The thermally-induced dehydroxylation and transformations of the 2:1 phyllosilicate pyrophyllite have been studied using infrared spectroscopy in the frequency range 350–11000 cm−1 and the temperature range 200–1500°C. The dehydroxylation of pyrophyllite to pyrophyllite dehydroxylate occurs between 500 and 900°C. It is characterized by a decrease in the intensity of the OH signals and phonon bands of pyrophyllite and the eventual disappearance of these features as well as the appearance of extra signals related to pyrophyllite dehydroxylate and an intermediate phase. Our results are consistent with previous observations that the SiO4 tetrahedral sheet structure still exists in pyrophyllite dehydroxylate, that the Si-O-Al linkages and 2:1 structure remain in the pyrophyllite dehydroxylate, and that AlO5 trigonal bipyramids form.

Two extra OH bands at 3690 and 3702 cm−1 and their overtones at 7208 and 7234 cm−1 are observed, for the first time, in samples annealed at the temperature range 550–900°C. Our results suggest that the formation and dehydroxylation of the extra OH species can be strongly affected by kinetic effects. The experimental evidence shows that the dehydroxylation of pyrophyllite is a two-stage process. The appearance of these additional OH bands is interpreted in terms of an unknown intermediate phase, and may be related to the second endothermic peak observed at high temperatures in DTA experiments. Pyrophyllite dehydroylate decomposes into a Si-rich amorphous phase and mullite in the temperature range 950–1100°C. Cristobalite is observed in the temperature range 1150–1500°C.

The paper investigates trace elements and crystal-rich fluid inclusions in spodumene from rare-metal pegmatites of the Kolmozero lithium deposit in the Kola region, Russia. The main lithium mineral in the pegmatites is spodumene, which occurs in three generations, designated as Spd-I, Spd-II and Spd-III. Iron, Na and Mn are the most typical element impurities in spodumene. The Fe/Mn ratio is 7.1 in Spd-I, 12.3 in Spd-II and 13.2 in Spd-III. Spd-II contains fluid and crystal-rich fluid inclusions. The crystal-rich fluid inclusions in Spd-II originally trapped CO2-bearing aqueous fluids with dissolved alkali carbonates. The crystal-rich fluid inclusions contain zabuyelite (Li2CO3) and cristobalite (SiO2) as solid phases, which have not been reported previously from the Kolmozero rare-metal pegmatites. These minerals are assumed to have resulted from a reaction between a CO2-bearing aqueous fluid and host Spd-II and are not related to the mineral-forming system of pegmatites.

Studies on type-V fulgurites are very sparse in the literature. This work reports on the characterization of natural exogenic fulgurites found at the archaeological site of Cerro de la Ermita (Tiedra, Valladolid, Spain), which was firstly a Celtiberian and then a Roman locum sacrum. Data from X-ray powder diffraction, X-ray fluorescence spectroscopy, Fourier-transform infrared spectroscopy and Raman spectroscopy suggest that the fulgurites consist of naquite, piroxenes, iron oxides, shocked quartz and neo-formed cristobalite.

Indurated volcanic soils (tepetates) of the Mexican Altiplano display thick columnar horizons, hard laminar horizons, and grey mottles at depth. X-ray diffraction (XRD) studies show a relative enrichment in cristobalite vs. halloysite in the indurated plates of the laminar horizons and in the clay fraction of the mottles. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) studies of these two soil components have shown that they are composed of small tubes of halloysite in which numerous globular grains ∼1 μm in diameter are embedded. Based on the relative abundance of cristobalite in pedological features and on the spatial relations between successive mineral phases, we interpret the cristobalite as a transformation of halloysite with a transitional amorphous phase. In the globular grains, large platy 1:1 clay minerals undergo a progressive transformation into platy particles of opal-A and opal-C. These are in turn transformed into cristobalite without further major change in their shape and appearance, except for a higher electron density than opal and clay.

Respirable forms of crystalline silica including the mineral cristobalite are known carcinogens and the subject of increasing regulation and codes of good practice. Some bentonites may contain cristobalite, but more commonly they contain opal-CT, or opal-C, which can be confused with cristobalite. In the light of increasing regulation there is a clear need for simple and reliable methods that can distinguish cristobalite from the opals in bentonites and other clay materials. Here we propose the use of a simple NaOH method that is easily applied to bulk samples of bentonites. The method consists of boiling the clay in 0.5 M NaOH for 10 min and measuring the weight of undissolved solid. The method is shown to be accurate for both the identification and quantification of opal in bentonites since these phases are soluble when thus treated. It is also a straightforward method to distinguish the opals from cristobalite as the latter is essentially insoluble. Adoption by industry of a simple operationally-defined method such as this would be preferable to ad hoc reliance on direct instrumental methods alone such as X-ray powder diffraction, as the latter almost always require a large element of judgement and experience on the part of the analyst, although direct methods do need to be used in a supporting role.

The crystal structure of the high-pressure phase-II of cristobalite has been solved by neutron diffraction (space group P21/c, a = 8.3780(11) Å, b = 4.6018(6) Å, c = 9.0568(13) Å, β = 124.949(7)°, at P = 3.5 GPa). This phase corresponds to a distortion of the high-temperature cubic β-phase, rather than of the ambient temperature and pressure tetragonal α-phase.

The atomic structure of chkalovite, Na2BeSi2O6, has been determined and refined by Simonov et al. (1976). It is orthorhombic, space group Fdd2, with cell parameters: a = 21.129 (5), b = 6.881 (2), and c = 21.188 (5)/Å. The structure is very similar to that of alpha-cristobalite (Dollase, 1965), comprising a framework of ordered BeO4 and SiO4 tetrahedra with the sodium atoms occupying sites within the cavities of the beryllosilicate framework. Taylor (1972) developed a tilting model for the cristobalite structure assuming regular tetrahedra. In addition to the single tilt system deduced for cristobalite (Taylor, 1972, 1984a) chkalovite has secondary tilt systems involving a slight adjustment of the structure by a small cooperative tilt or twist of some tetrahedra about one or more of their three-fold axes (see fig. 1 of Simonov et al., 1976).

We describe a model for framework silicates in which the SiO4 (and AlO4) tetrahedra are treated as perfectly rigid and freely jointed. From this model we are able to identify low-energy modes of distortion of the structure, which we call Rigid unit modes. These modes can act as soft modes to allow easy distortions at phase transition. We discuss three forces that will operate at a phase transition in conjunction with the candidate soft modes to determine which of the rigid unit modes will actually precipitate a phase transition, and illustrate these ideas by detailed discussions of the phase transitions in quartz, leucite and cristobalite. The model can also be used to estimate the transition temperature, and the theory highlights an important role for the stiffness of the tetrahedra.

Characterization of Brazilian agates containing a lower horizontally banded section and an upper chamber with bands parallel to the walls shows that these agates formed much later than the 135 Ma Paraná basalt host rock. Age differentiation between the two types of banding shows that the horizontal bands formed between 43 to 63 Ma ago with a final infill of wall-lining bands between 7 and 27 Ma later. The horizontal bands have a higher Al3+ concentration and a greater crystallite size than the wall-lining layers; they have a lower mogánite content and defect-site water content. The formation of these agates appears to be the result of a three-stage process. After the separate formation of horizontally banded and wall-lining agate, a silica infill seals the gap between the agate and the cavity wall. The detection of cristobalite in some specimens indicates that genesis of both the horizontally banded and wall-lining deposits in the Brazilian samples proceeds along an amorphous silica → opal-CT → opal-C → chalcedony pathway.

The Soufrière Hills stratovolcano on the Caribbean island of Montserrat has been erupting since 18th July 1995. An enormous amount of respirable volcanic ash has been suspended into the atmosphere by the eruptions and wind re-suspension of deposited ash. The large amount of fine, airborne particulate matter, in particular the component 10 μm equivalent aerodynamic diameter (PM10), is a cause of medical concern. Airborne levels have frequently exceeded the UK environmental standard for PM10, (50 μg/m3), although it is noted that this standard was primarily set for urban PM10. The crystalline silica in the ash is mostly cristobalite, at reported levels up to 20%. The UK government’s Chief Medical Officer, referring to Montserrat, has suggested that long-term exposure to high levels of volcanic ash could lead to silicosis. These concerns have prompted government-funded investigations into the potential toxicity of well characterized volcanic ash samples from Montserrat. Given the well established toxicity of cristobalite, particular attention was paid to the amount of this mineral in the ash samples. Three ash samples were tested: (1) a vulcanian eruption ash, (2) ash released in a domecollapse pyroclastic flow, and (3) ash from a major vulcanian explosion that was wind-transported to, and deposited on, the neighbouring island of Antigua. Comparative toxicological studies were carried out on respirable preparations of these three samples together with appropriate control mineral dusts that matched the major components of the Montserrat samples: anorthite, labradorite, cristobalite/ obsidian and cristobalite. Alpha quartz (DQ12) was the positive control. All samples, including the controls, were characterized to establish particle-size distributions, particle morphologies, and to confirm the mineralogy. Rats were challenged with 1 mg via intratracheal instillation, and groups sacrificed at three time points (1, 3 and 9 weeks). Health assessment was made by examining endpoints of increasing lung damage such as inflammation, permeability (oedema), changes in epithelium, and increase in the size of broncho-thoracic lymph nodes. The data indicate that Montserrat respirable ash, derived from dome collapse pyroclastic flows or vulcanian explosions, has minimal acute bioreactivity in the lung. The feldspar standards showed low bioreactivity, in stark contrast to the cristobalite standard that showed progressive increases in lung damage. These results suggest that either the mass of cristobalite present in the Montserrat ash was insufficient to cause an effect in the lung, or the cristobalite in the ash was, for some as yet unknown reason, markedly less bioreactive than our pure cristobalite standard.

The low-cristobalite-type modification of Al0.5Ga0.5PO4 is prepared by annealing the amorphous precipitate of stoichiometric phosphate at 1300 °C. The phase purity of the sample is ascertained by powder X-ray diffraction. The crystal structure is refined by Rietveld refinements of the neutron and X-ray diffraction data of the polycrystalline powder. This compound crystallizes in an orthorhombic lattice with unit cell parameters, a=7.0295(8), b=7.0132(8), and c=6.9187(4) Å, V=341.08(6) Å3, Z=4 (Space group C 2221, No. 20). The crystal structure analysis reveals the random distribution of the Al3+ and Ga3+ having tetrahedral coordination with typical M–O (M=Al3+:Ga3+) bond lengths as 1.74 Å. Similarly, the P5+ have tetrahedral coordination with typical P–O bond lengths 1.52–1.54 Å. The Mo4 and PO4 tetraheda are linked by common corners forming a three-dimensional framework lattice. The details of the crystal structure are presented in this paper.

Quantification of potentially toxic single mineral phases in natural dusts of heterogeneous composition is critical for health hazard assessment. For example, crystalline silica, a human carcinogen, can be present as respirable particles in volcanic ash such as quartz, cristobalite, or tridymite. A method to rapidly identify the proportions of crystalline silica within mixed dust samples, such as volcanic ash, is therefore required for hazard managers to assess the potential risk of crystalline silica exposure to local populations. Here we present a rapid method for quantifying the proportions of single phases in the mineral assemblage of mixed dusts using X-ray diffraction (XRD) with a fixed curved position-sensitive detector. The method is a modified version of the whole-pattern peak-stripping (PS) method (devised by Cressey and Schofield [Powder Diffr.11, 35–39 (1996)]) using an internal attenuation standard (IAS) but, unlike the PS method, it requires no knowledge of other phases present in the sample. Ten synthetic sample mixtures were prepared from known combinations of four pure phases (cristobalite, hematite, labradorite, and obsidian), chosen to represent problematic constituents of volcanic ash, and analyzed by XRD. Results of the IAS method were directly compared with those of the PS method. The proportions of cristobalite estimated using the methods were comparable and accurate to within 3 wt %. The new IAS method involved less sample preparation and processing and, therefore, was faster than the original PS method. It therefore offers a highly accurate rapid technique for determination of the proportions of individual phases in mixed dusts.

A new classification of opals through X-ray powder diffraction (XRPD) methodology, by analysing 75 new samples of opal came from different worldwide areas, is introduced. A brief historical summary of the application of XRPD analysis on opals and the most important XRPD results reported in literature were compared with the newly obtained XRPD data. A simple method for the classification of opals on the basis of their degrees of structural order-disorder calculated from the diffraction data is proposed. In addition, a clear boundary, which has not been previously described by others in literature, related to the presence (or absence) of two-peak characteristic of the cristobalite phase is identified. This boundary allows for a discrimination of opals C from CT.