[1] The dominant factors controlling the seasonal variations of ozone (O-3) and three major oxidized nitrogen species, peroxyacetyl nitrate (PAN), nitrogen oxides (NOx), and nitric acid (HNO3), in northeast Asia are investigated by using a three-dimensional global chemical transport model to analyze surface observations made at Rishiri Island, a remote island in northern Japan. The model was evaluated by comparing with observed seasonal variations, and with the relationships between O-3, CO, and PAN. We show that the model reproduces the chemical environment at Rishiri Island reasonably well, and that the seasonal cycles of O-3, CO, NOy species, and VOCs are well predicted. The impact of local emissions on some of these constituents is significant, but is not the dominant factor affecting the seasonal cycles. The seasonal roles of chemistry and transport in controlling O-3 and PAN are revealed by examining production/ destruction and import/ export/deposition fluxes in the boundary layer over the Rishiri region. For O-3, transport plays a key role throughout the year, and the regional photochemical contribution is at most 10% in summer. For PAN, in contrast, transport dominates in winter, while in-situ chemistry contributes as much as 75% in summer. It is suggested that the relative contribution of transport and in-situ chemistry is significantly different for O-3 and PAN, but that the wintertime dominance of transport due to the long chemical lifetimes of these species is sufficient to drive the seasonal cycles of springtime maximum and summertime minimum characteristic of remote sites

To improve the credibility of chemistry schemes employed in chemical transport models (CTMs) aiming at predicting ozone mixing ratios in urban, rural, and regional scales, validation of models not only by observational data of O3 and NOx but also by individual species of reactive nitrogen NOy is necessary because the formation and dissipation of O3 in the atmosphere occur via reactions accompanying the transformation of NOx and NOy. The disagreement of the simulated results of CTM with observational data of HNO3 and HONO have often been reported, and this paper reviews previous studies on the heterogeneous “renoxification” reaction of gaseous HNO3 to form NO, NO2, and/or HONO; the formation of HONO from the heterogeneous dark reaction of NO2 and H2O, and the photolysis of adsorbed HNO3 and NO3− on surfaces. For the further validation of CTMs with individual species of NOy, previous field studies of comprehensive observation of NOy speciation in ground-based and aircraft campaigns have also been reviewed. Studies combining observations of speciated NOy and model simulations need to be performed to improve chemistry models used in CTMs.