Fe-Mn partitioning between garnet and ilmenite: experimental calibration and applications

A new mineralogic geothermometer based on the partitioning of Fe and Mn between garnet and ilmenite has been calibrated by reversal experiments in the P-T range 600–900° C, 2 and 5 kbars and for fO₂=QFM. The results constitute a sensitive geothermometer applicable over a broad range of composition and conditions. Garnetilmenite thermometry has advantages relative to existing geothermometers because of its accurate calibration, marked temperature sensitivity and the chemical and structural simplicity of the crystalline solutions involved. Application to natural assemblages reveals that the garnet-ilmenite geothermometer yields temperatures that agree well with other estimates. The reactivity of, and relatively rapid Fe-Mn diffusion in ilmenite may lead to retrograde resetting of high temperature partition values, but these factors may be useful for estimating rock cooling rates. Analysis of the experimental data indicates minor positive deviations from ideality for Fe-Mn garnets and ilmenites. Absolute magnitudes of interaction parameters (W _AB) derived from a regression analysis are subject to considerable uncertainty. The partition coefficient is, however, strongly dependent on the difference between solution parameters. These differences are well constrained with a magnitude of W _FeMn ^ilm –W _FeMn ^gar 300 cal mol^–1. The accuracy and applicability of garnet-ilmenite thermometry will improve with the availability of better thermodynamic data for garnet crystalline solutions.Abbreviations and symbols used in text R universal gas constant (cal/mol/°K) - T absolute temperature (°K or °C) - P pressure (kbars) - V ⁰ volume change of reaction (1) - H _{1, T} ⁰ standard state enthalpy change of reaction (1) at 1 bar and the T of interest, in cal/mole - S _T ⁰ entropy change of reaction (1) at T of interest, in cal/mole/°K - G _P,T ⁰ standard free energy change of reaction (1) at the T and P of interest, in cal/mole - distribution coefficient for Fe-Mn partitioning between garnet and ilmenite - K apparent equilibrium coefficient for reaction (1) - _i ^j activity of component i in phase j - W _A-B binary A-B interaction (Margules) parameter - gar garnet - ilm ilmenite - biot biotite - ol olivine - opx orthopyroxene     

The heat-capacity of ilmenite and phase equilibria in the system Fe-T-O

Low temperature adiabatic calorimetry and high temperature differential scanning calorimetry have been used to measure the heat-capacity of ilmenite (FeTiO₃) from 5 to 1000 K. These measurements yield S₂₉₈⁰ = 108.9 J/(mol · K). Calculations from published experimental data on the reduction of ilmenite yield Δ₂₉₈⁰(I1) = ?1153.9 kJ/(mol · K). These new data, combined with available experimental and thermodynamic data for other phases, have been used to calculate phase equilibria in the system Fe-Ti-O. Calculations for the subsystem Ti-O show that extremely low values of $\text{?O}{}_2$ are necessary to stabilize TiO, the mineral hongquiite reported from the Tao district in China. This mineral may not be TiO, and it should be re-examined for substitution of other elements such as N or C. Consideration of solid-solution models for phases in the system Fe-Ti-O allows derivation of a new thermometer/oxybarometer for assemblages of ferropseudobrookite-pseudobrookite_ss and hematite-ilmenite_ss. Preliminary application of this new thermometer/oxybarometer to lunar and terrestrial lavas gives reasonable estimates of oxygen fugacities, but generally yields subsolidus temperatures, suggesting re-equilibration of one or more phases during cooling.     

Estimation of in-situ hydraulic diffusivity of rock masses

A method of estimating in-situ hydraulic diffusivity of rock masses by means of well-injection history and frequency of induced seismicity is presented. The method is based on the diffusion of injected fluid from a spherical cavity in a poroelastic half-space and the effective stress theory, as proposed byTerzaghi (1925, 1936) andHubbert andRubey (1959). Application of the method to two different regions, one in western New York and the other in Japan, resulted in estimated diffusivities of the order 10³ and 10⁴ cm²/sec, respectively. These values lie within the range of published estimates of in-situ diffusivity by other means, a summary of which is presented in tabular form. The calculated diffusivities suggest that the characteristic time of fluid diffusion is close to 0.1, rather than unity, as is sometimes assumed in the literature.     

A simple method of magnetic declination fluctuation correction for long single-streamer positioning in a seismic survey

In single‐streamer acquisition, the use of acoustic transducers to constrain the receiver positions is not possible, thus implying the use of compass birds to gather information on the streamer location. The compasses are, however, sensitive to the declination of the local magnetic field of the earth, and local fluctuations not accounted for can degrade the accuracy of reconstructed positions. In order to correct these small‐scale fluctuations, we propose a simple deterministic method to calculate a spatial correction to apply to the compasses that enhances the positioning accuracy. The local compass declination is calculated after a first reconstruction on the whole survey area. This method was applied with success to navigation data from a 3D survey offshore Japan, and the positioning accuracy was improved to the level of the DGPS accuracy.     

Experimental Research on the Load／Unload Response Ratio （LURR） Theory

Implementing acoustic emission experiments with large rock samples, LURR (Load/Unload Response Ratio) theory was studied. The loading conditions in the experiments were designed to simulate the complicated loading process of underground rocks. The damages emerging inside the rock samples were recorded by the acoustic emission technique during the loading process. The experimental results were consistent with prediction by LURR theory. Integrating the changing processes of LURR value Y and the location process of acoustic emission events showed agreement between the variation of LURR value Y and the damage evolution inside the rocks. Furthermore, the high value of Y emerged before the complete breakdown of materials. Therefore, the damage evolution of rock specimen can be quantitatively analyzed with LURR theory, thus the failure of the rock materials and the earthquake occurrence may be predicted. The experimental results gave a further verification of LURR theory.     

Relationship between shell weight and cadmium content in whole digestive gland of the Japanese scallop Patinopecten yessoensis (Jay)

Seasonal and age-specific variations of cadmium (Cd) concentration in the digestive gland were investigated in the Japanese scallop Patinopecten yessoensis from Peter the Great Bay, Sea of Japan, with different degrees of Cd pollution. The seasonal changes in Cd concentrations of the digestive gland were inversely proportional to the dry weight of the gland. Concentrations of Cd and total Cd content (mug Cd per organ) increased with age (age-specific) to the same extent in contaminated and uncontaminated areas. There was also a strong positive correlation between Cd content in the whole digestive gland and shell weight and it is proposed that this relationship can be used as a new criterion for comparative evaluation of Cd levels in scallops from different areas We hypothesize that Cd is uptaken into scallops in proportion to the amount of calcium that absorbed through ion channels, and in addition, Cd in the digestive gland is in immobile forms (e.g. metal-rich granules) that accumulate with age. Moderate environmental pollution has no effect on the relationship between Cd content and shell size and the observed decrease in growth performance of the scallops from polluted areas may be due to other factors.     

Spectroscopic and photometric observations of symbiotic nova PU Vul during 2009–2016

A new set of low-resolution spectral and UBVJHKL-photometric observations of the symbiotic nova PU Vul is presented. The binary has been evolving after its symbiotic nova outburst in 1977 and now it is in the nebular stage. It is found that the third orbital cycle(after 1977) was characterized by great changes in associated light curves. Now, PU Vul exhibits a sine-wave shape in all the light curves(with an amplitude in the U band of about 0.7 mag), which is typical for symbiotic stars in the quiescent state. Brightness variability due to pulsations of the cool component is now clearly visible in the VRI light curves. The amplitude of the pulsations increases from 0.5 mag in the V band to 0.8 mag in the I band. These two types of variability, as well as a very slow change in the physical parameters of the hot component due to evolution after the outburst of 1977, influence the spectral energy distribution(SED)of the system. The variability of emission lines is highly complex. Only hydrogen line fluxes vary with orbital phase. An important feature of the third orbital cycle is the first emergence of the OVI, 6828  Raman scattering line. We determine the temperature of the hot component by means of the Zanstra method applied to the He II, 4686  line. Our estimate is about 150 000 K for the spectrum obtained near orbital maximum in 2014. The VO spectral index derived near pulsation minimum corresponds to M6 spectral class for the cool component of PU Vul.     

Intrinsic nonlinearity and method of disturbed observations in inverse problems of celestial mechanics

Orbit determination from a small sample of observations over a very short observed orbital arc is a strongly nonlinear inverse problem. In such problems an evaluation of orbital uncertainty due to random observation errors is greatly complicated, since linear estimations conventionally used are no longer acceptable for describing the uncertainty even as a rough approximation. Nevertheless, if an inverse problem is weakly intrinsically nonlinear, then one can resort to the so-called method of disturbed observations (aka observational Monte Carlo). Previously, we showed that the weaker the intrinsic nonlinearity, the more efficient the method, i.e. the more accurate it enables one to simulate stochastically the orbital uncertainty, while it is strictly exact only when the problem is intrinsically linear. However, as we ascertained experimentally, its efficiency was found to be higher than that of other stochastic methods widely applied in practice. In the present paper we investigate the intrinsic nonlinearity in complicated inverse problems of Celestial Mechanics when orbits are determined from little informative samples of observations, which typically occurs for recently discovered asteroids. To inquire into the question, we introduce an index of intrinsic nonlinearity. In asteroid problems it evinces that the intrinsic nonlinearity can be strong enough to affect appreciably probabilistic estimates, especially at the very short observed orbital arcs that the asteroids travel on for about a hundredth of their orbital periods and less. As it is known from regression analysis, the source of intrinsic nonlinearity is the nonflatness of the estimation subspace specified by a dynamical model in the observation space. Our numerical results indicate that when determining asteroid orbits it is actually very slight. However, in the parametric space the effect of intrinsic nonlinearity is exaggerated mainly by the ill-conditioning of the inverse problem. Even so, as for the method of disturbed observations, we conclude that it practically should be still entirely acceptable to adequately describe the orbital uncertainty since, from a geometrical point of view, the efficiency of the method directly depends only on the nonflatness of the estimation subspace and it gets higher as the nonflatness decreases.     

Provenance of temper in a New Kingdom Egyptian pottery sherd: Evidence from the petrology and mineralogy of basalt fragments

A New Kingdom spinning bowl from Karnak (Luxor) Egypt is similar in form to spinning bowls commonly found at other Egyptian sites and has a bulk chemical composition in the range for other Egyptian marl vessels. These data support a domestic origin. The matrix of the bowl contains unaltered, sand-sized, mafic rock fragments with volcanic, subophitic textures. Over 20% of the sand-sized grains consist of angular, unweathered rock fragments, and of these ∼20% are volcanic. Apparently they were added as temper. Electron microprobe analyses show that augite, plagioclase, and, where present, pigeonite, in nine of these have compositions typical of mafic igneous rocks. Geothermometry confirms crystallization at ∼1100°C. Pyroxene discrimination diagrams indicate geological sources ranging from within-plate alkali basalts to within-plate, continental tholeiites. Suitable sources for the temper are rare in Egypt. Both alkaline and tholeiitic, postorogenic (unaltered) late Cenozoic basalts occur in the Cairo area, making this the most likely but not the only possible source for the temper. The pottery may have also originated in Cairo because raw rock materials were moved upstream less commonly than down the Nile. A Cairo provenance for the Karnak artifact is consistent with the everyday movement of people and goods along the Nile between the ancient twin capitals of Memphis and Thebes. These results and the common occurrence of volcanic rocks as temper indicate that microbeam analytical techniques may help narrow the provenance of ancient pottery. © 1998 John Wiley & Sons, Inc.