The crystal structure of zoned philipsbornite – hidalgoite, hexagonal (rhombohedral), Rm , Z = 3: a = 7.1142(4), c = 17.0973(9) A ˚ , V = 749.4(1) Å3, from the Tsumeb mine, Namibia, has been refined to R1 = 1.68% for 301 unique reflections collected on a Bruker D8 three-circle diffractometer equipped with a rotating-anode generator, multilayer optics and an APEX-II CCD detector. Chemical analysis by electron microprobe showed zoned crystals with a rim enriched in S and Fe relative to the core. The core composition is SO3 3.31, As2O5 30.57, Al2O3 23.05, FeO 1.44, PbO 33.94, H2Ocalc 9.58, total 101.79 wt.%, corresponding to Pb0.982+(Al2.92Fe0.132+)(AsO4)[(As0.72S0.27)O3.14(OH)0.85](OH)6; and the rim composition is SO3 8.88, As2O5 22.63, Al2O3 22.90, FeO 2.57, PbO 34.91, H2Ocalc 9.27, total 101.16 wt.%, corresponding to Pb0.992+(Al2.85Fe0.232+)(AsO4)[(As0.25S0.70)O3.30(OH)0.50](OH)6. Philipsbornite – hidalgoite has the alunite-type structure, sheets of corner-sharing octahedra, decorated on top and bottom by [(As,S)O4] and (AsO3OH) tetrahedra, that are linked into a three-dimensional structure by [12]-coordinated Pb2+ cations and hydrogen bonds. A new hydrogen-bonding scheme for the D2+G33+(T5+O4)(TO3OH)(OH)6 minerals is proposed.

Free energies of formation of divalent metal ion zippeïtes, M2(UO2)6(SO4)3(OH)10 ·nH2O, M = Mg,Co,Ni,Zn have been determined from solution studies and metal speciation calculations, in water. It is found that in the compounds, the number of molecules of water of crystallization is equal to 8. This is at variance with a previous report (Frondel et al., 1976), but it has been found that some at least of the water content of zippeite is either nonessential or very loosely bound in the structure. Based on the octahydrate formulation, values are −3506, −12695, −12683 and −12870±4 kJ mol−1 for the Mg,Co,Ni and Zn end-members, respectively. Almost all of the differences in the values are accounted for by those values for the metal ions alone with the exception of Znzippeïte where a discrepancy of some 22 kJ mol−1 is found. Even this value is small however, and the chemical studies indicate that extensive mutual solid solution between all end members is to be expected. These findings agree perfectly with observations on the composition of naturally occurring zippeite minerals of this group.

Khademite, ideally Al(SO4)F(H2O)5, from the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy, has been characterised through quantitative electron microprobe analysis, micro-Raman spectroscopy and single-crystal X-ray diffraction. Khademite occurs as colourless to whitish tabular crystals, up to 5 mm. Electron microprobe analysis (in wt.%, average of 20 spot analyses) gave: SO3 35.43, Al2O3 21.27, F 6.92, H2Ocalc 39.73, sum 103.35, –O = F 2.92, total 100.43. On the basis of 10 anions per formula unit, assuming the occurrence of 5 H2O groups and 1 (F+OH) atom per formula unit, its chemical formula can be written as Al0.96S1.02O4[F0.84(OH)0.16]Σ1.00⋅5H2O. The Raman spectrum of khademite is characterised by the occurrence of vibrational modes of SO4 groups and by broad and strong bands due to the O–H stretching modes. Khademite is orthorhombic, space group Pcab, with unit-cell parameters a = 11.1713(2), b = 13.0432(3), c = 10.8815(2) Å, V = 1585.54(5) Å3 and Z = 8. The crystal structure refinement converged to R1 = 0.0293 on the basis of 2359 unique reflections with Fo > 4σ(Fo) and 152 refined parameters. The crystal structure of khademite is characterised by the alternation, along b, of two distinct kinds of {010} layers, one formed by [001] rows of isolated Al-centred octahedra, connected to each other through H bonds, and the other showing isolated SO4 groups. Along b, oxygen atoms belonging to SO4 groups act as acceptor of H bonds from H2O groups coordinating Al atoms. The new data improved the description of the H bonds in khademite and led us to discuss about the possible existence of its (OH)-analogue, rostite. In addition, Raman spectroscopic data were collected on the same crystal used for the crystal-chemical characterisation, allowing a comparison with previous results.

The extended timescales involved in the decay of radioactive wastes to safe levels mean that geological disposal facilities must continue to function effectively long into the future. It is therefore essential to consider long-term climate evolution in post-closure performance assessments in order to evaluate a geological disposal system's response and robustness to a variety of potential environmental changes, driven by both natural and anthropogenic forcings. In this paper, we illustrate the multiple decay components that characterize the primary driver of climate change – atmospheric CO2 – in response to fossil fuel carbon emissions. We perform a multi-exponential analysis on a series of atmospheric CO2 decay curves predicted by an Earth system model and create an empirical response function that encapsulates the long-term (>1 kyr) removal of excess CO2 from the atmosphere. We present this response function as a simple tool for rapidly projecting the future atmospheric CO2 concentration resulting from any plausible cumulative release of CO2. We discuss the implications of the long 'tail' to this atmospheric CO2 decay curve, both in terms of future climate evolution as well as potential impacts on radioactive waste repositories.

Lxullianite is well known, at least by name, in this country, and indeed it enjoys an international reputation among petrologists. Its general characters have been described by Bonney and Sir John Flett, while reference to the type is to be found in most standard text-books on petrology. It is, however, a rock of outstanding interest and deserves fuller description and illustration than have yet been accorded it.

The preparation by Mr. A. V. Weatherhead of a large set of thin sections for teaching purposes has given the writer an opportunity of making a more detailed examination of the micropetrology of the rock, with special reference to the manner of the replacement of the several original components.

The first recognition of ankerite as a British mineral seems to have been made a little over fifty years ago by M. F. Heddle, who described and analysed a sample from the Ting of Norwick, Unst. The occurrence of the mineral in veins in the Carboniferous Limestone of Lilleshall, Shropshire, was recorded by C. J. Woodward, who gives analyses of two specimens. T. Crook noted the frequent occurrence of the mineral in British coal-fields and described specimens, with two analyses, from Lancashire, Yorkshire, Nottinghamshire, Leicestershire, and South Wales. F. S. Sinnatt and his collaborators, in their work on the mineral constituents of coal, devote a good deal of attention to the 'white partings' or ankerites, of which, as they say, 'no study has appeared in the literature'.

X-ray absorption spectroscopy (XAS) has been used to study the local structures of Fe, Co, Zn, and Mg in synthetic and natural staurolites. Results for the near-edge features (XANES) and refined EXAFS were used to deduce the crystallographic site(s) occupied for each element. The least squares refined, mean first shell metal-O bond lengths, coordination numbers, and Debye-Waller factors are in the ranges: Fe 1.97–1.99 Å, 3.5–4.1, 0.013–0.023 Å2; Co 1.97–1.98 Å, 3.5–3.9, 0.009–0.014 Å2; Zn 1.95–1.96 Å, 3.7–3.8, 0.008–0.009 Å2; and Mn 1.99 Å, 3.8, 0.012 Å2. No significant differences were found which depended on element concentration or whether the sampes are synthetic or natural. The refined bond length for Mg in end-member Mg-staurolite is 2.00 Å but EXAFS data did not allow refinement to give reliable coordination number and Debye-Waller factor estimates. The EXAFS data, together with staurolite and model compound XANES features, suggest that > about 90% of Fe, Co, Zn and Mn are concentrated in the tetrahedral T2 site, while in Mg-staurolite > about 75% of the total Mg is in T2 with the remainder in octahedral sites. In natural staurolite from Pizzo Forno (PF2), a greater proportion of Mg appears to be in octahedral coordination.

Zoned spherulites in greenalite-siderite-silica rocks of the Emilia-San Valentin lead-zinc deposit, Sierra de Cartagena, SE Spain, show a core of iron-rich talc, (Mgl.8Fel.2)Si4Ol0(OH)2, an intermediate zone of opal-chalcedony, and a rim of minnesotaite, (Fe2.7Mg0.3)Si4Ol0(OH)2. Crystalllization of the spherulites, presumably from undercooled silica sols carrying dissolved Mg and Fe, began with the non-equilibrium precipitation of metastable iron-rich talc; the residual fluids enveloping the growing spherulites became more iron-rich in composition until metastable equilibrium between iron-rich talc and iron-enriched residual liquid impeded the further growth of the iron-rich talc; the spherulites were then overgrown by colloidal silica flocculates and a rim of minnesotaite precipitated from the iron-enriched residual fluid. The proposed crystallization model implies that, if talc and minnesotaite represent an isomorphic series, under equilibrium conditions there is a broad immiscibility region in the series.

The development of low- and hightemperature alteration products in a 23 m section of ocean-floor basalts is described. Analcime, calcite and dioctahedral smectite are ubiquitous. Trioctahedral smectite, smectite-chlorite mixed layers, chabazite and scolecite occur in the deeper sections with Fe3+ oxides/hydroxides progressively becoming more abundant in the upper regions. The upper layers of the sequence show marked chemical reduction. High-temperature chemical changes include Na and Mg enrichment accompanied by Ca and Fe2+ losses. Superimposed low temperature changes include gains in Fe3+ K, Li, and Rb, and losses in Na, Ca, and Fe2+ Many trace elements also show consistent behaviour.

A transmission electron microscopy (TEM) investigation was undertaken in order to elucidate the nature of the structural disorder in a tobelite specimen from the sedimentary rocks of the Armorican sandstones (western France). This structural disorder may be the origin of residual electron-density maxima in difference-Fourier maps reported previously in single-crystal XRD studies of tobelite. The TEM investigation of tobelite confirmed that it is the 2M2 polytype in subfamily-B, but the ordered sequence is interrupted by numerous stacking faults parallel to (001), for which the stacking vectors belong to both subfamilies-A and -B of mica polytypes, with a prevalence of the latter. Chemical heterogeneity depending on the Si/Al ratio and Na and Mg concentration was observed at the nanoscale among different mica lamellae in a single crystal. The observed variations are consistent with a change in mica chemistry leading to interlayer vacancies which may cause shortening of the interlayer separation, as revealed by the single-crystal structure refinements.

A silver-palladium alloy with structural formula close to AgPd has been found in laterite from the Bahia lateritic gold deposit. The alloy occurs in a void of an iron oxide nodule, associated with goethite and hematite. The angular shape and protuberances of the alloy grains suggest crystal growth in a lateritic environment, indicating that the alloy is a secondary mineral precipitated during lateritisation. The oxidation of sulphides of the parent rocks probably favoured the migration of palladium and silver as transient thiosulphate and sulphite complexes. Destruction of the thiosulphate and sulphite ligands could result in precipitation of both palladium and silver as an alloy. Eh-pH phase diagrams for Pd-H2O-C1 and Ag-H2O-C1 systems show that both palladium and silver are stable in lateritic environments under lower redox potentials. Such an environment may exist at the top of the ferruginous zone due to the abundant organic matter near the surface.

Wycheproofite is a new hydrated sodium aluminium zirconium phosphate from a pegmatite vein in granite at Wycheproof, in northwestern Victoria, Australia. The mineral occurs as compact, finely fibrous masses in small cavities in the quartz/feldspar/muscovite/schorl-bearing pegmatite. The fibrous crystals are between 5 and 10 µm wide and up to several mm long. Accompanying minerals include two other zirconium phosphates — kosnarite and a new species, selwynite, the K-analogue of gainesite — as well as wardite, eosphorite, cyrilovite, leucophosphitc, rockbridgeite, a kidwellite-like mineral and saleeite. The wycheproofite aggregates are pale pinkish to brownish orange, with a vitreous to pearly lustre. The streak is colourless, fracture rough, cleavage not observed and the Mohs hardness is between 4 and 5. Optical data are incomplete due to the fibrous nature of the mineral; the indices of refraction are in the range 1.62–1.64. The measured density is 2.83 g cm−3. Chemical analysis gave (wt.%) Na2O 6.36, K2O 0.44, CaO 0.66, FeO 0.36, MnO 0.21, Al2O3 12.03, Cs2O 0.03, ZrO2 32.43, HfO2 1.24, P2O5 35.85, SiO2 0.23, F 0.34, H2O 9.0, less 0=F 0.14, Total 99.04. The simplified formula is NaAlZr(PO4)2(OH)2·H2O. Wycheproofite is triclinic with unit cell parameters a=10.926(5) Å, b = 10.986(5) Å, c = 12.479(9) Å, α= 71.37(4)°, β = 77.39(4)°, γ= 87.54(3)° V = 1375.9 Å3. For Z= 6, the calculated density is 2.81 g cm-3. The strongest lines in the X-ray powder diffraction pattern are [dobs (Å), Iobs,hkl] 2.603 (100) 040; 4.128 (80) 121; 3.711 (65) 023; 3.465 (60) 030; 8.865 (40) 101; 3.243 (35) 132. The crystal structure has not been solved due to the finely fibrous nature of the material available. The name is for the locality, which in the local Australian Aboriginal language means ‘witchie bushes growing on a hilltop’.

Data on the third occurrence of kosnarite, KZr2(PO4)3, at Wycheproof are also given.

Coaquandite, a new antimony oxy-sulphate hydrate, occurs as spheroidal knobs of silky fibres or, rarely, as tiny transparent colourless lamellar crystals on stibnite at the Pereta mine, Tuscany, Italy; it is associated with klebelsbergite, peretaite, valentinite, sulfur, gypsum, stibiconite, and senarmontite. Coquandite is triclinic P1, with a 11.434(7), b 29.77(4), c 11.314(4) Å, α 91.07(7)°, β 119.24(3)° γ 92.82(1)° . It has a cell volume of 3352(5)Å3 with Z = 12 and a calculated density of 5.78 g cm−3. The crystals, elongated along [001] and flattened on {010}, display polysynthetic twinning with (010) as the twin plane. Optically, they are biaxial (+) with z ≈ c, 2V ≫ 60° n = 2.08(5). The strongest lines of the X-ray powder pattern are [d in Å, (I), (hkl)] 14.84(50)(020), 9.27(41)(111, 110), 6.81(67)130, 3.304(93)(090), 3.092(100)(330).

Coquandite has also been found at the Cetine mine, Tuscany, Italy, and at the Lucky Knock mine, Tonasket, Okanogan County, Washington, USA. 22 microprobe chemical analyses (elemental microanalysis for H) gave Sb2O3 88.91, SO3 8.35, CaO 0.04, Na2O 0.03, H2O 1.43, total 98.76 wt.%, corresponding to the empirical formula (Sb + S = 7) Sb5.98Ca0.01Na0.01O7.96(SO4)1.02.0·78H2O, and to the idealised formula Sb6O8(SO4).H2O. The I.R. spectrum, which confirms the presence of water in the formula, is given.

A partial structural arrangement is also given: the Sb polyhedra lie in nine layers perpendicular to [010] and form 'hexagonally' shaped groups surrounded by SO4 tetrahedra.

The crystal structure of Ba2F2(S6+O3S2–), a natural thiosulphate weathering product of old smelting slags at the Surrender Mill, Yorkshire, England, UK, has been solved to R1 = 0.88% for 399 unique [Fo > 4α F] reflections and 0.91% for all 407 reflections. The compound is monoclinic, C2/m, a 15.3172(5), b 4.5898(1), c 4.6320(2) Å, β 101.449(1)º, V 319.17(2) Å3. The structure of Ba2F2(S6+O3S2–) consists of BaF2Ba layer fragments of the fluorite-type structure of frankdicksonite (BaF2) parallel to (100) alternating with layers of thiosulphate groups. The layer sequence in one unit cell is (S6+O3S2–)-BaF2Ba-(S6+O3S2–)-BaF2Ba. The structure resembles that of grandreefite, Pb2F2SO4.

Chromitite zones associated with ultramafic units of the Lysanskiy layered complex of dunite–peridotite–gabbro composition could well represent the primary source for the placers bearing platinum-group minerals (PGM) of the entire drainage of the River Sisim and its tributaries, the rivers Ko and Seyba, eastern Sayans. Alluvial gold present in the placers of River Seyba, as elsewhere in the Sisim Placer Zone, reflects mineralisation during a recent period of tectonic activity. We focus on the PGM in the Seyba suite, and in particular on the attributes of pentlandite enriched in platinum-group-elements (PGE) and the compositionally similar and recently defined ferhodsite, which were trapped in host grains of Os–Ir–Ru alloy. Both minerals formed from small volumes of fractionated Fe–Ni–Cu melt considerably enriched in the PGE. In the Seyba suite, as in several others, the amounts of PGE in ferhodsite exceeds that in pentlandite, which results in a greater proportion of vacancies than in pentlandite.

The mineral priderite has been examined by electron microprobe analysis and electron diffraction. The composition was approximately (K0.97Ba0.33)(Fe1.17Ti6.60Mg0.23)O16, which is in line with the observed superlattice periodicity of m = 5.88, there being inter-growths of m = 5 and m = 6 superstructures. A surprisingly high degree of lateral correlation between tunnel cations was noted.

The crystal structure of Na4[Cu4O2(SO4)4] MeCl (Me: Na,Cu,☐) has been solved by direct methods and refined to R1 = 0.028 using 2466 independent reflections. The compound is tetragonal with space group P4/n, a = 18.451(1)Å, c = 4.9520(2)Å, Z = 4. The two main building units running parallel to the c-axis comprise: (1) slabs containing SO4 and OCu4 tetrahedra; and (2) chains of corner sharing Me(Cl,O)6 octahedra. The displacement ellipsoids of the atoms occupying the Me sites and of the Cl ions indicate a short-range static disorder. Copper in the slabs exhibits a (4+1) coordination. Both elements form a tunnel structure in which additional Na atoms are incorporated for charge compensation. The structure is closely related to the mineral piypite (K4Cu4O2(SO4)4 MeCl (Me: Na,Cu,☐)): . Furthermore, the structure has a pronounced pseudo-translational symmetry: apart from some of the oxygen sites, all of the nineteen crystallographically distinct positions are related by a pseudo F centring.