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.     

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.     

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.     

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.     

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).     

Crustal velocity structure in the southern edge of the Central Alborz (Iran)

Inversion of local earthquake travel times and joint inversion of receiver functions and Rayleigh wave group velocity measurements were used to derive a simple model for the velocity crustal structure beneath the southern edge of the Central Alborz (Iran), including the seismically active area around the megacity of Tehran. The P and S travel times from 115 well-located earthquakes recorded by a dense local seismic network, operated from June to November 2006, were inverted to determine a 1D velocity model of the upper crust. The limited range of earthquake depths (between 2 km and 26 km) prevents us determining any velocity interfaces deeper than 25 km. The velocity of the lower crust and the depth of the Moho were found by joint inversion of receiver functions and Rayleigh wave group velocity data. The resulting P-wave velocity model comprises an upper crust with 3 km and 4 km thick sedimentary layers with P wave velocities (V_p) of ～5.4 and ～5.8 km s^?1, respectively, above 9 km and 8 km thick layers of upper crystalline crust (V_p ～6.1 and ～6.25 km s^?1 respectively). The lower crystalline crust is ～34 km thick (V_p ～ 6.40 km s^?1). The total crustal thickness beneath this part of the Central Alborz is 58 ± 2 km.     

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.     

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.     

Two extraterrestrial dust horizons found in the Dome Fuji ice core,East Antarctica

Two silicate-rich dust layers were found in the Dome Fuji ice core in East Antarctica, at Marine Isotope Stages 12 and 13. Morphologies, textures, and chemical compositions of constituent particles reveal that they are high-temperature melting products and are of extraterrestrial origin. Because similar layers were found ～ 2000 km east of Dome Fuji, at EPICA (European Project for Ice Coring in Antarctica)-Dome C, particles must have rained down over a wide area 434 and 481 ka. The strewn fields occurred over an area of at least 3 × 10⁶ km². Chemical compositions of constituent phases and oxygen isotopic composition of olivines suggest that the upper dust layer was produced by a high-temperature interaction between silicate-rich melt and water vapor due to an impact explosion or an aerial burst of a chondritic meteoroid on the inland East Antarctic ice sheet. An estimated total mass of the impactor, on the basis of particle flux and distribution area, is at least 3 × 10⁹ kg. A possible parent material of the lower dust layer is a fragment of friable primitive asteroid or comet. A hypervelocity impact of asteroidal/cometary material on the upper atmosphere and an explosion might have produced aggregates of sub-μm to μm-sized spherules. Total mass of the parent material of the lower layer must exceed 1 × 10⁹ kg. The two extraterrestrial horizons, each a few millimeters in thickness, represent regional or global meteoritic events not identified previously in the Southern Hemisphere.     

The origins and concentrations of water,carbon, nitrogen and noble gases on Earth

The isotopic compositions of terrestrial hydrogen and nitrogen are clearly different from those of the nebular gas from which the solar system formed, and also differ from most of cometary values. Terrestrial N and H isotopic compositions are in the range of values characterizing primitive meteorites, which suggests that water, nitrogen, and other volatile elements on Earth originated from a cosmochemical reservoir that also sourced the parent bodies of primitive meteorites. Remnants of the proto-solar nebula (PSN) are still present in the mantle, presumably signing the sequestration of PSN gas at an early stage of planetary growth. The contribution of cometary volatiles appears limited to a few percents at most of the total volatile inventory of the Earth. The isotope signatures of H, N, Ne and Ar can be explained by mixing between two end-members of solar and chondritic compositions, respectively, and do not require isotopic fractionation during hydrodynamic escape of an early atmosphere.The terrestrial inventory of ⁴⁰Ar (produced by the decay of ⁴⁰K throughout the Earth's history) suggests that a significant fraction of radiogenic argon may be still trapped in the silicate Earth. By normalizing other volatile element abundances to this isotope, it is proposed that the Earth is not as volatile-poor as previously thought. Our planet may indeed contain up to ~ 3000 ppm water (preferred range: 1000–3000 ppm), and up to ~ 500 ppm C, both largely sequestrated in the solid Earth. This volatile content is equivalent to an ~ 2 (± 1) % contribution of carbonaceous chondrite (CI-CM) material to a dry proto-Earth, which is higher than the contribution of chondritic material advocated to account for the platinum group element budget of the mantle. Such a (relatively) high contribution of volatile-rich matter is consistent with the accretion of a few wet planetesimals during Earth accretion, as proposed by recent dynamical models.The abundance pattern of major volatile elements and of noble gases is also chondritic, with two notable exceptions. Nitrogen is depleted by one order of magnitude relative to water, carbon and most noble gases, which is consistent with either N retention in a mantle phase during magma generation, or trapping of N in the core. Xenon is also depleted by one order of magnitude, and enriched in heavy isotopes relative to chondritic or solar Xe (the so-called “xenon paradox”). This depletion and isotope fractionation might have taken place due to preferential ionization of xenon by UV light from the early Sun, either before Earth's formation on parent material, or during irradiation of the ancient atmosphere. The second possibility is consistent with a recent report of chondritic-like Xe in Archean sedimentary rocks that suggests that this process was still ongoing during the Archean eon (Pujol et al., 2011). If the depletion of Xe in the atmosphere was a long-term process that took place after the Earth-building events, then the amounts of atmospheric ¹²⁹Xe and ^131–136Xe, produced by the short-lived radioactivities of ¹²⁹I (T_1/2 = 16 Ma) and ²⁴⁴Pu (T_1/2 = 82 Ma), respectively, need to be corrected for subsequent loss. Doing so, the I–Pu–Xe age of the Earth becomes ≤ 50 Ma after start of solar system formation, instead of ~ 120 Ma as computed with the present-day atmospheric Xe inventory.     

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.     

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.     

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.     

Potential application of activated carbon from maize tassel for the removal of heavy metals in water

Water-pollution problems worldwide have led to an acute shortage of clean and pure water for both domestic and human consumption. Various technologies and techniques are available for water treatment which includes the use of activated carbon. In this study activated carbons used for the removal of lead (II) ions from water samples were prepared from maize tassels (an agricultural waste residue) which were modified using physical and chemical activation. In the physical activation CO₂ was used as the activating agent, while in chemical activation H₃PO₄ with an impregnation ratio ranging from 1 to 4 was employed. The maize tassel was pyrolysed at different temperatures ranging from 300 °C to 700 °C in an inert atmosphere for a period of 60 min and activated at 700 °C for 30 min. The effects of activation temperature, impregnation ratio and duration were examined. The resultant modified tassels were characterised by measuring their particle-size distribution, porosities, pore volume, and pore-size distribution using scanning electron microscopy (SEM). The activated carbon produced by chemical activation had the highest BET surface area ranging from 623 m² g⁻¹ to 1 262 m² g⁻¹. The surface chemistry characteristics of the modified tassels were determined by FT–IR spectroscopy and Boehm’s titration method. The experimental data proved that properties of activated carbon depend on final temperature of the process, impregnation ratio and duration of the treatment at final temperature. The adsorption studies showed that chemically prepared activated carbon performed better than physically prepared activated carbon.     

Mercury emissions and stable isotopic compositions at Vulcano Island (Italy)

Sampling and analyses methods for determining the stable isotopic compositions of Hg in an active volcanic system were tested and optimized at the volcanic complex of Vulcano (Aeolian Islands, Italy). Condensed gaseous fumarole Hg_(fum)^T, plume gaseous elemental Hg_(g)⁰ and plume particulate Hg_(p)^II were obtained at fumaroles F0, F5, F11, and FA. The average total Hg emissions, based on Hg^T/SO₂ in condensed fumarolic gases and plumes, range from 2.5 to 10.1 kg y^? 1, in agreement with published values [Ferrara, R., Mazzolai, B., Lanzillotta, E., Nucaro, E., Pirrone, N., 2000. Volcanoes as emission sources of atmospheric mercury in the Mediterranean Basin. Sci. Total Environ. 259(1–3), 115–121; Aiuppa, A., Bagnato, E., Witt, M.L.I., Mather, T.A., Parello, F., Pyle, D.M., Martin, R.S., 2007. Real-time simultaneous detection of volcanic Hg and SO₂ at La Fossa Crater, Vulcano (Aeolian Islands, Sicily). Geophys. Res. Lett. 34(L21307).]. Plume Hg_(p)^II increases with distance from the fumarole vent, at the expense of Hg_(g)⁰ and indicates significant in-plume oxidation and condensation of fumarole Hg_(fum)^T.Relative to the NIST SRM 3133 Hg standard, the stable isotopic compositions of Hg are δ²⁰²Hg_(fum)^T = ? 0.74‰ ± 0.18 (2SD, n = 4) for condensed gaseous fumarole Hg_(fum)^T, δ²⁰²Hg_(g)⁰ = ? 1.74‰ ± 0.36 (2SD, n = 1) for plume gaseous elemental Hg_(g)⁰ at the F0 fumarole, and δ²⁰²Hg_(p)^II = ? 0.11‰ ± 0.18 (2SD, n = 4) for plume particulate Hg_(p)^II. The enrichment of Hg_(p)^II in the heavy isotopes and Hg_(g)⁰ in the light isotopes relative to the total condensed fumarolic Hg_(fum)^T gas complements the speciation data and demonstrates a gas-particle fractionation occurring after the gas expulsion in ambient T° atmosphere. A first order Rayleigh equilibrium condensation isotope fractionation model yields a fractionation factor α_cond-gas of 1.00135 ± 0.00058.     

Large-scale sedimentary bedforms and sediment dynamics on a glaciated tectonic continental shelf: Examples from the Pacific margin of Canada

The Pacific margin of Canada has been subjected to tectonism, dramatic sea level change and vigorous storm and tidal energy since glacial times resulting in a complex seafloor. Extensive multibeam mapping of this shelf has provided an opportunity to understand how these processes have impacted sedimentology and morphology. Bathymetric restriction of the tidally dominated flow between the inland seas and the open Pacific has resulted in the development of very large subaqueous dune fields and terrace moats. For example, in the southern Strait of Georgia nearly symmetrical dunes with wavelengths between 100 and 300 m, dune heights up to 28 m, cover the seafloor in 170–210 m water depth. In northern Hecate Strait a 72 km² area of large 2D dunes occurs at the transition with Dixon Entrance which opens to the Pacific Ocean and steep (>10°) wave-cut terraces and drowned spits, a result of sea level changes during the Holocene, are now being undercut to generate moats 7 m deep, in a narrowing shelf trough. Currents, with velocities ranging between 0.2 and 2.2 m s^?1, are dominated by semi-diurnal tidal streams that are continually modified by wind and estuarine circulation. There appears to be a clear association of grain size, water depth and flow velocity controlling the size of the subaqueous dunes.     

Latitudinal patterns of export production recorded in surface sediments of the Chilean Patagonian fjords (41–55°S) as a response to water column productivity

The Chilean Patagonian fjords region (41–56°S) is characterized by highly complex geomorphology and hydrographic conditions, and strong seasonal and latitudinal patterns in precipitation, freshwater discharge, glacier coverage, and light regime; all of these directly affect biological production in the water column. In this study, we compiled published and new information on water column properties (primary production, nutrients) and surface sediment characteristics (biogenic opal, organic carbon, molar C/N, bulk sedimentary δ¹³C_org) from the Chilean Patagonian fjords between 41°S and 55°S, describing herein the latitudinal pattern of water column productivity and its imprint in the underlying sediments. Based on information collected at 188 water column and 118 sediment sampling sites, we grouped the Chilean fjords into four main zones: Inner Sea of Chiloé (41° to ～44°S), Northern Patagonia (44° to ～47°S), Central Patagonia (48–51°S), and Southern Patagonia (Magellan Strait region between 52° and 55°S). Primary production in the Chilean Patagonian fjords was the highest in spring–summer, reflecting the seasonal pattern of water column productivity. A clear north–south latitudinal pattern in primary production was observed, with the highest average spring and summer estimates in the Inner Sea of Chiloé (2427 and 5860 mg C m^?2 d^?1) and Northern Patagonia (1667 and 2616 mg C m^?2 d^?1). This pattern was closely related to the higher availability of nutrients, greater solar radiation, and extended photoperiod during the productive season in these two zones. The lowest spring value was found in Caleta Tortel, Central Patagonia (91 mg C m^?2 d^?1), a site heavily influenced by glacier meltwater and river discharge loaded with glacial sediments. Biogenic opal, an important constituent of the Chilean fjord surface sediments (Si_OPAL ～1–13%), reproduced the general north–south pattern of primary production and was directly related to water column silicic acid concentrations. Surface sediments were also rich in organic carbon content and the highest values corresponded to locations far away from glacier influence, sites within fjords, and/or semi-enclosed and protected basins, reflecting both autochthonous (water column productivity) and allochthonous sources (contribution of terrestrial organic matter from fluvial input to the fjords). A gradient was observed from the more oceanic sites to the fjord heads (west–east) in terms of bulk sedimentary δ¹³C_org and C/N ratios; the more depleted (δ¹³C_org ?26‰) and higher C/N (23) values corresponded to areas close to rivers and glaciers. A comparison of the Chilean Patagonian fjords with other fjord systems in the world revealed high variability in primary production for all fjord systems as well as similar surface sediment geochemistry due to the mixing of marine and terrestrial organic carbon.     

Siberian gas venting and the end-Permian environmental crisis

The end of the Permian period is marked by global warming and the biggest known mass extinction on Earth. The crisis is commonly attributed to the formation of the Siberian Traps Large Igneous Province although the causal mechanisms remain disputed. We show that heating of Tunguska Basin sediments by the ascending magma played a key role in triggering the crisis. Our conclusions are based on extensive field work in Siberia in 2004 and 2006. Heating of organic-rich shale and petroleum bearing evaporites around sill intrusions led to greenhouse gas and halocarbon generation in sufficient volumes to cause global warming and atmospheric ozone depletion. Basin scale gas production potential estimates show that metamorphism of organic matter and petroleum could have generated > 100,000 Gt CO₂. The gases were released to the end-Permian atmosphere partly through spectacular pipe structures with kilometre-sized craters. Dating of a sill intrusion by the U–Pb method shows that the gas release occurred at 252.0 ± 0.4 million years ago, overlapping in time with the end-Permian global warming and mass extinction. Heating experiments to 275 °C on petroleum-bearing rock salt from Siberia suggests that methyl chloride and methyl bromide were significant components of the erupted gases. The results indicate that global warming and ozone depletion were the two main drivers for the end-Permian environmental crisis. We demonstrate that the composition of the heated sedimentary rocks below the flood basalts is the most important factor in controlling whether a Large Igneous Provinces causes an environmental crisis or not. We propose that a similar mechanism could have been responsible for the Triassic-Jurassic (~ 200 Ma) global warming and mass extinction, based on the presence of thick sill intrusions in the evaporite deposits of the Amazon Basin in Brazil.     

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.     

High resolution OSL dating back to MIS 5e in the central Sea of Okhotsk

Marine sediments contain important archives of past ocean and climate changes, but at high latitudes the absence of carbonate has prevented the construction of accurate chronological models. We have begun a study to (1) determine the accuracy of luminescence ages in deep-sea marine sediments, e.g. by comparison with marine oxygen isotope stratigraphy where possible, (2) describe changes in sedimentation rate through time, and (3) test whether it is possible to date back to marine isotope stage 5e (MIS 5e). We show here that optical dating of fine grains of quartz from the central Sea of Okhotsk is able to provide an accurate and precise chronology for the reconstruction of the palaeoceanic and palaeoclimatic environment at our site. The upper 6.5 m of the 18.42 m long core MR0604-PC07A is believed, based on its magnetic susceptibility and the oxygen isotope (δ¹⁸O) records to contain the last ～150 ka. Forty OSL samples were taken from this upper part of the core. The single-aliquot regenerative-dose (SAR) procedure is used for equivalent dose (D_e) determination. The luminescence characteristics of fine-grained quartz (4–11 μm) extracted from the core are described. The OSL signal is dominated by the fast component and a dose recovery test shows that we can accurately measure a known dose given in the laboratory prior to any heat treatment. Dose rates were determined using high-resolution gamma spectrometry, and vary between 0.4 and 1.6 Gy/ka. The OSL ages from this section lie between ～140 ka and ～15 ka and are in very good agreement with the δ¹⁸O stratigraphy up to MIS 5e. A clear change in sedimentation rate is identified: between ～139 and 110 ka, the sedimentation rate was ～0.09 m/ka, but then from ～110 to 15 ka, the sedimentation rate decreases to a constant value of ～0.04 m/ka. Our data confirm that OSL dating using widely distributed fine-grain quartz has great potential for dating deep-sea sediments. Because luminescence methods use clastic materials, they do not depend on the presence of biogenic carbonate. As a result it is now likely that we can establish a chronology in regions of the ocean that were previously undatable.