One of the most challenging aspects of understanding the flow of gas and water during testing in clay-rich low-permeability materials is the difficulty in visualizing localized flow. Whilst understanding has been increased using X-ray Computed-tomography (CT) scanning, synchrotron X-ray imaging and Nuclear Magnetic Resonance (NMR) imaging, real-time testing is problematic under realistic in situ conditions confining pressures, which require steel pressure vessels. These methods tend not to have the nano-metre scale resolution necessary for clay mineral visualization, and are generally not compatible with the long duration necessary to investigate flow in such materials. Therefore other methods are necessary to visualize flow paths during post-mortem analysis of test samples. Several methodologies have been established at the British Geological Survey (BGS), in order to visualize flow paths both directly and indirectly. These include: (1) the injection of fluorescein-stained water or deuterium oxide; (2) the introduction of nanoparticles that are transported by carrier gas; (3) the use of radiologically tagged gas; and (4) the development of apparatus for the direct visualization of clay. These methodologies have greatly increased our understanding of the transport of water and gas through intact and fractured clay-rich materials. The body of evidence for gas transport through the formation of dilatant pathways is now considerable. This study presents observations using a new apparatus to directly visualize the flow of gas in a kaolinite paste. The results presented provide an insight into the flow of gas in clay-rich rocks. The flow of gas through dilatant pathways has been shown in a number of argillaceous materials (Angeli et al., 2009; Autio et al., 2006; Cuss et al., 2014; Harrington et al., 2012). These pathways are pressure induced and an increase in gas pressure leads to the dilation of pathways. Once the gas breakthrough occurs, pressure decreases and pathways begin to close. This new approach is providing a unique insight into the complex processes involved during the onset, development and closure of these dilatant gas pathways.

Unit cell dimensions and refractive indices have been determined for synthetic pyroxenes in the system CaMgSi2O6-CaFeSi2O6-NaFeSi2O6, which have been crystallized and annealed on the nickel-bunsenite (Ni-NiO) oxygen buffer curve at 700 °C and a total pressure of 2 kb. The data presented confirms the many postulates that a complete solid solution series does exist in the subsolidus region of the ‘ternary’ system. The unit cell dimensions show an almost linear change with composition between the end members. The determined cell parameters for a series of analysed natural alkali pyroxenes have been compared with the data for the synthetic pyroxenes and close agreement was found between both sets of data. The variation of the unit cell dimensions and refractive indices has been examined in relation to the possible ionic substitutions taking place in the pyroxenes.

Diffusion into the rock matrix is potentially an important retardation mechanism for nuclides leached from an underground radioactive waste repository in a fractured hard rock. A technique for measuring the intrinsic diffusion coefficient and rock capacity factor is briefly described. Simple solutions to migration model equations are used, together with diffusion results and typical hydrogeological parameters, to estimate the impact of matrix diffusion on radionuclide migration. It is shown that retardation factors in excess of 100 and reductions in the peak concentration by 3–4 orders of magnitude are possible for non-sorbed ions, which would otherwise be carried by the flow and not retarded at all.

The new mineral species arsiccioite, AgHg2TlAs2S6, was discovered in the baryte-pyrite-iron oxide ore deposit exploited at the Monte Arsiccio mine, near Sant’Anna di Stazzema (Apuan Alps, Tuscany, Italy). It occurs as anhedral grains scattered in microcrystalline baryte, associated with cinnabar, laffittite, protochabournéite, pyrite, realgar, Hg-bearing sphalerite and stibnite. Arsiccioite is red, with a metallic to sub-metallic lustre. Minimum and maximum reflectance data for COM wavelengths in air are [λ (nm): R (%)]: 471.1: 29.0/29.4; 548.3: 27.6/28.3; 586.6: 26.1/26.5; 652.3: 24.2/24.6. Electron microprobe analyses give (wt.%): Cu 0.78(6), Ag 8.68(21), Zn 0.47(27), Fe 0.04(1), Hg 35.36(87), Cd 0.20(5), Tl 18.79(33), As 10.77(19), Sb 4.75(10), S 18.08(21), Se 0.07(5), total 97.99(44). On the basis of ΣMe = 6 a.p.f.u., the chemical formula is Ag0.87(2)Cu0.13(1)Zn0.08(4)Fe0.01(1)Hg1.91(5)Cd0.02(1)Tl1.00(2) (As1.56(2)Sb0.42(1))S1.98S6.12(6)Se0.01(1). Arsiccioite is tetragonal, I2m, with a 10.1386(6), c 11.3441(5) Å, V 1166.1(2) Å3, Z = 4. The main diffraction lines of the powder diagram are [d(in Å), visually estimated intensity, hkl]: 4.195, m, 211; 3.542, m, 103; 3.025, vs, 222; 2.636, m, 114; 2.518, s, 400 and 303. The crystal structure of arsiccioite has been refined by single-crystal X-ray data to a final R1 = 0.030, on the basis of 893 observed reflections. It shows a three dimensional framework of (Hg,Ag)- centred tetrahedra (1 M1 + 2 M2), with channels parallel to [001] hosting TlS6 and (As,Sb)S3 disymmetric polyhedra. Arsiccioite is derived from its isotype routhierite M1CuM2Hg2TlAs2S6 through the double heterovalent substitution M1Cu+ + M2Hg2+ → M1Hg2+ + M2Ag+. This substitution obeys a steric constraint, with Ag+, the largest cation relative to Hg2+ and Cu+, entering the largest M2 site. The ideal crystal chemical formula of arsiccioite is M1HgM2(Hg0.5Ag0.5)2TlAs2S6. The crystal chemistry of the routhierite isotypic series is discussed. Finally, the distribution of Hg ore minerals in the Apuan Alps is reviewed.

The upper stability of margarite has been determined to be 450 °C at 1 kb and 530 °C at 2 kb total pressure (PH2O = Ptotal). Other experiments delimit in a general way the lower stability of this mineral and its paragenesis in more SiO2 rich compositions. The presence of the 060 reflection at 1·475 Å can be used to distinguish between margarite and paragonite or muscovite.

Petrographic and compositional variations in the Lower Main Zone (LMZ) of the western Bushveld Complex indicate changing regimes of magma replenishment. The lowermost unit of the LMZ, designated N-I, is an enigmatic sequence of leuconoritic cumulates, characterized primarily by up-sequence increases in both orthopyroxene Mg# and whole-rock Sr isotope initial ratio. The Sr isotope profile of N-I is ascribed to injection and progressive integration of small influxes of fresh magma with high (Main Zone-type) Sr isotope initial ratios. The basal Fe-enrichment in N-I, on the other hand, is ascribed to a separate, later mechanism involving the downward migration of late-stage Fe-rich liquids. The overlying two units, N-II and G-I, delineated chiefly in terms of basal Mg-enrichment of orthopyroxene, are ascribed to injections of fresh magma into the chamber. Poikilitic orthopyroxene grains in the basal parts of both N-II and G-I suggest entrainment and partial resorption of plagioclase grains from the semi-crystalline resident material into which the fresh magma was intruded.

Roxbyite (Cu1.74–1.82S), a new mineral, was isolated from drill core from the Olympic Dam deposit, from copper flotation concentrates from the Olympic Dam pilot plant, and from reaction residues obtained by treating certain concentrates with sulphuric acid. Powder X-ray diffraction data and the composition of the mineral are similar to results reported previously for the unnamed mineral of composition Cu1.83S (with a trace of iron) from the El Teniente deposit in Chile, and to copper sulphides of composition CuxS, 1.75 ⩽ x ⩽ 1.86, prepared electrochemically by several workers. A Weissenberg single-crystal study shows roxbyite to be monoclinic with a = 53.79, b = 30.90, c = 13.36Å, β = 90.0° and space group alternatives C2/m, Cm or C2. Some iron in the structure may stabilize the mineral.

A number of new alkaline-earth-rare-earth silicate and germanate compounds with the apatite-type structure have been synthesized including a new calcium lanthanum silicate, Ca4La6(SiO4)6(OH)2, which has a 9·63 Å, c 7·12, and c/a 0·740. This has a random distribution of Ca2+ and La3+ over the (4f) and (6h) sites in the lattice. X-ray data are given for Ca4La6(SiO4)6(OH)2 together with cell dimensions for other synthetic silicate and germanate apatites. Silicate apatites with partially occupied or vacant halogen (2a) sites analogous to those of the pyro- morphites have been prepared, and a classification for silicate apatites based on synthetic end-members is proposed.

The coexistence of clinopyroxene (Wo18 En32 Fs44 Rh06) and pigeonite (W08 En35 Fs50 Rh07) in a meta-ironstone from Scourie is described. By comparison with experimental data, the temperature at which they were in equilibrium is estimated as at least 1000°C. The exsolution history of the two pyroxenes is documented. As the rock is an unambiguous metasediment, its presence among granulite facies rocks containing evidence of metamorphism at pressures greater than 10 kbar constrains at least part of the Scourie complex to a supracrustal origin and indicates that tectonic processes of burial were operative in the late Archaean.

Lapilli and spatter of natrocarbonatite extruded from the T56B cone of Oldoinyo Lengai (Tanzania) in August 2003 are unusually rich in apatite, silicate, oxide and sulphide minerals. These minerals occur primarily within inclusions of quenched natrocarbonatite in gregoryite and fractures in nyerereite-gregoryite intergrowths. Silicates include members of the sodian cuspidine–niobian cuspidine–niocalite solid-solution series and manganoan monticellite. Oxides are represented by members of the magnesioferrite–jacobsite–magnetite solid-solution series. Sulphides occurring in decreasing order of abundance include: ferroan alabandite, manganoan ferroan sphalerite, galena and pyrrhotite. Petrographic and compositional data for these minerals are interpreted to indicate that all are high-temperature (<900–650°C), early-crystallizing phases from relatively-unevolved natrocarbonatite magma, with the sulphides forming prior to the silicates, and the latter before gregoryite. Sulphur fugacityand oxygen fugacity of natrocarbonatite magma are considered to decrease and increase, respectively, during the formation of the sulphide-oxide assemblage. Crystallization of cuspidine-niocalite, monticellite and Si-bearing apatite rapidly depletes natrocarbonatite magma of its initial low silica content, preventing crystallization of late-stage groundmass silicates.

The crystal structure of sophiite, Zn2(SeO3)Cl2 (a = 10.251(4), b = 15.223(2), c = 7.666(5) Å, Z = 8) was solved in space group Pccn from single crystal X-ray data, and refined to R = 0.053 for 666 Fo > 4oFo. The mineral belongs to layer compounds. The threefold coordinated Se atom is at the apex of a pyramid, the base of which is formed by three O atoms; Se-O = 1.69 Å. Zn cations occupy two positions with distorted tetrahedral and octahedral coordinations. In the tetrahedra, Zn cations are surrounded by two O (2.02 Å) and two Ci (2.224 Å) atoms. Zn octahedra contain four O atoms (2.07 Å) and two CI atoms (2.701 Å). The atomic arrangement is characterized by rings containing two Se pyramids linked by their corners to two Zn tetrahedra. The rings are linked by their edges and corners to Zn octahedra to form layers parallel to (010). The layers are interconnected by residual Van der Waals bonds.

Experimental results on thermal phase transformations and deformations, crystal optics and other physical properties of sophiite are presented. A structural aspect of their anisotropy is discussed.

Most fungi synthesize siderophores as chelating agents which form soluble complexes with Fe3+ with very high stability constants, thus solubilizing ferric Fe. Ericoid mycorrhizal fungi release ferricrocin or fusigen as the main siderophores. Ferricrocin was also shown to be produced by the ectomycorrhizal fungi, Cenococcum geophilum and Hebeloma crustuliniforme. Arbuscular mycorrhizal fungi are reported to enhance Fe-uptake rates of associated host plants which can be taken as an indication that mycorrhizal siderophores of a yet unknown structure may be involved. Mycorrhizal fungi of orchids were shown to produce as the main siderophores, both well known ferrichrome-type siderophores or the novel linear trishydroxamate basidiochrome.

The equilibrium structures of cubic, tetragonal and orthorhombic phases of magnesium silicate perovskite are found from first principles electronic structure calculations. Zone centre and zone boundary phonons of each phase are also calculated from ab initio forces from finite displacments, and phase transitions between the phases are analysed in terms of phonon instabilities, and coupling between modes. Both the cubic and tetragonal phases have strongly unstable modes dominated by rotation of the SiO6 octahedra, which freeze in to ultimately form the orthorhombic phase. First priniciples molecular dynamics simulations at finite temperatures are used to further investigate the stability of the intermediate tetragonal phase and the coupling between participating phonon modes. The implications for a transition temperature between orthorhombic and tetragonal phases are discussed.

The FTIR spectra of synthetic BaMg(CO3)2 (norsethite) are measured at ambient temperature and atmospheric pressure, and the influence of formation conditions on the FTIR spectra is investigated. The results are compared with those for natural norsethite from Långban (Sweden) and Rosh Pinah (Namibia). The Raman spectrum of synthetic norsethite is reported, too. A number of first-order internal modes of the carbonate ion group (ν1, ν2, ν3, ν4) are found to be infrared and Raman active. Additonally, the (ν1+ν3) and (ν1+ν4) combination modes and the (2*ν2) overtone are observed in the FTIR and Raman spectrum, respectively. The carbon isotopic-shift coefficient for ν2 due to the substitution of 12C by 13C (ν2(13CO32-)/ν2(12CO32-) = 0.971 ± 0.002), observed by FTIR spectroscopy, agrees with the theoretical value of 0.969.

Electron probe microanalyses carried out on thirty areas of lithiophorite (Al,Li)MnO2(OH)2 from five Australian localities indicate wide variations in its Ni, Co, Cu, and Zn content. The concentration of these elements varies inversely with the alumina content, though there is a marked change in their concentration at 18% alumina, suggesting the existence of two varieties of lithiophorite with differing concentration of transition elements. EPMA line scans also indicate definite changes in Co content in lithiophorite grains less than 0.2 mm in dimension. The variations in alumina and transition elements may be explained if lithiophorite is considered to be an irregular mixed-layer-lattice intergrowth of pure lithiophorite with members of the recently discovered asbolane-type minerals.

Feldspars, paracelsian and danburite, harmotome and phillipsite have alumino-silicate frameworks that consist of three out of the seventeen simplest ways of cross-linking chains of the feldspar type. The four-membered rings that form the feldspar type of chain are parallel and have two adjacent tetrahedra pointing one way and the other two the other way. Chains are produced by sharing oxygen atoms of oppositely-pointing tetrahedra of parallel four-membered rings. Cross-linking of chains produces frameworks containing parallel eight-membered rings. If alternate tetrahedra in the rings point the same way, a new type of chain is produced, and there are four simple ways of joining these chains together to make a framework. If all four tetrahedra in a ring point the same way, only one structure can be developed, which has been proposed already by Barrer et al. for the zeolite Na-P1 and other members of the harmotome family. If three tetrahedra in the ring point the same way, very many simple structures can be constructed, and the seven simplest of these are described. It is suggested from comparison of cell dimensions that gismondine and, perhaps, yugawaralite may belong to this series of hypotheti- cal structures. It is also suggested that some of the complexity and confusion in the harmotome group of zeolites may arise from hitherto unrecognized members of this hypothetical group. Major angular distortions from the ideal shape occur for the naturally-occurring silicates belonging to these structural groups.

The 2 km × 5 m Newmains Dyke in the Scottish Southern Uplands consists mainly of primitive (mg number > 70), at least partly mantle-derived lamprophyre (vogesite spessartite, SiO2 50–60%), with hornblende-pyroxene-rich cumulates (SiO2 < 50%) and small amounts of quartz syenitic to granite residua (60–73% SiO2). The lamprophyres and cumulates yield an Rb-Sr whole-rock isochron age of 395±9 Ma (MSWD 2.0), and (87Sr/86Sr)i 0.70514±5—identical values to the nearby Criffell granitic pluton. After some 65% hornblende + clinopyroxene fractionation of parent lamprophyre magma, a volatile phase separated and metasomatically enriched the country rock greywackes in K, Ba, and Rb. The remaining quartz syenitic liquids became contaminated by 87Sr from these greywackes, which have a mean (87Sr/86Sr)395 value of 0.70789±114. Further fractionation of the contaminated syenitic liquids gave the granitic rocks, which have (87Sr/86Sr)395 values of 0.7056–64. The dyke appears to demonstrate in situ some of the hidden processes previously invoked to explain the evolution of the Criffell pluton itself.

The North Qôroq centre comprises a series of nested nepheline syenite intrusions and forms part of the mid-late Proterozoic Gardar province of South Greenland. Within the centre fractionation has produced varied rock types ranging from augite-syenite to lujavrite, a eudialyte microsyenite. Samples of eudialyte from the lujavrites of unit SN1B of the centre show evidence for two-stage alteration. This alteration ranges from slight modification along crystal margins to complete breakdown and replacement by new pseudomorphing phases. Modification to crystal margins is accompanied by increasing Nb and Zr contents and is related to metasomatism produced by the intrusion of younger syenite units of the North Qôroq centre. More extensive alteration is as a result of metasomatism followed by lower-temperature supergene alteration. Simplified reactions for this breakdown include eudialyte + metasomatic fluid = allanite + nepheline; eudialyte + metasomatic fluid = titanite + aegirine + møsandrite + wöhlerite; eudialyte + fluid = zirfesite + fluid. Mass balance calculations for altered compared with unaltered samples of lujavrite show that alteration took place at approximately constant volume with an overall increase in Fe (+2.41 g/100g), Si and K (+0.65 and +0.61 g/100g), whilst Na (−2.67 g/100g) and all trace elements, particularly La, Y, Nb and Zr (−5.6 to −166 g/10000g) are lost from the system.