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 mol/L), by colorimetric means. Experimental results and thermodynamic considerations presented here, show that Fe(II) oxidation in anaerobic conditions is first-order w.

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.

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.

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).

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.

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.

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).