Megacrysts and xenoliths in kimberlite,Elliott County,Kentucky: A mantle sample from beneath the Permian Appalachian Plateau

Two kimberlite pipes in Elliott County contain rare ultramafic xenoliths and abundant megacrysts of olivine (Fo_85–93), garnet (0.21–9.07% Cr₂O₃), picroilmenite, phlogopite, Cr-poor clinopyroxene (0.56–0.88% Cr₂O₃), and Cr-poor orthopyroxene (<0.03–0.34% Cr₂O₃) in a matrix of olivine (Fo_88–92), picroilmenite, Cr-spinel, magnetite, perovskite, pyrrhotite, calcite, and hydrous silicates. Rare clinopyroxene-ilmenite intergrowths also occur. Garnets show correlation of mg (0.79–0.86) and CaO (4.54–7.10%) with Cr₂O₃ content; the more Mg-rich garnets have more uvarovite in solution. Clinopyroxene megacrysts show a general decrease in Cr₂O₃ and increase in TiO₂ (0.38–0.56%) with decreasing mg (0.87–0.91). Clinopyroxene megacrysts are more Cr-rich than clinopyroxene in clinopyroxene-ilmenite intergrowths (0.06–0.38% Cr₂O₃) and less Cr-rich than peridotite clinopyroxenes (1.39–1.46% Cr₂O₃). Orthopyroxene megacrysts and orthopyroxene inclusions in olivine megacrysts form two populations: high-Ca, high-Al (1.09–1.16% CaO and 1.16–1.18% Al₂O₃) and low-Ca, low-Al (0.35–0.46% CaO and 0.67–0.74% Al₂O₃). Three orthopyroxenes belonging to a low-Ca subgroup of the high-Ca, high-Al group were also identified (0.86–0.98% CaO and 0.95–1.01% Al₂O₃). The high-Ca, high-Al group (Group I) has lower mg (0.88–0.90) than low-Ca, low-Al group (Group II) with mg=0.92–0.93; low mg orthopyroxenes (Group Ia) have lower Cr₂O₃ and higher TiO₂ than high mg orthopyroxenes (Group II). The orthopyroxene megacrysts have lower Cr₂O₃ than peridotite orthopyroxenes (0.46–0.57% Cr₂O₃). Diopside solvus temperatures indicate equilibration of clinopyroxene megacrysts at 1,165°–1,390° C and 1,295°–1,335° C for clinopyroxene in clinopyroxene-ilmenite intergrowths. P-T estimates for orthopyroxene megacrysts are bimodal: high-Ca, high-Al (Group I) orthopyroxenes equilibrated at 1,165°–1,255° C and 51–53 kb (± 5kb) and the low-Ca, low-Al (Group II) orthopyroxenes equilibrated at 970°–1,020°C and 46–56 kb (± 5kb). Garnet peridotites equilibrated at 1,240°–1,360° C and 47–49 kb. Spinel peridotites have discordant temperatures of 720°–835° C (using spinel-olivine Fe/Mg) and 865°–1,125° C (Al in orthopyroxene).Megacrysts probably precipitated from a fractionating liquid at >150 km depth. They are not disaggregated peridotite because: (1) of large crystal size (up to 1.5 cm), (2) compositions are distinctly different from peridotite phases, and (3) they display fractionation trends. The high mg, low T orthopyroxenes and the clustering of olivine rims near Fo_89–90 reflect liquid changes to higher MgO contents due to (1) assimilation of wall-rock and/or (2) an increase in Fe³⁺/Fe²⁺ and subsequently MgO/FeO as a result of an increase in f _o.     

Temperature dependence of goethite dissolution promoted by trihydroxamate siderophores

This article reports an investigation of the temperature dependence of goethite dissolution kinetics in the presence of desferrioxamine B (DFO-B), a trihydroxamate siderophore, and its acetyl derivative, desferrioxamine D1 (DFO-D1). At 25 and 40°C, DFO-D1 dissolved goethite at twice the rate of DFO-B, whereas at 55°C, the behavior of the two ligands was almost the same. Increasing the temperature from 25 to 55°C caused little or no significant change in DFO-B or DFO-D1 adsorption by goethite. A pseudo-first-order rate coefficient for dissolution, calculated as the ratio of the mass-normalized dissolution rate coefficient to the surface excess of siderophore, was approximately the same at 25 and 40°C for both siderophores. At 55°C, however, this rate coefficient for DFO-D1 was about half that for DFO-B. Analysis of the temperature dependence of the mass-normalized dissolution rate coefficient via the Arrhenius equation led to an apparent activation energy that was larger for DFO-B than for DFO-D1, but much smaller than that reported for the proton-promoted dissolution of goethite. A compensation law was found to relate the pre-exponential factor to the apparent activation energy in the Arrhenius equation, in agreement with what has been noted for the proton-promoted dissolution of oxide minerals and for the complexation of Fe³⁺ by DFO-B and simple hydroxamate ligands in aqueous solution. Analysis of these results suggested that the siderophores adsorb on goethite with a only single hydroxamate group in bidentate ligation with an Fe(III) center.     

Manganese(III) binding to a pyoverdine siderophore produced by a manganese(II)-oxidizing bacterium

The possible roles of siderophores (high affinity chelators of iron(III)) in the biogeochemistry of manganese remain unknown. Here we investigate the interaction of Mn(III) with a pyoverdine-type siderophore (PVD_MnB1) produced by the model Mn(II)-oxidizing bacterium Pseudomonas putida strain MnB1. PVD_MnB1 confirmed typical pyoverdine behavior with respect to: (a) its absorption spectrum at 350-600 nm, both in the absence and presence of Fe(III), (b) the quenching of its fluorescence by Fe(III), (c) the formation of a 1:1 complex with Fe(III), and (d) the thermodynamic stability constant of its Fe(III) complex. The Mn(III) complex of PVD_MnB1 had a 1:1 Mn:pvd molar ratio, showed fluorescence quenching, and exhibited a light absorption spectrum (A_max = 408-410 nm) different from that of either PVD_MnB1-Fe(III) or uncomplexed PVD_MnB1. Mn(III) competed strongly with Fe(III) for binding by PVD_MnB1 in culture filtrates (pH 8, 4°C). Equilibration with citrate, a metal-binding ligand, did not detectably release Mn from its PVD_MnB1 complex at a citrate/PVD_MnB1 molar ratio of 830 (pH 8, 4°C), whereas pyrophosphate under the same conditions removed 55% of the Mn from its PVD_MnB1 complex. Most of the PVD_MnB1-complexed Mn was released by reaction with ascorbate, a reducing agent, or with EDTA, a ligand that is also oxidized by Mn(III). Data on the competition for binding to PVD_MnB1 by Fe(III) vs. Mn(III) were used to determine a thermodynamic stability constant (nominally at 4°C) for the neutral species MnHPVD_MnB1 (log K = 47.5 ± 0.5, infinite dilution reference state). This value was larger than that determined for FeHPVD_MnB1 (log K = 44.6 ± 0.5). This result has important implications for the metabolism, solubility, speciation, and redox cycling of manganese, as well as for the biologic uptake of iron.     

Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

Computer animation of center of mass coordinates obtained from 800 ps molecular dynamics simulations of Cs-smectite hydrates (1/3 and 2/3 water monolayers) provided information concerning the structure and dynamics of the interlayer region that could not be obtained through traditional simulation analysis methods. Cs⁺ formed inner sphere complexes with the mineral surface, and could be seen to jump from one attracting location near a layer charge site to the next, while water molecules were observed to migrate from the hydration shell of one ion to that of another. Neighboring ions maintained a partial hydration shell by sharing water molecules, such that a single water molecule hydrated two ions simultaneously for hundreds of picoseconds. Cs-montmorillonite hydrates featured the largest extent of this sharing interaction, because interlayer ions were able to inhabit positions near surface cavities as well as at their edges, close to oxygen triads. The greater positional freedom of Cs⁺ within the montmorillonite interlayer, a result of structural hydroxyl orientation and low tetrahedral charge, promoted the optimization of distances between cations and water molecules required for water sharing. Preference of Cs⁺ for locations near oxygen triads was observed within interlayer beidellite and hectorite. Water molecules also could be seen to interact directly with the mineral surface, entering its surface cavities to approach attracting charge sites and structural hydroxyls. With increasing water content, water molecules exhibited increased frequency and duration of both cavity habitation and water sharing interactions. Competition between Cs⁺ and water molecules for surface sites was evident. These important cooperative and competitive features of interlayer molecular behavior were uniquely revealed by animation of an otherwise highly complex simulation output.     

Feldspathic clasts in Yamato-86032: Remnants of the lunar crust with implications for its formation and impact history

Low concentrations of Th and Fe in the Yamato (Y)-86032 bulk meteorite support earlier suggestions that Y-86032 comes from a region of the moon far distant from the Procellarum KREEP Terrain (PKT), probably from the lunar farside. ³⁹Ar–⁴⁰Ar, Rb–Sr, Sm–Nd, and Sm-isotopic studies characterize the chronology of Y-86032 and its precursors in the mega regolith. One of the rock types present in a light gray breccia lithology is an anorthosite characterized by plagioclase with An 93, i.e., more sodic than lunar FANs, but with very low ⁸⁷Rb/⁸⁶Sr and ⁸⁷Sr/⁸⁶Sr similar to those of FANs. (FAN stands for Ferroan Anorthosite). This “An93 anorthosite” has Nd-isotopic systematics similar to those of nearside norites. A FAN-like “An97 anorthosite” is present in a second light-colored feldspathic breccia clast and has a more negative ε_Nd value consistent with residence in a LREE-enriched environment as would be provided by an early plagioclase flotation crust on the Lunar Magma Ocean (LMO). This result contrasts with generally positive values of ε_Nd for Apollo 16 FANs suggesting the possibility of assymetric development of the LMO. Other possible explanations for the dichotomy in ε_Nd values are advanced in the text. The Y-86032 protolith formed at least 4.43 ± 0.03 Ga ago as determined from a Sm–Nd isochron for mineral fragments from the breccia clast composed predominantly of An93 anorthosite and a second clast of more varied composition. We interpret the mineral fragments as being predominatly from a cogenetic rock suite. An ³⁹Ar–⁴⁰Ar age of 4.36–4.41 ± 0.035 Ga for a third clast composed predominantly of An97 anorthosite supports an old age for the protolith. Initial ¹⁴³Nd/¹⁴⁴Nd in that clast was −0.64 ± 0.13 ε-units below ¹⁴³Nd/¹⁴⁴Nd in reservoirs having chondritic Sm/Nd ratios, consistent with prior fractionation of mafic cumulates from the LMO. A maximum in the ³⁹Ar–⁴⁰Ar age spectrum of 4.23 ± 0.03 Ga for a second sample of the same feldspathic breccia clast probably reflects some diffusive ⁴⁰Ar loss. Lack of solar wind and lunar atmosphere implanted Ar in the light gray breccia clast allows determination of an ³⁹Ar/⁴⁰Ar age of 4.10 ± 0.02 Ga, which is interpreted as the time of initial brecciation of this litholgy. After correction for implanted lunar atmosphere ⁴⁰Ar, impact melt and dark regolith clasts give Ar ages of 3.8 ± 0.1 Ga implying melt formation and final breccia assembly 3.8 Ga ago. Some breccia lithologies were exposed to thermal neutron fluences of 2 × 10¹⁵ n/cm², only about 1% of the fluence experienced by some other lunar highlands meteorites. Other lithologies experienced neutron fluences of 1 × 10¹⁵ n/cm². Thus, Y-86032 spent most of the time following final brecciation deeply buried in the megaregolith. The neutron fluence data are consistent with cosmogenic ³⁸Ar_cos cosmic ray exposure ages of 10 Ma. Variations among differing lithologies in the amount of several regolith exposure indicators, including cosmogenic noble gas abundances, neutron capture induced variations in Sm isotopic abundances, and Ir contents, are consistent with a period of early (>3.8 Ga ago) lunar regolith exposure, subsequent deep burial at >5 m depth, and ejection from the moon 7–10 Ma ago.     

云南瓦渣钨矿区老君山花岗岩体的SHRIMP锆石U-Pb定年、地球化学特征及成因探讨

云南省瓦渣钨矿区位于老君山花岗岩体的东北接触带,属于滇东南-桂西白垩纪钨锡多金属成矿区中的组成部分。该矿床与矿区西部大面积分布的老君山第一期中粗粒二云二长花岗岩在时间和成因上有着密切联系。本文通过SHRIMP锆石U-Pb测年、岩石主量元素、微量元素和稀土元素的系统研究,进而探讨该花岗岩的形成年龄和动力学背景、岩石物质来源以及形成温度和压力。研究表明,与瓦渣钨矿床有关的中粗粒二云二长花岗岩属于高钾钙碱性岩系,为强过铝质S型花岗岩。岩体形成时代为83.3±1.5Ma,属于晚白垩世,形成于岩石圈伸展环境,其源岩为富粘土的泥质来源,其形成温度为875～900℃,压力约为7×108Pa,相当于深度为26km。     

GPS/INS navigation precision and its effect on airborne radio occultation retrieval accuracy

An airborne radio occultation (RO) system has been developed to retrieve atmospheric profiles of refractivity, moisture, and temperature. The long-term objective of such a system is deployment on commercial aircraft to increase the quantity of moisture observations in flight corridors in order to improve weather forecast accuracy. However, there are several factors important to operational feasibility that have an impact on the accuracy of the airborne RO results. We investigate the effects of different types of navigation system noise on the precision of the retrieved atmospheric profiles using recordings from the GNSS Instrument System for Multistatic and Occultation Sensing (GISMOS) test flights, which used an Applanix POS/AV 510 Global Positioning System (GPS)/Inertial Navigation System (INS). The data were processed using a carrier phase differential GPS technique, and then the GPS position and inertial measurement unit data were combined in a loosely coupled integrated inertial navigation solution. This study quantifies the velocity precision as a function of distance from GPS reference network sites, the velocity precision with or without an inertial measurement unit, the impact of the quality of the inertial measurement unit, and the compromise in precision resulting from the use of real-time autonomous GPS positioning. We find that using reference stations with baseline lengths of up to 760?km from the survey area has a negligible impact on the retrieved refractivity precision. We also find that only a small bias (less than 0.5% in refractivity) results from the use of an autonomous GPS solution rather than a post-processed differential solution when used in an integrated GPS/INS system. This greatly expands the potential range of an operational airborne radio occultation system, particularly over the oceans, where observations are sparse.     

Brachinites: Igneous rocks from a differentiated asteroid

Abstract— We have done petrologic studies of brachinites Allan Hills (ALH) 84025, Elephant Moraine (EET) 99402, and EET 99407; bulk geochemical studies of EET 99402 and EET 99407; Ar‐Ar studies of Brachina and EET 99402; and a Xe isotopic study of Brachina. Textural, mineral compositional, and bulk compositional evidence show that EET 99402 and EET 99407 are paired. ALH 84025, EET 99402, and EET 99407 have igneous textures. Petrofabric analyses of ALH 84025 and EET 99407 demonstrate the presence of lineations and probable foliations of olivine grains that support formation as igneous cumulates. Mineral minor element chemistry and bulk rock incompatible lithophile element contents of the brachinites are distinct from those of acapulcoitelodranite clan meteorites, a suite of high‐grade metamorphic rocks and anatectic residues. The differences demonstrate a higher blocking temperature of equilibration for the brachinites and that cumulus plagioclase is present in EET 99402, EET 99407, and probably ALH 84025, thus indicating an igneous origin. Brachinites are differentiated, ultramafic achondrites, and are not part of a suite of primitive achondrites. We infer that their parent asteroid is a differentiated body. Brachina has an excess of ¹²⁹Xe correlated with reactor‐produced ¹²⁸Xe, demonstrating that short‐lived ¹²⁹I was present at the time of formation. This, plus literature data, attests to early formation of the brachinites, within a few Ma of the formation of chondrites. Ar‐Ar age data show that Brachina and EET 99407 were degassed about 4.13 Ga ago, possibly by a common impact event. EET 99402 and EET 99407 show petrographic evidence for shock, including possible conversion of plagioclase to maskelynite followed by devitrification. Brachina is unshocked, making a direct association between the Ar‐Ar age and textures ambiguous.     

The SEASWAB experiment

Abstract

SEASWAB is one element of the Delta Project of the U.S. Geological Survey, a cooperative effort with several universities and other governmental agencies to investigate the processes that cause marine‐sediment instability. The basic purpose of the SEASWAB experiment was to obtain field measurements of sediment motion and pore‐pressure variations in soft sediment affected by wave‐pressure perturbations. This article serves as an introduction to the six papers that follow and that together make up a report on the results of SEASWAB.     

Low-frequency dilatational wave propagation through fully-saturated poroelastic media

The strong coupling of applied stress and pore fluid pressure, known as poroelasticity, is relevant to a number of applied problems arising in hydrogeology and reservoir engineering. The standard theory of poroelastic behavior in a homogeneous, isotropic, elastic porous medium saturated by a viscous, compressible fluid is due to Biot, who derived a pair of coupled partial differential equations that accurately predict the existence of two independent dilatational (compressional) wave motions, corresponding to in-phase and out-of-phase displacements of the solid and fluid phases, respectively. The Biot equations can be decoupled exactly after Fourier transformation to the frequency domain, but the resulting pair of Helmholtz equations cannot be converted to partial differential equations in the time domain and, therefore, closed-form analytical solutions of these equations in space and time variables cannot be obtained. In this paper we show that the decoupled Helmholtz equations can in fact be transformed to two independent partial differential equations in the time domain if the wave excitation frequency is very small as compared to a critical frequency equal to the kinematic viscosity of the pore fluid divided by the permeability of the porous medium. The partial differential equations found are a propagating wave equation and a dissipative wave equation, for which closed-form solutions are known under a variety of initial and boundary conditions. Numerical calculations indicate that the magnitude of the critical frequency for representative sedimentary materials containing either water or a nonaqueous phase liquid is in the kHz–MHz range, which is generally above the seismic band of frequencies. Therefore, the two partial differential equations obtained should be accurate for modeling elastic wave phenomena in fluid-saturated porous media under typical low-frequency conditions applicable to hydrogeological problems.