Atmospheric nitrate formation pathways in urban and rural atmosphere of Northeast China: Implications for complicated anthropogenic effects

Effects of human activities on atmospheric nitrate (NO3-) formation remain unclear, though the knowledge is critical for improving atmospheric chemistry models and nitrogen deposition reduction strategies. A potentially useful way to explore this is to compare NO3- oxidation processes in urban and rural atmospheres based upon the oxygen stable isotope composition of NO3- (Delta O-17-NO3-). Here we compared the Delta O-17-NO3- from three-years of daily-based bulk deposition in urban (Shenyang) and forested rural sites (Qingyuan) in northeast China and quantified the relative contributions of different formation pathways based on the SIAR model. Our results showed that the Delta O-17 in Qiangyuan (26.2 +/- 3.3 parts per thousand) is significantly higher (p < 0.001) than in Shenyang (24.0 +/- 4.0 parts per thousand), and significantly higher in winter (Shenyang: 26.1 +/- 6.7 parts per thousand, Qingyuan: 29.6 +/- 2.5 parts per thousand) than in summer (Shenyang: 22.7 +/- 2.9 parts per thousand, Qingyuan: 23.8 +/- 2.4 parts per thousand) in both sites. The lower values in the urban site are linked with conditions that favored a higher relative contribution of nitrogen dioxide reaction with OH pathway (0.760.91) than in rural site (0.47-0.62), which should be induced by different levels of human activities in the two sites. The seasonal variations of Delta O-17-NO3- in both sites are explained by a higher relative contribution of ozonemediated oxidation chemistry and unfavorable conditions for the OH pathway during winter relative to summer, which is affected by human activities and seasonal meteorological condition change. Based on Delta O-17, wintertime conditions led to a contribution of O-3 related pathways (NO3 + DMS/HC and N2O5 hydrolysis) of 0.63 in Qingyuan and 0.42 in Shenyang, while summertime conditions led to 0.15 in Qingyuan and 0.05 in Shenyang. Our comparative study on Delta O-17-NO3- between urban and rural sites reveals different anthropogenic effects on nitrate formation processes on spatial and temporal scales, illustrating different responses of reactive nitrogen chemistry to changes in human activities.