Monthly variations in nitrogen isotopes of ammonium and nitrate in wet deposition at Guangzhou, south China

Monthly nitrogen isotopes of ammonium and nitrate in wet deposition in the city of Guangzhou, and the causes of their variability, are reported in this paper. Nitrate δ15N showed nearly constant values around zero in the dry season (October to April), but oscillating values from negative to positive in the rainy season (May to September). By contrast, ammonium δ15N displayed lower values during the rainy season than in the dry season. The rural area north of the city was considered as the prominent source of ammonium and nitrate in spring and early summer (May and June), as suggested by their concurrent negative isotopic trends and higher NH4+/NO3− ratios. From July to September, different dominating sources from the city, i.e., fossil fuel combustion for nitrate, and sewage and waste emission for ammonium, caused disparate δ15N trends of the two species, showing positive nitrate δ15N, but still negative ammonium δ15N. During the cool dry season, the high values of ammonium δ15N and concurrently low NH4+/NO3− ratios suggested the decrease in NH3 volatilization and relatively important thermogenic origin of ammonium, but the intermediate nitrate δ15N values around zero may be a result of a balanced emission of NOx from the city and the rural areas. The isotopic effects of chemical conversion of NOx to nitrate and washout of nitrate were ruled out as significant causes of nitrate δ15N variability, but ammonium washout, during which 15N is assumed to be preferentially removed, may partly contribute to the ammonium δ15N variability.