Department of Earth System Science

Sulfur dioxide (SO₂) in synthetic air and diluted ambient air was measured as part of the Gas-Phase Sulfur Intercomparison Experiment (GASIE) using the high performance liquid chromatography (HPLC)/fluorescence technique. SO₂ was analyzed by equilibrating the gaseous sample with aqueous SO₂, sulfite, and bisulfite, then converting the aqueous S(IV) to an isoindole derivative. The derivative was separated by reversed phase HPLC and detected via fluorescence. The system was calibrated with mixtures of SO₂ in zero air prepared from an SO₂ permeation device through a two-stage dilution system. The instrument has a 4-min. sample integration time and a measurement period of 9-min. During the GASIE intercomparison the lower limit of detection averaged 3.6 parts per trillion by volume (pptv). The precision of replicate measurements over the entire intercomparison period was better than 5% at the 20 pptv level. Instrument performance was unaffected by the interferent gases included in the GASIE protocol (H₂O, O₃, NO_x, DMS, CO, CO₂, and CH₄). During diluted ambient air tests, the HPLC/fluorescence technique exhibited an approximately 10% reduction in response relative to some other techniques. The cause of this apparent calibration change is not understood.