In this paper, we propose an analytical methodology for attributing provenance to natural lapis lazuli pigments employed in works of art, and for distinguishing whether they are of natural or synthetic origin. A multitechnique characterization of lazurite and accessory phases in lapis lazuli stones from Afghan, Siberian and Chilean quarries, on the pigments obtained by their purification, and on synthetic ultramarine pigments was performed. According to the results obtained, infrared spectroscopy is not a suitable technique for distinguishing the provenance of lapis lazuli, but a particular absorbance band makes it relatively easy to determine whether it is of natural or synthetic origin. On the other hand, EDS elemental composition and XRD patterns show the presence of specific mineral phases associated with specific lapis lazuli sources, and can be used to distinguish the provenance of the stones as well as-albeit to a lesser extent-the corresponding purified blue pigments. In contrast, FEG-SEM observations clearly show different stone textures depending on their provenance, although these distinctive features do not persist in the corresponding pigments. PCA analyses of EDS data allow Afghan lapis lazuli stone to be distinguished from Chilean and Siberian ones, and can distinguish between the pigments resulting from their purification as well as synthetic blue ones. Although this methodology was developed using a limited number of samples, it was tested on lapis lazuli pigments collected from three paintings (from the fourteenth to sixteenth centuries) in order to perform a preliminary validation of the technique, and based on the results, the provenance of the blue pigments employed in those artworks is proposed. Finally, upon analytically monitoring the process of purifying lapis lazuli to obtain the corresponding pigments, it was found that ion-exchange reactions occur between the alkali modifiers of silicate/aluminosilicate phases and free carboxylic acids present in the doughy mixture of natural terpenes and ground stone, namely pastello. These reactions favor (i) the retention of silicate phases in the organic mixture and (ii) the selective extraction of lazurite due to the formation of Brønsted acidic sites [Al(OH)Si], which are responsible for its high hydrophilicity in comparison to the one of the other species present in the lapis lazuli stone.

Colemanite (ideally CaB3O4(OH)3·H2O, space group P21/a, unit‐cell parameters: a ~ 8.74, b ~ 11.26, c ~ 6.10 Å, β ~ 110.1°) is one of the principal mineralogical components of borate deposits and the most important mineral commodity of boron. Its high‐pressure behavior is here described, for the first time, by means of in situ single‐crystal synchrotron X‐ray diffraction with a diamond anvil cell up to 24 GPa (and 293 K). Colemanite is stable, in its ambient‐conditions polymorph, up to 13.95 GPa. Between 13.95 and 14.91 GPa, an iso‐symmetric first‐order single‐crystal to single‐crystal phase transition (reconstructive in character) toward a denser polymorph (colemanite‐II) occurs, with: aCOL‐II=3·aCOL, bCOL‐II=bCOL, and cCOL‐II=2·cCOL. Up to 13.95 GPa, the bulk compression of colemanite is accommodated by the Ca‐polyhedron compression and the tilting of the rigid three‐membered rings of boron polyhedra. The phase transition leads to an increase in the average coordination number of both the B and Ca sites. A detailed description of the crystal structure of the high‐P polymorph, compared to the ambient‐conditions colemanite, is given. The elastic behaviors of colemanite and of its high‐P polymorph are described by means of III‐ and II‐order Birch‐Murnaghan equations of state, respectively, yielding the following refined parameters: KV0=67(4) GPa and KV′=5.5(7) [βV0=0.0149(9) GPa−1] for colemanite; KV0=50(8) GPa [βV0=0.020(3) GPa−1] for its high‐P polymorph.

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The crystal chemistry of two dimorphic hydrated sodium beryllium silicates, epididymite [a = 12.7334(4), b = 13.6298(5), c = 7.3467(3) Å, V = 1275.04 Å 3 , space group Pnma)] and eudidymite [a = 12.6188(10), b = 7.3781(5), c = 13.9940(9) Å, β = 103.762(5)°, V = 1265.47 Å 3 , space group C2/c] from Malosa, Malawi, has been reinvestigated by means of energy dispersive X-ray spectroscopy, thermo-gravimetric analysis, inductively coupled plasma-optical emission spectroscopy and single-crystal neutron diffraction. Two anisotropic structure refinements have been performed with final agreement index R 1 = 0.0317 for 137 refined parameters and 2261 unique reflections with F o > 4σ(F o ) for epididymite, and R 1 = 0.0478 for 136 refined parameters and 1732 unique reflections with F o > 4σ(F o ) for eudidymite. The analysis of the difference-Fourier maps of the nuclear density of the two dimorphs confirms the presence of extra-framework water molecules in both, and not hydroxyl groups as wrongly reported in previous studies and in several crystal-structure databases. The correct chemical formula of edipidymite and eudidymite is Na 2 Be 2 Si 6 O 15 ·H 2 O (Z = 4). The configuration of the water molecules and the hydrogen bonds are fully described for both the dimorphs. The chemical analyses show that a small, but significant, amount of Al and Fe (most likely substituting for Si in the tetrahedral sites) and K (substituting for Na as an extra-framework cation) occurs in both dimorphs.

Colemanite, CaB3O4(OH)3H2O, is the most common hydrous Ca-borate, as well as a major mineral commodity of boron. In this study, we report a thorough chemical analysis and the low-temperature behavior of a natural sample of colemanite, by means of a multi-methodological approach. From the chemical point of view, the investigated sample resulted to be relatively pure, its composition being very close to the ideal one, with only a minor substitution of Sr 2+ for Ca 2+ . At about 270.5 K a displacive phase transition from the centrosymmetric P21/a to the acentric P21 space group occurs.On the basis of in situ single-crystal synchrotron X-ray (down to 104 K) and neutron diffraction (at 20 K) data, the hydrogen-bonding configuration of both the polymorphs and the structural modifications at the atomic scale at varying temperatures are described. The asymmetric distribution of ionic charges along the [010] axis, allowed by the loss of the inversion center, is likely responsible for the reported ferroelectric behavior of colemanite below the phase transition temperature.

Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. AbSTRACTThe largest field of Alpine Oligocene pegmatite dikes is in the Central Alps within the Southern Steep Belt (SSB) of the Alpine nappes; it extends for about 100 km in an E-W direction and 15 km in a N-S direction north of the Periadriatic Fault, from the Bergell pluton (to the east) to the Ossola valley (to the west). The pegmatite field geographically overlaps (1) the highest temperature domain of the Lepontine Barrovian metamorphic dome and (2) the zone of Alpine migmatization. We have studied pegmatites in two areas: (1) the Codera area on the western border of the Bergell pluton and (2) the Bodengo area between the Mera and the Mesolcina valleys. Most pegmatites show a simple mineral assemblage consisting of K-feldspar, quartz, and muscovite ± biotite, and only a minor percentage of the dikes (< 5%) contains Sn-Nb-Ta-Y-REE-U oxide, Y-REE phosphate, Mn-Fe-phosphate, Ti-Zr-silicate, Be-Y-REE-U-silicate and oxide minerals (beryl, chrysoberyl, bertrandite, bavenite, and milarite), garnet (almandine-spessartine), tourmaline (schorl to rare elbaite), bismuthinite, magnetite, and rarely dumortierite and helvite. The mineral assemblages, geological context, and chemical compositions allow the distinction between LCT (lithium, cesium, tantalum) and mixed LCT-NYF (niobium, yttrium, fluorine) pegmatites (with only one exception of an NYF dike in the Bodengo area). The LCT pegmatites of the Central Alps did not reach a high degree of geochemical evolution. The most fractionated pegmatites are found in the Codera area and contain Mn-rich elbaite, triplite, pink-beryl, and Cs-Rb-rich feldspar. In the Bodengo area pegmatites locally contain miarolitic cavities and the most evolved pegmatites correspond to the berylcolumbite-phosphate type. From a structural point of view two main types of pegmatites can be distinguished: (1) pegmatites that were involved in ductile deformation and (2) pegmatites that postdated the main ductile deformation of the SSB. Many pegmatites of the Codera valley belong to the first structural type: they were emplaced at relatively high ambient temperature (ca. 500 °C) and locally show a pervasive recrystallization of quartz and a mylonitic structure. The Codera dikes trend about 70° and are steeply dipping. In the Bodengo area the main set of pegmatites (trending approximately N-S to NNE-SSW) crosscuts the ductile deformation structures of the SSB, but the area also includes an earlier generation of boudinaged and folded pegmatite dikes. The undeformed ...

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Dalnegroite, ideally Tl4Pb2(As12Sb8)Σ20S34, is a new mineral from Lengenbach, Binntal, Switzerland. It occurs as anhedral to subhedral grains up to 200 μm across, closely associated with realgar, pyrite, Sb-rich seligmanite in a gangue of dolomite. Dalnegroite is opaque with a submetallic lustre and shows a brownish-red streak. It is brittle; the Vickers hardness (VHN25) is 87 kg mm-2(range: 69—101) (Mohs hardness ∼3—3½). In reflected light, dalnegroite is highly bireflectant and weakly pleochroic, from white to a slightly greenish-grey. In cross-polarized light, it is highly anisotropic with bluish to green rotation tints and red internal reflections.According to chemical and X-ray diffraction data, dalnegroite appears to be isotypic with chabournéite, Tl5-xPb2x(Sb,As)21-xS34. It is triclinic, probable space groupP1, witha= 16.217(7) Å,b= 42.544(9) Å,c= 8.557(4) Å, α = 95.72(4)°, β = 90.25(4)°, γ = 96.78(4)°,V= 5832(4) Å3,Z= 4.The nine strongest powder-diffraction lines [d(Å) (I/I0) (hkl)] are: 3.927 (100) (10 0); 3.775 (45) (22); 3.685 (45) (60); 3.620 (50) (440); 3.124 (50) (2); 2.929 (60) (42); 2.850 (70) (42); 2.579 (45) (02); 2.097 (60) (024). The mean of 11 electron microprobe analyses gave elemental concentrations as follows: Pb 10.09(1) wt.%, Tl 20.36(1), Sb 23.95(1), As 21.33(8), S 26.16(8), totalling 101.95 wt.%, corresponding to Tl4.15Pb2.03(As11.86Sb8.20)S34. The new mineral is named for Alberto Dal Negro, Professor in Mineralogy and Crystallography at the University of Padova since 1976.