Iron solid-phase differentiation along a redox gradient in basaltic soils

Iron compounds in soil are multifunctional, providing physical structure, ion sorption sites, catalytic reaction-centers, and a sink for respiratory electrons. Basaltic soils contain large quantities of iron that reside in different mineral and organic phases depending on their age and redox status. We investigated changes in soil iron concentration and its solid-phase speciation across a single-aged (400 ky) lava flow subjected to a gradient in precipitation (2200-4200 mm yr⁻¹) and hence redox history. With increasing rainfall and decreasing Eh, total Fe decreased from about 25% to <1% of the soil mass. Quantitative speciation of soil solid-phase iron was constrained by combining ⁵⁷Fe Mössbauer spectroscopy (MBS) at 295 and 4.2 K with powder X-ray diffraction, selective chemical extractions, and magnetic susceptibility measurements. This approach allowed us to partition iron into (1) nanoparticulate and microcrystalline Fe^III-(oxy)hydroxides, (2) microcrystalline and bulk Fe^III-oxides, (3) organic/silicate bound Fe^III, and (4) ferrous iron. The Fe^III-(oxy)hydroxide fraction dominated solid-phase Fe, exhibiting a crystallinity continuum based on magnetic ordering temperature. The continuum extended from well-ordered microcrystalline goethite through nanocrystalline Fe^III-(oxy)hydroxides to a nano Fe^III-(oxy)hydroxide phase of extremely low crystallinity. Magnetic susceptibility was correlated (R² = 0.77) with Fe^III-oxide concentration, consistent with a contribution of maghemite to the otherwise hematite dominated Fe-oxide fraction. The Fe^III-(oxy)hydroxide fraction of total Fe decreased with increasing rainfall and was replaced by corresponding increase in the organic/silicate Fe^III fraction. The crystallinity of the Fe^III-(oxy)hydroxides also decreased with increasing rainfall and leaching, with the most disordered members of the crystallinity continuum, the nano Fe^III-(oxy)hydroxides, gaining proportional abundance in the wetter sites. This finding runs counter to the conventional kinetic expectation of preferential removal of the most disordered minerals in a reductive dissolution-dominated environment. We suggest the persistence of highly disordered Fe phases reflects the dynamic redox conditions of these upland soils in which periods of anoxia are marked by high water-throughput and Fe²⁺(aq) removal, while periodic Fe oxidation events occur in the presence of high concentrations of organic matter. Our ⁵⁷Fe Mössbauer study shows basalt-derived nano-scale Fe^III phases are more disordered than current synthetic analogs and have nano-structural characteristics that are linked to their formation environment.     

The effect of Si on metal-silicate partitioning of siderophile elements and implications for the conditions of core formation

We have determined the liquid metal-liquid silicate partitioning of Ni, Co, Mo, W, V, Cr and Nb at 1.5 GPa/1923 K and 6 GPa/2123 K under conditions of constant silicate melt composition with variable amounts of Si in the Fe-rich metallic liquid. Partitioning of Ni, Co, Mo, W and V is sensitive to the Si content of the metal with, in all five cases, increasing Si tending to make the element more lithophile than for conditions where the metal is Si-free. In contrast, metal-silicate partitioning of Cr and Nb is, at constant silicate melt composition, insensitive to the Si content of the metal.The implications of our data are that if, as indicated by the Si isotopic composition of the silicate Earth ( [Georg et al., 2007] and [Fitoussi et al., 2009]), the core contains significant amounts of Si, the important siderophile elements Ni, Co, W and Mo were more lithophile during accretion and core formation than previously believed.We use our new data in conjunction with published metal-silicate partitioning results to develop a model of continuous accretion and core segregation taking explicit account of the partitioning of Si (this study) and O (from Ozawa et al., 2008) between metal and silicate and their effects on metal-silicate partitioning of siderophile elements. We find that the effect of Si on the siderophile characteristics of Ni, Co and W means that the pressures of core segregation estimated from these elements are ∼5 GPa lower than those derived from experiments in which the metal contained negligible Si (e.g., Wade and Wood, 2005). The core-mantle partitioning of Cr and Nb requires that most of Earth accretion took place under conditions which were much more reducing than those implied by the current FeO content of the mantle and that the oxidation took place late in the accretionary process. Paths of terrestrial accretion, oxidation state and partitioning which are consistent with the current mantle contents of Ni, Co, W, V, Cr and Nb lead to Si and O contents of the core of ∼4.3 wt.% and 0.15%, respectively.     

GSD‐1G and MPI‐DING Reference Glasses for In Situ and Bulk Isotopic Determination

This paper contains the results of an extensive isotopic study of United States Geological Survey GSD‐1G and MPI‐DING reference glasses. Thirteen different laboratories were involved using high‐precision bulk (TIMS, MC‐ICP‐MS) and microanalytical (LA‐MC‐ICP‐MS, LA‐ICP‐MS) techniques. Detailed studies were performed to demonstrate the large‐scale and small‐scale homogeneity of the reference glasses. Together with previously published isotopic data from ten other laboratories, preliminary reference and information values as well as their uncertainties at the 95% confidence level were determined for H, O, Li, B, Si, Ca, Sr, Nd, Hf, Pb, Th and U isotopes using the recommendations of the International Association of Geoanalysts for certification of reference materials. Our results indicate that GSD‐1G and the MPI‐DING glasses are suitable reference materials for microanalytical and bulk analytical purposes.     

Geochemistry analysis and evolution of a bolson aquifer,basin and range province in the southwestern united states

This paper expands significantly on the major-ion geochemical characterization, evolution, and differentiation of groundwater in the Presidio-Redford Bolson (PRB) Aquifer of Texas as presented in Chowdhury et al. (2008). For 19 groundwater samples from the PRB Aquifer, the author calculated major cation–anion balance errors, equilibrium carbon dioxide partial pressure values and saturation indices for selected minerals. Comparison of major-ion analyses for groundwater from basin margin wells with those for basin center wells is documented and illustrated with ion-concentration maps and Piper and Stiff diagrams and reveals significant increases in concentrations of chloride, sulfate and sodium coupled with notable decrease of calcium in bolson-center well samples. These geochemical changes suggest dissolution of aquifer minerals and cation exchange as groundwater migrates downgradient to the bolson center. The US Geological Survey (USGS) computer code, NETPATH, was used to interpret probable net geochemical mass-balance reactions that potentially have occurred within the PRB Aquifer along groundwater flowpaths from bolson margin to bolson center. For all four upgradient–downgradient well pairs studied, at least three NETPATH models contain cation exchange values; calcium is being exchanged for sodium. The Rio Grande Alluvium Aquifer and Rio Grande River are notably minor sources of recharge to the PRB Aquifer, based on Chowdhury et al. (2008) and geochemical evaluations of this study.     

Developing a long-term outlook for the Great Barrier Reef,Australia: A framework for adaptive management reporting underpinning an ecosystem-based management approach

The Great Barrier Reef Outlook Report 2009 was the first produced in response to a newly legislated requirement for five-yearly reports on the status of and outlook for the Great Barrier Reef. It adopted an ecosystem approach, assessing all habitats and species, ecosystem processes and major uses. By then considering the factors affecting the ecosystem, coupled with an assessment of management effectiveness, it provided a risk-based forward-looking projection for the ecosystem. Rarely has such a comprehensive, ecosystem-based report been produced to guide government action. With no pre-determined path to follow for interpreting the legislative requirements, the Great Barrier Reef Marine Park Authority (GBRMPA) developed a repeatable structure and method for Great Barrier Reef Outlook Reports that impartially and consistently considers the evidence and clearly presents the findings. The GBRMPA worked closely with relevant Australian and Queensland Government agencies as well as researchers, industry representatives and the community while developing the report. That such a report must be produced every five years allows an overview of the effectiveness of management responses to be regularly assessed. It also provides a transparent means of highlighting and tracking emerging risks facing the Great Barrier Reef.     

Evaluation of the frequency of skipped spawning in Norwegian spring-spawning herring

Based upon an under-representation of second time spawners on the spawning grounds between 1935 and 1973, researchers have suggested that Norwegian spring-spawning (NSS) herring (Clupea harengus) frequently skip their second spawning event. In order to evaluate this claim with direct evidence, herring were collected over a period of three years from statutory surveys and commercial catches over a wide area covering the feeding, over-wintering and spawning grounds. The development stage of the ovaries was assessed and the intensity of atresia quantified. Only a negligible number of the analysed herring caught were considered likely to skip spawning, thus this phenomenon does not appear to be a common feature of the NSS herring stock at present. In addition, considering the reproductive strategy of herring, it seems doubtful that skipping the second spawning event has ever frequently occurred in this stock.     

Atom‐probe analyses of nanodiamonds from Allende

Atom‐probe tomography (APT) is currently the only analytical technique that, due to its spatial resolution and detection efficiency, has the potential to measure the carbon isotope ratios of individual nanodiamonds. We describe three different sample preparation protocols that we developed for the APT analysis of meteoritic nanodiamonds at sub‐nm resolution and present carbon isotope peak ratios of meteoritic and synthetic nanodiamonds. The results demonstrate an instrumental bias associated with APT that needs to be quantified and corrected to obtain accurate isotope ratios. After this correction is applied, this technique should allow determination of the distribution of ¹²C/¹³C ratios in individual diamond grains, solving the decades‐old question of the origin of meteoritic nanodiamonds: what fraction, if any, formed in the solar system and in presolar environments? Furthermore, APT could help us identify the stellar sources of any presolar nanodiamonds that are detected.     

New OSL dating of UK loess: indications of two phases of Late Glacial dust accretion in SE England and climate implications

Windblown dust deposits or loess, locally known in the UK as brickearth, blanket many parts of southern England outside the limits of the British and Irish Ice Sheet. The best‐studied loess exposures occur in Kent, southeast England, where the deposits are believed to be Late Glacial in age. New sedimentological evidence is presented for phases of accretion with two distinct units, a calcareous brickearth exhibiting periglacial cryoturbation and a non‐calcareous, massive brickearth. Optically stimulated luminescence (OSL) dating has been applied to chemically isolated modal quartz silts to derive a chronology for sediment accretion and to better understand the palaeoclimatic significance of these deposits. © British Geological Survey/Natural Environment Research Council copyright 2007. Reproduced with the permission of BGS/NERC. Published by John Wiley & Sons, Ltd.     

A radar survey of main-belt asteroids: Arecibo observations of 55 objects during 1999-2003

We report Arecibo observations of 55 main-belt asteroids (MBAs) during 1999-2003. Most of our targets had not been detected previously with radar, so these observations more than double the number of radar-detected MBAs. Our bandwidth estimates constrain our targets' pole directions in a manner that is geometrically distinct from optically derived constraints. We present detailed statistical analyses of the disk-integrated properties (radar albedo and circular polarization ratio) of the 84 MBAs observed with radar through March 2003; all of these observations are summarized in the online supplementary information. Certain conclusions reached in previous studies are strengthened: M asteroids have higher mean radar albedos and a wider range of albedos than do other MBAs, suggesting that both metal-rich and metal-poor M-class objects exist; and C- and S-class MBAs have indistinguishable radar albedo distributions, suggesting that most S-class objects are chondritic. Also in accord with earlier results, there is evidence that primitive asteroids from outside the C taxon (F, G, P, and D) are not as radar-bright as C and S objects, but a convincing statistical test must await larger sample sizes. In contrast with earlier work, we find S-class MBAs to have higher circular polarization ratios than other MBAs, indicating greater near-surface structural complexity at decimeter scales, due to different mineralogy (material strength or loss tangent), a different impactor population, or both.