Temperature dependencies of the degradation of NO, NO2 and HONO on a photocatalytic dispersion paint.

The photocatalytic decomposition of nitrogen oxides (NOx) has attracted significant interest as a potential measure of reducing NOx levels in the urban atmosphere. Since photocatalytic activity is highly variable depending on atmospheric conditions, the uptake of NO, NO2 and HONO was studied on a commercial photocatalytic dispersion paint in a flow photoreactor as a function of the relative humidity and temperature. Since the relative humidity is a function of the surface's temperature, here both dependencies were carefully decoupled for the first time. In addition, for the first time the temperature dependence of the whole NOx reaction system including the important intermediate HONO was investigated. While for NO and NO2 strong negative humidity dependencies were observed, the photocatalytic uptake of HONO increased with humidity. For constant relative humidity no temperature dependence of the photocatalytic oxidation of NO was observed, whereas the photocatalytic NO2 uptake decreased with increasing temperature, which is explained by a temperature dependent adsorption equilibrium of the surface active NO2. HONO uptake showed a positive temperature dependence confirming the proposed photocatalysis of nitrite in a layer of adsorbed water on the surface of the photocatalyst. The missing/negative temperature dependencies of the photocatalysis of NO/NO2 are overcompensated by their strong negative relative humidity dependencies, leading to increasing uptake for both pollutants when photocatalytic surfaces are heated by solar irradiation in the atmosphere.

Determination of the emission indices for NO, NO2 , HONO, HCHO, CO, and particles emitted from candles.

In the present study, emission indices for NO, NO2 , HONO, HCHO, CO, particle mass, and particle numbers including particle size distributions for three different offering candles were determined. The candles investigated showed similar emission characteristics with emission indices (g/kg) in good agreement with former candle emission studies. An average HONO/NOx emission ratio of 6.6 ± 1.1% was obtained, which is much higher compared to most other combustion sources, indicating that candles may be a significant indoor source of this important trace gas. The particle size distributions indicate that the majority of the emitted particles are in the size range 7 - 15 nm. Three modes were observed during burning the candles with very different emission profiles: a "normal burning" mode characterized by low particle number emission rates and small particles; an initial "sooting" behavior after ignition, and a final "smoldering" phase upon candle extinction with higher particle number emission rates and larger particles. The particle emission upon extinction is dependent on the extinction method. The NOx emission indices were applied in a simple box model to calculate typical indoor NOx concentration levels from candle emissions, which were in excellent agreement with direct measurements in a typical indoor environment.

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.

Reply to the 'Comment on "Investigations on HONO formation from photolysis of adsorbed HNO3 on quartz glass surfaces"' by M. N. Sullivan, L. T. Chu and L. Zhu, Phys. Chem. Chem. Phys., 2018, 20, DOI: 10.1039/C8CP04497J.

In their comment to our recent paper about low HONO and NO2 formation by photolysis of adsorbed HNO3 Sullivan et al. confirmed their former results of HNO3 adsorption on silica under dry conditions using a quartz crystal microbalance. The authors concluded that the differences between their results and our conclusions are caused by the different experimental conditions, i.e. adsorption under very dry conditions compared to our experiments at 50% r.h. While we agree that adsorption of the highly water soluble HNO3 will strongly depend on humidity, there is still the conflict in the photolysis frequency of adsorbed HNO3 under atmospheric conditions to which the authors referred in their previous publications (see their atmospheric implication sections) and to which also our paper refers. If their results on both the adsorption cross sections of HNO3 (two to three orders of magnitude larger compared to the gas phase) and the quantum yield for NO2 formation (close to unity) are applicable under conditions prevailing in the atmosphere, then the photolytic lifetime of HNO3 on surfaces would be only ∼5 min for atmospheric solar flux (0° SZA), which is highly unlikely.

Assessing chemistry schemes and constraints in air quality models used to predict ozone in London against the detailed Master Chemical Mechanism.

Air pollution is the environmental factor with the greatest impact on human health in Europe. Understanding the key processes driving air quality across the relevant spatial scales, especially during pollution exceedances and episodes, is essential to provide effective predictions for both policymakers and the public. It is particularly important for policy regulators to understand the drivers of local air quality that can be regulated by national policies versus the contribution from regional pollution transported from mainland Europe or elsewhere. One of the main objectives of the Coupled Urban and Regional processes: Effects on AIR quality (CUREAIR) project is to determine local and regional contributions to ozone events. A detailed zero-dimensional (0-D) box model run with the Master Chemical Mechanism (MCMv3.2) is used as the benchmark model against which the less explicit chemistry mechanisms of the Generic Reaction Set (GRS) and the Common Representative Intermediates (CRIv2-R5) schemes are evaluated. GRS and CRI are used by the Atmospheric Dispersion Modelling System (ADMS-Urban) and the regional chemistry transport model EMEP4UK, respectively. The MCM model uses a near-explicit chemical scheme for the oxidation of volatile organic compounds (VOCs) and is constrained to observations of VOCs, NOx, CO, HONO (nitrous acid), photolysis frequencies and meteorological parameters measured during the ClearfLo (Clean Air for London) campaign. The sensitivity of the less explicit chemistry schemes to different model inputs has been investigated: Constraining GRS to the total VOC observed during ClearfLo as opposed to VOC derived from ADMS-Urban dispersion calculations, including emissions and background concentrations, led to a significant increase (674% during winter) in modelled ozone. The inclusion of HONO chemistry in this mechanism, particularly during wintertime when other radical sources are limited, led to substantial increases in the ozone levels predicted (223%). When the GRS and CRIv2-R5 schemes are run with the equivalent model constraints to the MCM, they are able to reproduce the level of ozone predicted by the near-explicit MCM to within 40% and 20% respectively for the majority of the time. An exception to this trend was observed during pollution episodes experienced in the summer, when anticyclonic conditions favoured increased temperatures and elevated O3. The in situ O3 predicted by the MCM was heavily influenced by biogenic VOCs during these conditions and the low GRS [O3] : MCM [O3] ratio (and low CRIv2-R5 [O3] : MCM [O3] ratio) demonstrates that these less explicit schemes under-represent the full O3 creation potential of these VOCs. To fully assess the influence of the in situ O3 generated from local emissions versus O3 generated upwind of London and advected in, the time since emission (and, hence, how far the real atmosphere is from steady state) must be determined. From estimates of the mean transport time determined from the NOx : NOy ratio observed at North Kensington during the summer and comparison of the O3 predicted by the MCM model after this time, ∼60% of the median observed [O3] could be generated from local emissions. During the warmer conditions experienced during the easterly flows, however, the observed [O3] may be even more heavily influenced by London's emissions.

Investigations on HONO formation from photolysis of adsorbed HNO3 on quartz glass surfaces.

During the last few decades, nitrous acid (HONO) has attracted significant attention as a major source of the OH radical, the detergent of the atmosphere. However, the different daytime sources identified in the laboratory are still the subject of controversial discussion. In the present study, one of these postulated HONO sources, the heterogeneous photolysis of nitric acid (HNO3), was studied on quartz glass surfaces in a photo flow-reactor under atmospherically relevant conditions. In contrast to other investigations, a very low HNO3 photolysis frequency for HONO formation of J(HNO3→ HONO) = 2.4 × 10(-7) s(-1) (0° SZA, 50% r.h.) was determined. If these results can be translated to atmospheric surfaces, HNO3 photolysis cannot explain the significant HONO levels in the daytime atmosphere. In addition, it is demonstrated that even the small measured yields of HONO did not result from the direct photolysis of HNO3 but rather from the consecutive heterogeneous conversion of the primary photolysis product NO2 on the humid surfaces. The secondary NO2 conversion was not photo-enhanced on pure quartz glass surfaces in good agreement with former studies. A photolysis frequency for the primary reaction product NO2 of J(HNO3→ NO2) = 1.1 × 10(-6) s(-1) has been calculated (0° SZA, 50% r.h.), which indicates that renoxification by photolysis of adsorbed HNO3 on non-reactive surfaces is also a minor process in the atmosphere.

Role of nitrite in the photochemical formation of radicals in the snow.

Photochemical reactions in snow can have an important impact on the composition of the atmosphere over snow-covered areas as well as on the composition of the snow itself. One of the major photochemical processes is the photolysis of nitrate leading to the formation of volatile nitrogen compounds. We report nitrite concentrations determined together with nitrate and hydrogen peroxide in surface snow collected at the coastal site of Barrow, Alaska. The results demonstrate that nitrite likely plays a significant role as a precursor for reactive hydroxyl radicals as well as volatile nitrogen oxides in the snow. Pollution events leading to high concentrations of nitrous acid in the atmosphere contributed to an observed increase in nitrite in the surface snow layer during nighttime. Observed daytime nitrite concentrations are much higher than values predicted from steady-state concentrations based on photolysis of nitrate and nitrite indicating that we do not fully understand the production of nitrite and nitrous acid in snow. The discrepancy between observed and expected nitrite concentrations is probably due to a combination of factors, including an incomplete understanding of the reactive environment and chemical processes in snow, and a lack of consideration of the vertical structure of snow.

Photocatalytic fixation of NOx in soils.

Nitrogen oxides (NOx = NO + NO2) are important atmospheric pollutants that are directly harmful to human health. Recently in urban and industrial areas, synthetic materials have been developed and deployed to photocatalytically oxidize NOx to nitrate (NO3-) in order to improve air quality. We show that the natural presence of small amounts (≤5%) of titanium oxides, such as anatase and rutile, can also drive NOx oxidation to nitrate in soils under UV-visible irradiation. The NO uptake coefficients ranged between 0.1 × 10-6 for sandy soils to 6.4 × 10-5 in the case of tropical clay soils; the latter comparable in efficiency to current industrial man-made catalysts. This photocatalytic N-fixation mechanism offers a new strategy for NOx mitigation from the atmosphere by transforming it into nitrate, and simultaneously provides an energy efficient source of essential fertilizer to agriculture.

Photosensitized reduction of nitrogen dioxide on humic acid as a source of nitrous acid.

Nitrous acid is a significant photochemical precursor of the hydroxyl radical, the key oxidant in the degradation of most air pollutants in the troposphere. The sources of nitrous acid in the troposphere, however, are still poorly understood. Recent atmospheric measurements revealed a strongly enhanced formation of nitrous acid during daytime via unknown mechanisms. Here we expose humic acid films to nitrogen dioxide in an irradiated tubular gas flow reactor and find that reduction of nitrogen dioxide on light-activated humic acids is an important source of gaseous nitrous acid. Our findings indicate that soil and other surfaces containing humic acid exhibit an organic surface photochemistry that produces reductive surface species, which react selectively with nitrogen dioxide. The observed rate of nitrous acid formation could explain the recently observed high daytime concentrations of nitrous acid in the boundary layer, the photolysis of which accounts for up to 60 per cent of the integrated hydroxyl radical source strengths. We suggest that this photo-induced nitrous acid production on humic acid could have a potentially significant impact on the chemistry of the lowermost troposphere.

Guaiacol Nitration in a Simulated Atmospheric Aerosol with an Emphasis on Atmospheric Nitrophenol Formation Mechanisms.

Atmospheric nitrophenols are pollutants of concern due to their toxicity and light-absorption characteristics and their low reactivity resulting in relatively long residence times in the environment. We investigate multiphase nitrophenol formation from guaiacol in a simulated atmospheric aerosol and support observations with the corresponding chemical mechanisms. The maximal secondary organic aerosol (SOA) yield (42%) is obtained under illumination at 80% relative humidity. Among the identified nitrophenols, 4-nitrocatechol (3.6% yield) is the prevailing species in the particulate phase. The results point to the role of water in catechol and further 4-nitrocatechol formation from guaiacol. In addition, a new pathway of dark nitrophenol formation is suggested, which prevailed in dry air and roughly yielded 1% nitroguaiacols. Furthermore, the proposed mechanism possibly leads to oligomer formation via a phenoxy radical formation by oxidation with HONO.

Daytime sources of nitrous acid (HONO) in the atmospheric boundary layer.

Nitrous acid (HONO) is an important precursor of the hydroxyl radical (OH), the self-cleaning agent of the atmosphere and a key species in the formation of harmful photooxidants during summer smog. Recent field measurements using very sensitive HONO instruments have shown that daytime HONO concentrations are much higher than has been assumed previously and that the contribution of HONO to the radical formation was underestimated in the past. A strong photochemical HONO source has been proposed, which contributes to the primary OH radical production up to 56 %. These exciting results initiated new laboratory studies, in which new sources of HONO have been identified. It is demonstrated that HONO is photochemically formed 1) on surfaces treated with nitric acid, 2) by reduction of NO(2) on photosensitized organic surfaces like humic acids and c) in the gas phase photolysis of ortho-substituted nitroaromatics. Although significant uncertainties still exist on the exact mechanisms, these additional sources might explain daytime observations in the atmosphere and demonstrate that HONO should be generally measured in field campaigns, besides other radical sources.

The photolysis of ortho-nitrophenols: a new gas phase source of HONO.

Formation of nitrous acid (HONO) in the gas phase has been observed for the first time in a flow tube photoreactor upon irradiation (lambda = 300-500 nm) of 2-nitrophenol and methyl substituted derivatives using a selective and sensitive instrument (LOPAP) for the detection of HONO. Formation of HONO by heterogeneous NO2 photochemistry has been excluded, since production of NO2 under the experimental conditions is negligible. Variation of the surface to volume ratio and the nitrophenol concentration showed that the photolysis occurred in the gas phase indicating that HONO formation is initiated by intramolecular hydrogen transfer from the phenolic OH group to the nitro group. From the measured linear dependence of the HONO formation rate on the reactant's concentration and photolysis light intensity, a non-negligible new HONO source is proposed for the urban atmosphere during the day. Unexpectedly high HONO mixing ratios have been observed recently in several field campaigns during the day. It is proposed that the photolysis of aromatic compounds containing the ortho-nitrophenol entity could help to explain, at least in part, this high contribution of HONO to the oxidation capacity of the urban atmosphere.