Transport Of Aqueous Species Research Articles

Distinguishing different surface interactions for nucleotides adsorbed onto hematite and goethite particle surfaces through ATR-FTIR spectroscopy and DFT calculations.

Geochemical interfaces can impact the fate and transport of aqueous species in the environment including biomolecules. In this study, we investigate the surface chemistry of adsorbed nucleotides on two different minerals, hematite and goethite, using infrared spectroscopy and density functional theory (DFT) calculations. Attenuated total reflectance-Fourier transform infrared spectroscopy is used to probe the adsorption of deoxyadenosine monophosphate (dAMP), deoxyguanosine monophosphate (dGMP), deoxycytidine monophosphate (dCMP), and deoxythymidine monophosphate (dTMP) onto either hematite or goethite particle surfaces. The results show preferential adsorption of the phosphate group to either surface. Remarkably, surface adsorption of the four nucleotides onto either hematite or goethite have nearly identical experimental spectra in the phosphate region (900 to 1200 cm-1) for each mineral surface yet are distinctly different between the two minerals, suggesting differences in binding of these nucleotides to the two mineral surfaces. The experimental absorption frequencies in the phosphate region were compared to DFT calculations for nucleotides adsorbed through the phosphate group to binuclear clusters in either a monodentate or bidentate bridging coordination. Although the quality of the fits suggests that both binding modes may be present, the relative amounts differ on the two surfaces with preferential bonding suggested to be monodentate coordination on hematite and bidentate bridging on goethite. Possible reasons for these differences are discussed.

Strong Enhancement of Nanoconfined Water Mobility by a Structure Breaking Salt.

For the majority of the water present on earth, the two most important factors influencing its behavior are confinement, in either inorganic or organic matrixes, and the presence of solutes. Here, we investigate the effect of confinement in 3 nm pores on water diffusivity in aqueous solutions with archetypical solutes, a structure making (kosmotrope) NaCl and a structure breaking (chaotrope) KCl, up to 1.0 M in concentration. The water diffusivity in bulk aqueous solutions in such a concentration range is known to decrease very slightly in the presence of NaCl and increase very slightly in the presence of KCl. However, here we observe the water diffusivity in confined H2O-KCl increases by a factor of 2 compared to the pure water diffusivity in the same confinement. This unusually strong cumulative effect of confinement and a structure breaking additive may have profound implications for the mobility and transport of aqueous species in nature.

Measurement of Volume Change and Mass Transfer During Serpentinization: Insights From the Oman Drilling Project

AbstractSerpentinization plays a key role on the evolution of the physicochemical properties of the mantle lithosphere. The rate of serpentinization reactions is controlled by the transport of fluid, which itself depends on volume change during reaction. Element transfer can strongly modify the magnitude and sign of volume change. Here, we measure solid volume change and element transport perpendicular to a serpentine vein in a serpentinized dunite collected at depth during the Oman Drilling Project. The sample is extensively replaced (extent of reaction > 80%) by a serpentine/brucite mixture parallel to a main serpentine vein network. The Mg content of serpentine and brucite indicates reaction with a small amount of fluid at temperatures below 100°C. Concentrations of fluid‐mobile trace elements (Na, Ca, Sr, Rb, and Ba) decrease perpendicular to the main vein. Primary olivine contains parallel platelets of a clinopyroxene/magnetite symplectite. Tomography at the nanoscale reveals that these inclusions do not react during serpentinization but are cracked and displaced. We use these inert markers to measure a 59% to 74% positive volume change that is close to the 52% expected for reaction in a closed system. Chemical data indicate no change in major element composition during reaction except for the addition of water. The initial olivine zoning in Al, Ti, V, Sc, and Cr is still preserved in serpentine and brucite. Serpentinization can thus be a local replacement process during which the solid volume homogeneously increases at the micrometer scale and the transport of aqueous species is limited.

Molecular Simulation of Structure and Diffusion at Smectite–Water Interfaces: Using Expanded Clay Interlayers as Model Nanopores

In geologic settings relevant to a number of extraction and potential sequestration processes, nanopores bounded by clay mineral surfaces play a critical role in the transport of aqueous species. Solution structure and dynamics at clay–water interfaces are quite different from their bulk values, and the spatial extent of this disruption remains a topic of current interest. We have used molecular dynamics simulations to investigate the structure and diffusion of aqueous solutions in clay nanopores approximately 6 nm thick, comparing the effect of clay composition with model Na-hectorite and Na-montmorillonite surfaces. In addition to structural properties at the interface, water and ion diffusion coefficients were calculated within each aqueous layer at the interface, as well as in the central bulk-like region of the nanopore. The results show similar solution structure and diffusion properties at each surface, with subtle differences in sodium adsorption complexes and water structure in the first adsorbed...

Uraninite oxidation and dissolution induced by manganese oxide: A redox reaction between two insoluble minerals

The longevity of subsurface U(IV) produced by reduction of U(VI) during in situ bioremediation can be limited by reoxidation to more mobile U(VI) species. Coupling of the biogeochemical cycles of U and Mn may affect the fate and transport of uranium. Manganese oxides can act as a powerful oxidant that accelerates the oxidative dissolution of UO2. This study investigated the physical and chemical factors controlling the interaction between UO2 and MnO2, which are both poorly soluble minerals. A multi-chamber reactor with a permeable membrane was used to eliminate direct contact of the two minerals while still allowing transport of aqueous species. The oxidation of UO2 was not significantly enhanced by MnO2 if the two solids were physically separated. Complete mixing of MnO2 with UO2 led to a much greater extent and rate of U oxidation. When direct contact is not possible, the reaction slowly progresses through release of soluble U(IV) with its adsorption and oxidation on MnO2. Continuously-stirred tank reactors (CSTRs) were used to quantify the steady-state rates of UO2 dissolution induced by MnO2. MnO2 dramatically promoted UO2 dissolution, but the degree of promotion leveled off once the MnO2:UO2 ratio exceeded a critical value. Substantial amounts of U(VI) and Mn(II) were retained on MnO2 surfaces. The total production of Mn(II) was less than that of U(VI), indicating that the fate of Mn products and their impact on UO2–MnO2 reaction kinetics were complicated and may involve formation of Mn(III) phases. At higher dissolved inorganic carbon concentrations, UO2 oxidation by MnO2 was faster and less U(VI) was adsorbed to MnO2. Such an inverse relationship suggested that U(VI) may passivate MnO2 surfaces. A conceptual model was developed to describe the oxidation rate of UO2 by MnO2. This model is potentially applicable to a broad range of water chemistry conditions and is relevant to other environmental redox processes involving two poorly soluble minerals.

The Link Between Mineral Dissolution/Precipitation Kinetics and Solution Chemistry

Research Article| January 01, 2009 The Link Between Mineral Dissolution/Precipitation Kinetics and Solution Chemistry Jacques Schott; Jacques Schott Laboratoire d’Etude des Mécanismes et Transferts en Géologie, Observatoire Midi-Pyrénées, CNRS-Université de Toulouse, Toulouse, France, schott@lmtg.obs-mip.fr Search for other works by this author on: GSW Google Scholar Oleg S. Pokrovsky; Oleg S. Pokrovsky Laboratoire d’Etude des Mécanismes et Transferts en Géologie, Observatoire Midi-Pyrénées, CNRS-Université de Toulouse, Toulouse, France, schott@lmtg.obs-mip.fr Search for other works by this author on: GSW Google Scholar Eric H. Oelkers Eric H. Oelkers Laboratoire d’Etude des Mécanismes et Transferts en Géologie, Observatoire Midi-Pyrénées, CNRS-Université de Toulouse, Toulouse, France, schott@lmtg.obs-mip.fr Search for other works by this author on: GSW Google Scholar Author and Article Information Jacques Schott Laboratoire d’Etude des Mécanismes et Transferts en Géologie, Observatoire Midi-Pyrénées, CNRS-Université de Toulouse, Toulouse, France, schott@lmtg.obs-mip.fr Oleg S. Pokrovsky Laboratoire d’Etude des Mécanismes et Transferts en Géologie, Observatoire Midi-Pyrénées, CNRS-Université de Toulouse, Toulouse, France, schott@lmtg.obs-mip.fr Eric H. Oelkers Laboratoire d’Etude des Mécanismes et Transferts en Géologie, Observatoire Midi-Pyrénées, CNRS-Université de Toulouse, Toulouse, France, schott@lmtg.obs-mip.fr Publisher: Mineralogical Society of America First Online: 09 Mar 2017 © The Mineralogical Society Of America Reviews in Mineralogy and Geochemistry (2009) 70 (1): 207–258. https://doi.org/10.2138/rmg.2009.70.6 Article history First Online: 09 Mar 2017 Cite View This Citation Add to Citation Manager Share Icon Share Facebook Twitter LinkedIn MailTo Tools Icon Tools Get Permissions Search Site Citation Jacques Schott, Oleg S. Pokrovsky, Eric H. Oelkers; The Link Between Mineral Dissolution/Precipitation Kinetics and Solution Chemistry. Reviews in Mineralogy and Geochemistry 2009;; 70 (1): 207–258. doi: https://doi.org/10.2138/rmg.2009.70.6 Download citation file: Ris (Zotero) Refmanager EasyBib Bookends Mendeley Papers EndNote RefWorks BibTex toolbar search Search Dropdown Menu toolbar search search input Search input auto suggest filter your search All ContentBy SocietyReviews in Mineralogy and Geochemistry Search Advanced Search Recent years have seen the growing development and application of reactive transport models to describe, at different spatial and temporal scales, natural and industrial processes involving water-rock interactions such as continental weathering and its impact on ocean chemistry and climate, cycling of metals and the formation of ore deposits, porosity formation/reduction and oil migration in sedimentary basins, transport and geological sequestration of CO2, and geothermal power generation. The successful application of these models requires a comprehensive and robust kinetic data base of mineral-water interactions. To address this need significant efforts have been made over the past two decades... You do not have access to this content, please speak to your institutional administrator if you feel you should have access.

Modelling of the Interaction Between an Engineered Clay Barrier and Concrete Structures in a Deep Storage Vault

AbstractThe degradation of concrete structures in a storage vault will release an alkaline plume influencing the geochemical evolution of clay engineered barriers or plugs. The studied configuration has a representative scale and is composed of a rectangular clay barrier interfaced on one side with a cement block and on the other side with an external granitic field. A clay model including major and accessory minerals is used; cement material is supposed to be made of portlandite and CSH minerals. The clay barrier and the cement block are assumed to be initially saturated and in equilibrium with their respective interstitial water. Diffusive transport of aqueous species coupled to chemistry is simulated in a one dimension space up to 10000 y. The feed-back of the porosity evolution on the transport properties is not taken into account. The temperature is supposed to be constant (25°C). Calculations are performed with the TRIO-EF coupled transport-chemistry code.The main results deal with the evolution of the pH profile across the clay barrier, the dissolution of clay minerals and the precipitation of new solid phases in the clay such as albite, gibbsite and CSH. These simulations show that the pH excursion includes only a minor part of the clay barrier at 10 000 y and that the CSH precipitation retards the alkaline plume progression. The appearance of local accumulations of newly precipitated minerals might reduce strongly the porosity. Future developpements of this work include: (i) the completion of the geochemical model by introducing other minerals in concrete (other CSH phases and sulfo-aluminates) and ion exchange sites within the clay, (ii) the implementation of a precipitation/dissolution model in order to describe on a realistic way the porosity profile evolution and possible clogging phenomena.

Numerical Simulation of the Interaction Between Granitic Groundwater, Engineered Clay Barrier and Iron Canister

AbstractThe geochemical evolution of a clay engineered barrier subjected simultaneously to granitic groundwater on its external boundary and to a steady flux of iron released by canister corrosion on the other boundary is simulated for time periods up to 1000 y. A multisite ion-exchange model combined with dissolution/precipitation of accessory minerals (calcite, gypsum, quartz, goethite, pyrite, pyrrhotite, iron silicate, magnetite) is used to describe the geochemical evolution of the clay barrier. Diffusive transport of aqueous species and dissolved gases is simulated in a one dimension space. Retroaction of chemical reactions on the corrosion process of the canister is not included in the model. The temperature is assumed to be constant (25°C). Calculations are performed with the IMPACT geochemical coupled code. Two main scenarios are considered: (i) the reduction of sulfates (gypsum) is kinetically hindered, (ii) the reduction of sulfates is possible and leads to the precipitation of sulfides. Main results obtained are dealing with H2(gas) generation and control, pH transient and buffering effect of the clay barrier system. These simulations show that the hydrogen partial pressure in the clay barrier could possibly stay for long periods of time at a very low level due to interactions with mineral buffers or sinks. In the sulfate reduction scenario, a transient pH, xcursion is predicted at the vicinity of the canister. Future developpements of this work include the taking into account of a temperature gradient. Improvement of the geochemical model and reaction pathway is also necessary and will be done with the guidance of on going experimental work.