Tropospheric ozone chemistry. The impact of cloud chemistry

Abstract. Chemical rate constants determine the composition of the atmosphere and how this composition has changed over time. They are central to our understanding of climate change and air quality degradation. Atmospheric chemistry models, whether online or offline, box, regional or global use these rate constants. Expert panels synthesise laboratory measurements, making recommendations for the rate constants that should be used. This results in very similar or identical rate constants being used by all models. The inherent uncertainties in these recommendations are, in general, therefore ignored. We explore the impact of these uncertainties on the composition of the troposphere using the GEOS-Chem chemistry transport model. Based on the JPL and IUPAC evaluations we assess 50 mainly inorganic rate constants and 10 photolysis rates, through simulations where we increase the rate of the reactions to the 1σ upper value recommended by the expert panels. We assess the impact on 4 standard metrics: annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime. Uncertainty in the rate constants for NO2 + OH M → HNO3, OH + CH4 → CH3O2 + H2O and O3 + NO → NO2 + O2 are the three largest source of uncertainty in these metrics. We investigate two methods of assessing these uncertainties, addition in quadrature and a Monte Carlo approach, and conclude they give similar outcomes. Combining the uncertainties across the 60 reactions, gives overall uncertainties on the annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime of 11, 12, 17 and 17 % respectively. These are larger than the spread between models in recent model inter-comparisons. Remote regions such as the tropics, poles, and upper troposphere are most uncertain. This chemical uncertainty is sufficiently large to suggest that rate constant uncertainty should be considered when model results disagree with measurement. Calculations for the pre-industrial allow a tropospheric ozone radiative forcing to be calculated of 0.412 ± 0.062 Wm−2. This uncertainty (15 %) is comparable to the inter-model spread in ozone radiative forcing found in previous model-model inter-comparison studies where the rate constants used in the models are all identical or very similar. Thus the uncertainty of tropospheric ozone radiative forcing should expanded to include this additional source of uncertainty. These rate constant uncertainties are significant and suggest that refinement of supposedly well known chemical rate constants should be considered alongside other improvements to enhance our understanding of atmospheric processes.

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The Impact of Future Emission Policies on Tropospheric Ozone using a Parameterised Approach

10.5194/acp-2017-1220 ◽

2018 ◽

Cited By ~ 1

Author(s):

Steven Turnock ◽

Oliver Wild ◽

Frank Dentener ◽

Yanko Davila ◽

Louisa Emmons ◽

...

Keyword(s):

Air Quality ◽

Tropospheric Ozone ◽

Radiative Forcing ◽

Source Attribution ◽

The Future ◽

Future Emission ◽

Tropospheric O3 ◽

Near Term ◽

The Impact ◽

Surface O3

Abstract. This study quantifies future changes in tropospheric ozone (O3) using a simple parameterisation of source-receptor relationships based on simulations from a range of models participating in the Task Force on Hemispheric Transport of Air Pollutants (TF-HTAP) experiments. Surface and tropospheric O3 changes are calculated globally and across 16 regions from perturbations in precursor emissions (NOx, CO, VOCs) and methane (CH4) abundance. A source attribution is provided for each source region along with an estimate of uncertainty based on the spread of the results from the models. Tests against model simulations using HadGEM2-ES confirm that the approaches used within the parameterisation are valid. The O3 response to changes in CH4 abundance is slightly larger in TF-HTAP Phase 2 than in the TF-HTAP Phase 1 assessment (2010) and provides further evidence that controlling CH4 is important for limiting future O3 concentrations. Different treatments of chemistry and meteorology in models remains one of the largest uncertainties in calculating the O3 response to perturbations in CH4 abundance and precursor emissions, particularly over the Middle East and South Asian regions. Emission changes for the future ECLIPSE scenarios and a subset of preliminary Shared Socio-economic Pathways (SSPs) indicate that surface O3 concentrations will increase by 1 to 8 ppbv in 2050 across different regions. Source attribution analysis highlights the growing importance of CH4 in the future under current legislation. A global tropospheric O3 radiative forcing of +0.07 W m−2 from 2010 to 2050 is predicted using the ECLIPSE scenarios and SSPs, based solely on changes in CH4 abundance and tropospheric O3 precursor emissions and neglecting any influence of climate change. Current legislation is shown to be inadequate in limiting the future degradation of surface ozone air quality and enhancement of near-term climate warming. More stringent future emission controls provide a large reduction in both surface O3 concentrations and O3 radiative forcing. The parameterisation provides a simple tool to highlight the different impacts and associated uncertainties of local and hemispheric emission control strategies on both surface air quality and the near-term climate forcing by tropospheric O3.

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Supplementary material to "The Impact of Future Emission Policies on Tropospheric Ozone using a Parameterised Approach"

10.5194/acp-2017-1220-supplement ◽

2018 ◽

Author(s):

Steven Turnock ◽

Oliver Wild ◽

Frank Dentener ◽

Yanko Davila ◽

Louisa Emmons ◽

...

Keyword(s):

Tropospheric Ozone ◽

Future Emission ◽

Supplementary Material ◽

The Impact

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Impact of biogenic hydrocarbons on tropospheric chemistry: results from a global chemistry-climate model

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-5-10517-2005 ◽

2005 ◽

Vol 5 (5) ◽

pp. 10517-10612 ◽

Cited By ~ 8

Author(s):

G. A. Folberth ◽

D. A. Hauglustaine ◽

J. Lathière ◽

F. Brocheton

Keyword(s):

Tropospheric Ozone ◽

Radiative Forcing ◽

Climate Model ◽

Primary Source ◽

Tropospheric Chemistry ◽

Secondary Source ◽

Peroxy Radicals ◽

Substantial Impact ◽

The Impact ◽

Global Mean

Abstract. We present a description and evaluation of LMDz-INCA, a global three-dimensional chemistry-climate model, pertaining to its recently developed NMHC version. In this substantially extended version of the model a comprehensive representation of the photochemistry of non-methane hydrocarbons (NMHC) and volatile organic compounds (VOC) from biogenic, anthropogenic, and biomass-burning sources has been included. The tropospheric annual mean methane (9.2 years) and methylchloroform (5.5 years) chemical lifetimes are well within the range of previous modelling studies and are in excellent agreement with estimates established by means of global observations. The model provides a reasonable simulation of the horizontal and vertical distribution and seasonal cycle of CO and key non-methane VOC, such as acetone, methanol, and formaldehyde as compared to observational data from several ground stations and aircraft campaigns. LMDz-INCA in the NMHC version reproduces tropospheric ozone concentrations fairly well throughout most of the troposphere. The model is applied in several sensitivity studies of the biosphere-atmosphere photochemical feedback. The impact of surface emissions of isoprene, acetone, and methanol is studied. These experiments show a substantial impact of isoprene on tropospheric ozone and carbon monoxide concentrations revealing an increase in surface O3 and CO levels of up to 30 ppbv and 60 ppbv, respectively. Isoprene also appears to significantly impact the global OH distribution resulting in a decrease of the global mean tropospheric OH concentration by approximately 0.9×105 molecules cm−3 or roughly 10% and an increase in the global mean tropospheric methane lifetime by approximately four months. A global mean ozone net radiative forcing due to the isoprene induced increase in the tropospheric ozone burden of 0.09W m−2 is found. The key role of isoprene photooxidation in the global tropospheric redistribution of NOx is demonstrated. LMDz-INCA calculates an increase of PAN surface mixing ratios ranging from 75 to 750 pptv and 10 to 250 pptv during northern hemispheric summer and winter, respectively. Acetone and methanol are found to play a significant role in the upper troposphere/lower stratosphere (UT/LS) budget of peroxy radicals. Calculations with LMDz-INCA show an increase in HOx concentrations region of 8 to 15% and 10 to 15% due to methanol and acetone biogenic surface emissions, respectively. The model has been used to estimate the global tropospheric CO budget. A global CO source of 3019 TgCO yr−1 is estimated. This source divides into a primary source of 1533 TgCO yr−1 and secondary source of 1489 TgCO yr−1 deriving from VOC photooxidation. Global VOC-to-CO conversion efficiencies of 90% for methane and between 20 and 45% for individual VOC are calculated by LMDz-INCA.

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Meteorological and fire impacts on tropospheric ozone concentration over tropical forest in the Congo Basin

10.5194/egusphere-egu21-13301 ◽

2021 ◽

Author(s):

Inês Vieira ◽

Hans Verbeeck ◽

Félicien Meunier ◽

Marc Peaucelle ◽

Lodewijk Lefevre ◽

...

Keyword(s):

Tropical Forest ◽

Ozone Concentration ◽

Primary Productivity ◽

Tropospheric Ozone ◽

Congo Basin ◽

Solar Irradiation ◽

Ozone Concentrations ◽

Ozone Precursor ◽

The Impact ◽

Ozone Levels

<p>Tropospheric ozone is a greenhouse gas, and high tropospheric ozone levels can directly impact plant growth and human health. In the Congo basin, simulations predict high ozone concentrations, induced by high ozone precursor (VOC and NOx) concentrations and high solar irradiation, which trigger the chemical reactions that form ozone. Additionally, biomass burning activities are widespread on the African continent, playing a crucial role in ozone precursor production. How these potentially high ozone levels impact tropical forest primary productivity remains poorly understood, and field-based ozone monitoring is completely lacking from the Congo basin. This study intends to show preliminary results from the first full year of in situ measurements of ozone concentration in the Congo Basin (i.e., Yangambi, Democratic Republic of the Congo). We show the relationships between meteorological variables (temperature, precipitation, radiation, wind direction and speed), fire occurrence (derived from remote sensing products) and ozone concentrations at a new continuous monitoring station in the heart of the Congo Basin. First results show higher daily mean ozone levels (e.g. 43 ppb registered in January 2020) during dry season months (December-February). We identify a strong diurnal cycle, where minimum values of ozone (almost near zero) are registered during night hours, and maximum values (near 100 ppb) are registered during the daytime. We also verify that around 2.5% of the ozone measurements exceeds a toxicity level (potential for ozone to damage vegetation) of 40 ppb. In the longer term, these measurements should improve the accuracy of future model simulations in the Congo Basin and will be used to assess the impact of ozone on the tropical forest&#8217;s primary productivity.</p>

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On the impact of future climate change on tropopause folds and tropospheric ozone

Atmospheric Chemistry and Physics ◽

10.5194/acp-19-14387-2019 ◽

2019 ◽

Vol 19 (22) ◽

pp. 14387-14401 ◽

Cited By ~ 2

Author(s):

Dimitris Akritidis ◽

Andrea Pozzer ◽

Prodromos Zanis

Keyword(s):

Atmospheric Chemistry ◽

Tropospheric Ozone ◽

Eastern Mediterranean ◽

Stratospheric Ozone ◽

Lower Troposphere ◽

Future Climate Change ◽

Identification Algorithm ◽

The Future ◽

Projected Changes ◽

The Impact

Abstract. Using a transient simulation for the period 1960–2100 with the state-of-the-art ECHAM5/MESSy Atmospheric Chemistry (EMAC) global model and a tropopause fold identification algorithm, we explore the future projected changes in tropopause folds, stratosphere-to-troposphere transport (STT) of ozone, and tropospheric ozone under the RCP6.0 scenario. Statistically significant changes in tropopause fold frequencies from 1970–1999 to 2070–2099 are identified in both hemispheres, regionally exceeding 3 %, and are associated with the projected changes in the position and intensity of the subtropical jet streams. A strengthening of ozone STT is projected for the future in both hemispheres, with an induced increase in transported stratospheric ozone tracer throughout the whole troposphere, reaching up to 10 nmol mol−1 in the upper troposphere, 8 nmol mol−1 in the middle troposphere, and 3 nmol mol−1 near the surface. Notably, the regions exhibiting the largest changes of ozone STT at 400 hPa coincide with those with the highest fold frequency changes, highlighting the role of the tropopause folding mechanism in STT processes under a changing climate. For both the eastern Mediterranean and Middle East (EMME) and Afghanistan (AFG) regions, which are known as hotspots of fold activity and ozone STT during the summer period, the year-to-year variability of middle-tropospheric ozone with stratospheric origin is largely explained by the short-term variations in ozone at 150 hPa and tropopause fold frequency. Finally, ozone in the lower troposphere is projected to decrease under the RCP6.0 scenario during MAM (March, April, and May) and JJA (June, July, and August) in the Northern Hemisphere and during DJF (December, January, and February) in the Southern Hemisphere, due to the decline of ozone precursor emissions and the enhanced ozone loss from higher water vapour abundances, while in the rest of the troposphere ozone shows a remarkable increase owing mainly to the STT strengthening and the stratospheric ozone recovery.

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