Fast gas chromatography with luminol chemiluminescence detection for the simultaneous determination of nitrogen dioxide and peroxyacetyl nitrate in the atmosphere

Abstract

An instrument has been designed and constructed for the simultaneous determination of nitrogen dioxide (NO2) and peroxyacetyl nitrate (PAN) in atmospheric samples. The instrument’s design is based on separation by fast gas chromatography (GC) with a 30 ft capillary column (DB-1) followed by detection by luminol chemiluminescence. The chemiluminescent reaction between NO2 or PAN and luminol takes place at the gas–liquid interface on the surface of a solid support. The chemiluminescent emission at 425 nm is detected with a photon counting module. The instrument is controlled by a 1.8 GHz Notebook computer with a WINDOWS 2000 operating system and a custom software application programmed in LABVIEW. Detection limits are in the low parts per trillion (ppt) with a time resolution of 30 s to 1 min. The instrument was operated during the Mexico City Metropolitan Area/Mexico City Megacity 2003 collaborative air quality study. Results for NO2 from this fast GC method were compared with results from a co-located differential optical absorption spectrometer (DOAS) and a tunable diode laser absorption spectromenter (TDLAS). The results support the application of the new luminol-based instrument for atmospheric measurements.

Air quality in North America's most populous city – overview of the MCMA-2003 campaign

“…A novel fast gas chromatograph/luminal chemiluminescence instrument designed to detect nitrogen dioxide and peroxyacetyl nitrate (PAN) was developed at ANL and deployed at both the CENICA supersite and on the ARI mobile laboratory (Marley et al, 2004). Cross comparisons of NO 2 with long-path DOAS and co-located point TILDAS instruments showed good agreement.…”

A gas chromatograph for quantification of peroxycarboxylic nitric anhydrides calibrated by thermal dissociation cavity ring-down spectroscopy

“…Accurate measurements of MPAN are particularly challenging, because TD-CIMS is relatively insensitive to MPAN, and because ions other than methacrylate (CH 2 = C(CH 3 )CO − 2 ), e.g., trifluoromethoxy anions (CF 3 O − , generated from CF 3 OH that outgasses from Teflon tubing) and crotonate (CH 3 CH = CHCO − 2 , generated from peroxycrotonyl nitrate, CPAN), interfere at m/z 85 (Zheng et al, 2011;Mielke and Osthoff, 2012). PANs have also been quantified by proton transfer mass spectrometry (Hansel and Wisthaler, 2000;Hastie et al, 2010) and by quantifying the NO 2 generated from their thermal dissociation (usually by the difference relative to background NO 2 ) using luminol chemiluminescence (CL) (Nikitas et al, 1997;Marley et al, 2004), laser-induced fluorescence (LIF) (Day et al, 2002;Wooldridge et al, 2010), or cavity ring-down spectroscopy (CRDS) (Paul and Osthoff, 2010;Paul et al, 2009). In spite of the development of these new PAN measurement techniques, PAN-GCs remain attractive because of their relative simplicity, compactness, robustness, good sensitivity, and lack of interferences, properties that are desirable for long-term and unattended operations (e.g., Mills et al, 2007;Zhang et al, 2009;Fischer et al, 2010;Zhang et al, 2012).…”

Evaluation of nitrogen dioxide chemiluminescence monitors in a polluted urban environment

“…Other more specific NO 2 detection techniques have been developed, including a photolysis technique to specifically convert NO 2 to NO that avoids using a metal catalyst while still employing the chemiluminescence reaction (Kley and McFarland, 1980), an LIF technique (Thornton et al, 2000;Thornton et al, 2003), a fast gas chromatography luminol chemiluminescence detection (Marley et al, 2004), Differential Optical Absorption Spectroscopy (DOAS) (Platt, 1994;Platt and Perner, 1980), cavity ring down (Osthoff et al, 2006) and a Tunable Infrared Laser Differential Absorption Spectroscopy (TILDAS) technique (Li et al, 2004) (also described below). Several recent reviews provide a more complete description of these and other NO 2 measurement techniques (Demerjian, 2000;McClenny et al, 2002;Parrish and Fehsenfeld, 2000).…”