No abstract

No abstract

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.

No abstract

In this study, the immobilization mechanisms of Sn(IV) onto calcium silicate hydrates (C-S-H) and hardened cement paste (HCP) have been investigated by combining wet chemistry experiments with X-ray absorption spectroscopy (XAS). Evidence is presented which demonstrates the formation of a Sn(IV) inner-sphere surface complex on C-S-H with a CaO/SiO2 weight ratio of 0.7. Two possible structural models, implying a corner sharing between the Sn octahedra and Q1 or Q2b Si tetrahedra, have been developed based on the experimentally determined structural parameters. In HCP, the formation of a different type of Sn(IV) inner-sphere complex has been observed, indicating that C-S-H may not be the uptake-controlling phase for Sn(IV) in the cement matrix. An alternative structural model for Sn(IV) binding in HCP has been developed, assuming that ettringite is the uptake-controlling phase. At high Sn(IV) concentrations, Sn(IV) immobilization in HCP occurs due to the formation of CaSn(OH)6.