Investigation of water vapor effects on the detection of nitric acid vapor with the tungstic acid technique

An automated tungstic acid technique (TAT) has been successfully used to measure gaseous HNO₃ in the presence of water vapor. The TAT is based on the diffusion of gaseous HNO₃ to the interior walls of a tube coated with tungsten VI oxide (WO₃), where it is selectively chemisorbed. The collected HNO₃ sample is thermally desorbed from the WO₃ surface, as NO, and measured by a chemiluminescent oxides of nitrogen analyzer. The integrated analyzer response is directly proportional to the nitric acid collected.

Based on nitric acid hydration characteristics, a decrease in the diffusion coefficient and thus collection efficiency for denuder type measurement techniques may result with increased atmospheric water vapor (i.e., relative humidity). This study emphasizes the effect of water vapor (i.e., relative humidity) as a potential interferent for HNO₃ collection with the TAT system.

The effect of water vapor (< 78% RH) on the collection efficiency for HNO₃ with the tungstic acid technique is negligible at 25°C, but is significant only at elevated sampling temperatures. This threshold effect is further substantiated and eliminated when a modified sampling collection system was designed with coolant capabilities. The new design has been tested to sub-part-per-billion (NO_x analyzer detection limit) levels with minimal loss of gaseous HNO₃ signal, thereby increasing sensitivity to atmospheric HNO₃ concentrations and maintaining the gas/aerosol sample integrity.