Luca Peruzzo

The application of electron backscatter diffraction and orientation contrast imaging in the SEM to textural problems in rocks

Abstract In a scanning electron microscope (SEM) an electron beam sets up an omni-directional source of scattered electrons within a specimen. Diffraction of these electrons will occur simultaneously on all lattice planes in the sample and the backscattered electrons (BSE), which escape from the specimen, will form a diffraction pattern that can be imaged on a phosphor screen. This is the basis of electron backscatter diffraction (EBSD). Similar diffraction effects cause individual grains of different orientations to give different total BSE. SEM images that exploit this effect will show orientation contrast (OC). EBSD and OC imaging are SEM-based crystallographic tools. EBSD enables measurement of the crystallographic orientation of individual rock-forming minerals as small as 1 μm, and the calculation of misorientation axes and angles between any two data points. OC images enable mapping of all misorientation boundaries in a specimen and thus provide a location map for EBSD analyses. EBSD coupled to OC imaging in the SEM enables complete specimen microtextures and mesotextures to be determined. EBSD and OC imaging can be applied to any mineral at a range of scales and enable us to expand the microstructural approach, so successful in studies of quartz rocks, for example, to the full range of rock-forming minerals. Automated EBSD analysis of rocks remains problematic, although continuing technical developments are enabling progress in this area. EBSD and OC are important new tools for petrologists and petrographers. Present and future applications of EBSD and OC imaging include phase identification, studying deformation mechanisms, constraining dislocation slip systems, empirical quantification of microstructures, studying metamorphic processes, studying magmatic processes, and constraining geochemical microsampling. In all these cases, quantitative crystallographic orientation data enable more rigorous testing of models to explain observed microstructures.

Some garnet microstructures: an illustration of the potential of orientation maps and misorientation analysis in microstructural studies

The microstructures of two contrasting garnet grains are mapped using automated electron backscatter diffraction. In both cases there is a very strong crystallographic preferred orientation, with measurements clustered round a single dominant orientation. Each garnet grain is divided into domains with similar orientations, limited by boundaries with misorientations of 2° or more. In both samples most of misorientation angles measured across orientation domain boundaries are significantly lower than those measured between random pairs of orientation domains. One sample is a deformed garnet that shows considerable distortion within the domains. Lines of orientation measurements within domains and across domain boundaries show small circle dispersions around rational crystallographic axes. The domain boundaries are likely to be subgrain boundaries formed by dislocation creep and recovery. The second sample is a porphyroblast in which the domains have no internal distortion and the orientation domain boundaries have random misorientation axes. These boundaries probably formed by coalescence of originally separate garnets. We suggest that misorientations across these boundaries were reduced by physical relative rotations driven by boundary energy. The data illustrate the potential of orientation maps and misorientation analysis in microstructural studies of any crystalline material.

Tetragonal Almandine-Pyrope Phase, TAPP: finally a name for it, the new mineral jeffbenite

Abstract Jeffbenite, ideally Mg3Al2Si3O8, previously known as tetragonal-almandine-pyrope-phase (ʻTAPPʼ), has been characterized as a new mineral from an inclusion in an alluvial diamond from São Luiz river, Juina district of Mato Grosso, Brazil. Its density is 3.576 g/cm3 and its microhardness is ~7. Jeffbenite is uniaxial (-) with refractive indexes ω = 1.733(5) and ε = 1.721(5). The crystals are in general transparent emerald green. Its approximate chemical formula is (Mg2.62Fe2+0.27)(Al1.86Cr0.16)(Si2.82Al0.18)O12 with very minor amounts of Mn, Na and Ca. Laser ablation ICP-MS showed that jeffbenite has a very low concentration of trace elements. Jeffbenite is tetragonal with space group I4̄2d, cell edges being a = 6.5231(1) and c = 18.1756(3) Å. The main diffraction lines of the powder diagram are [d(in Å), intensity, hkl]: 2.647, 100, 2 0 4; 1.625, 44, 3 2 5; 2.881, 24, 2 1 1; 2.220, 19, 2 0 6; 1.390, 13, 4 2 4; 3.069, 11, 2 0 2; 2.056, 11, 2 2 4; 1.372, 11, 2 0 12. The structural formula of jeffbenite can be written as (M1)(M2)2(M3)2(T1)(T2)2O12 with M1 dominated by Mg, M2 dominated by Al, M3 dominated again by Mg and both T1 and T2 almost fully occupied by Si. The two tetrahedra do not share any oxygen with each other (i.e. jeffbenite is classified as an orthosilicate). Jeffbenite was approved as a new mineral by the IMA Commission on New Minerals and Mineral Names with the code IMA 2014-097. Its name is after Jeffrey W. Harris and Ben Harte, two world-leading scientists in diamond research. The petrological importance of jeffbenite is related to its very deep origin, which may allow its use as a pressure marker for detecting super-deep diamonds. Previous experimental work carried out on a Ti-rich jeffbenite establishes that it can be formed at 13 GPa and 1700 K as maximum P-T conditions.

Crystal chemistry of cement-asbestos

Abstract A study of a representative number of cement-asbestos (CA) samples removed from different localities in Italy has been accomplished with a combination of analytical techniques, including XRF, XRPD, SEM/EDS, micro-Raman, and electron backscattered diffraction (EBSD), to elucidate the mineralogical and chemical variability of this class of building materials on a large scale. We describe a complex mineralogy including phases of cement hydration, residual non-hydrated components, and a relevant fraction attributed to various processes of deterioration. With the aid of the CaO-MgOSiO2 compositional diagram, three groups of CAs have been identified on the basis of their chemical parameters. This result is important for environmental and waste management issues

Raberite, Tl5Ag4As6SbS15, a new Tl-bearing sulfosalt from Lengenbach quarry, Binn valley, Switzerland: description and crystal structure

Abstract Raberite, ideally Tl5Ag4As6SbS15, is a new mineral from Lengenbach quarry in the Binn Valley, Valais, Switzerland. It occurs very rarely as euhedral crystals up to 150 μm across associated with yellow needle-like smithite, realgar, hatchite and probable trechmannite, edenharterite, jentschite and two unidentified sulfosalts. Raberite is opaque with a metallic lustre and has a dark brown-red streak. It is brittle with a Vickers hardness (VHN10) of 52 kg mm-2 (range 50-55) corresponding to a Mohs hardness of 2½-3. In reflected light raberite is moderately bireflectant and very weakly pleochroic from light grey to a slightly greenish grey. It is very weakly anisotropic with greyish to light blue rotation tints between crossed polars. Internal reflections are absent. Reflectance percentages for the four COM wavelengths [listed as Rmin, Rmax, (λ)] are 30.6, 31.8 (471.1 nm), 28.1, 29.3 (548.3 nm), 27.1, 28.0 (586.6 nm), and 25.8, 26.9 (652.3 nm). Raberite is triclinic, space group P1̄, with a = 8.920(1), b = 9.429(1), c = 20.062(3) Å, α = 79.66(1), β = 88.84(1), γ = 62.72(1)º, V = 1471.6(4) Å3 and Z = 2. The crystal structure [R1 = 0.0827 for 2110 reflections with I > 2σ(I)] consists of columns of nine-coordinate Tl atoms forming irregular polyhedra extending along [001] and forming sheets parallel to (010). The columns are decorated by corner-sharing MS3 pyramids (M = As, Sb) and linked by AgS3 triangles. Of the seven M positions, one is dominated by Sb and the others by As; the mean M-S bond distances reflect As ↔ Sb substitution at these sites. The eight strongest lines in the powder diffraction pattern [dcalc in Å (I) (hkl)] are: 3.580 (100) (11̄3); 3.506 (58) (1̄2̄3); 3.281 (73) (006); 3.017 (54) (1̄23); 3.001 (98) (133); 2.657 (51) (226); 2.636 (46) (300); 2.591 (57) (330). A mean of 9 electron microprobe analyses gave Tl 39.55(13), Ag 18.42(8), Cu 0.06(2), As 17.08(7), Sb 5.61(6), S 19.15(11); total 99.87 wt.%, which corresponds to Tl4.85Ag4.28Cu0.02As5.72Sb1.16S14.97 with 31 atoms per formula unit. The new mineral has been approved by the IMA-CNMNC Commission (IMA 2012-017) and is named for Thomas Raber, an expert on Lengenbach minerals.

Detection of Calcium Crystals in Knee Osteoarthritis Synovial Fluid: A Comparison Between Polarized Light and Scanning Electron Microscopy.

BackgroundThe identification of calcium crystals in synovial fluid (SF) of patients with osteoarthritis (OA) represents an important step in understanding the role of these crystals in synovial inflammation and disease progression. ObjectivesThis study aimed to investigate the presence of calcium pyrophosphate (CPP) and basic calcium phosphate (BCP) crystals in SF collected from patients with symptomatic knee OA by scanning electron microscopy (SEM) coupled to x-ray energy dispersive spectroscopy, compensated polarized light microscopy (CPLM), and alizarin red staining. MethodsSeventy-four patients with knee OA were included in the study. Synovial fluid samples were collected after arthrocentesis and examined under CPLM for the assessment of CPP crystals. Basic calcium phosphate crystals were evaluated by alizarin red staining. All the samples were examined by SEM. The concordance between the 2 techniques was evaluated by Cohen &kgr; agreement coefficient. ResultsCalcium pyrophosphate and BCP crystals were found, respectively, in 23 (31.1%) and 13 (17.5%) of 74 OA SFs by SEM analysis. Calcium pyrophosphate crystals were identified in 23 (31.1%) of 74 samples by CPLM, whereas BCP crystals were suspected in 27 (36.4%) of 74 samples. According to &kgr; coefficient, the concordance between CPLM and SEM was 0.83 for CPP, and that between alizarin red and SEM was 0.68 for BCP. ConclusionsThe results of our study showed a high level of concordance between the 2 microscope techniques as regards CPP crystal identification and a lower agreement for BCP crystals. Although this finding highlights the difficulty in identifying BCP crystals by alizarin red staining, the use of SEM remains unsuitable to apply in the clinical setting. Because of the in vitro inflammatory effect of BCP crystals, further work on their analysis in SF could provide important information about the OA process.

What drives the distribution in nature of 3T vs. 2M1 polytype in muscovites and phengites? A general assessment based on new data from metamorphic and igneous granitoid rocks

Abstract Petrologic, chemical, and polytype data are presented for dioctahedral potassic micas from Kfeldspar- bearing metamorphic and igneous rocks of acidic composition unaffected by high-pressure (HP) conditions. The paper aims to demonstrate that: (1) under non-HP conditions, in both metamorphic and igneous plutonic environments, a given bulk-rock compositional constraint imposes a more or less marked phengitic composition to dioctahedral potassic mica; and (2) this muscovite crystallizes as 2M1, notwithstanding its phengitic composition. The samples (157 in number) are from widespread provenances. We conclude that the growth of 3T polytype of muscovite is not a function of mica composition. This is consistent with the recent crystallographic knowledge on polytypism, cation ordering, elastic properties, and structural deformational mechanisms of muscovite, which address the stabilization of 3T with pressure.

Deveroite-(Ce): a new REE-oxalate from Mount Cervandone, Devero Valley, Western-Central Alps, Italy

Abstract Deveroite-(Ce), ideally Ce2(C2O4)3·10H2O, is a new mineral (IMA 2013-003) found in the alpine fissures of Mount Cervandone, overlooking the Devero Valley, Piedmont, Italy. It occurs as sprays of colourless elongated tabular, acicular prisms only on cervandonite-(Ce). It has a white streak, a vitreous lustre, is not fluorescent and has a hardness of 2-2.5 (Mohs’ scale). The tenacity is brittle and the crystals have a perfect cleavage along {010}. The calculated density is 2.352 g/cm3. Deveroite-(Ce) is biaxial (-) with 2V of ~77º, is not pleochroic and the extinction angle (β ^ c) is ~27º. No twinning was observed. Electron microprobe analyses gave the following chemical formula: (Ce1.01Nd0.33La0.32Pr0.11Y0.11Sm0.01Pb0.04U0.03Th0.01Ca0.04)2.01(C2O4)2.99·9.99H2O. Although synchrotron radiation was not used to solve the structure of deveroite-(Ce) the extremely small size of the sample (13 μm × 3 μm× 1 μm) did not allow us to obtain reliable structural data. However, it was possible to determine the space group (monoclinic, P21/c) and the unit-cell parameters, which are: a = 11.240(8) Å, b = 9.635(11) Å, c = 10.339(12) Å, β = 114.41(10)º, V = 1019.6 Å3. The strongest lines in the powder diffraction pattern [d in Å (I)(hkl)] are: 10.266(100)(100); 4.816(35.26)(211̄); 3.415(27.83)(300); 5.125(24.70)(200); and 4.988(22.98)(111). Deveroite-(Ce) is named in recognition of Devero valley and Devero Natural Park.

Electron Backscatter Diffraction in Conservation Science: Phase Identification of Pigments in Paint Layers

Electron backscatter diffraction (EBSD) was used in Conservation Science for characterization of ancient materials collected from works of art. The results demonstrate the feasibility of EBSD analysis on heterogeneous matrices as very small samples of paint layers collected from paintings. Two reference pigments were selected from those used by artists to investigate the relationship existing between EBSD pattern quality and properties of the investigated material (i.e., average atomic number, density, and Mohs hardness). The technique was also tested to investigate the pigment phases on two real samples collected from Romaninos Santa Giustina altarpiece, an oil on wood painting dated 1514 (Civic Museum, Padova, Italy). Results show for the first time the acquisition of EBSD patterns from painting samples mounted in resin, i.e., painting cross sections, opening a new powerful tool to elucidate the pigment phases avoiding large sampling on works of arts and to further study the complex mechanisms of pigment deterioration.

Three-dimensional distribution of primary melt inclusions in garnets by X-ray microtomography

Abstract X-ray computed microtomography (X-μCT) is applied here to investigate in a non-invasive way the three-dimensional (3D) spatial distribution of primary melt and fluid inclusions in garnets from the metapelitic enclaves of El Hoyazo and from the migmatites of Sierra Alpujata, Spain. Attention is focused on a particular case of inhomogeneous distribution of inclusions, characterized by inclusion-rich cores and almost inclusion-free rims (i.e., zonal arrangement), that has been previously investigated in detail only by means of 2D conventional methods. Different experimental X-μCT configurations, both synchrotron radiation- and X-ray tube-based, are employed to explore the limits of the technique. The internal features of the samples are successfully imaged, with spatial resolution down to a few micrometers. By means of dedicated image processing protocols, the lighter melt and fluid inclusions can be separated from the heavier host garnet and from other non-relevant features (e.g., other mineral phases or large voids). This allows evaluating the volumetric density of inclusions within spherical shells as a function of the radial distance from the center of the host garnets. The 3D spatial distribution of heavy mineral inclusions is investigated as well and compared with that of melt inclusions. Data analysis reveals the occurrence of a clear peak of melt and fluid inclusions density, ranging approximately from ⅓ to ½ of the radial distance from the center of the distribution and a gradual decrease from the peak outward. Heavy mineral inclusions appear to be almost absent in the central portion of the garnets and more randomly arranged, showing no correlation with the distribution of melt and fluid inclusions. To reduce the effect of geometric artifacts arising from the non-spherical shape of the distribution, the inclusion density was calculated also along narrow prisms with different orientations, obtaining plots of pseudo-linear distributions. The results show that the core-rim transition is characterized by a rapid (but not step-like) decrease in inclusion density, occurring in a continuous mode. X-ray tomographic data, combined with electron microprobe chemical profiles of selected elements, suggest that despite the inhomogeneous distribution of inclusions, the investigated garnets have grown in one single progressive episode in the presence of anatectic melt. The continuous drop of inclusion density suggests a similar decline in (radial) garnet growth, which is a natural consequence in the case of a constant reaction rate. Our results confirm the advantages of high-resolution X-μCT compared to conventional destructive 2D observations for the analysis of the spatial distribution of micrometer-scale inclusions in minerals, owing to its non-invasive 3D capabilities. The same approach can be extended to the study of different microstructural features in samples from a wide variety of geological settings.