Intercomparison of near real time monitors of PM2.5 nitrate and sulfate at the U.S. Environmental Protection Agency Atlanta Supersite

Abstract

Five new instruments for semicontinuous measurements of fine particle (PM2.5) nitrate and sulfate were deployed in the Atlanta Supersite Experiment during an intensive study in August 1999. The instruments measured bulk aerosol chemical composition at rates ranging from every 5 min to once per hour. The techniques included a filter sampling system with automated water extraction and online ion chromatographic (IC) analysis, two systems that directly collected particles into water for IC analysis, and two techniques that converted aerosol nitrate or sulfate either catalytically or by flash vaporization to gaseous products that were measured with gas analyzers. During the one‐month study, 15‐min integrated nitrate concentrations were low, ranging from about 0.1 to 3.5 μg m −3 with a mean value of 0.5 μg m −3 . Ten‐minute integrated sulfate concentrations varied between 0.3 and 40 μg m −3 with a mean of 14 μg m −3 . By the end of the one‐month study most instruments were in close agreement, with r‐squared values between instrument pairs typically ranging from 0.7 to 0.94. Based on comparison between individual semicontinuous devices and 24‐hour integrated filter measurements, most instruments were within 20–30% for nitrate (∼0.1–0.2 μg m −3 ) and 10–15% for sulfate (1–2 μg m −3 ). Within 95% confidence intervals, linear regression fits suggest that no biases existed between the semicontinuous techniques and the 24‐hour integrated filter measurements of nitrate and sulfate;, however, for nitrate, the semicontinuous intercomparisons showed significantly less variability than intercomparisons amongst the 24‐hour integrated filters.