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Laboratory experiments suggest that water-soluble products from the gas-phase oxidation of volatile organic compounds can partition into atmospheric waters where they are further oxidized to form low volatility products, providing an alternative route for oxidation in addition to further oxidation in the gas-phase. These products can remain in the particle phase after water evaporation forming what is termed as aqueous secondary organic aerosol (aqSOA). However, few studies have attempted to observe ambient aqSOA. Therefore, a suite of measurements, including near real-time WSOC (water-soluble organic carbon), inorganic anions/cations, organic acids, and gas-phase glyoxal, were made during the PEGASOS (Pan-European Gas-AeroSols-climate interaction Study) 2012 campaign in the Po Valley, Italy to search for evidence of aqSOA. Our analysis focused on two specific periods: Period A on 19-21 June and Period B on 3-5 July to represent the first and second halves of the study, respectively. The large scale circulation was predominately from the west in both periods. Plus back trajectory analysis suggested all sites sampled similar air masses during both periods allowing for comparison of Periods A and B. The data collected during both periods were divided into times of increasing relative humidity (RH) and decreasing RH with the aim of diminishing the influence of dilution and mixing on SOA concentrations and other measured variables. Evidence for local aqSOA formation was only observed during Period A. When this occurred, there was a correlation of WSOC with organic aerosol (R² = 0.86), aerosol liquid water (R² = 0.69), RH (R² = 0.45), and aerosol nitrate (R² = 0.71). Additionally, this was only observed during times of increasing RH, which coincided with dark conditions. Comparisons of WSOC with oxygenated organic aerosol (OOA) factors determined from application of positive matrix factorization analysis on the aerosol mass spectrometer observations of the submicron non-refractory organic particle composition suggested that the WSOC in Periods A and B differed (Period A WSOC vs. OOA-2 R² = 0.85 and OOA-4 R² = 0.03 whereas Period B WSOC vs. OOA-2 R² = 0.03 and OOA-4 R² = 0.64). OOA-2 had a high O/C (oxygen/carbon) ratio of 0.77, providing evidence that aqueous processing was occurring during Period A. Key factors for local aqSOA production during Period A appear to include: air mass stagnation, which allows aqSOA precursors to accumulate in the region; the formation of substantial local particulate nitrate during the overnight hours, which enhances water uptake by the aerosol; and the presence of significant amounts of ammonia, which may contribute to ammonium nitrate formation and subsequent water uptake and/or play a more direct role in the aqSOA chemistry. [ABSTRACT FROM AUTHOR]

The global nitrogen (N) cycle at the beginning of the 21st century has been shown to be strongly influenced by the inputs of reactive nitrogen (Nr) from human activities, including combustion-related NOx, industrial and agricultural N fixation, estimated to be 220 TgNyr-1 in 2010, which is approximately equal to the sum of biological N fixation in unmanaged terrestrial and marine ecosystems. According to current projections, changes in climate and land use during the 21st century will increase both biological and anthropogenic fixation, bringing the total to approximately 600 TgNyr-1 by around 2100. The fraction contributed directly by human activities is unlikely to increase substantially if increases in nitrogen use efficiency in agriculture are achieved and control measures on combustion-related emissions implemented. Some N-cycling processes emerge as particularly sensitive to climate change. One of the largest responses to climate in the processing of Nr is the emission to the atmosphere of NH3, which is estimated to increase from 65 TgNyr-1 in 2008 to 93 TgNyr-1 in 2100 assuming a change in global surface temperature of 5 °C in the absence of increased anthropogenic activity. With changes in emissions in response to increased demand for animal products the combined effect would be to increase NH3 emissions to 135 TgNyr-1. Another major change is the effect of climate changes on aerosol composition and specifically the increased sublimation of NH4NO3 close to the ground to form HNO3 and NH3 in a warmer climate, which deposit more rapidly to terrestrial surfaces than aerosols. Inorganic aerosols over the polluted regions especially in Europe and North America were dominated by (NH4)2SO4 in the 1970s to 1980s, and large reductions in emissions of SO2 have removed most of the SO2-4 from the atmosphere in these regions. Inorganic aerosols from anthropogenic emissions are now dominated by NH4NO3, a volatile aerosol which contributes substantially to PM10 and human health effects globally as well as eutrophication and climate effects. The volatility of NH4NO3 and rapid dry deposition of the vapour phase dissociation products, HNO3 and NH3, is estimated to be reducing the transport distances, deposition footprints and inter-country exchange of Nr in these regions. There have been important policy initiatives on components of the global N cycle. These have been regional or country-based and have delivered substantial reductions of inputs of Nr to sensitive soils, waters and the atmosphere. To date there have been no attempts to develop a global strategy to regulate human inputs to the nitrogen cycle. However, considering the magnitude of global Nr use, potential future increases, and the very large leakage of Nr in many forms to soils, waters and the atmosphere, international action is required. Current legislation will not deliver the scale of reductions globally for recovery from the effects of Nr deposition on sensitive ecosystems, or a decline in N2O emissions to the global atmosphere. Such changes would require substantial improvements in nitrogen use efficiency across the global economy combined with optimization of transport and food consumption patterns. This would allow reductions in Nr use, inputs to the atmosphere and deposition to sensitive ecosystems. Such changes would offer substantial economic and environmental co-benefits which could help motivate the necessary actions. [ABSTRACT FROM AUTHOR]

High resolution aerosol mass spectrometer measurements have been performed, for the first time, at the Mt. Cimone Global Atmospheric Watch (GAW) station between June and July 2012, within the EU project PEGASOS and the ARPA--Emilia Romagna project SUPERSITO. Sub-micron aerosol was dominated by organics (63%) with sulphate, ammonium and nitrate contributing for the remaining 20, 9 and 7%, respectively. Organic aerosol (OA) was in general highly oxygenated, consistent with the remote character of the site; our observations suggest that oxidation and secondary organic aerosol (SOA) formation processes occurred during aerosol transport to high altitudes. All of the aerosol component concentrations as well as the OA elemental ratios showed a clear daily trend, driven by the evolution of the planetary boundary layer (PBL) and by the mountain wind regime. Higher loadings and lower OA oxidation levels were observed during the day, when the site was within the PBL, and therefore affected by relatively fresh aerosol transported from lower altitudes. Conversely, lower loadings and higher OA oxidation levels were observed at night, when the top of Mt. Cimone resided in the free troposphere although affected by the transport of residual layers on several days of the campaign. Analysis of the elemental ratios in a Van Krevelen space shows that OA oxidation follows a slope comprised between -0.5 and -1, consistent with addition of carboxylic groups, with or without fragmentation of the parent molecules. The increase of carboxylic groups during OA ageing is confirmed by the increased contribution of organic fragments containing more than one oxygen atom in the free troposphere night-time mass spectra. Finally, positive matrix factorization was able to deconvolve the contributions of relatively fresh OA (OOAa) originating from the PBL, more aged OA (OOAb) present at high altitudes during periods of atmospheric stagnation, and very aged aerosols (OOAc) transported over long distances in the free troposphere. [ABSTRACT FROM AUTHOR]

Airborne measurements of the aerosol hygroscopic and optical properties as well as chemical composition were performed in the Netherlands and northern Italy on board of a Zeppelin NT airship during the PEGASOS field campaigns in 2012. The vertical changes in aerosol properties during the development of the mixing layer were studied. Hygroscopic growth factors (GF) at 95% relative humidity were determined using the white-light humidified optical particles spectrometer (WHOPS) for dry diameters of 300 and 500nm particles. These measurements were supplemented by an aerosol mass spectrometer (AMS) and an aethalometer providing information on the aerosol chemical composition. Several vertical profiles between 100 and 700ma.g. were flown just after sunrise close to the San Pietro Capofiume ground station in the Po Valley, Italy. During the early morning hours the lowest layer (newly developing mixing layer) contained a high nitrate fraction (20 %) which was coupled with enhanced hygroscopic growth. In the layer above (residual layer) small nitrate fractions of ~ 2% were measured as well as low GFs. After full mixing of the layers, typically around noon and with increased temperature, the nitrate fraction decreased to 2% at all altitudes and led to similar hygroscopicity values as found in the residual layer. These distinct vertical and temporal changes underline the importance of airborne campaigns to study aerosol properties during the development of the mixed layer. The aerosol was externally mixed with 22 and 67% of the 500nm particles in the range GF<1.1 and GF>1.5, respectively. Contributors to the non-hygroscopic mode in the observed size range are most likely mineral dust and biological material. Mean hygroscopicity parameters (κ) were 0.34, 0.19 and 0.18 for particles in the newly forming mixing layer, residual layer and fully mixed layer, respectively. These results agree well with those from chemical analysis which found values of α = 0.27, 0.21 and 0.19 for the three layers. The highest κ values in the new mixed layer and lower values in the fully developed mixed layer were additionally confirmed by ground measurements. [ABSTRACT FROM AUTHOR]

High resolution aerosol mass spectrometer measurements have been performed, for the first time, at the Mt. Cimone Global Atmospheric Watch (GAW) station between June and July 2012, within the EU project PEGASOS and the ARPA-Emilia Romagna project SUPERSITO. Sub-micron aerosol was dominated by organics (63 %) with sulphate, ammonium and nitrate contributing for the remaining 20, 9 and 7 %, respectively. Organic aerosol (OA) was in general highly oxygenated, consistent with the remote character of the site; our observations suggest that oxidation and secondary organic aerosol (SOA) formation processes occurred during aerosol transport to high altitudes. All of the aerosol component concentrations as well as the OA elemental ratios showed a clear daily trend, driven by the evolution of the planetary boundary layer (PBL) and by the mountain wind regime. Higher loadings and lower OA oxidation levels were observed during the day, when the site was within the PBL, and therefore affected by relatively fresh aerosol transported from lower altitudes. Conversely, lower loadings and higher OA oxidation levels were observed at night, when the top of Mt. Cimone resided in the free troposphere although affected by the transport of residual layers on several days of the campaign. Analysis of the elemental ratios in a Van Krevelen space shows that OA oxidation follows a slope comprised between -0.5 and -1, consistent with addition of carboxylic groups, with or without fragmentation of the parent molecules. The increase of carboxylic groups during OA ageing is confirmed by the increased contribution of organic fragments containing more than one oxygen atom in the free troposphere night-time mass spectra. Finally, positive matrix factorization was able to deconvolve the contributions of relatively fresh OA (OOAa) originating from the PBL, more aged OA (OOAb) present at high altitudes during periods of atmospheric stagnation, and very aged aerosols (OOAc) transported over long distances in the free troposphere. [ABSTRACT FROM AUTHOR]

Chemical and dynamical processes lead to the formation of aerosol layers in the upper planetary boundary layer (PBL) and above it. Through vertical mixing and entrainment into the PBL these layers may contribute to the ground-level particulate matter (PM); however, to date a quantitative assessment of such a contribution has not been carried out. This study investigates this aspect by combining chemical and physical aerosol measurements with WRF/Chem (Weather Research and Forecasting with Chemistry) model simulations. The observations were collected in the Milan urban area (northern Italy) during the summer of 2007. The period coincided with the passage of a meteorological perturbation that cleansed the lower atmosphere, followed by a high-pressure period favouring pollutant accumulation. Lidar observations revealed the formation of elevated aerosol layers and evidence of their entrainment into the PBL. We analysed the budget of ground-level PM2.5 (particulate matter with an aerodynamic diameter less than 2.5 μm) with the help of the online meteorology-chemistry WRF/Chem model, focusing in particular on the contribution of upper-level processes. Our findings show that an important player in determining the upper-PBL aerosol layer is particulate nitrate, which may reach higher values in the upper PBL (up to 30% of the aerosol mass) than in the lower PBL. The nitrate formation process is predicted to be largely driven by the relative-humidity vertical profile, which may trigger efficient aqueous nitrate formation when exceeding the ammonium nitrate deliquescence point. Secondary PM2.5 produced in the upper half of the PBL may contribute up to 7-8 μg m-3 (or 25%) to ground-level concentrations on an hourly basis. The residual aerosol layer above the PBL is also found to potentially play a large role, which may occasionally contribute up to 10-12 μg m-3 (or 40%) to hourly ground-level PM2.5 concentrations during the morning hours. Although the results presented here refer to one relatively short period in one location, this study highlights the importance of considering the interplay between chemical and dynamical processes occurring within and above the PBL when interpreting ground-level aerosol observations. [ABSTRACT FROM AUTHOR]

The literature on atmospheric particulate matter (PM), or atmospheric aerosol, has increased enormously over the last two decades and amounts now to some 1500-2000 papers per year in the refereed literature. This is in part due to the enormous advances in measurement technologies, which has allowed for an increasingly accurate understanding of the chemical composition and of the physical properties of atmospheric particles and of their processes in the atmosphere. The growing scientific interest in atmospheric aerosol particles is due to their high importance for environmental policy. In fact, particulate matter constitutes one of the most challenging problems both for air quality and climate change policies. In this context, this paper reviews the most recent results within the atmospheric aerosol science, and the policy needs, which have driven much of the increase in monitoring and mechanistic research over the last two decades. The synthesis reveals many new processes and developments in the science underpinning climate-aerosol interactions and effects of PM on human health and the environment. But, while airborne particulate matter is responsible for globally important effects on premature human mortality, we still do not know the relative importance of different chemical components of PM for these effects. Likewise, the magnitude of the overall effects of PM on climate remains highly uncertain. Despite the uncertainty there are many things that could be done to mitigate local and global problems of atmospheric PM. Recent analyses have shown that reducing BC emissions, using known control measures would reduce global warming and delay the time when anthropogenic effects on global temperature would exceed 2 °C. Likewise, cost effective control measures on ammonia, an important agricultural precursor gas for secondary inorganic aerosols (SIA), would reduce regional eutrophication and PM concentrations in large areas of Europe, China, and the USA. Thus there is much that could be done to reduce effects of atmospheric PM on the climate and the health of the environment and human population. A prioritized list of actions to mitigate the full range of effects of PM is currently undeliverable due to shortcomings in knowledge of aerosol science among which the roles of PM in global climate and the relative roles of different PM precursor sources and their response to climate and land use change over the remaining decades of this century are prominent. [ABSTRACT FROM AUTHOR]

Atmospheric aerosols have been sampled and characterised at the Mace Head north-east (NE) Atlantic atmospheric research station since 1958, with many interesting phenomena being discovered. However, with the range of new discoveries and scientific advances, there has been a range of concomitant criticisms challenging the representativeness of aerosol sampled at the station compared to that of aerosol over the pristine open-ocean. Two recurring criticisms relate to the lack of representativeness due to potentially enhanced coastal sources, possibly leading to artificially high values of aerosol concentrations, and to the influence of long-range transport of anthropogenic or continental aerosol and its potential dominance over, or perturbation of, a natural marine aerosol signal. Here, we review the results of previous experimental studies on marine aerosols over the NE Atlantic and at Mace Head with the aim of evaluating their representativeness relative to that of a pristine openocean aerosol, i.e. with negligible anthropogenic/continental influence. Particular focus is given to submicron organic matter (OM) aerosol. In summary, no correlation was found between OM and black carbon (BC) in marine air conforming to clean-air sampling criteria, either at BC levels of 0-15 or 15-50 ng m-3, suggesting that OM concentrations, up to observed peak values of 3.8 μg m-3, are predominantly natural in origin. Sophisticated carbon isotope analysis and aerosol mass spectral finger printing techniques corroborate the conclusion that there is a predominant natural source of OM, with 80 % biogenic source apportionment being observed for general clean-air conditions, rising to ~ 98 % during specific primary marine organic plumes when peak OM mass concentrations > 3 μgm-3 are observed. Similarly, a maximum contribution of 20 % OM mass coming from non-marine sources was established by dual carbon isotope analysis. Further, analysis of a series of experiments conducted at Mace Head conclude that negligible coastal, surf zone, or tidal effects are discernible in the secondary or primary aerosol mass residing in the submicron size range for sampling heights of 7 m and above. The Mace Head marine-air criteria ensure anthropogenic and coastal effects are sufficiently minimised so as to guarantee a predominant, and sometimes overwhelming, natural marine aerosol contribution to the total aerosol population when the criteria are adhered to. [ABSTRACT FROM AUTHOR]

The use of co-located multiple spectroscopic techniques can provide detailed information on the atmospheric processes regulating aerosol chemical composition and mixing state. So far, field campaigns heavily equipped with aerosol mass spectrometers have been carried out mainly in large conurbations and in areas directly affected by their outflow, whereas lesser efforts have been dedicated to continental areas characterized by a less dense urbanization. We present here the results obtained in San Pietro Capofiume, which is located in a sparsely inhabited sector of the Po Valley, Italy. The experiment was carried out in summer 2009 in the framework of the EUCAARI project ("European Integrated Project on Aerosol, Cloud Climate Aerosol Interaction"). For the first time in Europe, six state-of-the-art techniques were used in parallel: (1) on-line TSI aerosol time-of-flight mass spectrometer (ATOFMS), (2) on-line Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS), (3) soot particle aerosol mass spectrometer (SP-AMS), (4) on-line high resolution time-of-flight mass spectrometer-thermal desorption aerosol gas chromatograph (HR-ToFMS-TAG), (5) off-line twelve-hour resolution proton nuclear magnetic resonance (H-NMR) spectroscopy, and (6) chemical ionization mass spectrometry (CIMS) for the analysis of gas-phase precursors of secondary aerosol. Data from each aerosol spectroscopic method were analysed individually following ad-hoc tools (i.e. PMF for AMS, Art-2a for ATOFMS). The results obtained from each techniques are herein presented and compared. This allows us to clearly link the modifications in aerosol chemical composition to transitions in air mass origin and meteorological regimes. Under stagnant conditions, atmospheric stratification at night and early morning hours led to the accumulation of aerosols produced by anthropogenic sources distributed over the Po Valley plain. Such aerosols include primary components such as black carbon (BC), only partly internally mixed with secondary semivolatile compounds such as ammonium nitrate and amines. Other organic components originating from anthropogenic sources at night include monocarboxylic acids which correspond to an AMS factor analogous to the "cooking" organic aerosol (COA) already identified in urban areas. In daytime, enhanced mixing in the planetary boundary layer (PBL) along with increasing temperature determined dramatic changes in aerosol composition caused by the evaporation of semivolatile components and by the entrainment of aged aerosols transported downwards from residual layers. In other words, the entrainment of aged air masses is responsible for the accumulation of low-volatility oxygenated organic aerosol (LV-OOAs) and also for the recycling of primary species such as black carbon. The LV-OOA concentrations were shown to correlate to the simple meteorological tracers of humid PBL air produced by daytime convection over land areas. In particular, both PMF-AMS and PMF-NMR could resolve two components of LV-OOA: one from long-range transport from Central Europe, the second from recirculated PBL air from the Po Valley. According to organic aerosol source apportionment by PMFAMS, anthropogenic aerosols accumulating in the lower layers overnight accounted for 38% of organic aerosol mass on average, another 21% was accounted for by aerosols recirculated in residual layers but still originating in North Italy, while a substantial fraction (41 %) was due to the most aged aerosols imported from transalpine areas. Overall, the deployment of six state-of-the-art spectrometric techniques provided a comprehensive picture of the nature and source contributions of aerosols and aerosol precursors at a European rural site with unprecedented level of details. [ABSTRACT FROM AUTHOR]

Atmospheric organic aerosols are generally classified as primary and secondary (POA and SOA) according to their formation processes. An actual separation, however, is challenging when the timescales of emission and gas-toparticle formation overlap. The presence of SOA formation in biomass burning plumes leads to scientific questions about whether the oxidized fraction of biomass burning aerosol is rather of secondary or primary origin, as some studies would suggest, and about the chemical compositions of oxidized biomass burning POA and SOA. In this study, we apply nuclear magnetic resonance (NMR) spectroscopy to investigate the functional group composition of fresh and aged biomass burning aerosols during an intensive field campaign in the Po Valley, Italy. The campaign was part of the EUCAARI project and was held at the rural station of San Pietro Capofiume in spring 2008. Factor analysis applied to the set of NMR spectra was used to apportion the wood burning contribution and other organic carbon (OC) source contributions, including aliphatic amines. Our NMR results, referred to the polar, water-soluble fraction of OC, show that fresh wood burning particles are composed of polyols and aromatic compounds, with a sharp resemblance to wood burning POA produced in wood stoves, while aged samples are clearly depleted of alcohols and are enriched in aliphatic acids with a smaller contribution of aromatic compounds. The comparison with biomass burning organic aerosols (BBOA) determined by high-resolution aerosol mass spectrometry (HRTOF- AMS) at the site shows only a partial overlap between NMR BB-POA and AMS BBOA, which can be explained by either the inability of BBOA to capture all BB-POA composition, especially the alcohol fraction, or the fact that BBOA account for insoluble organic compounds unmeasured by the NMR. Therefore, an unambiguous composition for biomass burning POA could not be derived from this study, with NMR analysis indicating a higher O/C ratio compared to that measured for AMS BBOA. The comparison between the two techniques substantially improves when adding factors tracing possible contributions from biomass burning SOA, showing that the operational definitions of biomass burning organic aerosols are more consistent between techniques when including more factors tracing chemical classes over a range of oxidation levels. Overall, the non-fossil total carbon fraction was 50-57 %, depending on the assumptions about the 14C content of non-fossil carbon, and the fraction of organic carbon estimated to be oxidized organic aerosol (OOA) from HR-TOF-AMS measurements was 73-100% modern. [ABSTRACT FROM AUTHOR]

The interaction of aerosol with atmospheric water affects the processing and wet removal of atmospheric particles. Understanding such interaction is mandatory to improve model description of aerosol lifetime and ageing. We analyzed the aerosol-water interaction at high relative humidity during fog events in the Po Valley, in the framework of the ARPA-ER Supersite project. For the first time in this area, the changes in particle chemical composition caused by fog are discussed along with changes in particle microphysics. During the experiment, 14 fog events were observed. The average mass scavenging efficiency was 70% for nitrate, 68% for ammonium, 61% for sulfate, 50% for organics, and 39% for black carbon. After fog formation, the interstitial aerosol was dominated by particles smaller than 200 nm Dva (vacuum aerodynamic diameter) and enriched in carbonaceous aerosol, mainly black carbon and water insoluble organic aerosol (WIOA). For each fog event, the size segregated scavenging efficiency of nitrate and organic aerosol (OA) was calculated by comparing chemical species size distribution before and after fog formation. For both nitrate and OA, the size segregated scavenging efficiency followed a sigmoidal curve, with values close to zero below 100 nm Dva and close to 1 above 700 nm Dva. OA was able to affect scavenging efficiency of nitrate in particles smaller than 300 nm Dva. A linear correlation between nitrate scavenging and particle hygroscopicity (κ) was observed, indicating that 44-51% of the variability of nitrate scavenging in smaller particles (below 300 nm Dva) was explained by changes in particle chemical composition. The size segregated scavenging curves of OA followed those of nitrate, suggesting that organic scavenging was controlled by mixing with water-soluble species. In particular, functional group composition and OA elemental analysis indicated that more oxidized OA was scavenged more efficiently than less oxidized OA. Nevertheless, the small variability of organic functional group composition during the experiment did not allow us to discriminate the effect of different organic functionalities on OA scavenging. [ABSTRACT FROM AUTHOR]

Continuous measurements of physical and chemical properties at the Mt. Cimone (Italy) GAW-WMO (Global Atmosphere Watch, World Meteorological Organization) Global Station (2165ma.s.l.) have allowed the detection of the volcanic aerosol plume resulting from the Eyjafjallajökull (Iceland) eruption of spring 2010. The event affected the Mt. Cimone site after a transport over a distance of more than 3000 km. Two main transport episodes were detected during the eruption period, showing a volcanic fingerprint discernible against the free tropospheric background conditions typical of the site, the first from April 19 to 21 and the second from 18 to 20 May 2010. This paper reports the modification of aerosol characteristics observed during the two episodes, both characterised by an abrupt increase in fine and, especially, coarse mode particle number. Analysis of major, minor and trace elements by different analytical techniques (ionic chromatography, particle induced X-ray emission-particle induced gamma-ray emission (PIXE-PIGE) and inductively coupled plasma mass spectrometry (ICP-MS)) were performed on aerosols collected by ground-level discrete sampling. The resulting database allows the characterisation of aerosol chemical composition during the volcanic plume transport and in background conditions. During the passage of the volcanic plume, the fine fraction was dominated by sulphates, denoting the secondary origin of this mode, mainly resulting from in-plume oxidation of volcanic SO2. By contrast, the coarse fraction was characterised by increased concentration of numerous elements of crustal origin, such as Fe, Ti, Mn, Ca, Na, and Mg, which enter the composition of silicate minerals. Data analysis of selected elements (Ti, Al, Fe, Mn) allowed the estimation of the volcanic plume's contribution to total PM10, resulting in a local enhancement of up to 9.5 μgm-3, i.e. 40% of total PM10 on 18 May, which was the most intense of the two episodes. These results appear significant, especially in light of the huge distance of Mt. Cimone from the source, confirming the widespread diffusion of the Eyjafjallajökull ashes over Europe. [ABSTRACT FROM AUTHOR]

The atmospheric organic aerosol composition is characterized by a great diversity of functional groups and chemical species, challenging simple classification schemes. Traditional offline chemical methods identify chemical classes based on the retention behaviour on chromatographic columns and absorbing beds. Such an approach led to the isolation of complex mixtures of compounds such as the humiclike substances (HULIS). More recently, online aerosol mass spectrometry (AMS) was employed to identify chemical classes by extracting fragmentation patterns from experimental data series using statistical methods (factor analysis), providing simplified schemes for the classification of oxygenated organic aerosols (OOAs) on the basis of the distribution of oxygen-containing functionalities. The analysis of numerous AMS data sets suggested the occurrence of very oxidized OOAs which were postulated to correspond to HULIS. However, only a few efforts were made to test the correspondence of the AMS classes of OOAs with the traditional classifications from the offline methods. In this paper, we consider a case study representative of polluted continental regional background environments. We examine the AMS factors for OOAs identified by positive matrix factorization (PMF) and compare them to chemical classes of water-soluble organic carbon (WSOC) analysed offline on a set of filters collected in parallel. WSOC fractionation was performed by means of factor analysis applied to proton nuclear magnetic resonance (NMR) spectroscopic data, and by applying an ion-exchange chromatographic method for direct quantification of HULIS. Results show that the very oxidized low-volatility OOAs from AMS correlate with the NMR factor showing HULIS features and also with true "chromatographic" HULIS. On the other hand, UV/VISabsorbing polyacids (or HULIS sensu stricto) isolated on ion-exchange beds were only a fraction of the AMS and NMR organic carbon fractions showing functional groups attributable to highly substituted carboxylic acids, suggesting that unspeciated low-molecular weight organic acids contribute to HULIS in the broad sense. [ABSTRACT FROM AUTHOR]

Continuous measurements of physical and chemical properties at the Mt. Cimone GAW-WMO Global Station (2165ma.s.l.) allowed the detection of the volcanic aerosol plume resulting from the Eyjafjallajökull eruption of spring 2010. The event affected the site after a transport over a distance of more than 3000 km. Two main transport episodes were detected during the eruption period, showing a volcanic fingerprint discernible against the free tropospheric background conditions typical of the site, the first from 19 to 21 April and the second from 18 to 20 May 2010. The paper reports the modification of aerosol characteristics observed during the two episodes, both characterized by an abrupt increase in fine and, especially, coarse mode particle number. Analysis of major, minor and trace elements by different analytical techniques (Ionic Chromatography, PIXE-PIGE and ICP-MS) were performed on aerosols collected by ground level discrete sampling. The resulting database allows the characterization of aerosol chemical composition during the volcanic plume transport and in background conditions. During the passage of the volcanic plume, the fine fraction was dominated by sulphates, denoting the secondary origin of this mode, mainly resulting from inplume oxidation of volcanic SO2. By contrast, the coarse fraction was characterized by increased concentration of numerous elements of crustal origin, such as Fe, Ti, Mn, Ca, Na, and Mg, which enter the composition of silicate minerals. Data analysis of selected elements (Ti, Al, Fe, Mn) allowed the estimation of the volcanic plume's contribution to total PM10, resulting in a local enhancement of up to 9.5 µgm-3, i.e. 40% of total PM10, on 18 May, which was the most intense of the two episodes. These results appear significant, especially in the light of the huge distance of Mt. Cimone from the source, confirming the widespread diffusion of the Eyjafjallajokull ashes over Europe. [ABSTRACT FROM AUTHOR]

Atmospheric aerosols have been sampled and characterised at the Mace Head North East (N.E.) Atlantic atmospheric research station since 1958, with many interesting phenomena being discovered. However, with the range of new discoveries and scientific advances, there has been a range of concomitant criticisms challenging the representativeness of aerosol sampled at the station to that of aerosol over the open ocean. Two recurring criticisms relate to the lack of representativeness due to enhanced coastal sources, thereby leading to artificially high values to aerosol parameters, and to the influence of long-range transport of anthropogenic aerosol and its potential dominance over, or drowning-out of, a natural marine aerosol signal. Here we review the results of previous experimental studies into marine aerosols over the N.E. Atlantic and at Mace Head with the aim of evaluating their representativeness relative to that of an open ocean aerosol with negligible anthropogenic influence. Particular focus is given to organic matter (OM) aerosol. In summary, no correlation was found between OM and black carbon (BC) either at BC levels of 0-15 or 15-50 ngm-3, suggesting that OM concentrations up to peak values of 3.8 μgm-3 are predominantly natural in origin. Sophisticated carbon isotope analysis and aerosol mass spectral finger printing corroborate the natural source of OM with 80% biogenic source apportionment being observed for general clean air conditions, rising to 98% during specific primary marine organic plumes when peak concentrations >3 μgm-3 are observed. A range of other experiments are discussed which corroborate the dominance of a marine signal under Mace Head clean air criteria along. Further, analysis of a series of experiments conducted at Mace Head conclude that negligible coastal, surf zone, or tidal effects are discernible in the submicron size range for sampling heights of 7m and above. The Mace Head clean air criteria ensures anthropogenic and coastal effects are sufficiently minimised so as to guarantee a dominant, if not at times, an overwhelming natural marine aerosol signal. [ABSTRACT FROM AUTHOR]

The chemistry of submicron particles was investigated at San Pietro Capofiume (SPC) measurement station in the Po Valley, Italy, in spring 2008. The measurements were performed by using both off-line and on-line instruments. Organic carbon (OC) and elemental carbon, organic acids and biomass burning tracers were measured off-line by using a 24-h PM1 filter sampling. More detailed particle chemistry was achieved by using a Aerodyne high resolution time-off-light aerosol mass spectrometer (HR-ToF-AMS) and analyzing the data by positive matrix factorization (PMF). Oxalic acid had the highest concentrations of organic acids (campaign-average 97.4 ng m-3) followed by methane sulfonic, formic, malonic, and malic acids. Samples were also analyzed for glyoxylic, succinic, azelaic and maleic acids. In total, the nine acids composed 1.9 and 3.8% of OC and water-soluble OC, respectively (average), in terms of carbon atoms. Levoglucosan concentration varied from 17.7 to 495 ng m-3 with the concentration decreasing in the course of the campaign most likely due to the reduced use of domestic heating with wood. Six factors were found for organic aerosol (OA) at SPC by PMF: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), nitrogen-containing OA (NOA) and three different oxygenated OAs (OOA-a, OOA-b and OOA-c). Most of the OA mass was composed of OOAa, HOA and OOA-c (26, 24 and 22%, respectively) followed by OOA-b (13%), BBOA (8%) and N-OA (7%). As expected, OOAs were the most oxygenated factors with organic matter:organic carbon (OM: OC) ratios ranging from 1.9 to 2.2. The diurnal variability of the aerosol chemical composition was greatly affected by the boundary layer meteorology. Specifically, the effect of the nocturnal layer break-up in morning hours was most evident for nitrate and N-OA indicating that these compounds originated mainly from the local sources in the Po Valley. For sulfate and OOA-a the concentration did not change during the break-up suggesting their origin to be mostly regional. That resulted in much more oxidized OA in the daytime mixing layer than in the nocturnal surface layer. In this study, the high mass resolution and source-related aerosol chemistry from the HR-ToF-AMS was combined with the filter measurements in a total new extent elucidating novel features and sources of organic aerosol in the Po Valley region. [ABSTRACT FROM AUTHOR]

Measurements of aerosol chemical composition made on the island of Lampedusa, south of the Sicily channel, during years 2004-2008, are used to identify the in- fluence of heavy fuel oil (HFO) combustion emissions on aerosol particles in the Central Mediterranean. Aerosol samples influenced by HFO are characterized by elevated Ni and V soluble fraction (about 80% for aerosol from HFO combustion, versus about 40% for crustal particles), high V and Ni to Si ratios, and values of Vsol > 6 ng m-3. Evidence of HFO combustion influence is found in 17% of the daily samples. Back trajectories analysis on the selected events show that air masses prevalently come from the Sicily channel region, where an intense ship traffic occurs. This behavior suggests that single fixed sources like refineries are not the main responsible for the elevated V and Ni events, which are probably mainly due to ships emissions. Vsol, Nisol, and non-sea salt Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed. show a marked seasonal behaviour, with an evident summer maximum. Such a pattern can be explained by several processes: (i) increased photochemical activity in summer, leading to a faster production of secondary aerosols, mainly Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed. , from the oxidation of SO2 (ii) stronger marine boundary layer (MBL) stability in summer, leading to higher concentration of emitted compounds in the lowest atmospheric layers. A very intense event in spring 2008 was studied in detail, also using size segregated chemical measurements. These data show that elements arising from heavy oil combustion (V, Ni, Al, Fe) are distributed in the sub-micrometric fraction of the aerosol, and the metals are present as free metals, carbonates, oxides hydrates or labile complex with organic ligands, so that they are dissolved in mild condition (HNO3, pH1.5). Data suggest a characteristic Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed. ratio in the range 200-400 for HFO combustion aerosols in summer at Lampedusa. By using the value of 200 a lower limit for the HFO contribution to total sulphates is estimated. HFO combustion emissions account, as a summer average, at least for 1.2 µgm-3, representing about 30% of the total Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed. , 3.9% of PM10, 8% of PM2.5, and 11% of PM1. Within the used dataset, sulphate from HFO combustion emissions reached the peak value of 6.1 µgm-3 on 26 June 2008, when it contributed by 47% to Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed. , and by 15% to PM10. [ABSTRACT FROM AUTHOR]

The number concentration of cloud droplets determines several climatically relevant cloud properties. A major cause for the high uncertainty in the indirect aerosol forcing is the availability of cloud condensation nuclei (CCN), which in turn is highly sensitive to atmospheric new particle formation. Here we present the effect of new particle formation on anthropogenic aerosol forcing in present-day (year 2000) and future (year 2100) conditions. The present-day total aerosol forcing is increased from -1.0Wm-2 to -1.6Wm-2 when nucleation is introduced into the model. Nucleation doubles the change in aerosol forcing between years 2000 and 2100, from +0.6Wm-2 to +1.4Wm-2. Two climate feedbacks are studied, resulting in additional negative forcings of -0.1Wm-2 (+10% DMS emissions in year 2100) and -0.5Wm-2 (+50% BVOC emissions in year 2100). With the total aerosol forcing diminishing in response to air pollution control measures taking effect, warming from increased greenhouse gas concentrations can potentially increase at a very rapid rate. [ABSTRACT FROM AUTHOR]

The study investigates the sources of fine organic aerosol (OA) in the boreal forest, based on measurements including both filter sampling (PM1) and online methods and carried out during a one-month campaign held in Hyytiälä, Finland, in spring 2007. Two aerosol mass spectrometers (Q-AMS, ToF-AMS) were employed to measure on-line concentrations of major non-refractory aerosol species, while the water extracts of the filter samples were analyzed by nuclear magnetic resonance (NMR) spectroscopy for organic functional group characterization of the polar organic fraction of the aerosol. AMS and NMR spectra were processed separately by non-negative factorization algorithms, in order to apportion the main components underlying the submicrometer organic aerosol composition and depict them in terms of both mass fragmentation patterns and functional group compositions. The NMR results supported the AMS speciation of oxidized organic aerosol (OOA) into two main fractions, which could be generally labelled as more and less oxidized organics. The more oxidized component was characterized by a mass spectrum dominated by the m/z 44 peak, and in parallel by a NMR spectrum showing aromatic and aliphatic backbones highly substituted with oxygenated functional groups (carbonyls/carboxyls and hydroxyls). Such component, contributing on average 50% of the OA mass throughout the observing period, was associated with pollution outbreaks from the Central Europe. The less oxidized component was enhanced in concomitance with air masses originating from the North-to-West sector, in agreement with previous investigations conducted at this site. NMR factor analysis was able to separate two distinct components under the less oxidized fraction of OA. One of these NMR-factors was associated with the formation of terrestrial biogenic secondary organic aerosol (BSOA), based on the comparison with spectral profiles obtained from laboratory experiments of terpenes photooxidation. The second NMR factor associated with western air masses was linked to biogenic marine sources, and was enriched in low-molecular weight aliphatic amines. Such findings provide evidence of at least two independent sources originating biogenic organic aerosols in Hyytiälä by oxidation and condensation mechanisms: reactive terpenes emitted by the boreal forest and compounds of marine origin, with the latter relatively more important when predominantly polar air masses reach the site. This study is an example of how spectroscopic techniques, such as proton NMR, can add functional group specificity for certain chemical features (like aromatics) of OA with respect to AMS. They can therefore be profitably exploited to complement aerosol mass spectrometric measurements in organic source apportionment studies [ABSTRACT FROM AUTHOR]

The new global anthropogenic emission inventory (EDGAR-CIRCE) of gas and aerosol pollutants has been incorporated in the chemistry general circulation model EMAC (ECHAM5/MESSy Atmospheric Chemistry). A relatively high horizontal resolution simulation is performed for the years 2005-2008 to evaluate the capability of the model and the emissions to reproduce observed aerosol concentrations and aerosol optical depth (AOD) values. Model output is compared with observations from different measurement networks (CASTNET, EMEP and EANET) and AODs from remote sensing instruments (MODIS and MISR). A good spatial agreement of the distribution of sulfate and ammonium aerosol is found when compared to observations, while calculated nitrate aerosol concentrations show some discrepancies. The simulated temporal development of the inorganic aerosols is in line with measurements of sulfate and nitrate aerosol, while for ammonium aerosol some deviations from observations occur over the USA, due to the wrong temporal distribution of ammonia gas emissions. The calculated AODs agree well with the satellite observations in most regions, while negative biases are found for the equatorial area and in the dust outflow regions (i.e. Central Atlantic and Northern Indian Ocean), due to an underestimation of biomass burning and aeolian dust emissions, respectively. Aerosols and precursors budgets for five different regions (North America, Europe, East Asia, Central Africa and South America) are calculated. Over East-Asia most of the emitted aerosols (precursors) are also deposited within the region, while in North America and Europe transport plays a larger role. Further, it is shown that a simulation with monthly varying anthropogenic emissions typically improves the temporal correlation by 5-10% compared to one with constant annual emissions. [ABSTRACT FROM AUTHOR]

We discuss the use of a two-dimensional volatility-oxidation space (2-D-VBS) to describe organicaerosol chemical evolution. The space is built around two coordinates, volatility and the degree of oxidation, both of which can be constrained observationally or specified for known molecules. Earlier work presented the thermodynamics of organics forming the foundation of this 2-D-VBS, allowing us to define the average composition (C, H, and O) of organics, including organic aerosol (OA) based on volatility and oxidation state. Here we discuss how we can analyze experimental data, using the 2-D-VBS to gain fundamental insight into organic-aerosol chemistry. We first present a well-understood "traditional" secondary organic aerosol (SOA) system -- SOA from α-pinene + ozone, and then turn to two examples of "non-traditional" SOA formation -- SOA from wood smoke and dilute diesel-engine emissions. Finally, we discuss the broader implications of this analysis. [ABSTRACT FROM AUTHOR]

In this paper we describe and summarize the main achievements of the European Aerosol Cloud Climate and Air Quality Interactions project (EUCAARI). EUCAARI started on 1 January 2007 and ended on 31 December 2010 leaving a rich legacy including: (a) a comprehensive database with a year of observations of the physical, chemical and optical properties of aerosol particles over Europe, (b) comprehensive aerosol measurements in four developing countries, (c) a database of airborne measurements of aerosols and clouds over Europe during May 2008, (d) comprehensive modeling tools to study aerosol processes fron nano to global scale and their effects on climate and air quality. In addition a new Pan-European aerosol emissions inventory was developed and evaluated, a new cluster spectrometer was built and tested in the field and several new aerosol parameterizations and computations modules for chemical transport and global climate models were developed and evaluated. These achievements and related studies have substantially improved our understanding and reduced the uncertainties of aerosol radiative forcing and air quality-climate interactions. The EUCAARI results can be utilized in European and global environmental policy to assess the aerosol impacts and the corresponding abatement strategies. [ABSTRACT FROM AUTHOR]

In this paper we describe and summarize the main achievements of the European Aerosol Cloud Climate and Air Quality Interactions project (EUCAARI). EUCAARI started on 1 January 2007 and ended on 31 December 2010 leaving a rich legacy including: (a) a comprehensive database with a year of observations of the physical, chemical and optical properties of aerosol particles over Europe, (b) comprehensive aerosol measurements in four developing countries, (c) a database of airborne measurements of aerosols and clouds over Europe during May 2008, (d) comprehensive modeling tools to study aerosol processes fron nano to global scale and their effects on climate and air quality. In addition a new Pan-European aerosol emissions inventory was developed and evaluated, a new cluster spectrometer was built and tested in the field and several new aerosol parameterizations and computations modules for chemical transport and global climate models were developed and evaluated. These achievements and related studies have substantially improved our understanding and reduced the uncertainties of aerosol radiative forcing and air quality-climate interactions. The EUCAARI results can be utilized in European and global environmental policy to assess the aerosol impacts and the corresponding abatement strategies. [ABSTRACT FROM AUTHOR]