Changes in nitrate accumulation mechanisms as PM2.5 levels increase on the North China Plain: A perspective from the dual isotopic compositions of nitrate.

ABSTRACT

Nitrate (NO3-) has become recognized as the most important water-soluble ion in fine particulate (PM2.5), and has been proposed as a driving factor for regional haze formation. However, nitrate formation mechanisms are still poorly understood. In this study, PM2.5 samples were collected from September 2017 to August 2018 in Shijiazhuang, a city located on the North China Plain, and NO3-concentration, δ18O-NO3- and δ15N-NO3- values in PM2.5 were analyzed. NO3- concentrations increased as PM2.5 levels increased during both polluted and non-polluted days over the entire year. δ18O-NO3- values during cold months (63.5-103‰) were higher than those during warm months (50.3-85.4‰), these results suggested that the nitrate formation pathways shifted from the NO2 + OH (POH) in warm months to the N2O5 + H2O (PN2O5) and NO3 + VOCs (PNO3) pathways in cold months. Especially during cold months, δ18O-NO3- values increased from 65.2-79.9‰ to 80.7-96.2‰ when PM2.5 increased from ∼25 to >100 µg/m3, but when PM2.5 > 100 µg/m3, there were relatively small variations in δ18O-NO3-. These results suggested that nitrate formation pathways changed from POH to PN2O5 and PNO3 pathways when PM2.5 < 100 µg/m3, but that PN2O5 and PNO3 dominated nitrate production when PM2.5 > 100 µg/m3. Higher δ15N-NO3- values in warm months (-11.8-13.8‰) than in cold months (-0.7-22.6‰) may be attributed to differences in NOx emission sources and nitrogen isotopic fractionation among NOx and NO3-. These results provide information on the dual isotopic compositions of nitrate to understand nitrate formation pathways under different PM2.5 levels.