C. M. B. Henderson

Use of L-edge X-ray absorption spectroscopy to characterize multiple valence states of 3d transition metals; a new probe for mineralogical and geochemical research

Abstract2p (L2,3) X-ray absorption spectra are presented for a range of minerals to demonstrate the usefulness of L-edge spectroscopy as a symmetry- and valenceselective probe. 2p XAS provides a sensitive fingerprint of the electronic states of 3 d transition metals and can be applied to phases containing mixtures of such elements. Calculated spectra for 3dn → 2p5 3dn+1 transitions provide a basis for the interpretation of the measured spectra. Thus, in principle, multiple valence states of a particular 3 d metal can be precisely characterized from a single L-edge spectrum. Examples of vanadium L-edge spectra are presented for a range of minerals; these complex spectra hold information concerning the presence of vanadium in multiple valence states. The Cu L-edge spectrum of sulvanite (Cu3 VS4) indicates the presence of both Cu+ and Cu2+; the V L-edge spectrum of the same sample shows that both V2+ and V5+ are present. Spectral simulations representing mixtures of Fe d5 and Fe d6 states are used to quantify Fe3+/∑Fe in a spinel, a glass, and an amphibole, all of which contain Fe as a major component. To illustrate the sensitivity of 2p XAS in a dilute system, the Fe L-edge spectrum of amethyst (α-SiO2: Fe) has been recorded; this spectrum shows that ∼68% of the Fe in amethyst is Fe2+, and ∼32% is Fe3+. Although previous studies on amethyst using other spectroscopic methods cite evidence for Fe4+, there is no indication in the L-edge spectrum for Fe4+ in amethyst. Comparison of theoretical and experimental spectra not only allows the valence states of 3 d ions to be recognised, but also provides site-symmetry information and crystal field parameters for each ion site.

The probable occurrence of interstitial Al in hydrous, F-bearing and F-free aluminosilicate melts

AbstractExperiments carried out on the system SiO2-NaAlSi3O8-KAlSi3O8(Qz-Ab-Or) at 1 kbar in the presence of H2O and F show that the quartz-alkali feldspar field boundary is progressively displaced towards the feldspar join as F contents increase from 0 to 4 wt. %F. Increasing

Na-rich carbonate inclusions in perovskite and calzirtite from the Guli intrusive Ca-carbonatite, polar Siberia

P_{H_2 O}

Geological applications of synchrotron radiation

, in the absence of F, has already been shown to have a similar effect (Tuttle and Bowen 1958; Luth, Jahns, and Tuttle 1964). The increased size of the quartz field in the F-bearing system compared to the hydrous system is believed to be caused by progressive removal of Al from the tetrahedral network of the melt by complexing with F. The residual network in the melt is thus enriched in Si and this stabilizes precipitation of quartz rather than feldspar for certain bulk compositions. The common presence of quench cryolite (Na3AlF6) in certain experiments carried out with 4 wt.% F supports this interpretation and indicates that some Al in the melt may be present in six-fold coordination with F−. The effect of H2O in the absence of F may be similar, with Al being progressively removed from four-fold coordination as more H2O is dissolved in the melt. Although a proportion of Al in hydrous melts may occur in six-fold coordination, dry melts predominantly contain Al in four-fold coordination. This major difference in Al complexing may be one of the main causes for differences in the high-pressure phase relations of wet and dry Albearing silicate systems.

High-temperature study of octahedral cation exchange in olivine by neutron powder diffraction

The distribution of cations between tetrahedral (A) sites and octahedral (B) sites in ferrite spinels has been studied using K-edge x-ray absorption spectroscopy. The samples include natural and synthetic end-member magnetites (Fe₃O₄), a natural Mn- and Zn-rich magnetite (franklinite) and synthetic binary, ternary and quaternary ferrites of stoichiometry M(²+)M₂(³+)O₄, where M(²+) = Mg, Co, Ni, Zn and M(³+) = Fe, Al. XAS data were obtained for all metals. Complete, unfiltered, EXAFS spectra were refined to determine the percentage distribution of each element over the A and B sites and these data were combined with microprobe analyses to quantify the tetrahedral occupancy for each element in each sample. Measured site occupancies and an internally consistent set of (M-O)(A) and (M-O)(B) bond lengths were used to calculate unit-cell parameters, which show excellent agreement with measured values, pointing to the reliability of the measured occupancy factors. The average occupancies determined for the tetrahedral sites in ferrites are (atoms per formula unit) Mg 0.44, Co 0.24, Ni 0.11, Zn 0.76, Al 0.11 and Fe(³+) 0.92-0.19. The wide range found for Fe(³+) is consistent with it playing a relatively passive role by making good any A-site deficit left by the other competing cations.

Structural phase transitions and mixing behaviour of the Ba-aluminate (BaAl2O4)–Sr-aluminate (SrAl2O4) solid solution

Carbonate phases, some rich in Na2O and comparatively rich in SrO and BaO, occur as inclusions in perovskite and calzirtite (Ca2Zr5Ti2O16) in the carbonatite of the Guli complex, Siberia. This is the first record of alkali carbonates, akin to ‘nyerereite’ [Na2Ca(CO3)2], in plutonic igneous rocks. The inclusion populations suggest that the parental magma of the complex was Ca-rich but developed Na-rich differentiates during the latest stages. This points to the dominant calcic carbonatites of the complex not being derivatives of alkali-rich parental carbonatites. These alkali-rich carbonate inclusions (and rare inclusions of djerfisherite) have been preserved due to the resistance of perovskite and calzirtite to processes of leaching, hydrothermal alteration and weathering.

The structural environments of trace elements in dry and hydrous silicate glasses; a manganese and strontium K-edge X-ray absorption spectroscopic study

Metal K- and L3-, sulfur K- and arsenic K- and L3-edge X-ray absorption near-edge spectra of a series of metal disulfides, FeS2 (both pyrite and marcasite), CoS2, NiS2, and CuS2, and their isomorphs, FeAsS and CoAsS, are presented. The features in this region of these spectra are interpreted using band structure and molecular orbital calculations in terms of the transitions from the 1s or 2p3/2 state to unoccupied states. The 3d transition metal L3-edge spectra of these materials show dependence on the degree of multiplet splitting in the final state, and thus offer less information on the electronic ground state. There are substantial differences in the spectra of the isostructural materials, whereas the spectra of the isotopes pyrite and marcasite show several similarities, illustrating the dependence of near-edge region on electronic structure.

The thermal expansion of synthetic aluminosilicate-sodalites, M 8(Al6Si6O24)X 2

Abstract Synchrotron-based, Earth sciences research carried out over the last 5 years is reviewed with special attention being given to X-ray absorption studies; X-ray diffraction and X-ray fluorescence microprobe applications are considered more briefly. A comprehensive bibliography is included. The main part of the paper summarizes recent work carried out at the Daresbury SRS. K-edge XAS studies of glasses as models for silicate melts provide information on the local structural environments of Si, Fe 2+ and Fe 3+ . By analogy with synthetic “leucites” which contain Fe 2+ and Fe 3+ in tetrahedral framework sites, it seems that many model glasses also contain both oxidation states of Fe in the network, rather than as network modifiers. The structural sites occupied by the minor elements Mn, Zn and Ti in staurolite have been identified using XAFS; Mn and Zn substitute for Fe 2+ in the tetrahedral T 2 site, while Ti occupies the distorted M 2 octahedral site. L-edge spectroscopy is used to identify the valencies and electronic structures of Mn and Fe in minerals and the Fe 2+ :Fe 3+ ratio in a natural spinel is determined. The polarized nature of the synchrotron beam is exploited in determining the Fe X-ray absorption anisotropy in single crystal tourmaline and epidote. XRD powder studies include Rietveld-refinement structure determination and compressibility studies. Synthetic “leucites” having the stoichiometry K 2 MgSi 5 O 12 have distinctly different structures. The dry-synthesized form is cubic Ia3d with Si and Mg fully disordered on tetrahedral framework sites, while the hydrothermally-synthesized polymorph is monoclinic P2 1 /c with Si and Mg fully disordered on, respectively, 10 and 2 tetrahedral sites. The reversible tetragonal to orthorhombic phase transition in gillespite (BaFeSi 4 O 10 ) has been studied in a diamond anvil cell using ED detection and found to occur at 1.2 ± 0.1 GPa. The anomalous compressibility observed has been interpreted in terms of ferroelastic and coelastic phenomena and the related order parameters analysed using Landau theory. The compressibility of MgCO 3 , determined up to 20 GPa, has been combined with thermochemical data to obtain an “equation to state” for magnesite and it is found that magnesite is likely to be the main host for carbon in the Earths lower mantle.