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Nitrous acid (HONO) plays an important role in radical formation and photochemical oxidation processes in the boundary layer. However, its impact on the chemistry in a street canyon microenvironment has not been thoroughly investigated. In this study, we measured HONO in a street canyon in urban Hong Kong and used an observation-based box model (OBM) with the Master Chemical Mechanism (MCM v3.3.1) to investigate the contribution of HONO to local oxidation chemistry. The observed HONO mixing ratios were in the range of 0.4–13.9 ppbv, with an average of 3.91 ppbv in the daytime and 2.86 ppbv at night. A mean HONO/NOx emission ratio of 1.0% (±0.5%) from vehicle traffic was derived. OBM simulations constrained by the observed HONO showed that the maximum concentrations of OH, HO2, and RO2 reached 4.65 × 106, 4.40 × 106, and 1.83 × 106 molecules cm−3, which were 7.9, 5.0, and 7.5 times, respectively, the results in the case without HONO constrained. Photolysis of HONO contributed to 86.5% of the total primary radical production rates and led to efficient NO2 and O3 production under the condition of weak regional transport of O3. The formation of HNO3 contributed to 98.4% of the total radical termination rates. Our results suggest that HONO could significantly increase the atmospheric oxidation capacity in a street canyon and enhance the secondary formation of HNO3 and HCHO, which can damage outdoor building materials and pose health risks to pedestrians.

Although nitrous acid (HONO) plays an important role in the chemistry of polluted atmospheres, its atmospheric abundances and sources are still not well understood. This paper reports ambient measurements of HONO taken over four select months in different seasons at a suburban site in Hong Kong. The data were analyzed to elucidate the seasonal characteristics, emission ratios and rates of heterogeneous production. The monthly averaged HONO concentrations ranged from 0.35 ± 0.30 ppbv in late spring (May) to 0.93 ± 0.67 ppbv in late autumn (November). The similar variation patterns of HONO, NOx, and traffic flow from midnight to rush hours suggest that the HONO concentration was strongly influenced by vehicle emissions. The emission ratios (HONO/NOx) were derived from an analysis of 21 fresh plumes (NO/NOx > 0.80), with the range of 0.5–1.6%. The large variability in the emission ratios is attributed to the reaction of NO2 on black carbon (BC) emitted from vehicles, based on a strong correlation between the HONO/NOx and concurrently measured BC. The mean conversion rate of NO2 to HONO on ground surface during nighttime estimated on nine select days was 0.52 × 10−2 h−1, which is relatively low compared with other reported values. This paper highlights a large variability in vehicle emission ratios and heterogeneous conversions of NO2 at ground surface. Photochemical models must consider this variability to better simulate the primary sources of HONO and subsequent photochemistry in the lower part of the troposphere.

An optical analytical instrument based on light emitting diode (LED) incoherent broadband cavity enhanced absorption spectroscopy (LED-IBBCEAS) was developed for simultaneous measurements of HONO and NO2 in ambient air. Detection limits (for signal-to-noise ratio, SNR = 2) of 0.6 ppbv for HONO and 2 ppbv for NO2 were achieved with an optimum acquisition time of 120 s. Field intercomparison campaign at a suburban site of Tung Chung in Hong Kong was carried out. Daytime and nighttime concentrations of HONO and NO2 were recorded and compared with data from a long path absorption photometer (LOPAP) and a NOx analyzer equipped with a blue light converter. The test of such a LED-IBBCEAS setup by the measurement intercomparison with the well established HONO and NO2 measurement instruments, for the first time, in a real atmospheric environment, demonstrated the feasibility of the proposed technique for the measurement of environmental HONO and NO2 concentrations in a manner that is free of chemical and spectral interference. During the measurement period from 12:32 on May 12th to 12:32 on May 14th, 2012, the quantitative assessments from these techniques showed well agreed data. High temporal correlations of HONO with NOx and CO were observed, and possible formation sources of HONO are discussed. Occasional inconsistencies in the quantitative assessment of HONO were observed during the in-field campaign. The problems encountered by the IBBCEAS technique applied to field observation and the further improvements are discussed.