Differential scanning calorimetry in a piston-cylinder apparatus: Design and calibration

We have designed and calibrated a piston-cylinder cell assembly suitable for conductingin situ measurements of enthalpies of phase transitions at elevated pressures by heat-flux differential scanning calorimetry (DSC). The high-pressure DSC detector consists of a Pt-Pt13%Rh thermopile wrapped around a frame of fired pyrophyllite. Four thermocouple junctions, arranged radially around the sample capsule, are connected in series, with four reference thermocouple junctions located 3–4 mm above the sample and embedded in thermally inert ceramic. A W-W25%Re control thermocouple is situated directly above the top of the sample; the whole detector assembly is enclosed in a 1.5 mm thick cylindrical ceramic sleeve located at the center of a 8–10 mm long hot-zone in the tapered graphite furnace. Using this detector design and cell assembly, we have observed the thermal signal associated with the fusion of Au at 0.5 and 1.2 GPa, and have calculated a calibration factor (K) for this detector based on the gold melting curve ofMirwald andKennedy (1979). Detector sensitivity decreases by a factor of four over this pressure-temperature interval. The reproducibility of the enthalpy of fusion of gold at 0.5 GPa suggests that detector geometry is reproducible from one experiment to the next, and thus confirms the viability of this particular detector design for quantitative DSC measurements. Subsequent experiments will assess the dependence of (K) on temperature and pressure by measuring the enthalpies of fusion of additional metals (e.g., Ag, Cu, Al, Ge) and salts (e.g., NaCl, CsCl).     

Thermochemistry of some pyroxenes and related compounds

The enthalpies of formation of a number of crystalline silicates from the oxides at 986 K were determined by oxide melt solution calorimetry. The values of ΔH°_{f, 986}, in kcal/mol, are as follows: MgCaSi₂O₆, ? 34.3 ± 0.4; CoCaSi₂O₆, ? 26.7 ± 0.5; NiCaSi₂O₆, ? 27.1 ± 0.5; MnSiO₃, ? 6.3 ± 0.3; Mn₂SiO₄, ? 12.2 ± 0.3. In addition, for MnSiO₃ (rhodonite)→ MnSiO₃ (pyroxmangite), ΔH°₉₈₆ = + 0.06 ± 0.3₃kcal/mol and for MgCaSi₂O₆ (diopside) = MgCaSi₂O₆ (glass), ΔH°₉₈₆ = + 21.0 ± 0.3 kcal/ mol. For hedenbergite, FeCaSi₂O₆, ΔG°₁₃₅₀ = ?25.6 ± 1.5 kcal/mol. In terms of pyroxene phase equilibria and crystal chemistry, our thermochemical data support the generally accepted crystallographic arguments that (a) the C2/c clinopyroxene structure increases in stability with decreasing size of the ion occupying the Ml site in the MCaSi₂O₆ series, and (b) the energy (and enthalpy) differences between orthopyroxene, clinopyroxene, and pyroxenoid structures are generally quite small and often less than 500 cal/mol in magnitude.     

Luminescence chronology of non‐glacial sediments in Changeable Lake,Russian High Arctic,and implications for limited Eurasian ice‐sheet extent during the LGM

A 10.5 m core from Changeable Lake in the Severnaya Zemlya Archipelago just north of the Taymyr Peninsula intersects ca. 30 cm of diamicton at its base, interpreted as a basal till. Because the upper 10.13 m of this core consists of non‐glacial sediments, a maximum numeric age for these non‐glacial sediments would provide a clear lower limit to the timing of the last glaciation in the area of Changeable Lake. Radiocarbon (¹⁴C) dating of several materials from this core yielded widely scattered results. Consequently we applied photonic dating to sediments above the diamicton. The experimental single‐aliquot‐regenerative (SAR) dose fine‐grain method was applied to two samples, using the ‘double SAR’ approach. With one exception, these fine‐grain SAR results and the results of application of the SAR method to sand‐sized quartz grains from two samples, at ca. 9.95 m and ca. 10.05 m depth, are discrepant with age estimates from the multi‐aliquot infrared‐photon‐stimulated luminescence (IR‐PSL) method applied to fine grains. Multi‐aliquot IR‐PSL dating of 10 samples produces ages increasing monotonically from ca. 4 ka at 2 m to 53 ± 4 ka at 9.97 m. These self‐consistent multi‐aliquot IR‐PSL ages, along with limiting ¹⁴C ages of >47 ka at ca. 10 m, provide direct evidence that glacial ice did not advance over this lake basin during the Last Glacial Maximum, and thus delimit the northeastern margin of the Barents–Kara Sea ice‐sheet to somewhere west of this archipelago. The last regional glaciation probably occurred during marine isotope stage (MIS) 4 or earlier. Copyright © 2004 John Wiley & Sons, Ltd.     

Changes in geochemistry and mineralogy of thermally altered coal, Upper Hunter Valley, Australia

Igneous intrusions thermally and geochemically alter coal, commonly causing economic and safety problems for many coal mines. The effects of two dykes on the inorganic content of the Late Permian bituminous Upper Wynn seam were determined from analyses of 44 samples that were collected along transects approaching the intrusions. Petrographic and XRD data were used to determine sample mineralogy, and INAA and XRF spectrometry were utilised to determine the contents of 57 elements. The mineralogy of the unaltered coal, altered coal and dyke is dominated by carbonates, particularly dawsonite, which formed by epigenetic precipitation at a late stage, after thermal alteration. Ankerite and siderite are the products of thermal alteration and are restricted to the altered coal and dykes.Principal component analysis, correlations and compositional trends approaching the intrusions were used to subdivide the elements into groups and to identify the mineralogical affinity of each group. Geochemical data are more sensitive than mineralogy for defining the size of the alteration halo, and three zones ranging from unaltered coal, through altered coal to highly coked coal are recognised as each intrusion is approached.The alteration halos differ in extent (9.5 and 56 m wide), but their size is not a multiple of the size of the causative intrusion. At the contact between coal and intrusion, concentrations of elements with affinities to some aluminosilicates, oxides, carbonates, sulphides and organic components are enriched, while other aluminosilicate-related elements are depleted. In the altered coal towards the edge of the alteration halo, some aluminosilicate elements are enriched and oxide elements are depleted.     

Thermochemistry of the tremolite-edenite amphiboles using fluorine analogues,and applications to amphibole-plagioclase-quartz equilibria

Heats of mixing of synthetic C2/m fluortremolite-fluoredenite amphiboles measured at 985 K show a systematic deviation from ideal mixing consistent with a subregular solution model. The deviations from ideal mixing are interpreted in terms of Na ordering in the A-site and Na-Al interactions in edenite-poor compositions. Enthalpies of edenite substitution reactions in amphiboles and in SiO₂-NaAlO₂ glasses and framework silicates are comparable. Gibbs free energies of formation of fluortremolite and fluoredenite at 298K are -2,821.07±3.34 kcal mol^–1 and -2,889.59±2.40 kcal mol^–1 respectively. The former value is in good agreement with values calculated from both F-OH exchange experiments and from a natural fluortremolite-bearing metamorphic rock. Least-squares fitted sub-regular heat-of-mixing parameters are poorly constrained and unrealistically high, but estimated subregular mixing parameters consistent with 95% confidence interval uncertainties in the calorimetric data and with TEM constraints give activity-composition relations in good agreement with the A-site compositions of natural metamorphic and igneous hornblendes. These relations predict unmixing in edenite-rich compositions over a wide range of temperature, but lend no support to the existence of a hornblende-actinolite miscibility gap. Calibration of the reaction tremolite+ albite=edenite+4 quartz as a function ofP,T andX _ed ^amph indicates negativedP/dT slopes and a limited range of X _ed ^amph (0.3 to 0.5) in equilibrium with plagioclase and quartz over a wide range of pressure and temperature, consistent with metamorphic hornblende-plagioclase assemblages. The energetics of this reaction suggest, however, that amphibole-plagioclase disequilibrium may be common.     

Electrodialytic treatment of sewage sludge: influence on microbiological community

This study aimed to evaluate the changes in microbiological communities present in sewage sludge (SS) when subjected to an electric field. The establishment of these relations is important to design and optimize an electrotechnology that not only promotes a direct degradation of the emerging organic contaminants, through electrodegradation, but also stimulates their biodegradation. Different current intensities were used continuously or by steps, in a two compartment electrodialytic (ED) cell. Samples collected between May and July of 2015 were analysed, prior to ED treatment, and the 35 Taxa identified were divided in 12 groups. Initial samples, collected on May, were mainly constituted by stalked ciliates (86%), followed by shelled amoebae (8%), whereas the samples collected between June and July presented higher number of shelled amoebae, between 52 and 92%. Epistylis, Vorticella and Arcella gibbosa were the most frequent protozoa identified. Samples richness (R) was between 7 and 14, Simpson’s biodiversity index (D) between 0.45 and 0.69, and evenness between 0.42 and 0.65. At the end of the ED experiments, a decrease in the number of identified Taxa and individuals was observed and, consequently, SS biodiversity also decreased. This decline was more pronounced in the ED experiments conducted with currents above 50 mA (0.10 mA cm^?2). In terms of abundance, the final SS was mainly constituted by shelled amoebae that showed to be the most resistant to the conditions within the ED cell. The obtained results showed that the studied conditions within the ED cell were not appropriate to the microbiological communities, which influenced the final SS quality.