Aerobic and anaerobic oxidation of ferrous ions in near-neutral solutions.

Whilst the oxidation of Fe(II) in aerobic conditions has been studied thoroughly, an in-depth knowhow on the fate or stability of Fe(II) in solutions with near-neutral pH under anaerobic conditions is still lacking. Here, we experimentally investigated the kinetics of Fe(II) oxidation in solutions with pH ranging between ∼5 and 9, under aerobic (when solutions were in equilibrium with atmospheric oxygen) and anaerobic conditions (when the dissolved oxygen concentration was ∼10-10 mol/L), by colorimetric means. Experimental results and thermodynamic considerations presented here, show that Fe(II) oxidation in anaerobic conditions is first-order w.r.t. [Fe(II)], and proceeds with set of parallel reactions involving different hydrolysed and non-hydrolysed Fe(II) and Fe(III) species, similar to that observed in aerobic conditions. However, in the absence of oxygen, the cathodic reaction accompanying the anodic oxidation of Fe(II), is the reduction of H2O (l) releasing H2 (g). Hydrolysed Fe(II) species oxidise much faster than Fe2+ and their concentrations increases with pH, leading to increased Fe(II) oxidation rates. Additionally, we also show the importance of the type of buffer used to study Fe(II) oxidation. Therefore, for the oxidation of Fe(II) in near-neutral solutions, the speciation of Fe(II) and Fe(III), the presence of other anions and the pH of the solution are critical parameters that must be considered. We anticipate that our results and hypothesis will find use in reactive-transport models simulating different processes occurring in anaerobic conditions such as corrosion of the steel in concrete structures, or in nuclear waste repositories.

Mechanisms and thermodynamic modelling of iodide sorption on AFm phases.

Both, experimental and modelling evidence is presented in this study showing that interlayer anion exchange is the dominant sorption mechanism for iodide (I-) on AFm phases. AFm phases are Ca-Al(Fe) based layered double hydroxides (LDH) known for their large potential for the immobilization of anionic radionuclides, such as dose-relevant iodine-129, emanating from low- and intermediate-level radioactive waste (L/ILW) repositories. Monosulfate, sulfide-AFm, hemicarbonate and monocarbonate are safety-relevant AFm phases, expected to be present in the cementitious near-field of such repositories. Their ability to bind I- was investigated in a series of sorption and co-precipitation experiments. The sorption of I- on different AFm phases was found to depend on the type of the interlayer anion. Sorption Rd values are very similar for monosulfate, sulfide-AFm and hemicarbonate. A slightly higher uptake occurs by AFm phases with a singly charged anion in the interlayer (HS-AFm) as compared to AFm with divalent ions (monosulfate), whereas uptake by hemicarbonate is intermediate. No significant sorption occurs onto monocarbonate. Our derived thermodynamic solid solution models reproduce the experimentally obtained sorption isotherms on HS-AFm, hemicarbonate and monosulfate, indicating that anion exchange in the interlayer is the dominant mechanism and that the contribution of I- electrostatic surface sorption to the overall uptake is negligible.

A luminescence line-narrowing spectroscopic study of the uranium(VI) interaction with cementitious materials and titanium dioxide.

Non-selective luminescence spectroscopy and luminescence line-narrowing spectroscopy were used to study the retention of UO2(2+) on titanium dioxide (TiO2), synthetic calcium silicate hydrate (C-S-H) phases and hardened cement paste (HCP). Non-selective luminescence spectra showed strong inhomogeneous line broadening resulting from a strongly disordered UO2(2+) bonding environment. This problem was largely overcome by using luminescence line-narrowing spectroscopy. This technique allowed unambiguous identification of three different types of UO2(2+) sorbed species on C-S-H phases and HCP. Comparison with spectra of UO2(2+) sorbed onto TiO2 further allowed these species to be assigned to a surface complex, an incorporated species and an uranate-like surface precipitate. This information provides the basis for mechanistic models describing the UO2(2+) sorption onto C-S-H phases and HCP and the assessment of the mobility of this radionuclide in a deep geological repository for low and intermediate level radioactive waste (L/ILW) as this kind of waste is often solidified with cement prior to storage.

Uptake of Np(IV) by C-S-H phases and cement paste: an EXAFS study.

Nuclear waste disposal concepts developed worldwide foresee the use of cementitious materials for the immobilization of long-lived intermediate level waste (ILW). This waste form may contain significant amounts of neptunium-237, which is expected to be present as Np(IV) under the reducing conditions encountered after the closure of the repository. Predicting the release of Np(IV) from the cementitious near field of an ILW repository requires a sufficiently detailed understanding of its interaction with the main sorbing components of hardened cement paste (HCP). In this study, the uptake of Np(IV) by calcium silicate hydrates (C-S-H) and HCP has been investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy. The EXAFS studies on Np(IV)-doped C-S-H and HCP samples reveal that Np(IV) is predominantly incorporated in the structure of C-S-H phases having different Ca:Si ratios. The two main species identified correspond to Np(IV) in C-S-H with a Ca:Si mol ratio of 1.65 as in fresh cement and with a Ca:Si mol ratio of 0.75 as in highly degraded cement. The local structure of Np(IV) changes with the Ca:Si mol ratio and does not depend on pH. Furthermore, Np(IV) shows the same coordination environment in C-S-H and HCP samples. This study shows that C-S-H phases are responsible for the Np(IV) uptake by cementitious materials and further that incorporation in the interlayer of the C-S-H structure is the dominant uptake mechanism.

Determination of uranium(VI) sorbed species in calcium silicate hydrate phases: a laser-induced luminescence spectroscopy and batch sorption study.

Batch sorption experiments and time-resolved luminescence spectroscopy investigations were carried out to study the U(VI) speciation in calcium silicate hydrates for varying chemical conditions representing both fresh and altered cementitious environments. U(VI) uptake was found to be fast and sorption distribution ratios (R(d) values) were very high indicating strong uptake by the C-S-H phases. In addition a strong dependence of pH and solid composition (Ca:Si mol ratio) was observed. U(VI) luminescence spectroscopy investigations showed that the U(VI) solid speciation continuously changed over a period up to 6 months in contrast to the fast sorption kinetics observed in the batch sorption studies. Decay profile analysis combined with factor analysis of series of spectra of U(VI)-C-S-H suspensions, recorded with increasing delay times, revealed the presence of four luminescent U(VI) species in C-S-H suspensions, in agreement with the batch sorption data. Along with the aqueous UO(2)(OH)(4)(2-) species and a Ca-uranate precipitate, two different sorbed species were identified which are either bound to silanol groups on the surface or incorporated in the interlayer of the C-S-H structure.

Strontium uptake by cementitious materials.

Wet chemistry experiments and X-ray absorption fine structure (XAFS) measurements were carried out to investigate the immobilization of nonradioactive Sr and 85Sr in calcite-free and calcite-containing Portland cement. The partitioning of pristine Sr between hardened cement paste (HCP) and pore solution, and the uptake of 85Sr and nonradioactive Sr were investigated in batch-type sorption/desorption experiments. Sr uptake by HCP was found to be fast and nearly linear for both cements, indicating that differences in the compositions of the two cements have no influence on Sr binding. The partitioning of pristine Sr bound in the cement matrix and 85Sr between HCP and pore solution could be modeled in terms of a reversible sorption process using similar Kd values. These findings allow 85Sr uptake to be interpreted in terms of an isotopic exchange process with pristine Sr. Sr K-edge EXAFS measurements on Sr doped HCP and calcium silicate hydrate (C-S-H) samples reveal no significant differences in the local coordination environments of pristine Sr and Sr bound to the cement matrix upon sorption. The first coordination sphere consists of five to six oxygen atoms located at a distance of about 2.6 A, which corresponds to Sr-O distances in the hydration sphere of Sr2+ in alkaline solution. Sr binds to the cement matrix via two bridging oxygen atoms located at a distance of about 3.6 A. No further neighboring atoms could be detected, indicating that Sr is taken up as a partially hydrated species by HCP. Wet chemistry and spectroscopic data further indicate that Sr binding to C-S-H phases is likely to be the controlling uptake mechanism in the cement matrix, which allows Sr uptake by HCP to be predicted based on a Ca-Sr ion exchange model previously developed for Sr binding to C-S-H phases. The latter finding suggests that long-term predictions of Sr immobilization in the cementitious near field of repositories for radioactive waste can be based on a simplified sorption model with C-S-H phases.

Uptake of trivalent actinides (curium(III)) by hardened cement paste: a time-resolved laser fluorescence spectroscopy study.

The curium(III) interaction with cement was investigated using time-resolved laser fluorescence spectroscopy at trace concentrations. Four different Cm(III) species were identified: a nonfluorescing species which corresponds to curium hydroxide real colloids, which were characterized in detail by laser-induced breakdown detection (LIBD), a fluorescing Cm(III)/portlandite sorption species, and two fluorescing Cm(III)/calcium silicate hydrate (CSH) species. From the fluorescence emission lifetimes it is predicted that the two fluorescing Cm(III)/CSH species have one to two and no water molecules, respectively, left in their first coordination sphere, suggesting that these species are incorporated into the CSH structure.

Uptake of Cm(III) and Eu(III) by calcium silicate hydrates: a solution chemistry and time-resolved laser fluorescence spectroscopy study.

The interaction of the two chemical homologues [Cm(III) and Eu(III)] with calcium silicate hydrates (CSH phases) at pH 13.3 has been investigated in batch-type sorption studies using Eu(III) and complemented with time-resolved laser fluorescence spectroscopy (TRLFS) using Cm(III). The sorption data for Eu(III) reveal fast sorption kinetics and a strong uptake by CSH phases with distribution ratios of (6 +/- 3) x 10(5) L kg(-1). Three different Cm(III) species have been identified: A nonfluorescing species, which was identified as a curium hydroxide (surface) precipitate, and two fluorescing Cm(III)/CSH-sorbed species. The fluorescing sorbed species have characteristic emission spectra with main peak maxima at 618.9 and 620.9 nm and fluorescence emission lifetimes of 289 +/- 11 and 1482 +/- 200 micros, respectively. From the fluorescence lifetimes, it was calculated that the two fluorescing Cm(III) species have one or two and no water molecules left in their first coordination sphere, suggesting that these species are incorporated into the CSH structure. A structural model for Cm(III) and Eu(III) incorporation into CSH phases is proposed based on the substitution for Ca at two different types of sites in the CSH structure.