Investigation of the ultraviolet photolysis method for the determination of organic nitrogen in aerosol samples.

The research objective was to adapt the ultraviolet (UV)-photolysis method to determine dissolved organic nitrogen (DON) in aqueous extracts of aerosol samples. DON was assumed to be the difference in total concentration of inorganic nitrogen forms before and after sample irradiation. Using a 2(2) factorial design the authors found that the optimal conversion of urea, amino acids (alanine, aspartic acid, glycine, and serine), and methylamine for a reactor temperature of 44 degrees C occurred at pH 2.0 with a 24-hr irradiance period at concentrations <33 microM of organic nitrogen. Different decomposition mechanisms were evident: the photolysis of amino acids and methylamine released mainly ammonium (NH4+), but urea released a near equimolar ratio of NH4+ and nitrate (NO3-). The method was applied to measure DON in the extracts of aerosol samples from Tampa, FL, over a 32-day sampling period. Average dissolved inorganic (DIN) and DON concentrations in the particulate matter fraction PM10 were 78.1 +/- 29.2 nmol-Nm(-3) and 8.3 +/- 4.9 nmol-Nm(-3), respectively. The ratio between DON and total dissolved nitrogen ([TDN] = DIN + DON) was 10.1 +/- 5.7%, and the majority of the DON (79.1 +/- 18.2%) was found in the fine particulate matter (PM2.5) fraction. The average concentrations of DIN and DON in the PM2.5 fraction were 54.4 +/- 25.6 nmol-Nm(-3) and 6.5 +/- 4.4 nmol-Nm(-3), respectively.