scholarly journals Modelling the global tropospheric ozone budget: exploring the variability in current models

2007 ◽  
Vol 7 (1) ◽  
pp. 1995-2035 ◽  
Author(s):  
O. Wild
Keyword(s):  
Dry Deposition ◽  
Tropospheric Ozone ◽  
Transport Model ◽  
Recent Model ◽  
Ozone Production ◽  
Surface Deposition ◽  
Chemistry Transport Model ◽  
Model Studies ◽  
Coarse Model ◽  
Lightning Nox

Abstract. What are the largest uncertainties in modelling ozone in the troposphere, and how do they affect the calculated ozone budget? Published chemistry-transport model studies of tropospheric ozone differ significantly in their conclusions regarding the importance of the key processes controlling the ozone budget: influx from the stratosphere, chemical processing and surface deposition. This study surveys ozone budgets from previous studies and demonstrates that about two thirds of the increase in ozone production seen between early assessments and more recent model intercomparisons can be accounted for by increased precursor emissions. Model studies using recent estimates of emissions compare better with ozonesonde measurements than studies using older data, and the tropospheric burden of ozone is closer to that derived here from measurement climatologies, 335±10 Tg. However, differences between individual model studies remain large and cannot be explained by surface precursor emissions alone; cross-tropopause transport, wet and dry deposition, humidity, and lightning make large contributions to the differences seen between models. The importance of these processes is examined here using a chemistry-transport model to investigate the sensitivity of the calculated ozone budget to different assumptions about emissions, physical processes, meteorology and model resolution. The budget is particularly sensitive to the magnitude and location of lightning NOx emissions, which remain poorly constrained; the 3–8 TgN/yr range in recent model studies may account for a 10% difference in tropospheric ozone burden and a 1.4 year difference in CH4 lifetime. Differences in humidity and dry deposition account for some of the variability in ozone abundance and loss seen in previous studies, with smaller contributions from wet deposition and stratospheric influx. At coarse model resolutions stratospheric influx is systematically overestimated and dry deposition is underestimated; these differences are 5–8% at the 300–600 km grid-scales investigated here, similar in magnitude to the changes induced by interannual variability in meteorology. However, a large proportion of the variability between models remains unexplained, suggesting that differences in model chemistry and dynamics have a large impact on the calculated ozone budget, and these should be the target of future model intercomparisons.

scholarly journals Modelling the global tropospheric ozone budget: exploring the variability in current models

2007 ◽  
Vol 7 (10) ◽  
pp. 2643-2660 ◽  
Author(s):  
O. Wild
Keyword(s):  
Dry Deposition ◽  
Tropospheric Ozone ◽  
Transport Model ◽  
Recent Model ◽  
Ozone Production ◽  
Chemistry Transport Model ◽  
Chemical Mechanisms ◽  
Model Studies ◽  
Coarse Model ◽  
Lightning Nox

Abstract. What are the largest uncertainties in modelling ozone in the troposphere, and how do they affect the calculated ozone budget? Published chemistry-transport model studies of tropospheric ozone differ significantly in their conclusions regarding the importance of the key processes controlling the ozone budget: influx from the stratosphere, chemical processing and surface deposition. This study surveys ozone budgets from previous studies and demonstrates that about two thirds of the increase in ozone production seen between early assessments and more recent model intercomparisons can be accounted for by increased precursor emissions. Model studies using recent estimates of emissions compare better with ozonesonde measurements than studies using older data, and the tropospheric burden of ozone is closer to that derived here from measurement climatologies, 335±10 Tg. However, differences between individual model studies remain large and cannot be explained by surface precursor emissions alone; cross-tropopause transport, wet and dry deposition, humidity, and lightning also make large contributions. The importance of these processes is examined here using a chemistry-transport model to investigate the sensitivity of the calculated ozone budget to different assumptions about emissions, physical processes, meteorology and model resolution. The budget is particularly sensitive to the magnitude and location of lightning NOx emissions, which remain poorly constrained; the 3–8 TgN/yr range in recent model studies may account for a 10% difference in tropospheric ozone burden and a 1.4 year difference in CH4 lifetime. Differences in humidity and dry deposition account for some of the variability in ozone abundance and loss seen in previous studies, with smaller contributions from wet deposition and stratospheric influx. At coarse model resolutions stratospheric influx is systematically overestimated and dry deposition is underestimated; these differences are 5–8% at the 300–600 km grid-scales investigated here, similar in magnitude to the changes induced by interannual variability in meteorology. However, a large proportion of the variability between models remains unexplained, suggesting that differences in chemical mechanisms and dynamical schemes have a large impact on the calculated ozone budget, and these should be the target of future model intercomparisons.

scholarly journals A new diagnostic for tropospheric ozone production

2017 ◽  
Author(s):  
Peter M. Edwards ◽  
Mathew J. Evans
Keyword(s):  
Air Quality ◽  
Tropospheric Ozone ◽  
Transport Model ◽  
Chemical Transport ◽  
Ozone Production ◽  
Chemical Transport Model ◽  
Organic Species ◽  
Earth’S Climate ◽  
Oxidation Of Organics

Abstract. Tropospheric ozone is important for the Earth’s climate and air quality. It is produced during the oxidation of organics in the presence of nitrogen oxides. Due to the range of organic species emitted and the chain like nature of their oxidation, this chemistry is complex and understanding the role of different processes (emission, deposition, chemistry) is difficult. We demonstrate a new methodology for diagnosing ozone production based on the processing of bonds contained within emitted molecules, the fate of which is determined by the conservation of spin of the bonding electrons. Using this methodology to diagnose ozone production in the GEOS-Chem chemical transport model, we demonstrate its advantages over the standard diagnostic. We show that the number of bonds emitted, their chemistry and lifetime, and feedbacks on OH are all important in determining the ozone production within the model and its sensitivity to changes. This insight may allow future model-model comparisons to better identify the root causes of model differences.

scholarly journals Snow-sourced bromine and its implications for polar tropospheric ozone

2010 ◽  
Vol 10 (16) ◽  
pp. 7763-7773 ◽  
Author(s):  
X. Yang ◽  
J. A. Pyle ◽  
R. A. Cox ◽  
N. Theys ◽  
M. Van Roozendael
Keyword(s):  
Tropospheric Ozone ◽  
Transport Model ◽  
Heterogeneous Reactions ◽  
Blowing Snow ◽  
Chemistry Transport Model ◽  
Sea Salt Aerosol ◽  
Catalytic Destruction ◽  
High Fraction ◽  
High Concentrations ◽  
Boundary Layer Ozone

Abstract. In the last two decades, significant depletion of boundary layer ozone (ozone depletion events, ODEs) has been observed in both Arctic and Antarctic spring. ODEs are attributed to catalytic destruction by bromine radicals (Br plus BrO), especially during bromine explosion events (BEs), when high concentrations of BrO periodically occur. However, neither the exact source of bromine nor the mechanism for sustaining the observed high BrO concentrations is completely understood. Here, by considering the production of sea salt aerosol from snow lying on sea ice during blowing snow events and the subsequent release of bromine, we successfully simulate the BEs using a global chemistry transport model. We find that heterogeneous reactions play an important role in sustaining a high fraction of the total inorganic bromine as BrO. We also find that emissions of bromine associated with blowing snow contribute significantly to BrO at mid-latitudes. Modeled tropospheric BrO columns generally compare well with the tropospheric BrO columns retrieved from the GOME satellite instrument (Global Ozone Monitoring Experiment). The additional blowing snow bromine source, identified here, reduces modeled high latitude lower tropospheric ozone amounts by up to an average 8% in polar spring.

scholarly journals Subtropical subsidence and surface deposition of oxidized mercury produced in the free troposphere

2017 ◽  
Vol 17 (14) ◽  
pp. 8999-9017 ◽  
Author(s):  
Viral Shah ◽  
Lyatt Jaeglé
Keyword(s):  
Boundary Layer ◽  
Dry Deposition ◽  
Wet Deposition ◽  
Transport Model ◽  
Lower Troposphere ◽  
Deposition Flux ◽  
Surface Deposition ◽  
Middle Troposphere ◽  
Western Us ◽  
Wet Deposition Flux

Abstract. Oxidized mercury (Hg(II)) is chemically produced in the atmosphere by oxidation of elemental mercury and is directly emitted by anthropogenic activities. We use the GEOS-Chem global chemical transport model with gaseous oxidation driven by Br atoms to quantify how surface deposition of Hg(II) is influenced by Hg(II) production at different atmospheric heights. We tag Hg(II) chemically produced in the lower (surface–750 hPa), middle (750–400 hPa), and upper troposphere (400 hPa–tropopause), in the stratosphere, as well as directly emitted Hg(II). We evaluate our 2-year simulation (2013–2014) against observations of Hg(II) wet deposition as well as surface and free-tropospheric observations of Hg(II), finding reasonable agreement. We find that Hg(II) produced in the upper and middle troposphere constitutes 91 % of the tropospheric mass of Hg(II) and 91 % of the annual Hg(II) wet deposition flux. This large global influence from the upper and middle troposphere is the result of strong chemical production coupled with a long lifetime of Hg(II) in these regions. Annually, 77–84 % of surface-level Hg(II) over the western US, South America, South Africa, and Australia is produced in the upper and middle troposphere, whereas 26–66 % of surface Hg(II) over the eastern US, Europe, and East Asia, and South Asia is directly emitted. The influence of directly emitted Hg(II) near emission sources is likely higher but cannot be quantified by our coarse-resolution global model (2° latitude  ×  2.5° longitude). Over the oceans, 72 % of surface Hg(II) is produced in the lower troposphere because of higher Br concentrations in the marine boundary layer. The global contribution of the upper and middle troposphere to the Hg(II) dry deposition flux is 52 %. It is lower compared to the contribution to wet deposition because dry deposition of Hg(II) produced aloft requires its entrainment into the boundary layer, while rain can scavenge Hg(II) from higher altitudes more readily. We find that 55 % of the spatial variation of Hg wet deposition flux observed at the Mercury Deposition Network sites is explained by the combined variation of precipitation and Hg(II) produced in the upper and middle troposphere. Our simulation points to a large role of the dry subtropical subsidence regions. Hg(II) present in these regions accounts for 74 % of Hg(II) at 500 hPa over the continental US and more than 60 % of the surface Hg(II) over high-altitude areas of the western US. Globally, it accounts for 78 % of the tropospheric Hg(II) mass and 61 % of the total Hg(II) deposition. During the Nitrogen, Oxidants, Mercury, and Aerosol Distributions, Sources, and Sinks (NOMADSS) aircraft campaign, the contribution of Hg(II) from the dry subtropical regions was found to be 75 % when measured Hg(II) exceeded 250 pg m−3. Hg(II) produced in the upper and middle troposphere subsides in the anticyclones, where the dry conditions inhibit the loss of Hg(II). Our results highlight the importance the subtropical anticyclones as the primary conduits for the production and export of Hg(II) to the global atmosphere.

scholarly journals Evaluation of tropospheric ozone columns derived from assimilated GOME ozone profile observations

2009 ◽  
Vol 9 (20) ◽  
pp. 8105-8120 ◽  
Author(s):  
A. T. J. de Laat ◽  
R. J. van der A ◽  
M. van Weele
Keyword(s):  
Tropospheric Ozone ◽  
Transport Model ◽  
Added Value ◽  
Chemistry Transport Model ◽  
Ozone Profile ◽  
Free Running ◽  
Tropospheric O3 ◽  
Total Column ◽  
Good Agreement

Abstract. Tropospheric O3 column estimates are produced and evaluated from spaceborne O3 observations by the subtraction of assimilated O3 profile observations from total column observations, the so-called Tropospheric O3 ReAnalysis or TORA method. Here we apply the TORA method to six years (1996–2001) of ERS-2 GOME/TOMS total O3 and ERS-2 GOME O3 profile observations using the TM5 global chemistry-transport model with a linearized O3 photochemistry parameterization scheme. Free running TM5 simulations show good agreement with O3 sonde observations in the upper-tropospheric and lower stratospheric region (UTLS), both for short day-to-day variability as well as for monthly means. The assimilation of GOME O3 profile observations counteracts the mid-latitude stratospheric O3 drift caused by the overstrong stratospheric meridional circulation in TM5. Assimilation of GOME O3 profile observations also improves the bias and correlations in the tropical UTLS region but slightly degrades the model-to-sonde correlations and bias of extra-tropical UTLS. We suggest that this degradation is related to the large ground pixel size of the GOME O3 measurements (960×100 km) in combination with retrieval and calibration errors. The added value of the assimilation of GOME O3 profiles compared to stand-alone model simulations lays in the long term variations of stratospheric O3, not in short term synoptic variations. The evaluation of daily and monthly tropospheric O3 columns obtained from total column observations and using the TORA methodology shows that the use of GOME UV-VIS nadir O3 profiles in combination with the spatial resolution of the model does not result in satisfactory residual tropospheric ozone columns.

scholarly journals Biomass burning influence on high latitude tropospheric ozone and reactive nitrogen in summer 2008: a multi-model analysis based on POLMIP simulations

2014 ◽  
Vol 14 (17) ◽  
pp. 24573-24621 ◽  
Author(s):  
S. R. Arnold ◽  
L. K. Emmons ◽  
S. A. Monks ◽  
K. S. Law ◽  
D. A. Ridley ◽  
...  
Keyword(s):  
Biomass Burning ◽  
High Latitude ◽  
Tropospheric Ozone ◽  
Transport Model ◽  
Chemical Transport ◽  
Ozone Production ◽  
The Arctic ◽  
Vertical Position ◽  
Chemical Transport Model ◽  
Fire Emissions

Abstract. We have evaluated tropospheric ozone enhancement in air dominated by biomass burning emissions at high laititudes (> 50˚ N) in July 2008, using 10 global chemical transport model simulations from the POLMIP multi-model comparison exercise. In model air masses dominated by fire emissions, Δ O3/ΔCO values ranged between 0.039 and 0.196 ppbv ppbv−1 (mean: 0.113 ppbv ppbv−1) in freshly fire-influenced air, and between 0.140 and 0.261 ppbv ppbv−1 (mean: 0.193 ppbv) in more aged fire-influenced air. These values are in broad agreement with the range of observational estimates from the literature. Model ΔPAN/ΔCO enhancement ratios show distinct groupings according to the meteorological data used to drive the models. ECMWF-forced models produce larger ΔPAN/ΔCO values (4.44–6.28 pptv ppbv−1) than GEOS5-forced models (2.02–3.02 pptv ppbv−1), which we show is likely linked to differences efficiency of vertical transport during poleward export from mid-latitude source regions. Simulations of a large plume of biomass burning and anthropogenic emissions exported from Asia towards the Arctic using a Lagrangian chemical transport model show that 4 day net ozone change in the plume is sensitive to differences in plume chemical composition and plume vertical position among the POLMIP models. In particular, Arctic ozone evolution in the plume is highly sensitive to initial concentrations of PAN, as well as oxygenated VOCs (acetone, acetaldehyde), due to their role in producing the peroxyacetyl radical PAN precursor. Vertical displacement is also important due to its effects on the stability of PAN, and subsequent effect on NOx abundance. In plumes where net ozone production is limited, we find that the lifetime of ozone in the plume is sensitive to hydrogen peroxide loading, due to the production of HO2 from peroxide photolysis, and the key role of HO2 + O3 in controlling ozone loss. Overall, our results suggest that emissions from biomass burning lead to large-scale photochemical enhancement in high latitude tropospheric ozone during summer.

scholarly journals Tropospheric ozone and ozone profiles retrieved from GOME-2 and their validation

2015 ◽  
Vol 8 (1) ◽  
pp. 385-398 ◽  
Author(s):  
G. M. Miles ◽  
R. Siddans ◽  
B. J. Kerridge ◽  
B. G. Latter ◽  
N. A. D. Richards
Keyword(s):  
Tropospheric Ozone ◽  
Transport Model ◽  
A Priori ◽  
Lower Troposphere ◽  
Rutherford Appleton Laboratory ◽  
Chemistry Transport Model ◽  
Ozone Profile ◽  
Retrieval Scheme ◽  
Hartley Band ◽  
Retrieval Bias

Abstract. This paper describes and assesses the performance of the RAL (Rutherford Appleton Laboratory) ozone profile retrieval scheme for the Global Ozone Monitoring Experiment 2 (GOME-2) with a focus on tropospheric ozone. Developments to the scheme since its application to GOME-1 measurements are outlined. These include the approaches developed to account sufficiently for UV radiometric degradation in the Hartley band and for inadequacies in knowledge of instrumental parameters in the Huggins bands to achieve the high-precision spectral fit required to extract information on tropospheric ozone. The assessment includes a validation against ozonesondes (sondes) sampled worldwide over 2 years (2007–2008). Standard deviations of the ensemble with respect to the sondes are considerably lower for the retrieved profiles than for the a priori, with the exception of the lowest subcolumn. Once retrieval vertical smoothing (averaging kernels) has been applied to the sonde profiles there is a retrieval bias of 6% (1.5 DU) in the lower troposphere, with smaller biases in the subcolumns above. The bias in the troposphere varies with latitude. The retrieval underestimates lower tropospheric ozone in the Southern Hemisphere (SH) (15–20% or ~ 1–3 DU) and overestimates it in the Northern Hemisphere (NH) (10% or 2 DU). The ability of the retrieval to reflect the geographical distribution of lower tropospheric ozone, globally (rather than just ozonesonde launch sites) is demonstrated by comparison with the chemistry transport model TOMCAT. For a monthly mean of cloud-cleared GOME-2 pixels, a correlation of 0.66 is found between the retrieval and TOMCAT sampled accordingly, with a bias of 0.7 Dobson Units. GOME-2 estimates higher concentrations in NH pollution centres but lower ozone in the Southern Ocean and South Pacific, which is consistent with the comparison to ozonesondes.

scholarly journals A new diagnostic for tropospheric ozone production

2017 ◽  
Vol 17 (22) ◽  
pp. 13669-13680 ◽  
Author(s):  
Peter M. Edwards ◽  
Mathew J. Evans
Keyword(s):  
Air Quality ◽  
Tropospheric Ozone ◽  
Transport Model ◽  
Chemical Transport ◽  
Ozone Production ◽  
Chemical Transport Model ◽  
Organic Species ◽  
Earth’S Climate ◽  
Oxidation Of Organics

Abstract. Tropospheric ozone is important for the Earth's climate and air quality. It is produced during the oxidation of organics in the presence of nitrogen oxides. Due to the range of organic species emitted and the chain-like nature of their oxidation, this chemistry is complex and understanding the role of different processes (emission, deposition, chemistry) is difficult. We demonstrate a new methodology for diagnosing ozone production based on the processing of bonds contained within emitted molecules, the fate of which is determined by the conservation of spin of the bonding electrons. Using this methodology to diagnose ozone production in the GEOS-Chem chemical transport model, we demonstrate its advantages over the standard diagnostic. We show that the number of bonds emitted, their chemistry and lifetime, and feedbacks on OH are all important in determining the ozone production within the model and its sensitivity to changes. This insight may allow future model–model comparisons to better identify the root causes of model differences.

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