187Os/186Os ratios were determined for in-situ laurite grains in Alpine-type chromitites and platinumgroup minerals (PGM) in the associated alluvial placers in Borneo, Indonesia/Malaysia. The Osisotope ratios of laurite grains in chromite defne an 187Os/186Os ratio for the 100 Ma mantle source of c. 1.04. Thelow 187Os/186Os ratios in all grains confirm the essential derivation of these platinum-group elements (PGE) from the mantle. A minor variation in 187Os/186Os ratios was detected among PGM from placers, but no variation was found within individual grains, including a grain with chemical inhomogeneity. The values are similar to those for PGM in the associated chromitites. The data are consistent with a detrital origin of PGM in placers: the placer PGM originated in the ultramafic section of ophiolities and the release of these grains from igneous rocks and their deposition in placers was almost entirely by mechanical processes.

Kuratite, ideally Ca4(Fe2+10Ti2)O4[Si8Al4O36], the Fe2+-analogue of rhönite and a new member of the sapphirine supergroup, was identified from the D'Orbigny angrite meteorite by electron microscopy and micro-Raman spectroscopy. Based on the least-squares refinement of 25 d-spacings measured from selected-area electron diffraction patterns of 11 zone axes, the symmetry of kuratite was shown to be triclinic (space group by analogy to rhönite) with a = 10.513(7), b = 10.887(7), c = 9.004(18) Å, α = 105.97(13), β = 96.00(12), γ = 124.82(04)°, V = 767 ± 2 Å3 and Z = 1 for the 40 oxygen formula. The empirical formula based on eight electron microprobe analyses is (Ca3.88Na0.02REE3+0.03Mn0.03Mg0.01Ni0.02Zn0.01Sr0.01)∑4.01 (Fe2+9.989.9Ti2.00)∑11.98(Si7.80Al3.52Fe3+0.64P0.05S0.02)∑12.03O39.98F0.01Cl0.01. The simplified formula is Ca4(Fe2+10Ti2)O4[Si8Al4O36]. Micro-Raman spectroscopy showed four main bands resembling those of lunar rhönite but with higher frequencies due to different chemical composition. Analogous to the occurrence of kuratite in terrestrial basaltic rocks, kuratite coexisting with Al, Ti-bearing hedenbergite, ulvöspinel, iron-sulfide, tsangpoite, Ca-rich fayalite and kirschsteinite in D'Orbigny angrite most probably was formed at >1000°C by rapid cooling of an interstitial melt, which is subsilicic, almost Mg-free but enriched in Al-P-Ca-Ti-Fe.

Ruizite is a new mineral found in the mesogene calc-silicate assemblage at the Christmas mine, Gila County, Arizona. Occurs with kinoite, apophyllite, smectite, and junitoite. Colour is orange inclining to brown with pale streak, H = 5, Sp. Gr. meas. = 2·9. Crystals monoclinic 2/m, elongate on [010]; a = 11·95 Å, b = 6·17, c = 9·03, β = 91° 22½′. Probable space group P21/c with Z = 4 giving Dcalc = 2·997. Strongest lines are 11·951 Å(10), 4·190 (7), 3·116 (6), 5·092 (5), 3·644 (4), 2·951 (4), 2·591 (4), 2·132 (4). Indices are α = 1·663, β = 1·715 ‖ [010], γ = 1·734, 44° to [001] in obtuse β; 2Vα = 60·2°; inclined dispersion p > v strong. Twinned on {100}. Analysis by wet methods gave CaO = 20·57%, Mn2O3 = 23·42, SiO2 = 39·14, H2O = 16·0 leading to or CaMn3+ (SiO3)2(OH). 2H2O.

Named for its discoverer, Joe Ana Ruiz of Mammoth, Arizona

I will consider mainly geothermobarometry in medium-grade pelitic rocks, including the garnet-biotite (GB) geothermometer, the Grossular-Al silicate-plagioclase (GASP) geobarometer, and the muscovite-almandine-biotite-sillimanite (MABS) geobarometer. For GB (Holdaway, 2000) experimental data and estimated biotite ΔWTi were used to optimize two exchange parameters and four biotite Margules parameters. Using stepwise linear regression, experimental vs. calculated T were constrained to lie on a line with slope of one and intercept of zero, maximizing r2. The best model involves experiments by Ferry and Spear (1978) and Perchuk and Lavrent’eva (1983), suggesting minimal viAl in the Ferry and Spear product biotite. For GASP (Holdaway, 2001), end-member experimental data do not adequately constrain the equilibrium. I used the GB model above, and allowed the end-member curve to rotate about the best-constrained part of the GASP end-member data. The end-member curve was further constrained with the kyanite-sillimanite (K-S) boundary using published chemical data on 76 pelitic schist samples from 11 localities, rejecting Low-Grs and low-An samples. The Fuhrman and Lindsley (1988) plagioclase model gives the best results. For MABS, work in progress involves 61 samples from the 11 localities which have muscovite analyses. Biotite Margules parameters were based on the GB model and McMullin et al. (1991). The MABS end-member curve was calibrated by comparison of P values determined using trial MABS data and GASP results. The P values for the 61 samples agree well with the K-S boundary, and sillimanite-bearing rocks of west-central Maine all fall in the sillimanite field. Preliminary biotite values are: GAnn = –5149198 – 412.05 T, WAlFe = –14023 + 28.14 T, WAlMg = –259582 + 308.44 T, WTiFe = 124842 – 98.67 T, WTiMg = –186148 + 271.72 T. For geobarometry, the Berman (1988, revised 1992) database was used with adjustable H and S of grossular for GASP and H and S of annite for MABS. The accuracy of currently available databases, activity models and mole fraction models is not adequate for good geothermobarometry, without further refinement. Adjustable parameters tend to compensate for error in activity models, mole fraction models and databases.

Silica sinter masses in the southern portion of the Pliocene Puhipuhi geothermal field of Northland, New Zealand, have recrystallized to microcrystalline quartz and moganite but many primary depositional fabrics of the sinters can still be recognized. Finely disseminated cinnabar, acicular stibnite, pyrite framboids and minor livingstonite are distributed through both massive sinter and stromatolitic fabrics with sulphide mineralization extending from fractured rocks about former spring vents into less disturbed sinter layers. The deposition of sulphides in the sinters is part of a continuum of mineralization resulting from the former hydrothermal regime and which extends to depth in the extinct geothermal system. Periodic changes in the hydrology, such as repeated fracturing following fracture sealing facilitated episodic sulphide deposition. Mercury is considered to have travelled in the liquid phase with antimony and precipitated directly as cinnabar. Remobilization of the sulphides, along with the recrystallization of the sinter masses, have produced complex textural relations. The multifaceted paragenesis of the sulphides is reflected in the range of their minor and trace element compositions revealed by electron microprobe analyses.

Ganophyllite and [Na+ + Al3+]-substituted tobermorite exhibited similar cation exchange properties and, in particular, selective cesium exchange. [Na+ + Al3+]-substituted tobermorite and ganophyllite showed a selective Cs exchange of 10.77 and 8.71 meq/100 g from 0.02N NaCl and of 11.08 and 9.04 meq/100 g from 0.02N CaCl2, respectively. The [Na+ + Al3+]-substituted tobermorite is structurally similar to ganophyllite: both are roughly analogous to 2:1 layer silicates, both have cross-linking tetrahedra across the interlayer region, and both have exchangeable cations located in zeolite-like sites in the interlayer region. The similarities in cation exchange properties imply that the residual charge configuration of the analogue 2 : 1 layer must be approximately equivalent also.

The Iblean Plateau (Southeastern Sicily, Italy) consists of a thick Meso-Cenozoic carbonate sequence with interbedded volcanic horizons (alkaline and tholeiitic basalts). The alkaline basalts contain ultramafic (peridotites and pyroxenites) and mafic xenoliths. The peridotites are spinel-bearing lherzolites and lherzolitic harzburgites, with porphyroblastic to protogranular texture. Pyroxenites consist of Cr-diopside-bearing and Al-augite-bearing websterites. The mineral chemistry of the nodules indicates temperatures between 700 and 1050°C.

Fluid inclusions containing CO2 and (sometimes) various proportions of silicate glass have been studied in olivine, orthopyroxene and clinopyroxene. The secondary inclusions occur as trails of CO2-rich inclusions, often cross-cutting deformation lamellae. The few primary inclusions, generally empty, show clear evidence of decrepitation. Of the 390 inclusions examined, 97% homogenized to the liquid phase (Th → L = −43.9 to +30.9°C); 3% homogenized to the vapour phase (Th → V = + 20.5 to +30.3°C, yelding CO2 densities in the range 0.20–1.13 g/cm3. Assuming a trapping temperature of 1100°C, the corresponding trapping pressure for a pure CO2 system lies in the range 0.6–11.0 kbar, i.e. a depth of ∼2.2 to 42 km.

The majority of CO2 trapping events in the xenoliths occurred from 2.2 to 11.0 kbar, with no major trapping events at pressures less than 2.3 kbar, indicating the absence of a shallow magma reservoir below the Iblean Plateau.

A new occurrence of barium silicates has been found in unmetamorphosed sedimentary rocks of central North Greenland. Two different barium minerals have been identified, the Ba-feldspar hyalophane, and an unknown and hitherto undescribed hydrated Ba-silicate with an anhydrous chemical composition identical to cymrite but with about 4 moles of water in the mineral structure. Both silicates are found in a black organic-rich chert sequence in close association with baryte. No replacement textures are observed between the three Ba-minerals.

The hydrated Ba-silicate in the unmetamorphosed rock sequence of the Navarana Fjord area is considered to represent a member in a sequence of Ba-silicates from the unknown Ba-silicate with four H2O in the structure (BaAl2Si2O8·4H2O), through cymrite with one H2O (BaAl2Si2O2O8·H2O) to celsian with none (BaAl2Si2O8). This sequence might reflect the continuous release of water during prograde diagenesis and metamorphism. The association between chert and Ba minerals in the sedimentary rocks of the Navarana Fjord area is believed to reflect an addition of silica and barium by hydrothermal solutions.

The sulphur-poor portions of the dry condensed Cu-Fe-Pd-S system were studied at 1000°C, 900°C and 725°C by synthesis in evacuated silicate glass tubes, along with textural observations and electron microprobe analyses of equilibrated reaction products. Sulphide melt coexists with Cu-Fe-Pd alloys, bornite, Fe1-xS and iss (intermediate solid solution, Cabri, 1973) and Pd4S. Compositional data were obtained for the associations bornite-alloy-melt, pyrrhotite-alloy-melt and for immiscible Cu-rich sulphide melts. Partition coefficients for all three metals were derived for the association alloy-melt. Formation of the two new Cu-Pd alloy minerals, skaergaardite and nielsenite, is discussed in terms of the present findings.

The major part of the Kap Edvard Holm complex consists of two series of conspicuously banded gabbroic rocks. The primary minerals of both lower and upper layered series show a progressive change in composition, from higher to lower temperature phases, with increasing height in the complex. Minor fluctuations in the differentiation of the two series occur but the division of the layered rocks into the lower and upper series is based on abrupt and major changes in the compositions of the pyroxenes, olivine and plagioclase. This break is correlated with the injection of a large volume of undifferentiated magma which occurred after much of the lower layered series had consolidated, and from which the rocks of the upper layered series were formed. Twelve pyroxenes, five from the lower and seven from the upper layered series have been analysed; the relationships between their optical properties and chemical composition, and between the cell parameters and composition are considered. The crystallization trend of the pyroxenes is compared with that of the Skaergaard calcium-rich pyroxenes; it is suggested that the restricted enrichment in iron shown by the Kap Edvard Holm pyroxenes may be related to the higher water-vapour pressures which prevailed during much of the period of crystallization.

In oxic waters, dissolved Fe exists dominantly as Fe(III) complexes with strongly coordinating, siderophore-like ligands. In this study, we have determined an equilibrium Fe isotope fractionation of 0.6% (∆56Fe) between inorganic Fe(III) and Fe(III) siderophore complexes using the siderophore desferrioxamine B as a model compound. The 57Fe tracer experiments show that the Fe isotopes ofthe siderophores exchange readily with dissolved inorganic Fe. The results indicate that organic ligands are likely to be important in the generation ofFe isotope signatures in oxic environments. For example, the isotopic composition ofmarine Fe-Mn nodules may largely be due to the presence of strongly coordinating ligands.

The net cationic charge of the octahedral and tetrahedral layers was calculated from the analyses of 100 biotites and 93 muscovites and compared to the observed hydroxyl contents (OH+F+Cl). The correlation coefficient between these parameters of −0·96 for biotites and −0·82 for muscovites demonstrates that the hydroxyl content in these micas varies in response to cationic substitutions. Thus substitutions in micas involve cation-hydroxyl replacement couples in addition to other modes previously recognized. Tetrasilicic phlogopite, K2Mg6Si8O22(OH)2, which is related to phlogopite by the substitution Al3+ + H+ = Si4+ was synthesized but is not a stable phase under the conditions investigated. This mica crystallizes as a 1M polymorph with a = 5·289(2) Å, b = 9·151(3) Å, c = 10·247(3) Å, β = 100°4(2).

Exchange reactions, such as Al3+ + H+ ⇌ Si4+, between phlogopite and pyroxenes at depth may provide a mechanism for release of H+ within the mantle.

Traces of a green chromian tourmaline occur in calcareous rocks in contact with serpentinite near Alpurai, Swat, West Pakistan. The petrography of the rocks and the optical properties of the tourmaline are presented along with its chemistry (it contains over 8 % Cr2O3 and about 0·2 % V2O3). The mineral is compared with other chromian tourmalines and its paragenesis discussed: it is thought to have been produced by silica-rich hydrothermal (or gaseous) solutions, which have crystallized as thin quartz veins in the calcareous rocks, introducing boron and other constituents.

Macphersonite is white, resinous to adamantine, hardness (Mohs) 2½−3, density 6.50–6.55 gm/cm3 and possesses a perfect cleavage on {010}. Optically it is negative with 2Vα 35–36°, α = 1.87, β = 2.00 and γ = 2.01, α = b, γ = c, and γ = a, dispersion r > v. Polysynthetic twinning, with either coarse or fine lamellae, is common, as are contact twins. Crystals are orthorhombic, tabular on b with a 10.37, b 23.10 and c 9.25 Å, cell volume 2215.8 Å3 and space group Pcab; Z is 8 formula units. The seven strongest lines in the X-ray powder pattern are 3.274 (50) 052; 3.234 (100) 251; 2.654 (90) 351,203; 2.598 (30) 172, 400; 2.310 (30) 004, 371, 0.10.0; 2.182 (30) 263; and 2.033 (30) 234, 452, 154, 1.10.2. Electronprobe-microanalysis-determined chemistry leads to the empirical formula (Pb4.08, Cu0.10, Cd0.07)Σ4.25S0.90 C2.18O10.55(OH)1.58 which yields the ideal formula Pb4(SO4)(CO3)2(OH)2 and hence macphersonite is a polymorph of leadhillite and susannite. The infrared spectrum shows basic similarities to leadhillite and susannite spectra with additional diagnostic absorption bands. Macphersonite shows an identical thermogravimetric behaviour to that of leadhillite. It is associated, in varying combinations, with leadhillite, susannite, cerussite, caledonite, pyromorphite, scotlandite, galena, and the ‘lead hydroxyapatite’ of Temple (1955). The new mineral mimics leadhillite.

The new mineral anatolyite Na6(Ca,Na)(Mg,Fe3+)3Al(AsO4)6 was found in the Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia. It is associated with potassic feldspar, hematite, tenorite, cassiterite, johillerite, tilasite, ericlaxmanite, lammerite, arsmirandite, sylvite, halite, aphthitalite, langbeinite, anhydrite, wulffite, krasheninnikovite, fluoborite, pseudobrookite and fluorophlogopite. Anatolyite occurs as aggregates (up to 2 mm across) of rhombohedral–prismatic, equant or slightly elongated along [001] crystals up to 0.2 mm. The mineral is transparent, pale brownish–pinkish, with vitreous lustre. It is brittle, cleavage was not observed and the fracture is uneven. The Mohs’ hardness is ca 4½. Dcalc is 3.872 g cm–3. Anatolyite is optically uniaxial (–), ω = 1.703(4) and ε = 1.675(3). Chemical composition (wt.%, electron microprobe) is: Na2O 16.55, K2O 0.43, CaO 2.49, MgO 5.80, MnO 0.16, CuO 0.69, ZnO 0.55, Al2O3 5.01, Fe2O3 7.94, TiO2 0.18, SnO2 0.17, SiO2 0.04, P2O5 0.55, As2O5 60.75, SO3 0.03, total 101.34. The empirical formula based on 24 O apfu is (Na5.90K0.10)Σ6.00(Ca0.50Na0.13Zn0.08Mn0.03)Σ0.74(Mg1.63Fe3+1.12Al0.15Cu0.10)Σ3.00(Al0.96Ti0.03Sn0.01)Σ1.00(As5.97P0.09Si0.01)Σ6.07O24. Anatolyite is trigonal, R$\bar{3}$c, a = 13.6574(10), c = 18.2349(17) Å, V = 2945.6(4) Å3 and Z = 6. The strongest reflections of the powder XRD pattern [d,Å(I)(hkl)] are: 7.21(33)(012), 4.539(16)(113), 4.347(27)(211), 3.421(20)(220), 3.196(31)(214), 2.981(17)(223), 2.827(100)(125) and 2.589(18)(410). The crystal structure was solved from single-crystal XRD data to R = 4.77%. The structure is based on a 3D heteropolyhedral framework formed by M4O18 clusters [M1 = Al and M2 = (Mg,Fe3+)] linked with AsO4 tetrahedra. (Ca,Na) and Na cations centre A1O6 and A2O8 polyhedra in voids of the framework. Anatolyite is isostructural with yurmarinite. The new mineral is named in honour of the outstanding Russian crystallographer, mineralogist and mathematician Anatoly Kapitonovich Boldyrev (1883–1946).

Rare phases of the Au–Ag–Sb system were recognized in the Krásná Hora Sb-Au deposit (Sb 1.5–3 wt.%; Au 3–5 ppm), Czech Republic which correspond to auriferous dyscrasite (up to 7 at.% Au), auriferous allargentum (up to 34 at.% Au), and an unnamed phase with composition similar to the eutectics (E1, E2) of the experimental Au–Ag–Sb system. The dominant ore mineral is stibnite with rare native antimony, native gold and a Ag-Au alloy. Textural relationships are well established: stibnite (early) →gold → aurostibite → native antimony (late). Gold is present in four generations: Au-1 (0–15 at.% Ag) is the most abundant type; Au-2 (20–70 at.% Ag) forms thin rims along intra-grain boundaries of Au-1; Au-3 and Au-4 are rare and almost pure (∼0 at.% Ag). The formationof most of the Au-2 and of Au-Ag-Sb phases is associated with Ag-mobilization coupled with the Au-1 to aurostibite transformation via dissolution-precipitation and solid-state diffusion processes at temperatures <200°C.

Ambient temperature X-ray diffraction data were collected at different pressures from two crystals of β-As4S4, which were made by heating realgar under vacuum at 295ºC for 24 h. These data were used to calculate the unit-cell parameters at pressures up to 6.86 GPa. Above 2.86 GPa, it was only possible to make an approximate measurement of the unit-cell parameters. As expected for a crystal structure that contains molecular units held together by weak van der Waals interactions, β-As4S4 has an exceptionally high compressibility. The compressibility data were fitted to a third-order Birch–Murnaghan equation of state with a resulting volume V0 = 808.2(2) Å3, bulk modulus K0 = 10.9(2) GPa and K' = 8.9(3). These values are extremely close to those reported for the low-temperature polymorph of As4S4, realgar, which contains the same As4S4 cage-molecule. Structural analysis showed that the unit-cell contraction is due mainly to the reduction in intermolecular distances, which causes a substantial reduction in the unit-cell volume (∼21% at 6.86 GPa). The cage-like As4S4 molecules are only slightly affected. No phase transitions occur in the pressure range investigated.

Micro-Raman spectra, collected across the entire pressure range, show that the peaks associated with As–As stretching have the greatest pressure dependence; the S–As–S bending frequency and the As–S stretching have a much weaker dependence or no variation at all as the pressure increases; this is in excellent agreement with the structural data.

The concept of force of crystallization is combined with that of depression of dissolution to explain diagenetic volume-for-volume replacement in both cases, either when the pressure is increased in early sedimentary settings, or when it is diminished in a late exposure. Also, a new textural criterion is added to the three classical ones in order to recognize diagenetic volume-for-volume replacement, and calculations are carried out to estimate the speed of the replacement.