HONO Emissions Research Articles

Comparison of Simultaneous Measurements of Indoor Nitrous Acid: Implications for the Spatial Distribution of Indoor HONO Emissions.

Despite its importance as a radical precursor and a hazardous pollutant, the chemistry of nitrous acid (HONO) in the indoor environment is not fully understood. We present results from a comparison of HONO measurements from a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) and a laser photofragmentation/laser-induced fluorescence (LP/LIF) instrument during the House Observations of Microbial and Environmental Chemistry (HOMEChem) campaign. Experiments during HOMEChem simulated typical household activities and provided a dynamic range of HONO mixing ratios. The instruments measured HONO at different locations in a house featuring a typical air change rate (ACR) (0.5 h–1) and an enhanced mixing rate (∼8 h–1). Despite the distance between the instruments, measurements from the two instruments agreed to within their respective uncertainties (slope = 0.85, R2 = 0.92), indicating that the lifetime of HONO is long enough for it to be quickly distributed indoors, although spatial gradients occurred during ventilation periods. This suggests that emissions of HONO from any source can mix throughout the house and can contribute to OH radical production in sunlit regions, enhancing the oxidative capacity indoors. Measurement discrepancies were likely due to interferences with the LP/LIF instrument as well as calibration uncertainties associated with both instruments.

The seasonal variations and potential sources of nitrous acid (HONO) in the rural North China Plain

Nitrous acid (HONO), an essential precursor of hydroxyl radicals (OH) in the troposphere, plays an integral role in atmospheric photochemistry. However, potential HONO sources remain unclear, particularly in rural areas, where long-term (including seasonal) measurements are scarce. HONO and related parameters were measured at a rural site in the North China Plain (NCP) during the winter of 2017 and summer and autumn of 2020. The mean HONO level was higher in winter (1.79 ± 1.44 ppbv) than in summer (0.67 ± 0.50 ppbv) and autumn (0.83 ± 0.62 ppbv). Source analysis revealed that the heterogeneous conversion (including photo-enhanced conversion) of NO2 on the ground surface dominated the daytime HONO production in the three seasons (43.1% in winter, 54.3% in summer, and 62.0% in autumn), and the homogeneous reaction of NO and OH contributed 37.8, 12.2, and 28.4% of the daytime HONO production during winter, summer, and autumn, respectively. In addition, the total contributions of other sources (direct vehicle emissions, particulate nitrate photolysis, NO2 uptake and its photo-enhanced reaction on the aerosol surface) to daytime HONO production were less than 5% in summer and autumn and 12.0% in winter. Unlike winter and autumn, an additional HONO source was found in summer (0.45 ± 0.21 ppbv h−1, 31.4% to the daytime HONO formation), which might be attributed to the HONO emission from the fertilized field. Among the primary radical sources (photolysis of HONO, O3, and formaldehyde), HONO photolysis was dominant, with contributions of 82.6, 49.3, and 63.2% in winter, summer, and autumn, respectively. Our findings may aid in understanding HONO formation in different seasons in rural areas and may highlight the impact of HONO on atmospheric oxidation capacity.

Reactive Nitrogen Hotspots Related to Microscale Heterogeneity in Biological Soil Crusts.

Biocrusts covering drylands account for major fractions of terrestrial biological nitrogen fixation and release large amounts of gaseous reactive nitrogen (Nr) as nitrous acid (HONO) and nitric oxide (NO). Recent investigations suggested that aerobic and anaerobic microbial nitrogen transformations occur simultaneously upon desiccation of biocrusts, but the spatio-temporal distribution of seemingly contradictory processes remained unclear. Here, we explore small-scale gradients in chemical concentrations related to structural characteristics and organism distribution. X-ray microtomography and fluorescence microscopy revealed mixed pore size structures, where photoautotrophs and cyanobacterial polysaccharides clustered irregularly in the uppermost millimeter. Microsensor measurements showed strong gradients of pH, oxygen, and nitrite, nitrate, and ammonium ion concentrations at micrometer scales in both vertical and lateral directions. Initial oxygen saturation was mostly low (∼30%) at full water holding capacity, suggesting widely anoxic conditions, and increased rapidly upon desiccation. Nitrite concentrations (∼6 to 800 μM) and pH values (∼6.5 to 9.5) were highest around 70% WHC. During further desiccation they decreased, while emissions of HONO and NO increased, reaching maximum values around 20% WHC. Our results illustrate simultaneous, spatially separated aerobic and anaerobic nitrogen transformations, which are critical for Nr emissions, but might be impacted by future global change and land management.

Strong impacts of biomass burning, nitrogen fertilization, and fine particles on gas-phase hydrogen peroxide (H2O2)

Gas-phase hydrogen peroxide (H2O2) plays an important role in atmospheric chemistry as an indicator of the atmospheric oxidizing capacity. It is also a vital oxidant of sulfur dioxide (SO2) in the aqueous phase, resulting in the formation of acid precipitation and sulfate aerosol. However, sources of H2O2 are not fully understood especially in polluted areas affected by human activities. In this study, we reported some high H2O2 cases observed during one summer and two winter campaigns conducted at a polluted rural site in the North China Plain. Our results showed that agricultural fires led to high H2O2 concentrations up to 9 ppb, indicating biomass burning events contributed substantially to primary H2O2 emission. In addition, elevated H2O2 and O3 concentrations were measured after fertilization as a consequence of the enhanced atmospheric oxidizing capacity by soil HONO emission. Furthermore, H2O2 exhibited unexpectedly high concentration under high NOx conditions in winter, which are closely related to multiphase reactions in particles involving organic chromophores. Our findings suggest that these special factors (biomass burning, fertilization, and ambient particles), which are not well considered in current models, are significant contributors to H2O2 production, thereby affecting the regional atmospheric oxidizing capacity and the global sulfate aerosol formation.

Global and Regional Patterns of Soil Nitrous Acid Emissions and Their Acceleration of Rural Photochemical Reactions

AbstractAbiotic and biotic releases of nitrous acid (HONO) from soils contribute substantially to the missing source of tropospheric HONO and hydroxyl radicals (OH). However, global and regional patterns of soil HONO emissions are rarely quantified, and the contributions of such emissions to atmospheric oxidization capacity are unclear. Here, we present that the best estimate of global soil HONO emissions in 2017 was 9.67 with a range of 7.36–11.99 Tg N yr−1, and cropland soils accounting for ∼79%. The analyses also indicate that regional soil HONO emissions enhanced ground OH concentrations by 10%–60% and ozone concentrations by 0.5–1.5 ppb in daytime in the ambient area of Shanghai, China. The impact of soil HONO emissions on OH budgets was more significant in rural than urban areas. These findings suggest that the soil HONO emissions, especially from cropland, could quicken photochemical reactions, and aggravate air pollution in rural areas.

Climate warming, but not Spartina alterniflora invasion, enhances wetland soil HONO and NOx emissions

Climate warming and invasive plant growth (plant invasion) may aggravate air pollution by affecting soil nitrogen (N) cycling and the emissions of reactive N gases, such as nitrous acid (HONO) and nitrogen oxides (NOx). However, little is known about the response of soil NOy (HONO + NOx) emissions and microbial functional genes to the interaction of climate warming and plant invasion. Here, we found that experimental warming (approximately 1.5 °C), but not Spartina alterniflora invasion, increased NOy emissions (0–140 ng N m−2 s−1) of treated wetland soils by 4–10 fold. Warming also decreased soil archaeal and fungal richness and diversity, shifted their community structure (e.g., decreased the archaeal classes Thermoplasmata and Iainarchaeia, and increased the archaeal genus Candidatus Nitrosoarchaeum, and the fungal classes Saccharomycetes and Tritirachiomycetes), and decreased the overall abundance of soil N cycling genes. Structural equation modeling revealed that warming-associated changes in edaphic factors and the microbial N cycling potential are responsible for the observed increase in soil NOy emissions. Collectively, the results showed that climate warming accelerates soil N cycling by stimulating large soil HONO and NOx emissions, and influences air quality by contributing to atmospheric reactive N and ozone cycling.

A source for the continuous generation of pure and quantifiable HONO mixtures

Abstract. A continuous source for the generation of pure HONO mixtures was developed and characterized, which is based on the Henry's law solubility of HONO in acidic aqueous solutions. With the help of a peristaltic pump, diluted nitrite and sulfuric acid solutions are mixed in a temperature-controlled stripping coil, which is operated with pure nitrogen or synthetic air at gas flow rates of 0.5–2 L min−1. Caused by the acidic conditions of the aqueous phase (pH ≈ 2.5), nitrite is almost completely converted into HONO, which partitions to the gas phase limited by its known solubility in water. The source shows a fast time response of ∼ 2 min (0 %–90 %) at higher concentrations and an excellent long-term stability (2σ noise < 1 %). The HONO emission of the source perfectly correlates with the nitrite concentration from the sub-ppb range up to 500 ppb. The rate of NOx formation increases quadratically with the HONO concentration from non-detectable values at atmospheric relevant HONO concentrations reaching a NOx content of 1.6 % at 500 ppb. A general equation based on Henry's law is developed, whereby the HONO concentration of the source can be calculated using measured experimental parameters, i.e. nitrite concentration, liquid flow rates, gas flow rate, pH of the solution, and temperature of the stripping coil. In the equation, the known Henry's law constant of HONO in sulfuric acid solutions is used. For the calculation of the effective Henry's law constant, the acid dissociation equilibrium of HONO / nitrite is used as a variable to adjust the theoretical HONO concentration to the measured values. From the average of all experimental data the equilibrium of HONO / nitrite is described well by pKa=1021.53/T-0.449. The pKa of 3.0 ± 0.1 (1σ) at 25 ∘C is in good agreement with the range of 2.8–3.28 published in former studies. A standard deviation between all measured and theoretical HONO concentrations of only ±3.8 % was observed, and a conservative upper-limit accuracy of the HONO concentration of better 10 % is estimated. Thus, for the first time, a stable HONO source is developed which can be used for the absolute calibration of HONO instruments.

Emissions of atmospherically reactive gases nitrous acid and nitric oxide from Arctic permafrost peatlands

Soils are important sources of nitric oxide (NO) and nitrous acid (HONO) in the atmosphere. These nitrogen (N)-containing gases play a crucial role in atmospheric chemistry and climate at different scales because of reactions modulated by NO and hydroxyl radicals (OH), which are formed via HONO photolysis. Northern permafrost soils have so far remained unexplored for HONO and NO emissions despite their high N stocks, capacity to emit nitrous oxide (N2O), and enhancing mineral N turnover due to warming and permafrost thawing. Here, we report the first HONO and NO emissions from high-latitude soils based on measurements of permafrost-affected subarctic peatlands. We show large HONO (0.1–2.4 µg N m−2h−1) and NO (0.4–59.3 µg N m−2h−1) emissions from unvegetated peat surfaces, rich with mineral N, compared to low emissions (⩽0.2 µg N m−2h−1 for both gases) from adjacent vegetated surfaces (experiments with intact peat cores). We observed HONO production under highly variable soil moisture conditions from dry to wet. However, based on complementary slurry experiments, HONO production was strongly favored by high soil moisture and anoxic conditions. We suggest urgent examination of other Arctic landscapes for HONO and NO emissions to better constrain the role of these reactive N gases in Arctic atmospheric chemistry.

Photolysis of 1-nitropyrene: HONO and NO formations, optical property changes and mechanism insights

The emissions of HONO and NOx (NOx = NO + NO2) from 1-nitropyrene (1NPy) photolysis were investigated using a cylindrical reactor under different environmental conditions, such as total irradiance, relative humidity (RH), temperature, and O2 content. The emission flux densities of HONO (FHONO) and NO (FNO) had a positive correlation with the total irradiance (0–7.32 × 1016 photons cm−2 s−1). FHONO exhibited its maximum value at RH of 55% and temperature of 298 K. FNO decreased with increasing RH (7%–80%), whereas it linearly increased with the temperature (278–318 K). O2 participated in the production of HONO, whereas NO formation was independent of the O2 content. During the photolysis, changes in the composition of 1NPy occurred, including the consumption of nitro groups and the formation of aromatic C=O groups and phenolic hydroxyls. The 1NPy photolysis led to the modification of optical properties, as shown by a decrease at 300–320 and 355–440 nm and an increase at 320–355 and 440–500 nm for the mass absorption efficiency (MAEλ). The 1NPy photolysis frequency for HONO (J1NPy→HONO) and NO (J1NPy→NO) was calculated to be (1.6 ± 0.3) × 10−7 and (2.2 ± 0.1) × 10−6 s−1, respectively. Based on the experimental results, the HONO source strength from the nitroaromatic compounds (NACs) photolysis was estimated to be lower than 0.11 ppt h−1, suggesting that the photolysis of NACs in aerosols may not well explain daytime HONO sources.

Indoor heterogeneous photochemistry of molds and their contribution to HONO formation.

To better understand the impact of molds on indoor air quality, we studied the photochemistry of microbial films made by Aspergillus niger species, a common indoor mold. Specifically, we investigated their implication in the conversion of adsorbed nitrate anions into gaseous nitrous acid (HONO) and nitrogen oxides (NOx ), as well as the related VOC emissions under different indoor conditions, using a high-resolution proton transfer reaction-time of flight-mass spectrometer (PTR-TOF-MS) and a long path absorption photometer (LOPAP). The different mold preparations were characterized by the means of direct injection into an Orbitrap high-resolution mass spectrometer with a heated electrospray ionization (ESI-Orbitrap-MS). The formation of a wide range of VOCs, having emission profiles sensitive to the types of films (either doped by potassium nitrate or not), cultivation time, UV-light irradiation, potassium nitrate concentration and relative humidity was observed. The formation of nitrous acid from these films was also determined and found to be dependent on light and relative humidity. Finally, the reaction paths for the NOx and HONO production are proposed. This work helps to better understand the implication of microbial surfaces as a new indoor source for HONO emission.

Water-driven microbial nitrogen transformations in biological soil crusts causing atmospheric nitrous acid and nitric oxide emissions

Biological soil crusts (biocrusts) release the reactive nitrogen gases (Nr) nitrous acid (HONO) and nitric oxide (NO) into the atmosphere, but the underlying microbial process controls have not yet been resolved. In this study, we analyzed the activity of microbial consortia relevant in Nr emissions during desiccation using transcriptome and proteome profiling and fluorescence in situ hybridization. We observed that < 30 min after wetting, genes encoding for all relevant nitrogen (N) cycling processes were expressed. The most abundant transcriptionally active N-transforming microorganisms in the investigated biocrusts were affiliated with Rhodobacteraceae, Enterobacteriaceae, and Pseudomonadaceae within the Alpha- and Gammaproteobacteria. Upon desiccation, the nitrite (NO2−) content of the biocrusts increased significantly, which was not the case when microbial activity was inhibited. Our results confirm that NO2− is the key precursor for biocrust emissions of HONO and NO. This NO2− accumulation likely involves two processes related to the transition from oxygen-limited to oxic conditions in the course of desiccation: (i) a differential regulation of the expression of denitrification genes; and (ii) a physiological response of ammonia-oxidizing organisms to changing oxygen conditions. Thus, our findings suggest that the activity of N-cycling microorganisms determines the process rates and overall quantity of Nr emissions.

Agricultural Fertilization Aggravates Air Pollution by Stimulating Soil Nitrous Acid Emissions at High Soil Moisture.

Nitrogen lost from fertilized soil is a potentially large source of atmospheric nitrous acid (HONO), a major precursor of the hydroxyl radical. Yet, the impacts of fertilizer types and other influencing factors on HONO emissions are unknown. As a result, the current state-of-the-art models lack an appropriate parameterization scheme to quantify the HONO impact on air quality after fertilization. Here, we report laboratory measurements of high HONO emissions from soils at a 75-95% water-holding capacity after applying three common fertilizers, which contrasts with previous lower predictions at high soil moisture. Urea use leads to the largest release of HONO compared to the other two commonly used fertilizers (ammonium bicarbonate and ammonium nitrate). The significant promotion effect of fertilization lasted up to 1 week. Implementation of the lab-derived parametrization in a chemistry transport model (CMAQ) significantly improved postfertilization HONO predictions at a rural site in the agriculture-intensive North China Plain and increased the regionally averaged daytime OH, O3, and daily fine particulate nitrate concentrations by 41, 8, and 47%, respectively. The results of our study underscore the necessity to include this large postfertilization HONO source in modeling air quality and atmospheric chemistry. Fertilizer structure adjustments may reduce HONO emissions and improve the air quality in polluted regions with intense agriculture.

Nitrous acid (HONO) emission factors for diesel vehicles determined using a chassis dynamometer

Vehicle exhaust gases are important sources of nitrous acid (HONO). In this study, HONO in diesel vehicle exhaust was measured by incoherent broadband cavity-enhanced absorption spectroscopy using a chassis dynamometer system. The mean HONO concentrations in exhaust gases emitted by passenger cars and light-duty trucks were high when the after treatment devices were not fully working during the warming up period. The HONO/NOx ratio is a good index of HONO formation. The HONO/NOx ratios were 9.7 × 10−3–18.1 × 10−3, and were higher than what we found in a previous study. The estimated HONO emission factors were 7.71–64.70 mg (kg fuel)−1, and were lower than were found in previous studies. The results indicated that the frequency particulate matter is removed from a diesel particle filter affects the HONO concentration in the emitted gases and the HONO emission factor.

Nitrous acid emission from soil bacteria and related environmental effect over the North China Plain

Soil bacteria could be one of the important sources for ambient HONO. However, the HONO emission from soil bacteria over North China Plain (NCP) with vast croplands has not yet been evaluated. In this study, high-resolution simulations are created to explore the HONO emission from soil bacteria over NCP and related influences on atmospheric chemistry. Ground measurements of critical air pollutants including O3, HONO, and PM2.5 compositions are incorporated to constrain the model simulations. Results show that abundant HONO is emitted from soil bacteria over NCP during summertime and the emission rate varies dramatically for different areas (about 0.2 kg km−2 d−1 - 2.0 kg km−2 d−1). The HONO emission rate presents clear diurnal cycles with peaks of 1.5 kg km−2 d−1 in the afternoon and valleys of 0.4 kg km−2 d−1 during the early morning hours. The resulting HONO concentration ranges from 0.2 μg m−3 to 1.4 μg m−3, which predominates the total HONO concentration in ambient air, particularly in western NCP. The soil bacteria source can significantly alter the diurnal cycles of ambient HONO and OH concentrations over NCP, but only slightly change O3 and PM2.5 concentrations via participating photochemistry and secondary aerosol formations. These results highlight the pressing need for the involvement of HONO emission from soil bacteria in modeling studies regarding atmospheric chemistry, particularly in rural areas.

Seasonality of nitrous acid near an industry zone in the Yangtze River Delta region of China: Formation mechanisms and contribution to the atmospheric oxidation capacity

HONO along with other trace gases and actinic flux were continuously measured in selected months from December 2015 to November 2016 near a major industrial zone of the Yangtze River Delta (YRD) region of China. The seasonalities of HONO and its formation mechanisms were explored. A box model was developed to assess the role of HONO chemistry in the atmospheric oxidative capacity in the study area. The model was constrained by in-situ observations to minimize simulation uncertainties. Our measurement results demonstrate that HONO mean concentration and diurnal profile varied noticeably between different seasons with the maximum (1.32 ± 0.92 ppbv) observed in winter, coincided with high mass loading of fine particles (PM2.5 = 114 ± 59.6 μg m−3). The averaged nighttime NO2 to HONO conversion ratios (hr−1) were (1.83 ± 0.73)% in spring, (2.91 ± 1.06)% in summer, (0.72 ± 0.44)% in autumn, and (0.84 ± 0.45)% in winter. The homogeneous reaction of OH + NO was responsible for a large portion of HONO production throughout the year but was relatively weaker compared to other mechanisms in winter. Heterogeneous reactions on ground surfaces were much stronger than those on aerosol surfaces, dominating nighttime HONO production, except in summer. Primary HONO emissions were only responsible for a small portion of the HONO budget. Particulate nitrate photolysis was a significant source of HONO and it showed very little variation in different seasons. OH budget analysis shows that O3 photolysis was a major contributor to the OH production in the study area while HONO photolysis provided an extra boost to the photochemical reactivity in the early morning, particularly during summer. However, HONO chemistry played a more important role in autumn and winter by dominating OH production throughout the day. Accordingly, effective control of NOx emissions dominated by industries can significantly reduce HONO production and thus weaken the atmospheric oxidative capacity in the study area.

Denitrification is the major nitrous acid production pathway in boreal agricultural soils

Nitrous acid (HONO) photolysis produces hydroxyl radicals—a key atmospheric oxidant. Soils are strong HONO emitters, yet HONO production pathways in soils and their relative contributions are poorly constrained. Here, we conduct 15N tracer experiments and isotope pool dilution assays on two types of agricultural soils in Finland to determine HONO emission fluxes and pathways. We show that microbial processes are more important than abiotic processes for HONO emissions. Microbial nitrate reduction (denitrification) considerably exceeded ammonium oxidation as a source of nitrite—a central nitrogen pool connected with HONO emissions. Denitrification contributed 97% and 62% of total HONO fluxes in low and high organic matter soil, respectively. Microbial ammonium oxidation only produced HONO in high organic matter soil (10%). Our findings indicate that microbial nitrate reduction is an important HONO production pathway in aerobic soils, suggesting that terrestrial ecosystems favouring it could be HONO emission hotspots, thereby influencing atmospheric chemistry.

Assessment of Daytime HONO Emission Source from Asphalt Surface to Urban Air

Existing studies suggest various potential daytime sources of atmospheric nitrous acid (HONO), including photolysis surface reactions and photo-enhanced NO2 conversion on organic surfaces. However, the understanding of daytime HONO sources is still inadequate. In this study, we report the HONO formation on asphalt surfaces under various NO2, VOCs (toluene and hexane), and UV irradiance conditions using a continuous flow chamber. Although no HONO formation was found without light exposure, the light threshold for HONO formation on the asphalt surface was very low, with a total UV (TUV) of 0.7 W m−2. HONO formation on the asphalt surface was linearly dependent on NO2 up to 300 ppb in the presence of VOCs, but no HONO formation was observed with humified air and NO2. HONO production was saturated at high hydrocarbon concentrations and light intensities. The calculated first-order NO2 conversion rate to HONO on the asphalt surface was 1.2 × 10−4 s −1. The observed mean HONO emission flux was 1.3 × 109 molecules cm−2 s −1 with a similar range of those on other urban covered surfaces. The calculated vertical HONO profile using the measured HONO emission flux and 1-D steady state model revealed that the asphalt surface may account for 13% of daytime HONO in the elevated on-road pollutant concentrations in Seoul. However, we show that its HONO contribution could be much higher on real-life road surfaces directly exposed to much higher NO2 emissions from vehicle exhaust.

Evidence for Strong HONO Emission from Fertilized Agricultural Fields and its Remarkable Impact on Regional O3 Pollution in the Summer North China Plain

Summertime HONO concentrations were synchronously measured at two (agricultural and nonagricultural) sites in the North China Plain (NCP). Daytime HONO (1.4 ± 0.6 ppbv) and HONO/NO2 ((12 ± 8)%) over the agricultural field after fertilization were found to be remarkably higher than those before fertilization, implying strong HONO emission from the fertilized fields. Synchronous enhancements of HONO and O3 after fertilization at both sites suggested that the emitted HONO accelerated the local and the regional O3 pollution. HONO budget analysis further revealed that its emission was significantly enhanced after fertilization. Soil HONO emission flux and its uncertainty were estimated and discussed. The estimated emission flux exhibited a distinct diurnal variation with a noontime maximum. The net OH production rate from HONO photolysis greatly exceeded that from O3 photolysis over the agricultural field, and their maximum ratio of 4.7 was obtained after fertilization. We provide field evidence that fertilized fields in the NCP act as a strong HONO source, which accelerates daytime photochemistry, leading to an increase of regional photo-oxidants such as O3. Considering the severe O3 pollution in the summer NCP and that the large area of the agricultural field is regularly treated with high fertilization amount in this region, HONO emission should be taken into account in the regional air quality deterioration.

High Gaseous Nitrous Acid (HONO) Emissions from Light-Duty Diesel Vehicles.

Nitrous acid (HONO) plays an important role in the budget of hydroxyl radical (•OH) in the atmosphere. Vehicular emissions are a crucial primary source of atmospheric HONO, yet remain poorly investigated, especially for diesel trucks. In this study, we developed a novel portable online vehicular HONO exhaust measurement system featuring an innovative dilution technique. Using this system coupled with a chassis dynamometer, we for the first time investigated the HONO emission characteristics of 17 light-duty diesel trucks (LDDTs) and 16 light-duty gasoline vehicles in China. Emissions of HONO from LDDTs were found to be significantly higher than previous studies and gasoline vehicles tested in this study. The HONO emission factors of LDDTs decrease significantly with stringent control standards: 1.85 ± 1.17, 0.59 ± 0.25, and 0.15 ± 0.14 g/kg for China III, China IV, and China V, respectively. In addition, we found poor correlations between HONO and NOx emissions, which indicate that using the ratio of HONO to NOx emissions to infer HONO emissions might lead to high uncertainty of HONO source budget in previous studies. Lastly, the HONO emissions are found to be influenced by driving conditions, highlighting the importance of conducting on-road measurements of HONO emissions under real-world driving conditions. More direct measurements of the HONO emissions are needed to improve the understanding of the HONO emissions from mobile and other primary sources.

Nitrous acid formation on Zea mays leaves by heterogeneous reaction of nitrogen dioxide in the laboratory

Nitrous acid (HONO) is of considerable interest because it is an important precursor of hydroxyl radicals (OH), a key species in atmospheric chemistry. HONO sources are still not well understood, and air quality models fail to predict OH as well as HONO mixing ratios. As there is little knowledge about the potential contribution of plant surfaces to HONO emission, this laboratory work investigated HONO formation by heterogeneous reaction of NO2 on Zea mays. Experiments were carried out in a flow tube reactor; HONO, NO2 and NO were measured online with a Long Path Absorption Photometer (LOPAP) and a NOx analyzer. Tests were performed on leaves under different conditions of relative humidity (5–58%), NO2 mixing ratio representing suburban to urban areas (10–80 ppbv), spectral irradiance (0–20 W m−2) and temperature (288–313 K). Additional tests on plant wax extracts from Zea mays leaves showed that this component can contribute to the observed HONO formation. Temperature and NO2 mixing ratios were the two environmental parameters that showed substantially increased HONO emissions from Zea mays leaves. The highest HONO emission rates on Zea mays leaves were observed at 313 K for 40 ppbv of NO2 and 40% RH and reached values of (5.6 ± 0.8) × 109 molecules cm−2 s−1. Assuming a mixing layer of 300 m, the HONO flux from Zea mays leaves was estimated to be 171 ± 23 pptv h−1 during summertime, which is comparable to what has been reported for soil surfaces.