Seasonal and shorter-term variations in particulate atmospheric nitrate in Baltimore

Fine particle nitrate concentrations were measured at 10-min intervals for approximately 9.5 months beginning on 14 February 2002, at the Baltimore Supersite Ponca St. location using an R&P 8400N semi-continuous monitor. The measurement results were used to characterize seasonal and shorter-term excursions in nitrate concentrations and determine their influence on PM2.5 concentrations. Over the 9.5-month study period, nitrate levels of 1.7±1.6 μg m−3 accounted for 11.4% of the PM2.5 mass. Monthly averages ranged from 0.8 μg m−3 in August to 2.9 μg m−3 in November, and accounted for 4.7–17.3% of monthly PM2.5 mass. Hourly averages, however, were often larger, especially in the colder months, owing to numerous relatively short-term transients, where hourly nitrate concentrations exceeded 5.0 μg m−3. These often occurred along with NOx and ultrafine particle transients during the morning commute hours.A total of 275 short-term transients (31.7% of the total) exceeding 1.0 μg m−3 were identified. These were associated with one of three sets of conditions. The first, most typical (177, i.e. 64.4% of the 275 incidences), is characterized by high NOx typically between 0500 and 0800EST and is attributed to early morning commute traffic activity. The second type occurred during the afternoon due to photochemical activity. The excursions in the afternoon occurred infrequently (only 9.5% of all the observed transients) during the study period and were characterized by less elevated nitrate concentrations than morning and nighttime transients. The third (72, i.e. 26.2% of the 275 transients) occurred at night, typically between 2000EST and 0200EST.Multiple linear regression analysis between nitrate excursions and volume size distributions indicates that particulate nitrate observed is closely related to the near accumulation (0.1–0.2 μm) and droplet modes (0.5–1.0 μm) in the morning hours, and associated with the droplet (0.5–1.0 μm) and coarse modes (1.0–2.5 μm) for nighttime transients, suggesting that processes governing particulate nitrate formation depend on time-of-day.