Casimiro Pio

Carbonaceous aerosol in urban and rural European atmospheres : estimation of secondary organic carbon concentrations

Abstract Aerosol samples from urban, rural and coastal areas in Europe were analysed for carbonaceous content by a thermaloptical transmission method. The fraction of particulate organic carbon with a secondary origin in gas/particle conversion of volatile organic compounds was estimated from the minimum ratio between particulate organic and black carbon, which occurred during periods of reduced photochemical activity. Values calculated by this method ranged from a minimum of 17%, in Birmingham, UK, during winter, to a maximum of 78% at a rural coastal area, in Portugal, with air masses transported directly from the ocean. A clear seasonal dependence was observed at both rural and urban environments, with minimum secondary organic carbon production during winter.

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.

Size-differentiated composition of inorganic atmospheric aerosols of both marine and polluted continental origin

Atmospheric aerosols were sampled with a high volume impactor/diffusion battery system and the collected fractions analysed for their major water-soluble inorganic constituents. Sulphate, nitrate and chloride showed bimodal distributions; sulphate and nitrate were mainly associated with NH4+, having approximately log-normal distributions with modes at 1.0 μm. In unpolluted maritime air, chlorides appeared as salts of sodium and magnesium with average modes at c. 5 μm, whilst in polluted air masses significant concentrations of ammonium chloride sub-μm aerosols were detected. Sodium nitrate and sodium sulphate aerosols having average modes of c. 3.5 μm were observed in mixed maritime/polluted air masses. The dimensions of these particles indicate formation from absorption of H2SO4 and HNO3 at the surface of marine NaCl particles. The concentration of H+ was very low, but the possibility of its neutralization by atmospheric ammonia during sampling was ruled out by parallel air sampling using an ‘ammonia denuder’.

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.

Seasonal trends and possible sources of brown carbon based on 2-year aerosol measurements at six sites in Europe

Brown carbon is a ubiquitous and unidentified component of organic aerosol which has recently come into the forefront of atmospheric research. This component is strongly linked to the class of humic-like substances (HULIS) in aerosol whose ultimate origin is still being debated. Using a simplified spectroscopic method the concentrations of brown carbon have been determined in aqueous extracts of fine aerosol collected during the CARBOSOL project. On the basis of the results of 2-year measurements of several aerosol constituents at six European sites, possible sources of brown carbon are inferred. Biomass burning ( possibly domestic wood burning) is shown to be a major source of brown carbon in winter. At elevated sites in spring, smoke from agricultural fires may be an additional source. Direct comparison of measured brown carbon concentrations with HULIS determined by an independent method reveals that the two quantities correlate well at low-elevation sites throughout the year. At high-elevation sites the correlation is still high for winter but becomes markedly lower in summer, implying different sources and/or atmospheric sinks of brown carbon and HULIS. The results shed some light on the relationships between atmospheric brown carbon and HULIS, two ill-defined and overlapping components of organic aerosol.

Land management and land-cover change have impacts of similar magnitude on surface temperature

The direct effects of land-cover change on surface climate are increasingly well understood, but fewer studies have investigated the consequences of the trend towards more intensive land management practices. Now, research investigating the biophysical effects of temperate land-management changes reveals a net warming effect of similar magnitude to that driven by changing land cover.

Composition of extractable organic matter of air particles from rural and urban Portuguese areas

Abstract Atmospheric particulate matter (PM 10 ) was collected simultaneously at three sites in the West Coast of Portugal, during an intensive campaign in August 1996. The sites were located in line with the breezes blowing from the sea. The collected aerosol was analysed in relation to black and organic carbon content. The particulate organic matter was extracted with solvents and characterised by gas chromatography and mass spectrometry (GC–MS). Most of the organic mass identified consists of alkanes, polycyclic aromatic hydrocarbons (PAH), ketones, aldehydes, alcohols and fatty acids with both biogenic and anthropogenic origin. Many photochemical products from volatile organic compounds emitted by vegetation were also detected. Biomarkers such as 6,10,14-trimethylpentadecanone, abieta-8,11,13-trien-7-one and Patchouli alcohol were observed at higher concentrations in the rural sites. Samples from the urban site present lower values of “carbon preference index” and higher concentrations of petrogenic/pyrogenic species, such as PAH. The PM 10 concentrations and the total organic extract measured for the more interior site were generally lower, indicating that dispersion and dry deposition into the forest canopy were more important during the transport of the air masses than aerosol production by condensation and photochemical reactions. On the contrary, the ratio between organic and black carbon was, in general, lower at sites near the coast, especially for compounds that evaporate at lower temperatures. The organic aerosol composition also seems to be strongly dependent on the meteorology.

Concentrations of particulate airborne polycyclic aromatic hydrocarbons and metals collected in Lahore, Pakistan

Abstract Hi-vol air sampling equipment was run at three sites (representative of “city”, “industrial” and “rural” sampling locations) in Lahore, Pakistan, for over a year. The extraction and quantitative analyses of all Lahore air samples was completed for a suite of metals, various anions, ammonium, elemental and organic carbon, as well as particle-associated polycyclic aromatic hydrocarbons (PAHs). A comparison of Lahore yearly mean pollutant concentrations with those obtained in Birmingham, U.K., shows that airborne metal levels in the Pakistani city are greater by at least one order of magnitude. The concentrations in Lahore obtained from this study are broadly in line with similar studies in Karachi as well as Calcutta and Bombay. Concentrations of particle-associated PAH are also around one order of magnitude higher than in U.K. samples, and, given the difference in ambient temperature, vapour-to-particle ratios of PAH are expected to be far higher in the hotter climate of Lahore. Minerals identified by X-ray diffraction (XRD) in the Lahore air samples were broadly in line with those determined at locations in other parts of the world.