Obsidian is volcanic glass that results from the rapid cooling of silica-rich melt. Nanoscale crystallites precipitate out of the melt prior to solidification and remain embedded in the amorphous matrix. These crystallites provide information on the flow kinetics and composition of the melt. Due to the sparsity and size of nanolites, studies often focus on supramicron crystallites. This research takes advantage of the conchoidal fracture of obsidian by knapping samples with nanometer-thin edges for transmission electron microscopy characterization. Nanolites in the amorphous matrix are studied using energy-dispersive spectroscopy (EDS) and electron diffraction. Certain alkali and alkaline-earth cations exhibit patterns of depletion near Fe-oxide nanolites. EDS is used to identify nanolites and variations in the composition of the matrix. Parallel beam diffraction and radial distribution function analysis of nearest-neighbor distances determine average bond lengths in the matrix near nanolites, showing that nanolites influence the nearby short-range ordering and atomic character of the matrix. Analysis reveals decreased mean nearest-neighbor distances in the matrix adjacent to nanolites compared to the bulk. Our methods exhibit the required sensitivity to detect variations in the composition and structure near nanolites, and our findings indicate that obsidian nanolites contribute to quantifiable localized changes in the amorphous structure.

The crystal structures of six gem-quality pargasites and fluoro-pargasites from Mogok, Myanmar, space group C2/m, Z = 2, have been refined to R1 indices of 2.20–2.90% using MoKα X-radiation. The unit formulae were calculated from the results of electron-microprobe analysis, and were used with the refined site-scattering values and the observed mean bond lengths to assign site populations. TAl occurs at both the T(1) and T(2) sites but is strongly ordered at T(1). [6]Al is partly disordered over the M(2) and M(3) sites but does not occur at the M(1) site. ANa is split between the A(2) and A(m) sites and K occurs at the A(m) site. The infrared spectra in the principal OH-stretching region were measured and the fine structure was fit to component bands. The component bands were assigned to short-range ion arrangements over the configuration symbol M(1)M(1)M(3)–O(3)–A–O(3):T(1)T(1) using the refined site-populations and the expected frequencies from previously assigned spectra in more simple amphibole compositions, and correspond to the local arrangements: (1) MgMgMg–OH–Na–OH:SiAl; (2) MgMgMg–OH–Na–F:SiAl; (3) MgMgAl–OH–Na–OH:SiAl and (4) MgMgAl–OH–Na–F:SiAl.

The general formula of the amphiboles of this series may be written as NaxMg2(Mg(5-y)Aly,)(Si(8-z)Alz)O22(OH)2, where Mg = Mg + Fe2+ + Mn2+ and Al = Al + Fe3+ + Ti. The individual <T–O> distances are linear functions of their [4]Al content, and the [4]Al content is strongly ordered in the following way: T1B > T1A » T2B » T2A. The <M1-O>, <M2-O> and <M3–O> distances are linear functions of the mean ionic radius of their constituent cations. End-member compositions may be written as follows: A☐Mg2Mg5Si8O22(OH)2O22(OH)2; A☐Mg2(Mg3Al2)(Si6Al2)O22(OH)2; ANaMg2Mg5(Si7Al) These compositions define a plane in xyz space across which the data of Schindler et al. (2008), measured on amphiboles from amphibolites, follow a tightly constrained trajectory. Anthophyllite–gedrite amphiboles equilibrated under significantly different P-T conditions (e.g. igneous rocks, contact-metamorphic rocks) follow trends that diverge from this trajectory, with greater Na and [4]Al contents and relatively smaller [6]Al contents. Detailed examination of the local bond topology involving the A and M2 sites indicates that the maximum degree of bond-valence compensation will occur for incorporation of ANa and M2Al in the ratio 4:10, and hence 2.5 ANa = M2Al in these amphiboles. This relation closely fits the data of Schindler et al. (2008), suggesting that the variation in chemical composition in anthophyllite–gedrite amphiboles is strongly constrained by the anion bond-valence requirements of the Pnma amphibole structure. We further suggest that different compositional trends for ortho-amphiboles equilibrated under different P-T conditions are the result of the valence-sum rule operating with (different) bond-lengths characteristic of these P-T conditions.

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 <M−O> 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 (shortrange- 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.

Solution calorimetry and phase equilibrium data for the diopside–jadeite system are assessed using a combination of the cluster variation method (CVM) and Redlich-Kister (RK) polynomial expansion. The CVM is used to model part of the free energy of mixing which depends on short-range order (SRO) and long-range order (LRO) effects. The SRO/LRO independent part of the free energy is modelled using an RK polynomial. The parameters of the RK and CVM models are obtained through the fit to the experimental data. The best-fit parameters are used to calculate activity-composition relations and a temperature-composition phase diagram of the diopside–jadeite system.

Short-range order in the oxygen co-ordination shell of the Ca ion in a glass of composition Ca3Mg4Al2Si7O24 is investigated by analysis of the extended X-ray absorption fine structure. The estimate of disorder in the short-range oxygen co-ordination is no greater than that for crystalline samples of diopside and bytownite. An estimate of the oxygen environment of calcium in the particular glass is included.

The crystal structure of byzantievite, Ba5(Ca,REE,Y)22(Ti,Nb)18(SiO4)4[(PO4),(SiO4)]4 (BO3)9O21[(OH),F]43(H2O)1.5, a new mineral from the moraine of the Dara-i-Pioz glacier, the Alai mountain ridge, Tien-Shan Mountains, northern Tajikistan, was solved by direct methods and refined to R1 = 13.14% based on 3794 observed [Fo >4σ|F|] unique reflections measured with Mo-Kα X-radiation on a Bruker P4 diffractometer equipped with a CCD detector. Byzantievite is hexagonal, space group R3, a = 9.1202(2) Å, c = 102.145(5) Å, V = 7358.0(5) Å3, Z = 3, Dcalc. = 4.151 g cm–3. The empirical formula (electron microprobe analysis) is Ba5.05[(Ca8.99Sr0.96Fe2+0.42Na0.20)Σ10.57(Ce3.46La1.54Nd1.20Pr0.30Sm0.26Dy0.41Gd0.32Th0.39U4+0.17)Σ8.05Y3.53]Σ22.15(Ti12.31Nb5.30)Σ17.61(SiO4)4.65(PO4)3.12(BO3)8.89O22.16(OH)38.21F4.89(H2O)1.5, Z = 3, calculated on the basis of 124.5 (O + F) a.p.f.u. The H2O and OH contents were calculated from structure refinement (F + OH = 43 a.p.f.u.; H2O = 1.5 a.p.f.u..), and B was determined by SIMS. The crystal structure is a framework of Ti-Ba-Ca-REE-dominant polyhedra and SiO4, PO4 and BO3 groups. In the crystal structure, there are 50 cation sites, 23 of which are fully occupied and 27 partly occupied: six of the 27 partly-occupied sites are >50% occupied, 21 <50% occupied. The crystal structure of byzantievite is an intercalation of three components, one fully ordered with 100% occupancy of cation sites, and two partly ordered with cation-site occupancies of 67% and 17% respectively. Byzantievite is the only known mineral that contains all three of the oxyanions (BO3), (SiO4) and (PO4) as essential components.

Atom probe tomography (APT) represents a significant step toward atomic resolution microscopy, analytically imaging individual atoms with highly accurate, though imperfect, chemical identity and three-dimensional (3D) positional information. Here, a technique to retrieve crystallographic information from raw APT data and restore the lattice-specific atomic configuration of the original specimen is presented. This lattice rectification technique has been applied to a pure metal, W, and then to the analysis of a multicomponent Al alloy. Significantly, the atoms are located to their true lattice sites not by an averaging, but by triangulation of each particular atom detected in the 3D atom-by-atom reconstruction. Lattice rectification of raw APT reconstruction provides unprecedented detail as to the fundamental solute hierarchy of the solid solution. Atomic clustering has been recognized as important in affecting alloy behavior, such as for the Al-1.1Cu-1.7Mg (at. %) investigated here, which exhibits a remarkable rapid hardening reaction during the early stages of aging, linked to clustering of solutes. The technique has enabled lattice-site and species-specific radial distribution functions, nearest-neighbor analyses, and short-range order parameters, and we demonstrate a characterization of solute-clustering with unmatched sensitivity and precision.