Photochemical Air Pollution Levels Research Articles

Formaldehyde and hydroperoxide distribution around the Arabian Peninsula – evaluation of EMAC model results with ship-based measurements

Abstract. Formaldehyde (HCHO), hydrogen peroxide (H2O2) and organic hydroperoxides (ROOH) play a key role in atmospheric oxidation processes. They act as sources and sinks for HOx radicals (OH + HO2), with OH as the primary oxidant that governs the atmospheric self-cleaning capacity. Measurements of these species allow for evaluation of chemistry-transport models which need to account for multifarious source distributions, transport, complex photochemical reaction pathways and deposition processes of these species. HCHO is an intermediate during the oxidation of volatile organic compounds (VOCs) and is an indicator of photochemical activity and combustion-related emissions. In this study, we use in situ observations of HCHO, H2O2 and ROOH in the marine boundary layer (MBL) to evaluate results of the general circulation model EMAC (ECHAM5/MESSy2 Atmospheric Chemistry; European Center HAMburg, Modular Earth Submodel System). The dataset was obtained during the Air Quality and Climate Change in the Arabian Basin (AQABA) ship campaign around the Arabian Peninsula in summer 2017. This region is characterized by high levels of photochemical air pollution, humidity and solar irradiation, especially in the areas around the Suez Canal and the Arabian Gulf. High levels of air pollution with up to 12 ppbv HCHO, 2.3 ppbv ROOH and relatively low levels of H2O2 (≤0.5 ppbv) were detected over the Arabian Gulf. We find that EMAC failed to predict absolute mixing ratios of HCHO and ROOH during high-pollution events over the Arabian Gulf, while it reproduced HCHO on average within a factor of 2. Dry deposition velocities were determined for HCHO and H2O2 at night with 0.77±0.29 cm s−1 for HCHO and 1.03±0.52 cm s−1 for H2O2 over the Arabian Sea, which were matched by EMAC. The photochemical budget of H2O2 revealed elevated HOx radical concentrations in EMAC, which resulted in an overestimation of H2O2 by more than a factor of 5 for the AQABA dataset. The underestimated air pollution over the Arabian Gulf was related to EMAC's coarse spatial resolution and missing anthropogenic emissions in the model.

Shipborne measurements of total OH reactivity around the Arabian Peninsula and its role in ozone chemistry

Abstract. The Arabian Peninsula is characterized by high and increasing levels of photochemical air pollution. Strong solar irradiation, high temperatures and large anthropogenic emissions of reactive trace gases result in intense photochemical activity, especially during the summer months. However, air chemistry measurements in the region are scarce. In order to assess regional pollution sources and oxidation rates, the first ship-based direct measurements of total OH reactivity were performed in summer 2017 from a vessel traveling around the peninsula during the AQABA (Air Quality and Climate Change in the Arabian Basin) campaign. Total OH reactivity is the total loss frequency of OH radicals due to all reactive compounds present in air and defines the local lifetime of OH, the most important oxidant in the troposphere. During the AQABA campaign, the total OH reactivity ranged from below the detection limit (5.4 s−1) over the northwestern Indian Ocean (Arabian Sea) to a maximum of 32.8±9.6 s−1 over the Arabian Gulf (also known as Persian Gulf) when air originated from large petroleum extraction/processing facilities in Iraq and Kuwait. In the polluted marine regions, OH reactivity was broadly comparable to highly populated urban centers in intensity and composition. The permanent influence of heavy maritime traffic over the seaways of the Red Sea, Gulf of Aden and Gulf of Oman resulted in median OH sinks of 7.9–8.5 s−1. Due to the rapid oxidation of direct volatile organic compound (VOC) emissions, oxygenated volatile organic compounds (OVOCs) were observed to be the main contributor to OH reactivity around the Arabian Peninsula (9 %–35 % by region). Over the Arabian Gulf, alkanes and alkenes from the petroleum extraction and processing industry were an important OH sink with ∼9 % of total OH reactivity each, whereas NOx and aromatic hydrocarbons (∼10 % each) played a larger role in the Suez Canal, which is influenced more by ship traffic and urban emissions. We investigated the number and identity of chemical species necessary to explain the total OH sink. Taking into account ∼100 individually measured chemical species, the observed total OH reactivity can typically be accounted for within the measurement uncertainty (50 %), with 10 dominant trace gases accounting for 20 %–39 % of regional total OH reactivity. The chemical regimes causing the intense ozone pollution around the Arabian Peninsula were investigated using total OH reactivity measurements. Ozone vs. OH reactivity relationships were found to be a useful tool for differentiating between ozone titration in fresh emissions and photochemically aged air masses. Our results show that the ratio of NOx- and VOC-attributed OH reactivity was favorable for ozone formation almost all around the Arabian Peninsula, which is due to NOx and VOCs from ship exhausts and, often, oil/gas production. Therewith, total OH reactivity measurements help to elucidate the chemical processes underlying the extreme tropospheric ozone concentrations observed in summer over the Arabian Basin.

Economic damages of ozone air pollution to crops using combined air quality and GIS modelling

This study aims at presenting a combined air quality and GIS modelling methodological approach in order to estimate crop damages from photochemical air pollution, depict their spatial resolution and assess the order of magnitude regarding the corresponding economic damages. The analysis is conducted within the Greater Thessaloniki Area, Greece, a Mediterranean territory which is characterised by high levels of photochemical air pollution and considerable agricultural activity. Ozone concentration fields for 2002 and for specific emission reduction scenarios for the year 2010 were estimated with the Ozone Fine Structure model in the area under consideration. Total economic damage to crops turns out to be significant and estimated to be approximately 43 M€ for the reference year. Production of cotton presents the highest economic loss, which is over 16 M€, followed by table tomato (9 M€), rice (4.2 M€), wheat (4 M€) and oilseed rape (2.8 M€) cultivations. Losses are not spread uniformly among farmers and the major losses occur in areas with valuable ozone-sensitive crops. The results are very useful for highlighting the magnitude of the total economic impacts of photochemical air pollution to the area’s agricultural sector and can potentially be used for comparison with studies worldwide. Furthermore, spatial analysis of the economic damage could be of importance for governmental authorities and decision makers since it provides an indicative insight, especially if the economic instruments such as financial incentives or state subsidies to farmers are considered.

The use of a modelling system as a tool for air quality management: Annual high-resolution simulations and evaluation

The high levels of air pollutants over the North-Western Mediterranean (NWM) exceed the thresholds set in current air quality regulations. They demand a detailed diagnosis of those areas where the exceedances of thresholds related to human health are found. In this sense, there is a need for modelling studies for the specific area of the NWM that take into account the annual cycle to address the diagnosis of air pollution. A new approach to the modelling of air quality in the NWM has been adopted by combining the WRF-EMICAT-CMAQ-DREAM modelling system to diagnose the current status of the levels of photochemical air pollution (focusing on ozone, O 3; nitrogen dioxide, NO 2; carbon monoxide, CO; and particulate matter, PM10) in the area during an annual cycle (year 2004). The complexity of the area of study requires the application of high spatial and temporal resolution (2 km and 1 h). The annual simulations need to cover the complex different meteorological situations and types of episodes of air pollution in the area of study. The outputs of the modelling system are evaluated against observations from 52 meteorological and 59 air quality stations belonging to the Environmental Department of the Catalonia Government (Spain), which involve a dense and accurate spatial distribution of stations in the territory (32,215 km 2). The results indicate a good behaviour of the model in both coastal and inland areas of the NWM, with a slight trend to the overestimation of tropospheric O 3 concentrations and the underestimation of other photochemical pollutants (NO 2, CO and PM10). The modelling diagnosis indicates that the main air quality-related problems in the NWM are the exceedances of the 1-hr O 3 information threshold set in the Directive 2002/3/EC (180 μg m − 3 ) as a consequence of the transport of O 3 precursors downwind the Barcelona Greater Area (BGA); and the exceedances of the annual value for the protection of human health for NO 2 and PM10 (40 μg m − 3 , Directive 1999/30/EC), both in the BGA, as a consequence of the high traffic-related emissions.

Multiscale modeling of air pollutants dynamics in the northwestern Mediterranean basin during a typical summertime episode

The complex behavior of photochemical pollutants in the northwestern Mediterranean basin (NWMB) is conditioned by the superposition of circulations of different scale and the pattern of emissions. Therefore a new approach to the modeling of air quality in the NWMB has been adopted by combining the global climate‐chemistry model ECHAM5/MESSy and the regional modeling system MM5‐EMICAT2000‐CMAQ to analyze the high levels of photochemical air pollution during a typical summertime episode. We show that this combination of models is well suited to address the range of scales involved. The complexity of the area requires the application of high spatial and temporal resolution (2 km and 1 hour) modeling to cover local to regional interactions. We address the local and large‐scale processes controlling tropospheric ozone in the NWMB, notably emissions and photochemistry, convective and advective transport, deposition processes, and stratosphere‐troposphere exchange. The simulation results indicate that the ozone buildup largely results from local photochemical production, which strongly exceeds the removal rates through transport and deposition. The contribution by advective transport is limited, associated with the stagnant meteorological conditions. In the lower troposphere, local recirculation systems are of key importance. The strength of the land‐sea breeze circulation and thermally or mechanically driven convection over the complex orography of the eastern Iberian coast can induce vertical transport and the layering of air pollution.

Numerical simulation of photochemical smog formation in Athens, Greece—A case study

High emission levels and the unfavourable topography are the main reasons for the alarming photochemical air pollution levels in Athens. An analysis of available air quality data proves that air pollution levels in Athens are largely affected by local wind circulation systems. The most frequent of these systems is dominated by the phenomenon of the sea breeze. Severe air pollution episodes occur, however, primarily under synoptic situations leading to stagnant conditions in the atmosphere over Athens. Photosmog formation in the Athens Basin is studied with the photochemical dispersion model MARS. The implicit solution algorithm incorporated in MARS is characterized by a variable time increment and a variable order. This solver allows avoiding unnecessary operator splitting by a coupled treatment of vertical diffusion and chemical kinetics. In this paper, MARS is used to analyse the situation on 25 May 1990, a day for which very high air pollution levels were reported in Athens. The simulation results elucidate the characteristics of a photosmog episode under stagnant conditions in Athens. In general, the model results reproduce satisfactorily the observed air pollution patterns.

The Relationship of Urgent Hospital Admissions for Respiratory Illnesses to Photochemical Air Pollution Levels in Montreal

The relationship between the number of daily urgent hospital admissions for respiratory illnesses (31 hospitals) and ambient air pollution in Montreal, Canada, was investigated for warm periods between 1984 and 1988. Air pollutants included 1-hr and 8-hr maximum ozone, estimated particulate matter ≤10 μm in aerometric diameter (PM10), and estimated sulfate (SO42−) fraction of PM10. Regression analyses controlled for seasonal and day-of-week trends, autocorrelation, temperature, and relative humidity. For July and August periods, there was a statistically significant (P < 0.01) univariate relationship of all respiratory admissions to 8-hr maximum ozone, which became nonsignificant when coregressed with temperature. Levels of ozone which never exceeded the U.S. National Ambient Air Quality Standard (NAAQS) of 120 ppb and high intercorrelations between ozone, particulates, and temperature may explain this finding. Asthma admissions in the May-October periods increased by 2.7% over mean levels for each 12 μg/m3 increase in PM(10) levels 3 days prior to the admission day (95% confidence interval, 0.7 to 4.8%). In the July and August periods, hospital admissions for respiratory illnesses excluding asthma were 9.6% higher (95% confidence interval, 0.5 to 18.7%) when estimated SO42− had exceeded 8.1 μg/m3 4 days prior to the admission day compared to days when SO42− was at or below this level. There were no significant (P < 0.05) associations of a reference group of nonrespiratory admissions to air pollution after controlling for weather. The above results were found despite levels of PM10 which never exceeded the NAAQS of 150 μg/m3. The associations found are relevant to public health, since hospital admissions are expected to be accompanied by considerably more frequent occurrences of less serious outcomes. The present findings suggest that particulate air pollution during photochemically active periods is related to respiratory morbidity in Montreal.

Athenian photochemical smog: intercomparison of simulations (APSIS), background and objectives

Athens is suffering under severe photochemical air pollution levels. The spatial variation of the photosmog characteristics in the Athens basin reveals that air pollution levels in Athens are largely affected by local wind circulation systems. A complete picture of wind field pattern and air pollutant dispersion in Athens can only be achieved with suitable mathematical models. In view of its complexity and its manifold peculiarities, the situation in Athens qualifies as a test case for prognostic mesoscale models and photochemical dispersion models. As the frame of model intercomparisons and of attempts to evaluate model simulation results, the APSIS project was initiated. With the participation of more than 30 scientific teams from four continents, this project is expected to contribute to the refinement of atmospheric environmental software.

Numerical simulation of the photochemical air pollution levels in Athens, Greece

This paper focuses on photochemical oxidant formation which is shown to be the most dominant feature of the Athenian air pollution problem. A simple but reliable photosmog model is used to simulate numerically the formation of photochemical oxidants on the basis of all available emission data. The resulting diurnal variation of the ozone concentration agrees fairly well with measurements. Predictions of the future development of the photosmog levels performed on the basis of realistic emission forecasts allow to conclude that no significant reduction of the photochemical air pollution in Athens can be expected in the next 25 years.

Cancer of the lung and los-angeles-type air pollution.Prospective study

A prospective study was conducted in Los Angeles California in an attempt to answer the question of whether longterm residents of Los Angeles at comparable smoking levels have a higher rate of pulmonary cancer than the longterm residents of other metropolitan areas of California. Questionnaires on cigarette smoking status residence history and other characteristics were mailed to men of the California Division of the American Legion. Subsequent checking of this population against the California mortality records for 1959 through 1962 revealed the number of deaths including those due to cancer of the lung and provided 336571 man years of observation. The pulmonary cancer gradient by smoking level was less pronounced than that found in other studies. Los Angeles and Bay Area and San Diego - the 2 major metropolitan areas - had higher mortality rates for cancer of the lung than remaining mixed rural and urban counties and these differences were relatively greater among nonsmokers. With controls for smoking and length of residence the risk of pulmonary cancer in Los Angeles where photochemical air pollution levels are highest was not greater than in Californias other major metropolitan areas.