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  • 1.
    Adeniyi, Omotayo
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Osmanaj, Blerina
    Umeå University, Faculty of Science and Technology, Department of Chemistry. Department of Chemistry, University of Prishtina, 10000 Prishtina, Kosovo.
    Manavalan, Gopinathan
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Samikannu, Ajaikumar
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Mikkola, Jyri-Pekka
    Umeå University, Faculty of Science and Technology, Department of Chemistry. Industrial Chemistry and Reaction Engineering, Johan Gadolin Process Chemistry Centre, Åbo Akademi University, Åbo-Turku, 20500, Finland.
    Avni, Berisah
    Department of Chemistry, University of Prishtina, 10000 Prishtina, Kosovo.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Tesfalidet, Solomon
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Engineering of layered iron vanadate nanostructure for electrocatalysis: simultaneous detection of methotrexate and folinic acid in blood serum2023In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, article id 142538Article in journal (Refereed)
    Abstract [en]

    In this study, nanostructure kazakhstanite-like iron vanadate (FexV3xOy.H2O) was synthesized and calcined at different temperatures (100-800 °C) in a nitrogen atmosphere. The material was used to modify screen-printed carbon electrodes to achieve an electrocatalytic effect on the surface. The relationship between calcination conditions and the catalytic performance of the electrode towards the oxidation of chemotherapeutic drugs, including methotrexate (MTX) and folinic acid (FA), was studied. Various spectroscopic, microscopic, and electrochemical methods were used to characterize the synthesized materials. The results show that calcination induces changes in the electronic structure, nanostructure morphology, electroactive surface area, and electrocatalytic performance of the material. Screen-printed carbon electrode modified with FexV3xOy calcinated at 450 °C (SPC/FexV3xOy-450) was used to develop a voltammetric sensor for the determination of MTX and FA in blood serum. The response of the SPC/FexV3xOy-450 towards the electrooxidation of MTX and FA was the highest in comparison to the bare SPC and SPC/FexV3xOy calcined at other temperatures. The SPC/FexV3xOy-450 exhibited a linear relationship over a wide concentration range: 0.005-200 µM for MTX and 0.05-200 µM for FA. The detection limit was 2.85 nM for MTX and 7.79 nM for FA. Compared to conventional methods, the SPC/FexV3xOy-450 sensor had a short response time (5 min) for simultaneous detection of MTX and FA without signal interferences from coexisting electroactive compounds. The accurate and precise determination of MTX in the presence of FA confirmed the potential clinical applications of SPC/FexV3xOy-450 for therapeutic drug monitoring during chemotherapy.

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  • 2.
    Annamalai, Alagappan
    et al.
    Umeå University, Faculty of Science and Technology, Department of Physics.
    Sandström, Robin
    Umeå University, Faculty of Science and Technology, Department of Physics.
    Gracia-Espino, Eduardo
    Umeå University, Faculty of Science and Technology, Department of Physics.
    Boulanger, Nicolas
    Umeå University, Faculty of Science and Technology, Department of Physics.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Muehlbacher, Inge
    Umeå University, Faculty of Science and Technology, Department of Physics.
    Wågberg, Thomas
    Umeå University, Faculty of Science and Technology, Department of Physics.
    Double donor Sb5+doped hematite (Fe3+) photoanodes for surface-enhanced PEC water splitting2018In: Abstracts of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 256Article in journal (Other academic)
  • 3.
    Annamalai, Alagappan
    et al.
    Umeå University, Faculty of Science and Technology, Department of Physics.
    Sandström, Robin
    Umeå University, Faculty of Science and Technology, Department of Physics.
    Gracia-Espino, Eduardo
    Umeå University, Faculty of Science and Technology, Department of Physics.
    Boulanger, Nicolas
    Umeå University, Faculty of Science and Technology, Department of Physics.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Mühlbacher, Inge
    Shchukarev, Andrey
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Wågberg, Thomas
    Umeå University, Faculty of Science and Technology, Department of Physics.
    Influence of Sb5+ as a Double Donor on Hematite (Fe3+) Photoanodes for Surface-Enhanced Photoelectrochemical Water Oxidation2018In: ACS Applied Materials and Interfaces, ISSN 1944-8244, E-ISSN 1944-8252, Vol. 10, no 19, p. 16467-16473Article in journal (Refereed)
    Abstract [en]

    To exploit the full potential of hematite (α-Fe2O3) as an efficient photoanode for water oxidation, the redox processes occurring at the Fe2O3/electrolyte interface need to be studied in greater detail. Ex situ doping is an excellent technique to introduce dopants onto the photoanode surface and to modify the photoanode/electrolyte interface. In this context, we selected antimony (Sb5+) as the ex situ dopant because it is an effective electron donor and reduces recombination effects and concurrently utilize the possibility to tuning the surface charge and wettability. In the presence of Sb5+ states in Sb-doped Fe2O3 photoanodes, as confirmed by X-ray photoelectron spectroscopy, we observed a 10-fold increase in carrier concentration (1.1 × 1020 vs 1.3 × 1019 cm–3) and decreased photoanode/electrolyte charge transfer resistance (∼990 vs ∼3700 Ω). Furthermore, a broad range of surface characterization techniques such as Fourier-transform infrared spectroscopy, ζ-potential, and contact angle measurements reveal that changes in the surface hydroxyl groups following the ex situ doping also have an effect on the water splitting capability. Theoretical calculations suggest that Sb5+ can activate multiple Fe3+ ions simultaneously, in addition to increasing the surface charge and enhancing the electron/hole transport properties. To a greater extent, the Sb5+- surface-doped determines the interfacial properties of electrochemical charge transfer, leading to an efficient water oxidation mechanism.

  • 4.
    Arbid, Yara
    et al.
    Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, France.
    Usman, Muhammad
    Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, France.
    Luong, N. Tan
    Umeå University, Faculty of Science and Technology, Department of Chemistry. Department of Physics, Chalmers University of Technology, Göteborg, Sweden.
    Mathon, Baptiste
    Treewater, Lyon, France.
    Cedat, Bruno
    Treewater, Lyon, France.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Hanna, Khalil
    Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, France; Department of Chemistry, Durham University, Durham, United Kingdom.
    Use of iron-bearing waste materials in laundry wastewater treatment2024In: Journal of Water Process Engineering, E-ISSN 2214-7144, Vol. 57, article id 104717Article in journal (Refereed)
    Abstract [en]

    This study evaluates the efficiency of a steel waste-derived magnetite (WM) for the treatment of laundry wastewater under various irradiation conditions (ultraviolet-A and C: UVA and UVC), both in the presence and absence of H2O2. Because WM can contain magnetite and elemental iron phases, its ability to remove ciprofloxacin and phenol, here used as model pollutants, and total organic carbon (TOC) from laundry wastewater was compared with that of synthetic magnetite (SM) and zero-valent iron (ZVI). We show that the mixed ZVI/H2O2 system under UVC degraded up to 80 % of the pollutant and 70 % of the TOC. WM had, on the other hand, a lower reactivity for pollutants due to the presence of inorganic impurities, yet removed up to 60 % of TOC. In all cases considered in this work, a higher degradation rate was observed under UVC irradiation than under UVA. Moreover, iron-based materials can adsorb heavy metals co-existing in the laundry wastewater. Recyclability tests showed no significant loss in the activity of WM or SM for up to 5 cycles in laundry wastewater. This study can have strong implications for the development of new remediation technologies relying on industrial solid wastes, especially in the context of a circular economy.

  • 5.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Colloids2017In: Encyclopedia of geochemistry: a comprehensive reference source on the chemistry of the Earth / [ed] William M. White, Cham: Springer, 2017, p. 1-4Chapter in book (Other academic)
    Abstract [en]

    Colloids are inorganic and organic fines of diverse compositions and sources. They are of widespread occurrence in continental, oceanic, and atmospheric environments. The high surface-to-bulk mass ratio of these particles is especially responsible for their large chemical reactivity and for their important roles in the biogeochemical cycling of elements in nature and even in atmospheric processes.

  • 6.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Hydrothermal solutions2017In: Encyclopedia of geochemistry: a comprehensive reference source on the chemistry of the Earth / [ed] William M. White, Cham: Springer, 2017, p. 1-6Chapter in book (Other academic)
  • 7.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Solubility2017In: Encyclopedia of geochemistry: a comprehensive reference source on the chemistry of the Earth / [ed] William M. White, Cham: Springer, 2017, p. 1-9Chapter in book (Other academic)
  • 8.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    The Variable Capacitance Model: A Strategy for Treating Contrasting Charge-Neutralizing Capabilities of Counterions at the Mineral/Water Interface2014In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 30, no 8, p. 2009-2018Article in journal (Refereed)
    Abstract [en]

    Thermodynamic models predicting ion adsorption at mineral/water interfaces can have limitations from the simplifying assumptions that compact plane thicknesses and capacitance values are constant, and that charge densities of electrolyte counterions of different charge-to-size ratios lie at the same planes of adsorption, or split between different planes. To address these limitations a thermodynamic adsorption modeling framework was developed to account for coexisting compact planes for each type of counterion complexes formed on a single mineral surface. This framework was developed to predict charge development at lepidocrocite (gamma-FeOOH) particle surfaces suspended in aqueous solutions of NaCl and NaClO4. The model incorporates properties of Cl-, ClO4-, and Na+ complexes formed at the (001) and (010) faces of this mineral obtained by molecular dynamics (MD) simulations. This concept was incorporated in a thermodynamic adsorption model that predicts an overall variable compact plane capacitance in terms of a linear combination of the capacitances of ion-specific EDL structures scaled for their relative surface loadings. These capacitance values are in turn constrained by compact plane thicknesses of every Cl-, ClO4-, and Na+ complex, based on their MD-derived structures and atomic densities. The model predicts experimental potential-determining (H+, OH-) data for submicrometer-sized synthetic lepidocrocite particles exhibiting both (001) and (010) faces. It also isolates electrostatic contributions from these faces. A computer code solving for this Variable Capacitance Model-VCM-is provided in the Supporting Information section of this article, and can be readily modified to predict molecular-level details of any other mineral/water interface systems using this methodology.

  • 9.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Water Structure and Hydrogen Bonding at Goethite/Water Interfaces: Implications for Proton Affinities2012In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 116, no 7, p. 4714-4724Article in journal (Refereed)
    Abstract [en]

    Molecular dynamics simulations of four crystallographic terminations of goethite (alpha-FeOOH) in contact with liquid water (300 K, 1 bar) were performed to resolve interfacial water structures in the vicinity of surface (hydr)oxo groups. Interfacial water molecules adopted highly surface-specific configurations on (010), 100), (110), and (021) planes of goethite. Water molecules generally had weaker hydrogen bond numbers and strengths, as well as smaller self-diffusion coefficients, than their bulk liquid counterparts. Relaxed surface Fe-O and H acceptor distances and populations were used to estimate proton affinity constants of singly-, and triply-coordinated (hydr)oxo groups using the multisite complexation model. These calculations confirmed that singly coordinated groups are mainly responsible for charge uptake under normal environmental conditions. However, revised proton affinity constants showed that protonation of doubly-coordinated hydroxo groups and one type of triply-coordinated oxo group may be favored in the presence of strongly binding negatively charged ligands. These calculations should facilitate elucidation of surface complexation mechanisms on this environmentally important material.

  • 10.
    Boily, Jean-Francois
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Fu, Li
    Tuladhar, Aashish
    Lu, Zhou
    Legg, Benjamin A.
    Wang, Zheming M.
    Wang, Hongfei
    Hydrogen bonding and molecular orientations across thin water films on sapphire2019In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 555, p. 810-817Article in journal (Refereed)
    Abstract [en]

    Hypothesis: Water vapor binding to metal oxide surfaces produces thin water films with properties controlled by interactions with surface hydroxo sites. Hydrogen bonding populations vary across films and induce different molecular orientations than at the surface of liquid water. Identifying these differences can open possibilities for tailoring film-mediated catalytic reactions by choice of the supporting metal oxide substrate.

    Experiments: The (0001) face of a single sapphire (α-Al2O3) sample exposed to water vapor and the surface of liquid water were probed by polarization dependent Sum Frequency Generation-Vibration Spectroscopy (SFG-VS). Molecular dynamics (MD) provided insight into the hydrogen bond populations and molecular orientations across films and liquid water.

    Findings: SFG-VS revealed a submonolayer film on sapphire exposed to 43% relative humidity (R.H.), and a multilayer film at 78% R.H. Polarization dependent SFG-VS spectra showed that median tilt angles of free OH bonds on the top of films are at ∼43° from the normal of the (0001) face but at 38° on neat liquid water. These values align with MD simulations, which also show that up to 36% of all OH bonds on films are free. This offers new means for understanding how interfacial reactions on sapphire-supported water films could contrast with those involving liquid water.

  • 11.
    Boily, Jean-Francois
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Kozin, Philipp A.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Particle Morphological and Roughness Controls on Mineral Surface Charge Development2014In: Geochimica et Cosmochimica Acta, ISSN 0016-7037, E-ISSN 1872-9533, Vol. 141, no 15 September, p. 567-578Article in journal (Other academic)
    Abstract [en]

    Effects of mineral particle morphology and roughness on potential determining ion (p.d.i.; H+, OH) loadings achieved at synthetic lepidocrocite (γ-FeOOH) surfaces were predominantly investigated by potentiometry and thermodynamic modeling. Nanosized rod- (RL) and lath-shaped (LL) particles exhibiting different proportions of the same predominant crystallographic faces acquired largely comparable pH, ionic strength and counterion (NaCl, NaClO4) dependencies on p.d.i. loadings. These results supported previous claims that faces ideally containing proton silent sites only, are likely populated by additional proton active sites. This concept was supported further by results of roughened LL-like particles (LLR) also showing highly congruent pH-, ionic strength- and composition-dependent p.d.i. loadings with those of LL and RL. These loadings thereby correspond to maximal levels allowed by net attractive and repulsive forces at each solution composition, irrespective of particle morphology. Contrasting equilibration times required to achieve these loadings revealed considerably slower exchange of p.d.i. and electrolyte ions near the point of zero charge in the rough LLR than in the more idealized LL and RL particles.

    Thermodynamic modeling was used to test various concepts accounting for these results. The model made use of a novel framework capable of isolating electrostatic contributions from different faces, and of accounting for ion-specific double-layer properties within a single crystallographic face. These efforts made use of capacitance values for each electrolyte ions within the framework of a recently developed Variable Capacitance Model. Attempts at modeling all three particle types were used to suggest that the (0 1 0) face contains ∼0.9 site nm−2 of proton active sites, a value notably constrained by recently published Na+, Cl, and ClO4 loadings derived by cryogenic X-ray photoelectron spectroscopy. The model presented in this work thus provides a means to predict p.d.i. loadings on multifaceted mineral particle surfaces, and can therefore be used to constrain further our understanding of mineral/water interface reactivity.

  • 12.
    Boily, Jean-Francois
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Lins, Roberto D
    Pacific Northwest National Laboratory, Richland Washington, USA .
    Electrostatic cooperativity of hydroxyl groups at metal oxide surfaces2009In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 113, no 38, p. 16568-16570Article in journal (Refereed)
    Abstract [en]

    The O−H bond distribution of hydroxyl groups at the {110} goethite (α-FeOOH) surface was investigated by molecular dynamics. This distribution was strongly affected by electrostatic interactions with neighboring oxo and hydroxo groups. The effects of proton surface loading, simulated by emplacing two protons at different distances of separation, were diverse and generated several sets of O−H bond distributions. DFT calculations of a representative molecular cluster were also carried out to demonstrate the impact of these effects on the orientation of oxygen lone pairs in neighboring oxo groups. These effects should have strong repercussions on O−H stretching vibrations of metal oxide surfaces.

  • 13.
    Boily, Jean-Francois
    et al.
    Umeå University, Faculty of Science and Technology, Chemistry.
    Lutzenkirchen, Johannes
    Balmes, Oliver
    Beattie, James
    Sjöberg, Staffan
    Umeå University, Faculty of Science and Technology, Chemistry.
    Modeling proton binding at the goethite (-FeOOH)-water interface2001In: Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 179, no 1, p. 11-27Article in journal (Refereed)
    Abstract [en]

    The basic charging behaviours of goethite particles with different surfaces area (23, 37 and 85 m2 g-1) in 0.003-2.0 M NaNO3 were interpreted using surface complexation theory with the basic Stern model (BSM). The affinity of the goethite surface functional groups for protons was evaluated using the multisite complexation model (MUSIC) framework considering singly, doubly, and triply-coordinated surface oxygens with respect to underlying Fe(III) atoms. The affinity of these functional groups for protons was investigated first by using a calibration curve devised in Hiemstra et al. [J. Colloid Interface Science, 184 (1996) 680]. The calibration curve correlates the proton affinity constants of aqueous metal monomers to the undersaturation of the coordination environment of oxygens by considering the actual bond valences of Fe&unknown;O bonds in goethite, short hydroxyl bonds and hydrogen bonds. The results show that the predictions are sensitive to the range of short hydroxyl bonds/hydrogen bonds found in the literature. The singly- and one type of the triply coordinated sites are, however, most likely responsible for the basic charging behavior of goethite in the pH 2-11. The proton affinity constants of the singly- and triply coordinated sites were also optimized using titration data at different ionic strengths by co-optimizing values for electrolyte ion pairs and the capacitance of the Stern Layer. The optimal proton binding constants were in the range of the predicted values using the aforementioned calibration curve, although the modeling parameters are interdependent. A narrow range of CStern and electrolyte ion pairs was chosen to model the charging behavior of goethite by considering, (i), the range of proton binding constants from the aforementioned calibration curve; and (ii), the success of the models to predict zeta potential measurements assuming that the shear plane coincides with the head of the diffuse layer. Modeling parameters were also produced with the '1pK approximation' whereby the proton affinity constant of the singly- and of the triply-coordinated sites were set to the pH of zero charge and CStern and the electrolyte ion binding constants were co-optimized. In both cases, the values of CStern and of the electrolyte ion binding constants are slightly larger for the 23 and 37 m2 g-1 goethites than for the 85 m2 g-1. This indicates a larger proton uptake capacity of the 23 and 37 m2 g-1 goethites, putatively resulting from the larger surface roughness at the termination of the particles.

  • 14.
    Boily, Jean-Francois
    et al.
    Umeå University, Faculty of Science and Technology, Chemistry.
    Persson, Per
    Umeå University, Faculty of Science and Technology, Chemistry.
    Sjöberg, Staffan
    Umeå University, Faculty of Science and Technology, Chemistry.
    Benzenecarboxylate surface complexation at the goethite (α-FEOOH)/water interface. III. The influence of particle surface area and the significance of modeling parameters2000In: Journal of colloid and interface science, Vol. 227, no 1, p. 132-40Article in journal (Refereed)
    Abstract [en]

    A surface complexation model describing the adsorption of three benzenecarboxylates (phthalate, trimellitate, and pyromellitate) on goethite (α-FeOOH) was calibrated on data using goethite particles of 37 and 43 m[2]/g surface area. The models predict potentiometric titration and batch adsorption data with the multisite complexation model coupled with the three-plane model to account for surface electrostatics. The modeling parameters were found to be similar to those calibrated on benzenecarboxylate adsorption data on goethite particles of 90 m[2]/g (Boily et al. Geochim. Cosmochim. Acta, in press). The significance of the benzenecarboxylate-dependent values of the modeling parameters is also discussed. The values of the capacitances of the inner- and outer-Helmholtz planes were shown to be important modeling parameters to model the benzenecarboxylate-dependent slopes of the adsorption edges. It was shown that the larger the charge of the ligand, the larger the capacitance of the outer-Helmholtz plane.

  • 15.
    Boily, Jean-Francois
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Shchukarev, Andrey
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    X-ray photoelectron spectroscopy of fast-frozen hematite colloids in aqueous solutions. 2. tracing the relationship between surface charge and electrolyte adsorption2010In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 114, no 6, p. 2613-2616Article in journal (Refereed)
    Abstract [en]

    Colloidal-sized hematite spheroids exposed to aqueous NaCl solutions were investigated by X-ray photoelectron spectroscopy using the fast-frozen technique. The O 1s region provided evidence for (de)protonation reactions of surface (hydr)oxo groups of OH-enriched/O-depleted hematite Surfaces. These results were also correlated to changes in sodium (Na 1s) and chloride (Cl 2p) contents with pH. Electrolyte ion surface loadings were successfully predicted using a classic thermodynamic adsorption model normalized for surface site density. These efforts pointed to ion-specific inner-Helmholtz plane capacitances.

  • 16.
    Boily, Jean-Francois
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Song, Xiaowei
    Direct identification of reaction sites on ferrihydrite2020In: Communications Chemistry, E-ISSN 2399-3669, Vol. 3, no 1, article id 79Article in journal (Refereed)
    Abstract [en]

    Hydroxyl groups are the cornerstone species driving catalytic reactions on mineral nanoparticles of Earth's crust, water, and atmosphere. Here we directly identify populations of these groups on ferrihydrite, a key yet misunderstood iron oxyhydroxide nanomineral in natural sciences. This is achieved by resolving an enigmatic set of vibrational spectroscopic signatures of reactive hydroxo groups and chemisorbed water molecules embedded in specific chemical environments. We assist these findings by exploring a vast array of configurations of computer-generated nanoparticles. We find that these groups are mainly disposed along rows at edges of sheets of iron octahedra. Molecular dynamics of nanoparticles as large as 10 nm show that the most reactive surface hydroxo groups are predominantly free, yet are hydrogen bond acceptors in an intricate network formed with less reactive groups. The resolved vibrational spectroscopic signatures open new possibilities for tracking catalytic reactions on ferrihydrite, directly from the unique viewpoint of its reactive hydroxyl groups. Ferrihydrite nanoparticles have many hydroxyl sites which can react with environmental contaminants and nutrients, but the surface structure of this common mineral is still not fully understood. Here, a combination of vibrational spectroscopy and molecular simulations identify hydroxyl groups exposed along rows at the edges of sheets of iron octahedra.

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  • 17.
    Boily, Jean-Francois
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Yesilbas, Merve
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Uddin, Munshi Md. Musleh
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Baiqing, Lu
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Trushkina, Yulia
    Salazar-Alvarez, German
    Thin Water Films at Multifaceted Hematite Particle Surfaces2015In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 31, no 48, p. 13127-13137Article in journal (Refereed)
    Abstract [en]

    Mineral surfaces exposed to moist air stabilize nanometer- to micrometer-thick water films. This study resolves the nature of thin water film formation at multifaceted hematite (alpha-Fe2O3) nanoparticle surfaces with crystallographic faces resolved by selected area electron diffraction. Dynamic vapor adsorption (DVA) in the 0-19 Torr range at 298 K showed that these particles stabilize water films consisting of up to 4-5 monolayers. Modeling of these data predicts water loadings in terms of an "adsorption regime" (up to 16 H2O/nm(2)) involving direct water binding to hematite surface sites, and of a "condensation regime" (up to 34 H2O/nm(2)) involving water binding to hematite-bound water nanodusters. Vibration spectroscopy identified the predominant hematite surface hydroxo groups (-OH, mu-OH, mu(3)-OH) through which first layer water molecules formed hydrogen bonds, as well as surface iron sites directly coordinating water molecules (i.e., as geminal eta-(OH2)(2) sites). Chemometric analyses of the vibration spectra also revealed a strong correspondence in the response of hematite surface hydroxo groups to DVA-derived water loadings. These findings point to a near-saturation of the hydrogen-bonding environment of surface hydroxo groups at a partial water vapor pressure of similar to 8 Torr (similar to 40% relative humidity). Classical molecular dynamics (MD) resolved the interfacial water structures and hydrogen bonding populations at five representative crystallographic faces expressed in these nanoparticles. Simulations of single oriented slabs underscored the individual roles of all (hydro)oxo groups in donating and accepting hydrogen bonds with first layer water in the "adsorption regime". These analyses pointed to the preponderance of hydrogen bond-donating -OH groups in the stabilization of thin water films. Contributions of mu-OH and mu(3)-OH groups are secondary, yet remain essential in the stabilization of thin water films. MD simulations also helped resolve crystallographic controls on water water interactions occurring in the "condensation regime". Water water hydrogen bond populations are greatest on the (001) face, and decrease in importance in the order (001) > (012) approximate to (110) > (014) >> (100). Simulations of a single (similar to 5 nm x similar to 6 nm x similar to 6 nm) nanometric hematite particle terminated by the (001), (110), (012), and (100) faces also highlighted the key roles that sites at particle edges play in interconnecting thin water films grown along contiguous crystallographic faces. Hydroxo water hydrogen bond populations showed that edges were the preferential loci of binding. These simulations also suggested that equilibration times for water binding at edges were slower than on crystallographic faces. In this regard, edges, and by extension roughened surfaces, are expected to play commanding roles in the stabilization of thin water films. Thus, in focusing on the properties of nanometric-thick water layers at hematite surfaces, this study revealed the nature of interactions between water and multifaced particle surfaces. Our results pave the way for furthering our understanding of mineral-thin water film interfacial structure and reactivity on a broader range of materials.

  • 18.
    Boily, Jean-François
    Umeå University, Faculty of Science and Technology, Chemistry.
    Elucidation of oxyanion coordination geometries at solid surfaces of varied electric field strengths2009In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 11, no 37, p. 8133-5Article in journal (Refereed)
    Abstract [en]

    Density functional theory calculations of oxyanions exposed to external electric fields revealed systematic variations in molecular geometries and vibration stretching frequencies. These variations can be used in laboratory studies to determine coordination geometries of oxyanions adsorbed on solid surfaces using infrared spectroscopy.

  • 19.
    Boily, Jean-François
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Chatman, Shawn
    Rosso, Kevin M
    Inner-Helmholtz potential development at the hematite (α-Fe2O3) (0 0 1) surface2011In: Geochimica et Cosmochimica Acta, ISSN 0016-7037, E-ISSN 1872-9533, Vol. 75, no 15, p. 4113-4124Article in journal (Refereed)
    Abstract [en]

    Electric potentials of the (0 0 1) surface of hematite were measured as a function of pH and ionic strength in solutions of sodium nitrate and oxalic acid using the single-crystal electrode approach. The surface is predominantly charge-neutral in the pH 4–14 range, and develops a positive surface potential below pH 4 due to protonation of μ-OH0 sites (pK1,1,0,int = −1.32). This site is resilient to deprotonation up to at least pH 14 (−pK−1,1,0,int ≫ 19). The associated Stern layer capacitance of 0.31–0.73 F/m2 is smaller than typical values of powders, and possibly arises from a lower degree of surface solvation. Acid-promoted dissolution under elevated concentrations of HNO3 etches the (0 0 1) surface, yielding a convoluted surface populated by sites. The resulting surface potential was therefore larger under these conditions than in the absence of dissolution. Oxalate ions also promoted (0 0 1) dissolution. Associated electric potentials were strongly negative, with values as large as −0.5 V, possibly from metal-bonded interactions with oxalate. The hematite surface can also acquire negative potentials in the pH 7–11 range due to surface complexation and/or precipitation of iron species (0.0038 Fe/nm2) produced from acidic conditions. Oxalate-bearing systems also result in negative potentials in the same pH range, and may include ferric-oxalate surface complexes and/or surface precipitates. All measurements can be modeled by a thermodynamic model that can be used to predict inner-Helmholtz potentials of hematite surfaces.

  • 20.
    Boily, Jean-François
    et al.
    Umeå University, Faculty of Science and Technology, Chemistry.
    Fein, Jeremy B
    Proton binding to humic acids and sorption of Pb(II) and humic acid to the corundum surface2000In: Chemical Geology, Vol. 168, no 3-4, p. 239-53Article in journal (Refereed)
    Abstract [en]

    An experimental investigation of proton binding to a humic acid, and of the co-adsorption of humic acid and Pb(II) to the corundum surface was conducted in 0.01 M NaNO3. We attempt to model the acid–base properties of the humic acid using both discrete and continuous distributions of proton affinity constants, also testing both nonelectrostatic and electrostatic approaches. The best-fitting models indicate that an average of three dominant proton-active functional groups are present on the humic acid with proton affinity constant logβ1,1,0 (int) equal to 2.6, 5.2 and 7.6. These values may be applied as intrinsic constants in a Constant Capacitance Model (CCM) or as means of distribution functions in a Langmuir–Freundlich isotherm where the humate is treated as a mixture of three monoprotic acids. The adsorption of humic acid onto corundum is best described using a Surface Complexation Model (SCM) with the Extended Constant Capacitance Model. The humate surface complexes, which best describe the experimental data, are the outer-sphere (>AlOH2+)0.1Hf1∑L(0.1–3.0+f1) and (>AlOH2+)0.1(H(f1+f2)∑L)(0.1–3.0+f1+f2) complexes, where f1 and f2 are the mole fractions of the sites with logβ1,1,0 (int)=7.6 and logβ1,1,0 (int)=5.2, respectively. Experimental data also show that the presence of calcium increases the adsorption of humate. The adsorption of Pb in the presence of humate was interpreted to proceed by the formation of the surface ternary complex >AlOH2+–L−z–Pb+2 at low to circumneutral pH. At high pH, aqueous Pb–humate complexation competes with Pb surface complexes and significantly reduces Pb adsorption.

  • 21.
    Boily, Jean-François
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Gassman, Paul L
    Peretyazhko, Tetyana
    Szanyi, János
    Zachara, John M
    FTIR spectral components of schwertmannite2010In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 44, no 4, p. 1185-1190Article in journal (Refereed)
    Abstract [en]

    Fourier transform infrared (FTIR) spectral components of three dominant groups of sulfate species in synthetic schwertmannite (Fe8O8(OH)6-x(SO4)x*nH2O) are presented. These components were extracted by multivariate curve resolution analysis of spectra obtained from N2(g)-dry samples initially reacted in aqueous solutions (pH 3-9) at room temperature. Each component contains complex sets of bands that correspond to mixtures of similar species. We tentatively assign these components to sulfate ions that are hydrogen- (components I and III) and iron-bonded (component I) to schwertmannite. Another component (II) is assigned to protonated sulfate species. Heating experiments to 130 degrees C moreover confirmed this possibility for component II. The spectral components extracted from this study can be used to identify dominant sulfate species in FTIR spectra of naturally occurring schwertmannite samples.

  • 22.
    Boily, Jean-François
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Ilton, Eugene S.
    An independent confirmation of the correlation of Uf4 primary peaks and satellite structures of UVI, UV and UIV in mixed valence uranium oxides by two-dimensional correlation spectroscopy2008In: Surface Science, ISSN 0039-6028, E-ISSN 1879-2758, Vol. 602, no 24, p. 3637-46Article in journal (Refereed)
    Abstract [en]

    Two-dimensional (2D) correlation spectroscopy was used to resolve the positions and correlations among U4f primary peaks and satellite structures of UIV, UV and UVI components on a dry mica surface. These different species resulted from the reduction of UVI, initially sorbed/precipitated from solution, upon exposure to a high flux of monochromatic Al Kα X-rays during X-ray photoelectron spectroscopy. Synchronous and asynchronous 2D maps of these results are consistent with previous assignments to UIV, UV and UVI components of the solid. The synchronous spectra confirmed the negative correlation between UVI and UIV components and the asynchronous spectra confirmed the role of UV as a reactive intermediate in the reduction reaction of UVI to UIV. Simulations of 2D correlation maps using synthetic spectra of the primary peaks showed that the presence of highly overlapped peaks centered within 2 eV of each other cannot be distinguished without the presence of additional cross-peaks. The maps have therefore confirmed the existence of three dominant oxidation states, and identified positions of UIV, UV and UVI U4f primary peaks and satellite structures that are consistent with previous peak-fitting efforts. Satellite structures also showed out-of-phase correlations among the different oxidation states, further confirming their use as reliable indicators of oxidation state.

  • 23.
    Boily, Jean-François
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Rosso, Kevin M
    Crystallographic controls on uranyl binding at the quartz/water interface2011In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 13, no 17, p. 7845-7851Article in journal (Refereed)
    Abstract [en]

    Molecular dynamics methods were used to simulate UO(2)(OH)(2)(0) binding to pairs of oxo sites (O(S)) on three low-index planes of α-SiO(2) in contact with water. Differences in binding site distributions on the (001), (010) and (101) planes produced distinct sets of stable U inner-sphere species. Steric constraints prevented bidentate coordination to the (001) surface, resulting in a mononuclear monodentate complex, [UO(2)(OH)(2)(H(2)O)(n)O(S)] (90% for n = 1 and 10% for n = 2 over 5 ns production runs). Binuclear bidentate coordination, [UO(2)(OH)(2)(H(2)O)(n)(O(S))(2)], was however favored on the (010) (99% for n = 0 and 1% for n = 1) and the (101) (72% for n = 0 and 28% for n = 1) planes. These results underscore a predominant four-coordinated equatorial shell for U when complexed to the quartz/water interface. Potential of mean force calculations uncovered a diversity of metastable outer- and inner-sphere complexes at local energy minima up to ∼0.4 nm from the surface. These calculations point to important differences in both energetic requirements and mechanisms for the approach of UO(2)(OH)(2)(0) to different quartz surfaces. Binding strengths are affected by binding site distribution, steric freedom, U hydration and OH orientation, and increase in the order (001) (3.7 kJ mol(-1)) < (101) (5.6 kJ mol(-1)) < (010) (6.5 kJ mol(-1)). A general binding mechanism involves (1) formation of monodentate outer-sphere complexes, (2) removal of oxo-bound waters, (3) formation of one (monodentate), then two (bidentate) direct U-O(S) bonds (inner-sphere), and (4) expulsion of excessive waters from the equatorial shell of U.

  • 24.
    Bottone, Anna
    et al.
    Umeå University, Faculty of Science and Technology, Department of Ecology and Environmental Sciences. Dep. of Ecology and Genetics, Uppsala Univ., Uppsala, Sweden.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Shchukarev, Andrey
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Andersson, Patrik L.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Klaminder, Jonatan
    Umeå University, Faculty of Science and Technology, Department of Ecology and Environmental Sciences.
    Sodium hypochlorite as an oxidizing agent for removal of soil organic matter before microplastics analyses2021In: Journal of Environmental Quality, ISSN 0047-2425, E-ISSN 1537-2537, Vol. 51, no 1, p. 112-122Article in journal (Refereed)
    Abstract [en]

    The omnipresence of microplastics (MPs) across Earth's surface has raised concerns about their environmental impact and created an urgent need for methods to identify them in complex soil and sedimentary matrices. However, detecting MPs in the O horizons of soils is difficult because plastic polymers share many physical and chemical properties with natural soil organic matter (SOM). In this study, we assessed whether sodium hypochlorite (NaOCl), a reagent that can oxidize SOM and simultaneously preserve mineral constituents, can be used for MP analysis and characterization in soil environments. In addition, we scrutinized how factors such as MP size, polymer type, extraction methods, and soil matrix affect the recovery of microplastic particles. We used both hydrophobic and density-dependent separation methods to assess the effects of our oxidation treatment on the recovery of MP. We observed that NaOCl effectively removed SOM without greatly altering the surface properties of resistant MP polymers (polypropylene, polylactic acid, low-density polyethylene, and polyethylene terephthalate), which were characterized using scanning electron microscopy and Fourier-transform infrared spectroscopy after SOM removal. The NaOCl treatment caused some chlorination and formation of additional C–OH bonds on polymer surfaces, which likely contributed to the reduced efficiency of the hydrophobic-based (oil) extraction. We conclude that NaOCl treatment can improve detection of MPs in SOM-rich soil and that recovery of MPs from soils is influenced by MP size, polymer type, extraction method, and soil type, which makes it challenging to develop a universal analytical method.

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  • 25.
    Cheng, Wei
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Hanna, K.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Water Vapor Binding on Organic Matter-Coated Minerals2019In: Environmental Science & Technology, ISSN 0013-936X, Vol. 53, no 3, p. 1252-1257Article in journal (Refereed)
    Abstract [en]

    Atmospheric water vapor binding to soils is a key process driving water availability in unsaturated terrestrial environments. Using a representative hydrophilic iron oxyhydroxide, this study highlights key mechanisms through which water vapor (i) adsorbs and (ii) condenses at mineral surfaces coated with Leonardite humic acid (LHA). Microgravimetry and vibrational spectroscopy showed that liquid-like water forms in the three-dimensional array of mineral-bound LHA when present at total C/Fe ratios well exceeding similar to 73 mg C per g Fe (26 C atoms/nm(2)). Below these loadings, minerals become even less hydrophilic than in the absence of LHA. This lowering in hydrophilicity is caused by the complexation of LHA water-binding sites to mineral surfaces, and possibly by conformational changes in LHA structure removing available condensation environments for water. An empirical relationship predicting the dependence of water adsorption densities on LHA loadings was developed from these results. Together with the molecular-level description provided in this work, this relationship should guide efforts in predicting water availability, and thereby occurrences of water-driven geochemical processes in terrestrial environments.

  • 26.
    Cheng, Wei
    et al.
    College of Resources and Environmental Science, South-Central Minzu University, Wuhan, China.
    Li, Jiabin
    College of Resources and Environmental Science, South-Central Minzu University, Wuhan, China.
    Sun, Jie
    College of Resources and Environmental Science, South-Central Minzu University, Wuhan, China.
    Luo, Tao
    Umeå University, Faculty of Science and Technology, Department of Chemistry. Université de Rennes, Ecole Nationale Supérieure de Chimie de Rennes, CNRS, ISCR-UMR 6226, Rennes, France.
    Marsac, Rémi
    Université de Rennes, CNRS, Géosciences Rennes─UMR 6118, Rennes, France.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Hanna, Khalil
    Université de Rennes, Ecole Nationale Supérieure de Chimie de Rennes, CNRS, ISCR-UMR 6226, Rennes, France.
    Nalidixic acid and Fe(II)/Cu(II) coadsorption at Goethite and Akaganéite surfaces2023In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 57, no 41, p. 15680-15692Article in journal (Refereed)
    Abstract [en]

    Interactions between aqueous Fe(II) and solid Fe(III) oxy(hydr)oxide surfaces play determining roles in the fate of organic contaminants in nature. In this study, the adsorption of nalidixic acid (NA), a representative redox-inactive quinolone antibiotic, on synthetic goethite (α-FeOOH) and akaganéite (β-FeOOH) was examined under varying conditions of pH and cation type and concentration, by means of adsorption experiments, attenuated total reflectance-Fourier transform infrared spectroscopy, surface complexation modeling (SCM), and powder X-ray diffraction. Batch adsorption experiments showed that Fe(II) had marginal effects on NA adsorption onto akaganéite but enhanced NA adsorption on goethite. This enhancement is attributed to the formation of goethite-Fe(II)-NA ternary complexes, without the need for heterogeneous Fe(II)-Fe(III) electron transfer at low Fe(II) loadings (2 Fe/nm2), as confirmed by SCM. However, higher Fe(II) loadings required a goethite-magnetite composite in the SCM to explain Fe(II)-driven recrystallization and its impact on NA binding. The use of a surface ternary complex by SCM was supported further in experiments involving Cu(II), a prevalent environmental metal incapable of transforming Fe(III) oxy(hydr)oxides, which was observed to enhance NA loadings on goethite. However, Cu(II)-NA aqueous complexation and potential Cu(OH)2 precipitates counteracted the formation of ternary surface complexes, leading to decreased NA loadings on akaganéite. These results have direct implications for the fate of organic contaminants, especially those at oxic-anoxic boundaries.

  • 27. Cheng, Wei
    et al.
    Lindholm, Jerry
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Holmboe, Michael
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Luong, N. Tan
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Shchukarev, Andrey
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Ilton, Eugene S.
    Hanna, Khalil
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Nanoscale hydration in layered manganese oxides2021In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 37, no 2, p. 666-674Article in journal (Refereed)
    Abstract [en]

    Birnessite is a layered MnO2 mineral capable of intercalating nanometric water films in its bulk. With its variable distributions of Mn oxidation states (MnIV, MnIII, and MnII), cationic vacancies, and interlayer cationic populations, birnessite plays key roles in catalysis, energy storage solutions, and environmental (geo)chemistry. We here report the molecular controls driving the nanoscale intercalation of water in potassium-exchanged birnessite nanoparticles. From microgravimetry, vibrational spectroscopy, and X-ray diffraction, we find that birnessite intercalates no more than one monolayer of water per interlayer when exposed to water vapor at 25 °C, even near the dew point. Molecular dynamics showed that a single monolayer is an energetically favorable hydration state that consists of 1.33 water molecules per unit cell. This monolayer is stabilized by concerted potassium–water and direct water–birnessite interactions, and involves negligible water–water interactions. Using our composite adsorption–condensation–intercalation model, we predicted humidity-dependent water loadings in terms of water intercalated in the internal and adsorbed at external basal faces, the proportions of which vary with particle size. The model also accounts for additional populations condensed on and between particles. By describing the nanoscale hydration of birnessite, our work secures a path for understanding the water-driven catalytic chemistry that this important layered manganese oxide mineral can host in natural and technological settings.

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  • 28.
    Cheng, Wei
    et al.
    College of Resources and Environmental Science, South-Central University for Nationalities, Wuhan, China.
    Marsac, Rémi
    Université Rennes, CNRS, Géosciences Rennes-UMR 6118, Rennes, France.
    Hanna, Khalil
    Université Rennes, Ecole Nationale Supérieure de Chimie de Rennes, UMR CNRS 6226, 11 Allée de Beaulieu, Cedex 7, Rennes, France; Institut Universitaire de France (IUF), MESRI, 1 rue Descartes, Paris, France.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Competitive Carboxylate-Silicate Binding at Iron Oxyhydroxide Surfaces2021In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 37, no 44, p. 13107-13115Article in journal (Refereed)
    Abstract [en]

    Dissolved silicate ions in wet and dry soils can determine the fate of organic contaminants via competitive binding. While fundamental surface science studies have advanced knowledge of binding in competitive systems, little is still known about the ranges of solution conditions, the time dependence, and the molecular processes controlling competitive silicate-organic binding on minerals. Here we address these issues by describing the competitive adsorption of dissolved silicate and of phthalic acid (PA), a model carboxylate-bearing organic contaminant, onto goethite, a representative natural iron oxyhydroxide nanomineral. Using surface complexation thermodynamic modeling of batch adsorption data and chemometric analyses of vibrational spectra, we find that silicate concentrations representative of natural waters (50-1000 μM) can displace PA bound at goethite surfaces. Below pH ∼8, where PA binds, every bound Si atom removes ∼0.3 PA molecule by competing with reactive singly coordinated hydroxo groups (-OH) on goethite. Long-term (30 days) reaction time and a high silicate concentration (1000 μM) favored silicate polymer formation, and increased silicate while decreasing PA loadings. The multisite complexation model predicted PA and silicate binding in terms of the competition for -OH groups without involving PA/silicate interactions, and in terms of a lowering of outer-Helmholtz potentials of the goethite surface by these anions. The model predicted that silicate binding lowered loadings of PA species, and whose two carboxylate groups are hydrogen- (HB) and metal-bonded (MB) with goethite. Vibrational spectra of dried samples revealed that the loss of water favored greater proportions of MB over HB species, and these coexisted with predominantly monomeric silicate species. These findings underscored the need to develop models for a wider range of organic contaminants in soils exposed to silicate species and undergoing wet-dry cycles.

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  • 29. Cheng, Wei
    et al.
    Zhou, Lian
    Marsac, Remi
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Hanna, Khalil
    Effects of organic matter-goethite interactions on reactive transport of nalidixic acid: Column study and modeling2020In: Environmental Research, ISSN 0013-9351, E-ISSN 1096-0953, Vol. 191, article id 110187Article in journal (Refereed)
    Abstract [en]

    The fractionation of natural organic matter (NOM) and its impact on the binding of quinolones to mineral surfaces and transport behavior under flow-through conditions have been scarcely investigated. In this study, the sorption and transport of a widely used quinolone antibiotic, Nalidixic acid (NA), were investigated in goethite-coated sand (GCS) columns over a wide concentration range (5-50 mg/L) of Leonardite humic acid (LHA), a representative NOM. Simultaneous injection of NA and LHA in GCS columns mutually alter transport of each other, i.e. NA mobility and LHA molecular fractionation. Preloading of GCS column with LHA dramatically facilitated the transport behavior of NA, where nonspecific interactions with LHA-covered goethite surfaces controlled NA mobility. Simulations using a two-site nonequilibrium model showed that a modified sorption rate constant was required to accurately describe the breakthrough curves of NA under these conditions. This altered rate constant suggests that nonspecific interactions of NA on bound LHA may take place as an additional binding mechanism affecting adsorption kinetics. NOM fractionation alters sorption mechanisms and kinetics of quinolone antibiotics, which in turn affect their fractionation. These results may have important implications for an accurate assessment of the fate of these types of antibiotics in aquatic environments.

  • 30.
    Ding, Xiangbin
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Song, Xiaowei
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Identification of fluoride and phosphate binding sites at FeOOH surfaces2012In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 116, no 41, p. 21939-21947Article in journal (Refereed)
    Abstract [en]

    Iron oxyhydroxide minerals occur widely in nature and play important roles in environmental and industrial processes. Owing to their high reactivity, these minerals can act as sinks and/or transformation centers for a variety of inorganic and organic ions. Interfacial reactions are often mediated by surface (hydr)oxo groups. These groups can be singly, doubly, or triply coordinated with respect to underlying Fe atoms. In order to investigate the reactivity of these differently coordinated groups, Fourier transform infrared (FTIR) spectroscopy was used to examine adsorption products formed on iron oxyhydroxide surfaces. The absence of water was required to probe the O-H stretching region after initial reactions in aqueous media. This work was specifically focused on synthetic, submicrometer-sized lepidocrocite and goethite particles reacted with aqueous solutions of sodium fluoride and monosodium phosphate. Langmuir-Freundlich adsorption isotherms were calibrated on adsorption data in aqueous media at various pH values to obtain the maximum sorption densities for these ions under these conditions. FTIR measurements of the resulting solids dried under N-2(g) show that fluoride and phosphate ions preferentially exchange with singly coordinated hydroxyls. Doubly coordinated groups can, however, be exchanged with fluoride ions at relatively high loading densities. Triply coordinated groups remain, in contrast, resilient to exchange. They may, however, stabilize phosphate species by hydrogen bonding. These findings add further constraints to our understanding of adsorption reactions and to the formulation of molecularly adequate thermodynamic models.

  • 31.
    Feng, Wenting
    et al.
    Umeå University, Faculty of Science and Technology, Department of Ecology and Environmental Sciences.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Erhagen, Bjoern
    Nilsson, Mats B.
    Klaminder, Jonatan
    Umeå University, Faculty of Science and Technology, Department of Ecology and Environmental Sciences.
    Millennia-old organic carbon in a boreal paleosol: chemical properties and their link to mineralizable carbon fraction2016In: Journal of Soils and Sediments, ISSN 1439-0108, E-ISSN 1614-7480, Vol. 16, no 1, p. 85-94Article in journal (Refereed)
    Abstract [en]

    Little is known about the biogeochemical properties of millennia-old soil organic matter (SOM) in boreal forest paleosols and whether these properties contribute to the persistence of several millennia-old SOM. In this study, we assessed the physicochemical properties of a well-drained paleosol and looked for links between these properties and the mineralizable carbon (C) fraction. We studied a well-drained paleosol located under a typical forest podzol in Northern Sweden, in which up to 7-kyr-old SOM was preserved according to C-14 dating. We assessed the elemental compositions of the outermost 2-mu m and 10-nm soil particle surfaces by using energy-dispersive X-ray scanning electron microscopy and X-ray photoelectron spectroscopy, respectively. We also conducted a 5-week laboratory incubation of samples from both the paleosol and the podzol to quantify their mineralizable C fractions and analyzed the thermal stability of soil samples before and after incubation by using temperature-programmed desorption coupled with mass spectrometry techniques. Proxies for weathering (i.e., total mineral surface area and Al/Si and Fe/Si ratios of particle surfaces) suggested that the paleosol was at the same weathering stage as the contemporary forming podzol. Mineral soil particle surfaces of both the paleosol and podzol were dominated by aliphatic and ether/alcohol C functional groups. The incubation and thermal analysis showed that the mineralizable C fraction of the paleosol was smaller than that of the podzol, and losses of thermally labile SOM due to microbial degradation during the incubations were only detected in the mineral free O horizon of the podzol. Moreover, the mineralizable C fraction of the sampled podzol-paleosol sequence was correlated to the proportion of ether/alcohol C functional groups at the outermost 10-nm soil particle surfaces. Based on the links between microbial decomposition and the chemistry of soil particle surfaces and the thermal stability difference between organic and mineral soils induced by microbial decomposition, we conclude that the intrinsic chemical properties of SOM and its chemical surroundings is important for SOM preservation over a millennia timescale in the studied soil.

  • 32.
    Feng, Wenting
    et al.
    Umeå University, Faculty of Science and Technology, Department of Ecology and Environmental Sciences.
    Klaminder, Jonatan
    Umeå University, Faculty of Science and Technology, Department of Ecology and Environmental Sciences.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Thermal Stability of Goethite-Bound Natural Organic Matter Is Impacted by Carbon Loading2015In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 119, no 51, p. 12790-12796Article in journal (Refereed)
    Abstract [en]

    Dissolved natural organic matter (NOM) sorption at mineral surfaces can significantly affect the persistence. of organic carbon in soils and sediments. Consequently, determining the mechanisms that stabilize sorbed NOM is crucial for predicting the persistence of carbon in nature. This study determined the effects of loadings and pH on the thermal stability of NOM associated: With synthetic goethite (alpha-FeOOH) particle surfaces, as a proxy for NOM mineral interactions taking place in nature.. NOM thermal stability was investigated using temperature programmed desorption (TPD) in the 30-700 degrees C range to collect vibration spectra of thermally decomposing goethite NOM assemblages, and to concomitantly analyze evolved gases using mass spectrometry Results showed that NOM thermal stability, indicated by the range of temperatures in which CO2 evolved during thermal decomposition, was greatest in unbound NOM and lowest when NOM was bound to goethite. NOM thermal Stability was also loading dependent. It decreased:when loadings were in increased the 0.01 to 042 mg C m(-2) range, where the upper value corresponds to a Langmuirian adsorption maximum. Concomitant Fourier transform infrared (FTIR) spectroscopy measurement showed that these lowered stabilities could be ascribed to direct NOM-goethite interactions that dominated the NOM binding environment. Mineral surface interactions at larger loadings involved, on the contrary, a smaller fraction of the sorbed NOM, thus increasing thermal stability toward that of its unbound counterpart. This study thus identifies a sorption threshold below which NOM sorption to goethite decreases NOM thermal stability, and above which no strong effects are Manifested. This should likely influence the fate of organic carbon exposed to thermal gradients in natural environments.

  • 33.
    Hakobyan, Shoghik
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Boily, Jean-François
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Ramstedt, Madeleine
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Proton and gallium(III) binding properties of a biologically active salicylidene acylhydrazide2014In: Journal of Inorganic Biochemistry, ISSN 0162-0134, E-ISSN 1873-3344, Vol. 138, p. 9-15Article in journal (Refereed)
    Abstract [en]

    Bacterial biofilm formation causes a range of problems in our society, especially in health care. Salicylidene acylhydrazides (hydrazones) are promising antivirulence drugs targeting secretion systems used during bacterial infection of host cells. When mixed with the gallium ion they become especially potent as bacterial and biofilm growth-suppressing agents, although the mechanisms through which this occurs are not fully understood. At the base of this uncertainty lies the nature of hydrazone-metal interactions. This study addresses this issue by resolving the equilibrium speciation of hydrazone-gallium aqueous solutions. The protonation constants of the target 2-oxo-2-[N-(2,4,6-trihydroxy-benzylidene)-hydrazino]-acetamide (ME0163) hydrazone species and of its 2,4,6-trihydroxybenzaldehyde and oxamic acid hydrazide building blocks were determined by UV-visible spectrophotometry to achieve this goal. These studies show that the hydrazone is an excessively strong complexing agent for gallium and that its antivirulence properties are predominantly ascribed to monomeric 1:1Ga-ME0163 complexes of various Ga hydrolysis and ME0163 protonation states. The chelation of Ga(III) to the hydrazone also increased the stability of the compounds against acid-induced hydrolysis, making this group of compounds very interesting for biological applications where the Fe-antagonist action of both Ga(III) and the hydrazone can be combined for enhanced biological effect.

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  • 34.
    Hakobyan, Shoghik
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Rzhepishevska, Olena
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Björn, Erik
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Boily, Jean-François
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Ramstedt, Madeleine
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Influence of Chelation Strength and Bacterial Uptake of Gallium Salicylidene Acylhydrazide on Biofilm Formation and Virulence by Pseudomonas aeruginosa2016In: Journal of Inorganic Biochemistry, ISSN 0162-0134, E-ISSN 1873-3344, Vol. 160, p. 24-32Article in journal (Refereed)
    Abstract [en]

    Development of antibiotic resistance in bacteria causes major challenges for our society and has prompted a great need for new and alternative treatment methods for infection. One promising approach is to target bacterial virulence using for example salicylidene acylhydrazides (hydrazones). Hydrazones coordinate metal ions such as Fe(III) and Ga(III) through a five-membered and a six-membered chelation ring. One suggested mode of action is via restricting bacterial Fe uptake. Thus, it was hypothesized that the chelating strength of these substances could be used to predict their biological activity on bacterial cells. This was investigated by comparing Ga chelation strength of two hydrazone complexes, as well as bacterial Ga uptake, biofilm formation, and virulence in the form of production and secretion of a toxin (ExoS) by Pseudomonas aeruginosa. Equilibrium constants for deprotonation and Ga(III) binding of the hydrazone N′-(5-chloro-2-hydroxy-3-methylbenzylidene)-2,4-dihydroxybenzhydrazide (ME0329), with anti-virulence effect against P. aeruginosa, were determined and compared to bacterial siderophores and the previously described Ga(III) 2-oxo-2-[N-(2,4,6-trihydroxy-benzylidene)-hydrazino]-acetamide (Ga-ME0163) and Ga-citrate complexes. In comparison with these two complexes, it was shown that the uptake of Ga(III) was higher from the Ga-ME0329 complex. The results further show that the Ga-ME0329 complex reduced ExoS expression and secretion to a higher extent than Ga-citrate, Ga-ME0163 or the non-coordinated hydrazone. However, the effect against biofilm formation by P. aeruginosa, by the ME0329 complex, was similar to Ga-citrate and lower than what has been reported for Ga-ME0163.

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  • 35. Hanna, K
    et al.
    Boily, Jean-François
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Sorption of two naphthoic acids to goethite surface under flow through conditions2010In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 44, no 23, p. 8863-8869Article in journal (Refereed)
    Abstract [en]

    While the transport of low molecular weight organic acids was widely investigated, little is known about the mobility of the carboxylated aromatic compounds containing double rings in natural porous media. This study combines macroscopic (batch and column), microscropic (vibration spectroscopy), and surface complexation modeling to evaluate the mobility of two PAH degradation products: naphthoic acid (1-naphthoic acid (NA) and 1-hydroxy-2-naphthoic acid (HNA)), in porous media consisting of goethite-coated sand. The loss of ligands from aqueous solution was attributed to (1) a hydrogen-bonded surface complex present over the entire 3−10 pH range as well as protonated (2) surface and (3) bulk precipitates below pH 5. Mobility in column experiments was strongly affected by ligand functionality. Adsorption breakthrough predictions that make use of surface complexation parameters accurately predicted NA mobility. Those for HNA however predicted much less adsorption reactions than in the batch sorption experiments. Additional breakthrough experiments and test calculations confirmed that these differences were not related to sorption kinetics. HNA adsorption breakthrough data could only be predicted by lowering intrinsic complexation constant of the formation of hydrogen-bonded species, thereby suggesting modifications of the diffuse layer properties under flow conditions. These findings have strong implications in the assessment and prediction of contaminant transport and environmental remediation.

  • 36. Hanna, K.
    et al.
    Martin, S.
    Quiles, F.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Sorption of Phthalic Acid at Goethite Surfaces under Flow-Through Conditions2014In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 30, no 23, p. 6800-6807Article in journal (Refereed)
    Abstract [en]

    The objectives of this investigation were to improve our understanding of organic acid transport in porous media by focusing on a model system involving phthalic acid and goethite-coated sand (GCS). This was specifically made by first recalibrating a molecularly sound phthalate surface complexation model to GCS and then applying this model to describe breakthrough curves (BTC) in a GCS packed column. ATR-FTIR spectra of phthalic acid adsorbed at goethite surfaces at pH 3.0 and 6.0 and at loadings from 2.0 to 40.8 mu mol/m(2) confirmed the coexistence of metal-bonded (MB) and hydrogen-bonded (HB) complexes at low pH and the predominance of HB complexes at high pH. This concept was incorporated into a surface complexation model used to describe BTC at influent pH (pH(in)) values of 3.0, 6.0, and 7.8. The BTC revealed strongly pH-dependent behaviors. At pH(in) 3.0, the BTC revealed one front/plateau behavior while at pH(in) 6.0 two fronts/plateaus occurred. The existence of a second front/plateau led to an overestimation of the sorbed amount compared to that observed in the batch and caused a failure in the prediction of BTC. Additional column investigations suggested that surface loadings of nonspecifically adsorbed complexes could vary with pH and ionic strength and that the two-step breakthrough behavior may have emerged as a result of the formation of surface species of different natures than those during the first step, with the latter even serving as attachment sites corresponding to the second step. These findings call for refinements in current day modeling approaches used in reactive transport studies.

  • 37.
    Haziri, Veton
    et al.
    Department of Chemistry, University of Prishtina, Prishtina, Serbia.
    Nha, Tu Pham Tran
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Berisha, Avni
    Department of Chemistry, University of Prishtina, Prishtina, Serbia.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    A gateway for ion transport on gas bubbles pinned onto solids2021In: Communications Chemistry, E-ISSN 2399-3669, Vol. 4, no 1, article id 43Article in journal (Refereed)
    Abstract [en]

    Gas bubbles grown on solids are more than simple vehicles for gas transport. They are charged particles with surfaces populated with exchangeable ions. We here unveil a gateway for alkali metal ion transport between oxygen bubbles and semi-conducting (iron oxide) and conducting (gold) surfaces. This gateway was identified by electrochemical impedance spectroscopy using an ultramicroelectrode in direct contact with bubbles pinned onto these solid surfaces. We show that this gateway is naturally present at open circuit potentials, and that negative electric potentials applied through the solid enhance ion transport. In contrast, positive potentials or contact with an insulator (polytetrafluoroethylene) attenuates transport. We propose that this gateway is generated by overlapping electric double layers of bubbles and surfaces of contrasting (electro)chemical potentials. Knowledge of this ion transfer phenomenon is essential for understanding electric shielding and reaction overpotential caused by bubbles on catalysts. This has especially important ramifications for predicting processes including mineral flotation, microfluidics, pore water geochemistry, and fuel cell technology.

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  • 38.
    Haziri, Veton
    et al.
    Department of Chemistry, University of Prishtina, Prishtina, Kosovo; Department of Food Science and Biotechnology, UBT College, Prishtina, Kosovo.
    Phal, Sereilakhena
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Berisha, Avni
    Department of Chemistry, University of Prishtina, Prishtina, Kosovo; Materials Science—Nanochemistry Research Group, NanoAlb—Unit of Albanian Nanoscience and Nanotechnology, Tirana, Albania.
    Tesfalidet, Solomon
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Oxygen Interactions with Covalently Grafted 2D Nanometric Carboxyphenyl Thin Films: An Experimental and DFT Study2022In: Coatings, ISSN 2079-6412, Vol. 12, no 1, article id 49Article in journal (Refereed)
    Abstract [en]

    Surface modification is a hot topic in electrochemistry and material sciences because it affects the way materials are used. In this paper, a method for covalently attaching carboxyphenyl (PhCOOH) groups to a gold electrode is presented. These groups were grafted onto the electrode surface electrochemically via reduction of aryldiazonium salt. The resulting grafted surface was characterized using cyclic voltammetry (CV) before and after the functionalization procedure to validate the presence of the grafted layer. The grafting of PhCOOH groups was confirmed by analyzing electrode thickness and composition by ellipsometry and X-ray photoelectron spectroscopy (XPS). Density functional theory (DFT) calculations indicated that the grafted layers provide a stable platform and resolved, for the first time, their interactions with oxygen.

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  • 39. Henriksson, Nils
    et al.
    Marshall, John
    Lundholm, Jonas
    Boily, Asa
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Nasholm, Torgny
    Improved in vivo measurement of alternative oxidase respiration in field-collected pine roots2019In: Physiologia Plantarum, ISSN 0031-9317, E-ISSN 1399-3054, Vol. 167, no 1, p. 34-47Article in journal (Refereed)
    Abstract [en]

    Cellular respiration via the alternative oxidase pathway (AOP) leads to a considerable loss in efficiency. Compared to the cytochrome pathway (COP), AOP produces 0-50% as much ATP per carbon (C) respired. Relative partitioning between the pathways can be measured in vivo based on their differing isotopic discriminations against O-18 in O-2. Starting from published methods, we have refined and tested a new protocol to improve measurement precision and efficiency. The refinements detect an effect of tissue water content (P < 0.0001), which we have removed, and yield precise discrimination endpoints in the presence of pathway-specific respiratory inhibitors [CN- and salicylhydroxamic acid (SHAM)], which improves estimates of AOP/COP partitioning. Fresh roots of Pinus sylvestris were sealed in vials with a CO2 trap. The air was replaced to ensure identical starting conditions. Headspace air was repeatedly sampled and isotopically analyzed using isotope-ratio mass spectrometry. The method allows high-precision measurement of the discrimination against O-18 in O-2 because of repeated measurements of the same incubation vial. COP and AOP respiration discriminated against O-18 by 15.1 +/- 0.3 parts per thousand and 23.8 +/- 0.4 parts per thousand, respectively. AOP contributed to root respiration by 23 +/- 0.2% of the total in an unfertilized stand. In a second, nitrogen-fertilized, stand AOP contribution was only 14 +/- 0.2% of the total. These results suggest the improved method can be used to assess the relative importance of COP and AOP activities in ecosystems, potentially yielding information on the role of each pathway for the carbon use efficiency of organisms.

  • 40. Ilton, Eugene S
    et al.
    Boily, Jean-François
    Umeå University, Faculty of Science and Technology, Chemistry.
    Buck, Edgar C
    Skomurski, Frances N
    Rosso, Kevin M
    Cahill, Christopher L
    Bargar, John R
    Felmy, Andrew R
    Influence of Dynamical Conditions on the Reduction of U(VI) at the Magnetite-Solution Interface2010In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 44, no 1, p. 170-6Article in journal (Refereed)
    Abstract [en]

    The heterogeneous reduction of U(VI) to U(IV) by ferrous iron is believed to be a key process influencing the fate and transport of U in the environment. The reactivity of both sorbed and structural Fe(II) has been studied for numerous substrates, including magnetite. Published results from U(VI)-magnetite experiments have been variable, ranging from no reduction to clear evidence for the formation of U(IV). In this contribution, we used XAS and high resolution (+/-cryogenic) XPS to study the interaction of U(VI) with nanoparticulate magnetite. The results indicated that U(VI) was partially reduced to U(V) with no evidence of U(IV). However, thermodynamic calculations indicated that U phases with average oxidation states below (V) should have been stable, indicating that the system was not in redox equilibrium. A reaction pathway that involves incorporation and stabilization of U(V) and U(VI) into secondary phases is invoked to explain the observations. The results suggest an important and previously unappreciated role of U(V) in the fate and transport of uranium in the environment.

  • 41. Ilton, Eugene S
    et al.
    Wang, Zheming
    Boily, Jean-François
    Qafoku, Odeta
    Rosso, Kevin M
    Smith, Steven C
    The Effect of pH and Time on the Extractability and Speciation of Uranium(VI) Sorbed to SiO(2)2012In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 46, no 12, p. 6604-6611Article in journal (Refereed)
    Abstract [en]

    The effect of pH and contact time on uranium extractability from quartz surfaces was investigated using either acidic or carbonate (CARB) extraction solutions, time-delayed spikes of different U isotopes ((238)U and (233)U), and liquid helium temperature time-resolved laser-induced fluorescence spectroscopy (TRLFS). Quartz powders were reacted with (238)U(VI) bearing solutions equilibrated with atmospheric CO(2) at pH 6, 7, and 8. After 42 days, the suspensions were spiked with (233)U(VI) and reacted for an additional 7 days. Sorbed U was then extracted with either dilute nitric acid or CARB. For the CARB, but not the acid, extraction there was a systematic decrease in extraction efficiency for both isotopes from pH 6 to 8, which was mimicked by less desorption of (238)U, after the (233)U spike, from pH 6 to 8. The efficiency of (233)U extraction was consistently greater than that of (238)U, indicating a strong temporal component to the strength of U association with the surface that was accentuated with increasing pH. TRLFS revealed a strong correlation between CARB extraction efficiency and sorbed U speciation as a function of pH and time. Collectively, the observations show that aging and pH are critical factors in determining the form and strength of uranium-silica interactions.

  • 42.
    Kanematsu, Masakazu
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Waychunas, Glenn A.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Silicate Binding and Precipitation on Iron Oxyhydroxides2018In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 52, no 4, p. 1827-1833Article in journal (Refereed)
    Abstract [en]

    Silica-bearing waters in nature often alter the reactivity of mineral surfaces via deposition of Si complexes and solids. In this work, Fourier transform infrared (FTIR) spectroscopy was used to identify hydroxo groups at goethite (alpha-FeOOH) and lepidocrocite (gamma-FeOOH) surfaces that are targeted by ligand exchange reactions with monomeric silicate species. Measurements of samples first reacted in aqueous solutions then dried under N-2(g) enabled resolution of the signature O-H stretching bands of singly (-OH), doubly (mu-OH), and triply coordinated (mu(3)-OH) groups. Samples reacted with Si for 3 and 30 d at pH 4 and 7 revealed that -OH groups were preferentially exchanged by silicate and that mu-OH and mu(3)-OH groups were not exchanged. Based on knowledge of the disposition of -OH groups on the major crystallographic faces of goethite and lepidocrocite, and the response of these groups to ligand exchange prior oligomerization, our work points to the predominance of rows of mononuclear monodentate silicate species, each separated by at least one -OH group. These species are the attachment sites from which oligomerization and polymerization reactions occur, starting at loadings exceeding similar to 1 Si/nm(2) and corresponding to soluble Si concentrations that can be as low as similar to 0.7 mM after 30 d reaction time. Only above such loadings can reaction products grow away from rows of -OH groups and form hydrogen bonds with nonexchangeable mu-OH and mu(3)-OH groups. These findings have important repercussions for our understanding of the fate of waterborne silicate ions exposed to minerals.

  • 43.
    Kim, Junhyung
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Lindholm, Jerry
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Holmboe, Michael
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Solvent and lipophilic solute effects on the swelling behavior of an organoclayManuscript (preprint) (Other academic)
  • 44.
    Kozin, Philipp A.
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Boily, Jean-François
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Mineral surface charge development in mixed electrolyte solutions2014In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 418, p. 246-253Article in journal (Refereed)
    Abstract [en]

    Abstract Effects of competing counterions with different charge-to-size ratios on potential-determining ion (pdi; H+, OH−) adsorption at mineral/water interfaces were resolved in mixtures of aqueous solutions of NaCl and NaClO4 solutions. These effects were monitored on two synthetic goethite (α-FeOOH) particle preparations with distinct charge uptake capacities arising from differences in surface roughness. Charge development at these mineral surfaces was chiefly explored by high precision potentiometric titrations at 25 °C. These measurements confirmed that the greater charge-to-size ratio chloride ion not only promoted greater surface charge, but also had pronounced effects in perchlorate-dominated solutions. Cryogenic X-ray photoelectron spectroscopic measurements confirmed that perchlorate retains significant loadings at the goethite surface, even in the presence of chloride. Molecular dynamics simulations of the (1 1 0) plane of goethite exposed to these mixed solutions showed that chloride compressed the interfacial region containing electrolyte ions. Perchlorate, on the other hand, is not only present over a thicker region of the interface but also promotes an additional outer-sphere sodium species. These findings were used to develop a thermodynamic adsorption model predicting charge development at these mineral surfaces. The model involves a new formulation accounting for coexisting ion-specific regions each with their distinct compact plane capacitance values. The model can predict charge development in any mixtures of NaCl and NaClO4 contacted with goethite particles of contrasting charge uptake capacities without any additional parameters. This model can also be applied to a broader range of material surfaces.

  • 45.
    Kozin, Philipp A
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Boily, Jean-François
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Proton Binding and Ion Exchange at the Akaganéite/Water Interface2013In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 117, no 12, p. 6409-6419Article in journal (Refereed)
    Abstract [en]

    Proton exchange in nanosized synthetic akaganéite particles suspended in aqueous media and in ionic strengths of 3–100 mM NaCl and NaClO4 was monitored by high precision potentiometry at 25 °C. Proton budgets in the pH 3–10 range pertain to simultaneously occurring surface complexation and bulk ionic exchange reactions. Surface complexation reactions involve proton binding to (hydr)oxo groups of the dominant crystallographic planes of the particles. These are responsible for the colloidal attributes of the akaganéite particles, as confirmed by electrophoretic mobility measurements. Bulk ionic exchange involves the codiffusion of protons and chloride ions through the tunnel structure of the hollandite-type akaganéite bulk. Chloride ions migrate to bulk complexation sites that are ideally defined by eight surrounding hydroxyl groups, ≡(OH)8. Protons are in turn considered to be bound to neighboring oxo groups, ≡O. Collectively, the complexes are referred as [≡(OH)8···Cl······HO≡]. A thermodynamic model accounting for these two processes was developed to predict the pH (3–9), ionic strength (3–100 mM), and ionic medium (NaCl, NaClO4) dependence of the potentiometric data. This model is supported by new zeta potential data pointing to an isoelectric point of 9.6–10.3 for pristine akaganéite particles and by Fourier transform infrared spectra showing the impact of pH and ionic medium on bulk proton-chloride loadings. Our proposed stoichiometry for a chloride-rich solid of β-FeOOH·(HCl)0.192 corresponds to a maximal occupancy of 75% for chloride ions in the [≡(OH)8···Cl······HO≡] bulk complexation sites. Samples equilibrated in pure aqueous solutions should have a composition of β-FeOOH·(HCl)0.151, corresponding to a 60% occupancy for chloride ions due to a partial exchange of HCl. Our model can be used to predict compositional changes in the akaganéite bulk and surfaces upon any variations in pH and ionic media considered in this work.

  • 46.
    Kozin, Philipp A.
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Salazar-Alvarez, German
    Materials and Environmental Chemistry, Stockholm University, 114 18 Stockholm, Sweden.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Oriented Aggregation of Lepidocrocite and Impact on Surface Charge Development2014In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 30, no 30, p. 9017-9021Article in journal (Refereed)
    Abstract [en]

    The impact of lepidocrocite (gamma-FeOOH) nanoparticle aggregation on mineral surface charge development was resolved in aqueous solutions of NaCl and NaClO4. Synthetic rod-like particles exhibiting charged edge (100) and neutrally/low-charged (010) faces self-aggregated in salt-free solutions. Aggregation was notably imaged by high-resolution transmission electron microscopy, and inferred by decreases in N-2(g)-B.E.T. specific surface area from 94 m(2)/g to 77 m(2)/g after 12 months, and to 66 m(2)/g after 33 months storage. Potential determining (H+, OH-) ions loadings in the 4-11 pH range were unchanged only if the particles remained aggregated in NaCI but only if they were disaggregated in NaClO4. These differences, alongside molecular simulations and experimental ion loadings resolved in other studies from our group, point to important controls on background electrolyte ion identity on the aggregation and charge development in lepidocrocite. These results may apply further to other mineral surfaces of comparable surface (hydr)oxo populations.

  • 47.
    Kozin, Philipp A.
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Salazar-Alvarez, German
    Boily, Jean-François
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Oriented Aggregation of Lepidocrocite and Its Impact on Surface Charge DevelopmentManuscript (preprint) (Other academic)
  • 48.
    Kozin, Philipp A
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Shchukarev, Andrey
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Boily, Jean-François
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Electrolyte Ion Binding at Iron Oxyhydroxide Mineral Surfaces2013In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 29, no 39, p. 12129-12137Article in journal (Refereed)
    Abstract [en]

    Electrolyte ion loadings at the surfaces of synthetic goethite (α-FeOOH) and lepidocrocite (γ-FeOOH) particles that were pre-equilibrated in aqueous solutions of 10 mM NaCl and NaClO4 at 25 °C were investigated by cryogenic X-ray photoelectron spectroscopy (XPS). Atomic concentrations of Cl(-), ClO4(-), and Na(+) were correlated to potential determining ion (pdi; H(+), OH(-)) loadings obtained by potentiometric titrations. While Cl(-) promoted more pdi adsorption than ClO4(-), due to its greater charge-to-size ratio, both ions followed the same loading dependence on pdi adsorption, in contrast to previous studies supporting the concept for negligible perchlorate adorption. Lepidocrocite particles exhibited a stronger response of electrolyte adsorption to pdi loadings due electrolyte ion adsorption on the proton inactive (010) plane. These particles also acquired greater sodium loadings than goethite. These loadings were moreover considerably enhanced by perchlorate adsorption, possibly due to a thickening of the interfacial region in NaClO4 on the (010) plane. Finally, goethite particles with rougher surfaces acquired greater pdi and ion loadings than on those with smoother surfaces. No strong differences could be discerned between Cl(-) and ClO4(-) loadings on these materials. This work thus identified key aspects underpinning the relationship between pdi and electrolyte loadings at FeOOH mineral surfaces of environmental and technological importance.

  • 49.
    Lindholm, Jerry
    et al.
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Boily, Jean-Francois
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Holmboe, Michael
    Umeå University, Faculty of Science and Technology, Department of Chemistry.
    Deconvolution of Smectite Hydration Isotherms2019In: ACS Earth and Space Chemistry, E-ISSN 2472-3452, Vol. 3, no 11, p. 2490-2498Article in journal (Refereed)
    Abstract [en]

    Sorption isotherm models have traditionally served as an invaluable tool to characterize synthesized and natural mineral particles. However, for particles susceptible to substantial hydration, such as the swelling smectite clay minerals and other layered minerals displaying intercalation of discrete water monolayers, traditional isotherm models inadequately describe the total water uptake as a result of the change in available surface sites and area during the hydration process. With the goal of deconvoluting the water uptake behavior of swelling smectite minerals, this research presents a novel composite isotherm model that describes water uptake by surface adsorption, condensation, and stepwise intercalation. A set of eight montmorillonite samples ion-exchanged with different countercations (Li+, Na+, K+, Cs+, Mg2+, Ca2+, Sr2+, and Cu2+) were used to develop this model, which was based on gravimetric uptake measurements and X-ray diffraction data of basal spacings obtained from relative humidity conditions up to 98% relative humidity.

  • 50. Lower, Brian H
    et al.
    Yongsunthon, Ruchirej
    Shi, Liang
    Wildling, Linda
    Gruber, Hermann J
    Wigginton, Nicholas S
    Reardon, Catherine L
    Pinchuk, Grigoriy E
    Droubay, Timothy C
    Boily, Jean-François
    Umeå University, Faculty of Science and Technology, Chemistry.
    Lower, Steven K
    Antibody Recognition Force Microscopy Shows that Outer Membrane Cytochromes OmcA and MtrC Are Expressed on the Exterior Surface of Shewanella oneidensis MR-12009In: Applied and environmental microbiology, ISSN 1098-5336, Vol. 75, no 9, p. 2931-5Article in journal (Refereed)
    Abstract [en]

    Antibody-recognition force microscopy showed that OmcA and MtrC are expressed on the exterior surface of living Shewanella oneidensis MR-1 cells when Fe(III), including solid phase hematite (Fe2O3), was the terminal electron acceptor. OmcA was localized to the interface between the cell and mineral. MtrC displayed a more uniform distribution across the cell surface. Both cytochromes were associated with an extracellular polymeric substance.

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