We present experimental data for the Pm3m-I4/mcm phase transitions in the perovskite crystals KMn1-xCaxF3 and SrTiO3. Comparison of calorimetric data (latent heat and specific heat) with order parameter data (measured with X-ray rocking methods) indicates that these transitions follow mean-field behaviour, and may be described using Landau potentials where the free energy expansion includes terms up to Q6. This potential is characteristic of transitions close to the tricritical point. Comparison of the behaviour of SrTiO3 and KMnF3 indicates that KMnF3 is closer to the tricritical point; a small amount of substitution of Ca for Mn causes the transition to cross the tricritical point from first order to second order behaviour.

In situ high temperature single crystal X-ray diffraction (XRD) experiments have been performed on a chemically quasi-ideal omphacite sample up to 1000°C. The lattice parameters were studied as a function of temperature, and their thermal expansion coefficients determined. The b and c cell edges show discontinuities as a function of temperature which are interpreted here in terms of intracrystalline cation diffusion processes. Structure refinements have been carried out using data collected at room temperature, at 800°C and at ambient conditions after cooling. The structural behaviour as a function of temperature of chemically quasi-ideal omphacites is compared with those of jadeite and diopside.

At the abandoned pyrite mine at Genna Luas (Sardinia, Italy), melanterite is the most environmentally important secondary phase associated with pyrite oxidation. A complete cycle, including formation on pyrite surface, dissolution in water, precipitation from water and subsequent alteration, can be observed. The oxidation of pyrite to melanterite is related mainly to the ‘intrinsic’ features of the Genna Luas pyrite, such as its cryptocrystalline pseudo-colloidal texture. During melanterite formation on pyrite there is transient storage of Fe2+, SO42- and acidity. This is controlled mainly by wetting-drying seasonal cycles. Laboratory experiments have shown that the simple dissolution of melanterite is an acidity-generating process which affects the geochemistry of water and, indirectly, contributes to the supply of the Fe3+ required for the aqueous oxidation of pyrite. According to this geochemical model, the interaction between rainwaters and ground pyritic materials accumulated in heaps generates hyperacidic saline waters (pH = 0.6; TDS = 300 g/l) with very high SO42+ contents (203 g/l), Fe2+ contents (73 g/l), Zn contents (11 g/l), and numerous potentially toxic elements. Melanterite precipitates from these waters (SIMelanterite = 0.15, calculated using PHRQPITZ software), giving rise to attractive emerald green crystal aggregates which, when exposed to air, alter to a fine white powder composed mainly of melanterite, and minor amounts of rozenite and szomolnokite.

Combined cathodoluminescence (CL) and transmitted light microscopy were used to characterize quartz from flat and steeply dipping quartz veins and from veinlets in banded host rocks from the giant Muruntau Au quartz vein deposit, Kyzyl Kum Desert, western Uzbekistan. The CL examinations were carried out using a ‘hot-cathode’ CL microscope linked to a highly sensitive digital video camera. The multi-stage deformed flat quartz veins and the steeply dipping hydrothermal formations at Muruntau are characterized by quartz with different CL colours, internal structures and degree of secondary alteration. Primary growth zoning of quartz, indiscernible in conventional polarized light was found to occur only in steeply dipping veins. The bulk of the high-grade Au mineralized ‘central’ quartz veins is dominated by one generation of hydrothermal quartz; intense brecciation of these veins is indicated by the occurrence of fragments of zoned quartz crystals. Primary growth zoning in quartz may be revealed not only by variations in the intensity of blue CL and/or by primary fluid inclusions arranged within the zones, but also by secondary inclusions and recrystallization phenomena developed along boundary surfaces between the zones. Using the results from CL imaging and microstructural analysis of the quartz, fluid inclusions investigated earlier were assigned to genetic types; the evidence of probably primary inclusions is of considerable importance for further studies of the geochemical conditions during vein formation. Considering geological and mineralogical data, CL studies of vein quartz may help to reveal the history of precipitation, deformation and recrystallization processes in the Muruntau Au ore field.

We make the first report of fluid inclusion data from a black dolomite matrix breccia from the Irish orefield which confirm a relatively high-temperature hydrothermal origin. Breccia matrix dolomite formed from NaCl-dominated fluids with temperatures primarily in the range 150–220°C and salinities of 13–20 wt.% NaCl equivalent, comparable with inferred ore-stage fluids at the Silvermines, Tynagh, Lisheen and Navan deposits. The spread in salinity is considered to be due to mixing of a moderate salinity (~12 wt.%), higher temperature fluid, probably derived from the Lower Palaeozoic metasedimentary basement, with a low temperature brine. Non-stoichiometric, black dolomites are therefore considered to be a product of relatively high-temperature hydrothermal processes involving the principal orefluid in Ireland, and thus their occurrence is believed to be a prime exploration indicator.

Earlier, coarse white dolomite, texturally similar to regional dolomite cements commonly observed in the Irish Midlands, precipitated from fluids in the temperature range 140–200°C and salinities of 10.3–13.5 wt.% NaCl equivalent. This is comparable with the higher temperature, moderate salinity end-member inferred for the black dolomite. These data call into question a uniquely low-temperature burial origin for coarse white dolomite cements in Ireland. Paragenetically late low-Mg calcites were formed as a result of an influx of relatively low salinity fluids.

Manganoan berthierine, sometimes only a few layers thick, is preserved interlayered with manganoan chlorite (chamosite) in small recrystallized patches in cherty metapelagites matamorphosed in the prehnite–pumpellyite facies at Meyers Pass, Torlesse Terrane, South Canterbury, New Zealand. The Mn occupies 11–12% of the octahedral sites, making this the most Mn–rich berthierine reported so far. The ratio (Fe+Mn)(Fe+Mn+Mg), 0.67–0.70, is at the lower end of those of previously reported occurrences, making these amongst the most Mg-rich berthierines known. Manganoan berthierine and interlayered manganoan chlorite also make up ~11–13% of the cryptocrystalline groundmass in which the berthierine is believed to have crystallized under early diagenetic conditions near a deep-ocean–sediment interface. The occurrence of berthierine in the recrystallized patches lends support to the possibility of a stability field at the temperature of prehnite-pumpellyite facies recrystallization in association with chlorite of similar but not identical composition.

Phase relations in the S-poor portions of the dry condensed Pt-Ir-Fe-S system were determined at 1000° and 1100°C with a particular emphasis on delineation of the solid solubility fields of the Pt-Ir-Fe alloys. At both temperatures, a broad field of γ(Ir,Fe,Pt) alloy coexists with γ-(Pt,Fe), Pt3Fe and PtFe which dissolve respectively at least 5.1, 29.3 and 24.0 at.% Ir at 1100°C (2.2, 23.6 and ≤17.2 at.% Ir at 1000°C). Gaps between the nearly Ir-free Pt-Fe alloys γ(Pt,Fe), Pt3Fe s.s., PtFe s.s. and γ(Fe,Pt) were estimated as 20–23 at.%, 40–42 at.% and 54.2–~57 at.% Fe at 1100°C (18–23, 39.5–42.5 and 59–62 at.% Fe at 1000°C). The first gap agrees with data from natural phases by Cabri et al. (1996). The Fe-rich sulphide melt dissolves only traces of Pt and Ir; Fe1–xS dissolves up to 5.8 at.% Ir at 1100°C and 3.4 at.% Ir at 1000°C. These solubilities and the compositions of coexisting alloys (before low-temperature exsolution) may serve as geothermometers. The S-rich melt dissolves up to 8.2 at.% Pt and 2.5 at.% Ir (measured on a solidified melt) at 1100°C. The Fe-Ir thiospinel dissolves up to 2.2 at.% Pt (for the composition Fe21.6Ir18.9Pt2.2S57.3 at 1100°C). The 25–28 at.% Fe portions of Pt3Fe with <10 at.% Ir partake in all important sulphide (± melt)-alloy assemblages (with PtS, Ir2S3, pyrrhotite, S-rich melt and thiospinel). Therefore, their use in recognizing distinct natural assemblages of genetic importance is of limited value.

The single-crystal X-ray structure of tungstenian wulfenite-I41/a containing 10 mol.% WO3 from the San Francisco mine, Sonora, Mexico, space group I41/a, a = 5.436(2), c = 12.068(8)Å and Z = 4, has been refined to R = 0.052. The Mo and W are disordered over special position 4a (0,0,0) in the lattice. Tungstenian wulfenite-I4̄ (‘chillagite’) from the Christmas Gift mine, Chillagoe, Queensland, Australia (Museum of Victoria specimen M16934), crystallizes in the closely related tetragonal space group I4̄, with a = 5.441(1), c = 12.068(6) Å and Z = 4. The structure was refined to R = 0.038. Refined site occupancy factors show that Mo and W are not distributed equally over the two crystallographically independent Mo/W positions, being 0.136(2) for Mo and 0.114(2) for W in special position 2a (0,0,0) and 0.184(2) for Mo and 0.066(2) for W in special position 2c (0,Ý,Ü). These give a composition corresponding to wulfenite64stolzite36, in agreement with analytical data. The Mo/W distributions in the unit cell provide one explanation for the origin of hemihedrism in the wulfenite-stolzite series.

The crystal structure of synthetic shannonite, Pb2O(CO3), orthorhombic, P212121, a = 5.1465(7), b = 9.014(1), c = 9.315(1)Å, V = 432.12(10)Å3, Z = 4, has been solved by direct methods and refined to R = 0.054. There are two symmetrically distinct Pb2+ cations in irregular coordination polyhedra due to the effect of stereoactive s2 lone-electron pairs. The structure can be described as composed of chains of [OPb2] composition running parallel to [100] that are built by corner-sharing of OPb3 oxocentred triangles. The [OPb2] chains are surrounded by CO3 groups to form complex [OPb2](CO3) chains that are linked into a 3-dimensional framework by additional Pb–O bonds. The structure has channels that are parallel to [100] in which the lone-electron pairs of the Pb2+ cations are probably located.

The crystal structure of synthetic ‘plumbonacrite’, Pb5O(OH)2(CO3)3, hexagonal, P63cm, a = 9.0921(7), c = 24.923(3)Å, V = 1784.3(3)Å3, Z = 6, has been solved by direct methods and refined to R = 0.049. There are six symmetrically independent Pb2+ positions in the structure, the coordination polyhedra of which are strongly distorted due to the effect of s2 lone-electron pairs on the Pb2+ cations. The Pb(6) position is disordered with a Pb–Pb distance of 1.24 Å . The structure of ‘plumbonacrite’ is built from complex Pb–O layers parallel to the (001) plane similar to those observed in polymorphs of Pb4(OH)2(SO4)(CO3)2. The structure of these layers can be described in terms of Pb–O,OH motifs and CO3 groups. The smallest structural subunit is the oxocentred [OPb4] tetrahedron that shares three of its Pb-Pb edges with three [(OH)Pb3] distorted triangles to form [O(OH)3Pb7] clusters. These clusters are surrounded by CO3 groups, forming more complex clusters. Due to the disorder in the Pb(6) site, the clusters comprising this site are linked with each other via OH(10) groups to give continuous sheets of Pb–O,OH bonds which are parallel to the (001) plane. The [O(OH)3Pb7] clusters in ‘plumbonacrite’ may be important in more complex Pb carbonate oxo/hydroxo complexes that may exist in aqueous environments.

The crystal structures of synthetic Pb3O2(CO3) and NaPb2(OH)(CO3)2, have been solved by direct methods and refined to R = 0.062 and 0.024, respectively. Pb3O2(CO3) is orthorhombic, Pnma, a = 22.194(3), b = 9.108(1), c = 5.7405(8) Å, V = 1160.4(3) Å3, Z = 8. There are four symmetrically distinct Pb2+ cations in irregular coordination polyhedra due to the effect of stereoactive s2 lone electron pairs. The structure is based upon double [O2Pb3] chains of [O(1)Pb4] and [O(2)Pb4] oxocentred tetrahedra and CO3 groups. The [O2Pb3] chains are parallel to the c axis, whereas the CO3 groups are parallel to the (010) plane. NaPb2(OH)(CO3)2 is hexagonal, P63mc, a = 5.276(1), c = 13.474(4)Å, V = 324.8(1) Å3, Z = 2 and has been solved by direct methods. There are two symmetrically distinct Pb2+ cations in asymmetric coordination polyhedra due to the effect of stereoactive s2 lone-electron pairs. The single symmetrically unique Na+ cation is in trigonal prismatic coordination. The structure is based on hexagonal sheets of Pb atoms. Within these sheets, Pb atoms are located at vertices of a 36 net, such that each Pb atom has six adjacent Pb atoms that are ~5.3 Å away. Two sheets are stacked in a close-packing arrangement, forming layers that contain the (CO3) groups. The layers are linked by OH groups that are linearly coordinated by two Pb2+ cations. Na+ cations are located between the layers. The structure is closely related to the structures of other lead hydroxide carbonates (leadhillite, macphersonite, susannite, hydrocerussite, ‘plumbonacrite’).

Near infrared absorption (NIR) spectra of natural morphologically cubic polycrystalline diamonds (cuboid) were obtained at room temperature, and the stretching plus bending combination band of molecular water was observed. The spectrum consisted of the main band at 5180 cm-1 due to liquid water and a shoulder at 5000 cm-1. The 5000 cm-1 band suggests the presence of a phase with stronger hydrogen bonding in inclusions in the diamond. This shoulder absorption decreased on heating to 120°C. The combination band of H2O at high pressure and temperature was measured using a resistively heated diamond cell and the pressure dependence of the peak position was obtained. Comparison with the present experimental results indicates that the spectral changes induced by heating of the cuboid corresponded to melting of a high-pressure form of ice, and the shoulder absorption at 5000 cm-1 arises from ice VI at 1.9 GPa. On the other hand, the liquid water, a main component of the fluid inclusions in the cuboid, was not under high pressure judging from the frequency of the combination band. This contrast might relate to the texture of the cuboid diamond. The spectral observation enables us to estimate the residual pressure of mantle fluid encapsulated in these diamonds. The diamond-cell data also provide high-P-T NIR fingerprint spectra that could be useful for identifying H2O phases and confining pressures in other samples.

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.

Rappoldite, the Co-analogue of helmutwinklerite, and zincgartrellite, the Zn-dominant analogue of gartrellite, are two new members of the tsumcorite group. Both minerals are triclinic, their structures are closely related to the parent structure, i.e. the ‘tsumcorite type’ (C2/m, Z = 2). The lower symmetry is caused by two different crystal-chemical requirements. Order phenomena of the hydrogen bonds cause the ‘helmutwinklerite type’ (P1̄, Z= 4), ordering of Cu2+and Fe3+ is responsible for the ‘gartrellite type’ (P1̄, Z = 1).

Rappoldite was found on samples from the Rappold mine near Schneeberg, Saxony, Germany. The new species forms red to red-brown prismatic and tabular crystals up to 1 mm long. Dcalc. = 5.28 g/cm3. 2Vz = 85(5)°, nx = 1.85 (calc.), ny = 1.87(2) and nz = 1.90(2); dispersion is distinct with r > v; orientation is Y ∼∥ [1̄ 20] and X ∼ ∥ c. The empirical formula derived from electron microprobe analyses is (Pb1.01Ca0.01)Σ1.02(Co0.99Ni0.62Zn0.35Fe0.02)Σ1.98[(AsO4)1.99(SO4)0.01]Σ2.00[(OH)0.02(H2O)1.98]Σ2.00 or Pb(Co,Ni)2(AsO4)2·2H2O. Single-crystal X-ray studies showed average C2/m symmetry. Weak superstructure reflections are responsible for triclinic symmetry and enlarged cell metrics (refined from powder data): a= 11.190(2)Å, b= 10.548(2)Å, c= 7.593(1)Å, α = 100.38(1)8, β = 109.59(2)8, γ = 98.96(1)8, V= 807.6 Å3, Z= 4. The superstructure results from the hydrogen-bond scheme, but faint streaks indicate some disorder. All investigated rappoldite crystals are twinned by reflection on (23̄0) which corresponds to the mirror plane of the average C2/m cell. Helmutwinklerite is isotypic with rappoldite and probably also with pure thometzekite; sulphatian thometzekite is monoclinic.

Zincgartrellite forms green-yellow rosette-like aggregates on samples from the Tsumeb mine, Namibia. The Dcalc. = 5.30 g/cm3. 2Vx = 87(5)°, nx = 1.91(2), ny = 1.94 (calc.) and nz = 1.97(2). Electron-microprobe analyses and Mössbauer data yielded the empirical formula (Pb0.97Ca0.04)Σ1.01(Zn0.91Cu0.51Fe0.59Al0.03)Σ2.04[(AsO4)1.96(SO4)0.01]Σ1.97[(OH)0.81(H2O)1.31]Σ2.12 or Pb(Zn,Fe,Cu)2(AsO4)2(H2O,OH)2. The structural formula is Pb(ZnxFe1–x)(ZnxCu1–x)(AsO4)2(OH)1–x(H2O)1+xwith 0.4 < x < 0.8. Gartrellite is defined by x < 0.4. Helmutwinklerite has x near to 1 and is defined by a cell with fourfold volume. Single-crystal X-ray studies of zincgartrellite proved space group P1̄ caused by ordering of Fe3+ and Cu at one atomic site. Cell parameters (refined from powder data): a= 5.550(1)Å, b= 5.620(1)Å, c= 7.621(1)Å, α = 68.59(1), β = 69.17(1), γ = 69.51(1)°, V= 200.1 Å3, Z= 1.

Ion probe data are documented for zircons from tuffs within the early Llandovery, the mid-Caradoc and the Ludlow. 206Pb/238U ages for tuff magmatism have been interpreted using mixture-modelling to distinguish inheritance and Pb loss. Comparisons with the reference zircon SL13 have been improved through a direct determination of the component of secondary ion discrimination caused by changes in target potential.

Interpretation of the SHRIMP data for the Birkhill ash (Scotland, Llandovery) is ambiguous. The more conservative possibility is that most zircons are 439 Ma, in close agreement with the previous isotope dilution ages for the same zircon concentrate. The other is that the 439 Ma group should be split into an inherited population at ˜447 Ma, with a minority at ˜434 Ma that corresponds with the ash volcanism. Although imprecise, the latter is detectably younger than the multi-grain MSID age, which itself might be a composite of the same two ages.

Most zircon analyses from the mid Caradoc Pont-y-ceunant Ash, Wales, fit an age-group at 452.5 Ma, similar to its published 206Pb/238U age by MSID, with a definite older age group at ˜476 Ma but none showing Pb loss. By contrast, those from the Millbrig bentonite (Virginia) of the same age mainly fall in a well-defined post-eruption age group at 435 Ma, while the remainder give 456 Ma. Most zircon analyses from the Kinnekulle bentonite, Sweden, fall into an apparent 464 Ma group which exceeds other estimates for the mid-Caradoc magmatism. It is interpreted to be a composite age, caused by an inability to resolve it into a younger magmatic and older inherited group owing to the larger analytical errors of the Kinnekulle data. The best SHRIMP estimate for the mid-Caradoc volcanism is 452.6±1.7 Ma found by combining the ages for the three volcanic units. During unmixing of the combined ages, the Kinnekulle ages are redistributed and the 464 Ma ‘group’ vanishes. Precambrian grains are present in all the above volcanics.

The original and new zircon analyses from the Laidlaw Volcanics (Canberra, Australia) of Ludlow age, are dominated by three groups of inherited zircons at ˜436 Ma, ˜450 Ma and ˜476 Ma, which makes it unfavourable for time-scale definition using zircons. The youngest zircon age group is 417.5 Ma (˜30%), but this is not associated with overgrowths on older grains or with wholly younger grains. Instead, it is composed of sporadic low ages within older grains suggestive of Pb loss rather than magmatic zircon growth. Nevertheless, the age for volcanism is 420.7±1.1 Ma based on published Rb-Sr and K-Ar dating, so that the youngest zircon group does appear to be associated with volcanism.

One zircon U-Pb age for the Frasnian by MSID is much older than a precise age by other decay schemes, and another for the Lochkovian is significantly older than a recent SHRIMP age for the same Stage. By small changes in the common Pb composition, both MSID ages can be changed from single volcanic ages affected by Pb loss to an inherited and younger volcanic age, which removes the conflict with the other determinations.

A zircon-based geological time-scale is constructed from the Ordovician to the Carboniferous using the time-points presented and discussed in Parts I and II of this paper.

Replacement phenomena in amblygonite–montebrasite in rare-element pegmatites from the Karibib-Usakos area, Namibia, have been investigated using the electron microprobe. The first African occurrence and analysis of the very rare mineral natromontebrasite NaAl(PO4)(OH,F) is reported from the Daheim pegmatite. In the Okatjimukuju pegmatite, montebrasite has been replaced by a number of phases including crandallite CaAl3(PO4)2(OH)5·H2O and brazilianite NaAl3(PO4)2(OH)4. In one example, montebrasite has been almost completely replaced by brazilianite which has also been found to contain not only crandallite but also its solid solution analogues: goyazite SrAl3(PO4)2(OH)5·H2O and gorceixite BaAl3(PO4)2(PO3OH)(OH)6. Apatite is common at the contacts with montebrasite and associated minerals and texturally is intimately intergrown with crandallite, goyazite and gorceixite at Okatjimukuju. The occurrence of these minerals offers insight into the chemistry of post-magmatic fluids in these pegmatites.

Metasediments of the Tayvallich Subgroup of the Dalradian at Kinnairds Head, Fraserburgh are metamorphosed to sillimanite + K-feldspar grade and form part of the classic high-T low-P Buchan metamorphic terrain. Pelitic samples constrain peak-metamorphic conditions to 615±13°C and 2.2±0.2 kbar. At or close to the metamorphic peak, irregular garnetiferous aplites and autopegmatite bodies intruded the metasediments. Thin marble bands within the sequence are dominated by calcite with diopside, and equilibrated with relatively CO2-rich, internally buffered fluids. Where these are in close proximity to granitoid pegmatites, wollastonite dominates the matrix, and fractures and veins running through the rock contain concentrations of grossular and vesuvianite. With increasing distance from the pegmatite, vesuvianite and then grossular disappear, and wollastonite is only patchily developed. Such occurrences require a flushing of the marble by metasomatic (siliceous and aluminous) aqueous fluids which were derived from the de-watering of the adjacent pegmatite as it crystallized. The large quantities of dissolved silica led to pervasive wollastonite formation for several metres. The smaller quantities of Al reacted to form Ca-Al-silicates which were confined to the fractures.