Alexandre Caseiro

Source apportionment of PM2.5 organic aerosol over Europe: Primary/secondary, natural/anthropogenic, and fossil/biogenic origin

On the basis of a 2-year comprehensive data set obtained within the CARBOSOL project, seasonal source apportionment of PM2.5 aerosol is attempted for five rural/remote sites in Europe. The approach developed combines radiocarbon measurements with bulk measurements of organic carbon (OC), elemental carbon (EC), and two organic tracers ( levoglucosan and cellulose). Source types are lumped into primary emissions from fossil fuel combustion and biomass burning, bioaerosol, and secondary organic aerosol from precursors emitted by fossil and nonfossil sources. Bulk concentration ratios reported for these source types in the literature are used to estimate the source contributions which are constrained by measured radiocarbon concentrations. It has been found that while fossil-related sources predominate EC throughout the year at all sites, the sources of OC are primarily biogenic and markedly different between summer and winter. In winter biomass burning primary emission is the main source, with sizable additional contribution from fossil fuel combustion. In contrast, in summer secondary organic aerosol (SOA) from nonfossil sources becomes predominant (63-76% of TC), with some contribution of SOA from fossil fuel combustion. The results agree well with recent findings of other authors who established the predominance of biogenic SOA for rural sites in summer in Europe. An uncertainty analysis has been conducted, which shows that the main conclusions from this study are robust.

Levoglucosan levels at background sites in Europe for assessing the impact of biomass combustion on the European aerosol background

Atmospheric levoglucosan has been determined as a proxy for “biomass smoke” in samples from six background stations on a west–east transect extending from the Atlantic (Azores) to the mid-European background site KPZ (K-Puszta, Hungary). Concentration levels of levoglucosan (biannual averages) in the west–east transect range from 0.005 μg/m3 at the oceanic background site AZO (Azores) to 0.52 μg/m3 at AVE (Aveiro, Portugal). The atmospheric concentration of “biomass smoke” (biannual averages) was derived from the levoglucosan data with wood-type-specific conversion factors. Annual averages of wood smoke levels ranged from 0.05 μg/m3 at AZO to 4.3 μg/m3 at AVE. Winter (DJF) averages at the low-level sites AVE and KPZ were 10.8 and 6.7 μg/m3, respectively. Relative contributions of biomass smoke to organic matter (OM) range from around 9–11% at the elevated sites SIL, PDD and SBO, as well as for AZO, to 36% at the low-level site AVE and 28% at KPZ. Surprisingly high relative concentrations of biomass smoke in OM (68 and 47%) were observed for wintry conditions at the continental low-level CARBOSOL sites AVE and KPZ. Thus biomass smoke is a very important constituent of the organic material in the mid and west European background with summer contributions to organic matter of around 1–6% and winter levels of around 20% at the elevated mountain sites and 47–68% at rural flat terrain sites, not including secondary organic aerosol from biomass combustion sources.

Climatology of aerosol composition (organic versus inorganic) at nonurban sites on a west‐east transect across Europe

in central Europe. Aerosols were analyzed for 210 Pb, inorganic ions, elemental (EC) and organic (OC) carbon, water soluble organic carbon (WSOC), macromolecular type (humic-like) organic substances (HULIS), C2–C5 diacids, cellulose, and levoglucosan. Pooled aerosol filters were also used for the identification of different families of organic compounds by gas chromatography/mass spectrometry, GC/MS, as well as 14 C determinations. The data resulted in a climatological overview of the aerosol composition over Europe in the various seasons, from west to east, and from the boundary layer to the free troposphere. The paper first summarizes the characteristics of the sites and collected samples and then focuses on the aerosol mass partitioning (mass closure, inorganic versus organic, EC versus OC, water soluble versus insoluble OC), giving an insight on the sources of carbonaceous aerosol present in rural and natural background areas in Europe. It also introduces the main role of other companion papers dealing with CARBOSOL aerosol data that are also presented in this issue.

Modeling carbonaceous aerosol over Europe: Analysis of the CARBOSOL and EMEP EC/OC campaigns

In this paper the European Monitoring and Evaluation Programme (EMEP) MSC-W model is used to assess our understanding of the sources of carbonaceous aerosol in Europe ( organic carbon (OC), elemental carbon (EC), or their sum, total carbon (TC)). The modeling work makes use of new data from two extensive measurement campaigns in Europe, those of the CARBOSOL project and of the EMEP EC/OC campaign. As well as EC and OC measurements, we are able to compare with levoglucosan, a tracer of wood-burning emissions, and with the source apportionment ( SA) analysis of Gelencser et al. ( 2007), which apportioned TC into primary versus secondary and fossil fuel versus biogenic origin. The model results suggest that emissions of primary EC and OC from fossil fuel sources are probably captured to better than a factor of two at most sites. Discrepancies for wintertime OC at some sites can likely be accounted for in terms of missing wood-burning contributions. Two schemes for secondary organic aerosol (SOA) contribution are included in the model, and we show that model results for TC are very sensitive to the choice of scheme. In northern Europe the model seems to capture TC levels rather well with either SOA scheme, but in southern Europe the model strongly underpredicts TC. Comparison against the SA results shows severe underprediction of the SOA components. This modeling work confirms the difficulties of modeling SOA in Europe, but shows that primary emissions constitute a significant fraction of ambient TC.

Impact of maritime air mass trajectories on the Western European coast urban aerosol.

Lisbon is the largest urban area in the Western European coast. Due to this geographical position the Atlantic Ocean serves as an important source of particles and plays an important role in many atmospheric processes. The main objectives of this study were to (1) perform a chemical characterization of particulate matter (PM2.5) sampled in Lisbon, (2) identify the main sources of particles, (3) determine PM contribution to this urban area, and (4) assess the impact of maritime air mass trajectories on concentration and composition of respirable PM sampled in Lisbon. During 2007, PM2.5 was collected on a daily basis in the center of Lisbon with a Partisol sampler. The exposed Teflon filters were measured by gravimetry and cut into two parts: one for analysis by instrumental neutron activation analysis (INAA) and the other by ion chromatography (IC). Principal component analysis (PCA) and multilinear regression analysis (MLRA) were used to identify possible sources of PM2.5 and determine mass contribution. Five main groups of sources were identified: secondary aerosols, traffic, calcium, soil, and sea. Four-day backtracking trajectories ending in Lisbon at the starting sampling time were calculated using the HYSPLIT model. Results showed that maritime transport scenarios were frequent. These episodes were characterized by a significant decrease of anthropogenic aerosol concentrations and exerted a significant role on air quality in this urban area.

Variations in wood burning organic marker concentrations in the atmospheres of four European cities

The particulate emissions from biomass burning are a growing concern due to the recent evidence of their ubiquitous and important contribution to the ambient aerosol load. A possible strategy to apportion the biomass burning share of particulate matter is the use of organic molecular tracers. Anhydrosugars (levoglucosan, mannosan and galactosan), together with two organic acids (dehydroabietic and pimaric acids), were previously reported as organic markers for particulate wood burning emissions. These five compounds were studied in four European cities (Helsinki, Copenhagen, Birmingham and Oporto), at both a Roadside and an Urban Background station, during a summer and a winter campaign in the fine (PM(2.5)) and the coarse (PM(10-2.5)) size-fractions of the ambient aerosol. Levoglucosan concentrations were highest in the city of Oporto. In winter, levoglucosan was more present in the fine fraction but in summer, concentrations were similar in both size fractions. Levoglucosan concentrations in the fine size fraction were higher in winter, but no seasonal differences were observed for the coarse size fraction. The lack of difference between the Roadside and Urban Background levoglucosan concentrations points towards a regional nature of this type of pollution. Wood burning was estimated to contribute to about 3.1% of the winter PM(10) mass in Oporto, and to 3.7% in Copenhagen. Mannosan followed the trends exhibited by levoglucosan. The ratio between the levoglucosan and mannosan concentrations allowed determination of a preference for softwood over hardwood in all four cities. Galactosan, pimaric acid and dehydroabietic acid were found to be minor compounds.

Composition and source apportionment of atmospheric aerosols in Portugal during the 2003 summer intense forest fire period

The summer of 2003 was characterized by an intense heat wave across Europe that resulted in a large number of deaths and intense and extended forest fires. In Portugal, during this period more than 300000 ha of forests were destroyed by fire, during a short period, emitting enormous quantities of pollutants to the atmosphere. These emissions have presumably important effects in terms of regional human health and on the atmospheric radiation balance. During the summer of 2003 aerosol samples were taken in the Aveiro region, Portugal, and analysed for total mass and a series of inorganic and organic compounds, including tracers of biomass burning such as potassium and levoglucosan. Based on air mass trajectories, the aerosol size distribution, the levels of particulate mass and the aerosol composition, observed during periods with and without forest fires, the contribution of forest fires to the regional aerosol load is inferred. The absolute and relative variability of the aerosol inorganic and organic components are used to evaluate the importance of forest fire emissions as sources responsible for the presence in the summer atmosphere of compounds such as particulate tracers. The results permit also to have, at least, a semi quantitative estimation of the emission factors of biomass burning tracers such as potassium and levoglucosan to the organic aerosol load in air mass plumes resulting from forest fires. The calculation of emission factors from natural forest fires (without the bias of laboratory and prescribed burnings) is a useful complement for a correct inventory of the impact of these nowadays common summer events on the contamination of regional and global atmosphere.

Quantifying Source Contribution to Ambient Particulate Matter in Austria with Chemical Mass Balance Receptor Modeling

In this work, we apply the CMB model to a set of samples collected in Vienna. Those samples were chemically characterised for a wide range of chemical species as were samples from aerosol sources. The set of samples represent periods in which the threshold value of the PM10 level was exceeded, thus providing an insight over the causes of such episodes.