Aerosol Thermodynamics: Nitrate Loss from Regulatory PM2.5 Filters in California

Fine particulate matter (PM2.5) mass concentrations reported by regulatory networks are declining across the United States. It is well established that ammonium nitrate contributes substantially to the PM2.5 mass in the western United States, and that Teflon filters commonly used by regulatory monitors are subject to negative mass artifacts due to ammonium nitrate volatilization. This study focuses on the San Joaquin Valley (SJV), an environmental justice (EJ) and agricultural region with persistently poor air quality. The SJV is a serious nonattainment area of PM2.5 National Ambient Air Quality Standards (NAAQS) with substantial nitrate mass concentrations. We explicitly model the chemical thermodynamic equilibrium of the ammonium nitrate-nitric acid systems and quantify volatilization across California as a function of the deliquescence point relative humidity (%DRH). Nitrate loss is estimated at all federal reference method (FRM) and federal equivalent method (FEM) monitors from 2001 to 2021. Nearly 20% of PM2.5 mass is lost from filters in the SJV area, especially during winter and fall when particulate nitrate mass is most abundant. All decadal PM2.5 trends calculated from reported measurements in Kern, Tulare, and Fresno counties in the SJV show greater decline in PM2.5 mass when nitrate loss is accounted for, up to a factor of 20 in Kern county. This suggests PM2.5 mass concentrations reported in regulatory networks are biased low relative to the actual atmospheric burden, notably in an EJ area that lags behind most of the country's air quality improvements.