Florian M. Schwandner

Deposition of reactive nitrogen during the Rocky Mountain Airborne Nitrogen and Sulfur (RoMANS) study.

Increases in reactive nitrogen deposition are a growing concern in the U.S. Rocky Mountain west. The Rocky Mountain Airborne Nitrogen and Sulfur (RoMANS) study was designed to improve understanding of the species and pathways that contribute to nitrogen deposition in Rocky Mountain National Park (RMNP). During two 5-week field campaigns in spring and summer of 2006, the largest contributor to reactive nitrogen deposition in RMNP was found to be wet deposition of ammonium (34% spring and summer), followed by wet deposition of nitrate (24% spring, 28% summer). The third and fourth most important reactive nitrogen deposition pathways were found to be wet deposition of organic nitrogen (17%, 12%) and dry deposition of ammonia (14%, 16%), neither of which is routinely measured by air quality/deposition networks operating in the region. Total reactive nitrogen deposition during the spring campaign was determined to be 0.45 kg ha(-1) and more than doubled to 0.95 kg ha(-1) during the summer campaign.

High-sensitivity microchip electrophoresis determination of inorganic anions and oxalate in atmospheric aerosols with adjustable selectivity and conductivity detection

A sensitive and selective separation of common anionic constituents of atmospheric aerosols, sulfate, nitrate, chloride, and oxalate, is presented using microchip electrophoresis. The optimized separation is achieved in under 1 min and at low background electrolyte ionic strength (2.9 mM) by combining a metal-binding electrolyte anion (17 mM picolinic acid), a sulfate-binding electrolyte cation (19 mM HEPBS), a zwitterionic surfactant with affinity towards weakly solvated anions (19 mM N-tetradecyl,N,N-dimethyl-3-ammonio-1-propansulfonate), and operation in counter-electroosmotic flow (EOF) mode. The separation is performed at pH 4.7, permitting pH manipulation of oxalates mobility. The majority of low-concentration organic acids are not observed at these conditions, allowing for rapid subsequent injections without the presence of interfering peaks. Because the mobilities of sulfate, nitrate, and oxalate are independently controlled, other minor constituents of aerosols can be analyzed, including nitrite, fluoride, and formate if desired using similar separation conditions. Contact conductivity detection is utilized, and the limit of detection for oxalate (S/N=3) is 180 nM without stacking. Sensitivity can be increased with field-amplified sample stacking by injecting from dilute electrolyte with a detection limit of 19 nM achieved. The high-sensitivity, counter-EOF operation, and short analysis time make this separation well-suited to continuous online monitoring of aerosol composition.