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 degrees S, 123.3 degrees E, 3233 m), during December 2011 to January 2012. Profiles of NOx mixing ratios of the lower 100m 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 (O-3). 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 O-3 mixing ratios resulting from increased net O-3 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 (F-NOx). During 23 December 2011-12 January 2012, median F-NOx was twice that during the same period in 20092010 due to significantly larger atmospheric turbulence and a slightly stronger snowpack source. A tripling of F-NOx 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 O-3 and associated increase in NO3- photolysis rates. A source of uncertainty in model estimates of F-NOx is the quantum yield of NO3- photolysis in natural snow, which may change over time as the snow ages

Formaldehyde (HCHO) in air, snow and interstitial air at Concordia (East Antarctic plateau) in summer

During the 2011/12 and 2012/13 austral summers, HCHO was investigated for the first time in ambient air, snow, and interstitial air at the Concordia site, located near Dome C on the East Antarctic Plateau, by deploying an Aerolaser AL-4021 analyzer. Snow emission fluxes were estimated from vertical gradients of mixing ratios observed at 1 cm and 1 m above the snow surface as well as in interstitial air a few centimeters below the surface and in air just above the snowpack. Typical flux values range between 1 and 2 × 1012 molecules m−2 s−1 at night and 3 and 5 × 1012 molecules m−2 s−1 at noon. Shading experiments suggest that the photochemical HCHO production in the snowpack at Concordia remains negligible compared to temperature-driven air–snow exchanges. At 1 m above the snow surface, the observed mean mixing ratio of 130 pptv and its diurnal cycle characterized by a slight decrease around noon are quite well reproduced by 1-D simulations that include snow emissions and gas-phase methane oxidation chemistry. Simulations indicate that the gas-phase production from CH4 oxidation largely contributes (66%) to the observed HCHO mixing ratios. In addition, HCHO snow emissions account for ~ 30% at night and ~ 10% at noon to the observed HCHO levels

Study of the unknown HONO daytime source at a European suburban site during the MEGAPOLI summer and winter field campaigns

International audienceNitrous acid measurements were carried out during the MEGAPOLI summer and winter field campaigns at SIRTA observatory in Paris surroundings. Highly variable HONO levels were observed during the campaigns, ranging from 10 ppt to 500 ppt in summer and from 10 ppt to 1.7 ppb in winter. Significant HONO mixing ratios have also been measured during daytime hours, comprised between some tenth of ppt and 200 ppt for the summer campaign and between few ppt and 1 ppb for the winter campaign. Ancillary measurements, such as NOx , O3 , photolysis frequencies, meteorological parameters (pressure, temperature, relative humidity , wind speed and wind direction), black carbon concentration , total aerosol surface area, boundary layer height and soil moisture, were conducted during both campaigns. In addition, for the summer period, OH radical measurements were made with a CIMS (Chemical Ionisation Mass Spectrometer). This large dataset has been used to investigate the HONO budget in a suburban environment. To do so, calculations of HONO concentrations using PhotoStationary State (PSS) approach have been performed, for daytime hours. The comparison of these calculations with measured HONO concentrations revealed an underestimation of the calculations making evident a missing source term for both campaigns. This unknown HONO source exhibits a bell-shaped like average diurnal profile with a maximum around noon of approximately 0.7 ppb h−1 and 0.25 ppb h−1 , during summer and winter respectively. This source is the main HONO source during daytime hours for both campaigns. In both cases, this source shows a slight positive correlation with J (NO2) and the product between J (NO2) and soil moisture. This original approach had, thus, indicated that this missing source is photolytic and might be heterogeneous occurring at ground surface and involving water content available on the ground. Published by Copernicus Publications on behalf of the European Geosciences Union. 2806 V. Michoud et al.: Study of the unknown HONO daytime sourc

Large mixing ratios of atmospheric nitrous acid (HONO) at Concordia (East Antarctic plateau) in summer: a strong source from surface snow?

During the austral summer 2011/2012 atmospheric nitrous acid was investigated for the second time at the Concordia site (75°06' S, 123°33' E) located on the East Antarctic plateau by deploying a long path absorption photometer (LOPAP). Hourly mixing ratios of HONO measured in December 2011/January 2012 (35 ± 5.0 pptv) were similar to those measured in December 2010/January 2011 (30.4 ± 3.5 pptv). The large value of the HONO mixing ratio at the remote Concordia site suggests a local source of HONO in addition to weak production from oxidation of NO by the OH radical. Laboratory experiments demonstrate that surface snow removed from Concordia can produce gas phase HONO at mixing ratios half that of NOx mixing ratio produced in the same experiment at typical temperatures encountered at Concordia in summer. Using these lab data and the emission flux of NOx from snow estimated from the vertical gradient of atmospheric concentrations measured during the campaign, a mean diurnal HONO snow emission ranging between 0.5 and 0.8 × 109 molecules cm−2 s−1 is calculated. Model calculations indicate that, in addition to around 1.2 pptv of HONO produced by the NO oxidation, these HONO snow emissions can only explain 6.5 to 10.5 pptv of HONO in the atmosphere at Concordia. To explain the difference between observed and simulated HONO mixing ratios, tests were done both in the field and at lab to explore the possibility that the presence of HNO4 had biased the measurements of HONO

Oxygen isotope mass balance of atmospheric nitrate at Dome C, East Antarctica, during the OPALE campaign

Variations in the stable oxygen isotope composition of atmospheric nitrate act as novel tools for studying oxidative processes taking place in the troposphere. They provide both qualitative and quantitative constraints on the pathways determining the fate of atmospheric nitrogen oxides (NO + NO₂ = NO_<i>x</i>). The unique and distinctive ¹⁷O excess (Δ¹⁷O = <i>δ</i>¹⁷O − 0.52 × <i>δ</i>¹⁸O) of ozone, which is transferred to NO_<i>x</i> via oxidation, is a particularly useful isotopic fingerprint in studies of NO_<i>x</i> transformations. Constraining the propagation of ¹⁷O excess within the NO_<i>x</i> cycle is critical in polar areas, where there exists the possibility of extending atmospheric investigations to the glacial–interglacial timescale using deep ice core records of nitrate. Here we present measurements of the comprehensive isotopic composition of atmospheric nitrate collected at Dome C (East Antarctic Plateau) during the austral summer of 2011/2012. Nitrate isotope analysis has been here combined for the first time with key precursors involved in nitrate production (NO_<i>x</i>, O₃, OH, HO₂, RO₂, etc.) and direct observations of the transferrable Δ¹⁷O of surface ozone, which was measured at Dome C throughout 2012 using our recently developed analytical approach. Assuming that nitrate is mainly produced in Antarctica in summer through the OH + NO₂ pathway and using concurrent measurements of OH and NO₂, we calculated a Δ¹⁷O signature for nitrate on the order of (21–22 ± 3) ‰. These values are lower than the measured values that ranged between 27 and 31 ‰. This discrepancy between expected and observed Δ¹⁷O(NO₃⁻) values suggests the existence of an unknown process that contributes significantly to the atmospheric nitrate budget over this East Antarctic region. However, systematic errors or false isotopic balance transfer functions are not totally excluded

Measurements of OH and RO₂ radicals at Dome C, East Antarctica

Concentrations of OH radicals and the sum of peroxy radicals, RO2, were measured in the boundary layer for the first time on the East Antarctic Plateau at the Concordia Station (Dome C, 75.10° S, 123.31° E) during the austral summer 2011/2012. The median concentrations of OH and RO2 radicals were 3.1 × 106 molecule cm−3 and 9.9 × 107 molecule cm−3, respectively. These values are comparable to those observed at the South Pole, confirming that the elevated oxidative capacity of the Antarctic atmospheric boundary layer found at the South Pole is not restricted to the South Pole but common over the high Antarctic plateau. At Concordia, the concentration of radicals showed distinct diurnal profiles with the median maximum of 5.2 × 106 molecule cm−3 at 11:00 and the median minimum of 1.1 × 106 molecule cm−3 at 01:00 for OH radicals and 1.7 × 108 molecule cm−3 and 2.5 × 107 molecule cm−3 for RO2 radicals at 13:00 and 23:00, respectively (all times are local times). Concurrent measurements of O3, HONO, NO, NO2, HCHO and H2O2 demonstrated that the major primary source of OH and RO2 radicals at Dome C was the photolysis of HONO, HCHO and H2O2, with the photolysis of HONO contributing ∼75% of total primary radical production. However, photochemical modelling with accounting for all these radical sources overestimates the concentrations of OH and RO2 radicals by a factor of 2 compared to field observations. Neglecting the OH production from HONO in the photochemical modelling results in an underestimation of the concentrations of OH and RO2 radicals by a factor of 2. To explain the observations of radicals in this case an additional source of OH equivalent to about 25% of measured photolysis of HONO is required. Even with a factor of 4 reduction in the concentrations of HONO, the photolysis of HONO represents the major primary radical source at Dome C. Another major factor leading to the large concentration of OH radicals measured at Dome C was large concentrations of NO molecules and fast recycling of peroxy radicals to OH radicals

Intercomparison of peroxy radical instruments at the HELIOS atmospheric simulation chamber

International audiencePeroxy radicals (HO 2 and RO 2 ) are key species in atmospheric chemistry, which together with the hydroxyl radical (OH), are involved in oxidation processes leading to the formation of secondary pollutants such as ozone and organic aerosols. Monitoring these short-lived species during intensive field campaigns and comparing the measured concentrations to box model simulations allow assessing the reliability of chemical mechanisms implemented in atmospheric models. However, ambient measurements of peroxy radicals are still considered challenging and only a few techniques have been used for field measurements. Three complementary instruments capable of ambient measurements of pe roxy radicals have been deployed together at the HELIOS atmospheric simulation chamber (Orléans, France) in October 2018. These instruments rely on the PEroxy Radical Chemical Amplification (PERCA), Laser Induced Fluorescence-Fluorescent Assay by Gas Expansion (LIF-FAGE), and Chemical Ionisation Mass Spectrometry (CIMS) techniques. Several chamber experiments have been conducted under dark and irradiated conditions, including oxidation experiments of dihydrogen, methane, pentene, isoprene, and α-pinene. In this presentation, the agreement between the different instruments will be discussed in the light of supporting measurements of volatile organic compounds and inorganic species (O3, NO, NO2), photolysis frequencies, as well as box modelling of the chamber chemistry

Intercomparison of peroxy radical instruments at the HELIOS atmospheric simulation chamber

International audiencePeroxy radicals (HO 2 and RO 2 ) are key species in atmospheric chemistry, which together with the hydroxyl radical (OH), are involved in oxidation processes leading to the formation of secondary pollutants such as ozone and organic aerosols. Monitoring these short-lived species during intensive field campaigns and comparing the measured concentrations to box model simulations allow assessing the reliability of chemical mechanisms implemented in atmospheric models. However, ambient measurements of peroxy radicals are still considered challenging and only a few techniques have been used for field measurements. Three complementary instruments capable of ambient measurements of pe roxy radicals have been deployed together at the HELIOS atmospheric simulation chamber (Orléans, France) in October 2018. These instruments rely on the PEroxy Radical Chemical Amplification (PERCA), Laser Induced Fluorescence-Fluorescent Assay by Gas Expansion (LIF-FAGE), and Chemical Ionisation Mass Spectrometry (CIMS) techniques. Several chamber experiments have been conducted under dark and irradiated conditions, including oxidation experiments of dihydrogen, methane, pentene, isoprene, and α-pinene. In this presentation, the agreement between the different instruments will be discussed in the light of supporting measurements of volatile organic compounds and inorganic species (O3, NO, NO2), photolysis frequencies, as well as box modelling of the chamber chemistry

Role of Criegee intermediates in the formation of sulfuric acid at a Mediterranean (Cape Corsica) site under influence of biogenic emissions

International audienceReaction of stabilized Criegee intermediates (SCIs) with SO2 was proposed as an additional pathway of gaseous sulfuric acid (H2SO4) formation in the atmosphere, supplementary to the conventional mechanism of H2SO4 production by oxidation of SO2 in reaction with OH radicals. However, because of a large uncertainty in mechanism and rate coefficients for the atmospheric formation and loss reactions of different SCIs, the importance of this additional source is not well established. In this work, we present an estimation of the role of SCIs in H2SO4 formation at a western Mediterranean (Cape Corsica) remote site, where comprehensive field observations including gas-phase H2SO4, OH radicals, SO2, volatile organic compounds (VOCs) and aerosol size distribution measurements were performed in July–August 2013 as a part of the project ChArMEx (Chemistry-Aerosols Mediterranean Experiment). The measurement site was under strong influence of local emissions of biogenic volatile organic compounds, including monoterpenes and isoprene generating SCIs in reactions with ozone, and, hence, presenting an additional source of H2SO4 via SO2 oxidation by the SCIs. Assuming the validity of a steady state between H2SO4 production and its loss by condensation on existing aerosol particles with a unity accommodation coefficient, about 90 % of the H2SO4 formation during the day could be explained by the reaction of SO2 with OH. During the night the oxidation of SO2 by OH radicals was found to contribute only about 10 % to the H2SO4 formation. The accuracy of the derived values for the contribution of OH + SO2 reaction to the H2SO4 formation is limited mostly by a large, at present factor of 2, uncertainty in the OH + SO2 reaction rate coefficient. The contribution of the SO2 oxidation by SCIs to the H2SO4 formation was evaluated using available measurements of unsaturated VOCs and steady-state SCI concentrations estimated by adopting rate coefficients for SCI reactions based on structure–activity relationships (SARs). The estimated concentration of the sum of SCIs was in the range of (1–3) × 103 molec. cm−3. During the day the reaction of SCIs with SO2 was found to account for about 10 % and during the night for about 40 % of the H2SO4 production, closing the H2SO4 budget during the day but leaving unexplained about 50 % of the H2SO4 formation during the night. Despite large uncertainties in used kinetic parameters, these results indicate that the SO2 oxidation by SCIs may represent an important H2SO4 source in VOC-rich environments, especially during nighttime