Daniele Morgavi

Elemental Imaging and Petro-Volcanological Applications of an Improved Laser Ablation Inductively Coupled Quadrupole Plasma Mass Spectrometry

We report on the performance of the a new LA-ICP-MS instrumentation installed at the Physics and Geology Department of Perugia University empathizing its capabilities in elemental imaging and the progresses in trace element in situ determination and U/Pb geochronology. The analytical device consists in a Thermo Fisher Scientific iCAP Q quadrupole mass spectrometer coupled with a Teledyne/Photon Machine ArF Excimer G2 laser ablation system. Results show that, in trace element configuration at 40 micron, precisions are better than 6.5% whereas accuracies are better than 10%. Results also show improved precisions with respect the X7 + UP213 instrumentation in U/Pb geochronological studies. On this regard, concordia ages for the Plesovice and R33 Zircons analyzed as unknowns are in close agreement with the accepted values for these reference materials highlighting the accuracy of the method. The potentials in 2D element imaging are also reported and successfully tested on a zoned plagioclase from the alkali basaltic Santa Venera lava Flow. Results evidences that expanding the analysis to the second dimension will lead to more reliable and accurate results and it is going to open new prospective for the modeling of igneous systems.

Time evolution of chemical exchanges during mixing of rhyolitic and basaltic melts

We present the first set of chaotic mixing experiments performed using natural basaltic and rhyolitic melts. The mixing process is triggered by a recently developed apparatus that generates chaotic streamlines in the melts, mimicking the development of magma mixing in nature. The study of the interplay of physical dynamics and chemical exchanges between melts is carried out performing time series mixing experiments under controlled chaotic dynamic conditions. The variation of major and trace elements is studied in detail by electron microprobe and Laser Ablation ICP-MS. The mobility of each element during mixing is estimated by calculating the decrease in the concentration variance in time. Both major and trace element variances decay exponentially, with the value of exponent of the exponential function quantifying the element mobility. Our results confirm and quantify how different chemical elements homogenize in the melt at differing rates. The differential mobility of elements in the mixing system is considered to be responsible for the highly variable degree of correlation (linear, nonlinear, or scattered) of chemical elements in many published inter-elemental plots. Elements with similar mobility tend to be linearly correlated, whereas, as the difference in mobility increases, the plots become progressively more nonlinear and/or scattered. The results from this study indicate that the decay of concentration variance is in fact a robust tool for obtaining new insights into chemical exchanges during mixing of silicate melts. Concentration variance is (in a single measure) an expression of the influence of all possible factors (e.g., viscosity, composition, and fluid dynamic regime) controlling the mobility of chemical elements and thus can be an additional petrologic tool to address the great complexity characterizing magma mixing processes.

Approximate chemical analysis of volcanic glasses using Raman spectroscopy.

The effect of chemical composition on the Raman spectra of a series of natural calcalkaline silicate glasses has been quantified by performing electron microprobe analyses and obtaining Raman spectra on glassy filaments (~450 µm) derived from a magma mingling experiment. The results provide a robust compositionally‐dependent database for the Raman spectra of natural silicate glasses along the calcalkaline series. An empirical model based on both the acquired Raman spectra and an ideal mixing equation between calcalkaline basaltic and rhyolitic end‐members is constructed enabling the estimation of the chemical composition and degree of polymerization of silicate glasses using Raman spectra. The model is relatively insensitive to acquisition conditions and has been validated using the MPI‐DING geochemical standard glasses1 as well as further samples. The methods and model developed here offer several advantages compared with other analytical and spectroscopic methods such as infrared spectroscopy, X‐ray fluorescence spectroscopy, electron and ion microprobe analyses, inasmuch as Raman spectroscopy can be performed with a high spatial resolution (1 µm2) without the need for any sample preparation as a nondestructive technique. This study represents an advance in efforts to provide the first database of Raman spectra for natural silicate glasses and yields a new approach for the treatment of Raman spectra, which allows us to extract approximate information about the chemical composition of natural silicate glasses using Raman spectroscopy. We anticipate its application in handheld in situ terrestrial field studies of silicate glasses under extreme conditions (e.g. extraterrestrial and submarine environments).

High-temperature apparatus for chaotic mixing of natural silicate melts

A unique high-temperature apparatus was developed to trigger chaotic mixing at high-temperature (up to 1800 °C). This new apparatus, which we term Chaotic Magma Mixing Apparatus (COMMA), is designed to carry out experiments with high-temperature and high-viscosity (up to 10(6) Pa s) natural silicate melts. This instrument allows us to follow in time and space the evolution of the mixing process and the associated modulation of chemical composition. This is essential to understand the dynamics of magma mixing and related chemical exchanges. The COMMA device is tested by mixing natural melts from Aeolian Islands (Italy). The experiment was performed at 1180 °C using shoshonite and rhyolite melts, resulting in a viscosity ratio of more than three orders of magnitude. This viscosity ratio is close to the maximum possible ratio of viscosity between high-temperature natural silicate melts. Results indicate that the generated mixing structures are topologically identical to those observed in natural volcanic rocks highlighting the enormous potential of the COMMA to replicate, as a first approximation, the same mixing patterns observed in the natural environment. COMMA can be used to investigate in detail the space and time development of magma mixing providing information about this fundamental petrological and volcanological process that would be impossible to investigate by direct observations. Among the potentials of this new experimental device is the construction of empirical relationships relating the mixing time, obtained through experimental time series, and chemical exchanges between the melts to constrain the mixing-to-eruption time of volcanic systems, a fundamental topic in volcanic hazard assessment.

Quantifying magma mixing with the Shannon entropy: Application to simulations and experiments

Abstract We introduce a new quantity to petrology, the Shannon entropy, as a tool for quantifying mixing as well as the rate of production of hybrid compositions in the mixing system. The Shannon entropy approach is applied to time series numerical simulations and high-temperature experiments performed with natural melts. We note that in both cases the Shannon entropy increases linearly during the initial stages of mixing and then saturates toward constant values. Furthermore, chemical elements with different mobilities display different rates of increase of the Shannon entropy. This indicates that the hybrid composition for the different elements is attained at different times generating a wide range of spatio-compositional domains which further increase the apparent complexity of the mixing process. Results from the application of the Shannon entropy analysis are compared with the concept of Relaxation of Concentration Variance (RCV), a measure recently introduced in petrology to quantify chemical exchanges during magma mixing. We derive a linear expression relating the change of concentration variance during mixing and the Shannon entropy. We show that the combined use of Shannon entropy and RCV provides the most complete information about the space and time complexity of magma mixing. As a consequence, detailed information about this fundamental petrogenetic and volcanic process can be gathered. In particular, the Shannon entropy can be used as complement to the RCV method to quantify the mobility of chemical elements in magma mixing systems, to obtain information about the rate of production of compositional heterogeneities, and to derive empirical relationships linking the rate of chemical exchanges between interacting magmas and mixing time.

Combining machine learning techniques, microanalyses and large geochemical datasets for tephrochronological studies in complex volcanic areas: New age constraints for the Pleistocene magmatism of central Italy

Characterization, correlation and provenance determination of tephra samples in sedimentary sections (tephrochronological studies) are powerful tools for establishing ages of depositional events, volcanic eruptions, and tephra dispersion. Despite the large literature and the advancements in this research field, the univocal attribution of tephra deposits to specific volcanic sources remains too often elusive. In this contribution, we test the application of a machine learning technique named Support Vector Machine to attempt shedding new light upon tephra deposits related to one of the most complex and debated volcanic regions on Earth: the Pliocene-Pleistocene magmatism in Italy. The machine learning algorithm was trained using one of the most comprehensive global petrological databases (GEOROC); 17 chemical elements including major (SiO2, TiO2, Al2O3, Fe2O3T, CaO, MgO, MnO, Na2O, K2O, P2O5) and selected trace (Sr, Ba, Rb, Zr, Nb, La, Ce) elements were chosen as input parameters. We first show the ability of support vector machines in discriminating among different Pliocene-Pleistocene volcanic provinces in Italy and then apply the same methodology to determine the volcanic source of tephra samples occurring in the Caio outcrop, an Early Pleistocene sedimentary section located in Central Italy. Our results show that: 1) support vector machines can successfully resolve high-dimensional tephrochronological problems overcoming the intrinsic limitation of two- and three-dimensional discrimination diagrams; 2) support vector machines can discriminate among different volcanic provinces in complex magmatic regions; 3) in the specific case study, support vector machines indicate that the most probable source for the investigated tephra samples is the so-called Roman Magmatic Province. These results have strong geochronological and geodynamical implications suggesting new age constraints (1.4 Ma instead of 0.8 Ma) for the starting of the volcanic activity in the Roman Magmatic Province.

Experimental constraints on the rheology, eruption and emplacement dynamics of analog lavas comparable to Mercury's northern volcanic plains

We present new viscosity measurements of a synthetic silicate system considered an analogue for the lava erupted on the surface of Mercury. In particular, we focus on the northern volcanic plains (NVP), which correspond to the largest lava flows on Mercury and possibly in the Solar System. High-temperature viscosity measurements were performed at both superliquidus (up to 1736 K) and subliquidus conditions (1569–1502 K) to constrain the viscosity variations as a function of crystallinity (from 0 to 28%) and shear rate (from 0.1 to 5 s-1). Melt viscosity shows moderate variations (4 –16 Pa s) in the temperature range 1736–1600 K. Experiments performed below the liquidus temperature show an increase in viscosity as shear rate increases from 0.1 to 5 s-1, resulting in a shear thinning behaviour, with a decrease in viscosity of ca. 1 log unit. The low viscosity of the studied composition may explain the ability of NVP lavas to cover long distances, on the order of hundreds of kilometres in a turbulent flow regime. Using our experimental data we estimate that lava flows with thickness of 1, 5 and 10 m are likely to have velocities of 4.8, 6.5 and 7.2 m/s respectively, on a 5° ground slope. Numerical modelling incorporating both the heat loss of the lavas and its possible crystallization during emplacement allows us to infer that high effusion rates (> 10000 m3/s) are necessary to cover the large distances indicated by satellite data from the MESSENGER spacecraft.

Enhancement of eruption explosivity by heterogeneous bubble nucleation triggered by magma mingling.

We present new evidence that shows magma mingling can be a key process during highly explosive eruptions. Using fractal analysis of the size distribution of trachybasaltic fragments found on the inner walls of bubbles in trachytic pumices, we show that the more mafic component underwent fracturing during quenching against the trachyte. We propose a new mechanism for how this magmatic interaction at depth triggered rapid heterogeneous bubble nucleation and growth and could have enhanced eruption explosivity. We argue that the data support a further, and hitherto unreported contribution of magma mingling to highly explosive eruptions. This has implications for hazard assessment for those volcanoes in which evidence of magma mingling exists.

Exponential decay of concentration variance during magma mixing: Robustness of a volcanic chronometer and implications for the homogenization of chemical heterogeneities in magmatic systems

Abstract The mixing of magmas is a fundamental process in the Earth system causing extreme compositional variations in igneous rocks. This process can develop with different intensities both in space and time, making the interpretation of compositional patterns in igneous rocks a petrological challenge. As a time-dependent process, magma mixing has been suggested to preserve information about the time elapsed between the injection of a new magma into sub-volcanic magma chambers and eruptions. This allowed the use of magma mixing as an additional volcanological tool to infer the mixing-to-eruption timescales. In spite of the potential of magma mixing processes to provide information about the timing of volcanic eruptions its statistical robustness is not yet established. This represents a prerequisite to apply reliably this conceptual model. Here, new chaotic magma mixing experiments were performed at different times using natural melts. The degree of reproducibility of experimental results was tested repeating one experiment at the same starting conditions and comparing the compositional variability. We further tested the robustness of the statistical analysis by randomly removing from the analysed dataset a progressively increasing number of samples. Results highlight the robustness of the method to derive empirical relationships linking the efficiency of chemical exchanges and mixing time. These empirical relationships remain valid by removing up to 80% of the analytical determinations. Experimental results were applied to constrain the homogenization time of chemical heterogeneities in natural magmatic system during mixing. The calculations show that, when the mixing dynamics generate millimetre thick filaments, homogenization timescales of the order of a few minutes are to be expected.

Syneruptive sequential fragmentation of pyroclasts from fractal modeling of grain size distributions of fall deposits: the Cretaio Tephra eruption (Ischia Island, Italy)

Abstract In this work we use fractal statistics in order to decipher the mechanisms acting during explosive volcanic eruptions by studying the grain size distribution (GSD) of natural pyroclastic-fall deposits. The method was applied to lithic-rich proximal deposits from a stratigraphic section of the Cretaio Tephra eruption (Ischia Island, Italy). Analyses were performed separately on bulk material, juvenile, and lithic fraction from each pyroclastic layer. Results highlight that the bulk material is characterized by a single scaling regime whereas two scaling regimes, with contrasting power-law exponents, are observed for the juvenile and the lithic fractions. On the basis of these results, we infer that the bulk material cannot be considered as a good proxy for deducing eruption dynamics because it is the result of mixing of fragments belonging to the lithic and juvenile fraction, both of which underwent different events of fragmentation governed by different mechanisms. In addition, results from fractal analyses of the lithic fraction suggest that it likely experienced a fragmentation event in which the efficiency of fragmentation was larger for the coarser fragments relative to the finer ones. On the contrary, we interpret the different scaling regimes observed for the juvenile fraction to be due to sequential events of fragmentation in the conduit, possibly enhanced by the presence of lithic fragments in the eruptive mixture. In particular, collisional events generated increasing amounts of finer particles modifying the original juvenile GSDs and determining the development of two scaling regimes in which the finer fragments record a higher efficiency of fragmentation relative to the coarser ones. We further suggest that in lithic-rich proximal fall deposits possible indications about the original GSDs of the juvenile fraction might still reside in the coarser particles fraction.