The long-lived fission product 126Sn (105 years) (Weast (1972)) is of substantial interest in the context of nuclear waste disposal in deep underground repositories. However, the prevalent redox state, the aqueous speciation as well as the reactions at the mineral-water interface under the expected anoxic conditions are a matter of debate. Therefore, in this PhD thesis I present work on the reactions of SnII with three Fe-bearing minerals as a function of pH, time, and SnII loading under anoxic condition with O2 level < 2 ppmv. The first mineral, goethite, contains only trivalent Fe (FeIIIOOH), the second, magnetite, contains both FeII and FeIII (FeIIFeIII2O4), and the third, mackinawite (FeIIS), contains only divalent Fe.
The uptake behavior of the three mineral surfaces was investigated by batch sorption studies. Tin redox state was investigated by Sn-K X-ray absorption near-edge structure (XANES) spectroscopy, and the local, molecular structure of the expected Sn surface complexes and precipitates was studied by extended X-ray absorption fine-structure (EXAFS) spectroscopy. Selected samples were also investigated by transmission electron microscopy (TEM) to elucidate the existence and nature of secondary, Fe- and /or Sn containing solids, and by Mössbauer spectroscopy to study FeII and FeIII in the minerals. Based on the such-obtained molecular-level information, surface complexation models (SCM) were fitted to the batch sorption data to derive surface complexation constants.
In the presence of the FeIII-bearing minerals magnetite and goethite, I observed a rapid uptake and oxidation of SnII to SnIV. The local structure determined by EXAFS showed two Sn-Fe distances of about 3.15 and 3.60 Å in line with edge and corner sharing arrangements between octahedrally coordinated SnIV and the Fe(O,OH)6 octahedra at the magnetite and goethite surfaces. While the respective coordination numbers suggested formation of tetradentate inner-sphere complexes between pH 3 and 9 for magnetite, bidentate inner-sphere complexes (single edge-sharing (1E) and corner-sharing (2C)) prevail at the goethite surface at pH > 3, with the relative amount of 2C increasing with Sn loading.
The interfacial electron transfer between sorbed SnII and structural FeIII potentially leads to dissolution of FeII and transformation to secondary FeII/FeIII oxide minerals. There is no clear evidence to confirm the reductive dissolution in the Sn/ magnetite system, Rietveld refinement of XRD patterns, however, indicates an increase of FeII/FeIII ratio in the magnetite structure. For the Sn/goethite system, dissolved FeII increased with SnII loading at the lowest pH investigated, indicative of reductive dissolution. At pH >5, spherical and cubic particles of magnetite were observed by TEM, and their number increased with SnII loading. Based on previous finding, this secondary mineral transformation of goethite should proceed via dissolution and recrystallization.
The molecular structure and oxidation state of sorbed Sn were then used to fit the batch sorption data of magnetite and goethite with SCM. The sorption data on magnetite were fit with the diffuse double layer model (DLM) employing two different complexes, the first ( = -14.97±0.35) prevailing from pH 2 to 9, and the second ( = -17.72±0.50), which forms at pH > 9 by co-adsorption of FeII, thereby increasing sorption at this high pH. The sorption data on goethite were fitted with the charge distribution–multisite complexation model (CD-MUSIC). Based on the EXAFS-derived presence of two different bidentate inner-sphere complexes ((≡FeOH)(≡Fe3O)Sn(OH)3 (1E) and (≡FeOH)2Sn(OH)3) (2C)), sorption affinity constants of 15.5 ±1.4 for the 1E complex and of 19.2 ±0.6 for the 2C complex were obtained. The model is not only able to predict sorption across the observed pH range, but also the transition from a roughly 50/50 distribution of the two complexes at 12.5 µmol/g Sn loading, to the prevalence of the 2C complex at higher loading, in line with the EXAFS data.
The retention mechanism of SnII by mackinawite is significantly dependent on the solution pH, reflecting the transient changes of the mackinawite surface in the sorption process. At pH <7, SnII is retained in its original oxidation state. It forms a surface complex, which is characterized by two short (2.38 Å) Sn-S bonds, which can be interpreted as the bonds towards the S-terminated surface of mackinawite, and two longer Sn-S bonds (2.59 Å), which point most likely towards the solution phase, completing the tetragonal SnS4 innersphere sorption complex. Precipitation of SnS or formation of a solid solution with mackinawite could be excluded. At pH > 9, SnII is completely oxidized by an FeII/FeIII (hydr)oxide, most likely green rust, forming on the surface of mackinawite. Six O atoms at 2.04 Å and 6 Fe atoms at 3.29 Å demonstrate a structural incorporation by green rust, where SnIV substitutes for Fe in the crystal structure. The transition between SnII and SnIV and between sulfur and oxygen coordination takes place between pH 7 and 8, in accordance with the transition from the mackinawite stability field to more oxidized Fe-bearing minerals. The uptake processes of SnII by mackinawite are largely in line with the uptake processes of divalent cations of other soft Lewis-acid metals like Cd, Hg and Pb.
Very different Sn retention mechanisms were hence active, including oxidation to SnIV and formation of tetradentate and bidentate surface complexes of the SnIV hydroxo moieties on goethite and magnetite, and in the case of mackinawite a SnII sulfide species forming a bidentate surface complex at low pH, and structural incorporation of SnIV by an oxidation product, green rust, at high pH. In all three mineral systems and largely independent on the retention mechanisms, inorganic SnII was strongly retained, with Rd values always exceeding 5, across the relatively wide pH range relevant for the near and far-field of nuclear waste respositories. For the goethite and magnetite systems, the retention could be well modeled with surface complexation models based on the molecular structural data. This is an important contribution to the safety case for future nuclear waste repositories, since such SCMs provide reliable means for predicting the radioactive dose released by 126Sn from nuclear waste into the biosphere across a wide range of physicochemical conditions typical for the engineered as well as natural barriers.
| Identifer | oai:union.ndltd.org:DRESDEN/oai:qucosa.de:bsz:14-qucosa-175316 |
| Date | 28 July 2015 |
| Creators | Dulnee, Siriwan |
| Contributors | Technischen Universität Dresden, Fakultät Mathematik und Naturwissenschaften, Dr. Andreas Scheinost, Prof. Dr. Eckhard Worch, Prof. Dr. Gert Bernhard |
| Publisher | Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden |
| Source Sets | Hochschulschriftenserver (HSSS) der SLUB Dresden |
| Language | English |
| Detected Language | English |
| Type | doc-type:doctoralThesis |
| Format | application/pdf |
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