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The literature on atmospheric particulate matter (PM), or atmospheric aerosol, has increased enormously over the last 2 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 have 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 for climate change policies. In this context, this paper reviews the most recent results within the atmospheric aerosol sciences and the policy needs, which have driven much of the increase in monitoring and mechanistic research over the last 2 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. However, while airborne particulate matter is responsible for globally important influences on premature human mortality, we still do not know the relative importance of the 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 black carbon (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 the effects of atmospheric PM on the climate and the health of the environment and the human population. A prioritized list of actions to mitigate the full range of effects of PM is currently undeliverable due to shortcomings in the knowledge of aerosol science; among the shortcomings, 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. In any case, the evidence from this paper strongly advocates for an integrated approach to air quality and climate policies.

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 Tg N yr-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 Tg N yr-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 Tg N yr-1 in 2008 to 93 Tg N yr-1 in 2100 assuming a change in global surface temperature of 5 degree 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 Tg N yr-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 SO42- 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.

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 within the framework of the Agenzia Regionale per la Prevenzione e l'Ambiente (ARPA) – Emilia Romagna 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. 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.

For oceans to be a significant source of primary organic aerosol (POA), sea spray aerosol (SSA) must be highly enriched with organics relative to the bulk seawater. We propose that organic enrichment at the air-sea interface, chemical composition of seawater, and the aerosol size are three main parameters controlling the organic mass fraction of sea spray aerosol (OMSSA). To test this hypothesis, we developed a new marine POA emission function based on a conceptual relationship between the organic enrichment at the air-sea interface and surface wind speed. The resulting parameterization is explored using aerosol chemical composition and surface wind speed from Atlantic and Pacific coastal stations, and satellite-derived ocean concentrations of chlorophyll-a, dissolved organic carbon, and particulate organic carbon. Of all the parameters examined, a multi-variable logistic regression revealed that the combination of 10 m wind speed and surface chlorophyll-a concentration ([Chl-a]) are the most consistent predictors of OMSSA. This relationship, combined with the published aerosol size dependence of OMSSA, resulted in a new parameterization for the organic mass fraction of SSA. Global emissions of marine POA are investigated here by applying this newly-developed relationship to existing sea spray emission functions, satellite-derived [Chl-a], and modeled 10 m winds. Analysis of model simulations shows that global annual submicron marine organic emission associated with sea spray is estimated to be from 2.8 to 5.6 Tg C yr−1. This study provides additional evidence that marine primary organic aerosols are a globally significant source of organics in the atmosphere.

The organic chemical composition of atmospheric submicron particles in the marine boundary layer was characterized over the northeast Atlantic Ocean in summer 2006, during the season of phytoplankton blooms, in the frame of the Marine Aerosol Production (MAP) experiment. First measurements of water‐insoluble organic carbon (WIOC) in marine aerosol particles by nuclear magnetic resonance (NMR) spectroscopy showed that it is structurally similar to lipids, resembling the organic fraction of sea spray formed during bubble‐bursting experiments. The composition of the water‐soluble organic carbon (WSOC) fraction was investigated by liquid chromatography – mass spectrometry and by 1D‐ and 2D‐NMR spectroscopy, and showed a less hydrophilic fraction containing traces of fatty acids and rich of alkanoic acids formed by lipid degradation, and a more hydrophilic fraction, containing more functionalized species encompassing short‐chain aliphatic acids and sulfate esters of hydroxyl‐carboxylic acids. The more oxidized fraction of WSOC accounts for the oxidized organic aerosol components, which can form by either gas‐to‐particle conversion or extensive chemical aging of lipid‐containing primary particles, as also suggested by the parallel measurements using online mass spectrometric techniques (presented in a companion paper), showing oxidized organic substances internally mixed with sea salt particles. These measurements are also compared with online measurements using an Aerosol Time‐Of‐Flight Mass Spectrometer (ATOFMS) and Aerodyne Aerosol Mass Spectrometer (AMS). Given the large variability in the chemical composition of marine organic aerosol particles, a multitechnique approach is recommended to reduce method‐dependent categorizations and oversimplifications and to improve the comparability with the results obtained in different oceanic areas. Key Points Marine organic aerosol is a mixture of primary and secondary components Water‐insoluble organics in marine aerosol are related to primary production Aging of primary organic aerosol is as important as gas‐to‐particle conversion

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-of-flight 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 (N-OA) and three different oxygenated OAs (OOA-a, OOA-b and OOA-c). Most of the OA mass was composed of OOA-a, 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.

Sulphuric acid and organic vapours have been identified as the key components in the ubiquitous secondary new particle formation in the atmosphere. In order to assess their relative contribution and spatial variability, we analysed altogether 36 new particle formation events observed at four European measurement sites during EUCAARI campaigns in 2007-2009. We tested models of several different nucleation mechanisms coupling the formation rate of neutral particles (J) with the concentration of sulphuric acid ([H2 SO4 ]) or low-volatility organic vapours ([org]) condensing on sub-4 nm particles, or with a combination of both concentrations. Furthermore, we determined the related nucleation coefficients connecting the neutral nucleation rate J with the vapour concentrations in each mechanism. The main goal of the study was to identify the mechanism of new particle formation and subsequent growth that minimizes the difference between the modelled and measured nucleation rates. At three out of four measurement sites - Hyytiälä (Finland), Melpitz (Germany) and San Pietro Capofiume (Italy) - the nucleation rate was closely connected to squared sulphuric acid concentration, whereas in Hohenpeissenberg (Germany) the low-volatility organic vapours were observed to be dominant. However, the nucleation rate at the sulphuric acid dominant sites could not be described with sulphuric acid concentration and a single value of the nucleation coefficient, as K in J=K [H2 SO4 ]2 , but the median coefficients for different sites varied over an order of magnitude. This inter-site variation was substantially smaller when the heteromolecular homogenous nucleation between H2 SO4 and organic vapours was assumed to take place in addition to homogenous nucleation of H2 SO4 alone, i.e., J=KSA1 [H2 SO4 ]2 +KSA2 [H2 SO4 ][org]. By adding in this equation a term describing homomolecular organic vapour nucleation, Ks3 [org]2 , equally good results were achieved. In general, our results suggest that organic vapours do play a role, not only in the condensational growth of the particles, but also in the nucleation process, with a site-specific degree.

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.

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 humic-like 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/VIS-absorbing 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.

Dual carbon isotope analysis of marine aerosol samples has been performed for the first time demonstrating a potential in organic matter apportionment between three principal sources: marine, terrestrial (non-fossil) and fossil fuel due to unique isotopic signatures. The results presented here, utilising combinations of dual carbon isotope analysis, provides conclusive evidence of a dominant biogenic organic fraction to organic aerosol over biologically active oceans. In particular, the NE Atlantic, which is also subjected to notable anthropogenic influences via pollution transport processes, was found to contain 80 % organic aerosol matter of biogenic origin directly linked to plankton emissions. The remaining carbonaceous aerosol was of terrestrial origin. By contrast, for polluted air advected out from Europe into the NE Atlantic, the source apportionment is 30 % marine biogenic, 40 % fossil fuel, and 30 % continental non-fossil fuel. The dominant marine organic aerosol source in the atmosphere has significant implications for climate change feedback processes.