Volatile Fluxes Research Articles

The influence of plate tectonic style on melt production and CO2 outgassing flux at mid-ocean ridges

Ocean ridges are one of the primary connections between Earth's mantle and surface. Therefore, understanding the evolution of ocean ridge processes through Earth history is important for understanding how Earth's surface and mantle have evolved. We combine an analytic model of mantle convection with a petrologic model of mantle melting in the presence of CO2 to compute the mantle temperature, plate speed, melt production, and CO2 outgassing flux at ocean ridges for the past 4 billion years. We explore a large suite of realistic mantle and lithospheric parameters to map out a full range of possible thermal histories. Our results show that in order to satisfy thermal constraints, the Earth must have started in a sluggish-lid mode of plate tectonics and transitioned to an active-lid mode. Furthermore, we show that plate speed and CO2 outgassing flux do not necessarily scale with mantle temperature, and that it is possible to reach present-day mantle temperatures and plate speeds with a simple force balance that does not invoke any feedbacks (e.g. grain size evolution, dehydration stiffening) or a fully stagnant-lid mode of convection in the Precambrian. The solutions show a range of evolutionary behaviors depending on the parameters chosen. The transition from sluggish- to active-lid can be smooth, abrupt, or somewhere in between. A smooth transition is difficult to distinguish from a purely active-lid evolutionary path based on temperature, plate speed, melt production, and CO2 outgassing flux. In contrast, an abrupt transition leads to a large increase in the average plate speed with a corresponding increase in melt production and CO2 outgassing flux. As an abrupt transition would have a much larger effect on CO2 outgassing and melt production than a change in ridge length, we investigate the impact of rapidly changing plate speeds and do not consider changes in ridge length. Finally, we show that carbon recycling is required for a large part of Earth history in order to explain present-day CO2 outgassing. Our model highlights the importance of understanding the style of mantle convection when calculating melt production and volatile fluxes through Earth's history.

How do volatiles escape their shallow magmatic hearth?

Only a small fraction (approx. 1-20%) of magmas generated in the mantle erupt at the surface. While volcanic eruptions are typically considered as the main exhaust pipes for volatile elements to escape into the atmosphere, the contribution of magma reservoirs crystallizing in the crust is likely to dominate the volatile transfer from depth to the surface. Here, we use multiscale physical modelling to identify and quantify the main mechanisms of gas escape from crystallizing magma bodies. We show that most of the outgassing occurs at intermediate to high crystal fraction, when the system has reached a mature mush state. It is particularly true for shallow volatile-rich systems that tend to exsolve volatiles through second boiling, leading to efficient construction of gas channels as soon as the crystallinity reaches approximately 40-50 vol.%. We, therefore, argue that estimates of volatile budgets based on volcanic activity may be misleading because they tend to significantly underestimate the magmatic volatile flux and can provide biased volatile compositions. Recognition of the compositional signature and volumetric dominance of intrusive outgassing is, therefore, necessary to build robust models of volatile recycling between the mantle and the surface. This article is part of the Theo Murphy meeting issue 'Magma reservoir architecture and dynamics'.

Accessory minerals and evolution of tin-bearing S-type granites in the western segment of the Gemeric Unit (Western Carpathians)

Abstract The S-type accessory mineral assemblage of zircon, monazite-(Ce), fluorapatite and tourmaline in the cupolas of Permian granites of the Gemeric Unit underwent compositional changes and increased variability and volume due to intensive volatile flux. The extended S-type accessory mineral assemblage in the apical parts of the granite resulted in the formation of rare-metal granites from in-situ differentiation and includes abundant tourmaline, zircon, fluorapatite, monazite-(Ce), Nb–Ta–W minerals (Nb–Ta rutile, ferrocolumbite, manganocolumbite, ixiolite, Nb–Ta ferberite, hübnerite), cassiterite, topaz, molybdenite, arsenopyrite and aluminophosphates. The rare-metal granites from cupolas in the western segment of the Gemeric Unit represent the topaz–zinnwaldite granites, albitites and greisens. Zircon in these evolved rare-metal Li–F granite cupolas shows a larger xenotime-(Y) component and heterogeneous morphology compared to zircons from deeper porphyritic biotite granites. The zircon Zr/Hfwt ratio in deeper rooted porphyritic granite varies from 29 to 45, where in the differentiated upper granites an increase in Hf content results in a Zr/Hfwt ratio of 5. The cheralite component in monazite from porphyritic granites usually does not exceed 12 mol. %, however, highly evolved upper rare-metal granites have monazites with 14 to 20 mol. % and sometimes > 40 mol. % of cheralite. In granite cupolas, pure secondary fluorapatite is generated by exsolution of P from P-rich alkali feldspar and high P and F contents may stabilize aluminophosphates. The biotite granites contain scattered schorlitic tourmaline, while textural late-magmatic tourmaline is more alkali deficient with lower Ca content. The differentiated granites contain also nodular and dendritic tourmaline aggregations. The product of crystallization of volatile-enriched granite cupolas are not only variable in their accessory mineral assemblage that captures high field strength elements, but also in numerous veins in country rocks that often contain cassiterite and tourmaline. Volatile flux is documented by the tetrad effect via patterns of chondrite normalized REEs (T1,3 value 1.46). In situ differentiation and tectonic activity caused multiple intrusive events of fluid-rich magmas rich in incompatible elements, resulting in the formation of rare-metal phases in granite roofs. The emplacement of volatile-enriched magmas into upper crustal conditions was followed by deeper rooted porphyritic magma portion undergoing second boiling and re-melting to form porphyritic granite or granite-porphyry during its ascent.

Xenon isotopic constraints on the history of volatile recycling into the mantle.

The long-term exchange of volatile species (such as water, carbon, nitrogen and the noble gases) between deepEarth and surface reservoirs controls the habitability of the Earth's surface. The present-day volatile budget of the mantle reflects the integrated history of outgassing and retention of primordial volatiles delivered to the planet during accretion, volatile species generated by radiogenic ingrowth and volatiles transported into the mantle from surface reservoirs over time. Variations in the distribution of volatiles between deep Earth and surface reservoirs affect the viscosity, cooling rate and convective stress state of the solid Earth. Accordingly, constraints on the flux of surface volatiles transported into the deep Earth improve our understanding of mantle convection and plate tectonics. However, the history of surface volatile regassing into the mantle is not known. Here we use mantle xenon isotope systematics to constrain the age of initiation of volatile regassing into the deep Earth. Given evidence of prolonged evolution of the xenon isotopic composition of the atmosphere1,2, we find that substantial recycling of atmospheric xenon into the deep Earth could not have occurred before 2.5 billion years ago. Xenon concentrations in downwellings remained low relative to ambient convecting mantle concentrations throughout the Archaean era, and the mantle shifted from a net degassing to a net regassing regime after 2.5 billion years ago. Because xenon is carried into the Earth's interior in hydrous mineral phases3-5, our results indicate that downwellings were drier in the Archaean era relative to the present. Progressive drying of the Archean mantle would allow slower convection and decreased heat transport out of the mantle, suggesting non-monotonic thermal evolution of the Earth's interior.

Fossil Fuel-Derived Polycyclic Aromatic Hydrocarbons in the Taiwan Strait, China, and Fluxes across the Air-Water Interface.

On the basis of the application of compound-specific radiocarbon analysis (CSRA) and air-water exchange models, the contributions of fossil fuel and biomass burning derived polycyclic aromatic hydrocarbons (PAHs) as well as their air-water transport were elucidated. The results showed that fossil fuel-derived PAHs (an average contribution of 89%) presented the net volatilization process at the air-water interface of the Taiwan Strait in summer. Net volatile fluxes of the dominant fluorene and phenanthrene (>58% of the total PAHs) were 27 ± 2.8 μg m-2 day-1, significantly higher than the dry deposition fluxes (average 0.43 μg m-2 day-1). The Δ14C contents of selected PAHs (fluorene, phenanthrene plus anthracene, fluoranthene, and pyrene) determined by CSRA in the dissolved seawater ranged from -997 ± 4‰ to -873 ± 6‰, indicating that 89-100% (95 ± 4%) of PAHs were supplied by fossil fuels. The South China Sea warm current originating from the southwest China in summer (98%) and the Min-Zhe coastal current originating from the north China in winter (97%) input more fossil fuel PAHs than the Jiulong River estuary (90%) and Xiamen harbor water (93%). The more radioactive decayed 14C of fluoranthene (a 4-ring PAH) than that of phenanthrene and anthracene (3-ring PAHs) represented a greater fossil fuel contribution to the former in dissolved seawater.

Flux influenced morphology tailoring and emission color tuning to pure white in ZrO2:Eu3+phosphors

Influence of volatile fluxes like NH4Cl, B(OH)3 and their combination on the photo luminescence and morphological properties of ZrO2:Eu3+ phosphor was investigated. The samples were characterized by XRD, UV–visible spectroscopy, scanning electron microscopy and photoluminescence spectra. XRD pattern shows that the samples prepared using ammonium chloride and by combination of ammonium chloride, boric acid crystallizes in tetragonal phase, whereas samples prepared without flux and using boric acid, crystallizes in cubic phase. The results revealed that particle size, morphology, phase and photoluminescence emission color were largely influenced by the flux. Type of flux employed significantly influenced the morphology and emission color of the phosphor. Addition of two fluxes resulted in pure white-light emission, with CIE chromaticity coordinates of (0.327, 0.331), which is very close to the essential requirement to the NTSC (National Television System Committee) system for standard white light.

Volatile concentrations in olivine-hosted melt inclusions from meimechite and melanephelinite lavas of the Siberian Traps Large Igneous Province: Evidence for flux-related high-Ti, high-Mg magmatism

The origin of high-Mg melts remains one of the most highly debated questions in igneous petrology. There are two contrasting points of view, namely, (1) melt initiation in a rising high-temperature plume, and (2) mantle melting due to fluxing by water. To address this question we determined H2O, CO2, F, Cl and S concentrations in olivine-hosted melt inclusions of high-Mg volcanic rocks of the Siberian Traps Large Igneous Province that bracket the main pulse of volcanism at about 252–250 Ma, and can be classified as melanephelinites and meimechites. Both rock types belong to the high-Ti rock series. Correcting measured H2O, CO2, F, Cl and S concentrations in homogenized primary meimechite melt inclusions to primary meimechite melt composition using experimental melt compositions resulted in corrected melt-inclusion, volatile compositions of ~3.88 wt% H2O, ~1477 ppm CO2, ~4214 ppm F, ~2.08 wt% Cl and ~2490 ppm S. These values are viewed as minimum estimates for the original volatile concentrations in the melt because of the high probability for degassing during melt crystallization and/or during experiment homogenization. Olivine-hosted homogenized melt inclusions from melanephelinites yielded lower corrected concentrations of ~1.06 wt% H2O, ~998 ppm CO2, ~3242 ppm F, ~607 ppm Cl and ~2131 ppm S. We also measured water concentrations in clinopyroxenes of melanephelinites by FTIR, obtaining values as high as 133 ppm H2O, which corresponds to 0.91 wt% in the melt, in general agreement with data obtained by SIMS on the olivine-hosted melt inclusions. Olivine grains from melanephelinites are characterized by evolved compositions (Fo 0.80–0.86). Extrapolation to a primitive melanephelinite melt by simple fractional crystallization suggests that it could also contain high H2O concentrations (up to ~ 3 wt%). Analyzed meimechite and melanephelinite whole-rock samples are characterized by trace-element patterns that are typical of mantle-derived melts and by Sr-Nd isotope ratios that exclude crustal contamination or derivation from ancient lithospheric mantle. Thus, high volatile concentrations can be attributed to sublithospheric mantle source regions. This supports the notion that high-Mg melts form by volatile fluxing of the asthenospheric mantle rather than by decompression melting under relatively dry conditions of a rising abnormally high-temperature mantle plume.

The Magmatic Gas Signature of Pacaya Volcano, With Implications for the Volcanic CO2 Flux From Guatemala

AbstractPacaya volcano in Guatemala is one of the most active volcanoes of the Central American Volcanic Arc (CAVA). However, its magmatic gas signature and volatile output have received little attention to date. Here, we present novel volcanic gas information from in‐situ (Multi‐GAS) and remote (UV camera) plume observations in January 2016. We find in‐plume H2O/SO2 and CO2/SO2 ratios of 2‐20 and 0.6‐10.5, and an end‐member magmatic gas signature of 80.5 mol. % H2O, 10.4 mol. % CO2, and 9.0 mol. % SO2. The SO2 flux is evaluated at 885 ± 550 tons/d. This, combined with co‐acquired volcanic plume composition, leads to H2O and CO2 fluxes of 2,230 ± 1,390 and 700 ± 440, and a total volatile flux of ∼3,800 tons/d. We use these results in tandem with previous SO2 flux budgets for Fuego and Santiaguito to estimate the total volcanic CO2 flux from Guatemala at ∼1,160 ± 600 tons/day. This calculation is based upon CO2/total S (St) ratios for Fuego (1.5 ± 0.75) and Santiaguito (1.4 ± 0.75) inferred from a gas (CO2/St ratio) versus trace‐element (Ba/La ratio) CAVA relationship. The H2O‐poor and low CO2/St ratio (∼1.0‐1.5) signature of Pacaya gas suggests dominant mantle‐wedge derivation of the emitted volatiles. This is consistent with 3He/4He ratios in olivine hosted fluid inclusions (FIs), which range between 8.4 and 9.0 Ra (being Ra the atmospheric 3He/4He ratio) at the upper limit of MORB range (8 ± 1 Ra). These values are the highest ever measured in CAVA and among the highest ever recorded in arc volcanoes worldwide, indicating negligible 4He contributions from the crust/slab.

Plume composition and volatile flux of Nyamulagira volcano, Democratic Republic of Congo, during birth and evolution of the lava lake, 2014–2015

Very little is known about the volatile element makeup of the gaseous emissions of Nyamulagira volcano. This paper tries to fill this gap by reporting the first gas composition measurements of Nyamulagira’s volcanic plume since the onset of its lava lake activity at the end of 2014. Two field surveys were carried out on 1 November 2014, and 13–15 October 2015. We applied a broad toolbox of volcanic gas composition measurement techniques in order to geochemically characterize Nyamulagira’s plume. Nyamulagira is a significant emitter of SO2, and our measurements confirm this, as we recorded SO2 emissions of up to ~ 14 kt/d during the studied period. In contrast to neighbouring Nyiragongo volcano, however, Nyamulagira exhibits relatively low CO2/SO2 molar ratios ( 92% of total gas emissions). Strong variations in the volatile composition, in particular for the CO2/SO2 ratio, were measured between 2014 and 2015, which appear to reflect the simultaneous variations in volcanic activity. We also determined the molar ratios for Cl/S, F/S and Br/S in the plume gas, finding values of 0.13 and 0.17, 0.06 and 0.11, and 2.3·10?4 and 1·10?4, in 2014 and 2015, respectively. A total gas emission flux of 48 kt/d was estimated for 2014. The I/S ratio in 2015 was found to be 3.6·10?6. In addition, we were able to distinguish between hydrogen halides and non-hydrogen halides in the volcanic plume. Considerable amounts of bromine (18–35% of total bromine) and iodine (8–18% of total iodine) were found in compounds other than hydrogen halides. However, only a negligible fraction of chlorine was found as compounds other than hydrogen chloride.

Coupled analytical approach to predict piloted flaming ignition of non-charring polymers

Classical thermal theory of piloted ignition is extended by coupling the heat balance at the exposed sample surface and the finite-rate pyrolysis in the material volume. Approximate analytical solutions for the sample temperature are obtained for an arbitrary sample thickness, with the external radiative heating, surface re-radiation, heat of gasification, and the convective heat flux corrected for blowing taken into account. The volatile mass flux is evaluated by integrating the pyrolysis rate throughout the layer, with the assumption of high activation energy limit. Critical mass flux of combustible volatiles is used as the ignition criterion. This enables the ignition temperature to be evaluated instead of being pre-assumed as is done in the classical thermal theory. Coupled analytical approach proposed in this work is verified by comparisons to the numerical solution obtained by the Pyropolis model for the same problem setup. This approach has also been validated by comparisons to published experimental data (ignition temperatures and times to ignition) for three non-charring thermoplastics: polymethylmethacrylate, polyethylene and polypropylene.

Geochemistry, petrogenesis, and tectonic setting of the Almogholagh batholith in the Sanandaj–Sirjan zone, western Iran

The Almogholagh batholith in the northern Sanandaj-Sirjan magmatic–metamorphic zone comprises three intrusive bodies (gabbroic diorite, quartz syenite, and quartz monzonite) that were generated during the northeastward subduction of Neo-Tethys beneath the Iranian sector of the Eurasian plate. These bodies intruded at different time phases and are related to post-collision magmatism. The quartz syenite and quartz monzonite rocks with specifications of metaluminous, generally ferroan, alkalic to alkali-calcic types, high content of Na2O + K2O, Zr, Ce, Ga, Y, Nb, Ta, and rare earth elements, and depleted in Eu, Sr, and Ti show borderline characteristics between A1 and A2 types granitoids but with more affinity to A2 type. The gabbroic dioritic rocks show borderline specifications between A1 and I types rocks but with more affinity to I type. Distinctive spiked peak patterns in spider diagrams accompanied by (La/Yb)CN values equal to 2.44 to 6.11 and a Ba/La ratio >3 indicate the magmatism activity in the volcanic arc environment. The characteristics (Ba/Rb)PN < 1, (Ba/Th)PN < 1, and Th/Ta ratio from 3.18 to 8.42 suggest the magmatism activity of the continental margin setting. The specifications of post-collision magmatic activities, 143Nd/144Nd > 0.512638 in some samples, εtNd > 0, εtSr > 0, and high content of Nb, Ta, and Zr (589 ppm) demonstrate the involvement of the mantle source, subducted slab fluids, high flux of mantle-derived halogen-rich volatiles, and contamination within the crust during the petrogenesis of intrusions. After the initial collision, the operation of minor subduction (with slab break-off) or foundering of the lithospheric mantle (delamination) occurred because of asthenospheric upwelling and heat flows in the mantle in the Sanandaj-Sirjan zone. Stretch and local disruptions were created by these heat flows; simultaneously, magma was formed and ascended upward.

Noble gases recycled into the mantle through cold subduction zones

Subduction of hydrous and carbonated oceanic lithosphere replenishes the mantle volatile inventory. Substantial uncertainties exist on the magnitudes of the recycled volatile fluxes and it is unclear whether Earth surface reservoirs are undergoing net-loss or net-gain of H2O and CO2. Here, we use noble gases as tracers for deep volatile cycling. Specifically, we construct and apply a kinetic model to estimate the effect of subduction zone metamorphism on the elemental composition of noble gases in amphibole – a common constituent of altered oceanic crust. We show that progressive dehydration of the slab leads to the extraction of noble gases, linking noble gas recycling to H2O. Noble gases are strongly fractionated within hot subduction zones, whereas minimal fractionation occurs along colder subduction geotherms. In the context of our modelling, this implies that the mantle heavy noble gas inventory is dominated by the injection of noble gases through cold subduction zones. For cold subduction zones, we estimate a present-day bulk recycling efficiency, past the depth of amphibole breakdown, of 5–35% and 60–80% for 36Ar and H2O bound within oceanic crust, respectively. Given that hotter subduction dominates over geologic history, this result highlights the importance of cooler subduction zones in regassing the mantle and in affecting the modern volatile budget of Earth's interior.

Analysis of gas jetting and fumarole acoustics at Aso Volcano, Japan

The gas-thrust region of a large volcanic eruption column is predominately a momentum-driven, fluid flow process that perturbs the atmosphere and produces sound akin to noise from jet and rocket engines, termed “jet noise”. We aim to enhance understanding of large-scale volcanic jets by studying an accessible, less hazardous fumarolic jet. We characterize the acoustic signature of ~2.5-meter wide vigorously jetting fumarole at Aso Volcano, Japan using a 5-element infrasound array located on the nearby crater. The fumarole opened on 13 July 2015 on the southwest flank of the partially collapsed pyroclastic cone within Aso Volcano's Naka-dake crater and had persistent gas jetting, which produced significant audible jet noise. The array was ~220m from the fumarole and 57.6° from the vertical jet axis, a recording angle not typically feasible in volcanic environments. Array processing is performed to distinguish fumarolic jet noise from wind. Highly correlated periods are characterized by sustained, low-amplitude signal with a 7–10Hz spectral peak. Finite difference time domain method numerical modeling suggests the influence of topography near the vent and along the propagation path significantly affects the spectral content, complicating comparisons with laboratory jet noise. The fumarolic jet has a low estimated Mach number (0.3 to 0.4) and measured temperature of ~260°C. The Strouhal number for infrasound from volcanic jet flows and geysers is not known; thus we assume a peak Strouhal number of 0.19 based on pure-air laboratory jet experiments. This assumption leads to an estimated exit velocity of the fumarole of ~79 to 132m/s. Using published gas composition data from 2003 to 2009, the fumarolic vent area estimated from thermal infrared images, and estimated jet velocity, we estimate total volatile flux at ~160–270kg/s (14,000–23,000t/d).

How Large Igneous Provinces affect global climate, sometimes cause mass extinctions, and represent natural markers in the geological record

Large Igneous Provinces (LIPs) can have a significant global climatic effect as monitored by sedimentary trace and isotopic compositions that record paleo-seawater/atmosphere variations. Improved U-Pb dating (with better than 0.1Myr resolution) for several LIPs is confirming a long-proposed mass extinction-LIP link. The most dramatic climatic effect is global warming due to greenhouse-gases from LIPs. Subsequent cooling (and even global glaciations) can be caused by CO2 drawdown through weathering of LIP-related basalts, and/or by sulphate aerosols. Additional kill mechanisms that can be associated with LIPs include oceanic anoxia, ocean acidification, sea level changes, toxic metal input, essential nutrient decrease, producing a complex web of catastrophic environmental effects. Notably, the size of a LIP is not the only important factor in contributuing to environmental impact. Of particular significance are the rate of effusion, and the abundance of LIP-produced pyroclastic material and volatile fluxes that reach the stratosphere. While flood basalt degassing (CO2, SO2, halogens) is important (and is also from associated silicic volcanism), a significant amount of these gases are released from volatile-rich sedimentary rocks (e.g. evaporites and coal horizons) heated by the intrusive component of LIPs. Feedbacks are important, such as global warming leading to destabilization of clathrates, consequent release of further greenhouse gases, and greater global warming. In the broadest sense LIPs can affect (or even induce) shifts between Icehouse, Greenhouse and Hothouse climatic states. However, the specific effects, their severity, and their time sequencing is specific to each LIP. Based on the robust array of environmental effects due to LIPs, as demonstrated in the Phanerozoic record, it is suggested that LIP events represent useful time markers in the Precambrian Era as proxies for some significant global environmental changes that are preserved in the sedimentary record.

Volatiles beneath mid-ocean ridges: Deep melting, channelised transport, focusing, and metasomatism

Deep-Earth volatile cycles couple the mantle with near-surface reservoirs. Volatiles are emitted by volcanism and, in particular, from mid-ocean ridges, which are the most prolific source of basaltic volcanism. Estimates of volatile extraction from the asthenosphere beneath ridges typically rely on measurements of undegassed lavas combined with simple petrogenetic models of the mean degree of melting. Estimated volatile fluxes have large uncertainties; this is partly due to a poor understanding of how volatiles are transported by magma in the asthenosphere. Here, we assess the fate of mantle volatiles through numerical simulations of melting and melt transport at mid-ocean ridges. Our simulations are based on two-phase, magma/mantle dynamics theory coupled to an idealised thermodynamic model of mantle melting in the presence of water and carbon dioxide. We combine simulation results with catalogued observations of all ridge segments to estimate a range of likely volatile output from the global mid-ocean ridge system. We thus predict global MOR crust production of 66–73 Gt/yr (22–24 km3/yr) and global volatile output of 52–110 Mt/yr, corresponding to mantle volatile contents of 100–200 ppm. We find that volatile extraction is limited: up to half of deep, volatile-rich melt is not focused to the axis but is rather deposited along the LAB. As these distal melts crystallise and fractionate, they metasomatise the base of the lithosphere, creating rheological heterogeneity that could contribute to the seismic signature of the LAB.

Greenhouses Gases, Carbonyls, and Volatile Organic Compounds Surface Flux Emissions at Three Final Waste Disposal Sites Located in the Metropolitan Area of Costa Rica

The surface flux emissions for volatile organic compounds (VOC’s) (alcohols and aromatic species), priority carbonyls and greenhouse gases, were measured in three different final disposal sites for urban solid waste located in the metropolitan area of Costa Rica, between July and October 2014. The emissions fluxes were determined using the static sampling chamber technique coupled to two different adsorption tubes: active charcoal (Supelco, ORBO 32) to capture BTEX and alcohols; and 2,4-DNPH coated silica gel (SKC, 226-119) for carbonyls. As for the VOCs, the BTEX, Alcohols, and Carbonyls total fluxes were in the range of 3 to 258, 1 to 318 and 0.4 to 8.5 mg/(m2d&#237a), respectively. The magnitudes per site were in the following order La Carpio > El Huaso > Rio Azul. Ethanol and BTEX presented a high correlation in all the cases because possibly they are sharing the same sources or formation mechanisms. The emission fluxes spatial distributions among the sites were very variable and dependent on the location of the active cells and their age. Only La Carpio showed a more homogeneous distribution due to its middle age.

Mantle to surface degassing of carbon- and sulphur-rich alkaline magma at El Hierro, Canary Islands

Basaltic volcanoes transfer volatiles from the mantle to the surface of the Earth. The quantification of deep volatile fluxes relies heavily on estimates of the volatile content of primitive magmas, the best archive of which is provided by melt inclusions. Available data from volcanoes producing mafic alkaline lavas in a range of tectonic settings suggest high volatile fluxes, but information remains sparse, particularly for intraplate ocean islands. Here we present measurements of volatile and trace element concentrations, as well as sulphur speciation, in olivine-hosted melt inclusions and matrix glasses from quenched basanite lava balloon samples from the 2011–2012 submarine eruption at El Hierro, Canary Islands. The results reveal remarkably high concentrations of dissolved volatiles and incompatible trace elements in this magma, with ∼80 ppm Nb and up to 3420 ppm CO2, 3.0 wt.% H2O and 5080 ppm S. Reconstructed primitive CO2 contents, considering CO2/Nb systematics and possible CO2 sequestration in shrinkage bubbles, reach weight percent levels, indicating that carbon is a major constituent of Canary Island magmas at depth and that exsolution of a CO2-rich fluid begins in the mantle at pressures in excess of 1 GPa. Correlations between sulphur concentration, sulphur speciation and water content suggest strong reduction of an initially oxidised mantle magma, likely controlled by coupled H2O and S degassing. This late-stage redox change may have triggered sulphide saturation, recorded by globular sulphide inclusions in clinopyroxene and ulvöspinel. The El Hierro basanite thus had a particularly high volatile-carrying capacity and released a minimum of 1.3–2.1 Tg CO2 and 1.8–2.9 Tg S to the environment, causing substantial stress on the local submarine ecosystem. These results highlight the important contribution of alkaline ocean island volcanoes, such as the Canary Islands, to volatile fluxes from the mantle.

Boron desorption and fractionation in Subduction Zone Fore Arcs: Implications for the sources and transport of deep fluids

AbstractAt many subduction zones, pore water geochemical anomalies at seafloor seeps and in shallow boreholes indicate fluid flow and chemical transport from depths of several kilometers. Identifying the source regions for these fluids is essential toward quantifying flow pathways and volatile fluxes through fore arcs, and in understanding their connection to the loci of excess pore pressure at depth. Here we develop a model to track the coupled effects of boron desorption, smectite dehydration, and progressive consolidation within sediment at the top of the subducting slab, where such deep fluid signals likely originate. Our analysis demonstrates that the relative timing of heating and consolidation is a dominant control on pore water composition. For cold slabs, pore water freshening is maximized because dehydration releases bound water into low porosity sediment, whereas boron concentrations and isotopic signatures are modest because desorption is strongly sensitive to temperature and is only partially complete. For warmer slabs, freshening is smaller, because dehydration occurs earlier and into larger porosities, but the boron signatures are larger. The former scenario is typical of nonaccretionary margins where insulating sediment on the subducting plate is commonly thin. This result provides a quantitative explanation for the global observation that signatures of deeply sourced fluids are generally strongest at nonaccretionary margins. Application of our multitracer approach to the Costa Rica, N. Japan, N. Barbados, and Mediterranean Ridge subduction zones illustrates that desorption and dehydration are viable explanations for observed geochemical signals, and suggest updip fluid migration from these source regions over tens of km.

Transfer of volatiles and metals from mafic to felsic magmas in composite magma chambers: An experimental study

In order to determine the behavior of metals and volatiles during intrusion of mafic magma into the base of silicic, upper crustal magma chambers, fluid–rock partition coefficients (Dfluid/rock) of Li, B, Na, S, Cl, K, Mn, Fe, Rb, Sr, Ba, Ce, Cu, Zn, Ag, Cd, Mo, As, Se, Sb, Te, W, Tl, Pb and Bi were determined experimentally at 2kbar and 850°C close to the solidus of mafic magma. In a first step, volatile-bearing mafic glasses were prepared by melting a natural basaltic trachyandesite in the presence of volatile-bearing fluids at 1200°C/10kbar in piston cylinder presses. The hydrous glasses were then equilibrated in subsequent experiments at 850°C/2kbar in cold-seal pressure vessels, which caused 80–90% of the melt to crystallize. After 0.5–2.0days of equilibration, the exsolved fluid was trapped by means of in-situ fracturing in the form of synthetic fluid inclusions in quartz. Both the mafic rock residue and the fluid inclusions were subsequently analyzed by laser-ablation ICP-MS for major and trace elements. Reverse experiments were conducted by equilibrating metal-bearing aqueous solutions with rock powder and then trapping the fluid. In two additional experiments, information on relative element mobilities were obtained by reacting fluids that exsolved from crystallizing mafic magma with overlying silicic melts. The combined results suggest that under the studied conditions S, Cl, Cu, Se, Br, Cd and Te are most volatile (Dfluid/rock >10), followed by Li, B, Zn, As, Ag, Sb, Cs, W, Tl, Pb and Bi (Dfluid/rock=1–10). Less volatile are Na, Mg, K, Ca, Mn, Fe, Rb, Sr, Mo and Rb (Dfluid/rock 0.1–1), and the least fluid-mobile elements are Al, Si, Ti, Zr, Ba and Ce (Dfluid/rock <0.1). This trend is broadly consistent with relative element volatilities determined on natural high-temperature fumarole gases, although some differences exist. Based on the volatility data and measured mineral–melt and sulfide–melt partition coefficients, volatile fluxing in felsic natural samples may be identified by Cu, Se, Te and Cd-enrichment in magmatic sulfides, and by As, Se, Cd and Bi-enrichment in magmatic apatite.

Constraints from Phase Equilibrium Experiments on Pre-eruptive Storage Conditions in Mixed Magma Systems: a Case Study on Crystal-rich Basaltic Andesites from Mount Merapi, Indonesia

Mount Merapi is one of Indonesia’s and the world’s most hazardous volcanoes. Existing constraints on the location and the crystallization conditions of its pre-eruptive magma reservoir based on mineral and glass thermobarometry and geophysical surveys are inconclusive, yet of immediate importance for future hazard mitigation. Here, we use two series of phase equilibrium experiments to quantify the conditions of pre-eruptive magma storage and magma recharge in Merapi’s upper-crustal reservoir: (1) to characterize crystallization at total equilibrium conditions; (2) to characterize crystallization at local equilibrium conditions between crystal rims and host melt. We demonstrate that this experimental approach can constrain pre-eruptive crystallization conditions and their variation in crystal-rich, mixed magma systems, such as that of Merapi, for which standard crystallization experiments and mineral thermobarometry fail. In agreement with geophysical estimates, we infer that Mount Merapi’s pre-eruptive reservoir partially crystallizes at ≥100–200 ± 75 MPa and thus at relatively shallow depths of c. ≥4·5 to ∼9 km. Magmas are stored at ≥925–950 ± 25°C with a melt H2O content of ∼3–4 wt % and a vapour phase with an XH2O [H2O/(H2O + CO2)] of ∼0·5–0·6 ± 0·1. Pre-eruptive recharge magmas, in contrast, have a temperature >950 to <1000°C, a higher melt H2O content of ∼4–5 wt % and a vapour phase with a higher XH2O of ∼0·8 ± 0·1. We hypothesize that these variations in melt H2O content and vapour XH2O between resident and pre-eruptive recharge magmas relate to variable degrees of open-system degassing of magma parcels en route into the reservoir rather than to variations in volatile fluxing of the stored magmas.