Main-group pallasites: chemical composition, relationship to IIIAB irons, and origin

We used neutron activation to characterize the metal of 33 main-group pallasites (PMG), widely held to be samples of a core-mantle interface. Most PMG cluster in a narrow range of metal and silicate compositions, but 6 are assigned to an anomalous subset (PMG-am) because of their deviant metal compositions, and 4 others to another anomalous subset (PMG-as) because of their appreciably higher olivine Fa contents. Metal compositions in all PMG are closely related to those in evolved IIIAB irons, and are generally consistent with their formation in the IIIAB parent asteroid. On element-Au diagrams for incompatible elements the normal PMG plot near an extrapolation of IIIAB trends to higher Au concentrations. On element-Au plots of compatible elements such as Ir or Pt the loci of PMG spread out over a broader region explainable by mixing of evolved IIIAB magma with early-crystallized core or mantle-residue solids.Two features of PMG require special models: (1) Ga and Ge contents are generally high (≈1.5×) compared to the IIIAB-based mixing model: and (2) the FeO/(FeO + MgO) ratios span a surprisingly wide range, from 0.11-0.14 in normal PMG to 0.16 to 0.18 in PMG-as This range is larger than expected in a cumulate layer at the base of a mantle. We suggest that both features may be related to the interaction of PMG precursors with a highly evolved magmatic gas phase, and that some or all of these anomalies may have resulted from vapor deposits in voids near the core-mantle interface.An important boundary condition for understanding the detailed PMG origin at the core-mantle interface is the large difference between the solidus temperature of Fa11 olivine (≈2000 K) and the liquidus temperature of an evolved IIIAB melt containing >100 mg/g S and some P (≈1600 K). Following the mixing event that formed the PMG it is therefore reasonable that there would have been olivine rubble floating on top of the IIIAB-like magma, but with appreciable void space present just above the upper level reached by the magma. These voids would have contained gases released from the magma during its flow into the PMG region. We suggest that Ga and Ge, the two most volatile siderophiles in our element set, were added to PMG metal from the magmatic gas. We also suggest that the magmatic gas was oxidizing and that the PMG having high olivine fayalite contents formed in regions where the ratio of void to olivine was high, and that some metallic Fe was oxidized and entered the olivine (or the phosphoran olivine). In support of the latter idea is the observation that both Ni and Co are elevated in the PMG-as (Fa≥16) compared to values predicted by IIIAB trends.We analyzed two Eagle-Station pallasites (PES); after correction for weathering effects in Cold Bay, its composition is found to closely resemble that of Eagle Station but to represent a more evolved composition (i.e., lower Ir, higher Au). Vermillion and Yamato 8451 have been called pyroxene pallasites but have metal compositions (unrelated to those of the PMG or PES) that are too different from each other to even allow assignment to the same grouplet.     

Geochemical and Nd isotope composition of detrital sediments on the north margin of the South China Sea: provenance and tectonic implications

A major re‐organization of regional drainages in eastern Tibet and south‐western China took place in the Cenozoic as deformation from the growing Himalayas and Tibetan Plateau affected an increasingly wider area. The effects of these changes on the regional sediment routing systems is not well constrained. This study examines the geochemical and Nd signatures of sedimentary rocks from the Ying‐Qiong and Nanxiong basins on the northern margin of the South China Sea to constrain and identify any significant changes in sediment source. Upper Cretaceous to Lower Eocene sedimentary rocks in the Nanxiong Basin show higher Th/Sc, La/Sc, Th/Cr and Th/Co ratios and lower Eu/Eu* ratios than PAAS (post‐Archaean Australian Shale), which indicates that Palaeozoic sedimentary rocks of the South China Block were the main basin sediment source. In contrast, Oligocene to Pleistocene sedimentary rocks of the Ying‐Qiong Basin show an abrupt change in these trace‐element ratios between 16·3 and 10·4 Ma, indicating a mid‐Miocene shift in provenance. ɛ_Nd values from the Ying‐Qiong Basin (range = −11·1 to −2·1) reinforce this, with pre‐13·8 Ma sedimentary rocks having average ɛ_Nd of −5·6 (range = −2·1 to −7·4), and post‐13·8 Ma sedimentary rocks having average ɛ_Nd of −9·3 (range = −8·7 to −11·1). During the Oligocene, the centre of rifting transferred south and basins on the north margin of the South China Sea experienced rapid subsidence. Further uplift and erosion then exposed Mesozoic and Cenozoic granites that supplied large amounts of granitic detritus, especially to the Ying‐Qiong Basin. Then a change occurred at ca 13 Ma resulting in less input from local sources (i.e. the fault blocks formed by Mesozoic‐Cenozoic tectonics and magmatism) to an increasing contribution of older continental material, mostly from Indochina to the west of the South China Sea.     

Microscopic reversibility of Sm and Yb sorption onto smectite and kaolinite: Experimental evidence

The microscopic reversibility of the sorption of Sm and Yb onto kaolinite and smectite is investigated by introducing an isotopic disequilibrium between the clay and the solution. The experiments are performed at 25°C, in 0.025 or 0.5 M NaClO₄ and from pH 4 up to pH 7. The isotopic exchange is monitored as a function of time over a duration of 355 hours. The first stage of the experiment consists of equilibrating the clays with a natural or spiked lanthanide solution. The second stage consists of interchanging the solutions between twin phials (same clay, pH and ionic strength, but with different lanthanide isotopic compositions). The isotopic composition and concentration of aqueous lanthanides are analysed by ICP-MS. The results are as follows: (1) the lanthanide isotopic composition of the solution is rapidly modified and stabilised within 24 h; (2) the isotopic exchange between the solid and the solution is not always complete; (3) the degree of microscopic reversibility (isotopic exchange) decreases with increasing pH. These results are explained by the fact that exchange is easier for lanthanides linked to the surface as outer-sphere complexes (physical sorption), which predominate at low pH, than for atoms sorbed as inner-sphere complexes (chemical sorption) which predominate at high pH. The contrasted kinetics observed for the different kind of sites provide additional constraints for the modeling of migration processes in natural systems.     

An anisotropic Model for Structured Soils: Part I: Theory

The paper presents an incremental plasticity constitutive Model for Structured Soils (MSS–2) to describe the effects of structure (stress history and bonding) on the mechanical behaviour of cohesive soils. Such effects are high initial stiffness, dilatancy and peak strength, their appreciable reduction upon strain-induced de-structuring and the evolution of material anisotropy. The proposed model advances present practice in incremental elasto-plasticity for structured soils by incorporating: (a) distorted ellipsoids, rotated with respect to the isotropic axis, for the Structure Strength Envelope (bounding surface) and the Plastic Yield Envelope (yield surface) to describe the evolution of structure and anisotropy, (b) an Intrinsic Compressibility Framework and a corresponding Intrinsic Strength Envelope which represents a lower bound of the Structure Strength Envelope and is used as reference locus for the structureless material, (c) an improved damage mechanism to model structure degradation by plastic strains and (d) a non-associated flow rule controlled by structure. The proposed model is modular, its features can be activated simultaneously or selectively, and the 3-D tensorial formulation facilitates direct implementation in finite elements codes.     

Antinomies of generosity: Moral geographies and post-tsunami aid in Southeast Asia

The Indian Ocean Tsunami on Boxing Day 2004 generated a wave of private donations from Western countries - a paradigmatic case of generosity. However, more than a year after, a number of evaluation studies conclude that post-tsunami aid has achieved ambivalent results and that recipients of aid felt excluded from the reconstruction process, reduced to passive observers. This paper argues that there is a link between the abundance of generosity and the practices of aid: the practices of gift giving after the tsunami have developed a humiliating force for those who were at the recipient end of the gift chain, because the marketing of Western generosity by media and aid agencies reinforced those affected by the tsunami as “pure” victims, as “bare life” - passive recipients devoid of their status as fellow citizens on this planet. In a second step, the paper discusses the meta-ethics of these practices of generosity, thinking about the ambivalences inherent in bridging distance in encountering the “distant” other in our aid practices. Various forms of virtue ethics reflect this emphasis on the generous person, while neglecting the perspective of the person in need, and therefore implicitly reproduce those asymmetries of gift giving. In contrast to these conceptions, I want to argue that we need to ground our duty to help distant sufferers in their moral entitlement to be aided. This requires a meta-ethical approach that seeks a combination of a theory of justice with virtue ethics.     

Landscape governance: The “politics of scale” and the “natural” conditions of places

Governance has become an iridescent concept in recent years. The term is widely used in almost all social-science disciplines as well as in the political process. The intention of this paper is not so much to clarify these sometimes vague meanings but to highlight some characteristics of environmental governance connected with the restructuring of the spatial dimensions of politics. It starts from the assumption that the quest for multi-level decision making is particularly pressing for environmental governance. However, multi-level governance raises concern about the constitution of various spatial levels and their relationships with each other, as discussed under the term of “politics of scale”. Moreover, it is argued that for environmental governance the spatial reference is strongly connected with another challenge, which concerns the question of how to deal with the biophysical conditions of particular places. The term landscape governance is introduced to tackle this question without referring to an ontologically given space. Thus, landscape governance deals with the interconnections between socially constructed spaces (the politics of scale) and “natural” conditions of places. For this task, the concept of societal relationships with nature is introduced and applied to the term “landscape” as a bridging concept between social and natural sciences. The paper illustrates the approach of landscape governance with examples of problem-oriented interdisciplinary research at the UFZ-Centre for Environmental research in Leipzig, Germany.     

Environmental literacy in interpreting endangered sustainability: Case studies from Thailand and the Sudan

This paper examines how people explain reasons and impacts of environmental change in the low-rain savanna of the central Sudan and mountainous forest lands of northern Thailand. The explanations are analyzed by using the concept of environmental literacy, which refers to the people’s ability to grasp the environment and its interactions. The paper aims to study people’s conceptions of the environment, which compose one factor in directing their behavior. For the study, rural inhabitants in the State of North Kordofan, the Sudan, and the Chiang Mai Province in Thailand were interviewed.It was noted that an individual’s capability to understand the environment is alone insufficient to address environmental problems because the efficient alleviation of the problems requires collective actions at all levels, and because of factors beyond an individual’s control. However, the results supported the assumption that the local people have knowledge of their environment that may help in developing sustainable environmental management practices. The main advantages of using the environmental literacy concept are argued to be its dynamic and synthetic essence, its link to sustainable behavior, and wide applicability in various contexts within heterogeneous communities.     

Proximity effects on semiconducting mineral surfaces II:: Distance dependence of indirect interactions

In a previous study, we described proximity effects on surfaces of the semiconducting minerals galena and pyrite, whereby a chemical reaction at one surface site modifies the reactivity of a remote surface site several Ångstroms or even nanometers away (Becker et al., 2001). The modification of interest does not arise because of a direct “through space” interaction between the two sites, but rather an indirect interaction via the electronic structure of the substrate. Here we investigate the distance and direction dependence of proximity effects using quantum mechanical modeling. The direct and indirect interactions between co-adsorbed oxygen atoms and between adsorbed oxygen atoms and point defects on vacuum-terminated galena (100) surfaces were modeled. Density functional theory cluster and plane wave pseudopotential calculations were used to calculate the modifications to the adsorption energy as a function of separation. Energy-distance plots indicate that the proximity effect energy can become very strong at separations decreasing below about 5 to 6 Å, and persist at increasing separations up to 12 Å in a slowly decaying form. A strong attractive indirect interaction out-competes direct electrostatic repulsion for O-vacancy interactions. An oscillatory asymptotic behavior is found for co-adsorbed O-O indirect interactions, which indicates that the proximity effect energy can vary with surface crystallographic direction. It implies the presence of a strong organizing force on like adatoms that may explain the progressive oxidation of certain sulfide minerals by patchwork growth. These findings begin to pave the way for improved adsorption isotherms and extended surface complexation models that will include the specific influence of semiconductor-type proximity effects.     

Diffusion kinetics of Fe and Mg in aluminous spinel: experimental determination and applications

The diffusion coefficients of Fe²⁺ and Mg in aluminous spinel at ∼20 kb, 950 to 1325°C, and at 30 kb, 1125°C have been determined via diffusion couple experiments and numerical modeling of the induced diffusion profiles. The oxygen fugacity, fO₂, was constrained by graphite encapsulating materials. The retrieved self-diffusion coefficients of Fe²⁺ and Mg at ∼20 kb, 950 to 1325°C, fit well the Arrhenian relation, D = D₀exp(−Q/RT), where Q is the activation energy, with D₀(Fe) = 1.8 (±2.8) × 10⁻⁵, D₀(Mg) = 1.9 (±1.4) × 10⁻⁵ cm²/s, Q(Fe) = 198 ± 19, and Q(Mg) = 202 ± 8 kJ/mol. Comparison with the data at 30 kb suggests an activation volume of ∼5 cm³/mol. From analysis of compositional zoning in natural olivine-spinel assemblages in ultramafic rocks, previous reports concluded that D(Fe-Mg) in spinel with Cr/(Cr + Al) ≤0.5 is ∼10 times that in olivine. The diffusion data in spinel and olivine have been applied to the problems of preservation of Mg isotopic inhomogeneity in spinel within the plagioclase-olivine inclusions in Allende meteorite and cooling rates of terrestrial ultramafic rocks.     

Chemical evolution of seawater during the Phanerozoic: Implications from the record of marine evaporites

The chemical evolution of seawater during the Phanerozoic is still a matter of debate. We have assembled and critically analyzed the available data for the composition of fluid inclusions in marine halite and for the mineralogy of marine evaporites. The composition of fluid inclusions in primary marine halite reveals two major long-term cycles in the chemistry of seawater during the past 600 myr. The concentration of Mg²⁺, Ca²⁺, and SO₄²⁻ has varied quite dramatically. The Mg²⁺ concentration in seawater during most of the early Paleozoic and Jurassic to Cretaceous was as low as 30 to 40 mmol/kg H₂O; it reached maximum values ≥50 mmol/kg H₂O during the Late Neoproterozoic and Permian. The Ca²⁺ concentration in seawater during the Phanerozoic has reached maximum values two to three times greater than the concentration in seawater today (10.6 mmol/kg H₂O), whereas SO₄²⁻ concentrations may have been as low as 5 to 10 mmol/kg H₂O (a third to a fifth of the modern value) during the Jurassic and Early Paleozoic. The Mg²⁺/Ca²⁺ ratio in seawater ranged from 1 to 1.5 during the early to middle Paleozoic and Jurassic-Cretaceous to a near-modern value of 5.2 during the Late Neoproterozoic and Permian. This change in seawater Mg²⁺/Ca²⁺ ratio is consistent with the notion of alternating “calcite-aragonite seas” recorded in oölites and marine carbonate cements.Several models have been proposed to explain the chemical evolution of seawater. These have invoked significant changes in one or more of the major geochemical processes that control the composition of seawater. The pattern and magnitude of the variations in the composition of seawater proposed in this study are similar to those proposed elsewhere that suggest that seawater fluxes through midocean ridges have played a major role in the evolution of seawater during the past 600 myr. Two Phanerozoic supercycles of the Earth’s exogenic processes were recognized in the literature that are caused by mantle convection and plate activity. The composition of seawater has apparently undergone dramatic secular changes in phase with these supercycles and as a consequence of biological evolution. Analyses of fluid inclusions containing unevaporated seawater and a better understanding of the processes that affect the composition of seawater are needed to refine our understanding of the history of Phanerozoic seawater.     

Origin of iodine in volcanic fluids: I results from the Central American Volcanic Arc

The largest reservoir of crustal iodine is found in marine sediments, where it is closely associated with organic material. This presence, together with the existence of a long-lived, cosmogenic radioisotope ¹²⁹I (t_1/2 = 15.7 Ma), make this isotopic system well suited for the study of sediment recycling in subduction zones. Reported here are the results of ¹²⁹I/I ratios in volcanic fluids, collected during a comprehensive study of fluids and gases in the Central American Volcanic Arc. ¹²⁹I/I ratios, together with I, Br, and Cl concentrations, were determined in 79 samples from four geothermal centers and a number of crater lakes, fumaroles, hot springs, and surface waters in Costa Rica, Nicaragua, and El Salvador. Geothermal and volcanic fluids were found to have iodine concentrations substantially higher than values in seawater or meteoric waters. ¹²⁹I/I ratios in most of the geothermal fluids are below the preanthropogenic input ratio of 1500 × 10⁻¹⁵, demonstrating that recent anthropogenic additions are largely absent from the volcanic systems. The majority of the ¹²⁹I/I ratios are between 500 and 800 × 10⁻¹⁵. These ratios indicate minimum iodine ages between 25 and 15 Ma, in good agreement with the age of subducted sediments in this region. In all four geothermal systems, however, a few samples were found with iodine ages older than 40 Ma—that is, considerably below the expected age range for subducted sediments from the Cocos Plate. These samples probably reflect the presence of iodine derived from sediments in older accreted oceanic terraines. The iodine ages indicate that the magmatic end member for the volcanic fluids originates in the deeper parts of the subducted sediment column, with small additions from older iodine mobilized from the overlying crust. The high concentrations of iodine in geothermal fluids, combined with the observed iodine ages, demonstrate that remobilization in the main volcanic zone (and probably also in the forearc area) is an important part in the overall marine cycle of iodine and similar elements.     

Precise geochronology of phoscorites and carbonatites:: The critical role of U-series disequilibrium in age interpretations

We present the results of a comparative study of several geochronometer minerals (baddeleyite, zircon, apatite, phlogopite and tetraferriphlogopite) and isotopic systems (U-Pb, Th-Pb and Rb-Sr) from phoscorites (magnetite-forsterite-apatite-calcite rocks) and carbonatites of the Kovdor ultramafic-alkaline-carbonatite massif, Kola Peninsula, Russia. Uranium, thorium and their decay products are extremely fractionated by minerals that crystallise from carbonatite and phoscorite magma. We obtain high-precision ages from different chronometers, compare their accuracy, and evaluate the role of geochronological pitfalls of initial radioactive disequilibrium, differential migration of radiogenic isotopes, and inaccurate decay constants.Apatite yielded concordant U-Th-Pb ages between 376 and 380 Ma. The accuracy of the apatite ²³⁸U-²⁰⁶Pb ages is, however, compromised by uncertainty in the amount of radiogenic ²⁰⁶Pb produced from initial excess ²³⁰Th. The ²³⁵U-²⁰⁷Pb ages are relatively imprecise due to large common Pb correction and the uncertainty in the initial Pb isotopic composition. The Th-Pb system yields a more precise age of 376.4 ± 0.6 Ma.Zircon from two carbonatite samples is characterised by moderate to low U contents, high Th contents, and very high Th/U ratios up to 9000. The ²⁰⁶Pb*/²³⁸U systems in the zircon are strongly affected by the presence of excess ²⁰⁶Pb*, produced by decay of initial ²³⁰Th. The ²⁰⁸Pb*/²³²Th ages of zircon from both carbonatite samples are uniform and yield a weighted average of 377.52 ± 0.94 Ma.Baddeleyite U-Pb analyses are 3 to 6% normally discordant and have variable ²⁰⁷Pb*/²⁰⁶Pb* apparent ages. Eleven alteration-free baddeleyite fractions from three samples with no evidence for Pb loss yield uniform ²⁰⁶Pb*/²³⁸U ages with a weighted average of 378.54±0.23 Ma (378.64 Ma after correction for initial ²³⁰Th deficiency), which we consider the best estimate for age of the phoscorite-carbonatite body of the Kovdor massif. The ²⁰⁶Pb*/²³⁸U ages of baddeleyite fractions from five other samples spread between 378.5 and 373 Ma, indicating a variable lead loss up to 1.5%. The anomalously old ²⁰⁷Pb/²³⁵U and ²⁰⁷Pb/²⁰⁶Pb ages are consistent with the presence of excess radiogenic ²⁰⁷Pb* in the baddeleyite. We interpret this as a result of preferential partitioning of ²³¹Pa to baddeleyite.Fifteen phlogopite and tetraferriphlogopite fractions from five carbonatite and phoscorite samples yielded precise Rb-Sr isochron age of 372.2 ± 1.5 Ma, which is 5 to 7 m.y. younger than our best estimate based on U-Th-Pb age values. This difference is unlikely to be a result of the disturbance or late closure of Rb-Sr system in phlogopite, but rather suggests that the accepted decay constant of ⁸⁷Rb is too high.Comparative study of multiple geochronometer minerals from the Kovdor massif has revealed an exceptional complexity of isotopic systems. Reliable ages can be understood through systematic analysis of possible sources of distortion. No single geochronometer is sufficiently reliable in these rocks. Th-Pb and Rb-Sr can be a very useful supplement to U-Pb geochronometry, but the routine use of these geochronometers together will require more precise and accurate determination of decay constants for ²³²Th and ⁸⁷Rb.     

Clay mineral weathering and contaminant dynamics in a caustic aqueous system: II. Mineral transformation and microscale partitioning

Microscopic and spectroscopic studies were conducted to assess mineral transformation processes in aqueous suspensions of illite (Il), vermiculite (Vm) and montmorillonite (Mt) that were subjected to weathering in a simulated high-level radioactive tank waste leachate (0.05 m Al_T, 2 m Na⁺, 1 m NO₃⁻, pH ∼14, Cs⁺ and Sr²⁺ present as co-contaminants). Time series (0 to 369 d) experiments were conducted at 298 K, with initial [Cs]₀ and [Sr]₀ concentrations from 10⁻⁵ to 10⁻ mol kg⁻. Incongruent clay dissolution resulted in an accumulation of secondary aluminosilicate precipitates identified as nitrate-sodalite, nitrate-cancrinite and zeolite X, by molecular spectroscopy and electron microscopy (XRD, IR, NMR, SEM-EDS and TEM-EDS). Contaminant fate was dependent on competing uptake to parent clays and weathering products. TEM-EDS results indicated that high Il affinity for Cs was due to adsorption at frayed edge sites. The Il system also comprised Sr-rich aluminous precipitates after 369 d reaction time. In Mt systems, Cs and Sr were co-precipitated into increasingly recalcitrant spheroidal precipitates over the course of the experiment, whereas contaminant association with montmorillonite platelets was less prevalent. In contrast, Cs and Sr were found in association with weathered Vm particles despite the formation of spheroidal aluminosilicate precipitates that were comparable to those formed from Mt dissolution.