ALBERT

Description: The partitioning of REE,Y and Sc (R3+) between olivine and melt has been investigated experimentally during basalt-carbonate interaction. Three synthetic basalts (meltMg#72, meltMg#75 and meltMg#78) were doped with 0, 10 and 20 wt% CaCO3 and then equilibrated for 72 h at 1 atm, 1,150, 1,200 and 1,250 °C, and the QFM oxygen buffer. The thermal decomposition of CaCO3 produced CaO contents in the melt up to ~22 wt%. Regular relationships are found between the ionic radius and the partition coefficient (DR3+), showing typical near-parabolic patterns. DR3+ is weakly dependent on temperature, but decreases with increasing CaCO3 in the starting material (e.g., DSc decreases from 0.20 to 0.13). From the point of view of the lattice strain theory, DR3+ is described in terms of the radius of the crystal site (r0), the Young Modulus (E) due to the elastic response of that site to lattice strain caused by cation insertion, and the strain-free partition coefficient (D03+). The value of r0 decreases as Ca cations are accommodated into the more distorted M2 site of olivine via progressive CaFe substitutions. This mechanism is accompanied by a higher proportion of Mg cations entering into the smaller M1 site, making the optimum ionic radius smaller and favoring the crystallization of more forsteritic olivines from decarbonated melts. The enrichment of Ca in the crystal lattice is also proportional to the number of Si and Ca cations available in the melt. This causes E to be anticorrelated either with Ca in olivine or the activity of CaO in the melt. R3+ cations behave as network modifiers and, during basalt-carbonate interaction, the increasing abundance of non-bridging oxygens enhances the solubility of REE, Y and Sc in the melt. As a consequence, D03+ is negatively correlated with the degree of melt depolymerization. Additionally, the strain of the crystal lattice dominates the DR3+ parabolic patterns and D03+ is strongly controlled by forsterite and aluminium concentrations in olivine. The accommodation of REE, Y and Sc in the crystal lattice requires maintenance of local charge-balance by the generation of vacancies, in accord with a paired substitution of R3+ and a vacancy for Mg in octahedral sites.

Description: Published

Description: 327-340

Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici

Description: JCR Journal

Description: The purpose of this review study is to reappraise in a more comprehensive form the thermodynamic principles behind the partitioning of trace elements between clinopyroxene and melt. The original corollary is that the partitioning energetics controlling the crystal-melt exchange are described by two distinct but complementary contributions: ΔGpartitioning = ΔGstrain + ΔGelectrostatic. ΔGstrain is the excess of strain energy quantifying the elastic response of the crystallographic site to insertion of trace cations with radius different from that of the major cation at the site. ΔGelectrostatic is the excess of electrostatic energy requiring that an electrostatic energy penalty is paid when a trace cation entering the lattice site without strain has charge different from that of the resident cation. Lattice strain and electrostatic parameters for different isovalent groups of cations hosting the same lattice site from literature have been discussed in comparison with new partitioning data measured between Tschermak-rich clinopyroxenes and a primitive phonotephritic melt assimilating variable amounts of carbonate material. Through such a comparatively approach, we illustrate that the type and number of trace cation substitutions are controlled by both charge-balanced and -imbalanced configurations taking place in the structural sites of Tschermak-rich clinopyroxenes. A virtue of this complementary relationship is that the control of melt composition on the partitioning of highly charged cations is almost entirely embodied in the crystal chemistry and structure, as long as these crystallochemical aspects are the direct expression of both ΔGstrain and ΔGelectrostatic. A size mismatch caused by cation substitution is accommodated by elastic strain in the surrounding lattice of clinopyroxene, whereas the charge mismatch is enabled via increasing amounts of charge-balancing Tschermak components, as well as the electrostatic work done on transferring the trace cations from melt to crystallographic sites, and vice versa. The influence of the melt chemistry on highly-charged (3+ and 4+) cation partitioning is greatly subordinate to the lattice strain and electrostatic energies of substitutions, in agreement with the thermodynamic premise that both these energetic quantities represent simple-activity composition models for the crystal phase. The various charge-balanced and -imbalanced configurations change principally with aluminium in tetrahedral coordination and the clinopyroxene volume change produced by heterovalent cation substitutions. In contrast, for low-charged (1+ and 2+) cations, the role of melt chemistry cannot be properly deconvoluted from the structural changes of the crystal lattice. The incorporation of these cations into the clinopyroxene lattice depends on the number of structural sites critically important to accommodating network-modifying cations in the melt structure, implying that the partitioning energetics of monovalent and divalent cations are strictly controlled by both crystal and melt properties. We conclude that the competition between charge-balanced and charge-imbalanced substitutions may selectively change the ability of trace elements to be compatible or incompatible in the clinopyroxene structure, with important ramifications for the modeling of natural igneous processes in crustal magma reservoirs which differentiate under closed- and open-system conditions.

Description: Published

Description: 103351

Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici

Description: JCR Journal

Description: Estimating the quantity of CO2 diffusively emitted from the Earth's surface has important implications for volcanic surveillance and global atmospheric CO2 budgets. However, the identification and quantification of non-hydrothermal contributions to CO2 release can be ambiguous. Here, we describe a multi-parametric approach employed at the Nisyros caldera, Aegean Arc, Greece, to assess the relative influence of deep and shallow gases released from the soil. In April 2019, we measured diffuse soil surface CO2 fluxes, together with their carbon isotope compositions, and at a depth of 80 cm, the CO2 concentration, soil temperature, and the activities of radon and thoron. The contributions of deep CO2 and biogenic CO2 fluxes were distinguished on the basis of their carbon isotope compositions. A Principal Component Analysis (PCA), performed on the measured parameters, effectively discriminates between a deep- and a shallow degassing component. The total CO2 output estimated from a relatively small testing area was two times higher with respect to that observed in a previous survey (October 2018). The difference is ascribed to variation in the soil biogenic CO2 production, that was high in April 2019 (a wet period) and low or absent in October 2018 (a dry period). Accounting for seasonal biogenic activity is therefore critical in monitoring and quantifying CO2 emissions in volcanic areas, because they can partially- or completely overwhelm the volcanic-hydrothermal signal.

Description: Published

Description: 13782

Description: 6A. Geochimica per l'ambiente e geologia medica

Description: JCR Journal

Description: The geochemical evolution of olivine from primitive magmatic skarn environments has been studied by atmospheric pressure experiments carried out at 1250, 1200, and 1150 °C under QFM oxygen buffering conditions. The starting materials were three synthetic basalts (i.e., meltMg#78, meltMg#75, and meltMg#72) doped with variable amounts of CaCO3, in order to reproduce the natural concentration levels of CaO-rich magmas interacting with the skarn rock shells. Results from decarbonation experiments evidence that the crystallization of Fo-CaO-rich, NiO-poor olivines is more favored at higher temperatures when primitive basaltic magmas assimilate increasing amounts of carbonate materials. The number of large size Ca cations entering olivine crystal lattice is proportional to the amount of Ca-O-Si bonds available in the melt. Due to differences between Fe2+ and Mg cation radii, the Ca-Fe2+ substitutions into M2 crystallographic site are more facilitated than CaMg ones, thus enhancing the forsterite component in olivine. The partitioning behavior of Ni, Mg, Fe2+, Mn, and Ca between olivine and melt has been also investigated to better understand cation redistribution mechanisms at the magma‑carbonate reaction zone. In this context, some partitioning models from the literature have been refined to more accurately quantify the geochemical evolution of primitive skarn systems. Under the effect of CaCO3 assimilation, the partitioning of divalent cations, can be parameterized as a function of temperature, bulk composition (mostly, CaO and MgO contents in both olivine and melt) and melt structure (expressed as the number of non-bridging oxygens per tetrahedrally coordinated cations). Conversely, the exchange partition coefficients between Fe2+/Ca/Mn/Ni and Mg do not vary significantly as a function of temperature and meltMg#, due to the limited influence of these parameters on the melt structure. In turn, cation exchange reactions are primarily controlled by the strong depolymerizing effect of CaCO3 assimilation that increases the number of structural sites critically important to accommodating network-modifying cations in the melt phase. The comparison between cumulates and magmatic skarns from the Colli Albani Volcanic District (Italy) and experiments from this study provides quantitative constraints on the geochemical evolution of olivine phenocrysts and their melt inclusions as a function of carbonate assimilation.

Description: Published

Description: 104-121

Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici

Description: JCR Journal

Description: A correct description and quantification of the geochemical behaviour of REE+Y (rare earth elements and Y) and HFSE (high field strength elements) is a key requirement for modeling petrological and volcanological aspects of magma dynamics. In this context, mafic alkaline magmas (MAM) are characterized by the ubiquitous stability of clinopyroxene from mantle depths to shallow crustal levels. On one hand, clinopyroxene incorporates REE+Y and HFSE at concentration levels that are much higher than those measured for olivine, plagioclase, and magnetite. On the other hand, the composition of clinopyroxene is highly sensitive to variations in pressure,temperature, and melt-water content, according to exchange-equilibria between jadeite and melt, and between jadeite/Ca-Tschermak and diopside-hedenbergite. As a consequence, the dependence of the partition coefficient on the physicochemical state of the system results in a variety of DREE+Y and DHFSE values that are sensitive to the magmatic conditions at which clinopyroxenes nucleate and grow. In order to better explore magma dynamics using clinopyroxene chemical changes, an integrated P-T-H2Olattice strain model specific to MAM compositions has been developed. The model combines a set of refined clinopyroxene-based barometric, thermometric and hygrometric equations with thermodynamically-derived expressions for the lattice strain parameters, i.e., the strain-free partition coefficient (D0), the site radius (r0), andthe effective elastic modulus (E). Through this approach, it is found that the incorporation of REE+Y and HFSE into M2 and M1 octahedral sites of clinopyroxene is determined by a variety of physicochemical variables that may or may not change simultaneously during magma differentiation. The applicability of the P-T-H2O-lattice strain model to natural environments has been verified using clinopyroxene-melt pairs from a great number of volcanic eruptions at Mt. Etna volcano (Sicily, Italy). DREE+Y and DHFSE values recovered by the model have been used as input data to quantify fractional crystallization processes in natural MAM compositions. Results from calculation illustrate that the concentration of REE+Y and HFSE in the magma is primary controlled by the geochemical evolution of clinopyroxene in terms of major cation exchange-equilibria and trace cation lattice strain properties.

Description: Published

Description: 32-56

Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici

Description: 4V. Processi pre-eruttivi

Description: JCR Journal

Description: This study documents the compositional variations of phenocrysts from a basaltic trachyandesitic sill emplaced in the Valle del Bove at Mt. Etna volcano (Sicily, Italy). The physicochemical conditions driving the crystallization and emplacement of the sill magma have been reconstructed by barometers, oxygen barometers, thermometers and hygrometers based on clinopyroxene, feldspar (plagioclase + K-feldspar) and titanomagnetite. Clinopyroxene is the liquidus phase, recording decompression and cooling paths decreasing from 200 to 0.1 MPa and from 1050 to 940 °C, respectively. Plagioclase and K-feldspar cosaturate the melt in a lower temperature interval of ~1000–870 °C. Cation exchanges in clinopyroxene (Mg-Fe) and feldspar (Ca-Na) indicate that magma ascent is accompanied by progressive H2O exsolution (up to ~2.2 wt. %) under more oxidizing conditions (up to ΔNNO + 0.5). Geospeedometric constraints provided by Ti–Al–Mg cation redistributions in titanomagnetite indicate that the travel time (up to 23 h) and ascent velocity of magma (up to 0.78 m/s) are consistent with those inferred for other eruptions at Mt. Etna. These kinetic effects are ascribed to a degassing-induced undercooling path caused principally by H2O loss at shallow crustal conditions. Rare earth element (REE) modeling based on the lattice strain theory supports the hypothesis that the sill magma formed from primitive basaltic compositions after clinopyroxene (≤41%) and plagioclase (≤12%) fractionation. Early formation of clinopyroxene at depth is the main controlling factor for the REE signature, whereas subsequent degassing at low pressure conditions enlarges the stability field of plagioclase causing trace element enrichments during eruption towards the surface.

Description: Published

Description: id 126

Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici

Description: JCR Journal

Description: Understanding the mechanisms that control the accumulation of large silicic magma bodies in the upper crust is key to determining the potential of volcanoes to form caldera-forming eruptions. Located in one of the most populated regions on Earth, Camp Flegrei is an active and restless volcano that has produced two cataclysmic caldera-forming eruptions and numerous smaller eruptive events over the past 60,000 years. Here, we combine the results of an extensive petrological survey with a thermomechanical model to investigate how the magmatic system shifts from frequent, small eruptions to large caldera-forming events. Our data reveal that the most recent eruption of Monte Nuovo is characterized by highly differentiated magmas akin to those that fed the pre-caldera activity and the initial phases of the caldera-forming eruptions. We suggest that this eruption is an expression of a state shift in magma storage conditions, whereby substantial amounts of volatiles start to exsolve in the shallow reservoir. The presence of an exsolved gas phase has fundamental consequences for the physical properties of the reservoir and may indicate that a large magma body is currently accumulating underneath Campi Flegrei.

Description: Published

Description: eaat9401

Description: 1V. Storia eruttiva

Description: JCR Journal

Description: This study deals with the textural and compositional characteristics of the calc-alkaline stratigraphic sequencefrom Capo MarargiuVolcanicDistrict (CMVD;Sardiniaisland,Italy). The areaisdominatedbybasalticto interme-diate hypabyssal (dikes and sills) and volcanic rocks (lavaflows and pyroclastic deposits) emplaced during theOligo-Miocene orogenic magmatism of Sardinia. Interestingly, a basaltic andesitic dome hosts dark-grey,crystal-rich enclaves containing up ~50% of millimetre- to centimetre-sized clinopyroxene and amphibolecrystals. This mineral assemblage is in equilibrium with a high-Mg basalt recognised as the parental magma ofthe entire stratigraphic succession at CMVD. Analogously, centimetre-sized clots of medium- and coarse-grained amphibole + plagioclase crystals are entrapped in andesitic dikes that ultimately intrude the stratigraphicsequence. Amphibole-plagioclase cosaturation occurs at equilibrium with a differentiated basaltic andesite. Majorand trace element modelling indicates that the evolutionary path of magma is controlled by a two-step processdriven by early olivine + clinopyroxene and late amphibole + plagioclase fractionation. In this context, enclavesrepresent parts of a cumulate horizon segregated at the early stage of differentiation of the precursory high-Mg ba-salt. This is denoted by i) resorption effects and sharp transitions between Mg-rich and Mg-poor clinopyroxenes,indicative of pervasive dissolution phenomena followed by crystal re-equilibration and overgrowth, and ii) reac-tion minerals found in amphibole coronas formed at the interface with more differentiated melts infiltrating with-in the cumulate horizon, and carrying the crystal-rich material with them upon eruption.....

Description: Published

Description: 31-46

Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici

Description: JCR Journal

Description: Capo Marargiu Volcanic District (CMVD) is an Oligo-Miocene calc-alkaline complex located in north-western Sardinia (Italy) and characterized by the widespread occurrence of basaltic to andesitic domes. One of these domes hosts abundant crystal-rich enclaves with millimeter-to-centimeter-sized clinopyroxenes showing intriguing textural features as a result of complex magma dynamics. To better understand the mechanisms governing the early evolution of the CMVD magmatic system, such clinopyroxene phenocrysts have been investigated in terms of their major, trace element and isotopic compositions. Three distinct clinopyroxene populations have been identified, i.e., Type 1, Type 2, and Type 3. Type 1 appears as the sub-rounded cores of diopsidic clinopyroxenes with overgrowth textures corresponding to Type 2 and Type 3. These latter populations may also occur as single isolated crystals. Type 2 diopsidic pyroxene exhibits oscillatory zoning and spongy cellular textures with Type 3 overgrowths, whereas Type 3 are polycrystalline augitic glomerocrysts with occasional Type 2 overgrowths. The crystal overgrowths are striking evidence of magma recharge dynamics. Type 1 (cpxMg#83-92), Type 2 (cpxMg#75-82) and Type 3 (cpxMg#72-79) are, respectively, in equilibrium with Sardinian mantle-derived high-Mg basalts (HMB with meltMg#56-73), least differentiated basaltic andesites (BA with meltMg#45-56) and evolved basaltic andesites (EBA with meltMg#41-50). Type 1 and Type 2 are diopsidic phenocrysts which have evolved along a similar geochemical path (i.e., linear increase of Al, Ti, La, and Hf contents, as well as negligible Eu-anomaly) controlled by olivine + clinopyroxene + amphibole fractionation. This differentiation path is related to phenocryst crystallization from hydrous HMB and BA magmas stalling at moderate crustal pressures. The occurrence of globular sulfides within Type 1 suggests saturation of the HMB magma with a sulfide liquid under relatively low redox conditions. Moreover, Type 1 clinopyroxenes show variable 87Sr/86Sr ratios ascribable either to assimilation of crustal material by HMB magma or a mantle source variably contaminated by crustal components. In contrast, Type 3 augitic phenocrysts recorded the effect of plagioclase and titanomagnetite fractionation (i.e., low Al and Ti contents associated with high La and Hf concentrations, as well as important Eu-anomaly) from more degassed EBA magmas ponding at shallow depths. Rare titanite associated to Type 3 and titanomagnetite crystals point to high oxidizing conditions for EBA magmas. The 87Sr/86Sr ratios of both Type 2 and Type 3 are almost constant, suggesting a limited interaction of BA and EBA magmas with the country rock. The overall textural and compositional features of Type 1, Type 2 and Type 3 clinopyroxene phenocrysts lead to the conclusion that CMVD was characterized by a polybaric plumbing system where geochemically distinct magmas crystallized and mixed under variable environmental conditions

Description: Published

Description: 899–910

Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici

Description: JCR Journal

Description: Understanding the mechanisms responsible for the generation of chemical gradients in high-volume ignimbrites is key to retrieve information on the processes that control the maturation and eruption of large silicic magmatic reservoirs. Over the last 60 ky, two large ignimbrites showing remarkable zoning were emplaced during caldera-forming eruptions at Campi Flegrei (i.e., Campanian Ignimbrite, CI, ~ 39 ka and Neapolitan Yellow Tuff, NYT, ~ 15 ka). While the CI displays linear compositional, thermal and crystallinity gradients, the NYT is a more complex ignimbrite characterized by crystal-poor magmas ranging in composition from trachy-andesites to phonolites. By combining major and trace element compositions of matrix glasses and mineral phases from juvenile clasts located at different stratigraphic heights along the NYT pyroclastic sequence, we interpret such compositional gradients as the result of mixing/mingling between three different magmas: (1) a resident evolved magma showing geochemical characteristics of a melt extracted from a cumulate mush dominated by clinopyroxene, plagioclase and oxides with minor sanidine and biotite; (2) a hotter and more mafic magma from recharge providing high-An plagioclase and high-Mg clinopyroxene crystals and (3) a compositionally intermediate magma derived from remelting of low temperature mineral phases (i.e., sanidine and biotite) within the cumulate crystal mush. We suggest that the presence of a refractory crystal mush, as documented by the occurrence of abundant crystal clots containing clinopyroxene, plagioclase and oxides, is the main reason for the lack of erupted crystal-rich material in the NYT. A comparison between the NYT and the CI, characterized by both crystal-poor extracted melts and crystal-rich magmas representing remobilized portions of a “mature” (i.e., sanidine dominated) cumulate residue, allows evaluation of the capability of crystal mushes of becoming eruptible upon recharge.

Description: Published

Description: id 45

Description: 2V. Struttura e sistema di alimentazione dei vulcani

Description: JCR Journal