Net Chemical Production Research Articles

Implications of Sea Breezes on Air Quality Monitoring in a Coastal Urban Environment: Evidence From High Resolution Modeling of NO2 and O3

AbstractCoastal urban environments face unique challenges associated with air quality‐meteorology interactions. In this study, high resolution chemical transport modeling over the Greater Boston area was performed to improve our understanding of sea breezes impacts on the spatiotemporal variability of primary and secondary pollutants. We perform WRF‐Chem simulations at 3 km resolution over June 22 to 10 July 2019 (a period that included 10 sea breeze occurrences), and use Pandora tropospheric NO2 column, surface air quality monitoring, and vertical meteorological aircraft profiles for evaluation. The model generally reproduces observed spatiotemporal variability of air pollution during sea breezes well. Tropospheric columns of NO2 predicted by the model and observed by the Pandora instrument show that sea breezes are associated with rapid increases and steep gradients in tropospheric NO2 and confirm accumulation of local primary emissions. Spatial heterogeneity in tropospheric NO2 is strongly governed by inland penetration lengths of the sea breeze front. Process diagnostics show that three sea‐breeze days where O3 observations recorded hourly concentrations >70 ppb have both efficient net chemical O3 production in the boundary layer (>10 ppb/hr) and rapid O3 convergence in the near‐surface convergence zone (>20 ppb/hr). During sea breezes, interactions between photochemistry, the convergence zone inland penetration, and urban NOx titration effects, contribute to strong heterogeneity and high O3 inland that is not captured by the current monitoring network. We discuss monitoring needs and model applications for the sea breeze scenarios, with broad implications for air quality monitoring in coastal urban environments.

Multiphase processes in the EC-Earth model and their relevance to the atmospheric oxalate, sulfate, and iron cycles

Abstract. Understanding how multiphase processes affect the iron-containing aerosol cycle is key to predicting ocean biogeochemistry changes and hence the feedback effects on climate. For this work, the EC-Earth Earth system model in its climate–chemistry configuration is used to simulate the global atmospheric oxalate (OXL), sulfate (SO42-), and iron (Fe) cycles after incorporating a comprehensive representation of the multiphase chemistry in cloud droplets and aerosol water. The model considers a detailed gas-phase chemistry scheme, all major aerosol components, and the partitioning of gases in aerosol and atmospheric water phases. The dissolution of Fe-containing aerosols accounts kinetically for the solution's acidity, oxalic acid, and irradiation. Aerosol acidity is explicitly calculated in the model, both for accumulation and coarse modes, accounting for thermodynamic processes involving inorganic and crustal species from sea salt and dust. Simulations for present-day conditions (2000–2014) have been carried out with both EC-Earth and the atmospheric composition component of the model in standalone mode driven by meteorological fields from ECMWF's ERA-Interim reanalysis. The calculated global budgets are presented and the links between the (1) aqueous-phase processes, (2) aerosol dissolution, and (3) atmospheric composition are demonstrated and quantified. The model results are supported by comparison to available observations. We obtain an average global OXL net chemical production of 12.615 ± 0.064 Tg yr−1 in EC-Earth, with glyoxal being by far the most important precursor of oxalic acid. In comparison to the ERA-Interim simulation, differences in atmospheric dynamics and the simulated weaker oxidizing capacity in EC-Earth overall result in a ∼ 30 % lower OXL source. On the other hand, the more explicit representation of the aqueous-phase chemistry in EC-Earth compared to the previous versions of the model leads to an overall ∼ 20 % higher sulfate production, but this is still well correlated with atmospheric observations. The total Fe dissolution rate in EC-Earth is calculated at 0.806 ± 0.014 Tg yr−1 and is added to the primary dissolved Fe (DFe) sources from dust and combustion aerosols in the model (0.072 ± 0.001 Tg yr−1). The simulated DFe concentrations show a satisfactory comparison with available observations, indicating an atmospheric burden of ∼0.007 Tg, resulting in an overall atmospheric deposition flux into the global ocean of 0.376 ± 0.005 Tg yr−1, which is well within the range reported in the literature. All in all, this work is a first step towards the development of EC-Earth into an Earth system model with fully interactive bioavailable atmospheric Fe inputs to the marine biogeochemistry component of the model.

Measurement report: Fast photochemical production of peroxyacetyl nitrate (PAN) over the rural North China Plain during haze events in autumn

Abstract. Photochemical pollution over the North China Plain (NCP) is attracting much concern. We usually view peroxyacetyl nitrate (PAN) as the second most important photochemical pollutant featuring high mixing ratios during warm seasons. Our observations at a background site in the NCP identified high PAN concentrations, even during haze events in autumn. The substantial increasing ratios of PAN, by 244 % and 178 %, over the morning hours (08:00–12:00 local time) on 20 and 25 October 2020 were 10.6 and 7.7 times larger than those on clean days. Polluted days are characterized by higher temperature, higher humidity, and anomalous southerly winds compared with clean days. Enhanced local photochemistry has been identified as being the dominant factor that controls the PAN increase in the morning at the rural site, as the time when prevailing wind turns to a southerly wind is too late to promote direct transport of PAN from the polluted urban region. By removing the effect of direct transport of PAN, we provide a quantitative assessment of net PAN chemical production rate of 0.45 ppb h−1 for the mornings of polluted days, also demonstrating the strong local photochemistry. Using observations and calculated photolysis rates, we find that acetaldehyde oxidation by hydroxyl radical (OH) is the primary pathway of peroxyacetyl radical formation at the rural site. Acetaldehyde concentrations and production rates of HOx (HOx= OH + HO2) on polluted days are 2.8 and 2 times as large as those on clean days, leading to a remarkable increase in PAN in the morning. Formaldehyde (HCHO) photolysis dominates the daytime HOx production, thus contributing to fast photochemistry of PAN. Our observational results suggest the cause of a rapid increase in PAN during haze events in autumn at a rural site of the NCP and provide evidence of important role of HCHO photolysis in secondary pollutants at lower nitrogen oxide emissions. This highlights the urgency of carrying out strict volatile organic compound controls over the NCP during the cold season and not just in summer.

Heat transfer augmentation by recombination reactions in turbulent reacting boundary layers at elevated pressures

A study of a reacting boundary layer flow with heat transfer at conditions typical for configurations at elevated pressures has been performed using a set of direct numerical simulations. Effects of wall temperatures are investigated, representative for cooled walls of gas turbines and sub-scale rocket engines operating with hydrocarbon as fuels. The results show that exothermic chemical reactions induced by the low-enthalpy in the boundary layer take place predominantly in the logarthimic sub-layer. The majority of the heat release is attributed to the exothermic recombination of OH and CO to produce CO2 and H2O. The recombination reactions result in an increase of the wall heat loads by up to 20% compared to the inert flow. The gas composition experiences strong deviations from the chemical equilibrium conditions. In fact, a quenching of the major species is observed within the viscous sub-layer and the transition region. Analysis of chemical time-scales shows that the location of quenched composition coincides with the region where the Damköhler number decreases below unity. Within the viscous sub-layer, a secondary reaction zone is detected, involving the production of formyl and formaldehyde radicals that provide an additional source of energy release. The analysis of the reaction paths showed that reactions with zero activation energy are responsible for this change in gas composition, which also account for the initial branching of hydrocarbon fuels decomposition according to previous auto-ignition studies. The effect of the secondary recombination reactions is more prominent for the lower wall temperature case. Finally, the role of turbulent fluctuations on the species net chemical production rates is evaluated, showing a strong correlation between species and temperature fluctuations. This leads to a pronounced deviation of the mean reaction rates ω˙(Yk,T)¯ from the reaction rates obtained under the assumption of laminar finite rate.

Impact of the 2016 Southeastern US Wildfires on the Vertical Distribution of Ozone and Aerosol at Huntsville, Alabama

AbstractWe present an integrated analysis of measurements from ozonesonde, ozone (O3) Differential Absorption Lidar (DIAL), ceilometer, surface monitors, and space‐borne observations in conjunction with the regional chemical transport model Weather Research and Forecast Model with Chemistry (WRF‐Chem) to investigate the effect of biomass burning emissions on the vertical distribution of ozone and aerosols during an episode of the 2016 Southeastern United States wildfires. The ceilometer and DIAL measurements capture the vertical extent of the smoke plumes affecting the surface and upper air over Huntsville, AL. The model evaluation results suggest a scaling factor of 3–4 for the wildfire aerosol emissions in order to better match observed aerosol optical depth, fine particulate matter (PM2.5), and DIAL aerosol extinction. We use the scaled emissions together with WRF‐Chem tendency diagnostics to quantify the fire impacts and characterize the processes affecting the vertical ozone budget downstream of the wildfires. During the daytime at Huntsville on November 12 and 13, we estimate that fire emissions contribute 12–32 μg/m3 (44%–70%) to hourly surface PM2.5 and 7–8 ppb/10 h (30%–37%) to the surface ozone increase (ΔO3), respectively. Net chemical ozone production (PO3) is the main contributor to upper‐air ozone, which reaches 17–19 ppb/10 h with an estimated 14%–25% contribution from fire sources. Vertical mixing and advection are the major drivers of changes in surface ozone. Model analysis indicates that advection dominates ΔO3 due to fire emissions below 1 km on November 12, while local photochemistry dominates on November 13. These results quantify the different mechanisms through which fires can influence the vertical ozone budget and point out uncertainties in fire inventories that need to be addressed in light of the increasing role of wildfires on air quality.

Tropospheric ozone in CMIP6 simulations

Abstract. The evolution of tropospheric ozone from 1850 to 2100 has been studied using data from Phase 6 of the Coupled Model Intercomparison Project (CMIP6). We evaluate long-term changes using coupled atmosphere–ocean chemistry–climate models, focusing on the CMIP Historical and ScenarioMIP ssp370 experiments, for which detailed tropospheric-ozone diagnostics were archived. The model ensemble has been evaluated against a suite of surface, sonde and satellite observations of the past several decades and found to reproduce well the salient spatial, seasonal and decadal variability and trends. The multi-model mean tropospheric-ozone burden increases from 247 ± 36 Tg in 1850 to a mean value of 356 ± 31 Tg for the period 2005–2014, an increase of 44 %. Modelled present-day values agree well with previous determinations (ACCENT: 336 ± 27 Tg; Atmospheric Chemistry and Climate Model Intercomparison Project, ACCMIP: 337 ± 23 Tg; Tropospheric Ozone Assessment Report, TOAR: 340 ± 34 Tg). In the ssp370 experiments, the ozone burden increases to 416 ± 35 Tg by 2100. The ozone budget has been examined over the same period using lumped ozone production (PO3) and loss (LO3) diagnostics. Both ozone production and chemical loss terms increase steadily over the period 1850 to 2100, with net chemical production (PO3-LO3) reaching a maximum around the year 2000. The residual term, which contains contributions from stratosphere–troposphere transport reaches a minimum around the same time before recovering in the 21st century, while dry deposition increases steadily over the period 1850–2100. Differences between the model residual terms are explained in terms of variation in tropopause height and stratospheric ozone burden.

Tropospheric Ozone Assessment Report

Our understanding of the processes that control the burden and budget of tropospheric ozone has changed dramatically over the last 60 years. Models are the key tools used to understand these changes, and these underscore that there are many processes important in controlling the tropospheric ozone budget. In this critical review, we assess our evolving understanding of these processes, both physical and chemical. We review model simulations from the International Global Atmospheric Chemistry Atmospheric Chemistry and Climate Model Intercomparison Project and Chemistry Climate Modelling Initiative to assess the changes in the tropospheric ozone burden and its budget from 1850 to 2010. Analysis of these data indicates that there has been significant growth in the ozone burden from 1850 to 2000 (approximately 43 ± 9%) but smaller growth between 1960 and 2000 (approximately 16 ± 10%) and that the models simulate burdens of ozone well within recent satellite estimates. The Chemistry Climate Modelling Initiative model ozone budgets indicate that the net chemical production of ozone in the troposphere plateaued in the 1990s and has not changed since then inspite of increases in the burden. There has been a shift in net ozone production in the troposphere being greatest in the northern mid and high latitudes to the northern tropics, driven by the regional evolution of precursor emissions. An analysis of the evolution of tropospheric ozone through the 21st century, as simulated by Climate Model Intercomparison Project Phase 5 models, reveals a large source of uncertainty associated with models themselves (i.e., in the way that they simulate the chemical and physical processes that control tropospheric ozone). This structural uncertainty is greatest in the near term (two to three decades), but emissions scenarios dominate uncertainty in the longer term (2050–2100) evolution of tropospheric ozone. This intrinsic model uncertainty prevents robust predictions of near-term changes in the tropospheric ozone burden, and we review how progress can be made to reduce this limitation.

What have we missed when studying the impact of aerosols on surface ozone via changing photolysis rates?

Abstract. Previous studies have emphasized that the decrease in photolysis rate at the surface induced by the light extinction of aerosols could weaken ozone photochemistry and then reduce surface ozone. However, quantitative studies have shown that weakened photochemistry leads to a much greater reduction in the net chemical production of ozone, which does not match the reduction in surface ozone. This suggests that in addition to photochemistry, some other physical processes related to the variation of ozone should also be considered. In this study, the Weather Research and Forecasting with Chemistry (WRF-Chem) model coupled with the ozone source apportionment method was applied to determine the mechanism of ozone reduction induced by aerosols over central East China (CEC). Our results showed that weakened ozone photochemistry led to a significant reduction in ozone net chemical production, which occurred not only at the surface but also within the lowest several hundred meters in the planetary boundary layer (PBL). Meanwhile, a larger ozone gradient was formed in the vertical direction, which led to the high concentrations of ozone aloft being entrained by turbulence from the top of the PBL to the surface and partly counteracting the reduction in surface ozone. In addition, contribution from dry deposition was weakened due to the decrease in surface ozone concentration. The reduction in the ozone's sink also slowed down the rate of the decrease in surface ozone. Ozone in the upper layer of the PBL was also reduced, which was induced by much ozone aloft being entrained downward. Therefore, by affecting the photolysis rate, the impact of aerosols was a reduction in ozone not only at the surface but also throughout the entire PBL during the daytime over CEC in this study. The ozone source apportionment results showed that 41.4 %–66.3 % of the reduction in surface ozone came from local and adjacent source regions, which suggested that the impact of aerosols on ozone from local and adjacent regions was more significant than that from long-distance regions. The results also suggested that while controlling the concentration of aerosols, simultaneously controlling ozone precursors from local and adjacent source regions is an effective way to suppress the increase in surface ozone over CEC at present.

Integration of airborne and ground observations of nitryl chloride in the Seoul metropolitan area and the implications on regional oxidation capacity during KORUS-AQ 2016

Abstract. Nitryl chloride (ClNO2) is a radical reservoir species that releases chlorine radicals upon photolysis. An integrated analysis of the impact of ClNO2 on regional photochemistry in the Seoul metropolitan area (SMA) during the Korea–United States Air Quality Study (KORUS-AQ) 2016 field campaign is presented. Comprehensive multiplatform observations were conducted aboard the NASA DC-8 and at two ground sites (Olympic Park, OP; Taehwa Research Forest, TRF), representing an urbanized area and a forested suburban region, respectively. Positive correlations between daytime Cl2 and ClNO2 were observed at both sites, the slope of which was dependent on O3 levels. The possible mechanisms are explored through box model simulations constrained with observations. The overall diurnal variations in ClNO2 at both sites appeared similar but the nighttime variations were systematically different. For about half of the observation days at the OP site the level of ClNO2 increased at sunset but rapidly decreased at around midnight. On the other hand, high levels were observed throughout the night at the TRF site. Significant levels of ClNO2 were observed at both sites for 4–5 h after sunrise. Airborne observations, box model calculations, and back-trajectory analysis consistently show that these high levels of ClNO2 in the morning are likely from vertical or horizontal transport of air masses from the west. Box model results show that chlorine-radical-initiated chemistry can impact the regional photochemistry by elevating net chemical production rates of ozone by ∼25 % in the morning.

A model investigation into the atmospheric NOy chemistry in remote continental Asia

The OMI-observed tropospheric NO2 columns over highly polluted regions in East Asia showed high values during the cold seasons and low values during the warm seasons. On the contrary, the monthly trends over Mongolia are completely opposite to those in polluted regions in East Asia. This study was initiated by such an interesting contrast. To determine the key factors controlling such monthly trends over Mongolia, we used the WRF-CMAQ simulated data. In the analysis, we explored the budget of P‾NOx (columnar net NOx chemical production rates), taking into account atmospheric chemical production and removal of NOx as well as surface (soil) NOx emissions. For the polluted regions, NOx emissions show the largest values, followed by P‾RNO3in terms of the magnitudes. Among the negative contributors, the largest contribution is made by P‾RNO3 (columnar net NOx chemical production rates via the HNO3 and RNO3-related reactions) ranging between −42% and −77% during the warm months. Other negative contributions from P‾PANs(columnar net NOx chemical production rates via the formations and decompositions of PANs) and P‾Hetero.(columnar net NOx chemical production rates via the heterogeneous reactions of NO3 and N2O5) are relatively small. Unlike the situations over the polluted regions, the negative P‾RNO3 was offset completely by ENOx (emission of NOx) and positive P‾PANsover the remote continental regions of Mongolia. P‾PANs was also regarded as an important atmospheric process, and its positive contributions range between 5% and 51% over the remote continental regions of (south) Mongolia. From the analysis, it was found that NO2 produced via thermal decomposition of PANs in the remote continental regions of Mongolia contribute to the high NO2 columns during the warm seasons and low values during the cold seasons.

Comparison of surface ozone simulation among selected regional models in MICS-Asia III – effects of chemistry and vertical transport for the causes of difference

Abstract. In order to clarify the causes of variability among the model outputs for surface ozone in the Model Intercomparison Study Asia Phase III (MICS-Asia III), three regional models, CMAQ v.5.0.2, CMAQ v.4.7.1, and NAQPMS (abbreviated as NAQM in this paper), have been selected. Detailed analyses of monthly averaged diurnal variation have been performed for selected grids covering the metropolitan areas of Beijing and Tokyo and at a remote oceanic site, Oki. The chemical reaction mechanism, SAPRC99, used in the CMAQ models tended to give a higher net chemical ozone production than CBM-Z used in NAQM, agreeing with previous studies. Inclusion of the heterogeneous “renoxification” reaction of HNO3 (on soot surface)→NO+NO2 only in NAQM would give a higher NO concentration resulting in a better agreement with observational data for NO and nighttime O3 mixing ratios. In addition to chemical processes, the difference in the vertical transport of O3 was found to affect the simulated results significantly. Particularly, the increase in downward O3 flux from the upper layer to the surface after dawn was found to be substantially different among the models. Larger early morning vertical transport of O3 simulated by CMAQ 5.0.2 is thought to be the reason for higher daytime O3 in July in this model. All three models overestimated the daytime ozone by ca. 20 ppbv at the remote site Oki in July, where in situ photochemical activity is minimal.

Lower tropospheric ozone over India and its linkage to the South Asian monsoon

Abstract. Lower tropospheric (surface to 600 hPa) ozone over India poses serious risks to both human health and crops, and potentially affects global ozone distribution through frequent deep convection in tropical regions. Our current understanding of the processes controlling seasonal and long-term variations in lower tropospheric ozone over this region is rather limited due to spatially and temporally sparse observations. Here we present an integrated process analysis of the seasonal cycle, interannual variability, and long-term trends of lower tropospheric ozone over India and its linkage to the South Asian monsoon using the Ozone Monitoring Instrument (OMI) satellite observations for years 2006–2014 interpreted with a global chemical transport model (GEOS-Chem) simulation for 1990–2010. OMI observed lower tropospheric ozone over India averaged for 2006–2010, showing the highest concentrations (54.1 ppbv) in the pre-summer monsoon season (May) and the lowest concentrations (40.5 ppbv) in the summer monsoon season (August). Process analyses in GEOS-Chem show that hot and dry meteorological conditions and active biomass burning together contribute to 5.8 Tg more ozone being produced in the lower troposphere in India in May than January. The onset of the summer monsoon brings ozone-unfavorable meteorological conditions and strong upward transport, which all lead to large decreases in the lower tropospheric ozone burden. Interannually, we find that both OMI and GEOS-Chem indicate strong positive correlations (r=0.55–0.58) between ozone and surface temperature in pre-summer monsoon seasons, with larger correlations found in high NOx emission regions reflecting NOx-limited production conditions. Summer monsoon seasonal mean ozone levels are strongly controlled by monsoon strengths. Lower ozone concentrations are found in stronger monsoon seasons mainly due to less ozone net chemical production. Furthermore, model simulations over 1990–2010 estimate a mean annual trend of 0.19 ± 0.07 (p value < 0.01) ppbv yr−1 in Indian lower tropospheric ozone over this period, which are mainly driven by increases in anthropogenic emissions with a small contribution (about 7 %) from global methane concentration increases.

The chemical effects on the summertime ozone in the upper troposphere and lower stratosphere over the Tibetan Plateau and the South Asian monsoon region

We use the global three-dimensional Goddard Earth Observing System chemical transport model with the Universal tropospheric–stratospheric Chemistry eXtension mechanism to examine the contributions of the chemical processes to summertime O3 in the upper troposphere and lower stratosphere (UTLS) over the Tibetan Plateau and the South Asian monsoon region (TP/SASM). Simulated UTLS O3 concentrations are evaluated by comparisons with Microwave Limb Sounder products and net chemical production of O3 (NPO3) are evaluated by comparisons with model results in previous studies. Simulations show that the chemical processes lead to an increase in O3 concentration, which is opposite to the effect of O3 transport in the UTLS over the TP/SASM region throughout the boreal summer. NPO3 in UTLS over the TP/SASM region is the largest in summer. Elevated values (0.016–0.020 Tg year−1) of the seasonal mean NPO3 are simulated to locate at 100 hPa in the TP/SASM region, where the mixing ratios of O3 are low and those of O3 precursors (NOx, VOCs, and CO) are high. The high concentrations of O3 precursors (NOx, VOCs, and CO) together with the active photochemical reactions of NO2 in the UTLS over the TP/SASM region during summertime could be important reasons for the enhancement of $${\text{NP}}_{{{\text{O}}_{3} }}$$ over the studied region.

Simulating ozone dry deposition at a boreal forest with a multi-layer canopy deposition model

Abstract. A multi-layer ozone (O3) dry deposition model has been implemented into SOSAA (a model to Simulate the concentrations of Organic vapours, Sulphuric Acid and Aerosols) to improve the representation of O3 concentration and flux within and above the forest canopy in the planetary boundary layer. We aim to predict the O3 uptake by a boreal forest canopy under varying environmental conditions and analyse the influence of different factors on total O3 uptake by the canopy as well as the vertical distribution of deposition sinks inside the canopy. The newly implemented dry deposition model was validated by an extensive comparison of simulated and observed O3 turbulent fluxes and concentration profiles within and above the boreal forest canopy at SMEAR II (Station to Measure Ecosystem–Atmosphere Relations II) in Hyytiälä, Finland, in August 2010. In this model, the fraction of wet surface on vegetation leaves was parametrised according to the ambient relative humidity (RH). Model results showed that when RH was larger than 70 % the O3 uptake onto wet skin contributed ∼ 51 % to the total deposition during nighttime and ∼ 19 % during daytime. The overall contribution of soil uptake was estimated about 36 %. The contribution of sub-canopy deposition below 4.2 m was modelled to be ∼ 38 % of the total O3 deposition during daytime, which was similar to the contribution reported in previous studies. The chemical contribution to O3 removal was evaluated directly in the model simulations. According to the simulated averaged diurnal cycle the net chemical production of O3 compensated up to ∼ 4 % of dry deposition loss from about 06:00 to 15:00 LT. During nighttime, the net chemical loss of O3 further enhanced removal by dry deposition by a maximum ∼ 9 %. Thus the results indicated an overall relatively small contribution of airborne chemical processes to O3 removal at this site.

Simulation of tropical tropospheric ozone variation from 1982 to 2010: The meteorological impact of two types of ENSO event

AbstractThe effects of two types of ENSO events on tropical ozone (O3) variations from 1982 to 2010, and the mechanisms underlying these effects, were analyzed using observations and model simulations. Tropospheric column O3 anomalies (TCOA) during canonical El Niño were different from El Niño Modoki. Absolute TCOA values are larger during canonical El Niño than during El Niño Modoki in most regions. La Niña events were not separated into the different types because of their similarity in terms of sea surface temperature patterns. TCOA in La Niña showed a reversed dipole from canonical El Niño. During canonical El Niño, anomalous downward motion together with suppressed convection weakened O3 outflow from the troposphere, causing an increase in tropospheric O3 over western Pacific. Over central and eastern Pacific, decreased O3 concentrations resulted primarily from a change in net chemical production of O3. The change in net O3 chemical production relates to increased levels of HOx under wetter condition. During El Niño Modoki, transport and chemical fluxes were similar but weaker than during canonical El Niño. During La Niña, O3 anomalies and transport fluxes were the opposite of those during the El Niño Modoki. Stratospheric O3 played a key role in the development of O3 anomaly above 250 hPa during ENSO events, contributing >30% to the O3 anomalies. The change in free tropospheric O3 affected the O3 anomaly from 850 hPa to 200 hPa (60% of O3 anomaly). The contribution of O3 from planetary boundary layer was concentrated at the surface, with a contribution of <15%.

Drivers of changes in stratospheric and tropospheric ozone between year 2000 and 2100

Abstract. A stratosphere-resolving configuration of the Met Office's Unified Model (UM) with the United Kingdom Chemistry and Aerosols (UKCA) scheme is used to investigate the atmospheric response to changes in (a) greenhouse gases and climate, (b) ozone-depleting substances (ODSs) and (c) non-methane ozone precursor emissions. A suite of time-slice experiments show the separate, as well as pairwise, impacts of these perturbations between the years 2000 and 2100. Sensitivity to uncertainties in future greenhouse gases and aerosols is explored through the use of the Representative Concentration Pathway (RCP) 4.5 and 8.5 scenarios. The results highlight an important role for the stratosphere in determining the annual mean tropospheric ozone response, primarily through stratosphere–troposphere exchange (STE) of ozone. Under both climate change and reductions in ODSs, increases in STE offset decreases in net chemical production and act to increase the tropospheric ozone burden. This opposes the effects of projected decreases in ozone precursors through measures to improve air quality, which act to reduce the ozone burden. The global tropospheric lifetime of ozone (τO3) does not change significantly under climate change at RCP4.5, but it decreases at RCP8.5. This opposes the increases in τO3 simulated under reductions in ODSs and ozone precursor emissions. The additivity of the changes in ozone is examined by comparing the sum of the responses in the single-forcing experiments to those from equivalent combined-forcing experiments. Whilst the ozone responses to most forcing combinations are found to be approximately additive, non-additive changes are found in both the stratosphere and troposphere when a large climate forcing (RCP8.5) is combined with the effects of ODSs.

Effects of anthropogenic heat on ozone air quality in a megacity

Anthropogenic heat released into the atmosphere in urban areas affects the characteristics/structures of boundary layer and local circulation and thus can affect local air quality. In this study, the effects of anthropogenic heat on ozone (O3) air quality in the Seoul metropolitan area, Republic of Korea, are examined using the Community Multiscale Air Quality (CMAQ) model coupled with the Weather Research and Forecasting (WRF) model. The release of anthropogenic heat is found to increase O3 concentration by 3.8 ppb in the urban area, and this effect is larger in the nighttime (5.3 ppb) than in the daytime (2.4 ppb). As stronger anthropogenic heat is released, the urban boundary layer becomes deeper and NOx concentration becomes lower due to the dilution. The decrease in NOx concentration causes the chemical loss of O3 by the reaction with NO to be reduced. In addition to the enhanced net chemical production of O3 in the deepened urban boundary layer, the strengthened urban-breeze circulation by anthropogenic heat contributes to an increase in O3 concentration in the urban area. The O3-rich air in the surroundings of Seoul, where biogenic volatile organic compound (BVOC) emissions are high and NOx emissions are low, is brought into the urban area by the urban breeze. Moreover, in the daytime, the advection of oxidant products of BVOCs by the urban breeze contributes to an enhanced chemical production of O3 in the urban area. Anthropogenic heat also modifies the sea/land-breeze circulations, which, in turn, is found to influence O3 concentration in the urban area.

Factors affecting O3 and NO2photolysis frequencies measured in the eastern Mediterranean during the five‐year period 2002–2006

The photolysis frequencies of ozone (O3; to singlet oxygen, JO1D) and nitrogen dioxide (NO2; JNO2) were recorded at the remote coastal site Finokalia (35°20′N, 25°40′E), on the island of Crete, Greece, during the period 2002–2006. We present a study of their main climatological aspects and a quantification of the effect of aerosol and total ozone column on these frequencies. The 5‐yr mean Aerosol Optical Depth (AOD) at 380 nm in the area is equal to 0.27 ± 0.13 and reduces JNO2by 5%–14% at a solar zenith angle (sza) of 60°, compared to an aerosol‐free atmosphere. It also leads to a similar reduction of JO1D by 5%–15% at the 60° sza, for an average total ozone column (300–320 Dobson units (DU)). The effect of regional background AOD (∼0.1) is a reduction of JNO2 and JO1D by up to 6% for sza in the range 15° to75°, respectively. During high aerosol loads (AOD 0.5–0.7) the percentage reduction of Js was found to be as much as 30%–40% at high sza. The day‐to‐day variability of total ozone column over the area, of the order of 20 DU, was found to result in a 12% change in JO1D at 60° sza as compared with zero AOD conditions. A reduction of Js corresponding to a 24% decrease in the local noon JO1D value and a 5% decrease in local noon JNO2 were found to result in a 12% reduction in the 24 h mean net chemical production of O3, using a chemical box model.

CAM-chem: description and evaluation of interactive atmospheric chemistry in the Community Earth System Model

Abstract. We discuss and evaluate the representation of atmospheric chemistry in the global Community Atmosphere Model (CAM) version 4, the atmospheric component of the Community Earth System Model (CESM). We present a variety of configurations for the representation of tropospheric and stratospheric chemistry, wet removal, and online and offline meteorology. Results from simulations illustrating these configurations are compared with surface, aircraft and satellite observations. Major biases include a negative bias in the high-latitude CO distribution, a positive bias in upper-tropospheric/lower-stratospheric ozone, and a positive bias in summertime surface ozone (over the United States and Europe). The tropospheric net chemical ozone production varies significantly between configurations, partly related to variations in stratosphere-troposphere exchange. Aerosol optical depth tends to be underestimated over most regions, while comparison with aerosol surface measurements over the United States indicate reasonable results for sulfate , especially in the online simulation. Other aerosol species exhibit significant biases. Overall, the model-data comparison indicates that the offline simulation driven by GEOS5 meteorological analyses provides the best simulation, possibly due in part to the increased vertical resolution (52 levels instead of 26 for online dynamics). The CAM-chem code as described in this paper, along with all the necessary datasets needed to perform the simulations described here, are available for download at www.cesm.ucar.edu.

The impact of soil uptake on the global distribution of molecular hydrogen: chemical transport model simulation

Abstract. The global tropospheric distribution of molecular hydrogen (H2) and its uptake by the soil are simulated using a model called CHemical AGCM (atmospheric general circulation model) for the Study of the Environment and Radiative forcing (CHASER), which incorporates a two-layered soil diffusion/uptake process component. The simulated distribution of deposition velocity over land is influenced by regional climate, and has a global average of 3.3×10−2 cm s−1. In the region north of 30° N, the amount of soil uptake shows a large seasonal variation corresponding to change in biological activity due to soil temperature and change in diffusion suppression by snow cover. In the temperate and humid regions in the mid- to low- latitudes, the uptake is mostly influenced by the soil air ratio, which controls the gas diffusivity in the soil. In the semi-arid regions, water stress and high temperatures contribute to the reduction of biological activity, as well as to the seasonal variation in the deposition velocity. A comparison with the observations shows that the model reproduces both the distribution and seasonal variation of H2 relatively well. The global burden and tropospheric lifetime of H2 are 150 Tg and 2.0 yr, respectively. The seasonal variation in H2 mixing ratios at the northern high latitudes is mainly controlled by a large seasonal change in the soil uptake. In the Southern Hemisphere, seasonal change in net chemical production and inter-hemispheric transport are the dominant causes of the seasonal cycle, while large biomass burning contributes significantly to the seasonal variation in the tropics and subtropics. Both observations and the model show large inter-annual variations, especially for the period 1997–1998, associated with large biomass burning in the tropics and at Northern Hemisphere high latitudes. The soil uptake shows relatively small inter-annual variability compared with the biomass burning signal. Given that the thickness of biologically inactive layer plays an important role in the soil uptake of H2, its value in the model is chosen to achieve agreement with the observed H2 trends. Uncertainty of the estimated soil uptake flux in the semi-arid region is still large, reflecting the discrepancy in the observed and modeled seasonal variations.