Effect of solution composition on the recrystallization of kaolinite to feldspathoids in hyperalkaline conditions: limitations of pertechnetate incorporation by ion competition effects

The incorporation of pertechnetate (TcO4–) into feldspathoids produced by alkaline alteration of aluminosilicate clays may offer a potential treatment route for 99Tc-containing groundwater and liquors. Kaolinite was aged in NaOH to determine the effect of base concentration, temperature, and solution composition on mineral transformation and pertechnetate uptake. In all reactions, increased temperature and NaOH concentration increased the rate of kaolinite transformation to feldspathoid phases. In reactions containing only NaOH, sodalite was the dominant alteration product; however, small amounts (6–15%) of cancrinite also formed. In experiments containing NaOH/Cl and NaOH/NO3 mixtures, sodalite and nitrate cancrinite were crystallized (at 70°C), with no reaction intermediates. The addition of SO42– crystallized sulfatic sodalite at 40 and 50°C, but at higher temperatures (60 and 70°C) sulfatic sodalite transforms to vishnevite (sulfatic cancrinite). In experiments where a pertechnetate tracer was added (at ∼1.5 μmol l–1), only 3–5% of the 99Tc was incorporated into the feldspathoid phases. This suggests that the larger pertechnetate anion was unable to compete as favourably for the internal vacancies with the smaller OH–, NO3–, SO42– or Cl– anions in solution, making this method likely to be unsuitable for groundwater treatment.

On the Use of the Unusual Green Pigment Brochantite (Cu4(SO4)(OH)6) in the 16th-Century Portuguese-Flemish Paintings Attributed to The Master Frei Carlos Workshop

This paper reports an unusual green pigment, brochantite (Cu4(SO4)(OH)6), on 16th-century Portuguese-Flemish paintings, attributed to the Master Frei Carlos workshop. This green mineral is usually identified as an impurity or alteration product in the green pigments verdigris (Cu(CH3COO)2nCu(OH)2) or malachite (CuCO3 Cu(OH)2). However, after thorough investigation with a broad range of analytical techniques, it became clear that, in this case, brochantite was applied as a pigment. The abundance, pigment granulometry, and pigment morphology suggest intentional use by this Portuguese-Flemish Master as a natural pigment rather than its accidental use as an alteration product. This seems to be a distinguishable feature to other painters (Flemish and Portuguese) working in Portugal at the beginning of the 16th century.The multi-analytical study of these easel paintings was first performed by physical imaging techniques and material characterization was carried out by optical microscopy, micro-Fourier-transform infrared-spectroscopy, micro-Raman spectroscopy, scanning electron microscopy coupled with energy dispersive X-ray spectrometry, and micro-X-ray diffraction analysis (XRD).

Two-stage formation of kaolinite in shear-zone slates, southern Iberian Massif, SE Spain

Kaolinite aggregates are the major alteration product in the strongly deformed areas of a shear zone developed in contact-metamorphosed slates from the Southern Iberian Massif near Jaén (SE Spain). Muscovite and Fe-rich chlorite in strain shadows of broken andalusite crystals were observed in slates from less deformed areas. The presence of phyllosilicate packets nearly perpendicular to each other and veinlets parallel to {110} of andalusite reveal the importance of cleavage-controlled fracturing of andalusite to the mineral reactions. The compositional similarity between kaolinite and andalusite suggests a direct transformation of andalusite to kaolinite in the strongly altered area. The absence of clear preferred orientation of phyllosilicates relative to andalusite, and the compositional differences of andalusite with muscovite and chlorite from the less altered samples, indicate andalusite dissolution and chlorite-muscovite precipitation during a first mineral-growth stage. Muscovite-kaolinite and chlorite-kaolinite intergrowths indicate a later retrograde replacement stage.

Hydrotalcite Formed by Alteration of R7T7 Nuclear Waste Glass and Basaltic Glass in Salt Brine at 190°C

ABSTRACTThe R7T7 and synthetic basaltic glasses were submitted to corrosion in a saline MgCl2dominated solution at 190°C. For both glasses, the early alteration product is a hydrotalcite-like compound in which HPO42-, SO4-2and Cl-substitutes to CO32. The measured d003spacing is 7.68 Å for the hydrotalcite formed from R7T7 glass and 7.62 Å for the hydrotalcite formed from basaltic glass which reflect the high aluminium content. Chemical microanalyses show that the hydrotalcite is subsequently covered by a silica-rich gel which evolves into saponite after few months.