Survival of the Mýrdalsjökull ice cap through the Holocene thermal maximum: evidence from sulphur contents in Katla tephra layers (Iceland) from the last ∼8400 years

International audienceThe climate in Iceland was drier and warmer during the Holocene thermal maximum than it is today and it has been suggested that ice caps disappeared entirely. Katla, a volcano covered by the Mýrdalsjökull ice cap in southern Iceland, has erupted rather steadily throughout the Holocene. Preand post-eruption sulphur concentrations in its products have been determined in previous studies, through melt inclusions trapped in phenocrysts (pre-eruption mean values of 2155 ± 165 ppm) and fully degassed magmatic tephra (post-eruption mean values of 445 ± 130 ppm). The phreatomagmatic tephra has much more variable S contents (550-1775 ppm) and spans the compositional gap between magmatic tephra and melt inclusions. These variable sulphur values are attributed to arresting of degassing as the magma is quenched upon contact with external water in the shallow levels of the volcano conduit. Sulphur in Katla tephra can thus be used to evaluate whether Mýrdalsjökull survived the warm spells of the Holocene. In this study, sulphur concentrations in tephra layers representing the last ∼8400 years of the volcano's eruption history were measured, revealing concentrations in the phreatomagmatic range (600-1600 ppm). Hence, we conclude that over the last ∼8400 years, explosive activity at Katla has been dominated by phreatomagmatic eruptions, implying that the Mýrdalsjökull ice cap has been present throughout the Holocene

The impact of the 1783-1784 AD Laki eruption on global aerosol formation processes and cloud condensation nuclei

The 1783–1784 AD Laki flood lava eruption commenced on 8 June 1783 and released 122 Tg of sulphur dioxide gas over the course of 8 months into the upper troposphere and lower stratosphere above Iceland. Previous studies have examined the impact of the Laki eruption on sulphate aerosol and climate using general circulation models. Here, we study the impact on aerosol microphysical processes, including the nucleation of new particles and their growth to cloud condensation nuclei (CCN) using a comprehensive Global Model of Aerosol Processes (GLOMAP). Total particle concentrations in the free troposphere increase by a factor ~16 over large parts of the Northern Hemisphere in the 3 months following the onset of the eruption. Particle concentrations in the boundary layer increase by a factor 2 to 5 in regions as far away as North America, the Middle East and Asia due to long-range transport of nucleated particles. CCN concentrations (at 0.22% supersaturation) increase by a factor 65 in the upper troposphere with maximum changes in 3-month zonal mean concentrations of ~1400 cm<sup>−3</sup> at high northern latitudes. 3-month zonal mean CCN concentrations in the boundary layer at the latitude of the eruption increase by up to a factor 26, and averaged over the Northern Hemisphere, the eruption caused a factor 4 increase in CCN concentrations at low-level cloud altitude. The simulations show that the Laki eruption would have completely dominated as a source of CCN in the pre-industrial atmosphere. The model also suggests an impact of the eruption in the Southern Hemisphere, where CCN concentrations are increased by up to a factor 1.4 at 20° S. Our model simulations suggest that the impact of an equivalent wintertime eruption on upper tropospheric CCN concentrations is only about one-third of that of a summertime eruption. The simulations show that the microphysical processes leading to the growth of particles to CCN sizes are fundamentally different after an eruption when compared to the unperturbed atmosphere, underlining the importance of using a fully coupled microphysics model when studying long-lasting, high-latitude eruptions

Double tailed scorpiand-type calix[10]phyrin: Synthesis and proton-driven anion recognition features

Reported here is a large oligopyrrole macrocycle, a calix[10]phyrin bearing two diformyl substituents. The combination of conjugation provided by two pentapyrrolic subunits and flexibility resulting from the presence of sp3 hybridized meso bridges allows the system to adopt a double tailed, scorpiand-like structure with two near-symmetric binding pockets. In methanol solution, this macrocycle was found to interact with a number of test acids, including sulfuric acid, trifluoroacetic acid, phosphoric acid, hydrochloric acid, and fluoroboric acid, via a combination of protonation and counter anion binding. Species specific behavior was seen, allowing for the colorimetric-based discrimination between the acids. Efforts to model the underlying binding equilibria led to the conclusion that upon treatment with excess H2SO4, up to four protons and two counteranions are bound, whereas in the case of HCl the dominant species is a monoanionic complex. The responses of several other acids were rationalized in terms of these limiting scenarios

Rootless tephra stratigraphy and emplacement processes

Volcanic rootless cones are the products of thermohydraulic explosions involving rapid heat transfer from active lava (fuel) to external sources of water (coolant). Rootless eruptions are attributed to molten fuel–coolant interactions (MFCIs), but previous studies have not performed systematic investigations of rootless tephrostratigraphy and grain-size distributions to establish a baseline for evaluating relationships between environmental factors, MFCI efficiency, fragmentation, and patterns of tephra dispersal. This study examines a 13.55-m-thick vertical section through an archetypal rootless tephra sequence, which includes a rhythmic succession of 28 bed pairs. Each bed pair is interpreted to be the result of a discrete explosion cycle, with fine-grained basal material emplaced dominantly as tephra fall during an energetic opening phase, followed by the deposition of coarser-grained material mainly as ballistic ejecta during a weaker coda phase. Nine additional layers are interleaved throughout the stratigraphy and are interpreted to be dilute pyroclastic density current (PDC) deposits. Overall, the stratigraphy divides into four units: unit 1 contains the largest number of sediment-rich PDC deposits, units 2 and 3 are dominated by a rhythmic succession of bed pairs, and unit 4 includes welded layers. This pattern is consistent with a general decrease in MFCI efficiency due to the depletion of locally available coolant (i.e., groundwater or wet sediments). Changing conduit/vent geometries, mixing conditions, coolant and melt temperatures, and/or coolant impurities may also have affected MFCI efficiency, but the rhythmic nature of the bed pairs implies a periodic explosion process, which can be explained by temporary increases in the water-to-lava mass ratio during cycles of groundwater recharge.We acknowledge financial support from the National Science Foundation (NSF) grant EAR-119648, National Aeronautics and Space Administration (NASA) Mars Data Analysis Program (MDAP) grant NNG05GQ39G, NASA Mars Fundamental Research Program (MFRP) grant NNG05GM08G, NASA Postdoctoral Program (NPP), Geological Society of America (GSA), and Icelandic Centre for Research (RANNÍS). We are grateful to Stephen Scheidt for his help developing photogrammetric reconstructions of Cone 53 and we thank Richard Brown for his editorial handing of this manuscript as well as Peter Reynolds and Adrian Pittari for their constructive reviews.Peer Reviewe

The evolution and storage of primitive melts in the Eastern Volcanic Zone of Iceland: the 10 ka Grímsvötn tephra series (i.e. the Saksunarvatn ash)

Major, trace and volatile elements were measured in a suite of primitive macrocrysts and melt inclusions from the thickest layer of the 10 ka Grímsvötn tephra series (i.e. Saksunarvatn ash) at Lake Hvítárvatn in central Iceland. In the absence of primitive tholeiitic eruptions (MgO > 7 wt%) within the Eastern Volcanic Zone (EVZ) of Iceland, these crystal and inclusion compositions provide an important insight into magmatic processes in this volcanically productive region. Matrix glass compositions show strong similarities with glass compositions from the AD 1783–1784 Laki eruption, confirming the affinity of the tephra series with the Grímsvötn volcanic system. Macrocrysts can be divided into a primitive assemblage of zoned macrocryst cores (An78–An92, Mg#cpx = 82–87, Fo79.5–Fo87) and an evolved assemblage consisting of unzoned macrocrysts and the rims of zoned macrocrysts (An60–An68, Mg#cpx = 71–78, Fo70–Fo76). Although the evolved assemblage is close to being in equilibrium with the matrix glass, trace element disequilibrium between primitive and evolved assemblages indicates that they were derived from different distributions of mantle melt compositions. Juxtaposition of disequilibrium assemblages probably occurred during disaggregation of incompatible trace element-depleted mushes (mean La/Ybmelt = 2.1) into aphyric and incompatible trace element-enriched liquids (La/Ybmelt = 3.6) shortly before the growth of the evolved macrocryst assemblage. Post-entrapment modification of plagioclase-hosted melt inclusions has been minimal and high-Mg# inclusions record differentiation and mixing of compositionally variable mantle melts that are amongst the most primitive liquids known from the EVZ. Coupled high-field strength element (HFSE) depletion and incompatible trace element enrichment in a subset of primitive plagioclase-hosted melt inclusions can be accounted for by inclusion formation following plagioclase dissolution driven by interaction with plagioclase-undersaturated melts. Thermobarometric calculations indicate that final crystal–melt equilibration within the evolved assemblage occurred at ~1140 °C and 0.0–1.5 kbar. Considering the large volume of the erupted tephra and textural evidence for rapid crystallisation of the evolved assemblage, 0.0–1.5 kbar is considered unlikely to represent a pressure of long-term magma accumulation and storage. Multiple thermometers indicate that the primitive assemblage crystallised at high temperatures of 1240–1300 °C. Different barometers, however, return markedly different crystallisation depth estimates. Raw clinopyroxene–melt pressures of 5.5–7.5 kbar conflict with apparent melt inclusion entrapment pressures of 1.4 kbar. After applying a correction derived from published experimental data, clinopyroxene–melt equilibria return mid-crustal pressures of 4 ± 1.5 kbar, which are consistent with pressures estimated from the major element content of primitive melt inclusions. Long-term storage of primitive magmas in the mid-crust implies that low CO2 concentrations measured in primitive plagioclase-hosted inclusions (262–800 ppm) result from post-entrapment CO2 loss during transport through the shallow crust. In order to reconstruct basaltic plumbing system geometries from petrological data with greater confidence, mineral–melt equilibrium models require refinement at pressures of magma storage in Iceland. Further basalt phase equilibria experiments are thus needed within the crucial 1–7 kbar range

Diffusive over-hydration of olivine-hosted melt inclusions

The pre-eruptive water content of magma is often estimated using crystal-hosted melt inclusions. However, olivine-hosted melt inclusions are prone to post-entrapment modification by H+ diffusion as they re-equilibrate with their external environment. This effect is well established for the case of H+ loss from olivine-hosted inclusions that have cooled slowly in degassed magma. Here we present evidence for the opposite effect: the addition of H+ into inclusions that are held in melts that are enriched in H2O with respect to the trapped melts. The compositional variability in a suite of 211 olivine-hosted inclusions from the Laki and Skuggafjöll eruptions in Iceland's Eastern Volcanic Zone indicates that diffusive H+ gain governs the H2O content of incompatible trace element depleted inclusions. Individual eruptive units contain olivine-hosted inclusions with widely varying incompatible element concentrations but near-constant H2O. Furthermore, over 40% of the inclusions have H2O/Ce>380H2O/Ce>380, significantly higher than the H2O/Ce expected in primary Icelandic melts or mid-ocean ridge basalts (150–280). The fact that the highest H2O/Ce ratios are found in the most incompatible element depleted inclusions indicates that hydration is a consequence of the concurrent mixing and crystallisation of compositionally diverse primary melts. Hydration occurs when olivines containing depleted inclusions with low H2O contents are juxtaposed against more hydrous melts during mixing. Melt inclusions from a single eruption may preserve evidence of both diffusive H+ loss and H+ gain. Trace element data are therefore vital for determining H2O contents of melt inclusions at the time of inclusion trapping and, ultimately, the H2O content of the mantle source regions

Disparate impacts of the Eldgjá and Laki flood-lava eruptions

The Eldgjá eruption of ~ 939 AD is recognised as the largest in Iceland since Settlement, and ranks among the largest late-Holocene volcanic episodes on Earth. It disgorged > 21.0 km3 (Dense Rock Equivalent) of magma as lava flows (~ 19.7 km3) and tephra deposits (> 1.3 km3 DRE), comprising alternating phreatomagmatic (wet) and magmatic (dry) explosive phases. Tephra deposits up to four metres thick buried proximal areas, and extreme quantities of sulphur and other volatiles were released into the atmosphere. Little is known about the environmental and societal impacts of the eruption within Iceland as it took place during the initial decades of human settlement, and before written record-keeping in Iceland became prevalent. In this work, we review what is known of the Eldgjá eruption, making comparisons with the better documented Laki eruption of 1783–1784 AD (~ 15.1 km3 DRE). While the Eldgjá eruption was volumetrically greater, probably longer-lasting, and involved phreatomagmatic explosive phases, we reason that societal resilience to volcanic hazards was likely stronger in the 10th century compared with the 18th, reflecting differences in social and natural capital in Iceland. Accordingly, the impacts of the Eldgjá eruption cannot be inferred reliably from knowledge of the Laki episode and its aftermath

Two-Dimensional Molecular Patterning by Surface-Enhanced Zn-Porphyrin Coordination

In this contribution, we show how zinc-5,10,15,20-meso-tetradodecylporphyrins (Zn-TDPs) self-assemble into stable organized arrays on the surface of graphite, thus positioning their metal center at regular distances from each other, creating a molecular pattern, while retaining the possibility to coordinate additional ligands. We also demonstrate that Zn-TDPs coordinated to 3-nitropyridine display a higher tendency to be adsorbed at the surface of highly oriented pyrolytic graphite (HOPG) than noncoordinated ones. In order to investigate the two-dimensional (2D) self-assembly of coordinated Zn-TDPs, solutions with different relative concentrations of 3-nitropyridine and Zn-TDP were prepared and deposited on the surface of HOPG. STM measurements at the liquid-solid interface reveal that the ratio of coordinated Zn-TDPs over noncoordinated Zn-TDPs is higher at the n-tetradecane/HOPG interface than in n-tetradecane solution. This enhanced binding of the axial ligand at the liquid/solid interface is likely related to the fact that physisorbed Zn-TDPs are better binding sites for nitropyridines.

UK monitoring and deposition of tephra from the May 2011 eruption of Grímsvötn, Iceland

Mapping the transport and deposition of tephra is important for the assessment of an eruption’s impact on health, transport, vegetation and infrastructure, but it is challenging at large distances from a volcano (> 1000 km), where it may not be visible to the naked eye. Here we describe a range of methods used to quantify tephra deposition and impact on air quality during the 21–28 May 2011 explosive basaltic eruption of Grímsvötn volcano, Iceland. Tephra was detected in the UK with tape-on-paper samples, rainwater samples, rainwater chemistry analysis, pollen slides and air quality measurements. Combined results show that deposition was mainly in Scotland, on 23–25 May. Deposition was patchy, with adjacent locations recording different results. Tape-on-paper samples, collected by volunteer citizen scientists, and giving excellent coverage across the UK, showed deposition at latitudes >55°N, mainly on 24 May. Rainwater samples contained ash grains mostly 20–30 μm long (maximum recorded grainsize 80 μm) with loadings of up to 116 grainscm-2. Analysis of rainwater chemistry showed high concentrations of dissolved Fe and Al in samples from N Scotland on 24–27 May. Pollen slides recorded small glass shards (3–4 μm long) deposited during rainfall on 24–25 May and again on 27 May. Air quality monitoring detected increased particulate matter concentrations in many parts of the country. An hourly concentration of particles  53°N) on 24 May but no negative effects on health were reported. Although the eruption column reached altitudes of 20 km above sea level, air mass trajectories suggest that only tephra from the lowest 4 km above sea level of the eruption plume was transported to the UK. This demonstrates that even low plumes could deliver tephra to the UK and suggests that the relative lack of basaltic tephra in the tephrochronological record is not due to transport processes