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

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

Arctic contaminants and climate change

International audienceIn a recent Letter1, Ma et al. analysed eight persistent organic pollutants (POPs) at an Arctic monitoring station (Mount Zeppelin, 474 metres above sea level, Svalbard). They identified inclines in the latter parts of the linearly detrended concentration time-series (1993–2009). Their interpretation is that many POPs (besides the more volatile polychlorinated biphenyls and hexachlorobenzene) have become remobilized from Arctic repositories into the atmosphere as a consequence of climate change. However, it should be emphasized that other factors can cause the reported inclines, which reflect nonlinearities (or a degree of curvature) within the data

Tropospheric impacts of volcanic halogen emissions: first simulations of reactive halogen chemistry in the Eyjafjallajökull eruption plume

International audienceVolcanic plumes are regions of high chemical reactivity. Instrumented research aircraft that probed the 2010 Icelandic Eyjafjallajökull eruption plume identified in-plume ozone depletion and reactive halogens (Cl, BrO), the latter also detected by satellite. These measurements add to growing evidence that volcanic plumes support rapid reactive halogen chemistry, with predicted impacts including depletion of atmospheric oxidants and mercury deposition. However, attempts to simulate volcanic plume halogen chemistry and predict impacts are subject to considerable uncertainties. e.g. in rate constants for HOBr reactive uptake (see this session: EGU2013-6076), or in the high-temperature initialisation. Model studies attempting to replicate volcanic plume halogen chemistry are restricted by a paucity of field data that is required both for model tuning and verification, hence reported model 'solutions' are not necessarily unique. To this end, the aircraft, ground-based and satellite studies of the Eyjafjallajökull eruption provide a valuable combination of datasets for improving our understanding of plume chemistry and impacts. Here, PlumeChem simulations of Eyjafjallajökull plume reactive halogen chemistry and impacts are presented and verified by observations for the first time. Observed ozone loss, a function of plume strength and age, is quantitatively reproduced by the model. Magnitudinal agreement to reported downwind BrO and Cl is also shown. The model predicts multi-day impacts, with reactive bromine mainly as BrO, HOBr and BrONO 2 during daytime, and Br2 and BrCl at night. BrO/SO 2 is reduced in more dispersed plumes due to enhanced partitioning to HOBr, of potential interest to satellite studies of BrO downwind of volcanoes. Additional predicted impacts of Eyjafjallajökull volcanic plume halogen chemistry include BrO-mediated depletion of HO x that reduces the rate of SO 2 oxidation to H2SO4, hence the formation of sulphate aerosol. The model predicts NO x is rapidly converted into nitric acid (via BrONO 2). Such HNO 3-formation might contribute towards new particle formation, noting reported very high in-plume particle nucleation rates in Eyjafjallajökull plume. Thus, plume halogen chemistry influences on aerosol formation and growth are emphasized regarding studies of climatic and health impacts of volcanic aerosol. As the plume disperses, in-plume ozone concentrations partially recover due to entrainment of O 3-rich background air. However, the cumulative net impact on ozone depletion continues. Whilst the global tropospheric impact of Eyjafjallajokull is small, up-scaling of the model findings in the context of present day global volcanic degassing and recent historic eruptions indicates potential for significant impacts of global volcanic halogen emissions on tropospheric ozone, particularly during periods of enhanced volcanic activity. Notably, this model-observation study of Eyjafjallajökull plume exhibits contrasts to a related model-observation study that quantified ozone loss in Redoubt volcano eruption plume (Kelly et al., JVGR in press). Meteorological and volcanological causes for these differences in plume halogen evolution (hence impacts) are discussed. This has implications for wider atmospheric modelling efforts to quantify global impacts from volcanic halogen emissions and highlights the useful role of fully-flexible and computationally inexpensive models such as PlumeChem to inform larger (regional or global) model studies regarding model initialisation and particularly near-source plume chemistry

Ozone Depletion in Tropospheric Volcanic Plumes: From Halogen-Poor to Halogen-Rich Emissions

Volcanic halogen emissions to the troposphere undergo a rapid plume chemistry that destroys ozone. Quantifying the impact of volcanic halogens on tropospheric ozone is challenging, only a few observations exist. This study presents measurements of ozone in volcanic plumes from Kīlauea (HI, USA), a low halogen emitter. The results are combined with published data from high halogen emitters (Mt Etna, Italy; Mt Redoubt, AK, USA) to identify controls on plume processes. Ozone was measured during periods of relatively sustained Kīlauea plume exposure, using an Aeroqual instrument deployed alongside Multi-Gas SO2 and H2S sensors. Interferences were accounted for in data post-processing. The volcanic H2S/SO2 molar ratio was quantified as 0.03. At Halema‘uma‘u crater-rim, ozone was close to ambient in the emission plume (at 10 ppmv SO2). Measurements in grounding plume (at 5 ppmv SO2) about 10 km downwind of Pu‘u ‘Ō‘ō showed just slight ozone depletion. These Kīlauea observations contrast with substantial ozone depletion reported at Mt Etna and Mt Redoubt. Analysis of the combined data from these three volcanoes identifies the emitted Br/S as a strong but non-linear control on the rate of ozone depletion. Model simulations of the volcanic plume chemistry highlight that the proportion of HBr converted into reactive bromine is a key control on the efficiency of ozone depletion. This underlines the importance of chemistry in the very near-source plume on the fate and atmospheric impacts of volcanic emissions to the troposphere

A new look at the reactive uptake of HOBr onto acidic aerosols in the troposphere, with application to volcanic plumes and acidified marine aerosol

International audienceThe reactive uptake of HOBr onto halogen-rich aerosols to form Br 2 is a key process enabling the autocatalytic formation of tropospheric BrO with impacts on atmospheric oxidants and mercury deposition. However, experimental data quantifying HOBr reactive uptake on tropospheric aerosols is limited, and reported values vary in magnitude. Here, we combine the reported experimental data into a single framework. By considering the elementary reaction mechanism of HOBr(aq) with Cl − (aq) and H + (aq) as two consecutive bi-molecular reactions rather than a ter-molecular process, we re-evaluate the acid-dependency of the reaction rate. HOBr(g) uptake coefficients are then calculated, reproducing the high uptake coefficient (>0.2) measured on HCl-acidified sea-salt particles and – for the first time – also the lower uptake coefficient (0.01) reported on highly H 2 SO 4-acidified sea-salt particles. Our new HOBr uptake calculations also provide a first explanation for the observed Br − (aq) excess in highly acidified sub-micron sea-salt particles simultaneous to Br − (aq) depletion in less acidic supra-micron particles. Finally, the parameterisation is used to predict HOBr uptake in volcanic plumes in the free troposphere, demonstrating the HOBr uptake coefficient is high (accommodation limited) in the upper troposphere but is reduced by low halogen-solubility (a function of temperature and humidity) in sulphate aerosol at lower altitudes. The study indicates HOBr uptake can readily act to promote multi-day BrO chemistry in volcanic plumes dispersing into the free troposphere, both due to continuous degassing from elevated volcano summits (e.g. Etna) or episodic eruptions (e.g. Eyjafjal-lajokull). However, numerical models that assume the HOBr(aq) reaction kinetics are ter-molecular in acidified sea-salt or volcanic aerosol may overestimate the aqueous-phase reaction rate and HOBr uptake coefficient

Modelling the impacts of a nitrogen pollution event on the biogeochemistry of an Arctic glacier

A highly polluted rain event deposited ammonium and nitrate on Midtre Love´nbreen,Svalbard, European High Arctic, during the melt season in June 1999. Quasi-daily sampling of glacial runoff showed elevated ion concentrations of both ammonium (NH4+) and nitrate (NO3–), collectively dissolved inorganic nitrogen (DIN) in the two supraglacial meltwater flows, but only elevated NO3– in the subglacial outburst. Time-series analysis and flow-chemistry modelling showed that supra- and subglacial assimilation of NH4 + were major impacts of this deposition event. Supraglacial assimilation likely occurred while the pollution-event DIN resided within a/the supraglacial slush layer (estimated DIN half-life 40–50 hours, with the lifetime of NO3– exceeding that of NH4+ by 30%). Potentially, such processes could affect preservation of DIN in melt-influenced ice cores. Subglacial routing of event DIN and its multi-day storage beneath the glacier also enabled significant assimilation of NH4+ to occur here (60% of input), which may have been either released as particulate N later during the melt season, or stored until the following year. Our results complement existing mass-balance approaches to the study of glacial biogeochemistry, show how modelling can enable time-resolved interpretation of process dynamics within the biologically active melt season, and highlight the importance of episodic polluted precipitation events as DIN inputs to Arctic glacial ecosystems

Controlled meteorological (CMET) free balloon profiling of the Arctic atmospheric boundary layer around Spitsbergen compared to ERA-Interim and Arctic System Reanalyses

Observations from CMET (Controlled Meteorological) balloons are analysed to provide insights into tropospheric meteorological conditions (temperature, humidity, wind) around Svalbard, European High Arctic. Five Controlled Meteorological (CMET) balloons were launched from Ny-Ålesund in Svalbard (Spitsbergen) over 5–12 May 2011 and measured vertical atmospheric profiles over coastal areas to both the east and west. One notable CMET flight achieved a suite of 18 continuous soundings that probed the Arctic marine boundary layer (ABL) over a period of more than 10h. Profiles from two CMET flights are compared to model output from ECMWF Era-Interim reanalysis (ERA-I) and to a high-resolution (15km) Arctic System Reanalysis (ASR) product. To the east of Svalbard over sea ice, the CMET observed a stable ABL profile with a temperature inversion that was reproduced by ASR but not captured by ERA-I. In a coastal ice-free region to the west of Svalbard, the CMET observed a stable ABL with strong wind shear. The CMET profiles document increases in ABL temperature and humidity that are broadly reproduced by both ASR and ERA-I. The ASR finds a more stably stratified ABL than observed but captured the wind shear in contrast to ERA-I. Detailed analysis of the coastal CMET-automated soundings identifies small-scale temperature and humidity variations with a low-level flow and provides an estimate of local wind fields. We demonstrate that CMET balloons are a valuable approach for profiling the free atmosphere and boundary layer in remote regions such as the Arctic, where few other in situ observations are available for model validation.ISSN:1680-7375ISSN:1680-736