Petr Gadas

Elemental mapping in fossil tooth root section of Ursus arctos by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to map the matrix (Ca, P) and trace (Ba, Sr, Zn) elements in the root section of a fossilized brown bear (Ursus arctos) tooth. Multielemental analysis was performed on a (2.5 × 1.5)cm(2) area. For elemental distribution, a UP 213 laser ablation system was coupled either with a quadrupole or a time of flight ICP-MS. The cementum and dentine on the slice of the sample surface were clearly distinguishable, especially changes in elemental distribution in the summer and winter bands in the fossil root dentine. Migration and diet of U. arctos were determined on the basis of fluctuations in Sr/Zn ratio and their contents. Quantification was accomplished with standard reference material of bone meal (NIST 1486) and by the use of electron microprobe analysis (EMPA). Changes in Sr/Zn and Sr/Ba ratios relating to the season, and composition of food during the lifetime of the animal are discussed on basis of analysis of light stable isotopes. It was observed that there was an increase in the Sr/Zn ratio during the winter season caused by a reduction of food intake during hibernation. Above mentioned inferences drawn from elemental data obtained by LA-ICP-MS were confirmed independently by determination of carbon, nitrogen and strontium isotopes. Moreover, diagenesis and its interfering influence on the biogenic composition of cementum and dentine were resolved. According to the distribution and/or content of the element of interest, post-mortem alterations were revealed. Namely, U, Na, Fe, Mg and F predicate about the suitability of the selected area for determination of migration and diet.

Darrellhenryite, Na(LiAl2)Al6(BO3)3Si6O18(OH)3O, a new mineral from the tourmaline supergroup

Abstract Darrellhenryite, Na(LiAl2)Al6(BO3)3Si6O18(OH)3O, a new member of the tourmaline supergroup (related to the alkali-subgroup 4), is a new Li-bearing tourmaline species, which is closely related to elbaite through the substitution YAlW 0.5O1YLiW -0.5(OH)-1. It occurs in a complex (Li-bearing) petalite-subtype pegmatite with common lepidolite, Li-bearing tourmalines, and amblygonite at Nová Ves near Český Krumlov, southern Bohemia, Moldanubian Zone, Czech Republic. This zoned pegmatite dike cross-cuts a serpentinite body enclosed in leucocratic granulites. Pink darrellhenryite forms columnar crystals (sometimes in parallel arrangement) up to 3 cm long and up 2 cm thick, associated with albite (var. cleavelandite), minor quartz, K-feldspar, petalite, rare polylithionite, and locally rare pollucite. The optical properties and the single-crystal structure study (R1 = 0.019) of darrellhenryite are consistent with trigonal symmetry, w = 1.636(2), e = 1.619(2), birefringence: 0.017, space group R3m, a = 15.809(2), c = 7.089(1) Å, V = 1534.4(4) Å3, and Z = 3. The chemical analysis, in combination with the results from the single-crystal structure refinement, gives the formula X(Na0.58Ca0.01□0.41)1.00Y(Li1.05Al1.95)3.00ZAl6 (BO3)3T(Si6O18) V(OH)3W(O0.66F0.34)1.00, which can be simplified to an ideal formula of Na(LiAl2) Al6(BO3)3Si6O18(OH)3O. The strongest lines of the powder pattern [d in Å (I, hkl)] are 4.180 (39, 211), 3.952 (54, 220), 3.431 (73, 012), 2.925 (100, 122), 2.555 (90, 051), 2.326 (42, 511), 2.029 (42, 223), 2.021 (42, 152), 1.901 (50, 342), 1.643 (49, 603). The density is Dmeas = 3.03(3) g/cm3, Dcalc = 3.038 g/ cm3. Darrellhenryite is considered to have crystallized in Li- and B-rich but F-moderate environments in complex pegmatites; no influence of higher activity of O on the darrellhenryite formation is implied from its mineral assemblage. The name is for Darrell J. Henry, Professor of Geology at the Louisiana State University, Baton Rouge, U.S.A., an expert on the mineralogy, petrology, crystal chemistry, and nomenclature of tourmaline-supergroup minerals.

Lucchesiite, CaFe2+3Al6(Si6O18)(BO3)3(OH)3O, a new mineral species of the tourmaline supergroup

Abstract Lucchesiite, CaFe2+3 Al6(Si6O18)(BO3)3(OH)3O, is a new mineral of the tourmaline supergroup. It occurs in the Ratnapura District, Sri Lanka (6°35′N, 80°35′E), most probably from pegmatites and in Mirošov near Strážek, western Moravia, Czech Republic, (49°27′49.38″N, 16°9′54.34″E) in anatectic pegmatite contaminated by host calc-silicate rock. Crystals are black with a vitreous lustre, conchoidal fracture and grey streak. Lucchesiite has a Mohs hardness of ∼7 and a calculated density of 3.209 g/cm3 (Sri Lanka) to 3.243 g/cm3 (Czech Republic). In plane-polarized light, lucchesiite is pleochroic (O = very dark brown and E = light brown) and uniaxial (-). Lucchesiite is rhombohedral, space group R3m, a ≈ 16.00 Å, c ≈ 7.21 Å, V ≈ 1599.9 Å3, Z = 3. The crystal structure of lucchesiite was refined to R1 ≈ 1.5% using ∼2000 unique reflections collected with MoKα X-ray intensity data. Crystal-chemical analysis for the Sri Lanka (holotype) and Czech Republic (cotype) samples resulted in the empirical formulae, respectively: X(Ca0.69Na0.30K0.02)Σ1.01Y(Fe2+1.44Mg0.72Al0.48Ti4+0.33V3+0.02Mn0.01Zn0.01)Σ3.00Z(Al4.74Mg1.01Fe3+0.25)Σ6.00 [T(Si5.85Al0.15)Σ6.00O18](BO3)3V(OH)3W[O0.69F0.24(OH)0.07]Σ1.00 and X(Ca0.49Na0.45□0.05K0.01)Σ1.00Y(Fe2+1.14Fe3+0.95Mg0.42Al0.37Mn0.03Ti4+0.08Zn0.01)Σ3.00Z(Al5.11Fe3+0.38Mg0.52)Σ6.00[T(Si5.88Al0.12)Σ6.00O18] (BO3)3V[(OH)2.66O0.34]Σ3.00W(O0.94F0.06)Σ1.00. Lucchesiite is an oxy-species belonging to the calcic group of the tourmaline supergroup. The closest end-member composition of a valid tourmaline species is that of feruvite, to which lucchesiite is ideally related by the heterovalent coupled substitution ZAl3+ + O1O2- ↔ ZMg2+ + O1(OH)1-. The new mineral was approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA 2015-043).

Compositional evolution of grossular garnet from leucotonalitic pegmatite at Ruda nad Moravou, Czech Republic; a complex EMPA, LA-ICP-MS, IR and CL study

Five distinct paragenetic, morphological and compositional types of grossular garnet (G1, G2, G3, G4, G5) were distinguished within the individual (sub)units of the zoned leucotonalitic pegmatite cutting serpentinized lherzolite with rodingite dikes at Žďár near Ruda nad Moravou, Staré Město Unit, Northern Moravia. Detailed study using Electron Microprobe Analysis, Laser Ablation Inductively Coupled Plasma Mass Spectrometry, Cathodoluminiscence and Infrared Spectroscopy revealed distinct compositional trends in major, minor and trace elements. The contents of Fe3+, Mn, Mg and Ti increase from early garnet (G1) in the outermost grossular subunit through the interstitial garnet (G2) in the leucocratic subunit to graphic intergrowths of quartz+garnet (G3) in the coarse-grained unit. Then these constituents decrease in inclusions of garnet (G4) from the blocky unit and large crystals of garnet (G5) from the quartz core. Some trace elements (V, Ni, Y) exhibit the same trends, only Be evidently increases in garnet from border zone to the centre. Fluorine has negative correlation with Fe3+ as well as some trace elements (Ta, Pb). Concentrations of H2O in garnets, up to 0.22 wt.% H2O, are comparable with spessartine-almandine garnets from the Rutherford No. 2 pegmatite, Virginia, and grossular garnets from high-temperature calc-silicate rocks (skarns). Water contents correlate positively with Fe3+, but inversely with F. The use of water contents in garnet to elucidate the fluctuations of activity of H2O during the pegmatite formation is only limited; the incorporation of hydrous defects seems to be controlled instead by crystal-structural constraints. However, the sum of all volatile components (H2O + F) increases about twice from the outermost subunit to the centre of the pegmatite body.

Detection of fluorine using laser-induced breakdown spectroscopy and Raman spectroscopy

In general, the detection of F and other halogens is challenging through conventional techniques. In this paper, various approaches for the qualitative and quantitative analysis of F using the laser-induced breakdown spectroscopy (LIBS) technique were demonstrated. In LIBS, fluorine detection can be realized by means of atomic lines and molecular bands. For the purposes of our experiment, two sets of pellets with various contents of CaF2, CaCO3 and cellulose were analyzed using a lab-based LIBS system under a He atmosphere. The fluorine atomic line at 685.60 nm was correlated with CaF signals proving their close relationship. Consequently, the limits of detection were determined for both analytical signals. Moreover, conditions necessary for the quantification of F via CaF band signals were estimated. The dependence of the CaF signal on the varying ratio of Ca and F contents was investigated. Finally, a chip of a real CaF2 crystal was prepared and its surface was mapped with Raman and LIBS systems. The obtained elemental and molecular maps showed good numerical correlations. Thus, the yielded results validated the possibility to substitute the fluorine atomic line by non-conventional CaF molecular bands in the qualitative and quantitative LIBS analysis of fluorine.

Vránaite, ideally Al16B4Si4O38, a new mineral related to boralsilite, Al16B6Si2O37, from the Manjaka pegmatite, Sahatany Valley, Madagascar

Abstract The system B2O3-Al2O3-SiO2 (BAS) includes two ternary phases occurring naturally, boromullite, Al9BSi2O19, and boralsilite, Al16B6Si2O37, as well as synthetic compounds structurally related to mullite. The new mineral vránaite, a third naturally occurring anhydrous ternary BAS phase, is found with albite and K-feldspar as a breakdown product of spodumene in the elbaite-subtype Manjaka granitic pegmatite, Sahatany Valley, Madagascar. Boralsilite also occurs in this association, although separately from vránaite; both minerals form rare aggregates of subparallel prisms up to 100 μm long. Optically, vránaite is biaxial (–), nα = 1.607(1), nβ = 1.634(1), nγ = 1.637(1) (white light), 2Vx(calc) = 36.4°, X ≈ c; Y ≈ a; Z = b. An averaged analysis by EMP and LA-ICP-MS (Li, Be) gives (wt%) SiO2 20.24, B2O3 11.73, Al2O3 64.77, BeO 1.03, MnO 0.01, FeO 0.13, Li2O 1.40, Sum 99.31. Raman spectroscopy in the 3000–4000 cm−1 region rules out the presence of significant OH or H2O. Vránaite is monoclinic, space group I2/m, a = 10.3832(12), b = 5.6682(7), c = 10.8228(12) Å, β = 90.106(11)°; V = 636.97(13) Å3, Z = 1. In the structure [R1 = 0.0416 for 550 Fo > 4σFo], chains of AlO6 octahedra run parallel to [010] and are cross-linked by Si2O7 disilicate groups, BO3 triangles, and clusters of AlO4 and two AlO5 polyhedra. Two Al positions with fivefold coordination, Al4 and Al5, are too close to one another to be occupied simultaneously; their refined site-occupancy factors are 54% and 20% occupancy, respectively. Al5 is fivefold-coordinated Al when the Al9 site and both O9 sites are occupied, a situation giving a reasonable structure model as it explains why occupancies of the Al5 and O9 sites are almost equal. Bond valence calculations for the Al4 site suggest Li is likely to be sited here, whereas Be is most probably at the Al5 site. One of the nine O sites is only 20% occupied; this O9 site completes the coordination of the Al5 site and is located at the fourth corner of what could be a partially occupied BO4 tetrahedron, in which case the B site is shifted out of the plane of the BO3 triangle. However, this shift remains an inference as we have no evidence for a split position of the B atom. If all sites were filled (Al4 and Al5 to 50%), the formula becomes Al16B4Si4O38, close to Li1.08Be0.47Fe0.02Al14.65B3.89Si3.88O36.62 calculated from the analyses assuming cations sum to 24. The compatibility index based on the Gladstone-Dale relationship is 0.001 (“superior”). Assemblages with vránaite and boralsilite are inferred to represent initial reaction products of a residual liquid rich in Li, Be, Na, K, and B during a pressure and chemical quench, but at low H2O activities due to early melt contamination by carbonate in the host rocks. The two BAS phases are interpreted to have crystallized metastably in lieu of dumortierite in accordance with Ostwald Step Rule, possibly first as “boron mullite,” then as monoclinic phases. The presence of such metastable phases is suggestive that pegmatites crystallize, at least partially, by disequilibrium processes, with significant undercooling, and at high viscosities, which limit diffusion rates.

Mercury associated with size-fractionated urban particulate matter: three years of sampling in Prague, Czech Republic

An analysis of suspended particulate matter, with an emphasis on the Hg chemical forms, is presented. Dust samples originating from an area highly affected by traffic pollution in the city of Prague (Czech Republic) were sampled over a period of three years from air-conditioner filters and fractioned by size. The samples were morphologically characterised by scanning electron microscopy. The main method used for the analysis of constituent mercury compounds was sequential extraction by leaching solutions in combination with thermal desorption. The total mercury content ranged from 0.37 mg kg−1 to 0.82 mg kg−1. It emerged that the mercury was distributed in a wide spectrum of forms, and various trends in the distribution of these forms among the different size classes were observed. The fraction leached by nitric acid (consisting of elemental and complex-bound mercury) was the main constituent of total mercury. The highest content of this fraction was observed in the finest particle size class. The heterogeneity of morphology of the material increased with the size fraction.