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

Air–snow transfer of nitrate on the East Antarctic Plateau - Part 1: Isotopic evidence for a photolytically driven dynamic equilibrium in summer

Here we report the measurement of the comprehensive isotopic composition (δ15N, Δ17O and δ18O) of nitrate at the air–snow interface at Dome C, Antarctica (DC, 75°06' S, 123°19' E), and in snow pits along a transect across the East Antarctic Ice Sheet (EAIS) between 66° S and 78° S. In most of the snow pits, nitrate loss (either by physical release or UV photolysis of nitrate) is observed and fractionation constants associated are calculated. Nitrate collected from snow pits on the plateau (snow accumulation rate below 50 kg m−2 a−1) displays average fractionation constants of (−59±10) ‰, (+2.0±1.0) ‰ and (+8.7±2.4)‰ for δ15N, Δ17O and δ18O, respectively. In contrast, snow pits sampled on the coast show distinct isotopic signatures with average fractionation constants of (−16±14) ‰, (−0.2±1.5) ‰ and (+3.1±5.8) ‰, for δ15N, Δ17O and δ18O, respectively. Our observations corroborate that photolysis (associated with a 15N / 14N fractionation constant of the order of –48 ‰ according to Frey et al. (2009) is the dominant nitrate loss process on the East Antarctic Plateau, while on the coast the loss is less pronounced and could involve both physical release and photochemical processes. Year-round isotopic measurements at DC show a~close relationship between the Δ17O of atmospheric nitrate and Δ17O of nitrate in skin layer snow, suggesting a photolytically driven isotopic equilibrium imposed by nitrate recycling at this interface. Atmospheric nitrate deposition may lead to fractionation of the nitrogen isotopes and explain the almost constant shift of the order of 25 ‰ between the δ15N values in the atmospheric and skin layer nitrate at DC. Asymptotic δ15N(NO3−) values calculated for each snow pit are found to be correlated with the inverse of the snow accumulation rate (ln(δ15N as. + 1) = (5.76±0.47) ċ (kg m−2 a−1/ A) + (0.01±0.02)), confirming the strong relationship between the snow accumulation rate and the degree of isotopic fractionation, consistent with previous observations by Freyer et al. (1996). Asymptotic Δ17O(NO3−) values on the plateau are smaller than the values found in the skin layer most likely due to oxygen isotope exchange between the nitrate photoproducts and water molecules from the surrounding ice. However, the apparent fractionation in Δ17O is small, thus allowing the preservation of a portion of the atmospheric signal

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

Isotopic composition of atmospheric nitrate in a tropical marine boundary layer

Long-term observations of the reactive chemical composition of the tropical marine boundary layer (MBL) are rare, despite its crucial role for the chemical stability of the atmosphere. Recent observations of reactive bromine species in the tropical MBL showed unexpectedly high levels that could potentially have an impact on the ozone budget. Uncertainties in the ozone budget are amplified by our poor understanding of the fate of NOx (= NO + NO2), particularly the importance of nighttime chemical NOx sinks. Here, we present year-round observations of the multiisotopic composition of atmospheric nitrate in the tropical MBL at the Cape Verde Atmospheric Observatory. We show that the observed oxygen isotope ratios of nitrate are compatible with nitrate formation chemistry, which includes the BrNO3 sink at a level of ca. 20 ± 10% of nitrate formation pathways. The results also suggest that the N2O5 pathway is a negligible NOx sink in this environment. Observations further indicate a possible link between the NO2/NOx ratio and the nitrogen isotopic content of nitrate in this low NOx environment, possibly reflecting the seasonal change in the photochemical equilibrium among NOx species. This study demonstrates the relevance of using the stable isotopes of oxygen and nitrogen of atmospheric nitrate in association with concentration measurements to identify and constrain chemical processes occurring in the MBL