MIL 03443, a dunite from asteroid 4 Vesta: Evidence for its classification and cumulate origin

Abstract– The absence of dunite (>90 vol% olivine) in the howardite, eucrite, and diogenite (HED) meteorite suite, when viewed with respect to spectroscopic and petrologic evidence for olivine on Vesta, is problematic. Herein, we present petrologic, geochemical, and isotopic evidence confirming that Miller Range (MIL) 03443, containing 91 vol% olivine, should be classified with the HED clan rather than with mesosiderites. Similarities in olivine and pyroxene FeO/MnO ratios, mineral compositions, and unusual mineral inclusions between MIL 03443 and the diogenites support their formation on a common parent body. This hypothesis is bolstered by oxygen isotopic and bulk geochemical data. Beyond evidence for its reclassification, we present observations and interpretations that MIL 03443 is probably a crustal cumulate rock like the diogenites, rather than a sample of the Vestan mantle.     

Bounce Rock—A shergottite‐like basalt encountered at Meridiani Planum,Mars

Abstract– The Opportunity rover of the Mars Exploration Rover mission encountered an isolated rock fragment with textural, mineralogical, and chemical properties similar to basaltic shergottites. This finding was confirmed by all rover instruments, and a comprehensive study of these results is reported here. Spectra from the miniature thermal emission spectrometer and the Panoramic Camera reveal a pyroxene‐rich mineralogy, which is also evident in Mössbauer spectra and in normative mineralogy derived from bulk chemistry measured by the alpha particle X‐ray spectrometer. The correspondence of Bounce Rock’s chemical composition with the composition of certain basaltic shergottites, especially Elephant Moraine (EET) 79001 lithology B and Queen Alexandra Range (QUE) 94201, is very close, with only Cl, Fe, and Ti exhibiting deviations. Chemical analyses further demonstrate characteristics typical of Mars such as the Fe/Mn ratio and P concentrations. Possible shock features support the idea that Bounce Rock was ejected from an impact crater, most likely in the Meridiani Planum region. Bopolu crater, 19.3 km in diameter, located 75 km to the southwest could be the source crater. To date, no other rocks of this composition have been encountered by any of the rovers on Mars. The finding of Bounce Rock by the Opportunity rover provides further direct evidence for an origin of basaltic shergottite meteorites from Mars.     

THEMIS-VIS observations of clouds in the martian mesosphere: Altitudes, wind speeds, and decameter-scale morphology

We present measurements of the altitude and eastward velocity component of mesospheric clouds in 35 imaging sequences acquired by the Mars Odyssey (ODY) spacecraft’s Thermal Emission Imaging System visible imaging subsystem (THEMIS-VIS). We measure altitude by using the parallax drift of high-altitude features, and the velocity by exploiting the time delay in the THEMIS-VIS imaging sequence.We observe two distinct classes of mesospheric clouds: equatorial mesospheric clouds observed between 0° and 180° L_s; and northern mid-latitude clouds observed only in twilight in the 200–300° L_s period. The equatorial mesospheric clouds are quite rare in the THEMIS-VIS data set. We have detected them in only five imaging sequences, out of a total of 2048 multi-band equatorial imaging sequences. All five fall between 20° south and 0° latitude, and between 260° and 295° east longitude. The mid-latitude mesospheric clouds are apparently much more common; for these we find 30 examples out of 210 northern winter mid-latitude twilight imaging sequences. The observed mid-latitude clouds are found, with only one exception, in the Acidalia region, but this is quite likely an artifact of the pattern of THEMIS-VIS image targeting. Comparing our THEMIS-VIS images with daily global maps generated from Mars Orbiter Camera Wide Angle (MOC-WA) images, we find some evidence that some mid-latitude mesospheric cloud features correspond to cloud features commonly observed by MOC-WA. Comparing the velocity of our mesospheric clouds with a GCM, we find good agreement for the northern mid-latitude class, but also find that the GCM fails to match the strong easterly winds measured for the equatorial clouds.Applying a simple radiative transfer model to some of the equatorial mesospheric clouds, we find good model fits in two different imaging sequences. By using the observed radiance contrast between cloud and cloud-free regions at multiple visible-band wavelengths, these fits simultaneously constrain the optical depths and particles sizes of the clouds. The particle sizes are constrained primarily by the relative contrasts at the available wavelengths, and are found to be quite different in the two imaging sequences: r_eff = 0.1 μm and r_eff = 1.5 μm. The optical depths (constrained by the absolute contrasts) are substantial: 0.22 and 0.5, respectively. These optical depths imply a mass density that greatly exceeds the saturated mass density of water vapor at mesospheric temperatures, and so the aerosol particles are probably composed mainly of CO₂ ice. Our simple radiative transfer model is not applicable to twilight, when the mid-latitude mesospheric clouds were observed, and so we leave the properties of these clouds as a question for further work.     

Stable sulfur isotopes in the water column of the Cariaco Basin

Previous geochemical and microbiological studies in the Cariaco Basin indicate intense elemental cycling and a dynamic microbial loop near the oxic-anoxic interface. We obtained detailed distributions of sulfur isotopes of total dissolved sulfide and sulfate as part of the on-going CARIACO time series project to explore the critical pathways at the level of individual sulfur species. Isotopic patterns of sulfate (δ³⁴S_SO4) and sulfide (δ³⁴S_H2S) were similar to trends observed in the Black Sea water column: δ³⁴S_H2S and δ³⁴S_SO4 were constant in the deep anoxic water (varying within 0.6‰ for sulfide and 0.3‰ for sulfate), with sulfide roughly 54‰ depleted in ³⁴S relative to sulfate. Near the oxic-anoxic interface, however, the δ³⁴S_H2S value was ∼3‰ heavier than that in the deep water, which may reflect sulfide oxidation and/or a change in fractionation during in situ sulfide production through sulfate reduction (SR). δ³⁴S_H2S and Δ³³S_H2S data near the oxic-anoxic interface did not provide unequivocal evidence to support the important role of sulfur-intermediate disproportionation suggested by previous studies. Repeated observation of minimum δ³⁴S_SO4 values near the interface suggests ‘readdition’ of ³⁴S-depleted sulfate during sulfide oxidation. A slight increase in δ³⁴S_SO4 values with depth extended over the water column may indicate a reservoir effect associated with removal of ³⁴S-depleted sulfur during sulfide production through SR. Our δ³⁴S_H2S and Δ³³S_H2S data also do not show a clear role for sulfur-intermediate disproportionation in the deep anoxic water column. We interpret the large difference in δ³⁴S between sulfate and sulfide as reflecting fractionations during SR in the Cariaco deep waters that are larger than those generally observed in culturing studies.     

Geochemical and mineralogical evidence for Sahara and Sahel dust additions to Quaternary soils on Lanzarote,eastern Canary Islands,Spain

Africa is the most important source of dust in the world today, and dust storms are frequent on the nearby Canary Islands. Previous workers have inferred that the Sahara is the most important source of dust to Canary Islands soils, with little contribution from the Sahel region. Soils overlying a late Quaternary basalt flow on Lanzarote, Canary Islands, contain, in addition to volcanic minerals, quartz and mica, exotic to the island’s bedrock. Kaolinite in the soils also likely has an exotic origin. Trace‐element geochemistry shows that the soils are derived from varying proportions of locally derived basalt and African dust. Major‐element geochemistry, clay mineralogy and interpretation of satellite imagery suggest that dust additions to the Canary Islands come not only from the Sahara Desert, but also from the Sahel region.     

The Role of One- and Two-Electron Transfer Reactions in Forming Thermodynamically Unstable Intermediates as Barriers in Multi-Electron Redox Reactions

In the aquatic geochemical literature, a redox half-reaction is normally written for a multi-electron process (n > 2); e.g., sulfide oxidation to sulfate. When coupling two multi-electron half-reactions, thermodynamic calculations indicate possible reactivity, and the coupled half-reactions are considered favorable even when there is a known barrier to reactivity. Thermodynamic calculations should be done for one or two-electron transfer steps and then compared with known reactivity to determine the rate controlling step in a reaction pathway. Here, thermodynamic calculations are presented for selected reactions for compounds of C, O, N, S, Fe, Mn and Cu. Calculations predict reactivity barriers and agree with one previous analysis showing the first step in reducing O₂ to O₂ ^? with Fe²⁺ and Mn²⁺ is rate limiting. Similar problems occur for the first electron transfer step in these metals reducing NO₃ ^?, but if reactive oxygen species form or if two-electron transfer steps with O atom transfer occur, reactivity becomes favorable. H₂S and NH₄ ⁺ oxidation in a one-electron transfer step by O₂ is also not favorable unless activation of oxygen can occur. H₂S oxidation by Cu²⁺, Fe(III) and Mn(III, IV) phases in two-electron transfer steps is favorable but not in one-electron steps indicating that (nano)particles with bands of orbitals are needed to accept two electrons from H₂S. NH₄ ⁺ oxidation by Fe(III) and Mn(III, IV) phases is generally not favorable for both one- and two-electron transfer steps, but their reaction with hydroxylamine and hydrazine to form N₂O and N₂, respectively, is favorable. The anammox reaction using hydroxylamine via nitrite reduction is the most favorable for NH₄ ⁺ oxidation. Other chemical processes including photosynthesis and chemosynthesis are considered for these element–element transformations.     

Analysis and Simulation of Propagule Dispersal and Salinity Intrusion from Storm Surge on the Movement of a Marsh–Mangrove Ecotone in South Florida

Coastal mangrove–freshwater marsh ecotones of the Everglades represent transitions between marine salt-tolerant halophytic and freshwater salt-intolerant glycophytic communities. It is hypothesized here that a self-reinforcing feedback, termed a “vegetation switch,” between vegetation and soil salinity, helps maintain the sharp mangrove–marsh ecotone. A general theoretical implication of the switch mechanism is that the ecotone will be stable to small disturbances but vulnerable to rapid regime shifts from large disturbances, such as storm surges, which could cause large spatial displacements of the ecotone. We develop a simulation model to describe the vegetation switch mechanism. The model couples vegetation dynamics and hydrologic processes. The key factors in the model are the amount of salt-water intrusion into the freshwater wetland and the passive transport of mangrove (e.g., Rhizophora mangle) viviparous seeds or propagules. Results from the model simulations indicate that a regime shift from freshwater marsh to mangroves is sensitive to the duration of soil salinization through storm surge overwash and to the density of mangrove propagules or seedlings transported into the marsh. We parameterized our model with empirical hydrologic data collected from the period 2000–2010 at one mangrove–marsh ecotone location in southwestern Florida to forecast possible long-term effects of Hurricane Wilma (24 October 2005). The model indicated that the effects of that storm surge were too weak to trigger a regime shift at the sites we studied, 50 km south of the Hurricane Wilma eyewall, but simulations with more severe artificial disturbances were capable of causing substantial regime shifts.     

An analysis and comparison of observed Pleistocene South Carolina (USA) shoreline elevations with predicted elevations derived from Marine Oxygen Isotope Stages

Geological maps of South Carolina, covering > 6800 km², confirm the existence of eight preserved Pleistocene shorelines above current sea level: Marietta (+ 42.6 m), Wicomico (+ 27.4 m), Penholoway (+ 21.3 m), Ladson (+ 17.4 m), Ten Mile Hill (+ 10.7 m), Pamlico (+ 6.7 m), Princess Anne (+ 5.2 m), and Silver Bluff (+ 3 m). Current geochronologic data suggest that these eight shorelines correlate with Marine Oxygen Isotope Stages (MIS) as follows: Marietta—older than MIS 77; Wicomico—MIS 55–45; Penholoway—MIS 19 or 17; Ladson—MIS 11; Ten Mile Hill—MIS 7; Pamlico—MIS 5; Princess Anne—MIS 5; and Silver Bluff—MIS 5 or 3. Except for the MIS 5e Pamlico, and possibly the MIS 11 Ladson, the South Carolina elevations are higher than predicted by isotope proxy-based reconstructions. The < 4 m of total relief from the Pamlico to the Silver Bluff shoreline in South Carolina, for which other reconstructions suggest an expected relief of ~ 80 m, illustrates the lack of match. Our results suggest that processes affecting either post-depositional changes in shoreline elevations or the creation of proxy sea-level estimates must be considered before using paleo sea-level position on continental margins.