Co-sequestration of SO2 with supercritical CO2 in carbonates: An experimental study of capillary trapping,relative permeability,and capillary pressure

In this study we performed three categories of steady- and unsteady-state core-flooding experiments to investigate capillary trapping, relative permeability, and capillary pressure, in a scCO₂ + SO₂/brine/limestone system at elevated temperature and pressure conditions, i.e., 60 °C and 19.16 MPa. We used a Madison limestone core sample acquired from the Rock Springs Uplift in southwest Wyoming. We carried out two sets of steady-state drainage-imbibition relative permeability experiments with different initial brine saturations to study hysteresis. We found that the final scCO₂ + SO₂ drainage relative permeability was very low, i.e., 0.04. We also observed a rapid reduction in the scCO₂-rich phase imbibition relative permeability curve, which resulted in a high residual trapping. The results showed that between 62.8% and more than 76% of the initial scCO₂ + SO₂ at the end of drainage was trapped by capillary trapping mechanism (trapping efficiency). We found that at higher initial brine saturations, the trapping efficiency was higher. The maximum initial and residual scCO₂-rich phase saturations at the end of primary drainage and imbibition were 0.525 and 0.329, respectively. Each drainage-imbibition cycle was followed by a dissolution process to re-establish S_w = 1. The dissolution brine relative permeabilities for both cycles were also obtained. We characterized the scCO₂ + SO₂/brine capillary pressure hysteresis behavior through unsteady-state primary drainage, imbibition, and secondary drainage experiments. We observed negative imbibition capillary pressure curve indicative of possible wettability alteration throughout the experiments due to contact with scCO₂ + SO₂/brine fluid system. The trapping results were compared to those reported in literature for other carbonate core samples. We noticed slightly more residual trapping in our sample, which might be attributed to heterogeneity, different viscosity ratio, and pore-space topologies. The impact of dynamic effects, i.e., high brine flow rate imbibition tests, on trapping of the scCO₂-rich phase was also explored. We performed two imbibition experiments with relatively high brine flow rates. The residual scCO₂ saturation dropped to 0.291 and 0.262 at the end of the first and second imbibition tests, i.e., 11.5% and 20.4%, respectively, compared to 0.329 under capillary-dominated regime.     

UV camera measurements of fumarole field degassing (La Fossa crater,Vulcano Island)

The UV camera is becoming an important new tool in the armory of volcano geochemists to derive high time resolution SO₂ flux measurements. Furthermore, the high camera spatial resolution is particularly useful for exploring multiple-source SO₂ gas emissions, for instance the composite fumarolic systems topping most quiescent volcanoes. Here, we report on the first SO₂ flux measurements from individual fumaroles of the fumarolic field of La Fossa crater (Vulcano Island, Aeolian Island), which we performed using a UV camera in two field campaigns: in November 12, 2009 and February 4, 2010. We derived ~ 0.5 Hz SO₂ flux time-series finding fluxes from individual fumaroles, ranging from 2 to 8.7 t d^?1, with a total emission from the entire system of ~ 20 t d^?1 and ~ 13 t d^?1, in November 2009 and February 2010 respectively. These data were augmented with molar H₂S/SO₂, CO₂/SO₂ and H₂O/SO₂ ratios, measured using a portable MultiGAS analyzer, for the individual fumaroles. Using the SO₂ flux data in tandem with the molar ratios, we calculated the flux of volcanic species from individual fumaroles, and the crater as a whole: CO₂ (684 t d^?1 and 293 t d^?1), H₂S (8 t d^?1 and 7.5 t d^?1) and H₂O (580 t d^?1 and 225 t d^?1).     

A reassessment of current volcanic emissions from the Central American arc with specific examples from Nicaragua

The Central American volcanic arc supplies a significant proportion of the persistent annual global sulphur dioxide emissions from volcanoes. In November/December 2003, we completed a survey of the arc section from Mombacho to San Cristóbal in Nicaragua recording individual mean fluxes of 800, 530 and 220 Mg day^− 1 in the plumes from San Cristóbal, Telica and Masaya, respectively. An assessment of fluxes published since 1997 along the entire Central America arc yields a mean total arc flux of SO₂ of 4360 Mg day^− 1 or 8–16% of the annual estimated global volcanic SO₂ flux to the troposphere. New field data shows that Masaya volcano continues to show stable HCl/SO₂ and HF/SO₂ ratios, suggesting a sustained flux of these components of ∼ 220 and 30 Mg day^− 1, respectively (1997 to 2004). Masaya's plume composition also appears to have been stable, between 2001 and 2003, with respect to all the particulate species measured, with significant fluxes of SO₄²⁻ (4 Mg day^− 1), Na⁺ (0.9–1.3 Mg day^− 1) and K⁺ (0.7 Mg day^− 1). Extrapolating the Masaya plume species ratios to the entire Central American arc gives mean HCl and HF fluxes of 1300 and 170 Mg day^− 1 and a particulate sulphate flux of 40 Mg day^− 1 for 1997 to 2004, although without further understanding of the degassing processes and sources at depth of these different volatiles, these arc-scale estimates should be treated with caution. Combining our arc scale mean SO₂ flux with published measurements of volcanic gas compositions with respect to CO₂ and H₂O allows us to estimate mean CO₂ fluxes of 4400–9600 Mg day^− 1 and H₂O fluxes of 70,000–78,000 Mg day^− 1 for the arc. Preliminary comparisons of these estimates of outgassing rates with published volatile input fluxes into the Central American subduction zone, suggest that Cl is more efficiently recycled through the subduction zone than CO₂. The results for H₂O are inconclusive.     

Deep pooling of low degree melts and volatile fluxes at the 85°E segment of the Gakkel Ridge: Evidence from olivine-hosted melt inclusions and glasses

We present new analyses of volatile, major, and trace elements for a suite of glasses and melt inclusions from the 85°E segment of the ultra-slow spreading Gakkel Ridge. Samples from this segment include limu o pele and glass shards, proposed to result from CO₂-driven explosive activity. The major element and volatile compositions of the melt inclusions are more variable and consistently more primitive than the glass data. CO₂ contents in the melt inclusions extend to higher values (167–1596 ppm) than in the co-existing glasses (187–227 ppm), indicating that the melt inclusions were trapped at greater depths. These melt inclusions record the highest CO₂ melt concentrations observed for a ridge environment. Based on a vapor saturation model, we estimate that the melt inclusions were trapped between seafloor depths (～ 4 km) and ～ 9 km below the seafloor. However, the glasses are all in equilibrium with their eruption depths, which is inconsistent with the rapid magma ascent rates expected for explosive activity. Melting conditions inferred from thermobarometry suggest relatively deep (25–40 km) and cold (1240°–1325 °C) melting conditions, consistent with a thermal structure calculated for the Gakkel Ridge. The water contents and trace element compositions of the melt inclusions and glasses are remarkably homogeneous; this is an unexpected result for ultra-slow spreading ridges, where magma mixing is generally thought to be less efficient based on the assumption that steady-state crustal magma chambers are absent in these environments. All melts can be described by a single liquid line of descent originating from a pooled melt composition that is consistent with the aggregate melt calculated from a geodynamic model for the Gakkel Ridge. These data suggest a model in which deep, low degree melts are efficiently pooled in the upper mantle (9–20 km depth), after which crystallization commences and continues during ascent and eruption. Based on our melting model and the assumption that CO₂ is perfectly incompatible, we show that the highest CO₂ concentrations of the melt inclusions (～ 1600 ppm) are consistent with the calculated CO₂ concentrations of primary undegassed melts. The highest measured CO₂/Nb ratio (443) of Gakkel Ridge melt inclusions predicts a mantle CO₂ content of 134 ppm and would result in a global ridge flux of 2.0 × 10¹² mol CO₂/yr.     

Multiphysics modeling of CO2 sequestration in a faulted saline formation in Italy

The present work describes the results of a modeling study addressing the geological sequestration of carbon dioxide (CO₂) in an offshore multi-compartment reservoir located in Italy. The study is part of a large scale project aimed at implementing carbon capture and storage (CCS) technology in a power plant in Italy within the framework of the European Energy Programme for Recovery (EEPR). The processes modeled include multiphase flow and geomechanical effects occurring in the storage formation and the sealing layers, along with near wellbore effects, fault/thrust reactivation and land surface stability, for a CO₂ injection rate of 1 × 10⁶ ton/a. Based on an accurate reproduction of the three-dimensional geological setting of the selected structure, two scenarios are discussed depending on a different distribution of the petrophysical properties of the formation used for injection, namely porosity and permeability. The numerical results help clarify the importance of: (i) facies models at the reservoir scale, properly conditioned on wellbore logs, in assessing the CO₂ storage capacity; (ii) coupled wellbore-reservoir flow in allocating injection fluxes among permeable levels; and (iii) geomechanical processes, especially shear failure, in constraining the sustainable pressure buildup of a faulted reservoir.     

Volatile and trace elements in basaltic glasses from Samoa: Implications for water distribution in the mantle

We report volatile (H₂O, CO₂, F, S, Cl) and trace element data for submarine alkalic basalt glasses from the three youngest Samoan volcanoes, Ta'u, Malumalu and Vailulu'u. Most samples are visibly sulfide saturated, so have likely lost some S during fractionation. Cl / K ratios (0.04–0.15) extend to higher values than pristine MORBs, but are suspected to be partly due to source differences since Cl / K roughly varies as a function of ⁸⁷Sr / ⁸⁶Sr. There are no resolvable differences in the relative enrichment of F among sources, and compatibility of F during mantle melting is established to be nearly identical to Nd. Shallow degassing has affected CO₂ in all samples, and H₂O only in the most shallowly erupted samples from Vailulu'u. Absolute water contents are high for Samoa (0.63–1.50 wt.%), but relative enrichment of water compared to equally incompatible trace elements (Ce, La) is low and falls entirely below normal MORB values. H₂O / Ce (58–157) and H₂O / La (120–350) correlate inversely with ⁸⁷Sr / ⁸⁶Sr compositions (0.7045–0.7089). This leads us to believe that, because of very fast diffusion of hydrogen in mantle minerals, recycled lithospheric material with high initial water and trace element content will lose water to the drier ambient mantle during storage within the inner Earth. The net result is the counter-intuitive appearance of greater dehydration with greater mantle enrichment. We expect that subducted slabs will experience a two-stage dehydration history, first within subduction zones and then in the ambient mantle during long-term convective mixing.     

Exact solutions to radially symmetric two-phase flow for an arbitrary diffusivity

Over the past decade there have been a variety of exact solutions developed for one-dimensional two-phase flow, however when higher dimensions are considered there is a distinct scarcity of solutions. In this paper we consider the problem of radially symmetric two-phase flow, into an infinite medium of uniform initial saturation, subject to a constant flux V from a line source at the origin. We show that in the absence of gravity and when the two-phase diffusivity D is related to the fraction flow function f by βD = V df/dθ, where θ is the water content and β is a constant of proportionality, a new class of exact solutions can be found. In particular, when β = 2, we show that the solution is given by a simple quadrature for arbitrary D, and is fully integrable for specific functional forms of D. It has been shown by Weeks et al. [Weeks SW, Sander GC, Parlange J-Y. n-Dimensional first integral and similarity solutions for two-phase flow. ANZIAM J 2003;44:365–80] that when D obeys the above relation, a saturated zone does not grow around the line of injection, consequently we find for β = 1, the flow equation maps to one-dimensional single-phase flow under a saturated boundary condition. Consequently solutions developed for one-dimensional single-phase flow (exact or approximate) apply to radially symmetric two-phase flow. Solutions for β = 1 or 2 can be derived for either a wetting fluid displacing a non-wetting fluid, or a non-wetting fluid displacing a wetting fluid, however for arbitrary β numerical methods are required.     

Balancing the global oceanic neodymium budget: Evaluating the role of groundwater

The distinctly different, ε_Nd(0) values of the Atlantic, Indian, and Pacific Oceans requires that the residence time of Nd in the ocean (i.e., τ_Nd) be on the order of, or less than, the ocean mixing time of ∼ 500–1500 yr. However, estimates of τ_Nd, based on river influxes, range from 4000 to 15,000 yr, thus exceeding the ocean mixing time. In order to reconcile the oceanic Nd budget and lower the residence time by roughly a factor of 10, an additional, as yet unidentified, and hence “missing Nd flux” to the ocean is necessary. Dissolution of materials deposited on continental margins has previously been proposed as a source of the missing flux. In this contribution, submarine groundwater discharge (SGD) is examined as a possible source of the missing Nd flux. Neodymium concentrations (n = 730) and ε_Nd(0) values (n = 58) for groundwaters were obtained from the literature in order to establish representative groundwater values. Mean groundwater Nd concentrations and ε_Nd(0) values were used along with recent estimates of the terrestrial (freshwater) component of SGD (6% of river discharge on a global basis) to test whether groundwater discharge to the coastal oceans could account for the missing flux. Employing mean Nd concentrations of the compiled data base (i.e., 31.8 nmol/kg for all 730 analyses and 11.3 nmol/kg for 141 groundwater samples from a coastal aquifer), the global, terrestrial-derived SGD flux of Nd is estimated to range between 2.9 × 10⁷ and 8.1 × 10⁷ mol/yr. These estimates are of the same order of magnitude, and within a factor of 2, of the missing Nd flux (i.e., 5.4 × 10⁷ mol/yr). Applying the SGD Nd flux estimates, the global average ε_Nd(0) of SGD is predicted to be − 9.1, which is similar to our estimate for the missing Nd flux (− 9.2), and in agreement with the mean (± S.D.) ε_Nd(0) measured in groundwaters (i.e., ε_Nd(0) = −8.9 ± 4.2). The similarities in the estimated SGD Nd flux and corresponding ε_Nd(0) values to the magnitude and isotope composition of the missing Nd flux are compelling, and suggest that discharge of groundwater to the oceans could account for the missing Nd flux. Future investigations should focus on quantifying the Nd concentrations and isotope compositions of groundwater from coastal aquifers from a variety of coastal settings, as well as the important geochemical reactions that effect Nd concentrations in subterranean estuaries in order to better constrain contributions of SGD to the oceanic Nd budget.     

Quantification of the gas mass emitted during single explosions on Stromboli with the SO2 imaging camera

We performed measurements using an SO₂ imaging camera of the SO₂ gas mass emitted during five discrete explosive events on Stromboli volcano on 3 October 2006. The SO₂ gas mass released during discrete explosions was 15–40 kg per explosion, producing 3–8% of the total daily SO₂ gas emission, demonstrating that in terms of gas flux Strombolian explosions are a second-order phenomenon compared with quiescent degassing. Using the typical gas composition measured with OP-FTIR allows us to determine the total gas mass released during an explosion as 360–960 kg with a volume of 1500–4100 m³ at 1 bar. At the probable source pressure of gas slug formation of 75 MPa this gas amount would occupy a volume equivalent to a sphere with a radius of 0.8–1 m, comparable with estimates of Stromboli's conduit geometry.     

New insights into the origin and evolution of Lake Vida,McMurdo Dry Valleys,Antarctica — A noble gas study in ice and brines

Unlike other lakes in the McMurdo Dry Valleys, Antarctica, Lake Vida has a thick (~ 19 m) ice cover sealing a liquid brine body of unusually high salinity (~ 245 g/L) from the atmosphere. To constrain the conditions under which the atypical Lake Vida ice cover formed and evolved, 19 ice samples were collected down to a depth of ~ 14 m, together with three brine samples trapped in the ice at ~ 16 m for analysis of helium, neon, argon, krypton, and xenon concentrations. The broad pattern of noble gas concentrations for Lake Vida samples is fundamentally different from that of air saturated water (ASW) at 0 °C and an elevation of 340 m for salinities of 0 (ice) and 245 g/L (brine). Overall, ice samples are enriched in He and depleted in Ne with saturation relative to ASW averages of 1.38 and 0.82, respectively, and strongly depleted in Ar, Kr, and Xe with relative saturations of 0.10, 0.06, and 0.05, respectively. By contrast, brine samples are generally depleted in He and Ne (relative saturation averages of 0.33 and 0.27, respectively) but enriched in Ar, Kr, and Xe, with relative saturation averages of 1.45, 3.15, and 8.86, respectively. A three-phase freezing partitioning model generating brine, ice and bubble concentrations for all stable noble gases was tested and compared with our data. Measured brine values are best reproduced for a salinity value of 175 g/L, a pressure of 1.1 atm, and a bubble volume of 20 cm³ kg^?1. Sensitivity tests for ice + bubble samples show an ideal fit for bubble volumes of ~ 1–2 cm³ kg^?1. Our results show that the conditions under which ice and brine formed and evolved at Lake Vida are significantly different from other ice-covered lakes in the area. Our brine data suggest that Lake Vida may be transitioning from a wet to a dry-based lake, while the ice + bubble data suggest at least partial re-equilibration of residual liquid with the atmosphere as ice forms at the top of Lake Vida ice cover.     

Cave air ventilation and CO2 outgassing by radon-222 modeling: How fast do caves breathe?

In general, the rate and timing of calcite precipitation is in part affected by variations in cave air CO₂ concentrations. Knowledge of cave ventilation processes is required to quantify the effect variations in CO₂ concentrations have on speleothem deposition rates and thus paleoclimate records. In this study we use radon-222 (²²²Rn) as a proxy of ventilation to estimate CO₂ outgassing from the cave to the atmosphere, which can be used to infer relative speleothem deposition rates. Hollow Ridge Cave, a wild cave preserve in Marianna, Florida, is instrumented inside and out with multiple micro-meteorological sensor stations that record continuous physical and air chemistry time-series data. Our time series datasets indicate diurnal and seasonal variations in cave air ²²²Rn and CO₂ concentrations, punctuated by events that provide clues to ventilation and drip water degassing mechanisms. Average cave air ²²²Rn and CO₂ concentrations vary seasonally between winter (²²²Rn = 50 dpm L^? 1, where 1 dpm L^? 1 = 60 Bq m^? 3; CO₂ = 360 ppmv) and summer (²²²Rn = 1400 dpm L^? 1; CO₂ = 3900 ppmv). Large amplitude diurnal variations are observed during late summer and autumn (²²²Rn = 6 to 581 dpm L^? 1; CO₂ = 360 to 2500 ppmv).We employ a simple first-order ²²²Rn mass balance model to estimate cave air exchange rates with the outside atmosphere. Ventilation occurs via density driven flow and by winds across the entrances which create a ‘venturi’ effect. The most rapid ventilation occurs 25 m inside the cave near the entrance: 45 h^? 1 (1.33 min turnover time). Farther inside (175 m) exchange is slower and maximum ventilation rates are 3 h^? 1 (22 min turnover time). We estimate net CO₂ flux from the epikarst to the cave atmosphere using a CO₂ mass balance model tuned with the ²²²Rn model. Net CO₂ flux from the epikarst is highest in summer (72 mmol m^? 2 day^? 1) and lowest in late autumn and winter (12 mmol m^? 2 day^? 1). Modeled ventilation and net CO₂ fluxes are used to estimate net CO₂ outgassing from the cave to the atmosphere. Average net CO₂ outgassing is positive (net loss from the cave) and is highest in late summer and early autumn (about 4 mol h^? 1) and lowest in winter (about 0.5 mol h^? 1). Modeling of ventilation, net CO₂ flux from the epikarst, and CO₂ outgassing to the atmosphere from cave monitoring time-series can help better constrain paleoclimatic interpretations of speleothem geochemical records.     

Himalayan metamorphic CO2 fluxes: Quantitative constraints from hydrothermal springs

Hot springs in the Marsyandi Valley, Nepal, vent CO₂ sourced from metamorphic fluids that mix with shallow groundwaters before degassing near the Earth's surface. The δ¹³C of spring waters ranges up to + 13‰, while that of the coexisting free gas phase is close to ? 4‰. Empirical and thermodynamic modelling of this isotopic fractionation suggests > 97 ± 1% CO₂ degassing. The calculated minimum total CO₂ degassing in the Marsyandi catchment is 5.4 × 10⁹ mol/yr from a Cl-based estimate of the spring water discharge to the Marsyandi River and the fraction of CO₂ degassed. Extrapolated to the whole of the Himalayas, this implies a probable minimum metamorphic CO₂ flux of 0.9 × 10¹² mol/yr, or ～ 13% of solid Earth CO₂ degassing. The calculated flux is a factor of three greater than the estimated CO₂ drawdown by silicate weathering in the Himalayas. Himalayan metamorphic degassing contributes a significant fraction of the global solid Earth CO₂ flux and implies that metamorphism may cause changes in long-term climate that oppose those resulting from the orogenic forcing of chemical weatherability.     

Evapotranspiration in the Pampean Region using field measurements and satellite data

Evapotranspiration (LE) is an important factor for monitoring crops, water requirements, and water consumption at local and regional scale. In this paper, we applied the semi-empirical model to estimate the daily latent heat flux (LE_d = Rn_d + A − B(Ts − Ta)). LE_d has been estimated using satellite images (Thematic Mapper sensor) and a local dataset (incoming and outgoing short- and long-wave radiation) measured during three years. We first estimated the daily net Radiation (Rn_d) from a linear equation derived from the instantaneous net Radiation (Rn_d = CRn_i + D). Subsequently, coefficients A and B have been estimated for two different cover vegetations (pasture and soybean). For each vegetation cover, an error analysis combining Rn_d, A, B, and surface and air temperatures has been calculated. Results showed that Rn_d had good performance (nonbias and low RMSE). LE_d errors for pasture and soybean were ±28 W m⁻² and ±40 W m⁻² respectively.     

CO2-induced dissolution of low permeability carbonates. Part II: Numerical modeling of experiments

We used the 3D continuum-scale reactive transport models to simulate eight core flood experiments for two different carbonate rocks. In these experiments the core samples were reacted with brines equilibrated with pCO₂ = 3, 2, 1, 0.5 MPa (Smith et al., 2013 [27]). The carbonate rocks were from specific Marly dolostone and Vuggy limestone flow units at the IEAGHG Weyburn-Midale CO₂ Monitoring and Storage Project in south-eastern Saskatchewan, Canada. Initial model porosity, permeability, mineral, and surface area distributions were constructed from micro tomography and microscopy characterization data. We constrained model reaction kinetics and porosity–permeability equations with the experimental data. The experimental data included time-dependent solution chemistry and differential pressure measured across the core, and the initial and final pore space and mineral distribution. Calibration of the model with the experimental data allowed investigation of effects of carbonate reactivity, flow velocity, effective permeability, and time on the development and consequences of stable and unstable dissolution fronts.The continuum scale model captured the evolution of distinct dissolution fronts that developed as a consequence of carbonate mineral dissolution and pore scale transport properties. The results show that initial heterogeneity and porosity contrast control the development of the dissolution fronts in these highly reactive systems. This finding is consistent with linear stability analysis and the known positive feedback between mineral dissolution and fluid flow in carbonate formations. Differences in the carbonate kinetic drivers resulting from the range of pCO₂ used in the experiments and the different proportions of more reactive calcite and less reactive dolomite contributed to the development of new pore space, but not to the type of dissolution fronts observed for the two different rock types. The development of the dissolution front was much more dependent on the physical heterogeneity of the carbonate rock. The observed stable dissolution fronts with small but visible dissolution fingers were a consequence of the clustering of a small percentage of larger pores in an otherwise homogeneous Marly dolostone. The observed wormholes in the heterogeneous Vuggy limestone initiated and developed in areas of greater porosity and permeability contrast, following pre-existing preferential flow paths.Model calibration of core flood experiments is one way to specifically constrain parameter input used for specific sites for larger scale simulations. Calibration of the governing rate equations and constants for Vuggy limestones showed that dissolution rate constants reasonably agree with published values. However the calcite dissolution rate constants fitted to the Marly dolostone experiments are much lower than those suggested by literature. The differences in fitted calcite rate constants between the two rock types reflect uncertainty associated with measured reactive surface area and appropriately scaling heterogeneous distribution of less abundant reactive minerals. Calibration of the power-law based porosity–permeability equations was sensitive to the overall heterogeneity of the cores. Stable dissolution fronts of the more homogeneous Marly dolostone could be fit with the exponent n = 3 consistent with the traditional Kozeny–Carman equation developed for porous sandstones. More impermeable and heterogeneous cores required larger n values (n = 6–8).     

The pre-eruptive volatile contents of recent basaltic and pantelleritic magmas at Pantelleria (Italy)

Pantelleria Island, located in the Sicily Channel Rift Zone (Italy), is the type locality for the peralkaline rhyolitic rocks called pantellerites. In the last 50 ka, after the large Green Tuff caldera-forming eruption, volcanic activity at Pantelleria has consisted of effusive and explosive eruptions mostly vented inside and along the rim of the caldera and producing silicic lava flows, lava domes and poorly dispersed pantelleritic pumice fall deposits. Basaltic cinder cones and lava flows are only present outside the caldera in the NW sector of the island. The most recent basaltic (Cuddie Rosse, ～ 20 ka) and pantelleritic (Cuddia Randazzo and Cuddia del Gallo, ～ 6 ka) pyroclastic products were sampled to investigate magmatic volatile contents through the study of melt inclusions.The melt inclusions in pyroxene and olivine phenocrysts of Cuddie Rosse scoriae have an alkali basalt composition. The dissolved volatiles comprise 0.9–1.6 wt.% H₂O, several hundred ppm of CO₂, 1600–2000 ppm of sulphur and 500–900 ppm of chlorine. The water–carbon dioxide couple gives a confining pressure ～ 2 kbar prior to the eruption. This result indicates that episodes of magma ponding and crystallization occurred in the upper crust prior to eruption. The melt inclusions in feldspar, fayalite and aenigmatite phenocrysts of Cuddia del Gallo and Cuddia Randazzo pumice have a pantelleritic composition (Agpaitic Indices 1.3–2.1), up to 4.4 wt.% H₂O, 8700 ppm Cl, 6000 ppm F, and CO₂ below the detection limit. Sulphur averaging 420 ppm has been measured in Cuddia Randazzo melt inclusions. These data indicate relatively high volatile contents for these low-energy Strombolian-type eruptions. Melt inclusions in Cuddia del Gallo pumice show the most evolved composition (Agpaitic Indices 2–2.1) and the highest volatile content, in agreement with fluid saturation conditions in the magma chamber prior to the eruption. This implies a confining pressure of ～ 1 kbar for the top of the pantelleritic reservoir. The composition of melt inclusions and mineralogical assemblage of Cuddia Randazzo pumice indicate that it has a lower evolutionary degree (Agpaitic Indices 1.3–1.8) and lower pre-eruptive Cl and H₂O contents than Cuddia del Gallo pumice. An increase in pressure due to the exsolution of volatiles in the upper part of the pantelleritic reservoir may have triggered the Cuddia del Gallo explosive eruption. Evidence of widespread pre-eruptive mingling between trachytes and pantellerites suggests that the intrusion of trachytic magma into the pantelleritic reservoir likely played a major role in destabilizing the magma system just prior to the Cuddia Randazzo event.     

A CO2-rich gas trigger of explosive paroxysms at Stromboli basaltic volcano,Italy

In addition to rhythmic slug-driven Strombolian activity, Stromboli volcano occasionally produces discrete explosive paroxysms (2 per year on average for the most frequent ones) that constitute a major hazard and whose origin remains poorly elucidated. Partial extrusion of the volatile-rich feeding basalt as aphyric pumice during these events has led to consider their triggering by the fast ascent of primitive magma blobs from possibly great depth. Here I examine and discuss the alternative hypothesis that most of the paroxysms could be triggered and driven by the fast upraise of CO₂-rich gas pockets generated by bubble foam growth and collapse in the sub-volcano plumbing system. Data for the SO₂ and CO₂ crater plume emissions are used to show that Stromboli's feeding magma may originally contain as much as 2 wt.% of carbon dioxide and early coexists with an abundant CO₂-rich gas phase with high CO₂/SO₂ molar ratio (≥ 60 at 10 km depth below the vents, compared to ～ 7 in time-averaged crater emissions). Pressure-related modelling indicates that the time-averaged crater gas composition and output are well accounted for by closed system decompression of the basalt–gas mixture until the volcano–crust interface (～ 3 km depth), followed by open degassing and crystallization in the volcano conduits. However, both the low viscosity and high vesicularity of the basaltic magma permit bubble segregation and bubble foam growth at deep sill-like feeder discontinuities and at shallower physical boundaries (such as the volcano–crust interface) where the gas-rich aphyric basalt interacts with the unerupted crystal-rich and viscous magma drained back from the volcano conduits. Gas pressure build-up and bubble foam collapse at these boundaries will intermittently trigger the sudden upraise of CO₂-rich gas blobs that constitute the main driving force of the paroxysms. Deeper-sourced gas blobs, driving the most powerful explosions, will be the richest in CO₂ and have highest CO₂/SO₂ ratios. This mechanism is shown to account well for the dynamic, seismic and petrologic features of Stromboli's paroxysms and, hence, to provide a potential alternative interpretation for their genesis and their forecasting. Enhanced bubble foam leakage prior to a paroxysm, or foam emptying in several steps, should lead indeed to precursory upstream of CO₂-rich gas and increasing CO₂/SO₂ ratio in crater plume emissions. The recent detection of such signals prior to two explosions in December 2006 and March 2007 strongly supports this expectation and the model proposed in this study.     

Recycling of harbor sediment as lightweight aggregate

Sediment sampled from Taichung Harbor was mixed with local reservoir sediment at different weight ratios to prepare lightweight aggregate at 1050, 1100, and 1150 °C. A pressure of 3000 or 5000 psi was used to shape the powder mixtures into pellets before the heating processes. The results indicate that the leaching levels of trace metals from the lightweight aggregate samples are considerably reduced to levels less than Taiwan Environmental Protection Administration regulatory limits. Increasing final process temperature tends to reduce the bulk density and crushing intensity of lightweight aggregate with a concomitant increase in water sorption capability. Lightweight aggregate with the lowest bulk density, 0.49 g cm⁻³ for the 5000 psi sample, was obtained with the heating process to 1150 °C. Based on the X-ray absorption near edge structure results, FeSO₄ decomposition with a concomitant release of SO_x (x = 2, 3) is suggested to play an important role for the bloating process in present study.     

The oxidation state of sulfur in magmatic fluids

Sulfur compounds in volcanic gases are responsible for the global cooling after explosive eruptions and they probably controlled the early evolution of the Earth's atmosphere. We have therefore studied the oxidation state of sulfur in aqueous fluids under the pressure and temperature conditions and oxygen fugacities typical for magma chambers (0.5–3 kbar, 650–950 °C, Ni–NiO to Re–ReO₂ buffer conditions). Sulfur speciation was determined by Raman spectroscopy of quenched fluids trapped as inclusions in quartz. Our results show that sulfur in hydrothermal fluids and volcanic gases is much more oxidized than previously thought and in particular, some explosive eruptions may release a significant fraction of sulfur as SO₃ or its hydrated forms. In the pressure range from 500 to 2000 bar, the equilibrium constant K₁ of the reaction 2H₂S + 3O₂ = 2SO₂ + 2H₂O in aqueous fluids can be described by lnK₁ = ?(57.1 ± 7.1) + (173,480 ± 7592)T^? 1, where T is temperature in Kelvin. The equilibrium constant K₂ for the reaction SO₂ + ½O₂ = SO₃ in aqueous fluids, where SO₃ may include hydrated forms, such as H₂SO₄, was found to be strongly pressure dependent, with lnK₂ = ?(5.2 ± 5.7) + (19,243 ± 5993)T^? 1 at 1500 bar; lnK₂ = ?(11.1 ± 1.3) + (25,383 ± 1371)T^? 1 at 2000 bar and lnK₂ = ?(22.1 ± 2.2) + (37,082 ± 2248)T^? 1 at 2500 bar. Our data imply that volcanoes may directly inject hexavalent sulfur in the form of H₂SO₄ into the atmosphere, not only on Earth, but possibly also on Venus and on Mars, when it was still tectonically active. Remote measurements from satellites may have underestimated the sulfur yield of some recent eruptions. Moreover, the mechanisms of the interaction of volcanic gases with the stratosphere need to be reconsidered.