FAST GAS CHROMATOGRAPHY WITH LUMINOL DETECTION FOR MEASUREMENT OF NITROGEN DIOXIDE AND PANs

Fast capillary gas chromatography has been coupled to a luminol-based chemiluminescence detection system for the rapid monitoring of nitrogen dioxide and peroxyacyl nitrates. A first-generation instrument was described recently (Gaffney et al., 1998). This system is capable of monitoring nitrogen dioxide and peroxyacyl nitrates (PANs; to and including the C4 species) with 1-min time resolution. This is an improvement by a factor of five over gas chromatography methods with electron capture detection. In addition, the luminol method is substantially less expensive than laser fluorescent detection or mass spectroscopic methods. Applications in aircraft-based research have been published electronically and will appear shortly in Environmental Science and Technology (Gaffney et al., 1999a). An improved version of the instrument that has been designed and built makes use of a Hammamatsu photon-counting system. Detection limits of this instrumentation are at the low tens of ppt. The range of the instrument can be adjusted by modifying sampling volumes and detection counting times. A review of past work and of recent application of the instrumentation to field measurements of nitrogen dioxide and PANs is presented. The data clearly indicate that the luminol approach can determine the target species with time resolution of less than 1 min. Examples of applications for estimation of peroxyacetyl radical concentrations and nitrate radical formation rates are also presented. This instrumentation can further be used for evaluation of surfaces for loss of nitrogen dioxide and PANs, phenomena of possible importance for sampling interfaces and chamber wall design. Our high-frequency field data clearly indicate that the “real world” is not well mixed and that turbulent mixing and plume-edge chemistries might play an important role in urbanand regional-scale interactions. Dynamic flow systems might be required to evaluate such effects in newgeneration chamber studies.