Chemical amplification, peroxy radical measurement

Figure 11.55 shows an altitude profile for peroxy radicals measured above the boundary layer over southern Germany using chemical amplification with the mass spectrometric derivatization measurement of OH (Reiner et ciL, 1998). Concentrations are again seen to be in the range of 10x-109 cm-3. 

Another approach combines the mass spectrometric derivatization approach with chemical amplification (Reiner et al., 1997, 1998). In this instrument, H02 and R02 are converted to OH through the reactions in the chemical amplifier approach discussed below, and the OH is then converted to H2S04 by reaction with S02 and measured by chemical ionization mass spectrometry using NO, (HN03) clusters as described earlier. In this case, the use of isotopically labeled S02 is not necessary, since the ambient H2S04 concentration is much smaller than that of the peroxy radicals. 

Fewer intercomparison studies have been carried out for peroxy radicals than for OH. Two chemical amplification methods were compared during a measurement campaign in Brittany, France (Cantrell et al., 1996). Although the measurements tended to track one another, there is more scatter than might be expected, given the similar nature of the instruments. For example, a plot of the data from one instrument against those from the second had a slope of 0.71 but a correlation coefficient of only r = 0.36. In another study (Zenker et al., 1998), comparison of three chemical amplifier techniques to matrix isolation-ESR gave... 

Cantrell, C. A., D. H. Stedman, and G. J. Wendel, Measurement of Atmospheric Peroxy Radicals by Chemical Amplification, Anal. Chem., 56, 1496-1502 (1984). 

Chemical Amplification. The measurement of a small electrical signal is often accomplished by amplification to a larger, more easily measured one. This technique of amplification can also be applied to chemical systems. For peroxy radicals, Cantrell and Stedman (117) proposed, as a possible technique, the chemical conversion of peroxy radicals to N02 with amplification (i.e., more than one N02 per peroxy radical). This method has also been used for laboratory studies of H02 reactions on aqueous aerosols (21). The following chemical scheme was proposed as the basis of the instrument ... 

Because the luminol detection system is also sensitive to NO2, chemical amplification methods have been attempted to further decrease detection limits for PANs below the pptv range for trace-level measurements. With this approach, the PANs are thermally decomposed to NO2 in the presence of large amounts of NO (6 ppm) and CO (8%). Thermal decomposition of the PANs yields peroxy radicals which initiate a free-radical chain oxidation of NO to NO2, producing several NO2 molecules (approximately 180 (20) for each PAN decomposed. This technique has been used as a gas chromatography detector to achieve ultratrace detection limits without sample preconcentration. The detector exhibits a slightly nonlinear response relative to conventional BCD, attributed to the nonlinear response of the luminol reaction in the presence of NO at 6 ppm. 

As part of this study, two potential RO2 measurement techniques have been investigated the chemical amplification and tuneable diode laser absorption spectroscopy. The first approach has proven to be successful for the measurement of ambient mixing ratios of the sum of all peroxy radicals which react with NO to form NO2. 

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See also in sourсe #XX -- [ , , , , ]

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