The metapelitic garnet–biotite–muscovite–aluminosilicate–quartz (GBMAQ) geobarometer

In this contribution we have empirically calibrated the garnet–biotite–muscovite–aluminosilicate–quartz (GBMAQ) barometer using low- to medium–high-pressure, mid-grade metapelites. Application of the barometer suggests that the GBMAQ and GASP barometers show quite similar pressure estimates. Furthermore, metapelites within thermal contact aureole or very limited geographic area show no meaningful pressure diversity determined by the GBMAQ and GASP barometers which is the geological reality. The random error of the GBMAQ barometer is expected to be around ± 0.8 kbar, and this barometer shows no systematic bias with respect to either pressure, or temperature, or Al^VI in muscovite, or Fe in biotite, or Fe in garnet. The GBMAQ barometer is thermodynamically consistent with the garnet–biotite geothermometer because they share the same activity models of both garnet and biotite. This barometer is especially useful for assemblages with Ca-poor garnet or Ca-poor plagioclase or plagioclase-absent metapelites. Application of this barometer beyond the calibration ranges, i.e., P–T range and chemical ranges of the minerals, is not encouraged.     

An enlarged and updated internally consistent thermodynamic dataset with uncertainties and correlations: the system K2O–Na2O–CaO–MgO–MnO–FeO–Fe2O3–Al2O3–TiO2–SiO2–C–H2–O2

We present, as a progress report, a revised and much enlarged version of the thermodynamic dataset given earlier (Holland & Powell, 1985). This new set includes data for 123 mineral and fluid end-members made consistent with over 200 P–T–X_CO2–f_O2 phase equilibrium experiments. Several improvements and advances have been made, in addition to the increased coverage of mineral phases: the data are now presented in three groups ranked according to reliability; a large number of iron-bearing phases has been included through experimental and, in some cases, natural Fe:Mg partitioning data; H₂O and CO₂ contents of cordierites are accounted for with the solution model of Kurepin (1985); simple Landau theory is used to model lambda anomalies in heat capacity and the Al/Si order–disorder behaviour in some silicates, and Tschermak-substituted end-members have been derived for iron and magnesium end-members of chlorite, talc, muscovite, biotite, pyroxene and amphibole. For the subset of data which overlap those of Berman (1988), it is encouraging to find both (1) very substantial agreement between the two sets of thermodynamic data and (2) that the two sets reproduce the phase equilibrium experimental brackets to a very similar degree of accuracy. The main differences in the two datasets involve size (123 as compared to 67 end-members), the methods used in data reduction (least squares as compared to linear programming), and the provision for estimation of uncertainties with this dataset. For calculations on mineral assemblages in rocks, we aim to maximize the information available from the dataset, by combining the equilibria from all the reactions which can be written between the end-members in the minerals. For phase diagram calculations, we calculate the compositions of complex solid solutions (together with P and T) involved in invariant, univariant and divariant assemblages. Moreover we strongly believe in attempting to assess the probable uncertainties in calculated equilibria and hence provide a framework for performing simple error propagation in all calculations in thermocalc, the computer program we offer for an effective use of the dataset and the calculation methods we advocate.     

Study on the Cu–As–Sb–Ag–Bi–Pb–Te Sulfosalt Minerals from the Hydrothermal System of Southwestern Hokkaido,Japan

Shin‐Otoyo, Suttsu, Teine, Date, Chitose, and Koryu are sites rich in precious and base metal Miocene–Pleistocene epithermal deposits, and located in southwestern Hokkaido, Japan. The deposits are predominantly hosted by the Green Tuff Formation of Middle Miocene age. Ore petrographic study of these deposits shows the occurrence of variable quantities of Cu–As–Sb–Ag–Bi–Pb–Te sulfosalt minerals. Determination of mineralogical and chemical compositions of the sulfosalt minerals was undertaken to elucidate the time and spatial changes of the sulfide‐sulfosalt minerals. Various types of sulfosalt minerals identified from gold–silver and base metal quartz–sulfide veins represented some sulfosalt mineralization phases, such as the Cu–Fe–Sn–S phase of mawsonite and stannite; Cu–(As,Sb)–S phase of tetrahedrite–tennantite and luzonite–famatinite series minerals; (Cu,Ag)–Bi–Pb–S phase of emplectite, pavonite, friedrichite, aikinite, and lillianite–gustavite series minerals; (Ag,Cu)–(As,Sb)–S phase of proustite–pyrargyrite and pearceite–polybasite series minerals; and Bi–Te–S phase of tetradymite and kawazulite minerals. There are some trends in the paragenetic sequence of sulfosalt mineralization in southwestern Hokkaido (in complete or partial) as follows: sulfide → Cu–Fe–Sn–S → (Cu,Ag)–Bi–Pb–S → (Bi–Te–S) → Cu–(As,Sb)–S → ([Ag,Cu]–[As,Sb]–S). The formation of sulfosalt minerals is characterized by the introduction of some elements such as Sn, Bi, and Te at an earlier stage and an increase or decrease of some elements such as As and Sb, followed by the introduction of Ag at the later stage of ore mineral paragenesis sequence. Mineral composition of the Chitose and Koryu deposits are slightly different from those of Shin‐Otoyo, Suttsu, Teine, and Date due to their lack of Sn (tin) and Bi (bismuth) mineralization. The variable concentrations and relationships are not simply with redistributed trace elements from the original sulfide minerals of chalcopyrite, pyrite, galena, and sphalerite. Some heavier elements were also introduced during the replacement reaction, which is consistent with the occurrence of their associated minerals.     

Revised empirical garnet–biotite–muscovite–plagioclase geobarometer in metapelites

The garnet–biotite–muscovite–plagioclase (GBMP) barometer was empirically revised for P–T conditions of 1–14 kbar and 450–840 °C, using 263 metapelitic rock samples from all over the world. This barometer is based on activity models for garnet, biotite and plagioclase identical to those of the well‐calibrated garnet–biotite thermometer and the garnet–aluminosilicate–plagioclase–quartz (GASP) barometer. The GBMP barometer is less temperature dependent than the GASP barometer and can be applied to either Al₂SiO₅‐absent or Al₂SiO₅‐bearing metapelites. The total error of the GBMP barometer is estimated to be about ±1.2 kbar on considering input temperature error and analytical errors of chemical compositions of the phases involved. The random error of the GBMP barometer is evenly distributed with respect to pressure, temperature and mineral composition. Simultaneous application of the GBMP barometer and the garnet–biotite thermometer identifies the correct stability field for Al₂SiO₅‐bearing metapelites. Application of the GBMP barometer to metapelitic rocks within the same geological terranes or thermal contact aureoles yielded similar pressures within error. A spreadsheet for implementing the proposed GBMP geobarometer is supplied on the journal's website.     

Internally consistent data for sulphur‐bearing phases and application to the construction of pseudosections for mafic greenschist facies rocks in Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–CO2–O–S–H2O

The Holland and Powell internally consistent data set version 5.5 has been augmented to include pyrite, troilite, trov (Fe_0.875S), anhydrite, H₂S, elemental S and S₂ gas. Phase changes in troilite and pyrrhotite are modelled with a combination of multiple end‐members and a Landau tricritical model. Pyrrhotite is modelled as a solid solution between hypothetical end‐member troilite (trot) and Fe_0.875S (trov); observed activity–composition relationships fit well to a symmetric formalism model with a value for w_trot?trov of ?3.19 kJ mol^?1. The hypothetical end‐member approach is required to compensate for iron distribution irregularities in compositions close to troilite. Mixing in fluids is described with the van Laar asymmetric formalism model with a_ij values for H₂O–H₂S, H₂S–CH₄ and H₂S–CO₂ of 6.5, 4.15 and 0.045 kJ mol^?1 respectively. The derived data set is statistically acceptable and replicates the input data and data from experiments that were not included in the initial regression. The new data set is applied to the construction of pseudosections for the bulk composition of mafic greenschist facies rocks from the Golden Mile, Kalgoorlie, Western Australia. The sequence of mineral assemblages is replicated successfully, with observed assemblages predicted to be stable at X(CO₂) increasing with increasing degree of hydrothermal alteration. Results are compatible with those of previous work. Assemblages are insensitive to the S bulk content at S contents of less than 1 wt%, which means that volatilization of S‐bearing fluids and sulphidation are unlikely to have had major effects on the stable mineral assemblage in less metasomatized rocks. The sequence of sulphide and oxide phases is predicted successfully and there is potential to use these phases qualitatively for geobarometry. Increases in X(CO₂) stabilized, in turn, pyrite–magnetite, pyrite–hematite and anhydrite–pyrite. Magnetite–pyrrhotite is predicted at temperatures greater than 410 °C. The prediction of a variety of sulphide and oxide phases in a rock of fixed bulk composition as a function of changes in fluid composition and temperature is of particular interest because it has been proposed that such a variation in phase assemblage is produced by the infiltration of multiple fluids with contrasting redox state. The work presented here shows that this need not be the case.     

Outokumpu revisited: New mineral deposit model for the mantle peridotite-associated Cu–Co–Zn–Ni–Ag–Au sulphide deposits

The metaturbidites of the Palaeoproterozoic Jormua–Outokumpu thrust belt in eastern Finland enclose m- to km-scale ultramafic massifs that are distributed over an area of more than 5000 km². These bodies, which almost entirely consist of highly depleted mantle peridotites (now metaserpentinites and metaperidotites), are intimately associated with massive to semimassive, polymetallic Cu–Co–Zn–Ni–Ag–Au sulphide deposits that sustained mining in the region between 1913 and 1988. Currently, one deposit (Kylylahti) is proceeding into a definitive feasibility study emphasising the renewed economic interest for Outokumpu-type deposits.The origin of these Outokumpu-type Cu–Co–Zn–Ni–Ag–Au deposits is now re-interpreted to be polygenetic. First, their formation requires deposition of a Cu-rich proto-ore within peridotitic sea floor at  1950 Ma. Close modern analogues to the proto-ore setting include, for example, the Logatchev and Rainbow fields at the Mid-Atlantic Ridge, where venting of high-T–low-pH hydrothermal fluid resulted in accumulations of Cu–Zn–Co–Ag–Au sulphides on serpentinised ultramafic seafloor. Second, the Ni-rich composition of Outokumpu sulphide ores calls for a separate source for nickel: Some 40 Ma after the deposition of the Cu-rich proto-ore – concomitant with the obduction of the ultramafic massifs – disseminated Ni sulphides formed through chemical interaction between obducting peridotite massifs and adjacent black schists. This process was related to listwaenite–birbirite type carbonate–silica alteration at margins of the ultramafic massifs. Due to this alteration, silicate nickel was released from the primary Fe–Mg silicates and redeposited as Ni sulphides in the alteration fringes of the massifs.We propose that syntectonic mixing of these two “end-member” sulphides, i.e., the primary Cu-rich proto-ore and the secondary Ni-sulphide disseminations, resulted in the uncommon metal combination of the Outokumpu-type sulphides. Late tectonic solid-state re-mobilisation, related to the duplexing of the ore by isoclinal folding, upgraded the sulphides into economic deposits.     

Calculation of partial melting equilibria in the system Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O (NCKFMASH)

A thermodynamic model for haplogranitic melts in the system Na₂O–CaO–K₂O–Al₂O₃–SiO₂–H₂O (NCKASH) is extended by the addition of FeO and MgO, with the data for the additional end‐members of the liquid incorporated in the Holland & Powell (1998) internally consistent thermodynamic dataset. The resulting dataset, with the software thermocalc , is then used to calculate melting relationships for metapelitic rock compositions. The main forms for this are P–T and T–X pseudosections calculated for particular rock compositions and composition ranges. The relationships in these full‐system pseudosections are controlled by the low‐variance equilibria in subsystems of NCKFMASH. In particular, the solidus relationships are controlled by the solidus relationships in NKASH, and the ferromagnesian mineral relationships are controlled by those in KFMASH. However, calculations in NCKFMASH allow the relationships between the common metapelitic minerals and silicate melt to be determined. In particular, the production of silicate melt and melt loss from such rocks allow observations to be made about the processes involved in producing granulite facies rocks, particularly relating to open‐system behaviour of rocks under high‐grade conditions.     

Genesis of the Weiquan Ag–Polymetallic Deposit in East Tianshan, China: Evidence from Zircon U–Pb Geochronology and C–H–O–S–Pb Isotope Systematics

The Weiquan Ag-polymetallic deposit is located on the southern margin of the Central Asian Orogenic Belt and in the western segment of the Aqishan-Yamansu arc belt in East Tianshan,northwestern China. Its orebodies, controlled by faults, occur in the lower Carboniferous volcanosedimentary rocks of the Yamansu Formation as irregular veins and lenses. Four stages of mineralization have been recognized on the basis of mineral assemblages, ore fabrics, and crosscutting relationships among the ore veins. Stage I is the skarn stage(garnet + pyroxene), Stage Ⅱ is the retrograde alteration stage(epidote + chlorite + magnetite ± hematite 士 actinolite ± quartz),Stage Ⅲ is the sulfide stage(Ag and Bi minerals + pyrite + chalcopyrite + galena + sphalerite + quartz ± calcite ± tetrahedrite),and Stage IV is the carbonate stage(quartz + calcite ± pyrite). Skarnization,silicification, carbonatization,epidotization,chloritization, sericitization, and actinolitization are the principal types of hydrothermal alteration. LAICP-MS U-Pb dating yielded ages of 326.5±4.5 and 298.5±1.5 Ma for zircons from the tuff and diorite porphyry, respectively. Given that the tuff is wall rock and that the orebodies are cut by a late diorite porphyry dike, the ages of the tuff and the diorite porphyry provide lower and upper time limits on the age of ore formation. The δ~(13)C values of the calcite samples range from-2.5‰ to 2.3‰, the δ~(18)O_(H2 O) and δD_(VSMOW) values of the sulfide stage(Stage Ⅲ) vary from 1.1‰ to 5.2‰ and-111.7‰ to-66.1‰, respectively,and the δ~(13)C, δ~(18)O_(H2 O) and δD_(V-SMOW) values of calcite in one Stage IV sample are 1.5‰,-0.3‰, and-115.6‰, respectively. Carbon, hydrogen, and oxygen isotopic compositions indicate that the ore-forming fluids evolved gradually from magmatic to meteoric sources. The δ~(34)S_(V-CDT) values of the sulfides have a large range from-6.9‰ to 1.4‰, with an average of-2.2‰, indicating a magmatic source, possibly with sedimentary contributions. The ~(206)Pb/~(204)Pb, ~(207)Pb/~(204)Pb, and ~(208)Pb/~(204)Pb ratios of the sulfides are 17.9848-18.2785,15.5188-15.6536, and 37.8125-38.4650, respectively, and one whole-rock sample at Weiquan yields~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb, and ~(208)Pb/~(204)Pb ratios of 18.2060, 15.5674, and 38.0511,respectively. Lead isotopic systems suggest that the ore-forming materials of the Weiquan deposit were derived from a mixed source involving mantle and crustal components. Based on geological features, zircon U-Pb dating, and C-H-OS-Pb isotopic data, it can be concluded that the Weiquan polymetallic deposit is a skarn type that formed in a tectonic setting spanning a period from subduction to post-collision. The ore materials were sourced from magmatic ore-forming fluids that mixed with components derived from host rocks during their ascent, and a gradual mixing with meteoric water took place in the later stages.     

A new thermodynamic model for sapphirine: calculated phase equilibria in K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3

The activity–composition (a–x) relations of sapphirine are re‐evaluated in the light of a recent new internally‐consistent data set of phase end‐members for use in phase equilibria modelling, particularly of ultra‐high‐temperature (UHT) rocks. This is achieved with the aid of relatively oxidized sapphirine+quartz‐bearing granulites from Wilson Lake, Canada. Calculated P–T projections and compatibility diagrams in the K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (KFMASHTO) system are used to illustrate sapphirine+quartz‐bearing phase equilibria in the context of UHT metamorphism. These new a–x relations for sapphirine should allow pseudosection thermobarometry in NCKFMASHTO for estimating peak P–T conditions of sapphirine‐bearing rocks.     

Thermodynamic modelling of C–O–H fluids

H₂O, CO₂, CH₄, CO, H₂ and O₂ are the most important species in crustal fluids. The composition of these C–O–H fluids can be calculated if the pressure, temperature, carbon activity, and either the oxygen fugacity or the atomic H/O ratio of the fluid is known. The calculation methods are discussed and calculation results are illustrated with isobaric T–X_i, P–T, and isobaric–isothermal ternary C–O–H diagrams. Fluid inclusion compositions, in particular, the X_CO2/(X_CO2+X_CH4) ratio, can be used for C–O–H model calculations. However, care should be taken about possible post-entrapment changes, which may have modified the chemical composition of the fluid inclusion.     

Equilibria in the system Au–Ag–S–fluid: computed and experimental data

We present results of computations on the interaction of solid-phase electrum–argentite–pyrite (weight ratios 210⁻⁵/ 210⁻³/1 and 210⁻⁵/410⁻²/1) association with Cl-containing aqueous moderately acid solutions (0.5m NaCl, pH = 3.08) at 300 °C and 500 bars. These data are a physicochemical basis for predicting the geochemical behavior of Au and Ag during the hydrothermal-metasomatic transformation of Au-Ag-pyrite. We also propose a technique of study of this process based on the phase equilibria of the subsystem Au–Ag–S with the aqueous solution at different liquid/solid (l/s) ratios, with the use of new graphic diagrams. The relationship of the composition of the solid-phase association with l/s ratio in real boundary conditions (Au = 17 ppm, mAu/mAg = 10^–3.57–10^–2.28) is shown. The maximum l/s values for complete leaching of gold and silver (l/smax = 200–800) are estimated. It has been established that argentite is the first to dissolve when mAu/mAg(s) > mAu/mAg(sol), and electrum, when mAu/mAg(s) < mAu/mAg(sol).

The experimental results showed that at 300 °C, the conversion of electrum (N_Au = 300‰) nonequilibrated with pyrite into an Au-richer form (N_Au = 730‰) and argentite follows an intricate kinetic scheme. Using the Pilling-Bedwords kinetic equation for processing data yielded the process rate constant K = 2.8(±0.5)10⁻⁵ g²cm⁻⁴day⁻¹. With this equation, the time of the complete conversion of 200 μm thick flat gold grains is 604 days. These data evidence a significant role of kinetic factors in hydrothermal-metasomatic processes involving native gold, which requires combination of thermodynamic and kinetic approaches on the construction of geologo-genetic models for hydrothermal sulfide formation.     

Re–Os and U–Pb Geochronology of the Dawan Mo–Zn–Fe Deposit in Northern Taihang Mountains,China

The Dawan Mo–Zn–Fe deposit located in the Northern Taihang Mountains in the middle of the North China Craton (NCC) contains large Mo‐dominant deposits. The mineralization of the Dawan Mo–Zn–Fe deposit is associated with the Mesozoic Wanganzhen granitoid complex and is mainly hosted within Archean metamorphic rocks and Proterozoic–Paleozoic dolomites. Rhyolite porphyry and quartz monzonite both occur in the ore field and potassic alteration, strong silicic–phyllic alteration, and propylitic alteration occur from the center of the rhyolite porphyry outward. The Mo mineralization is spacially related to silicic and potassic alteration. The Fe orebody is mainly found in serpentinized skarn in the external contact zone between the quartz monzonite and dolomite. Six samples of molybdenite were collected for Re–Os dating. Results show that the Re–Os model ages range from 136.2 Ma to 138.1 Ma with an isochron age of 138 ± 2 Ma (MSWD = 1.2). U–Pb zircon ages determined by laser ablation inductively coupled plasma mass spectrometry yield crystallization ages of 141.2 ± 0.7 (MSWD = 0.38) and 130.7 ± 0.6 Ma (MSWD = 0.73) for the rhyolite porphyry and quartz monzonite, respectively. The ore‐bearing rhyolite porphyry shows higher K₂O/Na₂O ratios, ranging from 58.0 to 68.7 (wt%), than those of quartz monzonite. All of the rock samples are classified in the shoshonitic series and characterized by enrichment in large ion lithophile elements; depletion in Mg, Fe, Ta, Ni, P, and Y; enrichment in light rare earth elements with high (La/Yb)_n ratios. Geochronology results indicate that skarn‐type Fe mineralization associated with quartz monzonite (130.7 ± 0.6 Ma) formed eight million years later than Mo and Zn mineralization (138 ± 2 Ma) in the Dawan deposit. From Re concentrations in molybdenite and previously presented Pb and S isotope data, we conclude that the ore‐forming material of the deposit was derived from a crust‐mantle mixed source. The porphyry‐skarn type Cu–Mo–Zn mineralization around the Wanganzhen complex is related to the primary magmatic activity, and the skarn‐type Fe mineralization is formed at the late period magmatism. The Dawan Mo–Zn–Fe porphyry‐skarn ores are related to the magmatism that was associated with lithospheric thinning in the NCC.     

Geochronology of the Limu W–Sn–Nb–Ta‐Bearing Granite Pluton in South China

Limu W–Sn–Nb–Ta mining district is located in the Nanling Range W–Sn poly‐metallic mineralization belt in south China. The district includes a number of Sn–Nb–Ta and W–Sn ore occurrences; all of them are spatially associated with granite stocks of a largely‐unexposed pluton, the Limu granitic pluton. A granite sample collected from the Sn–Nb–Ta‐bearing Jinzhuyuan granite stock yields a zircon SHRIMP U–Pb age of 218.3 ± 2.4 Ma, a muscovite ⁴⁰Ar/³⁹Ar plateau age of 212.4 ± 1.4 Ma, and a muscovite ⁴⁰Ar/³⁹Ar isochron age of 213.2 ± 2.2 Ma. Another granite sample collected from the W–Sn‐bearing Sangehuangniu granite stock yields a zircon SHRIMP U–Pb age of 214 ± 5 Ma. The geochronological data provide new constraints on the age of the Limu granite pluton and the timing of the associated W–Sn–Nb–Ta mineralization—at least it sets a reasonable upper age limit for the mineralization of the W–Sn–Nb–Ta ores. The reported ages suggest an active Late Triassic granitic magmatism in Limu area which is part of a regional magmatic event near the end of the Indosinian orogeny in south China.     

Genesis of Pb–Zn Mineralization Beneath the Xiangshan Uranium Orefield,South China: Constraints from H–O–S–Pb Isotopes and Rb–Sr Dating

The volcanic‐hosted Xiangshan uranium orefield is the largest uranium deposit in South China. Recent exploration has discovered extensive Pb–Zn mineralization beneath the uranium orebodies. Detailed geological investigation reveals that the major metallic minerals include pyrite, sphalerite, galena, and chalcopyrite, whilst the major non‐metallic minerals include quartz, sericite, and calcite. New δ¹⁸O_fluid and δD_fluid data indicate that the ore‐forming fluids were mainly derived from magmatic, and the sulfide δ³⁴S values (2.2–6.9‰) suggest a dominantly magmatic sulfur source. The Pb isotope compositions are homogeneous (²⁰⁶Pb/²⁰⁴Pb = 18.120–18.233, ²⁰⁷Pb/²⁰⁴Pb = 15.575–15.698, and ²⁰⁸Pb/²⁰⁴Pb = 37.047–38.446). The ⁸⁷Sr/⁸⁶Sr ratios of sulfide minerals range from 0.7197 to 0.7204, which is much higher than volcanic rocks and fall into the range of metamorphic basement. Lead and strontium isotopic compositions indicate that the metallogenic materials probably were derived from metamorphic basement. Pyrite Rb–Sr dating of the ores yielded 131.3 ± 4.0 Ma, indicating that the Pb–Zn mineralization occurred in the Early Cretaceous.     

Composition and origin of intermediate solid solutions in the system thorite–xenotime–zircon–coffinite

A comprehensive survey of the accessory-mineral assemblages in Variscan granites of the German Erzgebirge and Pan-African granites from Jordan revealed the occurrence of intermediate solid solutions of the tetragonal thorite–xenotime–zircon–coffinite mineral group with partially novel compositions. These solid solutions preferentially formed in evolved and metasomatically altered, P-poor leucogranites of either I- or A-type affinity. Thorite from the Erzgebirge contained up to 18.8 wt.% Y₂O₃, 16.1 wt.% ZrO₂, and 23.3 wt.% UO₂. Xenotime and zircon have incorporated Th in abundances up to 36.3 wt.% and 41.8 wt.% ThO₂, respectively. Extended compositional gradation with only minor gaps is confined to hydrated members of this mineral group, and is observed to exist between thorite and xenotime, thorite and coffinite, and Y–HREE-bearing thorite and zircon. Complex, hydrous solid solutions containing elevated abundances of three or more of the endmembers are subordinate. Previously reported intermediate solid solutions between anhydrous zircon and xenotime, and anhydrous zircon and thorite, are not observed and are in conflict with experimental work demonstrating very limited miscibility between anhydrous species of endmember composition. The majority of hydrous intermediate solid solutions in the Th–Y–Zr–U system are likely thermodynamically unstable. Instead, they are probably metastable responses to unusual physico-chemical conditions involving various parameters and conditions, the relative importance of which is incompletely known. Leaching and dissolution of preexisting accessory phases during interaction with F-bearing hydrous fluids enriched in Th, Y(HREE), Zr, and/or U, and common deposition of the various elements at disequilibrium (supersaturation) seems to play a key role, but other processes may be of similar importance. Experimental work involving hydrous conditions and complex systems composed of more than two endmembers are needed to shed light into the stability relations of the chemically uncommon compositions treated in this study.     

The stability of sapphirine + quartz: calculated phase equilibria in FeO–MgO–Al2O3–SiO2–TiO2–O

The presence in rocks of coexisting sapphirine + quartz has been widely used to diagnose conditions of ultra‐high‐temperature (UHT) metamorphism (>900 °C), an inference based on the restriction of this assemblage to temperatures >980 °C in the conventionally considered FeO–MgO–Al₂O₃–SiO₂ (FMAS) chemical system. With a new thermodynamic model for sapphirine that includes Fe₂O₃, phase equilibra modelling using thermocalc software has been undertaken in the FeO–MgO–Al₂O₃–SiO₂–O (FMASO) and FeO–MgO–Al₂O₃–SiO₂– TiO₂–O (FMASTO) chemical systems. Using a variety of calculated phase diagrams for quartz‐saturated systems, the effects of Fe₂O₃ and TiO₂ on FMAS phase relations are shown to be considerable. Importantly, the stability field of sapphirine + quartz assemblages extends down temperature to 850 °C in oxidized systems and thus out of the UHT range.     

Calibration of the garnet–biotite–Al2SiO5–quartz geobarometer for metapelites

A garnet–biotite–Al₂SiO₅–quartz (GBAQ) geobarometer was empirically calibrated using more than 700 natural metapelites with a broad compositional range of garnet and biotite under P–T conditions of 450–950°C and 1–17 kbar. In the calibration, activity models of garnet and biotite identical to those in the garnet–biotite (GB) geothermometer of Holdaway [American Mineralogist 2000, 85: 881–892] were used. Therefore, the GBAQ geobarometer and the GB geothermometer can be simultaneously applied to iteratively estimate metamorphic P–T conditions. Successful applications of the GBAQ geobarometer to natural metapelites certify its validity. Most importantly, when plagioclase is absent or CaO components in garnet and/or plagioclase are deficient, this geobarometer may prove useful for estimating metamorphic pressures. The random error of the present GBAQ geobarometer is inferred to be around ±1.8 kbar. An electronic spreadsheet is available as Table S4 to apply the GBAQ geobarometer in combination with the GB geothermometer.     

Solid–liquid–air coupling in multiphase porous media

This paper addresses various issues concerning the modelling of solid–liquid–air coupling in multiphase porous media with an application to unsaturated soils. General considerations based on thermodynamics permit the derivation and discussion of the general form of field equations; two cases are considered: a three phase porous material with solid, liquid and gas, and a two phase porous material with solid, liquid and empty space. Emphasis is placed on the presentation of differences in the formulation and on the role of the gas phase. The finite element method is used for the discrete approximation of the partial differential equations governing the problem. The two formulations are then analysed with respect to a documented drainage experiment carried out by the authors. The merits and shortcomings of the two approaches are shown. Copyright © 2003 John Wiley & Sons, Ltd.     

Cu–Ni–Co–As (U) mineralization in the Anarak area of central Iran

Cu–Ni–Co–As–U mineralization in the Anarak area of central Iran occurs at the intersection of the Uroumieh-Dokhtar magmatic belt with the Great Kavir–Doruneh fault. In the area, the volcanism associated with the magmatic belt is shoshonitic in character. Chemical analyses indicate that these are subduction related magmas. Detailed investigations in the vicinity of the Talmessi mine indicate that mineralization occurred in two separate stages: a first stage of copper sulphide mineralization with a relatively simple mineralogy and associated with the Eocene magmatism, and a second stage of Cu–Ni–Co–As–U mineralization with a complex mineralogy, which probably formed during another phase of deformation in the Upper Miocene. This later deformation reactivated previously formed faults. The mineralogy, element association and isotopic composition of carbonates for the second phase of mineralization suggest a different origin to that of the first phase. The fluids are likely to be non-magmatic in origin, possibly showing an increased input from meteoric waters. The close spatial association with basic/ultrabasic igneous rocks indicates that these may be the source through alteration and remobilization. The arsenide mineralization in the Anarak area shows many features that are similar to those of the classic five-element deposits.     

Regional time-predictable modeling in the Hindukush–Pamir–Himalayas region

The seismic characteristic of Hindukush–Pamir–Himalaya (HPH) and its vicinity is very peculiar and has experienced many widely distributed large earthquakes. Recent work on the time-dependent seismicity in the Hindukush–Pamir–Himalayas is mainly based on the so-called “regional time-predictable model”, which is expressed by the relation log T=cM_p+a, where T is the inter-event time between two successive main shocks of a region and M_p is the magnitude of the preceded main shock. Parameter a is a function of the magnitude of the minimum earthquake considered and of the tectonic loading and c is positive (0.3) constant. In 90% of the cases with sufficient data, parameter c was found to be positive, which strongly supports the validity of the model. In the present study, a different approach, which assumes no prior regionalization of the area, is attempted to check the validity of the model. Nine seismic sources were defined within the considered region and the inter-event time of strong shallow main shock were determined and used for each source in an attempt at long-term prediction, which show the clustering and occurrence of at least three earthquakes of magnitude 5.5≤M_s≤7.5 giving two repeat times, satisfying the necessary and sufficient conditions of time-predictable model (TP model). Further, using the global applicability of the regional time- and magnitude-predictable model, the following relations have been obtained: log T_t=0.19 M_min+0.52M_p+0.29 log m₀−10.63 and M_f=1.31M_min−0.60M_p−0.72 log m₀+21.01, where T_t is the inter-event time, measured in years; M_min the surface wave magnitude of the smallest main shock considered; M_p the magnitude of preceding main shock; M_f the magnitude of the following main shock; and m₀ the moment rate in each source per year.

These relations may be used for seismic hazard assessment in the region. Based on these relations and taking into account the time of occurrence and the magnitude of the last main shock in each seismogenic source, time-dependent conditional probabilities for the occurrence of the next large (M_s≥5.5) shallow main shocks during the next 20 years as well as the magnitudes of the expected main shocks are determined.