Investigation of the thermodynamics of iron phosphate melts and stability of iron phosphate glasses: effects of composition and iron redox ratio

“Iron phosphate glasses with Fe/P = 0.33 - 0.67, O/P = 3.0 - 3.5 and Fe2+/ΣFe = 0.16- 0.52 were prepared by altering batch compositions and melt conditions. Thermal analyses indicate polyphosphate glasses with intermediate chain lengths are most stable against devitrification. Heterogeneous crystallization occurs on the glass surface and is dependent on iron valence state, particle size, heating rate, temperature and oxygen availability in the atmosphere. Oxidation of ferrous iron on the glass surface occurs at temperatures as low as Tg, and thus crystallization behavior and stability can be altered via post-melt heat treatments. A novel preparation of thin glass “bubbles” was developed to allow examination of iron phosphate glasses using optical spectroscopy. Absorption near ~476 nm was determined to be predictive of iron valence state, and a deconvolution method is proposed to analyze iron coordination environments. Two models were developed using optical basicity and a statistical, bonding-level representation of the glass structure to investigate the effects of composition on iron redox equilibria and aqueous dissolution behavior. A new approach of calculating heats of formation from group basicities yields a linear correlation with thermochemical data for equivalent crystalline compounds, and the thermodynamic model of iron redox equilibria predicts trends in melt viscosity with bulk basicity, chain length and alkali mixing. An empirical fit of the model predicts iron redox ratios of glasses prepared here within experimental uncertainty. The bond hydration model yields similar spread in predicted versus experimental dissolution rates as previously established models based on free energies of hydration, yet is based solely on composition with no requisite for thermochemical data.”--Abstract, page iii

Clump stars in the Solar Neighbourhood

Hipparcos data has allowed the identification of a large number of clump stars in the Solar Neighbourhood. We discuss our present knowledge about their distributions of masses, ages, colours, magnitudes, and metallicities. We point out that the age distribution of clump stars is ``biased'' towards intermediate-ages. Therefore, the metallicity information they contain is different from that provided by the local G dwarfs. Since accurate abundance determinations are about to become available, these may provide useful constraints to chemical evolution models of the local disc.Comment: 6 pages, proc. of the Sept. 20-24, 1999 Vulcano Workshop "The chemical evolution of the Milky Way: stars vs. clusters", eds. F. Matteucci, F. Giovanell

Connecting and dating with tephras: principles, functioning, and application of tephrochronology in Quaternary research

Tephrochronology, the characterisation and use of volcanic-ash layers as a unique chronostratigraphic linking, synchronizing, and dating tool, has become a globally-practised discipline of immense practical value in a wide range of subjects including Quaternary stratigraphy, palaeoclimatology, palaeoecology, palaeolimnology, physical geography, geomorphology, volcanology, geochronology, archaeology, human evolution, anthropology, and human disease and medicine. The advent of systematic studies of cryptotephras – the identification, correlation, and dating of sparse, fine-grained glass-shard concentrations ‘hidden’ within sediments or soils – over the past ~20 years has been revolutionary. New cryptotephra techniques developed in northwestern Europe and Scandinavia in particular and in North America most recently adapted or improved to help solve problems as they arose, have now been applied to sedimentary sequences (including ice) on all the continents. The result has been the extension of tephra isochrons over wide areas hundreds to several thousands of kilometres from source volcanoes. Taphonomic and other issues, such as quantifying uncertainties in correlation, provide scope for future work. Developments in dating and analytical methods have led to important advances in the application of tephrochronology in recent times. In particular: (i) the ITPFT (glass fission-track) method has enabled landscapes and sequences to be dated where previously no dates were obtainable or where dating was problematic; (ii) new EMPA protocols enabling narrow-beam analyses (<5 um) of glass shards, or small melt inclusions, have been developed, meaning that small (typically distal) glass shards or melt inclusions <~10 um in diameter can now be analysed more efficaciously than previously (and with reduced risk of accidentally including microlites in the analysis as could occur with wide-beam analyses); (iii) LA-ICPMS method for trace element analysis of individual shards <~10 um in diameter is generating more detailed ‘fingerprints’ for enhancing tephra-correlation efficacy (Pearce et al., 2011, 2014; Pearce, 2014); and (iv) the revolutionary rise of Bayesian probability age modelling has helped to improve age frameworks for tephras of the late-glacial to Holocene period especially

Connecting with tephras: principles, functioning, and applications of tephrochronology in Quaternary science

Tephrochronology is a unique method for linking and dating geological, palaeoecological, palaeoclimatic, or archaeological sequences or events. The method relies firstly on stratigraphy and the law of superposition, which apply in any study that connects or correlates deposits from one place to another. Secondly, it relies on characterising and hence identifying or ‘fingerprinting’ tephra layers using either physical properties evident in the field or those obtained from laboratory analysis, including mineralogical examination by optical microscopy or geochemical analysis of glass shards or crystals (e.g., Fe-Ti oxides, ferromagnesian minerals) using the electron microprobe and other tools. Thirdly, the method is enhanced when a numerical age is obtained for a tephra layer by (1) radiometric methods such as radiocarbon, fission-track, U-series, or Ar/Ar dating, (2) incremental dating methods including dendrochronology or varved sediments or layering in ice cores, or (3) age-equivalent methods such as palaeomagnetism or correlation with marine oxygen isotope stages or palynostratigraphy. Once known, that age can be transferred from one site to the next using stratigraphic methods and by matching compositional characteristics, i.e., comparing ‘fingerprints’ from each layer. Used this way, tephrochronology is an age-equivalent dating method