A spectrophotometric study of samarium (III) speciation in chloride solutions at elevated temperatures

The speciation of samarium (III) in chloride-bearing solutions was investigated spectrophotometrically at temperatures of 100-250 °C and a pressure of 100 bars. The simple hydrated ion, Sm³⁺, is predominant at ambient temperature, but chloride complexes are the dominant species at elevated temperatures. Cumulative formation constants for samarium chloride species were calculated for the following reactions:

     

An experimental study of the solubility and speciation of neodymium (III) fluoride in F-bearing aqueous solutions

The solubility of neodymium (III) fluoride was investigated at temperatures of 150, 200 and 250 °C, saturated water vapor pressure, and a total fluoride concentration (HF°_aq + F⁻) ranging from 2.0 × 10⁻³ to 0.23 mol/l. The results of the experiments show that Nd³⁺ and NdF²⁺ are the dominant species in solution at the temperatures investigated and were used to derive formation constants for NdF²⁺ and a solubility product for NdF₃. The solubility product of NdF₃(logK_sp=loga_Nd³⁺+3loga_F^-) is −24.4 ± 0.2, −22.8 ± 0.1, and −21.5 ± 0.2 at 250, 200 and 150 °C, respectively, and the formation constant of NdF²⁺(logβ=loga_NdF²⁺-loga_Nd³⁺-loga_F^-) is 6.8 ± 0.1, 6.2 ± 0.1, and 5.5 ± 0.2 at 250, 200 and 150 °C, respectively. The results of this study show that published theoretical predictions significantly overestimate the stability of NdF²⁺ and the solubility of NdF₃.The potential impact of the results on natural systems was evaluated for a hypothetical fluid with a composition similar to that responsible for REE mineralization in the Capitan pluton, New Mexico. In contrast to results obtained using the theoretical predictions of Haas [Haas J. R., Shock E. L., and Sassani D. C. (1995) Rare earth elements in hydrothermal systems: estimates of standard partial molal thermodynamic properties of aqueous complexes of the rare earth elements at high pressures and temperatures. Geochim. Cosmochim. Acta59, 4329-4350.], which indicate that NdF²⁺ is the dominant species in solution, calculations employing the data presented in this paper and previously published experimental data for chloride and sulfate species [Migdisov A. A., and Williams-Jones A. E. (2002) A spectrophotometric study of neodymium(III) complexation in chloride solutions. Geochim. Cosmochim. Acta66, 4311-4323; Migdisov A. A., Reukov V. V., and Williams-Jones A. E. (2006) A spectrophotometric study of neodymium(III) complexation in sulfate solutions at elevated temperatures. Geochim. Cosmochim. Acta70, 983-992.] show that neodymium chloride species predominate and that neodymium fluoride species are relatively unimportant. This suggests that accepted models for REE deposits that invoke fluoride complexation as the method of hydrothermal REE transport may need to be re-evaluated.     

Predicted equilibrium constants for solid and aqueous selenium species to 300 °C: applications to selenium-rich mineral deposits

In this study, an attempt has been made to assess aqueous speciation of selenium and solubility product constants of common selenides at elevated temperatures (up to 300 °C) by using various extrapolation methods. This study predicts that reduced selenium species are dominant species in many geological processes even under relatively oxidized conditions such as those dictated by the magnetite–hematite buffer. On the basis of extrapolated equilibrium constants and solubility product constants for common Se-bearing mineral phases, critical ∑Se/∑S ratios (molal ratios) in mineralizing fluids are proposed for independent selenium mineralization. The minimum ∑Se/∑S ratios in mineralizing fluids for independent selenium mineralization should be at least 10⁻⁶, 10⁻⁵ and 10⁻⁴ at 100, 200 and 300 °C, respectively. For giant independent selenium deposits such as the La'erma and Qiongmo Au–Se deposits in the western Qingling mountains, and Yutangba Se deposits in Hubei Province, China, the mineralizing fluids have reached much higher ∑Se/∑S ratios ranging from 10⁻¹ to 10⁻³ at 200 °C. This study also suggests that the equilibrium assemblage of pyrite–ferroselite among the common ore minerals requires the highest ∑Se/∑S ratios in mineralizing fluids, followed in decreasing order by the assemblages of stibnite–antimonselite, galena–clausthalite, cinnabar–tiemannite, and acanthite/argentite–naumannite. The assemblage of pyrite–ferroselite can also be formed under relatively oxidizing conditions where [∑H₂Se]/[∑H₂S] ratios can be high enough for the formation of independent ferroselite.     

The aqueous geochemistry of Zr and the solubility of some Zr-bearing minerals

Literature data on the thermodynamics of complexation of Zr with inorganic species, at 25°C, have been critically reviewed. The preponderance of published complexation constants deal with F⁻ and OH⁻ ions. Stability constants for the complexation reactions are relatively independent of ionic strength and thus recomended values for each ligand type are averages of the most reliable data. Complexation constants under elevated conditions (T 250°C andP_v = P_H2O) have been predicted for various Zr complexes (F⁻, Cl⁻, SO₄²⁻ and OH⁻) using Helgeson's electrostatic approach. Predominance diagrams (calculated for simple systems with these constants) suggest that, over a wide range of pH conditions, Zr(OH)_4(aq) will dominate the aqueous geochemistry of Zr except under very high activities of competing ligands (e.g., F⁻, SO₄²⁻).The solubilities of vlasovite [Na₂ZrSi₄O₁₁] and weloganite [Sr₃Na₂Zr(CO₃)₆·3H₂O have been measured in KCI solutions (0.5–1.0 M) at 50°C. Weloganite dissolution is complicated by the predictable precipitation of strontianite (SrCO₃) whereas vlasovite dissolves incongruently. Solubility products for the dissolution of welonganite and vlasovite are determined to be −28.96±0.14 and −20.40±1.18, respectively. Concentrations of Zr up to 10⁻³ m were present in the experimental solutions; the presence of large amounts of Zr in aqueous solutions support the possibility of extensive remobilization of Zr during hydrothermal mineralization.     

Tectonic controls on metamorphism, partial melting, and intrusion: timing and duration of regional metamorphism and magmatism in the Ni de Massif, Turkey

Mafic high-pressure granulite, eclogite and pyroxenite xenoliths have been collected from a Mesozoic volcaniclastic diatreme in Xinyang, near south margin of the Sino-Korean Craton (SKC). The high-pressure granulite xenoliths are mainly composed of fine-grained granoblasts of Grt+Cpx+Pl+Hbl±Kfs±Q±Ilm with relict porphyritic mineral assemblage of Grt+Cpx±Pl±Rt. P–T estimation indicates that the granoblastic assemblage crystallized at 765–890 °C and 1.25–1.59 GPa, corresponding to crustal depths of ca. 41–52 km with a geotherm of 75–80 mW/m². Calculated seismic velocities (V_p) of high-pressure granulites range from 7.04 to 7.56 km/s and densities (D) from 3.05 to 3.30 g/cm³. These high-pressure granulite xenoliths have different petrographic and geochemical features from the Archean mafic granulites. Elevated geotherm and petrographic evidence imply that the lithosphere of this craton was thermally disturbed in the Mesozoic prior to eruption of the host diatreme. These samples have sub-alkaline basaltic compositions, equivalent to olivine– and quartz–tholeiite. REE patterns are flat to variably LREE-enriched (La_N/Yb_N=0.98–9.47) without Eu anomaly (Eu/Eu*=0.95–1.11). They possess 48–127 ppm Ni and 2–20 ppm Nb with Nb/U and La/Nb ratios of 13–54 and 0.93–4.75, respectively, suggesting that these high-pressure granulites may be products of mantle-derived magma underplated and contaminated at the base of the lower crust. This study also implies that up to 10 km Mesozoic lowermost crust was delaminated prior to eruption of the Cenozoic basalts on the craton.     

HP–LT Variscan metamorphism in the Cubito-Moura schists (Ossa-Morena Zone, southern Iberia)

Multi-equilibrium thermobarometry shows that low-grade metapelites (Cubito-Moura schists) from the Ossa–Morena Zone underwent HP–LT metamorphism from 340–370 °C at 1.0–0.9 GPa to 400–450 °C at 0.8–0.7 GPa. These HP–LT equilibriums were reached by parageneses including white K mica, chlorite and chloritoid, which define the earliest schistosity (S₁) in these rocks. The main foliation in the schists is a crenulation cleavage (S₂), which developed during decompression from 0.8–0.7 to 0.4–0.3 GPa at increasing temperatures from 400–450 °C to 440–465 °C. Fe³⁺ in chlorite decreased greatly during prograde metamorphism from molar fractions of 0.4 determined in syn-S₁ chlorites down to 0.1 in syn-S₂ chlorites. These new data add to previous findings of eclogites in the Moura schists indicating that a pile of allochtonous rocks situated next to the Beja-Acebuches oceanic amphibolites underwent HP–LT metamorphism during the Variscan orogeny. To cite this article: G. Booth-Rea et al., C. R. Geoscience 338 (2006).     

Rare-earth elements in groundwaters from the Osamu Utsumi mine and Morro do Ferro analogue study sites, Poços de Caldas, Brazil

Data are presented on rare-earth elements (REE) in prefiltered (<450 nm) near-surface and deeper groundwaters and in corresponding particulate matter (>450 nm) from the Osamu Utsumi uranium mine and the Morro do Ferro thorium-REE-deposit. Groundwaters from both sites typically contain between 1–50 μg/l of total REE, but can reach values of up to 160 μg/l in the deepest borehole F4 (U-Mine: 150–415 m). Even higher REE concentrations of up to 29 mg/l were measured in acidic, sulfate-rich near-surface waters of the same site. The chondrite-normalized REE patterns in deeper, more reducing groundwaters and in their corresponding suspended particle fractions are similar to those observed in the bedrock (phonolites), indicating that bedrock leaching and secondary mineral sorption occurred without significant fractionation between these elements, in accordance with the only small variations in the stability constants of the expected REE-sulfate complexes in these waters. Groundwaters from the unsaturated zone of both sites show a very characteristic cerium depletion (less pronounced than that observed in the corresponding suspended particulate fractions), which is most probably related to the oxidation of Ce (III) under the prevailing E_h-conditions of these waters (600 to 800 mV), and to sorption/precipitation reactions of the much less soluble Ce(IV) species. Coarse particulate matter (>450 nm), composed mainly of amorphous ferric hydrous oxides, has a strong capacity for sorption of REE. This is shown by its very high REE concentrations, in some boreholes > 8,000 μg/g (total REE), and by the calculated association ratios R_a (ml/g), which are in the order of 10⁵ to 10⁶. The implications of these findings for the migration behavior of REE in both environments are discussed.     

Rare earth element sorption by basaltic rock: Experimental data and modeling results using the “Generalised Composite approach”

Sorption of the 14 rare earth elements (REE) by basaltic rock is investigated as a function of pH, ionic strength and aqueous REE concentrations. The rock sample, originating from a terrestrial basalt flow (Rio Grande do Sul State, Brazil), is composed of plagioclase, pyroxene and cryptocrystalline phases. Small amounts of clay minerals are present, due to rock weathering. Batch sorption experiments are carried out under controlled temperature conditions of 20 °C with the <125 μm fraction of the ground rock in solutions of 0.025 M and 0.5 M NaCl and at pH ranging from 2.7 to 8. All 14 REEs are investigated simultaneously with initial concentrations varying from 10⁻⁷ to 10⁻⁴ mol/L. Some experiments are repeated with only europium present to evaluate possible competitive effects between REE. Experimental results show the preferential retention of the heavy REEs at high ionic strength and circumneutral pH conditions. Moreover, results show that REE sorption increases strongly with decreasing ionic strength, indicating two types of sorption sites: exchange and specific sites. Sorption data are described by a Generalised Composite (GC) non-electrostatic model: two kinds of surface reactions are treated, i.e. cation exchange at >XNa sites, and surface complexation at >SOH sites. Total site density (>XNa + >SOH) is determined by measuring the cation exchange capacity (CEC = 52 μmol/m²). Specific concentrations of exchange sites and complexation sites are determined by fitting the Langmuir equation to sorption isotherms of REE and phosphate ions. Site densities of 22 ± 5 and 30 ± 5 μmol/m² are obtained for [>XNa] and [>SOH], respectively. The entire set of REE experimental data is modeled using a single exchange constant (log K_ex = 9.7) and a surface complexation constant that progressively increases from log K = −1.15 for La(III) to −0.4 for Lu(III).The model proves to be fairly robust in describing other aluminosilicate systems. Maintaining the same set of sorption constants and only adjusting the site densities, we obtain good agreement with the literature data on REE/kaolinite and REE/smectite sorption. The Generalised Composite non-electrostatic model appears as an easy and efficient tool for describing sorption by complex aluminosilicate mineral assemblages.     

Iron-Titanium Oxide Geothermometry and Petrogenesis of Lava Flows and Dykes from Mandla Lobe of the Eastern Deccan Volcanic Province, India

Compositional studies on different forms of magnetite, ulvospinel, ilmenite and hematite mineral phases occurring in 37 lava flows and 6 dykes of the Mandla lobe are presented in this paper. Ilmenite (0001) in equilibrium with titanomanetite show high values of temperature of equilibration, ranging from 1172–974°C, for high alumina quartz normative tholeiitic lava flows of Chemical Type - A; 1129–1229°C for low alumina quartz normative tholeiitic lava flows of Chemical Type - B; 1283–1124°C for tholeiitic lava flows of Chemical Type - F and 1243°C and 99O°C for two diopside olivine normative tholeiite flows of Chemical Type D. High olivine normative flows of Chemical Type - G and H show 1095°C and 1092°C respectively. Whereas, high hypersthene normative tholeiite flow of Chemical me C shows temperature of 1187°C. Data plots disposition over iron-titanium oxide equilibration temperature vs – logfo₂, diagram for Mandla lava flows and other parts of the Deccan (Igatpuri, Mahabaleshwer, Nagpur and Sagar areas) revealed that tholeiitic (evolved) basalt of the eastern Deccan volcanic province formed at high temperatures whereas, picritic (primitive) lavas of Igatpuri and tholeiitic basalt of Mahabaleshwar areas were formed at low temperatures. Mahabaleshwer basalts follow FMQ (fayalite-magnetite-quartz) buffer curve but, plots of the Mandla basalts lie above this curve indicating higher temperatures of crystallisation of ilmenite-titanomagnetite than that of the lava flows from other parts of Deccan 'Raps. The eastern Deccan Traps are most evolved types of lava as characterised by its low Mg-number and Ni content whereas, Igatpuri lava flows are picritic (primitive), having high Mg-number and Ni contents. Temperature vs FeO + Fe₂O₃ / FeO + Fe₂O₃ + MgO ratio data plots for Mandla and other Deccan lava flows and liquidus data for Hawaiian tholeiites, indicated that Igatpuri basalts lie parallel to the liquidus line of Hawaiian tholeiite but at lower temperatures. Large data plots of Mandla lava flows lie along the liquidus line of the Hawaiian lava. The highly vesicular nature of compound lava flows having large amount of volatile is responsible for low temperature values whereas, lava flows represented by high temperatures show high modal values of glass and opaque minerals.     

Speciation of rare earth elements in natural terrestrial waters: assessing the role of dissolved organic matter from the modeling approach

Humic Ion-Binding Model V, which focuses on metal complexation with humic and fulvic acids, was modified to assess the role of dissolved natural organic matter in the speciation of rare earth elements (REEs) in natural terrestrial waters. Intrinsic equilibrium constants for cation-proton exchange with humic substances (i.e., pK_MHA for type A sites, consisting mainly of carboxylic acids), required by the model for each REE, were initially estimated using linear free-energy relationships between the first hydrolysis constants and stability constants for REE metal complexation with lactic and acetic acid. pK_MHA values were further refined by comparison of calculated Model V “fits” to published data sets describing complexation of Eu, Tb, and Dy with humic substances. A subroutine that allows for the simultaneous evaluation of REE complexation with inorganic ligands (e.g., Cl⁻, F⁻, OH⁻, SO₄²⁻, CO₃²⁻, PO₄³⁻), incorporating recently determined stability constants for REE complexes with these ligands, was also linked to Model V. Humic Ion-Binding Model V’s ability to predict REE speciation with natural organic matter in natural waters was evaluated by comparing model results to “speciation” data determined previously with ultrafiltration techniques (i.e., organic acid-rich waters of the Nsimi-Zoetele catchment, Cameroon; dilute, circumneutral-pH waters of the Tamagawa River, Japan, and the Kalix River, northern Sweden). The model predictions compare well with the ultrafiltration studies, especially for the heavy REEs in circumneutral-pH river waters. Subsequent application of the model to world average river water predicts that organic matter complexes are the dominant form of dissolved REEs in bulk river waters draining the continents. Holding major solute, minor solute, and REE concentrations of world average river water constant while varying pH, the model suggests that organic matter complexes would dominate La, Eu, and Lu speciation within the pH ranges of 5.4 to 7.9, 4.8 to 7.3, and 4.9 to 6.9, respectively. For acidic waters, the model predicts that the free metal ion (Ln³⁺) and sulfate complexes (LnSO₄⁺) dominate, whereas in alkaline waters, carbonate complexes (LnCO₃⁺ + Ln[CO₃]₂⁻) are predicted to out-compete humic substances for dissolved REEs. Application of the modified Model V to a “model” groundwater suggests that natural organic matter complexes of REEs are insignificant. However, groundwaters with higher dissolved organic carbon concentrations than the “model” groundwater (i.e., >0.7 mg/L) would exhibit greater fractions of each REE complexed with organic matter. Sensitively analysis indicates that increasing ionic strength can weaken humate-REE interactions, and increasing the concentration of competitive cations such as Fe(III) and Al can lead to a decrease in the amount of REEs bound to dissolved organic matter.     

Geochemistry and origin of massif-type anorthosites

Samples of Proterozoic anorthosite complexes from the Adirondack Mountains of New York, Burwash Area of Ontario, and the Nain Complex of Labrador, ranging in composition from anorthosite to anorthositic gabbro, have been analyzed for major elements, Rb, Sr, Ba and nine rare-earth elements (REE), in order to set limits on the compositions and origins of their parent magmas. Similar rock types from the different areas have similar major and trace element compositions. The anorthosites have high Sr/Ba ratios, low REE abundances (Ce about 10, Yb about 0.5–1.5 times chondrites) and large positive Eu anomalies. The associated anorthositic gabbros have lower Sr/Ba ratios, REE abundances nearly an order of magnitude higher than the anorthosites, and small to negligible positive Eu anomalies.Model calculations using the adcumulate rocks with the lowest REE abundances and published distribution coefficients yield parent liquids having REE abundances and patterns similar to those of the associated anorthositic gabbros with the highest REE abundances. Rocks with intermediate REE abundances are the result of incorporation of a liquid component by a plagioclase-rich cumulate similar to the adcumulate samples. The analytical data and model calculations both suggest parent liquids having compositions of 50–54% SiO₂, greater than 20% Al₂O₃, about 1% K₂O, atomic Mg/(Mg+Fe²⁺) ratios (Mg No.'s) of less than 0.4, 15–30 ppm Rb, 400–600 ppm Sr and 400–600 ppm Ba, 40–50 times chondrites for Ce and 8–10 times chondrites for Yb.The low atomic Mg/(Mg+Fe²⁺) values for these rocks combined with geophysical evidence suggesting there are not large quantities of ferromagnesian material at depth, indicate that the anorthositic masses are not products of fractional crystallization of mafic melt derived from melting of the mantle. Rather, it is suggested that they are a result of partial melting of tholeiitic compositions at depths shallower than the basalt-eclogite transformation, leaving a pyroxene-dominated residue.     

Geochemical constraints on the modes of carbonate precipitation in peridotites from the Logatchev Hydrothermal Vent Field and Gakkel Ridge

The ultramafic-hosted Logatchev Hydrothermal Field (LHF) at 15°N on the Mid-Atlantic Ridge and the Arctic Gakkel Ridge (GR) feature carbonate precipitates (aragonite, calcite, and dolomite) in voids and fractures within different types of host rocks. We present chemical and Sr isotopic compositions of these different carbonates to examine the conditions that led to their formation. Our data reveal that different processes have led to the precipitation of carbonates in the various settings. Seawater-like ⁸⁷Sr/⁸⁶Sr ratios for aragonite in serpentinites (0.70909 to 0.70917) from the LHF are similar to those of aragonite from the GR (0.70912 to 0.70917) and indicate aragonite precipitation from seawater at ambient conditions at both sites. Aragonite veins in sulfide breccias from LHF also have seawater-like Sr isotope compositions (0.70909 to 0.70915), however, their rare earth element (REE) patterns show a clear positive europium (Eu) anomaly indicative of a small (< 1%) hydrothermal contribution. In contrast to aragonite, dolomite from the LHF has precipitated at much higher temperatures (~ 100 °C), and yet its ⁸⁷Sr/⁸⁶Sr ratios (0.70896 to 0.70907) are only slightly lower than those of aragonite. Even higher temperatures are calculated for the precipitation of deformed calcite veins in serpentine–talc fault schists form north of the LHF. These calcites show unradiogenic ⁸⁷Sr/⁸⁶Sr ratios (0.70460 to 0.70499) indicative of precipitation from evolved hydrothermal fluids. A simple mixing model based on Sr mass balance and enthalpy conservation indicates strongly variable conditions of fluid mixing and heat transfers involved in carbonate formation. Dolomite precipitated from a mixture of 97% seawater and 3% hydrothermal fluid that should have had a temperature of approximately 14 °C assuming that no heat was transferred. The much higher apparent precipitation temperatures based on oxygen isotopes (~ 100 °C) may be indicative of conductive heating, probably of seawater prior to mixing. The hydrothermal calcite in the fault schist has precipitated from a mixture of 67% hydrothermal fluid and 33% seawater, which should have had an isenthalpic mixing temperature of ~ 250 °C. The significantly lower temperatures calculated from oxygen isotopes are likely due to conductive cooling of hydrothermal fluid discharging along faults. Rare earth element patterns corroborate the results of the mixing model, since the hydrothermal calcite, which formed from waters with the greatest hydrothermal contribution, has REE patterns that closely resemble those of vent fluids from the LHF. Our results demonstrate, for the first time, that (1) precipitation from pure seawater, (2) conductive heating of seawater, and (3) conductive cooling of hydrothermal fluids in the sub-seafloor all can lead to carbonate precipitation within a single ultramafic-hosted hydrothermal system.     

An example of post-collisional mafic magmatism: the gabbro–anorthosite layered complex from the Tin Zebane area (western Hoggar, Algeria)

The Tin Zebane gabbro–anorthosite layered mafic intrusion represented by plagioclase-rich cumulates forms a set of small lenticular to round-shaped mainly undeformed bodies intruding the Pan-African high-pressure metamorphic rocks from western Hoggar (Tuareg shield, southwest Algeria). The coarse-grained anorthosites are mainly made of slightly zoned bytownite (An_86–74) with the higher anorthite content at the cores. Anorthosites are interlayered with leucogabbros and gabbros that show preserved magmatic structures and with olivine gabbros characterised by coronitic textures. The primary assemblage in gabbros includes plagioclase (An_93–70), olivine (Fo_77–70), zoned clinopyroxene (En_43–48Fs_05–13Wo_41–49 with Al₂O₃ up to 4.3 wt.%) and rare orthopyroxene (En_73–78). Pyroxenes and olivine are commonly surrounded by Ca-amphibole. The olivine–plagioclase contact is usually marked by a fine orthopyroxene–Cr-spinel–amphibole symplectite. A magnesian pigeonite (En_70–75Fs_19–20Wo_6–10) is also involved in corona. The coronitic minerals have equilibrated with the primary mineral rims at P–T–a_H2O conditions of 797 ± 42 °C for a_H2O=0.5 and 808 ± 44 °C for a_H2O=0.6 at 6.2 ± 1.4 kbar. The Tin Zebane gabbroic rocks are depleted in REE with a positive Eu anomaly, high Sr (>10 * chondrite) and Al₂O₃ concentrations (17–33%) that support plagioclase accumulation with the extreme case represented by the anorthosites. The REE patterns can be modelised using plagioclase, clinopyroxene and orthopyroxene REE signature, without any role played by accessory minerals. High MgO content points to olivine as a major cumulate phase. Anorthositic gabbros Sr and Nd isotopic initial ratios are typical of a depleted mantle source (Sr_i=0.70257–0.70278; _Nd=+5.9 to +7.8). This isotopic signature is identical to that of the 10-km wide 592 Ma old dyke complex composed of alkaline to peralkaline granites and tholeiitic gabbros and one single bimodal complex can be inferred. The source of the Tin Zebane basic rocks corresponds to the prevalent mantle (PREMA). The Tin Zebane complex was emplaced along the mega-shear zone bounding to the west the Archaean In Ouzzal metacraton. The model proposed suggests a linear lithospheric delamination along this rigid and cold terrane due to post-collisional transtensional movements. This allowed the asthenosphere to rise rapidly and to melt by adiabatic pressure release. Transtension along a rigid body allowed these mantle melts to reach the surface rapidly without any crustal contamination.     

As–(Ag) sulphide veins in the Spanish Central System: further evidence for a hydrothermal event of Permian age

The Spanish Central System (SCS) has been subjected to repeated deformation and fluid flow events which have produced both sulphide-bearing and barren vein systems. Although several hydrothermal episodes took place between 300 and 100 Ma, fluid circulation during the Permian was especially important, giving rise to a range of different types of deposits. This study presents a multidisciplinary approach leading to the characterisation of the chemistry and age of the hydrothermal fluids that produced the As–(Ag) mineralised stockwork of Mónica mine (Bustaviejo, Madrid). Fluid inclusion data indicate the presence of two different fluids. An initial ore stage (I) formed from a low- to moderate salinity (3–8 wt.% eq. NaCl) H₂O–NaCl–CO₂–CH₄ fluid, at minimum trapping temperature of 350±15 °C and 0.3 kbar. A second H₂O–NaCl fluid is found in three types of fluid inclusions: a high temperature and low salinity type (340±20 °C; 0.8–3.1 wt.% eq. NaCl) also associated to ore stage I, a moderate temperature and very low salinity type (160–255 °C; 0–1.5 wt.% eq. NaCl) represented in ore stage III, and a very low temperature and hypersaline type (60–70 °C; 30–35 wt.% NaCl), unrelated to the mineralising stages and clearly postdating the previous types. ⁴⁰Ar–³⁹Ar dating on muscovite from the early As–Fe stage (I) has provided an age of 286±4 Ma, synchronous with the late emplacement phases of La Cabrera plutonic massif (288±5 Ma) and with other Permian hydrothermal events like Sn–W skarns and W–(Sn) sulphide veins. δ¹⁸O of water in equilibrium with stage I quartz (5.3–7.7‰), δD of water in equilibrium with coexisting muscovite (−16.0‰ to −2.0‰), and sulphide δ³⁴S (1.5–3.6‰) values are compatible with waters that leached metamorphic rocks. The dominant mechanism of the As–(Ag) deposition was mixing and dilution processes between aqueous–carbonic and aqueous fluids for stage I (As–Fe), and nearly isobaric cooling processes for stages II (Zn–Cu–Sn) and III (Pb–Ag). The origin and hydrothermal evolution of As–(Ag) veins is comparable to other hydrothermal Permian events in the Spanish Central System.     

Gd-DTPA in the hydrosphere: Kinetics of transmetallation by ions of rare earth elements,Y and Cu

The kinetics of transmetallation of Gd³⁺ in diethylenetriaminpentaacetic acid (Gd-DTPA) by rare earth elements (except Yb), Y³⁺ and Cu²⁺ has been studied in test solutions ranging from pH 5 to 6.5 in order to understand the distribution and longevity of their chelates in the hydrosphere. Chelated and non-chelated species were separated by adsorption of the free ions by clay minerals before analysis by ICP-MS. This simple method allows determining the distribution of DTPA chelates at concentration levels as low as a few 10 pmol/l. The transmetallation constants at ionic strength of 0.01 mol/l and room temperature are commensurable with those derived from published formation constants of the corresponding DTPA complexes. It could be proved that DTPA chelates of rare earth elements, Y and Cu are stable at least over 6 months. The pattern of the second-order rate constants shows a strong tetrad effect, which is not displayed by the pattern of transmetallation constants. Based on these results, the rate of transmetallation of Gd-DTPA under natural conditions is derived. The resultant process yields 10% turn-over of initial Gd-DTPA within two months, if Cu²⁺ concentrations are below 1 nmol/l. At higher concentrations, the turn-over increases with elapsed time. Equilibrium among REE and Y is expected only after tens of years. This makes Gd-DTPA a powerful tracer in hydrological studies.     

Ar/Ar age and geochemistry of the post-collisional Miocene Yamadağ volcanics in the Arapkir area (Malatya Province), eastern Anatolia, Turkey

The Neogene Yamadağ volcanics occupy a vast area between Sivas and Malatya in eastern Anatolia, Turkey. These volcanic rocks are characterized by pyroclastics comprising agglomerates, tuffs and some small outcrops of basaltic–andesitic–dacitic rocks, overlain upward by basaltic and dacitic rocks, and finally by basaltic lava flows in the Arapkir area, northern Malatya Province. The basaltic lava flows in the Arapkir area yield a ⁴⁰Ar/³⁹Ar age of 15.8 ± 0.2 Ma, whereas the dacitic lava flows give ⁴⁰Ar/³⁹Ar ages ranging from 17.6 through 14.7 ± 0.1 to 12.2 ± 0.2 Ma, corresponding to the Middle Miocene. These volcanic rocks have subalkaline basaltic, basaltic andesitic; alkaline basaltic trachyandesitic and dacitic chemical compositions. Some special textures, such as spongy-cellular, sieve and embayed textures; oscillatory zoning and glass inclusions in plagioclase phenocrysts; ghost amphiboles and fresh biotite flakes are attributable to disequilibrium crystallization related to magma mixing between coeval magmas. The main solidification processes consist of fractional crystallization and magma mixing which were operative during the soldification of these volcanic rocks. The dacitic rocks are enriched in LILE, LREE and Th, U type HFSE relative to the basaltic rocks. The basaltic rocks also show some marked differences in terms of trace-element and REE geochemistry; namely, the alkaline basaltic trachyandesites have pronounced higher HFSE, MREE and HREE contents relative to the subalkaline basalts. Trace and REE geochemical data reveal the existence of three distinct magma sources – one subalkaline basaltic trachyandesitic, one alkaline basaltic and one dacitic – in the genesis of the Yamadağ volcanics in the Arapkir region. The subalkaline basaltic and alkaline basaltic trachyandesitic magmas were derived from an E-MORB type enriched mantle source with a relatively high- and low-degree partial melting, respectively. The magmatic melt of dacitic rocks seem to be derived from an OIB-type enriched lithospheric mantle with a low proportion of partial melting. The enriched lithospheric mantle source reflect the metasomatism induced by earlier subduction-derived fluids. All these coeval magmas were generated in a post-collisional extensional geodynamic setting in Eastern Anatolia, Turkey.     

Crustal architecture above the high-pressure belt of the Grenville Province in the Manicouagan area: new structural, petrologic and U–Pb age constraints

Recent U–Pb age determinations and P–T estimates allow us to characterize the different levels of a formerly thickened crust, and provide further constraints on the make up and tectono-thermal evolution of the Grenville Province in the Manicouagan area. An important tectonic element, the Manicouagan Imbricate zone (MIZ), consists of mainly 1.65, 1.48 and 1.17 Ga igneous rocks metamorphosed under 1400–1800 MPa and 800–900 °C at 1.05–1.03 Ga, during the Ottawan episode of the Grenvillian orogenic cycle, coevally with intrusion of gabbro dykes in shear zones. The MIZ has been interpreted as representing thermally weakened deep levels of thickened crust extruded towards the NW over a parautochthonous crustal-scale ramp. Mantle-derived melts are considered as in part responsible for the high metamorphic temperatures that were registered.New data show that mid-crustal levels structurally above the MIZ are represented by the Gabriel Complex of the Berthé terrane, that consists of migmatite with boudins of 1136±15 Ma gabbro and rafts of anatectic metapelite with an inherited monazite age at 1478±30 Ma. These rocks were metamorphosed at about the same time as the MIZ (metamorphic zircon in gabbro: 1046±2 Ma; single grains of monazite in anatectic metapelite: 1053±2 Ma) and under the same T range (800–900 °C) but at lower P conditions (1000–1100 MPa). They are mainly exposed in an antiformal culmination above a high-strain zone, which has tectonic lenses of high P–T rocks from the MIZ and is intruded by synmetamorphic gabbroic rocks. This zone is interpreted as part of the hangingwall of the MIZ during extrusion. A gap of 400 MPa in metamorphic pressures between the tectonic lenses and the country rocks, together with the broad similarity in metamorphic ages, are consistent with rapid tectonic transport of the high P–T rocks over a ramp prior to the incorporation of the mafic lenses in the hangingwall.Between the antiformal culmination of the Gabriel Complex and the MIZ 1.48 Ga old granulites of the Hart Jaune terrane are exposed. They are intruded by unmetamorphosed 1228±3 Ma gabbro sills and 1166±1 Ma anorthosite. Hart Jaune Terrane represents relatively high crustal levels that truncate the MIZ-Gabriel Complex contact and are preserved in a synformal structure.Farther south, the Gabriel Complex is overlain by the Banded Complex, a composite unit including 1403+32/−25 Ma granodiorite and 1238+16/−13−1202+40/−25 Ma granite. This unit has been metamorphosed under relatively low-P (800 MPa) granulite-facies conditions. Metamorphic U–Pb data, limited to zircon lower intercept ages (971±38 Ma and 996±27 Ma) and a titanite (990±5 Ma) age, are interpreted to postdate the metamorphic peak.The general configuration of units along the section is consistent with extrusion of the MIZ during shortening and, finally, normal displacement along discrete shear zones.     

Geochemistry and origin of lower crustal granulite facies rocks in the Serra do Caparaó region, Espirito Santo/Minas Gerais, Brazil

Rocks of the Serra do Caparaó region, on the border between the Brazilian states of Espirito Santo and Minas Gerais, comprise granulitic (charnockitic) sequences that have undergone Brasiliano-aged metamorphism (586 ± 2 Ma.). Thermobarometric results document pressures between 8.1 kb and 10.6 kb and temperatures up to 700 ± 50°C. Chemical analysis show a calc-alkaline (CAC) trend with granodioritic, tonalitic-trondhjemitic chemistry. K₂O/Rb data represent low- to mid-pressure charnockites corresponding to the undepleted granulite types. Discriminant analyses and diagrams indicate a source rock characteristic of sedimentary origin. REE patterns show slight to moderate fractionation and also slight negative as well as positive Eu anomalies. REE trends and the total amounts of REE of the acidic to basic rock series are similar to those of North American and Australian post-Archaean shales. The granulite facies rock series in the Serro do Caparaó region are interpreted as having originated from supracrustal rock series—i.e., graywackes, which represent sedimentary sequences derived from a Lower Proterozoic bimodal magmatic suite.     

Solubility of Pt and Pd sulfides and Au metal in aqueous bisulfide solutions

An experimental study of the solubility of Pt and Pd sulfides and Au metal in aqueous bisulfide solutions was conducted at temperatures from 200° to 350 °C and at saturated vapor pressure. A 500-mL Bridgemantype pressure vessel constructed of titanium, and equipped with a motor-driven magnetic stirrer was employed. The pH and the oxidation state were buffered by the coexistence of H₂S/HS^–/SO _inf4 ^sup2– . The pH at temperature was calculated to be in the range 5.91–9.43, and S was 0.3–2.2 m. Under the experimental conditions, the measured solubility of gold is about two to three orders of magnitude greater than that of either platinum and palladium, and the measured solubility of platinum is, in general, approximately equal to that of palladium, in molal units. The solubilities are found to be in the range: platinum 4–800 ppb, palladium 1–400 ppb, and gold 2–300 ppm. The solubility data can be modeled adequately using the following reactions: Au+H₂S+HH^–=Au(HS) ₂ ^– +1/2H₂ (K₁₄); PtS+HS^–+H⁺=Pt (HS) ₂ ⁰ (K₁₅); PdS+HS^–+H⁺=Pd (HS) ₂ ⁰ (K₁₆); PtS₂+H₂=Pt (HS) ₂ ⁰ (K₂₁).With equilibrium constants determined as follows (errors represent two standard deviations): Preliminary measurements of the solubilities of metallic Pt, Pd and Au as hydroxide complexes were also conducted using a second titanium pressure vessel, at temperatures of 200° to 350 °C and vapor saturation pressure, with pH and the oxidation state controlled or buffered by adding known amounts of NaOH and H₂ gas. The concentration of NaOH was in the range 0.01–1.3 m, and the partial pressure of H₂ at 200 °C was 62–275 bars, initially. Under the temperature and pressure conditions of these experiments, the solubility of platinum in 1 m NaOH solution is less than 100 ppb, that of palladium is less than 10 ppb and that of gold is less than 0.2 ppm; and in 0.01 m NaOH solutions, both Pt and Pd solubilities are less than 1 ppb. These data indicate that the contributions of hydroxide complexes to the total solubilities in the bisulfide runs, where the pH was in the range of 5.9–9.4, are negligible. The concentrations of both Pt and Pd as bisulfide complexes in the Salton Sea geothermal system predicted using the stability constants determined in this work agree very well with those values measured by McKibben et al. (1990). This calculation strongly suggests that the PGE are transported in moderately reducing, near neutral hydrothermal fluids as bisulfide complexes, as is gold. However, the much lower maximum solubility of the PGE relative to gold severely constrains models of re genesis, and may explain the relative rarity of hydrothermal PGE deposits compared to the relative abundance of hydrothermal Au deposits.     

Iron isotopes in acid mine waters and iron-rich solids from the Tinto–Odiel Basin (Iberian Pyrite Belt, Southwest Spain)

The isotopic composition of Fe was determined in water, Fe-oxides and sulfides from the Tinto and Odiel Basins (South West Spain). As a consequence of sulfide oxidation in mine tailings both rivers are acidic (1.45 < pH < 3.85) and display high concentrations of dissolved Fe (up to 420 mmol l^− 1) and sulphates (up to 1190 mmol l^− 1).The δ⁵⁶Fe of pyrite-rich samples from the Rio Tinto and from the Tharsis mine ranged from − 0.56 ± 0.08‰ to + 0.25 ± 0.1‰. δ⁵⁶Fe values for Fe-oxides precipitates that currently form in the riverbed varied from − 1.98 ± 0.10‰ to 1.57 ± 0.08‰. Comparatively narrower ranges of values (− 0.18 ± 0.08‰ and + 0.21 ± 0.14‰) were observed in their fossil analogues from the Pliocene–Pleistocene and in samples from the Gossan (the oxidized layer that formed through exposure to oxygen of the massive sulfide deposits) (− 0.36 ± 0.12‰ to 0.82 ± 0.07‰). In water, δ⁵⁶Fe values ranged from − 1.76 ± 0.10‰ to + 0.43 ± 0.05‰.At the source of the Tinto River, fractionation between aqueous Fe(III) and pyrite from the tailings was less than would be expected from a simple pyrite oxidation process. Similarly, the isotopic composition of Gossan oxides and that of pyrite was different from what would be expected from pyrite oxidation. In rivers, the precipitation of Fe-oxides (mainly jarosite and schwertmannite and lesser amounts of goethite) from water containing mainly (more than 99%) Fe(III) with concentrations up to 372 mmol l^− 1 causes variable fractionation between the solid and the aqueous phase (− 0.98‰ < Δ⁵⁶Fe_{solid–water} < 2.25‰). The significant magnitude of the positive fractionation factor observed in several Fe(III) dominated water may be related to the precipitation of Fe(III) sulphates containing phases.