Exploring dust heterogeneous chemistry over China: Insights from field observation and GEOS-Chem simulation

Highlights: • Dust heterogeneous reactions are enhanced with increased RH, especially when RH > 40%. • Model result with RH-dependent uptake coefficients reproduce observed DSO4 and DNIT. • DSO4 exhibits larger contributions to sulfate (>40%) over downwind regions. • Heterogeneous reactions contribute to 20-30% sulfate formation over North China. Dust heterogeneous chemistry plays an important role in tropospheric chemistry, but its parameterization in numerical models is often quite simplified, which hampers accurate prediction of particulate matter and its chemical component. In this study, we investigate the evolution of dust heterogeneous chemical process and its potential impacts on gaseous and aerosol components during a dust pollution episode from March 27 to April 2, 2015 over North China. Based on field measurements, the significant role of relative humidity (RH) in dust heterogeneous chemistry is found and a RH-dependent parameterization for uptake coefficients of HNO₃ and SO₂ is incorporated in GEOS-Chem to reproduce the dust heterogeneous chemical process. During the study period, observed dust sulfate (DSO4) and dust nitrate (DNIT) exhibit maximum concentrations of 9.1 and 22.8 μg m^-3 respectively, accompanied by high RH and gaseous precursor concentrations. DSO4 concentrations are positively related to RH. The observed dust sulfate oxidation ratio (DSOR) is elevated evidently with increased RH, especially when RH is higher than ~40%, implying that enhanced RH could promote heterogeneous oxidation of SO₂ to DSO4. Model simulation shows that when incorporating the RH-dependent parameterization, DNIT and DSO4 are generally well captured and the model performance of total sulfate oxidation ratio (TSOR) and total nitrate oxidation ratio (TNOR) are improved. High contribution of DNIT and DSO4 are found to be located over the regions close to source areas (>60%) and downwind regions (>40%), respectively. Sensitivity results show that SO₂ and HNO₃ reduce by 2-24 μg m^-3 and 1-18 μg m^-3 when considering dust heterogeneous impacts, thus leading to reduction in non-dust sulfate and non-dust nitrate concentrations. As a result, simulated NH₃ increases and ammonium reduces by more than 20%. Our study indicates that the contribution of heterogeneous reactions to sulfate formation is 20-30% over North China.