Description: Highlights • Temporally close-spaced double eruption within a couple of hundreds of years. • Magmas are variably tapped from zoned magma chambers during eruptions due to changing magma discharge rates and/or vent migration. • Eruptions started with a series of fallouts featuring stable eruption columns followed by fluctuating and partially collapsing eruption columns. • Eruptive volumes sum up to a total of 25.6 km3 and 40.5 km3 tephra volume, eruption column heights have been between 20–33 km. • Potential hazards from similar sized eruptions around Coatepeque Caldera are indicated even in the distal regions around San Salvador. Abstract The Coatepeque volcanic complex in El Salvador produced at least four Plinian eruptions within the last 80 kyr. The eruption of the 72 ka old Arce Tephra formed the Coatepeque Caldera and was one of the most powerful explosive eruptions in El Salvador. Hitherto it was thought that the Arce tephra had been emplaced only by one, mostly Plinian, eruptive event that ended with the deposition of a thick ignimbrite. However, our stratigraphic, geochemical, and zircon data reveal a temporally closely- spaced double eruption separated by a gap of only a couple of hundred years, and we therefore distinguish Lower and Upper Arce Tephras. Both eruptions produced in the beginning a series of fallout units generated from fluctuating eruption columns and turning wind directions. The final phase of the Upper Arce eruption produced surge deposits by several eruption column collapses before the terminal phase of catastrophic ignimbrite eruption and caldera collapse. Mapping of the individual tephra units including the occurrences of distal marine and lacustrine ash layers in the Pacific Ocean, the Guatemalan lowlands and the Caribbean Sea, result in 25.6 km3 tephra volume, areal distribution of 4 × 105 km2 and eruption column heights between 20–33 km for the Lower Arce eruption, and 40.5 km3 tephra volume, including 10 km3 for the ignimbrite, distributed across 6 × 105 km2 and eruption column heights of 23–28 km for the Upper Arce eruption. These values and the detailed eruptive sequence emphasize the great hazard potential of possible future highly explosive eruptions at Coatepeque Caldera, especially for this kind of double eruption.

Description: Highlights • Release of dissolved Sr2+ with low 87Sr/86Sr, as well as Ca2+ and Ba2+ suggests ongoing volcanic ash alteration. • A concurrent increase in Fe2+ and a depletion of CH4 with a decrease in C of CH4 and DIC suggest Fe-AOM. • We for the first time document the potential linkage between ash alteration and methane oxidation via Fe-AOM. • The rate of Fe-AOM is estimated to be ∼0.4 μmol cm−2 yr−1, equivalent to ∼12% of total CH4 removal. Abstract We present geochemical data collected from volcanic ash-bearing sediments on the upper slope of the northern Hikurangi margin during the RV SONNE SO247 expedition in 2016. Gravity coring and seafloor drilling with the MARUM-MeBo200 allowed for collection of sediments down to 105 meters below seafloor (mbsf). Release of dissolved Sr2+ with isotopic composition enriched in 86Sr (87Sr/86Sr minimum = 0.708461 at 83.5 mbsf) is indicative of ash alteration. This reaction releases other cations in the 30-70 mbsf depth interval as reflected by maxima in pore-water Ca2+ and Ba2+ concentrations. In addition, we posit that Fe(III) in volcanogenic glass serves as an electron acceptor for methane oxidation, a reaction that releases Fe2+ measured in the pore fluids to a maximum concentration of 184 μM. Several lines of evidence support our proposed coupling of ash alteration with Fe-mediated anaerobic oxidation of methane (Fe-AOM) beneath the sulfate-methane transition (SMT), which lies at ∼7 mbsf at this site. In the ∼30-70 mbsf interval, we observe a concurrent increase in Fe2+ and a depletion of CH4 with a well-defined decrease in C-CH4 values indicative of microbial fractionation of carbon. The negative excursions in C values of both DIC and CH4 are similar to that observed by sulfate-driven AOM at low SO concentrations, and can only be explained by the microbially-mediated carbon isotope equilibration between CH4 and DIC. Mass balance considerations reveal that the iron cycled through the coupled ash alteration and AOM reactions is consumed as authigenic Fe-bearing minerals. This iron sink term derived from the mass balance is consistent with the amount of iron present as carbonate minerals, as estimated from sequential extraction analyses. Using a numerical modeling approach we estimate the rate of Fe-AOM to be on the order of 0.4 μmol cm−2 yr−1, which accounts for ∼12% of total CH4 removal in the sediments. Although not without uncertainties, the results presented reveal that Fe-AOM in ash-bearing sediments is significantly lower than the sulfate-driven CH4 consumption, which at this site is 3.0 μmol cm−2 yr−1. We highlight that Fe(III) in ash can potentially serve as an electron acceptor for methane oxidation in sulfate-depleted settings. This is relevant to our understanding of C-Fe cycling in the methanic zone that typically underlies the SMT and could be important in supporting the deep biosphere.

Description: Despite the important role that volcanogenic aluminosilicate (VA) alteration has on elemental cycles in marine sediments, there is no mechanism to arrive at a global assessment of this process. To quantify the VA alteration rates from Japan, New Zealand (NZ), and Costa Rica, we developed a mass balance approach that is constrained by the strontium concentration and 87Sr/86Sr ratios in pore fluid, authigenic carbonates, and VA. We derived VA alteration rates ranging from 101 to 103 nmole Sr/m3 bulk sediment/yr with the highest rate obtained for Tuaheni, NZ (Site GeoB80202), which has the youngest sediment. We showed that 87Sr/86Sr ratios of VA derived from this mass balance approach are significantly higher than the reported ratios from volcanic glass samples, indicating a concomitant role of volcanogenic feldspar dissolution and/or authigenic clay formation. Most of the strontium released during VA alteration is precipitated as authigenic carbonate, with important implications for carbon inventories. The VA alteration rates derived from this approach can also be used to quantify the release of other critical elements, such as release of iron that can stimulate formation of Fe‑carbonates and/or fuel microbial activity at depth.

Description: Highlights • Masaya caldera is an unusual basaltic caldera in that it formed by voluminous magma extraction during explosive eruptions. We identify the nature, age and volume of these three eruptions of which the first, emplacing the San Antonio tephra, was by far most voluminous. • The by far largest fraction of the 9 km3 DRE erupted volume of this tephra was discharged during a Plinian eruption phase, which was bracketed by phreatomagmatic eruptions. We demonstrate that water contents measured in melt inclusions equilibrated during residence at shallow level shortly before eruption strongly underestimate original water contents during differentiation at higher pressure. We argue that the large fraction of exsolved H2O together with buoyancy pressure from connection to the deeper reservoir drove the eruptive high mass flux needed for the Plinian eruption phase. Masaya is unusual for a basaltic caldera because it formed by piston-subsidence in response to large-volume magma withdrawal by highly explosive eruptions, i.e. in a fashion typical of silicic calderas. The first and most voluminous of the three explosive eruptions formed the 6 ka old basaltic San Antonio Tephra (SAT). This eruption is also unusual in that most of the 9 km3 DRE basaltic magma was discharged by a plinian eruption. The subsequent eruptions of the basaltic Masaya Triple Layer (MTL, 2.1 ka) and the Masaya Tuff/Ticuantepe Lapilli (MT-TIL, 1.9 ka) each discharged 2 km3 DRE magma and enlarged the Masaya caldera. The SAT consists of a lower sequence of alternating scoria lapilli and ash layers, interpreted as an alternation between more or less phreatomagmatically influenced fallout events. These are followed by two prominent well-sorted lapilli layers: the first one formed by a climactic plinian eruption whose column height reached 21–29 km and discharged most of the total erupted mass including about 35 Mt. SO2. The second, lithic-rich lapilli layer probably formed by a phreatoplinian event when partial collapse of the magma chamber roof initiated increasing magma-water interaction which ultimately formed the upper sequence of phreatomagmatic cross-bedded surge deposits, accretionary lapilli-rich tuffs and a final fallout of dense lapilli. Phreatomagmatic activity may have been related to disruption of a hydrothermal system reflected in hydrothermally altered lithics, and/or by the caldera floor subsiding closer to the groundwater table. The bulk-rock chemical composition of the SAT is basaltic but the bimodal glass compositions demonstrate mixing of a basaltic with an andesitic melt probably in the conduit during eruption. The SAT basalt differentiated in a reservoir near the MOHO at 20 km depth by fractional crystallization of olivine, plagioclase, and minor clinopyroxene forming a tholeiitic fractionation trend. Minor intermediate-An plagioclase crystallized from the basaltic melt at H2O concentrations of about 2 wt% as measured by FTIR in melt inclusions. However, a key observation is that the melt inclusions are not in equilibrium with the high-An plagioclases hosting them. Re-equilibration of the inclusions requires initially higher water contents (about 5–6 wt%) which also fits the high Ba/La ~ 80 indicating input from the strongly hydrated subducting slab. Therefore, while the SAT magma evolved under hydrous conditions at depth, it was then stored at shallow level long enough to adjust to the low saturation pressure and to precipitate some intermediate-An plagioclase but still preserving its high temperature (around 1100 °C) and phenocryst-poor composition. Large overpressure due to connection to the deep-seated reservoir and water degassing during ascent limited the storage time at shallow level and drove the unusually intense and voluminous plinian-style eruption that facilitated piston-type collapse of the chamber roof.

Description: Highlights • Overview on geochemical composition of pore water and solid phase of sediments on the Azores Plateau. • Evidence for deep marine hydrothermal activity on the Azores Plateau. • Pore water data suggest ongoing anaerobic oxidation of methane and carbonate recrystallization. The Azores Plateau is an active magmatic region in the Central North Atlantic Ocean. In this study, we present a comprehensive data set of major element compositions and 87Sr/86Sr ratios of pore waters from surface sediments (0–9 mbsf) of the Azores Plateau. Based on distinct geochemical signatures we can separate normal marine from hydrothermally affected sediments. Normal marine sediments can further be differentiated by their ash content. Pore waters of ash rich gravity cores (GCs) do not show any deviations from seawater values except of a minor increase in Sr. In contrast, ash poor GCs generally show a trend for decreasing Ca with increasing depth, accompanied by a minor SO4 decrease and a more pronounced Sr increase. We suggest that these deviations are caused by processes such as anaerobic oxidation of methane and carbonate recrystallization. At four additional sample locations we observed a decrease in Mg and SO4 accompanied by a Ca increase in the pore waters, a pattern typical for hydrothermal fluids. The existence of hydrothermal systems in this region are corroborated by multi-channel seismic data, suggesting that sill or dyke intrusions are present in the subsurface close to the core locations. Overall, our observations offer preliminary indications for the existence of submarine hydrothermal systems on the Azores Plateau away from the Mid- Atlantic Ridge.

Description: Defining a precise timeline for past eruptions from explosive volcanoes in continental arcs is imperative to forecast future hazards and mitigate volcanic disasters in these often densely populated regions. However, establishing reliable ages for Quaternary eruptions in the Central American Volcanic Arc has been challenging due to the common lack or alteration of suitable K-rich phases for 40Ar/39Ar geochronology, but also from their position in time beyond the reach of 14C dating. This especially holds for the active Amatitlán caldera in Guatemala, from which at least six explosive silicic eruptions have produced tephra blanketing neighboring regions that are today inhabited by millions of people. Zircon, a common datable accessory mineral in Amatitlán caldera magmas, is used here to retrieve eruption ages by applying the novel zircon double-dating method (ZDD) that integrates 238U–230Th disequilibrium dating and (U–Th)/He thermochronology. This approach yielded the first-ever radioisotopic ages of 24 ± 3 ka and 48 ± 6 ka (1σ), respectively, of two of Amatitlán caldera's most recent eruptions (J-tephra and E-tephra). Remarkably, both zircon crystallization and ZDD eruption ages for the older and voluminous T-tephra and L-tephra units significantly post-date existing plagioclase 40Ar/39Ar dates by ca. 26 and 70 kyr, respectively. The ZDD eruption age for T-tephra is 93 ± 4 ka, whereas zircon crystallization ages for L-tephra yield a maximum model eruption age of ca. 124 ka. The strong eruption age divergence between ZDD and plagioclase 40Ar/39Ar dating argues for the presence of inherited or xenocrystic plagioclase in Amatitlán caldera eruptive products. Statistical analysis based on the updated eruptive history suggests a recurrence interval of ca. 17 kyr, which is significantly shorter than previously estimated. The new age data, thus, suggest a more frequent eruptive activity of Amatitlán caldera than formerly thought and underscores the necessity to better understand the current underlying magmatic system and to constrain its past eruptive history more precisely.

Description: Highlights • Funda Volcanic System produced at least 3 eruptions over a period of 〈200 years. • Volcanism was longer and more recurrent than previously reported. • Eruptive styles range from Strombolian (mild and violent) to phreatomagmatic. • Magma/groundwater interactions may have led to rapid changes in eruptive style. • Future hazard assessment need to effectively consider magma/groundwater interactions. Monogenetic volcanoes occur in many different geotectonic settings and are usually small and short-lived. They can experience a variety of eruptive styles, even during the same eruption. In monogenetic volcanic fields, volcanism usually migrates to different locations over time, making volcanic hazard assessment very challenging. The eruptive history of a volcanic region, including the size, style, and location of previous eruptions, provides valuable information to help predict the behaviour of future volcanic events and their associated hazards. Here, we reconstruct for the first time the eruptive history of the Funda Volcanic System (FVS), one of the most recent (∼3 ka) monogenetic eruptive centres of Flores Island (Azores), based on a detailed tephrostratigraphic work coupled with geochemical analysis of glass shards and radiocarbon dating. We identified at least three volcanic events at FVS spaced by time intervals of ∼100 yr. The first event (3430 cal yr BP) was a small Strombolian eruption, the second event (3330 cal yr BP) started as a violent Strombolian eruption and may have ended as phreatomagmatic, and the third event (3250 cal yr BP) was exclusively phreatomagmatic. Our results demonstrate that volcanism at the FVS was more prolonged and recurrent than previously reported. Moreover, we show that the FVS experienced different eruptive styles in a short timeframe, ranging from small basaltic eruptions to violent explosive phreatomagmatic events. Such diversity of eruptive styles results in different volcanic products, which have different hazard implications. Our new results contribute to the knowledge of the recent volcanic activity of Flores Island, and we anticipate them to be of paramount importance for future volcanic hazard assessment studies.

Description: Highlights • Regardless of eruptive style, Masaya magmas are compositionally similar. • Volatile contents are higher in Plinian samples, but low compared to CAVA magmas. • All Masaya magmas undergo extensive pre-eruptive degassing at low pressure. • Initial volatiles are higher than observed, but do not control eruptive style. • The state of the volcano's conduit modulates eruptive style in a top–down manner. Abstract Highly explosive Plinian eruptions of basaltic magma are enigmatic because low melt viscosities should inhibit such eruptive style. Masaya volcano, Nicaragua, is a persistently active basaltic system capable of a wide range of eruptive styles, from open-conduit lava lake activity to voluminous Plinian eruptions; it is thus an ideal natural laboratory to constrain potential controls on basaltic eruption style. Here we report the major, trace, and volatile (CO2, H2O, S, Cl, F) element composition of olivine-, plagioclase- and clinopyroxene-hosted melt inclusions as well as matrix glasses from lava lake ejecta and two Plinian tephra deposits—the 2.1 ka Masaya Triple Layer and the 1.8 ka Ticuantepe Lapilli—to test whether pre-eruptive volatile contents and degassing history may be linked to eruptive style. All samples display a relatively narrow and largely overlapping basaltic–basaltic andesitic compositional range ( wt.% SiO2, wt.% MgO) with similar trace element signatures (e.g., , ). However, lava lake and Plinian samples show systematic differences in pre-eruptive volatile contents, forming distinct groups with mean H2O contents of wt.% (lava lake), wt.% (Masaya Triple Layer), and wt.% (Ticuantepe Lapilli). Together, these groups generate broad positive correlations between S, Cl and H2O concentrations, with maximum values reaching 920 ppm, 1300 ppm and 2.3 wt.%, respectively, which are low compared to typical Central American arc magmas. Magma temperature estimates overlap and average at 30°C, while volatile saturation pressures are low, mainly 〈100 MPa, although only lava lake samples record pressures 〈31 MPa. These observations reiterate the compositionally buffered state of the volcano's magmatic system highlighted by previous work and demonstrate that — regardless of eruption style — all Masaya magmas undergo variable, but extensive, pre-eruptive degassing at low pressure. Geohygrometry, gas emissions, and H2O/Ce–Ba/La systematics suggest initial, undegassed H2O contents on the order of 3.9–5.5 wt.%. Our results imply that pre-eruptive volatile contents are not the culprit for Plinian events at Masaya. Instead, we propose that the volcano's vigorous magma supply is modulated in a top–down manner to produce a wide range of eruptive styles, whereby temporary sealing of the conduit may instigate a transition to explosive behavior. In this model, rapid magma ascent is triggered when the seal eventually breaks from degassing-induced pressurization, yielding high degrees of undercooling, rapid microlite growth, and a dramatic increase in magma viscosity and explosive eruption potential. There may thus be a thin line between open-conduit conditions and Plinian eruptions at Masaya.

Description: Extensive and protracted volcanism in the Carpathian-Pannonian Region climaxed during the Early to Middle Miocene with series of major ignimbrite-forming eruptions with their products dispersed across the Alpine-Mediterranean Region. The spatial and temporal dispersion of these volcanic horizons make them potentially important stratigraphic markers throughout the region, allowing better understanding of temporal and spatial changes in depositional environments and paleoclimate. Several of these Middle Miocene volcaniclastic layers are preserved in stratigraphically and environmentally variable sedimentary facies on Mt. Medvednica, located in the North Croatian Basin. In order to decipher the age, depositional environment and provenance of two volcaniclastic horizons intercalated within Central Paratethys marine sediments on Mt. Medvednica, we applied an integrated approach of volcanological, geochronological, and paleontological analyses. New high-precision zircon geochronology and volcanic glass geochemistry data allow to distinguish two primary rhyolitic volcaniclastic horizons derived from distinct eruptions, “Plaz“, and the “Bidrovec“, dated at 14.937 ± 0.012 Ma and 14.835 ± 0.012 Ma. Distinguished mineralogical and geochemical data enabled the correlation of the older (“Plaz”) horizon on Mt. Medvednica with the Demjén eruption, one of the six major Early–Middle Miocene ignimbrite-forming eruptions of the Carpathian-Pannonian Region. However, a correlation of the younger (“Bidrovec“) horizon and assignment to a specific eruption could not be established due to a lack of compositional data from coeval eruption products throughout the region. The newly gathered data establishes both “Plaz” and “Bidrovec” pyroclastic deposits as valuable marker horizons for regional reconstructions, and enable a better understanding of the eruption chronology and tephrostratigraphy of the Carpathian-Pannonian Region.

Description: The Carpathian-Pannonian Region (CPR) hosted some of the largest silicic volcanic eruptions in Europe during the Early and Middle Miocene, contemporaneously with major lithospheric thinning of the Pannonian Basin. This was recorded as an ignimbrite flare-up event from approximately 18.1–14.4 Ma. To gain in-depth perspectives on the eruption chronology, tephrostratigraphy, and petrogenesis at the onset of CPR silicic volcanism, we applied a multi-proxy approach to Lower Miocene rhyolitic ignimbrites and pyroclastic fall deposits from the northern CPR to the Dinaride Lake System. High-precision zircon U-Pb geochronology distinguished two Lower Miocene groups of volcaniclastic rocks at ∼ 18.1 Ma and ∼ 17.3 Ma. Based on combined tephrostratigraphic signatures we propose that the ∼ 18.1 Ma Kalnik and ∼ 17.3 Ma Eger eruptions produced widespread (intermediate to) large caldera-forming massive rhyolitic ignimbrites, deposited across northern and southwestern regions of the CPR. Due to easterly winds that carried volcanic ash hundreds of kilometers to the southwest, Eger eruption products also reached distal intra-montane Dinaride lacustrine basins, recorded as pyroclastic fall deposits. Heterogeneous major and trace elemental compositions of ∼ 18.1 Ma volcanic glass shards suggest that the Kalnik eruption was sourced from complex silicic magmatic systems, with simultaneous tapping of two discrete melt bodies during the eruption. The homogeneous geochemical composition of ∼ 17.3 Ma glasses is distinct from the older glasses. Integrated zircon and bulk glass Nd-Hf isotope compositions have a positive correlation, defining a regional mantle array, and are more radiogenic in the younger phase of volcanism. The recorded systematic isotopic change, moving from older more crustal signatures to younger more juvenile compositions, imply that during the period of lithospheric thinning of the Pannonian Basin the region underwent more complex variations in the interaction between metasomatized lithospheric mantle-derived magmas and various crustal components than previously recognized.