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  • 1
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    Crystal-chemical variations of spinel, clinopyroxene, and plagioclase in MORB basaltic melt induced by continuous cooling (2022)
    Elsevier
    Details
    Publication Date: 2022-03-16
    Description: In this study we present the compositional changes of clinopyroxene (cpx), plagioclase (plg), spinel (sp), and glass experimentally solidified from an Icelandic MORB melt. The starting material was cooled at Patm and fO2 of air, in the thermal range of cooling (ΔTc) between 1300 °C (superliquidus) to 800 °C (solidus) with rates (ΔT/Δt) of 1, 7, 60, 180, 1800, and 9000 °C/h. The run products obtained at 1, 7 and 60 °C/h are holocrystalline, whilst between 60 and 180 °C/h plg disappears, and texture of cpx + sp. shifts from faceted to dendritic. As cooling rate increases, we observe that Fe2O3 decreases and Al2O3 increases in sp. and Al2O3 + Fe2O3 increase and CaO + MgO decrease in cpx. These measured variations mirror changes induced by cooling rate in cation (atoms per formula unit, a.p.f.u.) and molecular abundances of these two crystalline phases. Plg composition shows clear linear trends versus cooling rate. The chemistry of sp., cpx and, to a minor extent, plg solidified from this basaltic liquid is thus strictly related to the cooling rate condition and is similar to those observed in previous investigations on alkaline and evolved basaltic systems. In particular, cpx is the only mineral phase profusely present at all the cooling rates, showing the greatest chemical variations in terms of oxides, cations, and components. The intra-crystalline glass (≤ 50 μm from crystal rims) obtained at 180–1800 °C/h shows compositional variations related to the surrounding crystal growth, evidencing strong supersaturation phenomena (such as dendritic texture) due to the establishment of a diffusion-controlled growth regime. Chemical attributes of mineral phases are also quantitatively related with the maximum (Gmax) and average (GCSD) growth rates of sp., cpx, and plg. When compared with the starting melt composition, the chemistry of cpx suggests the attainment of near-equilibrium crystallization conditions at cooling rate ≤ 60 °C/h, whereas disequilibrium effects are found at cooling rate 〉 60 °C/h. In contrast, plg is in disequilibrium with the initial melt chemistry in all experiments. By using thermometric models, the calculated crystallization of plg takes place at temperatures much lower than those of cpx, when the crystal content is high and the diffusion of cations in the melt is slow due to the higher (residual) melt viscosity. Under such conditions and due to the effect of cooling, the system cannot return to homogeneous concentrations and, consequently, plg more effectively records the disequilibrium partitioning of cations between the growing crystal surface. The data-set reported here captures the entire (superliquidus to solidus) and intrinsic (heterogeneous site-free silicate liquid) solidification behavior from an actual MORB melt from very rapid to extremely sluggish cooling rate. Finally, all analytical relationships found in this work enable careful reconstruction of the solidification conditions of MORB melts, providing novel geo-speedometers for them at high fO2.
    Description: Published
    Description: 120765
    Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici
    Description: JCR Journal
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 2
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    Crystallization kinetics of clinopyroxene and titanomagnetite growing from a trachybasaltic melt: New insights from isothermal time-series experiments (2020)
    Details
    Publication Date: 2021-11-08
    Description: In order to investigate the role of crystallization kinetics in mafic alkaline systems, textural measurements, mineral compositional changes and diffusion modelling calculations have been carried out on isothermal time-series experiments. The data were obtained at 400 MPa and 1100 °C under anhydrous (nominally 0 wt% H2O) and hydrous (2 wt% H2O added) conditions. A synthetic trachybasaltic melt was first heated up to the superliquidus temperature of 1300 °C and then rapidly cooled at 80 °C/min down to 1100 °C. The final target temperature was kept constant over variable dwell times in the range of 0.5–24 h. Results from textural analysis indicate the attainment of fast crystal growth kinetics at the shortest experimental run duration, with early achievement of stable crystal sizes for clinopyroxene and titanomagnetite. The surface area to volume ratio weakly decreases with increasing dwell time, according to the development of euhedral crystal morphologies. Crystal growth rates are also observed to progressively decrease from 0.5 to 24 h. Due to the effect of fast growth kinetics, the morphological maturation of clinopyroxene progresses by attachment of dendrite branches, infilling and overgrowth phenomena, leading to the formation of well-faced and euhedral crystals. The kinetically-controlled cation exchange (Si + Mg) → (TAl + Fe3+) controls the clinopyroxene compositional variation, expanding the stability of Tschermak component at the expense of diopside. Conversely, titanomagnetite is characterized by an almost constant composition that, however, is enriched in incompatible Al and Mg cations, as typically observed under rapid crystal growth conditions. Titanomagnetite crystals show always euhedral morphology that develops by heterogeneous nucleation on early-formed clinopyroxene dendrites. Overall, the effect of undercooling causes strong supersaturation phenomena in the trachybasaltic melt, resulting in enhanced nucleation kinetics and fast attainment of a high crystallinity. As the dwell time increases, the bulk system tends to minimize the interfacial free energy between crystals and surrounding melt. This results in the progressive replacement of the early dendritic shapes developed in a diffusion-limited growth regime, by the formation of euhedral morphologies typical of interface-limited regimes that still retain the chemical evidences of the dendritic stage as complex zoning patterns in clinopyroxene.
    Description: Published
    Description: 113-129
    Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici
    Description: JCR Journal
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 3
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    Kinetic partitioning of major-minor cations between olivine and Hawaiian tholeiitic basalt under variable undercooling and cooling rate conditions (2021)
    Elsevier
    Details
    Publication Date: 2021-12-15
    Description: In order to elucidate the kinetic partitioning of cations between olivine and basalt, we performed undercooling (−ΔT) and cooling rate (CR) experiments at atmospheric pressure and QFM-2 buffer. Starting from the superliquidus temperature of 1250 °C, a Hawaiian tholeiitic basalt was cooled at the rates of 4 (CR4), 20 (CR20), and 60 (CR60) °C/h to the final target temperatures of 1175 °C (−ΔT = 35 °C; −ΔT35) and 1125 °C (−ΔT = 85 °C; −ΔT85). Results show that polyhedral olivine morphologies are obtained at -ΔT35, whereas strong disequilibrium skeletal and/or dendritic textures form at -ΔT85. The amount of forsterite in olivine decreases from to 85% to 78% with increasing both -ΔT and CR. A diffusive boundary layer also develops in the melt next to the olivine surface and its composition becomes progressively enriched in Ca, owing to its incompatible behavior with the lattice site. Residual melts are progressively depleted in silica and enriched in alkali from CR4 to CR60, but silica-rich melts are observed with increasing -ΔT. In terms of Fe2+-Mg exchange, olivines obtained at -ΔT35 are always in equilibrium with the diffusive boundary layer, comprising both the interface melt next to the olivine surface and the far-field melt where all chemical gradients cease. At -ΔT85, however, the Fe2+-Mg exchange indicates two distinct equilibration stages between olivine core and far-field melt, and between olivine rim and interface melt. Partition coefficients (Kd) of Mg, Fe, Mn, Ca, and Cr calculated at the olivine-melt interface preferentially change as a function of -ΔT rather than CR. From -ΔT35 to -ΔT85, KdMg, KdFe, KdMn, and KdCr remarkably increase, whereas the opposite applies to KdCa. Through the application of equilibrium partitioning models, we found that Mg, Fe, Mn, and Ca are incorporated into the olivine lattice site at near-equilibrium proportions. This generally good agreement with modeling data demonstrates that diffusive mass transport of cations in our experiments occurred under the conditions of local equilibrium at the olivine surface. In contrast, marked deviations from the expected equilibrium are found for KCr in response to the major influence of crystal field stabilization energy on cation incorporation.
    Description: Published
    Description: 120485
    Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici
    Description: JCR Journal
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 4
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    High pressure experimental investigation of clinopyroxene dissolution in a K-basaltic melt (2022)
    Elsevier
    Details
    Publication Date: 2022-02-24
    Description: Dissolution of clinopyroxene (cpx) in a K-basaltic melt from the Campi Flegrei Volcanic District (Italy) has been investigated through dissolution and dissolution-crystallization experiments at pressure of 0.8 GPa, superliquidus temperature of 1350 ◦C, and dwell times between 0.5 and 1 h. The obtained dissolution rates range from 7.9⋅10− 6 cm s− 1 to 6.1⋅10− 6 cm s− 1 as a function of dwell time. In the dissolution-crystallization experiment (1300 ◦C; 0.8 GPa; 2 h), the formation of overgrowth rims accompanied by new cpx crystals suggests that the injection of recharge magmas in basaltic reservoir may lead to inverse or oscillatory zonation. The interaction between cpx and K-basaltic melt at ~1570 ◦C was studied by in situ radiography using synchrotron radiation combined with the Paris-Edinburgh press. This resulted in cpx resorption to occur depending on the temperature conditions with respect to the liquidus temperature of the cpx (TcpxL). The calculated cpx dissolution rates are ~5⋅10− 3 cm s− 1 at T ≤ TcpxL and ~ 3⋅10− 2 cm s− 1 at T ≥ TcpxL. The role of crystal dissolution in the estimation of magma residence times has been also tested for a natural magmatic system by interpolating the dissolution rates (~10− 5–10− 6 cm s− 1) with the textural data of cpx phenocrysts from the Agnano-Monte Spina pyroclastic deposit at Campi Flegrei caldera (Campanian region, Italy). Results from calculations indicate that the time required for partial or complete resorption of phenocrysts varies from ~0.5 to ~40 h, and that the effect of crystal dissolution may be relevant to estimate magma residence times whether signifcant dissolution occurs during magma mixing processes.
    Description: Published
    Description: 120533
    Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici
    Description: JCR Journal
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 5
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    A K-feldspar–liquid hygrometer specific to alkaline differentiated magmas (2020)
    Details
    Publication Date: 2021-11-08
    Description: We present a K-feldspar-liquid hygrometer specific to alkaline differentiated magmas that is calibrated through the regression analysis of sanidine and anorthoclase crystals coexisting with trachyte and phonolite melts. Partial-regression leverage plots were used to determine the minimum number of regression parameters that closely describe the variance of the dataset. The derived model was tested using K-feldspar-liquid pairs not included into the calibration dataset in order to address issues of systematic errors. When K-feldspar and plagioclase crystals coprecipitate from the same alkaline liquid under identical P-T-X-fO(2)-H2O conditions, the ability prediction of the new hygrometer is comparable to that of previous plagioclase-liquid models. To minimize the error of H2O estimate caused by the inadvertent use of disequilibrium data in natural samples, we have also calibrated a new test for equilibrium based on Or-Ab exchange between K-feldspar and coexisting melt. As an immediate application for both equilibrium and hygrometer models, we used as input data K-feldsparliquid pairs from alkaline explosive eruptions at the Phlegrean Fields. The estimates of H2O dissolved in natural trachyte and phonolite magmas closely match those determined by melt inclusion analysis and H2O solubility modeling. This leads to the conclusion that our new models can significantly contribute to a better quantitative characterization of the H2O content in differentiated alkaline magmas feeding large-volume explosive eruptions. (C) 2014 Elsevier B.V. All rights reserved.
    Description: Published
    Description: 1-8
    Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici
    Description: JCR Journal
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 6
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    Decoding multiple zoning patterns in clinopyroxene phenocrysts at Vulcano Island: A record of dynamic crystallization through interconnected reservoirs (2021)
    Elsevier
    Details
    Publication Date: 2021-12-15
    Description: Here we document how the different growth features and intracrystalline distributions of both major and trace cations in clinopyroxene phenocrysts are important recorders of the intricate magma dynamics at Vulcano Island (Aeolian Arc, Italy). The compositions of clinopyroxene phenocrysts from products erupted over the last ~54 ka cluster at different degrees of evolution, paralleling the polybaric-polythermal differentiation of mantle-derived mafic magmas into more evolved silicic melts. The hotter lower crust is the most favorable location for the storage of mafic magmas and the early crystallization of diopsidic (Mg#91) clinopyroxene (Pmax ≈ 750 MPa and Tmax ≈ 1220 °C). Diopsidic phenocrysts are depleted in both rare earth elements (REE) and high field strength elements (HFSE) but are enriched in transition elements (TE). The transfer and accumulation of primitive magmas in the colder upper crustal regions lead to the formation of an interconnected series of more differentiated magmatic reservoirs (P ≈ 100–450 MPa and T ≈ 1100–1180 °C) hosting discrete populations of clinopyroxene (Mg#84–85) with a broad spectrum of zonations and dissolution features. Recharge bands in clinopyroxene are markers of multiple inputs of primitive REE-HFSE-poor, TE-rich magmas from depth. Augitic phenocrysts (Mg#82) with strong negative Eu anomaly and REE + HFSE enrichments crystallizes from highly differentiated trachytic and rhyolitic melts stored at very shallow crustal conditions (P ≤ 50 MPa and T ≤ 1100 °C). These silicic reservoirs represent residual melts trapped-extracted from crystal-dominated mush regions in the uppermost part of the plumbing system. The residence time of clinopyroxene increases from ∼0.1 to ∼44 years from basalt to rhyolite, together with an increasing number of recharge bands. The mineral assemblage in more silicic and viscous mush melts is sufficiently resilient to record numerous mafic injections and high degrees of magma mixing, hybridization, and crystallization before eruption. Overall, the compositional zoning pattern of clinopyroxene presents a picture of plumbing system that extends through the crust and is characterized by distributions of melts and crystals which are progressively more evolved and heterogeneous in both space and time.
    Description: Published
    Description: 106517
    Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici
    Description: JCR Journal
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 7
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    Trachyte-phonolite transition at Dunedin Volcano: Fingerprints of magma plumbing system maturity and mush evolution (2021)
    Elsevier
    Details
    Publication Date: 2021-12-22
    Description: Phonolite-trachyte associations are a common feature of alkaline volcanoes in intraplate settings, and their coexistence challenges closed-system magmatic differentiation scenarios. Here we have investigated the mineralogical and petrochemical features of dikes, lavas, pyroclastic deposits, and comagmatic crystal-rich enclaves outcropping at Dunedin Volcano (Otago region, southern New Zealand). These alkaline magmatic products show both highly and mildly alkaline affinities, trending towards phonolitic and trachytic end-members, respectively. Intermediate rocks are phonotephrites + tephriphonolites (highly alkaline series) and mugearites + benmoreites (mildly alkaline series) with a phenocryst assemblage of clinopyroxene + plagioclase ± amphibole formed at low to mid-crustal levels (i.e., ~29–16 km). Phonolites are porphyritic rocks characterized by alkali feldspar ± amphibole ± clinopyroxene. Their whole-rock compositions are highly enriched in incompatible elements, with variable Ba + Sr contents. A weak negative to slightly positive Eu anomaly is also associated with 87Sr/86Sr ratios of 0.7028–0.7031, which are comparable to those of parental magmas. Geochemical models indicate that phonolites originate as interstitial melts that are generated via abundant alkali feldspar crystallization from a shallow crystalline mush (i.e., ~14–5 km). Strong melt differentiation and extraction is testified by crystal-rich enclaves, as remnants of the mush region. On the other hand, trachytes are phenocryst-poor products strongly depleted in Ba + Sr and with a marked negative Eu anomaly. Trachytes are characterized by 87Sr/86Sr ratios of 0.7040–0.7060, which are different from intermediate rocks and phonolites, and trend towards crustal isotopic compositions. Integrated mass balance, trace element, and energy-constrained modeling confirm that trachytes originate from mildly alkaline magmas interacting with the country rock during feldspar fractionation. We interpret the transition from trachyte to phonolite formation and eruption resulting from the maturation of the plumbing system through accumulation, cooling, and degassing of both highly and mildly alkaline magmas.
    Description: Published
    Description: 106545
    Description: 2V. Struttura e sistema di alimentazione dei vulcani
    Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici
    Description: 4V. Processi pre-eruttivi
    Description: JCR Journal
    Keywords: Crystalline mush evolution ; Alkaline magmas ; Crystal-rich enclaves ; Trachyte-phonolite transition ; Magma fractionation ; Crustal assimilation ; Dunedin Volcano
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 8
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    Intraplate Basalt Alkalinity Modulated by a Lithospheric Mantle Filter at the Dunedin Volcano (New Zealand) (2021)
    Oxford University Press
    Details
    Publication Date: 2021-12-22
    Description: Systematic variations in the crystal cargo and whole-rock isotopic compositions of mantle-derived basalts in the intraplate Dunedin Volcano (New Zealand) indicate the influence of a complex mantle-to-crust polybaric plumbing system. Basaltic rocks define a compositional spectrum from low-alkali basalts through mid-alkali basalts to high-alkali basalts. High-alkali basalts display clinopyroxene crystals with sector (hourglass) and oscillatory zoning (Mg#61–82) as well as Fe-rich green cores (Mg#43–69), whereas low-alkali basalts are characterized by clinopyroxenes with unzoned overgrowths (Mg#69–83) on resorbed mafic cores (Mg#78–88), coexisting with reversely zoned plagioclase crystals (An43–68 to An60–84 from core to rim). Complex magma dynamics are indicated by distinctive compositional variations in clinopyroxene phenocrysts, with Cr-rich zones (Mg#74–87) indicating continuous recharge by more mafic magmas. Crystallization of olivine, clinopyroxene and titanomagnetite occurred within a polybaric plumbing system extending from upper mantle to mid-crustal depths (485–1059 MPa and 1147–1286°C), whereas crystallization of plagioclase with subordinate clinopyroxene and titanomagnetite proceeded towards shallower crustal levels. The compositions of high-alkali basalts and mid-alkali basalts resemble those of ocean island basalts and are characterized by FOZO-HIMU isotopic signatures (87Sr/86Sri = 0.70277–0.70315, 143Nd/144Ndi = 0.51286–0.51294 and 206Pb/204Pb = 19.348–20.265), whereas low-alkali basalts have lower incompatible element abundances and isotopic compositions trending towards EMII (87Sr/86Sri = 0.70327–70397, 143Nd/144Ndi = 0.51282–0.51286 and 206Pb/204Pb = 19.278–19.793). High- and mid-alkali basalt magmas mostly crystallized in the lower crust, whereas low-alkali basalt magma recorded deeper upper mantle clinopyroxene crystallization before eruption. The variable alkaline character and isotope composition may result from interaction of low-alkaline melts derived from the asthenosphere with melts derived from lithospheric mantle, possibly initiated by asthenospheric melt percolation. The transition to more alkaline compositions was induced by variable degrees of melting of metasomatic lithologies in the lithospheric mantle, leading to eruption of predominantly small-volume, high-alkali magmas at the periphery of the volcano. Moreover, the lithosphere imposed a filtering effect on the alkalinity of these intraplate magmas. As a consequence, the eruption of low-alkali basalts with greater asthenospheric input was concentrated at the centre of the volcano, where the plumbing system was more developed.
    Description: Published
    Description: egab062
    Description: 2V. Struttura e sistema di alimentazione dei vulcani
    Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici
    Description: 4V. Processi pre-eruttivi
    Description: JCR Journal
    Keywords: alkali basalts ; Dunedin Volcano ; thermobarometry ; primary magma ; lithospheric mantle filter ; Igneous Petrology ; Thermobarometry ; Mantle melting and metasomatism ; Magmatic plumbing systems
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 9
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    Intra-eruptive trachyte-phonolite transition: Natural evidence and experimental constraints on the role of crystal mushes (2020)
    Details
    Publication Date: 2021-11-08
    Description: The generation of silica undersaturated phonolite from silica saturated trachytes is uncommon, as it implies the crossing of the thermal barrier and critical plane of silica undersaturation. Nevertheless, a co-genetic suite displaying compositional transition from benmoreite-trachyte to phonolite has been observed within the Al Shaatha pyroclastic sequence in the Harrat Rahat Volcanic Field (Kingdom of Saudi Arabia). We performed crystallization experiments on benmoreite and trachyte starting compositions to simulate the pressure-temperature-volatile conditions that generated the observed liquid line of descent. The experimental conditions were 200-500 MPa, 850-1150 degrees C, 0-10 wt% H2O, 0.0-0.5 wt% CO2, and NNO+2 oxygen buffer. The experimental mineral assemblage consists of clinopyroxene, feldspar, and titanomagnetite, as well as glass in variable proportions. The degree of crystallinity of hydrous runs is lower than that of anhydrous ones at analogous pressure and temperature conditions. Clinopyroxene crystallizes with compositions diopside-augite and augite-hedenbergite, respectively, at 500 and 200 MPa. The saturation of feldspar is primarily controlled by temperature and volatile content, with the more potassic composition equilibrating at low temperature (850-900 degrees C) and anhydrous (for benmoreite) or hydrous (for trachyte) conditions. At low pressure (200 MPa), temperatures below 850 degrees C, and anhydrous conditions, the degree of crystallization is extremely high (〉90%), and the residual glass obtained from trachyte experiments is characterized by peralkaline and sodic affinity. This finding is consistent with natural eruptive products containing interstitial phonolitic glass within an anorthoclase framework. The shift from trachyte to phonolite is therefore interpreted as the result of open system interaction between trachytic magma and intercumulus phonolitic melt, as well as of dissolution of anorthoclase from a crystal mush.
    Description: Published
    Description: 1750–1764
    Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici
    Description: JCR Journal
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 10
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    Carrier and dilution effects of CO2 on thoron emissions from a zeolitized tuff exposed to subvolcanic temperatures (2022)
    The Royal Society
    Details
    Publication Date: 2022-02-11
    Description: Radon (222Rn) and thoron (220Rn) are two isotopes belonging to the noble gas radon (sensu lato) that is frequently employed for the geochemical surveillance of active volcanoes. Temperature gradients operating at subvolcanic conditions may induce chemical and structural modifications in rock-forming minerals and their related 222Rn-220Rn emissions. Additionally, CO2 fluxes may also contribute enormously to the transport of radionuclides through the microcracks and pores of subvolcanic rocks. In view of these articulated phenomena, we have experimentally quantified the changes of 220Rn signal caused by dehydration of a zeolitized tuff exposed to variable CO2 fluxes. Results indicate that, at low CO2 fluxes, water molecules and hydroxyl groups adsorbed on the glassy surface of macro- and micropores are physically removed by an intermolecular proton transfer mechanism, leading to an increase of the 220Rn signal. By contrast, at high CO2 fluxes, 220Rn emissions dramatically decrease because of the strong dilution capacity of CO2 that overprints the advective effect of carrier fluids. We conclude that the sign and magnitude of radon (sensu lato) changes observed in volcanic settings depend on the flux rate of carrier fluids and the rival effects between advective transport and radionuclide dilution.
    Description: Published
    Description: 201539
    Description: 6V. Pericolosità vulcanica e contributi alla stima del rischio
    Description: JCR Journal
    Keywords: dilution by CO2 degassing; mineral dehydration; radon and thoron; zeolitized tuff
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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