Abstract: 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.

Abstract: 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.

Abstract: Year-round records of the ionic composition of Antarctic aerosol were obtained at the inland Dome C (DC) and coastal Neumayer (NM) sites, with additional observations of black carbon (BC) at NM. Discussions focus on the origin of ammonium in Antarctica. This first Antarctic atmospheric study of several species emitted by biomass burning (BB) indicates that BC and oxalate reach a maximum in October in relation to BB activity in the southern hemisphere. Ammonium reaches a maximum 2 months later, suggesting that BB remains a minor ammonium source there. The ammonium maximum in December coincides with the occurrence of diatom blooms in the austral ocean, suggesting that oceanic ammonia emissions are the main source of ammonium in Antarctica. The ammonium to sulfur-derived biogenic species molar ratio of 0.15 in summer suggests far lower ammonia emissions from the Antarctic oceans than midlatitude southern oceans.