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Volatile Metal Emissions from Volcanic Degassing and Lava–Seawater

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Volatile Metal Emissions from Volcanic Degassing and Lava–Seawater ARTICLE https://doi.org/10.1038/s43247-021-00145-3 OPEN Volatile metal emissions from volcanic degassing and lava–seawater interactions at Kīlauea Volcano, Hawai’i ✉ Emily Mason 1 , Penny E. Wieser 1, Emma J. Liu 2, Marie Edmonds 3, Evgenia Ilyinskaya 4, Rachel C. W. Whitty5, Tamsin A. Mather 5, Tamar Elias 6, Patricia Amanda Nadeau 6, Thomas C. Wilkes 7, Andrew J. S. McGonigle7, Tom D. Pering7, Forrest M. Mims 8, Christoph Kern 9, David J. Schneider10 & Clive Oppenheimer 11 Volcanoes represent one of the largest natural sources of metals to the Earth’s surface. 1234567890():,; Emissions of these metals can have important impacts on the biosphere as pollutants or nutrients. Here we use ground- and drone-based direct measurements to compare the gas and particulate chemistry of the magmatic and lava–seawater interaction (laze) plumes from the 2018 eruption of Kīlauea, Hawai’i. We find that the magmatic plume contains abundant volatile metals and metalloids whereas the laze plume is further enriched in copper and seawater components, like chlorine, with volatile metals also elevated above seawater con- centrations. Speciation modelling of magmatic gas mixtures highlights the importance of the S2− ligand in highly volatile metal/metalloid degassing at the magmatic vent. In contrast, volatile metal enrichments in the laze plume can be explained by affinity for chloride com- plexation during late-stage degassing of distal lavas, which is potentially facilitated by the HCl gas formed as seawater boils. 1 Department of Earth Sciences, University of Cambridge, Cambridge, UK. 2 Department of Earth Sciences, University College London, London, UK. 3 COMET, Department of Earth Sciences, University of Cambridge, Cambridge, UK. 4 COMET, School of Earth and Environment, University of Leeds, Leeds, UK. 5 COMET, Department of Earth Sciences, University of Oxford, Oxford, UK. 6 U.S. Geological Survey Hawaiian Volcano Observatory, Hilo, HI, USA. 7 Department of Geography, University of Sheffield, Sheffield, UK. 8 Geronimo Creek Observatory, Seguin, TX, USA. 9 U.S. Geological Survey Cascades Volcano Observatory, Vancouver, WA, USA. 10 U.S. Geological Survey Alaska Volcano Observatory, Fairbanks, AK, USA. 11 Department of Geography, ✉ University of Cambridge, Cambridge, UK. email: [email protected] COMMUNICATIONS EARTH & ENVIRONMENT | (2021) 2:79 | https://doi.org/10.1038/s43247-021-00145-3 | www.nature.com/commsenv 1 ARTICLE COMMUNICATIONS EARTH & ENVIRONMENT | https://doi.org/10.1038/s43247-021-00145-3 olcanoes have played a key role in shaping the composi- first of 24 fissures opened in the Leilani Estates subdivision on the tion of Earth’s atmosphere over geological time, influen- LERZ44, and by the end of May, activity had largely focused at a V ’ cing the planet s habitability through the outgassing of single vent known as Fissure 8 (19.4627 °N, 154.9091 °W, ~220-m hydrogen-, carbon- and sulphur-bearing species1–4. Volcanoes a.s.l., Fig. 1a, b). Lava flows from the 2018 LERZ eruption reached also supply significant amounts of volatile trace elements, the coast on 23 May 2018, creating a laze plume (Fig. 1c) as still- 44 including metals and metalloids, in the gas phase or as non- molten lava boiled and evaporated seawater . Peak SO2 emission silicate particulate matter (PM, also called aerosol)5–12. Volca- rates of more than 200 kt day−1 were recorded from the LERZ in nogenic metal emissions have been sampled and studied at many June and early July45, exceeding Kīlauea’s 2014 to 2017 average 6–13 46 volcanoes worldwide (e.g., refs. ), and early studies date back SO2 emission rate (combined summit and ERZ ) of 5.1 ± 0.3 kt 14,15 −1 to the 1960s and 70s (e.g., refs. ). During periods of intense day SO2, by two orders of magnitude. Population exposure to unrest or eruption, volcanic emission rates of metals such as poor air quality (SO2 and PM) during the 2018 LERZ eruption cadmium (Cd), copper (Cu) and zinc (Zn) can be equal to or, in surpassed that observed during the 1983 to early 2018 eruption some cases, orders of magnitude greater than daily anthropogenic episodes at Kīlauea20,47. Further, in terms of both eruption rates emissions from entire regions (e.g., the Mediterranean basin14)or (50–500 m3 s−1, dense rock equivalent)44,48 and erupted volume countries16, and volcanoes are one of the largest natural sources (~1.5 km3 in 94 days)49, the 2018 eruption was 1–2 orders of of many metals17. Some trace metals present in volcanic plumes magnitude larger than any other in the preceding 180 years of 49 can act as nutrients for living organisms at low levels, yet at activity in the LERZ . The lava effusion and SO2 emissions from higher concentrations are categorised by environmental agencies Fissure 8 declined dramatically on the 4 August 201844. as pollutants known to be harmful to health18,19. Basaltic volca- During the 2018 LERZ eruption of Kīlauea, we used ground- noes typically release relatively ash-poor plumes into the based and Unoccupied Aircraft System (UAS) platforms (Sup- troposphere9, exposing both proximal populations (up to a few plementary Note 1; ‘Methods’, Figs. S3, S4) to quantify the major tens of kilometres away, e.g., Kīlauea, Hawai’i, 1983–201820; and trace element compositions of gas and size-segregated PM Masaya, Nicaragua, 1993–present21) and distal populations emitted in the magmatic plume from the main active vent (Fis- thousands of km downwind (e.g., Laki, Iceland22) to sustained sure 8, Fig. 1b, Supplementary Data 1 Tables S7–S9), and the laze high levels of volcanogenic gases (e.g., SO2) and trace metal- plume generated at the ocean entry (Fig. 1c, Supplementary bearing PM. Understanding volcanic metal emissions also pro- Data 1 Tables S11–S13). Here, we quantify element volatility in vides important constraints on the environmental impact of large, the magmatic plume, and demonstrate the consistency of prehistoric basaltic eruptions, including flood basalts23,24. How- Kīlauea’s volatile metal fingerprint across different eruptive per- ever, metal abundance and speciation in volcanic gas and aerosol iods (Supplementary Data 1 Table S10). We also model speciation emissions remain poorly understood. during the oxidation and cooling of Kīlauea’s magmatic plume Basaltic ocean island volcanoes, such as those found on the close to the lava–air interface (Supplementary Data 2 Tables S20– Island of Hawai’i, can produce an additional source of gas and S27) and use these results to decipher the origin of the PM emissions as lava flows reach coastlines and rapidly boil and lava–seawater interaction plume. evaporate seawater, with significant implications for the marine biosphere25. Lava–seawater interactions, which produce acidic Results and discussion ‘laze’ plumes, have occurred throughout Earth’s history, often Element volatility at Kīlauea Volcano. Measured concentrations associated with some of the most dramatic manifestations of of elements in the magmatic plume (Supplementary Data 1 volcanism, such as: when lava flows from continental flood Tables S7–S9) can be used to estimate the relative volatility of basalts reached coastlines (e.g., Columbia River Basalt group26, each element during degassing (i.e., to what degree elements Deccan Traps27); in periods of sub-aerial eruption during ocean degas from magmas50). Emanation coefficients describe the plateau basalt emplacement (e.g., the Kerguelen28, Ontong – degree to which an element is lost during syn-eruptive degassing Java29 31, and Manihiki32,33 Plateaus); and during the early stages at the vent according to: of continental rifting34 (e.g., the North Atlantic Igneous 35 ε ¼ ½À ½ =½ ð Þ Province ). Fragments of silicate material can be generated X i X f X i 1 – – during lava seawater interactions through a fuel coolant-type ½ 36 where X i is the concentration of X in the melt just prior to syn- interaction as seawater invades lava tubes, and during the col- ½ fi lapse of lava deltas37. A major component of laze plumes after eruptive degassing, and X f is the nal degassed concentration of water (~98–99 mol% of the gas phase) is hydrogen chloride (HCl) element X in the melt, respectively (originally defined by Lambert gas38,39, and it has been suggested that HCl emission rates from et al.51). Emanation coefficients can be estimated in several ways, laze plumes at Kīlauea Volcano are comparable to or may exceed including: (1) using enrichment factors and the assumed constant that from coal-fired power plants in the United States38. How- emanation coefficient of Pb from molten basalt52 and; (2) com- ever, despite the hazards and potential impacts of lava ocean paring undegassed and degassed melts (e.g., ref. 53). ½ entry plumes on the biosphere, only a few detailed studies have In this study, X i is calculated by adding the concentration of a been carried out (e.g., refs. 40–42) and relatively little is known degassed element in the magmatic plume (using X/S ratios) to a ½ 50 about their chemistry compared to magmatic plumes. degassed matrix glass composition, i.e., X f (e.g., ref. ; data The 2018 eruption of Kīlauea—a basaltic shield volcano located sources in Supplementary Data 1 Table S14, ‘Methods’). We use in the south–east of the Island of Hawai’i (Fig. 1a)—presented a the calculated ε values to group elements into volatile (ε > 0.001%) rare opportunity to study the emissions of volatile trace metals in and refractory elements (ε < 0.001%; Fig. 2a, b). Within these substantial, genetically related, magmatic and laze plumes. Before groupings, and particularly within the volatile group, there 30 April 2018, the eruptive activity at Kīlauea was relatively stable remains a large amount of variability in ε values. These groupings at two locations: a lava lake within the Halema’uma’u summit were chosen because elements with ε > 0.001% have weighted ash crater (active since 2008), and the Pu′u ′Ō′ōcone and other vents fractions (WAFs) in our plume samples of 5% or less (i.e., they in the East Rift Zone (ERZ), as part of the long-lived Pu′u ′Ō′ō- are predominantly released as gases or non-silicate particles in the Kupianaha eruption of Kīlauea (1983–2018)43.
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