Mark Raven

Geology and characterization of two hydrothermal nontronites from weathered metamorphic rocks at the Uley graphite mine, South Australia

Mining operations during the early 1990s at Uley Graphite Mine near Port Lincoln on southern Eyre Peninsula, South Australia, uncovered abundant nontronite veins in deeply weathered granulite facies schist, gneiss, and amphibolite of Palaeoproterozoic age. Two types of nontronite are present: a bright yellowish-green clay (NAu-1) distributed as veinlets and diffuse alteration zones within kaolinized schist and gneiss, and a massive to earthy, dark-brown clay (NAu-2) infilling fracture networks mainly in amphibolite or basic granulite. The nontronites are the product of low-temperature hydrothermal alteration of primary minerals, biotite, and amphibole. The principal chemical difference between NAu-1 and NAu-2 is a higher alumina content in NAu-1, which was either inherited during hydrothermal alteration of biotite in the host rock or acquired through recrystallization of nontronite during subsequent weathering and associated kaolinization. Sufficient bulk samples of both NAu-1 and NAu-2 were collected to supplement reference nontronite of the Source Clay Repository of The Clay Minerals Society. The clay fraction of the bulk samples is typically >85%. NAu-1 contains minor kaolin and quartz which are easily removed to give a high purity nontronite of composition M+1.05[Si6.98Al1.02][Al0.29Fe3.68Mg0.04]O20(OH)4, similar to that of nontronite from Garfield, Washington. NAu-2 contains fewer total impurities but the presence of trace amounts of submicron carbonate and iron oxyhydroxide requires additional chemical treatment to produce a nontronite of purity comparable to NAu-1. Composition of NAu-2 was calculated as M+0.72[Si7.55Al0.45][Fe3.83Mg0.05]O20(OH)4, although infrared data indicate that at least some Fe is in tetrahedral coordination.

Mineralogy of a bentonite from Miles, Queensland, Australia and characterisation of its acid activation products

Abstract The mineralogy of a bentonite from Miles, Queensland, Australia, before and after acid treatment (by reflux in 5.3 M HCl at 80 °C) has been assessed by IR, XRD and chemical analysis. The

Microstructural and petrophysical characterization of Muderong Shale: application to top seal risking

Analysis of the Muderong Shale from the Carnarvon Basin suggests the shale is dominated by interstratified illite–smectite with a high percentage of illite interlayers. Capillary pressure measurements indicate that gas columns of c. 250 m could be sealed by such shale, although the choice of drying method used does influence the accuracy of this calculation. Freeze drying yielded the most consistent threshold pressure results, whereas air drying and vacuum drying showed a greater range of values. Similar calculations in regard to carbon dioxide sequestration indicate column heights of between 550 m and 750 m could be retained. Column height variation is primarily dependent on the contact angle of supercritical carbon dioxide with shale. Microstructurally, the shale is clay supported, exhibiting differential compaction of clays around more rigid grains and containing numerous high aspect ratio discontinuous fractures. These fractures do not affect the capillary properties of the shale, even when injection is fracture-parallel, suggesting they are unlikely to influence reservoir-scale fluid-flow properties. Comparison of the Muderong Shale laboratory data with hydrocarbon column heights from Carnarvon Basin discoveries indicate that top seal failure by capillary breakthrough is unlikely given the maximum lengths of hydrocarbon columns encountered to date. Potential for top seal failure is more likely to be influenced by formation integrity, pore pressure and in situ stress conditions.

Geomechanical and ultrasonic characterization of a Norwegian Sea shale

Anisotropy of velocity in shaly overburden is known to cause significant problems for geophysical interpretation, including depth conversion and fluid identification. In addition, mechanical and dynamic elastic shale behavior is not well understood because few tests have been performed on well-preserved samples. Multiple stage triaxial tests were performed upon horizontal core plugs of a shale from the Norwegian Sea with a view to evaluating rock strength and the evolution of ultrasonic response during rock deformation. In addition, standard rock physical properties were characterized as well as composition. The shale microfabric is seen to be strongly laminated, with alternating thick clay-rich laminae and thin silt-rich laminae. Occasional microfractures are also noted parallel to these laminations. The shale has low friction coefficient and cohesive strength, and shows anisotropy of these parameters when the maximum principal stress is oriented parallel to and at 45 � to the microfabric. The orientation of the maximum principal stress parallel to the intrinsic fabric and microcracks was seen to significantly impact on velocity normal to the fabric as stress parallel to the fabric increased. S-wave anisotropy was significantly affected by the increasing stress anisotropy. Stress orientation with respect to fabric orientation was therefore found to be an important control on the degree of anisotropy of dynamic elastic properties in this shale.

Infrared Attenuated Total Reflectance Spectroscopy: An Innovative Strategy for Analyzing Mineral Components in Energy Relevant Systems

The direct qualitative and quantitative determination of mineral components in shale rocks is a problem that has not been satisfactorily resolved to date. Infrared spectroscopy (IR) is a non-destructive method frequently used in mineral identification, yet challenging due to the similarity of spectral features resulting from quartz, clay, and feldspar minerals. This study reports on a significant improvement of this methodology by combining infrared attenuated total reflection spectroscopy (IR-ATR) with partial least squares (PLS) regression techniques for classifying and quantifying various mineral components present in a number of different shale rocks. The developed multivariate classification model was calibrated using pure component mixtures of the most common shale minerals (i.e., kaolinite, illite, montmorillonite, calcite, and quartz). Using this model, the IR spectra of 11 real-world shale samples were analyzed and evaluated. Finally, the performance of the developed IR-ATR method was compared with results obtained via X-ray diffraction (XRD) analysis.

Stress-dependent elastic properties of shales: measurement and modeling

Despite decades of research, current understanding of elastic properties of shales is insufficient as it is based on a limited number of observations caused by the time-consuming nature of testing resulting from their low permeability. Though it is well known that shales are highly anisotropic and assumed to be transversely isotropic (TI) media, few laboratory experiments have been carried out for measuring the five elastic constants that define TI media on well-preserved shales. Many previous measurements were made without control of pore pressure, which is crucial for the determination of shale elastic properties.

Geotechnical properties indicating environmental uses for an unusual Australian bentonite

Abstract Samples of bentonite from a large deposit at Arumpo in southern New South Wales were characterised chemically and mineralogically. The samples of highly pure clay mineral, representing a large part of the deposit, together with a sodium-saturated sample of Wyoming bentonite were analysed for their rheological and free swell properties. Their permeability under a range of applied vertical stresses was also determined using a modified oedometer. As mined, the Arumpo bentonite showed little viscosity and swelling when suspended in water. Surprisingly, however, its permeability at all applied vertical stresses was as low as that of the high swelling Na-bentonite from Wyoming. Although the permeability of the Arumpo bentonite decreased with an increase in applied vertical stress, its void ratio hardly changed. On the other hand, the void ratio of the Wyoming bentonite showed an almost four-fold decrease with the same change in applied vertical stress. Since Arumpo bentonite has a high concentration of very small particles, it had a high external surface area (230 m2 g−1), whereas the external surface area of the Wyoming bentonite sample was only 14 m2 g−1. The permeability of Arumpo bentonite is intrinsically low because of the close packing of its particles. By contrast, the literature shows that Wyoming bentonite requires extensive swelling in order to achieve a low permeability, and needs to be in the Na-exchanged form for this purpose. As the Arumpo bentonite has a low permeability that is not dependent on swelling, or on the nature of the exchangeable cation, the material can be used as a barrier to many contaminants that are more stable than swelling bentonites. Barriers made from the Arumpo bentonite should also show minimal cracking on drying.

Lead solubility in seawater: an experimental study

Environmental context Many trace metals including lead are only sparingly soluble in seawater and may exist in both dissolved and particulate forms (e.g. as precipitates). Aquatic organisms may experience different toxic effects from exposure to dissolved and particulate trace metals. This study reports the limits to lead solubility in seawater that influence the exposure to these forms of lead in the field and the laboratory. Abstract A combination of laboratory investigations and thermodynamic modelling were conducted in order to gain an understanding of the factors controlling lead solubility in seawater. In experiments where increasing amounts of lead were added to seawater (in order to avoid supersaturation) and equilibrated for up to 28 days, the maximum solubility was ~2mgL–1 (pH 8.15, 22°C). However, at higher added lead concentrations, which caused the rapid formation of lead precipitates, the solution chemistry became dynamic and the observed solubility was markedly lower, varying with both reaction time and precipitate concentration. For instance, when seawater solutions were spiked with 10mgL–1 of total lead, precipitation occurred immediately and only 1.6mgL–1 of dissolved lead was measured after 1h, with this concentration decreasing to 1.3mgL–1 after 28 days. The solubility of lead in artificial seawater (0.68mgL–1) was much lower than in natural seawater. This difference was attributed to the significant role played by natural organic matter in complexing dissolved lead. X-Ray diffraction and elemental analysis data suggest that the phase controlling lead solubility is a previously unidentified lead chlorocarbonate, which rapidly transforms to hydrocerussite on washing with deionised water. These observations are of particular relevance to toxicity tests where organisms are exposed to wide ranges of metal concentrations in order to obtain dose–response curves.

OUTCOMES OF 12 YEARS OF THE REYNOLDS CUP QUANTITATIVE MINERAL ANALYSIS ROUND ROBIN

In 2000, The Clay Minerals Society established a biennial quantitative mineralogy round robin. The so-called Reynolds Cup competition is named after Bob Reynolds for his pioneering work in quantitative clay mineralogy and exceptional contributions to clay science. The first contest was run in 2002 with 40 sets of three samples, which were prepared from mixtures of purified, natural, and synthetic minerals that are commonly found in clay-bearing rocks and soils and represent realistic mineral assemblages. The rules of the competition allow any method or combination of methods to be used in the quantitative analysis of the mineral assemblages. Throughout the competition, X-ray diffraction has been the method of choice for quantifying the mineralogy of the sample mixtures with a multitude of other techniques used to assist with phase identification and quantification. In the first twelve years of the Reynolds Cup competition (2002 to 2014), around 14,000 analyses from 448 participants have been carried out on a total of 21 samples. The data provided by these analyses constitute an extensive database on the accuracy of quantitative mineral analyses and also has given enough time for the progression of improvements in such analyses. In the Reynolds Cup competition, the accuracy of a particular quantification is judged by calculating a “bias” for each phase in an assemblage. Determining exactly the true amount of a phase in the assemblage would give a bias of zero. Generally, the higher placed participants correctly identified all or most of the mineral phases present. Conversely, the worst performers failed to identify or misidentified phases. Several contestants reported a long list of minor exotic phases, which were likely reported by automated search/match programs and were mineralogically implausible. Not surprisingly, clay minerals were among the greatest sources of error reported. This article reports on the first 12 years of the Reynolds Cup competition results and analyzes the competition data to determine the overall accuracy of the mineral assemblage quantities reported by the participants. The data from the competition were also used to ascertain trends in quantification accuracy over a 12 year period and to highlight sources of error in quantitative analyses.

POWDER X-RAY DIFFRACTION STUDY OF THE HYDRATION AND LEACHING BEHAVIOR OF NONTRONITE

Nontronite is a significant component of commercially important nickel laterite ores. Its behavior during high-pressure acid leaching of such ores may have an impact upon the efficiency of the process. The present study was conducted in order to further investigate the response of this material during high-pressure acid leaching. In situ synchrotron powder X-ray diffraction data were collected from a number of nontronite samples during hydration and leaching reactions at ambient and elevated temperatures. The present study followed previous high-pressure acid-leaching studies of nontronite where unexpected contraction and expansion behavior of the clay was observed by means of in situ X-ray diffraction. In the earlier studies the data sets only extended to ~20 Å so that when the nontronite expanded to greater than 19.5 Å (hydrated) the main 001 peak was only partially visible in the observed d-spacing range. The aim of the current work was to collect similar in situ diffraction data over a greater d-spacing range to observe more fully the movement of the main 001 reflection in order to better understand the changes taking place. This work was undertaken at the powder diffraction beamline of the Australian Synchrotron which was configured such that an upper d-spacing limit of ~34.5 Å could be achieved. Suggestions arising out of the previous work were confirmed along with additional information from testing of samples from the Source Clays Repository of The ClayMinerals Society. These results also show contradictory behavior of clays with the layer charge distributed over tetrahedral and octahedral sheets.