Assessing the Seasonal Dynamics of Nitrate and Sulfate Aerosols at the South Pole Utilizing Stable Isotopes

Atmospheric nitrate (NO3- = particulate NO3- + gas-phase nitric acid [HNO3]) and sulfate (SO42-) are key molecules that play important roles in numerous atmospheric processes. Here, the seasonal cycles of NO3- and total suspended particulate sulfate (SO4(TSP)2-) were evaluated at the South Pole from aerosol samples collected weekly for approximately 10 months (26 January to 25 October) in 2002 and analyzed for their concentration and isotopic compositions. Aerosol NO3- was largely affected by snowpack emissions in which [NO3-] and delta N-15(NO3-) were highest (49.3 +/- 21.4 ng/m(3), n = 8) and lowest (-47.0 +/- 11.7 parts per thousand, n = 5), respectively, during periods of sunlight in the interior of Antarctica. The seasonal cycle of Delta O-17(NO3-) reflected tropospheric chemistry year-round with lower values observed during sunlight periods and higher values observed during dark periods, reflecting shifts from HOx- to O-3-dominated oxidation chemistry. SO4(TSP)2- concentrations were highest during austral summer and fall (86.7 +/- 73.7 ng/m(3), n = 18) and are indicated to be derived from dimethyl sulfide (DMS) emissions, as delta S-34(SO42-)((TSP)) values (18.5 +/- 1.0 parts per thousand, n = 10) were similar to literature delta S-34(DMS) values. The seasonal cycle of Delta O-17(SO42-)((TSP)) exhibited minima during austral summer (0.9 +/- 0.1 parts per thousand, n = 5) and maxima during austral fall (1.3 +/- 0.3 parts per thousand, n = 6) and austral spring (1.6 +/- 0.1 parts per thousand, n = 5), indicating a shift from HOx- to O-3-dominated chemistry in the atmospheric derived SO42- component. Overall, the budgets of NO3- and SO4(TSP)2- at the South Pole were complex functions of transport, localized chemistry, biological activity, and meteorological conditions, and these results will be important for interpretations of oxyanions in ice core records in the interior of Antarctica.