Thermodynamic data from redox reactions at high temperatures. VI. Thermodynamic properties of CoO–MnO solid solutions from emf measurements

Activities of CoO in (Co,Mn)O solid solutions in contact with metallic Co have been determined on ten compositions ranging from 0.12 to 0.84 X_CoO in order to calibrate the divariant equilibrium between (Co,Mn)O oxide solutions and Co metal as an oxygen fugacity sensor for application in experimental petrology. Experiments were conducted over the temperature range 900–1300 K at 1 bar, using an electrochemical technique with oxygen-specific calcia-stabilized zirconia (CSZ) electrolytes. Co + CoO or Fe + FeO was used as the reference electrode. Compositions of the (Co,Mn)O solid solutions were measured after each run by electron microprobe, and these were checked for internal consistency by measuring the lattice parameter by X-ray diffraction. Activity–composition relations were fitted to the Redlich–Kister formalism. (Co,Mn)O solid solutions exhibit slight positive deviations from ideality, which are symmetrical (corresponding to a regular solution mixing model) across the entire composition range with A₀ ^G = 3690(±47) Jmol⁻¹. Excess entropies and enthalpies were also derived from the emf data and gave S^ex=0.77(±0.08) JK⁻¹mol⁻¹ and H^ex=4558(±90) Jmol⁻¹ respectively. The experimental data from this study have been used to formulate the (Co,Mn)O/Co oxygen fugacity sensor to give an expression: where μO₂ ^CoCoO=−492,186 + 509.322 T − 53.284 T lnT + 0.02518 T², taken from O'Neill and Pownceby (1993). Received: 10 September 1999 / Accepted: 4 April 2000     

Thermodynamic data from redox reactions at high temperatures. III. Activity-composition relations in Ni-Pd alloys from EMF measurements at 850–1250 K,and calibration of the NiO+Ni-Pd assemblage as a redox sensor

The assemblage NiO+Ni-Pd alloy has been calibrated as a precise oxygen fugacity sensor in the temperature range 850–1250 K at 1 bar, using an electrochemical technique with oxygen-specific CSZ electrolytes, and Ni+NiO and Cu+Cu₂O as the reference electrodes. Nine compositions were studied, ranging from 0.12 to 0.83 X _Ni ^alloy . Steady EMFs, implying equilibrium, were rapidly achieved in all cells, and were found to be reversible on increasing and decreasing temperature with a precision approaching 0.1 mV. The estimated accuracy of the measurements on each cell is ±0.2 mV (1, corresponding to ±0.003 log-bar units in fo₂ at 1273 K). Compositions of the Ni-Pd alloys were measured after each run by electron microprobe, and these compositions were then checked for internal consistency by measuring the lattice parameter by X-ray diffraction. Nickel-rich alloys show positive deviations from ideality and endothermic enthalpies of mixing, but palladium-rich compositions have exothermic enthalpies of mixing and strong negative deviations from ideality. The excess entropies of mixing are positive for all compositions, and correlate approximately with the excess volumes of mixing. The highly asymmetrical deviations from ideality are well described by a polynomial expression of the Redlich-Kister form, with three terms for the enthalpies, and two for the excess entropies and volumes of mixing. The experimental data from this study have been used to re-formulate the Ni-Pd oxygen fugacity sensor to give an expression; _O2 ^ss = _O2 ^NNO – 2RT ln X _Ni ^alloy – [2 · (1 – X _Ni ^alloy )² · [(–2165–7.958 · T) + (9409 – 0.888 · T) · (4 X _Ni ^alloy – 1) + 2089 · (6 X _Ni ^alloy – 1) · (2 X _Ni ^alloy – 1)]](850<T<1300) where _O2 ^ss is in J mol^-1, T is in kelvins, and the expression for _O2 ^NNO is that given by O'Neill and Pownceby (1993). Values in terms of log fo₂ may be obtained from the above by dividing by RT ln 10. The estimated standard error in _O2 ^ss is on the order of ±200 J mol^-1, which is approximately ±0.01 log-bar units in fo₂ at 1273 K.     

Revised estimate of δ34S for marine sulfates from the Upper Ordovician: data from the Williston Basin,North Dakota,U.S.A.

Analyses for δ³⁴S of 13 bedded, marine anhydrite samples from the “C” anhydrite member of the Red River Formation (Upper Ordovician) in the North Dakota portion of the Williston basin represent an addition of δ³⁴S data to a portion of the S isotope age curve with few data. Previously published estimates of δ³⁴S for Upper Ordovician marine sulfates apparently are limited to 4 samples from the Saskatchewan portion of the same basin. An adjusted mean value of +25.5‰ was calculated for all known Upper Ordovician δ³⁴S determinations. This value is approximately 2 to 3‰ lighter than the previous estimate, which suggests that δ³⁴S of the world ocean during the Upper Ordovician may have been lighter than previously thought. However, because all δ³⁴S data are from one sedimentary basin, additional S isotopic data from several globally-distributed evaporite basins are needed to evaluate this hypothesis and further constrain δ³⁴S for the Upper Ordovician. Similar re-examination of other portions of the S isotope age curve with limited amounts of data may increase our understanding of the secular variation in δ³⁴S.     

Early diagenesis in anaerobic lake sediments—II. Thermodynamic and kinetic factors controlling the formation of iron phosphate

The ion activity product of Fe and phosphate in interstitial waters from four sediment cores taken from Greifensee, Switzerland indicate the presence of vivianite [Fe₃(PO₄)₂ · 8 H₂O] in the solid phase. Analysis of the sediment using an electron microprobe and by electron microscopy revealed P-rich grains to be also enriched in Fe. The combined methods provide strong evidence that vivianite is forming authigenically in the sediments. Thermodynamic stability calculations demonstrate that the most stable Fe and phosphate minerals (pyrite, siderite and apatite) are not the ones controlling the pore water chemistry. The results emphasize the importance of rate processes of mineral formation in early diagenesis.Calculations based on the sediment phosphate concentration, and the degree of supersaturation of Fe and phosphate in the upper portion (0–15 cm) of the pore waters, indicate that the rate of vivianite mineral growth is controlled by a surface reaction rather than a diffusion mechanism. The response time of dissolved phosphate in the sediment pore waters with respect to mineral precipitation is on the order of 1–20 days. Less than 15% of the phosphate released by organic matter degradation at the sediment-water interface and below is retained in the sediments.     

Estimation of the composition of the Earth’s primary aqueous phase. 2. Synthesis from the mantle and igneous rock material. Comparison with synthesis from the carbonaceous chondrite material

Simulation results of the equilibrium state of systems water-carbonaceous chondrite material, water-primary mantle material, water-ultramafic rock material, and water-mafic rock material open with respect to carbon dioxide and methane at 25°C, 1 bar indicate that highly alkaline reduced aqueous solutions with K/Na > 1 can be formed only if water is in equilibrium with compositions close to those of continental crust and primitive mantle. Yu.V. Natochin’s hypothesis that the living cell can be formed only in an aqueous environment with K/Na > 1 leads to the conclusion that terrestrial life could arise and further evolve on the Earth during the differentiation of primary chondritic material into the Earth’s core and mantle (during the first few million years of the planet’s lifetime) in an alkaline (pH 9–10) reduced (Eh = −400–500 mV) aqueous solution at a temperature of 50–60°C, in equilibrium with an N₂-bearing atmosphere, which also contained CH₄ (partial pressure from 10⁻² to 10⁻⁸ bar), CO₂ (partial pressure from 10⁻⁵ to 10⁻⁸ bar), NH₃, H₂, H₂S, CO, and other gases.     

Trace and Rare Earth Element Distribution in Scheelite from the Cantung Tungsten Bearing Skarn Deposit, N.W.T. Canada: a Geometallurgical Analysis with Evidence from SEM and LA ICP-MS Analysis

Please refer to the attachment(s) for more details.     

On Liaoximordellidae Fam. Nov. (Coleoptera, Insecta) from the Jurassic of Western Liaoning, China

A new insect family Liaoximordellidae (fam. nov.) has been named for a well-preserved specimen which was collected from the Upper Jurassic outcropping west of Daxinfangzi Village, Lingyuan County, Liaoning Province. The specimen can not be put into Mordellidae or Praemordellidae because it possesses some original and intermediate characters in morphology. It serves the study of mordellid evolution. Besides, the fossil group associated with the insect is important for the stratigraphic division of the Mesozoic in western Liaoning.     

<Emphasis Type="Bold">Rhodophycean algae from the Lower Cretaceous of the Cauvery Basin,South India</Emphasis> by P.K. Misra,S. Kishore,S.K. Singh and A.K. Jauhri. Jour. Geol. Soc. India,v.73, 2009, pp.325–334

Discussion

Rhodophycean algae from the Lower Cretaceous of the Cauvery Basin, South India by P.K. Misra, S. Kishore, S.K. Singh and A.K. Jauhri. Jour. Geol. Soc. India, v.73, 2009, pp.325–334     

Thermodynamic properties of hematite — ilmenite — geikielite solid solutions

A solution model is developed for rhombohedral oxide solid solutions having compositions within the ternary system ilmenite [(Fe ₂₊ ^s Ti ₄₊ ^1–s ) ^A (Fe ₂₊ ^1–s Ti ₄₊ ^s ) ^B O₃]-geikielite [(Mg ₂₊ ^t Ti ₄₊ ^1–t ) ^A (Mg ₂₊ ^1–t Ti ₄₊ ^t ) ^B O₃]-hematite [(Fe³⁺) ^A (Fe³⁺) ^B O₃]. The model incorporates an expression for the configurational entropy of solution, which accounts for varying degrees of structural long-range order (0s, t1) and utilizes simple regular solution theory to characterize the excess Gibbs free energy of mixing within the five-dimensional composition-ordering space. The 13 model parameters are calibrated from available data on: (1) the degree of long-range order and the composition-temperature dependence of the transition along the ilmenite-hematite binary join; (2) the compositions of coexisting olivine and rhombohedral oxide solid solutions close to the Mg–Fe²⁺ join; (3) the shape of the miscibility gap along the ilmenite-hematite join; (4) the compositions of coexisting spinel and rhombohedral oxide solid solutions along the Fe²⁺–Fe³⁺ join. In the course of calibration, estimates are obtained for the reference state enthalpy of formation of ulvöspinel and stoichiometric hematite (–1488.5 and –822.0 kJ/mol at 298 K and 1 bar, respectively). The model involves no excess entropies of mixing nor does it incorporate ternary interaction parameters. The formulation fits the available data and represents an internally consistent energetic model when used in conjuction with the standard state thermodynamic data set of Berman (1988) and the solution theory for orthopyroxenes, olivines and Fe–Mg titanomagnetite-aluminate-chromate spinels developed by Sack and Ghiorso (1989, 1990a, b). Calculated activity-composition relations for the end-members of the series, demonstrate the substantial degree of nonideality associated with interactions between the ordered and disordered structures and the dominant influence of the miscibility gap across much of the ternary system. The predicted shape of the miscibility gap, and the orientation of tie-lines relating the compositions of coexisting phases, display the effects of coupling between the excess enthalpy of solution and the degree of long-range order. One limb of the miscibility gap follows the composititiontemperature surface corresponding to the ternary second-order transition.     

Two New“Notostracans”,Chenops gen.nov.and Jeholops gen.nov. (Crustacea:Branchiopoda:?Notostraca) from the Yixian Formation,Northeastern China

<正>The Early Cretaceous Jehol biota of northeastern China contains a diverse group of notostracans, including two genera,Chenops and Jeholops,described here.Chenops is characterized by a combination of an ovate carapace,narrow anal plate,equant distal endites and endopod on the anterior thoracic limbs.In addition to the new species,Chenops yixianensis,the genus also provisionally includes Prolepidurus oblongus Oleynikov, 1968.Jeholops,however,is monotypic,represented by the new species Jeholops hongi.It is characterized by a combination of kazacharthran and notostracan features unique to this taxon.Both new genera are provisionally placed in the taxon Notostraca.More detailed work exploring the morphology of exceptionally-preserved branchiopod crustaceans is needed.The difficulties in placing fossil notostracans into a phylogenetic framework are discussed.     

Geological Phenomenon of Yalguba Ridge Variolite from F. Yu. Levinson-Lessing’s Time until Today: Mineralogical and Geochemical Aspects

Geology of Ore Deposits - The Yalguba Ridge in Karelia is a reference geological object for studying Paleoproterozoic variolitic lavas. F. Yu. Levinson-Lessing—the prominent Russian...     

Chemical Composition of Ancient Celadon Material （1127-1279 A.D.） from Zhejiang, China and Its Implication

The microprobe EDXRF equipment was used for analysis of the major and trace elements in glaze layer-transitive layer-body layer of the celadon from the Altar Yao （Kiln） and Laohudong Yao in the Southern Song Dynasty （1127-1279 A.D.）, Zhejiang, China. The K values of the discriminant factor for the celadon wares are larger than 8, which means the celadon of the Altar Yao and Laohudong Yao are different from that of the Longquan Yao. The former two belong to the Guan Yao system （the Chinese imperial kilns）, but the latter to the Min Yao system （the Chinese popular kilns）. The principle component analysis shows their relationship between the Altar and Laohudong wares with provenance postulation. The thickness of the transitive layer in the Altar and Laohudong wares is obviously different, which reveals the microstructure characteristics of the celadon even though both kinds of wares belong to the imperial kiln system.     

Thermodynamic modeling of binary CH4–CO2 fluid inclusions

An equation of state (EOS) explicit in Helmholtz free energy has been improved to calculate the PVTx and vapor–liquid phase equilibrium properties of CH₄–CO₂ fluid mixture. This EOS, where four mixing parameters are used, is based on highly accurate EOSs recommended by NIST for pure components (CH₄ and CO₂) and contains a simple generalized departure function presented by Lemmon and Jacobsen (1999). Comparison with experimental data available indicates that the EOS can calculate both vapor–liquid phase equilibrium and volumetric properties of this binary fluid system with accuracy close to that of experimental data up to high temperature and pressure within full range of composition. The EOS of CH₄–CO₂ fluid, together with the updated Gibbs free energy model of solid CO₂ (dry ice), is applied to calculate the CH₄ content (x_CH4) and molar volume (V_m) of the CH₄–CO₂ fluid inclusion based on the assumption that the volume of an inclusion keeps constant during heating and cooling. $V_{\text{m}}-x_{{\text{CH}}_4}$ diagrams are presented, which describe phase transitions involving vapor, liquid and CO₂ solid phases of CH₄–CO₂ fluid inclusions. Isochores of CH₄–CO₂ inclusions at given $x_{{\text{CH}}_4}$ and V_m can be easily calculated from the improved EOS.     

<Emphasis Type="Bold">Paleoproterozoic Boninite-Like Rocks in an Intracratonic Setting from Northern Bastar Craton,Central India</Emphasis> by D.V. Subba Rao,V. Balaram,K. Naga Raju and D.N. Sridhar. Jour. Geol. Soc. India,v.72, 2008, pp.373–380

Discussion

Paleoproterozoic Boninite-Like Rocks in an Intracratonic Setting from Northern Bastar Craton, Central India by D.V. Subba Rao, V. Balaram, K. Naga Raju and D.N. Sridhar. Jour. Geol. Soc. India, v.72, 2008, pp.373–380     

<Emphasis Type="Bold">Synplutonic Mafic Dykes from Late Archaean Granitoids in the Eastern Dharwar Craton,Southern India</Emphasis> by M. Jayananda,T. Miyazaki,R.V. Gireesh,N. Mahesha and T. Kano. Jour. Geol. Soc. India,v.73, 2009, pp.117–130

Discussion

Synplutonic Mafic Dykes from Late Archaean Granitoids in the Eastern Dharwar Craton, Southern India by M. Jayananda, T. Miyazaki, R.V. Gireesh, N. Mahesha and T. Kano. Jour. Geol. Soc. India, v.73, 2009, pp.117–130