Surface complexation of U(VI) on goethite (α-FeOOH)     

David M. Sherman  Caroline L. Peacock  Christopher G. Hubbard 《Geochimica et cosmochimica acta》2008,72(2):298-310

Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation , sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)₂UO₂(H₂O)_n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO₂-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)₂UO₂(H₂O)₃ which can form on the dominant {101} surface. However, in the presence of CO₂, we find an enhancement of UO₂ sorption at low pH and attribute this to a (>FeO)CO₂UO₂ ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)₂UO₂CO₃. The three proposed surface complexes, (>FeOH)₂UO₂(H₂O)₃, >FeOCO₂UO₂, and (>FeOH)₂UO₂CO₃ are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO₂-OH-CO₃ aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO₂ environments at surface loadings of 0.02-2.0 wt% U.  相似文献   

Reaction mechanism of uranyl in the presence of zero-valent iron nanoparticles     

Olga Riba  Thomas B. Scott  Geoffrey C. Allen 《Geochimica et cosmochimica acta》2008,72(16):4047-4057

The current study provides an investigation of abiotic reduction of an oversaturated uranyl solution driven by iron nanoparticle oxidation. The reactivity of nano-scale zero-valent iron (ZVI) under mildly oxic conditions (1.2% O₂ and 0.0017% CO₂) was studied in 1000 ppm uranyl solution in the pH range 3-7, at reaction times from 10 min to 4 h. Reductive precipitation of UO₂ was observed as the main process responsible for the removal of uranium from solution with the kinetics of reaction becoming increasingly favourable at higher pH. Despite working with an oversaturated uranium solution, the precipitation of UO₂ occurred in preference to precipitation of UO₃·2H₂O (metaschoepite) at reaction times between 1 and 4 h and for uranyl solutions initially set up at pH ?5. Characterisation of both solid and solution phases was performed using X-ray photoelectron spectroscopy (XPS), focused ion beam (FIB) imaging, X-ray diffraction (XRD) and inductively coupled plasma atomic emission spectroscopy (ICP-AES).  相似文献   

Seasonal δS variations in two high elevation snow pits measured by S-S double spike thermal ionization mass spectrometry     

Jacqueline L. Mann  Christopher A. Shuman  Karl J. Kreutz 《Geochimica et cosmochimica acta》2008,72(15):3907-3927

δ³⁴S and sulfate concentrations were determined in snow pit samples using a thermal ionization mass spectrometric technique capable of 0.2‰ accuracy and requires ≈5 μg (0.16 μmol) natural S. The technique utilizes a ³³S-³⁶S double spike for instrumental mass fractionation correction, and has been applied to snow pit samples collected from the Inilchek Glacier, Kyrgyzstan and from Summit, Greenland. These δ³⁴S determinations provide the first high-resolution seasonal data for these sites, and are used to estimate seasonal sulfate sources. Deuterium (δD) and oxygen (δ¹⁸O) isotope data show that the Inilchek and Summit snow pit samples represent precipitation over ≈20 months.The δ³⁴S values for the Inilchek ranged from +2.6 ± 0.4‰ to +7.6 ± 0.4‰ on sample sizes ranging from 0.3 to 1.8 μmol S. δ³⁴S values for Greenland ranged from +3.6 ± 0.7‰ to +13.3 ± 5‰ for sample sizes ranging from 0.05 to 0.29 μmol S. The concentration ranged from 92.6 ± 0.4 to 1049 ± 4 ng/g for the Inilchek and 18 ± 9 to 93 ± 6 ng/g for the Greenland snow pit. Anthropogenic sulfate dominates throughout the sampled time interval for both sites based on mass balance considerations. Additionally, both sites exhibit a seasonal signature in both δ³⁴S and concentration. The thermal ionization mass spectrometric technique has three advantages compared to gas source isotopic methods: (1) sample size requirements of this technique are 10-fold less permitting access to the higher resolution S isotope record of low concentration snow and ice, (2) the double spike technique permits δ³⁴S and S concentration to be determined simultaneously, and (3) the double spike is an internal standard.  相似文献   

Experimental investigation of the effects of temperature and ionic strength on Mo isotope fractionation during adsorption to manganese oxides     

Laura E. Wasylenki  Bryan A. Rolfe  Thomas G. Spiro 《Geochimica et cosmochimica acta》2008,72(24):5997-6005

The Mo stable isotope system is being applied to study changes in ocean redox. Such applications implicitly assume that Mo isotope fractionation in aqueous systems is relatively insensitive to frequently changing environmental variables such as temperature (T) and ionic strength (I). A major driver of fractionation is the adsorption of Mo to Mn oxyhydroxide surfaces [Barling J. and Anbar A. D. (2004) Molybdenum isotope fractionation during adsorption by manganese oxides. Earth Planet. Sci. Lett.217(3-4), 315-329]. Here, we report the results of experiments that determine the extent to which Mo isotope fractionation during adsorption of Mo to the Mn oxyhydroxide mineral birnessite is sensitive to T and I. The results are compared to new predictions from quantum chemical computations. We measured fractionation from 1 to 50 °C at I = 0.1 m and found that Δ^97/95Mo_{dissolved-adsorbed} varies from 1.9‰ to 1.6‰ over this temperature range. Experiments were also performed at 25 °C in synthetic seawater (I = 0.7); fractionation at this condition was the same within analytical error as in low ionic strength experiments. These findings confirm that the Mo isotope fractionation during adsorption to Mn oxyhydroxides is relatively insensitive to variations and T and I over environmentally relevant ranges. To relate these findings to potential mechanisms of Mo isotope fractionation, we also report results for density functional theory computations of the fractionation between and various possible structures of molybdic acid as a function of temperature. Because no plausible species fractionates from with a magnitude matching the experiments, we are left with three possibilities to explain the fractionation: (1) solvation effects on the vibrational frequencies of aqueous species considered thus far are significant, such that our calculations in vacuo yield inaccurate fractionations; (2) a trace aqueous species not yet considered fractionates from and then adsorbs to birnessite; or (3) a surface complex not present in solution forms on birnessite in which Mo is not tetrahedrally coordinated. Our findings help validate assumptions underlying paleoceanographic applications of the Mo isotope system and also lead us closer to understanding the mechanism of isotope fractionation during adsorption of Mo to Mn oxyhydroxides.  相似文献   

Microbial mass-dependent fractionation of chromium isotopes   总被引：1，自引：0，他引：1  

Eric R. Sikora  Thomas M. Johnson  Thomas D. Bullen 《Geochimica et cosmochimica acta》2008,72(15):3631-3641

Mass-dependent fractionation of Cr isotopes occurs during dissimilatory Cr(VI) reduction by Shewanella oneidensis strain MR-1. Cells suspended in a simple buffer solution, with various concentrations of lactate or formate added as electron donor, reduced 5 or 10 μM Cr(VI) to Cr(III) over days to weeks. In all nine batch experiments, ⁵³Cr/⁵²Cr ratios of the unreacted Cr(VI) increased as reduction proceeded. In eight experiments covering a range of added donor concentrations up to 100 μM, isotopic fractionation factors were nearly invariant, ranging from 1.0040 to 1.0045, with a mean value somewhat larger than that previously reported for abiotic Cr(VI) reduction (1.0034). One experiment containing much greater donor concentration (10 mM lactate) reduced Cr(VI) much faster and exhibited a lesser fractionation factor (1.0018). These results indicate that ⁵³Cr/⁵²Cr measurements should be effective as indicators of Cr(VI) reduction, either bacterial or abiotic. However, variability in the fractionation factor is poorly constrained and should be studied for a variety of microbial and abiotic reduction pathways.  相似文献   

Exurbia from the bottom-up: Confronting empirical challenges to characterizing a complex system   总被引：2，自引：0，他引：2  

Daniel G. Brown  Derek T. Robinson  Li An  Moira Zellner  William Rand  Rick Riolo  Bobbi Low 《Geoforum》2008,39(2):805-818

We describe empirical results from a multi-disciplinary project that support modeling complex processes of land-use and land-cover change in exurban parts of Southeastern Michigan. Based on two different conceptual models, one describing the evolution of urban form as a consequence of residential preferences and the other describing land-cover changes in an exurban township as a consequence of residential preferences, local policies, and a diversity of development types, we describe a variety of empirical data collected to support the mechanisms that we encoded in computational agent-based models. We used multiple methods, including social surveys, remote sensing, and statistical analysis of spatial data, to collect data that could be used to validate the structure of our models, calibrate their specific parameters, and evaluate their output. The data were used to investigate this system in the context of several themes from complexity science, including have (a) macro-level patterns; (b) autonomous decision making entities (i.e., agents); (c) heterogeneity among those entities; (d) social and spatial interactions that operate across multiple scales and (e) nonlinear feedback mechanisms. The results point to the importance of collecting data on agents and their interactions when producing agent-based models, the general validity of our conceptual models, and some changes that we needed to make to these models following data analysis. The calibrated models have been and are being used to evaluate landscape dynamics and the effects of various policy interventions on urban land-cover patterns.  相似文献   

Church-based social capital, networks and geographical scale: Katrina evacuation, relocation, and recovery in a New Orleans Vietnamese American community     

Christopher A. Airriess  Wei Li  Karen J. Leong  Angela Chia-Chen Chen  Verna M. Keith 《Geoforum》2008,39(3):1333-1346

This research examines the role of social capital and networks to explain the evacuation, relocation, and recovery experiences of a Vietnamese American community in New Orleans, Louisiana in the aftermath of Hurricane Katrina. As the single largest community institution, the parish church’s complex bonding and bridging social capital and networks proved particularly critical in part because of its historically based ontological security. The process of evacuation, but especially relocation and recovery, was dependent on deploying co-ethnic social capital and networks at a variety of geographical scales. Beyond the local or community scale, extra-local, regional, and national scales of social capital and networks reproduced a spatially redefined Vietnamese American community. Part of the recovery process included constructing discursive place-based collective-action frames to successfully contest a nearby landfill that in turn engendered social capital and networks crossing ethnic boundaries to include the extra-local African American community. Engaging social capital and networks beyond the local geographical scale cultivated a Vietnamese American community with an emergent post-Katrina cultural and political identity.  相似文献   

Effective livelihood adaptation to climate change disturbance: Scale dimensions of practice in Mozambique   总被引：2，自引：0，他引：2  

Henny Osbahr  Chasca Twyman  W. Neil Adger  David S.G. Thomas 《Geoforum》2008,(6):1951-1964

Natural resource-dependent societies in developing countries are facing increased pressures linked to global climate change. While social-ecological systems evolve to accommodate variability, there is growing evidence that changes in drought, storm and flood extremes are increasing exposure of currently vulnerable populations. In many countries in Africa, these pressures are compounded by disruption to institutions and variability in livelihoods and income. The interactions of both rapid and slow onset livelihood disturbance contribute to enduring poverty and slow processes of rural livelihood renewal across a complex landscape. We explore cross-scale dynamics in coping and adaptation response, drawing on qualitative data from a case study in Mozambique. The research characterises the engagements across multiple institutional scales and the types of agents involved, providing insight into emergent conditions for adaptation to climate change in rural economies. The analysis explores local responses to climate shocks, food security and poverty reduction, through informal institutions, forms of livelihood diversification and collective land-use systems that allow reciprocity, flexibility and the ability to buffer shocks. However, the analysis shows that agricultural initiatives have helped to facilitate effective livelihood renewal, through the reorganisation of social institutions and opportunities for communication, innovation and micro-credit. Although there are challenges to mainstreaming adaptation at different scales, this research shows why it is critical to assess how policies can protect conditions for emergence of livelihood transformation.  相似文献   

Growing up green on serpentine soils: Biogeochemistry of serpentine vegetation in the Central Coast Range of California     

Christopher Oze  Catherine Skinner  Andrew W. Schroth  Robert G. Coleman 《Applied Geochemistry》2008,23(12):3391-3403

Serpentine soils derived from the weathering of ultramafic rocks and their metamorphic derivatives (serpentinites) are chemically prohibitive for vegetative growth. Evaluating how serpentine vegetation is able to persist under these chemical conditions is difficult to ascertain due to the numerous factors (climate, relief, time, water availability, etc.) controlling and affecting plant growth. Here, the uptake, incorporation, and distribution of a wide variety of elements into the biomass of serpentine vegetation has been investigated relative to vegetation growing on an adjacent chert-derived soil. Soil pH, electrical conductivity, organic C, total N, soil extractable elements, total soil elemental compositions and plant digestions in conjunction with spider diagrams are utilized to determine the chemical relationships of these soil and plant systems. Plant available Mg and Ca in serpentine soils exceed values assessed in chert soils. Magnesium is nearly 3 times more abundant than Ca in the serpentine soils; however, the serpentine soils are not Ca deficient with Ca concentrations as high as 2235 mg kg⁻¹. Calcium to Mg ratios (Ca:Mg) in both serpentine and chert vegetation are greater than one in both below and above ground tissues. Soil and plant chemistry analyses support that Ca is not a limiting factor for plant growth and that serpentine vegetation is actively moderating Mg uptake as well as tolerating elevated concentrations of bioavailable Mg. Additionally, results demonstrate that serpentine vegetation suppresses the uptake of Fe, Cr, Ni, Mn and Co into its biomass. The suppressed uptake of these metals mainly occurs in the plants’ roots as evident by the comparatively lower metal concentrations present in above ground tissues (twigs, leaves and shoots). This research supports earlier studies that have suggested that ion uptake discrimination and ion suppression in the roots are major mechanisms for serpentine vegetation to tolerate the chemistry of serpentine soils.  相似文献   

An operational multiscale system for hazards prediction, mapping, and response     

David P. Bacon  Nash’at N. Ahmad  Thomas J. Dunn  Michael C. Monteith  Ananthakrishna Sarma 《Natural Hazards》2008,44(3):317-327

By definition, a crisis is a situation that requires assistance to be managed. Hence, response to a crisis involves the merging of local and non-local emergency response personnel. In this situation, it is critical that each participant: (1) know the roles and responsibilities of each of the other participants; (2) know the capabilities of each of the participants; and (3) have a common basis for action. For many types of natural disasters, this entails having a common operational picture of the unfolding events, including detailed information on the weather, both current and forecasted, that may impact on either the emergency itself or on response activities. The Consequences Assessment Tool Set (CATS) is a comprehensive package of hazard prediction models and casualty and damage assessment tools that provides a linkage between a modeled or observed effect and the attendant consequences for populations, infrastructure, and resources, and, hence, provides the common operational picture for emergency response. The Operational Multiscale Environment model with Grid Adaptivity (OMEGA) is an atmospheric simulation system that links the latest methods in computational fluid dynamics and high-resolution gridding technologies with numerical weather prediction to provide specific weather analysis and forecast capability that can be merged into the geographic information system framework of CATS. This paper documents the problem of emergency response as an end-to-end system and presents the integrated CATS–OMEGA system as a prototype of such a system that has been used successfully in a number of different situations.  相似文献