Contributions of vehicular emissions and secondary formation to nitrous acid concentrations in ambient urban air in Tokyo in the winter.

Nitrous acid (HONO) plays an important role in the formation of OH radicals, which are involved in photochemical oxidation. HONO concentrations in ambient air at urban sites have previously been measured, but very few studies have been performed in central Tokyo. In this study, HONO concentrations in ambient air in southeast central Tokyo (near Tokyo Bay) in winter were determined by incoherent cavity enhanced absorption spectroscopy. The O3, NO, NO2, and SO2 concentrations were simultaneously determined. The NO concentrations were used to classify the parts of the study period into types I (high pollution), II (medium pollution), and III (low pollution). The maximum HONO concentrations in the type I, II, and III periods were 7.1, 4.5, and 3.0ppbv, respectively. These concentrations were comparable to concentrations previously found in other Asian megacities. The mean HONO concentration varied diurnally, and HONO was depleted between 00:00 and 03:00 each day. The sampling site is surrounded by roads with high traffic loads, but vehicular emissions were estimated to contribute <10% of the HONO concentrations. Two positive and negative relative humidity dependences of the HONO to NO2 ratio were confirmed, implying the existence of the two different secondary formation process of HONO. The NO2 to HONO conversion rates at night in the type I, II, and III periods were 6.3×10-3, 7.6×10-3, and 4.2×10-3h-1, respectively.