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Trace metal speciation in saline waters affected by geothermal brines. Final technical report. [GEOCHEM]

Description: The computer program GEOCHEM was developed and applied to calculate the speciation of trace elements, such as Li, B, Mn, Co, Ni, Cu, Zn, Pb, and As, in mixtures of geothermal brines with soil waters. A typical speciation calculation involved the simultaneous consideration of about 350 inorganic and organic complexes and about 80 possible solid phases that could form among the macro- and microconstituents in the mixtures. The four geothermal brines chosen for study were from the East Mesa, Heber, and Salton Sea KGRA's. Two examples of East Mesa brine were employed in order to illustrate the effect of brine variability within a given KGRA. The soil waters chosen for study were the Holtville, Rosita, and Vint soil solutions and the Vail 4 drain water. These waters were mixed with the four brines to produce 1%, 5%, and 10% brine combinations. The combinations then were analyzed with the help of GEOCHEM and were interpreted in the context of two proposed general contamination scenarios. The results of the speciation calculations pointed to the great importance, in brine, of sulfide as a precipitating agent for trace metals and of borate as a trace metal-complexing ligand. In general, precipitation and/or exchange adsorption in soil were found to reduce the levels of trace metals well below harmful concentrations. The principal exceptions were Li and B, which did not precipitate and which were at or very hear harmful levels in the soil water-brine mixtures.
Date: July 1, 1979
Creator: Sposito, G.
Partner: UNT Libraries Government Documents Department

Trace metal speciation in saline waters affected by geothermal brines. [GEOCHEM]

Description: A description is given of the chemical equilibrium computer program GEOCHEM, which has been developed to calculate trace element speciation in soil, irrigation, drainage, or Salton Sea waters affected by geothermal brine. GEOCHEM is applied to irrigation water-brine mixtures and to Salton Sea water-brine mixtures in order to compute the chemical speciation of the elements Cd, Cu, Hg, Ni, Pb, and Zn, along with the oxyanions of As and B. The results suggest that the computer simulation can have an important effect on a program for managing brine spills. Appendices include published papers on related research.
Date: November 1, 1977
Creator: Sposito, G. & Page, A.L.
Partner: UNT Libraries Government Documents Department

Connecting the molecular scale to the continuum scale for diffusion processes in smectite-rich porous media

Description: In this paper, we address the manner in which the continuum-scale diffusive properties of smectite-rich porous media arise from their molecular- and pore-scale features. Our starting point is a successful model of the continuum-scale apparent diffusion coefficient for water tracers and cations which decomposes it as a sum of pore-scale terms describing diffusion in macropore and interlayer 'compartments.' We then apply molecular dynamics (MD) simulations to determine molecular-scale diffusion coefficients D{sub interlayer} of water tracers and representative cations (Na{sup +}, Cs{sup +}, Sr{sup 2+}) in Na-smectite interlayers. We find that a remarkably simple expression relates D{sub interlayer} to the pore-scale parameter {delta}{sub nanopore} {<=} 1, a constrictivity factor that accounts for the lower mobility in interlayers as compared to macropores: {delta}{sub nanopore} = D{sub interlayer}/D{sub 0}, where D{sub 0} is the diffusion coefficient in bulk liquid water. Using this scaling expression, we can accurately predict the apparent diffusion coefficients of tracer H{sub 2}O, Na{sup +}, Sr{sup 2+} and Cs{sup +}+ in compacted Na-smectite-rich materials.
Date: December 1, 2009
Creator: Bourg, I.C. & Sposito, G.
Partner: UNT Libraries Government Documents Department

Reactivity of biogenic manganese oxide for metal sequestration and photochemistry: Computational solid state physics study

Description: Many microbes, including both bacteria and fungi, produce manganese (Mn) oxides by oxidizing soluble Mn(II) to form insoluble Mn(IV) oxide minerals, a kinetically much faster process than abiotic oxidation. These biogenic Mn oxides drive the Mn cycle, coupling it with diverse biogeochemical cycles and determining the bioavailability of environmental contaminants, mainly through strong adsorption and redox reactions. This mini review introduces recent findings based on quantum mechanical density functional theory that reveal the detailed mechanisms of toxic metal adsorption at Mn oxide surfaces and the remarkable role of Mn vacancies in the photochemistry of these minerals.
Date: February 1, 2010
Creator: Kwon, K.D. & Sposito, G.
Partner: UNT Libraries Government Documents Department

Steady-State Dissolution Kinetics of Goethite in the Presence of Desferrioxamine B and Oxalate Ligands: Implications for the Microbial Acquisition of Iron

Description: OAK-B135 Results of laboratory experiments on the dissolution of the mineral, goethite, in the presence of hydroxamate siderophores and oxalate are presented showing a synergistic effect between the two ligands on mineral dissolution kinetics.
Date: December 18, 2003
Creator: Sposito, G.
Partner: UNT Libraries Government Documents Department

Temperature Dependence of Goethite Dissolution Promoted by Trihydroxamate Siderophores

Description: OAK-B135 Results of laboratory experiments are presented on the dissolution behavior of the mineral, goethite, in the presence of siderophores as affected by temperature changes between 25 and 55 Celsius. Data also are presented on the relationship between the parameters in the Arrhenius equation describing the temperature effects.
Date: December 18, 2003
Creator: Sposito, G.
Partner: UNT Libraries Government Documents Department

Isotopic mass-dependence of noble gas diffusion coefficients inwater

Description: Noble gas isotopes are used extensively as tracers inhydrologic and paleoclimatic studies. These applications requireknowledge of the isotopic mass (m) dependence of noble gas diffusioncoefficients in water (D), which has not been measured but is estimatedusing experimental D-values for the major isotopes along with an untestedrelationship from kinetic theory, D prop m-0.5. We applied moleculardynamics methods to determine the mass dependence of D for four noblegases at 298 K, finding that D prop m-beta with beta<0.2, whichrefutes the kinetic theory model underlying all currentapplications.
Date: June 25, 2007
Creator: Bourg, I.C. & Sposito, G.
Partner: UNT Libraries Government Documents Department

CANCELLED Molecular dynamics simulations of noble gases in liquidwater: Solvati on structure, self-diffusion, and kinetic isotopeeffect

Description: Despite their great importance in low-temperaturegeochemistry, self-diffusion coefficients of noble gas isotopes in liquidwater (D) have been measured only for the major isotopes of helium, neon,krypton and xenon. Data on the self-diffusion coefficients of minor noblegas isotopes are essentially non-existent and so typically are estimatedby a kinetic theory model in which D varies as the inverse square root ofthe isotopic mass (m): D proportional to m-0.5. To examine the validityof the kinetic theory model, we performed molecular dynamics (MD)simulations of the diffusion of noble gases in ambient liquid water withan accurate set of noble gas-water interaction potentials. Our simulationresults agree with available experimental data on the solvation structureand self-diffusion coefficients of the major noble gas isotopes in liquidwater and reveal for the first time that the isotopic mass-dependence ofall noble gas self-diffusion coefficients has the power-law form Dproportional to m-beta with 0<beta<0.2. Thus our results callinto serious question the widespread assumption that the square rootmodel can be applied to estimate the kinetic fractionation of noble gasisotopes caused by diffusion in ambient liquid water.
Date: May 25, 2007
Creator: Bourg, I.C. & Sposito, G.
Partner: UNT Libraries Government Documents Department

Mechanisms of nickel sorption by a bacteriogenic birnessite

Description: A synergistic experimental-computational approach was used to study the molecular-scale mechanisms of Ni sorption at varying loadings and at pH 6-8 on the biogenic hexagonal birnessite produced by Pseudomonas putida GB-1. We found that Ni is scavenged effectively by bacterial biomass-birnessite assemblages. At surface excess values below 0.18 mol Ni kg{sup -1} sorbent (0.13 mol Ni mol{sup -1} Mn), the biomass component of the sorbent did not interfere with Ni sorption on mineral sites. Extended X-ray absorption fine structure (EXAFS) spectra showed two dominant coordination environments: Ni bound as a triple-corner-sharing (Ni-TCS) complex at vacancy sites and Ni incorporated (Ni-inc) into the MnO{sub 2} sheet, with the latter form of Ni favored at high sorptive concentrations and decreased proton activity. In parallel to our spectral analysis, first-principles geometry optimizations based on density functional theory (DFT) were performed to investigate the structure of Ni surface complexes at vacancy sites. Excellent agreement was achieved between EXAFS- and DFT-derived structural parameters for Ni-TCS and Ni-inc. Reaction-path calculations revealed a pH-dependent energy barrier associated with the transition from Ni-TCS to Ni-inc. Our results are consistent with the rate-limited incorporation of Ni at vacancy sites in our sorption samples, but near-equilibrium state of Ni in birnessite phases found in nodule samples. This study thus provides direct and quantitative evidence of the factors governing the occurrence of Ni adsorption versus Ni incorporation in biogenic hexagonal birnessite, a key mineral in the terrestrial manganese cycle.
Date: April 1, 2010
Creator: Pena, J.; Kwon, K.D.; Refson, K.; Bargar, J.R. & Sposito, G.
Partner: UNT Libraries Government Documents Department

Isotopic mass-dependence of metal cation diffusion coefficients in liquid water

Description: Isotope distributions in natural systems can be highly sensitive to the mass (m) dependence of solute diffusion coefficients (D) in liquid water. Isotope geochemistry studies routinely have assumed that this mass dependence either is negligible (as predicted by hydrodynamic theories) or follows a kinetic-theory-like inverse square root relationship (D {proportional_to} m{sup -0.5}). However, our recent experimental results and molecular dynamics (MD) simulations showed that the mass dependence of D is intermediate between hydrodynamic and kinetic theory predictions (D {proportional_to} m{sup -{beta}} with 0 {&lt;=} {beta} &lt; 0.2 for Li{sup +}, Cl{sup -}, Mg{sup 2+}, and the noble gases). In this paper, we present new MD simulations and experimental results for Na{sup +}, K{sup +}, Cs{sup +}, and Ca{sup 2+} that confirm the generality of the inverse power-law relation D {proportional_to} m{sup -{beta}}. Our new findings allow us to develop a general description of the influence of solute valence and radius on the mass dependence of D for monatomic solutes in liquid water. This mass dependence decreases with solute radius and with the magnitude of solute valence. Molecular-scale analysis of our MD simulation results reveals that these trends derive from the exponent {beta} being smallest for those solutes whose motions are most strongly coupled to solvent hydrodynamic modes.
Date: January 11, 2009
Creator: Bourg, I.C.; Richter, F.M.; Christensen, J.N. & Sposito, G.
Partner: UNT Libraries Government Documents Department

Modeling the diffusion of Na+ in compacted water-saturated Na-bentonite as a function of pore water ionic strength

Description: Assessments of bentonite barrier performance in waste management scenarios require an accurate description of the diffusion of water and solutes through the barrier. A two-compartment macropore/nanopore model (on which smectite interlayer nanopores are treated as a distinct compartment of the overall pore space) was applied to describe the diffusion of {sup 22}Na{sup +} in compacted, water-saturated Na-bentonites and then compared with the well-known surface diffusion model. The two-compartment model successfully predicted the observed weak ionic strength dependence of the apparent diffusion coefficient (D{sub a}) of Na{sup +}, whereas the surface diffusion model did not, thus confirming previous research indicating the strong influence of interlayer nanopores on the properties of smectite clay barriers. Since bentonite mechanical properties and pore water chemistry have been described successfully with two-compartment models, the results in the present study represent an important contribution toward the construction of a comprehensive two-compartment model of compacted bentonite barriers.
Date: August 15, 2008
Creator: Bourg, I.C.; Sposito, G. & Bourg, A.C.M.
Partner: UNT Libraries Government Documents Department

On the role of Mn(IV) vacancies in the photoreductive dissolution of hexagonal birnessite

Description: Photoreductive dissolution of layer type Mn(IV) oxides (birnessite) under sunlight illumination to form soluble Mn(II) has been observed in both field and laboratory settings, leading to a consensus that this process is a key driver of the biogeochemical cycling of Mn in the euphotic zones of marine and freshwater ecosystems. However, the underlying mechanisms for the process remain unknown, although they have been linked to the semiconducting characteristics of hexagonal birnessite, the ubiquitous Mn(IV) oxide produced mainly by bacterial oxidation of soluble Mn(II). One of the universal properties of this biogenic mineral is the presence of Mn(IV) vacancies, long-identified as strong adsorption sites for metal cations. In this paper, the possible role of Mn vacancies in photoreductive dissolution is investigated theoretically using quantum mechanical calculations based on spin-polarized density functional theory (DFT). Our DFT study demonstrates unequivocally that Mn vacancies significantly reduce the band-gap energy for hexagonal birnessite relative to a hypothetical vacancy-free MnO{sub 2} and thus would increase the concentration of photo-induced electrons available for Mn(IV) reduction upon illumination of the mineral by sunlight. Calculations of the charge distribution in the presence of vacancies, although not fully conclusive, show a clear separation of photo-induced electrons and holes, implying a slow recombination of these charge-carriers that facilitates the two-electron reduction of Mn(IV) to Mn(II).
Date: June 1, 2009
Creator: Kwon, K.D.; Refson, K. & Sposito, G.
Partner: UNT Libraries Government Documents Department

Molecular dynamics simulations of the electrical double layer on smectite surfaces contacting concentrated mixed electrolyte (NaCl-CaCl2)

Description: We report new molecular dynamics results elucidating the structure of the electrical double layer (EDL) on smectite surfaces contacting mixed NaCl-CaCl{sup 2} electrolyte solutions in the range of concentrations relevant to pore waters in geologic repositories for CO{sub 2} or high-level radioactive waste (0.34-1.83 mol{sub c} dm{sup -3}). Our results confirm the existence of three distinct ion adsorption planes (0-, {beta}-, and d-planes), often assumed in EDL models, but with two important qualifications: (1) the location of the {beta}- and d-planes are independent of ionic strength or ion type and (2) 'indifferent electrolyte' ions can occupy all three planes. Charge inversion occurred in the diffuse ion swarm because of the affinity of the clay surface for CaCl{sup +} ion pairs. Therefore, at concentrations 0.34 mol{sub c} dm{sup -3}, properties arising from long-range electrostatics at interfaces (electrophoresis, electro-osmosis, co-ion exclusion, colloidal aggregation) will not be correctly predicted by most EDL models. Co-ion exclusion, typically neglected by surface speciation models, balanced a large part of the clay mineral structural charge in the more concentrated solutions. Water molecules and ions diffused relatively rapidly even in the first statistical water monolayer, contradicting reports of rigid 'ice-like' structures for water on clay mineral surfaces.
Date: April 1, 2011
Creator: Bourg, I.C. & Sposito, G.
Partner: UNT Libraries Government Documents Department

Ion exchange phenomena

Description: Ion exchange phenomena involve the population of readily exchangeable ions, the subset of adsorbed solutes that balance the intrinsic surface charge and can be readily replaced by major background electrolyte ions (Sposito, 2008). These phenomena have occupied a central place in soil chemistry research since Way (1850) first showed that potassium uptake by soils resulted in the release of an equal quantity of moles of charge of calcium and magnesium. Ion exchange phenomena are now routinely modeled in studies of soil formation (White et al., 2005), soil reclamation (Kopittke et al., 2006), soil fertilitization (Agbenin and Yakubu, 2006), colloidal dispersion/flocculation (Charlet and Tournassat, 2005), the mechanics of argillaceous media (Gajo and Loret, 2007), aquitard pore water chemistry (Tournassat et al., 2008), and groundwater (Timms and Hendry, 2007; McNab et al., 2009) and contaminant hydrology (Chatterjee et al., 2008; van Oploo et al., 2008; Serrano et al., 2009).
Date: May 1, 2011
Creator: Bourg, I.C. & Sposito, G.
Partner: UNT Libraries Government Documents Department

Low-frequency dilatational wave propagation through unsaturated porous media containing two immiscible fluids

Description: An analytical theory is presented for the low-frequency behavior of dilatational waves propagating through a homogeneous elastic porous medium containing two immiscible fluids. The theory is based on the Berryman-Thigpen-Chin (BTC) model, in which capillary pressure effects are neglected. We show that the BTC model equations in the frequency domain can be transformed, at sufficiently low frequencies, into a dissipative wave equation (telegraph equation) and a propagating wave equation in the time domain. These partial differential equations describe two independent modes of dilatational wave motion that are analogous to the Biot fast and slow compressional waves in a single-fluid system. The equations can be solved analytically under a variety of initial and boundary conditions. The stipulation of 'low frequency' underlying the derivation of our equations in the time domain is shown to require that the excitation frequency of wave motions be much smaller than a critical frequency. This frequency is shown to be the inverse of an intrinsic time scale that depends on an effective kinematic shear viscosity of the interstitial fluids and the intrinsic permeability of the porous medium. Numerical calculations indicate that the critical frequency in both unconsolidated and consolidated materials containing water and a nonaqueous phase liquid ranges typically from kHz to MHz. Thus engineering problems involving the dynamic response of an unsaturated porous medium to low excitation frequencies (e.g. seismic wave stimulation) should be accurately modeled by our equations after suitable initial and boundary conditions are imposed.
Date: February 1, 2007
Creator: Lo, W.-C.; Sposito, G. & Majer, E.
Partner: UNT Libraries Government Documents Department

Surface complexation of Pb(II) by hexagonal birnessite nanoparticles

Description: Natural hexagonal birnessite is a poorly-crystalline layer type Mn(IV) oxide precipitated by bacteria and fungi which has a particularly high adsorption affinity for Pb(II). X-ray spectroscopic studies have shown that Pb(II) forms strong inner-sphere surface complexes mainly at two sites on hexagonal birnessite nanoparticles: triple corner-sharing (TCS) complexes on Mn(IV) vacancies in the interlayers and double edge-sharing (DES) complexes on lateral edge surfaces. Although the TCS surface complex has been well characterized by spectroscopy, some important questions remain about the structure and stability of the complexes occurring on the edge surfaces. First-principles simulation techniques such as density functional theory (DFT) offer a useful way to address these questions by providing complementary information that is difficult to obtain by spectroscopy. Following this computational approach, we used spin-polarized DFT to perform total-energy-minimization geometry optimizations of several possible Pb(II) surface complexes on model birnessite nanoparticles similar to those that have been studied experimentally. We first validated our DFT calculations by geometry optimizations of (1) the Pb-Mn oxyhydroxide mineral, quenselite (PbMnO{sub 2}OH), and (2) the TCS surface complex, finding good agreement with experimental structural data while uncovering new information about bonding and stability. Our geometry optimizations of several protonated variants of the DES surface complex led us to conclude that the observed edge-surface species is very likely to be this complex if the singly-coordinated terminal O that binds to Pb(II) is protonated. Our geometry optimizations also revealed that an unhydrated double corner-sharing (DCS) species that has been proposed as an alternative to the DES complex is intrinsically unstable on nanoparticle edge surfaces, but could become stabilized if the local coordination environment is well-hydrated. A significant similarity exists in the structural parameters for the TCS complex and those for a DCS edge-surface complex that is protonated in the same manner as the optimal DES complex, ...
Date: October 15, 2010
Creator: Kwon, K.; Refson, K. & Sposito, G.
Partner: UNT Libraries Government Documents Department

Microbial acquisition of iron from ferric iron bearing minerals

Description: This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). Iron is a universal requirement for all life forms. Although the fourth most abundant element in the geosphere, iron is virtually insoluble at physiological pH in oxidizing environments, existing mainly as very insoluble oxides and hydroxides. Currently it is not understood how iron is solubilized and made available for biological use. This research project addressed this topic by conducting a series of experiments that utilized techniques from both soil microbiology and mineral surface geochemistry. Microbiological analysis consisted of the examination of metabolic and physiological responses to mineral iron supplements. At the same time mineral surfaces were examined for structural changes brought about by microbially mediated dissolution. The results of these experiments demonstrated that (1) bacterial siderophores were able to promote the dissolution of iron oxides, (2) that strict aerobic microorganisms may use anaerobic processes to promote iron oxide dissolution, and (3) that it is possible to image the surface of iron oxides undergoing microbial dissolution.
Date: December 31, 1998
Creator: Hersman, L.E. & Sposito, G.
Partner: UNT Libraries Government Documents Department

Magnetic ordering in tetragonal FeS: Evidence for strong itinerant spin fluctuations

Description: Mackinawite is a naturally occurring layer-type FeS mineral important in biogeochemical cycles and, more recently, in the development of microbial fuel cells. Conflicting results have been published as to the magnetic properties of this mineral, with Moessbauer spectroscopy indicating no magnetic ordering down to 4.2 K but density functional theory (DFT) predicting an antiferromagnetic ground state, similar to the Fe-based high-temperature superconductors with which it is isostructural and for which it is known that magnetism is suppressed by strong itinerant spin fluctuations. We investigated this latter possibility for mackinawite using photoemission spectroscopy, near-edge x-ray absorption fine structure spectroscopy, and DFT computations. Our Fe 3{sub s} core-level photoemission spectrum of mackinawite showed a clear exchange-energy splitting (2.9 eV) consistent with a 1 {micro}{sub B} magnetic moment on the Fe ions, while the Fe L-edge x-ray absorption spectrum indicated rather delocalized Fe 3{sub d} electrons in mackinawite similar to those in Fe metal. Our DFT computations demonstrated that the ground state of mackinawite is single-stripe antiferromagnetic, with an Fe magnetic moment (2.7 {micro}{sub B}) that is significantly larger than the experimental estimate and has a strong dependence on the S height and lattice parameters. All of these trends signal the existence of strong itinerant spin fluctuations. If spin fluctuations prove to be mediators of electron pairing, we conjecture that mackinawite may be one of the simplest Fe-based superconductors.
Date: November 1, 2010
Creator: Kwon, K.D.; Refson, K.; Bone, S.; Qiao, R.; Yang, W.; Liu, Z. et al.
Partner: UNT Libraries Government Documents Department