C–O–H–S fluids and granitic magma : how S partitions and modifies CO2 concentrations of fluid-saturated felsic melt at 200 MPa

Author Posting. © The Author(s), 2011. This is the author's version of the work. It is posted here by permission of Springer for personal use, not for redistribution. The definitive version was published in Contributions to Mineralogy and Petrology 162 (2011): 849-865, doi:10.1007/s00410-011-0628-1.Hydrothermal volatile-solubility and partitioning experiments were conducted with fluid-saturated haplogranitic melt, H2O, CO2, and S in an internally heated pressure vessel at 900°C and 200 MPa; three additional experiments were conducted with iron-bearing melt. The run-product glasses were analyzed by electron microprobe, FTIR, and SIMS; and they contain ≤ 0.12 wt% S, ≤ 0.097 wt.% CO2, and ≤ 6.4 wt.% H2O. Apparent values of log ƒO2 for the experiments at run conditions were computed from the [(S6+)/(S6++S2-)] ratio of the glasses, and they range from NNO-0.4 to NNO+1.4. The C-O-H-S fluid compositions at run conditions were computed by mass balance, and they contained 22-99 mol% H2O, 0-78 mol% CO2, 0-12 mol% S, and < 3 wt% alkalis. Eight S-free experiments were conducted to determine the H2O and CO2 concentrations of melt and fluid compositions and to compare them with prior experimental results for C-O-H fluid-saturated rhyolite melt, and the agreement is excellent. Sulfur partitions very strongly in favor of fluid in all experiments, and the presence of S modifies the fluid compositions, and hence, the CO2 solubilities in coexisting felsic melt. The square of the mole fraction of H2O in melt increases in a linear fashion, from 0.05-0.25, with the H2O concentration of the fluid. The mole fraction of CO2 in melt increases linearly, from 0.0003-0.0045, with the CO2 concentration of C-O-H-S fluids. Interestingly, the CO2 concentration in melts, involving relatively reduced runs (log ƒO2 ≤ NNO+0.3) that contain 2.5-7 mol% S in the fluid, decreases significantly with increasing S in the system. This response to the changing fluid composition causes the H2O and CO2 solubility curve for C-O-H-S fluid-saturated haplogranitic melts at 200 MPa to shift to values near that modeled for C-O-H fluid-saturated, S-free rhyolite melt at 150 MPa. The concentration of S in haplogranitic melt increases in a linear fashion with increasing S in C-O-H-S fluids, but these data show significant dispersion that likely reflects the strong influence of ƒO2 on S speciation in melt and fluid. Importantly, the partitioning of S between fluid and melt does not vary with the (H2O/H2O+CO2) ratio of the fluid. The fluid-melt partition coefficients for H2O, CO2, and S and the atomic (C/S) ratios of the run-product fluids are virtually identical to thermodynamic constraints on volatile partitioning and the H, S, and C contents of pre-eruptive magmatic fluids and volcanic gases for subduction-related magmatic systems thus confirming our experiments are relevant to natural eruptive systems.This research was supported in part by National Science Foundation awards EAR 0308866 and EAR-0836741 to J.D.W

Crystal and melt inclusion timescales reveal the evolution of magma migration before eruption

Volatile element concentrations measured in melt inclusions are a key tool used to understand magma migration and degassing, although their original values may be affected by different re-equilibration processes. Additionally, the inclusion-bearing crystals can have a wide range of origins and ages, further complicating the interpretation of magmatic processes. To clarify some of these issues, here we combined olivine diffusion chronometry and melt inclusion data from the 2008 eruption of Llaima volcano (Chile). We found that magma intrusion occurred about 4 years before the eruption at a minimum depth of approximately 8 km. Magma migration and reaction became shallower with time, and about 6 months before the eruption magma reached 3–4 km depth. This can be linked to reported seismicity and ash emissions. Although some ambiguities of interpretation still remain, crystal zoning and melt inclusion studies allow a more complete understanding of magma ascent, degassing, and volcano monitoring data.NRF (Natl Research Foundation, S’pore)MOE (Min. of Education, S’pore)Published versio

Melt inclusion record of the conditions of ascent, degassing, and extrusion of volatile-rich alkali basalt during the powerful 2002 flank eruption of Mount Etna (Italy)

Two unusual, highly explosive flank eruptions succeeded on Mount Etna in July August 2001 and in October 2002 to January 2003, raising the possibility of changing magmatic conditions. Here we decipher the origin and mechanisms of the second eruption from the composition and volatile (H2O, CO2, S, Cl) content of olivine-hosted melt inclusions in explosive products from its south flank vents. Our results demonstrate that powerful lava fountains and ash columns at the eruption onset were sustained by closed system ascent of a batch of primitive, volatile-rich ( 4 wt %) basaltic magma that rose from 10 km depth below sea level (bsl) and suddenly extruded through 2001 fractures maintained opened by eastward flank spreading. This magma, the most primitive for 240 years, probably represents the alkali-rich parental end-member responsible for Etna lavas’ evolution since the early 1970s. Few of it was directly extruded at the eruption onset, but its input likely pressurized the shallow plumbing system several weeks before the eruption. This latter was subsequently fed by the extrusion and degassing of larger amounts of the same, but slightly more evolved, magma that were ponding at 6–4 km bsl, in agreement with seismic data and with the lack of preeruptive SO2 accumulation above the initial depth of sulphur exsolution ( 3 km bsl). We find that while ponding, this magma was flushed and dehydrated by a CO2-rich gas phase of deeper derivation, a process that may commonly affect the plumbing system of Etna and other alkali basaltic volcanoes

S–Cl–F degassing pattern of water-rich alkali basalt: Modelling and relationship with eruption styles on Mount Etna volcano

Our knowledge of the degassing pattern of sulphur, chlorine and fluorine during ascent and eruption of basaltic magmas is still fragmental and mainly limited to water-poor basalts. Here we model and discuss the pressure-related degassing behaviour of S, Cl and F during ascent, differentiation and extrusion of H2O–CO2-rich alkali basalt on Mount Etna (Sicily) as a function of eruptive styles. Our modelling is based on published and new melt inclusion data for dissolved volatiles (CO2, H2O, S, Cl, F) in quenched explosive products from both central conduit (1989–2001) and lateral dyke (2001 and 2002) eruptions. Pressures are obtained from the dissolved H2O and CO2 concentrations, and vapour–melt partition coefficients of S, Cl and F are derived from best fitting of melt inclusion data for each step of magma evolution. This allows us to compute the compositional evolution of the gas phase during either open or closed system degassing and to compare it with the measured composition of emitted gases. We find that sulphur, chlorine and fluorine begin to exsolve at respective pressures of ∼140 MPa, ∼100 MPa and ≤10 MPa during Etna basalt ascent and are respectively degassed at >95%, 22–55%, and ∼15% upon eruption. Pure open system degassing fails to explain gas compositions measured during either lateral dyke or central conduit eruptions. Instead, closed-system ascent and eruption of the volatile-rich basaltic melt well accounts for the time-averaged gas composition measured during 2002-type lateral dyke eruptions (S/Cl molar ratio of 5±1, 35% bulk Cl loss). Extensive magma fragmentation during the most energetic fountaining phases enhances Cl release (55%) and produces a lower S/Cl ratio of 3.7, as actually measured. Comparatively slower magma rise in the central conduits of Etna favours both sulphide saturation of the melt and greater chlorine release (55%), resulting in a distinct S/Cl evolution path and final ratio in eruptive gas. In both eruption types, any previous bubble–melt separation at depth leads to increased S/Cl and S/F ratios in emitted gas. High S/Cl ratios measured during some discrete eruptive events can thus be explained by transitions from closed (deep) to open (shallow) system degassing, with differential gas transfer extending down to ∼2 km depth below the vents. This depth coincides with the base of the volcanic pile where structural discontinuities and the high magma vesicularity (60%) may favour separate gas flow. Finally, the excess S–Cl–F gas discharge through Etna summit craters during non-eruptive periods requires a mixed supply from shallow magma degassing in the volcanic conduits and deeper-derived SO2-rich bubbles from the sub-volcano plumbing system. Our modelling provides a useful reference framework for interpreting the monitored variations of S, Cl and F in Mount Etna gas emissions as a function of volcanic activity. More broadly, the observations made for S, Cl and F degassing on Etna may apply to other basaltic volcanoes with water-rich magmas, such as in arcs

J. Geophys. Res.-Solid Earth

International audienc

S–Cl–F degassing pattern of water-rich alkali basalt: Modelling and relationship with eruption styles on Mount Etna volcano

Our knowledge of the degassing pattern of sulphur, chlorine and fluorine during ascent and eruption of basaltic magmas is still fragmental and mainly limited to water-poor basalts. Here we model and discuss the pressure-related degassing behaviour of S, Cl and F during ascent, differentiation and extrusion of H2O–CO2-rich alkali basalt on Mount Etna (Sicily) as a function of eruptive styles. Our modelling is based on published and new melt inclusion data for dissolved volatiles (CO2, H2O, S, Cl, F) in quenched explosive products from both central conduit (1989–2001) and lateral dyke (2001 and 2002) eruptions. Pressures are obtained from the dissolved H2O and CO2 concentrations, and vapour–melt partition coefficients of S, Cl and F are derived from best fitting of melt inclusion data for each step of magma evolution. This allows us to compute the compositional evolution of the gas phase during either open or closed system degassing and to compare it with the measured composition of emitted gases. We find that sulphur, chlorine and fluorine begin to exsolve at respective pressures of ∼140 MPa, ∼100 MPa and ≤10 MPa during Etna basalt ascent and are respectively degassed at >95%, 22–55%, and ∼15% upon eruption. Pure open system degassing fails to explain gas compositions measured during either lateral dyke or central conduit eruptions. Instead, closed-system ascent and eruption of the volatile-rich basaltic melt well accounts for the time-averaged gas composition measured during 2002-type lateral dyke eruptions (S/Cl molar ratio of 5±1, 35% bulk Cl loss). Extensive magma fragmentation during the most energetic fountaining phases enhances Cl release (55%) and produces a lower S/Cl ratio of 3.7, as actually measured. Comparatively slower magma rise in the central conduits of Etna favours both sulphide saturation of the melt and greater chlorine release (55%), resulting in a distinct S/Cl evolution path and final ratio in eruptive gas. In both eruption types, any previous bubble–melt separation at depth leads to increased S/Cl and S/F ratios in emitted gas. High S/Cl ratios measured during some discrete eruptive events can thus be explained by transitions from closed (deep) to open (shallow) system degassing, with differential gas transfer extending down to ∼2 km depth below the vents. This depth coincides with the base of the volcanic pile where structural discontinuities and the high magma vesicularity (60%) may favour separate gas flow. Finally, the excess S–Cl–F gas discharge through Etna summit craters during non-eruptive periods requires a mixed supply from shallow magma degassing in the volcanic conduits and deeper-derived SO2-rich bubbles from the sub-volcano plumbing system. Our modelling provides a useful reference framework for interpreting the monitored variations of S, Cl and F in Mount Etna gas emissions as a function of volcanic activity. More broadly, the observations made for S, Cl and F degassing on Etna may apply to other basaltic volcanoes with water-rich magmas, such as in arcs.Published772-786reserve

Melt inclusion record of the conditions of ascent, degassing, and extrusion of volatile-rich alkali basalt during the powerful 2002 flank eruption of Mount Etna (Italy)

Two unusual, highly explosive flank eruptions succeeded on Mount Etna in July August 2001 and in October 2002 to January 2003, raising the possibility of changing magmatic conditions. Here we decipher the origin and mechanisms of the second eruption from the composition and volatile (H2O, CO2, S, Cl) content of olivine-hosted melt inclusions in explosive products from its south flank vents. Our results demonstrate that powerful lava fountains and ash columns at the eruption onset were sustained by closed system ascent of a batch of primitive, volatile-rich ( 4 wt %) basaltic magma that rose from 10 km depth below sea level (bsl) and suddenly extruded through 2001 fractures maintained opened by eastward flank spreading. This magma, the most primitive for 240 years, probably represents the alkali-rich parental end-member responsible for Etna lavas’ evolution since the early 1970s. Few of it was directly extruded at the eruption onset, but its input likely pressurized the shallow plumbing system several weeks before the eruption. This latter was subsequently fed by the extrusion and degassing of larger amounts of the same, but slightly more evolved, magma that were ponding at 6–4 km bsl, in agreement with seismic data and with the lack of preeruptive SO2 accumulation above the initial depth of sulphur exsolution ( 3 km bsl). We find that while ponding, this magma was flushed and dehydrated by a CO2-rich gas phase of deeper derivation, a process that may commonly affect the plumbing system of Etna and other alkali basaltic volcanoes.PublishedB04203reserve

2001 flank eruption of the alkali- and volatile-rich primitive basalt responsible for Mount Etna's evolution in the last three decades

Since the early 1970s enhanced eruptive activity of Mount Etna has been accompanied by selective geochemical changes in erupted lavas, among which a gradual increase of alkalis whose origin is still debated. Here we provide further insight into the origin of this recent evolution, based on a detailed study of the chemistry and dissolved volatile content of melt inclusions trapped in olivine crystals of unusual plagioclase-poor primitive basalt that was extruded during a highly explosive flank eruption in July–August 2001. Two types of lava were erupted simultaneously along a N–S fracture system. Trachybasalts from the upper vents (2950–2700 m) were simply drained out by fracturing of the central volcanic conduit. They are identical to summit crater lavas and contain Mg-poor olivines (Fo70–72) with evolved and volatile-poor melt inclusions that represent late-stage crystallisation during shallow open conduit degassing. In contrast, plagioclase-poor basalt (80% of total) extruded through the lower vents (2550–2100 m) derived from lateral dyke intrusion of a more primitive and volatile-rich magma across the sedimentary basement. This primitive melt is best preserved in rare Fo82.4–80.5 skeletal olivines present in lapilli deposits from the most powerful activities at the 2550 m vent. Its high dissolved contents of H2 O (3.4 wt.%), CO2 (0.11 to 0.41 wt.%), S (0.32 wt.%), Cl (0.16 wt.%) and F (0.094 wt.%) point to its closed system ascent from ∼400 to 250 MPa (∼12 to 6.5 km depth b.s.l.). However, the predominance of euhedral olivine phenocrysts with common reverse zoning (cores Fo76–78 and rims Fo78–80) and decrepited inclusions shows that most of the erupted basalt derived from a slightly more evolved, crystallizing body of the same magma that was invaded by the uprising primitive melt prior to erupting. The few preserved inclusions in these olivines indicate pre-eruptive storage of that magma body at about 5 km depth b.s.l., in coherence with seismic data. We propose that the 2001 flank eruption resulted from gradual overpressuring of Etna's shallow plumbing system due to the influx of volatile-rich primitive basalt that may have begun several months in advance. We find that this basalt is much richer in alkalis (2.0 wt.% K2 O) and has higher S/Cl (2.0) but lower Cl/K and Cl/F ratios than all pre-1970s Etnean lavas (1.4 wt.% K2 O, S/Cl=1.5), as further exemplified by melt inclusions in entrained olivine xenocrysts. Combining these new observations with previously published data, we argue that the 2001 basalt represents a new alkali-rich basic end-member feeding Mt. Etna, only few amount of which had previously been extruded during a 1974 peripheral eruption and, more recently, during brief paroxysmal summit events. Over the last three decades this new magma has progressively mixed with and replaced the former K-poorer trachybasalts filling the plumbing system, leading to extrusion of gradually more primitive and alkali-richer lavas. Its geochemical singularities cannot result from shallow crustal contaminations. Instead, they suggest the involvement of an alkali-richer but Cl-poorer arc-type component during recent magma genesis beneath Etna.Published1-17partially_ope

2001 flank eruption of the alkali- and volatile-rich primitive basalt responsible for Mount Etna's evolution in the last three decades

Since the early 1970s enhanced eruptive activity of Mount Etna has been accompanied by selective geochemical changes in erupted lavas, among which a gradual increase of alkalis whose origin is still debated. Here we provide further insight into the origin of this recent evolution, based on a detailed study of the chemistry and dissolved volatile content of melt inclusions trapped in olivine crystals of unusual plagioclase-poor primitive basalt that was extruded during a highly explosive flank eruption in July–August 2001. Two types of lava were erupted simultaneously along a N–S fracture system. Trachybasalts from the upper vents (2950–2700 m) were simply drained out by fracturing of the central volcanic conduit. They are identical to summit crater lavas and contain Mg-poor olivines (Fo70–72) with evolved and volatile-poor melt inclusions that represent late-stage crystallisation during shallow open conduit degassing. In contrast, plagioclase-poor basalt (80% of total) extruded through the lower vents (2550–2100 m) derived from lateral dyke intrusion of a more primitive and volatile-rich magma across the sedimentary basement. This primitive melt is best preserved in rare Fo82.4–80.5 skeletal olivines present in lapilli deposits from the most powerful activities at the 2550 m vent. Its high dissolved contents of H2 O (3.4 wt.%), CO2 (0.11 to 0.41 wt.%), S (0.32 wt.%), Cl (0.16 wt.%) and F (0.094 wt.%) point to its closed system ascent from ∼400 to 250 MPa (∼12 to 6.5 km depth b.s.l.). However, the predominance of euhedral olivine phenocrysts with common reverse zoning (cores Fo76–78 and rims Fo78–80) and decrepited inclusions shows that most of the erupted basalt derived from a slightly more evolved, crystallizing body of the same magma that was invaded by the uprising primitive melt prior to erupting. The few preserved inclusions in these olivines indicate pre-eruptive storage of that magma body at about 5 km depth b.s.l., in coherence with seismic data. We propose that the 2001 flank eruption resulted from gradual overpressuring of Etna's shallow plumbing system due to the influx of volatile-rich primitive basalt that may have begun several months in advance. We find that this basalt is much richer in alkalis (2.0 wt.% K2 O) and has higher S/Cl (2.0) but lower Cl/K and Cl/F ratios than all pre-1970s Etnean lavas (1.4 wt.% K2 O, S/Cl=1.5), as further exemplified by melt inclusions in entrained olivine xenocrysts. Combining these new observations with previously published data, we argue that the 2001 basalt represents a new alkali-rich basic end-member feeding Mt. Etna, only few amount of which had previously been extruded during a 1974 peripheral eruption and, more recently, during brief paroxysmal summit events. Over the last three decades this new magma has progressively mixed with and replaced the former K-poorer trachybasalts filling the plumbing system, leading to extrusion of gradually more primitive and alkali-richer lavas. Its geochemical singularities cannot result from shallow crustal contaminations. Instead, they suggest the involvement of an alkali-richer but Cl-poorer arc-type component during recent magma genesis beneath Etna