Ozone Dry Deposition Research Articles

Monte Carlo analyses of the uncertainties in the predictions from global tropospheric ozone models: Tropospheric burdens and seasonal cycles

Abstract Because ozone is a highly reactive trace gas, estimates of its contribution to climate forcing must rely on global chemistry-transport models. These models employ many uncertain input parameters representing the sources and sinks for tropospheric ozone. Ten thousand quasi-randomly Monte Carlo sampled model runs employing a zonally-averaged global ozone model were completed and the output uncertainties were estimated in the burdens and turnovers of methane, carbon monoxide and ozone, together with the uncertainties in the ozone seasonal cycles. Multiple regression was then used to attribute the uncertainty in each output metric to each of the 183 uncertain input parameters which represented emission source sectors, chemical and photochemical rate coefficients, dry deposition velocities and biases in temperature and water vapour concentrations. We have tentatively identified sixteen chemical and photochemical rate coefficients, eight emission source sectors, ozone dry deposition and biases in temperature and water vapour as contributing most to the uncertainties in our chosen output metrics. Ten out of the sixteen chemical processes turned out to be the most important processes in the fast, photochemical balance of the troposphere. Emissions from NOx, methane, carbon monoxide and isoprene had the potential to contribute in a major way to model output uncertainties. There are, however, many limitations to our study, not the least being our use of a two-dimensional (altitude-latitude) ozone model. We have not been able to resolve the apparent conflicts between our model and the observations of ozone seasonal cycles and these must await a more rigorous treatment of tropospheric ozone sources and sinks before they can be resolved.

Influence of Dynamic Ozone Dry Deposition on Ozone Pollution

AbstractIdentifying the contributions of chemistry and transport to observed ozone pollution using regional‐to‐global models relies on accurate representation of ozone dry deposition. We use a recently developed configuration of the NOAA GFDL chemistry‐climate model—in which the atmosphere and land are coupled through dry deposition—to investigate the influence of ozone dry deposition on ozone pollution over northern midlatitudes. In our model, deposition pathways are tied to dynamic terrestrial processes, such as photosynthesis and water cycling through the canopy and soil. Small increases in winter deposition due to more process‐based representation of snow and deposition to surfaces reduce hemispheric‐scale ozone throughout the lower troposphere by 5–12 ppb, improving agreement with observations relative to a simulation with the standard configuration for ozone dry deposition. Declining snow cover by the end of the 21st‐century tempers the previously identified influence of rising methane on winter ozone. Dynamic dry deposition changes summer surface ozone by −4 to +7 ppb. While previous studies emphasize the importance of uptake by plant stomata, new diagnostic tracking of depositional pathways reveals a widespread impact of nonstomatal deposition on ozone pollution. Daily variability in both stomatal and nonstomatal deposition contribute to daily variability in ozone pollution. Twenty‐first century changes in summer deposition result from a balance among changes in individual pathways, reflecting differing responses to both high carbon dioxide (through plant physiology versus biomass accumulation) and water availability. Our findings highlight a need for constraints on the processes driving ozone dry deposition to test representation in regional‐to‐global models.

Dry Deposition of Ozone over Land: Processes, Measurement, and Modeling.

Dry deposition of ozone is an important sink of ozone in near surface air. When dry deposition occurs through plant stomata, ozone can injure the plant, altering water and carbon cycling and reducing crop yields. Quantifying both stomatal and nonstomatal uptake accurately is relevant for understanding ozone's impact on human health as an air pollutant and on climate as a potent short-lived greenhouse gas and primary control on the removal of several reactive greenhouse gases and air pollutants. Robust ozone dry deposition estimates require knowledge of the relative importance of individual deposition pathways, but spatiotemporal variability in nonstomatal deposition is poorly understood. Here we integrate understanding of ozone deposition processes by synthesizing research from fields such as atmospheric chemistry, ecology, and meteorology. We critically review methods for measurements and modeling, highlighting the empiricism that underpins modeling and thus the interpretation of observations. Our unprecedented synthesis of knowledge on deposition pathways, particularly soil and leaf cuticles, reveals process understanding not yet included in widely-used models. If coordinated with short-term field intensives, laboratory studies, and mechanistic modeling, measurements from a few long-term sites would bridge the molecular to ecosystem scales necessary to establish the relative importance of individual deposition pathways and the extent to which they vary in space and time. Our recommended approaches seek to close knowledge gaps that currently limit quantifying the impact of ozone dry deposition on air quality, ecosystems, and climate.

Effects of Dry Deposition on Surface Ozone over South Asia Inferred from a Regional Chemical Transport Model

Dry deposition is a major sink for tropospheric ozone; nevertheless, studies on its effects on ozone distribution are very limited over the rapidly developing South Asian region. We performed numerical simulations using the regional model WRF-Chem (Weather Research and Forecasting Model coupled with chemistry) to investigate the effect of dry deposition on surface ozone over this region by switching dry deposition ON–OFF in the model. Dry deposition of ozone is found to reduce ozone mixing ratios by up to ∼40% over the Indo-Gangetic Plain (IGP) and parts of western and central India. Additional enhancements (by up to ∼5 ppbv) in ozone are simulated when dry deposition for all gaseous species is switched off. We find a significant contrast on the effects of dry deposition from station to station as well as on the diurnal timescales over this region. The enhancements in ozone, caused by the absence of dry deposition, are lower over urban stations during nighttime, as compared to the rural and high-altitude stations. Significant enhancements in ozone levels in the absence of dry deposition over the mostly agrarian IGP underpin the importance of dry deposition particularly in the vegetated areas. The South Asian ecosystem is seen to act as an important sink of surface ozone via the dry deposition. The analyses partially fill a gap in the studies of dry deposition over the South Asian region, where this sink is anticipated to get perturbed following the changes in land use and land cover.

Importance of dry deposition parameterization choice in global simulations of surface ozone

Abstract. Dry deposition is a major sink of tropospheric ozone. Increasing evidence has shown that ozone dry deposition actively links meteorology and hydrology with ozone air quality. However, there is little systematic investigation on the performance of different ozone dry deposition parameterizations at the global scale and how parameterization choice can impact surface ozone simulations. Here, we present the results of the first global, multidecadal modelling and evaluation of ozone dry deposition velocity (vd) using multiple ozone dry deposition parameterizations. We model ozone dry deposition velocities over 1982–2011 using four ozone dry deposition parameterizations that are representative of current approaches in global ozone dry deposition modelling. We use consistent assimilated meteorology, land cover, and satellite-derived leaf area index (LAI) across all four, such that the differences in simulated vd are entirely due to differences in deposition model structures or assumptions about how land types are treated in each. In addition, we use the surface ozone sensitivity to vd predicted by a chemical transport model to estimate the impact of mean and variability of ozone dry deposition velocity on surface ozone. Our estimated vd values from four different parameterizations are evaluated against field observations, and while performance varies considerably by land cover types, our results suggest that none of the parameterizations are universally better than the others. Discrepancy in simulated mean vd among the parameterizations is estimated to cause 2 to 5 ppbv of discrepancy in surface ozone in the Northern Hemisphere (NH) and up to 8 ppbv in tropical rainforests in July, and up to 8 ppbv in tropical rainforests and seasonally dry tropical forests in Indochina in December. Parameterization-specific biases based on individual land cover type and hydroclimate are found to be the two main drivers of such discrepancies. We find statistically significant trends in the multiannual time series of simulated July daytime vd in all parameterizations, driven by warming and drying (southern Amazonia, southern African savannah, and Mongolia) or greening (high latitudes). The trend in July daytime vd is estimated to be 1 % yr−1 and leads to up to 3 ppbv of surface ozone changes over 1982–2011. The interannual coefficient of variation (CV) of July daytime mean vd in NH is found to be 5 %–15 %, with spatial distribution that varies with the dry deposition parameterization. Our sensitivity simulations suggest this can contribute between 0.5 to 2 ppbv to interannual variability (IAV) in surface ozone, but all models tend to underestimate interannual CV when compared to long-term ozone flux observations. We also find that IAV in some dry deposition parameterizations is more sensitive to LAI, while in others it is more sensitive to climate. Comparisons with other published estimates of the IAV of background ozone confirm that ozone dry deposition can be an important part of natural surface ozone variability. Our results demonstrate the importance of ozone dry deposition parameterization choice on surface ozone modelling and the impact of IAV of vd on surface ozone, thus making a strong case for further measurement, evaluation, and model–data integration of ozone dry deposition on different spatiotemporal scales.

Update and evaluation of the ozone dry deposition in Oslo CTM3 v1.0

Abstract. High concentrations of ozone in ambient air are hazardous not only to humans but to the ecosystem in general. The impact of ozone damage on vegetation and agricultural plants in combination with advancing climate change may affect food security in the future. While the future scenarios in themselves are uncertain, there are limiting factors constraining the accuracy of surface ozone modeling also at present: the distribution and amount of ozone precursors and ozone-depleting substances, the stratosphere–troposphere exchange, as well as scavenging processes. Removal of any substance through gravitational settling or by uptake by plants and soil is referred to as dry deposition. The process of dry deposition is important for predicting surface ozone concentrations and understanding the observed amount and increase of tropospheric background ozone. The conceptual dry deposition velocities are calculated following a resistance-analogous approach, wherein aerodynamic, quasi-laminar, and canopy resistance are key components, but these are hard to measure explicitly. We present an update of the dry deposition scheme implemented in Oslo CTM3. We change from a purely empirical dry deposition parameterization to a more process-based one which takes the state of the atmosphere and vegetation into account. We examine the sensitivity of the scheme to various parameters, e.g., the stomatal conductance-based description of the canopy resistance and the choice of ozone surface resistance, and evaluate the resulting modeled ozone dry deposition with respect to observations and multi-model studies. Individual dry deposition velocities are now available for each land surface type and agree generally well with observations. We also estimate the impact on the modeled ozone concentrations at the surface. We show that the global annual total ozone dry deposition decreases with respect to the previous model version (−37 %), leading to an increase in surface ozone of more than 100 % in some regions. While high sensitivity to changes in dry deposition to vegetation is found in the tropics and the Northern Hemisphere, the largest impact on global scales is associated with the choice of prescribed ozone surface resistance over the ocean and deserts.

Sensitivity of Ozone Dry Deposition to Ecosystem‐Atmosphere Interactions: A Critical Appraisal of Observations and Simulations

AbstractThe response of ozone (O3) dry deposition to ecosystem‐atmosphere interactions is poorly understood but is central to determining the potential for extreme pollution events under current and future climate conditions. Using observations and an interactive dry deposition scheme within two dynamic vegetation land models (Geophysical Fluid Dynamics Laboratory LM3.0/LM4.0) driven by observation‐based meteorological forcings over 1948–2014, we investigate the factors controlling seasonal and interannual variability (IAV) in O3 deposition velocities (Vd,O3). Stomatal activity in this scheme is determined mechanistically, depending on phenology, soil moisture, vapor pressure deficit, and CO2 concentration. Soil moisture plays a key role in modulating the observed and simulated Vd,O3 seasonal changes over evergreen forests in Mediterranean Europe, South Asia, and the Amazon. Analysis of multiyear observations at forest sites in Europe and North America reveals drought stress to reduce Vd,O3 by ~50%. Both LM3.0 and LM4.0 capture the observed Vd,O3 decreases due to drought; however, IAV is weaker by a factor of 2 in LM3.0 coupled to atmospheric models, particularly in regions with large precipitation biases. IAV in summertime Vd,O3 to forests, driven primarily by the stomatal pathway, is largest (15–35%) in semiarid regions of western Europe, eastern North America, and northeastern China. Monthly mean Vd,O3 for the highest year is 2 to 4 times that of the lowest, with significant implications for surface O3 variability and extreme events. Using Vd,O3 from LM4.0 in an atmospheric chemistry model improves the simulation of surface O3 abundance and spatial variability (reduces mean biases by ~10 ppb) relative to the widely used Wesely scheme.

Influences of planetary boundary layer mixing parameterization on summertime surface ozone concentration and dry deposition over North China

We present a regional modeling study that analyzes how planetary boundary layer (PBL) and surface layer parameterizations influence surface ozone concentrations and dry deposition fluxes over the Beijing-Tianjin-Hebei region in summer (July 2015). We use the Weather Research and Forecasting Model coupled to Chemistry (WRF-Chem) to simulate surface ozone concentration and dry deposition, and examine three PBL schemes: the Yonsei University (YSU), Mellor–Yamada–Janjić (MYJ), and Asymmetric Convective Model version 2 (ACM2) schemes. The model sensitivity to surface layer schemes is also tested by coupling the ACM2 PBL scheme with either the revised MM5-similarity scheme or the Pleim-Xiu surface layer scheme. Key physical and chemical factors for ozone dry deposition parameterization are analyzed to explore the root causes of model discrepancies. We find that all simulations overestimate the summertime daily mean ozone concentrations over North China (42 ppbv in observations vs. 43–50 ppbv in model results for July 2015) that are caused by high biases in daytime ozone and partly compensated by low biases in nighttime ozone. The YSU scheme has the largest overestimate in daily mean ozone concentration, but best reproduces the ozone diurnal cycle. The ACM2 scheme shows the largest underestimates of surface ozone over North China during nighttime, which can be explained by its weakest vertical mixing leading to high NOx concentrations and strong ozone titration near surface. The choices of PBL and surface layer schemes lead to over 20% differences in ozone dry deposition fluxes due to differences in simulated surface ozone concentrations and dry deposition velocities. We find the differences in dry deposition velocity are mainly caused by differences in Monin-Obukhov length during nighttime and surface temperature during daytime. Our study emphasizes the needs to better understand these key PBL and surface factors for reducing the uncertainties in model simulation of surface ozone concentration and dry deposition.

Exploring 2016–2017 surface ozone pollution over China: source contributions and meteorological influences

Abstract. Severe surface ozone pollution over major Chinese cities has become an emerging air quality concern, raising a new challenge for emission control measures in China. In this study, we explore the source contributions to surface daily maximum 8 h average (MDA8) ozone over China in 2016 and 2017, the 2 years with the highest surface ozone averaged over Chinese cities in record. We estimate the contributions of anthropogenic, background, and individual natural sources to surface ozone over China using the GEOS-Chem chemical transport model at 0.25∘×0.3125∘ horizontal resolution with the most up-to-date Chinese anthropogenic emission inventory. Model results are evaluated with concurrent surface ozone measurements at 169 cities over China and show generally good agreement. We find that background ozone (defined as ozone that would be present in the absence of all Chinese anthropogenic emissions) accounts for 90 % (49.4 ppbv) of the national March–April mean surface MDA8 ozone over China and 80 % (44.5 ppbv) for May–August. It includes large contributions from natural sources (80 % in March–April and 72 % in May–August). Among them, biogenic volatile organic compound (BVOC) emissions enhance MDA8 ozone by more than 15 ppbv in eastern China during July–August, while lightning NOx emissions and ozone transport from the stratosphere both lead to ozone enhancements of over 20 ppbv in western China during March–April. Over major Chinese city clusters, domestic anthropogenic sources account for about 30 % of the May–August mean surface MDA8 ozone and reach 39–73 ppbv (38 %–69 %) for days with simulated MDA8 ozone > 100 ppbv in the North China Plain, Fenwei Plain, Yangtze River Delta, and Pearl River Delta city clusters. These high ozone episodes are usually associated with high temperatures, which induce large BVOC emissions and enhance ozone chemical production. Our results indicate that there would be no days with MDA8 ozone > 80 ppbv in these major Chinese cities in the absence of domestic anthropogenic emissions. We find that the 2017 ozone increases relative to 2016 are largely due to higher background ozone driven by hotter and drier weather conditions, while changes in domestic anthropogenic emissions alone would have led to ozone decreases in 2017. Meteorological conditions in 2017 favor natural source contributions (particularly soil NOx and BVOC ozone enhancements) and ozone chemical production, increase the thermal decomposition of peroxyacetyl nitrate (PAN), and further decrease ozone dry deposition velocity. More stringent emission control measures are thus required to offset the adverse effects of unfavorable meteorology, such as high temperature, on surface ozone air quality.

Spatiotemporal Controls on Observed Daytime Ozone Deposition Velocity Over Northeastern U.S. Forests During Summer

AbstractSpatiotemporal variability in ozone dry deposition is often overlooked despite its implications for interpreting and modeling tropospheric ozone concentrations accurately. Understanding the influences of stomatal versus nonstomatal deposition processes on ozone deposition velocity is important for attributing observed changes in the ozone depositional sink and associated damage to ecosystems. Here, we aim to identify the stomatal versus nonstomatal deposition processes driving observed variability in ozone deposition velocity over the northeastern United States during June–September. We use ozone eddy covariance measurements from Harvard Forest in Massachusetts, which span a decade, and from Kane Experimental Forest in Pennsylvania and Sand Flats State Forest in New York, which span one growing season each, along with observation‐driven modeling. Using a cumulative precipitation indicator of soil wetness, we infer that high soil uptake during dry years and low soil uptake during wet years may contribute to the twofold interannual variability in ozone deposition velocity at Harvard Forest. We link stomatal deposition and humidity to variability in ozone deposition velocity on daily timescales. The humidity dependence may reflect higher uptake by leaf cuticles under humid conditions, noted in previous work. Previous work also suggests that uptake by leaf cuticles may be enhanced after rain, but we find that increases in ozone deposition velocity on rainy days are instead mostly associated with increases in stomatal conductance. Our analysis highlights a need for constraints on subseasonal variability in ozone dry deposition to soil and fast in‐canopy chemistry during ecosystem stress.

A Deep Learning Parameterization for Ozone Dry Deposition Velocities

AbstractThe loss of ozone to terrestrial and aquatic systems, known as dry deposition, is a highly uncertain process governed by turbulent transport, interfacial chemistry, and plant physiology. We demonstrate the value of using Deep Neural Networks (DNN) in predicting ozone dry deposition velocities. We find that a feedforward DNN trained on observations from a coniferous forest site (Hyytiälä, Finland) can predict hourly ozone dry deposition velocities at a mixed forest site (Harvard Forest, Massachusetts) more accurately than modern theoretical models, with a reduction in the normalized mean bias (0.05 versus ~0.1). The same DNN model, when driven by assimilated meteorology at 2° × 2.5° spatial resolution, outperforms the Wesely scheme as implemented in the GEOS‐Chem model. With more available training data from other climate and ecological zones, this methodology could yield a generalizable DNN suitable for global models.

Investigation of ozone deposition to vegetation under warm and dry conditions near the Eastern Mediterranean coast

Dry deposition of ozone (O3) to vegetation is an important removal pathway for tropospheric O3, while O3 uptake through plant stomata negatively affects vegetation and leads to climate change. Both processes are controlled by vegetation characteristics and ambient conditions via complex mechanisms. Recent studies have revealed that these processes can be fundamentally impacted by coastal effects, and by dry and warm conditions in ways that have not been fully characterized, largely due to lack of measurements under such conditions. Hence, we hypothesized that measuring dry deposition of O3 to vegetation along a sharp spatial climate gradient, and at different distances from the coast, can offer new insights into the characterization of these effects on O3 deposition to vegetation and stomatal uptake, providing important information for afforestation management and for climate and air-quality model improvement. To address these hypotheses, several measurement campaigns were performed at different sites, including pine, oak, and mixed Mediterranean forests, at distances of 20–59 km from the Eastern Mediterranean coast, under semiarid, Mediterranean and humid Mediterranean climate conditions. The eddy covariance technique was used to quantify vertical O3 flux (Ftot) and its partitioning to stomatal flux (Fst) and non-stomatal flux (Fns). Whereas Fst tended to peak around noon under humid Mediterranean and Mediterranean conditions in summer, it was strongly limited by drought under semiarid conditions from spring to early winter, with minimum average Fst/Ftot of 8–11% during the summer. Fns in the area was predominantly controlled by relative humidity (RH), whereas increasing Fns with RH for RH < 70% indicated enhancement of Fns by aerosols, via surface wetness stimulation. At night, efficient turbulence due to sea and land breezes, together with increased RH, resulted in strong enhancement of Ftot. Extreme dry surface events, some induced by dry intrusion from the upper troposphere, resulted in positive Fns events.

Ionic-Strength Effects on the Reactive Uptake of Ozone on Aqueous Pyruvic Acid: Implications for Air–Sea Ozone Deposition

A vertical wetted-wall flow-tube technique was used to explore the ionic strength effects at the air-water interface in mediating the sea-surface reaction between ozone (O3) and pyruvic acid (PA). The uptake coefficients of ozone on aqueous PA increase substantially with the concentrations of bromide (Br-) ions, clearly indicating that the dry deposition of ozone could be significantly enhanced due to the presence of carbonyl compounds such as PA at the bromide-rich sea surface. Based on the observed uptake coefficients, the estimated deposition velocity of ozone (100 ppb) for a nanomolar range of PA concentrations is ∼1 × 10-3 m s-1, which represents a significant contribution to the known deposition velocity of ozone at the sea surface. The analysis of reaction products by ultra-high-resolution Fourier transform-ion cyclotron resonance mass spectrometry suggests the formation of oligomers during both the dark and light-induced heterogeneous reactions between gaseous O3 and PA occurring at the surface of a dilute aqueous phase (representative of cloud droplets). The detected high-molecular-weight compounds are much more complex than the oligomeric species identified during the photolytic degradation of bulk aqueous PA alone.

Measurement-based investigation of ozone deposition to vegetation under the effects of coastal and photochemical air pollution in the Eastern Mediterranean

Dry deposition of ozone (O3) to vegetation is an important pathway for its removal from the troposphere, and it can lead to adverse effects in plants and changes in climate. However, our mechanistic understanding of O3 dry deposition is insufficient to adequately account for it in global and regional models, primarily because this process is highly complicated by feedback mechanisms and sensitivity to specific characteristics of vegetative environment and atmospheric dynamics and composition. We hypothesized that measuring dry deposition of O3 to vegetation near the Eastern Mediterranean (EM) coast, where large variations in meteorological conditions and photochemical air pollution frequently occur, would enable identifying the mechanisms controlling O3 deposition to vegetation. Moreover, we have only limited knowledge of O3 deposition to vegetation occurring near a coastline, under air pollution, or in the EM. This study investigated O3 deposition to mixed Mediterranean vegetation between the summers of 2015 and 2017, 3.6 km away from the EM coast, using the eddy covariance technique to quantify vertical flux of O3 and its partitioning to stomatal and non-stomatal flux, concurrent with nitrogen oxide (NOx), sulfur dioxide and carbon monoxide. Surprisingly, nighttime O3-deposition velocity (Vd) was smaller than daytime Vd by only ~20–37% on average for all measurement periods, primarily related to moderate nighttime atmospheric stability due to proximity to the seashore. We provide evidence for the role of sea-salt aerosols in enhancing O3 deposition via surface-wetness buildup at low relative humidity near the coast, and for daytime enhancement of O3 deposition by the combined effects of biogenic volatile organic compound emission and surface-wetness buildup. We further show that NOx emitted from elevated emission sources can reduce O3 deposition, and even lead to a positive O3 flux, demonstrating the importance of adequately taking into account the impact of air pollution on O3 deposition to vegetation.

A revised global ozone dry deposition estimate based on a new two-layer parameterisation for air–sea exchange and the multi-year MACC composition reanalysis

Abstract. Dry deposition at the Earth's surface is an important sink of atmospheric ozone. Currently, dry deposition of ozone to the ocean surface in atmospheric chemistry models has the largest uncertainty compared to deposition to other surface types, with implications for global tropospheric ozone budget and associated radiative forcing. Most global models assume that the dominant term of surface resistance in the parameterisation of ozone dry deposition velocity at the oceanic surface is constant. There have been recent mechanistic parameterisations for air–sea exchange that account for the simultaneous waterside processes of ozone solubility, molecular diffusion, turbulent transfer, and first-order chemical reaction of ozone with dissolved iodide and other compounds, but there are questions about their performance and consistency. We present a new two-layer parameterisation scheme for the oceanic surface resistance by making the following realistic assumptions: (a) the thickness of the top water layer is of the order of a reaction–diffusion length scale (a few micrometres) within which ozone loss is dominated by chemical reaction and the influence of waterside turbulent transfer is negligible; (b) in the water layer below, both chemical reaction and waterside turbulent transfer act together and are accounted for; and (c) chemical reactivity is present through the depth of the oceanic mixing layer. The new parameterisation has been evaluated against dry deposition velocities from recent open-ocean measurements. It is found that the inclusion of only the aqueous iodide–ozone reaction satisfactorily describes the measurements. In order to better quantify the global dry deposition loss and its interannual variability, modelled 3-hourly ozone deposition velocities are combined with the 3-hourly MACC (Monitoring Atmospheric Composition and Climate) reanalysis ozone for the years 2003–2012. The resulting ozone dry deposition is found to be 98.4 ± 30.0 Tg O3 yr−1 for the ocean and 722.8 ± 87.3 Tg O3 yr−1 globally. The new estimate of the ocean component is approximately a third of the current model estimates. This reduction corresponds to an approximately 20 % decrease in the total global ozone dry deposition, which (with all other components being unchanged) is equivalent to an increase of approximately 5 % in the modelled tropospheric ozone burden and a similar increase in tropospheric ozone lifetime.

Impacts of different characterizations of large-scale background on simulated regional-scale ozone over the continental United States.

This study analyzes simulated regional-scale ozone burdens both near the surface and aloft, estimates process contributions to these burdens, and calculates the sensitivity of the simulated regional-scale ozone burden to several key model inputs with a particular emphasis on boundary conditions derived from hemispheric or global-scale models. The Community Multiscale Air Quality (CMAQ) model simulations supporting this analysis were performed over the continental US for the year 2010 within the context of the Air Quality Model Evaluation International Initiative (AQMEII) and Task Force on Hemispheric Transport of Air Pollution (TF-HTAP) activities. CMAQ process analysis (PA) results highlight the dominant role of horizontal and vertical advection on the ozone burden in the mid-to-upper troposphere and lower stratosphere. Vertical mixing, including mixing by convective clouds, couples fluctuations in free-tropospheric ozone to ozone in lower layers. Hypothetical bounding scenarios were performed to quantify the effects of emissions, boundary conditions, and ozone dry deposition on the simulated ozone burden. Analysis of these simulations confirms that the characterization of ozone outside the regional-scale modeling domain can have a profound impact on simulated regional-scale ozone. This was further investigated by using data from four hemispheric or global modeling systems (Chemistry - Integrated Forecasting Model (C-IFS), CMAQ extended for hemispheric applications (H-CMAQ), the Goddard Earth Observing System model coupled to chemistry (GEOS-Chem), and AM3) to derive alternate boundary conditions for the regional-scale CMAQ simulations. The regional-scale CMAQ simulations using these four different boundary conditions showed that the largest ozone abundance in the upper layers was simulated when using boundary conditions from GEOS-Chem, followed by the simulations using C-IFS, AM3, and H-CMAQ boundary conditions, consistent with the analysis of the ozone fields from the global models along the CMAQ boundaries. Using boundary conditions from AM3 yielded higher springtime ozone columns burdens in the middle and lower troposphere compared to boundary conditions from the other models. For surface ozone, the differences between the AM3-driven CMAQ simulations and the CMAQ simulations driven by other large-scale models are especially pronounced during spring and winter where they can reach more than 10 ppb for seasonal mean ozone mixing ratios and as much as 15 ppb for domain-averaged daily maximum 8 h average ozone on individual days. In contrast, the differences between the C-IFS-, GEOS-Chem-, and H-CMAQ-driven regional-scale CMAQ simulations are typically smaller. Comparing simulated sur face ozone mixing ratios to observations and computing seasonal and regional model performance statistics revealed that boundary conditions can have a substantial impact on model performance. Further analysis showed that boundary conditions can affect model performance across the entire range of the observed distribution, although the impacts tend to be lower during summer and for the very highest observed percentiles. The results are discussed in the context of future model development and analysis opportunities.

Investigating Dry Deposition of Ozone to Vegetation

AbstractAtmospheric ozone loss through dry deposition to vegetation is a critically important process for both air quality and ecosystem health. The majority of atmospheric chemistry models calculate dry deposition using a resistance‐in‐series parameterization by Wesely (1989), which is dependent on many environmental variables and lookup table values. The uncertainties contained within this parameterization have not been fully explored, ultimately challenging our ability to understand global scale biosphere‐atmosphere interactions. In this work, we evaluate the GEOS‐Chem model simulation of ozone dry deposition using a globally distributed suite of observations. We find that simulated daytime deposition velocities generally reproduce the magnitude of observations to within a factor of 1.4. When correctly accounting for differences in land class between the observations and model, these biases improve, most substantially over the grasses and shrubs land class. These biases do not impact the global ozone burden substantially; however, they do lead to local absolute changes of up to 4 ppbv and relative changes of 15% in summer surface concentrations. We use MERRA meteorology from 1979 to 2008 to assess that the interannual variability in simulated annual mean ozone dry deposition due to model input meteorology is small (generally less than 5% over vegetated surfaces). Sensitivity experiments indicate that the simulation is most sensitive to the stomatal and ground surface resistances, as well as leaf area index. To improve ozone dry deposition models, more measurements are necessary over rainforests and various crop types, alongside constraints on individual depositional pathways and other in‐canopy ozone loss processes.

Evaluation of ozone deposition models over a subalpine forest in Niwot Ridge, Colorado

In this study, we evaluated three conceptually similar ozone gas deposition models. These dry deposition models are frequently used with chemical transport models for calculations over large spatial domains. However, large scale applications of surface-atmosphere exchange of reactive gases require modeling results as accurate as possible to avoid nonlinear accumulation of errors in the spatially representative results. In this paper, model evaluation and comparison against measured data over a coniferous forest at Niwot Ridge AmeriFlux site (Colorado, USA) is carried out. At this site, no previous model calibration took place for any of the models, therefore, we can test and compare their performances under similar conditions as they would perform in a spatial application. Our results show systematic model errors in all the three cases, model performance varies with time of the day, and the errors show a pronounced seasonal pattern as well. The introduction of soil moisture content stress in the model improved model performance regarding the magnitude of fluxes, but the correlation between measured and modeled ozone deposition values remains low. Our results suggest that ozone dry deposition model results should be interpreted carefully in large scale applications, where the accuracy can vary with land cover sometimes are biased. © 2018, Hungarian Meteorological Service. All rights reserved.

An Attempt to Partition Stomatal and Non-stomatal Ozone Deposition Parts on a Short Grassland

To evaluate the damaging effect of tropospheric ozone on vegetation, it is important to evaluate the stomatal uptake of ozone. Although the stomatal flux is a dominant pathway of ozone deposition onto vegetated surfaces, non-stomatal uptake mechanisms such as soil and cuticular deposition also play a vital role, especially when the leaf area index $${LAI}< 4$$ . In this study, we partitioned the canopy conductance into stomatal and non-stomatal components. To calculate the stomatal conductance of water vapour for sparse vegetation, we firstly partitioned the latent heat flux into effects of transpiration and evaporation using the Shuttleworth–Wallace (SW) model. We then derived the stomatal conductance of ozone using the Penman–Monteith (PM) theory based on the similarity to water vapour conductance. The non-stomatal conductance was calculated by subtracting the stomatal conductance from the canopy conductance derived from directly-measured fluxes. Our results show that for short vegetation (LAI $$=$$ 0.25) dry deposition of ozone was dominated by the non-stomatal flux, which exceeded the stomatal flux even during the daytime. At night the stomatal uptake of ozone was found to be negligibly small. In the case of vegetation with $${LAI}\approx 1$$ , the daytime stomatal and non-stomatal fluxes were of the same order of magnitude. These results emphasize that non-stomatal processes must be considered even in the case of well-developed vegetation where cuticular uptake is comparable in magnitude with stomatal uptake, and especially in the case of vegetated surfaces with $${LAI}< 4$$ where soil uptake also has a role in ozone deposition.

Advanced error diagnostics of the CMAQ and Chimere modelling systems within the AQMEII3 model evaluation framework.

The work here complements the overview analysis of the modelling systems participating in the third phase of the Air Quality Model Evaluation International Initiative (AQMEII3) by focusing on the performance for hourly surface ozone by two modelling systems, Chimere for Europe and CMAQ for North America. The evaluation strategy outlined in the course of the three phases of the AQMEII activity, aimed to build up a diagnostic methodology for model evaluation, is pursued here and novel diagnostic methods are proposed. In addition to evaluating the "base case" simulation in which all model components are configured in their standard mode, the analysis also makes use of sensitivity simulations in which the models have been applied by altering and/or zeroing lateral boundary conditions, emissions of anthropogenic precursors, and ozone dry deposition. To help understand of the causes of model deficiencies, the error components (bias, variance, and covariance) of the base case and of the sensitivity runs are analysed in conjunction with timescale considerations and error modelling using the available error fields of temperature, wind speed, and NO x concentration. The results reveal the effectiveness and diagnostic power of the methods devised (which remains the main scope of this study), allowing the detection of the timescale and the fields that the two models are most sensitive to. The representation of planetary boundary layer (PBL) dynamics is pivotal to both models. In particular, (i) the fluctuations slower than ~ 1.5 days account for 70-85 % of the mean square error of the full (undecomposed) ozone time series; (ii) a recursive, systematic error with daily periodicity is detected, responsible for 10-20 % of the quadratic total error; (iii) errors in representing the timing of the daily transition between stability regimes in the PBL are responsible for a covariance error as large as 9 ppb (as much as the standard deviation of the network-average ozone observations in summer in both Europe and North America); (iv) the CMAQ ozone error has a weak/negligible dependence on the errors in NO2, while the error in NO2 significantly impacts the ozone error produced by Chimere; (v) the response of the models to variations of anthropogenic emissions and boundary conditions show a pronounced spatial heterogeneity, while the seasonal variability of the response is found to be less marked. Only during the winter season does the zeroing of boundary values for North America produce a spatially uniform deterioration of the model accuracy across the majority of the continent.