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In 2023 human populations experienced multiple record-breaking climate events, with widespread impacts on human health and well-being. These events include extreme heat domes, drought, severe storms, flooding, and wildfires. Due to inherent lags in the climate system, we can expect such extremes to continue for multiple decades after reaching net zero carbon emissions. Unfortunately, despite these significant current and future impacts, funding for research in climate and health has lagged behind that for other geoscience and biomedical research. While some initial efforts from funding agencies are evident, there is still a significant need to increase the resources available for multidisciplinary research in the face of this issue. As a group of experts at this important intersection, we call for a more concerted effort to encourage interdisciplinary and policy-relevant investigations into the detrimental health effects of continued climate change., Competing Interests: The authors declare no conflicts of interest relevant to this study., (© 2024 The Authors. GeoHealth published by Wiley Periodicals LLC on behalf of American Geophysical Union.)

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., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Disasters may impact air quality through the generation of high levels of potentially pathogenic particulate matter (PM), for example, in a volcanic eruption. Depending on the concentrations of particles in the air, their size and composition, and the duration of exposure, high levels of PM can create significant public health issues. It has been argued that air pollution, in and of itself, is a public health crisis. One possible intervention to reduce exposure to high levels of PM during an air pollution disaster (APD) is using facemasks. However, agencies may be reluctant to recommend or distribute facemasks for community use during APDs for a variety of reasons, including concerns about liability. There has been no analysis of these concerns. This paper analyzes whether agencies may have a legal duty of care in negligence to provide warnings about the health risks associated with APDs and/or to recommend facemasks as a protective mechanism for community use to reduce exposure to PM. It is also the first to examine the potential for liability in negligence, when a decision is made to distribute facemasks for community use during an APD and the receiver alleges that they sustained a personal injury and seeks compensation.

This paper critically appraises the extrapolation of concentration-response functions (CRFs) for fine and coarse particulate matter, PM 2.5 and PM 10 , respectively, used in outdoor air pollution health impact assessment (HIA) studies to assess the extent of health impacts in communities exposed to volcanic emissions. Treating volcanic ash as PM, we (1) consider existing models for HIA for general outdoor PM, (2) identify documented health effects from exposure to ash in volcanic eruptions, (3) discuss potential issues of applying CRFs based on the composition and concentration of ash-related PM, and (4) critically review available case studies of volcanic exposure scenarios utilizing HIA for outdoor air pollution. We identify a number of small-scale studies focusing on populations exposed to volcanic ash; exposure is rarely quantified, and there is limited evidence concerning the health effects of PM from volcanic eruptions. That limited evidence is, however, consistent with the CRFs typically used for outdoor air pollution HIA. Two health assessments of exposure to volcanic emissions have been published using population- and occupational-based CRFs, though each application entails distinct assumptions and limitations. We conclude that the best available strategy, at present, is to apply outdoor air pollution risk estimates to scenarios involving volcanic ash emissions for the purposes of HIA. However, due to the knowledge gaps on, for example, the health effects from exposure to volcanic ash and differences in ash composition, there is inherent uncertainty in this application. To conclude, we suggest actions to enable better prediction and assessment of health impacts of volcanic emissions., Competing Interests: The authors declare no conflicts of interest relevant to this study., (©2020. The Authors.)

Air pollution is a major health problem and children are particularly vulnerable to the adverse effects. Facemasks are one form of protection but, to be effective, they need to filter out airborne pollutants, fit the face well and be wearable. In this pilot study, we assess the perceived wearability of three facemasks (Vogmask, TuHao and ReSpimask) marketed in the UK as being designed to protect children against exposure to air pollution. Twenty-four primary school children wore each facemask during a standardised walking and running activity. After each activity, the children were asked to rate facemask wearability in terms of parameters, such as perceived comfort, hotness, breathability and fit. At the end of the trial, the children compared and identified their preferred facemask. The main complaint about the facemasks was the children's faces being too hot. The ReSpimask was most frequently reported as being perceived to be the hardest to breathe through. The TuHao facemask was the only adjustable strap mask assessed but was reported to be difficult to adjust. Facemasks with a nose clip were frequently rated highest for fit (TuHao and Vogmask). The patterned, cloth fabric Vogmask had significantly higher ratings for appearance and perceived fit. The results show children's perceptions of facemasks are highly affected by the facemask's design, hotness and perceived breathability. By making children's facemasks more appealing, breathable, cooler and improving their fit, wearability may be improved., Competing Interests: The authors declare no conflict of interest. Vogmask, California and Respilon, Czech Republic donated masks free of charge, but had no participation or influence in the design of the study, data analysis, its interpretation and the writing and publication of this manuscript. The Bristol Medical School, University of Bristol, provided funding for the purchase of the remaining masks. They had no role in the design of the study, the collection, analyses, or interpretation of data, in writing of the manuscript, or in the decision to publish the results.

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 (SO 2 ) 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 SO 2 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 SO 2 -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 SO 2 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., (Copyright © 2019 The Authors. Published by Elsevier Inc. All rights reserved.)

Communities living near active volcanoes may be exposed to respiratory hazards from volcanic ash. Understanding their perception of the risks and the actions they take to mitigate against those risks is important for developing effective communication strategies. To investigate this issue, the first comparative study of risk perceptions and use of respiratory protection was conducted on 2003 residents affected by active volcanoes from three countries: Japan (Sakurajima volcano), Indonesia (Merapi and Kelud volcanoes) and Mexico (Popocatépetl volcano). The study was designed to test the explanatory value of a theoretical framework which hypothesized that use of respiratory protection (i.e., facemask) would be motivated by two cognitive constructs from protection motivation theory: threat appraisal (i.e., perceptions of harm/ worry about ash inhalation) and coping appraisal (i.e., beliefs about mask efficacy). Using structural equation modelling (SEM), important differences in the predictive ability of the constructs were found between countries. For example, perceptions of harm/ worry were stronger predictors of mask use in Japan and Indonesia than they were in Mexico where beliefs about mask efficacy were more important. The SEM also identified differences in the demographic variants of mask use in each country and how they were mediated by the cognitive constructs. Findings such as these highlight the importance of contextualising our understanding of protection motivation and, thus, the value of developing targeted approaches to promote precautionary behaviour., Competing Interests: Declarations of Interest None.

Inhalation of ash can be of great concern for affected communities, during and after volcanic eruptions. Governmental and humanitarian agencies recommend and distribute a variety of respiratory protection (RP), commonly surgical masks but, also, industry-certified N95-style masks. However, there is currently no evidence on how wearable they are within affected populations or how protective wearers perceive them being against volcanic ash (which will influence the likelihood of uptake of recommended interventions). Volunteers living near Mt. Sinabung, Sumatra, Indonesia, participated in a field wearability study, which included a high-efficiency mask certified to industry standards (N95-equiv.); a standard, pleated surgical mask (Surgical); a Basic flat-fold mask (Flat-fold), and the surgical mask plus a scarf tied over the top (Surgical Plus) to improve fit. These types of RP had all performed well during earlier laboratory filtration efficiency tests. The N95-equiv. mask had performed significantly better than the other RP in the subsequent total inward leakage volunteer trials, whilst the Flat-fold and Surgical masks performed poorly, letting in a third of PM 2.5 particles (data published elsewhere). Thirty volunteers wore each mask for a 15-min walk before being asked to rate the comfort, breathability and perceived protection and fit of each. After wearing all of the masks, volunteers compared and identified their preferred type of protection. The feedback received from the volunteers suggested that the Surgical Plus and N95-equiv. masks were rated as being significantly hotter and more humid than other masks. The Flat-fold was rated to have better breathability than the other masks. The N95-equiv. mask was ranked as providing the best level of effectiveness of the four masks tested. Ultimately, when asked which type of mask they would choose to wear during ashfall, 33% selected the Flat-fold mask due to its comfort and simplicity, with the Surgical Plus being the least likely to be chosen of the four tested. The study findings are of benefit to agencies who need to make informed decisions on the procurement and distribution of RP for use by those affected in future eruptions and the provision of advice to communities on their usage.

Inhalation of ash can be of great concern for affected communities, during and after volcanic eruptions. Governmental and humanitarian agencies recommend and distribute a variety of respiratory protection (RP), most commonly surgical masks. However, there is currently no evidence on how effective such masks are in protecting wearers from volcanic ash. In Part I of this study (Mueller et al., 2018), we assessed the filtration efficiency (FE) of 17 materials from different forms of RP against volcanic ash and a surrogate, low-toxicity dust, Aloxite. Based on those results, we now present the findings from a volunteer simulation study to test the effect of facial fit through assessment of Total Inward Leakage (TIL). Four different disposable RP types that demonstrated very high median FE (≥96% for Aloxite; ≥89% for volcanic ash) were tested without provision of training on fit. These were an industry-certified mask (N95-equiv.); a surgical mask from Japan designed to filter PM 2.5 ; a flat-fold basic mask from Indonesia; and a standard surgical mask from Mexico, which was also tested with an added medical bandage on top, as an additional intervention to improve fit. Ten volunteers (6 female, 4 male) were recruited. Each RP type was worn by volunteers under two different conditions simulating cleaning-up activities during/after volcanic ashfall. Each activity lasted 10 min and two repeats were completed for each RP type per activity. Dust (as PM 2.5 ) concentration inside and outside the mask was measured with two TSI SidePak aerosol monitors (Models AM510 and AM520, TSI, Minnesota, USA) to calculate TIL. A questionnaire was administered after each test to collect perceptions of fit, comfort, protection and breathability. The best-performing RP type, across both activities, was the industry-certified N95-equiv. mask with 9% mean TIL. The standard surgical mask and the basic flat-fold mask both performed worst (35% TIL). With the additional bandage intervention, the surgical mask mean TIL improved to 24%. The PM 2.5 surgical mask performed similarly, with 22% TIL. The N95-equiv. mask was perceived to provide the best protection, but was also perceived as being uncomfortable and more difficult to breathe through. This study provides a first objective evidence base for the effectiveness of a selection of RP types typically worn around the world during volcanic crises. The findings will help agencies to make informed decisions on the procurement and distribution of RP in future eruptions., (Copyright © 2018 The Authors. Published by Elsevier GmbH.. All rights reserved.)

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/cm 2 and 0.39 ± 0.09 μg/cm 2 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% CO 2 ). 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., (Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.)

During volcanic eruptions and their aftermath, communities may be concerned about the impacts of inhaling volcanic ash. Access to effective respiratory protection (RP) is therefore important for many people in volcanic areas all over the world. However, evidence to support the use of effective RP during such crises is currently lacking. The aim of this study was to build the first evidence base on the effectiveness of common materials used to protect communities from ash inhalation in volcanic crises. We obtained 17 forms of RP, covering various types of cloth through to disposable masks (typically used in occupational settings), which communities are known to wear during volcanic crises. The RP materials were characterised and subjected to filtration efficiency (FE) tests, which were performed with three challenge dusts: ashes from Sakurajima (Japan) and Soufrière Hills (Montserrat) volcanoes and aluminium oxide (Aloxite), chosen as a low-toxicity surrogate dust of similar particle size distribution. FE tests were conducted at two concentrations (1.5 mg/m 3 and 2.5 mg/m 3 ) and two flow rates (equivalent to 40 and 80 l/min through 15.9 cm 2 sections of each RP type). Each material was held in a sample holder and PM 2.5 dust concentrations were measured both outside the mask material and inside the sample holder to determine FE. A limited number of tests were undertaken to assess the effect on FE of wetting a bandana and a surgical mask, as well as folding a bandana to provide multiple filter layers. Overall, four RP materials performed very well against volcanic ash, with median FEs in excess of 98% (N95-equiv., N99-equiv., PM 2.5 surgical (Japan), and Basic flat-fold (Indonesia)). The two standard surgical masks tested had median FEs of 89-91%. All other materials had median FEs ranging from 23 to 76% with no cloth materials achieving >44%. Folding a bandana resulted in better FE (40%; 3× folded) than single-layered material (29%). Wetting the bandana and surgical mask material did not improve FE overall. This first evidence base on the FE of common materials used to protect communities in volcanic crises from ash inhalation has been extended in a companion study (Steinle et al., 2018) on the total inward leakage of the best-performing masks when worn by human volunteers. This will provide a complete assessment of the effectiveness of these RP types., (Copyright © 2018 The Authors. Published by Elsevier GmbH.. All rights reserved.)

Objectives: Many residents in Beijing use disposable face masks in an attempt to protect their health from high particulate matter (PM) concentrations. Retail masks may be certified to local or international standards, but their real-life performance may not confer the exposure reduction potential that is marketed. This study aimed to evaluate the effectiveness of a range of face masks that are commercially available in China., Methods: Nine masks claiming protection against fine PM (PM 2.5 ) were purchased from consumer outlets in Beijing. The masks' filtration efficiency was tested by drawing airborne diesel exhaust through a section of the material and measuring the PM 2.5 and black carbon (BC) concentrations upstream and downstream of the filtering medium. Four masks were selected for testing on volunteers. Volunteers were exposed to diesel exhaust inside an experimental chamber while performing sedentary tasks and active tasks. BC concentrations were continuously monitored inside and outside the mask., Results: The mean per cent penetration for each mask material ranged from 0.26% to 29%, depending on the flow rate and mask material. In the volunteer tests, the average total inward leakage (TIL) of BC ranged from 3% to 68% in the sedentary tests and from 7% to 66% in the active tests. Only one mask type tested showed an average TIL of less than 10%, under both test conditions., Conclusions: Many commercially available face masks may not provide adequate protection, primarily due to poor facial fit. Our results indicate that further attention should be given to mask design and providing evidence-based guidance to consumers., Competing Interests: Competing interests: The Institute of Occupational Medicine undertakes a wide range of commercial testing related to occupational and environmental health, some of which has been for respirator manufacturers., (© Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2018. All rights reserved. No commercial use is permitted unless otherwise expressly granted.)

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 (SiO 2 ) 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: Exposure to crystalline silica (SiO 2 ), 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., (Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.)

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 m 2  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.

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/cm 2 , 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.

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., (Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.)

Background: Diatomaceous earth (DE) is mined globally and is potentially of occupational respiratory health concern due to the high crystalline silica content in processed material. DE toxicity, in terms of variability related to global source and processing technique, is poorly understood. This study addresses this variability using physicochemical characterisation and in vitro toxicology assays., Methods: Nineteen DE samples sourced from around the world, comprising unprocessed, calcined and flux-calcined DE, were analysed for chemical and mineral composition, particle size and morphology, and surface area. The potential toxicity of DE was assessed by its haemolytic capacity, and its ability to induce cytotoxicity or cytokine release by J774 macrophages., Results: The potential toxicity of DE varied with source and processing technique, ranging from non-reactive to as cytotoxic and haemolytic as DQ12. Crystalline silica-rich, flux-calcined samples were all unreactive, regardless of source. The potential toxicity of unprocessed and calcined samples was variable, and did not correlate with crystalline silica content. Calcium-rich phases, iron content, amorphous material, particle size and morphology all appeared to play a role in sample reactivity. An increased surface area was linked to an increased reactivity in vitro for some sample types., Conclusions: Overall, no single property of DE could be linked to its potential toxicity, but crystalline silica content was not a dominant factor. Occlusion of the potentially toxic crystalline silica surface by an amorphous matrix or other minerals and impurities in the crystal structure are suggested to pacify toxicity in these samples. In vivo verification is required, but these data suggest that crystalline silica content alone is not a sufficient indicator of the potential DE hazard.

Extreme geological events, such as earthquakes, are a significant global concern and sometimes their consequences can be devastating. Geographic information plays a critical role in health protection regarding hazards, and there are a range of initiatives using geographic information to communicate risk as well as to support early warning systems operated by geologists. Nevertheless we consider there to remain shortfalls in translating information on extreme geological events into health protection tools, and suggest that social scientists have an important role to play in aiding the development of a new generation of toolkits aimed at public health practitioners. This viewpoint piece reviews the state of the art in this domain and proposes potential contributions different stakeholder groups, including social scientists, could bring to the development of new toolkits., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Cristobalite is a common mineral in volcanic ash produced from dome-forming eruptions. Assessment of the respiratory hazard posed by volcanic ash requires understanding the nature of the cristobalite it contains. Volcanic cristobalite contains coupled substitutions of Al 3+ and Na + for Si 4+ ; similar co-substitutions in synthetic cristobalite are known to modify the crystal structure, affecting the stability of the α and β forms and the observed transition between them. Here, for the first time, the dynamics and energy changes associated with the α-β phase transition in volcanic cristobalite are investigated using X-ray powder diffraction with simultaneous in situ heating and differential scanning calorimetry. At ambient temperature, volcanic cristobalite exists in the α form and has a larger cell volume than synthetic α-cristobalite; as a result, its diffraction pattern sits between ICDD α- and β-cristobalite library patterns, which could cause ambiguity in phase identification. On heating from ambient temperature, volcanic cristobalite exhibits a lower degree of thermal expansion than synthetic cristobalite, and it also has a lower α-β transition temperature (∼473 K) compared with synthetic cristobalite (upwards of 543 K); these observations are discussed in relation to the presence of Al 3+ and Na + defects. The transition shows a stable and reproducible hysteresis loop with α and β phases coexisting through the transition, suggesting that discrete crystals in the sample have different transition temperatures.

Sugarcane combustion generates fine-grained particulate that has the potential to be a respiratory health hazard because of its grain size and composition. In particular, conversion of amorphous silica to crystalline forms during burning may provide a source of toxic particles. In this study, we investigate and evaluate the toxicity of sugarcane ash and bagasse ash formed from commercial sugarcane burning. Experiments to determine the main physicochemical properties of the particles, known to modulate biological responses, were combined with cellular toxicity assays to gain insight into the potential reactions that could occur at the particle-lung interface following inhalation. The specific surface area of the particles ranged from ∼16 to 90 m(2) g(-1) . The samples did not generate hydroxyl- or carbon-centered radicals in cell-free tests. However, all samples were able to 'scavenge' an external source of hydroxyl radicals, which may be indicative of defects on the particle surfaces that may interfere with cellular processes. The bioavailable iron on the particle surfaces was low (2-3 μmol m(-2) ), indicating a low propensity for iron-catalyzed radical generation. The sample surfaces were all hydrophilic and slightly acidic, which may be due to the presence of oxygenated (functional) groups. The ability to cause oxidative stress and membrane rupture in red blood cells (hemolysis) was found to be low, indicating that the samples are not toxic by the mechanisms tested. Cytotoxicity of sugarcane ash was observed, by measuring lactate dehydrogenase release, after incubation of relatively high concentrations of ash with murine alveolar macrophage cells. All samples induced nitrogen oxide release (although only at very high concentrations) and reactive oxygen species generation (although the bagasse samples were less potent than the sugarcane ash). However, the samples induced significantly lower cytotoxic effects and nitrogen oxide generation when compared with the positive control., (Copyright © 2012 Wiley Periodicals, Inc.)

The six week eruption of Eyjafjallajökull volcano in 2010 produced heavy ash fall in a sparsely populated area of southern and south eastern Iceland and disrupted European commercial flights for at least 6 days. We adopted a protocol for the rapid analysis of volcanic ash particles, for the purpose of informing respiratory health risk assessments. Ash collected from deposits underwent a multi-laboratory physicochemical and toxicological investigation of their mineralogical parameters associated with bio-reactivity, and selected in vitro toxicology assays related to pulmonary inflammatory responses. Ash from the eruption of Grímsvötn, Iceland, in 2011 was also studied. The results were benchmarked against ash from Soufrière Hills volcano, Montserrat, which has been extensively studied since the onset of eruptive activity in 1995. For Eyjafjallajökull, the grain size distributions were variable: 2-13 vol% of the bulk samples were <4 µm, with the most explosive phases of the eruption generating abundant respirable particulate matter. In contrast, the Grímsvötn ash was almost uniformly coarse (<3.5 vol%<4 µm material). Surface area ranged from 0.3 to 7.7 m2 g(-1) for Eyjafjallajökull but was very low for Grímsvötn (<0.6 m2 g(-1)). There were few fibre-like particles (which were unrelated to asbestos) and the crystalline silica content was negligible in both eruptions, whereas Soufrière Hills ash was cristobalite-rich with a known potential to cause silicosis. All samples displayed a low ability to deplete lung antioxidant defences, showed little haemolysis and low acute cytotoxicity in human alveolar type-1 like epithelial cells (TT1). However, cell-free tests showed substantial hydroxyl radical generation in the presence of hydrogen peroxide for Grímsvötn samples, as expected for basaltic, Fe-rich ash. Cellular mediators MCP-1, IL-6, and IL-8 showed chronic pro-inflammatory responses in Eyjafjallajökull, Grímsvötn and Soufrière Hills samples, despite substantial differences in the sample mineralogy and eruptive styles. The value of the pro-inflammatory profiles in differentiating the potential respiratory health hazard of volcanic ashes remains uncertain in a protocol designed to inform public health risk assessment, and further research on their role in volcanic crises is warranted., (Copyright © 2013 The Authors. Published by Elsevier Inc. All rights reserved.)

Background: Respirable crystalline silica (RCS) continues to pose a risk to human health worldwide. Its variable toxicity depends on inherent characteristics and external factors which influence surface chemistry. Significant population exposure to RCS occurs during volcanic eruptions, where ashfall may cover hundreds of square km and exposure may last years. Occupational exposure also occurs through mining of volcanic deposits. The primary source of RCS from volcanoes is through collapse and fragmentation of lava domes within which cristobalite is mass produced. After 30 years of research, it is still not clear if volcanic ash is a chronic respiratory health hazard. Toxicological assays have shown that cristobalite-rich ash is less toxic than expected. We investigate the reasons for this by determining the physicochemical/structural characteristics which may modify the pathogenicity of volcanic RCS. Four theories are considered: 1) the reactivity of particle surfaces is reduced due to co-substitutions of Al and Na for Si in the cristobalite structure; 2) particles consist of aggregates of cristobalite and other phases, restricting the surface area of cristobalite available for reactions in the lung; 3) the cristobalite surface is occluded by an annealed rim; 4) dissolution of other volcanic particles affects the surfaces of RCS in the lung., Methods: The composition of volcanic cristobalite crystals was quantified by electron microprobe and differences in composition assessed by Welch's two sample t-test. Sections of dome-rock and ash particles were imaged by scanning and transmission electron microscopy, and elemental compositions of rims determined by energy dispersive X-ray spectroscopy., Results: Volcanic cristobalite contains up to 4 wt. % combined Al(2)O(3) and Na(2)O. Most cristobalite-bearing ash particles contain adhered materials such as feldspar and glass. No annealed rims were observed., Conclusions: The composition of volcanic cristobalite particles gives insight into previously-unconsidered inherent characteristics of silica mineralogy which may affect toxicity. The structural features identified may also influence the hazard of other environmentally and occupationally produced silica dusts. Current exposure regulations do not take into account the characteristics that might render the silica surface less harmful. Further research would facilitate refinement of the existing simple, mass-based silica standard by taking into account composition, allowing higher standards to be set in industries where the silica surface is modified.

Sugarcane leaves contain amorphous silica, which may crystallise to form crystalline silica polymorphs (cristobalite or quartz), during commercial sugarcane harvesting where sugarcane plants are burned. Respirable airborne particulate containing these phases may present an occupational health hazard. Following from an earlier pilot study (J. S. Le Blond, B. J. Williamson, C. J. Horwell, A. K. Monro, C. A. Kirk and C. Oppenheimer, Atmos. Environ., 2008, 42, 5558-5565) in which experimental burning of sugarcane leaves yielded crystalline silica, here we report on actual conditions during sugarcane burning on commercial estates, investigate the physico-chemical properties of the cultivated leaves and ash products, and quantify the presence of crystalline silica. Commercially grown raw sugarcane leaf was found to contain up to 1.8 wt% silica, mostly in the form of amorphous silica bodies (with trace impurities e.g., Al, Na, Mg), with only a small amount of quartz. Thermal images taken during several pre-harvest burns recorded temperatures up to 1056 degrees C, which is sufficient for metastable cristobalite formation. No crystalline silica was detected in airborne particulate from pre-harvest burning, collected using a cascade impactor. The sugarcane trash ash formed after pre-harvest burning contained between 10 and 25 wt% SiO(2), mostly in an amorphous form, but with up to 3.5 wt% quartz. Both quartz and cristobalite were identified in the sugarcane bagasse ash (5-15 wt% and 1-3 wt%, respectively) formed in the processing factory. Electron microprobe analysis showed trace impurities of Mg, Al and Fe in the silica particles in the ash. The absence of crystalline silica in the airborne emissions and lack of cristobalite in trash ash suggest that high temperatures during pre-harvest burning were not sustained long enough for cristobalite to form, which is supported by the presence of low temperature sylvite and calcite in the residual ash. The occurrence of quartz and cristobalite in bagasse ash is significant as the ash is recycled onto the fields where erosion and/or mechanical disturbance could break down the deposits and re-suspend respirable-sized particulate. Appropriate methods for treatment and disposal of bagasse ash must, therefore, be employed and adequate protection given to workers exposed to these dusts.

Volcanic ash has the potential to cause acute and chronic respiratory diseases if the particles are sufficiently fine to enter the respiratory system. Characterization of the grain-size distribution (GSD) of volcanic ash is, therefore, a critical first step in assessing its health hazard. Quantification of health-relevant size fractions is challenging without state-of-the-art technology, such as the laser diffractometer. Here, several methods for GSD characterization for health assessment are considered, the potential for low-cost measurements is investigated and the first database of health-pertinent GSD data is presented for a suite of ash samples from around the world. Methodologies for accurate measurement of the GSD of volcanic ash by laser diffraction are presented by experimental analysis of optimal refractive indices for different magmatic compositions. Techniques for representative sampling of small quantities of ash are also experimentally investigated. GSD results for health-pertinent fractions for a suite of 63 ash samples show that the fraction of respirable (<4 microm) material ranges from 0-17 vol%, with the variation reflecting factors such as the style of the eruption and the distance from the source. A strong correlation between the amount of <4 and <10 microm material is observed for all ash types. This relationship is stable at all distances from the volcano and with all eruption styles and can be applied to volcanic plume and ash fallout models. A weaker relationship between the <4 and <63 microm fractions provides a novel means of estimating the quantity of respirable material from data obtained by sieving.

A novel, low-cost passive sampling procedure for monitoring of volcanogenic hydrogen sulfide is reported. The technique is based on absorption of H2S onto treated sections of photographic paper, which are housed in plastic film canisters during exposure. The H2S reacts with silver halide in the photographic paper, causing a colour-change reaction from white, through brown, to black, depending on concentration of atmospheric H2S. The sampler is sensitive to << 30 ppb to approximately 1000 ppb of H2S. Here we present results from a series of optimization and quantification experiments. An active sampling procedure for rapid H2S measurement is also reported, based on absorption of H2S onto Whatman No. 41 cellulose filters treated with silver nitrate, and was shown to be quantitative using a single filter at flow rates <1.0 L min(-1) for collection of <200 microg of sulfide (as H2S). Determination of sulfide collected on the substrates was performed using a rapid flow-injection technique based on the fluorescence quenching of fluorescein mercuric acetate (FMA) by sulfide. This was optimized at a FMA concentration of 8 mg L(-1), at which 100% quenching was obtained at a solution sulfide concentration of 3 mg L(-1).

The fine-grained character of volcanic ash generated in the long-lived eruption of the Soufrière Hills volcano, Montserrat, West Indies, raises the issue of its possible health hazards. Surface- and free-radical production has been closely linked to bioreactivity of dusts within the lung. In this study, electron paramagnetic resonance (EPR) techniques have been used, for the first time, on volcanic ash to measure the production of radicals from the surface of particles. Results show that concentrations of hydroxyl radicals (HO*) in respirable ash are two to three times higher than a toxic quartz standard. The dome-collapse ash contains cristobalite, a crystalline silica polymorph that may cause adverse health effects. EPR experiments indicate, however, that cristobalite in the ash does not contribute to HO* generation. Our results show that the main cause of reactivity is removable divalent iron (Fe2+), which is present in abundance on the surfaces of the particles and is very reactive in the lung. Our analyses show that fresh ash generates more HO* than weathered ash (which has undergone progressive oxidation and leaching of iron from exposed surfaces), an effect replicated experimentally by incubating fresh ash in dilute acid. HO* production experiments also indicate that iron-rich silicate minerals are responsible for surface reactivity in the Soufrière Hills ash.