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Abstract. Tropospheric ozone results from in situ chemical formation and stratosphere–troposphere exchange (STE), with the latter being more important in the middle and upper troposphere than in the lower troposphere. Ozone photochemical formation is nonlinear and results from the oxidation of methane and non-methane hydrocarbons (NMHCs) in the presence of nitrogen oxide (NOx=NO+NO2). Previous studies showed that O3 short- and long-term trends are nonlinearly controlled by near-surface anthropogenic emissions of carbon monoxide (CO), volatile organic compounds (VOCs), and nitrogen oxides, which may also be impacted by the long-range transport (LRT) of O3 and its precursors. In addition, several studies have demonstrated the important role of STE in enhancing ozone levels, especially in the midlatitudes. In this article, we investigate tropospheric ozone spatial variability and trends from 2005 to 2019 and relate those to ozone precursors on global and regional scales. We also investigate the spatiotemporal characteristics of the ozone formation regime in relation to ozone chemical sources and sinks. Our analysis is based on remote sensing products of the tropospheric column of ozone (TrC-O3) and its precursors, nitrogen dioxide (TrC-NO2), formaldehyde (TrC-HCHO), and total column CO (TC-CO), as well as ozonesonde data and model simulations. Our results indicate a complex relationship between tropospheric ozone column levels, surface ozone levels, and ozone precursors. While the increasing trends of near-surface ozone concentrations can largely be explained by variations in VOC and NOx concentration under different regimes, TrC-O3 may also be affected by other variables such as tropopause height and STE as well as LRT. Decreasing or increasing trends in TrC-NO2 have varying effects on TrC-O3, which is related to the different local chemistry in each region. We also shed light on the contribution of NOx lightning and soil NO and nitrous acid (HONO) emissions to trends of tropospheric ozone on regional and global scales.
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Lifetimes and timescales of tropospheric ozone
The lifetime of tropospheric O3 is difficult to quantify because we model O3 as a secondary pollutant, without direct emissions. For other reactive greenhouse gases like CH4 and N2O, we readily model lifetimes and timescales that include chemical feedbacks based on direct emissions. Here, we devise a set of artificial experiments with a chemistry-transport model where O3 is directly emitted into the atmosphere at a quantified rate. We create 3 primary emission patterns for O3, mimicking secondary production by surface industrial pollution, that by aviation, and primary injection through stratosphere–troposphere exchange (STE). The perturbation lifetimes for these O3 sources includes chemical feedbacks and varies from 6 to 27 days depending on source location and season. Previous studies derived lifetimes around 24 days estimated from the mean odd-oxygen loss frequency. The timescales for decay of excess O3 varies from 10 to 20 days in northern hemisphere summer to 30 to 40 days in northern hemisphere winter. For each season, we identify a single O3 chemical mode applying to all experiments. Understanding how O3 sources accumulate (the lifetime) and disperse (decay timescale) provides some insight into how changes in pollution emissions, climate, and stratospheric O3 depletion over this century will alter tropospheric O3. This work incidentally found 2 distinct mistakes in how we diagnose tropospheric O3, but not how we model it. First, the chemical pattern of an O3 perturbation or decay mode does not resemble our traditional view of the odd-oxygen family of species that includes NO2. Instead, a positive O3 perturbation is accompanied by a decrease in NO2. Second, heretofore we diagnosed the importance of STE flux to tropospheric O3 with a synthetic “tagged” tracer O3S, which had full stratospheric chemistry and linear tropospheric loss based on odd-oxygen loss rates. These O3S studies predicted that about 40% of tropospheric O3 was of stratospheric origin, but our lifetime and decay experiments show clearly that STE fluxes add about 8% to tropospheric O3, providing further evidence that tagged tracers do not work when the tracer is a major species with chemical feedbacks on its loss rates, as shown previously for CH4.
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- Award ID(s):
- 2135749
- PAR ID:
- 10569668
- Publisher / Repository:
- UC Press
- Date Published:
- Journal Name:
- Elem Sci Anth
- Volume:
- 12
- Issue:
- 1
- ISSN:
- 2325-1026
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1525/elementa.2023.00112
