G. Della Ventura

Application of micro-FTIR imaging in the Earth sciences

AbstractIn this paper we describe recent applications of micro-infrared imaging in the Earth sciences. We address, in particular, the use of Fourier-transform infrared (FTIR) spectroscopy in characterizing the zoning and speciation of H and C in a variety of geological materials, including microporous minerals, nominally anhydrous volcanic minerals (NAMs), and crystal inclusions. These investigations show that use of the modern techniques of FTIR imaging enables detection of the zoning of volatile species across the studied samples, and possible configuration changes of structurally-bound carbon molecular species (e.g., CO2 vs CO3) during crystal growth. Such features, which are not accessible with other micro-analytical techniques, may provide information about the physicochemical properties which act as constraints in the genesis of the samples, and important information about the evolution of the geological system. Tests performed with focal-plane-array detectors (FPA) show that resolution close to the diffraction limit can be achieved if the amounts of the target molecules in the sample are substantially different. We also point out the possibility of using FTIR imaging for investigations under non-ambient conditions. FigureFTIR-FPA image of fluid inclusions within a haüyine matrix

On the crystal structure and crystal chemistry of pollucite, (Cs,Na)16Al16Si32O96·nH2O: A natural microporous material of interest in nuclear technology

Abstract The crystal structure and crystal chemistry of two natural pollucite samples, from Buckfield, Oxford County, Maine (sample M3), and from Kanzit Mawaie, Laghman, Nooristan, Afghanistan (sample N5), have been investigated by means of wavelength-dispersive X-ray microanalysis, thermogravimetric analysis, single-crystal X-ray and neutron diffraction, and single-crystal Fourier-transform infrared spectroscopy. The X-ray and neutron diffraction patterns of the two pollucite crystals show a metrically cubic unit cell [with aM3 = 13.6914(6) Å and aN5 = 13.6808(6) Å by neutron diffraction data; the deviation from isometry is <1.5σ(li), where li is the unrestrained unit-cell length] and the reflection conditions are consistent with the space group Ia3d. Anisotropic neutron structural refinements gave final agreement indices: R1 = 0.0543 for 32 refined parameters and 372 unique reflections with Fo > 4σ(Fo) for M3 and R1 = 0.0693 for 31 refined parameters and 331 unique reflections with Fo > 4σ(Fo) for N5. The structure refinements show a disordered Si/Al-distribution in the tetrahedral framework. The analysis of the difference-Fourier maps of the nuclear density confirms the presence of extraframework water molecules with oxygen sharing the Cs site (at 1/8, 1/8, 1/8, Wyckoff-16b position). However, the minima, ascribable to the proton sites, are very weak in density. Two possible proton positions, leading to a reasonable H2O configuration, are given, and the possible hydrogen bonding is described. Sodium is located at 1/4, 1/8, 0 (Wyckoff-24c position). The main IR absorption bands in the regions typical of H2O are assigned, and the presence of hydroxyls in the studied samples is ruled out. Neutron diffraction and FTIR data agree with the presence of very weak hydrogen bonds in the structure. The detailed description of the crystal structure and crystal chemistry of pollucite (e.g., Si/Al-distribution, configuration of the extra-framework content, possible hydrogen bonding scheme) reported in this study is the key to understand the high thermo-elastic stability of pollucite, the immobility of Cs at non-ambient conditions, and the extremely low leaching rate of Cs, which make this open-framework silicate a promising material with potential use for fixation and deposition of Cs radioisotopes

Fantappièite, a new mineral of the cancrinite-sodalite group with a 33-layer stacking sequence: Occurrence and crystal structure

Abstract This paper reports the occurrence and the crystal structure of fantappièite, a new member of the cancrinite-sodalite group of minerals from Torre Stracciacappe, Trevignano community (Rome, Latium, Italy). The mineral occurs within a volcanic ejectum consisting of dominant sanidine with minor plagioclase, biotite, augitic clinopyroxene, andradite, and iron oxides. Fantappièite (0.7 mm as largest size) is observed within miarolitic cavities of the rock as transparent colorless crystals, showing complex morphologies and striated faces. It is non-pleochroic and uniaxial negative, nω = 1.5046(5) and nε = 1.5027(5). Dcalc is 2.471 g/cm3. Fantappièite is trigonal, space group P3̄; the cell parameters are: a = 12.8742(6), c = 87.215(3) Å, V = 12518.8(9) Å3, Z = 1. The empirical chemical formula is: (Na84.12Ca30.00K15.95Fe0.19Ti0.13Mn0.10Mg0.09)(Si99.36Al98.64)O396(SO4)30.24(CO3)0.29Cl0.84F0.82∙5.18H2O, which corresponds to the ideal formula [Na82.5Ca33K16.5]Σ=132(Si99Al99O396)(SO4)33·6H2O. The five strongest reflections in the X-ray powder pattern are [d in Å (I %) (hkl)]: 3.70 (100) (3 0 0), 3.60 (80) (1 0 23), 2.641 (65) (0 0 33), 6.85 (60) (0 1 10), 6.40 (55) (1 1 0). The single-crystal FTIR spectrum rules out OH groups and shows the presence of H2O and CO2 molecules, as well. The structure can be described as a stacking sequence of 33 layers of six-membered rings of tetrahedra along the c axis. The stacking sequence is ACBACABACBACBACBCACBACBACBABCBACB…, where A, B, and C represent the positions of the rings within the layers. This sequence gives rise to liottite, sodalite, and cancrinite cages, alternating along c. Sulfate groups occur within the liottite cages associated by Na, K, and Ca, while highly disordered sulfate groups are located within the sodalite cages. H2O groups occur within the cancrinite cages, bonded to Ca and Na cations. Split positions are found for Na-Ca sites, and are related to disordering of the sulfate groups in the sodalite cages.

Crystal-chemistry of zirconolite and calzirtite from Jacupiranga, Sao Paulo (Brazil)

Abstract A specimen of zirconolite, collected from the type locality of the mineral originally described as zirkelite at Jacupiranga, São Paulo, Brazil has been re-examined and its mineral chemistry more completely characterized. All crystals studied are metamict and display very fine lamellar oscillatory zoning (1-3 μm in width) superimposed on a sector zonation. Such zoning, observed in backscattered electron images, is primarily related to differences in the concentration of Th. In comparison with other reported zirconolite samples from a variety of geological occurrences, Jacupiranga zirconolite has higher Ca, Th, (Nb + Ta) and lower Ti and REE, which is consistent with its occurrence in carbonatitic rocks. The compositional variation with respect to an ideal zirconolite is described by two main coupled substitutions: (Th,U)4+ + (Fe,Mg)2+ ⇌ Ca2+ + Ti4+, and (Th,U)4+ + (REE)3+ + (Nb,Ta)5+ + (Fe,Mg)2+ ⇌ (Ca)2+ + 3(Ti)4+. Calzirtite, Ca2Zr5Ti2O16, although intergrown with zirconolite and with identical major components, shows much less compositional variability with only minor amounts of Nb and Ta substituting for Ti. Unlike zirconolite, the REE and actinide elements are not easily accommodated in the calzirtite structure.

Low-T neutron powder-diffraction and synchrotron-radiation IR study of synthetic amphibole Na(NaMg)Mg5Si8O22(OH)2

Abstract ANaB(NaMg)CMg5Si8O22(OH,D)2 amphibole was hydrothermally synthesized at 850 °C and 0.3 GPa. SEM, EPMA, and X-ray powder-diffraction data showed the experimental product to consist of a high amphibole yield (90.95%), plus minor quartz and rare enstatite. Neutron powder-diffraction data were collected using a time-of-flight diffractometer at room T and at 8 K, respectively, and structure refinement was carried out using the Rietveld method. The space group of the amphibole is P21/m at both temperatures, as confirmed by the presence of b-type reflections (h + k = 2n + 1). FTIR OH- and OD-stretching spectra at both room and low T (30 K) show two main absorptions, which are assigned to two non-equivalent OH groups in the structure, and a third lower-frequency band, assigned to A-site vacant environments (local cummingtonite environments). At room- and low-T, the cell parameters are (in Å): a 9.7188(1) and 9.7016(2), b 17.9385(3) and 17.8953(4), c 5.2692(1) and 5.2574(1); β (°) is 102.526(1) and 102.597(2). Cell volumes (Å3) are 896.78(2) at room T and 890.80(2) at 8 K, with a relative reduction of less than 1%. Accurate structural positions for the hydrogen atoms were obtained from diffraction data. The O5A-O6A-O5A and O5B-O6B-O5B angles, diagnostic of the A- and B-chains kinking along c, are 190.0° and 159.2° at 293 K and 193.8° and 156.8° at 8 K, respectively. The orientation of the thermoelastic strain ellipsoid was calculated and the principal unit-strain tensor components are reported. A comparison between the low-temperature data reported here and the high-temperature data for a similar amphibole composition, reported by Cámara et al. (2003) up to 643 K, is discussed.

Non-metamict betafite from Le Carcarelle (Vico volcanic complex, Italy): occurrence and crystal-structure

Abstract Non-metamict betafite, a pyrochlore-group mineral with general formula A2-mB2XO6Y(O,OH,F)1-n·pH2O and 2 Ti > Nb+Ta and U > 20% at the A site, has been found at Le Carcarelle, (Latium, Italy). It occurs within miarolitic cavities of a foid-bearing syenitic ejectum enclosed within the pyroclastic formation known as “ignimbrite C″, which belongs to the main effusive phase of the Vico volcanic complex. The host rock is composed of K-feldspar, biotite, augitic clinopyroxene, magnetite and minor sodalite. Electron microprobe analyses gave the following crystal-chemical formula: (Ca1.24Na0.17U0.49REE0.03)∑=1.93 (Ti1.05Nb0.76Zr0.14Fe0.04Ta0.01)∑=2.00O6(O,OH). Compared with other occurrences reported in the mineralogical literature, betafite from Le Carcarelle is extremely enriched in U and depleted in Th. Due to its young age of formation (~150 k.y.), this betafite sample is highly crystalline, thus allowing structure refinement of unheated material. Betafite from Le Carcarelle is cubic Fd3̄m, with a = 10.2637(13) Å, and V = 1081.21(35) Å3, and has a smaller A site (consistent with the higher U content), and a larger and more distorted B site (consistent with the higher Ti content) than calciobetafite from Campi Flegrei, Italy (Mazzi and Munno, 1983). Analysis of the atomic displacement parameters provides evidence for static disorder at the X site.

Crystal-chemistry and short-range order of fluoro-edenite and fluoro-pargasite: a combined X-ray diffraction and FTIR spectroscopic approach

Abstract This study addresses the crystal chemistry of a set of five samples of F-rich amphiboles from the Franklin marble (USA), using a combination of microchemical (Electron microprobe analysis (EMPA)), single-crystal refinement (SREF) and Fourier transform infrared (FTIR) spectroscopy methods. The EMPA data show that three samples fall into the compositional field of fluoro-edenite (Hawthorne et al., 2012), whereas two samples are enriched in high-charged C cations and - although very close to the CR3+ boundary - must be classified as fluoro-pargasite. Magnesium is by far the dominant C cation, Ca is the dominant B cation (with BNa in the range 0.00-0.05 a.p.f.u., atoms per formula unit) and Na is the dominant A cation, with A□ (vacancy) in the range 0.07-0.21 a.p.f.u.; WF is in the range 1.18 - 1.46 a.p.f.u. SREF data show that: TAl is completely ordered at the T(1) site; the M(1) site is occupied only by divalent cations (Mg and Fe2+); CAl is disordered between the M(2) and M(3) sites; ANa is ordered at the A(m) site, as expected in F-rich compositions. The FTIR spectra show a triplet of intense and sharp components at ~3690, 3675 and 3660 cm-1, which are assigned to the amphibole and the systematic presence of two very broad absorptions at 3560 and 3430 cm-1. These latter are assigned, on the basis of polarized measurements and FPA (focal plane array) imaging, to chlorite-type inclusions within the amphibole matrix. Up to eight components can be fitted to the spectra; band assignment based on previous literature on similar compositions shows that CAl is disordered over the M(2) and M(3) sites, thus supporting the SREF conclusions based on the bond distance analysis. The measured frequencies of all components are typical of O-H groups pointing towards Si-O(7)-Al tetrahedral linkages, thus allowing characterization of the SRO (short-range-order) of TAl in the double chain. Accordingly, the spectra show that in the fluoro-edenite/ pargasite structure, the T cations. Si and Al, are ordered in such a way that Si-O(7)-Si linkages regularly alternate with Si-O(7)-Al linkages along the double chain.

FTIR transmission spectroscopy of sideronatrite, a sodium-iron hydrous sulfate

Abstract This paper relates an infrared (IR) (6000-2500; 1400-400 cm−1) spectroscopic study of sideronatrite, Na2Fe3+(SO4)2(OH)·3H2O. Spectra in the 600-1250 cm−1 range are dominated by fundamental S-O absorption bands. Factor-group analysis based on the space group P212121 (D24 ) is in accordance with the observed band multiplicity. A broad and convolute absorption centred around 3400 cm−1 and a sharp band at 3605 cm−1 are observed in the 2900-3900 cm−1 frequency region. The resolution of the broad band is significantly improved at liquid nitrogen temperature; seven components can be fitted to the pattern and these can be assigned to H2O/OH molecules in the structure. All components in the broad band and the sharp absorption at 3605 cm−1 are strongly polarized for E//a, in accordance with the structure analysis results. Infrared transmission spectroscopy is a useful tool to identify these sulfate minerals occurring in specific geological environments.

The high-temperature P21/m → C2/m phase transitions in synthetic amphiboles along the richterite–(BMg)–richterite join

Abstract The thermal behavior of three amphiboles along the join “Mg-richterite” [MRIC: ANaB(NaMg) CMg5 TSi8O22 W(OH)2]-richterite [RIC: ANaB(NaCa)CMg5TSi8O22W(OH)2] was investigated by in situ synchrotron radiation powder diffraction between 90 and 873 K. The studied samples have Bsite compositions Na1Mg1 (sample RN1), Na0.97Mg0.8Ca0.24(sample RN2), and Na0.97Mg0.58Ca0.45 (sample RN6). The evolution of cell parameters as a function of T shows a discontinuity in the two Mg-richer samples (RN1 and RN2), which is interpreted as evidence of a P21/m → C2/m phase transition, whereas the Ca-richer sample (RN6) shows no evidence of a phase transition. The transition in samples RN1 and RN2 follows a different thermodynamic behavior, being tricritical in end-member “Mg-richterite” (RN1) and second order in the BCa-bearing amphibole RN2. A thermodynamic analysis done according to the Landau formalism and allowing for order parameter saturation, gives Tc = 462(3) and 378(1) K, and saturation temperature θs =116(21) and 141(7) for RN1 and RN2, respectively. Comparison with data from literature shows that the thermal strain of C-centered amphiboles with constant A-, C-, T-, and W-site occupancy equal to Na, Mg5, Si8, and (OH)2, respectively, and a B-site occupied by variable amounts of Li, Na, Mg, and/or Ca, mainly expands about 70° from c toward the a cell-edge onto the 010 plane. Conversely, the spontaneous strain accompanying the thermal transition shows that the maximum expansion is oriented about 25° from c and is coupled with a contraction close to the a cell direction. On the other side, transition induced by solid solution at room-T follows an almost opposite deformation pattern. The present data confirm the hypothesis of a first-order character of the transition induced by the increase of the B-site dimension for increasing BCa contents, similarly to the closely related P21/c → C2/c transition in pyroxenes

Site occupancy in richterite-winchite from Libby, Montana, USA, by FTIR spectroscopy

Abstract Three natural amphibole samples collected from the former vermiculite mine near Libby, Montana, USA, have been analysed by Rietveld X-ray powder diffraction (XRPD) refinement and Fourier transform infrared spectroscopy (FTIR) in the OH-stretching region. The same materials have been analysed previously by electron microprobe analysis (EMPA), Mössbauer spectroscopy and structure refinement (SREF) single crystal X-ray diffraction (SC-XRD), which revealed that these amphiboles have a crystal chemical formula very close to an intermediate composition between winchite and richterite, i.e. AA0.5BNaCaCMg4.5M3+0.5TSi8O22(OH)2 (A = Na and/or K; M3+ = Fe3+ and/or Al). The Rietveld analysis showed the powder samples used for the experiments here to be composed only of amphibole. This in turn allowed us to use FTIR OH-stretching data to derive cation ordering on these powder samples. The three FTIR spectra are quite similar and up to four components can be fitted to the patterns. The two lower-frequency components (labelled A and B) can be attributed to a local O(3)-H dipole surrounded byM(1)M(3)Mg3 and M(1)M(3)Mg2Fe2+ (respectively), an empty A site and TSi8 environments; on the contrary, the higher-frequency C and D bands indicate the presence of an occupied A site. The FTIR OH-stretching data alone allow us to calculate the site occupancy of the A, M(1)-M(3) and T sites with confidence, as compared with previously published data. By contrast M(4)- and M(2)-site occupancies are more difficult to evaluate. This study takes advantage of the large database of well characterized synthetic amphiboles, built over the last two decades. The comparison of vibrational spectroscopy data with micro-chemical and crystallographic data reported in this study demonstrate that the FTIR OH-stretching method alone is a valuable and rapid method to derive or at least sensibly constrain site occupancy for natural amphiboles. A much more detailed cation site occupancy can be obtained by combining micro-chemical and FTIR OH-stretching data.