Camaronesite (IMA 2012-094), [Fe3+(H2O)2(PO3OH)]2(SO4)·1–2H2O, is a new mineral from near the village of Cuya in the Camarones Valley, Arica Province, Chile. The mineral is a low-temperature, secondary mineral occurring in a sulfate assemblage with anhydrite, botryogen, chalcanthite, copiapite, halotrichite, hexahydrite, hydroniumjarosite, pyrite, römerite, rozenite and szomolnokite. Lavender-coloured crystals up to several mm across form dense intergrowths. More rarely crystals occur as drusy aggregates of tablets up to 0.5 mm in diameter and 0.02 mm thick. Tablets are flattened on {001} and exhibit the forms {001}, {104}, {015} and {018}. The mineral is transparent with white streak and vitreous lustre. The Mohs hardness is 2½, the tenacity is brittle and the fracture is irregular, conchoidal and stepped. Camaronesite has one perfect cleavage on {001}. The measured and calculated densities are 2.43(1) and 2.383 g/cm3, respectively. The mineral is optically uniaxial (+) with ω = 1.612(1) and ε = 1.621(1) (white light). The pleochroism is O (pale lavender) > E (colourless). Electron-microprobe analyses provided Fe2O331.84, P2O529.22, SO315.74, H2O 23.94 (based on O analyses), total 100.74 wt.%. The empirical formula (based on 2 P a.p.f.u.) is: Fe1.94(PO3OH)2(S0.96O4)(H2O)4·1.46H2O. The mineral is slowly soluble in concentrated HCl and extremely slowly soluble in concentrated H2SO4. Camaronesite is trigonal, R32, with cell parameters:a = 9.0833(5), c = 42.944(3) Å, V = 3068.5(3) Å3 and Z = 9. The eight strongest lines in the X-ray powder diffraction pattern are [dobs Å (I)(hkl)]: 7.74(45)(101), 7.415(100)(012), 4.545(72)(110), 4.426(26)(018), 3.862(32)(021,202,116), 3.298(93)(027,119), 3.179(25)(208) and 2.818(25)(1·1·12,125). In the structure of camaronesite (R1 = 2.28% for 1138 Fo > 4σF), three types of Fe octahedra are linked by corner sharing with (PO3OH) tetrahedra to form polyhedral layers perpendicular to c with composition [Fe3+(H2O)2(PO3OH)]. Two such layers are joined through SO4 tetrahedra (in two half-occupied orientations) to form thick slabs of composition [Fe3+(H2O)2(PO3OH)]2(SO4). Between the slabs are partially occupied H2O groups. The only linkages between the slabs are hydrogen bonds. The most distinctive component in the structure consists of two Fe octahedra linked to one another by three PO4 tetrahedra yielding an [Fe2(PO4)3] unit. This unit is also the key component in the sodium super-ionic conductor (NASICON) structure and has been referred to as the lantern unit. The polyhedral layers in the structure of camaronesite are similar to those in the structure of taranakite. The Raman spectrum exhibits peaks consistent with sulfate, phosphate, water and OH groups.

In December, 2007, after 30 years of operations, the mine of Meirama ceased extraction of brown lignite. Since then operations have begun which will lead to the formation of a big mining lake (~2 km2 surface and up to 180 m deep) after controlled flooding of the open pit. In the process of flooding, both surface and ground waters are involved, each with their own chemical signature. According to the information available, the diversion of surface waters towards the pit hole should lead to the formation of a water body of acceptable quality. However, an unassisted flooding process could eventually form an acidic lake.

Chemical analyses of nine K-feldspars and thirteen albites, along with their optical, physical, and X-ray data are presented. The obliquity values Δ = 12·5(d131-d13¯1) of the K-feldspars are found to be independent of the contents of silica and volatiles in the rocks. The role of temperature as the primary factor affecting the obliquity values is stressed. The relationship between the (An + Ab) content of the potassic phase of K-feldspars and 2Vα is shown diagrammatically.

The mineral truscottite was discovered at the Lebong Donok mine, Benkulen, Sumatra, by Hövig in 1914. He considered it to be a hydrated calcium silicate of composition CaO.2SiO2.1/2H2O. Later work by Grutterink suggested a different formula, 2(Ca,Mg)O.3SiO2.2H2O, the water content being reduced to 1-3 molecules after drying at 120°. Grutterink noted that the composition, general character, and optical properties indicated a similarity to gyrolite. Flint, McMurdie, and Wells concluded from X-ray powder photographs that the two species were identical, although they detected quartz as an impurity in the truscottite examined. All known specimens of truscottite come from the original locality, and no further investigations have been reported.

In Part I (Vinograd, 2002) the relationship between temperature, composition and free energy of the diopside–jadeite solid solution was described using a CVM model. Here the same relationship is described using a combination of Redlich-Kister (RK) polynomials and Gaussian functions. The use of the Gaussians permits an accurate description of the free energy dip centred at Jd50, which is caused by the long-range ordering, while the effect of the short-range ordering can be easily modelled using the RK polynomial The simplified RK-Gaussian description is extended to the three-component diopside–jadeite–hedenbergite solid solution. The polynomial description permits an easy incorporation of the derived activity-composition relations into phase-equilibrium computation software.

The single-crystal X-ray structure of a sulphate-bearing buttgenbachite, Cu36Cl7.8(NO3)1.3(SO4)0.35(OH)62.2.5.2H2O, from Likasi, Democratic Republic of Congo, has been determined at 100 and 288 K. The basic framework of the structure is the same as has been previously reported for buttgenbachite, except for the identification of a hydrogen-bonded chloride ion (occupancy 0.6) at the origin instead of a Cu ion with partial occupancy. The nature of nitrate positional disorder along channels in the c direction and how this relates to the presence of other species such as chloride ions and water molecules and, most importantly, sulphate ions has been elucidated. One nitrate ion, with an occupancy of 0.18, lies at 2/3,l/3,l/4 and shares the site with a chloride ion (occupancy 0.30) and also a sulphate ion (occupancy 0.09); a second nitrate, with an occupancy of 0.24, lies at 2/3,1/3,0.084 and shares the site with a water molecule (occupancy 0.06). As a result, a formula of Cu36Cl7.8(NO3)1.3(SO4)0.35(OH)62.2.5.2H2O is obtained. Re-refinement of deposited data for a supposed connellite crystal from the Toughnut mine,Tombstone, Arizona gives a related, but different, pattern of anion substitution. No sulphate could be detected in the structure and it is evident that this structure refers to buttgenbachite. A nitrate nitrogen atom and a chloride ion are disordered at 2/3,l/3,l/4, the overall site being fully occupied. A chloride ion with ∼0.5 occupancy is sited at the origin and the formula Cu36Cl7.9(NO3)1.1(OH)63.4H2O is indicated. Re-refinement of a deposited data set for another buttgenbachite crystal from the Likasi mine reveals a partially occupied nitrate centred at 2/3,l/3, z and a partially occupied chloride at 2/3,l/3,l/4. Either 0.5Cl–, OH–, H2O or H3O+ is located at the origin. If the latter is the case, the stoichiometry for this buttgenbachite is Cu36Cl6.5(NO3)1.5(OH)64.5.5H2O. The present study has highlighted the fact that a range of compositions for buttgenbachite exists, depending on the pH and relative activities of chloride, nitrate and sulphate ions in solutions from which the mineral crystallizes.

Noélbensonite, a new mineral, is the barium manganese analogue of lawsonite. It is described from the Woods ornamental rhodonite mine, 30 km NNE of Tamworth, New South Wales, Australia, where it occurs as aggregates of blocky to sometimes lamellar crystals ranging from a few micrometres to (rarely) 100 µm in length. It replaces NaMn amphibole, namansilite, and pectolite, and also occurs as tiny monomineralic veinlets 0.05–0.25 mm thick. Rare euhedral crystals are dominated by {100} and {011}, with (011) ^ = 68°. The mineral is orthorhombic, space group apparently Cmcm; a = 6.325(1), b = 9.120(1), c = 13.618(1) Å, V = 785.6(1) Å3, with a : b : c = 0.694 : 1 : 1.493. Noélbensonite is brittle, fracture irregular, Mohs hardness about 4, cleavage and twinning not observed, colour dark brown, streak paler yellow-brown, lustre earthy on some veinlet surfaces to brilliantly vitreous, calculated density 3.87 g/cm3, refractive indices α = 1.82(1),β (calculated from 2V) = 1.835(10), γ = 1.85(1), biaxial negative 2Vα = 46°(3°), strong dispersion r > v, straight extinction to plane of flattening, {100}, α ∥ c, β ∥ b, γ ∥ a with pleochroism in very thin sections: α = orange yellow, β = orange, γ = brownish orange, absorption γ > β ⇐p; α. The average of 23 electron microprobe analyses (wt.%) is SiO2 26.02, Al2O3 0.17, TiO2 0.01, Fe2O3 0.19, Mn2O3 34.76, CaO 0.31, Na2O 0.14, BaO 29.08, SrO 1.51, H2Ocalc 7.87, total 100.06, leading to the simplified formula . Up to 15% Sr and 9% Ca substitute for Ba in the large-cation sites. The strongest lines in the X-ray powder diffraction pattern are [(Iobs) dobs/Å hkl] (100) 4.85 111; (50) 4.557 020; (59) 4.322 021; (77) 3.416 113,004; (80) 2.869 202; (47) 2.849 114; (82) 2.729 024; (45) 2.543 132; (48) 2.428 222; (38) 2.255 223,041. The name is for William Noél Benson (1885–1957), in honour of his classic researches in the New England Fold Belt and of his tenure of the Chair of Geology at the University of Otago.

The high-pressure monazite – scheelite structure transition has been observed at P >4.57 GPa in CaSeO4 by synchrotron X-ray powder diffraction. It is a first-order transition with a 4.5% volume change and is severely hindered kinetically. Scheelite-type CaSeO4 remains to a maximum experimental pressure of 42.2 GPa and no (002) reflection, specifically indicative of a subgroup transition to a fergusonite-type structure, is observed. Scheelite-type CaSeO4 remains at ambient conditions, where the tetragonal unit cell has parameters of a = 5.04801(11) c = 11.6644(5) Å and V = 297.21(3) Å3 with Dcalc = 4.090 g cm–3. The diffraction pattern of the recovered material was refined in space group I41/a to Rp = 0.98%, wRp = 1.91%, GoF = 0.59, RFobs = 5.04%, wRFobs = 4.27%. The oxygen is located on the general 16f site at (0.2578(8) 0.3699(14) 0.5755(4)) and shares four identical bonds with Se (4a: ½ ½ ½) at 1.644(5) Å. The Ca (4b: 0, 0, ½) is eight-coordinated via O at 4 × 2.440(6) Å and 4 × 2.504(5) Å. This is further evidence of the dissimilarity of sulfate and selenate at high pressure and temperature conditions and the closer resemblance of the selenates to the orthophosphates, arsenates and vanadates, where this type of transition sequence has been described.

The new mineral joanneumite was found at Pabellón de Pica Mountain, Iquique Province, Tarapacá Region, Chile, where it occurs as violet microcrystalline aggregates up to 2 mm in size in small cracks in a gabbroic rock, which is covered by a guano deposit. Associated minerals are salammoniac, dittmarite, möhnite and gypsum. Joanneumite is non-fluorescent and the Mohs hardness is 1. The calculated density is 2.020 g cm–3. The infrared spectrum of joanneumite shows the frequencies of NH3 and isocyanurate groups and the absence of absorptions of H2O molecules and OH– ions. The chemical composition (electron microprobe data, the hydrogen was calculated from the structural formula, wt.%) is C 20.33, N 31.11, O 28.34, Cu 17.27, Zn 0.24, H 2.82, total 100.11. The empirical formula is Cu0.96Zn0.01N7.84C5.98O6.25H9.96 and the idealized formula is CuN8C6O6H10 with the structural formula Cu(C3N3O3H2)2(NH3)2. Due to the lack of suitable single crystals the synthetic analogue of joanneumite was prepared for the single-crystal structure refinement. The crystal structure was solved and refined to R = 0.025 based upon 1166 unique reflections with I > 2σ (I). Joanneumite is triclinic, space group P1̄, a = 4.982(1), b = 6.896(1), c = 9.115(2) Å, α = 90.53(3), β = 97.85(3), γ = 110.08(3)°, V = 290.8(1) Å3, Z = 1 obtained from single-crystal data at 100 K, which are in good agreement with cell parameters from powder diffraction data of joanneumite at 293 K: a = 5.042(1), b = 6.997(1), c = 9.099(2) Å, α = 90.05(3), β = 98.11(2), γ = 110.95(3)° and V = 296.3(1) Å3. The eight strongest lines of the powder X-ray diffraction pattern are [d, Å (I,%) (hkl)] 6.52 (68) (010), 5.15 (47) (011), 4.66 (21) (100, 110), 4.35 (9) (1̄11), 3.29 (6) (1̄20), 3.22 (7) (1̄1̄1), 3.140 (100) (1̄21), 2.074 (7) (1̄32). The crystal structure of joanneumite is identical with the structure of synthetic bis(isocyanurato) diamminecopper(II).

The new mineral feynmanite, Na(UO2)(SO4)(OH)·3.5H2O, was found in both the Blue Lizard and Markey mines, San Juan County, Utah, USA, where it occurs as a secondary phase on pyrite-rich asphaltum in association with chinleite-(Y), gypsum, goethite, natrojarosite, natrozippeite, plášilite, shumwayite (Blue Lizard) and wetherillite (Markey). The mineral is pale greenish yellow with a white streak and fluoresces bright greenish white under a 405 nm laser. Crystals are transparent with a vitreous lustre. It is brittle, with a Mohs hardness of ~2, irregular fracture and one perfect cleavage on {010}. The calculated density is 3.324 g cm–3. Crystals are thin needles or blades, flattened on {010} and elongate on [100], exhibiting the forms {010}, {001}, {101} and {10$\bar{1}$}, and are up to ~0.1 mm in length. Feynmanite is optically biaxial (–), with α = 1.534(2), β = 1.561(2) and γ = 1.571(2) (white light); 2Vmeas. = 62(2)°; no dispersion; and optical orientation: X = b, Y ≈ a,Z ≈ c. It is weakly pleochroic: X = colourless, Y = very pale green yellow and Z = pale green yellow (X < Y < Z). Electron microprobe analyses (WDS mode) provided (Na0.84Fe0.01)(U1.01O2)(S1.01O4)(OH)·3.5H2O. The five strongest powder X-ray diffraction lines are [dobs Å(I)(hkl)]: 8.37(100)(010), 6.37(33)($\bar{1}$01,101), 5.07(27)($\bar{1}$11,111), 4.053(46)(004,021) and 3.578(34)(120). Feynmanite is monoclinic, has space group P2/n, a = 6.927(3), b = 8.355(4), c = 16.210(7) Å, β = 90.543(4)°, V = 938.1(7) Å3 and Z = 4. The structure of feynmanite (R1 = 0.0371 for 1879 Io > 2σI) contains edge-sharing pairs of pentagonal bipyramids that are linked by sharing corners with SO4 groups, yielding a [(UO2)2(SO4)2(OH)2]2– sheet based on the phosphuranylite anion topology. The sheet is topologically identical to those in deliensite, johannite and plášilite. The dehydration of feynmanite to plášilite results in interlayer collapse involving geometric reconfiguration of the sheets and the ordering of Na.

Hundholmenite-(Y) occurs as pale brown, subhedral crystals up to 1 mm across, embedded in REE–bearing fluorite, in a granitic pegmatite at Hundholmen, Tysfjord, Nordland County, north Norway. Two other occurrences in the same area are the granitic pegmatites at Stetind and Lagmannsvik. The simplified formula, obtained from wavelength-dispersive EMP analyses and boron determination by ICP-AES, is (Y,REE,Ca,Na)15(Al,Fe3+)CaxAs1–x3+ (Si,As5+)Si6B3(O,F)48 (x = 0.78). The mineral is trigonal, R3m, with a = 10.675(6), c = 27.02(2) Å , V = 2667(5) Å 3, Z = 3. The crystal structure was refined to R1 = 0.037 for 1720 observed reflections. Hundholmenite-(Y) is isostructural with okanoganite-(Y) and vicanite-(Ce), and the differences in site populations are discussed. The strongest seven reflections of the X-ray powder-diffraction pattern [dobs in Å , (I) (hkl)] are: 4.38 (33) (202), 3.114 (43) (214), 2.972 (100) (027), 2.947 (76) (125), 2.924 (66) (303, 033), 2.681 (36) (220) and 1.978 (37) (235). The mineral is optically uniaxial (–) with o 1.7578(5) and e 1.7487(5). The Mohs hardness is ~5–6; Dcalc = 5.206(9) g/cm3.

The crystal structure and chemical formula of zvyaginite, ideally Na2ZnTiNb2(Si2O7)2O2(OH)2(H2O)4, a lamprophyllite-group mineral of the seidozerite supergroup from the type locality, Mt. Malyi Punkaruaiv, Lovozero alkaline massif, Kola Peninsula, Russia have been revised. The crystal structurewas refined with a new origin in space group C1, a = 10.769(2), b = 14.276(3), c = 12.101(2) Å, α = 105.45(3), β = 95.17(3), γ = 90.04(3)°, V = 1785.3(3.2) Å3, R1 = 9.23%. The electron-microprobe analysis gave the following empirical formula [calculated on 22 (O + F)]: (Na0.75Ca0.09K0.04□1.12)Σ2 (Na1.12Zn0.88Mn0.17Fe2+0.04□0.79)Σ3 (Nb1.68Ti1.25Al0.07)Σ3 (Si4.03O14)O2 [(OH)1.11F0.89]Σ2(H2O)4, Z = 4. Electron-diffraction patterns have prominent streaking along c* and HRTEM images show an intergrowth of crystalline zvyaginite with two distinct phases, both of which are partially amorphous. The crystal structure of zvyaginite is an array of TS (Titanium-Silicate) blocks connected via hydrogen bonds between H2O groups. The TS block consists of HOH sheets (H = heteropolyhedral, O = octahedral) parallel to (001). In the O sheet, the [6]MO(1,4,5) sites are occupied mainly by Ti, Zn and Na and the [6]MO(2,3) sites are occupied by Na at less than 50%. In the H sheet, the [6]MH(1,2) sites are occupied mainly by Nb and the [8]AP(1) and [8]AP(2) sites are occupied mainly by Na and □. The MH and AP polyhedra and Si2O7 groups constitute the H sheet. The ideal structural formula is Na□Nb2NaZn□Ti(Si2O7)2O2(OH)2(H2O)4. Zvyaginite is a Zn-bearing and Na-poor analogue of epistolite, ideally (Na□)Nb2Na3Ti(Si2O7)2O2(OH)2(H2O)4. Epistolite and zvyaginite are related by the following substitution in the O sheet of the TS-block: (Naþ 2 )epi↔Zn2+ zvy +□zvy. The doubling of the t1 and t2 translations of zvyaginite relative to those of epistolite is due to the order of Zn and Na along a (t1) and b (t2) in the O sheet of zvyaginite.

Electrostatic calculations estimated the energy of hypothetical ion clustering in intermediate plagioclase feldspars. The calculated energy appears too great to allow segregation of Ca and Na atoms into domains upon annealing without a corresponding movement of Al and Si from an original disordered structure. The calculated energy may be sufficiently small that Ca and Na atoms can disorder partially without movement of Al and Si upon heating a low-plagioclase to high temperatures.

Iron oxides resulting from the corrosion of large quantities of steel that are planned to be installed throughout a deep geological disposal facility (GDF) are expected to be one of the key surfaces of interest for controlling radionuclide behaviour under disposal conditions. Over the lengthy timescales associated with a GDF, the system is expected to become anoxic so that reduced Fe(II) phases will dominate. Batch experiments have therefore been completed in order to investigate how a model reduced Fe-oxide surface (wüstite, Fe1–xO) alters as a function of exposure to aqueous solutions with compositions representative of conditions expected within a GDF. Additional experiments were performed to constrain the effect that highly alkaline solutions (up to pH 13) have on the adsorption behaviour of the uranyl (UO22+) ion onto the surfaces of both wüstite and portlandite [Ca(OH)2; representative of the expected cementitious phases]. Surface co-ordination chemistry and speciation were determined by ex situ X-ray absorption spectroscopy measurements (both X-ray absorption near-edge structure analysis (XANES) and extended X-ray absorption fine structure analysis (EXAFS)). Diffraction, elemental analysis and XANES showed that the bulk solid composition and Fe oxidation state remained relatively unaltered over the time frame of these experiments (120 h), although under alkaline conditions possible surface hydroxylation is observed, due presumably to the formation of surface hydroxyl complexes. The surface morphology, however, is altered significantly with a large degree of roughening and an observed decrease in the average particle size. Reduction of U(VI) to U(IV) occurs during adsorption in almost all cases and this is interpreted to indicate that wüstite may be an effective reductant of U during surface adsorption. This work also shows that increasing the carbonate concentration in reactant solutions dramatically decreases the adsorption coefficients for U on both wüstite and portlandite, consistent with U speciation and surface reactivity determined in other studies. Finally, the EXAFS results include new details about exactly how U bonds to this metal oxide surface.

Wooldridgeite, ideally Na2(P2O7)2(H2O)10, orthorhombic, a = 11.938(1), b = 32.854(2), c = 11.017(1) Å , V = 4321.2(8) Å3, a:b:c = 0.3634:1:0.3353, space group Fdd2, Z = 8, is a new mineral from Judkins Quarry, Nuneaton, Warwickshire, England. Associated minerals are calcite, chalcopyrite, bornite and baryte. It occurs as equant crystals forming rhombic dipyramids; no twinning was observed. It is transparent blue-green with a very pale-blue streak, a vitreous lustre, and does not fluoresce under long- or short-wave ultraviolet light. Wooldridgeite has a Mohs hardness of 2–3, is brittle with an irregular fracture, and has no cleavage. The calculated density is 2.279 g/cm3. In transmitted light, wooldridgeite is colourless, non-pleochroic, and shows no dispersion. It is biaxial negative with α = 1.508(1), β = 1.511(1), γ = 1.517(1), 2V(meas.) = 76.2(5), 2V(calc.) = 71(10)8, X = b, Y = c, Z = a. The strongest five reflections in the X-ray powder diffraction pattern are [d(Å), (I), (hkl)]: 8.23(30)(040), 6.52(100)(131), 4.05(40)(260), 3.255(40)(262); 2.924(40)(371). Electron-microprobe analysis of wooldridgeite gave P2O5 39.37, CuO 20.24, MgO 0.24, CaO 7.73, Na2O 8.33, K2O 0.17, H2O(calc.) 24.72, sum 100.80 wt.%; the corresponding unit formula (based on 24 anions) is (Na1.96K0.03)Ca1.00(Cu1.85Mg0.04)P4.04O14(H2O)10 where the H2O groups were assigned from knowledge of the crystal structure; the infrared absorption spectrum also indicates the presence of H2O in the structure. The mineral is named for James Wooldridge (1923–1995), a fervent amateur mineral collector who discovered this mineral.

The new mineral oskarssonite (IMA2012-088), with ideal formula AlF3, was found in August 2009 at the surface of fumaroles on the Eldfell volcano, Heimaey Island, Iceland (GPS coordinates 63°25′58.9″N 20°14′50.3″W). It occurs as sub-micron-sized crystals forming a white powder in association with anhydrite, bassanite, gypsum, jarosite, anatase, hematite, opal, ralstonite, jakobssonite and meniaylovite. Chemical analyses by energy-dispersive spectrometry with a scanning electronmicroscope produced the following mean elemental composition: Al, 31.70; F, 58.41; O, 9.22; total 99.33 wt.%. The empirical chemical formula is AlF2.6(OH)0.5 which suggests partial substitution of F by OH. Oskarssonite is rhombohedral, space group Rc, with ah = 4.9817(4) Å, c = 12.387(1) Å, Vuc = 266.23(5) Å3, Z = 6. The five strongest lines in the powder diffraction diagram [d in Å(I) (hkl)] are as follows: 3.54 (100) (012), 2.131 (13) (113), 1.771 (20) (024), 1.59 (15) (116), 1.574 (10) (122). Rietveld refinement confirms the identity of oskarssonite with the synthetic rhombohedral form of AlF3. Its structure can be described as a rhombohedral deformation of the idealized cubic perovskitetype octahedral framework of corner-sharing AlF6 groups. Oskarssonite appears in the surface part of the fumaroles where fluorides are abundant. At greater depths (below 10 cm) sulfates dominate among the fumarolic minerals. In accordance with its occurrence, we surmise that oskarssonite forms in the later stages of the fumarolic activity in an environment poor in alkalies and Mg. Ralstonite (NaxMgxAl1−xF3(H2O)y), which, unlike oskarssonite, contains Na and Mg as important constituents, dominated in the first-formed fumaroles, but now, 41 years after the eruption of Eldfell, is only a minor phase. The new mineral is named after the Icelandic volcanologist Niels Oskarsson.

The fusion crusts of meteorites form due to heating during atmospheric entry and have mineralogies which are strongly influenced by changes in oxidation state. We have studied the fusion crusts of the most reduced primitive meteorite group, the enstatite chondrites, since they should demonstrate pronounced changes on oxidation. The fusion crusts are dominated by highly unequilibrated assemblages of sulphide, metal and oxide with compositions indicative of progressive oxidation by the reaction with atmospheric oxygen. Troilite becomes depleted in Ti, Cr and Mn, and enriched in Ni with increasing oxidation. Enrichments in the Ni-contents of kamacite and depletions in Si-content also occur with oxidation, although contemporaneous enrichments in Si within metal droplets occurs by partial melting. Assemblages dominated by Fe-oxide are found within fusion crusts as reaction rims on metal, as veins and within troilite-metal assemblages as droplets and formed by oxidation of metal during heating. Despite the evidence for large increases in redox state during heating, fusion crusts also contain lithophile sulphides indicating a high degree of disequilibrium during the atmospheric reprocessing of enstatite chondrite materials. Based on comparisons with experimental phase relations, ablation rates of 0.08–0.25 cm s−1 are predicted from the thermal gradients recorded in fusion crusts; these rates are broadly similar to those suggested for other meteorite groups.

Fluorcaphite [SrCaCa3(PO4)3F] is a rare strontium-calcium member of the apatite supergroup which was previously known only from the Khibiny and Lovozero alkaline complexes. This paper presents evidence of a third fluorcaphite occurrence. It was found in hydrothermally altered Lower Cretaceous teschenite, which forms an intrusive body (probably a sill) in the Lower Cretaceous siliciclastic flysch sediments at Tichá near Frenštát pod Radhoštěm, Silesian Unit, Outer Western Carpathians (Czech Republic). Fluorcaphite occurs as an accessory mineral in hydrothermal veins and in an adjacent alteration zone within the host teschenite. Vein-hosted fluorcaphite forms euhedral crystals and skeletal crusts enclosed in analcime while the teschenite-hosted fluorcaphite forms small overgrowths on older phenocrysts of magmatic apatite. Fluorcaphite from Tichá contains 0.50–1.97 Sr apfu, 2.96–4.49 Ca apfu, 0.59–1.09 F apfu and significantly lower Na (0.01–0.05 apfu) and LREE contents (up to 0.07 apfu). Fluorcaphite formed under hydrothermal conditions after solidification of the host teschenite during post-magmatic hydrothermal activity at temperatures probably between ∼150 and 300°C. The initial 87Sr/86Sr ratio of vein-hosted analcime +fluorcaphite (0.7063) is significantly higher than those of the host teschenite (0.7041). We therefore suggest a mix of strontium sources in the vein analcime+fluorcaphite: (1) from the host teschenite plus (2) from external source(s) including the Lower Cretaceous seawater and/or surrounding sedimentary rocks of the Silesian Unit. These data indicate an open-system fluid regime and the participation of various fluid sources during the alteration event giving rise to fluorcaphite.

Pyrrhotite Fe1–xS is the main sulfide component of platinum-group element (PGE) ores and commonly contains from a few tenths to a few dozen ppm of disseminated Pt. Here we report an X-ray absorption spectroscopy investigation into the state of Pt in synthetic pyrrhotite in combination with theoretical spectra modelling. The pyrrhotite crystals were obtained by means of the salt flux technique, using a eutectic mixture of alkali metal halides as the transport media. Analysis of the chemical composition of synthesised crystals showed that an increase of the temperature and sulfur fugacity yields higher concentrations of Pt in pyrrhotite. The Pt content reached 0.6 wt.% at the maximum temperature and sulfur fugacity (t = 720°C, log $f_{{\rm S}_ 2}$ = –0.1) achieved in a Pt-saturated system. X-ray absorption near-edge structure (XANES) analysis of Pt L3-edge spectra revealed that Pt is present in pyrrhotite in the 4+ and 2+ ‘formal’ oxidation states. Theoretical modelling of XANES and interpretation of extended X-ray absorption fine structure (EXAFS) spectra showed that Pt4+ substitutes for Fe in the crystal lattice of pyrrhotite, whereas Pt2+ forms PtS-like clusters disseminated in the pyrrhotite matrix. Atoms of isomorphous Pt4+ are surrounded by 6 S atoms at a distance of 2.39 ± 0.02 Å. According to theoretical simulations using the FDMNES program, the second coordination sphere of the solid-solution Pt contains one vacancy in the Fe sublattice within the Fe-layer. The Pt2+S-like clusters can be considered as a quench product. High sulfur fugacity stabilises the solid-solution Pt and prevents the formation of the PtS-like clusters during cooling. The maximum content of the solid-solution Pt in pyrrhotite is ca. 50 times lower than in pyrite and can be approximated by a straight line in the log C(Pt) vs. 1/T plot, it increases from 1 ppm at 350°C to 3 wt.% at 900°C.

The Icelandic crust is characterized by low δ18O values that originate from pervasive high-temperature hydrothermal alteration by 18O-depleted meteoric waters. Igneous rocks in Iceland with δ18O values significantly higher than unaltered oceanic crust (~5.7‰) are therefore rare. Here we report on rhyolitic intra-caldera samples from a cluster of Neogene central volcanoes in Borgarfjörður Eystri, Northeast Iceland, that show whole-rock δ18O values between +2.9 and +17.6‰ (n = 6), placing them among the highest δ18O values thus far recorded for Iceland. Extra-caldera rhyolite samples from the region, in turn, show δ18O whole-rock values between +3.7 and +7.8‰ (n = 6), consistent with the range of previously reported Icelandic rhyolites. Feldspar in the intra-caldera samples (n = 4) show δ18O values between +4.9 and +18.7‰, whereas pyroxene (n = 4) shows overall low δ18O values of +4.0 to +4.2‰, consistent with regional rhyolite values. In combination with the evidence from mineralogy and rock H2O contents, the high whole-rock δ18O values of the intra-caldera rhyolites appear to be the result of pervasive isotopic exchange during subsolidus hydrothermal alteration with 18O-enriched water. This alteration conceivably occurred in a near-surface hot spring environment at the distal end of an intra-caldera hydrothermal system, and was probably fed by waters that had already undergone significant isotope exchange with the country rock. Alternatively, 18O-enriched alteration fluids may have been produced during evaporation and boiling of standing water in former caldera lakes, which then interacted with the intra-caldera rock suites. Irrespective of the exact exchange processes involved, a previously unrecognized and highly localized δ18O-enriched rock composition exists on Iceland and thus probably within the Icelandic crust too.