The November 2002 eruption of Piton de la Fournaise,Réunion: tracking the pre-eruptive thermal evolution of magma using melt inclusions

The November 2002 eruption of Piton de la Fournaise in the Indian Ocean was typical of the activity of the volcano from 1999 to 2006 in terms of duration and volume of magma ejected. The first magma erupted was a basaltic liquid with a small proportion of olivine phenocrysts (Fo₈₁) that contain small numbers of melt inclusions. In subsequent flows, olivine crystals were more abundant and richer in Mg (Fo_83–84). These crystals contain numerous melt and fluid inclusions, healed fractures, and dislocation features such as kink bands. The major element composition of melt inclusions in this later olivine (Fo_83–84) is out of equilibrium with that of its host as a result of extensive post-entrapment crystallization and Fe²⁺ loss by diffusion during cooling. Melt inclusions in Fo₈₁ olivine are also chemically out of equilibrium with their hosts but to a lesser degree. Using olivine–melt geothermometry, we determined that melt inclusions in Fo₈₁ olivine were trapped at lower temperature (1,182 ± 1°C) than inclusions in Fo_83–84 olivine (1,199–1,227°C). This methodology was also used to estimate eruption temperatures. The November 2002 melt inclusion compositions suggest that they were at temperatures between 1,070°C and 1,133°C immediately before eruption and quenching. This relatively wide temperature range may reflect the fact that most of the melt inclusions were from olivine in lava samples and therefore likely underwent minor but variable amounts of post-eruptive crystallization and Fe²⁺ loss by diffusion due to their relatively slow cooling on the surface. In contrast, melt inclusions in tephra samples from past major eruptions yielded a narrower range of higher eruption temperatures (1,163–1,181°C). The melt inclusion data presented here and in earlier publications are consistent with a model of magma recharge from depth during major eruptions, followed by storage, cooling, and crystallization at shallow levels prior to expulsion during events similar in magnitude to the relatively small November 2002 eruption.     

The solubility of molybdenum dioxide and trioxide in HCl-bearing water vapour at 350 °C and pressures up to 160 bars

The solubility and speciation of the assemblage MoO₂-MoO₃ in water vapour were investigated in experiments conducted at 350 °C, P_total from 59 to 160 bar and fHCl from 0 to 3.4 bar (0-2.0 mol%). Measured solubility at these conditions ranges from 22 to 2500 ppm (∑fMo from 4.4 × 10⁻⁴ to 6.5 × 10⁻² bar). The concentration of Mo in the vapour at fHCl below 0.1 bar is similar to that in pure water vapour, but increases by two orders of magnitude at fHCl above 0.1 bar. The fugacity of gaseous Mo species is independent of chloride concentration at fHCl below 0.1 bar, but increases with increasing fHCl above this pressure. The dominant Mo species at fHCl below 0.1 bar is interpreted to be the same as it is in pure water vapour, and to form as a result of the reaction

(A1)     

The solubility and speciation of molybdenum in water vapour at elevated temperatures and pressures: Implications for ore genesis

The solubility of molybdenum trioxide in liquid-undersaturated water vapour has been investigated experimentally at 300, 320, and 360 °C and 39-154 bars. Results of these experiments show that the solubility of MoO₃ in water vapour is between 1 and 29 ppm, which is 19-20 orders of magnitude higher than the vapour pressure of MoO₃(g). Molybdenum solubility increases exponentially with f_H2O, suggesting the formation of a gaseous hydrated complex of the type MoO₃·nH₂O by the reaction:

(A.1)     

The role of collisional tectonics in the metallogeny of the Central Andean tin belt

The Inner Arc of the Central Andes, broadly corresponding to the Eastern Cordillera, is the location of a rich Tertiary and Triassic Sn–W–(Ag-base metal) metallogenic province, commonly referred to as the Bolivian tin belt. We propose that the Tertiary metallogeny, which generated most of the tin ores, was a direct consequence of discrete “collisions” between the South American plate and the Nazca slab and sub-slab mantle, during the ongoing Andean orogeny. Evidence supporting this proposal include: (1) the coincidence of the tin province and the Inner Arc in a marked “hump” in the Andean orogen, which may represent tectonic indentation; (2) the symmetry of the tin province with respect to the Bolivian orocline, the axis of which corresponds to the direction of highest compression; (3) the relative symmetry of the magmatism and tin mineralization with respect to this axis; (4) the concurrent timing of mineralization and compressional pulses; (5) the similar host rock geochemistry and ore lead isotope data, testifying to a common crustal reservoir; and (6) the striking similarity of the igneous suites, associated with the ore deposits to those from “typical” collisional orogens. A number of studies have called upon a persistent tin anomaly to explain the metallogeny of the region. We propose, instead, that the latter is better explained by periodic compressional interaction between the Farallon/Nazca oceanic plate and the South American continent. This led to the generation of peraluminous magmas, which during fractional crystallization exsolved the fluids responsible for the voluminous Sn–W mineralization.     

Real-time measurement of volcanic SO2 emissions: validation of a new UV correlation spectrometer (FLYSPEC)

A miniaturized, lightweight and low-cost UV correlation spectrometer, the FLYSPEC, has been developed as an alternative for the COSPEC, which has long been the mainstay for monitoring volcanic sulfur dioxide fluxes. Field experiments have been conducted with the FLYSPEC at diverse volcanic systems, including Masaya (Nicaragua), Poás (Costa Rica), Stromboli, Etna and Vulcano (Italy), Villarica (Chile) and Kilauea (USA). We present here those validation measurements that were made simultaneously with COSPEC at Kilauea between March 2002 and February 2003. These experiments, with source emission rates that ranged from 95 to 1,560 t d⁻¹, showed statistically identical results from both instruments. SO₂ path-concentrations ranged from 0 to >1,000 ppm-m with average correlation coefficients greater than r ²=0.946. The small size and low cost create the opportunity for FLYSPEC to be used in novel deployment modes that have the potential to revolutionize the manner in which volcanic and industrial monitoring is performed.     

Partitioning of boron among melt, brine and vapor in the system haplogranite–H2O–NaCl at 800 °C and 100 MPa

Fluid-saturated experiments were conducted to investigate the partitioning of boron among haplogranitic melt, aqueous vapor and brine at 800 °C and 100 MPa. Experiments were carried out in cold-seal pressure vessels for 1 to 21 days, and utilized powdered synthetic subaluminous haplogranite glass doped with 1000 ppm B (crystalline H₃BO₃) and variable amounts of NaCl and H₂O at a fluid/haplogranite mass RATIO=1:1. Run-product glasses were analyzed for boron concentration by secondary ion mass spectrometry (SIMS) and for major elements and chlorine by electron microprobe. The composition of the coexisting fluid was calculated by mass balance. Boron partition coefficients between aqueous vapor and hydrous granitic melt range from 3.1 to 6.3, and demonstrate a clear preference of boron for the vapor over the hydrous melt. Partition coefficients between brine and hydrous granitic melt vary from 0.45 to 1.1, suggesting that boron has no preference for the brine or the melt. The bulk fluid–melt partition coefficients for low-salinity and high-salinity experiments are D_B^(vapor/melt)=4.6±1.3 and D_B^(brine/melt)=0.91±0.49, respectively. The corresponding vapor–brine partition coefficient is 5.0±3.1, demonstrating that boron partitions preferentially into the vapor over the brine at the conditions of this study. The preferential incorporation of boron in the aqueous vapor is controlled by borate speciation and solution mechanism. The dominant borate species in aqueous fluids, H₃BO₃^o, is highly soluble in aqueous vapor (X_B2O3=0.187); however, B₂O₃ is immiscible in NaCl liquid. Consequently, concentrations of boron in aqueous vapor are significantly higher than in the coexisting brine. Furthermore, Na–B complexing in the melt at high chlorine fluid contents stabilizes boron in the melt thereby contributing to the non-preferential partitioning of boron between brine and melt. The commonly observed association of tourmalinization (boron metasomatism), brecciation and ore deposition in nature is consistent with the preferential partitioning of boron into aqueous vapor of magmatic-hydrothermal systems predicted by this study.     

Gravity changes and passive SO2 degassing at the Masaya caldera complex, Nicaragua

An understanding of the mechanisms responsible for persistent volcanism can be acquired through the integration of geophysical and geochemical data sets. By interpreting data on micro-gravity, ground deformation and SO₂ flux collected at Masaya Volcano since 1993, it is now clear that the characteristically cyclical nature of the activity is not driven by intrusion of additional magma into the system. Rather, it may be due in large part to the blocking and accumulation of gas by restrictions in the volcano substructure. The history of crater collapse and formation of caverns beneath the crater floor would greatly facilitate the trapping and storage of gas in a zone immediately beneath San Pedro and the other craters. Another mechanism that may explain the observed gravity and gas flux variations is the convective overturn of shallow, pre-existing, degassed, cooled, dense magma that is replaced periodically by lower density, hot, gas-rich magma from depth. Buoyant gas-rich magma rises from depth and is emplaced near the surface, resulting in the formation and fluctuation of a low-density gas-rich layer centred beneath Nindirí and Santiago craters. As this magma vigorously degasses, it must cool, increase in density and eventually sink. Five stages of activity have been identified at Masaya since 1853 and the most recent data suggest that the system may have been entering another period of reduced degassing in 2000. This type of analysis has important implications for hazard mitigation because periods of intense degassing are associated with poor agricultural yields and reduced quality of life. A better understanding of persistent cyclically active volcanoes will allow for more effective planning of urban development and agricultural land use.     

Genomic resources for the spotted ragged-tooth shark Carcharias taurus

Genomic data can be a useful tool in the management and conservation of biodiversity. Here, we report the development of genomic resources for the spotted ragged-tooth shark Carcharias taurus using genome-wide DNA data from Illumina next-generation sequencing. We explored two commonly used genetic marker types: microsatellites and mitochondrial DNA. A total of 4 394 putative microsatellites were identified, of which 10 were tested on 24 individuals and found to have ideal properties for population genetic analyses. Additionally, we reconstructed the first complete mitochondrial genome of a South African spotted ragged-tooth shark, and highlight the most informative gene regions to facilitate future primer design. The data reported here may serve as a resource for future studies and can ultimately be applied in the sustainable conservation and fisheries management of this apex predator.     

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.