Measurement of peroxycarboxylic nitric anhydrides (PANs) during the ITCT 2K2 aircraft intensive experiment

Abstract

[1] Measurements of peroxycarboxylic nitric anhydrides (PANs), peroxyacetic nitric anhydride (CH 3 C(O)OONO 2 ; PAN), and peroxypropionic nitric anhydride (CH 3 CH 2 C(O)OONO 2 ; PPN) were made in the spring of 2002, off the west coast of North America, as part of the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) project. Long-range transport of Asian emissions was observed in which PAN and PPN mixing ratios were as high as 650 pptv and 90 pptv, respectively. Moreover, these two species constituted as much as 80% of the odd nitrogen (NO y ) in those air masses, and median PAN/NO y was more than 60% at altitudes of 4 km and above. Systematic differences in the ratio of PPN to PAN were observed in air masses that had been impacted by Asian urban emissions relative to those impacted by biomass burning. Mixing ratios of PAN and PPN were also elevated in the marine boundary layer close to the west coast of California, possibly because of photochemical production driven by maritime NO x emissions.

Seasonal and diurnal variations of atmospheric peroxyacetyl nitrate, peroxypropionyl nitrate, and carbon tetrachloride in Beijing

“…The slope (or the ratio of PPN/PAN) of 0.152 was well within the range (0.135-0.172) reported in polluted areas (Grosjean et al, 1993;Kourtidis et al, 1993;Ridley et al, 1990). The VOCs precursors for PAN have been recognized to be emitted from both anthropogenic and biogenic sources whereas the precursors for PPN (propanal and 1-butene) are predominantly from anthropogenic sources (Grosjean et al, 2001;Roberts et al, 2004). Therefore, the ratio of PPN/PAN has been widely used as an indicator for distinguishing the contribution of anthropogenic hydrocarbons from biogenic hydrocarbons to atmospheric PANs.…”

“…Therefore, the ratio of PPN/PAN has been widely used as an indicator for distinguishing the contribution of anthropogenic hydrocarbons from biogenic hydrocarbons to atmospheric PANs. Through the regression of a linear multivariate correlation involving PAN and PPN, Roberts et al (2002Roberts et al ( , 2004 concluded that when the ratio of PPN/PAN is between 13.5% and 17.2%, PANs formation was dominated by anthropogenic hydrocarbons, while dominated by biogenic hydrocarbons when the ratio is lower than 10%. The average ratio of PPN/PAN (15.2%) obtained by this study implied that the PANs formation in Beijing was dominated by anthropogenic hydrocarbons emission.…”

“…PANs are thermal unstable compounds, they are quite stable in the midand upper troposphere under low temperature, and can be transported over long distances from polluted continental regions into the remote areas where they release NOx under high temperature (Honrath et al, 1996;Kondo et al, 1997;Singh et al, 1996), and hence PANs act as important temporary NOx reservoirs and control the photochemical production of O 3 in the remote troposphere (Singh and Hanst, 1981). Due to the particular importance of PANs on atmospheric chemistry, a great number of PANs measurements have been conducted intensively in developed countries, including the urban regions (Grosjean et al, 2001;Marley et al, 2007;Roberts et al, 1995) and remote area (Hartsell et al, 1994;Roberts et al, 2004;Singh et al, 1990Singh et al, , 1992Williams and Grosjean, 1991). However, only few researches involving with PANs are implemented in developing countries of Asia (Lee et al, 2008;Watanabe et al, 1998;Zhang and Tang, 1994;Wang et al, 2010;Zhang et al, 2009).…”

Changes in the photochemical environment of the temperate North Pacific troposphere in response to increased Asian emissions

“…[9] Experimental details regarding the various PAN data sets are reported by Parrish et al [1992], Jaffe et al [2001], Kotchenruther et al [2001a], and Roberts et al [2004], who estimated accuracies from 15 to 30% depending upon the study and the PAN levels. The 1985 study represent the only relatively early measurements, but fortunately two, wellrespected measurement groups simultaneously measured PAN, and the results agreed well [Parrish et al, 1992].…”

Development of a photochemical source for the production and calibration of acyl peroxynitrate compounds

“…The most atmospherically abundant and well-understood of the APNs is acetyl peroxynitrate (PAN, CH 3 C(O)O 2 NO 2 ) formed from the oxidation of VOCs (Roberts, 2007;Fischer et al, 2014;Singh et al, 1992;LaFranchi et al, 2009;Moxim et al, 1996;Phillips et al, 2013;Roberts et al, 2004Roberts et al, , 2007Williams et al, 1997). Recent research has become increasingly focused on less-well-studied APNs due to their involvement in several key atmospheric processes.…”