Hans Puxbaum

Inventorying emissions from nature in Europe

As part of the work of the Economic Commission for Europe of the United Nations Task Force on Emission Inventories, a new set of guidelines has been developed for assessing the emissions of sulphur, nitrogen oxides, NH3, CH4, and nonmethane volatile organic compounds (NMVOC) from biogenic and other natural sources in Europe. This paper gives the background to these guidelines, describes the sources, and gives our recommended methodologies for estimating emissions. We have assembled land use and other statistics from European or national compilations and present emission estimates for the various natural/biogenic source categories based on these. Total emissions from nature derived here amount to ∼1.1 Tg S yr−1, 6–8 Tg CH4 yr−1, 70 Gg NH3 (as N) yr−1, and 13 Tg NMVOC yr−1. Estimates of biogenic NO x emissions cover a wide range, from 140 to 1500 Gg NO x (as N) yr−1. In terms of relative contribution to total European emissions for different pollutants, then NMVOC from forests and vegetation are clearly the most important emissions source. Biogenic NO x emissions (although heavily influenced by nitrogen inputs from anthropogenic activities) are very important if the higher estimates are reliable. CH4 from wetlands and sulphur from volcanoes are also significant emissions in the European budgets. On a global scale, European biogenic emissions are not significant, a consequence of the climate and size (7% of global land area) of Europe and of the destruction of natural ecosystems since prehistoric times. However, for assessing local budgets and for photochemical oxidant modeling, natural/biogenic emissions can play an important role. The most important contributor in this regard is undoubtedly forest VOC emissions, although this paper also indicates that NMVOC emissions from nonforested areas also need to be further evaluated. This paper was originally conceived as a contribution to the collection of papers arising as a result of the Workshop on Biogenic Hydrocarbons in the Atmospheric Boundary Layer, August 24–27, 1997. (Several papers arising from this workshop have been published in Journal of Geophysical Research, 103(D19) 1998.)

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.

Bacterial growth in supercooled cloud droplets

It is well known that the atmosphere is a conveyor of microorganisms, and that bacteria can act as ice or cloud condensation nuclei, but clouds have not been considered as a site where organisms can live and reproduce. Here we show that bacteria in cloud droplets collected at high altitudes are actively growing and reproducing at temperatures at or below 0°C. Since ∼60% of the earth surface is covered by clouds, cloud water should be considered as a microbial habitat.

The contribution of bacteria and fungal spores to the organic carbon content of cloud water, precipitation and aerosols

To estimate the contribution of bacterial and fungal carbon to the carbon content of atmospheric samples, the number concentrations of bacteria and fungal spores in cloud water, snow, rain and aerosol samples collected at a continental background site in the Austrian Alps were determined. Based on these number concentrations, bacterial and fungal carbon was calculated and related to the total carbon (TC) and organic carbon (OC) contents of the samples. In cloud water samples, an average of4.5 x 10 3 spores ml -1 was found, which corresponds to 1.5% of OC. The average bacterial abundance was 2.0 × 10 4 cells ml -1 corresponding to 0.01% ofOC. In snow samples, the average concentrations of bacteria and fungi were 3.1 x 10 3 cells ml -1 corresponding to 0.015% of TC and 6.2 x 10 2 spores ml -1 corresponding to 1.8% of TC, respectively. In aerosol samples, average concentration of bacteria amounted to 1.2 x 10 4 cells m -3 , which corresponds to 0.03% of OC, while fungal concentrations averaged to 7.3 x 10 2 spores m -3 3 or 0.9% ofOC. As fungal spores occur predominantly in the size range > 2.1 μm aerodynamic equivalent diameter (a.e.d.), their contribution to the coarse size fraction (2.1-10 μm) was investigated and amounted up to 9.9% ofOC.

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.

Aerosol chemical characteristics of a mega-city in Southeast Asia (Dhaka–Bangladesh)

Elemental carbon (EC), organic carbon (OC), organic acids, major inorganic ions and trace elements were determined in aerosol samples collected under pre-monsoon conditions (March–April 2001) in Dhaka (Bangladesh). Using the Fe content of the aerosol to reconstruct the aerosol mass from soil-type mineralic material, a mass balance of the Dhaka aerosol was achieved. From this follows that on the average around 76% of the aerosol is from soil-type material, around 18% of carbonaceous material, and around 6% soluble ions and trace elements (without iron) o0.3%. Enrichment factors (Fe as a reference element) indicated that coal fly ash is a likely main source for Cd, Pb and Zn in the Dhaka aerosol, while As appears to be of geogenic origin. Organic acids contributed only 0.72% C to OC and were much less abundant relative to OC than at European sites. The trace elements levels in Dhaka were much lower than at comparable Southeast Asian mega-cities (e.g. Lahore, Pakistan), but considerably higher than reported for European and US cities under present day conditions. The correlation between EC and OC was quite high (R 2 ¼ 0:81) indicating a potential joint source of emission for carbonaceous aerosols. The EC/total carbon (TC) and K/EC ratios indicated that biomass combustion was not a main contributor to EC in Dhaka, which implicates that fossil fuel combustion is the major contributor to EC levels in the Dhaka aerosol. The differences in the EC/TC and K/EC ratios in the three mega-cities in Southeast Asia (data available from Dhaka, Bangladesh; Lahore, Pakistan; and Mumbai, India) indicate that the aerosol source mix in Southeast Asian cities varies considerably at a national or even regional scale.

A Critical Evaluation of Interlaboratory Data on Total, Elemental, and Isotopic Carbon in the Carbonaceous Particle Reference Material, NIST SRM 1649a

Because of increased interest in the marine and atmospheric sciences in elemental carbon (EC), or black carbon (BC) or soot carbon (SC), and because of the difficulties in analyzing or even defining this pervasive component of particulate carbon, it has become quite important to have appropriate reference materials for intercomparison and quality control. The NIST “urban dust” Standard Reference Material® SRM 1649a is useful in this respect, in part because it comprises a considerable array of inorganic and organic species, and because it exhibits a large degree of (14C) isotopic heterogeneity, with biomass carbon source contributions ranging from about 2 % (essentially fossil aliphatic fraction) to about 32 % (polar fraction). A primary purpose of this report is to provide documentation for the new isotopic and chemical particulate carbon data for the most recent (31 Jan. 2001) SRM 1649a Certificate of Analysis. Supporting this is a critical review of underlying international intercomparison data and methodologies, provided by 18 teams of analytical experts from 11 institutions. Key results of the intercomparison are: (1) a new, Certified Value for total carbon (TC) in SRM 1649a; (2) 14C Reference Values for total carbon and a number of organic species, including for the first time 8 individual PAHs; and (3) elemental carbon (EC) Information Values derived from 13 analytical methods applied to this component. Results for elemental carbon, which comprised a special focus of the intercomparison, were quite diverse, reflecting the confounding of methodological-matrix artifacts, and methods that tended to probe more or less refractory regions of this universal, but ill-defined product of incomplete combustion. Availability of both chemical and 14C speciation data for SRM 1649a holds great promise for improved analytical insight through comparative analysis (e.g., fossil/biomass partition in EC compared to PAH), and through application of the principle of isotopic mass balance.

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.