A spectrophotometric study of Nd(III), Sm(III) and Er(III) complexation in sulfate-bearing solutions at elevated temperatures

The speciation of Nd(III), Sm(III), and Er(III) in sulfate-bearing solutions has been determined spectrophotometrically at temperatures from 25 to 250 °C and a pressure of 100 bars. The data obtained earlier on the speciation of Nd in sulfate-bearing solutions (Migdisov et al., 2006) have been re-evaluated and corrected using a more appropriate activity model and are compared with the corresponding data for Sm(III) and Er(III) and new data for Nd(III). Based on this comparison, the dominant species in the solution are interpreted to be and , with the latter complex increasing in importance at higher temperature. Equilibrium constants were calculated for the following reactions:

     

Phylogeography of the pelagic fish Seriola lalandi at different scales: confirmation of inter-ocean population structure and evaluation of southern African genetic diversity

The study investigated the global and regional phylogeography of the yellowtail kingfish Seriola lalandi by examining genetic diversity and population genetic structure of this species at inter-and intra-ocean level and on a regional scale. DNA fragments of two mitochondrial genes, cytochrome b (Cytb) and cytochrome c oxidase subunit I (COI) and one nuclear gene, recombination activating gene 1 (RAG1), were sequenced to investigate the global-scale phylogeography of this species. The population genetic structure within the South Pacific, as well as along the South African coastline, was examined further using six microsatellite markers. Three distinct clades were identified for S. lalandi, which correspond with previously described subspecies of the North-East Pacific, North-West Pacific and the Southern Hemisphere. Within the latter, additional divergence was observed between the South Pacific and the South-East Atlantic regions. Divergence estimates were indicative of a Pacific origin for S. lalandi populations, because of Pleistocene vicariant events. Microsatellite analyses revealed overall significant genetic differentiation between South African and South Pacific samples. This corroborates recent findings on the global phylogeography of the species. No population differentiation was observed within South Africa, indicating high levels of gene flow.     

A fluid inclusion study of the porphyry-greisen,tungsten-molybdenum deposit at Mount Pleasant,New Brunswick,Canada

Homogenization temperatures and salinity data are presented for fluid inclusions from hydrothermal gangue minerals (quartz and fluorite) associated with porphyry wolframite-molybdenite-arsenopyrite-sphaleritebismuth-chalcopyrite-cassiterite mineralization within the Fire Tower ore zone, Mt Pleasant, New Brunswick. The data indicate that ore mineral precipitation occurred within a temperature range of 260° to 490°C from moderate to high salinity (10–42 wt% NaCl equivalent) aqueous fluids. Two stages of hydrothermal activity characterized by high (>30 wt% NaCl equivalent) salinity fluids are recognized; one which occurred at relatively high temperature (350°–490°C); and one which took place at lower temperature (180°–250°C). The high salinity, high temperature stage is interpreted to be the result of resurgent boiling. Dilution of these early fluids by convecting meteoric water resulted in low to moderate salinity fluids, which dominate the inclusion population. The low temperature, high salinity fluid inclusions are interpreted to represent late residual fluids derived from boiling which occurred as a result of a change in the pressure regime from dominantly lithostatic to hydrostatic conditions.     

An experimental study of the stability of copper chloride complexes in water vapor at elevated temperatures and pressures

The solubility of copper chloride in liquid-undersaturated HCl-bearing water vapor was investigated experimentally at temperatures of 280 to 320°C and pressures up to 103 bars. Results of these experiments show that the solubility of copper in the vapor phase is significant and increases with increasing f_H2O, but is retrograde with respect to temperature. This solubility is attributed to the formation of hydrated copper-chloride gas species, interpreted to have a copper-chlorine ratio of 1:1 (e.g., CuCl, Cu₃Cl₃, etc.) and a hydration number varying from 7.6 at 320°C, to 6.0 at 300°C, and 6.1 at 280°C. Complex formation is proposed to have occurred through the reaction:

A1     

Pit crater structure and processes governing persistent activity at Masaya Volcano, Nicaragua

 Persistent activity at Masaya Volcano, Nicaragua, is characterised by cycles of intense degassing, lava lake development and pit crater formation. It provides a useful site to study the processes which govern such activity, because of its easy accessibility and relatively short cycles (years to decades). An understanding of the present activity is important because Masaya is visited by large numbers of tourists, is located close to major cities and has produced voluminous lavas, plinian eruptions and ignimbrites in the recent past. We provide structural and geophysical data that characterise the "normal" present state of activity. These indicate that the ongoing degassing phase (1993 to present) was not caused by fresh magma intrusion. It was associated with shallow density changes within the active Santiago pit crater. The activity appears to be associated predominantly with shallow changes in the pit crater structure. More hazardous activity will occur only if there are significant departures from the present gravity, deformation and seismic signatures. Received: 16 May 1997 / Accepted: 29 October 1997     

An experimental study of the solubility and speciation of the Rare Earth Elements (III) in fluoride- and chloride-bearing aqueous solutions at temperatures up to 300 °C

The solubility of REE(III) fluoride solids was determined in fluoride- and chloride-bearing solutions at 150, 200 and 250 °C and saturated water vapor pressure. These experimental data, together with experimental data from previously published studies, were used to evaluate formation constants for chloride- and fluoride-bearing aqueous species of the entire REE(III) group at temperatures up to 300 °C. The data show that the stability of these species differs significantly from that predicted theoretically. For example, contrary to the theoretical predictions, LREEF²⁺ species are more stable than HREEF²⁺ species at elevated temperature. The behavior of the chloride-bearing species is similar. Parameters for the Helgeson–Kirkham–Flowers (HKF) equation of state were determined for REEF²⁺, REECl²⁺ and REECl₂⁺ complexes using these experimental data and permit calculation of formation constants of these species at conditions not investigated experimentally. These data now permit the mobility of all REE in fluoride- and chloride-bearing hydrothermal systems to be reliably evaluated at intermediate temperatures and pressures.     

Factors controlling copper solubility and chalcopyrite deposition in the Sungun porphyry copper deposit, Iran

The Sungun porphyry copper deposit is hosted in a Diorite/granodioritic to quartz-monzonitic stock that intruded Eocene volcanosedimentary and Cretaceous carbonate rocks. Copper mineralization is associated mainly with potassic alteration and to a lesser extent with sericitic alteration. Based on previously published fluid inclusion and isotopic data by Hezarkhani and Williams-Jones most of the copper is interpreted to have deposited during the waning stages of orthomagmatic hydrothermal activity at temperatures of 400 to 300 °C. These data also indicate that the hydrothermal system involved meteoric waters, and boiled extensively. In this work, thermodynamic data are used to delineate the stability fields of alteration and ore assemblages as a function of fS₂, fO₂ and pH. The solubility of chalcopyrite was evaluated in this range of conditions using recently published experimental data. During early potassic alteration (>450 °C), Copper solubility is calculated to have been >50 000 ppm, whereas the copper content of the initial fluid responsible for ore deposition is estimated, from fluid inclusion data, to have been 1200–3800 ppm. This indicates that initially the fluid was highly undersaturated with respect to chalcopyrite, which agrees with the observation that veins formed at T > 400 °C contain molybdenite but rarely chalcopyrite. Copper solubility drops rapidly with decreasing temperature, and at 400 °C is approximately 1000 ppm, within the range estimated from fluid inclusion data, whereas at 350 °C it is only 25 ppm. These calculations are consistent with observations that the bulk of the chalcopyrite deposited at Sungun is hosted by veins formed at temperatures of 360 ± 60 °C. Other factors that, in principle, may reduce chalcopyrite solubility are increases in pH, and decreases in fO₂ and aCl⁻. Our analysis shows, however, that most of the change in pH occurred at high temperature when chalcopyrite was grossly undersaturated in the fluid, and that the direction of change in fO₂ increased chalcopyrite solubility. We propose that the Sungun deposit formed mainly in response to the sharp temperature decrease that accompanied boiling, and partly as a result of the additional heat loss and decrease in aCl⁻, which occurred as a result of mixing of acidic Cu-bearing magmatic waters with cooler meteoric waters of lower salinity. Received: 8 July 1998 / Accepted: 8 April 1999     

A Nd- and O-isotope study of the REE-rich peralkaline Strange Lake granite: implications for Mesoproterozoic A-type magmatism in the Core Zone (NE-Canada)

It is well established that A-type granites enriched in high field strength elements, such as Zr, Nb and the REE, form in anorogenic tectonic settings. The sources of these elements and the processes controlling their unusual enrichment, however, are still debated. They are addressed here using neodymium and oxygen isotope analyses of samples from the 1.24 Ga Strange Lake pluton in the Paleoproterozoic Core Zone of Québec-Labrador, an A-type granitic body characterized by hyper-enrichment in the REE, Zr, and Nb. Age-corrected εNd values for bulk rock samples and sodic amphiboles (mainly arfvedsonite) from the pluton range from ?0.6 to ?5.7, and ?0.3 to ?5.3, respectively. The εNd values for the Napeu Kainiut quartz monzonite, which hosts the pluton, range from ?4.8 to ?8.1. The ¹⁴⁷Sm/¹⁴⁴Nd ratios of the suite and the host quartz monzonite range from 0.0967 to 0.1659, large variations that can be explained by in situ fractionation of early LREE-minerals (Strange Lake), and late hydrothermal HREE remobilization. Oxygen isotope analyses of quartz of both Strange Lake and the host yielded δ¹⁸O values between +8.2 and +9.1, which are considerably higher than the mantle value of 5.7 ± 0.2‰. Bulk rock oxygen isotope analyses of biotite-gneisses in the vicinity of the Strange Lake pluton yielded δ¹⁸O values of 6.3, 8.6 and 9.6‰. The negative εNd values and positive δ¹⁸O values of the Strange Lake and Napeu Kainiut samples indicate that both magmas experienced considerable crustal contamination. The extent of this contamination was estimated, assuming that the contaminants were sedimentary-derived rocks from the underlying Archean Mistinibi (para-) gneiss complex, which is characterized by low εNd and high δ¹⁸O values. Mixing of 5–15% of a gneiss, having an εNd value of ?15 and a δ¹⁸O value of +11, with a moderately enriched mantle source (εNd = +0.9, δ¹⁸O = +6.3) would produce values similar to those obtained for the Strange Lake granites. Based on analogies between the Nain Plutonic Suite and the Gardar alkaline igneous province (SW-Greenland), we conclude that the Strange Lake pluton and associated REE-mineralized anorogenic bodies formed from a combination of subduction-induced fertilization of the sublithospheric mantle, crustal extension and in situ magma evolution.     

Vapour transport of rare earth elements (REE) in volcanic gas: Evidence from encrustations at Oldoinyo Lengai

Fumarolic encrustations and natrocarbonatite lava from the active crater of Oldoinyo Lengai volcano, Tanzania, were sampled and analysed. Two types of encrustation were distinguished on the basis of their REE content, enriched (~ 2800–5600 × [REE_chondrite]) and depleted (~ 100–200 × [REE_chondrite]) relative to natrocarbonatite (1700–1900 × [REE_chondrite]. REE-enriched encrustations line the walls of actively degassing fumaroles, whereas REE-depleted encrustations occur mainly along cracks in and as crusts on cooling natrocarbonatite lava flows; one of the low REE encrustation samples was a stalactite from the wall of a possible fumarole. The encrustations are interpreted to have different origins, the former precipitating from volcanic gas and the latter from meteoric/ground water converted to steam by the heat of the overlying lava flow(s). REE-profiles of encrustations and natrocarbonatite are parallel, suggesting that there was no preferential mobilization of specific REE by either volcanic vapour or meteoric water vapour. The elevated REE-content of the first group of encrustations suggests that direct REE-transport from natrocarbonatite to volcanic vapour is possible. The REE trends observed in samples precipitating directly from the volcanic vapour cannot be explained by dry volatility based on the available data as there is no evidence in the encrustation compositions of the greatly enhanced volatility predicted for Yb and Eu. The observed extreme REE-fractionation with steep La/Sm slopes parallel to those of the natrocarbonatite reflects solvation and complexation reactions in the vapour phase that did not discriminate amongst the different REE or similar transport of REE in both the natrocarbonatite magma and its exsolving vapour. The low concentrations of REE in the encrustations produced by meteoric vapour suggest that the temperature was too low or that this vapour did not contain the ligands necessary to permit significant mobilization of the REE.