Effect of adsorbed metal ions on the transport of Zn- and Ni-EDTA complexes in a sand and gravel aquifer     

Douglas B. Kent  James A. DavisLinda C.D. Anderson  Brigid A. ReaJennifer A. Coston 《Geochimica et cosmochimica acta》2002,66(17):3017-3036

Adsorption, complexation, and dissolution reactions strongly influenced the transport of metal ions complexed with ethylenediaminetetraacetic acid (EDTA) in a predominantly quartz-sand aquifer during two tracer tests conducted under mildly reducing conditions at pH 5.8 to 6.1. In tracer test M89, EDTA complexes of zinc (Zn) and nickel (Ni), along with excess free EDTA, were injected such that the lower portion of the tracer cloud traveled through a region with adsorbed manganese (Mn) and the upper portion of the tracer cloud traveled through a region with adsorbed Zn. In tracer test S89, Ni- and Zn-EDTA complexes, along with excess EDTA complexed with calcium (Ca), were injected into a region with adsorbed Mn. The only discernable chemical reaction between Ni-EDTA and the sediments was a small degree of reversible adsorption leading to minor retardation. In the absence of adsorbed Zn, the injected Zn was displaced from EDTA complexes by iron(III) [Fe(III)] dissolved from the sediments. Displacement of Zn by Fe(III) on EDTA became increasingly thermodynamically favorable with decreasing total EDTA concentration. The reaction was slow compared to the time-scale of transport. Free EDTA rapidly dissolved aluminum (Al) from the sediments, which was subsequently displaced slowly by Fe. In the portion of tracer cloud M89 that traveled through the region contaminated with adsorbed Zn, little displacement of Zn complexed with EDTA was observed, and Al was rapidly displaced from EDTA by Zn desorbed from the sediments, in agreement with equilibrium calculations. In tracer test S89, desorption of Mn dominated over the more thermodynamically favorable dissolution of Al oxyhydroxides. Comparison with results from M89 suggests that dissolution of Al oxyhydroxides in coatings on these sediment grains by Ca-EDTA was rate-limited whereas that by free EDTA reached equilibrium on the time-scale of transport. Rates of desorption are much faster than rates of dissolution of Fe oxyhydroxides from sediment-grain surfaces and, therefore, adsorbed metal ions can strongly influence the speciation of ligands like EDTA in soils and sediments, especially over small temporal and spatial scales.  相似文献   

Uranium co-precipitation with iron oxide minerals   总被引：2，自引：0，他引：2  

Martine C. DuffJessica Urbanik Coughlin  Douglas B. Hunter 《Geochimica et cosmochimica acta》2002,66(20):3533-3547

In oxidizing environments, the toxic and radioactive element uranium (U) is most soluble and mobile in the hexavalent oxidation state. Sorption of U(VI) on Fe-oxides minerals (such as hematite [α-Fe₂O₃] and goethite [α-FeOOH]) and occlusion of U(VI) by Fe-oxide coatings are processes that can retard U transport in environments. In aged U-contaminated geologic materials, the transport and the biological availability of U toward reduction may be limited by coprecipitation with Fe-oxide minerals. These processes also affect the biological availability of U(VI) species toward reduction and precipitation as the less soluble U(IV) species by metal-reducing bacteria.To examine the dynamics of interactions between U(VI) and Fe oxides during crystallization, Fe-oxide phases (containing 0.5 to 5.4 mol% U/(U + Fe)) were synthesized by means of solutions of U(VI) and Fe(III). Wet chemical (digestions and chemical extractions) and spectroscopic techniques were used to characterize the synthesized Fe oxide coprecipitates after rinsing in deionized water. Leaching the high mol% U solids with concentrated carbonate solution (for sorbed and solid-phase U(VI) species) typically removed most of the U, leaving, on average, about 0.6 mol% U. Oxalate leaching of solids with low mol% U contents (about 1 mol% U or less) indicated that almost all of the Fe in these solids was crystalline and that most of the U was associated with these crystalline Fe oxides. X-ray diffraction and Fourier-transform infrared (FT-IR) spectroscopic studies indicate that hematite formation is preferred over that of goethite when the amount of U in the Fe-oxides exceeds 1 mol% U (∼4 wt% U). FT-IR and room temperature continuous wave luminescence spectroscopic studies with unleached U/Fe solids indicate a relationship between the mol% U in the Fe oxide and the intensity or existence of the spectra features that can be assigned to UO₂²⁺ species (such as the IR asymmetric υ₃ stretch for O = U = O for uranyl). These spectral features were undetectable in carbonate- or oxalate-leached solids, suggesting solid phase and sorbed U(VI)O₂²⁺ species are extracted by the leach solutions. Uranium L₃-edge x-ray absorption spectroscopic (XAFS) analyses of the unleached U-Fe oxide solids with less than 1 mol% U reveal that U(VI) exists with four O atoms at radial distances of 2.19 and 2.36 Å and second shell Fe at a radial distance at 3.19 Å.Because of the large ionic radius of UO₂²⁺ (∼1.8 Å) relative to that of Fe³⁺ (0.65 Å), the UO₂²⁺ ion is unlikely to be incorporated in the place of Fe in Fe(III)-oxide structures. Solid-phase U(VI) can exist as the uranyl [U(VI)O₂²⁺] species with two axial U-O double bonds and four or more equatorial U-O bonds or as the uranate species (such as γ-UO₃) without axial U-O bonds. Our findings indicate U⁶⁺ (with ionic radii of 0.72 to 0.8 Å, depending on the coordination environment) is incorporated in the Fe oxides as uranate (without axial O atoms) until a point of saturation is reached. Beyond this excess in U concentration, precipitating U(VI) forms discrete crystalline uranyl phases that resemble the uranyl oxide hydrate schoepite [UO₂(OH)₂·2H₂O]. Molecular modeling studies reveal that U⁶⁺ species could bond with O atoms from distorted Fe octahedra in the hematite structure with an environment that is consistent with the results of the XAFS. The results provide compelling evidence of U incorporation within the hematite structure.  相似文献   

Consequences of diffuse and channelled porous melt migration on uranium series disequilibria     

M Jull  P.B Kelemen  K Sims 《Geochimica et cosmochimica acta》2002,66(23):4133-4148

Magmas erupted at mid-ocean ridges (MORB) result from decompression melting of upwelling mantle. However, the mechanism of melt transport from the source region to the surface is poorly understood. It is debated whether melt is transported through melt-filled conduits or cracks on short time scales (<∼ 10³ yrs), or whether there is a significant component of slow, equilibrium porous flow on much longer time scales (>∼ 10³-10⁴ yrs). Radiogenic excess ²²⁶Ra in MORB indicates that melt is transported from the melting region on time scales less than the half life of ²²⁶Ra (∼1600 yrs), and has been used to argue for fast melt transport from the base of the melting column. However, excess ²²⁶Ra can be generated at the bottom of the melt column, during the onset of melting, and at the top of the melt column by reactive porous flow. Determining the depth at which ²²⁶Ra is generated is critical to interpreting the rate and mechanism of magma migration. A recent compilation of high quality U-series isotope data show that in many young basalts, ²²⁶Ra excess in MORB is negatively correlated with ²³⁰Th excess. The data suggest that ²²⁶Ra excess is generated independently of ²³⁰Th excess, and cannot be explained by “dynamic” or fractional melting, where observed radiogenic excesses are all generated at the base of the melt column. One explanation is that the negative correlation of activity ratios is a result of mixing of slow moving melt that has travelled through reactive, low-porosity pathways and relatively fast moving melt that has been transported in unreactive high-porosity channels. We investigate this possibility by calculating U-series disequilibria in a melting column in which high-porosity, unreactive channels form within a low-porosity matrix that is undergoing melting. The results show that the negative correlation of ²²⁶Ra and ²³⁰Th excesses observed in MORB can be produced if ∼60% of the total melt flux travels through the low-porosity matrix. This melt maintains ²²⁶Ra excesses via chromatographic fractionation of Ra and Th during equilibrium transport. Melt that travels through the unreactive, high-porosity channels is not able to maintain significant ²²⁶Ra excesses because Ra and Th are not fractionated from each other during transport and the transport time for melt in the channels to reach the top of the melt column is longer than the time scale for ²²⁶Ra excesses to decay. Mixing of melt from the high porosity channels with melt from the low-porosity matrix at the top of the melting column can produce a negative correlation of ²²⁶Ra and ²³⁰Th excesses with the slope and magnitude observed in MORB. This transport process can also account for other aspects of the geochemistry of MORB, such as correlations between La/Yb, α_Sm/Nd, and Th/U and ²²⁶Ra and ²³⁰Th excess.  相似文献   

New graptolite faunas from the Llandovery, lower Silurian of the Graveyard Creek Subprovince, Broken River region, Queensland, Australia     

R.B. RickardsJ.S. Jell 《Proceedings of the Geologists' Association. Geologists' Association》2002,113(2):111-120

  相似文献   

Climate change impacts on U.S. Coastal and Marine Ecosystems   总被引：1，自引：0，他引：1  

Donald Scavia  John C. Field  Donald F. Boesch  Robert W. Buddemeier  Virginia Burkett  Daniel R. Cayan  Michael Fogarty  Mark A. Harwell  Robert W. Howarth  Curt Mason  Denise J. Reed  Thomas C. Royer  Asbury H. Sallenger  James G. Titus 《Estuaries and Coasts》2002,25(2):149-164

Increases in concentrations of greenhouse gases projected for the 21st century are expected to lead to increased mean global air and ocean temperatures. The National Assessment of Potential Consequences of Climate Variability and Change (NAST 2001) was based on a series of regional and sector assessments. This paper is a summary of the coastal and marine resources sector review of potential impacts on shorelines, estuaries, coastal wetlands, coral reefs, and ocean margin ecosystems. The assessment considered the impacts of several key drivers of climate change: sea level change; alterations in precipitation patterns and subsequent delivery of freshwater, nutrients, and sediment; increased ocean temperature; alterations in circulation patterns; changes in frequency and intensity of coastal storms; and increased levels of atmospheric CO₂. Increasing rates of sea-level rise and intensity and frequency of coastal storms and hurricanes over the next decades will increase threats to shorelines, wetlands, and coastal development. Estuarine productivity will change in response to alteration in the timing and amount of freshwater, nutrients, and sediment delivery. Higher water temperatures and changes in freshwater delivery will alter estuarine stratification, residence time, and eutrophication. Increased ocean temperatures are expected to increase coral bleaching and higher CO₂ levels may reduce coral calcification, making it more difficult for corals to recover from other disturbances, and inhibiting poleward shifts. Ocean warming is expected to cause poleward shifts in the ranges of many other organisms, including commercial species, and these shifts may have secondary effects on their predators and prey. Although these potential impacts of climate change and variability will vary from system to system, it is important to recognize that they will be superimposed upon, and in many cases intensify, other ecosystem stresses (pollution, harvesting, habitat destruction, invasive species, land and resource use, extreme natural events), which may lead to more significant consequences.  相似文献   

G-Probe-1 - An International Proficiency Test for Microprobe Laboratories - Report on Round 1 : February 2002 (TB-1 Basaltic Glass)     

Philip J. Potts  Michael Thompson  Stephen Wilson 《Geostandards and Geoanalytical Research》2002,26(2):197-235

Results are presented for round one of a new international proficiency testing programme designed for microprobe laboratories involved in the routine analysis of silicate minerals. The sample used for this round was TB-1, a basaltic glass fused and prepared by the USGS. Thirty nine laboratories contributed data to this round, the majority of major element results being undertaken by EPMA and the majority of trace elements by LA-ICP-MS. Assigned values were derived from the median of results produced by nine selected laboratories that analysed powdered material by conventional ICP-MS, INAA and XRF techniques using bulk powders of the sample. Submitted microprobe results were evaluated using a target precision calculated using the Horwitz function, adopting the same criteria as those used for "applied" geochemistry laboratories in the companion GeoPT proficiency testing programme for laboratories involved in the routine bulk analysis of silicate rocks. An evaluation of results from participating microprobe laboratories indicated that overall, data were compatible with this precision function. A comparison between the performance of bulk and microprobe techniques used in the analysis of the basaltic glass showed remarkably good agreement, with significant bias only observed for the major oxide MgO.  相似文献   

STRESS-METAMORPHISM AND ISOTOPIC AGE OF SHEAR ZONE GRANITOID TECTONITES OF IRTYSH SHEAR ZONE (ALTAI REGION)   总被引：1，自引：0，他引：1  

B.M.Chikov  V.A.Ponomachuk  S.V.Zinoviev  B.N.Lapin  A.T.Titov  A.V.Travin  S.V.Palessky 《大地构造与成矿学(英文版)》2002,26(1):36-51

The Irtysh shear zone (ISZ) of Altai region is the lineament structure of the collision-suture type, where granites of Kalba complex and granodiorites of Zmeinogorsk complex are exposed to regional gneiss-formation and stress-metamorphic alterations. This study is based on detailed structural observations at special grounds using optical and electron microscopy, and on the behavior analysis of isotopic systems from altered granitoids.Within the ISZ area we have established the continuous rows of granitoid stress-metamorphism from initial recrystallization of protolite, its cataclasis and mechanical flaring up to complete recrystallization with alteration of mineral composition and formation of the streaky complexes of granite tectonites of blastomylonite and blastocataclasite types. The directed alteration of rocks has several impulse and is expressed by a change in morphology of mineral grains and their relations, magnification of deformation component in the rock structure, and formation of new mineral phases on the basis of initial ones without surface fluidization. At transformation of isotopic systems from granitoid, their feldspars,biotite and hornblende, we can observe “rejuvenation“ of the rock substrate from 270- 290 Ma for Kalba granitoids to 220-235 Ma for their tectonites, and for Rudny Altai granodiorites, their ages changes from 285-317 Ma to 232-257 Ma for their tectonites.  相似文献   

Integrated Two-Dimensional Modeling of Fluid Flow and Compaction in a Sedimentary Basin     

Zhangxin Chen  Richard E. Ewing  Hao Lu  Stephen L. Lyons  Serguei Maliassov  Michael B. Ray  Tong Sun 《Computational Geosciences》2002,6(3-4):545-564

In this paper we employ mixed finite elements and numerically study an integrated two-dimensional model of fluid flow and compaction in a sedimentary basin. This model describes a single phase incompressible flow in a two-dimensional section of a sedimentary basin with vertical compaction. At each time step, an iterative algorithm is used to solve this model. The determination of the grid movement is based on the mass conservation and movement of sediments in the basin, while the mixed method is utilized to solve the fluid flow over the moving grid. Numerical experiments are presented to verify this iterative algorithm and show representative solutions for the model under consideration.  相似文献   

Unstructured, Control-Volume Distributed, Full-Tensor Finite-Volume Schemes with Flow Based Grids     

Michael G. Edwards 《Computational Geosciences》2002,6(3-4):433-452

Locally conservative flux-continuous, full-tensor, discretization schemes are presented for general unstructured grids. The schemes are control-volume distributed, where flow variables and rock properties are assigned to the polygonal control-volumes derived from the primal grid. A relationship between these finite volume schemes and the mixed finite element method is established. An extension for unstructured grids is described that leads to a general symmetric positive definite discretization matrix for both quadrilateral and triangular grids. A novel flow based gridding approach for unstructured mesh generation is also proposed for heterogeneous reservoir domains. Results computed with the flux continuous schemes on unstructured flow-based grids demonstrate the advantages of the methods.  相似文献   

Wave velocities and attenuation of shaley sandstones as a function of pore pressure and partial saturation   总被引：3，自引：0，他引：3  

Nam H. Pham  †  José M. Carcione  Hans B. Helle  Bjørn Ursin 《Geophysical Prospecting》2002,50(6):615-627

We obtain the wave velocities and quality factors of clay‐bearing sandstones as a function of pore pressure, frequency and partial saturation. The model is based on a Biot‐type three‐phase theory that considers the coexistence of two solids (sand grains and clay particles) and a fluid mixture. Additional attenuation is described with the constant‐Q model and viscodynamic functions to model the high‐frequency behaviour. We apply a uniform gas/fluid mixing law that satisfies the Wood and Voigt averages at low and high frequencies, respectively. Pressure effects are accounted for by using an effective stress law. By fitting a permeability model of the Kozeny– Carman type to core data, the model is able to predict wave velocity and attenuation from seismic to ultrasonic frequencies, including the effects of partial saturation. Testing of the model with laboratory data shows good agreement between predictions and measurements.  相似文献