Discriminating stromatolite formation modes using rare earth element geochemistry: Trapping and binding versus in situ precipitation of stromatolites from the Neoproterozoic Bitter Springs Formation, Northern Territory, Australia

Stromatolites consist primarily of trapped and bound ambient sediment and/or authigenic mineral precipitates, but discrimination of the two constituents is difficult where stromatolites have a fine texture. We used laser ablation-inductively coupled plasma-mass spectrometry to measure trace element (rare earth element – REE, Y and Th) concentrations in both stromatolites (domical and branched) and closely associated particulate carbonate sediment in interspaces (spaces between columns or branches) from bioherms within the Neoproterozoic Bitter Springs Formation, central Australia. Our high resolution sampling allows discrimination of shale-normalised REE patterns between carbonate in stromatolites and immediately adjacent, fine-grained ambient particulate carbonate sediment from interspaces. Whereas all samples show similar negative La and Ce anomalies, positive Gd anomalies and chondritic Y/Ho ratios, the stromatolites and non-stromatolite sediment are distinguishable on the basis of consistently elevated light REEs (LREEs) in the stromatolitic laminae and relatively depleted LREEs in the particulate sediment samples. Additionally, concentrations of the lithophile element Th are higher in ambient sediment samples than in stromatolites, consistent with accumulation of some fine siliciclastic detrital material in the ambient sediment but a near absence in the stromatolites. These findings are consistent with the stromatolites consisting dominantly of in situ carbonate precipitates rather than trapped and bound ambient sediment. Hence, high resolution trace element (REE + Y, Th) geochemistry can discriminate fine-grained carbonates in these stromatolites from coeval non-stromatolitic carbonate sediment and demonstrates that the sampled stromatolites formed primarily from in situ precipitation, presumably within microbial mats/biofilms, rather than by trapping and binding of ambient sediment. Identification of the source of fine carbonate in stromatolites is significant, because if it is not too heavily contaminated by trapped ambient sediment, it may contain geochemical biosignatures and/or direct evidence of the local water chemistry in which the precipitates formed.

In Situ Observation of the Thermal Decomposition of Weddelite by Heating Stage Environmental Scanning Electron Microscopy

The morphological and chemical changes occurring during the thermal decomposition of weddelite, CaC2O4·2H2O, have been followed in real time in a heating stage attached to an Environmental Scanning Electron Microscope operating at a pressure of 2 Torr, with a heating rate of 10 °C/min and an equilibration time of approximately 10 min. The dehydration step around 120 °C and the loss of CO around 425 °C do not involve changes in morphology, but changes in the composition were observed. The final reaction of CaCO3 to CaO while evolving CO2 around 600 °C involved the formation of chains of very small oxide particles pseudomorphic to the original oxalate crystals. The change in chemical composition could only be observed after cooling the sample to 350 °C because of the effects of thermal radiation.

In situ preparation and protein delivery of silicate/alginate composite microspheres with core-shell structure

It is predicted that with increased life expectancy in the developed world, there will be a greater demand for synthetic materials to repair or regenerate lost, injured or diseased bone (Hench & Thompson 2010). There are still few synthetic materials having true bone inductivity, which limits their application for bone regeneration, especially in large-size bone defects. To solve this problem, growth factors, such as bone morphogenetic proteins (BMPs), have been incorporated into synthetic materials in order to stimulate de novo bone formation in the center of large-size bone defects. The greatest obstacle with this approach is that the rapid diffusion of the protein from the carrier material, leading to a precipitous loss of bioactivity; the result is often insufficient local induction or failure of bone regeneration (Wei et al. 2007). It is critical that the protein is loaded in the carrier material in conditions which maintains its bioactivity (van de Manakker et al. 2009). For this reason, the efficient loading and controlled release of a protein from a synthetic material has remained a significant challenge. The use of microspheres as protein/drug carriers has received considerable attention in recent years (Lee et al. 2010; Pareta & Edirisinghe 2006; Wu & Zreiqat 2010). Compared to macroporous block scaffolds, the chief advantage of microspheres is their superior protein-delivery properties and ability to fill bone defects with irregular and complex shapes and sizes. Upon implantation, the microspheres are easily conformed to the irregular implant site, and the interstices between the particles provide space for both tissue and vascular ingrowth, which are important for effective and functional bone regeneration (Hsu et al. 1999). Alginates are natural polysaccharides and their production does not have the implicit risk of contamination with allo or xeno-proteins or viruses (Xie et al. 2010). Because alginate is generally cytocompatible, it has been used extensively in medicine, including cell therapy and tissue engineering applications (Tampieri et al. 2005; Xie et al. 2010; Xu et al. 2007). Calcium cross-linked alginate hydrogel is considered a promising material as a delivery matrix for drugs and proteins, since its gel microspheres form readily in aqueous solutions at room temperature, eliminating the need for harsh organic solvents, thereby maintaining the bioactivity of proteins in the process of loading into the microspheres (Jay & Saltzman 2009; Kikuchi et al. 1999). In addition, calcium cross-linked alginate hydrogel is degradable under physiological conditions (Kibat PG et al. 1990; Park K et al. 1993), which makes alginate stand out as an attractive candidate material for the protein carrier and bone regeneration (Hosoya et al. 2004; Matsuno et al. 2008; Turco et al. 2009). However, the major disadvantages of alginate microspheres is their low loading efficiency and also rapid release of proteins due to the mesh-like networks of the gel (Halder et al. 2005). Previous studies have shown that a core-shell structure in drug/protein carriers can overcome the issues of limited loading efficiencies and rapid release of drug or protein (Chang et al. 2010; Molvinger et al. 2004; Soppimath et al. 2007). We therefore hypothesized that introducing a core-shell structure into the alginate microspheres could solve the shortcomings of the pure alginate. Calcium silicate (CS) has been tested as a biodegradable biomaterial for bone tissue regeneration. CS is capable of inducing bone-like apatite formation in simulated body fluid (SBF) and its apatite-formation rate in SBF is faster than that of Bioglass® and A-W glass-ceramics (De Aza et al. 2000; Siriphannon et al. 2002). Titanium alloys plasma-spray coated with CS have excellent in vivo bioactivity (Xue et al. 2005) and porous CS scaffolds have enhanced in vivo bone formation ability compared to porous β-tricalcium phosphate ceramics (Xu et al. 2008). In light of the many advantages of this material, we decided to prepare CS/alginate composite microspheres by combining a CS shell with an alginate core to improve their protein delivery and mineralization for potential protein delivery and bone repair applications

In situ SANS study of the surface and pore filling adsorption of subcritical and supercritical CO2 in porous silica as a function of pore size

We applied small-angle neutron scattering (SANS) and ultra small-angle neutron scattering (USANS) to monitor evolution of the CO2 adsorption in porous silica as a function of CO2 pressure and temperature in pores of different sizes. The range of pressures (0 < P < 345 bar) and temperatures (T=18 OC, 35 OC and 60 OC) corresponded to subcritical, near critical and supercritical conditions of bulk fluid. We observed that the adsorption behavior of CO2 is fundamentally different in large and small pores with the sizes D > 100 Å and D < 30 Å, respectively. Scattering data from large pores indicate formation of a dense adsorbed film of CO2 on pore walls with the liquid-like density (ρCO2)ads≈0.8 g/cm3. The adsorbed film coexists with unadsorbed fluid in the inner pore volume. The density of unadsorbed fluid in large pores is temperature and pressure dependent: it is initially lower than (ρCO2)ads and gradually approaches it with pressure. In small pores compressed CO2 gas completely fills the pore volume. At the lowest pressures of the order of 10 bar and T=18 OC, the fluid density in smallest pores available in the matrix with D ~ 10 Å exceeds bulk fluid density by a factor of ~ 8. As pressure increases, progressively larger pores become filled with the condensed CO2. Fluid densification is only observed in pores with sizes less than ~ 25 – 30 Å. As the density of the invading fluid reaches (ρCO2)bulk~ 0.8 g/cm3, pores of all sizes become uniformly filled with CO2 and the confinement effects disappear. At higher densities the fluid in small pores appears to follow the equation of state of bulk CO2 although there is an indication that the fluid density in the inner volume of large pores may exceed the density of the adsorbed layer. The equivalent internal pressure (Pint) in the smallest pores exceeds the external pressure (Pext) by a factor of ~ 5 for both sub- and supercritical CO2. Pint gradually approaches Pext as D → 25 – 30 Å and is independent of temperature in the studied range of 18 OC ≤ T ≤ 60 OC. The obtained results demonstrate certain similarity as well as differences between adsorption of subcritical and supercritical CO2 in disordered porous silica. High pressure small angle scattering experiments open new opportunities for in situ studies of the fluid adsorption in porous media of interest to CO2 sequestration, energy storage, and heterogeneous catalysis.

An in situ high pressure FT-IR study of CO2/H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol synthesis catalysts

In situ FT-IR spectroscopy allows the methanol synthesis reaction to be investigated under actual industrial conditions of 503 K and 10 MPa. On Cu/SiO2 catalyst formate species were initially formed which were subsequently hydrogenated to methanol. During the reaction a steady state concentration of formate species persisted on the copper. Additionally, a small quantity of gaseous methane was produced. In contrast, the reaction of CO2 and H2 on ZnO/SiO2 catalyst only resulted in the formation of zinc formate species: no methanol was detected. The interaction of CO2 and H2 with Cu/ZnO/SiO2 catalyst gave formate species on both copper and zinc oxide. Methanol was again formed by the hydrogenation of copper formate species. Steady-state concentrations of copper formate existed under actual industrial reaction conditions, and copper formate is the pivotal intermediate for methanol synthesis. Collation of these results with previous data on copper-based methanol synthesis catalysts allowed the formulation of a reaction mechanism

In situ observation of structural changes in polycrystalline silver catalysts by environmental scanning electron microscopy

Morphology changes induced in polycrystalline silver catalysts as a result of heating in either oxygen, water or oxygen-methanol atmospheres have been investigated by environmental scanning electron microscopy (ESEM), FT-Raman spectroscopy and temperature programmed desorption (TPD). The silver catalyst of interest consisted of two distinct particle types, one of which contained a significant concentration of sub-surface hydroxy species (in addition to surface adsorbed atomic oxygen). Heating the sample to 663 K resulted in the production of 'pin-holes' in the silver structure as a consequence of near-surface explosions caused by sub-surface hydroxy recombination. Furthermore, 'pin-holes' were predominantly found in the vicinity of surface defects, such as platelets and edge structures. Reaction between methanol and oxygen also resulted in the formation of 'pin-holes' in the silver surface, which were inherently associated with the catalytic process. A reaction mechanism is suggested that involves the interaction of methanol with sub-surface oxygen species to form sub-surface hydroxy groups. The sub-surface hydroxy species subsequently erupt through the silver surface to again produce 'pin-holes'.

In situ imaging of catalytic etching on silver during methanol oxidation conditions by environmental scanning electron microscopy

Polycrystalline silver is used to catalytically oxidise methanol to formaldehyde. This paper reports the results of extensive investigations involving the use of environmental scanning electron microscopy (ESEM) to monitor structural changes in silver during simulated industrial reaction conditions. The interaction of oxygen, nitrogen, and water, either singly or in combination, with a silver catalyst at temperatures up to 973 K resulted in the appearance of a reconstructed silver surface. More spectacular was the effect an oxygen/methanol mixture had on the silver morphology. At a temperature of ca. 713 K pinholes were created in the vicinity of defects as a consequence of subsurface explosions. These holes gradually increased in size and large platelet features were created. Elevation of the catalyst temperature to 843 K facilitated the wholescale oxygen induced restructuring of the entire silver surface. Methanol reacted with subsurface oxygen to produce subsurface hydroxyl species which ultimately formed water in the subsurface layers of silver. The resultant hydrostatic pressure forced the silver surface to adopt a "hill and valley" conformation in order to minimise the surface free energy. Upon approaching typical industrial operating conditions widespread explosions occurred on the catalyst and it was also apparent that the silver surface was extremely mobile under the applied conditions. The interaction of methanol alone with silver resulted in the initial formation of pinholes primarily in the vicinity of defects, due to reaction with oxygen species incorporated in the catalyst during electrochemical synthesis. However, dramatic reduction in the hole concentration with time occurred as all the available oxygen became consumed. A remarkable correlation between formaldehyde production and hole concentration was found.

In situ Raman studies of the selective oxidation of methanol to formaldehyde and ethene to ethylene oxide on a polycrystalline silver catalyst

The combined techniques of in situ Raman microscopy and scanning electron microscopy (SEM) have been used to study the selective oxidation of methanol to formaldehyde and the ethene epoxidation reaction over polycrystalline silver catalysts. The nature of the oxygen species formed on silver was found to depend critically upon the exact morphology of the catalyst studied. Bands at 640, 780 and 960 cm-1 were identified only on silver catalysts containing a significant proportion of defects. These peaks were assigned to subsurface oxygen species situated in the vicinity of surface dislocations, AgIII=O sites formed on silver atoms modified by the presence of subsurface oxygen and O2 - species stabilized on subsurface oxygen-modified silver sites, respectively. The selective oxidation of methanol to formaldehyde was determined to occur at defect sites, where reaction of methanol with subsurface oxygen initially produced subsurface OH species (451 cm-1) and adsorbed methoxy species. Two distinct forms of adsorbed ethene were identified on oxidised silver sites. One of these was created on silver sites modified by the interaction of subsurface oxygen species, and the other on silver crystal planes containing a surface coverage of atomic oxygen species. The selective oxidation of ethene to ethylene oxide was achieved by the reaction between ethene adsorbed on modified silver sites and electrophilic AgIII=O species, whereas the combustion reaction was perceived to take place by the reaction of adsorbed ethene with nucleophilic surface atomic oxygen species. Defects were determined to play a critical role in the epoxidation reaction, as these sites allowed the rapid diffusion of oxygen into subsurface positions, and consequently facilitated the formation of the catalytically active AgIII=O sites.

An investigation of goethite-seeded Al(OH)3 precipitation using in situ X-ray diffraction and Rietveld-based quantitative phase analysis

An in situ X-ray diffraction investigation of goethite-seeded Al(OH)3 precipitation from synthetic Bayer liquor at 343 K has been performed. The presence of iron oxides and oxyhydroxides in the Bayer process has implications for alumina reversion, which causes significant process losses through unwanted gibbsite precipitation, and is also relevant for the nucleation and growth of scale on mild steel process equipment. The gibbsite, bayerite and nordstrandite polymorphs of Al(OH)3 precipitated from the liquor; gibbsite appeared to precipitate first, with subsequent formation of bayerite and nordstrandite. A Rietveld-based approach to quantitative phase analysis was implemented for the determination of absolute phase abundances as a function of time, from which kinetic information for the formation of the Al(OH)3 phases was determined.

Electrocatalytic and SERS activity of Pt rich Pt-Pb nanostructures formed via the utilisation of in-situ underpotential deposition of lead

The controlled synthesis of nanostructured materials remains an ongoing area of research, especially as the size, shape and composition of nanomaterials can greatly influence their properties and applications. In this work we present the electrodeposition of highly dendritic platinum rich platinum-lead nanostructures, where lead acetate acts as an inorganic shape directing agent via underpotential deposition on the growing electrodeposit. It was found that these nanomaterials readily oxidise at potentials below monolayer oxide formation, which significantly impacts on the methanol electrooxidation reaction and correlates with the incipient hydrous oxide adatom mediator (IHOAM) model of electrocatalysis. Additionally these materials were tested for their surface enhanced Raman scattering (SERS) activity, where the high density of sharp tips provides promise for their application as SERS substrates.

Ceramic membranes for separation of proteins and DNA by in situ growth of alumina nanofibres with a nanomesh of metal oxide nanofibres

Ceramic membranes were fabricated by in situ synthesis of alumina nanofibres in the pores of an alumina support as a separation layer, and exhibited a high permeation selectivity for bovine serum albumin relative to bovine hemoglobin (over 60 times) and can effectively retain DNA molecules at high fluxes.

Synthesis of 4-arm star poly(L-Lactide) oligomers using an in situ-generated calcium-based initiator

Using an in situ-generated calcium-based initiating species derived from pentaerythritol, the bulk synthesis of well-defined 4-arm star poly(L-lactide) oligomers has been studied in detail. The substitution of the traditional initiator, stannous octoate with calcium hydride allowed the synthesis of oligomers that had both low PDIs and a comparable number of polymeric arms (3.7 – 3.9) to oligomers of similar molecular weight. Investigations into the degree of control observed during the course of the polymerization found that the insolubility of pentaerythritol in molten L-lactide resulted in an uncontrolled polymerization only when the feed mole ratio of L-lactide to pentaerythritol was 13. At feed ratios of 40 and greater, a pseudo-living polymerization was observed. As part of this study, in situ FT-Raman spectroscopy was demonstrated to be a suitable method to monitor the kinetics of the ring-opening polymerization (ROP) of lactide. The advantages of using this technique rather than FT-IR-ATR and 1H NMR for monitoring L-lactide consumption during polymerization are discussed.

The insured's non-disclosure in the formation of insurance contracts : a comparative perspective

The requirements that an insured disclose all facts material to a transaction as well as not misrepresent material facts in the formation of an insurance contract are universal requirements of insurance law. The nature and extent of these obligations varies from one jurisdiction to the next. Disclosure in the insurance context is distinct from the general approach in commercial contracts, and in others between persons dealing at arm's length. It is the purpose of this article therefore to examine, on a comparative basis, the approaches adopted in the Anglo-Commonwealth context of England, Australia New Zealand and Singapore to the resolution of disclose issues in the formation of insurance contracts. Particular attention is focused on the Insurance Contracts Act 1984 (Australia) as this statue effects the most significant overhaul of the common law and the National Consumer Council in the United Kingdom has advocated that similar reforms be adopted.