Tectonic controls on the genesis of ignimbrites from the Campanian Volcanic Zone, southern Italy

Summary ¶The Campanian Plain is an 80×30km region of southern Italy, bordered by the Apennine Chain, that has experienced subsidence during the Quaternary. This region, volcanologically active in the last 600ka, has been identified as the Campanian Volcanic Zone (CVZ). The products of three periods of trachytic ignimbrite volcanism (289–246ka, 157ka and 106ka) have been identified in the Apennine area in the last 300ka. These deposits probably represent distal ash flow units of ignimbrite eruptions which occurred throughout the CVZ. The resulting deposits are interstratified with marine sediments indicating that periods of repeated volcano-tectonic emergence and subsidence may have occurred in the past. The eruption, defined as the Campanian Ignimbrite (CI), with the largest volume (310km³), occurred in the CVZ 39ka ago. The products of the CI eruption consist of two units (unit-1 and unit-2) formed from a single compositionally zoned magma body. Slightly different in composition, three trachytic melts constitute the two units. Unit-1 type A is an acid trachyte, type B is a trachyte and type C of unit-2 is a mafic trachyte.The CI, vented from pre-existing neotectonic faults, formed during the Apennine uplift. Initially the venting of volatile-rich type A magma deposited the products to the N–NE of the CVZ. During the eruption, the Acerra graben already affected by a NE–SW fault system, was transected by E–W faults, forming a cross-graben that extended to the gulf of Naples. E–W faults were then further dislocated by NE–SW transcurrent movements. This additional collapse significantly influenced the deposition of the B-type magma of unit-1, and the C-type magma of unit-2 toward the E–SE and S, in the Bay of Naples. The pumice fall deposit underlying the CI deposits, until now thought to be associated with the CI eruption, is not a strict transition from plinian to CI-forming activity. It is derived instead from an independent source probably located near the Naples area. This initial volcanic activity is assumed to be a precursor to the CI trachytic eruptions, which vented along regional faults.Received October 23, 2002; revised version accepted July 29, 2003     

Converging P-T paths of Mesozoic HP-LT metamorphic units (Diego de Almagro Island, Southern Chile): evidence for juxtaposition during late shortening of an active continental margin

Summary On Diego de Almagro Island in Chilean Patagonia (51°30S), a convergent strike slip zone, the Seno Arcabuz shear zone, separates the Diego de Almagro Metamorphic Complex from very low grade metagreywackes in the east, which were intruded by Jurassic granitoids. The Diego de Almagro Metamorphic Complex is composed of a metapsammopelitic sequence containing blueschist intercalations in the west and (garnet) amphibolite lenses in the east. Peak metamorphic conditions (stage I) at 9.5–13.5kbar, 380–450°C in the blueschist and at 11.2–13.2, 460–565°C in the amphibolite indicate subduction and accretion at different positions within the deepest part of the accretionary wedge. A K–Ar age of 117±28Ma of amphibole approximately dates the peak of metamorphism in the amphibolite. The early retrograde stage of metamorphism occurred under static conditions and resulted in localized equilibration (stage II) at 6.3–9.6kbar, 320–385°C in the blueschist and 6.1–8.4kbar, 310–504°C in the amphibolite. Both P-T paths converge within a midcrustal level.In contrast, an orthogneiss of trondhjemitic composition occurring within the Seno Arcabuz shear zone is associated with a garnet mica-schist containing a high temperature/intermediate pressure assemblage formed at 4.9–6.5kbar, 580–690°C. A muscovite K–Ar age of 122.2±4.6Ma dates cooling after this event which is related to a concomitant magmatic arc. These rocks were overprinted by a mylonitic deformation, which is caused by convergent strike slip shearing and ends during formation of a retrograde phengite-chlorite-stilpnomelane assemblage at a minimum pressure of approximately 5.7kbar (at 300°C).Zircon fission track ages from rocks of the Seno Arcabuz shear zone are 64.9±2.7 and 64.9±2.7Ma; they record the end of shearing in the Seno Arcabuz shear zone that juxtaposed all rocks in the middle crust. Zircon fission track ages ranging from 78 to 105Ma in the South Patagonian batholith to the east indicate earlier cooling through 280°C. The rocks of the Diego de Almagro Metamorphic Complex were initially slowly exhumed and resided at a midcrustal level before being emplaced via shearing in the Seno Arcabuz shear zone. Apatite fission track ages (54±8Ma) from the Seno Arcabuz shear zone show that exhumation and cooling rates increased after this event. The incorporation of continental crust within the subduction system was a late process, which modified the Cretaceous accretionary wedge, resulting in considerable shortening of the convergent margin.     

Metagranitoids from the eastern part of the Central Rhodopean Dome (Bulgaria): U–Pb, Rb–Sr and 40Ar/39Ar timing of emplacement and exhumation and isotope-geochemical features

Summary Geochronological data (U–Pb, Rb–Sr and ⁴⁰Ar/³⁹Ar) are used to unravel the Late Alpine high-grade metamorphism, migmatisation and exhumation of Variscan granitoids within the core of the Central Rhodopean dome, Bulgaria. The age of the granitoid protolith is 300±11Ma, as determined by U–Pb analyses on single zircons selected from the core of the dome structure.Rb–Sr whole rock data define an errorchron with a large scatter of the data points due to the Late Alpine metamorphic overprint. The slope of the reference line indicates a Variscan magmatic event. Strontium characteristics are used to discriminate the samples most influenced by metamorphism from those, which reflect possible differences in the protolith age of the granitoids.Petrological-geochemical data, the initial strontium ratio of 0.708±0.001, and _Hf zircon values ranging from –2.58 to –3.82 point to a mixed, but crust-dominated origin of the Variscan magmas; young crustal material and mantle fragments were sources for the I-type metagranitoids.The exhumation of the granitoids from depths greater than 20–25km to about 5km below the surface was a rapid geological process. It started with the formation of granitic eutectic minimum melts at the temperature peak of metamorphism. Monazite crystallisation at about 650°C continued during isothermal decompression to possible depths of about 10–12km. An age of 35.83±0.40Ma was determined using conventional U–Pb isotope methods on four multigrain monazite fractions. A maximum average age of 36.6–37.5Ma (assuming same error uncertainties) for crystallisation of the metamorphic monazites was calculated assuming 10 to 20% monazite resetting during the subsequent Oligocene volcanism and hydrothermal activity in the region of the Central Rhodopean Dome. The rocks were then cooled to about 350–300°C at 35.35±0.22Ma according to ⁴⁰Ar/³⁹Ar ages of biotites and below 300°C at 35.31±0.25Ma (Rb–Sr data), as indicated by crystallisation of adularia in an open vein subsequent to pegmatite intrusion. A minimum exhumation rate of 3–5km per 1 million years can therefore be calculated for the exhumation of the metagranitoids during the period from 38–35Ma.     

Solid solution of rare earth elements in synthetic titanite: a reconnaissance study

Summary Titanite varieties doped with rare earth elements (REE) have been prepared by ceramic synthesis and quenching in air. Their crystal structure was determined by Rietveld analysis of the powder X-ray diffraction patterns. Two different substitution schemes, Ca_1–xNa_x/2Sm_x/2TiSiO₅ and Ca_1–xDy_xTi_1–x SiO₅, are studied at x=0.2. Both synthetic varieties of titanite adopt space group A2/a. This implies that both single-site and complex multivalent substitutional schemes destroy the coherence of the off-centering of octahedral chains in the titanite structure resulting in a P2₁/aA2/a phase transition. Unit cell dimensions obtained for the REE-bearing titanite varieties are as follows: a=7.0541(1)Å; b=8.7247(1)Å; c=6.5664(1)Å; =113.732(1)° for Ca_0.8Na_0.1Sm_0.1TiSiO₅; and a=7.0021(1)Å; b=8.7256(1)Å; c=6.5427(1)Å; =113.294(1)° for . Both REE-doped titanite samples and a control sample of the pure titanite end member have similar unit cell parameters and consist of polyhedra distorted to a similar extent with the exception of more-distorted SiO₄ tetrahedron in CaSiTiO₅. The structural data suggest that the Ca_1–xNa_x/2Sm_x/2TiSiO₅ and Ca_1–xDy_xTi_1–xFe_xSiO₅ solid solutions adopting the titanite structure might extend to x sufficiently greater than 0.2 and involve both heavier and lighter trivalent rare earth elements.Permanent address: Geological Institute KSC RAS, 14 Fersmana St., Apatity, 184200 Russia     

Sedimentary provenance of Mid-Devonian clastic sediments in the Teplá-Barrandian Unit (Bohemian Massif): U–Pb and Pb–Pb geochronology of detrital zircons by laser ablation ICP-MS

Summary The provenance of the Mid-Devonian clastic sediments in the Teplá-Barrandian Unit (TBU) of the Bohemian Massif was investigated by laser ablation ICP-MS U–Pb zircon dating, bulk sediment geochemistry and mineralogical study of the heavy mineral fraction. In contrast to the island arc provenance of the TBU Neoproterozoic sediments, the Early Palaeozoic sediments contain significant amounts of differentiated crustal material. The detrital zircon populations in the Barrandian Mid-Devonian siltstones and sandstones show ages ranging from Archaean (3.0Ga) to Early Palaeozoic (0.39Ga). Major age maxima are at 2.6Ga, 2.0–2.25Ga, 0.62 and 0.51Ga. The youngest identified zircons so far correspond to Lower and Mid-Devonian ages. The extensive mechanical abrasion of zircons having Archaean (3.0, 2.8 and 2.6Ga) to Paleoproterozoic ages (2.25–2.0Ga) suggest their provenance from recycled old sedimentary sequences. The relatively large number of zircons with ages between 2.0 and 3.0Ga may indicate the presence of relicts of the Archaean/Paleoproterozoic crust in the source areas of the studied Mid-Devonian sediments. The absence of detrital zircon ages between 0.9 and 1.2Ga and the presence of zircon ages of 2.0–2.25 and 0.5–0.8Ga correspond to the zircon age pattern from the Gondwana-related North African, rather than Gondwana-related South American and Baltic terranes. The material was entering the basin predominantly from the west and consisted primarily of detrital material of Cambrian granitoids and recycled material of Neoproterozoic meta-sedimentary sequences.     

Formation of Ni–Cu–Platinum Group Element sulfide mineralization in the Sudbury Impact Melt Sheet

Summary The Ni–Cu–Platinum Group Element (PGE) sulfide deposits of the Sudbury Structure have provided a major portion of the worlds total nickel production and their host rocks have been the subject of numerous research studies, yet a number of perplexing problems remain to be solved. On the one hand, studies seeking to explain the formation of the Sudbury Structure have now converged on a genetic model which proposes that the Main Mass and Offset Dykes of the Sudbury Igneous Complex (SIC) were produced by crystallization of an impact-generated melt sheet. On the other hand, these models have yet to be fully reconciled with the production of the very large volume of magmatic Ni, Cu, Co, and PGE-rich sulfide mineralization and the associated mafic rock types. This paper explores this problem using new precious metal data from the Main Mass and Offset Dykes. These data are used to understand the relationships between these rocks, and to provide constraints on how the Ni–Cu–PGE sulfide ore deposits fit into the geological evolution of the Sudbury Structure.In the two drill cores selected for study in this project, the Mafic Norite has 1–5 modal percent pyrrhotite plus chalcopyrite, and elevated Ni (40–1000ppm), Cu (40–1140ppm), and PGE (1.9–7.8ppb Pd, 1.8–7.3ppb Pt); this is overlain by Felsic Norite that contains pyrrhotite, and has a wide range in concentration of Ni (13–257ppm), Cu (7–328ppm), and PGE (<0.01–6.4ppb Pd, <0.01–5ppb Pt). For a similar range of MgO, the upper portion of the Felsic Norite unit has 5–10 times lower Ni and Cu abundances than within-plate basalts and local crustal rocks, and PGE abundance levels are mostly below analytical determination limits. Stratigraphic studies of other compositional profiles around the SIC demonstrate that this depletion signature of Ni, Cu, and PGE is widespread and developed not only above mineralized embayments and offsets, but also above barren sections of the lower contact of the SIC.The depletion of the upper part of the Felsic Norite in Ni, Cu and PGE is presumably due to equilibration of the magma with magmatic sulfide, and accumulation of this dense sulfide liquid. Results of modeling indicate that the parental magma giving rise to the Mafic and Felsic Norites had initial Ni and Cu contents of 210 and 110ppm, respectively. In addition, Ni, Cu and PGE tenors calculated in 100% sulfide from the Copper Cliff Offset average 13% Cu, 6% Ni, 18ppm Pd, and 19ppm Pt indicating that these sulfides had formed by fractionation from magmas that contained 310ppm Ni, 310ppm Cu, 18ppb Pd and 19ppb Pt. These values are factors of 3 to 5 higher than the Ni, Cu, Pd, and Pt contents of the Onaping Formation with average values of 55ppm Ni, 48ppm Cu, and 4.9ppb Pd as well as the marginal sulfide-poor phase of the Worthington Offset quartz diorite, which has average values of 61ppm Ni, 59ppm Cu, 2.8ppb Pd and 4.0ppb Pt. Both the Onaping Formation and the marginal quartz diorite are believed to represent the initial composition of a large component of the melt sheet. There is therefore a fundamental problem in reconciling the initial metal contents of the SIC magma as indicated by the marginal phases of the Offset dykes and that of the Onaping Formation with the composition of the SIC magma at the times of formation of the sulfides as indicated by their Ni, Cu and PGE tenors.It is proposed that because the SIC melt sheet was initially superheated with a temperature of 1700°C, it was able to dissolve 5 times as much S as it could at its liquidus temperature of 1200°C. It was also initially composed of an emulsion of mafic and felsic melts (Marsh and Zieg, 1999), which may have formed discrete magma cells. As the temperature of the melt sheet decreased, some of these magma cells became S-saturated and the resultant Ni–Cu–PGE sulfides settled downwards and on reaching magma cells lower in the melt sheet were re-dissolved thereby raising the Ni, Cu and PGE contents of the lower magma cells. It was from these enriched magma cells that precipitation of the ore-forming Ni–Cu–PGE sulfide melts eventually took place.The mineral potential of Offset and embayment structures appears to be empirically linked to the thickness of the overlying noritic rocks; for example, the most heavily mineralized embayments and Offset Dykes are located in areas where the Felsic Norite is thickest. It appears unlikely that the entire 1–3km-thick melt sheet was convectively mixing throughout its lateral extent, and so the heterogeneity in sulfide distribution was retained after crystallization and cooling.     

K–Ar and Ar–Ar dating of the Palaeozoic metamorphic complex from the Mid-Bosnian Schist Mts., Central Dinarides, Bosnia and Hercegovina

Summary K–Ar and Ar–Ar whole rock and mineral ages are presented for 25 samples of metamorphic rocks from the Mid-Bosnian Schist Mts., representing one of the largest allochthonous Palaeozoic terranes incorporated within the Internal Dinarides. Four main age groups can be distinguished: 1) Variscan (343Ma), 2) post-Variscan (288–238Ma), 3) Early Cretaceous (mainly 121–92Ma), and 4) Eocene (59–35Ma) ages. Apart from this, an Oligocene (31Ma) age was obtained on Alpine vein hyalophane. The radiometric dating indicates a polyphase metamorphic evolution of the Palaeozoic formations and suggests a pre-Carboniferous age of the volcano-sedimentary protoliths, an Early Carboniferous age of Variscan metamorphism and deformation, post-Variscan volcanism, an Early Cretaceous metamorphic overprint related to out-of-sequence thrusting of the Palaeozoic complex, and an Eocene and Oligocene metamorphic overprint related to the main Alpine compressional deformation and subsequent strike-slip faulting, and uplift of the metamorphic core. Accordingly, the Mid-Bosnian Schist Mts. can be correlated in its multistage geodynamic evolution with some Palaeozoic tectonostratigraphic units from the Austroalpine domain in the Eastern Alps.Deceased     

Sr-rich minerals in a carbonatite skarn, Fuerteventura, Canary Islands (Spain)

Summary Metamorphosed carbonatites and related skarn deposits, located in Fuerteventura Basal Complex, contain unusual Sr-rich minerals. Maximum SrO concentration in the following minerals are: calcite, 7.23wt%; apatite, 5.22wt%; epidote, 11.64wt%; clinozoisite, 1.25wt%; allanite, 5.63wt%; britholite, 4.11wt% and a Sr–Na aluminosilicate (probably stronalsite), 16.44wt% SrO. Calcite and apatite are chemically similar to those found in carbonatites and are therefore considered to be of igneous origin. Textural evidence indicates that the first skarn stage garnet+diopside+Sr–Na aluminosilicate formed as the result of chemical interaction between carbonatites and adjacent silicate rocks. The formation of Sr-bearing epidote/clinozoisite, allanite and britholite appears to be related to the release of Sr into the fluid phase from the breakdown of high temperature assemblages during the retrograde skarn stage. During the final evolution stages, further alteration of britholite by bastnäsite and törnebohmite took place. The occurrence of REE minerals shows that the fluids responsible for this metasomatism must also have transported significant quantities of REE.     

Molybdenum mineralization at Alpeiner Scharte, Tyrol (Austria): results of in-situ U–Pb zircon and Re–Os molybdenite dating

Summary Vein-type Mo mineralization at Alpeiner Scharte occurs in the Penninic units of the western Tauern Window in the Eastern Alps. Three types of previously undated metagranitoids (central gneisses) are distinguished and preserve intrusive contacts with pre-Alpine metamorphosed supracrustal rocks. The granitic protoliths represent fractionated late to post-orogenic, calc-alkaline, I-type magmas with minor S-type components. The Mo veins are restricted to a biotite and alkali feldspar-rich gneiss variety and occur in E–W trending normally sub-vertical quartz veins with adjacent thin discontinuous garnet- and biotite-rich zones; the latter are interpreted as metamorphosed vein selvages. Prior to this work the age of the intrusive host rocks as well as the age of Mo mineralization were unknown.The pre-Alpine Mo deposit and its host rocks were affected by four Alpine deformation events (D₁–D₄) and Young-Alpine regional metamorphism. The P-T conditions of this metamorphic event were 550°C and 8kbar and are in agreement with results of previous regional studies.Zircon grains from two orthogneiss samples were dated with the U–Pb method using ion probe techniques. Zircons from the metagranitic host rock of the Mo-veins yielded an emplacement age of 306.8±3.8Ma (2). A second sample from a more leucocratic gneiss lacking Mo-veins gave 305.0±6.6Ma (2). Re–Os dating of molybdenite from the veins yielded an age of 306.8±3.1Ma, in good agreement with the U–Pb zircon ages.This study confirms one of two alternative hypotheses discussed in the literature. It supports the idea that vein-type Mo-mineralization in the western Tauern Window is genetically related to Late Carboniferous (Westphalian) granitoids that were emplaced during the late to post-orogenic stage of the Variscan orogeny. They do not constitute an Alpine metamorphic-hydrothermal deposit. This study further confirms the strength of the Re–Os molybdenite chronometer, in that it was unaffected by subsequent Alpine medium grade regional metamorphism.Present address: Kremstalstraße 32, A-4501 Neuhofen an der Krems, Austria     

Nickel tenor variations between Archaean komatiite-associated nickel sulphide deposits, Kambalda ore field, Western Australia: the metamorphic modification model revisited

Summary Geochemical data for 870 ore samples of 14 nickel sulphide (NiS) deposits from throughout the major Archaean Kambalda ore field, Western Australia, reveal highly heterogeneous Ni tenor (wt% Ni in 100wt% sulphide) variation that is difficult to explain solely by magmatic processes. The Ni tenor values for the deposits range from 6.2wt% Ni (Helmut deposit) to 19.7wt% Ni (Carnilya Hill deposit), close to the range for within single deposits (9.7–19.3wt% Ni). Contents of Ni and platinum-group elements (PGE) broadly increase with decreasing Fe and with increasing abundance of metamorphic pyrite+magnetite±silicates. In turn, the abundance of the metamorphic phases appears to be complexly related to structural setting, metamorphic grade, alteration type, and proximity to felsic intrusion. Chondrite-normalised multi-element plots of deposit compositions reveal relative depletions in Au, As, Bi, and Te.The relationship of increasing Ni content with secondary phase abundance indicates a strong role for metamorphic modification in the tenor variation. Replacement of pyrrhotite by pyrite+magnetite±chlorite during oxidation reduced the abundance of Fe sulphide relative to Ni sulphide and increased the Ni tenor of the residual sulphide. The extent of the oxidation reflects the extent of alteration fluid ingress along deformation structures and fabrics during talc-carbonate alteration, regional metamorphism, and felsic intrusion related to D3. The relative depletions of Au, As, Bi and Te combined with relative enrichments of these metals in nearby orogenic gold deposits mean that NiS deposits could represent metal reservoirs for Archaean gold hydrothermal systems.     

Pervasive rehydration of granulites during exhumation – an example from the Pulur complex, Eastern Pontides, Turkey

Summary High-grade gneisses from the Pulur complex in NE Turkey bear evidence for biotite-dehydration melting at 820°C and 0.7–0.8GPa, melt segregation and near-isothermal decompression to 0.4–0.5GPa. During further exhumation, the rocks underwent secondary pervasive rehydration at temperatures between 400 and 230°C and fluid pressures between 0.3 and 0.1GPa. Metamorphic peak conditions are dated at 331–327Ma, while hydrothermal retrogression occurred significantly later at 315–310Ma under static conditions. During the rehydration event, primary high-grade mineral assemblages including garnet, cordierite, sillimanite, spinel, biotite, plagioclase and ilmenite were extensively replaced by muscovite, paragonite, margarite, corundum, diaspore, chlorite, kaolinite, pumpellyite, prehnite, epidote, titanite, anatase, pyrite and chalcopyrite. Secondary mineral assemblages indicate that the infiltrating fluids were characterized by low fO₂, very low X_CO2 (<0.002), variable activities of Ca²⁺, K⁺, Na⁺ and H⁺ and relatively high activities of H₂S and CH₄. Quartz veins that might have acted as pathways for the fluids are rare. Ubiquitous veinlets consisting of (i) albite, (ii) chlorite+calcite+quartz or (iii) K-feldspar+calcite+quartz were formed after the pervasive rehydraton event by precipitation from aqueous solutions that were somewhat richer in CO₂.     

Synthetic polycrystalline aragonite to calcite transformation kinetics: experiments at pressures close to the equilibrium boundary

Summary ¶This study experimentally investigated the transformation kinetics of synthetic polycrystalline aragonite to calcite at four temperature/pressure conditions (330°C/200MPa, 380°C/325MPa, 430°C/580MPa, and 480°C/875MPa), close to the calcite-aragonite equilibrium phase boundary. The extents of transformation measured as a function of time in a synthetic system, using in-situ annealed, high purity samples, are consistent with the kinetic model for grain-boundary nucleation and interface-controlled growth. The growth rates are slightly lower than those previously determined for a natural polycrystalline sample at 330 and 380°C. The activation energy (158kJ/mol) for calcite growth from synthetic samples is lower than that (247kJ/mol) from natural samples, but is close to the previously reported value (163kJ/mol) from a single crystal aragonite. The extrapolation of our experimental data to natural conditions reveals unusually fast transformation rates, in contrast to those of natural samples. The presence of deformational strain, fractures, defects or impurities in natural samples, and other factors may account for the discrepancy. This study suggests that the retrograde metamorphism of aragonite to calcite may proceed in a wide range of rates also depending on other geological factors than temperature and pressure.Received July 15, 2002; revised version accepted May 15, 2003     

Mineralogy and composition of the chromitites and their platinum-group minerals from Ortaca (Muğla-SW Turkey): evidence for ophiolitic chromitite genesis

Summary A large number of podiform chromitite bodies of massive, disseminated and nodular type have been located in ultramafic units, composed of depleted mantle harzburgite and dunite of the Marmaris Peridotite from Ortaca (Mula, SW Turkey). The chromite ore bodies are surrounded by dunite envelopes of variable thickness, exhibiting transitional boundaries to harzburgite host rocks. Chromitites, containing a large number of inclusions, i.e. silicates, base metal sulphides and alloys, and platinum-group minerals (PGM) have a wide range of chemical composition. The Cr# [Cr/(Cr+Al)] values of most chromitites are high (0.61–0.81) and Mg# [Mg/(Mg+Fe²⁺)] values range between 0.65 and 0.71 with TiO₂ content lower than 0.24wt.%, which may reflect the crystallization of chromites from boninitic magmas in supra-subduction setting environment.Platinum-group minerals (PGM) such as laurite, erlichmanite and Os–Ir alloys, silicates such as olivine, clinopyroxene and amphibole, and base metal sulphides (BM-S), alloys (BM-A) and arsenides (BM-As) are found as inclusions in chromite or in the serpentine matrix. Platinum-group element (PGE) concentrations of the Ortaca chromitites (OC) are low in all samples. Total PGE (Ir+Ru+Rh+Pt+Pd) ranges from 63ng/g to 266ng/g and Pd/Ir ratios range between 0.23 and 4.75. PGE content is higher and the Pd/Ir ratio lower in Cr-rich chromitites compared to Al-rich ones. There is a strong negative correlation between the Cr# and Pd/Ir ratios (r=–0.930). The PGE patterns show a negative slope from Ru to Pt and a positive slope from Pt to Pd. The low PGE content in the majority of the OC may reflect a lack of sulphur saturation during an early stage of their crystallization. The laurite compositions show a wide range of Ru–Os substitution caused by relatively low temperature and increasing f(S₂) during the chromite crystallization. The high Cr# of and hydrous silicate mineral inclusions in chromite imply that chromite crystallized in a supra-subduction setting.     

Phosphorus-rich topaz from fractionated granites (Podlesí, Czech Republic)

Summary A detailed electron microprobe study of P, F, Ge and Ga-contents in rock-forming topaz was performed on a suite of Variscan granites at Podlesí in the western Kruné Hory Mts., Czech Republic. Topaz crystals from the relatively less evolved biotite- and protolithionite granites display homogeneous cathodo-luminescence (CL) intensities, whereas topaz from the marginal pegmatite, highly fractionated zinnwaldite granite and greisens show intense oscillatory zoning. Phosphorus contents reach 1.15wt% P₂O₅ in topaz from the zinnwaldite granite. Many topaz crystals are distinctly zoned with a maximum P content in the transition zone between core and rim. Phosphorus is incorporated into the topaz lattice by berlinite substitution: Al³⁺+P⁵⁺=Si⁴⁺+Si⁴⁺. The majority of analysed topazes are highly saturated in F, reaching 90–97% of the theoretical maximum saturation. Topaz from the marginal pegmatite only reaches 87–90% of F-saturation. There is a positive correlation between P_topaz and P_{whole rock}, but no correlation between F_topaz and F_{whole rock}. No difference has been found in P and F contents between magmatic and the hydrothermal (=greisen stage) topaz. Contents of Ge and Ga vary from around the detection limit (50ppm) up to 200ppm Ge and 100ppm Ga, respectively.     

Mineralogy and geochemistry of Al-phosphate and Al-borosilicate-bearing metaquartzites of the northern Serra do Espinhaço (State of Bahia, Brazil)

Summary The investigated Al-phosphate- and Al-borosilicate-bearing metaquartzite horizon belongs to the Middle Proterozoic Serra de Vereda member of the São Marcos Formation of the northern Espinhaço fold belt. Outcrops are located in the NNW–SSE trending hills of the Serra de Canas/Cana Brava (Northern Serra do Espinhaço, State of Bahia, NE Brazil) about 10km west of the town of Boquira. Sky blue lazulite and deep blue to lilac dumortierite are enriched in layers which sometimes show relic cross bedding. The occurrence of hematite patches and layers is typical. In rocks of type A, phosphorus contents range from 1.89wt.% to 10.73wt.% P₂O₅ and boron contents are mostly below 10ppm whereas in the rocks of type B phosphorus contents are below 1% and boron contents reach 2600ppm with a mean value of 1139ppm. REE distribution patterns of rocks are predominantly controlled by the amount of xenotime, monazite and zircon. Oxygen thermometry on quartz and hematite and the stability of kyanite, augelite, trolleite and berlinite allow to estimate the minimum metamorphic peak P-T conditions at 475°C and 3.8kbar i.e. within the stability field of scorzalite–lazulite and dumortierite. The association of Al-phosphates with hematite layers provides evidence for the deposition of the metaquartzite protolith in a seawater-fed sabkha-like sand flat fringing the Espinhaço rift. It is proposed that apatite, Al-phosphates and Al-borosilicates were chemically precipitated together with iron hydroxides from pore fluids. The antithetic behaviour of phosphorus and boron contents in the metaquartzites is the consequence of an influx of toxic boron-rich water that drastically affected algae populations and consequently reduced phosphorus precipitation.     

Comparison between measured and predicted values of axial end bearing and skin capacity of piles bored in cohesionless soils in the Arabian Gulf Region

The axial base and skin capacities of piles bored in cohesion less soils are often estimated using empirical, semi-empirical and theoretical methods. The aim of this paper is to assess the applicability and evaluate the accuracy of different predictions methods available in the literature, via comparison with data from 43 field pile load tests conducted on shafts drilled in the region of the United Arab Emirates. Janbu's theoretical method (1989) with the parameter (=75°) and Vesics theoretical method (1975) yielded accurate predictions for the base resistances. Burlands approach (1973) overpredicts the skin capacities with an average predicted-to-estimated ratio (q _p /q _e) of three times greater than the unity while using values of the coefficient of earth pressure (k=05k _o ) and the angle of soil-pile friction (=23).     

Telluride mineralogy of the low-sulfidation epithermal Emperor gold deposit, Vatukoula, Fiji

Summary ¶The epithermal, low sulfidation Emperor gold telluride deposit in Fiji, hosted by Late Miocene-Early Pliocene shoshonitic rocks, is spatially related to a low-grade porphyry Cu system on the western flank of the Tavua Caldera. Gold is largely in the form of invisible gold in arsenian pyrite but 10 to 50% of gold is in the form of precious metal tellurides. Gold mineralization occurs in steeply dipping dikes and faults, flat-dipping structures (<45°), referred to locally as flatmakes, and at the intersection of two or more structures referred to as shatter zones. Petrographic, electron microprobe, and scanning electron microscope analyses of ores from some of the more recently discovered orebodies, Matanagata, Matanagata East, and R1 reveal that tellurium-bearing minerals, sylvanite, calaverite, krennerite, petzite, hessite, coloradoite, melonite, native tellurium, and rare benleonardite, formed during various hydrothermal stages, hosted in quartz, and to a lesser extent arsenian pyrite and tetrahedrite group minerals. Sylvanite followed by krennerite are the two most common tellurides in these orebodies. These tellurides show no systematic spatial distribution within flatmakes but there appears to be a higher concentration of tellurides where the flatmake intersects steep structures. Gold-rich tellurides preceded the formation of silver-rich tellurides and were constrained at 250°C in log fS₂ and log fTe₂ space at –12.7 to –10.1 and –9.4 to –7.8, respectively, based on sulfide and telluride stabilities, and the composition of sphalerite. Ore forming components, such as Au, Ag, Te, Cu, V, and S, were likely derived from Late Miocene-Early Pliocene monzonites in and adjacent to the Tavua caldera.Received January 14, 2003; revised version accepted June 26, 2003     

Platinum-group element alloy inclusions in chromites from Archaean mafic-ultramafic units: evidence from the Abitibi and the Agnew-Wiluna Greenstone Belts

Summary The paper investigates the role of primary magmatic phases in the fractionation and concentration of PGE in Archaean mafic and ultramafic systems. The composition of chromites and olivines in sulphur-poor (S<0.6wt%) komatiites from the Agnew-Wiluna Belt (Western Australia), and of chromite concentrated from komatiitic basalt, ferropicritic basalt and tholeiitic basalt from the Abitibi Belt (Canada) were analysed. The results of laser ablation ICP-MS analyses show that PGE-bearing alloys are not stable in crystallising komatiite and that ruthenium is soluble in chromite during crystallisation. Conversely, analyses of chromites separated from Theos Flow tholeiitic basalt indicate that Ir–Os–(±Pt) enrichments (>200ppb) reflect the presence of PGM. Chromites from Freds Flow komatiitic basalt contain Ir-rich clusters, whereas Pt enrichments (>370ppb) in Boston Creek ferropicritic basalt reflect the presence of Pt-rich compounds. The presence of PGE-bearing alloys in Theos Flow and Freds Flow is due to late S-supersaturation, whereas the presence of Pt-rich compounds in Boston Creek Flow reflects high state of melt oxidisation. The lack of PGE-bearing alloys in the olivines and chromites of komatiites can be explained by thermal instability of PGM, depletion in PGE at the mantle source, early S-supersaturation, the oxidisation conditions of the melt, or a combination of these factors.     

Trace hydrogen zoning in diopside

Summary ¶The trace hydrogen content of a colourless to light-green zoned diopside single-crystal from Zillertal was investigated by IR microspectroscopy. The light-green part of the crystal reveals pleochroic OH absorption bands centred at 3645, 3463, and 3358cm^–1 which are attributed to structural OH defects. The OH absorptions of the colourless crystal part are characterised by weak bands at 3645 and 3662cm^–1 and by a strong band at 3676cm^–1. The bands at 3662 and 3676cm^–1 are attributed to the presence of amphibole lamellae. The analytical water content due to the structural OH defect concentration of the light-green crystal part amounts to 0.0016wt.%, that of the colourless part is lowered by a factor of about 50. According to optical absorption spectra, the light-green colour of the crystal is essentially caused by an Fe²⁺–Fe³⁺ charge transfer. The relatively high concentration of OH defects in the light-green crystal part associated with higher Al contents relative to the colourless part suggests that OH is incorporated as hydrodiopside component, CaMg(SiAlO₅OH). It is concluded that increasing water activity during the crystallisation process causes the formation of amphibole lamellae under consumption of nearly all of the water available in the fluid phase. It is further concluded that the observed hydrogen content of diopside represents a primary incorporation and not the result of late hydrothermal alteration processes.Received July 11, 2002; accepted October 30, 2002 Published online February 24, 2003     

Application of mineral thermometers and barometers to granitoid igneous rocks: the Etive Complex, W Scotland

Summary The Etive complex, one of the Caledonian Newer Granites of Scotland, is a ring complex of Devonian age, ranging in composition from pyroxene-diorite to leucogranite. Six samples, representing the major rock units in the southern parts of the Etive complex were chosen for mineral chemical studies and for estimation of the pressure and temperature conditions of magmatic crystallisation. Application of Al- in-hornblende barometry and crossite contents of amphiboles indicates a pressure <3kbar for the intrusion, in good agreement with published independent pressure estimates of 2kbar from mineral equilibria in metasedimentary hornfelses in the Etive thermal aureole. Thermometry, using ternary and binary feldspar systems, yields low temperatures, which probably reflect late-stage, post-magmatic re-equilibration of these minerals. Several geothermometers have been applied to the Quarry Diorite, the outermost intrusion of the complex. The highest temperature for the rocks comes from orthopyroxene–clinopyroxene solvus thermometry, and is 1000°C; this is interpreted to reflect the initial crystallisation of the diorite magma immediately after its emplacement. The maximum temperature from hornblende-plagioclase thermometer is 816°C, which probably reflects late-stage crystallisation of the magma.