Search

Nitrous acid (HONO) plays an important role in the budget of hydroxyl radical (OH) in the atmosphere. However, current chemical transport models (CTMs) typically underestimate ambient concentrations of HONO due to a dearth of high resolution primary HONO emission inventories. To address this issue, we have established a highly resolved bottom-up HONO emission inventory for CTMs in Guangdong province, utilizing the best available domestic measured emission factors and newly obtained activity data. Our results indicate that emissions from various sources in 2020, including soil, on-road traffic, non-road traffic, biomass burning, and stationary combustion, were estimated at 21.5, 10.0, 8.2, 2.5, and 0.7 kt, respectively. Notably, the HONO emissions structure differed between the Pearl River Delta (PRD) and the non-PRD regions. Specifically, traffic sources were the dominant contributors (62 %) to HONO emissions in the PRD, whereas soil sources accounted for the majority (65 %) of those in the non-PRD. Among on-road traffic sources, diesel vehicles played a significant role, contributing 99.7 %. Comparisons with previous methods suggest that HONO emissions from diesel vehicles are underestimated by approximately 2.5 times. Higher HONO emissions, dominated by soil emissions, were observed in summer months, particularly in August. Furthermore, diesel vehicle emissions were pronounced at night, likely contributing to the nighttime accumulation of HONO and the morning peak of OH. The emission inventories developed in this study can be directly applied to widely used CTMs, such as CMAQ, CAMx, WRF-Chem, and NAQPMS, to support the simulation of OH formation and secondary air pollution.

Nitrous acid (HONO) is an important component of the global nitrogen cycle and can regulate the atmospheric oxidative capacity. Soil is an important source of HONO. [HONO]*, the equilibrium gas-phase concentration over the aqueous solution of nitrous acid in the soil, has been suggested as a key parameter for quantifying soil fluxes of HONO. However, [HONO]* has not yet been well-validated and quantified. Here, we present a method to retrieve [HONO]* by conducting controlled dynamic chamber experiments with soil samples applied with different HONO concentrations at the chamber inlet. We show a bi-directional soil–atmosphere exchange of HONO and confirm the existence of [HONO]* over soil: when [HONO]* is higher than the atmospheric HONO concentration, HONO will be released from soil; otherwise, HONO will be deposited. We demonstrate that [HONO]* is a soil characteristic, which is independent of HONO concentrations in the chamber but varies with different soil water contents. We illustrate the robustness of using [HONO]* for quantifying soil fluxes of HONO, whereas the laboratory-determined chamber HONO fluxes can largely deviate from those in the real world for the same soil sample. This work advances the understanding of the soil–atmosphere exchange of HONO and the evaluation of its impact on the atmospheric oxidizing capacity., Version of record

Tobacco-specific nitrosamines (TSNAs) are emitted during smoking and form indoors by nitrosation of nicotine. Two of them, N'-nitrosonornicotine (NNN) and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), are human carcinogens with No Significant Risk Levels (NSRLs) of 500 and 14 ng day-1, respectively. Another TSNA, 4-(methylnitrosamino)-4-(3-pyridyl) butanal (NNA), shows genotoxic and mutagenic activity in vitro. Here, we present additional evidence of genotoxicity of NNA, an assessment of TSNA dermal uptake, and predicted exposure risks through different pathways. Dermal uptake was investigated by evaluating the penetration of NNK and nicotine through mice skin. Comparable mouse urine metabolite profiles suggested that both compounds were absorbed and metabolized via similar mechanisms. We then investigated the effects of skin constituents on the reaction of adsorbed nicotine with nitrous acid (epidermal chemistry). Higher TSNA concentrations were formed on cellulose and cotton substrates that were precoated with human skin oils and sweat compared to clean substrates. These results were combined with reported air, dust, and surface concentrations to assess NNK intake. Five different exposure pathways exceeded the NSRL under realistic scenarios, including inhalation, dust ingestion, direct dermal contact, gas-to-skin deposition, and epidermal nitrosation of nicotine. These results illustrate potential long-term health risks for nonsmokers in homes contaminated with thirdhand tobacco smoke.

Nitrous acid (HONO) is an important component of the global nitrogen cycle and can regulate the atmospheric oxidative capacity. Soil is an important source of HONO. [HONO]*, the equilibrium gas-phase concentration over the aqueous solution of nitrous acid in the soil, has been suggested as a key parameter for quantifying soil fluxes of HONO. However, [HONO]* has not yet been well-validated and quantified. Here, we present a method to retrieve [HONO]* by conducting controlled dynamic chamber experiments with soil samples applied with different HONO concentrations at the chamber inlet. We show a bi-directional soil–atmosphere exchange of HONO and confirm the existence of [HONO]* over soil: when [HONO]* is higher than the atmospheric HONO concentration, HONO will be released from soil; otherwise, HONO will be deposited. We demonstrate that [HONO]* is a soil characteristic, which is independent of HONO concentrations in the chamber but varies with different soil water contents. We illustrate the robustness of using [HONO]* for quantifying soil fluxes of HONO, whereas the laboratory-determined chamber HONO fluxes can largely deviate from those in the real world for the same soil sample. This work advances the understanding of the soil–atmosphere exchange of HONO and the evaluation of its impact on the atmospheric oxidizing capacity., Version of record

The ROx (=OH + HO2 + RO2) budget and O3 production at an urban site in central China (Wuhan) during autumn were simulated and analyzed for the first time using a UW Chemical Model 0-D box model constrained by in situ observational data. The daytime average OH, HO2, and RO2 concentrations were 2.2 × 106, 1.0 × 108, and 5.2 × 107 molecules cm−3, respectively. The average daytime O3 production rate was 8.8 ppbv h−1, and alkenes were the most important VOC species for O3 formation (contributing 45%) at this site. Our sensitivity test indicated that the atmospheric environment in Wuhan during autumn belongs to the VOC-limited regime. The daily average HONO concentration at this site during the study period reached 1.1 ppbv and played an important role in the oxidative capacity of the atmosphere. Without the source of excess HONO, the average daytime OH, HO2, RO2, and O3 production rates decreased by 36%, 26%, 27%, and 31% respectively. A correlation between the HONO to NO2 heterogeneous conversion efficiency and PM2.5 × SWR was found at this site; based on this relationship, if the PM2.5 concentration met the World Health Organization air quality standard (25 µg m−3), the O3 production rate in this city would decrease by 19% during late autumn. The burning of agricultural biomass severely affected the air quality in Wuhan during summer and autumn. Agricultural burning was found to account for 18% of the O3 formation during the study period. Our results suggest that VOC control and a ban on agricultural biomass burning should be considered as high-priority measures for improving the air quality in this region.

The ROx (=OH + HO2 + RO2) budget and O3 production at an urban site in central China (Wuhan) during autumn were simulated and analyzed for the first time using a UW Chemical Model 0-D box model constrained by in situ observational data. The daytime average OH, HO2, and RO2 concentrations were 2.2 × 106, 1.0 × 108, and 5.2 × 107 molecules cm−3, respectively. The average daytime O3 production rate was 8.8 ppbv h−1, and alkenes were the most important VOC species for O3 formation (contributing 45%) at this site. Our sensitivity test indicated that the atmospheric environment in Wuhan during autumn belongs to the VOC-limited regime. The daily average HONO concentration at this site during the study period reached 1.1 ppbv and played an important role in the oxidative capacity of the atmosphere. Without the source of excess HONO, the average daytime OH, HO2, RO2, and O3 production rates decreased by 36%, 26%, 27%, and 31% respectively. A correlation between the HONO to NO2 heterogeneous conversion efficiency and PM2.5 × SWR was found at this site; based on this relationship, if the PM2.5 concentration met the World Health Organization air quality standard (25 µg m−3), the O3 production rate in this city would decrease by 19% during late autumn. The burning of agricultural biomass severely affected the air quality in Wuhan during summer and autumn. Agricultural burning was found to account for 18% of the O3 formation during the study period. Our results suggest that VOC control and a ban on agricultural biomass burning should be considered as high-priority measures for improving the air quality in this region.

The ROx (=OH + HO2 + RO2) budget and O3 production at an urban site in central China (Wuhan) during autumn were simulated and analyzed for the first time using a UW Chemical Model 0-D box model constrained by in situ observational data. The daytime average OH, HO2, and RO2 concentrations were 2.2 × 106, 1.0 × 108, and 5.2 × 107 molecules cm−3, respectively. The average daytime O3 production rate was 8.8 ppbv h−1, and alkenes were the most important VOC species for O3 formation (contributing 45%) at this site. Our sensitivity test indicated that the atmospheric environment in Wuhan during autumn belongs to the VOC-limited regime. The daily average HONO concentration at this site during the study period reached 1.1 ppbv and played an important role in the oxidative capacity of the atmosphere. Without the source of excess HONO, the average daytime OH, HO2, RO2, and O3 production rates decreased by 36%, 26%, 27%, and 31% respectively. A correlation between the HONO to NO2 heterogeneous conversion efficiency and PM2.5 × SWR was found at this site; based on this relationship, if the PM2.5 concentration met the World Health Organization air quality standard (25 µg m−3), the O3 production rate in this city would decrease by 19% during late autumn. The burning of agricultural biomass severely affected the air quality in Wuhan during summer and autumn. Agricultural burning was found to account for 18% of the O3 formation during the study period. Our results suggest that VOC control and a ban on agricultural biomass burning should be considered as high-priority measures for improving the air quality in this region.

We present OH observations from Nitrogen, Aerosol Composition, and Halogens on a Tall Tower 2011 (NACHTT-11) held at the Boulder Atmospheric Observatory in Weld County, Colorado. Average OH levels at noon were ~ 2.7 × 106 molecules cm-3 at 2 m above ground level. Nitrous acid (HONO) photolysis was the dominant OH source (80.4%) during this campaign, while alkene ozonolysis (4.9%) and ozone photolysis (14.7%) were smaller contributions to OH production. To evaluate recycling sources of OH from HO2 and RO2, an observationally constrained University of Washington Chemical Mechanism (UWCM) box model (version 2.1) was employed to simulate ambient OH levels over several scenarios. For the base run, not constrained by observed HONO, the model significantly underestimated OH by a factor of 5.3 in the morning (9:00–11:00) and by a factor of 3.2 in the afternoon (13:00–15:00). The results suggest that known chemistry cannot constrain HONO and, subsequently, OH during the observational period. When HONO is constrained in the model by observations (< 50 m), the discrepancy between observation and model simulation improves to a factor of 1.3 in the morning and a factor 1.1 in the afternoon, within the 35% estimated instrumental uncertainty. However, the model produces both a morning and afternoon maximum in OH, in contrast to the observations, which show strong evidence for morning OH production but no distinct morning maximum. Two additional OH sources were also considered, although they do not improve the differences in modeled and measured temporal OH profiles. First, the impact of daytime HONO gradients near the ground surface (< 20 m) was evaluated. Strong HONO gradients were observed between 06:00 and 09:00 MST (mountain standard time), especially within 20 m of the surface. When constrained to HONO observed below 20 m (rather than 50 m), the model produced an even larger morning OH maximum, in contrast to the observations. Second, Cl atoms from ClNO2 photolysis prod

We present OH observations from Nitrogen, Aerosol Composition, and Halogens on a Tall Tower 2011 (NACHTT-11) held at the Boulder Atmospheric Observatory in Weld County, Colorado. Average OH levels at noon were ~ 2.7 × 106 molecules cm-3 at 2 m above ground level. Nitrous acid (HONO) photolysis was the dominant OH source (80.4%) during this campaign, while alkene ozonolysis (4.9%) and ozone photolysis (14.7%) were smaller contributions to OH production. To evaluate recycling sources of OH from HO2 and RO2, an observationally constrained University of Washington Chemical Mechanism (UWCM) box model (version 2.1) was employed to simulate ambient OH levels over several scenarios. For the base run, not constrained by observed HONO, the model significantly underestimated OH by a factor of 5.3 in the morning (9:00–11:00) and by a factor of 3.2 in the afternoon (13:00–15:00). The results suggest that known chemistry cannot constrain HONO and, subsequently, OH during the observational period. When HONO is constrained in the model by observations (< 50 m), the discrepancy between observation and model simulation improves to a factor of 1.3 in the morning and a factor 1.1 in the afternoon, within the 35% estimated instrumental uncertainty. However, the model produces both a morning and afternoon maximum in OH, in contrast to the observations, which show strong evidence for morning OH production but no distinct morning maximum. Two additional OH sources were also considered, although they do not improve the differences in modeled and measured temporal OH profiles. First, the impact of daytime HONO gradients near the ground surface (< 20 m) was evaluated. Strong HONO gradients were observed between 06:00 and 09:00 MST (mountain standard time), especially within 20 m of the surface. When constrained to HONO observed below 20 m (rather than 50 m), the model produced an even larger morning OH maximum, in contrast to the observations. Second, Cl atoms from ClNO2 photolysis prod

type:text, An open top chamber experiment was carried out in the summer of 2003 to examine the effect of nitrous acid (HONO) gas on the physiological status of Scots pine saplings (Pinus sylvestris). Four-year-old pine trees were exposed to two different levels of HONO gas (at ca. 2.5 ppb and 5.0 ppb) and a control (filtered air) from early evening to early morning (18:00–6:00), in duplicate open top chambers. Significant decreases in the ratios of chlorophylls a to b, an increase in the carbon to nitrogen (C/N) ratio, and a reduction of maximum yield of PS II (Fv/Fm) in pine needles were also observed after the 2 months' fumigation. Cation contents of pine needles were also decreased by the fumigation with HONO gas. The results could be explained by the harmful effects of OH radicals, generated from photolysis of HONO gas, and/or aqueous phase HONO (NO2-/HONO), on the photosynthetic capacity of pine needles.

An open top chamber experiment was carried out in the summer of 2003 to examine the effect of nitrous acid (HONO) gas on the physiological status of Scots pine saplings (Pinus sylvestris). Four-year-old pine trees were exposed to two different levels of HONO gas (at ca. 2.5 ppb and 5.0 ppb) and a control (filtered air) from early evening to early morning (18:00–6:00), in duplicate open top chambers. Significant decreases in the ratios of chlorophylls a to b, an increase in the carbon to nitrogen (C/N) ratio, and a reduction of maximum yield of PS II (Fv/Fm) in pine needles were also observed after the 2 months' fumigation. Cation contents of pine needles were also decreased by the fumigation with HONO gas. The results could be explained by the harmful effects of OH radicals, generated from photolysis of HONO gas, and/or aqueous phase HONO (NO2-/HONO), on the photosynthetic capacity of pine needles.

An open top chamber experiment was carried out in the summer of 2003 to examine the effect of nitrous acid (HONO) gas on the physiological status of Scots pine saplings (Pinus sylvestris). Four-year-old pine trees were exposed to two different levels of HONO gas (at ca. 2.5 ppb and 5.0 ppb) and a control (filtered air) from early evening to early morning (18:00–6:00), in duplicate open top chambers. Significant decreases in the ratios of chlorophylls a to b, an increase in the carbon to nitrogen (C/N) ratio, and a reduction of maximum yield of PS II (Fv/Fm) in pine needles were also observed after the 2 months' fumigation. Cation contents of pine needles were also decreased by the fumigation with HONO gas. The results could be explained by the harmful effects of OH radicals, generated from photolysis of HONO gas, and/or aqueous phase HONO (NO2-/HONO), on the photosynthetic capacity of pine needles.

The research performed with support by AFOSR grant F49620-95-1-0310 for the period April 1, 1995 to September 30, 1998 is described. Theoretical methods and atomic-level models were developed for studies of fundamental processes and properties of potential HEDM materials. The long-term goal of this research is to perform molecular dynamics and Monte Carlo simulations of the various kinds of processes, including chemical reactions, for systems that display the properties inherent in high-energy high-density materials. This research lays the groundwork for that by providing the theoretical and computational methods as well as accurate molecular and crystal models for important types of energetic systems; for example, molecules such as NTO (5-Nitro-2,4-dihydro-3H-1,2,4-triazol-3-one) and ADN (ammonium dinitramide). Classical dynamics simulations of molecular isomerization in a solid (Ar matrix) were performed for a prototypical energy material (HONO). A significant part of this project was the refinement of chemical dynamics methods for multidimensional problems. A new method was introduced in this work that can be used for accurate treatment of quantum effects such as tunneling in many-atom systems. A fundamental analysis of the failure in some cases of classical mechanics to accurately account for the behavior of zero-point energy was also presented. A method based on simple transtion-state theory was developed for computing the rates of mass migration in solids; it was demonstrated for various kinds of atoms in rare gas matrices, and the results are in good agreement with experiment.

An open top chamber experiment was carried out in the summer of 2003 to examine the effect of nitrous acid (HONO) gas on the physiological status of Scots pine saplings (Pinus sylvestris). Four-year-old pine trees were exposed to two different levels of HONO gas (at ca. 2.5 ppb and 5.0 ppb) and a control (filtered air) from early evening to early morning (18:00–6:00), in duplicate open top chambers. Significant decreases in the ratios of chlorophylls a to b, an increase in the carbon to nitrogen (C/N) ratio, and a reduction of maximum yield of PS II (Fv/Fm) in pine needles were also observed after the 2 months' fumigation. Cation contents of pine needles were also decreased by the fumigation with HONO gas. The results could be explained by the harmful effects of OH radicals, generated from photolysis of HONO gas, and/or aqueous phase HONO (NO2-/HONO), on the photosynthetic capacity of pine needles.