On the changes in surface ozone over the twenty-first century: sensitivity to changes in surface temperature and chemical mechanisms.

In this study, we show using a state-of-the-art Earth system model, UKESM1, that emissions and climate scenario depending, there could be large changes in surface ozone by the end of the twenty-first century, with unprecedentedly large increases over South and East Asia. We also show that statistical modelling of the trends in future ozone works well in reproducing the model output between 1900 and 2050. However, beyond 2050, and especially under large climate change scenarios, the statistical model results are in poorer agreement with the fully interactive Earth system model output. This suggests that additional processes occurring in the Earth system model such as changes in the production of ozone at higher temperatures or changes in the influx of ozone from the stratosphere, which are not captured by the statistical model, have a first order impact on the evolution of surface ozone over the twenty-first century. We show in a series of idealized box model simulations, with two different chemical schemes, that changes in temperature lead to diverging responses between the schemes. This points at the chemical mechanisms as being a source of uncertainty in the response of ozone to changes in temperature, and so climate, in the future. This underscores the need for more work to be performed to better understand the response of ozone to changes in temperature and constrain how well this relationship is simulated in models. This article is part of a discussion meeting issue 'Air quality, past present and future'.

Observational-based assessment of contributions to maximum ozone concentrations in the western United States.

Archived Ozone Design Values (ODVs) provide smoothed temporal records of maximum ozone concentrations impacting monitoring sites throughout the US. Utilizing time series of ODVs recorded at sites along the US West Coast, we separately estimate ODV contributions from US background ozone and from production driven by US anthropogenic precursor emissions. Sondes launched from Trinidad Head in northern California measure the vertical distribution of baseline ozone transported ashore from the Pacific; this profile is reflected in the increase of the US background ODV contribution with monitoring site elevation in both rural and urban areas. The ODVs that would result from US background ozone alone are small at coastal, sea level locations (average ~45 ppb), but increase with altitude; above 1 km US background ODVs can exceed 60 ppb. US background ozone contributions now constitute the majority of the maximum ODVs throughout the US west coast region, including the Los Angeles urban area, which records the country's highest ODVs. US anthropogenic emissions presently cause enhancements of 35 to 55 ppb to the maximum ODVs in the Los Angeles area; thus, local emission controls can further reduce ozone even though the background contribution is larger. In other US west coast urban areas ODV enhancements from US anthropogenic emissions are much smaller than the US background ODV contribution. The past decrease in US anthropogenic ODV enhancements from emission controls is larger than generally realized - a factor of more than 6 from 1980 to 2020, while US background ODV contributions varied to only a small extent over those four decades. Wildfire impacts on ODVs are significant in urban areas of the Pacific Northwest, but not over the vast northern US rural region. There is an indication that agricultural emissions of nitrogen oxides in California's Salinas Valley increase downwind maximum ODVs by 5-10 ppb.Implications: In 2020 the ozone design values (ODVs) resulting from transported background ozone alone are now larger than the ODV enhancements from US anthropogenic precursor emissions, even in the Los Angeles urban area, where the nation's highest ODVs are recorded. The US anthropogenic ODV enhancements have been reduced by more than a factor of 6 from 1980 to 2020. The maximum US background ODV contributions have varied somewhat, but in each of the US west coast urban areas it was 60 ppb or larger in 2000. These contributions are so large that reducing maximum urban ODVs to the 70 ppb required by the 2015 ozone NAAQS is very difficult. There remains relatively little room for further reducing ODVs through domestic emission controls alone. From this perspective, degraded US ozone air quality in the western US is primarily due to the US background ozone contribution, with the US anthropogenic enhancement making a significant, but smaller contribution. Notably, the US background ODV has slowly decreased (~1 ppb decade-1; Parrish, Derwent, and Faloona 2021) since the mid-2000s; cooperative, international emission control efforts aimed at continuing or even accelerating this background ozone decrease may be an effective approach to further ODV reductions, since the US background ODV is largely due to a hemisphere-wide, transported reservoir of ozone with contributions from all northern midlatitude continents. Given the major contribution of background ozone to observed ODVs, future reviews of the ozone NAAQS will be better informed if observational-based estimates of background ODV contributions are considered, in addition to model-derived estimates upon which past reviews have solely relied.

Long-term baseline ozone changes in the Western US: A synthesis of analyses.

Quantification of the magnitude and long-term changes in ozone concentrations transported into the U.S. is important for effective air quality policy development. We synthesize multiple published trend analyses of western U.S. baseline ozone, and show that all results are consistent with an overall, non-linear change - a rapid increase (~5 ppb/decade) during the 1980s that slowed in the 1990s, maximized in the mid-2000s, and was followed by a slow decrease (~1 ppb/decade) thereafter. This non-linear change accounts for ~2/3 of the variance in 28 published linear trend analyses; we attribute the other 1/3 of the variance to unquantified autocorrelation in the analyzed data sets that result primarily from meteorologically driven interannual ozone variability. Recent systematic changes in baseline ozone on the U.S. West Coast have been relatively small - the standard deviation of the 2-year means over the 1990-2017 period is 1.5 ppb. International efforts to reduce anthropogenic precursor emissions from all northern mid-latitude sources could possibly reduce baseline ozone concentrations, thereby improving U.S. ozone air quality.Implications: Ozone is an air pollutant with significant human and ecological health impacts. Air masses transported into the western U.S. from over the Pacific Ocean carry ozone concentrations that are, on average, a large fraction of the U.S. health standard. The US EPA policy assessment conducted for the recent review of the ozone National Ambient Air Quality Standard (NAAQS) found that 2016 regional average MDA8 ozone concentrations in the western US maximized in summer at ~52 ppb and that ~40 ppb of that maximum was contributed by ozone of natural and transported anthropogenic contributions. Thus, quantifying these trans-boundary background ozone concentrations has been identified as an important issue for a complete understanding of US air quality. Published analyses of temporal trends of these transported ozone concentrations vary widely, from early reports of increases to more recent reports of decreases. We show that the long-term ozone changes are nonlinear, with substantial concentration increases (as large as ~5 ppb/decade) before the mid-2000s when a maximum is reached, followed by a small decrease of ~1 ppb/decade thereafter. Superimposed on the overall changes is significant interannual variability that makes accurate determination of systematic trends over decade-scale time periods uncertain. The end of the previously increasing trends, and the recent decrease in transported ozone concentrations, is a good news for U.S. air quality, as it eases the difficulty of achieving the ozone air quality standard.

Reactivity scales as comparative tools for chemical mechanisms.

Incremental ozone impacts or reactivities have been calculated for selected organic compounds using a Master Chemical Mechanism (MCMv3.1) and compared with those calculated elsewhere with the SAPRC-07 chemical mechanism. The comparison of incremental reactivities has been completed for 116 organic compounds representing the alkanes, alkenes, aldehydes, ketones, aromatics, oxygenates, and halocarbons. Both mechanisms have constructed a consistent and coherent description of reactivity within each class of organics. MCMv3.1 and SAPRC-07 have represented some features of the available body of understanding concerning the atmospheric oxidation of organic compounds in a consistent and quantitative manner, although significant differences were found for 14 organic compounds. These differences represent species-dependent facets of their atmospheric chemistry that have not been adequately resolved in the available literature experimental data.

Photochemical trajectory modelling of ozone during the summer PUMA campaign in the UK West Midlands.

A Photochemical Trajectory Model (PTM), coupled with the Master Chemical Mechanism, is set up for summertime conditions and used to simulate pollutant levels measured in Birmingham, UK during the summer Pollution in the Urban Midlands Atmosphere (PUMA) campaign. In general, ozone is modelled well by the PTM, with reasonably good correlation and approximately 90% of afternoon and evening concentrations within a factor of two of measurements. The contribution of local biogenic emissions in the West Midlands to ozone formation during this period was also assessed and found to be of minor importance. Initially, the ozone episode of 26th June 1999, where levels of up to 87 ppb were observed was not reproduced by the UK PTM model. Sensitivity studies showed that the major cause for this was transport uncertainty in the origin and pathway of the air during conditions of slow moving anticyclonic conditions. The results indicate that the ozone episode was caused by recirculation of air polluted within the UK, with additional precursor emissions over the Netherlands, Belgium and France.

Particulate sulphate and nitrate in Southern England and Northern Ireland during 2002/3 and its formation in a photochemical trajectory model.

Daily measurements of sulphate and nitrate are reported from Harwell in southern England and Belfast in Northern Ireland for the period 2002/3. When the higher percentiles are compared with the mean concentration, nitrate reveals considerably greater episodicity than either sulphate or PM(10) (measured by TEOM). A photochemical trajectory model using the Master Chemical Mechanism scheme has been used to predict daily concentrations of both nitrate and sulphate aerosol over the period March to August 2002 at the Belfast and Harwell sites. This has been carried out for daily samples using 72, 96 and 120 h air mass back trajectories obtained from both the British Atmospheric Data Centre and the HYSPLIT on-line service. Additionally, model simulations have been conducted for 5 trajectories generated through clustering of the trajectories for individual days. This reveals an under-prediction of the model associated particularly with trajectories originating from the European mainland. In general, the model performs reasonably well in simulating concentrations of both nitrate and sulphate, which is surprising given that the model does not account for processes requiring the presence of liquid water. This suggests that aqueous phase oxidation processes may not make a major contribution to airborne sulphate concentrations in the U.K. in the spring and summer months. It appears that inclusion of explicit ammonium nitrate formation chemistry may be essential to reliable prediction of episodic nitrate peaks.

European abatement of surface ozone in a global perspective.

EU's programme Clean Air for Europe (CAFE) is presently revising the policy on air quality which will lead to the adoption of a thematic strategy on air pollution under the Sixth Environmental Action Programme by mid-2005. For the abatement of surface ozone it is becoming evident that processes outside European control will be crucial for meeting long-term aims and air quality guidelines in Europe in the future. Measurements and modelling results indicate that there is a strong link between climate change and surface ozone. A warmer and dryer European climate is very likely to lead to increased ozone concentrations. Furthermore, increased anthropogenic emissions in developing economies in Asia are likely to raise the hemispheric background level of ozone. A significant increase in the background concentration of ozone has been observed at several sites in Northern Europe although the underlying causes are not settled. The photochemical formation of tropospheric ozone from increased concentrations of methane and CO may also lead to a higher ozone level on a global scale. Gradually, these effects may outweigh the effect of the reduced European ozone precursor emissions. This calls for a global or hemispheric perspective in the revision of the European air quality policy for ozone.

The contribution from shipping emissions to air quality and acid deposition in Europe.

A global three-dimensional Lagrangian chemistry-transport model STOCHEM is used to describe the European regional acid deposition and ozone air quality impacts along the Atlantic Ocean seaboard of Europe, from the SO2, NOx, VOCs and CO emissions from international shipping under conditions appropriate to the year 2000. Model-derived total sulfur deposition from international shipping reaches over 200 mg S m(-2) yr(-1) over the southwestern approaches to the British Isles and Brittany. The contribution from international shipping to surface ozone concentrations during the summertime, peaks at about 6 ppb over Ireland, Brittany and Portugal. Shipping emissions act as an external influence on acid deposition and ozone air quality within Europe and may require control actions in the future if strict deposition and air quality targets are to be met.

Regional and global impacts of Criegee intermediates on atmospheric sulphuric acid concentrations and first steps of aerosol formation.

Carbonyl oxides ("Criegee intermediates"), formed in the ozonolysis of alkenes, are key species in tropospheric oxidation of organic molecules and their decomposition provides a non-photolytic source of OH in the atmosphere (Johnson and Marston, Chem. Soc. Rev., 2008, 37, 699, Harrison et al, Sci, Total Environ., 2006, 360, 5, Gäb et al., Nature, 1985, 316, 535, ref. 1-3). Recently it was shown that small Criegee intermediates, C.I.'s, react far more rapidly with SO2 than typically represented in tropospheric models, (Welz, Science, 2012, 335, 204, ref. 4) which suggested that carbonyl oxides could have a substantial influence on the atmospheric oxidation of SO2. Oxidation of 502 is the main atmospheric source of sulphuric acid (H2SO4), which is a critical contributor to aerosol formation, although questions remain about the fundamental nucleation mechanism (Sipilä et al., Science, 2010, 327, 1243, Metzger et al., Proc. Natl. Acad. Sci. U. S. A., 2010 107, 6646, Kirkby et al., Nature, 2011, 476, 429, ref. 5-7). Non-absorbing atmospheric aerosols, by scattering incoming solar radiation and acting as cloud condensation nuclei, have a cooling effect on climate (Intergovernmental Panel on Climate Change (IPCC), Climate Change 2007: The Physical Science Basis, Cambridge University Press, 2007, ref. 8). Here we explore the effect of the Criegees on atmospheric chemistry, and demonstrate that ozonolysis of alkenes via the reaction of Criegee intermediates potentially has a large impact on atmospheric sulphuric acid concentrations and consequently the first steps in aerosol production. Reactions of Criegee intermediates with SO2 will compete with and in places dominate over the reaction of OH with SO2 (the only other known gas-phase source of H2SO4) in many areas of the Earth's surface. In the case that the products of Criegee intermediate reactions predominantly result in H2SO4 formation, modelled particle nucleation rates can be substantially increased by the improved experimentally obtained estimates of the rate coefficients of Criegee intermediate reactions. Using both regional and global scale modelling, we show that this enhancement is likely to be highly variable spatially with local hot-spots in e.g. urban outflows. This conclusion is however contingent on a number of remaining uncertainties in Criegee intermediate chemistry.

Secondary organic aerosol formation from a large number of reactive man-made organic compounds.

A photochemical trajectory model has been used to examine the relative propensities of a wide variety of volatile organic compounds (VOCs) emitted by human activities to form secondary organic aerosol (SOA) under one set of highly idealised conditions representing northwest Europe. This study applied a detailed speciated VOC emission inventory and the Master Chemical Mechanism version 3.1 (MCM v3.1) gas phase chemistry, coupled with an optimised representation of gas-aerosol absorptive partitioning of 365 oxygenated chemical reaction product species. In all, SOA formation was estimated from the atmospheric oxidation of 113 emitted VOCs. A number of aromatic compounds, together with some alkanes and terpenes, showed significant propensities to form SOA. When these propensities were folded into a detailed speciated emission inventory, 15 organic compounds together accounted for 97% of the SOA formation potential of UK man made VOC emissions and 30 emission source categories accounted for 87% of this potential. After road transport and the chemical industry, SOA formation was dominated by the solvents sector which accounted for 28% of the SOA formation potential.

Historical reconstruction of mercury pollution across the Tibetan Plateau using lake sediments.

The Tibetan Plateau is described as the "Roof of the World" averaging over 4000 m above sea level; it is remote, isolated, and presumed to be a pristine region. In order to study the history of atmospheric mercury (Hg) pollution and its spatial variation across the Plateau, lakes were chosen from three areas forming a north to south transect. Sediment cores were taken from three sites in each area and dated using the radionuclides 210Pb and 137Cs. Analysis of the cores yielded the first comprehensive Hg reconstructions for the Plateau, showing clear Hg pollution at all sites. The first indication of Hg pollution is much earlier than the onset of the industrial revolution in Europe, but the most significant pollution increase is from the 1970s, followed by a further marked increase from the 1990s. The mean post-2000 atmospheric pollution Hg accumulation rates for the sampling sites were estimated at between 5.1 and 7.9 microg m(-2) yr(-1). The increase in Hg pollution over the last few decades is synchronous with the recent economic development in Asia (especially China and India), and pollution Hg levels continue to increase. Furthermore, contemporary sediment Hg accumulation rate data are in broad agreement with Hg deposition values derived from global models that attribute pollution to sources mainly within southeast Asia. As most of the sites are exceptionally remote and situated above the atmospheric boundary layer, these results underline the need to understand the local Hg cycle in both regional and global context.

Modelling the ambient distribution of organic compounds during the august 2003 ozone episode in the southern UK.

A photochemical trajectory model containing speciated emissions of 124 non-methane volatile organic compounds (VOC), and a comprehensive description of the chemistry of VOC degradation, has been used to simulate the chemical evolution of boundary layer air masses arriving at a field campaign site in the southern UK during a widespread and prolonged photochemical pollution event in August 2003. The simulated concentrations and distributions of organic compounds at the arrival location are compared with observations of a series of hydrocarbons and carbonyl compounds, which were measured using GC-FID and multidimensional GC methods. The comparison of the simulated and observed distributions of 34 emitted hydrocarbons provides some support for the magnitude and applied emissions speciation of anthropogenic hydrocarbons, but is indicative of an under representation of the input of biogenic hydrocarbons, particularly at elevated temperatures. Simulations of the detailed distribution of ca. 1250 carbonyl compounds, formed primarily from the degradation of the 124 emitted VOC, focus on 61 aldehydes, ketones, dicarbonyls, hydroxycarbonyls and aromatic aldehydes which collectively account for ca. 90% of the simulated total molar concentration of carbonyls. The simulated distributions indicate that the photolysis of formaldehyde and alpha-dicarbonyls make major contributions to free radical production for the arrival conditions of five case study trajectories. The simulated concentrations of hydroxycarbonyls demonstrate preferential formation of the 1,4-substituted isomers (compared with 1,2- and 1,3-isomers of the same carbon number), which are formed during the initial oxidation sequence of longer chain alkanes.