The formation and chronology of the PAT 91501 impact-melt L chondrite with vesicle-metal-sulfide assemblages

The L chondrite Patuxent Range (PAT) 91501 is an 8.5-kg unshocked, homogeneous, igneous-textured impact melt that cooled slowly compared to other meteoritic impact melts in a crater floor melt sheet or sub-crater dike [Mittlefehldt D. W. and Lindstrom M. M. (2001) Petrology and geochemistry of Patuxent Range 91501 and Lewis Cliff 88663. Meteoritics Planet. Sci. 36, 439-457]. We conducted mineralogical and tomographic studies of previously unstudied mm- to cm-sized metal-sulfide-vesicle assemblages and chronologic studies of the silicate host. Metal-sulfide clasts constitute about 1 vol.%, comprise zoned taenite, troilite, and pentlandite, and exhibit a consistent orientation between metal and sulfide and of metal-sulfide contacts. Vesicles make up ∼2 vol.% and exhibit a similar orientation of long axes. ³⁹Ar-⁴⁰Ar measurements probably date the time of impact at 4.461 ± 0.008 Gyr B.P. Cosmogenic noble gases and ¹⁰Be and ²⁶Al activities suggest a pre-atmospheric radius of 40-60 cm and a cosmic ray exposure age of 25-29 Myr, similar to ages of a cluster of L chondrites. PAT 91501 dates the oldest known impact on the L chondrite parent body. The dominant vesicle-forming gas was S₂ (∼15-20 ppm), which formed in equilibrium with impact-melted sulfides. The meteorite formed in an impact melt dike beneath a crater, as did other impact melted L chondrites, such as Chico. Cooling and solidification occurred over ∼2 h. During this time, ∼90% of metal and sulfide segregated from the local melt. Remaining metal and sulfide grains oriented themselves in the local gravitational field, a feature nearly unique among meteorites. Many of these metal-sulfide grains adhered to vesicles to form aggregates that may have been close to neutrally buoyant. These aggregates would have been carried upward with the residual melt, inhibiting further buoyancy-driven segregation. Although similar processes operated individually in other chondritic impact melts, their interaction produced the unique assemblage observed in PAT 91501.     

Molecular dynamics simulations of kinetic isotope fractionation during the diffusion of ionic species in liquid water

Interpretation of isotope ratios, a powerful tool in geochemical investigations of fluid-rock systems, requires an understanding of all relevant processes that fractionate isotopes. One such process, diffusion in liquid water, has remained problematic despite its potential significance as a major cause of kinetic isotope fractionation. Recent laboratory experiments published by [Richter, F. M., Mendybaev, R. A., Christensen, J. N., Hutcheon, I. D., Williams, R. W., Sturchio, N. C., and Beloso Jr., A. D. (2006) Kinetic isotopic fractionation during diffusion of ionic species in water. Geochim. Cosmochim. Acta70, 277-289.] have shown clearly for the first time that lithium and chloride isotopes are fractionated by diffusion in liquid water, whereas magnesium isotopes are not. In the present paper, we present the results of molecular dynamics simulations of lithium, chloride, and magnesium diffusion in liquid water that were designed to provide molecular-scale insight into the experimental findings of Richter et al. (2006). Our results indicate that the self-diffusion coefficients of lithium, chloride, and magnesium isotopes follow an inverse power-law dependence on ion mass (, where D_i is the self-diffusion coefficient of a solute with isotopic mass m_i). The power-law exponents (β) deduced for lithium, chloride, and magnesium from the diffusivity data of Richter et al. (2006) are consistent with the mass dependencies found in our simulations. Further analysis of our simulation results showed that the experimental β-values are inversely related to the residence times of water molecules in the first solvation shells of the diffusing ions, as expected from mode-coupling and renormalized kinetic theories.     

The exceptionally stable cobalt(III)–desferrioxamine B complex

The biogeochemistry of trivalent iron, manganese, and cobalt in the oceans is dominated by soluble complexes formed with high-affinity organic ligands that are believed to be microbial siderophores or similar biogenic chelating agents. Desferrioxamine B (DFOB), a trihydroxamate siderophore found in both terrestrial and marine environments, has served as a useful model for a large class of microbial siderophores in studies of 1:1 complexes formed with trivalent iron and manganese. However, no data exist concerning DFOB complexes with Co(III), which we hypothesize should be as strong as those with Fe(III) and Mn(III) if the current picture of the ocean biogeochemistry of the three trivalent metals is accurate. We investigated the complexation reaction between DFOB and Co(III) in aqueous solution at seawater pH using base and redox titrations, and then characterized the resulting 1:1 complex Co(III)HDFOB⁺ using X-ray absorption, resonance Raman spectroscopy, and quantum mechanical structural optimizations. We found that the complex stability constant for Co(III)HDFOB⁺ (log K _{[Co(III)HDFOB⁺]} = 37.5 ± 0.4) is in fact five and seven orders of magnitude larger than that for Fe(III)HDFOB⁺ (log K_{[Fe(III)HDFOB⁺]} = 32.02) and Mn(III)HDFOB⁺ (log K_{[Mn(III)HDFOB}⁺_] = 29.9), respectively. Spectroscopic data and the supporting theoretical structural optimizations elucidated the molecular basis for this exceptional stability. Although not definitive, our results nevertheless are consistent with the evolution of siderophores as a response by bacteria to oxygenation, not only because of sharply decreasing concentrations of Fe(III), but also of Co(III).     

Use of paleolimnology to document the effect of lake shoreland development on water quality

Four Wisconsin, USA lakes were examined with paleolimnological techniques to determine the effects of shoreland development on water quality. Geochemical parameters such as aluminum, iron, manganese, phosphorus, nitrogen, and carbon were used to document watershed inputs while redox sensitive elements provided information on changes in hypolimnetic oxygen levels. Changes in the diatom community were used to assess the impacts of development upon the lakes' trophic status as well as changes in the littoral community. We assessed the relative sensitivity of high vs. low ANC lakes.The initial shoreland development, late in the 19^th or early in the 20^th century, involved seasonal cabins and minimal disturbance of the shoreland. This development phase had minimal impact upon the lakes compared to that during the mid- and late-twentieth century. Increased levels of iron and aluminum indicated the highest input of sediment occurred during the construction phase of converting shoreland homes from seasonal to year-round usage. Phosphorus deposition increased moderately in the high alkalinity lakes but more so in the low alkalinity lakes. In the low alkalinity stratified lake, increased levels of iron and manganese in the last decade indicated more anoxia in the hypolimnion. Phosphorus levels have also increased during this time period most likely as a result of elevated phosphorus release from the sediments.In the high alkalinity lakes, as the nutrient levels increased, diatom production initially shifted from benthic taxa of the family Fragilariaceae to metalimnetic taxa and as nutrients increased further, epilimnetic species. In the low alkalinity lakes, prior to settlement the major site of diatom prodution was the open water. Coincidental with the early shoreland development was an increase of macrophyte density as indicated by the epiphytic diatom Achnanthidium minutissimum ((Kützing) Czarnecki (= Achnanthes minutissima Kützing). The water quality in the high alkalinity lakes showed some improvement following completion of the home construction phase, especially in the lake with lower development density. The low alkalinity lakes did not show improved water quality and appear more sensitive to shoreland development.     

Biological components of Ross Sea short-term particle fluxes in the austral summer of 1995–1996

The Ross Sea, a region of high seasonal production in the Southern Ocean, is characterized by blooms of the haptophyte Phaeocystis antarctica and of diatoms. The different morphology, structural composition and consumption of these two phytoplankton by grazing zooplankton may result in different carbon cycling dynamics and carbon flux from the euphotic zone. We sampled short-term (2 days) particle flux at 5 sites from 177.6°W to 165°E along a transect at 76.5°S with traps placed below the euphotic zone at 200 m during December 1995–January 1996. We estimated carbon flux of as many eucaryotic organisms and fecal pellets as possible using microscopy for counts and measurements and applying volume:carbon conversions from the literature. Eucaryotic organisms contributed about 20–40% of the total organic carbon flux in both the central Ross Sea polynya and in the western polynya, and groups of organisms differed in contribution to the carbon flux at the different sites. Algal carbon flux ranged from 4.5 to 21.1 mg C m⁻² day⁻¹ and consisted primarily of P. antarctica (cell plus mucus) and diatom carbon at all sites. Different diatom species dominated the diatom flux at different sites. Carbon fluxes of small pennate diatoms may have been enhanced by scavenging, by sinking senescent P. antarctica colonies. Heterotrophic carbon flux ranged from 9.2 to 37.6 mg C m⁻² day⁻¹ and was dominated by athecate heterotrophic dinoflagellate carbon in general and by carbon flux of a particular large athecate dinoflagellate at two sites. Fecal pellet carbon flux ranged from 4.6 to 54.5 mg C m⁻² day⁻¹ and was dominated by carbon from ovoid/angular pellets at most sites. Analysis of fecal pellet contents suggested that large protozoans identified by light microscopy contributed to ovoid/angular fecal pellet fluxes. Carbon flux as a percentage of daily primary production was lowest at sites where P. antarctica predominated in the water column and was highest at sites where fecal pellet flux was highest. This indicates the importance of grazers in carbon export.     

Interaction of oblique waves with an infinite cylinder

A Green's function procedure is applied to compute the oblique wave interaction with a cylinder of arbitrary section on the free surface in water of infinite depth. Also, the hydrodynamic coefficients associated with the motion of the cylinder oscillating in its three degrees of freedom, periodic along its axis, are treated. A computer program based on the present procedure is found to be accurate and efficient. The results are applicable to the analysis of floating breakwaters, floating bridges, ship hulls and other elongated structures on a free surface.     

Can beach dune ridges of the Texas Gulf Coast preserve climate signals?

A study of the evolution of North Padre Island (southern Texas Gulf Coast) dunes was carried out using LIDAR topographic data, dune vibracores through the center of the dunes, and grab samples of shoreface sand at four locations along a cross-shore profile. Grain-size analyses of the vibracores show vertical variations in shoreface sand deposition over decimeter depth intervals. A dune ridge growth model is introduced that describes the dune vertical accretion rate as a function of island progradation and freshwater lens expansion. This model allows indirect dating of the dune core samples based on a known island progradation rate (1?m/year), and height and spacing of the dunes calculated from the topographic data. A sand provenance model is also proposed that links the sand deposition in the dunes with sand sourced from various depths along the shoreface profile, depending on storm activity. We present evidence linking the changes in storm-sand deposition in the dune cores with yearly climatic fluctuations in the Gulf of Mexico associated with landfalling tropical storm activity in the period from 1942?C1965. This record of storm-induced sand variability is negatively correlated with El Ni?o-Southern Oscillation (Pacific) sea surface temperature variability, and positively correlated with North Atlantic decadal sea surface temperature variability.     

Solar-proton-produced neon in shergottite meteorites and implications for their origin

Abstract— Measured Ne isotopes in samples of shergottite ALHA77005 show variations in ²¹Ne/²²Ne ratios and ²¹Ne abundances that are consistent with the presence of two cosmogenic components: a component produced by nuclear interactions of galactic cosmic rays (GCR) and a component produced at shallow shielding depths (～0–3 cm) by energetic solar flare protons (SCR). We suggest that the ²¹Ne/²²Ne ratio generally can be used to distinguish between SCR and GCR components in many meteorite types. Analysis of cosmogenic Ne produced in chondrite mineral separates, eucrites, and anorthositic lunar rocks, all having diverse major element compositions, indicate that the GCR ²¹Ne/²²Ne ratio increases modestly with relative Mg content. Data for hundreds of chondrite analyses suggest that SCR Ne is present in no more than a very small fraction of chondrites. Examination of literature data for other shergottites, however, indicate that all of these meteorites contain SCR Ne but that it is apparently absent in other SNC meteorites. The ubiquitous presence of SCR Ne in shergottites, in contrast to most other types of meteorites, suggests that the martian origin of shergottites gave them different orbital parameters compared to other meteorites. This in turn may have contributed to slower entry velocities and lesser surface ablation in the atmosphere or even to higher SCR production rates.