Core formation and the oxidation state of the Earth: Additional constraints from Nb, V and Cr partitioning

We have combined metal-silicate partitioning data from the literature with new experimental results at 1.5-8 GPa and 1480-2000 °C to parameterize the effects of pressure, temperature and composition on the partitioning of V, Cr and Nb between liquid Fe metal (with low S and C content) and silicate melt.Using information from the steelmaking literature to correct for interactions in the metal phase, we find that, for peridotitic silicate melts, metal-silicate partition coefficients are given by:

     

The age of the martian meteorite Northwest Africa 1195 and the differentiation history of the shergottites

Samarium-neodymium isotopic analyses of unleached and acid-leached mineral fractions from the recently identified olivine-bearing shergottite Northwest Africa 1195 yield a crystallization age of 347 ± 13 Ma and an value of +40.1 ± 0.9. Maskelynite fractions do not lie on the Sm-Nd isochron and appear to contain a martian surface component with low ¹⁴⁷Sm/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd ratios that was added during shock. The Rb-Sr system is disturbed and does not yield an isochron. Terrestrial Sr appears to have affected all of the mineral fractions, although a maximum initial ⁸⁷Sr/⁸⁶Sr ratio of 0.7016 is estimated by passing a 347 Ma reference line through the maskelynite fraction that is least affected by contamination. The high initial value and the low initial ⁸⁷Sr/⁸⁶Sr ratio, combined with the geologically young crystallization age, indicate that Northwest Africa 1195 is derived from a source region characterized by a long-term incompatible-element depletion.The age and initial Sr and Nd isotopic compositions of Northwest Africa 1195 are very similar to those of Queen Alexandra Range 94201, indicating these samples were derived from source regions with similar Sr-Nd isotopic systematics. These similarities suggest that these two meteorites share a close petrogenetic relationship and might have been erupted from a common volcano. The meteorites Yamato 980459, Dar al Gani 476, Sayh al Uhaymir 005/008, and Dhofar 019 also have relatively old ages between 474 and 575 Ma and trace element and/or isotopic systematics that are indicative of derivation from incompatible-element-depleted sources. This suggests that the oldest group of meteorites is more closely related to one another than they are to the younger meteorites that are derived from less incompatible-element-depleted sources. Closed-system fractional crystallization of this suite of meteorites is modeled with the MELTS algorithm using the bulk composition of Yamato 980459 as a parent. These models reproduce many of the major element and mineralogical variations observed in the suite. In addition, the rare earth element systematics of these meteorites are reproduced by fractional crystallization using the proportions of phases and extents of crystallization that are calculated by MELTS. Other shergottites that demonstrate enrichments in incompatible-elements and have evolved Sr and Nd isotopic systematics have some geochemical systematics that are similar to those observed in the depleted group. Most notably, although they exhibit a very limited range of incompatible trace element and isotopic compositions, they have highly variable major element compositions. This is also consistent with evolution from a common mantle source region by variable amounts of fractional crystallization. If this scenario is correct, it suggests that the combined effects of source composition and fractional crystallization are likely to account for the major element, trace element, and isotopic diversity of all shergottites.     

Biotite weathering and nutrient uptake by ectomycorrhizal fungus, Suillus tomentosus, in liquid-culture experiments

Ectomycorrhiza-forming fungi (EMF) alter the nutrient-acquisition capabilities of vascular plants, and may play an important role in mineral weathering and the partitioning of products of weathering in soils under nutrient-limited conditions. In this study, we isolated the weathering function of Suillus tomentosus in liquid-cultures with biotite micas incubated at room temperature. We hypothesized that the fungus would accelerate weathering by hyphal attachment to biotite surfaces and transmission of nutrient cations via direct exchange into the fungal biomass. We combined a mass-balance approach with scanning electron microscopy (SEM) and atomic force microscopy (AFM) to estimate weathering rates and study dissolution features on biotite surfaces. Weathering of biotite flakes was about 2-3 orders of magnitude faster in shaken liquid-cultures with fungus compared to shaken controls without fungus, but with added inorganic acids. Adding fungus in nonshaken cultures caused a higher dissolution rate than in inorganic pH controls without fungus, but it was not significantly faster than organic pH controls without fungus. The K⁺, Mg²⁺ and Fe²⁺ from biotite were preferentially partitioned into fungal biomass in the shaken cultures, while in the nonshaken cultures, K⁺ and Mg²⁺ was lost from biomass and Fe²⁺ bioaccumulated much less. Fungal hyphae attached to biotite surfaces, but no significant surface changes were detected by SEM. When cultures were shaken, the AFM images of basal planes appeared to be rougher and had abundant dissolution channels, but such channel development was minor in nonshaken conditions. Even under shaken conditions the channels only accounted for only 1/100 of the total dissolution rate of 2.7 × 10⁻¹⁰ mol of biotite m⁻² s⁻¹. The results suggest that fungal weathering predominantly occurred not by attachment and direct transfer of nutrients via hyphae, but because of the acidification of the bulk liquid by organic acids, fungal respiration (CO₂), and complexation of cations which accelerated dissolution of biotite. Results further suggest that both carbohydrate source (abundant here) and a host with which nutrients are exchanged (missing here) may be required for EMF to exert an important weathering effect in soils. Unsaturated conditions and physical dispersal of nutrient-rich minerals in soils may also confer a benefit for hyphal growth and attachment, and promote the attachment-mediated weathering which has been observed elsewhere on soil mineral surfaces.     

Water and sanitation in the Buenos Aires metropolitan region: Fragmented markets, splintering effects?

This paper discusses the provision of water and sanitation services and the related urban impacts in Buenos Aires circa 2005. The first part of the paper focuses on the metropolitan region (BAMR) which is larger than the area served by the Aguas Argentinas S.A. (AASA) concession (i.e. the capital and its conurbano). It highlights a form of institutional fragmentation that is reflected in the diverse management practices of the numerous service providers and results in differentiated levels of and access to services. The paper discusses the technical, economic and regulatory factors that have historically resulted in this institutional fragmentation. The second part of the article focuses on AASA’s water concession agreement. It demonstrates that, although the agreement had an in-built splintering logic, its implementation led to a more “integrated approach” based on the “reality on the ground”. On the whole, the conclusion regarding the application of the splintering urbanism concept to Buenos Aires is a mixed one and depends on the scale of observation. Although at regional level (BAMR), a form of “institutional fragmentation” would appear to be obvious, it is the result of a long and complex historical process and, while recent neo-liberal reforms in service provisions have “cemented” this fragmentation, they did not actually cause it. If we take the AASA service area in isolation, the trend in the decade following the contracting out of the service has been one of improved service provision and access—although this was not achieved through increased integration of the supply system. Finally, in the case of the Buenos Aires metropolitan region, the splintering urbanism thesis defended by Marvin and Graham needs to be nuanced in several significant ways.     

EPR investigation of the methyl radical,the hydrogen atom and carbon oxide radicals in Maxixe-type beryl

The EPR spectra of Maxixe-type beryl contain a large number of overlapping signals. The angular dependence of the 1:3:3:1 signal typical for the CH₃ radical shows that this radical is located at the center of the channel cavity with its symmetry axis parallel to the crystal c-axis and is rotating around this axis. Its EPR spectrum is axially symmetric with g _// = 2.00263, g _⊥ = 2.00249 and A_// = 2.288 mT, A_⊥ = 2.256 mT. These anisotropies have the opposite signs of those found for surface-adsorbed methyl radicals. Hydrogen atoms are located at position 2a at the center of the beryl cavity and the EPR parameters of the narrow doublet signal are A ₀ = 1,407 MHz and g = 2.00230. Another doublet signal, which is broader and has axial symmetry with g _// = 2.00265, g _⊥ = 2.00625 and A_// = 0.895 mT, A_⊥ = 0.885 mT, could come from a HCO₃ radical. One narrow and easily saturated signal with g _// = 2.00227 and g _⊥ = 2.00386 is interpreted to arise from a carbon monoxide radical in the beryl channel, oriented with its axis parallel to the crystal c-axis. Additional weak doublet lines, which have similar g values as the carbon monoxide radical, are created by nearby hydrogens. A powder spectrum with g _// = 2.0017 and g _⊥ = 2.0004 appears upon UV irradiation of the single crystal and is easily saturated. This spectrum is interpreted to arise from a carbon dioxide radical, which rotates around its symmetry axis.     

Prolonged Magmatic and Tectonic Development of the Caribbean Igneous Province Revealed by a Diving Submersible Survey

Using the diving submersible survey NAUTICA we investigated the central part of the Caribbean large igneous province (CLIP) to observe and sample internal portions of this proposed oceanic plateau. Most of the samples are gabbroic and doleritic rocks; basalts are scarce. Radiometric dating by ⁴⁰Ar/³⁹Ar incremental heating experiments indicate that the intrusive rocks are Campanian in age (81–75 Ma). In some places these intrusive rocks underlie older Santonian (85–83 Ma) extrusive basaltic rocks, suggesting that the Campanian rocks represent a sill injection and an underplating episode. Results of the diving program supplemented by information from ODP and DSDP drilling sites document a 20 m.y. period (94–75 Ma) of igneous activity in the submerged portion of the Caribbean large igneous province (CLIP). In the northern part of the Beata Ridge late Campanian and/or post Campanian uplift is documented by prominent Maastrichtian (71–65 Ma) erosion and the establishment of a Paleocene-middle Eocene (65–49 Ma) carbonate platform. During and after the uplift an extensional period is indicated by seismic images and the subsidence (3 km depth) of the carbonate platform. Paleocene ages (55–56 Ma) determined on some volcanic samples are attributed to localised decompression mantle melting that accompanied the extension. We document a prolonged period of magmatic and tectonic events that do not fit with the current models of short-lived plateau formation during mantle plume initiation but shares many similarities with the constructional histories of other oceanic large igneous provinces.