Investigations of emissions and heterogeneous formation of HONO in a road traffic tunnel

Simultaneous measurements of nitrous acid (HONO) and nitrogen dioxide (NO2) using a differential optical absorption spectroscopy system, nitrogen oxide (NO) by an in situ chemiluminescence analyser and carbon dioxide (CO2) by a gas chromatographic technique were carried out in the Wuppertal Kiesbergtunnel. At high traffic density HONO concentrations of up to 45 ppbV were observed. However, at low traffic density unexpectedly high HONO concentrations of up to 10 ppbV were measured caused by heterogeneous HONO formation on the tunnel walls. In addition to the tunnel campaigns, emission measurements of HONO, NO2, NO and CO2 from different single vehicles (a truck, a diesel and a gasoline passenger car) were also performed. For the correction of the HONO emission data, the heterogeneous HONO formation on the tunnel walls was quantified by two different approaches (a) in different NO2 emission experiments in the tunnel without traffic and (b) on tunnel wall residue in the laboratory. The HONO concentration corrected for heterogeneous formation on the tunnel walls, in relation to the CO2 concentration can be used to estimate the amount of HONO, which is directly emitted from the vehicle fleet. From the measured data, emission ratios (e.g. HONO/NOx) and emission indices (e.g. mg HONO kg−1 fuel) were calculated. The calculated emission index of 88±18 mg HONO kg−1 fuel allows an estimation of the HONO emission rates from traffic into the atmosphere. Furthermore, the heterogeneous formation of HONO from NO2 on freshly emitted exhaust particles is discussed.