Formation of metal in Grosvenor Mountains 95551 and comparison to ordinary chondrites

Siderophile element abundances in individual metal grains in the ungrouped chondrite Grosvenor Mountains (GRO) 95551 and in the ordinary chondrites Tieschitz H3.6, Soko-Banja LL4, and Allegan H5 were measured with laser ablation-inductively coupled plasma mass spectrometry. Matrix metal in GRO 95551 falls into two distinct compositional groups, a high-Ni group with 7.2 ± 0.4 wt% Ni and a low-Ni group with 3.7 ± 0.1 wt% Ni, indicating that kamacite/taenite equilibration at ∼1020 K was followed by rapid cooling. The nonrefractory siderophile elements P, Co, Cu, Ga, Ge, As, Pd, and Au also partition between the high-Ni and low-Ni metal in a manner consistent with kamacite/taenite fractionation, but the refractory siderophiles Ru, Re, Os, Ir, and Pt show correlated variations that are unrelated to kamacite/taenite partitioning and indicate that variations in refractory components of the metal were not completely erased during equilibration at ∼1020 K. The Ni-normalized bulk metal composition of GRO 95551 is refractory depleted and volatile rich relative to Bencubbin and related metal-rich chondrites but bears strong similarities to equilibrated ordinary chondrite metal. GRO 95551 represents a new chondrite type with chemical affinity to the ordinary chondrites. Individual metal grains in unequlibrated ordinary chondrites also have correlated variations in refractory siderophile contents that cannot be produced by redox processes alone; these variations span three orders of magnitude and diminish with increasing metamorphic grade of the ordinary chondrites.     

Surface structure effects on direct reduction of iron oxides by Shewanella oneidensis

The atomic and electronic structure of mineral surfaces affects many environmentally important processes such as adsorption phenomena. They are however rarely considered relevant to dissimilatory bacterial reduction of iron and manganese minerals. In this regard, surface area and thermodynamics are more commonly considered. Here we take a first step towards understanding the nature of the influence of mineral surface structure upon the rate of electron transfer from Shewanella oneidensis strain MR-1 outer membrane proteins to the mineral surface and the subsequent effect upon cell “activity.” Cell accumulation has been used as a proxy for cell activity at three iron oxide single crystal faces; hematite (001), magnetite (111) and magnetite (100). Clear differences in cell accumulation at, and release from the surfaces are observed, with significantly more cells accumulating at hematite (001) compared to either magnetite face whilst relatively more cells are released into the overlying aqueous phase from the two magnetite faces than hematite. Modeling of the electron transfer process to the different mineral surfaces from a decaheme (protoporphyrin rings containing a central hexacoordinate iron atom), outer membrane-bound cytochrome of S. oneidensis has been accomplished by employing both Marcus and ab initio density functional theories. The resultant model of electron transfer to the three oxide faces predicts that over the entire range of expected electron transfer distances the highest electron transfer rates occur at the hematite (001) surface, mirroring the observed cell accumulation data. Electron transfer rates to either of the two magnetite surfaces are slower, with magnetite (111) slower than hematite (001) by approximately two orders of magnitude. A lack of knowledge regarding the structural details of the heme-mineral interface, especially in regards to atomic distances and relative orientations of hemes and surface iron atoms and the conformation of the protein envelope, precludes a more thorough analysis. However, the results of the modeling concur with the empirical observation that mineral surface structure has a clear influence on mineral surface-associated cell activity. Thus surface structure effects must be accounted for in future studies of cell-mineral interactions.     

Rare Earth Element and yttrium compositions of Archean and Paleoproterozoic Fe formations revisited: New perspectives on the significance and mechanisms of deposition

The ocean and atmosphere were largely anoxic in the early Precambrian, resulting in an Fe cycle that was dramatically different than today’s. Extremely Fe-rich sedimentary deposits—i.e., Fe formations—are the most conspicuous manifestation of this distinct Fe cycle. Rare Earth Element (REE) systematics have long been used as a tool to understand the origin of Fe formations and the corresponding chemistry of the ancient ocean. However, many earlier REE studies of Fe formations have drawn ambiguous conclusions, partially due to analytical limitations and sampling from severely altered units. Here, we present new chemical analyses of Fe formation samples from 18 units, ranging in age from ca. 3.0 to 1.8 billion years old (Ga), which allow a reevaluation of the depositional mechanisms and significance of Precambrian Fe formations. There are several temporal trends in our REE and Y dataset that reflect shifts in marine redox conditions. In general, Archean Fe formations do not display significant shale-normalized negative Ce anomalies, and only Fe formations younger than 1.9 Ga display prominent positive Ce anomalies. Low Y/Ho ratios and high shale-normalized light to heavy REE (LREE/HREE) ratios are also present in ca. 1.9 Ga and younger Fe formations but are essentially absent in their Archean counterparts. These marked differences in Paleoproterozoic versus Archean REE + Y patterns can be explained in terms of varying REE cycling in the water column.Similar to modern redox-stratified basins, the REE + Y patterns in late Paleoproterozoic Fe formations record evidence of a shuttle of metal and Ce oxides across the redoxcline from oxic shallow seawater to deeper anoxic waters. Oxide dissolution—mainly of Mn oxides—in an anoxic water column lowers the dissolved Y/Ho ratio, raises the light to heavy REE ratio, and increases the concentration of Ce relative to the neighboring REE (La and Pr). Fe oxides precipitating at or near the chemocline will capture these REE anomalies and thus evidence for this oxide shuttle. In contrast, Archean Fe formations do not display REE + Y patterns indicative of an oxide shuttle, which implies an absence of a distinct Mn redoxcline prior to the rise of atmospheric oxygen in the early Paleoproterozoic. As further evidence for reducing conditions in shallow-water environments of the Archean ocean, REE data for carbonates deposited on shallow-water Archean carbonate platforms that stratigraphically underlie Fe formations also lack negative Ce anomalies. These results question classical models for deposition of Archean Fe formations that invoke oxidation by free oxygen at or above a redoxcline. In contrast, we add to growing evidence that metabolic Fe oxidation is a more likely oxidative mechanism for these Fe formations, implying that the Fe distribution in Archean oceans could have been controlled by microbial Fe uptake rather than the oxidative potential of shallow-marine environments.     

Field Measurement of Suction, Water Content, and Water Permeability

This paper presents a review of techniques for field measurement of suction, water content, and water hydraulic conductivity (permeability). Main problems in the use of field tensiometers are addressed and hints on how to improve tensiometer performance are given. Advantages and limitations of instruments for indirect measurement of suction including electrical conductivity sensors, thermal conductivity sensors, dielectric permittivity sensors, filter paper, and psychrometer are discussed. Techniques for water content measurement based on dielectric methods are then presented. These include time and amplitude domain reflectometry and capacitance. Finally, a brief overview of methods for measurement of water permeability in the field is presented.     

Antarctic sea-ice relationships with indices of the atmospheric circulation of the Southern Hemisphere

A link between the Antarctic sea-ice extent and low-frequency atmospheric variations, particularly ENSO, has been suggested by recent modeling and empirical studies. This question is examined here using a high-resolution (by week, by region) data base of Antarctic sea-ice extent for the 1973–1982 period. Although of relatively short duration by Northern Hemisphere standards, such a data base offers an opportunity rare in Southern Hemisphere climate studies. The seaice variations are examined in the context of longer-term indices of the large-scale atmospheric circulation. These are a Southern Oscillation Index (SOI) and an index of sea-level pressure (SLP) wavenumber one in the Southern Hemisphere extratropics. The indices are updated through 1982, and their associations with regional-scale pressure indices in the Australia-New Zealand sector are also examined. The 1973–1982 period is anomalous when compared with the period 1951–1972. Correlation analysis of the monthly sea ice and circulation index values reveals that much of the apparent link between the ice and the SOI suggested in previous studies arises from autocorrelations present in both data sets and the strong annual cycle of sea-ice extent. Removing these effects from the data and re-running the correlations reveals that most of the resulting significant associations between the ice and one or other of the circulation indices can probably be explained on the basis of chance. In order to reconcile these findings with previous studies that show some strong ice-circulation interactions on regional scales, only those months in which significant correlations occur between both largescale circulation indices and the sea ice are examined further. These occur preferentially in the Ross and Weddell sectors, which constitute the regions contributing most to the variability of Antarctic sea ice. The analysis suggests that the sea-ice-extent changes lag the SOI by several months but may precede changes in extratropical SLP wavenumber one. Confirmation of these tentative regional ice extent-circulation teleconnections necessarily awaits the forward extension of the high-resolution sea-ice data base beyond the 10 years available here.This paper is based on material presented at the Conference on Mechanisms of Interannual and Longer-Term Climatic Variations held at the University of Melbourne, Australia: December 8–12, 1986.     

A Comparative Plume Study of DRO,GRO, Benzene,and MTBE: Implications for Risk Management

Groundwater remediation and no-further action decision making at petroleum underground storage tank (UST) sites has largely been based on an understanding of plume length, plume stability, and attenuation rates for key hydrocarbon constituents. Regulatory guidance to support and guide such decisions is based in part on plume studies involving individual hydrocarbon constituents, namely benzene and methyl tert-butyl ether (MTBE). Questions remain regarding whether current guidance is applicable to chemical mixtures such as gasoline range organics (GRO), diesel range organics (DRO), and oxygen containing organic compounds (OCOCs) resulting from hydrocarbon biodegradation. To help address this concern, data from California's GeoTracker database were used to estimate maximum plume lengths, plume stability, and attenuation rates of DRO (which can be used as an analytical surrogate for OCOCs) and GRO relative to benzene and MTBE. The distributions of maximum plume lengths were similar for the four constituents with medians ranging from 27 to 32 m. The fraction of monitoring wells with a decreasing concentration trend ranged from 19% for DRO to 40% for MTBE, while fewer than 7% of the wells had an increasing concentration trend for any of the constituents. Median attenuation rates ranged from 0.10% day⁻¹ for DRO to 0.17% day⁻¹ for MTBE. The results suggest attenuation based risk management is appropriate for DRO and GRO plumes at most petroleum UST sites.