The space symmetry of prehnite, a mineral which occurs in cavities and veins within skarn from the Tieshan iron mineral deposit, Daye, Hubei province, central China, has been determined using selected area electron diffraction (SAED) and convergent-beam electron diffraction (CBED) on the submicrometer scale. Our results confirm that natural prehnite may belong to space group Pncm. The unit-cell parameters of the prehnite investigated ( a = 0.458 nm, b = 0.555 nm and c = 1.853 nm) have been calculated using the multicrystal diffraction rings of gold, the internal standard.

Backscattered electron imaging of cordierite-muscovite intergrowths near the margin of a schist xenolith in trachytic tephra of the Wehr Volcano, East Eifel area, Germany, show that they have undergone disequilibrium melting to form spinel + biotite + sillimanite/?mullite + peraluminous melt. Textures indicate that in the initial stage of reaction, spinel, biotite and sillimanite/?mullite formed with melt produced in cordierite and spinel + ?mullite with melt after muscovite, providing evidence of two different reaction pathways. Fe-Mg distributions between biotite/spinel, cordierite/spinel, cordierite/ biotite suggest a melting temperature of ∼770°C, implying overstepping of various calculated and experimentally determined mineral breakdown curves of between 30 and 170°C during short-term heating before the xenolith was quenched on eruption.

The previously unknown crystal structure of the basic lead nitrate Pb2(OH)3(NO3) has been determined using single-crystal X-ray diffraction data (Mo-Kα radiation, CCD area detector). The compound is orthorhombic, space group Immm, with a = 8.314(2), b = 8.545(2), c = 17.210(3) Å (R1 = 2.78% for 940 ‘observed’ reflections with Fo > 4σ(Fo)). The layered structure contains a previously unknown cuboid [Pb8(OH)12]4+ cluster and NO3 groups. The study used crystals formed by anthropogenic processes on a medieval mine dump, probably involving black gunpowder used in the blasting of ore. Pb2(OH)3(NO3) is associated with a second nitrate, Pb13O8(OH)6(NO3)4, which was previously designated as “Pb3O3(OH)4(NO3)2” or “Pb3(OH)5(NO3)”. It is rhombohedral, space group , with a = 10.263(1), c = 25.454(5) Å, and a structure solution is in complete agreement with an independent single-crystal study by Li et al. (2001). Probable hydrogen bonds in Pb2(OH)3(NO3) are indicated. Reported data on clusters and lead hydroxide and oxide nitrates are summarized and discussed critically. The probable conditions of formation of the studied samples are evaluated.

Lattice parameters and crystal structures of the synthetic spinels Co3O4, CoCr2O4, and solid solutions in the binary join Co3O4-CoCr2O4, have been determined by powder X-ray diffraction structural refinements. In all these spinels the cation distribution is completely normal at room temperature, and the tetrahedrally coordinated cation site is occupied only by Co2+. The ionic radius of Co2+(tet) increases from 0.556(3) in Co3O4 to 0.599(4) in CoCr2O4. In the spinel structure, the interatomic distance between the tetrahedral cations and oxygen are geometrically independent of those between the octahedral cations and oxygen; thus the variation in effective ionic radii is ascribed to next-nearest neighbour effects, induced by covalent tendencies in the low-spin Co3+-O bond. The results demonstrate that the assumption of constant ionic radii even within an isomorphic group such as the oxide spinels needs to be made with caution.

Oxidative dissolution of a primary Mn-silicate phase (rhodonite) was studied via synchrotron X-ray techniques. The study was designed to combine the element-specific chemical technique of Glancing Incidence X-ray Absorption Spectroscopy (GIXAS) with the surface structural technique of X-ray scattering in order to produce the first depth resolved study of Mn-silicate low-temperature reactivity. A chemo-mechanically polished polycrystalline rhodonite sample was characterized and then reacted with pH 3.5 nitric acid. The surface originally had a mosaic structure and 15.5 (±1) Å r.m.s. roughness. Surface composition was not measurably different from bulk rhodonite before reaction, indicating that the surface preparation regimen had not produced an altered surface. After 1 h of reaction, the roughness of the mineral surface decreased and reflectivity oscillations developed, resulting from the formation of a leached layer. This layer was 74.7 (±2) Å thick with an electron density equal to 72% of that of bulk rhodonite (equal to the loss of ~1 in 2 Mn atoms). Both the primary and the buried interfaces had similar roughnesses; 4.9 and 4.5 (±1.0) Å , respectively. Diffuse scatter indicated that the correlation length between surface features also decreased. The GIXAS analysis showed that the Mn remaining in the surface had become oxidized, with the degree of oxidation decreasing as a function of depth. Oxidation penetrated at least 140 Å into the structure. A further 2.5 h of reaction at pH 3.5 caused dissolution of the leached layer and reduced the thickness of this altered region to 16.0 (±2) Å , while surface roughness increased slightly to 6.2 (±1.0) Å . Depletion of Mn in this region increased only slightly relative to the first reaction step; the electron density was 67% that of bulk rhodonite, equivalent to the loss of 2 in 3 Mn atoms. The thickness of the oxidized region however, persisted. Analysis by XPS on the same specimen corroborates the X-ray results.

Adiabatic self-heating tests were carried out on five New Zealand coal samples ranging in rank from lignite to high-volatile bituminous. Kinetic parameters of oxidation were obtained from the self-heating curves assuming Arrhenius behaviour. The activation energy E (kJ mol–1) and the pre-exponential factor A (s–1) were determined in the temperature range of 70–140°C. The activation energy exhibited a definite rank relationship with a minimum E of 55 kJ mol–1 occurring at a Suggate rank of ∼6.2 corresponding to subbituminous C. Either side of this rank there was a noticeable increase in the activation energy indicating lower reactivity of the coal. A similar rank trend was also observed in the R70 self-heating rate index values that were taken from the initial portion of the self-heating curve from 40 to 70°C. From these results it is clear that the adiabatic method is capable of providing reliable kinetic parameters of coal oxidation.

Heavy metal-bearing sediment particles enter river systems by discharge of mine or processing waste, tailings dam failures, remobilization of mining-contaminated alluvium and mine drainage. The mineralogy and geochemistry of these particles is dependent upon the original ore mineralogy, and on processes that have occurred in the source areas, during transport and deposition and during postdepositional early diagenesis. This paper reviews the research carried out to date on the sources, mineralogy, chemistry and fate of heavy metal-bearing particles in mining-affected river systems, and identifies six important avenues for further investigation.

Some samples of hollandite-type titanates from the Murun alkaline complex (Yakutia, Russia) contain appreciable amounts of Pb (up to 12.5 wt.% PbO). These titanates occur in a pegmatitic K-feldsparaegirine rock containing subordinate K-rich batisite, titanite, wadeite and other minerals. The Pb-bearing crystals coexist with hollandite-type phases devoid of detectable Pb and zoned from a Kdominant (priderite) core to a Ba-dominant (henrymeyerite) rim. Recalculation of the microprobe analyses on the stoichiometric basis indicates that most of the Fe occurs in this mineral in trivalent form, suggesting the existence of a solid solution between the Ba(Ti6Fe)O16, K2(Ti6Fe)O16 and Pb(Ti6Fe)O16 end-members. The maximum proportion of the latter end-member in the Murun titanates is ∽45 mol.%. The Ba-free compositions [Pb1.0–1.3(Ti,Fe)8O16] and intermediate members of the (Ba1–xPbx)(Ti6Fe)O16 series were synthesized at 1050 –1100ºC. The synthesis products comprise tetragonal hollandites of various stoichiometry intermixed with rutile, a pseudobrookite-type phase and (for the Ba-free compositions) minor macedonite. Electron microprobe analyses of the hollandites indicate that there is a continuous series of compositions between the two hexatitanate end-members, Ba(Ti6Fe)O16 and Pb(Ti6Fe)O16. The crystal structure of one intermediate member was refined by the Rietveld method in space group I4/m, and found to differ from the hollandite archetype (i.e. Pb-bearing Ba manganate) in that Pb is preferentially partitioned into the 2b tunnel site at (0,0,½), whereas Ba is partitioned into the larger 4e site at (0,0,∽0.8).

The Miocene, epithermal, Ag-rich polymetallic Santo Toribio deposit is hosted by the volcanics of the Quiruvilva-Pierina subbelt, Northern Peru, which also comprises the world-class, high sulphidation Pierina deposit. The Ag-rich, alabandite-bearing veins of the Santo Toribio deposit formed during two major stages. The early stage is characterized by deposition of arsenopyrite, pyrite, quartz, Mn- sphalerite, stannite, alabandite and minor miargyrite. Sphalerite associated with this stage is exceptionally enriched in Mn (up to 14.5 wt.%) and alabandite is optically and mineralogically zoned. Its brown zones have greater Fe+Sb and smaller Mn contents than the green zones and Fe+Sb replaces Mn in its structure. During this early stage, fs2 must have been high to allow the stabilization of alabandite relative to rhodochrosite. In the second stage, the physicochemical conditions changed and the CO2/S ratio increased, causing dissolution of alabandite and the deposition of abundant rhodochrosite and a second generation of arsenopyrite, pyrite and quartz, sphalerite with chalcopyrite inclusions, mirargyrite, ramdohrite, and finally stibnite. This polymetallic ore probably formed due to an abrupt decrease in H+ and/or Cl- concentration caused by boiling or dilution of the high-salinity hydrothermal fluids and constitutes an example of “intermediate sulfidation-state” epithermal deposits.

Conventional experiments designed to investigate the mechanical properties of polycrystalline geological materials are generally restricted to measurements of whole-rock properties. However, when comparing the measurements with theoretical models, it is frequently essential to understand how the deformation is accommodated at the grain-scale. This is particularly true for polymineralic rocks because in this case most theories express the whole-rock properties as some function of the properties of their constituent minerals, and hence the contribution which each phase makes to those properties must be measured if the theories are to be fully assessed. The penetrating nature of neutrons offers a method of addressing this problem. By performing deformation experiments in the neutron beam-line and collecting neutron diffraction patterns at different applied loads, the lattice parameters of all the mineral phases present may be determined as a function of load. The elastic strain experienced by each phase is then easily determined. Moreover, the strain in different lattice directions is also obtained. From this information a wide range of problems relevant for the characterization of the elastic and plastic deformation behaviour of polymineralic geological materials can be explored. An experimental technique for carrying out such experiments is described, and its validity is demonstrated by showing that the results obtained from deforming an elastically isotropic olivine + magnesiowüstite sample agree, to within very tight bounds, with the behaviour predicted by theory for elastically isotropic composites.

A dolostone layer is found in spatial association with the Emirli epithermal Sb-Au deposit in western Turkey. It occurs within an argillic alteration zone adjacent to the major Emirli fault zone, which is the controlling structure for the deposit, and is composed of large closely packed subhedral to anhedral planar and nonplanar dolomites. Pyrite is the only accessory mineral in the layer and occurs as disseminations and veinlets up to 100 μm wide. Dolomite crystals are petrographically homogeneous and have consistent deep-red cathodoluminescence (CL) colour with no zoning which implies single-stage dolomitization of a calcitic precursor which is partly preserved as remnant patches of orange-coloured CL zones. Some crystal boundaries have dark (or no) CL colour. Electron microprobe line-scan analyses across these regions indicate intense enrichment of Fe and Mg depletion, revealing late-stage Fe-metasomatism (ankeritization) especially prevalent near pyrite veinlets and disseminations.

Dolomite crystals are composed of 52.4–55.0 mol.% CaCO3, 29.9 –41.2 mol.% MgCO3, 1.8 – 14.4 mol.% FeCO3 and 0.75 –3.2 mol.% MnCO3 indicating ferroan dolomite. The relationship between Ca and Mg is not stoichiometric due to substitution of Mg2+ by Fe2+ after dolomitization, as demonstrated by a strong negative correlation between Fe and Mg. Whole-rock Fe contents of the dolostone layer increases toward the Emirli fault zone.

The δ13C(PDB) compositions of the Emirli dolomite, calcitic marbles, and graphite-schists are in the ranges of –1.6 to 0.8‰, 1.5 to 1.5‰ and –6.6 to –23.5%, respectively, indicating that dolomite was formed due to interaction of light-carbon-enriched fluids with calcitic marbles; light-carbon may have been derived from decarboxylation of the graphitic schist layers. δ18O(PDB) values of dolomite and marble range –15.2 to – 11.2‰ and –2.4 to – 3.5‰, respectively. This large isotopic difference between dolomite and marble was probably inherited from oxygen isotope exchange between the dolomitizing fluid and the precursor calcites, as well as other minerals enriched in light-oxygen.

Fluid inclusions in dolomite are two-phase, and homogenize into liquid within the temperature interval 242 – 362ºC with a mode of 290ºC, and have salinities of 1 – 3 wt.% NaCl equiv. Using this modal temperature, the average δ18O(PDB) composition of water in isotopic equilibrium with the Emirli dolostone was estimated to be –19.4±2.1‰, which is interpreted as an indication of modified surface-waters; this interpretation is also supported by low fluid salinity and Na and Sr contents. These fluids migrated along graben-related faults, penetrating deeper levels where they were transformed into hydrothermal fluids due to the high heat-flow of the Küçük Menderes graben system, and flowed-up mainly through the Emirli and Haliköy faults that control mineralization in local deposits of Sb-Au and Hg, respectively. Due to interaction with chlorite-bearing graphite-schists, the fluid may have dissolved Mg2+ from chlorite and been enriched in isotopically-light carbon due to decarboxylation of graphite. Dolomitization occurred as a result of the interaction of these fluids with a calcitic marble band adjacent to the Emirli fault zone. Subsequent introduction of Fe2+ caused ankeritization along dolomite crystal boundaries during first-stage Sb-Au mineralization.

An epidemiological and environmental study of the area around Biancavilla (CT, Italy) was prompted by a significant incidence of malignant pleural mesothelioma, which was not related to a specific occupational activity. An environmental dispersion of fibres was found and attributed to local quarry activities, whose extracted volcanic products also contained fibrous amphiboles and had been used extensively in the local building industry, especially in the period 1960–1970.

Abundant yellowish and grey-whitish asbestiform amphiboles with strongly asymmetric morphology were identified in this study, intimately associated with albitic feldspar, hematite and very minor orthopyroxene. These minerals fill the pores of the altered volcanic host rock (metasomatized benmoreitic lavas and pyroclastic rocks). The Rietveld method allowed a quantitative mineralogical analysis of the mineral mixture (24% amphiboles-asbestos, 73% feldspar and 3% hematite).

The crystal size and morphology of the grey-whitish amphibole fibres do not allow quantitative microprobe analyses; semi-quantitative EDS-SEM analyses of a prismatic mineral known to be fluoroedenite and the unknown fibrous crystals studied here suggest that they are the same mineral, although the fibres are generally depleted in Ca and Mg. The F content is the same in both occurrences. Unitcell parameters of the fibres are: a = 9.815(1), b = 17.992(3), c = 5.2733(6) Å , β = 104.547(9)º, V = 901.4(3)Å3, and the refractive indices are in the range 1.60 –1.63. Optical, chemical and Rietveld analyses of the fibres confirm their similarity with the yellow prismatic fluoro-edenite previously analysed.

Biancavilla is the first occurrence of amphibole fibres in a volcanic context (the Etnean volcanic complex). These fibres have a very anomalous composition (high ANa, IVAl and O3F contents) in comparison to other known oncogenic minerals.

Ikaite is a metastable hexahydrate of calcium carbonate, forming in aqueous conditions near freezing conditions. Neutron powder diffraction data of synthetic deuterated ikaite, collected at seven temperatures from 4 to 270 K, were refined. The linear thermal expansion coefficients are quite anisotropic, being smaller in the direction of the C—O bond. A review of the hydrogen-bonding scheme around the (CaCO03) ion pair is given and an additional weak potential hydrogen bond is suggested. Temperature-dependent growth of the atomic displacement factors of the carbonate O1 atom agrees with the previous suggestion of a possible low-frequency, hindered librational mode of the carbonate group.

Computer-controlled scanning electron microscopy (CCSEM) has been assessed for the determination of form and size distribution of heavy metals in urban contaminated soils. Metal distributions within individual particles were determined using X-ray element mapping. The sites selected for study were (1) around a landfill site, previously a colliery in Wolverhampton, UK and (2) a private garden adjacent to a railway in Nottingham, UK. Backscattered thresholding techniques were used to isolate the Pb-containing categories. The classification results for both Wolverhampton and Nottingham soils were generally similar but more Pb-containing classes were observed for the Nottingham samples when a comparison was made between results of the same size fractions. However, difficulties with the technique arose when particles showing chemically similar weathering crusts were assigned to the same class, despite having different internal compositions. The CCSEM data therefore need to be interpreted with caution and their application limited to situations in which particle internal complexity is not an issue.

The application of Raman spectroscopy to the study of the mixed cationic Pb-Cu and Pb-Cu-Ag minerals: boleite, cumengeite and diaboleite has enabled their molecular structures to be compared. Each of these three minerals shows different hydroxyl-stretching vibrational patterns, but some similarity exists in the Raman spectra of the hydroxyl-deformation modes. The low-wavenumber region is characterized by the bands assigned to the cation-chloride stretching and bending modes. Phosgenite is also a mixed chloride-carbonate mineral and a comparison is made with the molecular structure of the aforementioned minerals. Raman spectroscopy lends itself to the study of these types of minerals in complex mineral systems of secondary mineral formation.

All samples of silica sinter, <2 y old taken from the discharge drain of the Wairakei geothermal power station and the Rainbow Terrace of Orakei Korako, consist of non-crystalline opal-A. This silica phase deposits directly upon the concrete drain wall and filamentous templets, extending from this wall, afforded by the microbial community present in the drain, whose nature was determined by a culture- independent strategy that entailed construction, fingerprinting and sequencing of a 16S clone library. The bacterial community is dominated by five major groups of organisms, present in approximately equal proportions, and which account for ∼50% of the community. None of the 16S sequences from these dominant groups yielded a perfect match with 16S sequences for named organisms in the international databases. However one dominant group clusters with Hydrogenophilus thermoluteus, a thermophilic filamentous bacterium, and two cluster with putatively thermophilic members of the Cyanobacteria and green non-sulphur bacteria respectively. Initial opal-A deposits rapidly as agglomerations of silica nanospheres that, in turn, form chains of coalesced, oblate, microspheres <0.4 x 0.2 mm about the barbicel-like filaments, to produce a mat of fine woven strands. The majority of individual filaments are <8 μm long and 0.8 mm wide but may be up to 55 mm long by 1 mm wide. Where laminar flow dominates, most strands develop parallel to the drain current but some strands crisscross while others protrude above the mat surface. Where flow is turbulent, strands lack preferred orientation and some adopt a helical form. In general, following deposition, the values of the scattering broadband at half (FWHM) and three quarters (FWTM) of the maximum intensity decrease with increasing sample age. The behaviour of the band at one quarter maximum intensity (FWQM) is less consistent, but, in general, the youngest sinters possess the highest FWQM, FWHM and FWTM values that prove independent of fabric type. Opal-A silica matures following its removal from the parent fluid, especially where the sinter surface is filmed by water. A continual movement of silica is shown by a second generation of microspheres formed on the silica mat surface, by an increase in size of the initial microspheres, and by an increase in maximum intensity of the X-ray scattering broadbands. Similar silica aging behaviour occurs among young sinters developed upon microbial mats at Orakei Korako. The deposition and aging processes accord with the known behaviour of juvenile opaline silica in both natural and artificial systems whose pH, temperature and dissolved salt content are similar to Wairakei and Rainbow terrace: gelling of silica is favoured by the high pH (∼8.3) and temperature (∼60°C) of the Wairakei discharge fluid but the high dissolved salt content of the water (Na+ = 930 μg/g, Ca2+ = 12 μg/g, Cl = 1500 μg/g) and abundant microbial community facilitate rapid and copious flocculation of solid silica within the drain, in contrast to the slower accumulation on the natural sinter terrace at lower temperature (30—45°C) from less saline dilute bicarbonate-chloride waters (Na+ = 180 μg/g, Ca2+ = 0.2 μg/g, Cl = 400 μg/g, pH = 8.1).

The tropospheric dust loading in Upper Silesia (Poland) shows a steady, annually averaged supply of minerals from natural and anthropogenic sources, industrial dust emitters, domestic heating, transportation, but with superimposed seasonal changes for some dust types. Samples of airborne and deposited particles were collected at monthly intervals between 1996 and 2001 in several cities of Upper Silesia. Dust samples were examined by X-ray powder diffraction, analytical transmission electron microscopy, analytical scanning electron microscopy, and electron microprobe microanalysis. The most common dust included quartz, gypsum, coke, soot, hematite, magnetite, wüstite, bassanite, graphite and various K-, Fe- and Mg-bearing aluminosilicates, in order of decreasing abundance. Minor phases included α-iron, sulphur, sphalerite, halite, sylvite, hercynite, franklinite, baryte, dolomite, ankerite, apatite, olivine and feldspars. Quartz, and specific industrial minerals, e.g. spinels, sphalerite, olivine and iron, occurred throughout the year in almost constant abundances. The amounts of all other dust components show seasonal variations; gypsum, baryte and other sulphates are particularly abundant in winter. In general, minerals related to low-emission sources are abundant in the winter time, while both natural dusts and dust from high-emission sources are predominant during the summer.

Phase transitions in the BaAl2O4–SrAl2O4 solid solution have been analysed as a function of temperature and composition using infrared (IR) powder absorption spectroscopy. The improper ferroelectric phase transition P6322 → P63 (2A superstructure) in the BaAl2O4 end-member can be detected through a change in slope of the wavenumbers of hard modes at ∽450 K. A change in line widths at ∽520 K appears to correlate with the development of diffuse intensity in a*-b* planes of electron diffraction patterns reported elsewhere in the literature. The same shift in wavenumber of hard modes is not observed in spectra from samples with compositions corresponding to 60, 80 and 90% of BaAl2O4 component, but a change in line widths at ∽500 K has been tentatively explained in terms of a different phase transition, from a P6322 parent structure to a P63 (√3A superstructure) product. Strain analysis of published high-temperature lattice parameter data suggests that the hexagonal → monoclinic transition in Sr-rich members of the solid solution may consist of two discrete transitions, and a sequence P6322 → C2 → P21 is suggested. The second transition could be related to instabilities in the hexagonal solid solution. Autocorrelation analysis of the IR spectra reveals a large positive deviation from linear behaviour across the solid solution, which is interpreted in terms of microscopic strain effects. These microscopic strains are probably responsible for the different transformation behaviour shown by samples with different compositions across the solid solution.

Compreignacite, a naturally occurring potassium uranyl oxide hydrate, is an expected alteration product of spent nuclear fuel subjected to oxidative corrosion in the presence of water. Ion-exchange experiments were performed using natural crystals of compreignacite in a 2 M CsCl solution at 180°C for 24 h, and in a 100 ppm CsCl solution at 90°C for 14 days. Exchange of Cs into crystals of compreignacite was demonstrated by crystal-structure analysis for a crystal from 2 M solution and chemical analysis for crystals from both exchange experiments. The structure of Cs-exchanged compreignacite is hexagonal, space group P2m, a= 14.1014 (18) Å, c = 15.127(3) Å, V = 2605.1(7) Å2. It was solved by direct methods and refined on the basis of F2 for all unique reflections to a final R1 = 6.37%. The structure determination demonstrated almost complete exchange of Cs for K in the interlayer of the structure, as confirmed by compositional analysis of the crystals, and provided the formula Cs6[(UO2)12(OH)10O10](H2O)3.5, Z= 2. The structure of Cs-exchanged compreignacite contains α-U3O8-type sheets of uranyl pentagonal bipyramids that are topologically identical, although compositionally distinct, to those in compreignacite. Compreignacite crystals placed in 100 ppm CsCl solution also incorporated substantial Cs by ion exchange. Ion exchange experiments, using Cs-exchanged compreignacite from earlier experiments, in 2 M KCl solution at 90°C for 14 days showed that compreignacite will retain significant Cs in the presence of a solution rich in K. These experiments indicate that formation of compreignacite structure-type phases in a geological repository due to alteration of nuclear waste may significantly impact upon the mobility of Cs, either by direct incorporation of Cs into growing crystals, or by exchange of Cs into earlier-formed crystals of compreignacite when they contact Cs-bearing solutions.