The crystal structure of balićžunićite, Bi2O(SO4)2, a new mineral species from the La Fossa crater of Vulcano (Aeolian Islands, Italy), was solved from single-crystal X-ray diffraction data and refined to R = 0.0507. The structure is triclinic, space group P1, with a = 6.7386(3), b = 11.1844(5), c = 14.1754(7) Å, α = 80.082(2), β = 88.462(2)°, γ = 89.517(2)°, V = 1052.01(8) Å3 and Z = 6. The crystal structure consists of six independent Bi sites, six S sites and 27 O sites of which three are oxo oxygen atoms not bonded to sulfur. Bismuth and S atoms are arranged close to a eutectic pattern parallel to the (100) plane. The planes are stacked atom on atom such that Bi always overlays S and vice versa. This structural feature is shared with the known structure of the high-temperature polymorph of the same compound, stable at T >535°C. However, the sequences of Bi and S atoms in the two structures are different and so are the arrangements of oxygen atoms. Characteristic building blocks in the structure of balićžunićite are clusters of five Bi atoms which form nearly planar trapezoidal Bi5 groups with oxo oxygens located in the centres of the three Bi3 triangles, which form the trapezoids. The trapezoidal Bi5O39+ ions are joined along [100] with SO42– groups by means of strong bismuth-sulfate oxygen bonds, forming infinite [100] rods with composition Bi5O3(SO4)5–. One sixth of the Bi atoms do not participate in trapezoids, but form, with additional SO42– groups, rows of composition BiSO4+, also parallel to [100]. [Bi5O3(SO4)5–] rods form infinite layers parallel to (010) with [BiSO4+] rows located on the irregular surface of contact between adjacent layers. Bi atoms occur in four different coordination types, all showing the stereochemical influence of the Bi3+ lone electron pair. In this respect the crystal structure of balićžunićite shows greater variability than its high-temperature polymorph which has only two types of the Bi coordination spheres present in balićžunićite.

The crystal structure of the organic mineral refikite has been determined. The mineral was found in joints in bark and wood from pine trees in the 'V Borkách' peat deposit near the town of Krásno, Slavkovský les Mountains, western Bohemia, Czech Republic. It forms white to light-yellow polycrystalline crusts or randomly intergrown, transparent, colourless, very thin, acicular crystals up to 0.2–0.5 mm long. Sometimes, colourless-to-white elongated prismatic crystals up to 1–1.5 mm in size were encountered. The mineral is soft (Mohs hardness ∼1) and very brittle, with an uneven fracture. No visible cleavage was discerned. Crystals have a greasy-to-glassy lustre; fine crystal aggregates have a pearly lustre. Refikite, empirical formula C20H34O2 or C19H33COOH, is a derivative of abietic acid. It is orthorhombic, space group P21212, with a = 22.6520(7), b = 10.3328(3), c = 7.6711(2) Å, V = 1795.49(9) Å3, Z = 4. Refikite comprises two closely related compounds based on perhydrophenanthrene. The major component has two axial methyl groups, one terminal carboxylic group and one terminal propan-2-yl (isopropyl) group joined to the three fused rings in the same fashion as in abietic acid. However, the fused ring system is fully reduced (contains single bonds only). In the minor component, the terminal propan-2-yl group is replaced by a propen-2-yl (methylvinyl) group. The crystal structure is stabilized by strong O···H–O hydrogen bonds. High-resolution mass spectroscopy (HRMS) confirmed a molecular mass of 306 and the formula C20H34O2. Hydrogen-1 and carbon-13 nuclear magnetic resonance (NMR) spectroscopy showed the presence of four methyl groups in the major component; infrared (IR), Raman and NMR spectra are consistent with the structure. The HRMS, IR and Raman spectroscopy methods confirmed the presence of a minor component containing the propen-2-yl group replacing the propan-2-yl group. This is also reflected in a shortened C15–C17 single bond metric of 1.468(6) Å shown by single-crystal X-ray analysis. The trivial name of the major component of refikite is tetrahydroabietic acid or abietan-18-oic acid. This work represents the first proof of the existence of abietic acid derivatives as naturally occurring species.

The new oxalate mineral antipinite is found in a guano deposit located on the Pabellón de Pica Mountain, Iquique Province, Tarapacá Region, Chile. Associated minerals are halite, salammoniac, chanabayaite, joanneumite and clays. Antipinite occurs as blue, imperfect, short prismatic crystals up to 0.1 mm × 0.1 mm × 0.15 mm in size, as well as their clusters and random aggregates. The mineral is brittle. Mohs hardness is 2; Dmeas = 2.53(3), Dcalc = 2.549 g cm–3. The infrared spectrum shows the presence of oxalate anions and the absence of absorptions associated with H2O molecules, C–H bonds, CO32–, NO3– and OH– ions. Antipinite is optically biaxial (+), α = 1.432(3), β = 1.530(1), γ = 1.698(5), 2Vmeas = 75(10)°, 2Vcalc = 82°. The chemical composition (electron-microprobe data, C measured by gas chromatography of products of ignition at 1200°C, wt.%) is Na2O 15.95, K2O 5.65, CuO 27.34, C2O3 48.64, total 99.58. The empirical formula is K0.96Na3.04Cu2.03(C2.00O4)4 and the idealized formula is KNa3Cu2(C2O4)4. The crystal structure was solved and refined to R = 0.033 based upon 4085 unique reflections with I > 2σ(I). Antipinite is triclinic, space group P1, a = 7.1574(5), b = 10.7099(8), c = 11.1320(8) Å, α = 113.093(1), β = 101.294(1), γ = 90.335 (1)°, V = 766.51(3) Å3, Z = 2. The strongest reflections of the powder X-ray diffraction pattern [d, Å (I,%) (hkl)] are 5.22 (40) (111), 3.47 (100) (032), 3.39 (80) (210), 3.01 (30) (033, 220), 2.543 (40) (122, 034, 104), 2.481 (30) (213), 2.315 (30) (143, 310), 1.629 (30) (146, 414, 243, 160).

Khvorovite, ideally Pb42+Ca2[Si8B2(SiB)O28]F, is a new borosilicate mineral of the hyalotekite group from the Darai-Pioz alkaline massif in the upper reaches of the Darai-Pioz river, Tajikistan. Khvorovite was found in a pectolite aggregate in silexites (quartz-rich rocks). The pectolite aggregate consists mainly of pectolite, quartz and fluorite, with minor aegirine, polylithionite, turkestanite and baratovite; accessory minerals are calcite, pyrochlore-group minerals, reedmergnerite, stillwellite-(Ce), pekovite, zeravshanite, senkevichite, sokolovaite, mendeleevite-(Ce), alamosite, orlovite, leucosphenite and several unknown Cs-silicates. Khvorovite occurs as irregular grains, rarely with square or rectangular sections up to 150 μm, and grain aggregates up to 0.5 mm. Khvorovite is colourless, rarely white, transparent with a white streak, has a vitreous lustre and does not fluoresce under ultraviolet light. Cleavage and parting were not observed. Mohs hardness is 5–5.5, and khvorovite is brittle with an uneven fracture. The measured and calculated densities are 3.96(2) and 3.968 g/cm3, respectively. Khvorovite is biaxial (+) with refractive indices (λ = 589 nm) α = 1.659(3), βcalc. = 1.671(2), γ = 1.676(3); 2Vmeas. = 64(3)°, medium dispersion: r < v. Khvorovite is triclinic, space group I1¯, a = 11.354(2), b = 10.960(2), c = 10.271(2) Å, α = 90.32(3), β = 90.00(3), γ = 90.00(3)°, V = 1278(1) Å3, Z = 2. The six strongest lines in the powder X-ray diffraction pattern [d (Å), I, (hkl)] are: 7.86, 100, (110); 7.65, 90, (101); 7.55, 90, (011); 3.81, 90, (202); 3.55, 90, (301); 2.934, 90, (312, 312). Chemical analysis by electron microprobe gave SiO2 36.98, B2O3 6.01, Y2O3 0.26, PbO 40.08, BaO 6.18, SrO 0.43, CaO 6.77, K2O 1.72, Na2O 0.41, F 0.88, O=F –0.37, sum 99.35 wt.%. The empirical formula based on 29 (O+F) a.p.f.u. is (Pb2.762+Ba0.62K0.56Na0.16)Σ4.10(Ca1.86Sr0.06Y0.04Na0.04)Σ2[Si8B2(Si1.46B0.65)Σ2.11O28](F0.71O0.29), Z = 2 , and the simplified formula is (Pb2+, Ba, K)4Ca2[Si8B2(Si,B)2O28]F. The crystal structure of khvorovite was refined to R1 = 2.89% based on 3680 observed reflections collected on a four-circle diffractometer with MoKα radiation. In the crystal structure of khvorovite, there are four [4]-coordinated Si sites occupied solely by Si with <Si–O>= 1.617 Å. The [4]-coordinated B site is occupied solely by B, with <B–O> = 1.478 Å. The [4]-coordinated T site is occupied by Si and B (Si1.46B0.54), with <T–O> = 1.605 Å; it ideally gives (SiB) a.p.f.u. The Si, B and T tetrahedra form an interrupted framework of ideal composition [Si8B2(SiB)O28]11–. The interstitial cations are Pb2+, Ba and K (minor Na) [A(11–22) sites] and Ca [M site]. The two A sites are each split into two subsites ∼0.5 Å apart and occupied by Pb2+ and Ba + K. The [8]-coordinated M site is occupied mainly by Ca, with minor Sr, Y and Na. Khvorovite is a Pb2+ analogue of hyalotekite, (Ba,Pb2+,K)4(Ca,Y)2[Si8(B,Be)2(Si,B)2O28]F and a Pb2+-, Ca-analogue of kapitsaite-(Y), (Ba,K)4(Y,Ca)2[Si8B2(B,Si)2O28]F. It is named after Pavel V. Khvorov (b. 1965), a Russian mineralogist, to honour his contribution to the study of the mineralogy of the Darai-Pioz massif.

Ternary systems of 152Eu(III), bulk bentonite and ethylenediaminetetraacetic acid (EDTA) ([Eu] = 7.9 × 10–10 M; pH = 6.0–7.0) have been studied. Without EDTA, there was slow uptake in a two-stage process, with initial rapid sorption of Eu(III) (96%), followed by slower uptake of a much smaller fraction (3.0% over a period of one month). The reversibility of Eu(III) binding was tested by allowing Eu(III) to sorb to bentonite for 1–322 days. EDTA was added to the pre-equilibrated Eu bentonite systems at 0.01 M, a concentration that was sufficient to suppress sorption in a system where EDTA was present prior to the contact of Eu(III) with bentonite. A fraction of the Eu was released instantaneously (30–50%), but a significant amount remained bound. With time, the amount of Eu(III) retained by the bentonite reduced, with a slow fraction dissociation rate constant of approximately 4.3 × 10–8 s–1 (values in the range 2.2 × 10–8 – 1.0 × 10–7 s–1) for pre-equilibration times ≥7 days. Eventually, the amount of Eu(III) remaining bound to the bentonite was within error of that when EDTA was present prior to contact (4.5% ± 0.6), although in systems with pre-equilibration times >100 days, full release took up to 500 days. Europium interactions with colloidal bentonite were also studied, and the dissociation rate constant measured by a resin competition method. For the colloids, more Eu was found in the slowly dissociating fraction (60–70%), but the first-order dissociation rate constant was faster, with an average rate constant of 8.8 × 10–7 s–1 and a range of 7.7 × 10–7 –9.5 × 10–7 s–1. For both bulk and colloidal bentonite, although slow dissociation was observed for Eu(III), there was no convincing evidence for 'irreversible' binding.

The new mineral shilovite, the first natural tetrammine copper complex, was found in a guano deposit located on the Pabellón de Pica Mountain, near Chanabaya, Iquique Province, Tarapacá Region, Chile. It is associated with halite, ammineite, atacamite (a product of ammineite alteration) and thénardite. The gabbro host rock consists of amphibole, plagioclase and minor clinochlore, and contains accessory chalcopyrite. The latter is considered the source of Cu for shilovite. The new mineral occurs as deep violet blue, imperfect, thick tabular to equant crystals up to 0.15 mm in size included in massive halite. The mineral is sectile. Its Mohs hardness is 2. Dcalc is 1.92 g cm–3. The infrared spectrum shows the presence of NH3 molecules and NO3– anions. Shilovite is optically biaxial (+), α = 1.527(2), β = 1.545(5), γ = 1.610(2). The chemical composition (electron-microprobe data, H calculated from ideal formula, wt.%) is Cu 26.04, Fe 0.31, N 30.8, O 35.95, H 4.74, total 100.69. The empirical formula is H12.56(Cu1.09Fe0.01)N5.87O6.00. The idealized formula is Cu(NH3)4(NO3)2. The crystal structure was solved and refined to R = 0.029 based upon 2705 unique reflections having F > 4σ(F). Shilovite is orthorhombic, space group Pnn2, a = 23.6585(9), b = 10.8238(4), c = 6.9054(3) Å, V = 1768.3(1) Å3, Z = 8. The strongest reflections of the powder X-ray diffraction pattern [d, Å (I,%) (hkl)] are: 5.931 (41) (400), 5.841 (100) (011), 5.208 (47) (410), 4.162 (88) (411), 4.005 (62) (420), 3.462 (50) (002), 3.207 (32) (031), 2.811 (40) (412).

In this work a single crystal of synthetic hercynite, FeAl2O4, was investigated by X-ray diffraction up to 7.5 GPa and at room temperature, in order to determine its pressure–volume equation of state. The unit-cell volume decreases non-linearly with a reduction of 3.4% (i.e. 18.43 Å3). The pressure–volume data were fitted to a third-order Birch-Murnaghan equation of state providing the following coefficients: V0 = 542.58(3)Å3, KT0 = 193.9(1.7) GPa, K' = 6.0(5). These results are consistent with previous investigations of Cr and Al spinels measured with the same experimental approach but the KT0 differs significantly from the experimental determination carried out more than 40 years ago by Wang and Simmons (1972) by the pulse echo overlap method. Our new results were used to redetermine the FeAl2O4(hercynite) = FeO(wüstite) + Al2O3(corundum) equilibrium in P–T space and obtain geobarometric information for Cr-Al spinels found as inclusions in diamond.

Bobshannonite, Na2KBa(Mn,Na)8(Nb,Ti)4(Si2O7)4O4(OH)4(O,F)2, is a new TS-block mineral from Mont Saint-Hilaire, Québec, Canada. It occurs as blocky crystals 0.5–1 mm across,perched on sérandite and albite. Other associated minerals are epididymite, catapleiite, aegirine, kupletskite, rhodochrosite and rhabdophane-(Ce). Bobshannonite occurs as vitreous to frosty, transparent to translucent very pale brown to orange brown crystals, has a very pale brown streak, hackly fracture and does not fluoresce under cathode or ultraviolet light. Cleavage is {001} very good, no parting was observed, Mohs hardness is ∼4, it is brittle and Dcalc. = 3.787 g/cm3. Crystals are twinned extensively and do not extinguish in cross-polarized light. Bobshannonite is triclinic, C1, a = 10.839(6), b = 13.912(8), c = 20.98(1) Å, α = 89.99(1), β = 95.05(2), γ = 89.998(9)°, V = 3152(5) Å3. The six strongest reflections in the powder X-ray diffraction data [d (Å),I, (hkl)] are: 2.873, 100, (241, 241, 044, 044, 241, 241); 3.477, 60, (006); 3.193, 59, (224, 224); 2.648, 40, (402, 243, 243); 2.608, 35, (008, 226, 226); 1.776, 30, (249). Chemical analysis by electron microprobe gave Ta2O5 0.52, Nb2O5 19.69,TiO2 5.50, SiO2 26.31, Al2O3 0.06, BaO 7.92, ZnO 1.02, FeO 0.89, MnO 26.34, MgO 0.06, Rb2O 0.42, K2O 2.38, Na2O 4.05, F 0.70, H2Ocalc. 1.96, O = –0.29, total 97.53 wt.%, where the H2O content was calculated from the crystal-structure analysis. The empirical formula on the basis of 38 anions is Na1.89(K0.93Rb0.08)Σ1.01Ba0.95(Mn6.85Na0.52Zn0.23Fe0.232+Mg0.03Al0.02)Σ7.88(Nb2.73Ti1.27Ta0.04)Σ4.04(Si8.07O28)O9.32H4.01F0.68,Z = 4. The crystal structure was refined to R1 = 2.55% on the basis of 7277 unique reflections [F > 4σ(F)] and can be described as a combination of a TS (Titanium Silicate) block and an I (Intermediate) block. The TS block consists ofHOH sheets (H – heteropolyhedral, O – octahedral). The topology of the TS block is as in Group II of the Ti disilicates: Ti + Nb = 2 a.p.f.u. per (Si2O7)2 [as defined by Sokolova (2006)]. In the O sheet, ten[6]MO sitesare occupied mainly by Mn, less Na and minor Zn, Fe2+, Mg and Al, with <MO–ϕ> = 2.223 Å. In the H sheet, four [6]MH sites are occupied by Nb and Ti (Nb > Ti), with <MH–ϕ> = 1.975 Å,and eight [4]Si sites are occupied by Si, with <Si–O> = 1.625 Å. The MH octahedra and Si2O7 groups constitute the H sheet. The TS blocks link via common vertices of MH octahedra. In the I block, Ba and Kare ordered at the AP(1) and AP(2) sites with Ba:K = 1:1 and the two BP sites are occupied by Na. The ideal composition of the I block is Na2KBa a.p.f.u. Bobshannonite, perraultite, surkhobite and jinshajiangite are topologically identical Group-II TS-block minerals. Bobshannonite is the Nb-analogue of perraultite. The mineral is named bobshannonite after Dr. Robert (Bob) D. Shannon (b. 1935), in recognition of his major contributions to the field of crystal chemistry in particular and mineralogy in general through his development of accurate and comprehensive ionic radii and his work on dielectric properties of minerals.

Palladosilicide, Pd2Si, is a new mineral (IMA 2014-080) discovered in chromite-rich samples from the Kapalagulu intrusion, western Tanzania (30°03′51′′E 5°53′16′′S and 30°05′37′′E 5°54′26′′S) and from the UG-2 chromitite, Bushveld complex, South Africa. A total of 13 grains of palladosilicide, ranging in size from 0.7 to 39.1 μm (equivalent circle diameters), were found. Synthetic Pd2Si is hexagonal, space group P62m, with a = 6.496(5), c = 3.433(4) Å, V = 125.5(1) Å3, c:a = 0.529 with Z = 3. The strongest lines calculated from the powder pattern (Anderko and Schubert, 1953) are [d in Å (I) (hkl)] 2.3658 100 (111); 2.1263 37 (120); 2.1808 34 (021); 3.240 20 (110); 1.8752 19 (030); 1.7265 12 (002); 1.3403 11 (122); 1.2089 10 (231). The calculated density for three analyses varies from 9.562 to 9.753 g cm–3. Palladosilicide is considered to be equivalent to synthetic Pd2Si based on results from electron backscattered diffraction analyses. Reflectance data in air for the four Commission on Ore Mineralogy wavelengths are [λ nm, R1 (%) R2 (%)] 470 49.6 52.7; 546 51.2 53.8; 589 51.6 53.7; 650 51.7 53.3 and the mineral is bright creamy white against chromite, weakly bireflectant and displays no discernible pleochroism or twinning. It is weakly anisotropic, has weak extinction and rotation tints in shades of blue and olive green. Electron probe microanalyses of palladosilicide yield a simplified formula of Pd2Si.

The phase equilibria in the system Ag–Pd–Te were studied by the technique of using an evacuated silica glass tube at 350° and 450°C. Five ternary phases were synthesized: sopcheite (Pd3Ag4Te4), lukkulaisvaaraite (Pd14Ag2Te9),telargpalite (Pd2–xAg1+xTe) and the previously unknown phases Pd7.5–xAg0.5+ xTe3 and Pd2+xAg2–xTe.The synthetic telargpalite has a compositional range from 26 to 29 wt.% Ag, with the formula Pd2–xAg1+xTe, where x varies from 0.09 to 0.22. The phase Pd2+xAg2–xTe has a compositional range from 34 to 35 wt.% Ag, where x varies from 0.18 to 0.24. The phase Pd7.5–xAg0.5+xTe3 forms a solid solution from 4 to 11 wt.% Ag, where x varies from 0.02 to 0.83. Phases Pd20Te7and Pd13Te3 dissolve up to 3.5 and 2 wt.% Ag, respectively. Other binary palladium tellurides do not dissolve Ag. The phase Pd3Ag4Te4, an analogue of the mineral sopcheite, forms a stable association with hessite and kotulskite it also coexists with lukkulaisvaaraite. Sopcheite is stable up to 383°C. Natural occurrences of hessite, kotulskite and lukkulaisvaaraite together in equilibrium indicate formation above this temperature. Phase relations defined the mineral assemblages that can be expected to occur in nature.The phase Pd7.5–xAg0.5+xTe3 potentially represents a new mineral; it will probably be found in association with lukkulaisvaaraite and telargpalite or telluropalladinite, among other platinum-group minerals. The phasePd2+xAg2–x Te can be found in association with telargpalite. Mineral assemblages defined in this study can be expected in Cu-Ni-PGE mineral deposits, associated with mafic and ultramafic igneous rocks, particularly in mineralized zones with known silver-palladium tellurides.

Using type material from the Österby pegmatite in Dalarna, Sweden, the chemical composition and structural parameters of thalénite-(Y) [ideally Y3Si3O10(OH)] were examined by wavelength dispersive spectroscopy electron microprobe (WDS EMP) analysis and single-crystal X-ray diffraction. High contrast back-scatter electron images of the Österby material show at least two generations of thalénite-(Y). The formula of the primary thalénite-(Y) normalized to 11 anions is (Y2.58Dy0.11Yb0.09Gd0.06Er0.06Ho0.02Sm0.02Tb0.02Lu0.02Nd0.01Tm0.01)Σ3.00Si3.01O10F0.97OH0.03. The secondary thalénite-(Y), replacing the primary material, is weakly enhanced in Y and depleted in the lightest and the heaviest rare-earth elements, yielding the formula (Y2.63Dy0.12Yb0.06Gd0.06Er0.05Ho0.02Sm0.02Tb0.02Tm0.01Nd0.01Lu0.01)Σ3.00Si3.01O10F0.98OH0.02. Structural data for thalénite-(Y) from Österby clearly indicate the monoclinic space group P21/n, with a = 7.3464(4), b = 11.1726(5), c = 10.4180(5) Å, β = 97.318(4)°, V = 848.13(7) Å3, Z = 4, which is consistent with previous investigations. The structure was refined from single-crystal X-ray diffraction data to R1 = 0.0371 for 1503 unique observed reflections, and the final chemical composition obtained from the refinement, (Y2.64Dy0.36)Σ3.00F0.987[Si3O10], Z = 4, is in good agreement with the empirical formula resulting from electron microprobe (EMP) analysis. Both techniques reveal a strong dominance of F over OH, which means that the type material actually corresponds to the fluorine analogue. Moreover, new EMP analyses of samples of thalénite-(Y) from an additional seven localities (Åskagen and Reunavare in Sweden; White Cloud and Snow Flake in Colorado, USA; the Guy Hazel claim in Arizona, USA; Suishoyama and Souri in Japan) clearly show the prevalence of F over OH as well. Based on these observations, the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association has recommended a redefinition of the chemical composition of thalénite-(Y) to represent the F-dominant species with the ideal formula Y3Si3O10F, as it has historical priority. Consequently, the later described fluorthalénite-(Y) has to be discredited.

Two Pbca orthopyroxene samples, donpeacorite (DP N.1) and enstatite (B22 N.60) with chemical formulae Mn0.54Ca0.03Mg1.43Si2O6 (XMn = 0.27) and Fe0.54Ca0.03Mg1.43Si2O6 (XFe = 0.27), respectively, were investigated by single-crystal X-ray diffraction at high-temperature conditions.

The nearly identical XFe and XMn make the two samples the perfect candidates to investigate the effect of the compositional change at the M2 site (i.e. Fe-Mn substitution) on the thermal expansion behaviour of orthopyroxenes.

Therefore, the unit-cell parameter thermal expansion behaviour of both samples has been investigated in the temperature range between room T and 1073 K. No evidence for phase transitions was found over that range. The two samples have been previously disordered with an ex situ annealing at ∼1273 K.

The unit-cell parameters and volume thermal expansion data, collected on the disordered samples, have been fitted to a Fei Equation of State (EoS) and the following coefficients obtained: V0 = 853.35(4) Å3, αV,303K = 2.31(24) × 10–5 K–1 and V0 = 845.40(6) Å3, αV,303K = 2.51(25) × 10–5 K–1 for DP N.1 and B22 N.60, respectively.

While there is no difference in the volume thermal expansion coefficient as a function of composition and the expansion along the b direction is nearly identical for both samples, slight differences have been found along a and c lattice directions. The thermal expansion along the a direction is counterbalanced by that along c being responsible for the changes in lattice expansion scheme from αb > αc > αa at room T, to αc > αb > αa at high T. Therefore, as a result of the different behaviour along a and c, the unit-cell volume thermal expansion for both samples is identical within estimated standard deviations. The negligible effect of the Fe-Mn substitution on the bulk thermal expansion can be applied when dealing with geothermobarometry based on the elastic host-inclusion approach (e.g. Nestola et al., 2011; Howell et al., 2010; Angel et al., 2014 a, b, 2015). In fact, though the compressibility effect is still not known, the nearly identical thermal expansion coefficients will not affect the entrapment pressure (Pe).

The new minerals fermiite (IMA2014-068), Na4(UO2)(SO4)3·3H2O and oppenheimerite (IMA2014-073), Na2(UO2)(SO4)2·3H2O, were found in the Blue Lizard mine, San Juan County, Utah, USA, where they occur together as secondary alteration phases in association with blödite, bluelizardite, chalcanthite, epsomite, gypsum, hexahydrite, kröhnkite, manganoblödite, sideronatrite, tamarugite and wetherillite.

Fermiite descriptive details: pale greenish-yellow prisms; transparent; vitreous lustre; bright greenishwhite fluorescence; white streak; hardness (Mohs) 2½; brittle; conchoidal fracture; no cleavage; slightly deliquescent; easily soluble in RT H2O; densitymeas = 3.23(2) g cm–3; densitycalc = 3.313 g cm–3. Optically, biaxial (+), α = 1.527(1), β = 1.534(1), γ = 1.567(1) (white light); 2Vmeas. = 51(1)°, 2Vcalc. = 50°; dispersion r < v, distinct. Pleochroism: X, Y = colourless, Z = pale greenish yellow; X = Y < Z. Energy dispersive spectroscopic (EDS) analyses yielded the empirical formula Na3.88(U1.05O2)(S0.99O4)3(H2O)3. Fermiite is orthorhombic, Pmn21, a = 11.8407(12), b = 7.8695(5), c = 15.3255(19) Å, V = 1428.0(2) Å3 and Z = 4. The structure (R1 = 2.21% for 1951 Io > 3σI) contains [(UO2)(SO4)3] chains that are linked by bonds involving five different Na–O polyhedra to form a framework. The mineral is named for Italian-American theoretical and experimental physicist Dr. Enrico Fermi (1901–1954).

Oppenheimerite descriptive details: pale greenish-yellow prisms; transparent; vitreous lustre; bright greenish-white fluorescence; white streak; hardness (Mohs) 2½; slightly sectile; three good cleavages, {110}, {011} and {101}; irregular fracture; slightly deliquescent; easily soluble in RT H2O; densitycalc = 3.360 g cm–3. Optically, biaxial (+), α = 1.537(1), β = 1.555(1), γ = 1.594(1) (white light); 2Vmeas. = 72(2)°, 2Vcalc. = 70°; dispersion is r > v, moderate, inclined; optical orientation: X ≈ ⊥ {101}, Z ≈ [111]; pleochroism: X very pale greenish yellow, Y pale greenish yellow, Z greenish yellow; X < Y < Z. EDS analyses yielded the empirical formula Na1.94(U0.97O2)(S1.02O4)2(H2O)3. Oppenheimerite is triclinic, P1, a = 7.9576(6), b = 8.1952(6), c = 9.8051(7) Å, α = 65.967(5), β = 70.281(5), γ = 84.516(6)°, V = 549.10(8) Å3 and Z = 2. The structure (R1 = 3.07% for 2337 Io > 3σI) contains [(UO2)(SO4)2(H2O)] chains that are linked by bonds involving two different Na–O polyhedra to form a framework. The mineral is named for American theoretical physicist Dr. J. Robert Oppenheimer (1904–1967).

Corrosion of steel canisters, disposed of in a repository for high-level waste (HLW), leads to generation of hydrogen gas for a long period after the repository's closure. The accumulation of hydrogen gas may lead to significant desaturation and unacceptable build-up of pressure in the backfilled disposal tunnels if the gas cannot escape through the low-permeability host rock. Consequently, the investigation of gas migration is of high relevance in the assessment of the repository's performance.

In this paper, the results of numerical investigations on gas migration performed using the computer code TOUGH2 (USA) are presented. The objective was to investigate migration of gas generated in a single disposal tunnel of a conceptual geological repository in a clay formation, which was suggested for benchmark studies in the European Commission project FORGE (Fate Of Repository GasEs). The analysis was focused on evaluation of the impact of an initial temperature in the repository and of different tortuosity models on gas migration. It was revealed that gas migration results were dependent on tortuosity model, while temperature variation in the repository had minor impact.

Gatedalite, Zr(Mn22+Mn43+)SiO12, is a new mineral of the braunite group. It is found in hausmannite-impregnated skarn together with jacobsite, Mn-bearing calcite, tephroite, Mn-bearing phlogopite, långbanite, pinakiolite and oxyplumboroméite at the Långban Mn-Fe oxide deposit, Värmland, central Sweden. The mineral occurs as very rare, small (≤60 μm), grey, submetallic, irregularly rounded anhedral grains. Gatedalite has a calculated density of 4.783 g/cm3. It is opaque and weakly anisotropic with reflectivity in air varying between 17.1 and 20.8% in the visible spectral range. Gatedalite is tetragonal, space group I41/acd, with the unit-cell parameters a = 9.4668(6) Å, c = 18.8701(14) Å, V = 1691.1(2) Å3 and Z = 8. The crystal structure was refined to an R1 index of 5.09% using 1339 unique reflections collected with MoKαX-ray radiation. The five strongest powder X-ray diffraction lines [d in Å, (I), (hkl)] are: 2.730(100)(224), 2.367(12)(040), 1.6735(12)(440), 1.6707(29)(048) and 1.4267(16)(264). Electron microprobe analyses in combination with single-crystal structure refinement resulted in the empirical formula: (Zr0.494+Mn0.402+Mg0.07Ca0.02Zn0.01Ce0.013+)Σ1.00(Mn4.443+Fe0.593+Mn0.572+Mg0.41Al0.01)Σ6.02Si0.99O12. Gatedalite is a member of the braunite group (general formula AB6SiO12). It is related to braunite (Mn2+Mn63+SiO12) through the net cation exchange (Zr4+ + Mn2+) → 2Mn3+, which results from the substitutions Zr4+ → Mn2+ at the 8-fold coordinated site (A in the general formula) coupled with a 2Mn2+ → 2Mn3+ substitution at the 6-fold coordinated sites (B in the general formula).

Large quantities of irradiated graphite will arise from the decommissioning of the UK's Magnox power stations. Irradiated graphite contains 14C as well as other longer lived radionuclides (e.g. 36Cl). The potential use of magnetic sector secondary ion mass spectrometry (MS-SIMS) to examine the distribution of the 14C within trepanned graphite samples from a Magnox nuclear power station has been investigated. This work indicates that the methodology proposed has the potential to be used to analyse irradiated graphite samples with preliminary results highlighting a possible 14C enrichment in the carbonaceous deposit found on a channel wall sample. 14C concentrations in samples without this deposit were below the limits of detection of the instrument. The methodology used for these determinations ensured that possible mass interferences between 14C species and oxygen-bearing or nitrogen-bearing species were eliminated from the analysis. Future work will utilize the methodology proposed in this work on a larger number of samples.

A systematic investigation of agates from different occurrences in Europe, Northern and Southern America reveals that macrocrystalline quartz and chalcedony within them have an unusually high uranium content. Whereas agates may contain >70 ppm of U, quartz from magmatic and metamorphic rocks as well as pegmatite quartz commonly exhibit U concentrations at sub-ppm levels. Spatially resolved trace-element analyses by laser ablation inductively coupled plasma mass spectrometry show that the distribution of U within the agate samples is heterogeneous and coincides with the structural banding. The results indicate that U is incorporated into agate as uranyl ions. These ions, which are bound to the silica surface, are interpreted to originate from the parallel accumulation of Si and U by alteration processes of surrounding host rocks during agate formation.

The uranyl ion is the cause of greenish photoluminescence (PL) in agate, which can only be excited by short wavelengths (<300 nm). The green PL is due to the electron transition from an excited to a ground state of the uranyl ion and is shown by a typical emission line at ∼500 nm accompanied by several equidistant lines. These are due to the harmonic vibration of oxygen atoms along the uranyl axis. Luminescence can be detected in samples with a U content down to the 1 ppm level.

Manganese incorporation in synthetic hercynite, and partitioning between hercynite and silicate melt synthesized at 1.0 GPa, 1250°C, and at an fO2 buffered by Fe–FeO, has been studied by X-ray absorption spectroscopy and single-crystal X-ray structure refinement. Spectra indicate the presence of both Mn2+ and Mn3+ (and possibly also Mn4+) in synthetic hercynite and partitioning of Mn2+ into the melt phase, and Mn3+ into hercynite, respectively, under run conditions. X-ray refinement is consistent with partial disorder of Fe and Al across tetrahedral and octahedral sites. A higher than expected degree of Fe-Al disorder in the Mn-bearing hercynite can be explained by preferential incorporation of Mn2+ onto the tetrahedral site, and indicates that Fe-Al disorder in pure, stoichiometric hercynite cannot necessarily be used to determine closure temperatures in natural spinel. However, partitioning of Mn2+ and Mn3+ between melt and hercynite suggests that Mn incorporation in hercynite could be used as a measure of fO2 conditions in magmas during spinel crystallization.

The oxidation state of Fe and precipitates within olivine phenocrysts from an olivine-basalt from Kuroshima volcano, Goto Islands, Nagasaki Prefecture, Japan, were determined using electron microprobe analysis, 57Fe Mössbauer spectroscopy, Raman spectroscopy and transmission electron microscopy, to examine the formation process of the Fe-bearing precipitates.

The average Fo content of the olivine phenocrysts is 76.2 mol.%. The olivine phenocrysts occasionally have precipitate minerals at their rims, especially on rims near vesicles. The 57Fe Mössbauer spectrum of olivine separates consists of two doublets assigned to Fe2+ at the octahedral M1 and M2 sites, and a Fe3+ doublet at the M1 and M2 sites. The Fe2+:Fe3+ ratio is 90(5):10(1). The precipitates at the rims of the olivine phenocrysts consistof magnetite and enstatite showing coaxial relations with host olivine, and grow parallel to the olivine c axis. Moreover, clusters consisting of nanoscale domains of a few tens of nm in size occur in the host olivine. Their rounded form and appearance in transmission electron microscope images are similar to those of the magnetite precipitates, but they have an olivine structure and can be regarded as embryos of magnetite within the olivine.

The oxidation process of olivine phenocrysts under cooling conditions is: (1) formation of magnetite embryos on the rims of olivinephenocrysts; (2) formation of enstatite-like pyroxene domains by depletion of Fe in olivine due to the generation of magnetite embryos; (3) crystallization of magnetite and enstatite-like pyroxene precipitates.