Spectroscopic Investigation of Ni Speciation in Hardened Cement Paste

Laboratory for Waste Management (LES), Paul Scherrer Institut, Aargau, Switzerland
Environmental Science and Technology (Impact Factor: 5.33). 05/2006; 40(7):2275-82. DOI: 10.1021/es052240q
Source: PubMed


Cement-based materials play an important role in multi-barrier concepts developed worldwide for the safe disposal of hazardous and radioactive wastes. Cement is used to condition and stabilize the waste materials and to construct the engineered barrier systems (container, backfill, and liner materials) of repositories for radioactive waste. In this study, Ni uptake by hardened cement paste has been investigated with the aim of improving our understanding of the immobilization process of heavy metals in cement on the molecular level. X-ray absorption spectroscopy (XAS) coupled with diffuse reflectance spectroscopy (DRS) techniques were used to determine the local environment of Ni in cement systems. The Ni-doped samples were prepared at two different water/cement ratios (0.4, 1.3) and different hydration times (1 hour to 1 year) using a sulfate-resisting Portland cement. The metal loadings and the metal salts added to the system were varied (50 up to 5000 mg/kg; NO3(-), SO4(2-), Cl-). The XAS study showed that for all investigated systems Ni(ll) is predominantly immobilized in a layered double hydroxide (LDH) phase, which was corroborated by DRS measurements. Only a minor extent of Ni(ll) precipitates as Ni-hydroxides (alpha-Ni(OH)2 and beta-Ni(OH)2). This finding suggests that Ni-Al LDH, rather than Ni-hydroxides, is the solubility-limiting phase in the Ni-doped cement system.

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    • "In the case of Ni spot 3, the LC analysis indicate that predominantly Ni–Al LDH has formed (∼ 70%) together with some β-Ni(OH) 2 (∼30%). Comparison of further LC analysis, previously carried out for Ni bulk-XAS measurements [22], with the data from this study indicate that the Ni species observed on the micro-scale are relevant for the whole cement matrix. This comparison between bulk-and micro-XAS results is compulsory to assess the relevance of the speciation determined on the micro-scale. "
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    ABSTRACT: Synchrotron-based micro-X-ray fluorescence (XRF) combined with scanning electron microscopy-based energy dispersive micro-analysis (EDS) has been used to determine the elemental distribution of contaminants (e.g., Ni) and of chemical elements inherent to the cement matrix (e.g., Si, Ca, Al, S) in hardened cement paste. Detailed information on the cement microstructure was gained by using backscattered electron (BSE) imaging. The results obtained from the complementary use of micro-XRF, EDS and BSE reveal that Ni is primarily distributed around inner calcium silicate hydrates (inner-C-S-H) and that Ni is preferentially associated with Al. This suggests the formation of a Ni–Al phase and its direct association with inner-C-S-H. Further information on the chemical speciation of Ni in relation to Al and S was obtained at selected regions of interests in the cement matrix using synchrotron-based micro-X-ray absorption spectroscopy (XAS). Data analysis shows that Ni is predominantly immobilized in layered double hydroxides, while predominant formation of ettringite was indicated from the Al and S XAS data.The present study demonstrates that the combined use of micro-XRF, BSE, EDS and micro-XAS, opens up a powerful analytical approach to determine the distribution and the speciation of chemical elements in complex heterogeneous cementitious materials on the same region of interest with micro-scale resolution.
    Full-text · Article · Nov 2007 · Cement and Concrete Research
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    • "e Vespa et al. (2006) "
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    ABSTRACT: Cement is used to condition waste materials and for the construction and backfilling of repositories for low-and intermediate-level radioactive waste. In this study, Ni uptake by hardened cement paste has been investigated with the aim of improving our understanding of the immobilization process of Ni(ll) in cement on the microscale. Information on the cement microstructure, Ni distribution, Ni concentration, and speciation of the Ni phases formed in the cement system and their association with specific cement minerals has been gained by using scanning electron microscopy (SEM) and synchrotron-based micro-X-ray fluorescence (micro-XRF) and micro-X-ray absorption spectroscopy (micro-XAS). The Ni-doped samples were prepared at a water/cement ratio of 0.4 using a sulfate-resisting Portland cement and were hydrated for 30 days. The metal loadings of the system were varied from 50 up to 5000 mg/kg. SEM investigations show that for all metal loadings the Ni phases form rims around inner-calcium silicate hydrates, suggesting a direct association with this cement phase. The micro-XAS measurements further reveal that a mixture of Ni phases form at Ni-enriched regions. Data analysis indicates that Ni(ll) is predominantly immobilized in a layered double hydroxide-type phase (Ni-Al LDH) and only to a minor extent precipitates as Ni-hydroxides (alpha-Ni(OH)2 and beta-Ni(OH)2). At 50 mg/kg Ni loading, however, the p-XAS measurements suggest the presence of an additional Ni species. In the latter system Ni-Al LDH is found in Ni-rich regions, whereas at Ni-poor regions an unknown species is formed.
    Full-text · Article · Jan 2007 · Environmental Science and Technology
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