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Nitrous acid (HONO), an important precursor of the hydroxyl radical (OH), plays a key role in atmospheric chemistry, but its sources are still debated. The production of HONO on aerosol surfaces or on ground surfaces in nocturnal atmospheres remains controversial. The vertical profile provides vertical information on HONO and NO2 to understand the nocturnal HONO production and loss. In this study, we report the first high-resolution ( m) nocturnal vertical profiles of HONO and NO2 measured from in situ instruments on a movable container that was lifted on the side wiring of a 325 m meteorological tower in Beijing, China. High-resolution vertical profiles revealed the negative gradients of HONO and NO2 in nocturnal boundary layers, and a shallow inversion layer affected the vertical distribution of HONO. The vertical distribution of HONO was consistent with stratification and layering in the nocturnal urban atmosphere below 250 m. The increase in the HONO ∕ NO2 ratio was observed throughout the column from the clean episode to the haze episode, and relatively constant HONO∕NO2 ratios in the residual layer were observed during the haze episode. Direct HONO emissions from traffic contributed 29.3 % ± 12.4 % to the ambient HONO concentrations at night. The ground surface dominates HONO production by heterogeneous uptake of NO2 during clean episodes. In contrast, the HONO production on aerosol surfaces (30–300 ppt) explained the observed HONO increases (15–368 ppt) in the residual layer, suggesting that the aerosol surface dominates HONO production aloft during haze episodes, while the surface production of HONO and direct emissions into the overlying air are minor contributors. Average dry deposition rates of 0.74±0.31 and 1.55±0.32 ppb h−1 were estimated during the clean and haze episodes, respectively, implying that significant quantities of HONO could be deposited to the ground surface at night. Our results highlight the ever-changing contributions of aerosol and ground surfaces in nocturnal HONO production at different pollution levels and encourage more vertical gradient observations to evaluate the contributions from varied HONO sources.

The production of HONO on aerosol surfaces and ground surfaces in urban atmosphere is of interests. However, ground surface measurement commonly in our society is not able to distinguish these two parts. Here, for the first time, we reported high-resolution vertical profile measurements of HONO and NO2 in urban Beijing at night using an incoherent broadband cavity enhanced absorption spectrometer (IBBCEAS) amounted on a movable container which attached to a meteorological tower of 325m high. The mixing ratios of HONO during one haze episode (E1), the clean episode (C2) and another haze episode (E3) were 4.26±2.08, 0.83±0.65, and 3.54±0.91ppb, respectively. High-resolution vertical profiles revealed that the vertical distribution of HONO is consistent with stratification and layering in the nocturnal urban atmosphere below 250m. Direct emissions from combustion processes contributed 51.1% to ambient HONO concentration at night. The HONO production from the heterogeneous conversion of NO2 on the aerosol surfaces cannot explain HONO vertical measurements at night, indicating that the heterogeneous reaction of NO2 on ground surfaces dominated the nocturnal HONO production. The nocturnal HONO in the boundary layer is primarily derived from the heterogeneous conversion of NO2 at ground level and direct emissions; it is then transported throughout the column by vertical convection. ϕNO2→HONO, the HONO yield from deposited NO2, is used to evaluate HONO production from the heterogeneous conversion of NO2 at night. The derived ϕNO2→HONO values on 9 (C2), 10 (C2) and 11 December (E3) were 0.10, 0.08, and 0.09, respectively, indicating a significant production of HONO from heterogeneous reaction of NO2 at ground level. The similar ϕNO2→HONO values measured during clean and haze episodes suggest that the heterogeneous conversion potential of NO2 at ground level is consistent at night. Furthermore, the dry deposition loss of HONO to the ground surface and vertical mixing effects associated with convection reached a near steady state at midnight on 1112 December, indicating that significant quantities of HONO are deposited to the ground surface at night, and the ground surface is the source and sink of HONO at night.

Nitric oxide (NO) and nitrogen dioxide (NO2) are relevant to air quality due to their roles in tropospheric ozone (O3) production. In China, NOx emissions are very high and NOx emissions exhausted from on-road vehicles make up 20 % of total NOx emissions. In order to detect the NO and NO2 emissions on road, a dual-channel cavity ring-down spectroscopy (CRDS) system for NO2 and NO detection has been developed. In the system, NO is converted to NO2 by its reaction with excess O3 in the NOx channel, such that NO can be determined through the difference between two channels. The detection limits of NO2 and NOx for the system are estimated to be about 0.030 (1σ, 1 s) and 0.040 ppb (1σ, 1 s), respectively. Considering the error sources of NO2 absorption cross section and RL determination, the total uncertainty of NO2 measurements is about 5%. The performance of the system was validated against a chemiluminescence (CL) analyser (42i, Thermo Scientific, Inc.) by measuring the NO2 standard mixtures. The measurement results of NO2 showed a linear correction factor (R2) of 0.99 in a slope of 1.031±0.006, with an offset of (-0.940±0.323) ppb. An intercomparison between the system and a cavity-enhanced absorption spectroscopy (CEAS) instrument was also conducted separately for NO2 measurement in an ambient environment. Least-squares analysis showed that the slope and intercept of the regression line are 1.042±0.002 and (-0.393±0.040) ppb, respectively, with a linear correlation factor of R2=0.99. Another intercomparison conducted between the system and the CL analyser for NO detection also showed a good agreement within their uncertainties, with an absolute shift of (0.352±0.013) ppb, a slope of 0.957±0.007 and a correlation coefficient of R2=0.99. The system was deployed on the measurements of on-road vehicle emission plumes in Hefei, and the different emission characteristics were observed in the different areas of the city. The successful deployment of the system has demonstrated that the instrument can provide a new method for retrieving fast variations in NO and NO2 plumes.

We report the development of an instrument for simultaneous fast measurements of glyoxal (CHOCHO) and NO2 based on incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) in the 438–465 nm wavelength region. The highly reflective cavity mirrors were protected from contamination by N2 purge gas. The reduction of the effective cavity length was calibrated by measuring collision-induced oxygen absorption at ∼477 nm of pure oxygen gas input with and without the N2 mirror purge gas. The detection limits of the developed system were evaluated to be 23 parts per trillion by volume (pptv, 2σ) for CHOCHO and 29 pptv (2σ) for NO2 with a 30 s acquisition time. A potential cross-interference of NO2 absorption on accurate CHOCHO measurements has been investigated in this study, as the absorption of NO2 in the atmosphere could often be several hundred-fold higher than that of glyoxal, especially in contaminated areas. Due to non-linear spectrometer dispersion, simulation spectra of NO2 based on traditional convolution simulation did not match the measurement spectra well enough. In this work, we applied actual NO2 spectral profile measured by the same spectrometer as a reference spectral profile in subsequent atmospheric spectral analysis and retrieval of NO2 and CHOCHO concentrations. This effectively reduced the spectral fitting residuals. The instrument was successfully deployed for 24 d of continuous measurements of CHOCHO and NO2 in the atmosphere in a comprehensive field campaign in Beijing in June 2017.

Nitric oxide (NO) and nitrogen dioxide (NO2) are relevant to air quality due to their role in tropospheric ozone (O3) production. In China, NOx emission is high and exhausted from on-road vehicles makes up 20 % of total NOx emissions. Too much NOx are harmful to the human body and animals. In order to detect the NO and NO2 emissions on road, a dual-channel CRDS system for NO2 and NO detection is reported. In this system, NO is converted to NO2 by its reaction with excess O3 in NOx channel, such that NO can be determined through the difference between two channels. The detection limits of the developed CRDS system for NO2 and NOx measurements are estimated to be about 0.030 ppb (1σ, 1 s) and 0.040 ppb (1σ, 1 s), respectively. Considering the error sources of NO2 absorption cross section and RL determination, the total uncertainty of NO2 measurements is about 5 %. The CRDS method is capable of measuring species with high sensitivity and accuracy. The performance of the system was validated against a chemiluminescence (CL) analyzer (42i, Thermo Scientific, Inc.) when measuring the NO2 standard mixtures. The results of NO2 with standard mixtures sampled showed a linear correction factor (R2) of 0.99 in a slope of 1.031 ± 0.006, with an offset of (−0.940 ± 0.323) ppb. An intercomparison between the system and a cavity-enhanced absorption spectroscopy (CEAS) instrument for NO2 measurement was also conducted alone in ambient environment. Least-squares analysis showed that the slope and intercept of the regression line are 1.042 ± 0.002 and (−0.393 ± 0.040) ppb, respectively, with a linear correlation factor of R2 = 0.99. Another intercomparison conducted between the system and the CL analyzer for NO detection also showed a good agreement within their uncertainties, with an absolute shift of (0.352 ± 0.013) ppb, a slope of 0.957 ± 0.007 and a correlation coefficient of R2 = 0.99. The measurements of on-road vehicle emission plumes by this mobile CRDS instrument show the different emission characteristics in the urban and suburban areas of Hefei. The instrument provides a new method for retrieving fast variations of NO and NO2 plumes.

Gaseous nitrous acid (HONO) is an important source of OH radicals in the troposphere. However, its source, especially that during daytime hours remains unclear. We present an instrument for simultaneous unambiguous measurements of HONO and NO2 with high time resolution based on incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS). To achieve robust performance and system stability under different environment conditions, the current IBBCEAS instrument has been developed with significant improvements in terms of efficient sampling as well as resistance against vibration and temperature change, and the IBBCEAS instrument also has low power consumption and a compact design that can be easily deployed on different platforms powered by a high-capacity lithium ion battery. The effective cavity length of the IBBCEAS was determined using the absorption of O2-O2 to account for the “shortening” effect caused by the mirror purge flows. The wall loss for HONO was estimated to be 2.0 % via a HONO standard generator. Measurement precisions (2σ) for HONO and NO2 are about 180 and 340 ppt in 30 s, respectively. A field inter-comparison was carried out at a rural suburban site in Wangdu, Hebei Province, China. The concentrations of HONO and NO2 measured by IBBCEAS were compared with a long optical path absorption photometer (LOPAP) and a NOx analyzer (Thermo Fisher Electron Model 42i), and the results showed very good agreement, with correlation coefficients (R2) of HONO and NO2 being ∼0.89 and ∼0.95, respectively; in addition, vehicle deployments were also tested to enable mobile measurements of HONO and NO2, demonstrating the promising potential of using IBBCEAS for in situ, sensitive, accurate and fast simultaneous measurements of HONO and NO2 in the future.

We report the development of an instrument for simultaneous fast measurements of glyoxal (CHOCHO) and NO2 based on incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) in the 438–465 nm wavelength region. The highly-reflective cavity mirrors were protected from contamination by N2 purge gas. The reduction of the effective cavity length was calibrated by measuring collision-induced oxygen absorption at ∼477 nm of pure oxygen gas input with and without the N2 mirror purge gas. The detection limits of the developed system were evaluated to be 23 parts per trillion by volume (pptv, 2σ) for CHOCHO and 29 pptv (2σ) for NO2 with a 30-s acquisition time, respectively. A potential cross-interference of NO2 absorption on accurate CHOCHO measurements has been investigated in this study, as the absorption of NO2 in the atmosphere could often be several hundred-fold higher than that of glyoxal, especially in contaminated areas. Due to nonlinear spectrometer dispersion, simulation spectra of NO2 based on traditional convolution-simulation did not match the measurement spectra well enough. In this work, we applied actual NO2 spectral profile measured by the same spectrometer as a reference spectral profile in subsequent atmospheric spectral analysis and retrieval of NO2 and CHOCHO concentrations. This effectively reduced the spectral fitting residuals. The instrument was successfully deployed for 24 days of continuous measurements of CHOCHO and NO2 in atmosphere in a comprehensive field campaign in Beijing in June 2017.

Gaseous nitrous acid (HONO) is an important source of OH radicals in the troposphere. However, its source, especially that during daytime hours remains unclear. We present an instrument for simultaneous unambiguous measurements of HONO and NO2 with high time resolution based on incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS). To achieve robust performance and system stability under different environment conditions, the current IBBCEAS instrument has been developed with significant improvements in terms of efficient sampling as well as resistance against vibration and temperature change, and the IBBCEAS instrument also has low power consumption and a compact design that can be easily deployed on different platforms powered by a high-capacity lithium ion battery. The effective cavity length of the IBBCEAS was determined using the absorption of O2-O2 to account for the “shortening” effect caused by the mirror purge flows. The wall loss for HONO was estimated to be 2.0 % via a HONO standard generator. Measurement precisions (2σ) for HONO and NO2 are about 180 and 340 ppt in 30 s, respectively. A field inter-comparison was carried out at a rural suburban site in Wangdu, Hebei Province, China. The concentrations of HONO and NO2 measured by IBBCEAS were compared with a long optical path absorption photometer (LOPAP) and a NOx analyzer (Thermo Fisher Electron Model 42i), and the results showed very good agreement, with correlation coefficients (R2) of HONO and NO2 being ∼0.89 and ∼0.95, respectively; in addition, vehicle deployments were also tested to enable mobile measurements of HONO and NO2, demonstrating the promising potential of using IBBCEAS for in situ, sensitive, accurate and fast simultaneous measurements of HONO and NO2 in the future.