Ozone Deposition Research Articles

The impact of surfaces on indoor air chemistry following cooking and cleaning.

Cooking and cleaning are common sources of indoor air pollutants, including volatile organic compounds (VOCs). The chemical fate of VOCs indoors is determined by both gas-phase and multi-phase chemistry, and can result in the formation of potentially hazardous secondary pollutants. Chemical interactions at the gas-surface boundary play an important role in indoor environments due to the characteristically high surface area to volume ratios (SAVs). This study first characterises the VOC emissions from a typical cooking and cleaning activity in a semi-realistic domestic kitchen, using real-time measurements. While cooking emitted a larger amount of VOCs overall, both cooking and cleaning were sources of chemically reactive monoterpenes (peak mixing ratios 7 ppb and 2 ppb, respectively). Chemical processing of the VOC emissions from sequential cooking and cleaning activities was then simulated in a kitchen using a detailed chemical model. Results showed that ozone (O3) deposition was most effective onto plastic and soft furnishings, while wooden surfaces were the most effective at producing formaldehyde following multi-phase chemistry. Subsequent modelling of cooking and cleaning emissions using a range of measured kitchen SAVs revealed that indoor oxidant levels and the subsequent chemistry, are strongly influenced by the total and material-specific SAV of the room. O3 mixing ratios ranged from 1.3-7.8 ppb across 9 simulated kitchens, with higher concentrations of secondary pollutants observed at higher O3 concentration. Increased room volume, decreased total SAV, decreased SAVs of plastic and soft furnishings, and increased wood SAV contributed to elevated formaldehyde and total peroxyacetyl nitrates (PANs) mixing ratios, of up to 1548 ppt and 643 ppt, respectively, following cooking and cleaning. Therefore, the size and material composition of indoor environments has the potential to impact the chemical processing of VOC emissions from common occupant activities.

An improved estimate of inorganic iodine emissions from the ocean using a coupled surface microlayer box model

Abstract. Iodine at the ocean's surface impacts climate and health by removing ozone (O3) from the troposphere both directly via ozone deposition to seawater and indirectly via the formation of iodine gases that are released into the atmosphere. Here we present a new box model of the ocean surface microlayer that couples oceanic O3 dry deposition to inorganic chemistry to predict inorganic iodine emissions. This model builds on the previous work of Carpenter et al. (2013), improving both chemical and physical processes. This new box model predicts iodide depletion in the top few micrometres of the ocean surface due to rapid chemical loss to ozone competing with replenishment from underlying water. From this box model, we produce parameterized equations for HOI and I2 emissions, which are implemented into the global chemical transport model GEOS-Chem along with an updated sea surface iodide climatology. Compared to the previous model, inorganic iodine emissions from some tropical waters decrease by as much as half, while higher-latitude emissions increase by a factor of ≫10. With these large local changes, global total inorganic iodine emissions increased by ∼49 % (2.99 to 4.48 Tg) compared to the previous parameterization. This results in a negligible change in average tropospheric OH (<0.2 %) and tropospheric methane lifetime (<0.2 %). The annual mean tropospheric O3 burden decreases (−1.5 % to 325 Tg); however, higher-latitude surface O3 concentrations decrease by as much as 20 %.

Production of oxygenated volatile organic compounds from the ozonolysis of coastal seawater

Abstract. Dry deposition of ozone (O3) to the ocean surface and the ozonolysis of organics in the sea surface microlayer (SSML) are potential sources of volatile organic compounds (VOCs) to the marine atmosphere. We use a gas chromatography system coupled to a Vocus proton-transfer-reaction time-of-flight mass spectrometer to determine the chemical composition and product yield of select VOCs formed from ozonolysis of coastal seawater collected from Scripps Pier in La Jolla, California. Laboratory-derived results are interpreted in the context of direct VOC vertical flux measurements made at Scripps Pier. The dominant products of laboratory ozonolysis experiments and the largest non-sulfur emission fluxes measured in the field correspond to Vocus CxHy+ and CxHyOz+ ions. Gas chromatography (GC) analysis suggests that C5–C11 oxygenated VOCs, primarily aldehydes, are the largest contributors to these ion signals. In the laboratory, using a flow reactor experiment, we determine a VOC yield of 0.43–0.62. In the field at Scripps Pier, we determine a maximum VOC yield of 0.04–0.06. Scaling the field and lab VOC yields for an average O3 deposition flux and an average VOC structure results in an emission source of 10.7 to 167 Tg C yr−1, competitive with the DMS source of approximately 20.3 Tg C yr−1. This study reveals that O3 reactivity to dissolved organic carbon can be a significant carbon source to the marine atmosphere and warrants further investigation into the speciated VOC composition from different seawater samples and the reactivities and secondary organic aerosol (SOA) yields of these molecules in marine-relevant, low NOx conditions.

Observation of ozone deposition flux and its contribution to stomatal uptake over a winter wheat field in eastern China

Ground-level ozone (O3) poses a significant threat to food security in China. Therefore, it is imperative to conduct a comprehensive scientific evaluation of the potential hazards posed by O3 to agricultural crops. This study continuously observed variation in meteorological factors, O3 concentration, O3 deposition rate and flux, and quantified the distribution characteristics of O3 deposition flux in stomatal and non-stomatal pathways. Results suggested that the O3 dry deposition rate and flux in winter wheat fields exhibited relatively stable variations at night but pronounced fluctuations during the day. Their mean values were 0.31 cm s−1 and -0.0044 μmol m−2·s−1, respectively, with peak values occurring at 08:30 and 14:00. The cumulative O3 total flux during the main growth season of winter wheat was 26.1 mmol m−2, with stomatal and non-stomatal fluxes accounting for 7.7 mmol m−2 and 18.4 mmol m−2, respectively. The proportions of total O3 flux in stomatal and non-stomatal channels were 29.5% and 70.5%, respectively, with daytime proportions being 39.7% and 60.3%, respectively. These findings provide crucial insights for future accurate assessments of crop yield loss due to O3 at the earth's surface.

Improving model representation of rapid ozone deposition over soil in the central Tibetan Plateau

Ozone deposition velocity with a daily mean of 0.49 cm s−1 was observed in the Tibetan Plateau and rationalized by local meteorological and soil conditions. Our research suggested widespread ozone deposition velocity over soil of 0.1–0.7 cm s−1.

Ozone Fluxes Over a Boreal Lake Exhibit Enhanced Deposition at Nights

AbstractA few studies on ozone deposition over lake water are available and so far only one using the eddy covariance technique (Wesely et al., 1981, https://doi.org/10.1007/BF00122295). A 23‐day field campaign was held in August‐September 2012 at the Lake Kuivajärvi in Hyytiälä, Finland. The results showed a mean flux of −30 ± 1 ng m−2 s−1 and deposition velocity of 0.86 ± 0.05 mm s−1. Deposition velocity showed a weak diurnal cycle over the lake with elevated values during the nighttime. The daytime and nighttime portions of the data set differed statistically. Analysis showed that waterside convective mixing enhanced deposition and such conditions pre‐dominantly occurred during nighttime. We compared the measured deposition velocities with the dry deposition model of air‐sea exchange, adjusted for the chemical sinks relevant for the lake. We suggest that the buoyant mixing and unaccounted chemistry can be responsible for the difference between the model results and observations.

A single-point modeling approach for the intercomparison and evaluation of ozone dry deposition across chemical transport models (Activity 2 of AQMEII4).

A primary sink of air pollutants and their precursors is dry deposition. Dry deposition estimates differ across chemical transport models, yet an understanding of the model spread is incomplete. Here, we introduce Activity 2 of the Air Quality Model Evaluation International Initiative Phase 4 (AQMEII4). We examine 18 dry deposition schemes from regional and global chemical transport models as well as standalone models used for impact assessments or process understanding. We configure the schemes as single-point models at eight Northern Hemisphere locations with observed ozone fluxes. Single-point models are driven by a common set of site-specific meteorological and environmental conditions. Five of eight sites have at least 3 years and up to 12 years of ozone fluxes. The interquartile range across models in multiyear mean ozone deposition velocities ranges from a factor of 1.2 to 1.9 annually across sites and tends to be highest during winter compared with summer. No model is within 50 % of observed multiyear averages across all sites and seasons, but some models perform well for some sites and seasons. For the first time, we demonstrate how contributions from depositional pathways vary across models. Models can disagree with respect to relative contributions from the pathways, even when they predict similar deposition velocities, or agree with respect to the relative contributions but predict different deposition velocities. Both stomatal and nonstomatal uptake contribute to the large model spread across sites. Our findings are the beginning of results from AQMEII4 Activity 2, which brings scientists who model air quality and dry deposition together with scientists who measure ozone fluxes to evaluate and improve dry deposition schemes in the chemical transport models used for research, planning, and regulatory purposes.

Modeling ozone deposition on bulk grains and ozone deposition in columns of wheat grains

To better understand ozone deposition on bulk grains to control bacterium and insects, we investigated time-dependent deposition of ozone at various depths in columns of grains. We proposed a model of ozone deposition on bulk grains based on a material balance for ozone. The model included porosity, pore shape factor and velocity of ozone gas for bulk grains. The model was applied to determine the time-dependent deposition velocities of ozone at various depths in columns of wheat grains. Ozone deposition on wheat grains had two distinct phases. Phase 1 was characterized by high deposition velocities and then rapid decrease. In phase 2, the deposition velocities were kept constant with the time at various depths in the column. The saturation time based on the deposition model was 87.1h and the relative error was 2.4% for grade 4 hard red winter wheat with a moisture content of 10.3% at 22.0 °C. The surface reaction probability was the order of magnitude of 1 × 10−6 in the saturation state. This deposition model can be applied to optimize the ozone treatment for various kinds of grains.

An Analysis of CMAQ Gas Phase Dry Deposition over North America Through Grid-Scale and Land-Use Specific Diagnostics in the Context of AQMEII4.

The fourth phase of the Air Quality Model Evaluation International Initiative (AQMEII4) is conducting a diagnostic intercomparison and evaluation of deposition simulated by regional-scale air quality models over North America and Europe. In this study, we analyze annual AQMEII4 simulations performed with the Community Multiscale Air Quality Model (CMAQ) version 5.3.1 over North America. These simulations were configured with both the M3Dry and Surface Tiled Aerosol and Gas Exchange (STAGE) dry deposition schemes available in CMAQ. A comparison of observed and modeled concentrations and wet deposition fluxes shows that the AQMEII4 CMAQ simulations perform similarly to other contemporary regional-scale modeling studies. During summer, M3Dry has higher ozone (O3) deposition velocities (Vd) and lower mixing ratios than STAGE for much of the eastern U.S. while the reverse is the case over eastern Canada and along the West Coast. In contrast, during winter STAGE has higher O3 Vd and lower mixing ratios than M3Dry over most of the southern half of the modeling domain while the reverse is the case for much of the northern U.S. and southern Canada. Analysis of the diagnostic variables defined for the AQMEII4 project, i.e. grid-scale and land-use (LU) specific effective conductances and deposition fluxes for the major dry deposition pathways, reveals generally higher summertime stomatal and wintertime cuticular grid-scale effective conductances for M3Dry and generally higher soil grid-scale effective conductances (for both vegetated and bare soil) for STAGE in both summer and winter. On a domain-wide basis, the stomatal grid-scale effective conductances account for about half of the total O3 Vd during daytime hours in summer for both schemes. Employing LU-specific diagnostics, results show that daytime Vd varies by a factor of 2 between LU categories. Furthermore, M3Dry vs. STAGE differences are most pronounced for the stomatal and vegetated soil pathway for the forest LU categories, with M3Dry estimating larger effective conductances for the stomatal pathway and STAGE estimating larger effective conductances for the vegetated soil pathway for these LU categories. Annual domain total O3 deposition fluxes differ only slightly between M3Dry (74.4 Tg/year) and STAGE (76.2 Tg/yr), but pathway-specific fluxes to individual LU types can vary more substantially on both annual and seasonal scales which would affect estimates of O3 damages to sensitive vegetation. A comparison of two simulations differing only in their LU classification scheme shows that the differences in LU cause seasonal mean O3 mixing ratio differences on the order of 1 ppb across large portions of the domain, with the differences generally largest during summer and in areas characterized by the largest differences in the fractional coverages of the forest, planted/cultivated, and grassland LU categories. These differences are generally smaller than the M3Dry vs. STAGE differences outside the summer season but have a similar magnitude during summer. Results indicate that the deposition impacts of LU differences are caused both by differences in the fractional coverages and spatial distributions of different LU categories as well as the characterization of these categories through variables like surface roughness and vegetation fraction in look-up tables used in the land-surface model and deposition schemes. Overall, the analyses and results presented in this study illustrate how the diagnostic grid-scale and LU-specific dry deposition variables adopted for AQMEII4 can provide insights into similarities and differences between the CMAQ M3Dry and STAGE dry deposition schemes that affect simulated pollutant budgets and ecosystem impacts from atmospheric pollution.

Contrasting the Biophysical and Radiative Effects of Rising CO2 Concentrations on Ozone Dry Deposition Fluxes

AbstractThe dry deposition of ozone from the atmosphere to ecosystems is an important coupling mechanism between atmospheric chemistry and terrestrial biogeochemical processes. In most Earth system models, dry deposition is simulated using a resistor‐in‐series approach that aims to parameterize the governing biological, chemical, and physical processes through a series of functional approximations. Here, we evaluate the influence of carbon cycle‐climate responses on this parameterization using the results of the Energy Exascale Earth System Model v1.1 Biogeochemistry simulation campaign. This simulation campaign was designed in part to explore the biophysical and radiative effects of rising historical CO2 concentrations on the Earth system. We find that while the global annual ozone dry deposition is relatively insensitive to these effects, regionally the influence can be up to 10%. The strongest regional sensitivities in ozone dry deposition are predominantly in higher latitudes over land in the northern hemisphere and are dominated by the radiative effect of CO2, with little net influence of biophysical responses. Of all the impacts of the radiative effect of CO2, we point to the potential importance of accurately representing ozone deposition to snow in Earth System Models and provide recommendations for future simulation campaigns.

A Modelling Study of Indoor Air Chemistry: The Surface Interactions of Ozone and Hydrogen Peroxide

Indoor surfaces play a key role in indoor chemistry, including modification of indoor oxidant concentrations. This study utilises the INdoor CHEmical Model in Python (INCHEM-Py) to investigate the impact of surface transformations and their impact on indoor gas-phase chemistry. INCHEM-Py has been developed to simulate the surface deposition of ozone and hydrogen peroxide onto nine and six individual surfaces respectively in a typical bedroom, kitchen and office for normal indoor concentrations in the absence of household activities. The results show that 91 to 96% of these oxidants are deposited onto indoor surfaces under our simulated conditions. In the bedroom, 38 to 44% of indoor ozone and hydrogen peroxide is deposited onto soft fabric surfaces, with 41 to 54% of ozone deposition occurring on plastic surfaces in the kitchen and office. Total indoor concentrations of straight-chained aldehydes (C1-C10) ranged from ≈ 4 to 5 ppb, with nonanal having the highest individual concentration (1.7, 1.6 and 1.5 ppb in the bedroom, kitchen and office respectively), primarily as a result of emissions from plastics following ozone deposition. Aldehyde concentrations following hydrogen peroxide deposition were often less than 0.01 ppb. Understanding how reactions and deposition on different indoor surfaces impact indoor air chemistry will enable internal surface selection with a view to improving overall indoor air quality.

Iodine emission from the reactive uptake of ozone to simulated seawater.

The heterogeneous reaction of ozone and iodide is both an important source of atmospheric iodine and dry deposition pathway of ozone in marine environments. While the iodine generated from this reaction is primarily in the form of HOI and I2, there is also evidence of volatile organoiodide compound emissions in the presence of organics without biological activity occuring [M. Martino, G. P. Mills, J. Woeltjen and P. S. Liss, A new source of volatile organoiodine compounds in surface seawater, Geophys. Res. Lett., 2009, 36, L01609, L. Tinel, T. J. Adams, L. D. J. Hollis, A. J. M. Bridger, R. J. Chance, M. W. Ward, S. M. Ball and L. J. Carpenter, Influence of the Sea Surface Microlayer on Oceanic Iodine Emissions, Environ. Sci. Technol., 2020, 54, 13228-13237]. In this study, we evaluate our fundamental understanding of the ozonolysis of iodide which leads to gas-phase iodine emissions. To do this, we compare experimental measurements of ozone-driven gas-phase I2 formation in a flow tube to predictions made with the kinetic multilayer model for surface and bulk chemistry (KM-SUB). The KM-SUB model uses literature rate coefficients used in current atmospheric chemistry models to predict I2(g) formation in pH-buffered solutions of marine composition containing chloride, bromide, and iodide compared to solutions containing only iodide. Experimentally, I2(g) formation was found to be suppressed in solutions containing seawater levels of chloride compared to solutions containing only iodide, but the model does not predict this effect using literature rate constants. However, the model is able to predict this trend upon adjustment of two specific reaction rate constants. To more closely represent true oceanic conditions, we add an organic component to the proxy seawater solutions using material generated from Thalassiosira pseudonana phytoplankton cultures. Whereas the rate of ozone deposition is unaffected, the formation rate of I2(g) is strongly suppressed in the presence of biological organic material, indicative of a sink or reduction of reactive iodine formed during the oxidation process.

Comparison of model and ground observations finds snowpack and blowing snow aerosols both contribute to Arctic tropospheric reactive bromine

Abstract. Reactive halogens play a prominent role in the atmospheric chemistry of the Arctic during springtime. Field measurements and modeling studies suggest that halogens are emitted into the atmosphere from snowpack and reactions on wind-blown snow-sourced aerosols. The relative importance of snowpack and blowing snow sources is still debated, both at local scales and regionally throughout the Arctic. To understand the implications of these halogen sources on a pan-Arctic scale, we simulate Arctic reactive bromine chemistry in the atmospheric chemical transport model GEOS-Chem. Two mechanisms are included: (1) a blowing snow sea salt aerosol formation mechanism and (2) a snowpack mechanism assuming uniform molecular bromine production from all snow surfaces. We compare simulations including neither mechanism, each mechanism individually, and both mechanisms to examine conditions where one process may dominate or the mechanisms may interact. We compare the models using these mechanisms to observations of bromine monoxide (BrO) derived from multiple-axis differential optical absorption spectroscopy (MAX-DOAS) instruments on O-Buoy platforms on the sea ice and at a coastal site in Utqiaġvik, Alaska, during spring 2015. Model estimations of hourly and monthly average BrO are improved by assuming a constant yield of 0.1 % molecular bromine from all snowpack surfaces on ozone deposition. The blowing snow aerosol mechanism increases modeled BrO by providing more bromide-rich aerosol surface area for reactive bromine recycling. The snowpack mechanism led to increased model BrO across the Arctic Ocean with maximum production in coastal regions, whereas the blowing snow aerosol mechanism increases BrO in specific areas due to high surface wind speeds. Our uniform snowpack source has a greater impact on BrO mixing ratios than the blowing snow source. Model results best replicate several features of BrO observations during spring 2015 when using both mechanisms in conjunction, adding evidence that these mechanisms are both active during the Arctic spring. Extending our transport model throughout the entire year leads to predictions of enhanced fall BrO that are not supported by observations.

The Combined Impact of Canopy Stability and Soil NOx Exchange on Ozone Removal in a Temperate Deciduous Forest

AbstractDry deposition is an important ozone sink that impacts ecosystem carbon and water cycling. Ozone dry deposition in forests is regulated by vertical transport, stomatal uptake, and non‐stomatal processes including chemical removal. However, accurate descriptions of these processes in deposition parameterizations are hindered by sparse observational constraints on individual sink terms. Here we quantify the contribution of canopy‐atmosphere turbulent exchange and chemical ozone removal by soil‐emitted nitric oxide (NO) to ozone deposition in a North‐Italian broadleaf deciduous forest. We apply a multi‐layer canopy exchange model to interpret campaign observations of nitrogen oxides (NOx = NO + NO2) and ozone exchange above and inside the forest canopy. Two state‐of‐science parameterizations of in‐canopy vertical diffusivity, based on above‐canopy wind speed or stability, do not reproduce the observed exchange suppressed by canopy‐top radiative heating, resulting in overestimated dry deposition velocities of 10%–19% during daytime. Applying observation‐derived vertical diffusivities in our simulations largely resolves this overestimation. Soil emissions are an important NOx source despite the observed high background NOx levels. Soil NOx emissions decrease the gradient between canopy and surface layer NOx mixing ratios, which suppresses simulated NOx deposition by 80% compared to a sensitivity simulation without soil emissions. However, a sensitivity analysis shows that the enhanced chemical ozone sink by reaction with soil‐emitted NO is offset by increased vertical ozone transport from aloft and suppressed dry deposition. Our results highlight the need for targeted observations of non‐stomatal ozone removal and turbulence‐resolving deposition simulations to improve quantification and model representation of forest ozone deposition.

The influence of personal care products on ozone-skin surface chemistry.

Personal care products are increasingly being marketed to protect skin from the potentially harmful effects of air pollution. Here, we experimentally measure ozone deposition rates to skin and the generation rates and yields of oxidized products from bare skin and skin coated with various lotion formulations. Lotions reduced the ozone flux to the skin surface by 12% to 25%; this may be due to dilution of reactive skin lipids with inert lotion compounds or by reducing ozone diffusivity within the resulting mixture. The yields of volatile squalene oxidation products were 25% to 70% lower for a commercial sunscreen and for a base lotion with an added polymer or with antioxidants. Lower yields are likely due to competitive reactions of ozone with lotion ingredients including some ingredients that are not intended to be ozone sinks. The dynamics of the emissions of squalene ozonation product 6 methyl-2-heptenone (6MHO) suggest that lotions can dramatically reduce the solubility of products in the skin film. While some lotions appear to reduce the rate of oxidation of squalene by ozone, this evidence does not yet demonstrate that the lotions reduce the impact of air pollution on skin health.

Assessment and intercomparison of ozone dry deposition schemes over two ecosystems based on Noah-MP in China

Dry deposition of ozone (O3) is a major sink of O3 in near-surface air. The uncertainties in any existing dry deposition schemes are large. In this study, we incorporate four dry deposition schemes into the Noah with multi-parameterization options model (Noah-MP) to assess the importance of choice of different dry deposition schemes on simulated dry deposition velocity of O3 (Vd(O3)) over forest and agricultural ecosystems. Our simulated Vd(O3) values from different schemes were compared with observational data. All schemes performed similarly for agricultural ecosystems (correlation coefficient of approximately 0.4). For the forest ecosystem, Ball–Berry type schemes performed better than Jarvis-type schemes, with correlation coefficients for Vd(O3) between simulations and observations being approximately 0.55 and 0.38, respectively. To further improve the efficacy of the simulation of Vd(O3), we modified two canopy stomatal resistance mechanisms. For the Jarvis stomatal resistance mechanism, the minimum stomatal resistance was modified, with a mean bias of daytime reduction of by 39.3% for the forest ecosystem and 60.9% for the agricultural ecosystem. For Ball–Berry stomatal resistance mechanism, the stomatal resistance mechanism and nitrogen-limiting scheme for photosynthesis were modified. However, the results showed no significant improvement in the Vd(O3) simulation. The results demonstrate the importance of canopy resistance parameterization over agricultural and forest ecosystems, thus making a strong case for further evaluation and model improvement of O3 dry deposition in different ecosystems.

Indoor ozone removal and deposition using unactivated solid and liquid coffee.

Managing indoor ozone levels is important because ozone is a hazardous pollutant that has adverse effects on human health. Coffee is a popular daily beverage, and thus, coffee beans and spent coffee grounds are common in many places such as offices, homes, aircraft, cafeterias, and such. The most common material used to remove ozone is activated carbon which can be made from coffee beans or spent coffee grounds with proper activation processes. This paper presents a novel idea: to remove ozone at the level of an indoor environment using unactivated coffee products. This paper examines the ozone removal efficiency and the ozone deposition velocity at 130 ppb ozone for two types of coffee: solid coffee (powder) and liquid coffee (beverage). The activated carbon, the deionized water, and the seawater are also included for comparison and validation purposes. The tests show that the fine coffee powder has a removal efficiency of 58.5% and a deposition velocity of 0.62 cm/s. The liquid coffee has a removal efficiency of 34.4% and a deposition velocity of 0.23 cm/s. The chemical inspections indicate that the oxidation reactions with the carbohydrates in solid coffee and the metal/mineral elements in liquid coffee are responsible for ozone removal. These results have confirmed that ozone removal via coffee is effective, controlling indoor air quality by coffee products is thus becoming possible.

Nocturnal pollutant uptake contributes significantly to the total stomatal uptake of Mangifera indica

DO3SE (Deposition of Ozone for Stomatal Exchange), is a dry deposition model, designed to assess tropospheric ozone risk to vegetation, and is based on two alternative algorithms to estimate stomatal conductance: multiplicative and photosynthetic. The multiplicative model has been argued to perform better for leaf-level and regional-level application. In this study, we demonstrate that the photosynthetic model is superior to the multiplicative model even for leaf-level studies using measurements performed on Mangifera indica. We find that the multiplicative model overestimates the daytime stomatal conductance, when compared with measured stomatal conductance and prescribes zero conductance at night while measurements show an average conductance of 100 mmol(H2O)m−2s−1 between 9 p.m. and 4 a.m. The daytime overestimation of the multiplicative model can be significantly reduced when the model is modified to include a response function for ozone-induced stomatal closure. However, nighttime pollutant uptake fluxes can only be accurately assessed with the photosynthetic model which includes the stomatal opening at night during respiration and is capable of reproducing the measured nighttime stomatal conductance. At our site, the nocturnal flux contributes 64%, 39%, 46%, and 88% of the total for NO2 uptake in winter, summer, monsoon, and post-monsoon, respectively. For SO2, nocturnal uptake amounts to 35%, 28%, 28%, and 44% in winter, summer, monsoon, and post-monsoon, respectively while for ozone the nighttime uptake contributes 30%, 17%, 18%, and 29% of the total stomatal uptake in winter, summer, monsoon, and post-monsoon respectively.

New Evidence for the Importance of Non‐Stomatal Pathways in Ozone Deposition During Extreme Heat and Dry Anomalies

AbstractDry deposition could partially explain the observed response in ambient ozone to extreme hot and dry episodes. We examine the response of ozone deposition to heat and dry anomalies using three long‐term co‐located ecosystem‐scale carbon dioxide, water vapor and ozone flux measurement records. We find that, as expected, canopy stomatal conductance generally decreases during days with dry air or soil. However, during hot days, concurrent increases in non‐stomatal conductance are inferred at all three sites, which may be related to several temperature‐sensitive processes not represented in the current generation of big‐leaf models. This may offset the reduction in stomatal conductance, leading to smaller net reduction, or even net increase, in total deposition velocity. We find the response of deposition velocity to soil dryness may be related to its impact on photosynthetic activity, though considerable variability exists. Our findings emphasize the need for better understanding and representation of non‐stomatal ozone deposition.

Estimation of the historical dry deposition of air pollution indoors to the monumental paintings by Edvard Munch in the University Aula, in Oslo, Norway

The historical (1835–2020) deposition of major air pollutants (SO2, NOx, O3 and PM2.5) indoors, as represented by the monumental Edvard Munch paintings (c. 220 m2) installed in 1916 in the Oslo University Aula in Norway, were approximated from the outdoor air concentrations, indoor to outdoor concentration ratios and dry deposition velocities. The annual deposition of the pollutants to the paintings was found to have been 4–25 times lower than has been reported to buildings outdoors in the urban background in the centre of Oslo. It reflected the outdoor deposition but varied less, from 0.3 to 1.2 g m−2 a−1. The accumulated deposition since 1916, and then not considering the regularly performed cleaning of the paintings, was found to have been 43 ± 13 g m−2, and 110 ± 40 g m−2 in a similar situation since 1835. The ozone deposition, and the PM2.5 deposition before the 1960s, were a relatively larger part of the accumulated total indoor (to the paintings) than reported outdoor deposition. About 18 and 33 times more O3 than NOx and PM2.5 deposition was estimated to the paintings in 2020, as compared to the about similar reported outdoor dry deposition of O3 and NOx. The deposition of PM2.5 to the paintings was probably reduced with about 62% (50–80%) after installation of mechanical filtration in 1975 and was estimated to be 0.011 (± 0.006) g m−2 in 2020.Graphical