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The conditions under which halogens partition in favor of an exsolved fluid relative to the coexisting melt are key for understanding many magmatic processes, including volcanic degassing, evolution of crustal melt bodies, and ore formation. We report new F, Cl, and Br fluid/melt partition coefficients for intermediate to silicic melts, for which F and Br data are particularly lacking; and for varying CO2-H2O contents to assess the effects of changing fluid composition (XH2O) on Br fluid/melt partitioning for the first time. The experiments were conducted at pressures 50–120 MPa, temperatures 800–1100 °C, and volatile compositions [molar XH2O = H2O/(H2O +CO2)] of 0.55 to 1, with redox conditions around the Nickel-Nickel Oxygen buffer (fO2 ≈ NNO). Experiments were not doped with Cl, Br, or F and were conducted on natural crystal-bearing volcanic products at conditions close to their respective pre-eruptive state. The experiments therefore provide realistic constraints on halogen partitioning at naturally occurring, brine-undersaturated conditions. Measurements of Br, Cl, and F were made by Secondary Ion Mass Spectrometry (SIMS) on 13 experimental glass products spanning andesite to rhyolitic compositions, together with their natural starting materials from Kelud volcano, Indonesia, and Quizapu volcano, Chile. Fluid compositions were constrained by mass balance. Average bulk halogen fluid/melt partition coefficients and standard deviations are: DClfluid/melt = 3.4 (±3.7 1 s.d.), DFfluid/melt = 1.7 (±1.7), and DBrfluid/melt = 7.1 (±6.4) for the Kelud starting material (bulk basaltic andesite), and DClfluid/melt = 11.1 (±3.5), DFfluid/melt = 0.8 (±0.8), and DBrfluid/melt = 31.3 (±20.9) for Quizapu starting material (bulk dacite). The large range in average partition coefficients is a product of changing XH2O, pressure and temperature. In agreement with studies on synthetic melts, our data show an exponential increase of halogen Dfluid/melt with increasing ionic radius, with partitioning behavior controlled by melt composition according to the nature of the complexes forming in the melt (e.g., SiF4, NaCl, KBr). The fundamental chemistry of the different halogens (differing ionic size and electronegativities) controls the way in which partitioning responds to changes in melt composition and other variables. Experimental results confirm that more Cl partitions into the fluid at higher bulk Cl contents, higher melt Na, higher fluid XH2O ratios, and lower temperatures. Bromine shows similar behavior, though it seems to be more sensitive to temperature and less sensitive to Na content and XH2O. In contrast, F partitioning into the fluid increases as the melt silica content decreases (from 72 to 56 wt% SiO2), which we attribute to the lower abundance of Si available to form F complexes in the melt. These new data provide more insights into the conditions and processes that control halogen degassing from magmas and may help to inform the collection and interpretation of melt inclusions and volcano gas data.

There is a temporal correlation between the peak activity of the North Atlantic Igneous Province (NAIP) and the Paleocene–Eocene Thermal Maximum (PETM), suggesting that the NAIP may have initiated and/or prolonged this extreme warming event. However, corroborating a causal relationship is hampered by a scarcity of expanded sedimentary records that contain both climatic and volcanic proxies. One locality hosting such a record is Fur Island in Denmark, where an expanded pre- to post-PETM succession containing hundreds of NAIP ash layers is exceptionally well preserved. We compiled a range of environmental proxies, including mercury (Hg) anomalies, paleotemperature proxies, and lithium (Li) and osmium (Os) isotopes, to trace NAIP activity, hydrological changes, weathering, and seawater connectivity across this interval. Volcanic proxies suggest that NAIP activity was elevated before the PETM and appears to have peaked during the body of the δ13C excursion, but decreased considerably during the PETM recovery. This suggests that the acme in NAIP activity, dominated by flood basalt volcanism and thermogenic degassing from contact metamorphism, was likely confined to just ~200 kyr (ca. 56.0–55.8 Ma). The hundreds of thick basaltic ashes in the post-PETM strata likely represent a change from effusive to explosive activity, rather than an increase in NAIP activity. Detrital δ7Li values and clay abundances suggest that volcanic ash production increased basaltic reactive surface area, likely enhancing silicate weathering and atmospheric carbon sequestration in the early Eocene. Signals in lipid biomarkers and Os isotopes, traditionally used to trace paleotemperature and weathering changes, are used here to track seaway connectivity. These proxies indicate that the North Sea was rapidly cut off from the North Atlantic in under 12 kyr during the PETM recovery due to NAIP thermal uplift. Our findings reinforce the hypothesis that the emplacement of the NAIP had a profound and complex impact on Paleocene–Eocene climate, both directly through volcanic and thermogenic degassing, and indirectly by driving regional uplift and changing seaway connectivity.

Marine tetrapods occupy important roles in modern marine ecosystems and often gather in large aggregations driven by patchy prey distribution, 1 ,2 social or reproductive behaviors, 3 ,4 or oceanographic factors. 5 Here, we show that similar grouping behaviors evolved in an early marine tetrapod lineage, documented by dozens of specimens of the giant ichthyosaur Shonisaurus in the Luning Formation in West Union Canyon, Nevada, USA. 6 ,7 A concentration of at least seven skeletons closely preserved on a single bedding plane received the bulk of previous attention. However, many more specimens are preserved across ∼106 square meters and ∼200 stratigraphic meters of outcrop representing an estimated >105–6 years. Unlike other marine-tetrapod-rich deposits, this assemblage is essentially monotaxic; other vertebrate fossils are exceptionally scarce. Large individuals are disproportionately abundant, with the exception of multiple neonatal or embryonic specimens, indicating an unusual demographic composition apparently lacking intermediate-sized juveniles or subadults. Combined with geological evidence, our data suggest that dense aggregations of Shonisaurus inhabited this moderately deep, low-diversity, tropical marine environment for millennia during the latest Carnian Stage of the Late Triassic Period (237–227 Ma). Thus, philopatric grouping behavior in marine tetrapods, potentially linked to reproductive activity, has an antiquity of at least 230 million years.

Satellite instruments play a valuable role in detecting, monitoring and characterising emissions of ash and gas into the atmosphere during volcanic eruptions. Plumes of ash and sulfur dioxide (SO2) from the April 2021 eruption of La Soufrière volcano on St Vincent in the Eastern Caribbean were observed by a multiple satellite instruments. This study looks at these plumes with two satellite instruments: the Advanced Baseline Imager (ABI) on the Geostationary Operational Environmental Satellite (GOES), and the Infrared Atmospheric Sounding Interferometer (IASI) on the MetOp platforms. Using true and false colour images, and brightness temperature difference images produced from the ABI data, a minimum of 32 eruptive events were identified. The ABI images were used to determine the approximate start and end times and character of each event. In this way the eruption has been divided into four phases: (1) an initial explosive event, (2) a sustained event lasting over nine hours, (3) a pulsatory phase with 23 explosive events in a 54 hour period and (4) a waning sequence of explosive events. The IASI instrument was used to study the dispersion of SO2 from this eruption. The results showed a highly complex structure to the plume, in terms of the column amounts and height, which is likely linked to the multiple explosive events. The SO2 is shown to have largely been emitted between 13 and 19 km. This was primarily in the upper troposphere and around the height of the tropopause, but with some emission into the stratosphere. The SO2 was transported around the globe with parts of the plume reaching as far as 45° S and 45° N. The largest SO2 atmospheric burden measured with IASI was 0.31±0.09 Tg, recorded on the 13 April 2021 (descending orbits). The SO2 masses were converted into fluxes. The SO2 flux was shown to peak on 10 April and then shown to decrease over time. By summing the IASI SO2 flux results, it is estimated that a total of 0.57±0.44 Tg of SO2 was emitted to the atmosphere. However, due to the limitations associated with the retrieval this should be considered a minimum estimate of the total mass of SO2 emitted. An average e-folding time of 7.09±5.70 days was computed based on the IASI SO2 results: similar to other tropical eruptions of this magnitude. There are a number of similarities between the 1979 and 2021 eruptions at La Soufrière. For example, both eruptions consisted of a series of explosive events with varied heights including some emission into the stratosphere. The similarities between the 1979 and 2021 highlight the importance of studying these eruptions to be prepared for future activity.

Past large igneous province (LIP) emplacement is commonly associated with mantle plume upwelling and led to major carbon emissions. One of Earth’s largest past environmental perturbations, the Toarcian oceanic anoxic event (T-OAE; ~183 Ma), has been linked to Karoo-Ferrar LIP emplacement. However, the role of mantle plumes in controlling the onset and timing of LIP magmatism is poorly understood. Using global plate reconstruction models and Lower Toarcian sedimentary mercury (Hg) concentrations, we demonstrate (i) that the T-OAE occurred coevally with Karoo-Ferrar emplacement and (ii) that timing and duration of LIP emplacement was governed by reduced Pangean plate motion, associated with a reversal in plate movement direction. This new model mechanistically links Earth’s interior and surficial processes, and the mechanism is consistent with the timing of several of the largest LIP volcanic events throughout Earth history and, thus, the timing of many of Earth’s past global climate change and mass extinction events.

The latest Permian mass extinction (LPME) was triggered by magmatism of the Siberian Traps Large Igneous Province (STLIP), which left an extensive record of sedimentary Hg anomalies at Northern Hemisphere and tropical sites. Here, we present Hg records from terrestrial sites in southern Pangea, nearly antipodal to contemporaneous STLIP activity, providing insights into the global distribution of volcanogenic Hg during this event and its environmental processing. These profiles (two from Karoo Basin, South Africa; two from Sydney Basin, Australia) exhibit significant Hg enrichments within the uppermost Permian extinction interval as well as positive Δ

The caldera-forming Samalas eruption of the Samalas–Rinjani volcanic complex on Lombok, Indonesia, in 1257 CE ranks as one of the most explosive and sulphur-rich eruptions of the past thousand years. Along with other significant events (e.g. Tambora 1815, El Chichón 1982), Samalas 1257 forms a class of powerful eruptions of magmas of intermediate alkaline composition, which remain relatively understudied. This study aims to better understand the pre-eruptive magma reservoir conditions and volatile storage capacities of intermediate alkaline systems, using the 1257 Samalas eruption as a case study. Systematic partial-equilibrium experiments were run to constrain potential magma reservoir conditions (25–200 MPa and 850–1000°C) by examining changes in the chemistry and textures of experimental glass and mineral products. Natural trachydacite pumice from the 1257 Samalas eruption was used as the experimental charge for a series of water-saturated experiments run in cold-seal pressure vessels, buffered at an oxygen fugacity ƒO2 of NNO/NNO + 1 log units. Assessing the match between natural and experimental glass compositions and mineral phases and textures reveals that pre-eruptive magma reservoir conditions were between 875°C and 930°C and ca. 100–150 MPa (4.5 ± 1km depth). Breakdown of experimental amphibole at pressures below 75 MPa, and plagioclase instability at 950°C/100 MPa, provide the strongest constraints on phase stabilities that are consistent with the magma storage region. In the observed temperature and pressure range, the natural compositions of plagioclase, amphibole and orthopyroxene are replicated in experimentally precipitated rims. Clinopyroxene and high anorthite plagioclase (An>64) in the natural mineral assemblage could not be replicated in the experiments, implying that these compositions most likely did not grow in the shallow pre-eruptive reservoir of Mt Samalas. The pre-eruptive storage depths of trachydacite magma are significantly shallower than the postulated magma storage at the currently active basaltic-andesite magmatic system at Rinjani, and thus monitoring magma storage depth may be a useful indicator of changing magma composition in the future. Our findings show that highly explosive VEI 7 eruptions of intermediate alkaline magma can be fed from a relatively limited range of storage pressures (100–150 MPa), suggesting accumulation of magma in one place, rather than the rapid extraction of magma from a vertically extensive, transcrustal magma system.

Volcanic activity associated with the emplacement of Large Igneous Provinces (LIPs) has been linked to most Phanerozoic extinctions/episodes of major environmental change. In recent years, mercury (Hg) enrichments and elevated mercury/total organic carbon (Hg/TOC) ratios have been increasingly utilized as a marker of volcanism in sedimentary records deposited distally from LIPs. The proxy is based on the premise that volcanism is a major natural source of the element to the atmosphere, and that it was especially important prior to anthropogenic emissions. To date, end-Permian and end-Triassic records illustrate the strongest use of Hg as a marker of volcanic activity, supplemented by the use of Hg isotopes and other evidence for LIP eruptions and volatile emissions. Sedimentary records of several other events also document Hg enrichments in at least one region, suggestive of a regional- or global-scale perturbation to the Hg cycle at those times, potentially linked to volcanism. The Cenomanian– Turonian Oceanic Anoxic Event 2 appears to be the exception, with strata documenting peaks in Hg/TOC in a small minority of studied records, suggesting that there was only a minimal perturbation to the Hg cycle at that time. Even for events where a global Hg-cycle perturbation apparently occurred, varying Hg enrichments documented from individual archives of the same event indicate that the complex biogeochemical cycling of mercury can result in a strong influence of local/regional aquatic, biological, or sedimentary processes on the precise signature of any worldwide disturbance. Of additional intrigue is an apparent lack of correlation of Hg and Hg/TOC with other volcanic proxies such as osmium isotopes, suggesting that the two systems record different aspects of LIP volcanism and emplacement. Recent studies are beginning to investigate these above complexities, but further work is needed to fully explore the nuances of Hg in the geological record, and how it can be best employed as a proxy for LIP volcanism.

This study was supported by the Leverhulme Trust grant 2016–21 (Nature and impacts of Middle Pleistocene volcanism in the Ethiopian Rift). KF was supported by the UK's Natural Environment Research Council (NERC) grant NE/L013932/1 (RiftVolc: The Past, Present and Future of Rift Volcanism in the Main Ethiopian Rift), a Boise Fund grant from the Department of Zoology, University of Oxford, and acknowledges Fonds de Recherche Scientifique – FNRS MIS grant F.4515.20. Tephra work on the Chew Bahir cores in the Cambridge Tephra Lab by AA, AP and CL was made possible by NERC grant NE/K014560/1. Ar–Ar dating was supported by grants NIGFSC IP-1683-1116 and IP-1680-1116. The iCRAG lab is supported by SFI 13/RC/2092. The Main Ethiopian Rift (MER) is renowned as a focus of investigations into human origins. It is also the site of many large volcanic calderas, whose eruptions have spanned the timeframe of speciation, cultural innovation, and dispersal of our species. Yet, despite their significance for dating human fossils and cultural materials, the timing and geochemical signatures of some of the largest eruptions have remained poorly constrained at best. Here, through a programme of field surveys, geochemical analysis and 40Ar/39Ar dating, we report the ages of MER ignimbrites and link them to widespread tephra layers found in sequences of archaeological and paleoenvironmental significance. We date major eruptions of Fentale (76 ± 18 ka), Shala (ca. 145–155 ka), Kone (184 ± 42 ka and ca. 200 ± 12 ka) and Gedemsa (251 ± 47 ka) volcanoes, and correlate a suite of regionally important tephra horizons. Geochemical analysis highlights the predominantly peralkaline rhyolitic melt compositions (7.5–12 wt% Na2O + K2O, 70–76 wt% SiO2) across the central MER and remarkable similarity in incompatible trace element ratios, limiting the correlation of deposits via glass composition alone. However, by integrating stratigraphic and geochronological evidence from proximal deposits, lake sediment cores and distal outcrops at archaeological sites, we have traced ash layers associated with the ca. 177 ka Corbetti, ca. 145–155 ka Shala and ca. 108 ka Bora-Baricha-Tullu-Moye eruptions across southern Ethiopia. In addition to strengthening the tephrochronological framework that supports paleoenvironmental and archaeological work in the region, our findings have wider implications for evaluating the hypothesis of a middle Pleistocene ‘ignimbrite flare-up’ in the MER, and for evaluating the impacts of these great eruptions on landscapes, hydrology, and human ecology. Publisher PDF

Gas and particulate matter (PM) emissions from Masaya volcano, Nicaragua, cause substantial regional volcanic air pollution (VAP). We evaluate the suitability of low-cost SO2 and PM sensors for a continuous air-quality network. The network was deployed for six months in five populated areas (4–16 km from crater). The SO2 sensors failed and recorded erroneous values on multiple occasions, likely due to corrosion, requiring significant maintenance commitment. The PM sensors were found to be robust but data required correction for humidity. SO2 measurements could not be used as stand-alone tools to detect occurrence of VAP episodes (VAPE), but an SO2/PM correlation reliably achieved this at near-field stations, as confirmed by meteorological forecasts and satellite imagery. Above-background PM concentrations reliably identified VAPE at both near-field and far-field stations. We suggest that a continuous network can be built from a combination of low-cost PM and SO2 sensors with a greater number of PM-only sensors.

Understanding the timing of critical changes in volcanic systems, such as the beginning and end of eruptive behaviour, is a key goal of volcanic monitoring. Traditional approaches to forecasting these changes have used models motivated by the underlying physics of eruption onset, which assume that geophysical precursors will consistently display similar patterns prior to transition in volcanic state. We present a machine learning classification approach for detecting significant changes in patterns of volcanic activity, potentially signalling transitions during the onset or end of volcanic activity, which does not require a model of the physical processes underlying critical changes. We apply novelty detection, where models are trained only on data prior to eruption, to the precursory unrest at Augustine Volcano, Alaska in 2005. This approach looks promising for geophysically-monitored volcanic systems which have been in repose for some time, as no eruptive data is required for model training. We compare novelty detection results with multi32 class classification, where models are trained on examples of both non-eruptive and eruptive data. We contextualise the results of these classification models using constraints from petrological, satellite and visual observations from the 2006 eruption of Augustine Volcano. The transition from non-eruptive to eruptive behaviour we identify in mid-November 2005 is in agreement with previous estimates of the initiation of dike intrusion prior to the 2006 eruption. We find that models which include multiple types of data (seismic, deformation and gas emissions) can better distinguish between non-eruptive and eruptive data than models formulated on single data types.

The 6-month-long 2014–2015 Holuhraun eruption was the largest in Iceland for 200 years, emitting huge quantities of sulfur dioxide (SO2) into the troposphere, at times overwhelming European anthropogenic emissions. Weather, terrain and latitude made continuous ground-based or UV satellite sensor measurements challenging. Infrared Atmospheric Sounding Interferometer (IASI) data are used to derive the first time series of daily SO2 mass present in the atmosphere and its vertical distribution over the entire eruption period. A new optimal estimation scheme is used to calculate daily SO2 fluxes and average e-folding time every 12 h. For the 6 months studied, the SO2 flux was observed to be up to 200 kt day−1 and the minimum total SO2 erupted mass was 4.4±0.8 Tg. The average SO2 e-folding time was 2.4±0.6 days. Where comparisons are possible, these results broadly agree with ground-based near-source measurements, independent remote-sensing data and values obtained from model simulations from a previous paper. The results highlight the importance of using high-resolution time series data to accurately estimate volcanic SO2 emissions. The SO2 mass missed due to thermal contrast is estimated to be of the order of 3 % of the total emission when compared to measurements by the Ozone Monitoring Instrument. A statistical correction for cloud based on the AVHRR cloud-CCI data set suggested that the SO2 mass missed due to cloud cover could be significant, up to a factor of 2 for the plume within the first kilometre from the vent. Applying this correction results in a total erupted mass of 6.7±0.4 Tg and little change in average e-folding time. The data set derived can be used for comparisons to other ground- and satellite-based measurements and to petrological estimates of the SO2 flux. It could also be used to initialise climate model simulations, helping to better quantify the environmental and climatic impacts of future Icelandic fissure eruptions and simulations of past large-scale flood lava eruptions.

Long-lived basaltic volcanic eruptions are a globally important source of environmentally reactive, volatile metal pollutant elements such as selenium, cadmium and lead. The 2018 eruption of Kīlauea, Hawai’i produced exceptionally high discharge of metal pollutants, and was an unprecedented opportunity to track them from vent to deposition. Here we show, through geochemical sampling of the plume that volatile metal pollutants were depleted in the plume up to 100 times faster than refractory species, such as magnesium and iron. We propose that this rapid wet deposition of complexes containing reactive and potentially toxic volatile metal pollutants may disproportionately impact localised areas close to the vent. We infer that the relationship between volatility and solubility is an important control on the atmospheric behaviour of elements. We suggest that assessment of hazards from volcanic emissions should account for heterogeneous plume depletion of metal pollutants. Volatile metal pollutants in basaltic volcanic plumes can be deposited up to 100 times faster than refractory species, and may produce disproportionate impacts at proximal locations, according to extensive sampling of Kīlauea’s 2018 eruption plume.

Raikoke, a remote volcano in the Kuril Islands, erupted on the 21st June 2019. The eruption injected significant quantities of SO2 into the atmosphere along with volcanic ash. These plumes have been studied with tools developed for the Infrared Atmospheric Sounding Interferometer (IASI) by the Earth Observation Data Group (EODG) at the University of Oxford. IASI is a hyperspectral sensor onboard of three meteorological satellites (Metop A, B and C). Each instrument obtains near global coverage twice a day and has a spectral range which includes sensitivity to both SO2 and ash: making them useful for studying the Raikoke plumes. A fast linear SO2 retrieval was first applied to flag pixels with elevated amounts of SO2. With this tool it was possible to follow the Raikoke plume as it circulated the northern hemisphere above 30 degrees, with parts of the plume still visible around 2 months after the eruption took place. Next an iterative SO2 retrieval was used to quantify the amount and height of the SO2 in each pixel. In the first few days after the eruption took place, very high column amounts are recorded, in some cases exceeding 600 DU. Using this retrieval, a preliminary estimate of 1.6 Tg was obtained for the total amount of SO2 emitted (measured on the 23rd of June). Height information from this technique shows that there were probably multiple injection heights during the eruption and that SO2 was emitted into both the troposphere and stratosphere. The tropospheric plume remains visible for just a few days after the eruption, while the stratospheric portion of the plume persists for several weeks.

The Paleocene-Eocene Thermal Maximum (PETM) is recognized as one of the potential analogues in the geological record for present-day global warming. The aim of the International Continental Scientific Drilling Program (ICDP) project PVOLC is to test the hypothesis that voluminous magmatism in sedimentary basins in the NE Atlantic triggered the PETM. Two ICDP boreholes are planned to core the boundary in the Limfjorden area in Denmark in 2022. PVOLC will be conducted in conjunction with IODP Exp 396 on the mid-Norwegian continental margin. The North Atlantic Igneous Province (NAIP) was is a large igneous province (5–10 million km3 magma) that coincided with both the opening of the NE Atlantic Ocean and the greenhouse conditions of the early Paleogene. The close temporal correlations suggest a possible causal relationship between the NAIP and both the climatic and tectonic changes around 56– 54 Ma. In particular, the main acme of NAIP activity occurred across the Paleocene–Eocene Thermal Maximum (PETM), an extreme hyperthermal event that represents the warmest conditions of the last 60 million years. The NAIP is among several proposed candidates for driving global warming through CO2/CH4 emissions, both by magmatic degassing and through contact metamorphism around shallow intrusions in organic rich sedimentary basins. What is needed to refine the role of the NAIP during the PETM are key sedimentary sequences that contain abundant volcanic and climatic proxies in the same section, thereby allowing a precise geochronology of events to be attained. The sediments exposed on the Fur island, Denmark, are a key sequence of PETM and post-PETM strata with little thermal overprint and hundreds of well-preserved volcanic ash layers from the NAIP. The effects of Quaternary glaciotectonism have disturbed this key stratigraphic interval at Fur, but seismic surveys indicate that undisturbed strata are found a few km to the south. The ICDP PVOLC project plan is to drill both the Paleocene-Eocene and the Cretaceous-Paleocene boundaries, hopefully recovering pristine cores suitable for high-resolution geochemical and climatic studies.

Monitoring of volcanic emissions (gas, ash and aerosols) is crucial to our understanding of eruption mechanisms, as well as to developing mitigation strategies during volcanic eruptions. Ultraviolet (UV) spectrometers and cameras are now ubiquitous monitoring tools at most volcano observatories for quantifying sulphur dioxide (SO2) emissions. However, because they rely on scattered UV light as a source of radiation, their use is limited to daytime only, and measurement windows are often further restricted by unfavourable weather conditions. On the other end of the spectrum, Open Path Fourier Transform Infrared (OP-FTIR) instruments can be used to measure the concentrations of a series of volcanic gases, and they allow for night-time operation. However, the retrieval methods rely on the presence of a strong source of IR radiation in the background - either natural (lava flow, crater rim, the sun) or artificial – restricting their use to very specific observation geometries and a narrow range of eruptive conditions. Here we present a new approach to derive quantities of SO2, ash and aerosols from measurements of a drifting volcanic plume. Using the atmosphere as a background, we measured self-emitted IR radiation from plumes at Stromboli volcano (Italy) capturing both passive degassing and ash-rich explosive plumes. We use an iterative approach with a forward radiative transfer model (the Reference Forward Model – RFM) to quantify concentrations of sulphur dioxide (SO2), aerosols and ash in the line of sight of the spectrometer. This new method could significantly enhance the scientific return from OP-FTIR instruments at volcano observatories, ultimately expanding their deployment as part of permanent scanning networks (an alternative to DOAS instruments) to provide continuous data on the emissions of gas, ash and aerosols.

Over the past few years, mercury (Hg) concentrations in (predominantly) marine sediments have gained widespread attention as a far-field, high-temporal resolution proxy for deep-time enhanced volcanic activity. The primary focus of these Hg studies has been a range of events in the past 500 million years; mostly larger and smaller mass extinctions and periods of high-amplitude climate change. As a result, sedimentary Hg data reinforced the notion many of these events are indeed coeval with and hypothesized causally connected to large igneous provinces (LIPs). However, relatively poor constraints on long-term dispersal of emissions through the marine and terrestrial biosphere, accumulation and preservation mechanisms of Hg pose difficulties for its use as a qualitative proxy for enhanced volcanic emissions. As a result, using sedimentary Hg for detailed modeling of Hg cycling or past gaseous emissions of magmatic volatiles, e.g. carbon and sulfur, and by extension environmental impact, remains speculative.The use of Hg normalization to common Hg-binding sedimentary components such as organic carbon (TOC), Fe or Al provides a basic means of comparing relative Hg loading within a sedimentary sequence. Yet, normalizing Hg to these major sedimentary components relies on simple linear relations and this approach often leaves substantial variance. While the high Hg concentrations have usually been ascribed to variability in volcanic activity, there are likely other factors that may invoke changes in the Hg concentrations in sediments, or mask Hg emitted by volcanism such as amount or type and flux of organic matter being deposited in basins and oxygenation of water and local sediments.To evaluate potential confounding factors, we compiled published Hg, TOC and bulk and trace element data, modern and deep-time events, periods with and without known anomalous volcanic activity and cover a range of depositional settings. We find that the depositional setting, as inferred from lithology and bulk sediment chemistry exerts a major control on the overall concentrations of Hg. Differences in Hg loading between time-correlative deposits persist after normalization to major sedimentary components, likely as a result of a complex interplay between various spatial and environmental factors. Our data compilation further allows us to explore the potential of establishing a range for background Hg values and variability through different periods of geological deep-time. Collectively, such constraints can aid the understanding of changes induced by environmental factors or volcanic emissions and inform Hg-cycling models.

Arctic carbon cycling and its regional climate have been observed to deviate from global trends in the Late Jurassic and across the Jurassic–Cretaceous boundary interval, but appear to recouple with global trends in the Early Cretaceous (Galloway et al., 2019; Jelby et al., 2020). We investigate the possible link between these observed trends and volcanism by examining the mercury (Hg) and other element records from Arctic sites in Svalbard (Norway) and the Queen Elizabeth Islands, Canada. We assess whether pulsed phases of the High Arctic Large Igneous Province, or the globally significant emplacement of Paraná-Etendeka or Greater Ontong-Java Plateau, are expressed by stratigraphic Hg trends recorded in the studied sites of Arctic Canada and Svalbard, and how any signals correlate with the regional stable carbon-isotope (δ13C) record. We compare these new data to Hg and δ13C records from other globally distributed sites, focusing on the carbon isotope excursion (CIE) intervals: the Arctic-wide Volgian CIE (“VOICE”), the global Valanginian positive CIE (“Weissert Event”), and the global early Aptian CIE associated with Ocean Anoxic Event 1a (OAE1a).

Explosive, caldera-forming eruptions are exceptional and hazardous volcanic phenomena. The 1883 eruption of Krakatau is the largest such event for which there are detailed contemporary written accounts, allowing information on the eruptive progression to be integrated with the stratigraphy and geochemistry of its products. Freshly exposed sequences of the 1883 eruptive deposits of Krakatau, stripped of vegetation by a tsunami generated by the flank collapse of Anak Krakatau in 2018, shed new light on the eruptive sequence. Matrix glass from the base of the stratigraphy is chemically distinct and more evolved than the overlying sequence indicating the presence of a shallow, silicic, melt-rich region that was evacuated during the early eruptive activity from May 1883 onwards. Disruption of the shallow, silicic magma may have led to the coalescence and mixing of chemically similar melts representative of a range of magmatic conditions, as evidenced by complex and varied plagioclase phenocryst zoning profiles. This mixing, over a period of two to three months, culminated in the onset of the climactic phase of the eruption on 26th August 1883. Pyroclastic density currents (PDCs) emplaced during this phase of the eruption show a change in transport direction from north east to south west, coinciding with the deposition of a lithic lag breccia unit. This may be attributed to partial collapse of an elevated portion of the island, resulting in the removal of a topographic barrier. Edifice destruction potentially further reduced the overburden on the underlying magmatic system, leading to the most explosive and energetic phase of the eruption in the morning of 27th August 1883. This phase of the eruption culminated in a final period of caldera collapse, which is recorded in the stratigraphy as a second lithic lag breccia. The massive PDC deposits emplaced during this final phase contain glassy blocks up to 8 m in size, observed for the first time in 2019, which are chemically similar to the pyroclastic sequence. These blocks are interpreted as representing stagnant, shallow portions of the magma reservoir disrupted during the final stages of caldera formation. This study provides new evidence for the role that precursory eruptions and amalgamation of shallow crustal magma bodies potentially play in the months leading up to caldera-forming eruptions.

Funder: EPSRC-CASE studentship, Funder: NERC studentship, Funder: Leverhulme Trust; doi: https://doi.org/10.13039/501100000275, Funder: NERC-CASE studentship, Funder: Rolex Institute, Volcanoes represent one of the largest natural sources of metals to the Earth’s surface. Emissions of these metals can have important impacts on the biosphere as pollutants or nutrients. Here we use ground- and drone-based direct measurements to compare the gas and particulate chemistry of the magmatic and lava–seawater interaction (laze) plumes from the 2018 eruption of Kīlauea, Hawai’i. We find that the magmatic plume contains abundant volatile metals and metalloids whereas the laze plume is further enriched in copper and seawater components, like chlorine, with volatile metals also elevated above seawater concentrations. Speciation modelling of magmatic gas mixtures highlights the importance of the S2− ligand in highly volatile metal/metalloid degassing at the magmatic vent. In contrast, volatile metal enrichments in the laze plume can be explained by affinity for chloride complexation during late-stage degassing of distal lavas, which is potentially facilitated by the HCl gas formed as seawater boils.

Episodes of large igneous province (LIP) volcanism punctuate Earth history. LIPs are anomalous geologically rapid large‐volume accumulations of igneous rock on the Earth’s surface and in the shallow crust. Periods of LIP emplacement are often temporally associated with times of profound environmental and climatic change throughout Earth history, particularly during the last 300 million years. The fluxes of gas and particles emitted during LIP volcanism are key candidates for triggering these Earth system responses. Understanding these events, their feedbacks and impacts on the Earth system requires collaboration between the fields of volcanology, atmospheric science, ocean chemistry, sedimentology and palaeobiology amongst other fields. This presentation will explore how evidence of the environmental impacts of LIP volcanism and the processes leading to these effects is best combined often from disparate sources including: (1) temporal associations between the dates or proxies of LIPs and evidence of environmental change captured in the geological record; (2) historical records or monitoring studies of the effects of large‐scale recent volcanic activity such as the Laki eruption in 1783–1784 CE and its deposits; and (3) scaling up from observations and measurements of the environmental impacts of present‐day volcanism such as the 2014–2015 Holuhraun eruption and the 2018 Lower East Rift Zone eruption at Kīlauea, Hawai‘i. Recent progress in each of these areas sets the scene for future advances in our understanding of these profoundly important events in Earth’s history.

The Paleocene–Eocene Thermal Maximum (PETM) was a period of geologically-rapid carbon release and global warming ~56 million years ago. Although modelling, outcrop and proxy records suggest volcanic carbon release occurred, it has not yet been possible to identify the PETM trigger, or if multiple reservoirs of carbon were involved. Here we report elevated levels of mercury relative to organic carbon—a proxy for volcanism—directly preceding and within the early PETM from two North Sea sedimentary cores, signifying pulsed volcanism from the North Atlantic Igneous Province likely provided the trigger and subsequently sustained elevated CO2. However, the PETM onset coincides with a mercury low, suggesting at least one other carbon reservoir released significant greenhouse gases in response to initial warming. Our results support the existence of ‘tipping points’ in the Earth system, which can trigger release of additional carbon reservoirs and drive Earth’s climate into a hotter state., The Paleocene–Eocene boundary coincided with runaway global warming possibly analogous to future climate change, but the sources of greenhouse gasses have remained unresolved. Here, the authors reveal volcanism triggered initial warming, and subsequent carbon was released after crossing a tipping point.

Volcanoes are a large global source of almost every element, including ~20 environmentally reactive trace elements classified as metal pollutants (e.g. selenium, cadmium and lead). Fluxes of metal pollutants from individual eruptions can be comparable to total anthropogenic emissions from large countries such as China.The 2018 Lower East Rift Zone eruption of Kīlauea, Hawaii produced exceptionally high emission rates of major and trace chemical species compared to other basaltic eruptions over 3 months (200 kt/day of SO2; Kern et al. 2019). We tracked the volcanic plume from vent to exposed communities over 0-240 km distance using in-situ sampling and atmospheric dispersion modelling. This is the first time that trace elements in volcanic emissions (~60 species) are mapped over such distances. In 2019, we repeated the field campaign during a no-eruption period and showed that volcanic emissions had caused 3-5 orders of magnitude increase in airborne metal pollutant concentrations across the Island of Hawai’i.We show that the volatility of the elements (the ease with which they are degassed from the magma) controls their particle-phase speciation, which in turn determines how fast they are depleted from the plume after emission. Elements with high magmatic volatilities (e.g. selenium, cadmium and lead) have up to 6 orders of magnitude higher depletion rates compared to non-volatile elements (e.g. magnesium, aluminium and rare earth metals).Previous research and hazard mitigation efforts on volcanic emissions have focussed on sulphur and it has been assumed that other pollutants follow the same dispersion patterns. Our results show that the atmospheric fate of sulphur, and therefore the associated hazard distribution, does not represent an accurate guide to the behaviour and potential impacts of other species in volcanic emissions. Metal pollutants are predominantly volatile in volcanic plumes, and their rapid deposition (self-limited by their volatility) places disproportionate environmental burdens on the populated areas in the immediate vicinity of the active and, in turn, reduces the impacts on far-field communities.Reference: Kern, C., T. Elias, P. Nadeau, A. H. Lerner, C. A. Werner, M. Cappos, L. E. Clor, P. J. Kelly, V. J. Realmuto, N. Theys, S. A. Carn, AGU, 2019; https://agu.confex.com/agu/fm19/meetingapp.cgi/Paper/507140.

Satellite remote sensing has been widely used to make measurements of sulphur dioxide (SO2) emissions from volcanoes. The Infrared Atmospheric Sounding Interferometer (IASI) is one such instrument that has been used to examine the emissions from large explosive eruptions. Much less work has been done using IASI to study the emissions from smaller eruptions, non-eruptive degassing or anthropogenic sources, and similarly it is rarely used for examining long term trends in activity. Now, when there are three IASI instruments in orbit and with over ten years of data, is the perfect opportunity to explore these topics. This study applied a ‘fast’ linear retrieval developed for IASI in Oxford, across the globe for a ten-year period. Global annual averages were dominated by the emissions from large eruptions (e.g. Nabro in 2011) but elevated signals could also be identified from smaller volcanic sources and industrial centres, suggesting the technique has promise for detecting lower level emissions. A systematic approach was then taken, rotating the linear retrieval output for each orbit at over 100 volcanoes worldwide, with the wind direction at the volcano’s vent, or in cases where the plume was emitted at a greater height, using the observed plume direction. This isolates the elevated signal downwind of the volcano. The rotated outputs were then averaged over monthly, annual and multi-annual time periods. Analysis of the upwind and downwind values establishes whether there is an elevated signal and its intensity. An inventory was then constructed from these observations which show how these emissions varied over a ten-year period. Trends in SO2 emission were compared against fluxes generated for the Ozone Monitoring Instrument (OMI) and the number of thermal anomalies detected by the MODVOLC algorithm developed for MODIS. It was identified for example, that long term trends are more easily identified at high altitude volcanoes such as Popocatepetl, Sabancaya and Nevado del Ruiz. This is consistent with the idea that the instrument performs better in regions with lower levels of water vapour (e.g. above the boundary layer).

The 2018 eruption of Kīlauea volcano, Hawai'i, resulted in enormous gas emissions from the Lower East Rift Zone (LERZ) of the volcano. This led to important changes to air quality in downwind communities. We analyse and present measurements of atmospheric sulfur dioxide (SO2) and aerosol particulate matter < 2.5 µm (PM2.5) collected by the Hawai'i Department of Health (HDOH) and National Park Service (NPS) operational air quality monitoring networks between 2007 and 2018; and a community-operated network of low-cost PM2.5 sensors on the Island of Hawai'i. During this period, the two largest observed increases in Kīlauea's volcanic emissions were: the summit eruption that began in 2008 (Kīlauea emissions averaged 5 – 6 kt/day SO2 over the course of the eruption) and the LERZ eruption in May-August 2018 when SO2 emission rates likely reached 200 kt/day in June. Here we focus on characterising the airborne pollutants arising from the 2018 LERZ eruption and the spatial distribution and severity of air pollution events across the Island of Hawai'i. The LERZ eruption caused the most frequent and severe exceedances of Environmental Protection Agency 24-hour-mean PM2.5 air quality thresholds in Hawai'i since 2010. In Kona, for example, there were eight exceedances during the 2018 LERZ eruption, where there had been no exceedances in the previous eight years as measured by the HDOH and NPS networks. SO2 air pollution during the LERZ eruption was most severe in communities in the south and west of the island, with maximum 24-hour-mean mass concentrations of 728 µg/m3 recorded in Ocean View (100 km west of the LERZ emission source) in May 2018. Data from the low-cost sensor network correlated well with data from the HDOH PM2.5 instruments (Kona station, R2 = 0.89), demonstrating that these low-cost sensors provide a viable means to rapidly augment reference-grade instrument networks during crises.

The 2018 eruption on the Lower East Rift Zone of Kilauea volcano, Hawai’i released unprecedented fluxes of gases (>200 kt/d SO2) and aerosol into the troposphere [1,2]. The eruption affected air quality across the island and lava flows reached the ocean, forming a halogen-rich plume as lava rapidly boiled and evaporated seawater.We present the at-source composition – gas and size-segregated aerosol – of both the magmatic plume (emitted from ‘Fissure 8’, F8) and the lava-seawater interaction plume (ocean entry, OE), including major gas species, and major and trace elements in non-silicate aerosol. Trace metal and metalloid (TMM) emissions during the 2018 eruption were the highest recorded for Kilauea, and the magmatic ‘fingerprint’ of TMMs (X/SO2 ratios) in the 2018 plume is consistent with measurements made at the summit lava lake in 2008 [3], and with other rift and hotspot volcanoes [4,5].We show that the OE plume composition predominantly reflects seawater composition with a small contribution from plagioclase +/- ash. However, elevated concentrations of some TMMs (Bi, Cd, Cu, Zn, Ag) with affinity for Cl-speciation in the gas phase cannot be accounted for by the silicate correction and therefore may derive from degassing of lava in the presence of elevated Cl-. In the case of silver and copper, concentrations in the OE plume are elevated above both the F8 plume and seawater.At-vent speciation of TMMs in the F8 plume during oxidation (following a correction for ash contributions) was assessed using a Gibbs Energy Minimization algorithm (HSC chemistry, Outotec Research). We also demonstrate the sensitivity of speciation in the plume to the concentration of common ligand-forming elements, chlorine and sulfur. These results could be used as initial conditions in atmospheric reaction models to investigate how plume composition evolves as low-temperature chemistry takes over.References:[1] Neal C et al. (2019) Science[2] Kern C et al. (2019) AGU Fall meeting abstract V43C-0209[3] Mather T et al. (2012) GCA 83:292-323[4] Zelenzki et al. (2013) Chem Geol 357:95-116[5] Gauthier P-J et al. (2016) J Geophys 121:1610-1630

The close temporal correlation between the emplacement of large igneous provinces and environmental crises in the geological record suggests a causal relationship. One such example is the emplacement of the North Atlantic Igneous Province (NAIP) and the Paleocene-Eocene Thermal Maximum (PETM), an extreme climate change event that occurred ~56 Ma. The main pulse of activity from the NAIP is around this time, but current radioisotopic ages are too low-resolution to constrain whether this activity was before, during and/or after the PETM. An ideal locality for understanding the initiation and development of the PETM is the island of Fur, northwest Denmark. The sedimentary sequence consists of clays and diatomites deposited in an epicontinental, shallow marine sea. The high sedimentation rates and close proximity to the NAIP means there are numerous volcanic and climatic proxies in the strata that can be used to provide high-resolution records constraining the relative and absolute timings of these events.Here we present the findings of the project ‘Ashlantic’, which focuses on pre- to post-PETM strata. We adopt a multiproxy approach using volcanic tracers, including tephra horizons, Hg anomalies, and Os isotopes, to infer the intensity and timing of NAIP activity. Volcanic glass morphology and chemistry suggests a hydromagmatic origin for key tephra intervals, while U-Pb dating of magmatic zircon constrains the timing of NAIP activity and the development of the PETM. Detailed chemostratigraphic logs and datasets (e.g. δ13C analyses) define the onset and duration of the PETM, while clay chemistry, Li isotopes, total organic carbon (TOC), and the paleothermometer TEX86 are used to assess the climate response to global warming during the PETM. In concert, our results suggest that the NAIP was active just before, during, and after the PETM, but the relationship between the NAIP and the marine and terrestrial environments is complex. These findings call for further work, such as ICDP and/or IODP drilling of North Sea sediments.