Is there an ozone depletion in volcanic plumes?

<p>Volcanic plumes are known to contain reactive halogen species, especially bromine oxide. Therefore, local ozone (O<sub>3</sub>) depletion (OD) is expected inside volcanic plumes. This OD has been measured in several field studies and is also found in several modelling studies. Recently, in order to quantify O<sub>3</sub> mixing ratios in volcanic plumes, mainly UV absorption monitors have been used as these have become the standard technique for ambient O<sub>3</sub> monitoring. However, these instruments show a large positive interference with sulphur dioxide (SO<sub>2</sub>). In fact, these instruments are approximately only 100 times more sensitive to O<sub>3</sub> than to SO<sub>2</sub>. This poses a significant problem for volcanic measurements since SO<sub>2 </sub>mixing ratios can exceed O<sub>3 </sub>mixing ratios by factors of 1000 or more. Thus, laborious SO<sub>2</sub> filtering introducing further problems, as e.g. humidity dependence, needed to be employed.</p><p>In this work simultaneous O<sub>3</sub> measurements inside a fumarole were conducted with a compact and mobile (backpack-size, ~10kg) chemiluminescence (CL) ozone monitor and a conventional UV absorption monitor at the summit of Mt Etna volcano, Italy. In parallel, SO<sub>2</sub> and CO<sub>2</sub> measurements were carried out with a MultiGAS-instrument. The CL monitor was used since no interference from trace gases contained in volcanic plumes is expected. Indeed, in this first field study inside a fumarole, we observed no significant interference with volcanic SO<sub>2 </sub>concentrations for the CL monitor. Under field conditions the CL monitor’s detection limit was determined to be ~1 ppb (1σ) at an integration time of 1 second.</p><p>Additionally, a rough calculation to estimate the expected OD in volcanic plumes was made. Contrary to popular belief, this calculation suggests for typical bromine oxide concentrations no significant (i.e. <1%) reactive halogen catalysed O<sub>3</sub>-loss in volcanic plumes.</p>

Separating tropospheric and stratospheric BrO columns over the Arctic using TROPOMI data

<p>Halogen radicals can drastically alter the atmospheric chemistry. In the polar regions, this is made evident, among others, by the almost complete destruction of boundary layer ozone during polar springs. These recurrent episodes of catalytic ozone depletion, referred to as Ozone Depletion Events (ODE), are caused by enhanced concentrations of reactive bromine compounds. The proposed mechanism by which these are released into the atmosphere is called bromine explosions -  reactive bromine is formed autocatalytically from the condensed phase. Enhanced bromine oxide concentrations have been observed by ground-based measurements as well as from aircraft and satellite, where the large spatial coverage allows to study the spatial extent of the phenomenon and its correlation with meteorological data as well as climate change.</p><p>The spatial resolution of S-5P/TROPOMI of 3,5 km x 7 km allows improved localization of these events and to resolve finer structures compared to previous satellite measurements. Together with the better than daily coverage over the polar regions, this allows investigations of the spatio-temporal variability of enhanced BrO levels and their relation to different possible bromine sources and release mechanisms.</p><p>We present tropospheric BrO column densities retrieved from TROPOMI data using Differential Optical Absorption Spectroscopy (DOAS). Building on methods from statistical data analysis and machine learning, we separate the tropospheric partial column from the total column using solely data (BrO, O3 and NO2) measured by satellite. The observations are discussed with regards to sea ice coverage and meteorological influences.</p>

Tropospheric trace gas slant column densities derived from MAX-DOAS measurements on pacific transit cruises of the German research vessel Sonne in 2019

<p>Between January and July 2019 the German research vessel Sonne was on several cruises in the Pacific, crossing the ocean from Suva, Fiji to Manzanillo, Mexico in February (SO267-2) and from Vancouver, Canada to Singapore in June (SO268-3). A Multi Axis-Differential Optical Absorption Spectroscopy (MAX-DOAS) instrument was in operation outside the national exclusive economic zone (EEZ) regions allowing for profile measurements of trace gases and aerosol on the open seas under background conditions. Both transit cruises cover a wide range of marine biomes and climatic zones affecting the trace gas and particle composition of the atmosphere.</p><p>Ship measurements of Nitrogen Dioxide (NO<sub>2</sub>) and Sulphur Dioxide (SO<sub>2</sub>) are especially important for the validation of satellite measurements as the remote Pacific Ocean is typically used as a reference region. Off the coast of North America an enhanced signal of halogen species, i.e. bromine oxide (BrO) and iodine oxide (IO) was observed. The abundance of formaldehyde (HCHO) and its interrelation with the marine bio-activity could also be observed.</p>

Atmospheric nitrogen oxides (NO and NO₂) at Dome C, East Antarctica, during the OPALE campaign

Mixing ratios of the atmospheric nitrogen oxides NO and NO2 were measured as part of the OPALE (Oxidant Production in Antarctic Lands & Export) campaign at Dome C, East Antarctica (75.1° S, 123.3° E, 3233 m), during December 2011 to January 2012. Profiles of NOx mixing ratios of the lower 100 m of the atmosphere confirm that, in contrast to the South Pole, air chemistry at Dome C is strongly influenced by large diurnal cycles in solar irradiance and a sudden collapse of the atmospheric boundary layer in the early evening. Depth profiles of mixing ratios in firn air suggest that the upper snowpack at Dome C holds a significant reservoir of photolytically produced NO2 and is a sink of gas-phase ozone (O3). First-time observations of bromine oxide (BrO) at Dome C show that mixing ratios of BrO near the ground are low, certainly less than 5 pptv, with higher levels in the free troposphere. Assuming steady state, observed mixing ratios of BrO and RO2 radicals are too low to explain the large NO2 : NO ratios found in ambient air, possibly indicating the existence of an unknown process contributing to the atmospheric chemistry of reactive nitrogen above the Antarctic Plateau. During 2011–2012, NOx mixing ratios and flux were larger than in 2009–2010, consistent with also larger surface O3 mixing ratios resulting from increased net O3 production. Large NOx mixing ratios at Dome C arise from a combination of continuous sunlight, shallow mixing height and significant NOx emissions by surface snow (FNOx). During 23 December 2011–12 January 2012, median FNOx was twice that during the same period in 2009–2010 due to significantly larger atmospheric turbulence and a slightly stronger snowpack source. A tripling of FNOx in December 2011 was largely due to changes in snowpack source strength caused primarily by changes in NO3− concentrations in the snow skin layer, and only to a secondary order by decrease of total column O3 and associated increase in NO3− photolysis rates. A source of uncertainty in model estimates of FNOx is the quantum yield of NO3− photolysis in natural snow, which may change over time as the snow ages.

Active and widespread halogen chemistry in the tropical and subtropical free troposphere

Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O3), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O3 and methane (CH4) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10°N to 40°S), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric O3. The observed BrO concentrations increase strongly with altitude (∼3.4 pptv at 13.5 km), and are 2–4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5–6.4 pptv total inorganic bromine (Bry), or model overestimated Bry wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Bry source from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. The halogen-catalyzed loss of tropospheric O3 needs to be considered when estimating past and future ozone radiative effects.

Chemical ozone loss and ozone mini-hole event during the Arctic winter 2010/2011 as observed by SCIAMACHY and GOME-2

Record breaking loss of ozone (O3) in the Arctic stratosphere has been reported in winter–spring 2010/2011. We examine in detail the composition and transformations occurring in the Arctic polar vortex using total column and vertical profile data products for O3, bromine oxide (BrO), nitrogen dioxide (NO2), chlorine dioxide (OClO), and polar stratospheric clouds (PSC) retrieved from measurements made by SCIAMACHY (Scanning Imaging Absorption SpectroMeter for Atmospheric CHartography) on-board Envisat (Environmental Satellite), as well as total column ozone amount, retrieved from the measurements of GOME-2 (Global Ozone Monitoring Experiment) on MetOp-A (Meteorological Experimental Satellite). Similarly we use the retrieved data from DOAS (Differential Optical Absorption Spectroscopy) measurements made in Ny-Ålesund (78.55° N, 11.55° E). A chemical transport model (CTM) has been used to relate and compare Arctic winter–spring conditions in 2011 with those in the previous year. In late winter–spring 2010/2011 the chemical ozone loss in the polar vortex derived from SCIAMACHY observations confirms findings reported elsewhere. More than 70% of O3 was depleted by halogen catalytic cycles between the 425 and 525 K isentropic surfaces, i.e. in the altitude range ~16–20 km. In contrast, during the same period in the previous winter 2009/2010, a typical warm Arctic winter, only slightly more than 20% depletion occurred below 20 km, while 40% of O3 was removed above the 575 K isentrope (~23 km). This loss above 575 K is explained by the catalytic destruction by NOx descending from the mesosphere. In both Arctic winters 2009/2010 and 2010/2011, calculated O3 losses from the CTM are in good agreement to our observations and other model studies. The mid-winter 2011 conditions, prior to the catalytic cycles being fully effective, are also investigated. Surprisingly, a significant loss of O3 around 60%, previously not discussed in detail, is observed in mid-January 2011 below 500 K (~19 km) and sustained for approximately 1 week. The low O3 region had an exceptionally large spatial extent. The situation was caused by two independently evolving tropopause elevations over the Asian continent. Induced adiabatic cooling of the stratosphere favoured the formation of PSC, increased the amount of active chlorine for a short time, and potentially contributed to higher polar ozone loss later in spring.

Atmospheric mercury over sea ice during the OASIS-2009 campaign

Measurements of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate mercury (PHg) were collected on the Beaufort Sea ice near Barrow, Alaska, in March 2009 as part of the Ocean-Atmosphere-Sea Ice-Snowpack (OASIS) and OASIS-Canada International Polar Year programmes. These results represent the first atmospheric mercury speciation measurements collected on the sea ice. Concentrations of PHg averaged 393.5 pg m−3 (range 47.1–900.1 pg m−3) and RGM concentrations averaged 30.1 pg m−3 (range 3.5–105.4 pg m−3) during the two-week-long study. The mean concentration of GEM during the study was 0.59 ng m−3 (range 0.01–1.51 ng m−3) and was depleted compared to annual Arctic ambient boundary layer concentrations. It is shown that when ozone (O3) and bromine oxide (BrO) chemistry were active there is a positive linear relationship between GEM and O3, a negative one between PHg and O3, a positive correlation between RGM and BrO, and none between RGM and O3. For the first time, GEM was measured simultaneously over the tundra and the sea ice. The results show a significant difference in the magnitude of the emission of GEM from the two locations, with significantly higher emission over the tundra. Elevated chloride levels in snow over sea ice are proposed to be the cause of lower GEM emissions over the sea ice because chloride has been shown to suppress photoreduction processes of RGM to GEM in snow. Since the snowpack on sea ice retains more mercury than inland snow, current models of the Arctic mercury cycle may greatly underestimate atmospheric deposition fluxes because they are based predominantly on land-based measurements. Land-based measurements of atmospheric mercury deposition may also underestimate the impacts of sea ice changes on the mercury cycle in the Arctic. The predicted changes in sea ice conditions and a more saline future snowpack in the Arctic could enhance retention of atmospherically deposited mercury and increase the amount of mercury entering the Arctic Ocean and coastal ecosystems.