Oxidation capacity changes in the atmosphere of large urban areas in Europe: Modelling and experimental campaigns in atmospheric simulation chambers.

Air pollution is a major concern for human health and the environment. Consequently, environmental standards have become stricter to improve air quality. Thanks to this, the ambient levels of O3 precursors such as VOCs and NOX have decreased. However, O3 levels in Europe, especially during winter, have increased, potentially impacting on atmospheric oxidation capacity and the associated chemistry of tropospheric oxidants. In this work, we focus on recent changes in the oxidation capacity of urban atmospheres. The study is conducted with the results of the CMAQ modelling system with a regional resolution with 12 × 12 km2 across the entire European continent for the winter (January) and summer (July) of 2007 and 2015. The 2015 meteorological data is used for both years to emphasise emission changes during the studied period. We scrutinise the changes in ambient concentration levels of the main tropospheric oxidants (O3 and HOX radicals) in five representative cities, Valencia, Madrid, Milan, Berlin, and The Hague. The enhanced O3 formation in winter seems to be due to the low VOC/NOX ratio, while the opposite trend in summer may be related to a relatively high ratio. Additionally, photooxidation experiments are carried out in the EUPHORE chambers to study the effect of changes in NOX concentration and NO/NO2 ratio on the variation of the given oxidants at constant VOCs concentrations. For the baseline experiments, two scenarios are selected based on the model results of 2015: two representative winter and summer days of low and high pollution in Berlin and Madrid, respectively. The role of VOC/NOX and NO/NO2 ratios on atmospheric reactivity is discussed. As a result, it is first suggested that further decreases in ambient NOX levels are required to reduce ambient O3 levels. Moreover, additional factors should be considered when designing local-specific emission abatement strategies.

Summertime tropospheric ozone source apportionment study in the Madrid region (Spain).

The design of emission abatement measures to effectively reduce high ground-level ozone (O3) concentrations in urban areas is very complex. In addition to the strongly non-linear chemistry of this secondary pollutant, precursors can be released by a variety of sources in different regions, and locally produced O3 is mixed with that transported from the regional or continental scales. All of these processes depend also on the specific meteorological conditions and topography of the study area. Consequently, high-resolution comprehensive modeling tools are needed to understand the drivers of photochemical pollution and to assess the potential of local strategies to reduce adverse impacts from high tropospheric O3 levels. In this study, we apply the Integrated Source Apportionment Method (ISAM) implemented in the Community Multiscale Air Quality (CMAQ v5.3.2) model to investigate the origin of summertime O3 in the Madrid region (Spain). Consistent with previous studies, our results confirm that O3 levels are dominated by non-local contributions, representing around 70 % of mean values across the region. Nonetheless, precursors emitted by local sources, mainly road traffic, play a more important role during O3 peaks, with contributions as high as 25 ppb. The potential impact of local measures is higher under unfavorable meteorological conditions associated with regional accumulation patterns. These findings suggest that this modeling system may be used in the future to simulate the potential outcomes of specific emission abatement measures to prevent high-O3 episodes in the Madrid metropolitan area.

Analysis of emissions-driven changes in the oxidation capacity of the atmosphere in Europe.

Anthropogenic emissions in Europe have been gradually reduced thanks to a combination of factors, including restrictive regulation and policy implementation, fuel switching, technological developments, and improved energy efficiencies. Many measures have been specifically introduced to meet the annual and hourly limit value of NO2 for the protection of human health, mainly targeting traffic emissions. Due to NOX reduction policies in Europe, NO2 levels have generally declined, but O3 concentrations have been found to increase. This phenomenon would cause changes in the oxidant capacity of the atmosphere, altering the concentration of tropospheric oxidants in urban areas. The Community Multiscale Air Quality (CMAQ) modelling system has been used to study concentration changes of NO2, O3 and the main radicals in Europe between 2007 and 2015 for two months representatives of winter and summer conditions (January and July). In addition to describing the general situation in Europe, variations in pollutants along with NOX emission changes over 67 large European cities have been analysed by means of statistical methods. NOX emissions and NO2 concentrations decreased in both seasons during the period in all the selected cities. In most of them O3 concentrations increased in winter but decreased in summer. The concentration of the OH radical, the main oxidant during the daytime, shows an increase in winter. This is also the case for the main cities in summer although we found a general decrease in continent for this season. The NO3 radical, the main night-time oxidant, was found to increase in winter and decrease in summer. HNO3 shows a concentration decline in both seasons. The studied cities are classified in five groups by means of k-mean clustering procedure. We identified five groups with specific patterns, suggesting that the oxidant capacity of the European urban atmospheres has reacted differently to NOX emission abatement policies.

Impact of halogen chemistry on summertime air quality in coastal and continental Europe: application of the CMAQ model and implications for regulation.

Halogen (Cl, Br, and I) chemistry has been reported to influence the formation of secondary air pollutants. Previous studies mostly focused on the impact of chlorine species on air quality over large spatial scales. Very little attention has been paid to the effect of the combined halogen chemistry on air quality over Europe and its implications for control policy. In the present study, we apply a widely used regional model, the Community Multiscale Air Quality Modeling System (CMAQ), incorporated with the latest halogen sources and chemistry, to simulate the abundance of halogen species over Europe and to examine the role of halogens in the formation of secondary air pollution. The results suggest that the CMAQ model is able to reproduce the level of O3, NO2, and halogen species over Europe. Chlorine chemistry slightly increases the levels of OH, HO2, NO3, O3, and NO2 and substantially enhances the level of the Cl radical. Combined halogen chemistry induces complex effects on OH (ranging from -0.023 to 0.030 pptv) and HO2 (in the range of -3.7 to 0.73 pptv), significantly reduces the concentrations of NO3 (as much as 20 pptv) and O3 (as much as 10 ppbv), and decreases NO2 in highly polluted regions (as much as 1.7 ppbv); it increases NO2 (up to 0.20 ppbv) in other areas. The maximum effects of halogen chemistry occur over oceanic and coastal regions, but some noticeable impacts also occur over continental Europe. Halogen chemistry affects the number of days exceeding the European Union target threshold for the protection of human beings and vegetation from ambient O3. In light of the significant impact of halogen chemistry on air quality, we recommend that halogen chemistry be considered for inclusion in air quality policy assessments, particularly in coastal cities.

Population dynamics based on mobile phone data to improve air pollution exposure assessments.

Air pollution is one of the greatest challenges cities are facing today and improving air quality is a pressing need to reduce negative health impacts. In order to efficiently evaluate which are the most appropriate policies to reduce the impact of urban pollution sources (such as road traffic), it is essential to conduct rigorous population exposure assessments. One of the main limitations associated with those studies is the lack of information about population distribution in the city along the day (population dynamics). The pervasive use of mobile devices in our daily lives opens new opportunities to gather large amounts of anonymized and passively collected geolocation data allowing the analysis of population activity and mobility patterns. This study presents a novel methodology to estimate population dynamics from mobile phone data based on a user-centric mobility model approach. The methodology was tested in the city of Madrid (Spain) to evaluate population exposure to NO2. A comparison with traditional census-based methods shows relevant discrepancies at disaggregated levels and highlights the need to incorporate mobility patterns into population exposure assessments.

Application of a short term air quality action plan in Madrid (Spain) under a high-pollution episode - Part II: Assessment from multi-scale modelling.

Air pollution continues to be one of the main issues in urban areas. In addition to air quality plans and emission abatement policies, additional measures for high pollution episodes are needed to avoid exceedances of hourly limit values under unfavourable meteorological conditions such as the Madrid's short-term action NO2 protocol. In December 2016 there was a strong atmospheric stability episode that turned out in generalized high NO2 levels, causing the stage 3 of the NO2 protocol to be triggered for the first time in Madrid (29th December). In addition to other traffic-related measures, this involves access restrictions to the city centre (50% to private cars). We simulated the episode with and without measures under a multi-scale modelling approach. A 1 km2 resolution modelling system based on WRF-SMOKE-CMAQ was applied to assess city-wide effects while the Star-CCM+ (RANS CFD model) was used to investigate the effect at street level in a microscale domain in the city centre, focusing on Gran Vía Avenue. Changes in road traffic were simulated with the mesoscale VISUM model, incorporating real flux measurements during those days. The corresponding simulations suggest that the application of the protocol during this particular episode may have prevented concentrations to increase by 24 µg·m-3 (14% respect to the hypothetical no action scenario) downtown although it may have cause NO2 to slightly increase in the city outskirts due to traffic redistribution. Speed limitation and parking restrictions alone (stages 1 and 2 respectively) have a very limited effect. The microscale simulation provides consistent results but shows an important variability at street level, with reduction above 100 µg·m-3 in some spots inside Gran Vía. Although further research is needed, these results point out the need to implement short-term action plans and to apply a consistent multi-scale modelling assessment to optimize urban air quality abatement strategies.

The influence of ocean halogen and sulfur emissions in the air quality of a coastal megacity: The case of Los Angeles.

The oceans are the main source of natural halogen and sulfur compounds, which have a significant influence on the oxidizing capacity of the marine atmosphere; however, their impact on the air quality of coastal cities is currently unknown. We explore the effect of marine halogens (Cl, Br and I) and dimethyl sulfide (DMS) on the air quality of a large coastal city through a set of high-resolution (4-km) air quality simulations for the urban area of Los Angeles, US, using the Community Multiscale Air Quality (CMAQ model). The results indicate that marine halogen emissions decrease ozone and nitrogen dioxide levels up to 5ppbv and 2.5ppbv, respectively, in the city of Los Angeles. Previous studies suggested that the inclusion of chlorine in air quality models leads to the generation of ozone in urban areas through photolysis of nitryl chloride (ClNO2). However, we find that when considering the chemistry of Cl, Br and I together the net effect is a reduction of surface ozone concentrations. Furthermore, combined ocean emissions of halogens and DMS cause substantial changes in the levels of key urban atmospheric oxidants such as OH, HO2 and NO3, and in the composition and mass of fine particles. Although the levels of ozone, NO3 and HOx are reduced, we find a 10% increase in secondary organic aerosol (SOA) mean concentration, attributed to the increase in aerosol acidity and sulfate aerosol formation when combining DMS and bromine. Therefore, this new pathway for enhanced SOA formation may potentially help with current model under predictions of urban SOA. Although further observations and research are needed to establish these preliminary conclusions, this first city-scale investigation suggests that the inclusion of oceanic halogens and DMS in air quality models may improve regional air quality predictions over coastal cities around the world.

Microscale traffic simulation and emission estimation in a heavily trafficked roundabout in Madrid (Spain).

This paper presents the evaluation of emissions from vehicle operations in a domain of 300m×300m covering a complex urban roundabout with high traffic density in Madrid. Micro-level simulation was successfully applied to estimate the emissions on a scale of meters. Two programs were used: i) VISSIM to simulate the traffic on the square and to compute velocity-time profiles; and ii) VERSIT+micro through ENVIVER that uses VISSIM outputs to compute the related emissions at vehicle level. Data collection was achieved by a measurement campaign obtaining empirical data of vehicle flows and traffic intensities. Twelve simulations of different traffic situations (scenarios) were conducted, representing different hours from several days in a week and the corresponding NOX and PM10 emissions were estimated. The results show a general reduction on average speeds for higher intensities due to braking-acceleration patterns that contribute to increase the average emission factor and, therefore, the total emissions in the domain, especially on weekdays. The emissions are clearly related to traffic volume, although maximum emission scenario does not correspond to the highest traffic intensity due to congestion and variations in fleet composition throughout the day. These results evidence the potential that local measures aimed at alleviating congestion may have in urban areas to reduce emissions. In general, scenario-averaged emission factors estimated with the VISSIM-VERSIT+micro modelling system fitted well those from the average-speed model COPERT, used as a preliminary validation of the results. The largest deviations between these two models occur in those scenarios with more congestion. The design and resolution of the microscale modelling system allow to reflect the impact of actual traffic conditions on driving patterns and related emissions, making it useful for the design of mitigation measures for specific traffic hot-spots.

An integrated assessment of two decades of air pollution policy making in Spain: Impacts, costs and improvements.

This paper analyses the effects of policy making for air pollution abatement in Spain between 2000 and 2020 under an integrated assessment approach with the AERIS model for number of pollutants (NOx/NO2, PM10/PM2.5, O3, SO2, NH3 and VOC). The analysis of the effects of air pollution focused on different aspects: compliance with the European limit values of Directive 2008/50/EC for NO2 and PM10 for the Spanish air quality management areas; the evaluation of impacts caused by the deposition of atmospheric sulphur and nitrogen on ecosystems; the exceedance of critical levels of NO2 and SO2 in forest areas; the analysis of O3-induced crop damage for grapes, maize, potato, rice, tobacco, tomato, watermelon and wheat; health impacts caused by human exposure to O3 and PM2.5; and costs on society due to crop losses (O3), disability-related absence of work staff and damage to buildings and public property due to soot-related soiling (PM2.5). In general, air quality policy making has delivered improvements in air quality levels throughout Spain and has mitigated the severity of the impacts on ecosystems, health and vegetation in 2020 as target year. The findings of this work constitute an appropriate diagnosis for identifying improvement potentials for further mitigation for policy makers and stakeholders in Spain.

A methodology to estimate uncertainty for emission projections through sensitivity analysis.

UNLABELLED: Air pollution abatement policies must be based on quantitative information on current and future emissions of pollutants. As emission projections uncertainties are inevitable and traditional statistical treatments of uncertainty are highly time/resources consuming, a simplified methodology for nonstatistical uncertainty estimation based on sensitivity analysis is presented in this work. The methodology was applied to the "with measures" scenario for Spain, concretely over the 12 highest emitting sectors regarding greenhouse gas and air pollutants emissions. Examples of methodology application for two important sectors (power plants, and agriculture and livestock) are shown and explained in depth. Uncertainty bands were obtained up to 2020 by modifying the driving factors of the 12 selected sectors and the methodology was tested against a recomputed emission trend in a low economic-growth perspective and official figures for 2010, showing a very good performance. IMPLICATIONS: A solid understanding and quantification of uncertainties related to atmospheric emission inventories and projections provide useful information for policy negotiations. However, as many of those uncertainties are irreducible, there is an interest on how they could be managed in order to derive robust policy conclusions. Taking this into account, a method developed to use sensitivity analysis as a source of information to derive nonstatistical uncertainty bands for emission projections is presented and applied to Spain. This method simplifies uncertainty assessment and allows other countries to take advantage of their sensitivity analyses.

Air quality modeling and mortality impact of fine particles reduction policies in Spain.

BACKGROUND: In recent years, Spain has implemented a number of air quality control measures that are expected to lead to a future reduction in fine particle concentrations and an ensuing positive impact on public health. OBJECTIVES: We aimed to assess the impact on mortality attributable to a reduction in fine particle levels in Spain in 2014 in relation to the estimated level for 2007. METHODS: To estimate exposure, we constructed fine particle distribution models for Spain for 2007 (reference scenario) and 2014 (projected scenario) with a spatial resolution of 16×16km(2). In a second step, we used the concentration-response functions proposed by cohort studies carried out in Europe (European Study of Cohorts for Air Pollution Effects and Rome longitudinal cohort) and North America (American Cancer Society cohort, Harvard Six Cities study and Canadian national cohort) to calculate the number of attributable annual deaths corresponding to all causes, all non-accidental causes, ischemic heart disease and lung cancer among persons aged over 25 years (2005-2007 mortality rate data). We examined the effect of the Spanish demographic shift in our analysis using 2007 and 2012 population figures. RESULTS: Our model suggested that there would be a mean overall reduction in fine particle levels of 1µg/m(3) by 2014. Taking into account 2007 population data, between 8 and 15 all-cause deaths per 100,000 population could be postponed annually by the expected reduction in fine particle levels. For specific subgroups, estimates varied from 10 to 30 deaths for all non-accidental causes, from 1 to 5 for lung cancer, and from 2 to 6 for ischemic heart disease. The expected burden of preventable mortality would be even higher in the future due to the Spanish population growth. Taking into account the population older than 30 years in 2012, the absolute mortality impact estimate would increase approximately by 18%. CONCLUSIONS: Effective implementation of air quality measures in Spain, in a scenario with a short-term projection, would amount to an appreciable decline in fine particle concentrations, and this, in turn, would lead to notable health-related benefits. Recent European cohort studies strengthen the evidence of an association between long-term exposure to fine particles and health effects, and could enhance the health impact quantification in Europe. Air quality models can contribute to improved assessment of air pollution health impact estimates, particularly in study areas without air pollution monitoring data.

Emission inventories and modeling requirements for the development of air quality plans. Application to Madrid (Spain).

Modeling is an essential tool for the development of atmospheric emission abatement measures and air quality plans. Most often these plans are related to urban environments with high emission density and population exposure. However, air quality modeling in urban areas is a rather challenging task. As environmental standards become more stringent (e.g. European Directive 2008/50/EC), more reliable and sophisticated modeling tools are needed to simulate measures and plans that may effectively tackle air quality exceedances, common in large urban areas across Europe, particularly for NO2. This also implies that emission inventories must satisfy a number of conditions such as consistency across the spatial scales involved in the analysis, consistency with the emission inventories used for regulatory purposes and versatility to match the requirements of different air quality and emission projection models. This study reports the modeling activities carried out in Madrid (Spain) highlighting the atmospheric emission inventory development and preparation as an illustrative example of the combination of models and data needed to develop a consistent air quality plan at urban level. These included a series of source apportionment studies to define contributions from the international, national, regional and local sources in order to understand to what extent local authorities can enforce meaningful abatement measures. Moreover, source apportionment studies were conducted in order to define contributions from different sectors and to understand the maximum feasible air quality improvement that can be achieved by reducing emissions from those sectors, thus targeting emission reduction policies to the most relevant activities. Finally, an emission scenario reflecting the effect of such policies was developed and the associated air quality was modeled.

Implementation of a module for risk of ozone impacts assessment to vegetation in the Integrated Assessment Modelling system for the Iberian Peninsula. Evaluation for wheat and Holm oak.

A module to estimate risks of ozone damage to vegetation has been implemented in the Integrated Assessment Modelling system for the Iberian Peninsula. It was applied to compute three different indexes for wheat and Holm oak; daylight AOT40 (cumulative ozone concentration over 40 ppb), cumulative ozone exposure index according to the Directive 2008/50/EC (AOT40-D) and POD(Y) (Phytotoxic Ozone Dose over a given threshold of Y nmol m(-2) s(-1)). The use of these indexes led to remarkable differences in spatial patterns of relative ozone risks on vegetation. Ozone critical levels were exceeded in most of the modelling domain and soil moisture content was found to have a significant impact on the results. According to the outputs of the model, daylight AOT40 constitutes a more conservative index than the AOT40-D. Additionally, flux-based estimations indicate high risk areas in Portugal for both wheat and Holm oak that are not identified by AOT-based methods.