Layered titanate nanofibers as efficient adsorbents for removal of toxic radioactive and heavy metal ions from water

Titanate nanofibers with two formulas, Na2Ti3O7 and Na1.5H0.5Ti3O7, respectively, exhibit ideal properties for removal of radioactive and heavy metal ions in wastewater, such as Sr2+ , Ba2+ (as substitute of 226Ra2+), and Pb2+ ions. These nanofibers can be fabricated readily by a reaction between titania and caustic soda and have structures in which TiO6 octahedra join each other to form layers with negative charges; the sodium cations exist within the interlayer regions and are exchangeable. They can selectively adsorb the bivalent radioactive ions and heavy metal ions from water through ion exchange process. More importantly, such sorption finally induces considerable deformation of the layer structure, resulting in permanent entrapment of the toxic bivalent cations in the fibers so that the toxic ions can be safely deposited. This study highlights that nanoparticles of inorganic ion exchangers with layered structure are potential materials for efficient removal of the toxic ions from contaminated water.

Synthesis and modifications of metal oxide nanostructures and their applications

Transition metal oxides are functional materials that have advanced applications in many areas, because of their diverse properties (optical, electrical, magnetic, etc.), hardness, thermal stability and chemical resistance. Novel applications of the nanostructures of these oxides are attracting significant interest as new synthesis methods are developed and new structures are reported. Hydrothermal synthesis is an effective process to prepare various delicate structures of metal oxides on the scales from a few to tens of nanometres, specifically, the highly dispersed intermediate structures which are hardly obtained through pyro-synthesis. In this thesis, a range of new metal oxide (stable and metastable titanate, niobate) nanostructures, namely nanotubes and nanofibres, were synthesised via a hydrothermal process. Further structure modifications were conducted and potential applications in catalysis, photocatalysis, adsorption and construction of ceramic membrane were studied. The morphology evolution during the hydrothermal reaction between Nb2O5 particles and concentrated NaOH was monitored. The study demonstrates that by optimising the reaction parameters (temperature, amount of reactants), one can obtain a variety of nanostructured solids, from intermediate phases niobate bars and fibres to the stable phase cubes. Trititanate (Na2Ti3O7) nanofibres and nanotubes were obtained by the hydrothermal reaction between TiO2 powders or a titanium compound (e.g. TiOSO4·xH2O) and concentrated NaOH solution by controlling the reaction temperature and NaOH concentration. The trititanate possesses a layered structure, and the Na ions that exist between the negative charged titanate layers are exchangeable with other metal ions or H+ ions. The ion-exchange has crucial influence on the phase transition of the exchanged products. The exchange of the sodium ions in the titanate with H+ ions yields protonated titanate (H-titanate) and subsequent phase transformation of the H-titanate enable various TiO2 structures with retained morphology. H-titanate, either nanofibres or tubes, can be converted to pure TiO2(B), pure anatase, mixed TiO2(B) and anatase phases by controlled calcination and by a two-step process of acid-treatment and subsequent calcination. While the controlled calcination of the sodium titanate yield new titanate structures (metastable titanate with formula Na1.5H0.5Ti3O7, with retained fibril morphology) that can be used for removal of radioactive ions and heavy metal ions from water. The structures and morphologies of the metal oxides were characterised by advanced techniques. Titania nanofibres of mixed anatase and TiO2(B) phases, pure anatase and pure TiO2(B) were obtained by calcining H-titanate nanofibres at different temperatures between 300 and 700 °C. The fibril morphology was retained after calcination, which is suitable for transmission electron microscopy (TEM) analysis. It has been found by TEM analysis that in mixed-phase structure the interfaces between anatase and TiO2(B) phases are not random contacts between the engaged crystals of the two phases, but form from the well matched lattice planes of the two phases. For instance, (101) planes in anatase and (101) planes of TiO2(B) are similar in d spaces (~0.18 nm), and they join together to form a stable interface. The interfaces between the two phases act as an one-way valve that permit the transfer of photogenerated charge from anatase to TiO2(B). This reduces the recombination of photogenerated electrons and holes in anatase, enhancing the activity for photocatalytic oxidation. Therefore, the mixed-phase nanofibres exhibited higher photocatalytic activity for degradation of sulforhodamine B (SRB) dye under ultraviolet (UV) light than the nanofibres of either pure phase alone, or the mechanical mixtures (which have no interfaces) of the two pure phase nanofibres with a similar phase composition. This verifies the theory that the difference between the conduction band edges of the two phases may result in charge transfer from one phase to the other, which results in effectively the photogenerated charge separation and thus facilitates the redox reaction involving these charges. Such an interface structure facilitates charge transfer crossing the interfaces. The knowledge acquired in this study is important not only for design of efficient TiO2 photocatalysts but also for understanding the photocatalysis process. Moreover, the fibril titania photocatalysts are of great advantage when they are separated from a liquid for reuse by filtration, sedimentation, or centrifugation, compared to nanoparticles of the same scale. The surface structure of TiO2 also plays a significant role in catalysis and photocatalysis. Four types of large surface area TiO2 nanotubes with different phase compositions (labelled as NTA, NTBA, NTMA and NTM) were synthesised from calcination and acid treatment of the H-titanate nanotubes. Using the in situ FTIR emission spectrescopy (IES), desorption and re-adsorption process of surface OH-groups on oxide surface can be trailed. In this work, the surface OH-group regeneration ability of the TiO2 nanotubes was investigated. The ability of the four samples distinctively different, having the order: NTA > NTBA > NTMA > NTM. The same order was observed for the catalytic when the samples served as photocatalysts for the decomposition of synthetic dye SRB under UV light, as the supports of gold (Au) catalysts (where gold particles were loaded by a colloid-based method) for photodecomposition of formaldehyde under visible light and for catalytic oxidation of CO at low temperatures. Therefore, the ability of TiO2 nanotubes to generate surface OH-groups is an indicator of the catalytic activity. The reason behind the correlation is that the oxygen vacancies at bridging O2- sites of TiO2 surface can generate surface OH-groups and these groups facilitate adsorption and activation of O2 molecules, which is the key step of the oxidation reactions. The structure of the oxygen vacancies at bridging O2- sites is proposed. Also a new mechanism for the photocatalytic formaldehyde decomposition with the Au-TiO2 catalysts is proposed: The visible light absorbed by the gold nanoparticles, due to surface plasmon resonance effect, induces transition of the 6sp electrons of gold to high energy levels. These energetic electrons can migrate to the conduction band of TiO2 and are seized by oxygen molecules. Meanwhile, the gold nanoparticles capture electrons from the formaldehyde molecules adsorbed on them because of gold’s high electronegativity. O2 adsorbed on the TiO2 supports surface are the major electron acceptor. The more O2 adsorbed, the higher the oxidation activity of the photocatalyst will exhibit. The last part of this thesis demonstrates two innovative applications of the titanate nanostructures. Firstly, trititanate and metastable titanate (Na1.5H0.5Ti3O7) nanofibres are used as intelligent absorbents for removal of radioactive cations and heavy metal ions, utilizing the properties of the ion exchange ability, deformable layered structure, and fibril morphology. Environmental contamination with radioactive ions and heavy metal ions can cause a serious threat to the health of a large part of the population. Treatment of the wastes is needed to produce a waste product suitable for long-term storage and disposal. The ion-exchange ability of layered titanate structure permitted adsorption of bivalence toxic cations (Sr2+, Ra2+, Pb2+) from aqueous solution. More importantly, the adsorption is irreversible, due to the deformation of the structure induced by the strong interaction between the adsorbed bivalent cations and negatively charged TiO6 octahedra, and results in permanent entrapment of the toxic bivalent cations in the fibres so that the toxic ions can be safely deposited. Compared to conventional clay and zeolite sorbents, the fibril absorbents are of great advantage as they can be readily dispersed into and separated from a liquid. Secondly, new generation membranes were constructed by using large titanate and small ã-alumina nanofibres as intermediate and top layers, respectively, on a porous alumina substrate via a spin-coating process. Compared to conventional ceramic membranes constructed by spherical particles, the ceramic membrane constructed by the fibres permits high flux because of the large porosity of their separation layers. The voids in the separation layer determine the selectivity and flux of a separation membrane. When the sizes of the voids are similar (which means a similar selectivity of the separation layer), the flux passing through the membrane increases with the volume of the voids which are filtration passages. For the ideal and simplest texture, a mesh constructed with the nanofibres 10 nm thick and having a uniform pore size of 60 nm, the porosity is greater than 73.5 %. In contrast, the porosity of the separation layer that possesses the same pore size but is constructed with metal oxide spherical particles, as in conventional ceramic membranes, is 36% or less. The membrane constructed by titanate nanofibres and a layer of randomly oriented alumina nanofibres was able to filter out 96.8% of latex spheres of 60 nm size, while maintaining a high flux rate between 600 and 900 Lm–2 h–1, more than 15 times higher than the conventional membrane reported in the most recent study.

Bioactive inorganic materials/alginate composite microspheres with controllable drug-delivery ability

Alginate microspheres are considered a promising material as a drug carrier in bone repair due to excellent biocompatibility, but their main disadvantage is low drug entrapment efficiency and non-controllable release. The aim of this study was to investigate the effect of incorporating mesoporous bioglass (MBG), non-mesoporous bioglass (BG) or hydroxyapatite (HAp) into alginate microspheres on their drug-loading and release properties. X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and atomic emission spectroscopy (AES) were used to analyse the composition, structure and dissolution of bioactive inorganic materials and their microspheres. Dexamethasone (DEX)-loading and release ability of four microspheres were tested in phosphate buffered saline with varying pHs. Results showed that the drug-loading capacity was enhanced with the incorporation of bioactive inorganic materials into alginate microspheres. The MBG/Alginate microspheres had the highest drug loading ability. DEX release from alginate microspheres correlated to the dissolution of MBG, BG and HAp in PBS, and that the pH was an efficient factor in controlling the DEX release; a high pH resulted in greater DEX release, whereas a low pH delayed DEX release. In addition, MBG/alginate, BG/alginate and HAp/alginate microspheres had varying apatite-formation and dissolution abilities, which indicate that the composites would behave differently with respect to bioactivity. The study suggests that microspheres made of a composite of bioactive inorganic materials and alginate have a bioactivity and degradation profile which greatly improves their drug delivery capacity, thus enhancing their potential applications as bioactive filler materials for bone tissue regeneration.

Sodium niobate adsorbents doped with tantalum (TaV) for the removal of bivalence radioactive ions in waste waters

Sodium niobates doped with different amount of tantalum (TaV) were prepared via thermal reaction process. It was found pure nanofibril and bar-like solids can be obtained when tantalum was introduced into the reaction system. For the well-crystallized fibril solids, the Na+ ions are difficult to be exchanged, and the radioactive ions such as Sr2+ and Ra2+ ions just deposit on the surface of the fibers during the sorption process, resulting in lower sorption capacity and distribution coefficients (Kd)`. However, the bar-like solids are poorly-crystallized and have lots of exchangeable Na+ ions. They are able to remove highly hazardous bivalent radioactive isotopes such as Sr2+ and Ra2+ ions. Even in the presence of lots of Na+ ions, they also have higher Kd. More importantly, such sorption finally intelligently triggers considerable collapse of the structure, resulting in the entrapment of the toxic bivalent cations permanently in the solids so that they can be safely disposed. This study highlights new opportunities for the preparation of Nb-based adsorbents to efficiently remove the toxic radioactive ions from contaminated water.

The molecular structure of the mineral sarmientite Fe2(AsO4,SO4)2(OH)6•5H2O : implications for arsenic accumulation and removal

Sarmientite is an environmental mineral; its formation in soils enables the entrapment and immobilisation of arsenic. The mineral sarmientite is often amorphous making the application of X-ray diffraction difficult. Vibrational spectroscopy has been applied to the study of sarmientite. Bands are attributed to the vibrational units of arsenate, sulphate, hydroxyl and water. Raman bands at 794, 814 and 831 cm−1 are assigned to the ν3 (AsO4)3− antisymmetric stretching modes and the ν1 symmetric stretching mode is observed at 891 cm−1. Raman bands at 1003 and 1106 cm−1 are attributed to vibrations. The Raman band at 484 cm−1 is assigned to the triply degenerate (AsO4)3− bending vibration. The high intensity Raman band observed at 355 cm−1 (both lower and upper) is considered to be due to the (AsO4)3−ν2 bending vibration. Bands attributed to water and OH stretching vibrations are observed.

The Biodex Isokinetic Dynamometer for knee strength assessment in children : advantages and limitations

Objective: To critically appraise the Biodex System 4 isokinetic dynamometer for strength assessment of children. Methods: Appraisal was based on experiences from two independent laboratories involving testing of 213 children. Issues were recorded and the manufacturer was consulted regarding appropriate solutions. Results: The dynamometer had insufficient height adjustment for alignment of the knee for some children, requiring the construction of padding to better fit the child within the dynamometer. Potential for entrapment of the non-testing leg was evident in the passive and eccentric modes and a leg bracket restraint was constructed. Automated gravity correction did not operate when protocols were linked or data was exported to an external device. Conclusions: Limitations were noted, some of which were applicable to knee strength testing in general and others which were specific to use with children. However, most of these obstacles could be overcome, making the Biodex System 4 suitable for assessment of knee strength in children.

Micas in experimentally shocked gneiss

Biotites and muscovites from a gneiss have been experimentally shocked between 18 and 70 GPa using powder-propellant guns at NASA Johnson Space Center and at the California Institute of Technology. This study shows that shock in biotite and muscovite can produce homogeneous and devolatilized glasses within microseconds. Shock-deformed micas display fracturing, kinking, and complex extinction patterns over the entire pressure range investigated. However, these deformation features are not a sensitive pressure indicator. Localized melting of micas begins at 33 GPa and goes to completion at 70 GPa. Melted biotite and muscovite are optically opaque, but show extensive microvesiculation and flow when observed with the SEM. Electron diffraction confirms that biotite and muscovite have transformed to a glass. The distribution of vesicles in shock-vitrified mica shows escape of volatiles within the short duration of the shock experiment. Experimentally shocked biotite and muscovite undergo congruent melting. Compositions of the glasses are similar to the unshocked micas except for volatiles (H2O loss and K loss). These unusual glasses derived from mica may be quenched by rapid cooling conditions during the shock experiment. Based on these results, the extremely low H2O content of tektites may be reconciled with a terrestrial origin by impact. Release of volatiles in shock-melted micas affects the melting behavior of coexisting dry silicates during the short duration of the shock experiment. Transportation and escape of volatiles released from shock-melted micas may provide plausible mechanisms for the origin of protoatmospheres on terrestrial planets, hydrothermal activity on phyllosilicate-rich meteorite parent bodies, and fluid entrapment in meteorites.

Global indigenous studies in the first world: some reflections and epistemological matters

Indigenous studies in First World nation states such as Australia, Canada, New Zealand, the United States of America and Hawaii, appear to have acquired the status of a discipline, although the accounts of its formation vary. Indigenous studies is formally recognised as part of university curricula in these countries and is included in inter‐disciplinary contexts and degree programs or is offered as a program and a degree in its own right. Indigenous scholarship is being published in unprecedented numbers with publishing houses competing for manuscripts. Indigenous studies journals have proliferated having emerged in the 1970s though most were, and continue to be, edited by non‐Indigenous people. In addition, Indigenous studies professional associations have been established organising research related activities as well as convening conferences to enable intellectual engagement and the formation of national and international networks. The nature and extent of this institutionalisation and the conditions of existence, though often marginalised and under resourced, may allude to the coherence of Indigenous Studies as a discipline with global reach but what remains unclear are its epistemological boundaries and the degree to which it perpetuates cultural entrapment . This paper will reflect on some of these epistemological matters.

Effect of chemical conjugation of L-leucine to chitosan on the dispersibility and drug release of a dry powder inhaler nanoparticle formulation

Purpose: This study investigated the effect of chemical conjugation of the amino acid L-leucine to the polysaccharide chitosan on the dispersibility and drug release pattern of a polymeric nanoparticle (NP)-based controlled release dry powder inhaler (DPI) formulation. Methods: A chemical conjugate of L-leucine with chitosan was synthesized and characterized by Infrared (IR) Spectroscopy, Nuclear Magnetic Resonance (NMR) Spectroscopy, Elemental Analysis and X-ray Photoelectron Spectroscopy (XPS). Nanoparticles of both chitosan and its conjugate were prepared by a water-in-oil emulsification – glutaraldehyde cross-linking method using the antihypertensive agent, diltiazem (Dz) hydrochloride as the model drug. The surface morphology and particle size distribution of the nanoparticles were determined by Scanning Electron Microscopy (SEM) and Dynamic Light Scattering (DLS). The dispersibility of the nanoparticle formulation was analysed by a Twin Stage Impinger (TSI) with a Rotahaler as the DPI device. Deposition of the particles in the different stages was determined by gravimetry and the amount of drug released was analysed by UV spectrophotometry. The release profile of the drug was studied in phosphate buffered saline at 37 ⁰C and analyzed by UV spectrophotometry. Results: The TSI study revealed that the fine particle fractions (FPF), as determined gravimetrically, for empty and drug-loaded conjugate nanoparticles were significantly higher than for the corresponding chitosan nanoparticles (24±1.2% and 21±0.7% vs 19±1.2% and 15±1.5% respectively; n=3, p<0.05). The FPF of drug-loaded chitosan and conjugate nanoparticles, in terms of the amount of drug determined spectrophotometrically, had similar values (21±0.7% vs 16±1.6%). After an initial burst, both chitosan and conjugate nanoparticles showed controlled release that lasted about 8 to 10 days, but conjugate nanoparticles showed twice as much total drug release compared to chitosan nanoparticles (~50% vs ~25%). Conjugate nanoparticles also showed significantly higher dug loading and entrapment efficiency than chitosan nanoparticles (conjugate: 20±1% & 46±1%, chitosan: 16±1% & 38±1%, n=3, p<0.05). Conclusion: Although L-leucine conjugation to chitosan increased dispersibility of formulated nanoparticles, the FPF values are still far from optimum. The particles showed a high level of initial burst release (chitosan, 16% and conjugate, 31%) that also will need further optimization.

Horror

The monstrous landscape and the revenge of nature are recurring motifs in Australian cinema. In the horror genre, the idea of the monstrous landscape emerges from, and builds upon, an established tradition in Australian cinema in which landscape functions not just as a setting for action, but also as a character in its own right. Rather than a picturesque wilderness or countryside, or a serene natural world untainted by civilisation – representations common in landscape cinema celebrating positive aspects of the Australian ‘outback’ – the monstrous landscape is a dangerous, malevolent and threatening force. Drawing upon themes also common in Australian Gothic narratives such as entrapment in a hostile environment, isolation and fear of the unknown (Turcotte, 1988, see also Jonathan Rayner’s essay in this volume), the monstrous landscape acts according to its own logic indecipherable to non-Indigenous Australians and is represented in terms of its alien-ness and inhuman horror.

"Unruly women and semiotic spaces": Jay Verney's a mortality tale

Written at a time of significant changes for women and for women writers in Queensland, Australia, Jay Verney's A Mortality Tale (1994), privileges women's experiences of place and seeks to redeem the feminine from its entrapment in masculine stories/discourses of self and place. This chapter draws on Julia Kristeva's conceptualisation of the semiotic as a way of reading Verney's witty and reflective re-articulation of phallocentric orderings of spatiality and gender.

Synthesis and vesicle formation from hybrid bolaphile/amphiphile ion-pairs. Evidence of membrane property modulation by molecular design

Four new hybrid (bolaphile/amphiphile) ion-pairs were synthesized. Electron microscopy indicated that each of these forms bilayer membranes upon dispersion in aqueous media. Membrane properties have also been examined by differential scanning calorimetry, microcalorimetry, temperature-dependent fluorescence anisotropy measurements, and UV-vis spectroscopy. The T-m values for the vesicular 1, 2, 3, 4, and 5 were 38, 12, 85, 31.3, and 41.6 degrees C, respectively. Interestingly the T-m values for 1 and 3 were found to depend on their concentration. The entrapment of small solute and the release capability have also been examined to demonstrate that these bilayers form enclosed vesicles. X-ray diffraction of the cast films has been performed to understand the nature and the thickness of these membrane organizations. The membrane widths ranged from 33 to 47 Angstrom. Finally, the above observations have been analyzed in light of the results obtained from molecular modeling studies. Thus we have demonstrated that membrane properties can be modulated by simple structural changes at the amphiphile level. It was shown that by judicious incorporation of central, isomeric, disubstituted aromatic units as structural anchors into different bolaphiles, one can modulate the properties of the resulting vesicles.

Tarsal tunnel syndrome: A narrative literature review

Background Tarsal tunnel syndrome is classified as a focal compressive neuropathy of the posterior tibial nerve or one of its associated branches individually or collectively. The tunnel courses deep to fascia, the flexor retinaculum and within the abductor hallucis muscle of the foot/ankle. The condition is rare and regularly under-diagnosed leading to a range of symptoms affecting the plantar margins of the foot. There are many intervention strategies for treating tarsal tunnel syndrome with limited robust evidence to guide the clinical management of this condition. The role of conservative versus surgical interventions at various stages of the disease process remains unclear, and there is a need for a structured, step-wise approach in treating patients with this syndrome based on derived empirical evidence. This narrative review attempts to scrutinize the literature to date by clarifying initial presentation, investigations and definitive treatment for the purpose of assisting future informed clinical decision and prospective research endeavours. Process The literature searches that have been incorporated in compiling a rigorous review of this condition have included: the Cochrane Neuromuscular Group's Specialized Register (Cochrane Library 2013), the databases of EMBASE, AMED, MEDLINE, CINAHL, Physiotherapy evidence database (PEDRO), Biomed Central, Science Direct and Trip Database (1972 to the present). Reference listings of located articles were also searched and scrutinized. Authors and experts within the field of lower-limb orthopaedics were contacted to discuss applicable data. Subject-specific criteria searches utilizing the following key terms were performed across all databases: tarsal tunnel syndrome, tibial neuralgia, compression neuropathy syndromes, tibial nerve impingement, tarsal tunnel neuropathy, entrapment tibial nerve, posterior tibial neuropathy. These search strategies were modified with differing databases, adopting specific sensitivity-searching tools and functions unique to each. This search strategy identified 88 journal articles of relevance for this narrative literature review. Findings This literature review has appraised the clinical significance of tarsal tunnel syndrome, whilst assessing varied management interventions (non-surgical and surgical) for the treatment of this condition in both adults and children. According to our review, there is limited high-level robust evidence to guide and refine the clinical management of tarsal tunnel syndrome. Requirements for small-scaled randomized controlled trials in groups with homogenous aetiology are needed to analyse the effectiveness of specific treatment modalities. Conclusions It is necessary that further research endeavours be pursued for the clinical understanding, assessment and treatment of tarsal tunnel syndrome. Accordingly, a structured approach to managing patients who have been correctly diagnosed with this condition should be formulated on the basis of empirical evidence where possible.

Effectiveness of commercial harvesting in controlling feral-pig populations

Context. The feral pig (Sus scrofa) is a widespread pest species in Australia and its populations are commonly controlled to reduce damage to agriculture and the environment. Feral pigs are also a resource and harvested for commercial export as game meat. Although many other control techniques are used, commercial harvesting of feral pigs is often encouraged by land managers, because it carries little or no cost and is widely perceived to control populations. Aims. To use feral-pig harvesting records, density data and simple harvest models to examine the effectiveness of commercial harvesting to reduce feral-pig populations. Methods. The present study examined commercial harvest off-take on six sites (246-657 km2) in southern Queensland, and 20 large blocks (~2-6000 km2) throughout Queensland. The harvest off-take for each site was divided by monthly or average annual population size, determined by aerial survey, to calculate monthly and annual harvest rates.Asimple harvest model assuming logistic population growth was used to determine the likely effectiveness of harvesting. Key results. Commercial harvest rates were generally low (<~20%) and are likely to provide only modest reductions in population size. Additionally, harvest rates capable of substantial reductions (>50%) in long-term population size were isolated occurrences and not maintained across sites and years. High harvest rates were observed only at low densities. Although these harvest rates may be sufficiently high to hold populations at low densities, the population is likely to escape this entrapment following a flush in food supply or a reduction in harvest effort. Implications. Our results demonstrated that, at current harvest rates, commercial harvesting is ineffective for the landscape-scale control of feral-pig populations. Unless harvest rates can be significantly increased, commercial harvesting should be used as a supplement to, rather than as a substitute for, other damage-control techniques.

Thermal decomposition of titanyl oxalates-I : Barium titanyl oxalate

Thermal decomposition of barium titanyl oxalate tetrahydrate (BTO) has been investigated employing TGA, DTG and DTA techniques and gas and chemical analysis. The decomposition proceeds through five steps and is not affected much by the surrounding gas atmosphere. The first step which is the dehydration of the tetrahydrate is followed by a low-temperature decomposition of the oxalate groups. In the temperature range 190–250°C half a mole of carbon monoxide is evolved with the formation of a transient intermediate containing both oxalate and carbonate groups. The oxalate groups are completely destroyed in the range 250–450°C, resulting in the formation of a carbonate which retains free carbon dioxide in the matrix. The trapped carbon dioxide is released in the temperature range of 460–600°C. The final decomposition of the carbonate takes place between 600–750°C and yields barium titanate. The i.r. spectra, surface area measurements and X-ray, powder diffraction data support entrapment of carbon dioxide in the matrix.