Prediction of iodate adsorption and surface speciation on oxides by surface complexation modeling

Aqueous iodine species occur mainly as iodide (I⁻) and iodate (IO₃⁻), depending on redox conditions. The adsorption of IO₃⁻ on naturally occurring oxides under oxic conditions is of environmental concern. The adsorption behaviors of IO₃⁻ by hydrous ferric oxide (HFO), α-FeOOH, and γ-Al₂O₃ were examined in this study as functions of pH, ionic strength, and solid concentration. Adsorption data were analyzed using an extended triple-layer model (ETLM) for surface complexation modeling to infer IO₃⁻ adsorption reactions and equilibrium constants. Results of ETLM analysis suggest that adsorption of IO₃⁻ is both an outer-sphere and an inner-sphere process, as expressed by the following complexation reactions, which are consistent with the independent pressure jump kinetic results and adsorption enthalpy measurements

     

Paleomagnetic field intensity derived from meteorite magnetization

The paleomagnetic field intensity is estimated with the aid of the Koenigsberger-Thellier method for four ordinary chondrites and one carbonaceous chondrite by assuming that the stable NRM component of these meteorites is attributable to the TRM acquired in a low-temperature range (lower than about 400°C) during their extremely-slow cooling process. The results are summarized in Table IV, where the paleomagnetic field intensity ranges from 0.10 to 0.97 Oe.Possible effects of the extremely-slow cooling rate of meteorites and the secondary TRM acquisition of the surface fusion crust upon the original NRM of the meteorite interior are discussed.     

Meteorite magnetism and the early solar system magnetic field

The ferromagnetism of irons, stony-irons, E-, H-, L- and LL-chondrites and achondrites is due to a metallic phase comprising mostly Fe and Ni and small amounts of Co and P. The ferromagnetic constituent in non-metamorphosed C-chondrites is magnetite, but some metamorphosed C-chondrites contain FeNi metallic grains too.

Among the stony meteorites, the content of metals as determined by their saturation magnetization (I_S) sharply decreases in the order E → H → L → LL → achondrites, whereas the I_S value for magnetite and additional metals in C-chondrites ranges from the I_S value of achondrites to that of L-chondrites.

With an increase of Ni-content in the metallic phase in chondrites of the order E → H → L → LL → C, the relative amount of Ni-poor kamacite magnetization, I_S(), in the total I_S decreases in the same order, from I_S()/I_S 1 for E-chondrites to I_S()/I_S 0 for C-chondrites. Thus, E-, H-, L-, LL- and C-chondrites and achondrites are well separated in a diagram of I_S()/I_S versus I, which could be called a magnetic classification diagram for stony meteorites.

As the surface skin layer of all meteorites is anomalously magnetized, it must be removed and the natural remanent magnetization (NRM) of the unaltered interior only must be examined for the paleomagnetic study. The NMR of C-chondrites is highly stable and that of achondrites is reasonably stable against AF-demagnetization, whereas the NMR of E-chondrites and ordinary chondrites as well as stony-iron meteorites is not very stable in most cases. Although the NRM of iron meteorites is reasonably stable, it is not attributable to the extraterrestrial magnetic field.

The paleointensity for Allende C₃-chondrite is estimated to be about 1.0 Oe assuming that its NRM is of TRM origin. The paleointensity for other reasonably reliable C-chondrites (Orgueil, Mighei, Leoville and Karoonda) is also around 1 Oe.

The paleointensity for two achondrites has been determined to be about 0.1 Oe. The NRM of other achondrites also suggests that their paleointensity is roughly 0.1 Oe.

The NRM of ordinary chondrites is less stable than that of C-chondrites and achondrites so that the estimated paleointensity for ordinary chondrites is less reliable. The paleointensity for comparatively reliable ordinary chondrites ranges from 0.1 to 0.4 Oe.

The paleointensity values of 1 Oe for C-chondrites and 0.1 Oe for achondrites may represent the early solar nebula magnetic field about 4.5 × 10⁹ years ago. A possibility that the paleomagnetic field for achondrites was a magnetic field attributable to a dynamo within a metallic core of their parent planet may also not be rejected.     

Partitioning of elements between majorite garnet and melt and implications for petrogenesis of komatiite

Partitioning of elements between majorite garnet and ultrabasic melt has been studied at 16 GPa and 1950° C. Ca, Ti, La, Sm, Gd, Zr, Hf, Fe, Ni, Mn, K, and Na are enriched in the melt, whereas Al, Cr, V, Sc and Yb are concentrated in majorite garnet. Thus, majorite garnet fractionation by partial melting could produce chemical heterogeneities in these elements deviating from chondritic abundance. Using the partitioning behaviour of elements between majorite garnet and ultrabasic melt, the petrogenesis of komatiite is discussed. A simple model to explain the chemical varieties of komatiites is as follows. Aluminadepleted komatiite was generated by partial melting of the primitive mantle at 200–650 km depth, and alumina-enriched komatiite is the product of remelting of the residual solid at the same depths, whereas alumina-undepleted komatiite was formed by partial melting of the primitive upper mantle at depths shallower than 200 km. We suggest the possibility of large-scale chemical layering or heterogeneity in the early Archean upper mantle as an alternative model for komatiite genesis; shallower mantle depleted in majorite garnet and the underlying mantle enriched in majorite garnet. Alumina-depleted and alumina-enriched komatiites in the early Archean might be generated by a high degree of partial melting of the layered mantle. Such chemical layering could have been homogenized by the late Archean. This explains the observations that alumina-depleted and alumina-enriched komatiites were generally formed in the early Archean but alumina-undepleted komatiite was erupted in the late Archean.     

Skewed Water Temperature Occurrence Frequency in the Sea off Sanriku, Japan, and Intrusion of the Pure Kuroshio Water

Temperature and salinity data obtained by the Iwate Fisheries Technology Center were analyzed for the period 1971–1995. It was found that occurrence frequency distributions of temperature and salinity are very skewed at depths deeper than 200 m and that temperature sometimes exceeds m + 5σ (m: mean and σ: standard deviation. If such abnormally high temperatures are real the 3σ criterion cannot be adopted. Oceanic conditions were surveyed in 1972 and 1979, when temperatures exceeding m + 5σ were observed. It was found that the abnormally high temperature (and high salinity) water was the pure Kuroshio Water introduced into the region due to some special conditions such as abnormal approach of large warm-core ring to the Sanriku Coast or abnormal northward extension of the Kuroshio along the coast. These events are very rare, occurring only twice in the 25-year period analyzed, but the abnormally high temperature observed is real. This revised version was published online in July 2006 with corrections to the Cover Date.     

Precise estimation of pressure–temperature paths from zoned minerals using Markov random field modeling: theory and synthetic inversion

The chemical zoning profile in metamorphic minerals is often used to deduce the pressure–temperature (P–T) history of rock. However, it remains difficult to restore detailed paths from zoned minerals because thermobarometric evaluation of metamorphic conditions involves several uncertainties, including measurement errors and geological noise. We propose a new stochastic framework for estimating precise P–T paths from a chemical zoning structure using the Markov random field (MRF) model, which is a type of Bayesian stochastic method that is often applied to image analysis. The continuity of pressure and temperature during mineral growth is incorporated by Gaussian Markov chains as prior probabilities in order to apply the MRF model to the P–T path inversion. The most probable P–T path can be obtained by maximizing the posterior probability of the sequential set of P and T given the observed compositions of zoned minerals. Synthetic P–T inversion tests were conducted in order to investigate the effectiveness and validity of the proposed model from zoned Mg–Fe–Ca garnet in the divariant KNCFMASH system. In the present study, the steepest descent method was implemented in order to maximize the posterior probability using the Markov chain Monte Carlo algorithm. The proposed method successfully reproduced the detailed shape of the synthetic P–T path by eliminating appropriately the statistical compositional noises without operator’s subjectivity and prior knowledge. It was also used to simultaneously evaluate the uncertainty of pressure, temperature, and mineral compositions for all measurement points. The MRF method may have potential to deal with several geological uncertainties, which cause cumbersome systematic errors, by its Bayesian approach and flexible formalism, so that it comprises potentially powerful tools for various inverse problems in petrology.