Fe(II) reduction of pyrolusite (β-MnO<Subscript>2</Subscript>) and secondary mineral evolution

Iron (Fe) and manganese (Mn) are the two most common redox-active elements in the Earth’s crust and are well known to influence mineral formation and dissolution, trace metal sequestration, and contaminant transformations in soils and sediments. Here, we characterized the reaction of aqueous Fe(II) with pyrolusite (β-MnO₂) using electron microscopy, X-ray diffraction, aqueous Fe and Mn analyses, and ⁵⁷Fe Mössbauer spectroscopy. We reacted pyrolusite solids repeatedly with 3 mM Fe(II) at pH 7.5 to evaluate whether electron transfer occurs and to track the evolving reactivity of the Mn/Fe solids. We used Fe isotopes (56 and 57) in conjunction with ⁵⁷Fe Mössbauer spectroscopy to isolate oxidation of Fe(II) by Fe(III) precipitates or pyrolusite. Using these complementary techniques, we determined that Fe(II) is initially oxidized by pyrolusite and that lepidocrocite is the dominant Fe oxidation product. Additional Fe(II) exposures result in an increasing proportion of magnetite on the pyrolusite surface. Over a series of nine 3 mM Fe(II) additions, Fe(II) continued to be oxidized by the Mn/Fe particles suggesting that Mn/Fe phases are not fully passivated and remain redox active even after extensive surface coverage by Fe(III) oxides. Interestingly, the initial Fe(III) oxide precipitates became further reduced as Fe(II) was added and additional Mn was released into solution suggesting that both the Fe oxide coating and underlying Mn phase continue to participate in redox reactions when freshly exposed to Fe(II). Our findings indicate that Fe and Mn chemistry is influenced by sustained reactions of Fe(II) with Mn/Fe oxides.

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Towards a protocol for laser scanning of rock surfaces

The precision of height measurements derived from laser scanning a weathered rock surface was analysed. Different registration methods for comparing surfaces to deduce weathering were assessed and the most precise was found to be the method that used registration shapes as control, located in different planes relative to the scanned surface. In addition, the different sources of error in scanning precision were assessed by varying factors such as scan distance, lens configuration, scan angle and the nature of the topography being scanned. From this analysis it was possible to suggest what the optimal scanning conditions were for this particular experimental set‐up. The procedures outlined for assessing errors in the precision of height measurements are transferable to other scanning studies. Copyright © 2010 John Wiley & Sons, Ltd.     

Heavy metal contamination in coastal sediments and soils near the Brazilian Antarctic Station, King George Island

This paper investigates the natural and anthropogenic processes controlling sediment chemistry in Admiralty Bay, King George Island, Antarctica, emphasizing the area affected by the Brazilian Antarctic Station Comandante Ferraz (Ferraz). Total and bioavailable concentrations of sixteen elements were determined in 32 sediment and 14 soils samples. Factor analysis allowed us to distinguish three groups of samples: (1) Ferraz sediments, with higher content of total trace metals and organic matter; (2) control sediments, with intermediate characteristics; (3) Ferraz soils, with higher bioavailability of most metals due to its oxidizing condition and low organic matter content. Major elements such as Fe, Al, Ca and Ti presented similar levels in all three groups. Enrichment factor calculations showed that paints, sewage and petroleum contamination enhanced metal concentrations in Ferraz surface sediments as follows: B, Mo, and Pb (>90%); V and Zn (70-80%); Ni, Cu, Mg, and Mn (30-40%). Despite evidence of contamination in these sediments, the low bioavailability, probably caused by iron-sulfide, indicates small environmental risks.     

Rhenium–osmium systematics of the Mount Isa copper orebody and the Eastern Creek Volcanics,Queensland, Australia: implications for ore genesis

The syn-tectonic breccia-hosted Mount Isa Cu deposit in northwest Queensland is the largest sediment-hosted Cu deposit in Australia. Whole-rock samples of chalcopyrite-rich Cu ore form an isochron with a Re–Os age of 1,372 ± 41 Ma. This age is more than 100 Ma younger than the previously accepted age of Cu ore formation, an Ar–Ar mineral age for biotite separated from the host rocks within the alteration envelope to the Cu orebody. This discrepancy cannot be unequivocally resolved due to a lack of other absolute geochronological constraints for Cu mineralisation or the deformation event associated with Cu emplacement. The 1,372 ± 41 Ma date may reflect (a) the time of Cu deposition, (b) the time of a hydrothermal event that reset the Re–Os signature of the Cu ore or (c) mixing of the Re–Os isotope systematics between the host rocks and Cu-bearing fluids. However, a range of published Ar–Ar and Rb–Sr dates for potassic alteration associated with Cu mineralisation also records an event between 1,350 and 1,400 Ma and these are consistent with the 1,372 Ma Re–Os age. The 1.8 Ga Eastern Creek Volcanics are a series of tholeiitic basalts with a primary magmatic Cu enrichment which occur adjacent to the Mount Isa Cu deposit. The whole-rock Os isotopic signature of the Eastern Creek Volcanics ranges from mantle-like values for the upper Pickwick Member, to more radiogenic/crustal values for the lower Cromwell Member. The Re–Os isotope signature of the Cu ores overlaps with those calculated for the two volcanic members at 1,372 Ma; hence, the Os isotope data are supportive of the concept that the Os in the Cu ores was sourced from the Eastern Creek Volcanics. By inference, it is therefore postulated that the Eastern Creek Volcanics are the source of Cu in the Mount Isa deposit, as both Os and Cu are readily transported by oxidised hydrothermal fluids, such as those that are thought to have formed the Cu orebody. The Pickwick Member yields a Re–Os isochron age of 1,833 ± 51 Ma, which is within error of previously reported age constraints. The initial ¹⁸⁷Os/¹⁸⁸Os isotopic ratio of 0.114 ± 0.067 (γOs = −0.7) is slightly subchondritic, and together with other trace element geochemical constraints, is consistent with a subcontinental lithospheric mantle source. The Pickwick Member records a minimum age of ca. 1.95 Ga for melt depletion in the subcontinental lithospheric mantle beneath the Mount Isa Inlier prior to the extraction of the magmas which formed the Eastern Creek Volcanics. This corresponds with the end of subduction-related magmatism along the eastern margin of the Northern Australian Craton, which included the Mount Isa Inlier.     

Dating of raised marine and lacustrine deposits in east Greenland using beryllium‐10 depth profiles and implications for estimates of subglacial erosion

Here we combine ¹⁰Be depth profile techniques applied to late glacial ice‐contact marine and lacustrine deltas, as well as boulder exposure dating of associated features in the Scoresby Sound region, east Greenland, to determine both the surface age and the magnitude of cosmogenic nuclide inheritance. Boulder ages from an ice‐contact delta in northern Scoresby Sund show scatter typical of polar regions and yield an average age of 12.8 ± 0.5 ka – about 2 ka older than both our average profile surface age of 10.9 ± 0.7 ka from three depth profiles and a radiocarbon‐based estimate. On the other hand, boulder exposure ages from a set of moraines in southern Scoresby Sund show excellent internal consistency for polar regions and yield an average age of 11.6 ± 0.2 ka. The profile surface age from a corresponding ice‐contact delta is 8.1 ± 0.9 ka, while a second delta yields an age of 10.0 ± 0.4 ka. Measured ¹⁰Be inheritance concentrations from all depth profiles are internally consistent and are between 10% and 20% of the surface concentrations, suggesting a regional cosmogenic inheritance signal for the Scoresby Sound landscape. Based on the profile inheritance concentrations, we explore the first‐order catchment‐averaged bedrock erosion under the Greenland ice sheet, yielding estimates of total erosion during the last glacial cycle of the order of 2–30 m. Copyright © 2010 John Wiley & Sons, Ltd.     

Sediment geochemistry in coastal maritime Antarctica (Admiralty Bay, King George Island): Evidence from rare earths and other elements

We report the concentrations of 22 elements in short coastal sediment cores of Admiralty Bay (King George Island, Antarctica) determined by Neutron Activation Analysis. We focus the discussion on rare earth elements (REE) because their fractionation patterns in sediments relative to local sources may offer insights about weathering, transportation, deposition, and diagenetic processes. We found strong correlations between REE and Th, indicating detrital origin. Despite strong Eh gradients, the Th-normalized redox-sensitive elements (e.g., Eu, Ce, Fe, As, and others) showed little variability within the sedimentary environment. The exceptions were U (depleted in the upper few centimeters) and Br (enriched in the upper few centimeters). While U appears to be removed from seawater via uptake across the boundary of reducing sediments, the mechanisms driving Br accumulation are unclear, but perhaps related to increasing diatom production driven by regional warming. A comparison with published concentrations from rocks representing the regional eroding units showed that the characteristics of source rock could be recognized in the REE fractionation patterns in our sediments. These results imply no significant alteration during weathering and sediment transport in the coastal region of Admiralty Bay and the prevalence of strong periglacial erosion in ice-free areas of maritime Antarctica in spite of the relatively mild regional environmental setting (e.g., high moisture and high temperatures).     

Alkali and halogen chemistry in volcanic gases on Io

We use chemical equilibrium calculations to model the speciation of alkalis and halogens in volcanic gases emitted on Io. The calculations cover wide temperature (500-2000 K) and pressure (10⁻⁶ to 10⁺¹ bars) ranges, which overlap the nominal conditions at Pele (T=1760 K, P=0.01 bars). About 230 compounds of 11 elements (O, S, Li, Na, K, Rb, Cs, F, Cl, Br, I) are considered. The elemental abundances for O, S, Na, K, and Cl are based upon observations. CI chondritic elemental abundances relative to sulfur are used for the other alkalis and halogens (as yet unobserved on Io). We predict the major alkali species in Pele-like volcanic gases and the percentage distribution of each alkali are LiCl (73%), LiF (27%); NaCl (81%), Na (16%), NaF (3%); KCl (91%), K (5%), KF (4%); RbCl (93%), Rb (4%), RbF (3%); CsCl (92%), CsF (6%), Cs (2%). Likewise the major halogen species and the percentage distribution of each halogen are NaF (88%), KF (10%), LiF (2%); NaCl (89%), KCl (11%); NaBr (89%), KBr (10%), Br (1%); NaI (61%), I (30%), KI (9%). We predict the major halogen condensates and their condensation temperatures at P=0.01 bar are NaF (1115 K), LiF (970 K); NaCl (1050 K), KCl (950 K); KBr (750 K), RbBr (730 K), CsBr (645 K); and solid I₂ (200 K). We also model disequilibrium chemistry of the alkalis and halogens in the volcanic plume. Based on this work and our prior modeling for Na, K, and Cl in a volcanic plume, we predict the major loss processes for the alkali halide gases are photolysis and/or condensation onto grains. Their estimated photochemical lifetimes range from a few minutes for alkali iodides to a few hours for alkali fluorides. Condensation is apparently the only loss process for elemental iodine. On the basis of elemental abundances and photochemical lifetimes, we recommend searching for gaseous KCl, NaF, LiF, LiCl, RbF, RbCl, CsF, and CsCl around volcanic vents during eruptions. Based on abundance considerations and observations of brown dwarfs we also recommend a search of Io's extended atmosphere and the Io plasma torus for neutral and ionized Li, Cs, Rb, and F.     

Outgassing of ordinary chondritic material and some of its implications for the chemistry of asteroids, planets, and satellites

We used chemical equilibrium calculations to model thermal outgassing of ordinary chondritic material as a function of temperature, pressure, and bulk composition and use our results to discuss outgassing on asteroids and the early Earth. The calculations include ∼1000 solids and gases of the elements Al, C, Ca, Cl, Co, Cr, F, Fe, H, K, Mg, Mn, N, Na, Ni, O, P, S, Si, and Ti. The major outgassed volatiles from ordinary chondritic material are CH₄, H₂, H₂O, N₂, and NH₃ (the latter at conditions where hydrous minerals form). Contrary to widely held assumptions, CO is never the major C-bearing gas during ordinary chondrite metamorphism. The calculated oxygen fugacity (partial pressure) of ordinary chondritic material is close to that of the quartz-fayalite-iron (QFI) buffer. Our results are insensitive to variable total pressure, variable volatile element abundances, and kinetic inhibition of C and N dissolution in Fe metal. Our results predict that Earth's early atmosphere contained CH₄, H₂, H₂O, N₂, and NH₃; similar to that used in Miller—Urey synthesis of organic compounds.     

Heavy metal frost on Venus

Chemical equilibrium calculations of volatile metal geochemistry on Venus show that high dielectric constant compounds of lead and bismuth such as PbS (galena), Bi₂S₃ (bismuthite) or Pb-Bi sulfosalts condense in the venusian highlands and may be responsible for the low radar emissivities observed by Magellan and Pioneer Venus. Our calculations also show that elemental tellurium is unstable on Venus' surface and will not condense below 46.6 km. This is over 30 km higher than Maxwell Montes, the highest point on Venus' surface. Elemental analyses of Venus' highlands surface by laser induced breakdown spectroscopy (LIBS) and/or X-ray fluorescence (XRF) can verify the identity of the heavy metal frost on Venus. The Pb-Pb age of Venus could be determined by mass spectrometric measurements of the Pb²⁰⁷/Pb²⁰⁴ and Pb²⁰⁶/Pb²⁰⁴ isotopic ratios in Pb-bearing frosts. All of these measurements are technologically feasible now.     

The effect of submerged plateaux on Pleistocene gyral circulation and sea-surface temperatures in the Southwest Pacific

Uniquely in the Southern Hemisphere the New Zealand micro-continent spans the interface between a subtropical gyre and the Subantarctic Circumpolar Current. Its 20° latitudinal extent includes a complex of submerged plateaux, ridges, saddles and basins which, in the present interglacial, are partial barriers to circulation and steer the Subtropical (STF) and Subantarctic (SAF) fronts. This configuration offers a singular opportunity to assess the influence of bottom topography on oceanic circulation through Pleistocene glacial – interglacial (G/I) cycles, its effect on the location and strength of the fronts, and its ability to generate significant differences in mixed layer thermal history over short distances.For this study we use new planktic foraminiferal based sea-surface temperature (SST) estimates spanning the past 1 million years from a latitudinal transect of four deep ocean drilling sites. We conclude that: 1. the effect of the New Zealand landmass was to deflect the water masses south around the bathymetric impediments; 2. the effect of a shallow submerged ridge on the down-current side (Chatham Rise), was to dynamically trap the STF along its crest, in stark contrast to the usual glacial–interglacial (G–I) meridional migration that occurs in the open ocean; 3. the effect of more deeply submerged, downstream plateaux (Campbell, Bounty) was to dynamically trap the SAF along its steep southeastern margin; 4. the effects of saddles across the submarine plateaux was to facilitate the development of jets of subtropical and subantarctic surface water through the fronts, forming localized downstream gyres or eddies during different phases in the G–I climate cycles; 5. the deep Pukaki Saddle across the Campbell-Bounty Plateaux guided a branch of the SAF to flow northwards during each glacial, to form a strong gyre of circumpolar surface water in the Bounty Trough, especially during the mid-Pleistocene Climate Transition (MIS 22-16) when exceptionally high SST gradients existed across the STF; 6. the shallower Mernoo Saddle, at the western end of the Chatham Rise, provided a conduit for subtropical water to jet southwards across the STF in the warmest interglacial peaks (MIS 11, 5.5) and for subantarctic water to flow northwards during glacials; 7. although subtropical or subantarctic drivers can prevail at a particular phase of a G–I cycles, it appears that the Antarctic Circumpolar Current is the main influence on the regional hydrography.Thus complex submarine topography can affect distinct differences in the climate records over short distances with implications for using such records in interpreting global or regional trends. Conversely, the local topography can amplify the paleoclimate record in different ways in different places, thus enhancing its value for the study of more minor paleoceanographic influences that elsewhere are more difficult to detect. Such sites include DSDP 594, which like some other Southern Ocean sites, has the typical late Pleistocene asymmetrical saw-tooth G–I climate pattern transformed to a gap-tooth pattern of quasi-symmetrical interglacial spikes that interrupt extended periods of minimum glacial temperatures.