Geochemical and mineralogical impacts of H2SO4 on clays between pH 5.0 and −3.0

Natural and constructed clay liners are routinely used to contain waste and wastewater. The impact of acidic solutions on the geochemistry and mineralogy of clays has been widely investigated in relation to acid mine drainage systems at pH > 1.0. The impact of H₂SO₄ leachate characterized by pH < 1.0 and potentially negative pH values on the geochemistry and mineralogy of clays is, however, not clear. Thus, laboratory batch experiments were conducted on three natural clay samples with different mass ratios of smectite, illite and kaolinite to investigate the impact of H₂SO₄ on the geochemistry and mineralogy of aluminosilicates from pH 5.0 to −3.0. Batch testing was conducted at seven pH treatments (5.0, 3.0, 1.0, 0.0, −1.0, −2.0 and −3.0) using standardized H₂SO₄ solutions for four exposure periods (14, 90, 180, and 365 d). Aqueous geochemical and XRD analyses showed: increased dissolution of aluminosilicates with decreasing pH and increasing exposure period, that smectite was more susceptible to dissolution than illite and kaolinite, precipitation of an amorphous silica phase occurred at pH ? 0.0, and anhydrite precipitated in Ca-rich clays at pH ? −1.0. In addition, global dissolution rates were calculated for the clays and showed good agreement to literature smectite, illite and kaolinite dissolution rates, which suggests global dissolution rates for complex clays could be determined from monomineralic studies. A stepwise conceptual model of the impact of H₂SO₄ on aluminosilicate geochemistry and mineralogy between pH 5.0 and −3.0 is proposed.     

Dissolution of hausmannite (Mn3O4) in the presence of the trihydroxamate siderophore desferrioxamine B

That microbial siderophores may be mediators of Mn(III) biogeochemistry is suggested by recent studies showing that these well known Fe(III)-chelating ligands form very stable Mn(III) aqueous complexes. In this study, we examine the influence of desferrioxamine B (DFOB), a trihydroxamate siderophore, on the dissolution of hausmannite, a mixed valence Mn(II, III) oxide found in soils and freshwater sediments. Batch dissolution experiments were conducted both in the absence (pH 4-9) and in the presence of 100 μM DFOB (pH 5-9). In the absence of the ligand, there is a sharp decrease in the extent of proton-promoted dissolution above pH 5 and no appreciable dissolution above pH 8. The resulting aqueous Mn²⁺ activities were in good agreement with previous studies, indirectly supporting the accepted two-step mechanism involving the formation of manganite and reprecipitation of hausmannite. Desferrioxamine B enhanced hausmannite dissolution over the entire pH range investigated, both via the formation of a Mn(III) complex and through surface-catalyzed reductive dissolution. Above pH 8, non-reductive ligand-promoted dissolution dominated, whereas below pH 8, dissolution was non-stoichiometric with respect to DFOB. Concurrent proton-promoted, ligand-promoted, reductive, and induced dissolution was observed, with Mn release by either reductive or induced dissolution increasing linearly with decreasing pH. The fast kinetics of the DFOB-promoted dissolution of hausmannite, as compared to iron oxides, suggest that the siderophore-promoted dissolution of Mn(III)-bearing minerals may compete with the siderophore-promoted dissolution of Fe(III)-bearing minerals.     

The effect of high pH alkaline solutions on the mineral stability of the Boom Clay – Batch experiments at 60 °C

Boom Clay is currently viewed as a reference host formation for studies on deep geological disposal of radioactive waste in Belgium. The interactions between bulk rock Boom Clay and 0.1 M KOH, 0.1 M NaOH, 0.1 M Ca(OH)₂, young cement water and evolved cement water solutions, ranging in pH from 12.5 to 13.2, were examined as static batch experiments at 60 °C to simulate alkaline plume perturbations, which are expected to occur in the repository due to the presence of concrete. Both liquids and solids were investigated at specific times between 90 and 510 days in order to control the elemental budget and to search for potential mineralogical alterations. Also, the clay fraction was separated from the whole-rock Boom Clay at the end of each run and characterized for its mineralogical composition. Thereby, the importance of the mineral matrix to buffer the alkaline attack and the role of organic matter to protect clay minerals were also addressed. The results indicate that the degree of geochemical perturbation in Boom Clay is dependent on the initial pH of the applied solution together with the nature of the major cation in the reactant fluids. The higher the initial pH of the media, the stronger its interaction with Boom Clay. No major non-clay mineralogical alteration of the Boom Clay was detected, but dissolution of kaolinite, smectite and illite occurred within the studied experimental conditions. The dissolution of clays is accompanied by the decrease in the layer charge, followed by a decrease in the cation-exchange capacity. The highest TOC values coincide with the highest total elemental concentrations in the leachates, and correspondingly, the highest dissolution degree. However, no quantitative link could be established between the degree of organic matter decomposition and clay dissolution.     

Evidence for ligand hydrolysis and Fe(III) reduction in the dissolution of goethite by desferrioxamine-B

Desferrioxamine-B (DFOB) is a bacterial trihydroxamate siderophore and probably the most studied to date. However, the manner in which DFOB adsorbs at mineral surfaces and promotes dissolution is still under discussion. Here we investigated the adsorption and dissolution reactions in the goethite-DFOB system using both in situ infrared spectroscopic and quantitative analytical methods. Experiments were carried out at a total DFOB concentration of 1 μmol/m², at pH 6, and in the absence of visible light. Our infrared spectroscopic results indicated that the adsorption of DFOB was nearly complete after a 4-h reaction time. In an attempt to determine the coordination mode at the goethite surface, we compared the spectrum of adsorbed DFOB after a 4-h reaction time to the spectra of model aqueous species. However, this approach proved too simplistic in the case of such a complex ligand as DFOB, and we suggest that a more detailed investigation (IR in D₂O, EXAFS of adsorbed model complexes) is needed to elucidate the structure of the adsorbed siderophore. Between a 4-h and 4-day reaction time, we observed the growth of carboxylate stretching bands at 1548 and 1404 cm⁻¹, which are indicators of DFOB hydrolysis. Acetate, a product of DFOB hydrolysis at its terminal hydroxamate group, was quantified by ion chromatography. Its rate of formation was linear and nearly the same as the rate of Fe(III) dissolution. The larger hydrolysis product, a hydroxylamine fragment, was not detected by LC-MS. However, a signal due to the oxidized form of this fragment, a nitroso compound, was found to increase linearly with time, which is an indirect indication for Fe(III) reduction. Based on these findings, we propose that DFOB undergoes metal-enhanced hydrolysis at the mineral surface followed by the reduction of surface Fe(III). While Fe(II) was not detected in solution, this is likely because it remains adsorbed at the goethite surface or becomes buried in the goethite crystal by electron conduction. Taking into account the extent and similarity between the rates of hydrolysis and dissolution, we suggest that a reductive mechanism could play an important part in the dissolution of goethite by DFOB. This possibility has not been considered previously in the absence of light and at circumneutral pH.     

Dissolution of illite in saline-acidic solutions at 25 °C

The dissolution rate of illite, a common clay mineral in Australian soils, was studied in saline-acidic solutions under far from equilibrium conditions. The clay fraction of Na-saturated Silver Hill illite (K_1.38Na_0.05)(Al_2.87Mg_0.46Fe³⁺_0.39Fe²⁺_0.28Ti_0.07)[Si_7.02Al_0.98]O₂₀(OH)₄ was used for this study. The dissolution rates were measured using flow-through reactors at 25 ± 1 °C, solution pH range of 1.0-4.25 (H₂SO₄) and at two ionic strengths (0.01 and 0.25 M) maintained using NaCl solution. Illite dissolution rates were calculated from the steady state release rates of Al and Si. The dissolution stoichiometry was determined from Al/Si, K/Si, Mg/Si and Fe/Si ratios. The release rates of cations were highly incongruent during the initial stage of experiments, with a preferential release of Al and K over Si in majority of the experiments. An Al/Si ratio >1 was observed at pH 2 and 3 while a ratio close to the stoichiometric composition was observed at pH 1 and 4 at the higher ionic strength. A relatively higher K⁺ release rate was observed at I = 0.25 in 2-4 pH range than at I = 0.01, possibly due to ion exchange reaction between Na⁺ from the solution and K⁺ from interlayer sites of illite. The steady state release rates of K, Fe and Mg were higher than Si over the entire pH range investigated in the study. From the point of view of the dominant structural cations (Si and Al), stoichiometric dissolution of illite occurred at pH 1-4 in the higher ionic strength experiments and at pH ?3 for the lower ionic strength experiments. The experiment at pH 4.25 and at the lower ionic strength exhibited lower R_Al (dissolution rate calculated from steady state Al release) than R_Si (dissolution rate calculated from steady state Si release), possibly due to the adsorption of dissolved Al as the output solutions were undersaturated with respect to gibbsite. The dissolution of illite appears to proceed with the removal of interlayer K followed by the dissolution of octahedral cations (Fe, Mg and Al), the dissolution of Si is the limiting step in the illite dissolution process. A dissolution rate law showing the dependence of illite dissolution rate on proton concentration in the acid-sulfate solutions was derived from the steady state dissolution rates and can be used in predicting the impact of illite dissolution in saline acid-sulfate environments. The fractional reaction orders of 0.32 (I = 0.25) and 0.36 (I = 0.01) obtained in the study for illite dissolution are similar to the values reported for smectite. The dissolution rate of illite is mainly controlled by solution pH and no effect of ionic strength was observed on the dissolution rates.     

Investigation of acidic dissolution of mixed clays between pH 1.0 and −3.0 using Si and Al X-ray absorption near edge structure

Although widely investigated in relation to acid mine drainage systems at pH > 1.0, we know little about the impact of sulfuric acid (H₂SO₄) on the geochemistry and mineralogy of clays at pH < 1.0 (including negative pH values). Thus, laboratory batch experiments were conducted on three mixed clay samples with different mass ratios of phyllosilicates (smectite, illite, and kaolinite) to investigate the impact of H₂SO₄ from pH 1.0 to −3.0 for exposure periods of 14, 90, 180, and 365 days. Si and Al K- and L_2,3-edge X-ray absorption near edge structure (XANES) spectroscopy were employed on these samples to determine the chemical and structural changes that occur during acidic dissolution of phyllosilicates that cannot be distinguished using X-ray diffraction analyses. A series of silicate, phyllosilicate, and Al-bearing standard compounds were also studied to provide an explanation for the observed changes in the clay samples. The Si XANES results indicated the preferential dissolution of the phyllosilicates (pH ? 1.0, t ? 14 d), the persistence of quartz even at pH ? −3.0 and t ? 365 d, and the formation of an amorphous silica-like phase that was confined to the surface layer of the altered clay samples at pH ? 0.0 and t ? 90 d). Al XANES results demonstrated dissolution of Al-octahedral layers (pH ? 1.0, t ? 14 d), the persistence of four-fold relative to six-fold coordinated Al, and the precipitation of an Al-SO₄-rich phase (pH ? −1.0, t ? 90 d). An existing conceptual model of phyllosilicate dissolution under extremely acidic conditions was modified to include the results of this study.     

Experimental study of the effect of pH on the kinetics of montmorillonite dissolution at 25 °C

The effect of pH on the kinetics of smectite (K-montmorillonite) dissolution was investigated at 25 °C in batch and stirred flow-through reactors over the pH range of 1-13.5, in KNO₃ solutions. Dissolution rates were obtained based on the release of Si and Al at steady-state under far from equilibrium conditions. Dissolution was non-stoichiometric between pH 5 and 10, due to adsorption/precipitation of Al. Dissolution rates computed from batch and flow-through experiments were consistent, irrespective of the Si and Al concentrations. Sample pre-treatment and the interlayer cation do not affect the steady-state dissolution rate or stoichiometry of cation release. The rate dependence on pH can be described by:

     

Thermodynamic modelling of clay dehydration, stability and compositional evolution with temperature, pressure and H2O activity

We propose a thermodynamic approach to model the stepwise dehydration with increasing temperature or decreasing H₂O activity of K, Na, Ca and Mg-smectite. The approach relies on the relative stability of the different solid-solutions that describe the hydration of di- or trioctahedral-smectites containing 0, 1, 2 or 3 interlayer water layers. The inclusion of anhydrous mica end-members makes it possible to cover, with the same solid-solution model, the entire range of composition from low-charge smectite to mica, through high-charge smectite and illite. Non-ideal Margules parameters were used to describe the non-ideality of the solid solutions between the hydrated and dehydrated smectite end-members. Standard state properties of all smectite end-members as well as Ca- and Mg-muscovite and -phlogopite were initially estimated by oxide summation. These values were then refined and the other non-ideal interactions were estimated on the basis of different experimental data. The stepwise dehydration of smectite, and its stability and compatibility relations were calculated by Gibbs free energy minimising. Our results account for the progressive evolution of smectite to interlayered illite/smectite and then to mica, as observed in nature and experiments, and our model provides an explanation for the thermodynamic stability of smectite and illite/smectite compared to mica + kaolinite or pyrophyllite assemblages. The results suggest that the enthalpic contribution of interlayer water is a function of the ionic potential of the interlayer cation and the number of interlayer water molecules. This evolution makes possible to estimate the standard-state thermodynamic parameters and hydration-temperature behaviour of smectite of virtually all possible compositions. For the four-interlayer cations considered in the study, our model reproduces the 3 → 2 → 1 water-layer transitions that accompany a reduction of water activity or an increase of temperature at ambient pressure. The range of water content and interlayer distance calculated for the 3w, 2w and 1w states are also in fair agreement with the experimental values at ambient pressure.     

ATR-FTIR spectroscopic study of the adsorption of desferrioxamine B and aerobactin to the surface of lepidocrocite (γ-FeOOH)

The adsorption of two model siderophores, desferrioxamine B (DFOB) and aerobactin, to lepidocrocite (γ-FeOOH) was investigated by attenuated total reflection infrared spectroscopy (ATR-FTIR). The adsorption of DFOB was investigated between pH 4.0 and 10.6. The spectra of adsorbed DFOB indicated that two to three hydroxamic acid groups of adsorbed DFOB were deprotonated in the pH range 4.0-8.2. Deprotonation of hydroxamic acid groups of adsorbed DFOB at pH values well below the first acid dissociation constant of solution DFOB species (pK_a = 8.3) and well below the point of zero charge of lepidocrocite (pH_PZC = 7.4) suggested that the surface speciation at the lower end of this pH range (pH 4) is dominated by a surface DFOB species with inner-sphere coordination of two to three hydroxamic acids groups to the surface. Maximum adsorption of DFOB occurred at approximately pH 8.6, close to the first pK_a value of the hydroxamic acid groups, and decreased at lower and higher pH values.The spectra of adsorbed aerobactin in the pH range 3-9 indicated at least three different surface species. Due to the small spectral contributions of the hydroxamic acid groups of aerobactin, the interactions of these functional groups with the surface could not be resolved. At high pH, the spectral similarity of adsorbed aerobactin with free aerobactin deprotonated at the carboxylic acid groups indicated outer-sphere complexation of the carboxylate groups. With decreasing pH, a significant peak shift of the asymmetric carboxylate stretch vibration was observed. This finding suggested that the (lateral) carboxylic acid groups are coordinated to the surface either as inner-sphere complexes or as outer-sphere complexes that are strongly stabilized at the surface by hydrogen bonding at low pH.     

Towards a link between the energetic heterogeneities of the edge faces of smectites and their stability in the context of metallic corrosion

In the context of the potential confinement of high-level radioactive wastes (HLW) within the clay engineered barrier system (EBS) in deep geological formations, the evolution of the retention properties of smectite when interacting with Fe(0) needs to be assessed. If some potential natural analogues describing iron-clay reactivity are easily found, metallic iron-clay interactions are poorly described in studies regarding the Earth. Therefore, experimental investigations are needed. Several parameters influence Fe(0)-clay interactions, such as temperature, the interlayer composition of swelling clays, and the presence of octahedral Fe³⁺, etc. From a geometrical point of view, it is thought that clay destabilization is mainly controlled by phenomena starting at the edge faces of the particles. In the present work, the rates of the smectite-Fe(0) reaction at 80 °C were assessed by XRD, Mössbauer, and CEC analyses for three smectites. The investigations show marked differences in the degree of stability, which cannot be explained by the crystal-chemistry rules established in previous studies. Therefore, the Fe(0)-smectite interactions were studied in view of textural and energetic surface quantitative analyses. The studied smectites have equivalent nitrogen BET-specific surface areas, equivalent argon edge surface areas and slightly different basal surface areas. This similarity in particle shape indicates that the edge surface area cannot be accounted for when explaining the observed differences in reactivity. However, a correlation is obtained between smectite reactivity and the energetic heterogeneity of its edge faces. This is interpreted in terms of a multiplication of the number of sites on the edge faces, where the electron transfer between Fe(0) and the smectite structure can occur.     

Kaolinite and smectite dissolution rate in high molar KOH solutions at 35° and 80°C

Experiments measuring kaolinite and smectite dissolution rates were carried out using batch reactors at 35° and 80°C. No potential catalysts or inhibitors were present in solution. Each reactor was charged with 1 g of clay of the ≤2 μm fraction and 80, 160 or 240 ml of 0.1–4 M KOH solution. An untreated but sized kaolinite from St. Austell and two treated industrial smectites were used in the experiments. One smectite is a nearly pure montmorillonite, while the second has a significant component of beidellitic charge (35%). The change in solution composition and mineralogy was monitored as a function of time. Initially, the 3 clays dissolved congruently. No new formed phases were observed by XRD and SEM during the pure dissolution stage. The kaolinite dissolution is characterized by a linear release of silica and Al as a function of the log of time. This relationship can be explained by a reaction affinity effect which is controlled by the octahedral layer dissolution. Far from equilibrium, dissolution rates are proportional to a^0.56±0.12_OH⁻ at 35°C and to a^0.81±0.12_OH⁻ at 80°C. The activation energy of kaolinite dissolution increases from 33±8 kJ/mol in 0.1 M KOH solutions to 51±8 kJ/mol in 3 M KOH solutions. In contrast to kaolinite, the smectites dissolve at much lower rates and independently of the aqueous silica or Al concentrations. The proportionality of the smectite dissolution rate constant at 35 and 80°C was a^0.15±0.06_OH⁻. The activation energy of dissolution appears to be independent of pH for smectite and is found to be 52±4 kJ/mol. The differences in behavior between the two kinds of minerals can be explained by structural differences. The hydrolysis of the tetrahedral and the octahedral layer appears as parallel reactions for kaolinite dissolution and as serial reactions for smectite dissolution. The rate limiting step is the dissolution of the octahedral layer in the case of kaolinite, and the tetrahedral layer in the case of smectite.     

Stability of YREE complexes with the trihydroxamate siderophore desferrioxamine B at seawater ionic strength

Organic complexation of yttrium and the rare earth elements (YREEs), although generally believed to be important, is an understudied aspect of YREE solution speciation in the open ocean. We report the first series of stability constants for complexes of YREEs (except Ce and Pm) with the trihydroxamate siderophore desferrioxamine B (DFOB), representing a class of small organic ligands that have an extraordinary selectivity for Fe(III) and are found in surface seawater at low-picomolar concentrations. Constants were measured by potentiometric titration of DFOB (pH 3-10) in the presence of single YREEs, in simple media at seawater ionic strength (NaClO₄ or NaCl, I = 0.7 M). Under these circumstances, the terminal amine of DFOB does not deprotonate. The four acid dissociation constants of the siderophore were determined separately by potentiometric titration of DFOB alone.Values for the bidentate (log β₁), tetradentate (log β₂), and hexadentate (log β₃) complexes of La-Lu range from 4.88 to 6.53, 7.70 to 11.27, and 10.09 to 15.19, respectively, while Y falls between Gd and Tb in each case. Linear free-energy relations of the three stability constants with the first YREE hydrolysis constant, log , yield regression coefficients of >0.97. On the other hand, plots of the constants vs. the radius of the inner hydration sphere display an increasing deviation from linearity for the lightest REEs (La > Pr > Nd). This may signify steric constraints in DFOB folding around bulkier cations, a larger mismatch in coordination number, or a substantial degree of covalence in the YREE-hydroxamate bond.Complexes of the YREEs with DFOB are many orders of magnitude more stable than those with carbonate, the dominant inorganic YREE ligand in seawater. Speciation modeling with MINEQL indicates that, for an average seawater composition, the hexadentate complex could constitute as much as 28% of dissolved Lu at free DFOB concentrations as low as 10⁻¹³ M. Such conditions might occur when DFOB or other siderophores are present in excess over metals for which they have high affinity, like Fe(III) and Co(III), for example during plankton blooms. Even if it turns out that trihydroxamate siderophores are not the dominant organic YREE ligand in seawater, our results establish a benchmark for producing effects on YREE solution speciation comparable to that of DFOB: the free concentration of any weaker organic ligand L must exceed that of DFOB by a factor β₃/_Lβ₁, assuming its first order complex is formed in greatest abundance.     

Relation between the dissolution rates of single minerals and reservoir rocks in acidified pore waters

A series of kinetic experiments has been carried out to investigate the rates of dissolution (release of Al and Si) of common sandstone minerals in response to acidification of pore waters (pH = 3), using an experimental procedure designed to maximise the proportion of solid to fluid, and to minimise possible damage from agitation. The results have then been compared with those from experiments using disaggregated sandstones from two North Sea reservoirs. Experiments were carried out at 25 °C and 80 °C and in 0.01, 0.1 and 1 M NaCl solutions, with a pH of 3. Hydrochloric acid was used as the source of acidity and rate constants were determined based on both release of Al and Si. Mineral dissolution rates were closely comparable to literature values, despite the different experimental technique, except in the case of smectite where particle aggregation appears to have inhibited reaction. The dissolution rates calculated for reservoir sandstones based on their modal mineralogy and surface areas agree within a factor of 2 with the measured vales. Based on the reaction rates measured here, reservoir rocks rich in feldspar, illite and/or smectite are likely to react most rapidly with acidified pore waters.     

Effects of layer-charge distribution on the thermodynamic and microscopic properties of Cs-smectite

To explore the effects of layer-charge distribution on the thermodynamic and microscopic properties of Cs-smectites, classical molecular dynamic simulations are performed to derive the swelling curves, distributions and mobility of interlayer species, and Cs binding structures. Three representative smectites with distinct layer-charge distributions are used as model clay frameworks and interlayer water content is set within a wide range from 0 to 380 mg_water/g_clay. All the three smectites swell in a similar way, presenting the characteristic swelling plateaus and similar trends of swelling energetic profiles. The full-monolayer hydrate, corresponding to the global minima of the immersion energy, is the most stable hydrated state of Cs-smectites. The calculated diffusion coefficients of interlayer species disclose the confining effects in all smectites: both water molecules and ions diffuse slower than corresponding bulk cases and they are much more mobile in the direction parallel to the clay surfaces than perpendicular to them. The formed inner-sphere complex structures are very similar in different smectites: ions bind on the H-sites or T-sites and water molecules form cage-like caps covering the ions. Layer-charge distribution is found to have significant influences on the mobility of interlayer species and preference of ion binding sites. A general sequence is proposed to elucidate the preferences of various hexagonal sites (H-sites) and triangular sites (T-sites), that is, tetrahedrally substituted H-sites > nonsubstituted H-sites > tetrahedrally substituted T-sites > nonsubstituted T-sites, but the influence of octahedral substitutions on the preference of the neighboring sites is not obvious. Analysis of mobility indicates that H-sites are more stable Cs-fixation positions than T-sites and smectite with higher fraction of octahedral charges seems to be the most effective barrier material no matter how water content varies although all smectites can immobilize Cs ions in relatively dry conditions. These findings will not only facilitate basic research in geochemistry and material sciences, but also promote the barrier material designing.     

Metal corrosion and argillite transformation at the water-saturated,high-temperature iron–clay interface: A microscopic-scale study

In this study, microscopic and spectroscopic techniques (scanning electron microscopy coupled with energy-dispersive X-ray analysis, Raman microspectroscopy, micro X-ray fluorescence spectroscopy, micro X-ray fine structure adsorption spectroscopy, and micro laser-induced breakdown spectroscopy) were combined to decipher the chemical and mineralogical properties of a saturated Fe–clay interface reacted at 90 °C and 50 bar for 8 months. The results collectively confirm the presence of a corrosion layer and a clay transformation layer. The corrosion layer is made of a magnetite-containing internal sublayer and a Fe-phyllosilicate external sublayer enriched in Na, with traces of goethite presumably resulting from sample reaction with air. The clay transformation layer is made of predominantly Ca-rich siderite (FeCO₃). It is depleted in Al and K, suggesting dissolution of rock-forming minerals. The corroded thickness determined from the amount of Fe in corrosion and transformation layers and assuming zero porosity equals 19 ± 9 μm. These data indicate that the interfacial clay was transformed by dissolution of calcite and clay minerals and precipitation of siderite close to the original surface. Silica released upon clay dissolution diffused into the corrosion layer and coprecipitated with oxidized Fe to form Fe-phyllosilicate.     

Experimental study of terrestrial plant litter interaction with aqueous solutions

Quantification of silicon and calcium recycling by plants is hampered by the lack of physico-chemical data on reactivity of plant litter in soil environments. We applied a laboratory experimental approach for determining the silica and calcium release rates from litter of typical temperate and boreal plants: pine (Pinus laricio), birch (Betula pubescens), larch (Larix gmelinii), elm (Ulmus laevis Pall.), tree fern (Dicksonia squarrosa), and horsetail (Equisetum arvense) in 0.01 M NaCl solutions, pH of 2-10 and temperature equals to 5, 25 and 40 °C. Open system, mixed-flow reactors equipped with dialysis compartment and batch reactors were used. Comparative measurements were performed on intact larch needles and samples grounded during different time, sterilized or not and with addition or not of sodium azide in order to account for the effect of surface to mass ratio and possible microbiological activity on the litter dissolution rates. Litter degradation results suggest that the silica release rate is independent on dissolved organic carbon release (cell breakdown) which implies the presence of phytoliths in a pure “inorganic” pool not complexed with organic matter. Calcium and DOC are released at the very first stage of litter dissolution while Si concentration increases gradually suggesting the presence of Ca and Si in two different pools. The dry-weight normalized dissolution rate at circum-neutral pH range (approx. 1-10 μmol/g_DW/day) is 2 orders of magnitude higher than the rates of Si release from common soil minerals (kaolinite, smectite, illite). Minimal Ca release rates evaluated from batch and mixed-flow reactors are comparable with those of most reactive soil minerals such as calcite and apatite, and several orders of magnitude higher than the dissolution rates of major rock-forming silicates (feldspars, pyroxenes). The activation energy for Si liberation from plant litter is approx. 50 kJ/mol which is comparable with that of surface-controlled mineral dissolutions. It is shown that the Si release rate from the above-ground forest biomass is capable of producing the Si concentrations observed in soil solutions of surficial horizons and contribute significantly to the Si flux from the soil to the river.     

Enhancement and inhibition of iron photoreduction by individual ligands in open ocean seawater

In laboratory experiments, we investigated the effect of five individual Fe-binding ligands: phaeophytin, ferrichrome, desferrioxamine B (DFOB), inositol hexaphosphate (phytic acid), and protoporphyrin IX (PPIX) on the Fe(II) photoproduction using seawater of the open Southern Ocean. Addition of 10-100 nM Fe(III) to open Southern Ocean seawater without the model ligands and containing; 1.1 nM dissolved Fe(III), 1.75 ± 0.28 equivalents of nM Fe of natural ligands with a conditional stability constant (log K′) of 21.75 ± 0.34 and a concentration DOC of 86.8 ± 1.13 μM C leads to the formation of amorphous Fe(III) hydroxides. These amorphous Fe(III) hydroxides are the major source for the photoproduction of Fe(II). The addition of the model ligands changed the Fe(II) photoproduction considerably and in various ways. Phaeophytin showed higher Fe(II) photoproduction than ferrichrome and the control, i.e., amorphous Fe(III) hydroxides. Additions of phytic acid between 65 and 105 nM increased the concentration of photoproduced Fe(II) with 0.16 nM Fe(II) per nM phytic acid, presumably due to the co-aggregation of Fe(III) and phytic acid leading via an increasing colloidal surface to an increasing photoreducible Fe(III) fraction. DFOB and PPIX strongly decreased the photoproduced Fe(II) concentration. The low Fe(II) photoproduction with DFOB confirmed reported observations that Fe(III) complexed to DFOB is photo-stable. The PPIX hardly binds Fe(III) in the open Southern Ocean seawater but decreased the photoproduced Fe(II) concentration by complexing the Fe(II) with a binding rate constant of k_Fe(II)PPIX = 1.04 × 10⁻⁴ ± 1.53 × 10⁻⁵ s⁻¹ nM⁻¹ PPIX. Subsequently, PPIX is suggested to act as a photosensitizing producer of superoxide, thus increasing the dark reduction of Fe(III) to Fe(II). Our research shows that the photochemistry of Fe(III) and the resulting photoproduced Fe(II) concentration is strongly depending on the identity of the Fe-binding organic ligands and that a translation to natural conditions is not possible without further characterization of the natural occurring ligands.     

Glass-iron-clay interactions in a radioactive waste geological disposal: An integrated laboratory-scale experiment

Glass-iron-clay setups were reacted at 90 °C for 6-18 months to investigate the coupled interactions between glass alteration, Fe corrosion and clay transformation. The reacted interfaces were probed at the microscopic level using complementary characterization methods (scanning electron microscopy coupled with energy-dispersive X-ray analysis, micro-Raman spectroscopy, micro X-ray diffraction, micro X-ray fluorescence spectroscopy, and micro X-ray absorption near-edge structure spectroscopy). The 10-μm thick Fe foil was fully corroded within 10 months, exposing glass to the pore solution. Iron corrosion led to the formation of a layer containing mostly magnetite, siderite and Fe-rich phyllosilicates with one tetrahedral and one octahedral sheet (TO) or two tetrahedral and one octahedral (TOT) sheet per layer. The clay in contact with this corrosion layer was enriched in siderite (FeCO₃). Glass alteration resulted in the formation of a gel layer whose thickness increased with reaction time (from 20 μm after 6 months to 80 μm after 18 months) and a thin layer of secondary precipitates that concentrated lanthanides, P, and Mo. Assuming conservative behavior of Zr, the Si molar concentration in the gel is about 57% that in the glass. Glass dissolution remained at a rate close to the initial dissolution rate r₀. The data are consistent with glass dissolution sustained by the uptake of dissolved Si and charge-compensating cations on secondary (corrosion) products, thus maintaining the gel porosity open and facilitating the leaching of easily soluble elements.     

Synthetic coprecipitates of exopolysaccharides and ferrihydrite. Part II: Siderophore-promoted dissolution

Ferrihydrite (Fh) coprecipitated with exopolymers of plants and microbes may differ in its geochemical reactivity from its abiotic counterpart. We synthesized Fh in the presence and absence of acid polysaccharides (polygalacturonic acid (PGA), alginate, xanthan) and characterized the physical and structural properties of the precipitates formed [Mikutta C., Mikutta R., Bonneville S., Wagner F., Voegelin A., Christl I. and Kretzschmar R. (2008) Synthetic coprecipitates of exopolysaccharides and ferrihydrite. Part I: Characterization. Geochim. Cosmochim. Acta]. In this paper, we focus on the reactivity of PGA and alginate coprecipitates and pure Fh, and studied their interaction with the microbial siderophore desferrioxamine B (DFOB) in the presence and absence of low molecular weight organic (LMWO) acid anions (malate, citrate). Batch adsorption and dissolution experiments were performed in the dark at pH 7 in 10 mM NaClO₄ background electrolyte. In the dissolution experiments, different modes of ligand addition were applied (single, simultaneous, stepwise). With an estimated Langmuir sorption maximum of 15 mmol/mol Fe, a PGA coprecipitate with 11% C_org sorbed about four times as much DFOB as pure Fh, and the amount of DFOB sorbed was ∼4-fold larger than estimated from the sum of DFOB sorption to pure Fh and PGA alone. The apparent initial dissolution rates, R_app-initial, and pseudo-first order rate coefficients, k, of the coprecipitates exceeded those of pure Fh by up to two orders of magnitude. Citrate and malate exerted a strong synergistic effect on the DFOB-promoted dissolution of pure Fh, whereas synergistic effects of both anions were absent or negligible for the coprecipitates. R_app-initial of the citrate and DFOB-promoted dissolution of PGA coprecipitates increased with increasing molar C/Fe ratio of the coprecipitates, independent of the charge of the LMWO ligand. Our results indicate that polyuronates stabilize Fh particles sterically and /or electrostatically, thus increasing the mineral surface area accessible to LMWO ligands. In contrast, pure Fh was coagulated at pH 7 (pH_iep of Fh = 7.1), and hence only a small fraction of the Fh surface underwent dissolution. The increase in ligand-accessible surface area of Fh upon coprecipitation with acid polysaccharides seems to primarily control the kinetics of the ligand-promoted dissolution at neutral pH. In pH environments where the solubility of Fe(III) is very low, dissolution rates of Fe(III) (hydr)oxides in such coprecipitates may therefore exceed those of pure minerals by several orders of magnitude, despite a similar crystallinity of the minerals.     

Experimental investigation of main controls to methane adsorption in clay-rich rocks

In this study a series of CH₄ adsorption experiments on clay-rich rocks were conducted at 35 °C, 50 °C and 65 °C and at CH₄ pressure up to 15 MPa under dry conditions. The clay-dominated rock samples used are fresh samples from quarries and mines. Samples are individually dominated by montmorillonite, kaolinite, illite, chlorite, and interstratified illite/smectite. The experimental results show that clay mineral type greatly affects CH₄ sorption capacity under the experimental conditions. In terms of relative CH₄ sorption capacity: montmorillonite ? illite/smectite mixed layer > kaolinite > chlorite > illite. Physisorption is the dominant process for CH₄ absorption on clay minerals, as a result, there is a linear correlation between CH₄ sorption capacity and BET surface area in these clay-mineral dominated rocks. The abundance of micro-mesopores in the size range of a few to a few 10 s of nanometers in montmorillonite clay and illite–smectite interstratified clay results in large BET surface area values for these mineral species.