Chlorine isotope composition of volcanic rocks and gases at Stromboli volcano (Aeolian Islands, Italy): Inferences on magmatic degassing prior to 2014 eruption

Abstract Among the magmatic volatiles, chlorine (Cl) is degassed at shallow depths offering the opportunity to investigate the behavior of magmatic degassing close to the surface, and the possible occurrence of chemical and isotopic fractionation related to gas/melt partitioning. However, it is still unclear if the isotopic composition of Cl (δ 37 Cl) can be used as a proxy of magmatic degassing. In this work, we investigate the concentrations of chlorine and sulfur, and the Cl isotope composition of rocks and plume gases collected at Stromboli volcano, Aeolian Islands, Italy. This volcano was chosen because it is characterized by persistent eruptive activity (i.e., Strombolian explosions) and by the presence of magma at very shallow levels in the conduits. Rocks belonging to the different magmatic series erupted throughout the formation of the volcano have δ 37 Cl values ranging between − 1.0 and + 0.7‰. The isotopic composition seems independent of the Cl concentration of the rocks, but shows a negative correlation with SiO 2 content. Plume gases have a greater isotopic compositional variability than the rocks (− 2.2‰ ≤ δ 37 Cl ≤ + 1.5‰) and the composition seems related to the level of volcanic activity at Stromboli. Gases collected in 2011–2013 during days of ordinary eruptive activity are characterized by δ 37 Cl values ranging from + 0.3 to + 1.5‰ and S/Cl molar ratios between 1.4 and 2.2, similar to previous S/Cl measurements performed at Stromboli with other techniques. Plume gases collected in July 2014, in days of high-level eruptive activity preceding the onset of the 2014 effusive eruption, have negative δ 37 Cl values (− 2.2‰ ≤ δ 37 Cl ≤ − 0.1‰) and S/Cl between 0.9 and 1.2, which are among the lowest S/Cl values measured at this volcano. The amplitude of the volcanic tremor and the variation in the inclination of very long period (VLP) seismic signal polarization clearly indicate that in July 2014 the intensity and frequency of Strombolian explosions, as well as the level of magma in the conduits, were higher than normal. This suggests that when magmatic degassing occurs at very shallow depths (magma residing at few tens of meters below the craters), isotopic fractionation between gaseous and dissolved chlorine (lnα gas-melt  > 0) can occur, resulting in a depletion of 37 Cl in the melt. Finally, we argue that the range of δ 37 Cl values measured in rocks and gases at Stromboli overlaps most of the known mantle reservoirs (i.e., DMM, HIMU and EM-EM1), indicating that the transfer of chlorine from the mantle to the surface occurs without significant isotopic fractionation. This work opens new perspectives for better constraining the isotope signature of chlorine of different magmatic systems and mantle reservoirs on the Earth.

[1]  U. Platt,et al.  Active alkaline traps to determine acidic‐gas ratios in volcanic plumes: Sampling techniques and analytical methods , 2014 .

[2]  Luca D'Auria,et al.  Seismological Insights on the Shallow Magma System , 2013 .

[3]  J. Barnes,et al.  Stable chlorine isotope behavior during volcanic degassing of H2O and CO2 at Mono Craters, CA , 2014, Bulletin of Volcanology.

[4]  M. Martini,et al.  Source and path effects in the wave fields of tremor and explosions at Stromboli Volcano, Italy , 1997 .

[5]  Luca D'Auria,et al.  Slug Flow: Modeling in a Conduit and Associated Elastic Radiation , 2009, Encyclopedia of Complexity and Systems Science.

[6]  M. Laiolo,et al.  Probing Stromboli volcano from the mantle to paroxysmal eruptions , 2008 .

[7]  T. Plank,et al.  The volatile content of magmas from Arenal volcano, Costa Rica , 2006 .

[8]  M. Laiolo,et al.  Mafic and ultramafic xenoliths in San Bartolo lava field: New insights on the ascent and storage of Stromboli magmas , 2006 .

[9]  A. Sobolev,et al.  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) , 2006 .

[10]  Clive Oppenheimer,et al.  Sulfur Degassing From Volcanoes: Source Conditions, Surveillance, Plume Chemistry and Earth System Impacts , 2011 .

[11]  J. M. Moor,et al.  Temporal variations in fumarole gas chemistry at Poás volcano, Costa Rica , 2015 .

[12]  S. Ciliberto,et al.  Time constraints for modeling source dynamics of volcanic explosions at Stromboli , 2001 .

[13]  J. Charlou,et al.  Chlorine isotopic compositions of high temperature hydrothermal vent fluids over ridge axes , 2005 .

[14]  M. Ripepe,et al.  Effusive to explosive transition during the 2003 eruption of Stromboli volcano , 2005 .

[15]  N. Métrich,et al.  Volatile Abundances in Basaltic Magmas and Their Degassing Paths Tracked by Melt Inclusions , 2008 .

[16]  Z. Sharp,et al.  Chlorine isotope homogeneity of the mantle, crust and carbonaceous chondrites , 2007, Nature.

[17]  B. Scaillet,et al.  Experimental Crystallization of a High-K Arc Basalt: the Golden Pumice, Stromboli Volcano (Italy) , 2006 .

[18]  L. Francalanci,et al.  Chapter 13 Eruptive, volcano-tectonic and magmatic history of the Stromboli volcano (north-eastern Aeolian archipelago) , 2013 .

[19]  Z. Sharp,et al.  An experimental determination of chlorine isotope fractionation in acid systems and applications to volcanic fumaroles , 2010 .

[20]  Z. Sharp,et al.  Chlorine isotope vapor–liquid fractionation during experimental fluid-phase separation at 400 °C/23 MPa to 450 °C/42 MPa , 2006 .

[21]  P. Manetti,et al.  Volcanological and magmatological evolution of Stromboli volcano (Aeolian Islands): The roles of fractional crystallization, magma mixing, crustal contamination and source heterogeneity , 1989 .

[22]  J. Barnes,et al.  Chlorine isotope composition of volcanic gases and rocks at Mount Etna (Italy) and inferences on the local mantle source , 2013 .

[23]  A. Bertagnini,et al.  Conditions of Magma Storage, Degassing and Ascent at Stromboli: New Insights into the Volcano Plumbing System with Inferences on the Eruptive Dynamics , 2010 .

[24]  R. Moretti,et al.  Chlorine Partitioning Between a Basaltic Melt and H2O-CO2 Fluids at Mount Etna , 2009 .

[25]  A. Long,et al.  Natural chlorine isotope variations , 1984, Nature.

[26]  J. Barnes,et al.  Chlorine stable isotope variations across the Quaternary volcanic arc of Ecuador , 2014 .

[27]  M. Ripepe,et al.  Temperature and dynamics of degassing at Stromboli , 2007 .

[28]  Luca D'Auria,et al.  Changes in the VLP seismic source during the 2007 Stromboli eruption , 2009 .

[29]  J. Webster,et al.  Solubilities of sulfur, noble gases, nitrogen, chlorine, and fluorine in magmas , 1994 .

[30]  A. Bekker,et al.  The chlorine isotope composition of chondrites and Earth , 2013 .

[31]  Maurizio Ripepe,et al.  Strombolian explosive styles and source conditions: insights from thermal (FLIR) video , 2007 .

[32]  L. Francalanci,et al.  The volcanic activity of Stromboli in the 1906–1998 AD period: mineralogical, geochemical and isotope data relevant to the understanding of the plumbing system , 2004 .

[33]  P. Scandone,et al.  Seismotectonics of the Calabrian arc , 1982 .

[34]  J. Webster,et al.  Chloride and water solubility in basalt and andesite melts and implications for magmatic degassing , 1999 .

[35]  M. Liuzzo,et al.  The 2014 effusive eruption at Stromboli volcano (Italy): Inferences from soil CO2 flux and 3He/4He ratio in thermal waters , 2015 .

[36]  R. W. Le Maitre,et al.  A Chemical Classification of Volcanic Rocks Based on the Total Alkali-Silica Diagram , 1986 .

[37]  E. Salvioli-Mariani,et al.  Cordierite-anorthoclase hornfels xenoliths in Stromboli lavas (Aeolian Islands, Sicily): an example of a fast cooled contact aureole , 2003 .

[38]  A. Bertagnini,et al.  Crystallization Driven by Decompression and Water Loss at Stromboli Volcano (Aeolian Islands, Italy) , 2001 .

[39]  T. Caltabiano,et al.  Major eruptive style changes induced by structural modifications of a shallow conduit system: the 2007–2012 Stromboli case , 2014, Bulletin of Volcanology.

[40]  Bernard A. Chouet,et al.  Long-period volcano seismicity: its source and use in eruption forecasting , 1996, Nature.

[41]  Alejandro W. Rodriguez,et al.  Chlorine isotope and Cl–Br fractionation in fluids of Poás volcano (Costa Rica): Insight into an active volcanic–hydrothermal system , 2016 .

[42]  A. McGonigle,et al.  Passive vs. active degassing modes at an open-vent volcano (Stromboli, Italy) , 2012 .

[43]  L. Civetta,et al.  Magma dynamics during the 2007 Stromboli eruption (Aeolian Islands, Italy): Mineralogical, geochemical and isotopic data , 2009 .

[44]  C. Buonocunto,et al.  The Broadband Seismic Network of Stromboli Volcano, Italy , 2009 .

[45]  C. Federico,et al.  Anomalous magmatic degassing prior to the 5th April 2003 paroxysm on Stromboli , 2004 .

[46]  Z. Sharp,et al.  Chlorine isotope variations across the Izu-Bonin-Mariana arc , 2008 .

[47]  Giorgio Lacanna,et al.  The onset of the 2007 Stromboli effusive eruption recorded by an integrated geophysical network , 2009 .

[48]  A. Peccerillo,et al.  Transition from calc-alkaline to potassium-rich magmatism in subduction environments: geochemical and Sr, Nd, Pb isotopic constraints from the island of Vulcano (Aeolian arc) , 2000 .

[49]  S. Kohn,et al.  Experimental Simulation of Closed-System Degassing in the System Basalt–H2O–CO2–S–Cl , 2011 .

[50]  P. Zettwoog,et al.  Sulphur output and magma degassing budget of Stromboli volcano , 1994, Nature.

[51]  A. Renzulli,et al.  Pyrometamorphic Processes at the Magma–Hydrothermal System Interface of Active Volcanoes: Evidence from Buchite Ejecta of Stromboli (Aeolian Islands, Italy) , 2011 .

[52]  N. Casagli,et al.  Shifts in the eruptive styles at Stromboli in 2010–2014 revealed by ground-based InSAR data , 2015, Scientific Reports.

[53]  K. Haase,et al.  Chlorine isotope evidence for crustal recycling into the Earth's mantle , 2010 .

[54]  H. Eggenkamp δ37Cl : the geochemistry of chlorine isotopes , 1994 .

[55]  P. Manetti,et al.  Sr isotopic systematics in volcanic rocks from the island of Stromboli, Italy (aeolian arc) , 1988 .

[56]  S. Hurwitz,et al.  Tracing chlorine sources of thermal and mineral springs along and across the Cascade Range using halogen concentrations and chlorine isotope compositions , 2015 .

[57]  L. Francalanci,et al.  The Fate of High-Angle Dipping Slabs in the Subduction Factory: an Integrated Trace Element and Radiogenic Isotope (U, Th, Sr, Nd, Pb) Study of Stromboli Volcano, Aeolian Arc, Italy , 2007 .

[58]  J. M. Moor,et al.  Degassing at Anatahan volcano during the May 2003 eruption: Implications from petrology, ash leachates, and SO2 emissions , 2005 .

[59]  M. Ripepe,et al.  Monitoring Explosive Volcanic Activity Using Thermal Images, Stromboli Volcano, Italy , 2006 .

[60]  Mike Burton,et al.  Magmatic Gas Composition Reveals the Source Depth of Slug-Driven Strombolian Explosive Activity , 2007, Science.

[61]  Mike Burton,et al.  Spectroscopic evidence for a lava fountain driven by previously accumulated magmatic gas , 2005, Nature.

[62]  A. Bertagnini,et al.  Onset of the persistent activity at Stromboli Volcano (Italy) , 2000 .

[63]  P. Allard,et al.  S-Cl-F degassing pattern of water-rich alkali basalt: Modelling and relationship with eruption styles on Mount Etna volcano , 2006 .

[64]  Z. Sharp,et al.  A chlorine isotope study of DSDP/ODP serpentinized ultramafic rocks: Insights into the serpentinization process , 2006 .

[65]  A. Paonita,et al.  Sulfur isotopic compositions of fumarolic and plume gases at Mount Etna (Italy) and inferences on their magmatic source , 2012 .

[66]  I. Arienzo,et al.  Noble-gas signature of magmas from a heterogeneous mantle wedge: The case of Stromboli volcano (Aeolian Islands, Italy) , 2014 .

[67]  F. Giudicepietro,et al.  Source mechanisms of explosions at Stromboli Volcano, Italy, determined from moment‐tensor inversions of very‐long‐period data , 2003 .

[68]  D. Harlov,et al.  Iron-bearing chlor-fluorapatites in crustal xenoliths from the Stromboli volcano (Aeolian Islands, Southern Italy): an indicator of fluid processes during contact metamorphism , 2006 .

[69]  M. Ripepe,et al.  Infrasonic waves and volcanic tremor at Stromboli , 1996 .

[70]  Marco Liuzzo,et al.  A model of degassing for Stromboli volcano , 2010 .

[71]  A. Bertagnini,et al.  Stromboli volcano (Aeolian Archipelago, Italy): An open window on the deep-feeding system of a steady state basaltic volcano , 2003 .

[72]  R. Harmon,et al.  Oxygen isotope constraints on the crustal contribution to the subduction-related magmatism of the Aeolian Islands, southern Italy , 1990 .

[73]  Y. Muramatsu,et al.  Determination of halogens, with special reference to iodine, in geological and biological samples using pyrohydrolysis for preparation and inductively coupled plasma mass spectrometry and ion chromatography for measurement. , 1996, The Analyst.

[74]  L. Francalanci,et al.  A west-east geochemical and isotopic traverse along the volcanism of the Aeolian Island arc, southern Tyrrhenian Sea, Italy: Inferences on mantle source processes , 2007 .

[75]  P. Okubo,et al.  Location of long‐period events below Kilauea Volcano using seismic amplitudes and accurate relative relocation , 2003 .

[76]  M. Coleman,et al.  A cross-calibration of chlorine isotopic measurements and suitability of seawater as the international reference material , 2004 .

[77]  M. Coleman,et al.  The Chlorine Isotope Composition of Earth's Mantle , 2008, Science.

[78]  D. Hilton,et al.  Subducted lithosphere controls halogen enrichments in the Iceland mantle plume source , 2016 .

[79]  A. Bertagnini,et al.  Volcanology and Magma Geochemistry of the Present‐Day Activity: Constraints on the Feeding System , 2008 .

[80]  M. Ripepe,et al.  Air-wave phases in strombolian explosion quake seismograms: a possible indicator for the magma level? , 1994 .

[81]  E. Salvioli-Mariani,et al.  Glass-bearing crustal xenoliths (buchites) erupted during the recent activity of Stromboli (Aeolian Islands) , 2005 .

[82]  M. Tiepolo,et al.  Trace element and Pb–B–Li isotope systematics of olivine-hosted melt inclusions: insights into source metasomatism beneath Stromboli (southern Italy) , 2012, Contributions to Mineralogy and Petrology.

[83]  Gürdal Tuncel,et al.  Sources and source regions effecting the aerosol composition of the Eastern Mediterranean , 2008 .

[84]  Luca D'Auria,et al.  Real‐time monitoring and massive inversion of source parameters of very long period seismic signals: An application to Stromboli Volcano, Italy , 2006 .

[85]  L. Sagnotti,et al.  Holocene eruptive history of the Stromboli volcano: Constraints from paleomagnetic dating , 2008 .

[86]  M. Ripepe,et al.  Gas bubble dynamics model for shallow volcanic tremor , 1999 .

[87]  Z. Sharp,et al.  The Chlorine Isotope Composition of the Moon and Implications for an Anhydrous Mantle , 2010, Science.

[88]  B. Scaillet,et al.  Experimental Constraints on the Deep Magma Feeding System at Stromboli Volcano, Italy , 2009 .

[89]  Mike Burton,et al.  New insights into volcanic processes at Stromboli from Cerberus, a remote-controlled open-path FTIR scanner system , 2013 .

[90]  O. Crispi,et al.  Chlorine isotopes of thermal springs in arc volcanoes for tracing shallow magmatic activity , 2015 .

[91]  Luca D'Auria,et al.  Seismological monitoring of the February 2007 effusive eruption of the Stromboli volcano , 2007 .

[92]  A. Renzulli,et al.  Origin of high-silica liquids at Stromboli volcano (Aeolian Islands, Italy) inferred from crustal xenoliths , 2001 .

[93]  D. Hilton,et al.  Chlorine isotope variations along the Central American volcanic front and back arc , 2009 .