Marked long-term decline in ambient CO mixing ratio in SE England, 1997–2014:Evidence of policy success in improving air quality

Atmospheric CO at Egham in SE England has shown a marked and progressive decline since 1997, following adoption of strict controls on emissions. The Egham site is uniquely positioned to allow both assessment and comparison of ‘clean Atlantic background’ air and CO-enriched air downwind from the London conurbation. The decline is strongest (approximately 50ppb per year) in the 1997–2003 period but continues post 2003. A ‘local CO increment’ can be identified as the residual after subtraction of contemporary background Atlantic CO mixing ratios from measured values at Egham. This increment, which is primarily from regional sources (during anticyclonic or northerly winds) or from the European continent (with easterly air mass origins), has significant seasonality, but overall has declined steadily since 1997. On many days of the year CO measured at Egham is now not far above Atlantic background levels measured at Mace Head (Ireland). The results are consistent with MOPITT satellite observations and ‘bottom-up’ inventory results. Comparison with urban and regional background CO mixing ratios in Hong Kong demonstrates the importance of regional, as opposed to local reduction of CO emission. The Egham record implies that controls on emissions subsequent to legislation have been extremely successful in the UK

Mixing layer height as an indicator for urban air quality?

The mixing layer height (MLH) is a measure for the vertical turbulent exchange within the boundary layer, which is one of the controlling factors for the dilution of pollutants emitted near the ground. Based on continuous MLH measurements with a Vaisala CL51 ceilometer and measurements from an air quality network, the relationship between MLH and near-surface pollutant concentrations has been investigated. In this context the uncertainty of the MLH retrievals and the representativeness of ground-based in situ measurements are crucial. We have investigated this topic by using data from the BAERLIN2014 campaign in Berlin, Germany, conducted from June to August 2014. To derive the MLH, three versions of the proprietary software BL-VIEW and a novel approach COBOLT were compared. It was found that the overall agreement is reasonable if mean diurnal cycles are considered. The main advantage of COBOLT is the continuous detection of the MLH with a temporal resolution of 10 min and a lower number of cases when the residual layer is misinterpreted as mixing layer. We have calculated correlations between MLH as derived from the different retrievals and concentrations of pollutants (PM10, O-3 and NOx) for different locations in the metropolitan area of Berlin. It was found that the correlations with PM10 are quite different for different sites without showing a clear pattern, whereas the correlation with NOx seems to depend on the vicinity of emission sources in main roads. In the case of ozone as a secondary pollutant, a clear correlation was found. We conclude that the effects of the heterogeneity of the emission sources, chemical processing and mixing during transport exceed the differences due to different MLH retrievals. Moreover, it seems to be unrealistic to find correlations between MLH and near-surface pollutant concentrations representative for a city like Berlin (flat terrain), in particular when traffic emissions are dominant. Nevertheless it is worthwhile to use advanced MLH retrievals for ceilometer data, for example as input to dispersion models and for the validation of chemical transport models

Tropospheric ozone and its precursors from the urban to the global scale from air quality to short-lived climate forcer

Ozone holds a certain fascination in atmospheric science. It is ubiquitous in the atmosphere, central to tropospheric oxidation chemistry, yet harmful to human and ecosystem health as well as being an important greenhouse gas. It is not emitted into the atmosphere but is a byproduct of the very oxidation chemistry it largely initiates. Much effort is focused on the reduction of surface levels of ozone owing to its health and vegetation impacts, but recent efforts to achieve reductions in exposure at a country scale have proved difficult to achieve owing to increases in background ozone at the zonal hemispheric scale. There is also a growing realisation that the role of ozone as a short-lived climate pollutant could be important in integrated air quality climate change mitigation. This review examines current understanding of the processes regulating tropospheric ozone at global to local scales from both measurements and models. It takes the view that knowledge across the scales is important for dealing with air quality and climate change in a synergistic manner. The review shows that there remain a number of clear challenges for ozone such as explaining surface trends, incorporating new chemical understanding, ozone–climate coupling, and a better assessment of impacts. There is a clear and present need to treat ozone across the range of scales, a transboundary issue, but with an emphasis on the hemispheric scales. New observational opportunities are offered both by satellites and small sensors that bridge the scales

Assessing chemistry schemes and constraints in air quality models used to predict ozone in London against the detailed Master Chemical Mechanism

Air pollution is the environmental factor with the greatest impact on human health in Europe. Understanding the key processes driving air quality across the relevant spatial scales, especially during pollution exceedances and episodes, is essential to provide effective predictions for both policymakers and the public. It is particularly important for policy regulators to understand the drivers of local air quality that can be regulated by national policies versus the contribution from regional pollution transported from mainland Europe or elsewhere. One of the main objectives of the Coupled Urban and Regional processes: Effects on AIR quality (CUREAIR) project is to determine local and regional contributions to ozone events. A detailed zero-dimensional (0-D) box model run with the Master Chemical Mechanism (MCMv3.2) is used as the benchmark model against which the less explicit chemistry mechanisms of the Generic Reaction Set (GRS) and the Common Representative Intermediates (CRIv2-R5) schemes are evaluated. GRS and CRI are used by the Atmospheric Dispersion Modelling System (ADMS-Urban) and the regional chemistry transport model EMEP4UK, respectively. The MCM model uses a near-explicit chemical scheme for the oxidation of volatile organic compounds (VOCs) and is constrained to observations of VOCs, NOx, CO, HONO (nitrous acid), photolysis frequencies and meteorological parameters measured during the ClearfLo (Clean Air for London) campaign. The sensitivity of the less explicit chemistry schemes to different model inputs has been investigated: Constraining GRS to the total VOC observed during ClearfLo as opposed to VOC derived from ADMS-Urban dispersion calculations, including emissions and background concentrations, led to a significant increase (674% during winter) in modelled ozone. The inclusion of HONO chemistry in this mechanism, particularly during wintertime when other radical sources are limited, led to substantial increases in the ozone levels predicted (223%). When the GRS and CRIv2-R5 schemes are run with the equivalent model constraints to the MCM, they are able to reproduce the level of ozone predicted by the near-explicit MCM to within 40% and 20% respectively for the majority of the time. An exception to this trend was observed during pollution episodes experienced in the summer, when anticyclonic conditions favoured increased temperatures and elevated O3. The in situ O3 predicted by the MCM was heavily influenced by biogenic VOCs during these conditions and the low GRS [O3] : MCM [O3] ratio (and low CRIv2-R5 [O3] : MCM [O3] ratio) demonstrates that these less explicit schemes under-represent the full O3 creation potential of these VOCs. To fully assess the influence of the in situ O3 generated from local emissions versus O3 generated upwind of London and advected in, the time since emission (and, hence, how far the real atmosphere is from steady state) must be determined. From estimates of the mean transport time determined from the NOx : NOy ratio observed at North Kensington during the summer and comparison of the O3 predicted by the MCM model after this time, ∼60% of the median observed [O3] could be generated from local emissions. During the warmer conditions experienced during the easterly flows, however, the observed [O3] may be even more heavily influenced by London's emissions

BAERLIN2014-stationary measurements and source apportionment at an urban background station in Berlin, Germany

The "Berlin Air quality and Ecosystem Research: Local and long-range Impact of anthropogenic and Natural hydrocarbons" (BAERLIN2014) campaign was conducted during the 3 summer months (June-August) of 2014. During this measurement campaign, both stationary and mobile measurements were undertaken to address complementary aims. This paper provides an overview of the stationary measurements and results that were focused on characterization of gaseous and particulate pollution, including source attribution, in the Berlin-Potsdam area, and quantification of the role of natural sources in determining levels of ozone and related gaseous pollutants. Results show that biogenic contributions to ozone and particulate matter are substantial. One indicator for ozone formation, the OH reactivity, showed a 31% (0.82 +/- 0.44 s(-1) and 75% (3.7 +/- 0.90 s(-1) contribution from biogenic non-methane volatile organic com-pounds (NMVOCs) for urban background (2.6 +/- 0.68 s(-1) and urban park (4.9 +/- 1.0 s(-1) location, respectively, emphasizing the importance of such locations as sources of biogenic NMVOCs in urban areas. A comparison to NMVOC measurements made in Berlin approximately 20 years earlier generally show lower levels today for anthropogenic NMVOCs. A substantial contribution of secondary organic and inorganic aerosol to PM10 concentrations was quantified. In addition to secondary aerosols, source apportionment analysis of the organic carbon fraction identified the contribution of biogenic (plant-based) particulate matter, as well as primary contributions from vehicles, with a larger contribution from diesel compared to gasoline vehicles, as well as a relatively small contribution from wood burning, linked to measured levoglucosan

Observations of Diurnal to Weekly Variations of Monoterpene-Dominated Fluxes of Volatile Organic Compounds from Mediterranean Forests: Implications for Regional Modeling

The Estate of Castelporziano (Rome, Italy) hosts many ecosystems representative of Mediterranean vegetation, especially holm oak and pine forests and dune vegetation. In this work, basal emission factors (BEFs) of biogenic volatile organic compounds (BVOCs) obtained by Eddy Covariance in a field campaign using a proton transfer reaction-time-of-flight-mass spectrometer (PTR-TOF-MS) were compared to BEFs reported in previous studies that could not measure fluxes in real-time. Globally, broadleaf forests are dominated by isoprene emissions, but these Mediterranean ecosystems are dominated by strong monoterpene emitters, as shown by the new BEFs. The original and new BEFs were used to parametrize the model of emissions of gases and aerosols from nature (MEGAN v2.1), and model outputs were compared with measured fluxes. Results showed good agreement between modeled and measured fluxes when a model was used to predict radiative transfer and energy balance across the canopy. We then evaluated whether changes in BVOC emissions can affect the chemistry of the atmosphere and climate at a regional level. MEGAN was run together with the land surface model (community land model, CLM v4.0) of the community earth system model (CESM v1.0). Results highlighted that tropospheric ozone concentration and air temperature predicted from the model are sensitive to the magnitude of BVOC emissions, thus demonstrating the importance of adopting the proper BEF values for model parametrization

Analysis and comparison of trends in concentrations and emissions of VOC and CO and VOC:CO ratios in urban European cities

Since 2007, more than half of the world's population live in urban areas. Megacities, urban agglomerations with more than 10 million inhabitants, are rapidly increasing in number: in 1950 there were only two, New York and Tokyo with ~12 million, while by 2005 there were already 20, with Tokyo ranging the 35 millions. The urban atmospheres of these megacities are dominated by pollutants associated with vehicular emissions, as well as the formation of secondary pollutants responsible for photochemical smog. A comparative assessment of emissions and concentrations of volatile organic compounds (VOC) and carbon monoxide (CO) ratios in London (L) and Paris (P) is hereby presented. The work is based on three recent studies by Baker et al. (2008), Parrish et al. (2009) and von Schneidemesser et al. (in press) where concentrations of these compounds were analyzed for 28 US cities in the former and some global megacities in the second and third studies. Considering the fact that VOC provide information on the main emissions sources of cities, these studies found that even though concentrations of VOC varied greatly among cities, the ratio with the combustion tracer CO remained rather constant and was very useful for city comparison, as well as a good indicator of traffic emissions. VOC patterns in ambient air concentrations were observed to be similar in most cities, being able to consider that deviations from those patterns could be the result of measurement problems. Nevertheless, the representation of these emissions in global inventories has large uncertainties. The goal of our study is to compare and contrast emission inventory estimates with measured ambient concentrations of non-methane hydrocarbons (NMHC) and CO, as well as NMHC:CO ratios. Within the European CityZen project we have built an updated global emissions inventory with the best available datasets of anthropogenic, biomass burning and natural sources. As part of this research we will follow the same approach to compare emissions ratios between NMHC and CO for the megacities region of Paris and London and to compare these trends with measured ambient concentrations from three monitoring sites: Eltham (L) suburban station, Marylebone Road (L) kerbside station and Les Halles (P) urban station for the period 1997-2006