Platinum-group minerals (PGM) from placer deposits in Colombia, California, Oregon and Alaska were investigated with the electron microprobe, proton microprobe (μ-PIXE) and ion probe to analyse their major and trace element contents and 187Os/186Os isotopic ratios. Most of the grains in the samples investigated proved to be essentially homogeneous alloys of Pt-Fe and Os-Ir-Ru although a few of them contained inclusions of other PGM such as cooperite and laurite. Detailed analyses were undertaken on the Os-Ir-Ru alloy phases.

The 187Os/186Os isotope ratios fell into a range from 1.005 to 1.156 and are consistent with data published on PGM from other placer deposits from these regions. The ratios, together with the trace element data (and in particular the low rhenium content) determined by ion probe and μ-PIXE, indicate that crustal osmium was not incorporated in the grains and that no significant evolution of the 187Os/186Os ratios occurred during their history. These data, along with mineralogical and textural evidence, are consistent with a mantle origin for the grains through ultramafic intrusions, although the data do not entirely rule out alternative interpretations.

The concentrations of LREE and Zr in a granitic melt formed by anatexis of a metapelitic protolith will be buffered by the stability of monazite and zircon respectively. The rate at which equilibrium is reached between dissolving monazite and zircon and a static melt is limited by the rate at which Zr and LREE can diffuse away from dissolution sites. If melt extraction rates exceed the rates at which the LREE and Zr in the melt become homogenized by diffusion, extracted melts will be undersaturated with respect to these elements. Evidence from accessory phase thermometry suggests that for many Himalayan leucogranites generated by crustal anatexis, the melts equilibrated with restitic monazite and zircon prior to extraction. In contrast, discordant temperatures determined from accessory phase thermometry suggest that tourmaline leucogranites from the Zanskar region of NW India did not equilibrate prior to extraction. Quantitative interpretation of this discordance assumes that the melt was static prior to extraction, and that accessory phase inheritance was minimal. Modelling of the time-dependant homogenization process suggests that tourmaline leucogranites generated at 700°C probably remained in contact with restitic monazite in the protolith for less than 7 ka and certainly less than 50 ka. Such rapid extraction rates suggest that deformation-driven mechanisms were important in removing these melts from their source.

The petrographical, crystal-chemical and petrogenetical aspects of rutile rich in antimony (up to 33.75 wt.% Sb2O5; equal to 0.2 Sb5+ per O = 2) from St. Marcel-Praborna in the Aosta Valley, Italy, were re-examined. These compositions occur in two different petrographical environments (within the rock matrix or as microinclusions within Sb-rich titanite) in the manganese concentrations at this locality. The new data confirm our earlier hypothesis that two distinct petrogenetical/crystal-chemical processes both occurred: 1. Sb-metasomatism of pre-existing Sb-free rutile inclusions; and 2. creation of neoblastic Sb-rich rutile by the expulsion of Ti from pre-existing Sb-free titanite being metasomatized by Sb to form Sb-rich titanite. In the literature, Sb in minerals is variably considered as being trivalent and/or pentavalent. This work demonstrates that within rutile it is entirely Sb5+, substituting for Ti4+ by the following heterovalent cation exchange mechanism which is also the dominant one in the host Sb-rich titanite: 2 viR4+ = viR3+ + viR5+, where viR3+ = (Al,Cr,Mn,Fe)3+. A near-perfect correlation of ΣR5+vs. ΣR3+ (r > 0.98) is perturbed only by the presence of trace amounts of Ca2+, Sr2+ and Ba2+. Traces of Mn4+, Si4+ and/or (OH)− might also be present. These alkaline earth cations are the largest cations ever recorded in the rutile structure and are seemingly too large to occupy normal octahedral sites. The cation exchange mechanism involved might be that found in the ‘trirutile’ mineral group: 3 viR4+ = viR2+ + 2 viR5+. Alternatively these large divalent cations may be situated in the lozenge-shaped tunnels of the rutile structure, by analogy with other large cations occupying the wider subrectangular tunnels in the analogous cryptomelane/hollandite/priderite, romanéchite and todorokite mineral groups. This leads to a possible new cation exchange mechanism for the rutile structure: 2 viR4+ + tunelvacant = 2 viR3+ + tunnelR2+.

Perovskite group minerals, general formula ABX3, from the intrusive ultramafic alkaline Gardiner Complex, East Greenland, range from almost pure CaTiO3 (perovskite, sensu stricto), to the rare earth element (REE) variety, loparite-(Ce). Chemical zonation in the perovskites (sensu lato), is described by the substitutions 2Ca2+ = (Na+ + REE3+) on the A-site and 2Ti4+ = (Fe3+ + Nb5+) on the B-site. Other trace elements detected include Th, Sr, Al, Si, Zr, Ta and Sn. Excellent agreement was found between the determinations of the REE by electron microprobe and neutron activation analysis. Chondrite-normalized REE patterns display enrichment in the light rare earths for perovskite, loparite, apatite, melilite and diopside. Mean perovskite/apatite partition coefficients from four of the Gardiner rocks were calculated as La = 10.4, Ce = 13.8, Nd = 13.9, Sm = 9.9, Eu = 7.7, Gd = 5.2, Tb = 5.6, Tm = 5.5, Yb = 2.7 and Lu = 1.6, indicating that perovskite concentrates all REE to a much greater extent than apatite. Light-REE enrichment occurs in both perovskite and apatite.

The Nanga Parbat massif is a rapidly eroding, thrust-related antiform that is distinct from other regions of the Himalayan orogen in being both intruded by Late Miocene-Pliocene anatectic granites and permeated by a vigorous hydrothermal system. Exhumation is achieved by erosion during thrusting along the Liachar thrust in the apparent absence of extensional tectonics. At depths in excess of 20 km, small batches of leucogranitic melt have been generated by fluid-absent breakdown of muscovite from metapelitic lithologies. These melts ascend several kilometres prior to emplacement, aided by low geothermal gradients at depth and by interaction with meteoric water as they reach shallow levels. At intermediate depths (∼15 km) limited fluid infiltration is restricted to shear zones resulting in localised anatexis. Within the upper 8 km of crust, magmatic and meteoric fluid fluxes are channelised by active structures providing a feedback mechanism for focusing deformation. Leucogranite sheets show a range of pre-full crystallization and high-temperature crystal-plastic textures indicative of strain localisation onto these sheets and away from the country rocks. At subsolidus temperatures meteoric fluids promote strain localisation and may trigger cataclastic deformation. Since near-surface geothermal gradients are unusually steep, the macroscopic transition between distributed shearing and substantial, but localised, cataclastic deformation occurred at amphibolite-facies conditions (∼600°C). Even with the greatest topographic relief in the world, the meteoric system of Nanga Parbat is effectively restricted to the upper 8 km of the crust, strongly controlled by active structures.

Lithium may constitute an essential element in micas, yet it cannot be detected by the electron microprobe. Since Li is critical for correctly classifying micas and properly calculating their formulae, several methods have been proposed to overcome this analytical deficiency. We offer empirical relationships between Li2O and SiO2, MgO, F, and Rb in trioctahedral micas, and between Li2O and F as well as Rb in dioctahedral micas. The resultant regression equations enable lithium contents to be sufficiently well estimated from EPM analyses within the range of validity discussed.

Secondly, we introduce an easy to handle, new diagram with the axis variables [Mg-Li] and [Fetot + Mn + Ti-AlVI] for graphical representation and discuss its scientific rationale. Being based on absolute abundances of cations in the octahedral layer, the diagram provides a simple means to classify micas in terms of composition and octahedral site occupancy, and it also allows compositional relationships between Li-bearing and Li-free mica varieties as well as between trioctahedral and dioctahedral micas to be displayed on a single, two-dimensional diagram.

The large Fe-Nb-REE deposit at Bayan Obo is hosted by a dolomite marble within the thrust complex of marbles, quartzites and slates that belongs to the Bayan Obo Formation of mid-Proterozoic age. The dolomite is either a dolomitized sedimentary limestone subsequently mineralized and tectonically thrust and folded, or a dolomite (or dolomitized) carbonatite intrusion with late-stage recrystallization and mineralization that has been subsequently tectonically deformed.

O and C isotope data indicate that the sedimentary limestones and dolomites of the Bayan Obo Formation, which occur in the thrust stack together with quartzites and slates, have values of δO c. +20 per mil (SMOW) and δC c. zero. In contrast, the coarser grained facies of the large (0.5 × 10 km) dolomite marble which hosts the REE ore body has δO per mil values between +8 and +12 and δC values between −5 and −3, whereas the finer-grained recrystallized and REE-mineralized dolomite marble which occurs close to the ore bodies has δO between +12 to +16 and δC between −4 and zero. 87Sr/86Sr data confirm this distinction: >0.710 for the sedimentary rocks and <0.704 for the coarse- and fine-grained dolomite marbles.

These data are taken to indicate that the large and coarse-grained dolomite was an igneous carbonatite (as borne out by its fenitic contact rocks and trace element geochemistry), and that the finer grained dolomite recrystallized under the influence of mineralizing solutions which entrained groundwater. The stratiform features in the coarse-grained dolomite that are evident in the field are interpreted as tectonic layering.

The diagenetic to very low-grade metamorphic manganese ores of the Postmasburg manganese field provide a unique example of oxide-facies manganese ores in a Palaeoproterozoic palaeokarst setting. The ores are composed mainly of braunite group minerals, including braunite, partridgeite and bixbyite, with rare braunite II and Ca-poor, silica-depleted braunite. Iron-poor partridgeite is distinguished from Fe-rich bixbyite and the occurrence of Ca-poor, silica-depleted braunite is reported for the first time. Braunite and partridgeite formed during early diagenesis but remained stable under greenschist facies metamorphic conditions. In contrast, bixbyite is apparently a product of metasomatic remobilisation under peak metamorphic conditions. It is suggested that local variations of the metamorphic mineral association reflect variations of the host rock composition and that they are not related to changing P-T conditions of metamorphic alteration, a model promoted by previous authors. The phase chemistry of braunite, braunite II and bixbyite is explained by the existing polysomatic stacking model for the braunite group. However, the chemical composition of partridgeite and Ca-poor, silica-depleted braunite can only be explained by introducing a distinct module layer, with partridgeite composition, to the existing polysomatic stacking model.

Miargyrite is the low-temperature monoclinic derivative of a high temperature cubic galena/halite structure. The essential features of its crystal structure (Knowles, 1959) were confirmed, but the details of the bonding changed [new space group C121; a 12.824(1), b 4.4060(3), c 13.193(1) Å, β 98.567(6)°]. The octahedral connectivity of galena/halite is severely distorted: Ag(1), 2S each at 2.53, 2.66 & 3.39 Å; Ag(2), 2 each at 2.54, 2.62 and 3.44; Ag(3), 2.38, 2.40, 3.05, 3.05, 3.53, 3.58; Sb(1), 2.45, 2.50, 2.51, 3.22 3.28, 3.41; Sb(2), 2.45, 2.50, 2.51, 3.22, 3.28, 3.41. The short distances define the following coordinations: very distorted tetrahedral Ag(1) and (2); near-linear Ag(3) at 178.9(2)° trigonal-pyramidal Sb(1) and (2) at 92.0, 93.6 and 96.8°. The ten shortest S-S distances range from 3.61 to 3.77 Å.

Remarkable single crystal galena formations in the unique form of cylindrical or steep conical ‘pillars’ with ‘capitals’ of small rhombododecahedral single crystals of sphalerite, are described. It is suggested that the pillars result from a highly specific process of anisotropic mineral dissolution controlled by a system of internal channels in the original skeletal crystals and represent a kind of dissolution whiskers.

The tectonic position of the intraplate, alkaline volcanic province of N. Tanzania in a broad rift-controlled area astride the boundary between the Tanzania Craton and the circum-cratonic Mozambique Fold Belt, strongly resembles that of the Gardar province of S. Greenland. Earlier-identified petrological analogies between Gardar magmatism and that in the Kenya sector of the East African Rift Valley can be extended to volcanism in N. Tanzania, and analogies specifically with the Gardar agpaitic suite are strengthened by the occurrence of eudialyte and aenigmatite in some Tanzanian peralkaline, silicic volcanics.

The mineralogical status of ilmenite from a prominent modern placer deposit of India is illustrated using different techniques. Compositional, powder XRD, TGA and SEM analyses prove that consistent low temperature alteration took place in Chavara ilmenite leading to the formation of a pseudorutile-hydrated-ilmenite stage. Except for the indication of a geochemical zonation at the southern tip of the deposit, the Chavara ilmenite points to a common origin throughout its 22 km stretch along the coast. We advocate a major segregation activity by marine factors to the accumulated sediments in the shelf zone in order to originate such a huge deposit of homogeneous composition.

Austinite belongs to the adelite mineral group of calcium and lead arsenates, and has the conichalcite/descloizite type of crystal structure. The crystal structure of nearly pure austinite, CaZn(AsO4)OH, was redetermined (R = 0.014) and the absolute configuration identified. The space group P212121 and cell parameters a 7.5092(8), b 9.0438(9), c 5.9343(8) Å match previous data. Zinc octahedra share edges to form chains parallel to c. Arsenic tetrahedra share vertices with the Zn octahedra to generate a compact framework. Calcium square antiprisms share edges to make chains parallel to a that occupy the channels in the zinc-arsenic framework.

Several complex Cu-Pb-Bi, Cu-Pb-Bi-Sb and Ag-Pb-Bi sulphosalt minerals have been identified in samples from hydrothermal vein mineralisation associated with the Toroiaga sub-volcanic body in the Baia Borşa area of Maramureş County, northwest Romania. This is the first chemically-documented report of Bi-sulphosalts in the Neogene metallogenic province around Baia Mare. The investigated samples contain abundant amounts of matildite solid solution within galena, the Cu-Pb/Bi sulphosalts aikinite, friedrichite, krupkaite, hammarite, lindströmite and gladite as well as nuffieldite and berryite. Within the Ag-Pb/Bi group, the majority of analysed grains can be regarded as members of the lillianite homologous series. Three distinct lillianite homologues were identified, which correspond to (i) phases along the lillianite-gustavite solid solution join (Pb3Bi2S6-AgPbBi3S6), (ii) phases within solid solution field of heyrovskyite, and (iii) compositions which best correspond to ‘schirmerite’, sensu Makovicky and Karup-Møller (1977b), but may represent disordered gustavite, vikingite or eskimoite. Some of the analysed lillianite homologues contain excess Cu, which may occupy interstitial sites. Furthermore, a large proportion of the lillianite homologues display significant substitution of Sb for Bi within the limits predicted by experimental investigations. Cosalite, also showing a range of compositions including Sb-rich varieties is recognised. Izoklakeite, Cu2Pb22(Sb,Bi)22S57, is an abundant phase throughout the analysed samples, its composition is in good agreement with previously published analyses, except for excess Cu and Fe beyond the limits previously reported. The description of several minerals from this new occurrence and compositional data on them, including the Sb-bearing varieties, provides valuable additional information on compositional limits in natural samples.

Fibrous veins are generally interpreted in terms of the crack-seal mechanism. Several aspects of fibrous veins (fibrous structure, curved fibres, symmetry of antitaxial veins) are however better explained by vein formation without fracturing. Mass transfer to such veins would be by diffusional transport rather than by fluid flow through the veins. Deformation by dissolution-precipitation creep can provide the driving force for the necessary mass transfer. Veins form when mass transfer is heterogeneous and precipitation is localised.

Experiments were performed which enforced a chemical potential gradient, acting as the driving force for diffusional mass transfer. These experiments resulted in fibrous growths in aggregates of soluble salts (NaCl and KCl) saturated with brine. The experimental results support the theory that fibrous veins may form without fracturing and that rather than providing evidence for major fluid pathways, fibrous veins may instead represent localised precipitation during diffusional material transfer.

Blueschist-facies rocks with jadeite-K-feldspar-lawsonite paragenesis occur as exotic blocks in Miocene debris flows in the blueschist belt of northwest Turkey. The jadeite-K-feldspar rocks have a very fine grain size and although recrystallized locally retain a relict porphyritic volcanic texture. The former nepheline microphenocrysts, recognized from their characteristic shapes, are pseudomorphed by jadeite and K-feldspar, while the relict magmatic aegirine has rims of jadeite. The matrix of the rock consists of very fine-grained aggregates of jadeite, K-feldspar and lawsonite. In some blocks, jadeite makes up >60% of the mode. Jadeite, K-feldspar and lawsonite in the blocks are essentially pure end-member in composition. P-T estimates for these rocks are 8 ± 2 kbar and 300 ± 50°C. The preserved volcanic texture, relict aegirine and the bulk rock composition indicate that these rocks represent metamorphosed phonolites. The paragenesis in these rocks shows that jadeite-K-feldspar is a stable mineral pair in blueschist-facies P-T conditions.

Omphacite (Jd46.1–52.0Ae0–8.4Aug48.0–51.2) and diopside (Jd4.3–6.3Ae0–0.4Aug93.6–95.6) coexist in a vein cutting an omphacitite block in a serpentinite melange of the Oeyama ophiolite, central Chugoku Mountains. The compositional gap between omphacite and diopside is significantly wider than for other omphacitediopside pairs reported in the literature. The intergrowth texture of the omphacite-diopside vein suggests that the clinopyroxene pair was contemporaneously crystallized in the fracture from a Ca-bearing, alkali-rich fluid in a sub-solvus condition. Such a fluid may have been introduced from the surrounding serpentinized clinopyroxene-bearing harzburgite. The stability of omphacite and Al-rich pumpellyite in the matrix and the omphacite-diopside vein indicate that the earlier matrix recrystallization and later fracture filling may have both taken place under high-P-T condition during the melange-forming stage.

We discuss the use of regression diagnostics combined with nonlinear least-squares to refine cell parameters from powder diffraction data, presenting a method which minimizes residuals in the experimentally-determined quantity (usually 2θhkl or energy, Ehkl). Regression diagnostics, particularly deletion diagnostics, are invaluable in detection of outliers and influential data which could be deleterious to the regressed results. The usual practice of simple inspection of calculated residuals alone often fails to detect the seriously deleterious outliers in a dataset, because bare residuals provide no information on the leverage (sensitivity) of the datum concerned. The regression diagnostics which predict the change expected in each cell constant upon deletion of each observation (hkl reflection) are particularly valuable in assessing the sensitivity of the calculated results to individual reflections. A new computer program, implementing nonlinear regression methods and providing the diagnostic output, is described.

The Maimecha-Kotui province in the North of Siberian platform is the largest province of ultramafic alkaline rocks in the world. The province comprises thirty-seven central-type complexes together with numerous dykes. The majority of dykes are radially disposed around the ultramafic alkaline massifs. Data are presented for dykes of the Dolbykha carbonatite complex, which comprises olivine and melilite nephelinites; nosean, calcite and cancrinite phonolites; calcite trachytes and calcite carbonatites.

Some peralkaline phonolitic dykes contain carbonate-bearing globules with sizes of 1−2 mm to 17−20 mm. Globules consist of polycrystalline calcitic aggregates together with albite, phlogopite, apatite, Sr-lueshite, zircon, ancylite, ilmenite and strontianite. The phonolites have phenocrysts of albite, phlogopite and ilmenite. Albite, phlogopite, calcite and nepheline are also present in the groundmass. Analysis of these materials in the light of experimental data on the liquid immiscibility in carbonate-silicate systems suggests that separation of carbonatite from phonolitic melts took place due to immiscibility in the liquid state. I propose that carbonate melts contained originally significantly higher alkali contents which were subsequently lost into the fluid phase due to the incongruent dissolution of calcium-sodium carbonates in aqueous fluid at low temperatures. The discovery of nyerereite in the carbonatite of Polar Siberia confirms this conclusion. I infer that one of the mechanisms for the genesis of carbonatite melt in Polar Siberia was liquid immiscibility in strongly differentiated phonolitic magmas.

The generation of the carbonatites was probably controlled by the depth (and PCO2) of the crustal magma chamber where differentiation took place and probably also by the alkalinity of melts, and the rapidity of magma ascent to the surface.

New intersectorial isotope data are presented for two calcites. Mendip calcite shows no detectable δ13C and δ18O differences between synchronous {214} and {014} sectors. Nottingham calcite shows a δ13C difference of 1.0‰ and a δ18O difference of 0.5‰ between synchronous {401} and {0001} sectors. Data now available for 5 different calcites show the magnitude of intersectorial fractionation is variable; the effect on δ13C is twice that on δ18O. All five natural calcites also show erratic isotopic differences between symmetrically-equivalent synchronous sectors. Intersectorial isotopic fractionation is probably widespread but its cause and quantification require further work. Synchronous intracrystalline isotopic differences should be accommodated in the interpretation of isotopic data and should influence future sampling strategy.