Sector-zoned clinopyroxene is common in igneous rocks, but has been overlooked in the study of magmatic processes. Whilst concentric zoning is commonly used as a record of physicochemical changes in ...the melt feeding crystal growth, clinopyroxene is also highly sensitive to crystallisation kinetics. In sector-zoned crystals, the fidelity of compositional changes as recorders of magma history is dubious and the interplay between thermodynamic and kinetic controls remains poorly understood. Here we combine electron probe and laser ablation micro-chemical maps of titanaugite crystals from Mt. Etna (Sicily, Italy) to explore the origin of sector zoning at the major and trace element levels, and its implications for the interpretation of magmatic histories. Elemental maps afford the possibility to revisit sector zoning from a spatially controlled perspective. The most striking observation is a clear decoupling of elements into sectors vs. concentric zones within single crystals. Most notably, Al-Ti enrichments and Si-Mg depletions in the prism sectors {1 0 0}, {1 1 0} and {0 1 0} relative to the hourglass (or basal) sectors {−1 1 1} correlate with enrichments in rare earth elements and highly charged high field strength elements due to cation exchanges driven by kinetic effects. In contrast, transition metals (Cr, Ni, Sc) show little partitioning into sectors and strong enrichments in concentric zones following resorbed surfaces, interpreted as evidence of mafic recharge and magma mixing. Our results document that kinetic partitioning has minor effects on the compositional variations of cations with low charge relative to the ideal charge/radius of the structural site they occupy in the clinopyroxene lattice. We suggest that this may be due to a lower efficiency in charge balance mechanisms compared to highly charged cations. It follows that compatible metals such as Cr can be considered trustworthy recorders of mafic intrusions and eruption triggers even in sector-zoned crystals. We also observe that in alkaline systems where clinopyroxene crystallisation takes place at near-equilibrium conditions, sector zoning should have little effect on Na-Ca partitioning and in turn, on the application of experimentally calibrated thermobarometers. Our data show that whilst non-sector-zoned crystals form under relatively stagnant conditions, sector zoning develops in response to low degrees of undercooling, such as during slow magma ascent. Thus, we propose that the chemistry of sector-zoned crystals can provide information on magma history, eruption triggers, and possibly ascent rates.
Open-conduit basaltic volcanoes can be characterised by sudden large explosive events (paroxysms) that interrupt normal effusive and mild explosive activity. In June-August 2019, one major explosion ...and two paroxysms occurred at Stromboli volcano (Italy) within only 64 days. Here, via a multifaceted approach using clinopyroxene, we show arrival of mafic recharges up to a few days before the onset of these events and their effects on the eruption pattern at Stromboli, as a prime example of a persistently active, open-conduit basaltic volcano. Our data indicate a rejuvenated Stromboli plumbing system where the extant crystal mush is efficiently permeated by recharge magmas with minimum remobilisation promoting a direct linkage between the deeper and the shallow reservoirs that sustains the currently observed larger variability of eruptive behaviour. Our approach provides vital insights into magma dynamics and their effects on monitoring signals demonstrating the power of petrological studies in interpreting patterns of surficial activity.
The Present-day (<1.2 kyr) activity of Stromboli (Aeolian Islands, Southern Italy) is fed by a vertically-extended mush column with an open-conduit configuration. The eruptive products are the result ...of periodic supply of mafic magma (low porphyritic or Lp-magma) from depth into a homogeneous shallow reservoir (highly porphyritic or Hp-magma). Clinopyroxene phenocrysts from the 2003–2017 activity exhibit marked diopside-augite heterogeneities caused by continuous Lp-Hp magma mixing and antecryst recycling. Diopsidic bands record Lp-recharge injected into the shallow Hp-reservoir, whereas resorbed diopsidic cores testify to the continuous disruption and cannibalism of relic antecrysts from the mush. The transition between diopside (∼1175 °C) and augite (∼1130 °C) takes place at comparable P (∼190 MPa) and H2O (0.5–2.4 wt%) conditions. Short timescales (∼1 year) for diopsidic bands from the 2003 paroxysm document restricted temporal intervals between mafic injection, magma mixing and homogenization in the Hp-reservoir. Longer timescales (∼4–182 years) for diopsidic cores indicate protracted antecryst remobilization times. By comparing clinopyroxenes from the Present-day and Post-Pizzo eruptions, we argue a distinct phase in the life of Stromboli volcano is evident from the 2003 paroxysm onwards. More efficient mechanisms of mush disruption and cannibalism involve diopsidic antecrysts remobilized and transported by Lp-magmas permeating the mush, in concert with gravitational instability of the solidification front and melt migration within the shallow Hp-reservoir. Magmatic injections feeding the persistent Present-day activity are more intensively mixed and homogenized prior to eruption, reflecting small recharge volumes and/or a more mafic system in which the mafic inputs are less pronounced.
•Clinopyroxenes from the 2003–2017 eruptions at Stromboli have been investigated.•The crystal chemistry indicates continuous magma mixing and antecryst recycling.•Shorter timescales for clinopyroxene bands refer to the 2003 paroxysm event.•Longer timescales for clinopyroxene cores refer to the antecryst remobilization time.•Mush cannibalism is accompanied by magmas more intensively mixed prior to eruption.
We present a new empirical plagioclase-liquid hygrometer for estimating the amount of H2O dissolved in trachytic magmas. The hygrometer is based on the exchange reaction of anorthite between ...plagioclase and liquid, and is calibrated using crystallization experiments where the concentration of H2O in quenched glasses has been accurately determined based on Fourier Transform Infrared Spectroscopy (FTIR) analysis. The multiple linear regression of plagioclase-liquid cation fractions and components from experimental data obtained at 150–202 MPa, 850–1020 °C, 1.17–7.57 wt. % H2O and ΔNNO + 2.5 buffer, yields to a highly accurate model with uncertainty of only ±0.29 wt. % H2O. The model reliability has been demonstrated using an independent test data set consisting of crystallization experiments from the literature and thermodynamically derived compositions. The fairly good convergence between our model calibration and the test data set excludes systematic H2O overestimates or underestimates caused by miscalibration and data overfitting. The plagioclase-liquid hygrometer from this study has been applied to trachyandesitic (latitic) and trachytic products erupted over the last 1000 years at the La Fossa cone of Vulcano Island (Aeolian Islands, Southern Italy). Results from calculations indicate that the concentration of H2O in the latitic and trachytic melts is comprised between ~2.5 and ~3.5 wt. %. These values are in good agreement with data from melt inclusions and, overall, testify to low-pressure, open-system differentiation of trachytic magmas under strong degassing conditions.
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.
The compositional variation of clinopyroxene and the partitioning of major elements between clinopyroxene and melt are estimated as a function of the cooling rate. Clinopyroxenes were crystallized ...under variable cooling regimes (15, 9.4, 3, 2.1, and 0.5
°C/min from 1250 down to 1000
°C) and at isothermal conditions of 1000
°C from a basaltic composition at a pressure of 500
MPa under anhydrous and hydrous (H
2O
=
1.3
wt.%) conditions. The clinopyroxene chemistry shows that, as the cooling rate increases, crystals are progressively depleted in Ca, Mg, Fe
2+ and Si and enriched in Na, Fe
3+, Al (mainly Al
IV), and Ti. Di and Hd
versus CaTs and CaFeTs form a continuous binary solid solution characterized by higher amounts of tschermakitic components with increasing cooling rate. Two parameters (DH
=
Di
+
Hd and TE
=
CaTs
+
CaFeTs
+
En) are calculated to describe the effect of cooling rate on the clinopyroxene composition. The variation of DH/TE with increasing cooling rate evidences the kinetic process induced by rapid cooling in basic rocks under hydrous and anhydrous conditions.
Dynamic crystallization conditions affect the partitioning of major elements between clinopyroxene and melt; with increasing cooling rate, the value of crystal–melt partition coefficient departs from that obtained at the isothermal condition. However, in spite of these variations, the values of
cpx–meltKd
Fe–Mg remain almost constant. Therefore, the Fe
2–Mg exchange between clinopyroxene and melt is not suitable to prove the (dis)equilibrium conditions in basaltic cooling magmas, giving rise to possible mismatches in the application of thermobarometers. The results of our study are consistent with that observed at the margin of dikes or in the exterior portions of lavas, where the cooling rate is maximized and disequilibrium compositions of clinopyroxene have been found.
The magmatic architecture and physicochemical processes inside volcanoes influence the style and timescale of eruptions. A long-standing challenge in volcanology is to establish the rates and depths ...of magma storage and the events that trigger eruption. Magma feeder systems are remarkably crystal-rich, and the growth stratigraphy of minerals sampled by erupted magmas can reveal a wealth of information on pre-eruptive processes. Here we combine detailed textural and chemical data acquired on large (>5 mm), euhedral augite megacrysts from Roman era activity (Pizzo scoria cone, 2.4–1.8 ka) at Stromboli (Italy) to investigate the plumbing system prior to the onset of current steady-state activity. Our dataset includes novel laser ablation time-of-flight mass spectrometry (LA-ICP-TOFMS) maps, which rapidly visualise multi-element zoning patterns across entire megacryst sections. The clinopyroxene data are complemented with geochemical constraints on mineral and melt inclusions, and adhering glassy tephra. Megacrysts are sector and oscillatory zoned in trace elements, yet their major element compositions are relatively uniform and in equilibrium with shoshonite-buffered melts. Mild sector zoning documents dynamic crystallisation under conditions of low undercooling during magma residence and growth. Clinopyroxene-melt thermobarometric and hygrometric calibrations, integrated with thermodynamically derived equilibrium equations, accurately track the P-T-H2O path of magmas. The refined models return restricted crystallisation depths that are deeper than those reported previously for historical and current eruptions, but consistent with deep clinopyroxene-dominated crystallisation (≥10 km), resembling other water-rich alkaline mafic systems. Megacryst cores are overgrown by oscillatory zoned mantles recording continuous input of magma that failed to trigger eruption. Crystal rims are characterised by a mild increase in compatible transition metals Cr and Ni, and depletion in incompatible elements, indicative of pre-eruptive mafic replenishment and magma mixing. The volcanic system appears to have been dominated by protracted periods of replenishment, convection, and crystal residence, punctuated by rapid megacryst evacuation and eruption upon arrival of more mafic magma (days-weeks). Since the inception of current steady-state activity, eruption-triggering melts have become appreciably more mafic, suggesting that intrusion of primitive magma may be a key driver of the steady-state regime.
Abstract
Estimating the quantity of CO
2
diffusively emitted from the Earth’s surface has important implications for volcanic surveillance and global atmospheric CO
2
budgets. However, the ...identification and quantification of non-hydrothermal contributions to CO
2
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 CO
2
fluxes, together with their carbon isotope compositions, and at a depth of 80 cm, the CO
2
concentration, soil temperature, and the activities of radon and thoron. The contributions of deep CO
2
and biogenic CO
2
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 CO
2
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 CO
2
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 CO
2
emissions in volcanic areas, because they can partially- or completely overwhelm the volcanic-hydrothermal signal.
Hasandağ volcano (Central Anatolia, Turkey) has recently underwent an increase in local seismicity and fumarolic activity since 2013. In the past, this volcano has produced multiple large explosive ...eruptions during the last million years. The Belbaşhanı Pumice is the product of a sub-Plinian to Plinian eruption dated at ~ 417 ± 20.5 ka (
40
Ar/
39
Ar). Here, we present a complete volcanological study including stratigraphy, glass chemistry, pumice morphology, geochronology, and eruption source parameters with the associated uncertainties, to characterize the Belbaşhanı Pumice eruption. The eruption involved a column of 18–29 km in height, with the main dispersal axis towards the northeast. A pumice layer up to ~ 17-m-thick accumulated in proximal deposits along the Belbaşhanı path, and up to 2-m-thick in medial-distal areas (~ 18 km northeast from the vent). The high and tubular vesicularity of the pumice clasts indicates that the Belbaşhanı eruption was predominantly magmatic. The bulk volume of the Belbaşhanı Pumice fallout deposit has been estimated as 0.5 and 8 km
3
(with ~ 2 km
3
being the mean value), which corresponds to Volcanic Explosivity Index (VEI) of at least 4 and up to 6. Both isopach and isopleth maps indicate that the volcanic vent may have been located at the intersection of the Tuz Gölü fault and Ulukışla caldera, within the Hasandağ volcanic complex. The glass composition of Belbaşhanı Pumice confirms that the eruption belongs to the Hasandağ magmatic system. The reconstruction of the Belbaşhanı Pumice eruption represents an essential baseline in providing volcanological constraints for further investigations of tephra fallout hazard assessment in Central Anatolia, especially considering that a new Plinian eruption cannot be ruled out at Hasandağ volcano in the future. The chemical and geochronological datasets presented here could aid in refining tephrochronological correlations, with the goal of synchronizing paleoenvironmental and paleoclimatic records alongside archaeological sites.
This Special Issue of Minerals collects seven different scientific contributions highlighting how magma chamber processes and eruption dynamics studied either in the laboratory or in nature may ...ultimately control the evolutionary histories and geochemical complexities of igneous rocks ...
PDF
