Data on unveiling the occurrence of transient, multi-contaminated mafic magmas inside a rhyolitic reservoir feeding an explosive eruption (Nisyros, Greece)

This data article includes the description and the geochemical and mineralogical dataset of 67 pyroclastic rock samples from the Upper Pumice (UP) explosive activity of Nisyros volcano (eastern South Aegean Active Volcanic Arc). A detailed field and petrographic description of the studied outcrops and samples are reported, including representative photomicrographs and SEM images, whole-rock major and trace elements compositions of 31 representative samples and Sr-Nd isotope ratios on 22 selected samples. Analytical methods and conditions used for data acquisition are also reported. The UP eruption produced a stratigraphic sequence constituted by a basal fallout deposit, gradually substituted by pyroclastic density current (PDC) deposits; these are overlaid by a lag-breccia unit, and the sequence is closed by a grey ash flow level. The juvenile is mainly constituted by white-yellow, moderately crystalline pumice with rhyolitic composition and homogenous Sr-Nd isotope values. Variable amounts of dense, grey, crystalline juvenile lapilli clasts (CRC, Crystal-Rich Clast), with rounded shape and less evolved composition (andesite to dacite) are also present in the deposit. These mafic CRCs are peculiar due to their large variability in textures (from distinctive diktytaxitic to strongly fragmented structure without a defined fabric) and in the geochemical and isotopic composition. The data acquired were fundamental to reconstruct the complex and peculiar history of ascent, storage and differentiation/assimilation processes of these mafic melts before their intrusion into the shallow, rhyolitic magma chamber, with important implication on the possible eruption trigger during the more recent explosive phase of activity at Nisyros volcano. Moreover, the geochemical and isotopic analyses provide new original data to the general knowledge of the Aegean volcanics. All the data reported in this paper are related to the research article Braschi et al. (2022

Nitrogen, helium, and argon reveal the magmatic signature of fumarole gases and episodes of outgassing from upper-crustal magma reservoirs. The case of the Nisyros caldera (Aegean Arc, Greece)

The chemical composition of gases emitted by active volcanoes reflects both magma degassing and shallower processes, such as fluid-rock hydrothermal interaction and mixing with atmospheric-derived fluids. Untangling the magmatic fluid endmember within surface gas emission is therefore challenging, even with the use of well-known magma degassing tracers such as noble gases. Here, we investigate the deep magmatic fluid composition at the Nisyros caldera (Aegean Arc, Greece) by measuring nitrogen and noble gas abundances and isotopes in naturally degassing fumaroles. Gas samples were collected from 32 fumarolic vents at water-boiling temperature between 2018 and 2021. These fumaroles are admixtures of magmatic fluids typical of subduction zones, groundwater (or air saturated water, ASW), and air. The N2, He, and Ar composition of the magmatic endmember is calculated by reverse mixing modeling and shows N2/He = 31.8 ± 4.5, N2/Ar = 281.6, d15N = +7 ± 3 ‰, 3He/4He = 6.2 Ra (where Ra is air 3He/4He), and 40Ar/36Ar = 551.6 ± 19.8. Although N2/He is significantly low with respect to typical values for arc volcanoes (1,000–10,000), the contribution of subducted sediments to the Aegean Arc magma generation is reflected by the positive d15N values of Nisyros fumaroles. The low N2/He ratio indicates N2-depletion due to solubility-controlled differential degassing of an upper-crustal silicic (dacitic/ rhyodacitic) melt in a high-crystallinity reservoir. We compare our 2018–2021 data with N2, He, and Ar values collected from the same fumaroles during a hydrothermal unrest following the seismic crisis in 1996–1997. Results show additions of both magmatic fluid and ASW during this unrest. In the same period, fumarolic vents display an increase in magmatic species relative to hydrothermal gas, such as CO2/CH4 and He/CH4 ratios, an increase of 50 C in the equilibrium temperature of the hydrothermal system (up to 325 C), and greater amounts of vapor separation. These variations reflect an episode of magmatic fluid expulsion during the seismic crisis. The excess of heat and mass supplied by the magmatic fluid injection is then dissipated through boiling of deeper and peripheral parts of the hydrothermal system. Reverse mixing modeling of fumarolic N2-He-Ar has therefore important ramifications not only to disentangle the magmatic signature from gases emitted during periods of dormancy, but also to trace episodes of magmatic outgassing and better understand the state of the upper crustal reservoir

Vibrational spectra of C60C8H8 and C70C8H8 in the rotor-stator and polymer phases

C60-C8H8 and C70-C8H8 are prototypes of rotor-stator cocrystals. We present infrared and Raman spectra of these materials and show how the rotor-stator nature is reflected in their vibrational properties. We measured the vibrational spectra of the polymer phases poly(C60C8H8) and poly(C70C8H8) resulting from a solid state reaction occurring on heating. Based on the spectra we propose a connection pattern for the fullerene in poly(C60C8H8), where the symmetry of the C60 is D2h. On illuminating the C60-C8H8 cocrystal with green or blue light a photochemical reaction was observed leading to a similar product to that of the thermal polymerization.Comment: 26 pages, 8 figures, to appear in Journal of Physical Chemistry B 2nd version: minor changes in wording, accepted version by journa

GEOMORPHOLOGY, SEDIMENTOLOGY AND GEOCHEMISTRY IN THE MARINE AREA BETWEEN SIFNOS AND KIMOLOS ISLANDS, GREECE

Στην ελάχιστα μελετημένη θαλάσσια περιοχή μεταξύ των νησιών Σίφνου και Κιμώλου πραγματοποιήθηκε μια εκτεταμένη ωκεανογραφική μελέτη, με σκοπό την καταγραφή της υποθαλάσσιας μορφολογίας και των χαρακτηριστικών των επιφανειακών ιζημάτων, καθώς και της πηγής προέλευσης αυτών. Έγιναν καταγραφές με πολυδεσμικό βυθόμετρο και δειγματοληψίες επιφανειακών ιζημάτων με box corer με το Ω/Κ Αιγαίο και ακολούθησαν αναλύσεις μεγέθους κόκκων, ορυκτολογίας και γεωχημείας. Ένα μεγάλο βαθυμετρικό βύθισμα εντοπίστηκε βόρεια της Κιμώλου, με μέγιστο βάθος 743 μ., που συγκεντρώνει λεπτόκοκκα ιζήματα. Η κατανομή των ιζημάτων ως προς το μέγεθος κόκκων χαρακτηρίζεται από σταδιακή μείωση του μεγέθους από νότο προς βορρά. Η ορυκτολογική σύσταση περιλαμβάνει ασβεστίτη, Mg-ασβεστίτη, αραγωνίτη, δολομίτη, χαλαζία, Κ-άστριους, πλαγιόκλαστα, αμφίβολους και αργιλικά ορυκτά. Οι κύριες ιζηματολογικές επαρχίες που αναγνωρίστηκαν είναι 1) η ρηχή περιοχή πλησίον της Κιμώλου, με υψηλό περιεχόμενο σε Si, Al, K, Rb και Ba, 2) η βαθιά περιοχή δυτικά της Σίφνου, όπου εμφανίζεται και το μεγάλο βύθισμα, που χαρακτηρίζεται από υψηλό περιεχόμενο σε Fe, Ti, Na, Mg, S, Cr, Cu, Ni, V, Zn και 3) το στενό μεταξύ Σίφνου και Κιμώλου, με υψηλότερο περιεχόμενο σε Ca, S και Sr. Στο βύθισμα αυτό, παρατηρήθηκε σημαντικός εμπλουτισμός των ιζημάτων σε μαγγάνιο, ενώ τα οξείδια του Mn φαίνεται να προσροφούν διάφορα μέταλλα.An extensive oceanographic survey was conducted in the marine area between Kimolos and Sifnos Islands, a rather poorly-studied sector of the Aegean Sea, in order to gain better understanding of submarine geomorphological features and associated sediment provenance. Multi-beam bathymetry and surface sediment sampling with a box corer were carried out on board R/V Aegaeo, followed by grain-size analysis, XRD and XRF measurements. A large circular depression was identified north of Kimolos reaching a water depth of 743 m, filled with fine grained sediments. Surface sediment distribution is characterized by gradual decrease in grain-size from silty sand to silt in a S-N direction. The mineralogical composition comprises calcite, Mgcalcite, aragonite, dolomite, quartz, K feldspars, plagioclase, amphiboles and clay minerals. Major sediment provinces identified were: (i) the shallow sector proximal to Kimolos, characterized by higher contents in Si, Al, K, Rb and Ba; (ii) the deep area west of Sifnos, including the large depression, characterized by higher contents in Fe, Ti, Na, Mg, S, Cr, Cu, Ni, V, Zn; and (iii) the south passage between Kimolos and Sifnos, which exhibits higher Ca, S, and Sr contents. Manganese enrichment was observed in and around the bathymetric depression, where Mn oxides act efficiently as scavengers of a suite of metals

Influence of electrolyte co-additives on the performance of dye-sensitized solar cells

The presence of specific chemical additives in the redox electrolyte results in an efficient increase of the photovoltaic performance of dye-sensitized solar cells (DSCs). The most effective additives are 4-tert-butylpyridine (TBP), N-methylbenzimidazole (NMBI) and guanidinium thiocyanate (GuNCS) that are adsorbed onto the photoelectrode/electrolyte interface, thus shifting the semiconductor's conduction band edge and preventing recombination with triiodides. In a comparative work, we investigated in detail the action of TBP and NMBI additives in ionic liquid-based redox electrolytes with varying iodine concentrations, in order to extract the optimum additive/I2 ratio for each system. Different optimum additive/I2 ratios were determined for TBP and NMBI, despite the fact that both generally work in a similar way. Further addition of GuNCS in the optimized electrolytic media causes significant synergistic effects, the action of GuNCS being strongly influenced by the nature of the corresponding co-additive. Under the best operation conditions, power conversion efficiencies as high as 8% were obtained

Synthesis of a square-planar rhodium alkylidene N-heterocyclic carbene complex and its reactivity toward alkenes

The first rhodium alkylidene square-planar complex stabilized by an N-heterocyclic carbene ligand, RhCl(-CHPh)(IPr)PPh3 (2; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-carbene), has been prepared by reaction of RhCl(IPr)(PPh3)2 (1) with phenyldiazomethane and its dynamic behavior in solution studied. Treatment of 2 with alkenes results in the formation of the ¿2-olefin complexes RhCl(¿2-CH2-CHR)(IPr)PPh3 (3, R = H; 4, R = Ph; 5, R = OEt) and new olefins arising from the coupling of the alkylidene with the alkenes, likely via a metallacyclobutane intermediate