Clay mineral weathering and contaminant dynamics in a caustic aqueous system: I. Wet chemistry and aging effects

Caustic high level radioactive waste induces mineral weathering reactions that can influence the fate of radionuclides released in the vicinity of leaking storage tanks. The uptake and release of Cs^I and Sr^II were studied in batch reactors of 2:1 layer-type silicates—illite (Il), vermiculite (Vm) and montmorillonite (Mt)—under geochemical conditions characteristic of leaking tank waste at the Hanford Site in WA (0.05 m Al_T, 2 m Na⁺, 1 m NO₃⁻, pH ∼14, Cs and Sr 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 10⁻³ mol kg⁻¹. Clay mineral type affected the rates of (i) hydroxide promoted dissolution of Si, Al and Fe, (ii) precipitation of secondary solids and (iii) uptake of Cs and Sr. Initial Si release to solution followed the order Mt > Vm > Il. An abrupt decrease in soluble Si and/or Al after 33 d for Mt and Vm systems, and after 190 d for Il suspensions was concurrent with accumulation of secondary aluminosilicate precipitates. Strontium uptake exceeded that of Cs in both rate and extent, although sorbed Cs was generally more recalcitrant to subsequent desorption and dissolution. After 369 d reaction time, reacted Il, Vm and Mt solids retained up to 17, 47 and 14 mmol kg⁻¹ (0.18, 0.24 and 0.02 μmol m⁻²) of Cs, and 0, 27 and 22 mmol kg⁻¹ (0, 0.14 and 0.03 μmol m⁻²) Sr, respectively, which were not removed in subsequent Mg exchange or oxalic acid dissolution reactions. Solubility of Al and Si decreased with initial Cs and Sr concentration in Mt and Il, but not in Vm. High co-contaminant sorption to the Vm clay, therefore, appears to diminish the influence of those ions on mineral transformation rates.     

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.     

Catalysis by mineral surfaces: Implications for Mo geochemistry in anoxic environments

Fixation of Mo in sulfidic environments is believed to be preceded by conversion of geochemically passive MoO₄²⁻ to particle-reactive thiomolybdates (MoO_xS_4−x²⁻). In aqueous solution, these transformations are general-acid catalyzed, implying that proton donors can accelerate both the forward and reverse reactions. Here, we explore whether mineral surfaces also catalyze thiomolybdate interconversions. The rate of MoS₄²⁻ hydrolysis is investigated in the presence and absence of natural kaolinite (KGa-1b) and synthetic Al₂O₃ and SiO₂ phases. Comparison of rates achieved with these phases suggests that the Al oxyhydroxide component in kaolinite furnishes the catalytic activity. An anhydrous Al₂O₃ phase is catalytically inactive until hydrated (and therefore protonated). Surface kinetics with kaolinite at mildly alkaline pH are consistent with rate limitation by formation or decomposition of monomeric surface complexes; oligomeric surface intermediates may become important at MoS₄²⁻ > 20 μmol/L, higher than is likely to be found in nature. The pH dependence of the kaolinite-catalyzed reaction suggests that weak-acid surface sites promote hydrolysis. Intermediate thiomolybdates or molybdate appears to compete for active sites, inhibiting MoS₄²⁻ hydrolysis. Catalysis of MoOS₃²⁻ hydrolysis is also observed but has not been studied systematically. Thiomolybdate hydrolysis is inhibited slightly by sulfate and more strongly by phosphate. Low NaCl concentrations (<10⁻² mol/L) promote hydrolysis, but higher NaCl concentrations retard the reaction to a small extent. A mechanism is postulated involving expansion of the coordination number around Mo from 4 to 6 under the influence of the surface. The effective concentration of surface sites available to Mo in sediment pore waters is likely to be large enough to greatly accelerate thiomolybdate hydrolysis and sulfidation. Possibly this explains why Mo capture in seasonally or intermittently anoxic environments often occurs through processes operating within sediments but not in overlying waters.     

Major element chemistry of surface- and ground waters in basaltic terrain, N-Iceland.: I. primary mineral saturation

This contribution describes primary basalt mineral saturation in surface- and up to 90°C ground waters in a tholeiite flood basalt region in northern Iceland. It is based on data on 253 water samples and the mineralogical composition of the associated basalts. Surface waters are significantly under-saturated with plagioclase and olivine of the compositions occurring in the study area, saturation index (SI) values ranging from −1 to −10 and −5 to −20, respectively. With few exceptions these waters are also significantly under-saturated with pigeonite and augite of all compositions (SI = −1 to −7) and with ilmenite (SI = −0.5 to −6). The surface waters are generally over-saturated with respect to the titano-magnetite of the compositions occurring in the basalts of the study area, the range in SI being from −2 to +10. For crystalline OH-apatite, SI values in surface waters range from strong under-saturation (−10) to strong over-saturation (+5) but for crystalline F-apatite they lie in the range 0 to 15. Systematic under-saturation is, on the other hand, observed for “amorphous apatite,” i.e. an apatite of the kind Clark (1955) prepared by mixing Ca(OH)₂ and H₃PO₄ solutions. Like surface waters, ground waters are under-saturated with plagioclase and olivine, its degree increasing with increasing Ca content of the plagioclase and increasing Fe content of the olivine, the SI values being −2 to −7 and 0 to −4 for the Ca-richest and Ca-poorest plagioclase, respectively, and about −3 to −18 and 0 to −15 for forsterite and fayalite, respectively. Ground waters are generally close to saturation with pigeonite and augite of all compositions. However, some non-thermal ground waters in highland areas are strongly under-saturated. Above 25°C the ground waters are ilmenite under-saturated but generally over-saturated at lower temperatures. These waters are titano-magnetite over-saturated at temperatures below 70°C, the SI values decreasing with increasing temperature from about 6 to 8 at 10°C to 0 at 70°C. The ground waters are highly over-saturated with both crystalline OH- and F-apatite, or by approximately 10 to 15 SI units but close to saturation with “amorphous apatite” containing about equal amounts of F and OH. The results presented here for the pyroxenes carry an unknown error because available thermodynamic data do not permit but a simple solid solution model for the calculation of their solubility. Published values on the dissociation constants for ferrous iron hydroxide complexes are very variable and those for ferric iron are limited. This casts an error of an unknown magnitude on the calculated SI values for all iron bearing minerals. This error may not be large for waters with a pH of less than 9 but it is apparently high for waters with a higher pH. Improved experimental data on the stability of ferrous and ferric hydrolysis constants are needed to improve the accuracy by which Fe-mineral saturation can be calculated in natural waters.     

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.     

Variation in calcite dissolution rates:: A fundamental problem?

A comparison of published calcite dissolution rates measured far from equilibrium at a pH of ∼ 6 and above shows well over an order of magnitude in variation. Recently published AFM step velocities extend this range further still. In an effort to understand the source of this variation, and to provide additional constraint from a new analytical approach, we have measured dissolution rates by vertical scanning interferometry. In areas of the calcite cleavage surface dominated by etch pits, our measured dissolution rate is 10^−10.95 mol/cm²/s (PCO₂ 10^−3.41 atm, pH 8.82), 5 to ∼100 times slower than published rates derived from bulk powder experiments, although similar to rates derived from AFM step velocities. On cleavage surfaces free of local etch pit development, dissolution is limited by a slow, “global” rate (10^−11.68 mol/cm²/s). Although these differences confirm the importance of etch pit (defect) distribution as a controlling mechanism in calcite dissolution, they also suggest that “bulk” calcite dissolution rates observed in powder experiments may derive substantial enhancement from grain boundaries having high step and kink density. We also observed significant rate inhibition by introduction of dissolved manganese. At 2.0 μM Mn, the rate diminished to 10^−12.4 mol/cm²/s, and the well formed rhombic etch pits that characterized dissolution in pure solution were absent. These results are in good agreement with the pattern of manganese inhibition in published AFM step velocities, assuming a step density on smooth terraces of ∼9 μm⁻¹.     

Modeling of flowing film concentrators: Part 1. Water split behaviour

A large number of mineral processing equipment employs the basic principles of gravity concentration in a flowing fluid of a few millimetres thick in small open channels where the particles are distributed along the flow height based on their physical properties and the fluid flow characteristics. Fluid flow behaviour and slurry transportation characteristics in open channels have been the research topic for many years in many engineering disciplines. However, the open channels used in the mineral processing industries are different in terms of the size of the channel and the flow velocity used. Understanding of water split behaviour is, therefore, essential in modeling flowing film concentrators. In this paper, an attempt has been made to model the water split behaviour in an inclined open rectangular channel, resembling the actual size and the flow velocity used by the mineral processing industries, based on the Prandtl's mixing length approach.     

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.     

Comparative Re-Os systematics of chondrites: Implications regarding early solar system processes

A suite of 47 carbonaceous, enstatite, and ordinary chondrites are examined for Re-Os isotopic systematics. There are significant differences in the ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os ratios of carbonaceous chondrites compared with ordinary and enstatite chondrites. The average ¹⁸⁷Re/¹⁸⁸Os for carbonaceous chondrites is 0.392 ± 0.015 (excluding the CK chondrite, Karoonda), compared with 0.422 ± 0.025 and 0.421 ± 0.013 for ordinary and enstatite chondrites (1σ standard deviations). These ratios, recast into elemental Re/Os ratios, are as follows: 0.0814 ± 0.0031, 0.0876 ± 0.0052 and 0.0874 ± 0.0027, respectively. Correspondingly, the ¹⁸⁷Os/¹⁸⁸Os ratios of carbonaceous chondrites average 0.1262 ± 0.0006 (excluding Karoonda), and ordinary and enstatite chondrites average 0.1283 ± 0.0017 and 0.1281 ± 0.0004, respectively (1σ standard deviations). The new results indicate that the Re/Os ratios of meteorites within each group are, in general, quite uniform. The minimal overlap between the isotopic compositions of ordinary and enstatite chondrites vs. carbonaceous chondrites indicates long-term differences in Re/Os for these materials, most likely reflecting chemical fractionation early in solar system history.A majority of the chondrites do not plot within analytical uncertainties of a 4.56-Ga reference isochron. Most of the deviations from the isochron are consistent with minor, relatively recent redistribution of Re and/or Os on a scale of millimeters to centimeters. Some instances of the redistribution may be attributed to terrestrial weathering; others are most likely the result of aqueous alteration or shock events on the parent body within the past 2 Ga.The ¹⁸⁷Os/¹⁸⁸Os ratio of Earth’s primitive upper mantle has been estimated to be 0.1296 ± 8. If this composition was set via addition of a late veneer of planetesimals after core formation, the composition suggests the veneer was dominated by materials that had Re/Os ratios most similar to ordinary and enstatite chondrites.     

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.     

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.