F. Javier Huertas

Surface chemistry of K-montmorillonite: ionic strength, temperature dependence and dissolution kinetics.

The surface chemistry of K-montmorillonite was investigated by potentiometric titrations conducted at 25, 50 and 70 degrees C and at ionic strengths of 0.001, 0.01 and 0.1 M KNO(3). Proton adsorption decreases with electrolyte concentration at all pHs. The pH of zero net proton charge (PZNPC) decreases from 8.1 to 7.6 when the ionic strength increases from 0.001 to 0.1 M. Temperature has a very small effect on surface charge. A constant capacitance model that accounts for protonation/deprotonation of aluminol and silanol edge sites and basal plane H(+)/K(+) exchange is used to fit the experimental data. H(+) and OH(-) adsorption to specific surface sites appear to account for the pH-dependence of the K-montmorillonite dissolution.

Experimental study of the hydrothermal formation of kaolinite

Kaolinite was hydrothermally precipitated starting from amorphous aluminosilicates, with Si/Al ratio from 1.8 to 0.76, at temperatures of 150, 175, 200, 225, and 250°C, at time periods varying from 6 h to 60 days. The solutions were analysed for pH, Si, Al, and K, and their saturation state was calculated by using the computer program SOLMINEQ.88. The solids were studied by surface area, XRD and DTA–TG analyses. Kaolinite was the only crystalline phase found in the products of the runs and its formation and crystallinity depended on time, temperature, and Si/Al ratio of the starting material. The kaolinite yield increased as starting material was aged for longer times. Products synthesized at higher temperature contain more kaolinite which was more crystalline than in the experiments carried out at lower temperature. The gel with Si/Al=0.99 produced the most disordered kaolinite and better crystallinity was obtained from products richest in Al or Si. The process of kaolinite formation was the result of two stages. During the first one aggregates of domains having a kaolinite-like structure were formed. The second stage corresponded to the formation of hexagonally outlined platy crystals. The formation rates indicated that the first stage was approximately one order of magnitude faster than the second stage, with average activation energies of 82±5 kJ mol−1 and 71±5 kJ mol−1, respectively. Si/Al ratio of the starting material exerted only a slight influence on the activation energies. The precipitation rates obtained for the second stage were consistent with literature data and may be considered precipitation rates of kaolinite in hydrothermal environments.

SYNTHESIS OF KAOLINITE WITH A HIGH LEVEL OF Fe3+ FOR Al SUBSTITUTION

Fe-rich kaolinites were synthesized at 225°C in distilled water from gels with different Fe/Al ratios (0.15, 0.25, 0.35) and with Si/(Al + Fe) = 2. X-ray diffraction patterns of the reaction products showed that kaolinite was the only long-range crystalline phase synthesized. Analytical electron microscopy analyses of individual particles and Fourier transform infrared spectra indicated that Fe3+ was isomorphously incorporated into the kaolinite octahedral sheet and that tetrahedral substitution did not occur. The Fe content hosted in the synthetic kaolinites was similar to that incorporated into its corresponding starting gel. The highest Fe content in the particles reached 30 mol.% of the octahedral occupancy. Increases in the b parameter are proportional to increases in Fe for Al substitution. The extent of isomorphic substitution of Al by Fe is the highest ever reported for both natural and synthetic samples. At the nano-scale, there is no evidence of discontinuity in the solid-solution between the Si2Al2O7 and Si2Al1.4Fe0.6O7 end-members, such as short-range disorder or clustering of Fe and Al in domains.

Experimental alteration of volcanic tuff; smectite formation and effect on 18 O isotope composition

Three samples of volcanic tuff were hydrothermally altered at ∼82°C in a soxhlet apparatus for periods from 745 to 2706 h. The samples correspond to partially altered specimens of volcanic tuff with 6 wt. % (T3a) and 9 wt. % (T3b) smectite and to the calcination product of the latter (T3c). The calcination treatment melted the smectite in the sample. Untreated samples and alteration products were studied by X-ray diffraction (XRD), differential thermal analysis (DTA) and thermogravimetry (TG), scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis, and oxygen isotope analysis. DTA-TG of the <2-µm size fractions showed that there was a small increase of smectite relative to glass after alteration for samples T3a and T3b, with the amount of smectite increasing exponentially with time. No smectite formed in sample T3c. These results suggest that smectite acts as a nucleation site for the precipitation of new smectite. The amount of glass in the <2-µm size fraction increased, although slightly decreased relative to smectite. SEM-EDX analysis showed smectite with the approximate structural formula of Na0.22K0.08Mg0.12Ca0.03VI(Al1.47Fe0.05Mg0.48)IV(Si3.97Al0.03)O10(OH)2.Oxygen isotope composition of the <2-µm size fraction became enriched in 18O by alteration, the >2-µm size fraction of T3b did not vary, and that of T3c was depleted in 18O. Our results are consistent with three processes during alteration: 1) oxygen isotope exchange between volcanic glass and water, 2) neoformation of smectite, and 3) hydration and consequent hydroxylation of the calcined glass.

Effect of lactate, glycine, and citrate on the kinetics of montmorillonite dissolution

Abstract The montmorillonite dissolution in saline solutions that mimic synthetic lung fluids (SLF) was investigated to gain knowledge on the clearance mechanisms of inhaled clay particles. Dissolution rates were measured at pH 4 (macrophages) and 7.5 (interstitial fluids) at 37 °C in flow-through reactors. The effect of organic acids was investigated through the addition of lactate, citrate, and glycine (0.15, 1.5, and 15 mmol/L). Lactate or glycine does not markedly affect the montmorillonite dissolution rates at pH 4, but at pH 7.5 there exists a slight inhibitory effect of lactate on the dissolution, probably due to a reduction in the number of reactive surface sites caused by lactate adsorption. Citrate enhances the dissolution rate by 0.5 order of magnitude at pH 4 and more than 1 order of magnitude at pH 7.5, thus indicating the prevalence of the ligand-promoted over the proton-promoted dissolution mechanism under these experimental conditions. The kinetic data were used to estimate the reduction in size of an inhaled clay particle. At pH 7.5, a particle 500 nm in diameter could be reduced 25% in the presence of citrate, whereas the reduction in saline solution would only be 10% after 10 years. Ligand adsorption was measured in batch experiments at pH 2-11 and EQ3NR was used to model the capacity of the ligands to form soluble species of Al. Citrate, glycine, and lactate adsorb onto montmorillonite under acidic conditions, up to 23, 26, and 60 μmol/g, respectively. However, only citrate can complex the released aqueous Al at pH 4 and 7.5, which contributes to enhance dissolution rate and prevents precipitation of gibbsite at pH 7.5. The enhancement of the dissolution rate in acidic citrate solution very likely comes from the formation of surface complexes between the ligand and the edge surface of montmorillonite. In neutral conditions the effect may be also due to the decrease of the activity of Al3+ by formation of aqueous Al-citrate complexes.

Trace elements in different marine sediment fractions of the Gulf of Tunis (Central Mediterranean Sea)

Abstract Over several decades, the mouth of the Mejerda River (northern Tunisia) has received large amounts of mining tailings mainly containing Pb, Zn and Ba. We have measured the concentrations of major and trace elements (Al, Ti, P, K, Mg, Na, Ca, S, Fe, Cl, V, Cr, Co, Ni, Cu, Zn, Ga, Br, Rb, Sr, Y, Zr, Nb, I, Ba and Pb) in three different fractions of 45 surficial sediments using wavelength dispersive X-ray fluorescence. The size distribution of fine particles (<2 μm, 2–20 μm, 20–63 μm) revealed that clay and silt compounds were predominant (75–95%) in the deeper estuarine region. These condensed clay phases were mainly dioctahedral smectite, illite and kaolinite. The total organic carbon (TOC) concentration varies from 0.08 to 1.37 %. The C:N ratio varies from 1 to 17 indicating that the organic matter has a mixed marine and continental origin principal component analysis was used to determine the associations of trace elements with organic and/or inorganic phases of the sediment fractions. The correlations of Fe2O3, MnO2 and P2O5 with trace elements showed that amorphous Fe and Mn were the most active scavengers of dissolved metals from the Mejerda River. Cluster analysis clearly distinguished local trace element accumulations according to grain size fractions (< 2 μm and 2–20 μm) near the Ghar el Melh Lagoon and th River.

SYNTHESIS OF Ni-RICH 1:1 PHYLLOSILICATES

Rapid dissolution of partly amorphized kaolinite in the systems kaolinite + NiCl2, kaolinite + Ni(OH)2, and kaolinite + NiCl2 + Ni(OH)2, at a temperature of 200°C and at pH between 5.3 and 7.4, leads to the precipitation of Ni-poor kaolinite, Ni-rich kaolinite and Al-Ni-serpentine. Identification of the phases was carried out using a combination of X-ray diffraction and transmission/analytical electron microscopy. Ni-bearing kaolinite shows variable morphologies in the systems studied: stacks of kaolinite with relatively small Ni contents and fine-grained curved particles of Ni-rich kaolinite dominate in the Cl-bearing system; spherical particles with a disordered structure and relatively uniform Ni contents (in the order of 0.15 atoms per formula unit (a.p.f.u.)) and platy particles of Al-Ni-serpentine characterize the products formed in the Ni(OH)2-richest systems. The presence of Ni(OH)2 in the systems (with and without Cl) favors the dissolution process as well as rapid precipitation of spherical particles, and the formation of serpentine. A difference from Mg systems studied previously is a well defined phase intermediate in composition between kaolinite and serpentine which originated in the Ni-bearing systems. Increasing Ni content is clearly reflected in the parallel increase in the b cell parameter of kaolinite. The average composition of the coexisting Al-Ni-serpentine is: (Al1.24Ti0.01Fe0.02Ni1.31) (Si1.58Al0.42)O5(OH,Cl)2.

REACTION PATHWAYS OF CLAY MINERALS IN TROPICAL SOILS: INSIGHTS FROM KAOLINITE-SMECTITE SYNTHESIS EXPERIMENTS

Pedogenic smectite from a young (Holocene) tropical soil was reacted in Al-rich solution at 150ºC for a range of reaction times (3 to 120 days) in orderto study mechanisms and rates associated with the transformation of smectite to kaolinite via interstratified kaolinite-smectite (K-S). As has been observed in tropical soils, the overall reaction rate is logarithmic, with rapid initial transformation of smectite to K-S with ~50% smectite layers, followed by progressively slower transformation of intermediate K-S to kaolinite-rich K-S and eventually Fe-kaolinite. Sub-micron hexagonal non-Fe-bearing kaolinite forms in the final stage (after 120 days) as a minor mineral in an assemblage dominated by Fe-kaolinite. The pedogenic smectite used as starting material consisted of two end-members, Fe-beidellite and Al-smectite, enabling comparison of reaction pathways. Fe-beidellite transforms to K-S or Fe-kaolinite within 3 days, whereas Al-smectite transforms much more slowly, appearing to reach a maximum rate in intermediate stages. This difference is probably due to hydrolysis of relatively weak Mg-O and Fe-O bonds (relative to Al-O bonds) in Fe-beidellite octahedral sheets, which drives rapid reaction, whereas the driving force behind transformation of Al-smectite is more likely to be related to stripping of tetrahedral sheets which reaches its maximum rate at intermediate stages. Multiple analytical approaches have indicated that Al is rapidly fixed from solution into smectite interlayers within K-S, and that K-S and Fe-kaolinite inherit octahedral Fe and Mg from precursor smectite; as the reaction progresses, octahedral sheets become progressively more Al-rich and Fe and Mg are lost to solution. These results demonstrate that: (1) early-formed pedogenic smectite in tropical soils is expected to transform to kaolinite via interstratified K-S; (2) K-S has a strong potential to sequester plant-toxic Al in tropical soil; and (3) the presence in tropical soils of Fe-kaolinites with relatively large cation exchange capacities may be related to inheritance of octahedral sheets from precursor smectite and K-S.

Effect of oxalate and pH on chrysotile dissolution at 25 °C: An experimental study

Abstract The effect of pH on the kinetics of chrysotile dissolution was investigated at 25 °C in batch reactors over the pH range of 1 to 13.5, in oxalic solutions and buffered solutions of inorganic salts. Dissolution rates were obtained based on the release of Si and Mg. Results of the batch with inorganic buffers showed a strong dependence of dissolution rates on pH in the acid range. The logarithm of dissolution rates decreases with the pH with a slope of n = 0.27. Around neutral pH, a minimum is reached. From pH 8 to 12, rates increase again when pH increases, and follow a linear dependence with a shallow slope (n = 0.06). The Mg/Si ratio shows a non-stoichiometric dissolution reaction with a preferential release of Mg2+ at acidic pH; it decreases at neutral pH conditions according to Mg solubility. Our results suggest that the relative ease of the breaking of Mg-O bonds compared with Si-O bonds lead to dissolution via a series of steps involving Si and Mg, where Si release is the rate-limiting step. In the presence of 15 mmol L-1 oxalate, an intense catalytic effect from pH 1 to 6 is observed because of the capacity of the oxalate anion to form different complexes with Mg. The ratio of the rates derived from Mg and Si concentrations confirm an enhancement of non-stoichiometric dissolution compared with the series without oxalate. The mechanism of catalysis involves different processes depending on pH: At pH 1, XRD analysis confirms the formation of an amorphous silica phase dissolving all the Mg present in the chrysotile structure. At pH 2, XRD and FTIR results also confirm the precipitation of glushinskite, a magnesium oxalate phase. At pH 3 to 6, the presence of oxalate enhances dissolution almost by an order of magnitude compared with the experiments in inorganic buffered solutions. In this case, the mechanism could be due to the formation of aqueous or surface magnesium oxalate complexes. However, dissolution rates at neutral pH in the presence of oxalate are similar to those obtained in inorganic buffered solutions; the pH dependence at pH 8 to 13 is minimal. The increase in saturation and the drastic decrease in Mg solubility at these pH values could lead to precipitation of secondary phases coating the reactive mineral surface and inhibiting the surface. Results obtained in this study show that chrysotile dissolves faster in acid media and oxalate acts as a strong catalyst increasing the efficiency of magnesium release to solution at ambient temperature. These data may provide an excellent background to design and select optimal conditions in the previous acid treatment for carbon capture processes, as well as help to develop remediation process of asbestos contaminated sites.

In situ observation of biotite (001) surface dissolution at pH 1 and 9.5 by advanced optical microscopy

Summary Laser confocal differential interference contrast microscopy (LCM-DIM) allows for the study of the reactivity of surface minerals with slow dissolution rates (e.g., phyllosilicates). With this technique, it is possible to carry out in situ inspection of the reacting surface in a broad range of pH, ionic strength and temperature providing useful information to help unravel the dissolution mechanisms of phyllosilicates. In this work, LCM-DIM was used to study the mechanisms controlling the biotite (001) surface dissolution at pH 1 (11 and 25 °C) and pH 9.5 (50 °C). Step edges are the preferential sites of dissolution and lead to step retreat, regardless of the solution pH. At pH 1, layer swelling and peeling takes place, whereas at pH 9.5 fibrous structures (streaks) form at the step edges. Confocal Raman spectroscopy characterization of the reacted surface could not confirm if the formation of a secondary phase was responsible for the presence of these structures.