J.J. Ehrhardt

Adsorption studies of methylene blue and phenol onto vetiver roots activated carbon prepared by chemical activation

Vetiver roots have been utilized for the preparation of activated carbon (AC) by chemical activation with different impregnation ratios of phosphoric acid, X(P) (gH(3)PO(4)/g precursor): 0.5:1; 1:1 and 1.5:1. Textural characterization, determined by nitrogen adsorption at 77K shows that mixed microporous and mesoporous structures activated carbons (ACs) with high surface area (>1000 m(2)/g) and high pore volume (up to 1.19 cm(3)/g) can be obtained. The surface chemical properties of these ACs were investigated by X-ray photoelectron spectroscopy (XPS) and Boehm titration. Their textural and chemical characteristics were compared to those of an AC sample obtained by steam activation of vetiver roots. Classical molecules used for characterizing liquid phase adsorption, phenol and methylene blue (MB), were used. Adsorption kinetics of MB and phenol have been studied using commonly used kinetic models, i.e., the pseudo-first-order model, the pseudo-second-order model, the intraparticle diffusion model and as well the fractal, BWS (Brouers, Weron and Sotolongo) kinetic equation. The correlation coefficients (R(2)) and the normalized standard deviation Deltaq (%) were determined showing globally, that the recently derived fractal kinetic equation could best describe the adsorption kinetics for the adsorbates tested here, indicating a complex adsorption mechanism. The experimental adsorption isotherms of these molecules on the activated carbon were as well analysed using four isotherms: the classical Freundlich, Langmuir, Redlich-Peterson equations, but as well the newly published deformed Weibull Brouers-Sotolongo isotherm. The results obtained from the application of the equations show that the best fits were achieved with the Brouers-Sotolongo equation and with the Redlich-Peterson equation. Influence of surface functional groups towards MB adsorption is as well studied using various ACs prepared from vetiver roots and sugar cane bagasse. Opposite effects governing MB and phenol adsorption mechanism on ACs are demonstrated. The various effects involved in adsorption mechanisms of each molecule are demonstrated.

Surface chemistry and structural properties of mackinawite prepared by reaction of sulfide ions with metallic iron

Tetragonal FeS1−x mackinawite, has been synthesized by reacting metallic iron with a sodium sulfide solution and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), transmission Mossbauer spectroscopy (TMS) and X-ray photoelectron spectroscopy (XPS). Based on XRD and TEM analyses, synthetic mackinawite exhibits crystallization and is identical to the natural mineral. Unit cell parameters derived from XRD data are a = b = 0.3670 nm and c = 0.5049 nm. The bulk Fe:S ratio derived from the quantitative dispersive energy analysis is practically 1. XPS analyses, however, showed that mackinawite surface is composed of both Fe(II) and Fe(III) species bound to monosulfide. Accordingly, monosulfide is the dominant S species observed at the surface with lesser amount of polysulfides and elemental sulfur. TMS analysis revealed the presence of both Fe(II) and Fe(III) in the mackinawite structure, thus supporting the XPS analysis. We propose that the iron monosulfide phase synthesized by reacting metallic iron and dissolved sulfide is composed of Fe(II) and S(-II) atoms with the presence of a weathered thin layer covering the bulk material that consists of both Fe(II) and Fe(III) bound to S(-II) atoms and in a less extent of polysulfide and elemental sulfur.

Effects of different crystal faces on the surface charge of colloidal goethite (α-FeOOH) particles: an experimental and modeling study

The surface charge of colloidal particles is usually determined by potentiometric titration. These acid-base titrations make it possible to measure the pH of point-of-zero charge (pzc) for oxide minerals. This macroscopic property is the most important parameter used in surface complexation modeling to reproduce experimental data. The pzc values of goethite reported in the literature vary between 7.0 and 9.5. Carbonate adsorption and/or surface morphology are thought to account for this wide range. We demonstrate a procedure for the removal of the carbonate ions that initially adsorb on goethite and strongly affect the titration curves and pzc determination. We also investigated the crystal-face-specific reactivity of two morphologically different goethites. The z-profiles obtained from atomic force microscopy (AFM) images showed that the goethite with the smallest specific surface area (S = 49 m2/g, denoted G49) exhibits 70% of the (001) face, whereas this value is only 30% for the goethite with largest specific surface area (S = 95 m2/g, denoted G95). This morphologic difference results in slightly different pzc values: 9.0 for G49 goethite and 9.1 for G95 geothite. These experimental pzc values have been correlated with multisite complexation calculations using both the full-site and the 1-pK approaches. We used the full-site approach to consider all of the configurations of hydrogen bond interactions with surface site. The resulting mean charges gave estimated pzc values of 8.9 and 9.2 for the (001) and (101) faces, respectively. Considering these theoretical pzc values for individual faces and the face distributions obtained from AFM analysis, the calculated pzc values are in full agreement with the experimental pzc values. However, this morphologic difference is more expressed in surface charge values than in the pzc values. Indeed, the surface charge of G49 goethite is much higher than that of G95 goethite, and the 1-pK calculations make it possible to fit the titration data satisfactorily.

U(VI) sorption and reduction by Fe(II) sorbed on montmorillonite.

The influence of surface-bound Fe(II) on uranium oxidation state and speciation was studied as a function of time (6 min-72 h) and pH (6.1-8.5) in a U(VI)-Fe(II)-montmorillonite (Ca-montmorillonite, MONT) system under CO(2)-free, anoxic (O(2) <1 ppmv) conditions. The results show a rapid removal of U(VI) from the aqueous solution within 1 h under all pH conditions. U L(III)-edge X-ray absorption near-edge structure spectroscopy shows that 96% of the total sorbed U(VI) is reduced at pH 8.5. However, the extent of reduction significantly decreases at lower pH values as specifically sorbed Fe(II) concentration decreases. The reduction kinetics followed by X-ray photoelectron spectroscopy during 24 h at pH 7.5 demonstrates the presence of partially reduced surface species containing U(VI) and U(IV). Thermodynamically predicted mixed valence solids like U(3)O(8)/beta-U(3)O(7)/U(4)O(9) do not precipitate as verified by transmission electron microscopy and extended X-ray absorption fine-structure spectroscopy. This is also supported by the bicarbonate extraction results. The measured redox potentials of Fe(II)/Fe(III)-MONT suspensions are controlled by the Fe(II)/hydrous ferric oxide [HFO(s)] couple at pH 6.2 and by the Fe(II)/lepidocrocite [gamma-FeOOH(s)] couple at pH 7.5. The key finding of our study is the formation of a sorbed molecular form of U(IV) in abiotic reduction of U(VI) by sorbed Fe(II) at the surface of montmorillonite.

Mössbauer and XAS study of a green rust mineral; the partial substitution of Fe2+ by Mg2+

Abstract Layered double hydroxysalt green rusts, GRs, are very reactive compounds and their general formula, [Fe2(1-x) Fe3+x (OH)2]x+ [x/n An- ·m H2O]x-, where x is the ratio Fe3+/Fetot, reflects the structure in which brucite-like layers alternate with interlayers of anions An- and water molecules. A GR mineral was extracted from hydromorphic soils in Fougères (France) and studied by X-ray absorption spectroscopy (XAS) and transmission Mössbauer spectroscopy (TMS). The XAS spectrum at the Fe K absorption edge of this mineral proved to be very similar to that of synthetic GRs. However, the radial distribution function obtained for the GR mineral proved to be intermediate between those of GR(CO2-3) and pyroaurite, that is between the Fe2+-Fe3+ and Mg2+-Fe3+ hydroxycarbonates. Consequently, a partial substitution of Fe2+ by Mg2+ occurs, leading to the general formula of [Fe2+(1-x)Mg2+yFe3+x (OH)(2+2y)]x+ [x/n An-·m H2O]x- where An- is the interlayer anion. Unfortunately, the XAS spectra of various GR proved to be independent of the interlayer anion, and the nature of the anions present in the mineral GR could not be determined. The Mössbauer spectrum of the mineral, measured at 77 K, is composed of four quadrupole doublets: D1 and D2 due to Fe2+ [δ ≅ 1.26 mm/s and ΔEQ ≅ 2.5 and 2.9 mm/s, respectively] and D3 and D4 due to Fe3+ [δ ≅ 0.46 mm/s and ΔEQ ≅ 0.5 and 1.0 mm/s, respectively]. Finally, synthetic Mg2+-Fe2+-Fe3+ hydroxycarbonates could be prepared by coprecipitation from Mg and Fe salts and lead to Mössbauer spectra similar to that of the mineral. In particular, the partial substitution of Fe2+ by Mg2+ proved to be consistent with the existence of the unusual doublet D4.

Morphology and surface heterogeneities in synthetic goethites

In the framework on a study of the acido-basic and sorption properties of iron oxides, a thorough characterization of two types of goethite powders was performed in several laboratories joined in a common project. Chemical analysis by ICPAES; high-resolution SEM, TEM, and AFM observations; XRD with line width analysis; and argon and nitrogen sorption isotherms were used for that purpose. The main crystallographic faces of goethite particles could be identified as {001}, {101}, and {121}, and their abundance correlated with the distribution of low-pressure argon adsorption local isotherms. These results will be very useful for further studies on the relationship between surface reactivity in aqueous solution and orientation of solid surfaces.

Preparation and characterisation of raw chars and physically activated carbons derived from marine Posidonia oceanica (L.) fibres.

Industrial valorisation of low cost and renewable biomass as raw precursor of activated carbon for environmental applications is an interesting alternative to costly commercial activated carbons. In this study, the possible use of Mediterranean, Posidonia oceanica fibrous biomass, as a precursor for chars and physically activated carbons, is investigated. Firstly, the raw marine material was chemically and biochemically characterised throughout dry-basis elemental, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) analysis. Then, several P. oceanica chars were prepared and characterised under different pyrolysis times and temperatures. In addition, physically activated carbons (PACs) were produced via water steam flow under various activation periods. The results showed that the pyrolysis induces the creation of pores at different levels with respect to the involved temperature. Thereafter, the physical activation tends to enhance the development of the porous structure. In that issue, the performed Brunauer-Emmett-Teller (BET) and Barrett-Joiner-Halenda (BJH) analysis revealed that the prepared PACs have a mainly mesoporous inner morphology with a varying fraction of micropores.

Structural identification of europium(III) adsorption complexes on montmorillonite

A study of trivalent europium retention onto Na-montmorillonite is presented, combining both macroscopic and microscopic points of view. In order to investigate the metal sorption mechanisms at a molecular level and therefore experimentally identify both clay reactive sites and sorption equilibria, laser-induced fluorescence spectroscopy (LIF) and X-ray photoelectron spectroscopy (XPS) on europium ion loaded montmorillonite have been performed. Moreover, since this clay is an alumino-silicated mineral, we have interpreted our experimental results in terms of interactions between a metal ion and a cation exchange site, and distinct “aluminol” and “silanol” edge sites. Therefore, identical structural investigations have been carried out on both Eu/alumina and Eu/silica systems. These comparisons have allowed us to determine the nature of the europium surface complexes and thus led to an experimental definition of the sorption equilibria involved in the retention process. The obtained lifetime values and the Eu 3d XPS spectra of europium sorbed on the three solids have shown that this metal is sorbed, on the montmorillonite clay, on exchange sites as an outer-sphere complex and onto both “aluminol” and “silanol” edge sites as inner-sphere surface complexes, depending on the pH value and the ionic strength of the suspension.

XPS study of the sorption of Hg(II) onto pyrite FeS2

In this study, the sorption of Hg(II) onto pyrite was investigated as a function of the aqueous solution pH. X-ray photoelectron spectroscopy (XPS) was used to characterize the surfaces, and to identify the adsorbed species when possible. After 12 h of equilibration at a given initial pH (between 6 and 10.5), slabs of pyrite were in contact with Hg(II) solution (210 μM, constant ionic strength fixed with 0.01 M NaNO 3 ) for 24 h. The final pH ranged between 4.1 and 3.6. The solid samples were then dried and transferred into the XPS machine for surface analyses (Hg 4f, S 2p, O 1s and Fe 2p levels). Taking advantage of the differential charge effect when the surface was partly covered with Fe(III) oxyhydroxides, it was shown that Hg could be sorbed onto both pyritic zones and oxidized patches. On pyritic zones where no charge effect was observed, the Hg 4f 7/2 level was pointed out at 100.7 eV, ruling the presence of Hg(0) at the surface out. The S 2p level analyses clearly showed that the main component was S 2 2- , with some traces of polysulphur. Neither S(II) nor S(VI) were detected in any experiment, excluding the formation of HgS, sulphate and thiosulphate. Most observations were understood as the formation of two surface complexes between mercury and either the pyritic functional groups or the oxyhydroxide sites.

Immobilization of iodide on copper(I) sulfide minerals

In the goal of finding efficient scavengers for radioiodide in conditions (pH, pE) close to those encountered in deep geological sites, sorption of iodide ions on cuprous sulfide minerals (especially roxbyite, Cu(1.75)S) has been studied. Surface analysis by X-ray photoelectron spectroscopy has shown that commercial cuprous sulfides are covered by an oxidized overlayer (mainly in the form of CuSO(4)). Therefore, a synthetic procedure to get roxbyite (typically by mixing Na(2)S with an aqueous suspension of commercial Cu(2)O) was applied to produce pure samples with clean surfaces. Batch equilibration of cuprous sulfide particles suspended in aqueous solutions containing iodide species has revealed significant consumption of iodide. The sorption mechanism involves the formation of a surface complex via the exchange of surface hydroxyl groups by iodide anions, as highlighted by a transient pH increase during the immobilization process. Other copper and mixed copper-iron sulfides (e.g. CuS, CuFeS(2)), which are stable over wide pH and potential ranges are also likely to accumulate iodide species. Because of the specific interaction between iodide and copper(I) centers on the minerals, high distribution coefficients (>1000 ml/g) were observed.