Exploring Possible Missing Sinks of Nitrate and Its Precursors in Current Air Quality Models —A Case Simulation in the Pearl River Delta, China, Using an Observation-Based Box Model

Abstract

Nitrate and its precursor (gaseous HNO3) in China are generally overestimated by current chemical transport models in comparison to in-situ observations. In this study, we used an observation-based box model and in-situ measurements at a rural site in southern China to investigate possible missing sinks of nitrate. We found that a heterogeneous reaction of HNO3 to NOx on soot can better balance the NOx/HNO3 chemistry in models and improve model performance with regard to nitrate, particularly where an additional HONO source (the heterogeneous reaction of NO2 on soot) is incorporated into current models. Through a series of sensitivity simulations, the uptake coefficients of heterogeneous reactions were suggested to be 3.0 × 10−3 and 1 × 10−4 for HNO3 and HONO over southern China in fall, respectively. A 3-D simulation with the suggested uptake coefficients further confirmed that heterogeneous reactions significantly decreased the nitrate concentrations (PNO3) in southern China, by up to 10 μg m−3 (50%-80% of simulated PNO3) in polluted regions (e.g., the Yangtze River). In contrast to nitrate and HNO3, NOx concentrations in China were enhanced, which partly explained the underestimation of NO2 in current models compared to satellite observations.