Experimental transformation of kaolinite to halloysite

A well-characterized kaolinite has been hydrated in order to test the hypothesis that platey kaolinite will roll upon hydration. Kaolinite hydrates are prepared by repeated intercalation of kaolinite with potassium acetate and subsequent washing with water. On hydration, kaolinite plates roll along the major crystallographic directions to form tubes identical to proper tubular halloysite. Most tubes are elongated along the b crystallographic axis, while some are elongated along the a axis. Overall, the tubes exhibit a range of crystallinity. Well-ordered examples show a 2-layer structure, while poorly ordered tubes show little or no 3-dimensional order. Cross-sectional views of the formed tubes show both smoothly curved layers and planar faces. These characteristics of the experimentally formed tubes are shared by natural halloysites. Therefore, it is proposed that planar kaolinite can transform to tubular halloysite.

Poorly graphitized carbon as a new cosmothermometer for primitive extraterrestrial materials

The presence of carbon in primitive extraterrestrial materials has long been considered a useful indicator of prevailing geochemical conditions early in the formation of the Solar System. A recent addition to the suite of primitive materials available for study by cosmochemists includes particles collected from the stratosphere called chondritic porous (CP) aggregates1. Carbon-rich CP aggregates are less abundant in stratospheric collections and contain many low-temperature phases (such as layer silicates) as minor components2,3. We describe here the nature of the most abundant carbon phase in a carbon-rich CP aggregate (sample no. W7029* A) collected from the stratosphere as part of the Johnson Space Center (JSC) Cosmic Dust Program4. By comparison with experimental and terrestrial studies of poorly graphitized carbon (PGC), we show that the graphitization temperature, or the degree of ordering in the PGC, may provide a useful cosmothermometer for primitive extraterrestrial materials.

A multi-stage history for carbonaceous material in extraterrestrial chondritic porous aggregate W7029*A and a new cosmothermometer

A new set of primitive extraterrestrial materials collected in the Earth's stratosphere include Chondritic Porous Aggregates (CPA's) [1]. CPAs have a complex and variable mineralogy [1-3] that include 'organic compounds' [4,5] and poorly graphitised carbon (PGC)[6]. This study presents a continuation of our detailed Analytical Electron Microscope study on carbon-rich CPA W7029*A from the JSC Cosmic Dust Collection. This CPA is an uncontaminated sample that survived atmospheric entry without appreciable alteration [7] and which contains ~44% carbonaceous material. The carbonaceous composition of selected particles was confirmed by Electron Energy Loss Spectroscopy and Selected Area Electron Diffraction (SAED). Possible carbonaceous contaminants introduced by specimen preparation techniques are easily recognised from indigenous CPA carbon particles [8] and do not bias our interpretations.

Flotation process response of Ok Tedi fluorine bearing minerals

Orebodies at Ok Tedi contain a number of different fluorine bearing minerals. Some of these minerals report to concentrate and are responsible for the presence of the penalty element, fluorine, within the concentrate. Previous analytical work has tended to examine geological samples for content, rather than determine the metallurgical behaviour of the different mineralogical species. This investigation utilised X-Ray Diffraction combined with Scanning Electron Microscope/Electron Microprobe to identify the fluorine bearing minerals in flotation test products. Seven fluorine bearing minerals were identified, viz., talc, phlogopite, amphibole (tremolite and actinolite), sphene, apatite, biotite and clay. Talc was found exclusively in the skarn ore type. Phlogopite and amphiboles (tremolite and actinolite) were found to occur in both skarn and porphyry ores, while sphene, apatite, biotite and clay were found only in the porphyry ores. Of the fluorine bearing minerals observed, only talc exhibited natural hydrophobicity to any significant degree. Phlogopite and the amphibole minerals were found to be hydrophillic, whilst the remaining minerals occurred in insufficient quantities to determine the flotation behaviour. Ok Tedi copper concentrate fluorine content prior to skarn ore treatment in the mill (typically 350ppm) was previously identified as deriving from phlogopite, while talc was believed to be the source of intermittent high concentrate fluorine contents when skarn ores were treated. This paper provides supporting evidence for this belief, and reports the nature of fluorine bearing mineral flotation behaviour.

The role of randomly mixed-layered chlorite/smectite in the transformation of smectite to chlorite

Vesicular and groundmass phyllosilicates in a hydrothermally altered basalt from the Point Sal ophiolite, California, have been studied using transmission electron microscopy (TEM). Pore-filling phyllosilicates are texturally characterized as having coherent, relatively thick and defect-free crystals of chlorite (14 Å) with occasional 24-Å periodicities. Groundmass phyllosilicates are texturally characterized as 1) randomly oriented crystals up to 200 Å in width and 2) larger, more coherent crystals up to 1000 Å in width. Small crystallites contain predominantly 14-Å layers with some 24-Å units. Large crystals show randomly interlayered chlorite/smectite (C/S), with approximately 50% chlorite on average. Adjacent smectite-like layers are not uncommon in the groundmass phyllosilicates. Electron microprobe analyses show that Fe/Mg ratios of both groundmass and vesicular phyllosilicates are fairly constant. Termination of brucite-like interlayers has been identified in some of the TEM images. The transformation mechanisms represented by these layer terminations are 1) growth of a brucite-like interlayer within smectite interlayer regions and 2) the dissolution and reprecipitation of elements to form chlorite layers. Both mechanisms require an increase in volume as smectite transforms to chlorite. The data, combined with that from previously published reports, suggest that randomly interlayered C/S is a metastable phase formed in microenvironments with low water/rock ratios. Chlorite forms in microenvironments in the same sample dominated by higher water/rock ratios. The relatively constant number of Mg's in the structure (Mg#) of both structures indicates that in both microenvironments the bulk rock composition has influence over the composition of phyllosilicates.

Freshwater sensitivity of corrensite and chlorite/smectite in hydrocarbon reservoirs - an ESEM study

An Environmental Scanning Electron Microscope (ESEM) has been used to investigate the freshwater sensitivity of secondary corrensite (regularly interstratified chlorite/smectite) and chlorite-rich chlorite/smectite in order to determine whether hydrocarbon reservoirs hosting these clays should be regarded as freshwater sensitive. ESEM experiments involved an examination and close comparison of selected clay areas in three samples at high magnification before, during and after prolonged freshwater treatments. Corrensite and chlorine/smectite in the samples did not visibly swell when immersed in fresh water. After soaking in fresh water for up to three months, these clays retained their original morphology and associated porosity. Hence, the presence of corrensite or chlorite/smectite in a hydrocarbon reservoir need not indicate that the reservoir is freshwater sensitive. © 1994.

Kaolinite - NMF intercalates

Bulk and size-fractionated kaolinites from seven localities in Australia as well as the Clay Minerals Society Source Clays Georgia KGa-1 and KGa-2 have been studied by X-ray diffraction (XRD), laser scattering, and electron microscopy in order to understand the variation of particle characteristics across a range of environments and to correlate specific particle characteristics with intercalation behavior. All kaolinites have been intercalated with N-methyl formamide (NMF) after pretreatment with hydrazine hydrate, and the relative efficiency of intercalation has been determined using XRD. Intercalate yields of kaolinite: NMF are consistently low for bulk samples that have a high proportion of small-sized particles (i.e., <0.5 µm) and for biphased kaolinites with a high percentage (>60%) of low-defect phase. In general, particle size appears to be a more significant controlling factor than defect distribution in determining the relative yield of kaolinite: NMF intercalate.

Imaging fluid solid interactions in hydrocarbon reservoir rocks

The environmental scanning electron microscope (ESEM) has been used to image liquid hydrocarbons in sandstones and oil shales. Additionally, the fluid sensitivity of selected clay minerals in hydrocarbon reservoirs was assessed via three case studies: HCl acid sensitivity of authigenic chlorite in sandstone reservoirs, freshwater sensitivity of authigenic illite/smectite in sandstone reservoirs, and bleach sensitivity of a volcanic reservoir containing abundant secondary chlorite/corrensite. The results showed the suitability of using ESEM for imaging liquid hydrocarbon films in hydrocarbon reservoirs and the importance of simulating in situ fluid-rock interactions for hydrocarbon production programmes. In each case, results of the ESEM studies greatly enhanced prediction of reservoir/borehole reactions and, in some cases, contradicted conventional wisdom regarding the outcome of potential engineering solutions. (C) 1993 Wiley-Liss, Inc.

Calcite precipitation induced by clay-bleach cation exchange in andesitic reservoir rocks

Experiments were carried out on the sodium hypochlorite bleach sensitivity of a deep subsurface andesitic reservoir in order to predict possible deleterious mineral transformations during a downhole clean-up job. Experiments involved examination of core samples from the reservoir using an Environmental Scanning Electron Microscope (ESEM) with an attached Energy Dispersive Spectrometer (EDS) before and after the samples were immersed in bleach. Bleach immersion of whole-rock samples resulted in rapid (less than 1 min) precipitation of abundant 3.0-10.0-μm-wide calcite rhombs within clay-associated micropores and on clay and feldspar grain surfaces. Abundant microporefilling calcite rhombs also formed in pure separates of constituent chlorite/corrensite, whereas no calcite formed in a pure separate of constituent zeolite. These experiments indicate that corrensite is the likely calcium source in this experimental fluid-rock system. Formation of calcite occurs via a cation exchange reaction in which calcium in the smectitic interlayers of corrensite exchanges for sodium in the bleach. Serious formation damage due to calcite precipitation would have occurred in the andesite reservoir had it been exposed to bleach. This finding gives credence to earlier suggestions that cation exchange reactions have the potential to cause calcite precipitation in some sandstone reservoirs when exposed to drilling, completion or stimulation fluids. © 1993.

ESEM study of authigenic chlorite acid sensitivity in sandstone reservoirs

The effect of HCl on authigenic chlorite in three different sandstones has been examined uisng an Environmental Scanning Electron Microscope (ESEM), together with conventional analytical techniques. The ESEM enabled chlorites to be directly observed in situ at high magnifications during HCl treatment, and was particularly effective in allowing the same chlorite areas to be closely compared before and after acid treatment. Chlorites were reacted with 1M to 10M HCl at temperatures up to 80°C and for periods up to five months. After all treatments, chlorites show extensive leaching of iron, magnesium and aluminum, and their crystalline structure is destroyed. However, despite these major compositional and structural changes, chlorites show little or no visible evidence of acid attack, with precise morphological detail of individual plates preserved in all samples following acid treatments. Chlorite dissolution, sensu stricto, did not occur as a result of acidization of the host sandstones. Acid-treated chlorides are likely to exits in a structurally weakened state that may make them susceptible to physical disintegration during fluid flow. Accordingly, fines migration may be a significant engineering problem associated with the acidization of chlorite-bearing sandstones. © 1993.

ESEM study of illite/smectite freshwater sensitivity in sandstone reservoirs

The water sensitivity of authigenic smectite- and illite-rich illite/smectites in sandstone reservoirs has been investigated using an Environmental Scanning Electron Microscope (ESEM). The ESEM enabled the illite/smectites to be directly observed in situ at high magnification during freshwater immersion, and was also particularly effective in allowing the same selected illite/smectite areas to be closely compared before and after freshwater treatments. The tendency of authigenic smectite-rich illite/smectite to swell on contact with fresh water varies greatly. Smectite-rich illite/smectite may osmotically swell to many times its original volume to form a gel which greatly reduces porosity and permeability, or may undergo only a subtle morphological change which has little or no adverse effect on reservoir quality. Authigenic illite-rich illite/smectite in sandstones does not swell when immersed in fresh water. Even after prolonged soaking in fresh water, illite-rich illite/smectite particles retain their original morphology. Accordingly, illite-rich illite/smectite in sandstones is unlikely to cause formation damage if exposed to freshwater-based fluids. © 1993.

Characterisation of micrinite in the late triassic Callide Coal Measures

Samples from the Callide Coal Measures, Queensland, Australia, containing the minor maceral, micrinite, have been studied using optical and electron-optical techniques to determine the precise compositional and structural nature of micrinite when in association with vitrinite macerals. Emphasis has been placed on direct spatial correlation of optical and electron-optical data due to the fine grain size (<1μm) of micrinite and its relatively low abundance compared with other macerals in the Callide Basin coals. Precise elemental, morphological and structural data, including electron diffraction, provides unambiguous evidence for the presence of kaolinite in the component known as micrinite. Indeed, micrinite consists predominantly of fine-grained kaolinite (>90 per cent of the component) and, as such, should not be considered a maceral.

Integrated TEM, XRD and electron-microprobe investigation of mixed-layer chlorite smectite from the Point-Sal ophiolite, California

Five basalt samples from the Point Sal ophiolite, California, were examined using HRTEM and AEM in order to compare observations with interpretations of XRD patterns and microprobe analyses. XRD data from ethylene-glycol-saturated samples indicate the following percentages of chlorite in mixed-layer chlorite-smectite identified for each specimen: (i) L2036 almost-equal-to 50%, (ii) L2035 almost-equal-to 70 and 20%, (iii) 1A-13 almost-equal-to 70%, (iv) 1B-42 almost-equal-to 70%, and (v) 1B-55 = 100%. Detailed electron microprobe analyses show that 'chlorite' analyses with high Si, K, Na and Ca contents are the result of interlayering with smectite-like layers. The Fe/(Fe + Mg) ratios of mixed-layer phyllosilicates from Point Sal samples are influenced by the bulk rock composition, not by the percentage of chlorite nor the structure of the phyllosilicate. Measurements of lattice-fringe images indicate that both smectite and chlorite layers are present in the Point Sal samples in abundances similar to those predicted with XRD techniques and that regular alternation of chlorite and smectite occurs at the unit-cell scale. Both 10- and 14-angstrom layers were recorded with HRTEM and interpreted to be smectite and chlorite, respectively. Regular alternation of chlorite and smectite (24-angstrom periodicity) occurs in upper lava samples L2036 and 1A-13, and lower lava sample 1B-42 for as many as seven alternations per crystallite with local layer mistakes. Sample L2035 shows disordered alternation of chlorite and smectite, with juxtaposition of smectite-like layers, suggesting that randomly interlayered chlorite (< 0.5)-smectite exists. Images of lower lava sample 1B-55 show predominantly 14-angstrom layers. Units of 24 angstrom tend to cluster in what may otherwise appear to be disordered mixtures, suggesting the existence of a corrensite end-member having thermodynamic significance.