Zones of albitization 20 m wide are developed in the peraluminous, undeformed Proterozoic Bastfallshöjden granite, W. Bergslagen, central Sweden. During albitization Na, Si, Mg, Ni, Zn, and Ga are added, while Fe2+, Fe3+, Mn, K, Sc, Rb, Cs, Ba, Pb, U, and F are lost, together with the rare earth elements (REE) in decreasing amounts with increasing atomic number. Ti, Al, P, and Y were immobile. Trace element data for chlorites separated from hydrothermally altered country rocks and from a quartz-chlorite vein in the albitized granite show similar REE patterns indicating a common origin: the most altered granite has a similar REE pattern, probably resulting from interaction with the same hydrothermal fluid which produced the chlorites, in which seawater is thought to have been an important constituent.

Volatile species analysis of fluid inclusions in metamorphic quartz veins from the Llanbedr Formation, North Wales, show nitrogen to be an important component. Microthermometric and Laser Raman analysis indicates that the N2 is resident in a generation of very N2-rich inclusions and demonstrates the presence of both N2-rich and aqueous fluids during metamorphism of the Llanbedr Formation. N2-rich fluids do not appear to have been present in adjacent lithologies. Isotopic analysis of N2 in fluid inclusions and in the slates indicates that the N2 in the slates (thought to be present as substituting for K+ in muscovite and for Na+ in ) was probably originally derived from organic matter in the sediment and subsequently released to the fluid phase during metamorphism.

Mineral-fluid and fluid-phase equilibrium calculations show that the mineral assemblage in the slates could be in equilibrium with either N2-rich or aqueous fluid depending on redox conditions. The N2-rich and aqueous fluids in the veins could, therefore, have been trapped at different times under different conditions, though their coexistence as immiscible fluids is a possibility.

Ocean Drilling Program (ODP) Leg 147 recently drilled at Site 895 in Hess Deep (eastern Equatorial Pacific), where a structurally dissected section of the East Pacific Rise (EPR) is preserved, and intersected the mantle-crust transition zone of a fast-spreading centre for the first time. The core from Hole 895D (latitude 2°16.635′N, longitude 101°26.777′W) revealed that harzburgite is predominant over dunite in the top section of the Hole, but the reverse relationship is found lower in the section where dunite is closely associated with gabbroic rocks (gabbro and troctolite). Texture, mineralogy and mineral chemistry suggest a two-stage evolution for harzburgite preserved at the transition zone. Harzburgite with a porphyroclastic texture was produced by partial melting of peridotite to, or beyond the clinopyroxene-out phase boundary before or during asthenospheric (>1000°C) flow, which suggests a higher degree of mantle melting than normally expected below mid-ocean ridges. Subsequently, basaltic melt(s) interacted with this refractory harzburgite (olivine + orthopyroxene + spinel), which resulted in dissolution of orthopyroxene, re-equilibration and formation of olivine and spinel, and formation of clinopyroxene ± plagioclase, this is manifested as a progressive conversion of harzburgite to gabbroic rock through an intermediate dunite. At low melt/peridotite ratios, harzburgite was refertilised as the plagioclase component of the melt completely reacted with the peridotite matrix to produce clinopyroxene-spinel intergrowths and Al enrichment in ferromagnesian minerals. At high ratios, orthopyroxene completely dissolved incongruently, plagioclase appeared, and spinel was partially to completely resorbed; this produced olivine-bearing and olivine-free gabbroic rocks. Residual minerals in peridotites adjacent to gabbroic zones were enriched in Fe and Ti and depleted in Al.

Hydrohonessite has a composition that can be expressed by the formula [Ni8-x2+Fex+(OH)16] [x/2SO2-4.yH2O.zNiSO4], where x is approximately 2.6, y is 7, and z is 1. The X-ray powder diffraction pattern has strongest lines at 11.0 (10), 5.56 (5), 3.68 (4), and 2.709 Å (3), and can be indexed on a hexagonal unit cell with a = 3.09 Å and c = 10.80 Å. It is optically uniaxial negative with ɛ = 1.59 and ω = 1.63; bright yellow in hand specimen and transmitted light. Hydrohonessite is the hydrated equivalent of honessite, and is related to carrboydite, motukoreaite, and mountkeithite. These minerals are related to brucite and pyroaurite-type minerals in that they have a layered structure consisting of brucite-like layers separated by about 7 Å of interlayer material consisting predominantly of water, but also containing anions that balance the charge of the brucite-like layer. Hydrohonessite is a secondary mineral resulting from the weathering of Ni-Fe sulphides, and appears to be stable between pH 6 and 7.

Fluids can play a direct role in exhumation by influencing exhumation mechanisms and the driving processes for these mechanisms. In addition, the process of exhumation leads to the development of fluid-related features that in themselves may not drive exhumation. Fluids involved in exhumation are generally derived from dehydration reactions occurring during decompression, but at shallower crustal levels may also involve the introduction of exotic fluids. The composition of fluids attending exhumation are generally saline – CO2 mixtures, but N2, CH4, H2O mixtures have also been recorded. Studies of fluid features related to exhumation have found that fluids may contribute to density changes and the initiation of partial melting during decompression, as well as the development of extensive vein systems. However, the preservation of geochemical signatures related to fluid processes occurring prior to high-P and ultrahigh-P metamorphism indicates that large-scale pervasive fluid flow systems, in general, do not operate at any stage during the exhumation history. Large-scale channelled fluid flow may have operated in detachment faults and shear zones related to exhumation, and this requires further study. The most significant role of fluids during exhumation appears to be their controlling influence on the preservation of high-P or ultrahigh-P rocks.

Corundum xenocrysts from alkaline basalt fields differ in characteristics and hence lithospheric origins. Trace element, fluid/melt inclusion and oxygen isotope studies on two eastern Australian corundum deposits are compared to consider their origins. Sapphires from Weldborough, NE Tasmania, are magmatic (high-Ga, av. 200 ppm) and dominated by Fe (av. 3300 ppm) and variable Ti (av. 400 ppm) as chromophores. They contain Cl, Fe, Ga, Ti and CO2-rich fluid inclusions and give δ18O values (5.1–6.2‰) of mantle range. Geochronology on companion zircons suggests several sources (from 290 Ma to 47 Ma) were disrupted by basaltic melts (47 ± 0.6 Ma). Gem corundums from Barrington, New South Wales, also include magmatic sapphires (Ga av. 170 ppm; δ18O (4.6–5.8‰), but with more Fe (av. 9000 ppm) and less Ti (av. 300 ppm) as chromophores. Zircon dating suggests that gem formation preceded and was overlapped by Cenozoic basaltic melt generation (59–4 Ma). In contrast, a metamorphic sapphire-ruby suite (low-Ga, av. 30 ppm) here incorporates greater Cr into the chromophores (up to 2250 ppm). Fluid inclusions are CO2-poor, but melt inclusions suggest some alkaline melt interaction. The δ18O values (5.1–6.2‰) overlap magmatic sapphire values. Interactions at contact zones (T = 780–940°C) between earlier Permian ultramafic bodies and later alkaline fluid activity may explain the formation of rubies.

All samples of silica sinter, <2 y old taken from the discharge drain of the Wairakei geothermal power station and the Rainbow Terrace of Orakei Korako, consist of non-crystalline opal-A. This silica phase deposits directly upon the concrete drain wall and filamentous templets, extending from this wall, afforded by the microbial community present in the drain, whose nature was determined by a culture- independent strategy that entailed construction, fingerprinting and sequencing of a 16S clone library. The bacterial community is dominated by five major groups of organisms, present in approximately equal proportions, and which account for ∼50% of the community. None of the 16S sequences from these dominant groups yielded a perfect match with 16S sequences for named organisms in the international databases. However one dominant group clusters with Hydrogenophilus thermoluteus, a thermophilic filamentous bacterium, and two cluster with putatively thermophilic members of the Cyanobacteria and green non-sulphur bacteria respectively. Initial opal-A deposits rapidly as agglomerations of silica nanospheres that, in turn, form chains of coalesced, oblate, microspheres <0.4 x 0.2 mm about the barbicel-like filaments, to produce a mat of fine woven strands. The majority of individual filaments are <8 μm long and 0.8 mm wide but may be up to 55 mm long by 1 mm wide. Where laminar flow dominates, most strands develop parallel to the drain current but some strands crisscross while others protrude above the mat surface. Where flow is turbulent, strands lack preferred orientation and some adopt a helical form. In general, following deposition, the values of the scattering broadband at half (FWHM) and three quarters (FWTM) of the maximum intensity decrease with increasing sample age. The behaviour of the band at one quarter maximum intensity (FWQM) is less consistent, but, in general, the youngest sinters possess the highest FWQM, FWHM and FWTM values that prove independent of fabric type. Opal-A silica matures following its removal from the parent fluid, especially where the sinter surface is filmed by water. A continual movement of silica is shown by a second generation of microspheres formed on the silica mat surface, by an increase in size of the initial microspheres, and by an increase in maximum intensity of the X-ray scattering broadbands. Similar silica aging behaviour occurs among young sinters developed upon microbial mats at Orakei Korako. The deposition and aging processes accord with the known behaviour of juvenile opaline silica in both natural and artificial systems whose pH, temperature and dissolved salt content are similar to Wairakei and Rainbow terrace: gelling of silica is favoured by the high pH (∼8.3) and temperature (∼60°C) of the Wairakei discharge fluid but the high dissolved salt content of the water (Na+ = 930 μg/g, Ca2+ = 12 μg/g, Cl = 1500 μg/g) and abundant microbial community facilitate rapid and copious flocculation of solid silica within the drain, in contrast to the slower accumulation on the natural sinter terrace at lower temperature (30—45°C) from less saline dilute bicarbonate-chloride waters (Na+ = 180 μg/g, Ca2+ = 0.2 μg/g, Cl = 400 μg/g, pH = 8.1).

Mesothermal, gold-bearing quartz veins are widespread within allochthonous terranes of Alaska that are composed dominantly of greenschist-facies metasedimentary rocks. The most productive lode deposits are concentrated in south-central and southeastern Alaska; small and generally nonproductive gold-bearing veins occur upstream from major placer deposits in interior and northern Alaska. Oreforming fluids in all areas are consistent with derivation from metamorphic devolatilisation reactions, and a close temporal relationship exists between high-T tectonic deformation, igneous activity, and gold mineralization. Ore fluids were of consistently low salinity, CO2-rich, and had δ18O values of 7‰- 12‰ and δD values between −15‰ and −35‰. Upper-crustal temperatures within the metamorphosed terranes reached at least 450-500°C before onset of significant gold-forming hydrothermal activity. Within interior and northern Alaska, latest Paleozoic through Early Cretaceous contractional deformation was characterised by obduction of oceanic crust, low-T/high-P metamorphism, and a lack of gold vein formation. Mid-Cretaceous veining occurred some 50-100 m.y. later, during a subsequent high-T metamorphic/magmatic event, possibly related to extension and uplift. In southern Alaska, gold deposits formed during latter stages of Tertiary, subduction-related, collisional orogenesis and were often temporally coeval with calc-alkaline magmatism.

New field observations of certain harrisite occurrences are presented, including: interruption of layers; splitting of very thick layers into several smaller ones; existence of small isolated lenses and pods of harrisite and of upwardly extending tongues of harrisite; harrisite forming parts of the matrix of breccias; and isolated pods of harrisite along the western margin of the intrusion. These layers, lenses, tongues, and pods seem to have crystallized within the cumulus mush rather than at the mush magma boundary. It is proposed that the rock in these instances represents segregated, intercumulus melt which ‘ponded’ beneath relatively impermeable layers in the cumulus mush. Several ways in which supercooling may have arisen to cause skeletal olivine growth are considered and previous estimates are thought to need reduction by 10–20°C. It is suggested that segregation of upward-filtering melt in other layered intrusions might produce layers indistinguishable from ‘uniform’ cumulate.

At Niquelândia, Cr extracted from the soil (5,000–9,300 mg.kg-1) is likely the result of the Cr-bearing Fe-oxides compared to the Cr-spinels, showing that low Cr-containing minerals present in the dunite (enstatite, olivine and clay minerals) have been completely dissolved. The chromites, accumulated inside soil profiles, have undergone chemical weathering, leading to a Cr enrichment during soil genesis. Traces of dissolution inside the soil chromites suggest that they can be slowly weathered. In this case chromites could represent a diffuse source of available Cr(III) within the soil profiles.

A calcite-rich block in nephelinitic agglomerate at Oldoinyo Lengai comprises Sr-calcite, apatite, fluorite, a Ba-Mn oxide akin to romanrchite, and a distinctive Mn-Fe spinel. Formerly reported as sövite, on textural, mineralogical and stable isotope grounds it is now re-interpreted as a highly-altered natrocarbonatite lava. An implication of this study is that natrocarbonatite is not just a modern phenomenon, but has been extruded from Oldoinyo Lengai for at least around 1250 years.

Minute crystals of pure Mg-sapphirine approximating (Mg3.23Al4.74)vi(Al4.69Si1.31)ivO20, and thus having more aluminous compositions than the hitherto accepted 7:9:3 end member, were formed together with Mg-cordierite and corundum along narrow zones of the schist through reaction of the pre-existing high-pressure assemblages kyanite-gedrite and kyanite-talc. These sapphirines are considered to be metastable intermediate products growing under the influence of the structurally similar host mineral kyanite. Under equilibrium conditions they continued to react with kyanite to form the stable assemblage cordierite-corundum. Peraluminous sapphirines including those most recently synthesized may be metastable phases under all conditions of crystallization.

Losses of Fe and Na from a typical basaltic liquid during experiments using the wire-loop method have been determined for both Pt and Ag40Pd60 alloy wire by electron-microprobe analyses of the quenched glasses. The amount of Fe lost is dependent on the duration of the experiment and is particularly sensitive to the ratio of sample to metal in direct contact with it. Fe losses can be minimized by using the thinnest wire possible in conjunction with the largest amount of sample that will adhere to the wire and, if Ag-Pd wire is used, can be kept below the 1% level even in long experiments. Much more serious in terms of changes in the bulk composition are losses of Na, which appear to be in direct linear proportion to the length of the experiment and in inverse proportion to the mass of the sample. Even when samples in excess of 200 mg are used the Na losses are unlikely to be less than 5% except in experiments of less than a few days' duration or on samples with very low initial Na contents.

Fahlores [~(Cu,Ag)10(Zn,Fe)2Sb4S13] from the Keno Hill mining district, central Yukon, Canada record virtually the entire petrogenetic history of a Cretaceous hydrothermal system extending over 40 km outward from the Mayo Lake granitic pluton. These fahlores are an essential constituent of polymetallic sulphide veins developed in a graphitic Mississippian quartzite, where they occur in association with sphalerite, pyrargyrite, galena and siderite. Fahlores exhibit pronounced east-west zoning in average Ag/(Ag+Cu) and Zn/(Zn+Fe) values, with these simultaneously increasing and decreasing from east to west over 20 km of hydrothermal activity. These zonations are coupled with average Ag/(Ag+Cu) and Zn/(Zn+Fe) values in fahlore roughly paralleling the 300°C isotherm for fahlores in equilibrium with pyrargyrite, miargyrite and sphalerite in the simple system Ag2S-Cu2S-ZnS-FeS-Sb2S3. Early high-Ag, high-Zn fahlores from the eastern and western mines have Ag/(Ag+Cu) and Zn/(Zn+Fe) values requiring temperatures ≥400°C, in agreement with temperatures established from the As-content of arsenopyrite coexisting with pyrite, pyrrhotite and sphalerite. Ag/(Ag+Cu) and Zn/(Zn + Fe) values in later, main-stage fahlores are consistent with the 250–310°C range of temperatures established for boiling of Keno Hill fluids. Finally, Ag- and Fe-rich fahlores were produced by retrograde Fe-Zn exchange with sphalerite or crystallized from late-stage epithermal fluids which produced polybasite, stephanite, acanthite and wire silver. One such fahlore exhibits unmixing into high-Ag and low-Ag varieties. This is the first reported miscibility gap for freibergite fahlores and confirms the earlier prediction of such gaps.

Electron-microscope observations have been used to follow the low-temperature dehydration of boehmite, and show that a coherent skeleton of γ-Al2O3 with a porous texture is produced. For material fired in air the development of a number of pore systems is described. Of these the most important, as far as the dehydration process is concerned, is a lamellar pore system parallel to (001)γ and having a regular spacing of the order of 35–40. Å. A much faster dehydration process is induced by exposure to the electron beam and results in the formation of a more randomly oriented pore structure. The observed microstructure and the calculated internal surface area are compared with the results of previous adsorption studies.

A new variety of heterogenite was found in samples from Mindigi, Shaba, Zaïre. Photometric reflectance varies from 0·235 to 0·165 at λ 5890 Å in air. The bireflectance is 0·070, the degree of anisotropy is 0·7 and the main index in air is 2·7. A thermal weight-loss curve and a microprobe analysis are given and discussed, indicating the formula (Co,Ni) O.OH.

The new variety, referred to as heterogenite-H, is hexagonal with cell dimensions a 2·85, c 8·80, space group P63/mmc and cell-content 2 [(Co, Ni)O.OH)]. Indexed X-ray powder data are given. A crystal structure is suggested based on CoO.OH octahedra layers and indicating a polytypic relation between heterogenite-H, the 2H form, and normal heterogenite, the 3R form.

Post-Variscan vein-type Co-Ni-Bi ores of the Bieber deposit, Spessart mountains, Germany, which are related to the Permian Kupferschiefer, have been investigated by ore microscopy, X-ray powder diffraction and electron-probe microanalysis. The samples contain a variety of ore minerals, notably skutterudite, native bismuth, cobaltite, alloclasite, niccolite, maucherite, gersdorffite, rammelsbergite/pararammelsbergite, safflorite, loellingite and emplectite. The ores display structures indicative of multiple brecciation and complex zoned arsenide assemblages. Three sequential stages of deposition are identified, which are (1) the Cu stage, (2) the main Co-Ni-Bi stage, and (3) the late stage. The arsenide minerals, notably skutterudite, diarsenides and sulpharsenides, show a large range of compositional variation in Co-Ni-Fe space. A relatively limited number of skutterudite and diarsenide compositions lie outside the compositional fields established in the literature. Skutterudite and diarsenides are characterized by a significant substitution of As by S up to 0.44 a.p.f.u. and 0.31 a.p.f.u., respectively, which is larger than the range previously reported for these minerals. Sulpharsenide compositions can be grouped into three populations, which conform to cobaltian arsenopyrite, cobaltite and gersdorffite. They display highly variable As/S ratios between 0.95:1.00 and 1.29:0.73, consistent with experimental data. Estimates of the formation temperatures, based on the presence of dendritic native bismuth and emplectite, are in the range 100–300°C, similar to different post-Variscan mineralization styles widespread in Central Europe. Comparison of the Co-Ni-Bi vein assemblage with the framework of available paragenetic information and radiometric age data for regional mineralization events indicates an age of mineralization of ~150–160 Ma for the Bieber deposit.

We have developed a cluster variation method (CVM) model based on cuboctahedral and octahedral basis clusters containing 13 and 6 atoms, respectively, and applied it to the analysis of the thermodynamic mixing properties of (Zn,Fe)S solid solutions. The model, in which the internal energy of the lattice is approximated by next to nearest neighbour (nnn) pair interactions and many-body interactions associated with nearest neighbour (nn) equilateral triangles, describes the FeS contents of sphalerites equilibrated with pyrrhotite and pyrite, and with pyrrhotite and iron metal within experimental uncertainties. The model predicts moderate deviations from ideality; the mean values of the Lewis and Randall activity coefficient of FeS and ZnS are, 1.48 and 1.03, respectively. Predictions of the model are in qualitative agreement with cell-edge data. The model also predicts that sphalerites undergo long-range ordering to lower-symmetry structures at temperatures only slightly below those investigated experimentally, a result in agreement with inferences from an existing Mössbauer investigation of synthetic sphalerites.

More realistic models in which interactions are ascribed to larger species (nn triangular and centred square species) predict that such long-range ordering occurs at even higher temperatures and underscore the need for better characterization of the structures of (Zn,Fe)S minerals.

The compositions and textural relationships of the oxide minerals zirconolite, pyrochlore and baddeleyite are described. These occur as accessory minerals, often intergrown with each other, from a phoscorite rock associated with the Kovdor carbonatite complex. Both the zirconolite and baddeleyite have relatively high concentrations of Nb and Ta; the pyrochlore is rich in U and Ta. Backscattered electron images, coupled with detailed microprobe analyses, reveal complex compositional zoning in zirconolite and pyrochlore which reflect changes in the fluid composition during growth of these minerals. A comparison is made of incompatible element ratios Zr/Hf, Nb/Ta and Th/U between the three accessory minerals.

A suite of experimentally deformed single-crystal pyrite samples has been investigated using electron backscatter diffraction (EBSD). Single crystals were loaded parallel to <100> or <110> and deformed at a strain rate of 10-5 s-1, confining pressure of 300 MPa and temperatures of 600°C and 700°C. Although geometrically (Schmid factor) the {001}<100> slip system should not be activated in <100> loaded samples, lattice rotation and boundary trace analyses of the distorted crystals indicate this slip system is easier to justify. Determination of 75 MPa as the critical resolved shear stress (CRSS) for {001}<100> activation, in the <110> loaded crystals, suggests a crystal misalignment of ~5—15° in the <100> loaded crystals would be sufficient to activate the {001}<100> slip system. Therefore, {001}<100> is considered the dominant slip system in all of the single-crystal pyrite samples studied. Slip-system analysis of the experimentally deformed polycrystalline pyrite aggregates is consistent with the single-crystal findings, with the exception that {001}<11̄> also appears to be important, although less common than the {001}<100> slip system. The lack of crystal preferred orientation (CPO) development in the polycrystalline pyrite aggregates can be accounted for by the presence of two independent symmetrically equivalent slip systems more than satisfying the von Mises criterion.