Heterogeneous Conversion Of NO2 Research Articles

Exploring the HONO source during the COVID-19 pandemic in a megacity in China

HONO is a critical precursor of •OH, but its sources are controversial due to its complex formation mechanism. This study conducted comprehensive observations in Zhengzhou from April 26 to May 11, 2022. Low NOx concentrations were observed during the Covid epidemic period (EP) (10.4 ± 3.0 ppb), compared to the pre-epidemic period (PEP) (12.5 ± 3.8 ppb). The mean HONO concentration during EP (0.53 ± 0.34 ppb) was 0.09 ppb lower than that during PEP (0.62 ± 0.53 ppb). The decrease in HONO concentration during EP came mainly at night due to the reduction in the direct emission (Pemi) (0.03 ppb/hr), the homogeneous reaction between •OH and NO (POH+NO) (0.02 ppb/hr), and the heterogeneous conversion of NO2 on the ground (0.01 ppb/hr). Notably, there was no significant change in daytime HONO concentration. The daytime HONO budget indicated that the primary HONO sources during PEP were the nitrate photolysis (Pnitrate), followed by the POH+NO, Pemi, the photo-enhanced reaction of NO2 on the ground (Pground+hv) and aerosol surface (Paerosol+hv). The primary HONO sources were Pnitrate, POH+NO, Pemi, and Paerosol+hv during EP, respectively. The missing source has a high correlation with solar radiation, there might be other photo-related HONO sources or the contributions of photosensitized reactions were underestimated. In the extremely underestimated cases, HONO production rates from the Pnitrate, Pground+hv, and Paerosol+hv increased by 0.17, 0.10, and 0.10 ppb/hr during PEP, 0.23, 0.13, and 0.16 ppb/hr during EP, and Pnitrate was still the primary source during both PEP and EP.

Budget of atmospheric nitrous acid (HONO) during the haze and clean periods in Shanghai: Importance of heterogeneous reactions

Nitrous acid (HONO) plays a significant role in radical cycling and atmospheric oxidative chemistry. While the source and evolution of HONO in the Yangtze River Delta (YRD) region of China after 2018 remains largely unknown, this work monitored HONO and other air pollutants throughout 2019 at an urban site (Pudong, PD) and a suburban site (Qingpu, QP) in Shanghai. Episodes with high HONO mixing ratios but different PM2.5 levels, namely haze and clean episodes, were chosen for HONO budget analysis. Using an observation-based photochemical box model, relative importance of different sources and sinks of HONO were evaluated. Gas-phase reaction of NO with OH was found to be one of the most important daytime HONO formation sources, especially during the QPhaze period (accounting for 40.3 % of daytime HONO formation). In particular, heterogeneous conversion of NO2 on ground and aerosol surface was found to be the dominant source for nocturnal HONO. Photo-enhanced NO2 conversion on ground surface plays an important role in daytime HONO production (19.4 % in PDhaze vs. 27.6 % in PDclean, and 19.8 % in QPhaze vs. 25.9 % in QPclean). In addition, photo-enhanced NO2 conversion at the aerosol surface during haze episodes made more significant contributions to HONO formation compared to the clean periods (20.9 % in PDhaze vs. 17.1 % in PDclean, and 19.7 % in QPhaze vs. 11.2 % in QPclean). The role of multiphase reactions was found to be increasingly important in HONO generation with enhanced relative humidity (RH) during daytime. Significant unknown HONO source was further analyzed and found to be positively related with photolytic as well as multiphase pathways. Overall, our study sheds light on the budget of HONO in one of the biggest megacities in east China, which would help developing future mitigation strategies for urban HONO and atmospheric oxidation capacity.

Exploring HONO formation and its role in driving secondary pollutants formation during winter in the North China Plain

Daytime HONO photolysis is an important source of atmospheric hydroxyl radicals (OH). Knowledge of HONO formation chemistry under typical haze conditions, however, is still limited. In the Multiphase chemistry experiment in Fogs and Aerosols in the North China Plain in 2018, we investigated the wintertime HONO formation and its atmospheric implications at a rural site Gucheng. Three different episodes based on atmospheric aerosol loading levels were classified: clean periods (CPs), moderately polluted periods (MPPs) and severely polluted periods (SPPs). Correlation analysis revealed that HONO formation via heterogeneous conversion of NO2 was more efficient on aerosol surfaces than on ground, highlighting the important role of aerosols in promoting HONO formation. Daytime HONO budget analysis indicated a large missing source (with an average production rate of 0.66 ± 0.26, 0.97 ± 0.47 and 1.45 ± 0.55 ppbV/hr for CPs, MPPs and SPPs, respectively), which strongly correlated with photo-enhanced reactions (NO2 heterogeneous reaction and particulate nitrate photolysis). Average OH formation derived from HONO photolysis reached up to (0.92 ± 0.71), (1.75 ± 1.26) and (1.82 ± 1.47) ppbV/hr in CPs, MPPs and SPPs respectively, much higher than that from O3 photolysis (i.e., (0.004 ± 0.004), (0.006 ± 0.007) and (0.0035 ± 0.0034) ppbV/hr). Such high OH production rates could markedly regulate the atmospheric oxidation capacity and hence promote the formation of secondary aerosols and pollutants.

Physical and chemical characterization of urban grime: An impact on the NO2 uptake coefficients and N-containing product compounds.

Urban grime represents an important environmental surface for heterogeneous reactions in urban environment. Here, we assess the physical and chemical properties of urban grime collected during six consecutive months in downtown of Guangzhou, China. There is a significant variation of the uptake coefficients of NO2 on the urban grime as a function of the relative humidity (RH). In absence of water molecules (0% RH), the light-induced uptake coefficients of NO2 on urban grime samples collected during six months are very similar in order of ≈10-6. At 80% RH, depending on the sampling month the light-induced uptake coefficient of NO2 can reach one order of magnitude higher values (1.5 × 10-5, at 80% RH) compared to those uptakes at 0% RH. In presence of 80% RH, there are strong correlations between the measured NO2 uptakes and the concentrations of the water soluble carbon, soluble anions, polycyclic aromatic hydrocarbons and n-alkanes depicted in the urban grime. These correlations, demonstrate that surface adsorbed water on urban grime play an important role for the uptakes of NO2. The heterogeneous conversion of NO2 on two-month old urban grime under sunlight irradiation (68 W m-2, 300 nm < λ < 400 nm) at 60% RH leads to the formation of unprecedented HONO surface flux of 4.7 × 1010 molecules cm-2 s-1 which is higher than all previously observed HONO fluxes, thereby affecting the oxidation capacity of the urban atmosphere. During the heterogeneous chemistry of NO2 with urban grime, the unsaturated and N-containing organic compounds are released in the gas phase which can affect the air quality in the urban environment.

Budget of nitrous acid (HONO) at an urban site in the fall season of Guangzhou, China

Abstract. High concentrations of nitrous acid (HONO) have been observed in the Pearl River Delta (PRD) region of China in recent years, contributing to an elevated atmospheric oxidation capacity due to the production of OH through HONO photolysis. We investigated the budget of HONO at an urban site in Guangzhou from 27 September to 9 November 2018 using data from a comprehensive atmospheric observation campaign. During this period, measured concentrations of HONO were 0.02 to 4.43 ppbv, with an average of 0.74 ± 0.70 ppbv. An emission ratio (HONO/NOx) of 0.9 ± 0.4 % was derived from 11 fresh plumes. The primary emission rate of HONO at night was calculated to be between 0.04 ± 0.02 and 0.30 ± 0.15 ppbv h−1 based on a high-resolution NOx emission inventory. Heterogeneous conversion of NO2 on the ground surface (0.27 ± 0.13 ppbv h−1), primary emissions from vehicle exhaust (between 0.04 ± 0.02 and 0.30 ± 0.15 ppbv h−1, with a middle value of 0.16 ± 0.07 ppbv h−1), and the homogeneous reaction of NO + OH (0.14 ± 0.30 ppbv h−1) were found to be the three largest sources of HONO at night. Heterogeneous NO2 conversion on aerosol surfaces (0.03 ± 0.02 ppbv h−1) and soil emission (0.019 ± 0.009 ppbv h−1) were two other minor sources. Correlation analysis shows that NH3 and the relative humidity (RH) may have participated in the heterogeneous transformation of NO2 to HONO at night. Dry deposition (0.41 ± 0.31 ppbv h−1) was the main removal process of HONO at night, followed by dilution (0.18 ± 0.16 ppbv h−1), while HONO loss at aerosol surfaces was much slower (0.008 ± 0.006 ppbv h−1). In the daytime, the average primary emission Pemis was 0.12 ± 0.02 ppbv h−1, and the homogeneous reaction POH+NO was 0.79 ± 0.61 ppbv h−1, larger than the unknown source PUnknown (0.65 ± 0.46 ppbv h−1). Similar to previous studies, PUnknown appeared to be related to the photo-enhanced conversion of NO2. Our results show that primary emissions and the reaction of NO + OH can significantly affect HONO at a site with intensive emissions during both the daytime and nighttime. Uncertainty in parameter values assumed in the calculation of HONO sources can have a strong impact on the relative importance of HONO sources at night, and could be reduced by improving knowledge of key parameters such as the NO2 uptake coefficient. The uncertainty in the estimated direct emission can be reduced by using emission data with higher resolution and quality. Our study highlights the importance of better constraining both conventional and novel HONO sources by reducing uncertainties in their key parameters for advancing our knowledge of this important source of atmospheric OH.

Strong marine-derived nitrous acid (HONO) production observed in the coastal atmosphere of northern China

Despite its important roles in the formation of hydroxyl radical (OH) and ozone (O3), the characteristics and sources of nitrous acid (HONO) in the marine atmosphere are still poorly understood. In this study, the HONO production in maritime air masses was explored based on a field observation conducted at a coastal site in Qingdao, China in the summer of 2019. The “sea case” and the “land case” were carefully distinguished according to wind direction and backward air mass trajectory. About four times larger nocturnal NO2-to-HONO conversion rate and ~60% larger daytime Pother (production rate of HONO other than gas-phase OH + NO reaction) at noon were observed in the “sea case” compared to the “land case” (0.045 ± 0.014 h−1 versus 0.012 ± 0.007 h−1, and 1.83 ± 0.02 ppbv h−1 versus 1.14 ± 0.07 ppbv h−1, respectively). Correlation analysis implied that heterogeneous conversion of NO2 and photolysis of nitrogen-containing compounds were potentially important sources of marine atmospheric HONO in the nocturnal and daytime, respectively, though alkaline oceans are previously considered as sinks of HONO. The impacts of these marine-derived HONO on OH and O3 were comparable to or larger than that of the “land case”. These results suggest that strong marine-derived HONO production may have been overlooked previously, and more studies are required to explore its detailed formation mechanisms in the marine atmosphere.

HONO Budget and Its Role in Nitrate Formation in the Rural North China Plain.

Nitrous acid (HONO) is a major precursor of tropospheric hydroxyl radical (OH) that accelerates the formation of secondary pollutants. The HONO sources, however, are not well understood, especially in polluted areas. Based on a comprehensive winter field campaign conducted at a rural site of the North China Plain, a box model (MCM v3.3.1) was used to simulate the daytime HONO budget and nitrate formation. We found that HONO photolysis acted as the dominant source for primary OH with a contribution of more than 92%. The observed daytime HONO could be well explained by the known sources in the model. The heterogeneous conversion of NO2 on ground surfaces and the homogeneous reaction of NO with OH were the dominant HONO sources with contributions of more than 36 and 34% to daytime HONO, respectively. The contribution from the photolysis of particle nitrate and the reactions of NO2 on aerosol surfaces was found to be negligible in clean periods (2%) and slightly higher during polluted periods (8%). The relatively high OH levels due to fast HONO photolysis at the rural site remarkably accelerated gas-phase reactions, resulting in the fast formation of nitrate as well as other secondary pollutants in the daytime.

Characteristics, sources, and reactions of nitrous acid during winter at an urban site in the Central Plains Economic Region in China

Abstract. Nitrous acid (HONO) in the core city of the Central Plains Economic Region in China was measured using an ambient ion monitor from 9 to 31 January 2019. Measurement time intervals were classified into the following periods in accordance with the daily mean values of PM2.5: clean days (CDs), polluted days (PDs), and severely polluted days (SPDs). The HONO concentrations during CD, PD, and SPD periods were 1.2, 2.3, and 3.7 ppbv, respectively. The contributions of the homogeneous reaction, heterogeneous conversion, and direct emissions to HONO sources varied under different pollution levels. The mean values of the net HONO production of the homogeneous reaction (POH+NOnet) in CD, PD, and SPD periods were 0.13, 0.26, and 0.56 ppbv h−1, respectively. The average conversions of NO2 (CHONO) in CD, PD, and SPD periods were 0.72×10-2, 0.64×10-2, and 1.54×10-2 h−1, respectively, indicating that the heterogeneous conversion of NO2 was less important than the homogeneous reaction. Furthermore, the net production of the homogeneous reaction may have been the main factor in the increase of HONO under high-NOx conditions (i.e., when the concentration of NO was higher than that of NO2) at nighttime. Daytime HONO budget analysis showed that the mean values of the unknown source (Punknown) during CD, PD, and SPD periods were 0.26, 0.40, and 1.83 ppbv h−1, respectively. The values of POH+NOnet, CHONO, and Punknown in the SPDs period were comparatively larger than those in other periods, indicating that HONO participated in many reactions. The proportions of nighttime HONO sources also changed during the entire sampling period. Direct emissions and a heterogeneous reaction controlled HONO production in the first half of the night and provided a contribution that is larger than that of the homogeneous reaction. The proportion of homogenization gradually increased in the second half of the night due to the steady increase in NO concentrations. The hourly level of HONO abatement pathways, except for OH + HONO, was at least 0.22 ppbv h−1 in the SPDs period. The cumulative frequency distribution of the HONOemission∕HONO ratio (less than 20 %) was approximately 77 %, which suggested that direct emission was not important. The heterogeneous HONO production increased when the relative humidity (RH) increased, but it decreased when RH increased further. The average HONO∕NOx ratio (4.9 %) was more than twice the assumed globally averaged value (2.0 %).

Sources of atmospheric nitrous acid (HONO) in the European High Arctic

The atmospheric concentrations of nitrous acid (HONO) have been measured from 15 to 25 April 2010 at Ny-Alesund (Svalbard). The results were discussed from the stand point of diurnal variations and meteorological effects. No clear diurnal cycle for the HONO concentrations was observed during our measurements. HONO concentration showed strong and significant correlation with both nitrogen dioxide (NO2) and relative humidity (RH), suggesting the importance of heterogeneous processes as HONO source. The strong correlation between HONO and HONO to NO2 ratio suggested the occurrence of heterogeneous conversion from NO2 to HONO, or HONO direct emission processes, or both. We used a pseudo steady state approach, including homogeneous and heterogeneous reactions and the emissive fluxes of HONO from the snow surface. It allowed accounting for all observed HONO concentrations only from small period. Except on them, about 28 % of the measured HONO was explained. The results showed that the heterogeneous conversion of NO2 on humid surface was a major HONO source, especially during the night. However, the results indicated the occurrence of a daytime HONO source whose strength was enough to compete with the HONO photolysis.

The effects of acetaldehyde, glyoxal and acetic acid on the heterogeneous reaction of nitrogen dioxide on gamma-alumina.

Heterogeneous reactions of nitrogen oxides on the surface of aluminium oxide result in the formation of adsorbed nitrite and nitrate. However, little is known about the effects of other species on these heterogeneous reactions and their products. In this study, diffuse reflectance infrared spectroscopy (DRIFTS) was used to analyze the process of the heterogeneous reaction of NO2 on the surface of aluminium oxide particles in the presence of pre-adsorbed organic species (acetaldehyde, glyoxal and acetic acid) at 298 K and reveal the influence of these organic species on the formation of adsorbed nitrite and nitrate. It was found that the pre-adsorption of organic species (acetaldehyde, glyoxal and acetic acid) on γ-Al2O3 could suppress the formation of nitrate to different extents. Under the same experimental conditions, the suppression of the formation of nitrate by the pre-adsorption of acetic acid is much stronger than that by pre-adsorption of acetaldehyde and glyoxal, indicating that the influence of acetic acid on the heterogeneous reaction of NO2 is different from that of acetaldehyde and glyoxal. Surface nitrite is formed and identified to be an intermediate product. For the heterogeneous reaction of NO2 on the surface of γ-Al2O3 with and without the pre-adsorption of acetaldehyde and glyoxal, it is firstly formed and then gradually disappears as the reaction proceeds, but for the reaction with the pre-adsorption of acetic acid, it is the final main product besides nitrate. This indicates that the pre-adsorption of acetic acid would promote the formation of nitrite, while the others would not change the trend of the formation of nitrite. The possible influence mechanisms of the pre-adsorption of acetaldehyde, glyoxal and acetic acid on the heterogeneous conversion of NO2 on γ-Al2O3 are proposed and atmospheric implications based on these results are discussed.

Effect of Formaldehyde on the Heterogeneous Reaction of Nitrogen Dioxide on γ-Alumina.

Heterogeneous reactions of NO2 on various mineral aerosol particles have been investigated in many previous studies, but a fundamental understanding of how the adsorption of formaldehyde influences the heterogeneous reactions of NO2 remains unclear. In this work, the effect of formaldehyde preadsorption on heterogeneous reaction of NO2 on the surface of γ-Al2O3 at 298 K and ambient pressure was investigated by using diffuse reflectance infrared Fourier transform spectrometry (DRIFTS). It was found that the preadsorption of HCHO on γ-Al2O3 could suppress the formation of nitrate, and the rate of nitrate formation decreased with increasing amount of preadsorbed HCHO, whereas the following heterogeneous uptake of NO2 could suppress the hydration reaction of HCHO and promote the production of HCOO(-) during the reaction. Surface nitrite was formed and identified to be an intermediate product and gradually disappeared as the reaction proceeded. The amount of the formed nitrite decreased when the amount of HCHO increased. Uptake coefficients of heterogeneous reactions were calculated and found to be sensitive to the adsorption of HCHO. A possible mechanism for the influence of HCHO adsorption on the heterogeneous conversion of NO2 on γ-Al2O3 was proposed, and atmospheric implications based on these results were discussed.

Influence of biomass burning plumes on HONO chemistry in eastern China

Abstract. Nitrous acid (HONO) plays a key role in atmospheric chemistry by influencing the budget of hydroxyl radical (OH). In this study, a two-month measurement of HONO and related quantities were analyzed during a biomass burning season in 2012 at a suburban site in the western Yangtze River delta, eastern China. An overall high HONO concentration with the mean value of 0.76 ppbv (0.01 ppbv to 5.95 ppbv) was observed. During biomass burning (BB) periods, both HONO concentration and HONO/NO2 ratio were enhanced significantly (more than a factor of 2, p &lt; 0.01) compared with non-biomass burning (non-BB) periods. A correlation analysis showed that the HONO in BB plumes was more correlated with nitrogen dioxide (NO2) than that with potassium (a tracer of BB). Estimation by the method of potassium tracing suggests a maximum contribution of 17 ± 12% from BB emission to the observed HONO concentrations, and the other over 80% of the observed nighttime HONO concentrations during BB periods were secondarily produced by the heterogeneous conversion of NO2. The NO2-to-HONO conversion rate (CHONO) in BB plumes was almost twice as that in non-BB plumes (0.0062 hr−1 vs. 0.0032 hr−1). Given that the residence time of the BB air masses was lower than that of non-BB air masses, these results suggest BB aerosols have higher NO2 conversion potentials to form HONO than non-BB aerosols. A further analysis based on comparing the surface area at similar particle mass levels and HONO/NO2 ratios at similar surface area levels suggested larger specific surface areas and higher NO2 conversion efficiencies of BB aerosols. A mixed plume of BB and anthropogenic fossil fuel (FF) emissions was observed on 10 June with even higher HONO concentrations and HONO/NO2 ratios. The strong HONO production potential (high HONO/NO2 to PM2.5 ratio) was accompanied with a high sulfate concentration in this plume, suggesting a promotion of mixed aerosols to the HONO formation. In summary, our study suggests an important role of BB in atmospheric chemistry by affecting the HONO budget. This can be especially important in eastern China, where agricultural burning plumes are inevitably mixed with urban and industrial pollution.

Heterogeneous conversion of NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; on secondary organic aerosol surfaces: A possible source of nitrous acid (HONO) in the atmosphere?

Abstract. The heterogeneous conversion of NO2 on different secondary organic aerosols (SOA) was investigated with the focus on a possible formation of nitrous acid (HONO). In one set of experiments different organic aerosols were produced in the reactions of O3 with alpha-pinene, limonene or catechol and OH radicals with toluene or limonene, respectively. The aerosols were sampled on filters and exposed to humidified NO2 mixtures under atmospheric conditions. The estimated upper limits for the uptake coefficients of NO2 and the reactive uptake coefficients NO2 -&gt; HONO are in the range of 10-6 and 10-7, respectively. The integrated HONO formation for 1 h reaction time was &lt;1013 cm-2 geometrical surface and &lt;1017 g-1 particle mass. In a second set of experiments the conversion of NO2 into HONO in the presence of organic particles was carried out in an aerosol flow tube under atmospheric conditions. In this case the aerosols were produced in the reaction of O3 with beta-pinene, limonene or catechol, respectively. The upper limits for the reactive uptake coefficients NO2 -&gt; HONO were in the range of 7 x 10-7 - 9 x 10-6. The results from the present study show that heterogeneous formation of nitrous acid on secondary organic aerosols (SOA) is unimportant for the atmosphere.

Investigation of the heterogeneous NO2 conversion on perchloric acid surfaces

The heterogeneous conversion of NO2 on perchloric acid surfaces into HONO, HNO3 and N2O was investigated in a bubbler system under simulated atmospheric conditions. NO2, HONO and N2O were monitored time resolved by long-path tunable infrared diode laser absorption spectrometry using single vibrational rotational lines. The experimental results show that NO2 is heterogeneously converted on acid surfaces into HONO and consecutively into N2O. HONO formation in the reaction system occurs by the heterogeneous reaction of NO2 with water. The solubility of HONO in perchloric acid was determined at 298 K as a function of the acid concentration. The effective Henry's law constant (KHeff) is well described by: