The crystal structure of khinite, Pb2+Cu2+3Te6+O6(OH)2, orthorhombic, a = 5.7491(10), b = 10.0176(14), c = 24.022(3) Å, V = 1383.6(4) Å3, space group Fdd2, Z = 8, Dcalc = 6.29 g/cm3, from the Empire mine, Tombstone, Arizona, USA, has been solved by direct methods and refined to R1 = 3.2% on the basis of 636 unique observed reflections. There is one distinct Te site occupied by Te and coordinated by six O atoms in an octahedral arrangement with a <Te–O> distance of 1.962 Å. typical of Te6+. There are three octahedrally-coordinated Cu sites, each of which is occupied by Cu2+ with <Cu–O> distances of 2.132, 2.151 and 2.308 Å, respectively. Each Cu octahedron shows four short meridional bonds (~1.95 Å) and two long apical bonds (2.46–2.99 Å) characteristic of Jahn-Teller-distorted Cu2+ octahedra. There is one distinct Pb site occupied by Pb and coordinated by six O atoms and two (OH) groups with a <Pb–O, OH> distance of 2.690 Å. TeF6 and CuΦ6 octahedra share edges and corners to form an [MΦ2] (where Φ = O, OH) layer of composition [TeCu3Φ8]. These layers stack along the c axis at 6 A intervals with Pb atoms between the layers. Identical layers occur in the structure of parakhinite, Pb2+Cu2+Te6+O6(OH)2, hexagonal, a = 5.765(2), c = 18.001(9) Å, V =518.0(4) Å3, space group P32, Z = 3, Dcalc = 6.30 g/cm3. It is only the relative stacking of the TeCu3Φ8 layers in the c direction that distinguishes the two structures, and hence khinite and parakhinite are polytypes.

Weathering of terrestrial Ca- and Mg-bearing silicate minerals is an important control on atmospheric CO2 on geological time scales. It has been determined that vascular plants can accelerate mineral weathering as compared to non-vascular plants or non-vegetated surfaces. This indicates that the evolution of vascular plants, particularly the deep-rooted trees, may play a large role in the long-term carbon cycle and its regulation of the atmosphere. The weathering impact of the separate evolutionary appearances of the gymnosperms in the Palaeozoic and the angiosperms in the Mesozoic, and the shifting ecological dominance from the former to the latter, is currently poorly understood. This study aims to contribute to our understanding of the quantitative weathering rates of the angiosperms and gymnosperms by examining plant-mineral interactions of the two tree types in a temperate field setting underlain by granodiorite. Results include determinations of soil element fluxes and etching of minerals. The observed root-mineral interactions resulted in only slightly more weathering of Ca-bearing minerals by the angiosperms. However, we observed significantly more weathering of the Mg-bearing minerals by the gymnosperms. These results suggest that increasing dominance of the angiosperms in forests in the Mesozoic may have had a small or neutral impact on accelerating overall mineral weathering and regulating CO2, but that this impact may be lithology-dependent.

Brumadoite, ideally Cu3Te6+O4(OH)4-5H2O, is a new mineral from Pedra Preta mine, Serra das Eguas. Brumado, Bahia, Brazil. It occurs as microcrystalline aggregates both on and, rarely, pseudomorphous after coarse-grained magnesite, associated with mottramite and quartz. Crystals are platy, subhedral. 1—2 μm in size. Brumadoite is blue (near RHS 114B), has a pale blue streak and a vitreous lustre. It is transparent to translucent and does not fluoresce. The empirical formula is (Cu2.90Pb0.04Ca0.01)Σ2.95 (Te0.936+Si0.05)Σ0.98O3.92(OH)3.84.5.24H2O. Infrared spectra clearly show both (OH) and H2O. Microchemical spot tests using a KI solution show that brumadoite has tellurium in the 6+ state. The mineral is monoclinic, P2/m or P21. Unit-cell parameters refined from X-ray powder data are a 8.629(2) Å, b 5.805(2) Å, c 7.654(2) Å,β 0 103.17(2)°, F 373.3(2) Å3, Z= 2. The eight strongest X-ray powder-diffraction lines [d in Å,(I),(hkl)] are: 8.432,(100),(100); 3.162,(66),(2̄02); 2.385,(27),(220); 2.291,(12),(l̄22); 1.916,(11),(312); 1.666,(14),(4̄22,114); 1.452,(10),(323,040); 1.450,(10),(422,403). The name is for the type locality, Brumado, Bahia, Brazil. The new mineral species has been approved by the CNMNC (IMA 2008-028).

Although moissanite has been found in various rocks, reliable primary moissanite has been reported only from kimberlites and meteorites. The Dabie Mountain moissanite reported in this paper is the first occurrence of primary moissanite hosted by serpentinite. It differs from synthetic silicon carbide in optical properties, inclusions and infrared spectrum. The biaxiality of the Dabie Mountain moissanite is thought to be the result of intracrystal deformation. In reference to the ultrahigh pressure (7—8 GPa) signature of exsolution of rod-like apatite, clinopyroxene and rutile in garnets, and magnetite lamellae in olivine reported in the Dabieshan, we inferred that the moissanite from the Dabie Mountains was probably generated at a depth of 180 km; and then subducted to a depth of 210—250 km, where the moissanite became biaxial before its exhumation.

The crystal structures of lomonosovite, ideally Na10Ti4(Si2O7)2(PO4)2 O4, a = 5.4170(7) Å, b = 7.1190(9) Å, c = 14.487(2) Å, a = 99.957(3)°, β = 96.711(3)°, γ = 90.360(3)°, V= 546.28(4) Å3, Dcalc. = 3.175 g cm“3, and murmanite, ideally Na4Ti4(Si2O7)2O4(H2O)4, a = 5.3875(6) Å, b = 7.0579(7) Å, c = 12.176(1) Å, a = 93.511(2)°, 0 = 107.943(4)°, y = 90.093(2)°, V = 439.55(2) Å3, Dcalc. = 2.956 g.cm∼3, from the Lovozero alkaline massif, Kola Peninsula, Russia, have been refined in the space group P1̄ (Z = 1) to R values of 2.64 and 4.47%, respectively, using 4572 and 2222 observed |F°≥ 4σF| reflections collected with a single-crystal Bruker AXS SMART APEX diffractometer with a CCD detector and Mo-Kα. radiation. Electron microprobe analysis gave empirical formulae for lomonosovite (Na9.50Mn0.16Ca0.11)Σ9.77(Ti4+2.83Nb0.51Mn0.272+Zr0.11Mg0.11Fe2+0.10Fe3+0.06Ta0.01)Σ4.00(Si2.02O7)2(P0.98O4)2(O3.50F0.50)Σ4, Z = 1, calculated on the basis of 22(O+F) a.p.f.u., with H2O determined from structure refinement and Fe3+/(Fe2++Fe3+) ratios obtained by Mössbauer spectroscopy. The crystal structures of lomonosovite and murmanite are a combination of a titanium silicate (TS) block and an intermediate (I) block. The TS block consists of HOH sheets (H-heteropolyhedral, O-octahedral), and is characterized by a planar cell based on translation vectors, t1 and t2, with t1\ ∼5.5 and t2 ∼7 Å and ttA t2 close to 90°. The TS block exhibits linkage and stereochemistry typical for Group IV (Ti = 4 a.p.f.u.) of the Ti disilicate minerals: two H sheets connect to the O sheet such that two (Si2O7) groups link to Ti polyhedra of the O sheet adjacent along tx. In murmanite and lomonosovite, the invariant part of the TS block is of composition Na4Ti4(Si2O7)2O4. There is no evidence of vacancy-dominant cation sites or (OH) groups in the O sheet of lomonosovite or murmanite. In lomonosovite, the I block is a framework of Na polyhedra and P tetrahedra which gives 2[Na3 (PO)4] p.f.u. In murmanite, there are four (H2O) groups in the intermediate space between TS blocks. In lomonosovite, TS and I blocks alternate along c. In murmanite, TS blocks are connected via hydrogen bonding. The H atoms were located and details of the hydrogen bonding are discussed.

Cathodoluminescence (CL) imaging and spectroscopy are outstanding methods in several fields of geosciences. Cathodoluminescence can be examined using a wide variety of electron-beam equipment. Of special interest to geologists are optical microscopes (OMs) equipped with an electron gun. scanning electron microscopes (SEMs) and electron microprobes. Despite the similar kind of excitation, the results obtained may show marked differences. These are related to the use of focused or defocused as well as a scanned or stationary electron beam and the kind of signal acquisition. Images obtained by OM-CL (hot or cold acceleration) and SEM-CL differ due to different spatial resolution, true colour, grey-scale, or monochromatic detection, contrast inversion, phosphorescence effects, etc.

Instrumentation used for spectroscopic studies may differ in sequential or parallel signal acquisition, wavelength range, spectral resolution, and the kind of analytical spot limitation. This is particularly important when investigating transient CL, rare earth element (REE) emissions, or luminescence in the near UV and IR regions as well as samples with small grain sizes and contrasting CL behaviour of adjacent mineral phases.

In the present study, the influence of analytical parameters is demonstrated for certain mineral examples including zircon, fluorite, apatite, feldspar, quartz, corundum, kaolinite, and dickite.

Aluminium substitution into goethite, α-FeOOH, has been studied systematically by infrared spectroscopy over the frequency interval 150 to 700 cm-1. A range of synthetic compositions. (Fe1-xAlx)OOH, 0 ≤ x ≤ 0.0857, plus end-member diaspore (AlOOH) were examined. The IR spectrum of FeOOH over the range of interest can be deconvoluted into 9 peaks: 670, 633, 497, 451, 409, 396, 360, 290 and 268 cm-1. With addition of Al, the spectra become broader and the frequencies of the modes shift to higher values. An effective line width parameter Δcorr was determined by autocorrelation analysis for each spectrum and there is a significant increase in the Δcorr for compositions with >5.85 mol.% Al substitution, indicating that there is very significant structural strain associated with this solid solution at compositions where a significant number of Al sites will have an additional Al atom in the first cation coordination sphere. Trends in the values of Δcorr with composition mirrored published enthalpy of mixing values indicating that Al-goethite is metastable with respect to the goethite and diaspore end-members. The role of substitutional strain and possible partial order of Al is briefly discussed.

Presented here are quantitative dissolution rate data (volume of pyrite lost/time) for the inorganic oxidation of pyrite in synthetic, anaerobic and acidic (pH 2) hydrothermal vent fluids (HVF) from experiments where the volume loss was measured directly via Vertical Scanning Interferometry (VSI). The VSI-derived reaction rate was 2.12x10-10±1.14x10-1 mol/m2/min, which is ∼2 to 4 orders of magnitude slower than pyrite oxidation rates previously determined using traditional batch experiments where rates are calculated based on changes in solution chemistry. This lower rate stems primarily from differences in experimental conditions (i.e. water to rock ratios, vigorous vs. gentle stir rates, grain-size effects, time), yet the rates derived here are believed to be more representative of pyrite oxidation in natural environments where more static and high solution to solid rate conditions prevail, such as seafloor conditions or acid-mine-drainage environments.

Vaterite and aragonite polymorphs in freshwater cultured pearls from mussels of the genus Hyriopsis (Unionidae) were structurally and compositionally characterized by Raman spectroscopy, Micro computer tomography, high resolution field emission scanning electron microscopy, electron microprobe analysis and laser ablation inductively coupled plasma mass spectrometry. The appearance of vaterite in pearls is related to the initial stages of biomineralization, although we demonstrate that vaterite can not be a precursor to aragonite. It is not related to a particular crystal habit and therefore does not have a structural functionality in the pearls. Larger contents of elements typically bound to organic molecules, such as P and S in vaterite, as well as larger total organic contents in vaterite as opposed to aragonite in conjunction with larger concentrations of Mn2+ and Mg2+, imply a stabilizing role of organic macromolecules and X2+ ions for biological vaterite. Distribution coefficients between aragonite and vaterite for provenance-independent elements, such as Mn and Mg (0.27 and 0.04, respectively) agree very well with those observed in fish otoliths.

The crystal structure of seeligerite, Pb3IO4Cl3, from the San Rafael mine, Sierra Gorda, Chile, was solved in the space group Cmm2, and refined to R = 3.07%. The unit-cell parameters are: a = 7.971(2), b = 7.976(2), c = 27.341(5) Å, V = 1738.3(6) Å3 and Z = 8. The crystal structure consists of a stacking sequence along [001] of square-net layers of O atoms and square-net layers of Cl atoms with Pb+ and I+ cations located in the voids of the packing. As is typical of cations with a stereoactive lone-pair of electrons, Pb2+ and I5+ adopt strongly-asymmetrical configurations. Pb2+ cations occur in a variety of coordination polyhedra, ranging from anticubes and monocapped anticubes to pyramidal ‘one-sided’ coordinations. I5+ is coordinated by a square of four oxygen atoms: I1 and I3 exhibit a ‘one-sided’ coordination, whereas I2 has square-planar coordination.

The TEM investigation has revealed additional superlattice reflections (which were not registered by X-ray diffraction (XRD)) in the hk0 diffraction pattern of seeligerite based upon a 0.158 Å-1 square net, which can be interpreted as arising from a 20-cation super-sheet motif (12.6 Å x 12.6 Å), likely related to a further level of Pb-I order superimposed upon the 8-site motif identified by XRD.

Garnets, omphacite and the minerals of a clinopyroxene/amphibole/plagioclase symplectite in UHP eclogites from Yingshan, Dabieshan have been investigated by TEM and Micro-FTIR. TEM reveals that the predominant microstructures in eclogites and symplectite-forming minerals are chain multiplicity faults (CMFs), dislocation substructures, clusters of water molecules up to ∼50 nm in diameter and recrystallized grains ∼1.75 μm in diameter. This indicates dynamic recrystallization of omphacite, probably during an eclogite-facies metamorphic episode. The deformation structures in symplectite-forming minerals were produced by plastic deformation related to an amphibolite-facies retrograde metamorphic event. CMFs described in the present work demonstrate the existence of an infrequent ½<011> (010) slip system for P2/n omphacite from an UHP eclogite sample from Dabieshan. The frequent occurrence of CMFs in omphacite suggests that they indicate an important deformation mechanism in omphacite and shows that this slip system plays a significant role in the deformation and recovery of eclogite. The hydrous components of deformed minerals may cause plastic deformation of the rocks by dislocation movement and accelerate retrograde metamorphism. Micro-FTIR results show that all the garnets and omphacites contain structural water occurring as hydroxyl groups (OH) or water (H2O). The structural water contents in omphacite range from 110—710 ppm and in garnet from 0—180 ppm. Water released during decompression might supply an early-stage retrograde metamorphic fluid.

Otoliths, the earbones of teleost (bony) fish, are constructed from alternating layers of aragonite and protein. Laser ablation inductively coupled plasma mass spectrometry and proton-induced X-ray emission are used to obtain spatially well-resolved trace element line-scans that show trace-element concentrations are correlated with the annular structure. Zoned Sr and Zn signatures are common whereas other elements such as Cu, Pb, Li and Cs can be related to the proximity of mineral deposits. Aragonite in otoliths can incorporate a wide range of trace elements at the low-ppm level including alkali- and alkaline-earth elements and base metals; Se has also been detected in proximity to coal mines. These trace elements, in combination with the annular structures, are an important archive for recording information on environments occupied by fish, environmental change and exposure to pollutants.

The understanding of biogeochemical processes at the interface between geosphere, hydrosphere and biosphere is of paramount importance for many questions related to global climate and environmental change at very different time and spatial scales. In addition, soils are the principal resource for food production and the understanding of soil formation processes and biological interactions within soils is indispensable for the development of sustainable land-use strategies. In this contribution we present a research initiative, the multidisciplinary ‘BigLink’ Project, aiming at a better understanding of the links between weathering, soil formation and ecosystem evolution and how these biosphere-geosphere interactions are influenced (and themselves influence) climate and environmental change.

Six natural crystals from the Sludyanka crystalline complex belonging to the eskolaite (Cr2O3)–karelianite (V2O3)–hematite (Fe2O3) solid solution were studied by means of X-ray diffraction and electron microprobe. The Fe3+-poor samples show a general increase in a and c cell parameters with increasing mean cationic radius (MCR), consistent with that shown by the synthetic crystals along the eskolaite–karelianite join. The Fe3+-richer sample deviates significantly from the behaviour shown by the Fe3+-poor ones, similar to synthetic and natural hematites; with increasing MCR, the a and c cell parameters increase linearly along the eskolaite-karelianite join. However, for the samples rich in Fe3+, from karelianite to hematite, a shows a slightly steeper slope whereas the c parameter decreases strongly. The octahedral distortion increases slightly as a function of MCR along the eskolaite-karelianite join, whereas it increases markedly for Fe3+-rich samples. The evolution of the octahedral edges and of the octahedral distortions as a function of MCR are responsible for the behaviour of the unit-cell parameters along the eskolaite-karelianite-hematite join.

Vugs in late hydrothermal veins in the serpentinite at Gew-graze, Lizard, Cornwall, UK, contain serpentine spheres ≤0.7 mm in diameter composed of a crystallographically controlled radial array of well crystallized lizardite-1T crystals. Examinations with optical and scanning electron microscopy reveal that the spheres actually have polyhedral morphology. The polyhedral facets at the sphere surface are the (0001) terminations of individual single crystals of lizardite. Each lizardite crystal is a hexagonal prism and tapers inwards to the core. The angle from prism axis to prism axis is always ∼24°, and this angle is consistent even though individual prisms have not maintained contact during growth. The space between prisms is filled by smaller crystals of lizardite in more random orientations, forming a solid sphere. Collectively, the tapering prisms form a growth array that produces a surface tessellation consisting of mainly 6-fold neighbours, but with some 5-fold arrangements to accommodate a closed spherical structure. A ‘buckybalF, modified by adding face-centring points to each hexagon and pentagon, provides a useful model to describe the space filling adopted by the polyhedral lizardite spheres. Cross sections (close to an equatorial plane) through these polyhedral spheres resemble cross sections of polygonal serpentine, with 15 sectors at 24° to each other, though very much larger in diameter.

A detailed field study to determine quantitatively the distribution of K-feldspar megacrysts, mafic microgranular enclaves (MME) and metasedimentary xenoliths has been carried out in the Monte Capanne pluton (Elba, Italy) with a view to evaluating the utility of this approach to petrogenetic investigations. Mafic microgranular enclaves are inferred to result from interactions between mafic and felsic magmas, while xenoliths attest to crustal assimilation occurring in the Monte Capanne magma chamber. In particular, we emphasize, based on our field data, that both processes are intimately linked, such that xenolith dissolution during assimilation was triggered by replenishment with hot mafic magma. It is suggested that the previously defined ‘San Piero’ and ‘San Francesco’ facies do not differ substantially, and are thus amalgamated and renamed as the ‘Pomonte’ facies. Results also indicate that the abundance of K-feldspar megacrysts is positively correlated with the volumetric abundance of MME in the Sant’ Andrea facies, which we link to a recharging, mingling and textural coarsening event that occurred at a rather late stage of magma-chamber evolution prior to emplacement. This study demonstrates how petrogenetic processes can be deciphered by detailed field quantitative analyses of granite-forming components, thus complementing geochemical investigations.

Mineral phases and element localization were investigated in the vivid turquoise-coloured lichen, Lecanora polytropa, sampled from a psammite boulder in a wall supporting mine spoil at the abandoned copper mine, Riddarhyttan Kopparverke, southern Sweden. Normally pale yellowish (usnic acid), the lichen is turquoise coloured internally with bluish inclusions. X-ray mapping shows that Cu occurs on and within the lichen and does not coincide with P or S, suggesting that it is indeed associated with carbon or other elements not detected (or reported) using X-ray mapping. Scanning electron microscopy in back-scatter mode confirmed that the greatest Cu concentrations occur in the form of crystalline aggregates in coloured inclusions below the major internal turquoise layer with smaller Cu contents. X-ray diffraction with a position-sensitive detector (XRD-PSD) confirmed coloured crystalline aggregates consisted of the copper oxalate, moolooite. The study confirms the value of XRD-PSD as a non-destructive tool to characterize small (~50 μm) metal oxalate inclusions obtained from within lichen samples.

A REE-bearing fluorosilicate from the Tommot REE-Nb deposit in Yakutia, Russia, described without a name in 1966, is characterized here as a new species, proshchenkoite-(Y), of the vicanite group of borosilicates. Wavelength-dispersive electron probe analyses gave the following empirical formula: Y3.70REE7.54Ca1.55Na1.16Mn0.77Th0.10Pb0.01)Σ14.83(Fe2+0.83Mn0.15Ti0.02)Σ1.00Ca1.00(P0.70Si0.26As0.04)Σ1.00Si0.26B3.20(O34.55F13.45)Σ48. Boron was analysed with a nuclear microprobe method based on the nuclear reaction 11B(p,α)2α. The simplified formula is (Y,REE,Ca,Mn)15(Fe2+,Mn)Ca(P,Si)Si6B3O34F14. The mineral is trigonal, R3m, with a = 10.7527(7) Å, c = 27.4002(18) Å, V = 2743.6(6) Å 3, Z = 3. The crystal structure was refined to Rl = 0.042 for 1819 observed reflections. Proshchenkoite-(Y) is isostructural with okanoganite-(Y), vicanite-(Ce) and hundholmenite-(Y), and the differences in site occupancies are discussed. The strongest six reflections of the X-ray powder-diffraction pattern [dobs in Å, (I), (hkl)] are: 4.441, (36), (202); 3.144, (77), (214); 3.028, (45). (009); 2.968, (100), (027); 1.782, (32), (330); and 1.713, (32), (1.2.14). The mineral is optically uniaxial (—) with ω 1.734(2) and 8 1.728(2). The Mohs hardness is about 5; density measured on material subject to incipient metamictization is 4.72 g/cm3, as compared to Dcalc = 4.955 g/cm3.

The result of electron microprobe analyses of alleged okanoganite-(Y) from the type locality in Okanogan County, Washington, USA, is also presented. We find here also that P > Si at one of the sites, whereas the analytical data of Boiocchi et al. (2004) indicate Si > P. Consequently, the mineral we have analysed is the P analogue of okanoganite-(Y), another new species.

Scapolite oikocrysts, up to 3 cm in diameter, occur in cognate, cumulate nodules from the 2 Ma rift-related, alkali-basaltic Kula Volcanic Province in Western Turkey. Three scapolite-bearing nodules were found within deposits originating from two adjacent cones. They contain primocrysts of clinopyroxene, biotite, apatite and titanite, together with interstitial kaersutite, biotite, plagioclase and scapolite. Kula scapolites fall mid-way between the meionite (Ca4[Al6Si6O24]CO3) and marialite (Na4[Al3Si9O24]Cl) end-members (∼Me45—71). We believe this to be the first report of interstitial magmatic scapolite.

The sulphur-poor portions of the dry condensed Cu-Fe-Pd-S system were studied at 1000°C, 900°C and 725°C by synthesis in evacuated silicate glass tubes, along with textural observations and electron microprobe analyses of equilibrated reaction products. Sulphide melt coexists with Cu-Fe-Pd alloys, bornite, Fe1-xS and iss (intermediate solid solution, Cabri, 1973) and Pd4S. Compositional data were obtained for the associations bornite-alloy-melt, pyrrhotite-alloy-melt and for immiscible Cu-rich sulphide melts. Partition coefficients for all three metals were derived for the association alloy-melt. Formation of the two new Cu-Pd alloy minerals, skaergaardite and nielsenite, is discussed in terms of the present findings.