Oxidation state of iron in hydrous phono-tephritic melts

The oxidation state of iron in hydrous ultrapotassic (phono-tephritic) melts coexisting with mixed H2O-CO2 fluids was experimentally studied at 1200 and 1250{degree sign}C and pressures from 50 to 500 MPa. The oxygen fugacity (fO2) varied from NNO-2.9 to NNO+2.6 in logfO2, relative to the Ni-NiO oxygen buffer (NNO), as imposed by external redox conditions in experimental vessels and internal variations in water activity from 0.05 to 1 inside the capsules. The iron redox state of the quenched melts was determined by colorimetric wet-chemical analysis. This analytical method was optimized to measure the Fe2+/ΣFe ratio of mg-sized samples within ±0.03 (2σ). The accuracy and precision was tested with international reference materials and with standards analyzed by other methods. The Fe2+/ΣFe ratio of the experimental glasses covered a range of 0.41 to 0.85. A small negative effect of dissolved water on Fe2+/ΣFe at given fO2 was found, consistent with the thermodynamic model of Moretti (2005). No effect of pressure and temperature on the redox state of iron was resolvable in the investigated P-T range. Compared to hydrous ferrobasaltic melts that were studied previously under similar conditions, systematically lower Fe2+/ΣFe ratios were found for the phono-tephritic melts, in particular at low oxygen fugacities. This effect is attributed to the much higher K2O contents of the phono-tephrite (7.5 compared to 0.3 wt%), but the difference in ΣFeO (7.8 wt% in the phono-tephrite and 12.9 wt% in the ferrobasalt) may have an influence as well. Comparison of the experimentally obtained relationship between logfO2 and Fe3+/Fe2+ for the studied hydrous ultrapotassic melts with commonly used empirical and thermodynamic models suggest that these models can be successfully applied to phono-tephritc melts, although such compositions were not implemented in the model calibrations. Furthermore, the new data can be used to improve the models with respect to the effects of compositional variables, such as H2O or K2O, on the redox state of iron in silicate melts

A new test for equilibrium based on clinopyroxene-melt pairs: Clues on the solidification temperatures of Etnean alkaline melts at post-eruptive conditions

We have performed new global regression analyses to calibrate a model of equilibrium between clinopyroxene and co-existing melt. Then we have applied this model to a restricted but important range of clinopyroxene and melt compositions from Mt. Etna volcano. The degree of disequilibrium is determined through the comparison between components “predicted” for clinopyroxene via regression analyses of clinopyroxene-liquid pairs in equilibrium conditions, with those “measured” in the analyzed crystals. The model is tested using compositions not included into the calibration dataset, i.e., clinopyroxene-melt pairs obtained from equilibrium and cooling rate experiments conducted at ambient pressure on an Etnean trachybasalt. The experiments were duplicated at the NNO+1.5 and QFM oxygen buffering conditions estimated for magmas at Mt. Etna. Both equilibrium and disequilibrium clinopyroxene-melt pairs from the experiments were also used as input data for one of the most recent thermometers based on the Jd-DiHd exchange reaction. Results from calculations indicate that, under rapid cooling rate conditions, clinopyroxenes do not equilibrate with the melt. Consequently, the thermometers predict higher crystallization temperatures compared to the final experimental temperature, prior to rapid quenching of the experiment. The systematic difference between expected and measured compositions and temperatures allows us to calibrate a model that describes undercooling based on disequilibrium exchange reactions. We use this new tool to estimate the thermal history of naturally cooled lava flows and dikes at Mt. Etna volcano

Oxidation state of iron in hydrous phono-tephritic melts

The oxidation state of iron in hydrous ultrapotassic (phono-tephritic) melts coexisting with mixed H2O-CO2 fluids was experimentally studied at 1200 and 1250{degree sign}C and pressures from 50 to 500 MPa. The oxygen fugacity (fO2) varied from NNO-2.9 to NNO+2.6 in logfO2, relative to the Ni-NiO oxygen buffer (NNO), as imposed by external redox conditions in experimental vessels and internal variations in water activity from 0.05 to 1 inside the capsules. The iron redox state of the quenched melts was determined by colorimetric wet-chemical analysis. This analytical method was optimized to measure the Fe2+/ΣFe ratio of mg-sized samples within ±0.03 (2σ). The accuracy and precision was tested with international reference materials and with standards analyzed by other methods. The Fe2+/ΣFe ratio of the experimental glasses covered a range of 0.41 to 0.85. A small negative effect of dissolved water on Fe2+/ΣFe at given fO2 was found, consistent with the thermodynamic model of Moretti (2005). No effect of pressure and temperature on the redox state of iron was resolvable in the investigated P-T range. Compared to hydrous ferrobasaltic melts that were studied previously under similar conditions, systematically lower Fe2+/ΣFe ratios were found for the phono-tephritic melts, in particular at low oxygen fugacities. This effect is attributed to the much higher K2O contents of the phono-tephrite (7.5 compared to 0.3 wt%), but the difference in ΣFeO (7.8 wt% in the phono-tephrite and 12.9 wt% in the ferrobasalt) may have an influence as well. Comparison of the experimentally obtained relationship between logfO2 and Fe3+/Fe2+ for the studied hydrous ultrapotassic melts with commonly used empirical and thermodynamic models suggest that these models can be successfully applied to phono-tephritc melts, although such compositions were not implemented in the model calibrations. Furthermore, the new data can be used to improve the models with respect to the effects of compositional variables, such as H2O or K2O, on the redox state of iron in silicate melts

COMPORTAMENTO AD ALTA PRESSIONE DI TRASDUTTORI PIEZOELETTRICI PER APPLICAZIONI DI GEOFISICA SPERIMENTALE

L’investigazione del comportamento acustico di campioni di roccia implica l’uso di trasduttori piezoelettrici [Spinelli et al., 2009], sia in uso attivo (eccitazione e rilevazione) che passivo (rilevazione delle onde elastiche generate da fenomeni di fratturazione). In alcuni casi vengono imposte elevate pressioni per simulare le condizioni di sconfinamento del campione di roccia in profondità, utilizzando un liquido o un gas. La natura dei trasduttori piezoelettrici suggerisce che essi non debbano soffrire molto in ambienti in cui la variazioni di pressione o la pressione di esercizio sia un elemento non trascurabile e possono essere utilizzati in tali condizioni senza particolari precauzioni con evidenti vantaggi nella semplificazione del set-up sperimentale. Questa nota è la descrizione delle misure condotte per caratterizzare dei trasduttori piezoelettrici, nell’intervallo di pressione di interesse (0 - 1000 atm), da utilizzare per scopi sperimentali nell’ambito del progetto europeo ERC Starting Grant Project GLASS InteGrated Laboratories to investigate the mechanics of ASeismic vs. Seismic faulting. Per fare ciò due trasduttori sono stati incollati direttamente tra loro in modo da realizzare un quadripolo, con una porta d’ingresso e una di uscita, e ne è stata rilevata la caratteristica ingresso – uscita al variare della frequenza. Per il rilevamento delle caratteristiche elettriche sono stati usati differenti strumenti di misura: un generatore di segnali, un oscilloscopio e un analizzatore di reti vettoriale. Per imporre sui campioni una pressione controllata è stato allestito un apparato meccanico dedicato, formato da un insieme pistone-cilindro all’interno del quale viene alloggiata la coppia di trasduttori incollati. Nel cilindro viene inserito olio (adeguatamente incomprimibile ed elettricamente isolante) come vettore di pressione; la spinta sul pistone viene esercitata attraverso una pressa idraulica. Una particolare cura è stata posta nella costruzione del passacavo a tenuta per alte pressioni. Nei paragrafi che seguono verranno dapprima descritti i trasduttori usati per gli esperimenti e l’apparato meccanico, quindi si passerà alla presentazione delle misure effettuate in varie condizioni e con i vari strumenti

Viscosity of andesite melts and its implication for magma mixing prior to Unzen 1991-1995 eruption

The viscosity of an iron-bearing melt with composition similar to Unzen andesite was determined experimentally in the high (109-1010.5 Pa·s) and low (5-1000 Pa·s) viscosity range using a parallel plate viscometer and the falling sphere method, respectively. Falling sphere experiments were carried out in an internally heated argon pressure vessel and in a piston cylinder apparatus at 1323 to 1573 K and 200 to 2000 MPa. Creep experiments were performed in the temperature range of 747 - 845 K at 300 MPa. The water content of the melt varies from nominally dry to 6.2 wt% H2O. The Fe2+/Fetot ratio was determined for each sample in the quenched glass using a colorimetric method. Pressure has minor influence on the viscosity compared with the effect of temperature, water content (main compositional parameter controlling the viscosity) or with the Fe2+/Fetot ratio (especially important at low water content of the melt). Based on our new viscosity data and literature data with measured Fe2+/Fetot ratio we propose a new empirical equation to estimate the viscosity η (in Pa·s) of andesitic melts as a function of temperature T (in K), water content w (in wt%) and Fe2+/Fetot ratio. The derived relationship reproduces the experimental data (87 in total) in the viscosity range from 100.5 to 1013 Pa·s with a 1σ standard deviation of 0.17 log units. However, application of this calculation model is limited to Fe2+/Fetot>0.3 and to temperatures above Tg. Moreover, in the high viscosity range the variation of viscosity with water content is constrained only by few experimental data and needs verification by additional measurements. The viscosity data are used to interpret mixing processes in the Unzen magma chamber prior to 1991-1995 eruption. We demonstrate that the viscosities of the rhyolite and andesite melts from the two end-member magmas are nearly identical prior and during mixing, enabling efficient magma mixing

Metasomatism induced by alkaline magma in the upper mantle of northern Victoria Land (Antarctica): an experimental approach

Magma generation in the Ross Sea system is related to partial melting of strongly metasomatised mantle sources where amphibole most probably plays a crucial role. In this context, metasomatism induced by a mela-nephelinite melt in lithospheric mantle of the Mt. Melbourne Volcanic Province (northern Victoria Land – NVL, Antarctica) was investigated experimentally studying the effects of melt interaction with lherzolite at 1.5-2.0 GPa and T=975-1300°C, and wehrlite at 1.0 GPa and T=1050-1250°C. The experiments were designed to induce melt infiltration into the ultramafic rocks. The observed modifications in minerals are compared with those found in mantle xenoliths from NVL. The effects of metasomatic modifications are evaluated on the basis of run temperature, distance from the infiltrating melt and on the diffusion rates of chemical components. Both in lherzolite and wehrlite, clinopyroxene exhibits large compositional variations ranging from primary diopside to high Mg-Cr-(Na) augitic and omphacitic clinopyroxenes in lherzolite, and to low Mg and high Ti-Al-Fe-Na augites in wehrlite. Olivine (in wehrlite) and spinel (in lherzolite) also result compositionally modified, the former shows enrichments in Fe, the latter displays a higher Cr/(Cr+Al) ratio. The systematic variations in mineral compositions imply modifications of the chemistry of the infiltrating melt as recorded by the glass veinlets and patches observed in some charges. In experiments involving wehrlite paragenesis, the glass composition approaches that of melt patches associated to both amphibole-free and amphibole-bearing natural samples, and is related to olivine+clinopyroxene crystallisation coupled with primary clinopyroxene dissolution at the contact between the metasomatising melt and the solid matrix. Even if amphibole crystallisation was not attained in the experiments, we were able to explain the occurrence of amphibole in the natural system considering that in this case a hot metasomatising melt infiltrates a cooler matrix

The viscosity of shoshonitic melts (Vulcanello Peninsula, Aeolian Islands, Italy): insight on the magma ascent in dikes

The viscosity of shoshonitic melts from Vulcanello Peninsula (Vulcano Island, Italy) is experimentally determined at temperatures between 733 K and 1673 K. The water content of the melts varies from 0.03 to 4.75 wt% H2O. The micropenetration technique is employed at ambient pressure in the high viscosity range (109-1012 Pa·s). Falling sphere(s) experiments are performed at 500 and 2000 MPa in the low viscosity range (100.5-103 Pa·s). Results show a decrease of about 2 orders of magnitude in viscosity if ~ 3 wt% of water is added to the dry melt at 1300 K. At high temperature the viscosity of Vulcanello melts is intermediate between that of andesitic and basaltic melts. In contrast, at low temperatures (≤1050 K), the shoshonitic melt is characterized by a lower viscosity with respect to the two previous melts. Based on our new data set, a calculation model is proposed to predict the viscosity of the shoshonitic melts as a function of temperature and water content. The viscosity data are used to constrain the ascent velocity of shoshonitic magmas from Vulcanello within dikes. Using petrological data (temperature and crystal content of the magma) and volcanological information (geometrical parameters of the eruptive fissure and depth of magma storage), we estimate the time scale for the ascent of magma from the main reservoir to the surface. Results show time scales in the order of hours to few days. We conclude that the rapid ascent of poorly evolved melts from Moho depths should be taken into account for the hazard assessment of Vulcano Island

Magma–Carbonate Interaction Processes and Associated CO2 Release at Merapi Volcano, Indonesia: Insights from Experimental Petrology

There is considerable evidence for ongoing, late-stage interaction between the magmatic system at Merapi volcano, Indonesia, and local crustal carbonate (limestone). Calc-silicate xenoliths within Merapi basaltic-andesite eruptives display textures indicative of intense interaction between magma and crustal carbonate, and Merapi feldspar phenocrysts frequently contain individual crustally contaminated cores and zones. In order to resolve the interaction processes between magma and limestone in detail we have performed a series of time-variable de-carbonation experiments in silicate melt, at magmatic pressure and temperature, using a Merapi basaltic-andesite and local Javanese limestone as starting materials. We have used in-situ analytical methods to determine the elemental and strontium isotope composition of the experimental products and to trace the textural, chemical, and isotopic evolution of carbonate assimilation. The major processes of magmacarbonate interaction identified are: i) rapid decomposition and degassing of carbonate, ii) generation of a Ca-enriched, highly radiogenic strontium contaminant melt, distinct from the starting material composition, iii) intense CO2 vesiculation, particularly within the contaminated zones, iv) physical mingling between the contaminated and unaffected melt domains, and v) chemical mixing between melts. The experiments reproduce many of the features of magmacarbonate interaction observed in the natural Merapi xenoliths and feldspar phenocrysts. The Carich, high 87Sr/86Sr contaminant melt produced in the experiments is considered as a pre-cursor to the Ca-rich (often “hyper-calcic”) phases found in the xenoliths and the contaminated zones in Merapi feldspars. The xenoliths also exhibit micro-vesicular textures which can be linked to the CO2 liberation process seen in the experiments. This study, therefore, provides well-constrained petrological insights into the problem of crustal interaction at Merapi and points toward the substantial impact of such interaction on the volatile budget of the volcano

Carbonate assimilation in magmas: a reappraisal based on experimental petrology

The main effect of magma-carbonate interaction on magma differentiation is the formation of a silica-undersaturated, alkali-rich residual melt. Such a desilication process was explained as the progressive dissolution of CaCO3 in melt by consumption of SiO2 and MgO to form diopside sensu stricto. Magma chambers emplaced in carbonate substrata, however, are generally associated with magmatic skarns containing clinopyroxene with a high Ca-Tschermak activity in their paragenesis. Data are presented from magma-carbonate interaction experiments, demonstrating that carbonate assimilation is a complex process involving more components than so far assumed. Experimental results show that, during carbonate assimilation, a diopside-hedenbergite-Ca-Tschermak clinopyroxene solid solution is formed and that Ca-Tschermak/diopside and hedenbergite/diopside ratios increase as a function of the progressive carbonate assimilation. Accordingly, carbonate assimilation reaction should be written as follows, taking into account all the involved magmatic components: CaCO3solid+SiO2melt+MgOmelt+FeOmelt+Al2O3melt → (Di-Hd-CaTs)sssolid+CO2fluid The texture of experimental products demonstrates that carbonate assimilation produces three-phases (solid, melt, and fluid) whose main products are: i) diopside-hedenbergite-Ca-Tschermak clinopyroxene solid solution; ii) silica-undersaturated CaO-rich melt; and iii) C-O-H fluid phase. The silica undersaturation of the melt and, more importantly, the occurrence of a CO2-rich fluid phase, must be taken into account as they significantly affect partition coefficients and the redox state of carbonated systems, respectively

A general viscosity model of Campi Flegrei (Italy) melts

Viscosities of shoshonitic and latitic melts, relevant to the Campi Flegrei caldera magmas, have been experimentally determined at atmospheric pressure and 0.5 GPa, temperatures between 840 K and 1870 K, and H2O contents from 0.02 to 3.30 wt%. The concentric cylinder technique was employed at atmospheric pressure to determine viscosity of nominally anhydrous melts in the viscosity range of 101.5 - 103 Pa·s. The micropenetration technique was used to determine the viscosity of hydrous and anhydrous melts at atmospheric pressure in the high viscosity range (1010 Pa·s). Falling sphere experiments were performed at 0.5 GPa in the low viscosity range (from 100.35 to 102.79 Pa·s) in order to obtain viscosity data of anhydrous and hydrous melts. The combination of data obtained from the three different techniques adopted permits a general description of viscosity as a function of temperature and water content using the following modified VFT equation: where η is the viscosity in Pa·s, T the temperature in K, w the H2O content in wt%, and a, b, c, d, e, g are the VFT parameters. This model reproduces the experimental data (95 measurements) with a 1σ standard deviation of 0.19 and 0.22 log units for shoshonite and latite, respectively. The proposed model has been applied also to a more evolved composition (trachyte) from the same area in order to create a general model applicable to the whole compositional range of Campi Flegrei products. Moreover, speed data have been used to constrain the ascent velocity of latitic, shoshonitic, and trachytic melts within dikes. Using petrological data and volcanological information (geometrical parameters of the eruptive fissure and depth of magma storage), we estimate a time scale for the ascent of melt from 9 km to 4 km depth (where deep and shallow reservoirs, respectively, are located) in the order of few minutes. Such a rapid ascent should be taken into account for the hazard assessment in the Campi Flegrei area