the Apollo 14 regolith.