Ammonium in coastal Antarctic aerosol and snow: Role of polar ocean and penguin emissions

Year-round aerosol samples collected in the boundary layer at coastal Antarctic sites (Dumont D'Urville, Neumayer, and Halley) indicate a seasonal cycle of ammonium concentrations with a minimum in winter (April–September). A large intersite difference appears in the summer (November–February) maxima values, from ∼12.5 ng m−3 at Neumayer to 140–230 ng m−3 at Dumont D'Urville. At Dumont D'Urville, ammonium concentrations are the largest ever reported from Antarctic sites, and the large summer maxima are associated with large enrichments with respect to sea salt for potassium and calcium. In addition, seasonal ammonium variations at Dumont D'Urville are in phase with a well-marked seasonal cycle of oxalate concentrations which exhibit maxima of 5–10 ng m−3 in spring and summer and minima of less than 0.5 ng m−3 in winter. Such a composition of aerosols present in the boundary layer at Dumont D'Urville in summer is linked to the presence of a large Adélie penguin population from the end of October to March at the site. Ornithogenic soils (defined as guano-enriched soils), together with the bacterial decomposition of uric acid, are a source of ammonium, oxalate, and cation (such as potassium and calcium) aerosol, in addition to a subsequent large ammonia loss from ornithogenic soils to the atmosphere. The total breeding population of 5 million Adélie penguins widely distributed around the Antarctic continent may emit, at most, some 2.5 × 10−4 Mt of NH3-N during the summer months. In contrast, Halley and Neumayer Stations are far less exposed to penguin colony emissions. At Neumayer, ammonium concentrations peak from January to March and are in phase with the increase of biogenic sulfur species. Here the NH4+/(MSA + nss SO4−) molar ratio is close to 13% in summer aerosol and to 40% in winter aerosol. Using this summer ratio, which may be related to ammonia and sulfur oceanic emissions occurring south of 50°S in summer and estimated DMS emissions in these regions at this time, we derive an upper limit of 0.064 Mt NH3-N emitted per year by the high-latitude Southern Ocean in summer. This study indicates a very limited ammonia neutralization of acidic sulfate aerosols at high southern latitudes, except in the vicinity of ornithogenic soils occupied by large penguin colonies.

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