Philippa J.R. Uwins

Laboratory culture studies of Trichodesmium isolated from the Great Barrier Reef Lagoon, Australia

Cultures of Trichodesmium from the Northern and Southern Great Barrier Reef Lagoon (GBRL) have been established in enriched seawater and artificial seawater media. Some cultures have been maintained with active growth for over 6 years. Actively growing cultures in an artificial seawater medium containing organic phosphorus (glycerophosphate) as the principal source of phosphorus have also been established. Key factors that contributed to the successful establishment of cultures were firstly, the seed samples were collected from depth, secondly, samples were thoroughly washed and thirdly, incubations were conducted under relatively low light intensities (PAR ∼ 40–50 μmol quanta m−2 s−1). N2 fixation rates of the cultured Trichodesmium were found to be similar to those measured in the GBRL. Specific growth rates of the cultures during the exponential growth phase in all enriched media were in the range 0.2–0.3 day−1 and growth during this phase was characterised by individual trichomes (filaments) or small aggregations of two to three trichomes. Characteristic bundle formation tended to occur following the exponential growth phase, which suggests that the bundle formation was induced by a lack of a necessary nutrient e.g. Fe. Results from some exploratory studies showed that filament-dominated cultures of Trichodesmium grew over a range of relatively low irradiances (PAR ∼ 5–120 μmol quanta m−2 s−1) with the maximum growth occurring at ∼ 40–50 μmol quanta m−2 s−1. These results suggest that filaments of the tested strain are well adapted for growth at depth in marine waters. Other studies showed that growth yields were dependent on salinity, with maximum growth occurring between 30 and 37 psu. Also the cell yields decreased by an order of magnitude with the reduction of Fe additions from 450 to 45 nM. No active growth was observed with the 4.5 nM Fe addition.

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 (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.

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.

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.

Structural characterisation of kaolinite:NaCl intercalate and its derivatives

Kaolinite:NaCl intercalates with basal layer dimensions of 0.95 and 1.25 nm have been prepared by direct reaction of saturated aqueous NaCl solution with well-crystallized source clay KGa-1. The intercalates and their thermal decomposition products have been studied by XRD, solid-state 23Na, 27Al, and 29Si MAS NMR, and FTIR. Intercalate yield is enhanced by dry grinding of kaolinite with NaCl prior to intercalation. The layered structure survives dehydroxylation of the kaolinite at 500°–600°C and persists to above 800°C with a resultant tetrahedral aluminosilicate framework. Excess NaCl can be readily removed by rinsing with water, producing an XRD “amorphous” material. Upon heating at 900°C this material converts to a well-crystallized framework aluminosilicate closely related to low-carnegieite, NaAlSiO4, some 350°C below its stability field. Reaction mechanisms are discussed and structural models proposed for each of these novel materials.

THE INTERCALATION OF KAOLINITE BY ALKALI HALIDES IN THE SOLID STATE: A SYSTEMATIC STUDY OF THE INTERCALATES AND THEIR DERIVATIVES

Kaolinite: alkali halide intercalates have been successfully prepared by grinding the salt with kaolinite in the absence of water. Rate of intercalation is shown to correlate negatively with melting point of the salt. The basal dimensions of the intercalates increase with increasing size of the ion. As shown recently for kaolinite: NaCl intercalate, the layered structure survives the dehydroxylation of the kaolinite at 500°–600°C, at which point the excess alkali halide can be removed by rinsing to give an XRD-amorphous material. This amorphous material, of approximate stoichiometry MAlSiO4, reacts at surprisingly low temperatures to give crystalline phases, apparently of the same stoichiometry, with structures closely related to eucryptite (M = Li), carnegieite (M = Na), kalsilite (M = K), and leucite (M = K, Rb, Cs). The relationships between the structures of the reaction products are discussed.

Observations of water-clay reactions in water-sensitive sandstone and mudrocks using an environmental scanning electron microscope

The experimental in situ wetting and drying of water-sensitive mudrocks in an environmental scanning electron microscope (ESEM) is described. Fluids used in the tests were freshwater (tap water) and a KCl-based drilling mud. By examining the extent to which illite-smectite and smectite swell when treated with water, it has been possible to assess the importance of clay swelling as a drilling problem in these rocks. Smectite in mudrocks obtained from fresh outcrop (WH10 and WH13) and illite-smectite in sandstone (Sample B of Baker et al., 1992) reacted with fresh water to form a gel-like mass, a process which was only slowly reversed by drying. Less swelling was observed in the mudrocks containing Mg/Ca smectite than in those containing predominantly Na in the interlayer sites. Samples treated with KCl-based drilling mud showed no clay swelling with the exception of the most smectite-rich mudrock (1554). This is attributed to the clay having a residual coating of oil from the original oil-based mud used in drilling. Either a residue of this mud, or the solvents which were used to remove it from the cuttings prior to their being supplied to us may have interacted with the KCl-based drilling mud. The swelling rate for the samples used was pure Na-smectite>interstratified illite-Na smectite>Ca/Mg smectite>interstratified illite-Ca/Mg smectite.

Dynamic imaging of structural changes in silver catalysts by environmental scanning electron microscopy

Polycrystalline silver catalysts are used extensively for the partial oxidation of methanol to formaldehyde, which is then primarily incorporated in the synthesis process for adhesives and resins. In order to maximize formaldehyde production it is essential to gain a comprehensive understanding of the complex microstructural changes which occur in the catalyst during reaction conditions. However, conventional electron microscopic techniques are incapable of imaging catalysts at high temperatures and in the presence of a gaseous atmosphere. Therefore, an environmental scanning electron microscope (ESEM) has been used to image polycrystalline silver catalysts during simulated industrial conditions.

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

Abstract 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.

Freshwater sensitivity of glauconitic hydrocarbon reservoirs

Abstract Freshwater sensitivity tests were conducted on four glauconite/smectite mixed-layer clays (G/S) with 10–20% smectite content in order to determine whether G/S with low expandability has the potential to swell on contact with fresh water. Tests showed that three of the G/S samples underwent no visible swelling when immersed for up to 4 days in fresh water. In contrast, one sample was freshwater sensitive because, in addition to non-swelling G/S with low expandability, it contained a small component of highly smectitic G/S that rapidly swelled on contact with fresh water. These results indicate that the presence of G/S with low expandability in a hydrocarbon reservoir should not render the reservoir freshwater sensitive, but that individual reservoirs can contain a compositionally-heterogeneous population of G/S grains that may include a highly freshwater-sensitive, smectitic component.