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Published studies and internal NASA reports indicate that when native lunar dust is suspended in an aqueous solution a variety of metal and other ions are released. This release has implications for future lunar missions, ranging from effects on mission hardware, effects on life support systems, possible direct effects on human health, and effects on research experiments such as plant growth experiments, space biology experiments and any activities that may involve the use of water sourced from the lunar poles. Furthermore, such contaminants could become concentrated or chemically altered to a more hazardous form during a variety of lunar mission activities, including everything from space suit cleaning to lunar industrial materials extraction. The exact profile of the release of ions from lunar dust and the nature of the partially dissolved particles has not been explored. Any model of this dissolution must be based on an understanding of the unique micromorphology of lunar dust, including its glassy nature, agglutinate features, high surface area and the presence of small deposits of elemental iron (nanophase iron) located near the surface of the grain particles. Dust has a very high surface area available for interaction with water. For this reason, on first exposure to water, an immediate pulsed release of ions could occur, with more prolonged release taking place over months or years. The few studies that have been conducted previously have been limited in both the time scales examined and in the selection of ions that were measured. The proposed investigation is a comprehensive materials science investigation, using the most modern analytical tools to catalogue all metals given off from lunar dust in various aqueous solutions and their time profiles of release from the very short term to the very long term. The product of the proposed study will be a comprehensive database determined from NASA curated samples collected from the Apollo landing sites that can be applied to research in both living systems and non-living systems on the moon. The methods developed in the proposed study will also establish standards for analysis of lunar dust samples returned from future manned missions (Artemis and others) and future robotic missions. The knowledge gained from this basic materials science investigation will have broad impact on the design of engineered human safety and health systems.

Silicic volcanic eruptions range in style from gently effusive to highly explosive, and may switch style unpredictably during a single eruption. Direct observations of subaerial rhyolitic eruptions (Chaiten 2008, Cordón Caulle 2011–2012, Chile) challenged long-standing paradigms of explosive and effusive eruptive styles and led to the formulation of new models of hybrid activity. However, the processes that govern such hybrid explosive–effusive activity remain poorly understood. Here, we bring together observations of the well-studied 2011–2012 Cordón Caulle eruption with new textural and petrologic data on erupted products, and video and still imagery of the eruption. We infer that all of the activity – explosive, effusive, and hybrid – was fed by explosive fragmentation at depth, and that effusive behaviour arose from sticking and sintering, in the shallow vent region, of the clastic products of deeper, cryptic fragmentation. We use a scaling approach to determine that there is sufficient time available, during emplacement, for diffusive pyroclast degassing and sintering to produce a degassed plug that occludes the shallow conduit, feeding clastogenic, apparently effusive, lava-like deposits. Based on evidence from Cordón Caulle, and from other similar eruptions, we further argue that hybrid explosive–effusive activity is driven by episodic gas-fracking of the occluding lava plug, fed by the underlying pressurized ash- and pyroclast-laden region. The presence of a pressurized pocket of ash-laden gas within the conduit provides a mechanism for generation of harmonic tremor, and for syn-eruptive laccolith intrusion, both of which were features of the Cordón Caulle eruption. We conclude that the cryptic fragmentation models is more consistent with available evidence than the prevailing model for effusion of silicic lava that assume coherent non-fragmental rise of magma from depth to the surface without wholesale explosive fragmentation.

Freshly erupted volcanic ash contains a range of soluble elements, some of which can generate harmful effects in living cells and are considered potentially toxic elements (PTEs). This work investigates the leaching dynamics of ash-associated PTEs in order to optimize a method for volcanic ash respiratory hazard assessment. Using three pristine (unaffected by precipitation) ash samples, we quantify the release of PTEs (Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, V, Zn) and major cations typical of ash leachates (Mg, Na, Ca, K) in multiple simulated lung fluid (SLF) preparations and under varying experimental parameters (contact time and solid to liquid ratio). Data are compared to a standard water leach (WL) to ascertain whether the WL can be used as a simple proxy for SLF leaching. The main findings are: PTE concentrations reach steady-state dissolution by 24 h, and a relatively short contact time (10 min) approximates maximum dissolution; PTE dissolution is comparatively stable at low solid to liquid ratios (1:100 to 1:1000); inclusion of commonly used macromolecules has element-specific effects, and addition of a lung surfactant has little impact on extraction efficiency. These observations indicate that a WL can be used to approximate lung bioaccessible PTEs in an eruption response situation. This is a useful step towards standardizing in vitro methods to determine the soluble-element hazard from inhaled ash.

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.

Connecting caldera collapse The Kīlauea Volcano on the island of Hawai‘i erupted for 3 months in 2018. Neal et al. present a summary of the eruption sequence along with a variety of geophysical observations collected by the Hawaiian Volcano Observatory. The cyclic inflation, deflation, and eventual collapse of the summit was tied to lava eruption from lower East Rift Zone fissures. A total volume of 0.8 cubic kilometers of magma erupted, roughly the equivalent of 320,000 swimming pools, which matched the change in volume at the summit. Science , this issue p. 367

Funder: VUB Strategic Research Program, Exposure to volcanic ash is a long-standing health concern for people living near active volcanoes and in distal urban areas. During transport and deposition, ash is subjected to various physicochemical processes that may change its surface composition and, consequently, bioreactivity. One such process is the interaction with anthropogenic pollutants; however, the potential for adsorbed, deleterious organic compounds to directly impact human health is unknown. We use an in vitro bioanalytical approach to screen for the presence of organic compounds of toxicological concern on ash surfaces and assess their biological potency. These compounds include polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dlPCBs). Analysis of ash collected in or near urbanised areas at five active volcanoes across the world (Etna, Italy; Fuego, Guatemala; Kelud, Indonesia; Sakurajima, Japan; Tungurahua, Ecuador) using the bioassay inferred the presence of such compounds on all samples. A relatively low response to PCDD/Fs and the absence of a dlPCBs response in the bioassay suggest that the measured activity is dominated by PAHs and PAH-like compounds. This study is the first to demonstrate a biological potency of organic pollutants associated with volcanic ash particles. According to our estimations, they are present in quantities below recommended exposure limits and likely pose a low direct concern for human health.

Volcanic jet noise is the sound, often below the human audible range (St=Djf/Uj, connects frequency changes, f, to changes in the jet length (expanded jet diameter, Dj) and/or velocity scale (jet velocity, Uj). We examine the infrasound signal characteristics from the June 2019 VEI 4 eruptions of Raikoke, Kuril Islands and Ulawun, Papua New Guinea volcanoes with changes in crater geometry. We use data from the International Monitoring System (IMS) infrasound network and pre- and post-eruption satellite data (RADARSAT-2 and PlanetScope imaging for Raikoke and Ulawun, respectively). During both eruptions we observe a decrease in infrasound peak frequency during the transition to a Plinian phase, which remains through the end of the eruptions. The RADARSAT-2 data show a qualitative increase in the crater area at Raikoke; quantitative analysis is limited by shadows. At Ulawun, however, we estimate an increase in crater area from ~35,000 m2 on May 25, 2019 to ~66,000 m2 on July 17, 2019. We assume a constant Strouhal number and use the crater diameter as a proxy for expanded jet diameter. Our analysis suggests that the increase in crater diameter alone cannot account for the decrease in peak frequency during the Ulawun eruption. This suggests that the jet velocity also increased, which fits satellite data, and or the fluid properties (e.g. particle loading, nozzle geometry and roughness, etc.) changed. This is reasonable as the Ulawun eruption went Plinian, which likely involved an increase in jet velocity and erosion of the crater walls. This is the first study to corroborate the decrease in infrasound peak frequency with documented increase in crater area. The fortuitous satellite overpass timing, clear skies, and high spatial resolution enabled the quantitative examination of the Ulawun eruption.

National Science Foundation (NSF) EAR1724986 Comision Nacional de Investigacion Cientifica y Tecnologica (CONICYT) CONICYT FONDEF 15090013 "Centro de Excelencia en Geotermia de Los Andes," CEGA FONDECYT Postdoctoral Grant (Comision Nacional de Investigacion Cientifica y Tecnologica) 3170007 ICM grant "Millennium Nucleus for Metal Tracing Along Subduction" United States Geological Survey USGS Geothermal Energy Project

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.

We report the radiocarbon age, chemistry, and mineralogy of sinter deposits from Castle and Giant Geyser in the Upper Geyser Basin of Yellowstone National Park. At each geyser, we sampled following...

Volcanic ash presents a widespread and common hazard during and after eruptions. Complex interactions between solid ash surfaces and volcanic gases lead to the formation of soluble salts that may be mobilized in aqueous environments. A variety of stakeholders may be concerned about the effects of ash on human and animal health, drinking water supplies, crops, soils and surface runoff. As part of the immediate emergency response, rapid dissemination of information regarding potentially hazardous concentrations of soluble species is critical. However, substantial variability in the methods used to characterize leachable elements makes it challenging to compare datasets and eruption impacts. To address these challenges, the International Volcanic Health Hazard Network ( www.ivhhn.org ) organized a two-day workshop to define appropriate methods for hazard assessment. The outcome of this workshop was a ‘consensus protocol’ for analysis of volcanic ash samples for rapid assessment of hazards from leachable elements, which was subsequently ratified by leading volcanological organizations. The purpose of this protocol is to recommend clear, standard and reliable methods applicable to a range of purposes during eruption response, such as assessing impacts on drinking-water supplies and ingestion hazards to livestock, and also applicable to research purposes. Where possible, it is intended that the methods make use of commonly available equipment and require little training. To evaluate method transferability, an interlaboratory comparison exercise was organized among six laboratories worldwide. Each laboratory received a split of pristine ash, and independently analyzed it according to the protocol for a wide range of elements. Collated results indicate good repeatability and reproducibility for most elements, thus indicating that the development of this protocol is a useful step towards providing standardized and reliable methods for ash hazard characterization. In this article, we review recent ash leachate studies, report the outcomes of the comparison exercise and present a revised and updated protocol based on the experiences and recommendations of the exercise participants. The adoption of standardized methods will improve and facilitate the comparability of results among studies and enable the ongoing development of a global database of leachate information relevant for informing volcanic health hazards assessment.

Background Volcanic plumes are complex environments composed of gases and ash particles, where chemical and physical processes occur at different temperature and compositional regimes. Commonly, soluble sulphate- and chloride-bearing salts are formed on ash as gases interact with ash surfaces. Exposure to respirable volcanic ash following an eruption is potentially a significant health concern. The impact of such gas-ash interactions on ash toxicity is wholly un-investigated. Here, we study, for the first time, whether the interaction of volcanic particles with sulphur dioxide (SO2) gas, and the resulting presence of sulphate salt deposits on particle surfaces, influences toxicity to the respiratory system, using an advanced in vitro approach. Methods To emplace surface sulphate salts on particles, via replication of the physicochemical reactions that occur between pristine ash surfaces and volcanic gas, analogue substrates (powdered synthetic volcanic glass and natural pumice) were exposed to SO2 at 500 °C, in a novel Advanced Gas-Ash Reactor, resulting in salt-laden particles. The solubility of surface salt deposits was then assessed by leaching in water and geochemical modelling. A human multicellular lung model was exposed to aerosolised salt-laden and pristine (salt-free) particles, and incubated for 24 h. Cell cultures were subsequently assessed for biological endpoints, including cytotoxicity (lactate dehydrogenase release), oxidative stress (oxidative stress-related gene expression; heme oxygenase 1 and NAD(P)H dehydrogenase [quinone] 1) and its (pro-)inflammatory response (tumour necrosis factor α, interleukin 8 and interleukin 1β at gene and protein levels). Results In the lung cell model no significant effects were observed between the pristine and SO2-exposed particles, indicating that the surface salt deposits, and the underlying alterations to the substrate, do not cause acute adverse effects in vitro. Based on the leachate data, the majority of the sulphate salts from the ash surfaces are likely to dissolve in the lungs prior to cellular uptake. Conclusions The findings of this study indicate that interaction of volcanic ash with SO2 during ash generation and transport does not significantly affect the respiratory toxicity of volcanic ash in vitro. Therefore, sulphate salts are unlikely a dominant factor controlling variability in in vitro toxicity assessments observed during previous eruption response efforts.

Retrospective eruption characterization is valuable for advancing our understanding of volcanic systems and evaluating our observational capabilities, especially with remote technologies (defined here as a space-borne system or non-local, ground-based instrumentation which include regional and remote infrasound sensors). In June 2019, the open-system Ulawun volcano, Papua New Guinea, produced a VEI 4 eruption. We combined data from satellites (including Sentinel-2, TROPOMI, MODIS, Himawari-8), the International Monitoring System infrasound network, and GLD360 globally detected lightning with information from the local authorities and social media to characterize the pre-, syn- and post-eruptive behaviour. The Rabaul Volcano Observatory recorded ~24 h of seismicity and detected SO2 emissions ~16 h before the visually-documented start of the Plinian phase on 26 June at 04:20 UTC. Infrasound and SO2 detections suggest the eruption started during the night on 24 June 2019 at 10:39 UTC ~38 h before ash detections with a gas-dominated jetting phase. Local reports and infrasound detections show that the second phase of the eruption started on 25 June 19:28 UTC with ~6 h of jetting. The first detected lightning occurred on 26 June 00:14 UTC, and ash emissions were first detected by Himawari-8 at 01:00 UTC. Post-eruptive satellite imagery indicates new flow deposits to the south and north of the edifice and ash fall to the west and southwest. In particular, regional infrasound data provided novel insight into eruption onset and syn-eruptive changes in intensity. We conclude that, while remote observations are sufficient for detection and tracking of syn-eruptive changes, key challenges in data latency, acquisition, and synthesis must be addressed to improve future near-real-time characterization of eruptions at minimally-monitored or unmonitored volcanoes.

Siliceous sinter is formed by biogenic and abiogenic opal deposition around hot springs and geysers. Using Structure-from-Motion photogrammetry we generated three-dimensional models of Giant and Castle Geysers from the Upper Geyser Basin of Yellowstone National Park. We use these models to calculate an approximate mass of sinter for each (~2 and ~ 5 kton, respectively) and estimate a range of plausible long-term deposition rates for Castle Geyser (470 to 940 kg·yr−1). We estimate ~2% of the silica discharged from Castle Geyser is deposited as sinter in the cone and proximal terraces. We collected 15 sinter samples following the stratigraphy of each geyser from the older terrace to the younger cone and examined them using a variety of analytical methods. We find that young opaline sinter with high water content (

Raikoke, a small, unmonitored volcano in the Kuril Islands, erupted in June 2019. We integrate data from satellites (including Sentinel-2, TROPOMI, MODIS, Himawari-8), the International Monitoring System (IMS) infrasound network, and global lightning detection network (GLD360) with information from local authorities and social media to retrospectively characterize the eruptive sequence and improve understanding of the pre-, syn- and post- eruptive behavior. We observe six infrasound pulses beginning on 21 June at 17:49:55 UTC as well as the main Plinian phase on 21 June at 22:29 UTC. Each pulse is tracked in space and time using lightning and satellite imagery as the plumes drift eastward. Post-eruption visible satellite imagery shows expansion of the island's surface area, an increase in crater size, and a possibly-linked algal bloom south of the island. We use thermal satellite imagery and plume modeling to estimate plume height at 10–12 km asl and 1.5–2 × 106 kg/s mass eruption rate. Remote infrasound data provide insight into syn-eruptive changes in eruption intensity. Our analysis illustrates the value of interdisciplinary analyses of remote data to illuminate eruptive processes. However, our inability to identify deformation, pre-eruptive outgassing, and thermal signals, which may reflect the relatively short duration (~12 h) of the eruption and minimal land area around the volcano and/or the character of closed-system eruptions, highlights current limitations in the application of remote sensing for eruption detection and characterization.

Shallow‐water coral reef ecosystems, particularly those already impaired by anthropogenic pressures, may be highly sensitive to disturbances from natural catastrophic events, such as volcanic eruptions. Explosive volcanic eruptions expel large quantities of silicate ash particles into the atmosphere, which can disperse across millions of square kilometres and deposit into coral reef ecosystems. Following heavy ash deposition, mass mortality of reef biota is expected, but little is known about the recovery of post‐burial reef ecosystems. Reef regeneration depends partly upon the capacity of the ash deposit to be colonised by waterborne bacterial communities and may be influenced to an unknown extent by the physiochemical properties of the ash substrate itself. To determine the potential for volcanic ash to support pioneer bacterial colonisation, we exposed five well‐characterised volcanic and coral reef substrates to a marine aquarium under low light conditions for 3 months: volcanic ash, synthetic volcanic glass, carbonate reef sand, calcite sand and quartz sand. Multivariate statistical analysis of Automated Ribosomal Intergenic Spacer Analysis (ARISA) fingerprinting data demonstrates clear segregation of volcanic substrates from the quartz and coral reef substrates over 3 months of bacterial colonisation. Overall bacterial diversity showed shared and substrate‐specific bacterial communities; however, the volcanic ash substrate supported the most diverse bacterial community. These data suggest a significant influence of substrate properties (composition, granulometry and colour) on bacterial settlement. Our findings provide first insights into physicochemical controls on pioneer bacterial colonisation of volcanic ash and highlight the potential for volcanic ash deposits to support bacterial diversity in the aftermath of reef burial, on timescales that could permit cascading effects on larval settlement.

Communities resident in urban areas located near active volcanoes can experience volcanic ash exposures during, and following, an eruption, in addition to sustained exposures to high concentrations of anthropogenic air pollutants (e.g., vehicle exhaust emissions). Inhalation of anthropogenic pollution is known to cause the onset of, or exacerbate, respiratory and cardiovascular diseases. It is further postulated similar exposure to volcanic ash can also affect such disease states. Understanding of the impact of combined exposure of volcanic ash and anthropogenic pollution to human health, however, remains limited. The aim of this study was to assess the biological impact of combined exposure to respirable volcanic ash (from Soufrière Hills volcano (SHV), Montserrat and Chaitén volcano (ChV), Chile; representing different magmatic compositions and eruption styles) and freshly-generated complete exhaust from a gasoline vehicle. A multicellular human lung model (an epithelial cell-layer composed of A549 alveolar type II-like cells complemented with human blood monocyte-derived macrophages and dendritic cells cultured at the air-liquid interface) was exposed to diluted exhaust (1:10) continuously for 6 h, followed by immediate exposure to the ash as a dry powder (0.54 ± 0.19 μg/cm2 and 0.39 ± 0.09 μg/cm2 for SHV and ChV ash, respectively). After an 18 h incubation, cells were exposed again for 6 h to diluted exhaust, and a final 18 h incubation (at 37 °C and 5% CO2). Cell cultures were then assessed for cytotoxic, oxidative stress and (pro-)inflammatory responses. Results indicate that, at all tested (sub-lethal) concentrations, co-exposures with both ash samples induced no significant expression of genes associated with oxidative stress (HMOX1, NQO1) or production of (pro-)inflammatory markers (IL-1β, IL-8, TNF-α) at the gene and protein levels. In summary, considering the employed experimental conditions, combined exposure of volcanic ash and gasoline vehicle exhaust has a limited short-term biological impact to an advanced lung cell in vitro model.

Volcanic ash is a heterogeneous mineral dust that is typically composed of a mixture of amorphous (glass) and crystalline (mineral) fragments. It commonly contains an abundance of the crystalline silica (SiO2) polymorph cristobalite. Inhalation of crystalline silica can induce inflammation by stimulating the NLRP3 inflammasome, a cytosolic receptor complex that plays a critical role in driving inflammatory immune responses. Ingested material results in the assembly of NLRP3, ASC, and caspase-1 with subsequent secretion of the interleukin-1 family cytokine IL-1β. Previous toxicology work suggests that cristobalite-bearing volcanic ash is minimally reactive, calling into question the reactivity of volcanically derived crystalline silica, in general. In this study, we target the NLRP3 inflammasome as a crystalline silica responsive element to clarify volcanic cristobalite reactivity. We expose immortalized bone marrow-derived macrophages of genetically engineered mice and primary human peripheral blood mononuclear cells (PBMCs) to ash from the Soufrière Hills volcano as well as representative, pure-phase samples of its primary componentry (volcanic glass, feldspar, cristobalite) and measure NLRP3 inflammasome activation. We demonstrate that respirable Soufrière Hills volcanic ash induces the activation of caspase-1 with subsequent release of mature IL-1β in a NLRP3 inflammasome-dependent manner. Macrophages deficient in NLRP3 inflammasome components are incapable of secreting IL-1β in response to volcanic ash ingestion. Cellular uptake induces lysosomal destabilization involving cysteine proteases. Furthermore, the response involves activation of mitochondrial stress pathways leading to the generation of reactive oxygen species. Considering ash componentry, cristobalite is the most reactive pure-phase with other components inducing only low-level IL-1β secretion. Inflammasome activation mediated by inhaled ash and its potential relevance in chronic pulmonary disease was further evidenced in PBMC using the NLRP3 small-molecule inhibitor CP-456,773 (CRID3, MCC950). Our data indicate the functional activation of the NLRP3 inflammasome by volcanic ash in murine and human macrophages in vitro. Cristobalite is identified as the apparent driver, thereby contesting previous assertions that chemical and structural imperfections may be sufficient to abrogate the reactivity of volcanically derived cristobalite. This is a novel mechanism for the stimulation of a pro-inflammatory response by volcanic particulate and provides new insight regarding chronic exposure to environmentally occurring particles.

Background The eruptions of Eyjafjallajökull (2010) and Grímsvötn (2011), Iceland, triggered immediate, international consideration of the respiratory health hazard of inhaling volcanic ash, and prompted the need to estimate the potential hazard posed by future eruptions of Iceland’s volcanoes to Icelandic and Northern European populations. Methods A physicochemical characterization and toxicological assessment was conducted on a suite of archived ash samples spanning the spectrum of past eruptions (basaltic to rhyolitic magmatic composition) of Icelandic volcanoes following a protocol specifically designed by the International Volcanic Health Hazard Network. Results Icelandic ash can be of a respirable size (up to 11.3 vol.% < 4 μm), but the samples did not display physicochemical characteristics of pathogenic particulate in terms of composition or morphology. Ash particles were generally angular, being composed of fragmented glass and crystals. Few fiber-like particles were observed, but those present comprised glass or sodium oxides, and are not related to pathogenic natural fibers, like asbestos or fibrous zeolites, thereby limiting concern of associated respiratory diseases. None of the samples contained cristobalite or tridymite, and only one sample contained quartz, minerals of interest due to the potential to cause silicosis. Sample surface areas are low, ranging from 0.4 to 1.6 m2 g−1, which aligns with analyses on ash from other eruptions worldwide. All samples generated a low level of hydroxyl radicals (HO•), a measure of surface reactivity, through the iron-catalyzed Fenton reaction compared to concurrently analyzed comparative samples. However, radical generation increased after ‘refreshing’ sample surfaces, indicating that newly erupted samples may display higher reactivity. A composition-dependent range of available surface iron was measured after a 7-day incubation, from 22.5 to 315.7 μmol m−2, with mafic samples releasing more iron than silicic samples. All samples were non-reactive in a test of red blood cell-membrane damage. Conclusions The primary particle-specific concern is the potential for future eruptions of Iceland’s volcanoes to generate fine, respirable material and, thus, to increase ambient PM concentrations. This particularly applies to highly explosive silicic eruptions, but can also hold true for explosive basaltic eruptions or discrete events associated with basaltic fissure eruptions., This work was funded under the UK Natural Environment Research Council (NERC) Knowledge Exchange (KE) Fellowship NE/J500525/1 granted to R.E. Holdsworth at Durham University. DED was additionally supported by the ERC Advanced Grant no. 247076 awarded to D.B. Dingwell at LMU Munich.

Background Exposure to crystalline silica (SiO2), in the form of quartz, tridymite or cristobalite, can cause respiratory diseases, such as silicosis. However, the observed toxicity and pathogenicity of crystalline silica is highly variable. This has been attributed to a number of inherent and external factors, including the presence of impurities. In cristobalite-rich dusts, substitutions of aluminium (Al) for silicon (Si) in the cristobalite structure, and impurities occluding the silica surface, have been hypothesised to decrease its toxicity. This hypothesis is tested here through the characterisation and in vitro toxicological study of synthesised cristobalite with incremental amounts of Al and sodium (Na) dopants. Methods Samples of synthetic cristobalite with incremental amounts of Al and Na impurities, and tridymite, were produced through heating of a silica sol-gel. Samples were characterised for mineralogy, cristobalite purity and abundance, particle size, surface area and surface charge. In vitro assays assessed the ability of the samples to induce cytotoxicity and TNF-α production in J774 macrophages, and haemolysis of red blood cells. Results Al-only doped or Al+Na co-doped cristobalite contained between 1 and 4 oxide wt% Al and Na within its structure. Co-doped samples also contained Al- and Na-rich phases, such as albite. Doping reduced cytotoxicity to J774 macrophages and haemolytic capacity compared to non-doped samples. Al-only doping was more effective at decreasing cristobalite reactivity than Al+Na co-doping. The reduction in the reactivity of cristobalite is attributed to both structural impurities and a lower abundance of crystalline silica in doped samples. Neither non-doped nor doped crystalline silica induced production of the pro-inflammatory cytokine TNF-α in J774 macrophages. Conclusions Impurities can reduce the toxic potential of cristobalite and may help explain the low reactivity of some cristobalite-rich dusts. Whilst further work is required to determine if these effects translate to altered pathogenesis, the results have potential implications for the regulation of crystalline silica exposures.

Background There are justifiable health concerns regarding the potential adverse effects associated with human exposure to volcanic ash (VA) particles, especially when considering communities living in urban areas already exposed to heightened air pollution. The aim of this study was, therefore, to gain an imperative, first understanding of the biological impacts of respirable VA when exposed concomitantly with diesel particles. Methods A sophisticated in vitro 3D triple cell co-culture model of the human alveolar epithelial tissue barrier was exposed to either a single or repeated dose of dry respirable VA (deposited dose of 0.26 ± 0.09 or 0.89 ± 0.29 μg/cm2, respectively) from Soufrière Hills volcano, Montserrat for a period of 24 h at the air-liquid interface (ALI). Subsequently, co-cultures were exposed to co-exposures of single or repeated VA and diesel exhaust particles (DEP; NIST SRM 2975; 0.02 mg/mL), a model urban pollutant, at the pseudo-ALI. The biological impact of each individual particle type was also analysed under these precise scenarios. The cytotoxic (LDH release), oxidative stress (depletion of intracellular GSH) and (pro-)inflammatory (TNF-α, IL-8 and IL-1β) responses were assessed after the particulate exposures. The impact of VA exposure upon cell morphology, as well as its interaction with the multicellular model, was visualised via confocal laser scanning microscopy (LSM) and scanning electron microscopy (SEM), respectively. Results The combination of respirable VA and DEP, in all scenarios, incited an heightened release of TNF-α and IL-8 as well as significant increases in IL-1β, when applied at sub-lethal doses to the co-culture compared to VA exposure alone. Notably, the augmented (pro-)inflammatory responses observed were not mediated by oxidative stress. LSM supported the quantitative assessment of cytotoxicity, with no changes in cell morphology within the barrier model evident. A direct interaction of the VA with all three cell types of the multicellular system was observed by SEM. Conclusions Combined exposure of respirable Soufrière Hills VA with DEP causes a (pro-)inflammatory effect in an advanced in vitro multicellular model of the epithelial airway barrier. This finding suggests that the combined exposure to volcanic and urban particulate matter should be further investigated in order to deduce the potential human health hazard, especially how it may influence the respiratory function of susceptible individuals (i.e. with pre-existing lung diseases) in the population. Electronic supplementary material The online version of this article (doi:10.1186/s12989-016-0178-9) contains supplementary material, which is available to authorized users.

During European prehistory, hilltop enclosures made from polydisperse particle-and-block stone walling were exposed to temperatures sufficient to partially melt the constituent stonework, leading to the preservation of glassy walls called ‘vitrified forts’. During vitrification, the granular wall rocks partially melt, sinter viscously and densify, reducing inter-particle porosity. This process is strongly dependent on the solidus temperature, the particle sizes, the temperature-dependence of the viscosity of the evolving liquid phase, as well as the distribution and longevity of heat. Examination of the sintering behaviour of 45 European examples reveals that it is the raw building material that governs the vitrification efficiency. As Iron Age forts were commonly constructed from local stone, we conclude that local geology directly influenced the degree to which buildings were vitrified in the Iron Age. Additionally, we find that vitrification is accompanied by a bulk material strengthening of the aggregates of small sizes, and a partial weakening of larger blocks. We discuss these findings in the context of the debate surrounding the motive of the wall-builders. We conclude that if wall stability by bulk strengthening was the desired effect, then vitrification represents an Iron Age technology that failed to be effective in regions of refractory local geology.

The fusion dynamics of volcanic ash strongly impacts deposition in hot parts of jet engines. In this study, we investigate the sintering behavior of volcanic ash using natural ash of intermediate composition, erupted in 2012 at Santiaguito Volcano, Guatemala. A material science procedure was followed in which we monitored the geometrical evolution of cylindrical-shaped volcanic ash compact upon heating from 50 to 1400°C in a heating microscope. Combined morphological, mineralogical, and rheological analyses helped define the evolution of volcanic ash during fusion and sintering and constrain their sticking potential as well as their ability to flow at characteristic temperatures. For the ash investigated, 1240°C marks the onset of adhesion and flowability. The much higher fusibility of ash compared to that of typical test sands demonstrates for the need of a more extensive fusion characterization of volcanic ash in order to mitigate the risk posed on jet engine operation.

Ashfall into heavily populated areas during the October–November 2010 eruption of Merapi volcano, Indonesia created anxiety regarding the growing impacts to health as the eruption escalated and the hazard zone widened. We made a preliminary assessment of the respiratory hazards to human health of the tephra deposits (ashfall, lahar, and PDC surge) from the eruption using a laboratory protocol specifically developed to study the toxic potential of volcanic ash particles. Twenty samples collected from a range of locations were analysed for health-pertinent mineralogical parameters (grain size, crystalline silica content, morphology, surface area, bulk chemistry, and leachable elements) and bio-reactivity (hydroxyl radical generation, haemolytic potential, oxidative capacity, pro-inflammatory response). The grain size pertinent to respiratory health was variable, ranging from 1.4–15.6 vol.% sub-4 μm and 3.0–28.9 vol.% sub-10 μm diameter material. No fibre-like particles were observed. Cristobalite was present in all samples, ranging from 1.9–9.5 wt.%, but surface reactivity and in vitro toxicity assays showed low reactivity for all samples tested. The risk of direct exposure to ash from fallout was in any case low due to seasonal rains limiting its re-suspension and the immediate and effective clean-up of communities by local people who supplied the ash to the Indonesian construction industry for use as aggregate. However, mining of the lahar and thick PDC deposits in the valleys draining the volcano is performed on a vast, industrial scale, which could result in high occupational exposure to thousands of sand miners at Merapi during the dry seasons. Further study of the health hazard of the mined Merapi deposits is warranted

During explosive eruptions, a suspension of gas and pyroclasts rises rapidly within a conduit. Here, we have analysed textures preserved in the walls of a pyroclastic feeder dyke of the AD 1886 Tarawera basaltic Plinian fissure eruption. The samples examined consist of basaltic ash and scoria plastered onto a conduit wall of a coherent rhyolite dome and a welded rhyolitic dome breccia. We examine the textural evidence for the response of the wall material, built of ∼75 vol.% glass and ∼25 vol.% crystals (pore-free equivalent), to mass movement in the adjacent conduit. In the rhyolitic wall material, we quantify the orientation and aspect ratio of biotite crystals as strain markers of simple shear deformation, and interpret juxtaposed regions of vesiculation and vesicle collapse as evidence of conduit wall heating. Systematic changes occur close to the margin: (1) porosity is highly variable, with areas locally vesiculated or densified, (2) biotite crystals are oriented with their long axis parallel to the margin, (3) the biotites have greater aspect ratios close to the margin and (4) the biotite crystals are fractured. We interpret the biotite phenocryst deformation to result from crystal fracture, rotation and cleavage-parallel bookcase translation. These textural observations are inferred to indicate mechanical coupling between the hot gas-ash jet and the conduit wall and reheating of wall rock rhyolite. We couple these observations with a simple 1D conductive heating model to show what minimum temperature the conduit wall needs to reach in order to achieve a temperature above the glass transition throughout the texturally-defined deformed zone. We propose that conduit wall heating and resulting deformation influences conduit margin outgassing and may enhance the intensity of such large basaltic eruptions. Electronic supplementary material The online version of this article (doi:10.1007/s00445-016-1006-7) contains supplementary material, which is available to authorized users.

Regular eruptions from Sakurajima volcano, Japan, repeatedly cover local urban areas with volcanic ash. The frequency of exposure of local populations to the ash led to substantial concerns about possible respiratory health hazards, resulting in many epidemiological and toxicological studies being carried out in the 1980s. However, very few mineralogical data were available for determination of whether the ash was sufficiently fine to present a respiratory hazard. In this study, we review the existing studies and carry out mineralogical, geochemical and toxicological analyses to address whether the ash from Sakurajima has the potential to cause respiratory health problems. The results show that the amount of respirable (

Natural killer T (NKT) cells comprise a novel T-lymphocyte subset that can influence a wide variety of immune responses through their ability to secrete large amounts of a variety of cytokines. Although variation in NKT-cell number and function has been extensively studied in autoimmune disease-prone mice, in which it has been linked to disease susceptibility, relatively little is known of the natural variation of NKT-cell number and function among normal inbred mouse strains. Here, we demonstrate strain-dependent variation in the susceptibility of C57BL/6J and BALB/cJ mice to NKT-mediated airway hyperreactivity, which correlated with significant increases in serum interleukin-4 (IL-4) and IL-13 elicited by the synthetic glycosphingolipid alpha-galactosylceramide. Examination of NKT-cell function revealed a significantly greater frequency of cytokine-producing NKT cells in C57BL/6J versus BALB/cJ mice as well as significant differences in the kinetics of NKT-cell cytokine production. Extension of this analysis to a panel of inbred mouse strains indicated that variability in NKT-cell cytokine production was widespread. Similarly, an examination of NKT-cell frequency revealed a significantly greater number of liver NKT cells in the C57BL/6J mice versus BALB/cJ mouse livers. Again, examination of a panel of inbred mouse strains revealed that liver NKT-cell numbers were quite variable, spanning over a 100-fold range. Taken together, these results demonstrate the presence of widespread natural variation in NKT-cell number and function among common inbred mouse strains, which may have implications for the examination of the influence of NKT cells in immune responses and disease pathogenesis among different genetic backgrounds.

Ash from dome-forming volcanoes poses a unique hazard to millions of people worldwide due to an abundance of respirable cristobalite, a crystalline silica polymorph. Crystalline silica is an established respiratory hazard in other mixed dusts, but its toxicity strongly depends on sample provenance. Previous studies suggest that cristobalite-bearing volcanic ash is not as bio-reactive as may be expected for a dust containing crystalline silica. We systematically address the hazard posed by volcanic cristobalite by analysing a range of dome-related ash samples, and interpret the crystalline silica hazard according to the mineralogical nature of volcanic cristobalite. Samples are sourced from five well-characterized dome-forming volcanoes that span a range of magmatic compositions, specifically selecting samples rich in cristobalite (up to 16wt%). Isolated respirable fractions are used to investigate the in vitro response of THP-1 macrophages and A549 type II epithelial cells in cytotoxicity, cellular stress, and pro-inflammatory assays associated with crystalline silica toxicity. Dome-related ash is minimally reactive in vitro for a range of source compositions and cristobalite contents. Cristobalite-based toxicity is not evident in the assays employed, supporting the notion that crystalline silica provenance influences reactivity. Macrophages experienced minimal ash-induced cytotoxicity and intracellular reduction of glutathione; however, production of IL-1β, IL-6 and IL-8 were sample-dependent. Lung epithelial cells experienced moderate apoptosis, sample-dependent reduction of glutathione, and minimal cytokine production. We suggest that protracted interaction between particles and epithelial cells may never arise due to effective clearance by macrophages. However, volcanic ash has the propensity to incite a low, but significant, and sample-dependent response; the effect of this response in vivo is unknown and prolonged exposure may yet pose a hazard.

Advances in the collection and analysis of landslide inventory data have allowed for greater understanding of spatial distributions of landslides triggered by earthquakes. However, current approaches to analysing and modelling these phenomena do not account for the response of the individual potential landslide masses and their temporally evolving stability. This stems, in part, from the lack of a conceptual model describing the effect of seismic waves on the strength and stability of hillslopes, which can be applied at the regional scale and over long (multiple earthquake) time scales. Here we present such a conceptual model linking weakening via progressive failure, inertial displacements driven by seismic ground accelerations, and the repeating failure of sections of hillslopes through time. We explore the implications of the model for how various characteristics of earthquake-triggered landslide distributions are interpreted and understood. These include the apparently stochastic nature of spatial landslide occurrence, spatial patterns of landsliding, landslide magnitude-frequency distributions, global variability in numbers of landslides triggered by earthquakes, and in particular why in any earthquake smaller areas of hillslope fail than do not, even in regions of apparently high landslide susceptibility. Finally, we also propose means of testing the validity of this model relative to alternative hypotheses.

CD1d-restricted NKT cells make up an innate-like T cell subset that plays a role in amplifying the response of innate immune leukocytes to TLR ligands. The Slam locus contains genes that have been implicated in innate and adaptive immune responses. In this study, we demonstrate that divergent Slam locus haplotypes modulate the response of macrophages to the TLR4 ligand LPS through their control of NKT cell number and function. In response to LPS challenge in vivo, macrophage TNF production in Slam haplotype-2+ 129S1/SvImJ and 129X1/SvJ mice was significantly impaired in comparison with macrophage TNF production in Slam haplotype-1+ C57BL/6J mice. Although no cell-intrinsic differences in macrophage responses to LPS were observed between strains, 129 mice were found to be deficient in liver NKT cell number, in NKT cell cytokine production in response to the CD1d ligand α-galactosylceramide, and in NKT cell IFN-γ production after LPS challenge in vivo. Using B6.129c1 congenic mice and adoptive transfer, we found that divergent Slam haplotypes controlled the response to LPS in vivo, as well as the diminished NKT cell number and function, and that these phenotypes were associated with differential expression of signaling lymphocytic activation molecule family receptors on NKT cells. These data suggest that the polymorphisms that distinguish two Slam haplotypes significantly modulate the innate immune response in vivo through their effect on NKT cells.

Cristobalite is commonly found in the dome lava of silicic volcanoes but is not a primary magmatic phase; its presence indicates that the composition and micro-structure of dome lavas evolve during, and after, emplacement. Nine temporally and mineralogically diverse dome samples from the Soufrière Hills volcano (SHV), Montserrat, are analysed to provide the first detailed assessment of the nature and mode of cristobalite formation in a volcanic dome. The dome rocks contain up to 11 wt.% cristobalite, as defined by X-ray diffraction. Prismatic and platy forms of cristobalite, identified by scanning electron microscopy (SEM), are commonly found in pores and fractures, suggesting that they have precipitated from a vapour phase. Feathery crystallites and micro-crystals of cristobalite and quartz associated with volcanic glass, identified using SEM-Raman, are interpreted to have formed by varying amounts of devitrification. We discuss mechanisms of silica transport and cristobalite formation, and their implications for petrological interpretations and dome stability. We conclude: (1) that silica may be transported in the vapour phase locally, or from one part of the magmatic system to another; (2) that the potential for transport of silica into the dome should not be neglected in petrological and geochemical studies because the addition of non-magmatic phases may affect whole rock composition; and (3) that the extent of cristobalite mineralisation in the dome at SHV is sufficient to reduce porosity—hence, permeability—and may impact on the mechanical strength of the dome rock, thereby potentially affecting dome stability.