T. Thornberry et al., Observations of reactive oxidized nitrogen and speciation of NOy during the PROPHET summer 1998 intensive, J GEO RES-A, 106(D20), 2001, pp. 24359-24386
Measurements of NOy, NOx, PAN, PPN, MPAN, C-3-C-5 alkyl nitrates, total iso
prene nitrates, HNO3, HONO, and aerosol NO3- and NO2- were made during the
summer 1998 intensive of the Program for Research on Oxidants: Photochemist
ry, Emissions, and Transport (PROPHET). Mixing ratios of NOy, NOx, PAN, PPN
, and alkyl nitrates were observed to have a strong dependence on the direc
tion of transport to the site as was expected from the distribution of majo
r urban and industrial sources. A. peak in NOx and NOx/NOy during the morni
ng in southerly flow provides evidence for the transport of relatively unpr
ocessed emissions in layers above the nocturnal boundary layer. The differe
nce in PAN and PPN levels between north and south flow directions indicates
a net transport of reactive nitrogen to regions farther north. Isoprene ni
trates were observed to typically comprise less than 1% of NOy in spite of
the dominance of isoprene in local VOC chemistry, although due to the rapid
losses of isoprene nitrates through reaction, vertical mixing, and deposit
ion, their role in the processing of NOy may be significant. General agreem
ent was observed between NOy and the sum of the individually measured const
ituents during ten 24 hour periods, although a linear regression indicates
the potential for an interference in the individual measurements and a poss
ible shortfall in NOy. Measurements indicate that HONO may play a larger ro
le in the reactive nitrogen budget than previously expected for a rural sit
e. HONO/NO2 for a 24 hour period was observed to be 0.09-0.25 and suggests
the likelihood of a significant heterogeneous production pathway or pathway
s.