The low-frequency mechanical properties of pure and Ca-doped lead orthophosphate, (Pb1–xCax)3(PO4)2, have been studied using simultaneous dynamical mechanical analysis, X-ray diffraction (XRD), and optical video microscopy in the vicinity of the first-order ferroelastic phase transition. Both samples show mechanical softening at T > Tc, which is attributed to the presence of dynamic short-range order and microdomains. Stress-induced nucleation of the low-temperature ferroelastic phase within the hightemperature paraelastic phase was observed directly via optical microscopy at T ≈ Tc. Phase coexistence is associated with rapid mechanical softening and a peak in attenuation, P1, that varies systematically with heating rate and measuring frequency. A second peak, P2, occurs ≈3–5°C below Tc, accompanied by a rapid drop in the rate of mechanical softening. This is attributed to the change in mode of anelastic response from the displacement of the paraelastic/ferroelastic phase interface to the displacement of domain walls within the ferroelastic phase. Both the advancement/retraction of needles (W walls) and wall translation/rotation (W′ walls) modes of anelastic response were identified by optical microscopy and XRD. A third peak, P3, occurring ≈ 15°C below Tc, is attributed to the freezing-out of local flip disorder within the coarse ferroelastic domains. A fourth peak, P4, occurs at a temperature determined by the amplitude of the dynamic force. This peak is attributed to the crossover between the saturation (high temperature) and the superelastic(low temperature) regimes. Both samples display large superelastic softening due to domain wall sliding in the ferroelastic phase. Softening factors of 20 and 5 are observed in the pure and doped samples, respectively, suggesting that there is a significant increase in the intrinsic elastic constants (and hence the restoring force on a displaced domain wall) with increasing Ca content. No evidence for domain freezing was observed down to −150°C in either sample, although a pronounced peak in attenuation, P5, at T ≈ −100°C is tentatively attributed to the interaction between domain walls and lattice defects.

Both samples show similar high values of attenuation within the domain-wall sliding regime. It is concluded that the magnitude of attenuation for ferroelastic materials in this regime is determined by the intrinsic energy dissipation caused by the wall-phonon interaction, and not by the presence of lattice defects. This will have a large impact on attempts to predict the effect of domain walls on seismic properties of mantle minerals at high temperature and pressure.

The magnetic susceptibility of ordered and partially disordered manganogrunerites (composition and ) has been measured between room temperature and 5 K. The influence of disordering of metal cations over the M(1,2,3) sites of the octahedral ribbon in these amphiboles is to dilute Fe2+ within the ribbon. We observe a reduction in both θp and TN as a function of both increased Mg/(Mg+Fe) and metal cation disorder, linked to a reduction in the strength of magnetic coupling between and within the one-dimensional chains of the structure.

We demonstrate the potential of X-ray photo-emission electron microscopy (XPEEM) to reveal valence-state images of the spatial distribution and relative concentration of metals in specific oxidation states. Additionally, XPEEM allows X-ray absorption spectra to be extracted from chosen pixel areas of the images. Using an in-house-built XPEEM instrument we show an application of the method in providing valence-state images of complex mineral intergrowths. The image resolution achieved with this instrument of simple design was ∼5 μm and reasonable quality X-ray absorption spectra were extracted from areas of ∼5×5 μm. These initial results suggest that by using commercial XPEEM instruments on 3rd generation, high-brightness synchrotron sources a spatial resolution of 100 nm or better could be achieved, with the ability to extract high-quality X-ray absorption spectra from areas of 0.1 μm2. Given that standard thin sections or polished blocks can be studied by XPEEM, and that each XPEEM image records ∼1000 μm2, XPEEM can be used in conjunction with other analytical methods such as EMPA and TEM-EELS/PEELS.

Idiomorphic crystals (up to 3.5 mm) of ferroan platinum, cooperite and mertieite-II were found in a heavy-mineral concentrate from stream sediments of the Darya river in the Aldan Shield, Russia. Pt-Fe crystals display cubic and thin platy habits; occasionally they are twinned. The chemical composition ranges from Pt2.64Fe1.00 to Pt2.88Fe1.00 with Os, Ru, Ir, Rh and Pd below the analytical detection limit of the electron microprobe. X-ray diffractometry of Pt-Fe crystals suggests a F-centred cubic lattice, characteristic of ferroan platinum. Some of the ferroan platinum crystals have large (about 100 μm wide) cooperite overgrowth rims or are covered by a Au-Ag alloy. Cooperite also occurs as large euhedral crystals (up to 3 mm across, partly twinned). Crystals of mertieite-II are speckled with μm-sized (2–5 μm) inclusions of sperrylite and intergrown with minerals of cooperite-braggite solid solution, Pt-Pd-Hg alloy, keithconnite and Au-Ag alloy. Fractures along crystallographic planes of the mertieite-II crystals are filled with Pd-Pt-Fe-Sb-As-Hg-Te-Bi-bearing oxides. The coarse-grained PGM from the Darya have a geological setting similar to the Kondyor PGE placer 75 km to the northeast and are probably related to clinopyroxenite-hornblende-magnetite units of Alaskan-/Uralian-type intrusions.

Serpentine minerals and brucite in ultramafic rocks from the South Chamorro Seamount were characterized chemically to investigate the serpentinization of the Mariana forearc mantle. Relict primary minerals of the serpentinites are olivine, enstatite and minor Cr-spinel and diopside. The secondary minerals are mostly serpentine and brucite with minor magnetite. The serpentine minerals, mostly lizardite and chrysotile, display large compositional variations. Al2O3 and Cr2O3 contents depend generally upon the nature of the primary mineral from which the serpentine was derived. Both serpentine minerals and brucite exhibit wide Mg, Fe and Mn substitution: the Mg# ranges are 95.1–77.2 and 88.9–60.8, respectively. These mineralogical and chemical features allowed us to estimate an upper temperature limit for serpentinization of ∼200–300°C, in agreement with recent thermal models which suggest that the serpentinized mantle wedge of the Izu-Bonin-Mariana subduction zone is cold. The high degree of serpentinization (40–100%, average >75%), and the serpentine + brucite paragenesis of these ultramafics imply that the Mariana forearc mantle has a significantly reduced density and strength down to ∼30 km, which provides a driving mechanism for serpentinite diapirism. Pervasive serpentinization of the forearc by fluids released from the décollement zone also explains the low seismicity of the Izu-Bonin-Mariana subduction zone.

Pyrochlore has been considered as a waste form to immobilize high-level nuclear waste such as excess weapons-grade plutonium. In order to study the aqueous stability of pyrochlore, we have carried out hydrothermal experiments with a natural microlite (Nb + Ta > 2Ti; Ta ⩾ Nb) at 175°C in a neutral and acidic solution for 14 days. The starting material and the experimental products were studied by electron microprobe, backscattered electron (BSE) imaging, powder infrared (IR) and micro-Raman spectroscopy, and powder X-ray diffractrometry (XRD). The microlite has small U (∼200 ppm) and Th (∼800 ppm) contents and is crystalline. The hydrothermal treatment in a solution containing l mol/l HCl and l mol/l CaCl2 causes the partial replacement of the microlite (up to ∼10 μm) by a new pyrochlore phase. This new phase is characterized by a larger unit-cell volume and contains a large number of vacancies at the A site (A = Ca, Na) as well as anion vacancies, molecular water, and possibly OH groups. Analyses of the experimental fluid further revealed that U was also selectively lost to the solution. Treatment in pure water did not produce reaction zones detectable by BSE imaging or powder XRD. However, significant spectral changes in powder IR spectra of the reaction product and the detection of Na and Ca in the solution indicate that the microlite has also reacted in pure water. The experimental alteration features bear a remarkable resemblance to those seen in naturally altered microlite samples, suggesting that short-term experimental results can be applied to natural systems and vice versa in order to evaluate the long-term stability of a pyrochlore waste form.

La Colorada, in Zacatecas State, Mexico is an epithermal Ag-Zn-Pb system hosted in Mesozoic calcareous sedimentary rocks overlain by Tertiary volcanic rocks. The dominant vein is associated with a fault system that accommodates Tertiary normal and strike-slip faulting. The ore consists of fahlore [(Cu,Ag)10(Zn,Fe)2(Sb,As)4S13], polybasite [(Ag,Cu)16Sb2S11]–pearceite [(Ag,Cu)16As2S11] solid solution, pyrargyrite [Ag3SbS3]–proustite [Ag3AsS3] solid solution, acanthite-argentite [Ag2S], and native silver; associated sulphides include galena, sphalerite, chalcopyrite and pyrite. The Ag:Sb of the bulk concentrate from the mine is 1.076 and the Ag:Pb is 0.088. Compositions of the assemblages fahlore + pyrargyrite-proustite + sphalerite, and fahlore + polybasite-pearceite solid solution + (Ag,Cu)2S solid solution + sphalerite encapsulated in quartz and sphalerite indicate a primary depositional temperature of ∼325°C for a depth between 725 and 960 m below the inferred palaeosurface, which is in accord with fluid-inclusion data for higher elevations in the mine.

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)Σ=1.93 (Ti1.05Nb0.76Zr0.14Fe0.04Ta0.01)Σ=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 Fdm, 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.