216 research outputs found

    Size-dependent chemical ageing of oleic acid aerosol under dry and humidified conditions

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    Abstract. A chemical reaction chamber system has been developed for the processing of oleic acid aerosol particles with ozone under two relative humidity conditions: dry and humidified to 65 % R.H. The apparatus consists of an aerosol flow tube, in which the ozonolysis occurs, coupled to a scanning mobility particle sizer (SMPS) and an aerosol time-of-flight mass spectrometer (ATOFMS) which measure the evolving particle size and composition. Under both relative humidity conditions, ozonolysis results in a significant decrease in particle size and mass which is consistent with the formation of volatile products that partition from the particle to the gas phase. Mass spectra derived from the ATOFMS reveal the presence of the typically observed reaction products: azaleic acid, nonanal, oxononanoic acid and nonanoic acid, as well as a range of higher molecular weight products deriving from the reactions of reaction intermediates with oleic acid and its oxidation products. These include octanoic acid, and 9- and 10-oxooctadecanoic acid, as well as products of considerably higher molecular weight. Quantitative evaluation of product yields with the ATOFMS shows a marked dependence upon both particle size association (from 0.3 to 2.1 µm diameter) and relative humidity. Under dry conditions, the percentage residual oleic acid increases with increasing particle size, as does the percentage of higher molecular weight products, due to the poorer internal mixing of the larger particles. The main lower molecular weight products are nonanal and oxonononic acid. Under humidified conditions, the percentage unreacted oleic acid is greater, except in the smallest particle fraction, and oxononanoic acid dominates the product distribution, with little formation of high molecular weight products relative to the dry particles. It is postulated that water reacts with reactive intermediates, competing with the processes which produce high molecular weight products. Whilst the oleic acid model aerosol system is of limited relevance to complex internally mixed atmospheric aerosol, the generic findings presented in this paper give useful insights into the nature of heterogeneous chemical processes. </jats:p

    Sources and contributions of wood smoke during winter in London: Assessing local and regional influences

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    Determining the contribution of wood smoke to air pollution in large cities such as London is becoming increasingly important due to the changing nature of domestic heating in urban areas. During winter, biomass burning emissions have been identified as a major cause of exceedances of European air quality limits. The aim of this work was to quantify the contribution of biomass burning in London to concentrations of PM2:5 and determine whether local emissions or regional contributions were the main source of biomass smoke. To achieve this, a number of biomass burning chemical tracers were analysed at a site within central London and two sites in surrounding rural areas. Concentrations of levoglucosan, elemental carbon (EC), organic carbon (OC) and KC were generally well correlated across the three sites. At all the sites, biomass burning was found to be a source of OC and EC, with the largest contribution of EC from traffic emissions, while for OC the dominant fraction included contributions from secondary organic aerosols, primary biogenic and cooking sources. Source apportionment of the EC and OC was found to give reasonable estimation of the total carbon from non-fossil and fossil fuel sources based upon comparison with estimates derived from 14C analysis. Aethalometer-derived black carbon data were also apportioned into the contributions frombiomass burning and traffic and showed trends similar to those observed for EC. Mean wood smoke mass at the sites was estimated to range from 0.78 to 1.0 μgm-3 during the campaign in January–February 2012. Measurements on a 160m tower in London suggested a similar ratio of brown to black carbon (reflecting wood burning and traffic respectively) in regional and London air. Peaks in the levoglucosan and KC concentrations were observed to coincide with low ambient temperature, consistent with domestic heating as a major contributing local source in London. Overall, the source of biomass smoke in London was concluded to be a background regional source overlaid by contributions from local domestic burning emissions. This could have implications when considering future emission control strategies during winter and may be the focus of future work in order to better determine the contributing local sources

    Source apportionment of particle number size distribution in urban background and traffic stations in four European cities

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    Ultrafine particles (UFP) are suspected of having significant impacts on health. However, there have only been a limited number of studies on sources of UFP compared to larger particles. In this work, we identified and quantified the sources and processes contributing to particle number size distributions (PNSD) using Positive Matrix Factorization (PMF) at six monitoring stations (four urban background and two street canyon) from four European cities: Barcelona, Helsinki, London, and Zurich. These cities are characterised by different meteorological conditions and emissions. The common sources across all stations were Photonucleation, traffic emissions (3 sources, from fresh to aged emissions: Traffic nucleation, Fresh traffic – mode diameter between 13 and 37 nm, and Urban – mode diameter between 44 and 81 nm, mainly traffic but influenced by other sources in some cities), and Secondary particles. The Photonucleation factor was only directly identified by PMF for Barcelona, while an additional split of the Nucleation factor (into Photonucleation and Traffic nucleation) by using NOx concentrations as a proxy for traffic emissions was performed for all other stations. The sum of all traffic sources resulted in a maximum relative contributions ranging from 71 to 94% (annual average) thereby being the main contributor at all stations. In London and Zurich, the relative contribution of the sources did not vary significantly between seasons. In contrast, the high levels of solar radiation in Barcelona led to an important contribution of Photonucleation particles (ranging from 14% during the winter period to 35% during summer). Biogenic emissions were a source identified only in Helsinki (both in the urban background and street canyon stations), that contributed importantly during summer (23% in urban background). Airport emissions contributed to Nucleation particles at urban background sites, as the highest concentrations of this source took place when the wind was blowing from the airport direction in all cities.Ultrafine particles (UFP) are suspected of having significant impacts on health. However, there have only been a limited number of studies on sources of UFP compared to larger particles. In this work, we identified and quantified the sources and processes contributing to particle number size distributions (PNSD) using Positive Matrix Factorization (PMF) at six monitoring stations (four urban background and two street canyon) from four European cities: Barcelona, Helsinki, London, and Zurich. These cities are characterised by different meteorological conditions and emissions. The common sources across all stations were Photonucleation, traffic emissions (3 sources, from fresh to aged emissions: Traffic nucleation, Fresh traffic - mode diameter between 13 and 37 nm, and Urban - mode diameter between 44 and 81 nm, mainly traffic but influenced by other sources in some cities), and Secondary particles. The Photonucleation factor was only directly identified by PMF for Barcelona, while an additional split of the Nucleation factor (into Photonucleation and Traffic nucleation) by using NOx concentrations as a proxy for traffic emissions was performed for all other stations. The sum of all traffic sources resulted in a maximum relative contributions ranging from 71 to 94% (annual average) thereby being the main contributor at all stations. In London and Zurich, the relative contribution of the sources did not vary significantly between seasons. In contrast, the high levels of solar radiation in Barcelona led to an important contribution of Photonucleation particles (ranging from 14% during the winter period to 35% during summer). Biogenic emissions were a source identified only in Helsinki (both in the urban background and street canyon stations), that contributed importantly during summer (23% in urban background). Airport emissions contributed to Nucleation particles at urban background sites, as the highest concentrations of this source took place when the wind was blowing from the airport direction in all cities.Peer reviewe

    Urban aerosol size distributions over the Mediterranean city of Barcelona, NE Spain

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    Differential mobility particle sizer (DMPS) aerosol concentrations (N13−800) were collected over a oneyear- period (2004) at an urban background site in Barcelona, North-Eastern Spain. Quantitative contributions to particle number concentrations of the nucleation (33–39 %), Aitken (39–49 %) and accumulation mode (18–22 %) were estimated. We examined the source and time variability of atmospheric aerosol particles by using both K-means clustering and Positive Matrix Factorization (PMF) analysis. Performing clustering analysis on hourly size distributions, nine K-means DMPS clusters were identified and, by directional association, diurnal variation and relationship to meteorological and pollution variables, four typical aerosol size distribution scenarios were identified: traffic (69% of the time), dilution (15% of the time), summer background conditions (4% of the time) and regional pollution (12% of the time). According to the results of PMF, vehicle exhausts are estimated to contribute at least to 62–66% of the total particle number concentration, with a slightly higher proportion distributed towards the nucleation mode (34 %) relative to the Aitken mode (28–32 %). Photochemically induced nucleation particles make only a small contribution to the total particle number concentration (2–3% of the total), although only particles larger than 13 nm were considered in this study. Overall the combination of the two statistical methods is successful at separating components and quantifying relative contributions to the particle number population
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