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A unique data set derived from remote sensing, airborne, and ground-based in situ measurements is presented. This measurement report highlights the known complexity of comparing multiple aerosol optical parameters examined with different approaches considering different states of humidification and atmospheric aerosol concentrations. Mie-theory-based modeled aerosol optical properties are compared with the respective results of airborne and ground-based in situ measurements and remote sensing (lidar and photometer) performed at the rural central European observatory at Melpitz, Germany. Calculated extinction-to-backscatter ratios (lidar ratios) were in the range of previously reported values. However, the lidar ratio is a function of the aerosol type and the relative humidity. The particle lidar ratio (LR) dependence on relative humidity was quantified and followed the trend found in previous studies. We present a fit function for the lidar wavelengths of 355, 532, and 1064 nm with an underlying equation of fLR(RH, γ(λ))=fLR(RH=0,λ)×(1-RH)-γ(λ), with the derived estimates of γ(355 nm) = 0.29 (±0.01), γ(532 nm) = 0.48 (±0.01), and γ(1064 nm) = 0.31 (±0.01) for central European aerosol. This parameterization might be used in the data analysis of elastic-backscatter lidar observations or lidar-ratio-based aerosol typing efforts. Our study shows that the used aerosol model could reproduce the in situ measurements of the aerosol particle light extinction coefficients (measured at dry conditions) within 13 %. Although the model reproduced the in situ measured aerosol particle light absorption coefficients within a reasonable range, we identified many sources for significant uncertainties in the simulations, such as the unknown aerosol mixing state, brown carbon (organic material) fraction, and the unknown aerosol mixing state wavelength-dependent refractive index. The modeled ambient-state aerosol particle light extinction and backscatter coefficients were smaller than the measured ones. However, depending on the prevailing aerosol conditions, an overlap of the uncertainty ranges of both approaches was achieved.

An upgraded monitor for aerosols and gases in ambient air (MARGA) was applied for one year at the Central European TROPOS research site Melpitz investigating the gas- and particle-phase partitionin...

Trans-boundary PM10 transport into eastern Germany was quantified by comparing mean PM10 concentrations during western and eastern air mass inflow under similar meteorological conditions and calculating an “increment East” as a proxy for the trans-boundary PM10 fraction. Data of 10 measurement stations located in Berlin, Brandenburg, Mecklenburg-Western Pomerania and Saxony were used for winter 2016/17 and revealed trans-boundary PM10 increments of 0–30 μg m−3 on average, depending on meteorological conditions. On average over all days with positive increments, trans-boundary transport contributed 13 μg m−3 or 44% to the total PM10 concentration in the regional background. During pollution periods with elevated PM10 concentrations of >30 μg m−3 at rural background sites, this contribution lied between 44 and 62%, while it decreased to about 20% for moderate PM10 concentrations between 20 and 30 μg m−3 and was negligible for PM10 concentrations 80% of the trans-boundary PM10 fraction imported from eastern neighbouring countries can be explained by combustion emissions and formation of secondary particle mass, i.e. ammonium sulfate and organic matter, with the latter typically exceeding the contributions from combustion. Source contributions of these two PMF factors within the increment East were correlated, indicating combustion-related emissions of SO2 and volatile organic compounds leading to the observed secondary trans-boundary PM10 mass. Higher increment East values for cold than for warm days imply emissions from domestic heating in eastern European countries, presumably from the combustion of solid fuels such as wood and coal, as the dominant source for trans-boundary PM10 in eastern Germany. A case study for a traffic-impacted pollution hotspot in the city of Berlin showed an average contribution of about 30% from trans-boundary transport, while regional background, urban background and local traffic emissions explained about 40, 10, and 20% of PM10 mass concentrations during days with eastern air mass inflow where the increment East approach could be applied together with the incremental Lenschow approach. The results of this study reinforce the need of PM10 mitigation measures at different spatial scales, ranging from municipal to international levels.

To characterize the role of dew water for the ground surface HONO distribution, nitrous acid (HONO) measurements with a Monitor for AeRosols and Gases in ambient Air (MARGA) and a LOng Path Absorption Photometer (LOPAP) instrument were performed at the Leibniz Institute for Tropospheric Research (TROPOS) research site in Melpitz, Germany, from 19 to 29 April 2018. The dew water was also collected and analyzed from 8 to 14 May 2019 using a glass sampler. The high time resolution of HONO measurements showed characteristic diurnal variations that revealed that (i) vehicle emissions are a minor source of HONO at Melpitz station; (ii) the heterogeneous conversion of NO2 to HONO on the ground surface dominates HONO production at night; (iii) there is significant nighttime loss of HONO with a sink strength of 0.16±0.12 ppbv h−1; and (iv) dew water with mean NO2- of 7.91±2.14 µg m−2 could serve as a temporary HONO source in the morning when the dew droplets evaporate. The nocturnal observations of HONO and NO2 allowed the direct evaluation of the ground uptake coefficients for these species at night: γNO2→HONO=2.4×10-7 to 3.5×10-6, γHONO,ground=1.7×10-5 to 2.8×10-4. A chemical model demonstrated that HONO deposition to the ground surface at night was 90 %–100 % of the calculated unknown HONO source in the morning. These results suggest that dew water on the ground surface was controlling the temporal HONO distribution rather than straightforward NO2–HONO conversion. This can strongly enhance the OH reactivity throughout the morning time or in other planted areas that provide a large amount of ground surface based on the OH production rate calculation.

Size-resolved trace metal concentrations at four sites in Leipzig (Germany) and its surrounding were assessed between the winter of 2013 and the summer of 2015. The measurements were performed in parallel at; traffic dominated (Leipzig – Mitte, LMI), traffic and residential dominated (Eisenbahnstrasse, EIB), urban background (TROPOS, TRO) and regional background (Melpitz, MEL) sites. In total, 19 trace metals, i.e. K, Ca, Ti, Mn, Fe, Cu, Zn, As, Se, Ba, V, Pb, Ni, Cr, Sr, Sn, Sb, Co and Rb were analysed using total reflection x-ray fluorescence (TXRF). The major metals were Fe, K and Ca with concentrations ranging between; 31–440 ng/m3, 42–153 ng/m3 and 24–322 ng/m3, respectively, while the trace metals with the lowest concentrations were Co, Rb and Se with concentrations of; Traffic at LMI contributed to about 75% of Cr, Ba, Cu, Sb, Sn, Ca, Co, Mn, Fe and Ti concentrations while regional activities contributed to more than 70% of K, Rb, Pb, Se, As and V concentrations. Traffic dominated trace metals were often observed in the coarse mode while the regional background dominated trace metals were often observed in the fine mode. Trace metal sources were related to crustal matter and road dust re-suspension for metals such as Ca, Fe, Co, Sr, and Ti, brake and tire wear (Cu, Sb, Ba, Fe, Zn, Pb), biomass burning (K, Rb), oil and coal combustion (V, Zn, As, Pb). Crustal matter contributed 5–12% in winter and 8–19% in summer of the PM10 mass. Using Cu and Zn as markers for brake and tire wear, respectively, the estimated brake and tire wear contributions to the PM10 mass were 0.1–0.8% and 1.7–2.9%, respectively. The higher contributions were observed at the traffic sites while the lower contributions were observed at the regional background site. In total, non-exhaust emissions could account for about 10–22% of the PM10 mass in the summer and about 7–15% of the PM10 mass in the winter.

The heterogeneous hydrolysis of N2O5 on the surface of deliquescent aerosol leads to HNO3 formation and acts as a major sink of NOx in the atmosphere during night-time. The reaction constant of this heterogeneous hydrolysis is determined by temperature (T), relative humidity (RH), aerosol particle composition, and the surface area concentration (S). However, these parameters were not comprehensively considered in the parameterization of the heterogeneous hydrolysis of N2O5 in previous mass-based 3-D aerosol modelling studies. In this investigation, we propose a sophisticated parameterization (NewN2O5) of N2O5 heterogeneous hydrolysis with respect to T, RH, aerosol particle compositions, and S based on laboratory experiments. We evaluated closure between NewN2O5 and a state-of-the-art parameterization based on a sectional aerosol treatment. The comparison showed a good linear relationship (R = 0.91) between these two parameterizations. NewN2O5 was incorporated into a 3-D fully online coupled model, COSMO–MUSCAT, with the mass-based aerosol treatment. As a case study, we used the data from the HOPE Melpitz campaign (10–25 September 2013) to validate model performance. Here, we investigated the improvement of nitrate prediction over western and central Europe. The modelled particulate nitrate mass concentrations ([NO3−]) were validated by filter measurements over Germany (Neuglobsow, Schmücke, Zingst, and Melpitz). The modelled [NO3−] was significantly overestimated for this period by a factor of 5–19, with the corrected NH3 emissions (reduced by 50 %) and the original parameterization of N2O5 heterogeneous hydrolysis. The NewN2O5 significantly reduces the overestimation of [NO3−] by ∼ 35 %. Particularly, the overestimation factor was reduced to approximately 1.4 in our case study (12, 17–18 and 25 September 2013) when [NO3−] was dominated by local chemical formations. In our case, the suppression of organic coating was negligible over western and central Europe, with an influence on [NO3−] of less than 2 % on average and 20 % at the most significant moment. To obtain a significant impact of the organic coating effect, N2O5, SOA, and NH3 need to be present when RH is high and T is low. However, those conditions were rarely fulfilled simultaneously over western and central Europe. Hence, the organic coating effect on the reaction probability of N2O5 may not be as significant as expected over western and central Europe.

Particulate emissions from crop residue burning decrease the air quality as well as influence aerosol radiative properties on a regional scale. The North China Plain (NCP) is known for the large scale biomass burning (BB) of field residues, which often results in heavy haze pollution episodes across the region. We have been able to capture a unique BB episode during the international CAREBeijing-NCP intensive field campaign in Wangdu in the NCP (38.6°N, 115.2°E) from June to July 2014. It was found that aerosol particles originating from this BB event showed a significantly different mixing state compared with clean and non-BB pollution episodes. BB originated particles showed a narrower probability density function (PDF) of shrink factor (SF). And the maximum was found at shrink factor of 0.6, which is higher than in other episodes. The non-volatile particle number fraction during the BB episode decreased to 3% and was the lowest measured value compared to all other predefined episodes. To evaluate the influence of particle mixing state on aerosol single scattering albedo (SSA), SSA at different RHs was simulated using the measured aerosol physical-chemical properties. The differences between the calculated SSA for biomass burning, clean and pollution episodes are significant, meaning that the variation of SSA in different pollution conditions needs to be considered in the evaluation of aerosol direct radiative effects in the NCP. And the calculated SSA was found to be quite sensitive on the mixing state of BC, especially at low-RH condition. The simulated SSA was also compared with the measured values. For all the three predefined episodes, the measured SSA are very close to the calculated ones with assumed mixing states of homogeneously internal and core-shell internal mixing, indicating that both of the conception models are appropriate for the calculation of ambient SSA in the NCP.

Long-term measurements of particle number size distributions in combination with thermodenuder analysis have been performed since July 2003 at the Central European station of Melpitz, Germany. Up to the end of 2011, 20% of all investigated days during the 8.5 years of measurements showed new particle formation and subsequent growth. To investigate the role of various chemical compound candidates for condensational nanoparticle growth, we focused on nucleation events in which the measured size distributions with and without thermodesorption both showed growth patterns (accounting for up to ~85% of all nucleation events). In this study, particulate compounds that volatilize at 300°C were specifically defined as “volatile,” in contrast to “nonvolatile” compounds, which remain in the particulate phase after being heated to 300°C. A strong correlation between ambient temperature and growth rate associated with volatile substances (except gaseous sulfuric acid) was found, which implies the importance of organics (possibly oxidized biogenic organic compounds) in particle growth at Melpitz. The contributions of the volatile compounds to the growth rate due to condensation of gaseous sulfuric acid and organics were found to be about 19% and 47%, respectively. The remaining ~25% was attributed to nonvolatile residuals, which appear to form gradually during the particle growth process and are characterized as extremely low-volatility compounds. The growth rate associated with volatile components exhibited significant seasonal variation, with the highest value during summertime, whereas the growth rate associated with the nonvolatile fraction showed less fluctuation.

A reliable assessment of the optical properties of atmospheric black carbon is of crucial importance for an accurate estimation of radiative forcing. In this study we investigated the spatio-temporal variability of the mass absorption cross-section (MAC) of atmospheric black carbon, defined as light absorption coefficient (σap) divided by elemental carbon mass concentration (mEC). σap and mEC have been monitored at supersites of the ACTRIS network for a minimum period of one year. The 9 rural background sites considered in this study cover southern Scandinavia, central Europe and the Mediterranean. σap was determined using filter based absorption photometers and mEC using a thermal-optical technique. Homogeneity of the data-set was ensured by harmonization of all involved methods and instruments during extensive intercomparison exercises at the European Center for Aerosol Calibration (ECAC). Annual mean values of σap at a wavelength of 637 nm vary between 0.66 and 1.3 Mm−1 in southern Scandinavia, 3.7–11 Mm−1 in Central Europe and the British Isles, and 2.3–2.8 Mm−1 in the Mediterranean. Annual mean values of mEC vary between 0.084 and 0.23 μg m−3 in southern Scandinavia, 0.28–1.1 in Central Europe and the British Isles, and 0.22–0.26 in the Mediterranean. Both σap and mEC in southern Scandinavia and Central Europe have a distinct seasonality with maxima during the cold season and minima during summer, whereas at the Mediterranean sites an opposite trend was observed. Annual mean MAC values were quite similar across all sites and the seasonal variability was small at most sites. Consequently, a MAC value of 10.0 m2 g−1 (geometric standard deviation = 1.33) at a wavelength of 637 nm can be considered to be representative of the mixed boundary layer at European background sites, where BC is expected to be internally mixed to a large extent. The observed spatial variability is rather small compared to the variability of values in previous literature, indicating that the harmonization efforts resulted in substantially increased precision of the reported MAC. However, absolute uncertainties of the reported MAC values remain as high as ± 30–70% due to the lack of appropriate reference methods and calibration materials. The mass ratio between elemental carbon and non-light-absorbing matter was used as a proxy for the thickness of coatings around the BC cores, in order to assess the influence of the mixing state on the MAC of BC. Indeed, the MAC was found to increase with increasing values of the coating thickness proxy. This provides evidence that coatings do increase the MAC of atmospheric BC to some extent, which is commonly referred to as lensing effect. © 2016 The Authors, The research leading to these results has received funding from the European Union Seventh Framework Programme (ACTRIS, FP7/2007-2013, grant agreement no. 262254 ). ACTRIS-2 is a European Project supported by the European Commission Horizon 2020 Research and Innovation Framework Programme (ACTRIS-2, H2020-INFRAIA-2014-2015, grant agreement no. 654109 ). This work was also supported by grants from Labex OSUG@2020 (PhD investissements d'avenir – ANR10 LABX56) and from the European Research Council (ERC-CoG 615922-BLACARAT). Appendix A.

Carbonaceous aerosol (total carbon, TCp) was source apportioned at nine European rural background sites, as part of the European Measurement and Evaluation Programme (EMEP) Intensive Measurement Periods in fall 2008 and winter/spring 2009. Five predefined fractions were apportioned based on ambient measurements: elemental and organic carbon, from combustion of biomass (ECbb and OCbb) and from fossil-fuel (ECff and OCff) sources, and remaining non-fossil organic carbon (OCrnf), dominated by natural sources. OCrnf made a larger contribution to TCp than anthropogenic sources (ECbb, OCbb, ECff, and OCff) at four out of nine sites in fall, reflecting the vegetative season, whereas anthropogenic sources dominated at all but one site in winter/spring. Biomass burning (OCbb + ECbb) was the major anthropogenic source at the central European sites in fall, whereas fossil-fuel (OCff + ECff) sources dominated at the southernmost and the two northernmost sites. Residential wood burning emissions explained 30 %–50 % of TCp at most sites in the first week of sampling in fall, showing that this source can be the dominant one, even outside the heating season. In winter/spring, biomass burning was the major anthropogenic source at all but two sites, reflecting increased residential wood burning emissions in the heating season. Fossil-fuel sources dominated EC at all sites in fall, whereas there was a shift towards biomass burning for the southernmost sites in winter/spring. Model calculations based on base-case emissions (mainly officially reported national emissions) strongly underpredicted observational derived levels of OCbb and ECbb outside Scandinavia. Emissions based on a consistent bottom-up inventory for residential wood burning (and including intermediate volatility compounds, IVOCs) improved model results compared to the base-case emissions, but modeled levels were still substantially underestimated compared to observational derived OCbb and ECbb levels at the southernmost sites. Our study shows that natural sources are a major contributor to carbonaceous aerosol in Europe, even in fall and in winter/spring, and that residential wood burning emissions are equally as large as or larger than that of fossil-fuel sources, depending on season and region. The poorly constrained residential wood burning emissions for large parts of Europe show the obvious need to improve emission inventories, with harmonization of emission factors between countries likely being the most important step to improve model calculations for biomass burning emissions, and European PM2.5 concentrations in general.

This work reports the first statistical analysis of multi-annual data on tropospheric aerosols from the German Ultrafine Aerosol Network (GUAN). Compared to other networks worldwide, GUAN with 17 measurement locations has the most sites equipped with particle number size distribution (PNSD) and equivalent black carbon (eBC) instruments and the most site categories in Germany ranging from city street/roadside to High Alpine. As we know, the variations of eBC and particle number concentration (PNC) are influenced by several factors such as source, transformation, transport and deposition. The dominant controlling factor for different pollutant parameters might be varied, leading to the different spatio-temporal variations among the measured parameters. Currently, a study of spatio-temporal variations of PNSD and eBC considering the influences of both site categories and spatial scale is still missing. Based on the multi-site dataset of GUAN, the goal of this study is to investigate how pollutant parameters may interfere with spatial characteristics and site categories.

The carbonaceous aerosol accounts for an important part of total aerosol mass, affects human health and climate through its effects on physical and chemical properties of the aerosol, yet the understanding of its atmospheric sources and sinks is still incomplete. This study shows the state-of-the-art in modelling carbonaceous aerosol over Europe by comparing simulations performed with seven chemical transport models (CTMs) currently in air quality assessments in Europe: CAMx, CHIMERE, CMAQ, EMEP/MSC-W, LOTOS-EUROS, MINNI and RCGC. The simulations were carried out in the framework of the EURODELTA III modelling exercise and were evaluated against field measurements from intensive campaigns of European Monitoring and Evaluation Programme (EMEP) and the European Integrated Project on Aerosol Cloud Climate and Air Quality Interactions (EUCAARI). Model simulations were performed over the same domain, using as much as possible the same input data and covering four seasons: summer (1–30 June 2006), winter (8 January – 4 February 2007), autumn (17 September- 15 October 2008) and spring (25 February - 26 March 2009). The analyses of models’ performances in prediction of elemental carbon (EC) for the four seasons and organic aerosol components (OA) for the last two seasons show that all models generally underestimate the measured concentrations. The maximum underestimation of EC is about 60% and up to about 80% for total organic matter (TOM). The underestimation of TOM outside of highly polluted area is a consequence of an underestimation of secondary organic aerosol (SOA), in particular of its main contributor: biogenic secondary aerosol (BSOA). This result is independent on the SOA modelling approach used and season. The concentrations and daily cycles of total primary organic matter (TPOM) are generally better reproduced by the models since they used the same anthropogenic emissions. However, the combination of emissions and model formulation leads to overestimate TPOM concentrations in 2009 for most of the models. All models capture relatively well the SOA daily cycles at rural stations mainly due to the spatial resolution used in the simulations. For the investigated carbonaceous aerosol compounds, the differences between the concentrations simulated by different models are lower than the differences between the concentrations simulated with a model for different seasons. Keywords: Elemental carbon, Organic aerosol, Secondary organic aerosol, Model validation, Model inter-comparison

The mass loading and composition of atmospheric particles are important in determining their climate and health effects, and are typically measured by filter sampling. However, particle sampling under ambient conditions can lead to a shift in the size cut-off threshold induced by hygroscopic growth, and the influence of this on measurement of particle loading and composition has not been adequately quantified. Here, we propose a method to assess this influence based on κ-Köhler theory. A global perspective is presented based on previously reported annual climatological values of hygroscopic properties, meteorological parameters and particle volume size distributions. Measurements at background sites in Europe may be more greatly influenced by the cut-off shift than those from other continents, with a median influence of 10–20% on the total mass of sampled particles. However, the influence is generally much smaller (

Sea salt aerosol (SSA) is one of the major components of primary aerosols and has significant impact on the formation of secondary inorganic particles mass on a global scale. In this study, the fully online coupled WRF-Chem model was utilized to evaluate the SSA emission scheme and its influence on the nitrate simulation in a case study in Europe during 10–20 September 2013. Meteorological conditions near the surface, wind pattern and thermal stratification structure were well reproduced by the model. Nonetheless, the coarse-mode (PM1 − 10) particle mass concentration was substantially overestimated due to the overestimation of SSA and nitrate. Compared to filter measurements at four EMEP stations (coastal stations: Bilthoven, Kollumerwaard and Vredepeel; inland station: Melpitz), the model overestimated SSA concentrations by a factor of 8–20. We found that this overestimation was mainly caused by overestimated SSA emissions over the North Sea during 16–20 September. Over the coastal regions, SSA was injected into the continental free troposphere through an “aloft bridge” (about 500 to 1000 m above the ground), a result of the different thermodynamic properties and planetary boundary layer (PBL) structure between continental and marine regions. The injected SSA was further transported inland and mixed downward to the surface through downdraft and PBL turbulence. This process extended the influence of SSA to a larger downwind region, leading, for example, to an overestimation of SSA at Melpitz, Germany, by a factor of ∼ 20. As a result, the nitrate partitioning fraction (ratio between particulate nitrate and the summation of particulate nitrate and gas-phase nitric acid) increased by about 20 % for the coarse-mode nitrate due to the overestimation of SSA at Melpitz. However, no significant difference in the partitioning fraction for the fine-mode nitrate was found. About 140 % overestimation of the coarse-mode nitrate resulted from the influence of SSA at Melpitz. In contrast, the overestimation of SSA inhibited the nitrate particle formation in the fine mode by about 20 % because of the increased consumption of precursor by coarse-mode nitrate formation.

Cloud water samples were taken in September/October 2010 at Mt. Schmücke in a rural, forested area in Germany during the Lagrange-type Hill Cap Cloud Thuringia 2010 (HCCT-2010) cloud experiment. Besides bulk collectors, a three-stage and a five-stage collector were applied and samples were analysed for inorganic ions (SO42−,NO3−, NH4+, Cl−, Na+, Mg2+, Ca2+, K+), H2O2 (aq), S(IV), and dissolved organic carbon (DOC). Campaign volume-weighted mean concentrations were 191, 142, and 39 µmol L−1 for ammonium, nitrate, and sulfate respectively, between 4 and 27 µmol L−1 for minor ions, 5.4 µmol L−1 for H2O2 (aq), 1.9 µmol L−1 for S(IV), and 3.9 mgC L−1 for DOC. The concentrations compare well to more recent European cloud water data from similar sites. On a mass basis, organic material (as DOC × 1.8) contributed 20–40 % (event means) to total solute concentrations and was found to have non-negligible impact on cloud water acidity. Relative standard deviations of major ions were 60–66 % for solute concentrations and 52–80 % for cloud water loadings (CWLs). The similar variability of solute concentrations and CWLs together with the results of back-trajectory analysis and principal component analysis, suggests that concentrations in incoming air masses (i.e. air mass history), rather than cloud liquid water content (LWC), were the main factor controlling bulk solute concentrations for the cloud studied. Droplet effective radius was found to be a somewhat better predictor for cloud water total ionic content (TIC) than LWC, even though no single explanatory variable can fully describe TIC (or solute concentration) variations in a simple functional relation due to the complex processes involved. Bulk concentrations typically agreed within a factor of 2 with co-located measurements of residual particle concentrations sampled by a counterflow virtual impactor (CVI) and analysed by an aerosol mass spectrometer (AMS), with the deviations being mainly caused by systematic differences and limitations of the approaches (such as outgassing of dissolved gases during residual particle sampling). Scavenging efficiencies (SEs) of aerosol constituents were 0.56–0.94, 0.79–0.99, 0.71–98, and 0.67–0.92 for SO42−, NO3−, NH4+, and DOC respectively when calculated as event means with in-cloud data only. SEs estimated using data from an upwind site were substantially different in many cases, revealing the impact of gas-phase uptake (for volatile constituents) and mass losses across Mt. Schmücke likely due to physical processes such as droplet scavenging by trees and/or entrainment. Drop size-resolved cloud water concentrations of major ions SO42−, NO3−, and NH4+ revealed two main profiles: decreasing concentrations with increasing droplet size and “U” shapes. In contrast, profiles of typical coarse particle mode minor ions were often increasing with increasing drop size, highlighting the importance of a species' particle concentration size distribution for the development of size-resolved solute concentration patterns. Concentration differences between droplet size classes were typically < 2 for major ions from the three-stage collector and somewhat more pronounced from the five-stage collector, while they were much larger for minor ions. Due to a better separation of droplet populations, the five-stage collector was capable of resolving some features of solute size dependencies not seen in the three-stage data, especially sharp concentration increases (up to a factor of 5–10) in the smallest droplets for many solutes.

Elemental Carbon (EC) has a significant impact on human health and climate change. In order to evaluate the size segregation of EC emission in the EUCAARI inventory and investigate its influence on the simulation of EC long-range transportation in Europe, we used the fully coupled online Weather Research and Forecasting/Chemistry model (WRF-Chem) at a resolution of 2 km focusing on a region in Germany, in conjunction with a high-resolution EC emission inventory. The ground meteorology conditions, vertical structure and wind pattern were well reproduced by the model. The simulations of particle number and/or mass size distributions were evaluated with observations at the central European background site Melpitz. The fine mode particle concentration was reasonably well simulated, but the coarse mode was substantially overestimated by the model mainly due to the plume with high EC concentration in coarse mode emitted by a nearby point source. The comparisons between simulated EC and Multi-angle Absorption Photometers (MAAP) measurements at Melpitz, Leipzig-TROPOS and Bösel indicated that the coarse mode EC (ECc) emitted from the nearby point sources might be overestimated by a factor of 2–10. The fraction of ECc was overestimated in the emission inventory by about 10–30 % for Russia and 5–10 % for Eastern Europe (e.g., Poland and Belarus). This incorrect size-dependent EC emission results in a shorter atmospheric life time of EC particles and inhibits the long-range transport of EC. A case study showed that this effect caused an underestimation of 20–40 % in the EC mass concentration in Germany under eastern wind pattern.

Sources of elemental carbon (EC) and organic carbon (OC) in atmospheric aerosols (carbonaceous aerosols) were investigated by collection of weekly aerosol filter samples at six background sites in Northern Europe (Birkenes, Norway; Vavihill, Sweden; Risoe, Denmark; Cabauw and Rotterdam in The Netherlands; Melpitz, Germany) during winter 2013. Analysis of 14C and a set of molecular tracers were used to constrain the sources of EC and OC. During the four-week campaign, most sites (in particular those in Germany and The Netherlands) were affected by an episode during the first two weeks with high concentrations of aerosol, as continental air masses were transported westward. The analysis results showed a clear, increasing north to south gradient for most molecular tracers. Total carbon (TC = OC + EC) at Birkenes showed an average concentration of 0.5 ± 0.3 μg C m−3, whereas the average concentration at Melpitz was 6.0 ± 4.3 μg C m−3. One weekly mean TC concentration as high as 11 μg C m−3 was observed at Melpitz. Average levoglucosan concentrations varied by an order of magnitude from 25 ± 13 ng m−3 (Birkenes) to 249 ± 13 ng m−3 (Melpitz), while concentrations of tracers of fungal spores (arabitol and mannitol) and vegetative debris (cellulose) were very low, showing a minor influence of primary biological aerosol particles during the North European winter. The fraction of modern carbon generally varied from 0.57 (Melpitz) to 0.91 (Birkenes), showing an opposite trend compared to the molecular tracers and TC. Total concentrations of 10 biogenic and anthropogenic carboxylic acids, mainly of secondary origin, were 4–53 ng m−3, with the lowest concentrations observed at Birkenes and the highest at Melpitz. However, the highest relative concentrations of carboxylic acids (normalized to TC) were observed at the most northern sites. Levels of organosulphates and nitrooxy organosulphates varied more than two orders of magnitude, from 2 to 414 ng m−3, between individual sites and samples. The three sites Melpitz, Rotterdam and Cabauw, located closest to source regions in continental Europe, showed very high levels of organosulphates and nitrooxy organosulphates (up to 414 ng m−3) during the first two weeks of the study, while low levels (40% of TC), while use and combustion of fossil fuels was the second most important source. Furthermore, EC from biomass burning accounted for 7–16% of TC, whereas EC from fossil sources contributed to

An hourly quantification of inorganic water-soluble PM10 ions and corresponding trace gases was performed using the Monitor for AeRosols and Gases in ambient Air (MARGA) at the TROPOS research site in Melpitz, Germany. The data availability amounts to over 80% for the five-year measurement period from 2010 to 2014. Comparisons were performed for the evaluation of the MARGA, resulting in coefficients of determinations (slopes) of 0.91 (0.90) for the measurements against the SO2 gas monitor, 0.84 (0.88), 0.79 (1.39), 0.85 (1.20) for the ACSM NO3 −, SO4 2− and NH4 + measurements, respectively, and 0.85 (0.65), 0.88 (0.68), 0.91 (0.83), 0.86 (0.82) for the filter measurements of Cl−, NO3 −, SO4 2− and NH4 +, respectively. A HONO comparison with a batch denuder shows large scatter (R2 = 0.41). The MARGA HNO3 is underestimated compared to a batch and coated denuder with shorter inlets (slopes of 0.16 and 0.08, respectively). Less NH3 was observed in coated denuders for high ambient concentrations. Long-time measurements show clear daily and seasonal variabilities. Potential Source Contribution Function (PSCF) analysis indicates the emission area of particulate ions Cl−, NO3 −, SO4 2−, NH4 +, K+ and gaseous SO2 to lie in eastern European countries, predominantly in wintertime. Coarse mode sea salt particles are transported from the North Sea to Melpitz. The particles at Melpitz are nearly neutralised with a mean molar ratio of 0.90 for the five-year study. A slight increase of the neutralization ratio over the last three years indicates a stronger decrease of the anthropogenically emitted NO3 − and SO4 2− compared to NH4 +.

In the fine-particle mode (aerodynamic diameter < 1 μm) non-volatile material has been associated with black carbon (BC) and low-volatile organics and, to a lesser extent, with sea salt and mineral dust. This work analyzes non-volatile particles at the tropospheric research station Melpitz (Germany), combining experimental methods such as a mobility particle-size spectrometer (3–800 nm), a thermodenuder operating at 300 °C, a multi-angle absorption photometer (MAAP), and an aerosol mass spectrometer (AMS). The data were collected during two atmospheric field experiments in May–June 2008 as well as February–March 2009. As a basic result, we detected average non-volatile particle–volume fractions of 11 ± 3% (2008) and 17 ± 8% (2009). In both periods, BC was in close linear correlation with the non-volatile fraction, but not sufficient to quantitatively explain the non-volatile particle mass concentration. Based on the assumption that BC is not altered by the heating process, the non-volatile particle mass fraction could be explained by the sum of black carbon (47% in summer, 59% in winter) and a non-volatile organic contribution estimated as part of the low-volatility oxygenated organic aerosol (LV-OOA) (53% in summer, 41% in winter); the latter was identified from AMS data by factor analysis. Our results suggest that LV-OOA was more volatile in summer (May–June 2008) than in winter (February–March 2009) which was linked to a difference in oxidation levels (lower in summer). Although carbonaceous compounds dominated the sub-μm non-volatile particle mass fraction most of the time, a cross-sensitivity to partially volatile aerosol particles of maritime origin could be seen. These marine particles could be distinguished, however from the carbonaceous particles by a characteristic particle volume–size distribution. The paper discusses the uncertainty of the volatility measurements and outlines the possible merits of volatility analysis as part of continuous atmospheric aerosol measurements., Atmospheric Chemistry and Physics, 14 (18), ISSN:1680-7375, ISSN:1680-7367

Hygroscopic growth of aerosol particles is of significant importance in quantifying the aerosol radiative effect in the atmosphere. In this study, hygroscopic properties of ambient particles are investigated based on particle chemical composition at a suburban site in the North China Plain during the HaChi campaign (Haze in China) in summer 2009. The size-segregated aerosol particulate mass concentration as well as the particle components such as inorganic ions, organic carbon and water-soluble organic carbon (WSOC) are identified from aerosol particle samples collected with a ten-stage impactor. An iterative algorithm is developed to evaluate the hygroscopicity parameter κ from the measured chemical composition of particles. During the HaChi summer campaign, almost half of the mass concentration of particles between 150 nm and 1 μm is contributed by inorganic species. Organic matter (OM) is abundant in ultrafine particles, and 77% of the particulate mass with diameter (Dp) of around 30 nm is composed of OM. A large fraction of coarse particle mass is undetermined and is assumed to be insoluble mineral dust and liquid water. The campaign's average size distribution of κ values shows three distinct modes: a less hygroscopic mode (Dp < 150 nm) with κ slightly above 0.2, a highly hygroscopic mode (150 nm < Dp < 1 μm) with κ greater than 0.3 and a nearly hydrophobic mode (Dp > 1 μm) with κ of about 0.1. The peak of the κ curve appears around 450 nm with a maximum value of 0.35. The derived κ values are consistent with results measured with a high humidity tandem differential mobility analyzer within the size range of 50–250 nm. Inorganics are the predominant species contributing to particle hygroscopicity, especially for particles between 150 nm and 1 μm. For example, NH4NO3, H2SO4, NH4HSO4 and (NH4)2SO4 account for nearly 90% of κ for particles of around 900 nm. For ultrafine particles, WSOC plays a critical role in particle hygroscopicity due to the predominant mass fraction of OM in ultrafine particles. WSOC for particles of around 30 nm contribute 52% of κ. Aerosol hygroscopicity is related to synoptic transport patterns. When southerly wind dominates, particles are more hygroscopic; when northerly wind dominates, particles are less hygroscopic. Aerosol hygroscopicity also has a diurnal variation, which can be explained by the diurnal evolution of planetary boundary layer, photochemical aging processes during daytime and enhanced black carbon emission at night. κ is highly correlated with mass fractions of SO42−, NO3− and NH4+ for all sampled particles as well as with the mass fraction of WSOC for particles of less than 100 nm. A parameterization scheme for κ is developed using mass fractions of SO42−, NO3−, NH4+ and WSOC due to their high correlations with κ, and κ calculated from the parameterization agrees well with κ derived from the particle's chemical composition. Further analysis shows that the parameterization scheme is applicable to other aerosol studies in China.

The influence of aerosol water uptake on the aerosol particle light scattering was examined at the regional continental research site Melpitz, Germany. The scattering enhancement factor f (RH), defined as the aerosol particle scattering coefficient at a certain relative humidity (RH) divided by its dry value, was measured using a humidified nephelometer. The chemical composition and other microphysical properties were measured in parallel. f (RH) showed a strong variation, e.g. with values between 1.2 and 3.6 at RH=85% and λ=550 nm. The chemical composition was found to be the main factor determining the magnitude of f (RH), since the magnitude of f (RH) clearly correlated with the inorganic mass fraction measured by an aerosol mass spectrometer (AMS). Hysteresis within the recorded humidograms was observed and explained by long-range transported sea salt. A closure study using Mie theory showed the consistency of the measured parameters. Keywords: aerosol particle light scattering, hygroscopic growth, scattering enhancement, aerosol mass spectrometer, field measurements, optical closure study (Published: 14 March 2014) Citation: Tellus B 2014, 66 , 22716, http://dx.doi.org/10.3402/tellusb.v66.22716

The complexation of trace metal ions (TMI) was studied in size-segregated ambient aerosol particles collected at nine sites in Germany (urban, rural and coastal). Samples were analysed in terms of TMI (Fe, Mn, Cu), potential inorganic and organic ligands and pH. Using a thermodynamic model (E-AIM III), the concentrations of these compounds in the particle liquid phase were estimated. The resulting liquid phase concentrations were then used as input parameters for a speciation model (Visual MINTEQ) and the equilibrium complexation was calculated under realistic conditions. The complexation was found to be controlled by the availability of strong organic ligands, especially oxalate, whose occurrence in turn was governed by the formation of insoluble Ca-oxalate. Likewise, the pH influenced oxalate availability because it alters the concentrations of the chelating mono- and dianions. As a qualitative result, Fe3+ was found to be mainly complexed by oxalate, while Fe2+ and Mn2+ were rather associated with nitrate. Cu2+ showed mixed organic and nitrate complexation. Complexation by HULIS was only significant for Fe3+ and Cu2+ and was generally less important than other ligands like oxalate and nitrate. Oxalate was found to exist mainly in the solid phase while higher dicarboxylic acids mostly did not form complexes due to protonation. Complexation was shown to be influenced by season, air mass origin, particle size and sampling site.

Particle hygroscopic growth at 90% RH (relative humidity), cloud condensation nuclei (CCN) activity, and size-resolved chemical composition were concurrently measured in the Thüringer Wald mid-level mountain range in central Germany in the fall of 2010. The median hygroscopicity parameter values, κ, of 50, 75, 100, 150, 200, and 250 nm particles derived from hygroscopicity measurements are respectively 0.14, 0.14, 0.17, 0.21, 0.24, and 0.28 during the sampling period. The closure between HTDMA (Hygroscopicity Tandem Differential Mobility Analyzers)-measured (κHTDMA) and chemical composition-derived (κchem) hygroscopicity parameters was performed based on the Zdanovskii–Stokes–Robinson (ZSR) mixing rule. Using size-averaged chemical composition, the κ values are substantially overpredicted (30 and 40% for 150 and 100 nm particles). Introducing size-resolved chemical composition substantially improved closure. We found that the evaporation of NH4NO3, which may happen in a HTDMA system, could lead to a discrepancy in predicted and measured particle hygroscopic growth. The hygroscopic parameter of the organic fraction, κorg, is positively correlated with the O : C ratio (κorg = 0.19 × (O : C) − 0.03). Such correlation is helpful to define the κorg value in the closure study. κ derived from CCN measurement was around 30% (varied with particle diameters) higher than that determined from particle hygroscopic growth measurements (here, hydrophilic mode is considered only). This difference might be explained by the surface tension effects, solution non-ideality, gas-particle partitioning of semivolatile compounds, and the partial solubility of constituents or non-dissolved particle matter. Therefore, extrapolating from HTDMA data to properties at the point of activation should be done with great care. Finally, closure study between CCNc (cloud condensation nucleus counter)-measured (κCCN) and chemical composition (κCCN, chem) was performed using CCNc-derived κ values for individual components. The results show that the κCCN can be well predicted using particle size-resolved chemical composition and the ZSR mixing rule.

To identify current and future human health risks from urban air pollution, size-segregated particle samples were collected under various seasonal and meteorological conditions in Dresden, Germany. Sampling days were grouped into twelve categories depending on season, air mass origin and temperature. A comprehensive chemical characterisation and mass closure were performed. The particulate matter (PM) mass concentration and composition were shown to be highly dependent on these categories. The highest PM mass concentrations were found on cold winter days, mainly due to compounds of anthropogenic origin. The current annual mean PM mass concentration and composition were calculated using the occurrence frequencies of the categories (weighted mean). Information about future changes of the occurrence frequencies of the categories was deduced from climate models. Assuming that PM concentration and composition within a given category do not change, the annual mean PM mass concentration and composition were calculated for two scenarios (weighted mean, 2071–2100). As a result, it was found that the annual mean PM mass concentration is likely to decrease slightly by 2100, mainly due to a decrease of sulphate and soot mass concentrations. Generally, chemicals originating from anthropogenic emissions (PAHs, trace metals) are estimated to decrease. However, it is concluded that emission reduction measures are still necessary to control urban air quality including PM even if climate change will lead to a certain reduction in PM.

Size-segregated high-volume (HV) quartz filter samples were collected daily at the Melpitz rural site in Germany for PM10 (November 1992 until April 2012), and for PM2.5 and PM1 (January 2003 until April 2012, PM1 sampled every sixth day). The samples were analysed for mass concentration (gravimetrically), water-soluble ions (ion-chromatography) and since 2003 for organic carbon (OC) and elemental carbon (EC) (thermography). The long-term measurements first show a decreasing trend for PM10 (1993–2000) followed by a second period (2001–2011) with a mean mass concentration of about 22.4 μgm−3 and an inter-annual variation of about ± 2.9 μgm−3 (13% fluctuation margin). The absolute sulphate and calcium concentration (for the full period), as well as the EC concentration (time after 2003) decrease by about 50, 75 and 30% for PM10, respectively. The nitrate concentration remains constant all the time. For the daily objective weather type classification (OWTC, 1993–2002) the highest PM10 concentration was found for South-East (SE) and the lowest for North-West (NW) wind direction with 44 and 24 μgm−3, respectively. These concentrations decrease for 2003–2011 in comparison to 1993–2002 by about 21% and 26%, respectively. The highest PM10, PM2.5 and PM1 concentrations (2003–2011) were found for SE and the lowest for NW wind direction with about 34 and 17 μgm−3 (PM10), 28 and 19 μgm−3 (PM2.5) and 22 and 11 μgm−3 (PM1), respectively. The relative content of sulphate, OC and EC was the highest for SE wind direction. A differentiation into four categories for winter (Wi) and summer (Su) and air mass inflow from West (W) and East (E) was carried out. The highest PM concentrations were observed for WiE with the highest inter-annual fluctuation. In this category sulphate contents are largest. The lowest concentrations where found for SuW. The means for WiE show the strongest relative decreases, e.g. in PM10 sulphate (1993–2011) and EC (2003–2011) by about 60% and 40%, respectively. Nitrate is an indicator for NOx motor-car emissions. It shows a typical variation with maximum values in the middle of the week, especially for air mass inflow from West. In contrast, chloride mostly originating from sea spray doesn’t show such a concentration pattern. The PM2.5/PM10 as well the PM1/PM10-ratio have the highest median (0.878 and 0.654) during WiE and the lowest (0.718 and 0.578) during SuW, respectively. For the ratio PM2.5/PM10 a slightly increasing trend was found (about 0.71 and 0.83 for 1995 and 2011, respectively). The increase is stronger in summer than in winter.

The third intensive measurement period (IMP) organised by the European Monitoring and Evaluation Programme (EMEP) under the UNECE CLTRAP took place in summer 2012 and winter 2013, with PM10 filter samples concurrently collected at 20 (16 EMEP) regional background sites across Europe for subsequent analysis of their mineral dust content. All samples were analysed by the same or a comparable methodology. Higher PM10 mineral dust loadings were observed at most sites in summer (0.5–10 µg m−3) compared to winter (0.2–2 µg m−3), with the most elevated concentrations in the southern- and easternmost countries, accounting for 20–40 % of PM10. Saharan dust outbreaks were responsible for the high summer dust loadings at western and central European sites, whereas regional or local sources explained the elevated concentrations observed at eastern sites. The eastern Mediterranean sites experienced elevated levels due to African dust outbreaks during both summer and winter. The mineral dust composition varied more in winter than in summer, with a higher relative contribution of anthropogenic dust during the former period. A relatively high contribution of K from non-mineral and non-sea-salt sources, such as biomass burning, was evident in winter at some of the central and eastern European sites. The spatial distribution of some components and metals reveals the influence of specific anthropogenic sources on a regional scale: shipping emissions (V, Ni, and SO42−) in the Mediterranean region, metallurgy (Cr, Ni, and Mn) in central and eastern Europe, high temperature processes (As, Pb, and SO42−) in eastern countries, and traffic (Cu) at sites affected by emissions from nearby cities.

Although particulate organic and elemental carbon (OC and EC) are important constituents of the suspended atmospheric particulate matter (PM), measurements of OC and EC are much less common and more uncertain than measurements of e.g. the ionic components of PM. In the framework of atmospheric research infrastructures supported by the European Union, actions have been undertaken to determine and mitigate sampling artefacts, and assess the comparability of OC and EC data obtained in a network of 10 atmospheric observatories across Europe. Positive sampling artefacts (from 0.4 to 2.8 μg C/m3) and analytical discrepancies (between −50% and +40% for the EC/TC ratio) have been taken into account to generate a robust data set, from which we established the phenomenology of carbonaceous aerosols at regional background sites in Europe. Across the network, TC and EC annual average concentrations range from 0.4 to 9 μg C/m3, and from 0.1 to 2 μg C/m3, respectively. TC/PM10 annual mean ratios range from 0.11 at a Mediterranean site to 0.34 at the most polluted continental site, and TC/PM2.5 ratios are slightly greater at all sites (0.15–0.42). EC/TC annual mean ratios range from 0.10 to 0.22, and do not depend much on PM concentration levels, especially in winter. Seasonal variations in PM and TC concentrations, and in TC/PM and EC/TC ratios, differ across the network, which can be explained by seasonal changes in PM source contributions at some sites. © 2016 The Authors, EUSAAR (FP6/2001-2006, grant agreement no. RII3-GT-2006-026140), ACTRIS (FP7/2007-2013, grant agreement no. 262254), ACTRIS2 (H2020-INFRAIA-2014-2015, grant agreement no. 654109), EPA Ireland is acknowledged for the research support at Mace Head, the Norwegian Environment Agency for the measurements at Birkenes. Appendix A

Size-segregated particle samples were collected using a Berner 5-stage impactor (stages 1–5: 0.05–0.14–0.42–1.2–3.5–10 μm aerodynamic diameter). The means for all 169 days and for different categories of days were used for a characterization. The sorting criteria were (a) the distinction between winter (Wi, November to April) and summer (Su, May to October), (b) the distinction between air mass inflow from a sector West (W, 210 °–320 °) and from a sector East (E, 35 °–140 °). For the assignment of the air mass origin 96-h backward trajectories were used and four categories (WiW, WiE, SuW and SuE) with 48, 18, 42 and 29 days were established. The lowest mean particle mass concentrations were found for SuW and the highest for WiE with relative mass concentration distributions of 5.9, 28.2, 36.5, 18.0, and 11.4 % and 3.5, 22.7, 52.6, 16.7, and 4.5 % for stages 1–5, respectively. The mass closure for water soluble ions, water, organic material (OM) and elemental carbon (EC) accounts for 81–99 % of the gravimetric mass in Wi and for 60–81 % for Su, depending on the stage. The fractions of nitrate were relatively high for WiW while sulphate fractions are high for WiE. The estimated concentrations of secondary organic carbon (SOA) on stage 3 for WiW, WiE, SuW and SuE were 0.32, 1.25, 0.27 and 0.58 μgm−³, respectively. The highest amount of SOA is found for WiE, representing 59 % of organic carbon (OC). The highest difference in the percentages of SOA in OC was found between winter (WiW 55 %, WiE 59 %) and summer (SuW and SuE 74 %) indicating photochemical processes during long-range transport. The mean Carbon Preference Indices (CPI) are highest for SuE (stage 4: 7.57 and stage 5: 9.82) resulting mainly from plant wax abrasion in the surrounding forests. For WiE the mean PAH concentration on stage 3 (9.7 ngm−3) is about five times higher than for WiW, indicating long range transport following domestic heating and other combustion processes.

Ammonium nitrate and several organic compounds such as dicarboxylic acids (e.g. succinic acid, glutaric acid), some Polycyclic Aromatic Hydrocarbon (PAHs) or some n-alkanes are semi-volatile. The transition of these compounds between the gas and particulate phase may significantly change the aerosol particles radiative properties, the heterogeneous chemical properties, and, naturally, the total particulate mass concentration. To better assess these time-dependent effects, three intensive field experiments were conducted in 2008–2009 at the Central European EMEP research station Melpitz (Germany) using an Aerodyne Aerosol Mass Spectrometer (AMS). Data from all seasons highlight organic matter as being the most important particulate fraction of PM1 in summer (59%) while in winter, the nitrate fraction was more prevalent (34.4%). The diurnal variation of nitrate always showed the lowest concentration during the day while its concentration increased during the night. This night increase of nitrate concentration was higher in winter (ΔNO3− = 3.6 μg m−3) than in summer (ΔNO3− = 0.7 μg m−3). The variation in particulate nitrate was inherently linked to the gas-to-particle-phase equilibrium of ammonium nitrate and the dynamics of the atmosphere during day. The results of this study suggest that during summer nights, the condensation of HNO3 and NH3 on pre-existing particles represents the most prevalent source of nitrate, whereas during winter, nighttime chemistry is the predominant source of nitrate. During the summer 2008's campaign, a clear diurnal evolution in the oxidation state of the organic matter became evident (Organic Mass to Organic Carbon ratio (OM/OC) ranging from 1.65 during night to 1.80 during day and carbon oxidation state (OSc) from −0.66 to −0.4), which could be correlated to hydroxyl radical (OH) and ozone concentrations, indicating a photochemical transformation process. In summer, the organic particulate matter seemed to be heavily influenced by regional secondary formation and transformation processes, facilitated by photochemical production processes as well as a diurnal cycling of the substances between the gas and particulate phase. In winter, these processes were obviously less pronounced (OM/OC ranging from 1.60 to 1.67 and OSc from −0.8 to −0.7), so that organic matter apparently originated mainly from aged particles and long range transport.

Gaseous sulphuric acid is a key precursor for new particle formation in the atmosphere. Previous experimental studies have confirmed a strong correlation between the number concentrations of freshly formed particles and the ambient concentrations of sulphuric acid. This study evaluates a body of experimental gas phase sulphuric acid concentrations, as measured by Chemical Ionization Mass Spectrometry (CIMS) during six intensive measurement campaigns and one long-term observational period. The campaign datasets were measured in Hyytiälä, Finland, in 2003 and 2007, in San Pietro Capofiume, Italy, in 2009, in Melpitz, Germany, in 2008, in Atlanta, Georgia, USA, in 2002, and in Niwot Ridge, Colorado, USA, in 2007. The long term data were obtained in Hohenpeissenberg, Germany, during 1998 to 2000. The measured time series were used to construct proximity measures ("proxies") for sulphuric acid concentration by using statistical analysis methods. The objective of this study is to find a proxy for sulfuric acid that is valid in as many different atmospheric environments as possible. Our most accurate and universal formulation of the sulphuric acid concentration proxy uses global solar radiation, SO2 concentration, condensation sink and relative humidity as predictor variables, yielding a correlation measure (R) of 0.87 between observed concentration and the proxy predictions. Interestingly, the role of the condensation sink in the proxy was only minor, since similarly accurate proxies could be constructed with global solar radiation and SO2 concentration alone. This could be attributed to SO2 being an indicator for anthropogenic pollution, including particulate and gaseous emissions which represent sinks for the OH radical that, in turn, is needed for the formation of sulphuric acid.

The fractions of local traffic (LT), urban background (UBG) and regional background (RBG) of the particle pollution at a traffic-influenced kerbside in Dresden, Germany, were determined by measurements of size-segregated mass concentration, chemical composition and particle size distributions in a network of five measurement stations partly existing and partly set up for this study. Besides the kerbside station, one urban background site and three rural sites were included in the study. Using data from these different sites, the LT, UBG, and RBG contributions were calculated, following the approach of Lenschow et al. (2001). At the kerbside site, 19% of the total number concentration (DpSt = 10–600 nm) could be attributed to the RBG, 15% to the UBG, and 66% to the LT immediately nearby. Particle mass concentrations up to Dpaer = 420 nm RBG amounts to 68%, UBG to 21%, and LT only to 11%. Highest mass concentrations were observed at all stations in autumn and winter during easterly inflow directions. The local traffic fraction of PM10 mass at the kerbside station was found to be 30% for westerly inflow, but only 7% for southeasterly inflow due to the dominating transport fraction from up to 80% of the particle mass at this inflow direction. Size-resolved investigation showed the main fractions in both the particle size ranges of Dpaer = 0.42 to 1.2 and 0.14 to 0.42 μm at all stations. The main components sulphate, ammonium and total carbon showed higher concentrations at south-eastern/eastern inflow in autumn at all stations, while nitrate at the kerbside and urban background site was higher during westerly inflow in winter. The chemical composition at the regional background site at westerly inflow (12% nitrate, 8% sulphate, 11% total carbon) was significantly different from that at easterly inflow (3% nitrate, 15% sulphate, 22% total carbon). The prevailing part of the ionic mass was always found in the fine particle range of Dpaer = 0.14 to 1.2 μm at all stations. For all inflow directions highest total carbon concentrations were observed at the kerbside station, especially in the ultra-fine size range of Dpaer = 0.05 to 0.14 μm with up to 30% of the whole carbon. PAH concentrations were always higher at south-eastern/eastern inflow especially during wintertime. Trace metal components and silicon were found mainly in the coarse mode fraction at the kerbside resulting from abrasion or resuspension.

Nucleation experiments starting from the reaction of OH radicals with SO2 have been performed in the IfT-LFT flow tube under atmospheric conditions at 293±0.5 K for a relative humidity of 13–61%. The presence of different additives (H2, CO, 1,3,5-trimethylbenzene) for adjusting the OH radical concentration and resulting OH levels in the range (4–300) ×105 molecule cm−3 did not influence the nucleation process itself. The number of detected particles as well as the threshold H2SO4 concentration needed for nucleation was found to be strongly dependent on the counting efficiency of the used counting devices. High-sensitivity particle counters allowed the measurement of freshly nucleated particles with diameters down to about 1.5 nm. A parameterization of the experimental data was developed using power law equations for H2SO4 and H2O vapour. The exponent for H2SO4 from different measurement series was in the range of 1.7–2.1 being in good agreement with those arising from analysis of nucleation events in the atmosphere. For increasing relative humidity, an increase of the particle number was observed. The exponent for H2O vapour was found to be 3.1 representing an upper limit. Addition of 1.2×1011 molecule cm−3 or 1.2×1012 molecule cm−3 of NH3 (range of atmospheric NH3 peak concentrations) revealed that NH3 has a measureable, promoting effect on the nucleation rate under these conditions. The promoting effect was found to be more pronounced for relatively dry conditions, i.e. a rise of the particle number by 1–2 orders of magnitude at RH = 13% and only by a factor of 2–5 at RH = 47% (NH3 addition: 1.2×1012 molecule cm−3). Using the amine tert-butylamine instead of NH3, the enhancing impact of the base for nucleation and particle growth appears to be stronger. Tert-butylamine addition of about 1010 molecule cm−3 at RH = 13% enhances particle formation by about two orders of magnitude, while for NH3 only a small or negligible effect on nucleation in this range of concentration appeared. This suggests that amines can strongly influence atmospheric H2SO4-H2O nucleation and are probably promising candidates for explaining existing discrepancies between theory and observations.

In anthropogenically influenced atmospheres, sulphur dioxide (SO2) is the main precursor of gaseous sulphuric acid (H2SO4), which in turn is a main precursor for atmospheric particle nucleation. As a result of socio-economic changes, East Germany has seen a dramatic decrease in anthropogenic SO2 emissions between 1989 and present, as documented by routine air quality measurements in many locations. We have attempted to evaluate the influence of changing SO2 concentrations on the frequency and intensity of new particle formation (NPF) using two different data sets (1996–1997; 2003–2006) of experimental particle number size distributions (diameter range 3–750 nm) from the atmospheric research station Melpitz near Leipzig, Germany. Between the two periods SO2 concentrations decreased by 65% on average, while the frequency of NPF events dropped by 45%. Meanwhile, the average formation rate of 3 nm particles decreased by 68% on average. The trends were statistically significant and therefore suggest a connection between the availability of anthropogenic SO2 and freshly formed new particles. In contrast to the decrease in new particle formation, we found an increase in the mean growth rate of freshly nucleated particles (+22%), suggesting that particle nucleation and subsequent growth into larger sizes are delineated with respect to their precursor species. Using three basic parameters, the condensation sink for H2SO4, the SO2 concentration, and the global radiation intensity, we were able to define the characteristic range of atmospheric conditions under which particle formation events take place at the Melpitz site. While the decrease in the concentrations and formation rates of the new particles was rather evident, no similar decrease was found with respect to the generation of cloud condensation nuclei (CCN; particle diameter >100 nm) as a result of atmospheric nucleation events. On the contrary, the production of CCN following nucleation events appears to have increased by tens of percents. Our aerosol dynamics model simulations suggest that such an increase can be caused by the increased particle growth rate.

PM 10 measurements were started in November 1992 at Melpitz site. The mean PM 10 concentration in 1993 was 38 μg m −3 in the summer season (May until October) and about 44 μg m −3 in the winter season (November until April). The mean PM 10 level decreased until 1999 and varies now in ranges from 20–34 μg m −3 to 17–24 μg m −3 (minimum and maximum mean values for 1999–2008) in winter and summer seasons, respectively. High volume filter samples of particles PM 10 , PM 2.5 and PM 1 were characterized for mass, water-soluble ions, organic and elemental carbon from 2004 until 2008. The percentage of PM 2.5 in PM 10 varies between summer (71.6%) and winter seasons (81.9%). Mean concentrations of PM 10 , PM 2.5 and PM 1 in Melpitz were 20, 15, and 13 μg m −3 in 2004, 22, 18, and 13 μg m −3 in 2005, 24, 19, and 12 μg m −3 in 2006 and 22, 17, and 12 μg m −3 in 2007, respectively. In the four winters the rural background concentration PM 10 at Melpitz exceeded the daily 50 μg m −3 limit for Europe on 8, 8, 7 and 6 days, respectively. Findings for a simple two-sector-classification of the samples (May 2004 until April 2008) using 96-h backward trajectories for the identification of source regions are: Air masses were transported most of time (60%) from the western sector and secondly (17%) from the eastern sector. The lowest daily mean mass concentration PM 10 were found during western inflow in summer (17 μg m −3 ) containing low amounts of sulphate (2.4 μg m −3 ), nitrate (1.7 μg m −3 ), ammonium (1.1 μg m −3 ) and TC (3.7 μg m −3 ). In opposite the highest mean mass concentration PM 10 was found during eastern inflow in winter (35 μg m −3 ) with high amounts of sulphate (6.1 μg m −3 ), nitrate (5.4 μg m −3 ), ammonium (3.8 μg m −3 ) and TC (9.4 μg m −3 ). An estimation of secondary formed OC (SOA) shows 0.8–0.9 μg m −3 for air masses from West and 2.1–2.2 μg m −3 from East. The seasonal difference can be neglected. The half-hourly measurements of the particle mass concentration PM 10 evaluated as mean daily courses using a TEOM ® show low values (14–21 μg m −3 ) in summer and winter for air masses transported from West and the highest concentrations (31–38 μg m −3 ) in winter for air masses from East. The results demonstrate the influence of meteorological parameters on long-range transport, secondary particle mass formation and re-emission which modify mass concentration and composition of PM 10 , PM 2.5 and PM 1 . Melpitz site is located in the East of Germany faraway from strong local anthropogenic emissions (rural background). Therefore, this site is suitable for investigation of the influence of long-range transport of air pollution in continental air masses from the East with source regions inside and outside of the European Union.

Atmospheric aerosol particle size distributions at a continental background site in Eastern Germany were examined for a one-year period. Particles were classified using a twin differential mobility particle sizer in a size range between 3 and 800 nm. As a novelty, every second measurement of this experiment involved the removal of volatile chemical compounds in a thermodenuder at 300°C. This concept allowed to quantify the number size distribution of non-volatile particle cores – primarily associated with elemental carbon, and to compare this to the original non-conditioned size distribution. As a byproduct of the volatility analysis, new particles originating from nucleation inside the thermodenuder can be observed, however, overwhelmingly at diameters below 6 nm. Within the measurement uncertainty, every particle down to particle sizes of 15 nm is concluded to contain a non-volatile core. The volume fraction of non-volatile particulate matter (non-conditioned diameter < 800 nm) varied between 10 and 30% and was largely consistent with the experimentally determined mass fraction of elemental carbon. The average size of the non-volatile particle cores was estimated as a function of original non-conditioned size using a summation method, which showed that larger particles (>200 nm) contained more non-volatile compounds than smaller particles (

Ambient concentrations of NH3, HNO3, HNO2, HCl, SO2, particulate NH 4 + , NO 3 - , and SO 4 2 - were simultaneously measured from October 2001 to April 2003 at the Oberbarenburg research site (Erzgebirge, Germany). Seasonal variations of gas phase concentrations were often related to meteorological parameters and specific source strength. The particulate species (PM2.5) displayed weak seasonal trends, but periods with low mixing heights resulted in significantly elevated concentrations. Mean NH3, HNO2, HNO3, and SO2 concentrations in air (μg m−3) were about 0.48, 0.30, 0.80, and 5.9, respectively. With a PM2.5-mass fraction of 11.3 μg m−3, the Erzgebirge was moderately polluted. Average particle bound NH 4 + - (1.5 μg m−3) and NO 3 - - (2.2 μg m−3) concentrations were 2–3-times higher than the corresponding gas phase concentrations. In summer, preferentially (NH4)2SO4 existed, while the dominance of NH4NO3-aerosol increased in spring. The thermodynamic equilibrium constant for the system NH3/HNO3/NH4NO3 agrees well with the measured concentration product considering the co-existence of SO 4 2 - . The particulate phase is often favoured under ambient temperature and humidity. Nearly all species exhibited maximum concentrations from February to April 2003, during a stable high-pressure system. In March and April 2003, the secondary ions contributed more than 90% to the PM2.5 fraction. This was particularly due to increased NO 3 - - concentrations. The formation of NO 3 - was supported by a large supply of free NH3.

Within the EUROTRAC-2 subproject AEROSOL, the intensive field campaign INTERCOMP2000 was conducted to compare aerosol samplers and methods to measure various aerosol properties. Here a comparison of mass concentrations measured with different PM2.5 and PM10 samplers as well as cascade impactors is described. Different filter types were used. In general, the PM2.5 and PM10 mass concentrations obtained on filters agree well. The data agree within 18.1% (PM2.5, all data). If data obtained with the TEOM (18% low) and on Whatman QM-A quartz fibre filters (low face velocity, 38% high) are excluded, PM2.5 data agree within 8.1%. For PM10, the agreement is within 6.6% (again excluding the Whatman QM-A quartz fibre filters, 22% high) or 12.1% (all data). For the impactor samples, the data agreed within 6.3% (excluding the ELPI, which was 92% high) and 8.7% for PM2.5 and PM10.

Measurements were performed at the research site Melpitz (87 m a.s.l., 51 °32′ N and 12°54′E), 41 km north east of the Leipzig conurbation in spring 2000 to measure atmospheric nitrous and nitric acid concentrations, to compare available methods for these acids, and to investigate the distribution of particulate nitrate vs gaseous HNO3. Two different wet denuder methods were run side by side during the experiment: a wet effluent diffusion denuder (WEDD) and a rotating wet annular denuder (RWAN). The concentrations obtained for HONO with both methods agreed very well. At low relative humidity (RH) values, a good agreement was also observed for HNO3 between the two methods. However, significant differences were observed at RH values >80%. Both methods allow the measurement of atmospheric HONO and HNO3 with a fine time resolution even at very low concentration levels. Measurable daytime values for nitrous acid were observed and there were indications for heterogeneous formation. Storage of HONO or nitrite, respectively, on wet surfaces can be a source for observed daytime HONO.

The field campaign INTERCOMP2000 was organised within the EUROTRAC-2 subproject AEROSOL for characterisation of aerosol at a rural site. The groups involved used a wide range of measurement methods for aerosol particles. Although the focus was on critical aerosol properties like mass, nitrate and carbon, in this paper particular attention is given to the role of inorganic soluble material being main part of the cloud condensation nuclei. Here, we compare methods used in Europe also for inorganic ion mass concentrations: three high-volume samplers (2 Digitel and 1 Sierra Andersen, equipped with quartz fibre filters), four low-volume samplers (1 Rupprecht Patashnik with Teflon filter; 3 stacked filter units with Teflon, cellulose ester or Whatman 41 filter), and 2 low-pressure impactors (Berner type with Tedlar foils). Ten parallel 24 h samples were compared. The data for the main ions nitrate, sulphate and ammonium agree well for the PM10 as well for PM2.5 aerosol fraction; relative standard deviation of about 20–40% were found. The single values for calcium, sodium and chloride which contribute only minor to the soluble inorganic mass scatter very strongly around the calculated averages: about 50% in PM10 mode, and even 100% in PM2.5 mode. While laboratory calibrations typically indicate performance close to design specifications, methods during field operation are subject to a number of sampling and handling artefacts. We know that the different sampling principles used in this study, and the analytical procedures done by each group with their own methodology will cause a main part of the observed uncertainties. In reality, due to different reasons (availability, costs, manpower, different analysis from the same sample, size and time resolution, etc) in many networks and field studies a high variability of methods for aerosol characterisation is used and often those experimental figures will be used for statistical interpretations. Thus, our paper will emphasise that harmonisation among different PM measurements is the “order of the day”.

For a period of 10 years (1993–2002) daily PM10 samples were collected on quartz filters by a PM10 high-volume sampler (Sierra-Andersen). In addition, since 1995 weekly filter samples of PM10, PM2.5 and since 1999 PM1 filter samples were collected by a low-volume sampler (‘Partisol 2000’, Rupprecht and Patashnik) on Teflon filters at the IfT research station Melpitz (12°56′E, 51°32′N) located in the downwind plume of the Leipzig conurbation in central Europe. The resulting time series were compared based on weekly means (particle mass r=0.90, NO3− mass r=0.94, SO42− mass r=0.92 and NH4+ mass r=0.90) and integrated in a historical mass trend (since 1983) for Saxony. In the data (1983–1990) the total particle mass concentration (TSP) shows big scatter with a mean of about 75 μg m−3. Since the re-unification of Germany in 1990 a decrease in PM10-concentration to a mean of 20–30 μg m−3 is observed. The mass concentration of PM10 shows a decreasing trend from a yearly maximum value in 1996 (39 μg m−3) to a mean value for 1999–2002 of about 23 μg m−3. The highest values were observed just before the winter of 1997/1998. No pronounced concentration peaks were found in the following winters. Reasons are the rapid modernization of power plants and the decreasing number of coal heating systems in the Leipzig conurbation and its surroundings as well as a lack of strong inversion situations. The NO3−/SO42−-ratio shows a typical increasing trend caused by the decreasing SO42−-mass concentration in PM10 which originates in the dramatic decrease of SO2 concentrations. From the weekly low-volume samples the mass contributions of PM1, PM2.5–PM1 and PM10–PM2.5 to PM10 (100%) for 1999–2002 were about 61%, 20% and 19% for winter and 42%, 13% and 45% for summer, respectively. Most of the PM2.5 mass is PM1. During summers the weekly ratio of coarse particles (PM10–PM2.5) to fine particles (PM2.5) was higher (about 1.4) than the winter value (about 0.3). An additional impactor for PM1 at the low-volume sampler contains a quartz filter for the weekly determination of organic carbon (OC) and elemental carbon (EC) using a thermographic method. About 30% of the PM1 mass is total carbon (TC=OC+EC). The percentage of EC to TC seems to be increasing in the summer from 1999 to 2002.

In the course of two field campaigns, size-segregated particle samples were collected at nine sites in Germany, including traffic, urban, rural, marine and mountain sites. During the chemical characterisation of the samples some of them were found to contain an unknown substance that was later identified as hydroxymethanesulfonic acid (HMSA). HMSA is known to be formed during the reaction of S(IV) (HSO3− or SO32−) with formaldehyde in the aqueous phase. Due to its stability, HMSA can act as a reservoir species for S(IV) in the atmosphere and is therefore of interest for the understanding of atmospheric sulfur chemistry. However, no HMSA data are available for atmospheric particles from central Europe, and even on a worldwide scale data are scarce. Thus, the present study now provides a representative data set with detailed information on HMSA concentrations in size-segregated central European aerosol particles. HMSA mass concentrations in this data set were highly variable: HMSA was found in 224 out of 738 samples (30%), sometimes in high mass concentrations exceeding those of oxalic acid. On average over all 154 impactor runs, 31.5 ng m−3 HMSA was found in PM10, contributing 0.21% to the total mass. The results show that the particle diameter, the sampling location, the sampling season and the air mass origin impact the HMSA mass concentration. Highest concentrations were found in the particle fraction 0.42–1.2 μm, at urban sites, in winter and with eastern (continental) air masses, respectively. The results suggest that HMSA is formed during aging of pollution plumes. A positive correlation of HMSA with sulfate, oxalate and PM is found (R2 > 0.4). The results furthermore suggest that the fraction of HMSA in PM slightly decreases with increasing pH.

The present study comprises a large body of physical and chemical mass-related aerosol data which were collected over the industrialized basin of Leipzig, Germany, during the time period 1983 to 1997. For the period 1996/1997 consistent mass size distributions over the range 0.01 to 10 μm (PM10) were determined with a differential mobility analyzer and an aerodynamic particle sizer. The modal size distribution parameters were compared to similar lognormal data from the United States of the 1970s, yielding lower concentrations and coarse particle geometric diameters. In both accumulation and coarse mode, narrower distributions than over the United States were found which may be real or due to instrumental limitations in the 1970s. Within the range of measurement uncertainties and with reasonable assumptions about particle densities, chemical mass closure could be achieved with results of daily PMl0 samples. However, the results of a harmonic analysis of the physical and chemical time series indicated that there may be significant aerosol components which were not covered by our analyses, possibly organic compounds. Since 1990 a significant downward trend in gravimetric mass concentration and since 1993 clear changes in aerosol composition were found which are consistent with similar findings in precipitation samples over eastern Germany.

A simple parameterization describing the ozone depletion in thenocturnal residual layer by a parameter related to the mixing potential ofthe boundary layer was tested over homogeneous terrain in EasternGermany, on the basis of continuous SODAR and near-surface ozonemeasurements. For a summer smog episode in July 1994 the proposedrelationship could not be confirmed. This is attributed to the meteorologicaland transport situation as well as to the site-dependent characteristics.

The atmospheric concentration of elemental carbon (EC) in Europe during the six-year period 2005-2010 has been simulated with the EMEP MSC-W model. The model bias compared to EC measurements was less than 20% for most of the examined sites. The model results suggest that fossil fuel combustion is the dominant source of EC in most of Europe but that there are important contributions also from residential wood burning during the cold seasons and, during certain episodes, also from open biomass burning (wildfires and agricultural fires). The modelled contributions from open biomass fires to ground level concentrations of EC were small at the sites included in the present study, EC measurements and modelled EC were also compared to optical measurements of black carbon (BC). The relationships between EC and BC (as given by mass absorption cross section, MAC, values) differed widely between the sites, and the correlation between observed EC and BC is sometimes poor, making it difficult to compare results using the two techniques and limiting the comparability of BC measurements to model EC results. A new bottom-up emission inventory for carbonaceous aerosol from residential wood combustion has been applied. For some countries the new inventory has substantially different EC emissions compared to earlier estimates. For northern Europe the most significant changes are much lower emissions in Norway and higher emissions in neighbouring Sweden and Finland. For Norway and Sweden, comparisons to source-apportionment data from winter campaigns indicate that the new inventory may improve model-calculated EC from wood burning. Finally, three different model setups were tested with variable atmospheric lifetimes of EC in order to evaluate the model sensitivity to the assumptions regarding hygroscopicity and atmospheric ageing of EC. The standard ageing scheme leads to a rapid transformation of the emitted hydrophobic EC to hygroscopic particles, and generates similar results when assuming that all EC is aged at the point of emission. Assuming hydrophobic emissions and no ageing leads to higher EC concentrations. For the more remote sites, the observed EC concentration was in between the modelled EC using standard ageing and the scenario treating EC as hydrophobic. This could indicate too-rapid EC ageing in the model in relatively clean parts of the atmosphere. © Author(s) 2013. CC Attribution 3.0 License.

Atmospheric aerosol samples from a boreal forest (Hyytiala, April 2007), a rural site in Hungary (K-puszta, summer 2008), a polluted rural area in Italy (San Pietro Capofiume, Po Valley, April 2008), a moderately polluted rural site in Germany located on a meadow (Melpitz, May 2008), a natural park in Spain (Montseny, March 2009) and two urban background locations (Zurich, December 2008, and Barcelona, February/March 2009) were collected. Aliphatics, polycyclic aromatic hydrocarbons, carbonyls, sterols, n-alkanols, acids, phenolic compounds and anhydrosugars in aerosols were chemically characterised by gas chromatography-mass spectrometry, along with source attribution based on the carbon preference index (CPI), the rations between the unresolved and the chromatographically resolved aliphatics, the contribution of wax n-alkanes, n-alkanols and n-alkanoic acids from plants, diagnostic ratios of individual target compounds and source-specific markers to organic carbon ratios. In spite of transboundary pollution episodes, Hyytiala registered the lowest levels among all locations. CPI values close to 1 for the aliphatic fraction of the Montseny aerosol suggest that the anthropogenic input may be associated with the transport of aged air masses from the surrounding industrial/urban areas, which superimpose the locally originated hydrocarbons with biogenic origin. Aliphatic and aromatic hydrocarbons in samples from San Pietro Capofiume reveal that fossil fuel combustion is a major source influencing the diel pattern of concentrations. This source contributed to 25-45% of the ambient organic carbon (OC) at the Po Valley site. Aerosols from the German meadow presented variable contributions from both biogenic and anthropogenic sources. The highest levels of vegetation wax components and biogenic secondary organic aerosol (SOA) products were observed at K-puszta, while anthropogenic SOA compounds predominated in Barcelona. The primary vehicular emissions in the Spanish city accounted for around 25-30% of the OC in aerosols. Besides the traffic input (10% of OC), residential wood burning was found to be another dominant emission source contributing to the atmospheric aerosol (up to 38% of OC) at the Swiss urban location. It was estimated that around 10% of the OC mass in the urban sites originates from cooking emissions. Aerosols from the urban area of Zurich presented a much higher PAH content, and benzo(a)pyrene equivalent concentrations sometimes exceeding the mandatory limit. (C) 2012 Elsevier Ltd. All rights reserved.

The first EMEP intensive measurement periods were held in June 2006 and January 2007. The measurements aimed to characterize the aerosol chemical compositions, including the gas/aerosol partitioning of inorganic compounds. The measurement program during these periods included daily or hourly measurements of the secondary inorganic components, with additional measurements of elementaland organic carbon (EC and OC) and mineral dust in PM1, PM2.5 and PM10. These measurements have provided extended knowledge regarding the composition of particulate matter and the temporal and spatial variability of PM, as well as an extended database for the assessment of chemical transport models. This paper summarise the first experiences of making use of measurements from the first EMEP intensive measurement periods along with EMEP model results from the updated model version to characterise aerosol composition. We investigated how the PM chemical composition varies between the summer and the winter month and geographically., JRC.H.2-Air and Climate

Five years of PM10 and PM2.5 ambient air measurements at a roadside, an urban, and a regional background site in Leipzig (Germany) were analyzed for violations of the legal PM10 limit value (1999/30/EC, 1999). The annual mean PM10 concentrations at the three sites were well below the legal threshold of 40 μg m−3 (32.6, 22.0 and 21.7 μg m−3, respectively). However, at the roadside site, the daily maximum value of 50 μg m−3 was exceeded on 232 days (13 % of all days) in 2005–2009, which corresponds to 57 days more than warranted by the EC directive. We analysed the meteorological and local source factors that eventually led to these surplus exceedences. Not surprisingly, the highest pollutant concentrations and most exceedance days were observed in winter. Average concentrations for exceedance and non exceedance days of 64 and 28 μg m−3 at roadside and 40 and 19 μg m−3 in the regional background were observed, suggesting urban contributions of 24 and 8 μg m−3, respectively. Statistical and back trajectory cluster analysis yielded the essential result that PM10 concentrations were regionally enhanced during high pressure conditions, characterized by very low temperature, dry air masses, very low wind speeds, and stable stratification. The latter factor was instrumental in generating high PM10 concentrations at roadside as well as in the regional background through pollution trapping below the atmospheric inversion. During winter exceedance days, the highest organic and elemental carbon mass concentrations were measured. The fewest exceedance days were observed during fast moving air masses from the west, characterized by slightly unstable stratification and lower air pressure. During wintrily exceedance days, about half of PM10 at roadside was originating from regional transport and half from the urban-related sources. This result indicates that both are equally important in generating exceedance days in case of favourable meteorological conditions and cannot be separately considered. Our conclusion is that a combined effort of local, national and international reduction measures could most likely avoid systematic exceedances of the daily limit value in the future.

Sea salt aerosol can significantly affect the air quality. Sea salt can cause enhanced concentrations of particulate matter and change particle chemical composition, in particular in coastal areas, and therefore should be accounted for in air quality modelling. We have used an EMEP Unified model to calculate sea salt concentrations and depositions over Europe, focusing on studying the effects of uncertainties in sea salt production and lifetime on calculation results. Model calculations of sea salt have been compared with EMEP observations of sodium concentrations in air and precipitation for a four year period, from 2004 to 2007, including size (fine/coarse) resolved EMEP intensive measurements in 2006 and 2007. In the presented calculations, sodium air concentrations are between 8% and 46% overestimated, whereas concentrations in precipitation are systematically underestimated by 65–70% for years 2004–2007. A series of model tests have been performed to investigate the reasons for this underestimation, but further studies are needed. The model is found to reproduce the spatial distribution of Na+ in air and precipitation over Europe fairly well, and to capture most of sea salt episodes. The paper presents the main findings from a series of tests in which we compare several different sea spray source functions and also look at the effects of meteorological input and the efficiency of removal processes on calculated sea salt concentrations. Finally, sea salt calculations with the EMEP model have been compared with results from the SILAM model and observations for 2007. While the models produce quite close results for Na+ at the majority of 26 measurement sites, discrepancies in terms of bias and temporal correlation are also found. Those differences are believed to occur due to differences in the representation of source function and size distribution of sea salt aerosol, different meteorology used for model runs and the different models' resolution. This study contributes to getting a better insight on uncertainties associated with sea salt calculations and thus facilitates further improvement of aerosol modelling on both regional and global scales.

This paper synthesizes data on aerosol (particulate matter, PM) physical and chemical characteristics, which were obtained over the past decade in aerosol research and monitoring activities at more than 60 natural background, rural, near-city, urban, and kerbside sites across Europe. The data include simultaneously measured PM10 and/or PM2.5 mass on the one hand, and aerosol particle number concentrations or PM chemistry on the other hand. The aerosol data presented in our previous works (Van Dingenen et al., 2004; Putaud et al., 2004) were updated and merged to those collected in the framework of the EU supported European Cooperation in the field of Scientific and Technical action COST633 (Particulate matter: Properties related to health effects). A number of conclusions from our previous studies were confirmed. There is no single ratio between PM2.5 and PM10 mass concentrations valid for all sites, although fairly constant ratios ranging from 0.5 to 0.9 are observed at most individual sites. There is no general correlation between PM mass and particle number concentrations, although particle number concentrations increase with PM2.5 levels at most sites. The main constituents of both PM10 and PM2.5 are generally organic matter, sulfate and nitrate. Mineral dust can also be a major constituent of PM10 at kerbside sites and in Southern Europe. There is a clear decreasing gradient in SO4 2- and NO3 - contribution to PM10 when moving from rural to urban to kerbside sites. In contrast, the total carbon/PM10 ratio increases from rural to kerbside sites. Some new conclusions were also drawn from this work: the ratio between ultrafine particle and total particle number concentration decreases with PM2.5 concentration at all sites but one, and significant gradients in PM chemistry are observed when moving from Northwestern, to Southern to Central Europe. Compiling an even larger number of data sets would have further increased the significance of our conclusions, but collecting all the aerosol data sets obtained also through research projects remains a tedious task. © 2009 Elsevier Ltd. All rights reserved., This paper is a contribution to the COST Action 633 “Particulate matter: Properties related to health effects”.