Observation and modelling of ozone-destructive halogen chemistry in a passively degassing volcanic plume

Acknowledgements. As well as the financial support noted below, the authors would like to acknowledge the following. Computer modelling benefited from access to IDRIS HPC resources (GENCI allocation A007017141) and the IPSL mesoscale computing cen- tre (CICLAD: Calcul Intensif pour le CLimat, l’Atmosphère et la Dynamique). Aircraft measurements were carried out within the Global Mercury Observation System project (GMOS; http://www. gmos.eu, last access: 12 August 2021), and we acknowledge the contribution of the GMOS teams of CNR IIA, Italy, and Helmholtz- Zentrum Geesthacht, Germany. GMOS was financially supported by the European Union within the seventh framework programme (FP-7; project ENV.2010.4.1.3-2). The authors would like to thank Louis Marelle and Jennie Thomas for their assistance with the model development. The model presented in this paper is a devel- opment of work undertaken as part of Luke Surl’s PhD, which was funded by the UK’s Natural Environment Research Council and su- pervised by Deanna Donohoue and Roland von Glasow. The authors would like to thank the two anonymous referees for suggesting var- ious improvements to this paper. Financial support. This paper is a result of a project that has re- ceived funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement no. 800062 as well as ANR Projet de Recherche Collaborative VOLC-HAL-CLIM (Volcanic Halogens: from Deep Earth to Atmospheric Impacts), ANR-18-CE01-0018.Peer reviewedPublisher PD

On bromine, nitrogen oxides and ozone depletion in the tropospheric plume of Erebus volcano (Antarctica)

International audienceSince the discovery of bromine oxide (BrO) in volcanic emissions, there has been speculation concerning its role in chemical evolution and notably ozone depletion in volcanic plumes. We report the first measurements using Differential Optical Absorption Spectroscopy (DOAS) of BrO in the tropospheric plume of the persistently degassing Erebus volcano (Antarctica). These are the first observations pertaining to emissions from an alkaline phonolitic magma. The observed BrO/SO2 ratio of 2.5 x 10-4 is similar to that measured at andesitic arc volcanoes. The high abundance of BrO is consistent with high abundances of F and Cl relative to sulfur in the Erebus plume. Our estimations of HBr flux and BrO production rate suggest that reactive bromine chemistry can explain a 35% loss of tropospheric O3 observed in the Erebus plume at approximately 30 km from source (Oppenheimer et al., 2010). Erebus also has a permanent lava lake, which could result in generation of NOx by thermal fixation of atmospheric N2 at the hot lava surface. Any NOx emission could play a potent role in reactive bromine chemistry. However, the presence of NO2 could not be detected in the plume, about 400 m above the lake, in our DOAS observations of 2005. Nor could we reproduce spectroscopic retrievals that reportedly identified NO2 in DOAS observations from 2003 made of the Erebus plume (Oppenheimer et al., 2005). Based on the NO2 detection limit of our analysis, we can state an upper limit of the NO2/SO2 ratio of ≤ 0.012, an order of magnitude lower than previously reported. Our new result supports a rapid oxidation of NOx in the young plume and is more consistent with measurements of NOy species measured using an instrumented aircraft flying in the plume. Model simulations, tuned for Erebus, were performed to reproduce the BrO/SO2 observed in the young plume and to investigate the impact of NOx emissions at source on the subsequent formation of BrO in the plume. They support our hypothesis of rapid conversion of NOx to NOy in the vicinity of the lava lake. This study thus places new constraints on the interaction between reactive nitrogen and bromine species in volcanic plumes, and its effects on ozone

Measurements by Controlled Meteorological Balloons in Coastal Areas of Antarctica

An experiment applying controlled meteorological (CMET) balloons near the coast of Dronning Maud Land, Antarctica, in January 2013 is described. Two balloons were airborne for 60 and 106 hours with trajectory lengths of 885.8 km and 2367.4 km, respectively. The balloons carried out multiple controlled soundings on the atmospheric pressure, temperature and humidity up to 3.3 km. Wind speed and direction were derived from the balloon drift. Observations were compared with radiosonde sounding profiles from the Halley Research Station, and applied in evaluating simulations carried out with the weather research and forecasting (WRF) mesoscale atmospheric model. The most interesting feature detected by the CMET balloons was a mesoscale anticyclone over the Weddell Sea and the coastal zone, which was reproduced by the WRF model with reduced intensity. The modelled wind speed was up to 10 m s-1 slower and the relative humidity was 20-40% higher than the observed values. However, over the study period the WRF results generally agreed with the observations. The results suggest that CMET balloons could be an interesting supplement to Antarctic atmospheric observations, particularly in the free troposphere

Advances in Bromine Speciation in Volcanic Plumes

Volcanoes are a significant halogen source to the atmosphere. After water, carbon dioxide and sulfur compounds, halogens are often the most abundant gases in volcanic plumes. In the past, less attention was given to the heavy halogens bromine and iodine. However, the discovery of bromine monoxide (BrO) in volcanic plumes led to new interest especially in volcanic bromine chemistry and its impact on atmospheric processes. The BrO detection came along with advances in volcanic remote sensing techniques, in particular, robust DOAS applications and the possibility of continuous measurements by automated instruments located at safe distances from the volcano. As one of the consequences, the volcanic community developed an increased interest to use BrO/SO2 ratios as a potential tracer of volcanic activity. BrO is a secondary volcanic gas, but the only bromine species in volcanic plumes, which has been measured by remote sensing techniques today. For a better understanding on bromine chemistry in volcanic plumes and to gain information on the original amount of emitted bromine by only measuring BrO, additional techniques were developed (alkaline traps, diffusion denuders) and adapted for drone-based sampling to determine further gaseous bromine species (i.e. Br2, HBr, HOBr, interhalogens) at various plume ages. Additionally models of plume-atmospheric chemistry were developed to help the interpretation of field-measurements. Model studies simulating plume conditions indicated that a complex atmospheric chemistry mechanism transforms emitted HBr into BrO and other reactive bromine species such as BrOH, Br2, BrCl, BrONO2 or BrNO2. To reproduce the very rapid formation of BrO observed in volcanic plumes, the volcanic emission input to the (low-temperature) plume chemistry models also needs to consider the high-temperature near-vent plume conditions, as represented by thermodynamic models. The formation of BrO and other reactive bromine species depend not only on the amount of bromine emitted but also on plume mixing processes, relative humidity, and aerosol particle acidity. However, uncertainties remain in the validation of the plume chemistry models by a lack of field-measurements. This review provides a comprehensive summary on volcanic bromine data of the last 15 years achieved from established and cutting edge measurement techniques as well as their treatment and interpretation in recent model experiments. It points out controversially discussed relation of bromine degassing to volcanic activity and puts a light on remaining uncertainties

Insights into volcanic hazards and plume chemistry from multi-parameter observations: the eruptions of Fimmvörðuháls and Eyjafjallajökull (2010) and Holuhraun (2014–2015)

The eruptions of Eyjafjallajökull volcano in 2010 (including its initial effusive phase at Fimmvörðuháls and its later explosive phase from the central volcano) and Bárðarbunga volcano in 2014–2015 (at Holuhraun) were widely reported. Here, we report on complementary, interdisciplinary observations made of the eruptive gases and lavas that shed light on the processes and atmospheric impacts of the eruptions, and afford an intercomparison of contrasting eruptive styles and hazards. We find that (i) consistent with other authors, there are substantial differences in the gas composition between the eruptions; namely that the deeper stored Eyjafjallajökull magmas led to greater enrichment in Cl relative to S; (ii) lava field SO2 degassing was measured to be 5–20% of the total emissions during Holuhraun, and the lava emissions were enriched in Cl at both fissure eruptions—particularly Fimmvörðuháls; and (iii) BrO is produced in Icelandic plumes in spite of the low UV levels

Spatial and Temporal Variations in SO 2 and PM 2.5 Levels Around Kīlauea Volcano, Hawai'i During 2007–2018

Among the hazards posed by volcanoes are the emissions of gases and particles that can affect air quality and damage agriculture and infrastructure. A recent intense episode of volcanic degassing associated with severe impacts on air quality accompanied the 2018 lower East Rift Zone (LERZ) eruption of Kīlauea volcano, Hawai'i. This resulted in a major increase in gas emission rates with respect to usual emission values for this volcano, along with a shift in the source of the dominant plume to a populated area on the lower flank of the volcano. This led to reduced air quality in downwind communities. We analyse open-access data from the permanent air quality monitoring networks operated by the Hawai'i Department of Health (HDOH) and National Park Service (NPS), and report on measurements of atmospheric sulfur dioxide (SO2) between 2007 and 2018 and PM2.5 (aerosol particulate matter with diameter <2.5 μm) between 2010 and 2018. Additional air quality data were collected through a community-operated network of low-cost PM2.5 sensors during the 2018 LERZ eruption. From 2007 to 2018 the two most significant escalations in Kīlauea's volcanic emissions were: the summit eruption that began in 2008 (Kīlauea emissions averaged 5–6 kt/day SO2 from 2008 until summit activity decreased in May 2018) and the LERZ eruption in 2018 when SO2 emission rates reached a monthly average of 200 kt/day during June. In this paper we focus on characterizing the airborne pollutants arising from the 2018 LERZ eruption and the spatial distribution and severity of volcanic air pollution events across the Island of Hawai'i. The LERZ eruption caused the most frequent and severe exceedances of the Environmental Protection Agency (EPA) PM2.5 air quality threshold (35 μg/m3 as a daily average) in Hawai'i in the period 2010–2018. In Kona, for example, the maximum 24-h-mean mass concentration of PM2.5 was recorded as 59 μg/m3 on the twenty-ninth of May 2018, which was one of eight recorded exceedances of the EPA air quality threshold during the 2018 LERZ eruption, where there had been no exceedances in the previous 8 years as measured by the HDOH and NPS networks. SO2 air pollution during the LERZ eruption was most severe in communities in the south and west of the island, as measured by selected HDOH and NPS stations in this study, with a maximum 24-h-mean mass concentration of 728 μg/m3 recorded in Ocean View (100 km west of the LERZ emission source) in May 2018. Data from the low-cost sensor network correlated well with data from the HDOH PM2.5 instruments, confirming that these low-cost sensors provide a robust means to augment reference-grade instrument networks

Observed in-plume gaseous elemental mercury depletion suggests significant mercury scavenging by volcanic aerosols

Terrestrial volcanism is known to emit mercury (Hg) into the atmosphere. However, despite many years of investigation, its net impact on the atmospheric Hg budget remains insufficiently constrained, in part because the transformations of Hg in volcanic plumes as they age and mix with background air are poorly understood. Here we report the observation of complete gaseous elemental mercury (GEM) depletion events in dilute and moderately aged (&amp; SIM;3-7 hours) volcanic plumes from Piton de la Fournaise on Reunion Island. While it has been suggested that co-emitted bromine could, once photochemically activated, deplete GEM in a volcanic plume, we measured low bromine concentrations in both the gas- and particle-phase and observed complete GEM depletion even before sunrise, ruling out a leading role of bromine chemistry here. Instead, we hypothesize that the GEM depletions were mainly caused by gas-particle interactions with sulfate-rich volcanic particles (mostly of submicron size), abundantly present in the dilute plume. We consider heterogeneous GEM oxidation and GEM uptake by particles as plausible manifestations of such a process and derive empirical rate constants. By extrapolation, we estimate that volcanic aerosols may scavenge 210 Mg y(-1) (67-480 Mg y(-1)) of Hg from the atmosphere globally, acting effectively as atmospheric mercury sink. While this estimate is subject to large uncertainties, it highlights that Hg transformations in aging volcanic plumes must be better understood to determine the net impact of volcanism on the atmospheric Hg budget and Hg deposition pathways

Un voyage dans des nuages tourbillonnants de gaz et de particules

National audienceLa nocivité des panaches volcaniques est bien connue, tout comme l'impact climatique des émissions de soufre. Maisles volcans émettent également des halogènes dont les impacts atmosphériques sont en cours d’investigation grâce auxrecherches inter-laboratoires

Halogen Chemistry in Volcanic Plumes (Invited)

International audienceVolcanoes release vast amounts of gases and particles in the atmosphere. Volcanic halogens (HF, HCl, HBr, HI) are co-emitted alongside SO2, and observations show rapid formation of BrO and OClO in the plume as it disperses into the troposphere. The development of 1D and Box models (e.g. PlumeChem) that simulate volcanic plume halogen chemistry aims to characterise how volcanic reactive halogens form and quantify their atmospheric impacts. Following recent advances, these models can broadly reproduce the observed downwind BrO/SO2 ratios using "bromine-explosion" chemistry schemes, provided they use a "high-temperature initialisation" to inject radicals (OH, Cl, Br and possibly NOx) which "kick-start" the low-temperature chemistry cycles that convert HBr into reactive bromine (initially as Br2). The modelled rise in BrO/SO2 and subsequent plateau/decline as the plume disperses downwind reflects cycling between reactive bromine, particularly Br-BrO, and BrO-HOBr-BrONO2. BrCl is produced when aerosol becomes HBr-depleted. Recent model simulations suggest this mechanism for reactive chlorine formation can broadly account for OClO/SO2 reported at Mt Etna. Predicted impacts of volcanic reactive halogen chemistry include the formation of HNO3 from NOx and depletion of ozone. This concurs with HNO3 widely reported in volcanic plumes (although the source of NOx remains under question), as well as observations of ozone depletion reported in plumes from several volcanoes (Mt Redoubt, Mt Etna, Eyjafjallajokull). The plume chemistry can transform mercury into more easily deposited and potentially toxic forms, for which observations are limited. Recent incorporation of volcanic halogen chemistry in a 3D regional model of degassing from Ambrym (Vanuatu) also predicts how halogen chemistry causes depletion of OH to lengthen the SO2 lifetime, and highlights the potential for halogen transport from the troposphere to the stratosphere. However, the model parameter-space is vast and only partially constrained by available observations. Reactions on aerosol are a key driver of the chemistry and are affected by uncertainties in both the HOBr reactive uptake coefficient and the aerosol surface area. Recent work has explored the reactive uptake of HOBr on sulfate-rich aerosol, whilst field-measurements at Mt Etna have aimed to quantify the size-resolved primary aerosol emission, towards improving model representations of this highly non-linear volcanic plume halogen chemistry

Halogen Chemistry in Volcanic Plumes (Invited)

International audienceVolcanoes release vast amounts of gases and particles in the atmosphere. Volcanic halogens (HF, HCl, HBr, HI) are co-emitted alongside SO2, and observations show rapid formation of BrO and OClO in the plume as it disperses into the troposphere. The development of 1D and Box models (e.g. PlumeChem) that simulate volcanic plume halogen chemistry aims to characterise how volcanic reactive halogens form and quantify their atmospheric impacts. Following recent advances, these models can broadly reproduce the observed downwind BrO/SO2 ratios using "bromine-explosion" chemistry schemes, provided they use a "high-temperature initialisation" to inject radicals (OH, Cl, Br and possibly NOx) which "kick-start" the low-temperature chemistry cycles that convert HBr into reactive bromine (initially as Br2). The modelled rise in BrO/SO2 and subsequent plateau/decline as the plume disperses downwind reflects cycling between reactive bromine, particularly Br-BrO, and BrO-HOBr-BrONO2. BrCl is produced when aerosol becomes HBr-depleted. Recent model simulations suggest this mechanism for reactive chlorine formation can broadly account for OClO/SO2 reported at Mt Etna. Predicted impacts of volcanic reactive halogen chemistry include the formation of HNO3 from NOx and depletion of ozone. This concurs with HNO3 widely reported in volcanic plumes (although the source of NOx remains under question), as well as observations of ozone depletion reported in plumes from several volcanoes (Mt Redoubt, Mt Etna, Eyjafjallajokull). The plume chemistry can transform mercury into more easily deposited and potentially toxic forms, for which observations are limited. Recent incorporation of volcanic halogen chemistry in a 3D regional model of degassing from Ambrym (Vanuatu) also predicts how halogen chemistry causes depletion of OH to lengthen the SO2 lifetime, and highlights the potential for halogen transport from the troposphere to the stratosphere. However, the model parameter-space is vast and only partially constrained by available observations. Reactions on aerosol are a key driver of the chemistry and are affected by uncertainties in both the HOBr reactive uptake coefficient and the aerosol surface area. Recent work has explored the reactive uptake of HOBr on sulfate-rich aerosol, whilst field-measurements at Mt Etna have aimed to quantify the size-resolved primary aerosol emission, towards improving model representations of this highly non-linear volcanic plume halogen chemistry