Short-Time-Response measurements of nitrogen dioxide and peroxyacetyl nitrate by fast capillary gas chromatography with luminol detection.

The interaction of hydrocarbons and nitrogen oxides in sunlight to produce photochemical smog has been well studied over the years. In the past, the workhorse for the measurement of NO{sub 2}and NO was the chemiluminescent reaction with ozone. This method has detection limits of approximately 0.5 ppb in most commercial instruments, but it cannot detect NO{sub 2} directly; the instrument detects NO and uses hot catalytic surfaces to decompose all other nitrogen oxides (including NO{sub 2}) to NO for detection (l). The main problem with the method is the inherent difficulty in detecting excited NO{sub 2}, which emits over a broad region beginning at approximately 660 nm and has a maximum at 1270 nm, thus requiring a red-shifted photomultiplier for detection. The use of luminol for direct chemiluminescent detection of NO{sub 2} was demonstrated to have greater inherent sensitivity (detection limits of 5 ppt) than the indirect ozone chemiluminescence detection (2). In the luminol system, a gas-liquid reaction leads to light emission with a maximum at approximately 425 nm, at the maximum sensitivity for most photomultiplier tubes. This emission is responsible for the increased detection sensitivities. The biggest problem with this method for direct measurement of NO{sub 2} has been interference due to other soluble oxidants, particularly peroxyacyl nitrates (PANs)