Measuring inorganic nitrate species with short time resolution from an aircraft platform by dual‐channel ozone chemiluminescence

Abstract

A measurement technique for determining nitrate (the sum of nitric acid and particulate nitrate) with a few seconds time resolution in plumes is needed to resolve within‐plume features. A technique using dual ozone‐chemiluminescent NO detectors with a selective nitrate scrubber in one sampling train is promising if used with an appropriate sampling inlet, and if nitrate is the desired analyte. We report the design of, and preliminary results from a dual channel ozone‐chemiluminescent system, each channel containing a gold‐CO catalyzed converter which reduces all odd nitrogen species (NOy) quantitatively to NO; one channel also contains a nylon filter to remove nitrate from the air stream prior to the converter (this signal is termed NOy*). This system was deployed successfully in a Bell 205 helicopter during the 1995 Southern Oxidants Study Nashville Ozone Study. The converters were mounted forward near the air intake, and zero air and calibration gases admitted simultaneously to both channels during flight operations. The difference signal between the two channels (NOy‐NOy*) indicated apparent nitrate levels in the sampled air with a time resolution of <5 s and a limit of detection of about 1 ppbv. Nitrate levels observed with this system in plumes and background air during the Nashville Ozone Study were highly correlated with ozone and varied from below detection limits to ≈20 ppbv. Nitrate levels were also highly correlated with the calculated difference between NOy and the sum of NO and NO2 (NOz). Higher nitrate levels as a fraction of NOz were found in power plant plumes (≥60%) compared with urban plumes (≈50%) and background air, consistent with apparently lower ozone production efficiencies in power plant plumes vis‐à‐vis urban plumes.