Using atmospheric chemistry and storm track information to explain the variation of nitrate stable isotopes in precipitation at a site in central Pennsylvania,USA

Stable isotopes of NO₃^? (δ¹⁵N–NO₃^? and δ¹⁸O–NO₃^?) were monitored in precipitation at a central Pennsylvania site during six storm events in 2005 to determine whether information on atmospheric oxidants (e.g., O₃, NO₂, and NO_x), and storm tracks (using the NOAA HYSPLIT model) were capable of explaining observed seasonal and within-storm isotopic variation. Results showed that δ¹⁵N–NO₃^? and δ¹⁸O–NO₃^? in precipitation varied significantly during individual storm events. Seasonally, δ¹⁵N–NO₃^? and δ¹⁸O–NO₃^? in precipitation followed a pattern of depletion during the summer months and enrichment during the winter months. NO₃^? precursor concentrations and atmospheric oxidants were useful for explaining the seasonal and within-storm variation of δ¹⁵N–NO₃^? for all six storm events as evidenced by negative relationships with NO₂:NO_x ratios and ozone (O₃). In comparison, δ¹⁸O–NO₃^? was positively related to O₃ in three dormant season storms, which suggested that the O₃ oxidation pathway was important for producing the high δ¹⁸O–NO₃^? observed in wintertime precipitation. Storm track information was especially useful for describing differences in δ¹⁵N–NO₃^?. Cool-sector storms originating from the E/NE produced slightly negative δ¹⁵N–NO₃^? values characteristic of automobile emissions, whereas warm-sector storms with tracks from the SW/S/SE produced slightly positive δ¹⁵N–NO₃^? values characteristic of coal-fired emissions. Lightning also may have been an important source of atmospheric NO₃^? during two warm-sector thunderstorms. This study showed that (1) information about oxidant levels can be useful to predict the seasonal and within-storm variation of NO₃^? stable isotopes in precipitation, and (2) knowledge of storm tracks (warm-sector versus cool-sector) may be important for determining sources of NO₃^? in wet deposition.