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Brown carbon is a type of carbonaceous aerosol with strong light absorption in the ultraviolet and visible wavelengths that leads to radiative forcing. However, it is difficult to correlate the chemical composition of brown carbon with its atmospheric light absorption properties, which translates into significant uncertainty. Thus, a time-dependent density functional theory (TD-DFT) approach was used to model the real-world absorption properties of 14 polycyclic aromatic hydrocarbons (PAHs) over three regions of the Basque Country (Spain): Bilbao, Urretxu, and Azpeitia. The data were corrected for atmospheric concentration. The results show that the absorption spectra over each region are qualitatively identical, with the absorption intensities being significantly higher over Bilbao than over Azpeitia and Urretxu. Furthermore, it was found that the light absorption by PAHs should be more relevant for radiative forcing when it occurs at UVA and (sub)visible wavelengths. Finally, among the 14 studied PAHs, benzo[b]fluoranthene, pyrene, fluoranthene, benzo[a]pyrene, and benzo[k]fluoranthene and benzoperylene were identified as the molecules with larger contributions to radiative forcing.

Two approaches were applied for characterization of organic compounds in the atmospheric aerosols. These were chemical and statistical grouping analysis. We applied chemical group analysis as a new approach using the GC×GC data. Based on the principle of GC×GC, analytes in two dimensional data were divided into 6 chemical group depending on their volatility and polarity. Using this classification standards, all analytes were classified as one of 6 chemical groups, HP-VOC, LP-VOC, HP-SVOC, LP-SVOC, HP-NVOC and LP-NVOC. The relationship between the sum of the peak areas of each chemical group with other variables such as the concentrations of OC, EC, OCPOC, OC/EC and OCSOC were studied. However, no apparent relationship was observed. The principle component analysis (PCA) was carried out to find out the relationship among the analytes based on their sources. The OVOCs were dominant compounds in 3 out of 4 factors in summer. In winter, factor 1 was related to secondary organic aerosol and factor 3 was related to primary emission sources. The proposed approach looks promising in characterization of chemical groups but have limitations at current stage which are discussed.

International initiatives have successfully brought down the emissions, and hence also the related negative impacts on environment and human health, from shipping in Emission Control Areas (ECAs). However, the question remains as to whether increased shipping in the future will counteract these emission reductions. The overall goal of this study is to provide an up-to-date view on future ship emissions and provide a holistic view on atmospheric pollutants and their contribution to air quality in the Nordic (and Arctic) area. The first step has been to set up new and detailed scenarios for the potential developments in global shipping emissions, including different regulations and new routes in the Arctic. The scenarios include a Baseline scenario and two additional SOx Emission Control Areas (SECAs) and heavy fuel oil (HFO) ban scenarios. All three scenarios are calculated in two variants involving Business-As-Usual (BAU) and High-Growth (HiG) traffic scenarios. Additionally a Polar route scenario is included with new ship traffic routes in the future Arctic with less sea ice. This has been combined with existing Current Legislation scenarios for the land-based emissions (ECLIPSE V5a) and used as input for two Nordic chemistry transport models (DEHM and MATCH). Thereby, the current (2015) and future (2030, 2050) air pollution levels and the contribution from shipping have been simulated for the Nordic and Arctic areas. Population exposure and the number of premature deaths attributable to air pollution in the Nordic area have thereafter been assessed by using the health assessment model EVA (Economic Valuation of Air pollution). It is estimated that within the Nordic region approximately 9900 persons died prematurely due to air pollution in 2015 (corresponding to approximately 37 premature deaths for every 100 000 inhabitants). When including the projected development in both shipping and land-based emissions, this number is estimated to decrease to approximately 7900 in 2050. Shipping alone is associated with about 850 premature deaths during present-day conditions (as a mean over the two models), decreasing to approximately 600 cases in the 2050 BAU scenario. Introducing a HFO ban has the potential to lower the number of cases associated with emissions from shipping to approximately 550 in 2050, while the SECA scenario has a smaller impact. The “worst-case” scenario of no additional regulation of shipping emissions combined with a high growth in the shipping traffic will, on the other hand, lead to a small increase in the relative impact of shipping, and the number of premature deaths related to shipping is in that scenario projected to be around 900 in 2050. This scenario also leads to increased deposition of nitrogen and black carbon in the Arctic, with potential impacts on environment and climate.

International audience; The gas-phase reaction of trans-2-pentenal (T2P) with Cl atoms was studied at atmospheric pressure and room temperature. A rate coefficient of (2.56 ± 0.83) × 10-10 cm3 molecule-1 s-1 was obtained using the relative rate method and isoprene, cyclohexane and ethanol as reference compounds. The kinetic study was carried out using a 300-L Teflon bag simulation chamber (IMT Lille Douai-France) and a 16-L Pyrex cell (UCLM-Ciudad Real-Spain), both coupled to the Fourier transform infrared (FTIR) technique. Gas-phase products and secondary organic aerosol (SOA) formation were studied at UCLM using a 16-L Pyrex cell and a 264-L quartz simulation chamber coupled to the FTIR and gas-chromatography-mass spectrometry (GC-MS) techniques. HCl, CO, and propanal were identified as products formed from the studied reaction and quantified by FTIR, the molar yield of the latter being (5.2 ± 0.2)%. Formic acid was identified as a secondary product and was quantified by FTIR with a yield of (6.2 ± 0.4)%. In addition, 2-chlorobutanal and 2–pentenoic acid were identified, but not quantified, by GC-MS as products. The SOA formation was investigated using a fast mobility particle sizer spectrometer. The observed SOA yields reached maximum values of around 7% at high particle mass concentrations. This work provides the first study of the formation of gaseous and particulate products for the reaction of Cl with T2P. A reaction mechanism is suggested to explain the formation of the observed gaseous products. The results are discussed in terms of structure-reactivity relationship, and the atmospheric implications derived from this study are commented as well.

Matrix-induced signal suppression or enhancements are known phenomena in electrospray ionization mass spectrometry. Very few studies report on method development for organic aerosols analyses with the evaluation of the matrix effects. The matrix effects lead to errors in the quantification of the analytes and affect the detection capability, precision, and accuracy of an analysis method. The present study reports on the matrix effects in the analysis of organic chemical compounds present in atmospheric aerosol particles collected on quartz filters. A total number of 19 analytes, including different classes of organic compounds, such as monoaromatic phenols and derivatives (e.g., catechol, 4-methylcatechol, 3-methoxycatechol, 4-nitrocatechol, 4-nitrophenol, 2,4-dinitrophenol, 2,6-dimethyl-4-nitrophenol), carboxylic acids (terebic acid, adipic acid, pimelic acid, phthalic acid, vanillic acid), and sulfonic acids (e.g., camphor-10-sulfonic acid), was investigated by high-performance liquid chromatography coupled to electrospray ionization time-of-flight mass spectrometry (HPLC/ESI-ToF-MS). The HPLC and ESI set-up parameters used in this study were previously optimized for the investigated compounds. Different volumes of a standard mixture were added to sample extracts, with final solutions concentrations in the 50–1500 μg L−1 range. For the investigated concentration range, the observed matrix effect was independent of the standard concentration level. For quartz filter extracts, the average matrix effect determined on a concentration-based method was 109.5 ± 6.1%. Both signal suppression and enhancement effects were observed for different compounds. For other analytes, the influence of the matrix effect is variable, suggesting that the use of an internal standard is not sufficient for the matrix effects correction. Competition between analyte ions and matrix components in the gas-phase ionization processes occurring in electrospray might explain signal suppression while generated coeluted isobaric compounds might induce signal enhancement.

The current understanding of water-soluble organic aerosol (OA) composition, sources, transformations, and effects is still limited to outdoor scenarios. However, the OA is also an important component of particulate matter indoors, whose complexity impairs a full structural and molecular identification. The current limited knowledge on indoor OA, and particularly on its water-soluble organic matter (WSOM) fraction is the basis of this feature paper. Inspired by studies on outdoor OA, this paper discusses and prioritizes issues related to indoor water-soluble OA and their effects on human health, providing a basis for future research in the field. The following three main topics are addressed: (1) what is known about the origin, mass contribution, and health effects of WSOM in outdoor air particles; (2) the current state-of-the-art on the WSOM in indoor air particles, the main challenges and opportunities for its chemical characterization and cytotoxicity evaluation; and (3) why the aerosol WSOM should be considered in future indoor air quality studies. While challenging, studies on the WSOM fraction in air particles are highly necessary to fully understand its origin, fate, toxicity, and long-term risks indoors.

We analysed δ13C of total carbon (TC) and δ15N of total nitrogen (TN) in submicron (PM1) and size segregated aerosol particles (PM0.056–2.5) collected during a cruise in the Baltic Sea from 9 to 17 November 2012. PM1 were characterized by the highest δ13C (–26.4‰) and lowest δ15N (–0.2 and 0.8‰) values when air masses arrived from the southwest direction (Poland). The obtained δ13C values indicated that combined emissions of coal and diesel/gasoline combustion were the most likely sources of TC. The depleted δ15N values indicated that TN originated mainly from liquid fuel combustion (road traffic, shipping) during this period. The lowest δ13C and highest δ15N values were determined in PM1 samples during the western airflow when the air masses had no recent contact with land. The highest δ15N values were probably associated with chemical aging of nitrogenous species during long-range transport, the lowest δ13C values could be related to emissions from diesel/gasoline combustion, potentially from ship traffic. The δ13C analysis of size-segregated aerosol particles PM0.056–2.5 revealed that the lowest δ13C values were observed in the size range from 0.056 to 0.18 µm and gradual 13C enrichment occurred in the size range from 0.18 to 2.5 µm due to different sources or formation mechanisms of the aerosols.

The main emission source in Central and Southern Chilean cities is biomass combustion from residential heating and cooking due to old combustion technologies that are still widely utilized. In order to improve our understanding of biomass burning pollution and how it ages in the atmosphere, emissions from a pellet and wood stoves were studied with the aid of a photochemical chamber. Firewood combustion is an inefficient process that produces higher chamber loading of primary emission (gases and particles) compared to pellets. When these emissions are exposed to UV irradiation secondary particles are formed. However, with both fuels the secondary particle concentration was negligible with regards to the primary initial particle concentration. Observations show that when the initial mass is the same, firewood combustion emissions are more rapidly oxidized compared to emissions from pellet combustion. Particle aging evolution inside the chamber was evaluated using fragment tracer signals, via the mass fractions f44 vs f43 and f44 vs f60 triangles plots. For the same UV irradiation time, it was found that primary particles emitted form from firewood combustion show a slower aging rate compared to those emitted from pellet combustion, but this is due to high primary loading from wood combustion. Particle aging observed inside the chamber was similar to that found it in ambient urban air of Santiago de Chile in spring of 2011, indicating that chamber measurements can be a good indicator for some atmospheric processes. Levoglucosan, a well-known tracer for biomass combustion was also studied. It was found that wood stoves yielded higher levels than pellet stoves. This is due to the higher fuel combustion efficiency in pellet stoves, which yield low levoglucosan levels, making it difficult to use it for evaluation of the impact of pellet emissions on pollution.

Although atmospheric organic N compounds are considered to be important, especially in new particle formation and their contribution to brown carbon, these species are not that well understood. This can be partially attributed to their chemical complexity. Therefore, the aim of this study was to assess the characteristics of organic N compounds utilising comprehensive two-dimensional gas chromatography coupled with a time-of-flight mass spectrometer (GCxGC-TOFMS) in aerosol samples that were collected at a savanna-grassland background region and to determine the possible sources. 135 atmospheric organic N compounds were tentatively characterised and semi-quantified, which included amines, nitriles, amides, urea, pyridine derivatives, amino acids, nitro-and nitroso compounds, imines, cyanates and isocyanates, and azo compounds. Amines contributed to 51% of the semi-quantified concentrations, while nitriles, pyridine derivatives, and amides comprised 20%, 11%, and 8%, respectively, of the semi-quantified concentrations. Amines, nitriles, amides, and pyridine derivatives concentrations were higher during the dry season, which were attributed to meteorology and open biomass burning. Anthropogenic sources impacting air masses measured at Welgegund, as well as regional agricultural activities, were considered as the major sources of amines, while the regional influence of household combustion was most likely the main source of nitriles, amides, and pyridine derivatives. The other organic N species were most likely related to the influence of local and regional agricultural activities.

18 pages, 4 figures, 2 tables, supplement https://doi.org/10.5194/acp-19-10239-2019-supplement, There are limited measurements of the chemical composition, abundance and sources of atmospheric particles in the High Arctic To address this, we report 93 d of soot particle aerosol mass spectrometer (SP-AMS) data collected from 20 February to 23 May 2015 at Villum Research Station (VRS) in northern Greenland (81?360 N). During this period, we observed the Arctic haze phenomenon with elevated PM1 concentrations ranging from an average of 2.3, 2.3 and 3.3 μg m in February, March and April, respectively, to 1.2 μg m in May. Particulate sulfate (SO2 4-) accounted for 66 % of the non-refractory PM1 with the highest concentration until the end of April and decreasing in May. The second most abundant species was organic aerosol (OA) (24 %). Both OA and PM1, estimated from the sum of all collected species, showed a marked decrease throughout May in accordance with the polar front moving north, together with changes in aerosol removal processes. The highest refractory black carbon (rBC) concentrations were found in the first month of the campaign, averaging 0.2 μg m. In March and April, rBC averaged 0.1 μg m while decreasing to 0.02 μg m in May. Positive matrix factorization (PMF) of the OA mass spectra yielded three factors: (1) a hydrocarbon-like organic aerosol (HOA) factor, which was dominated by primary aerosols and accounted for 12 % of OA mass, (2) an Arctic haze organic aerosol (AOA) factor and (3) a more oxygenated marine organic aerosol (MOA) factor. AOA dominated until mid-April (64 %-81 % of OA), while being nearly absent from the end of May and correlated significantly with SO2-4, suggesting the main part of that factor is secondary OA. The MOA emerged late at the end of March, where it increased with solar radiation and reduced sea ice extent and dominated OA for the rest of the campaign until the end of May (24 %-74 % of OA), while AOA was nearly absent. The highest O=C ratio (0.95) and S=C ratio (0.011) was found for MOA. Our data support the current understanding that Arctic aerosols are highly influenced by secondary aerosol formation and receives an important contribution from marine emissions during Arctic spring in remote High Arctic areas. In view of a changing Arctic climate with changing sea-ice extent, biogenic processes and corresponding source strengths, highly time-resolved data are needed in order to elucidate the components dominating aerosol concentrations and enhance the understanding of the processes taking place, This research has been financially supported by the Danish Environmental Protection Agency and Danish Energy Agency with means from the MIKA/DANCEA funds for environmental support to the Arctic Region (project nos. MST-113-0079, 2016-3025, MST-112-00298) and the Danish Council for In dependent Research (project NUMEN, grant no. DFF-FTP-4005-00485B).

The OH-initiated heterogeneous oxidation of semi-solid saccharide particles with varying bulk compositions was investigated in an atmospheric pressure flow tube at 30% relative humidity. Reactive uptake coefficients were determined from the rate loss of the saccharide reactants measured by mass spectrometry at different monosaccharide (methyl-&beta, d-glucopyranoside, C7H14O6) and disaccharide (lactose, C12H22O11) molar ratios. The reactive uptake for the monosaccharide was found to decrease from 0.53 &plusmn, 0.10 to 0.05 &plusmn, 0.06 as the mono-to-disaccharide molar ratio changed from 8:1 to 1:1. A reaction&ndash, diffusion model was developed in order to determine the effect of chemical composition on the reactive uptake. The observed decays can be reproduced using a Vignes relationship to predict the composition dependence of the reactant diffusion coefficients. The experimental data and model results suggest that the addition of the disaccharide significantly increases the particle viscosity leading to slower mass transport phenomena from the bulk to the particle surface and to a decreased reactivity. These findings illustrate the impact of bulk composition on reactant bulk diffusivity which determines the rate-limiting step during the chemical transformation of semi-solid particles in the atmosphere.

© 2015 American Chemical Society. In the troposphere, the heterogeneous lifetime of an organic molecule in an aerosol exposed to hydroxyl radicals (OH) is thought to be weeks, which is orders of magnitude slower than the analogous gas phase reactions (hours). Here, we report an unexpectedly large acceleration in the effective heterogeneous OH reaction rate in the presence of NO. This 10-50 fold acceleration originates from free radical chain reactions, propagated by alkoxy radicals that form inside the aerosol by the reaction of NO with peroxy radicals, which do not appear to produce chain terminating products (e.g., alkyl nitrates), unlike gas phase mechanisms. A kinetic model, constrained by experiments, suggests that in polluted regions heterogeneous oxidation plays a much more prominent role in the daily chemical evolution of organic aerosol than previously believed.

In this work we report the study of the ozonolysis of 2,5-dihydrofuran and 2,3-dihydrofuran and the reaction conditions leading to the formation of secondary organic aerosols. The reactions have been carried out in a Teflon chamber filled with synthetic air mixtures at atmospheric pressure and room temperature. The ozonolysis only produced particles in the presence of SO2. Rising relative humidity from 0 to 40% had no effect on the production of secondary organic aerosol in the case of 2,5-dihydrofuran, while it reduced the particle number and particle mass concentrations from the 2,3-dihydrofuran ozonolysis. The water-to-SO2 rate constant ratio for the 2,3-dihydrofuran Criegee intermediate was derived from the secondary organic aerosol (SOA) yields in experiments with different relative humidity values, kH2O/kSO2 = (9.8 ± 3.7) × 10-5. The experimental results show that SO3 may not be the only intermediate involved in the formation or growth of new particles in contrast to the data reported for other Criegee intermediate-SO2 reactions. For the studied reactions, SO2 concentrations remained constant during the experiments, behaving as a catalyst in the production of condensable products. Computational calculations also show that the stabilised Criegee intermediates from the ozonolysis reaction of both 2,5-dihydrofuran and 2,3-dihydrofuran may react with SO2, resulting in the regeneration of SO2 and the formation of low-volatility organic acids., Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas

We focused this research on the composition of the organic aerosols transported in the two main airflows of the subtropical North Atlantic free troposphere: (i) the Saharan Air Layer - the warm, dry and dusty airstream that expands from North Africa to the Americas at subtropical and tropical latitudes - and (ii) the westerlies, which flow from North America over the North Atlantic at mid- and subtropical latitudes. We determined the inorganic compounds (secondary inorganic species and elemental composition), elemental carbon and the organic fraction (bulk organic carbon and organic speciation) present in the aerosol collected at Izaña Observatory, ∼2400m.a.s.l. on the island of Tenerife. The concentrations of all inorganic and almost all organic compounds were higher in the Saharan Air Layer than in the westerlies, with bulk organic matter concentrations within the range 0.02-4.0μ-3. In the Saharan Air Layer, the total aerosol population was by far dominated by dust (93% of bulk mass), which was mixed with secondary inorganic pollutants ( < 5%) and organic matter (∼1.5%). The chemical speciation of the organic aerosols (levoglucosan, dicarboxylic acids, saccharides, n-alkanes, hopanes, polycyclic aromatic hydrocarbons and those formed after oxidation of α-pinene and isoprene, determined by gas chromatography coupled with mass spectrometry) accounted for 15% of the bulk organic matter (determined by the thermo-optical transmission technique); the most abundant organic compounds were saccharides (associated with surface soils), secondary organic aerosols linked to oxidation of biogenic isoprene (SOA ISO) and dicarboxylic acids (linked to several primary sources and SOA). When the Saharan Air Layer shifted southward, Izaña was within the westerlies stream and organic matter accounted for 28% of the bulk mass of aerosols. In the westerlies, the organic aerosol species determined accounted for 64% of the bulk organic matter, with SOA ISO and dicarboxylic acids being the most abundant; the highest concentration of organic matter (3.6μ-3) and of some organic species (e.g. levoglucosan and some dicarboxylic acids) were associated with biomass burning linked to a fire in North America. In the Saharan Air Layer, the correlation found between SOA ISO and nitrate suggests a large-scale impact of enhancement of the formation rate of secondary organic aerosols due to interaction with anthropogenic NO emissions. © 2017 Author(s)., This study was performed within the context of the projects AEROATLAN (CGL2015-66299-P; MINECO/FEDER) and TEAPARTICLE (CGL2011-29621), supported by the Ministry of Economy and Competitiveness of Spain and the European Regional Development Fund (ERDF). The authors acknowledge the NOAA Air Resources Laboratory (ARL) for the provision of the HYSPLIT back-trajectories used in this publication. The excellent work performed by the staff of the Atmospheric Research Centre (Concepción Bayo, Cándida Hernández, Fernando de Ory, Virgilio Carreño, Rubén del Campo and SIELTEC Canarias) and of the Institute of Environmental Assessment and Water Research (Roser Chaler, Dori Fanjul, and Bibiano Hortelano) is appreciated. M. Isabel García acknowledges the grant of the Canarian Agency for Research, Innovation and Information Society (ACIISI), co-funded by the European Social Funds. Measurements at Izaña Observatory are performed within the context Global Atmospheric Watch networks with the financial support of the State Meteorological Agency of Spain (AEMET).

Aerosol samples were collected in autumn 2007 on day- and nighttime basis in the northern receptor site of Beijing, China. The samples were analyzed for total carbon (TC) and water-soluble dicarboxylic acids (C-2-C-12), oxocarboxylic adds (C-2-C-9), glyoxal and methylglyoxal to better understand the photochemical aging of organic aerosols in the vicinity of Beijing. Concentrations of TC are 50% greater in daytime when winds come from Beijing than in nighttime when winds come from the northern forest areas. Most diacids showed higher concentrations in daytime, suggesting that the organics emitted from the urban Beijing and delivered to the northern vicinity in daytime are subjected to photo-oxidation to result in diacids. However, oxalic acid (C-2), which is the most abundant diacid followed by C-3 or C-4, became on average 30% more abundant in nighttime together with azelaic, omega-oxooctanoic and omega-oxononanoic acids, which are specific oxidation products of biogenic unsaturated fatty acids. Methylglyoxal, an oxidation product of isoprene and a precursor of oxalic acid, also became 29% more abundant in nighttime. Based on a positive correlation between C-2 and glyoxylic acid (omega C-2) in nighttime when relative humidity significantly enhanced, we propose a nighttime aqueous phase production of C-2 via the oxidation of omega C-2. We found an increase in the contribution of diacids to TC by 3 folds during consecutive clear days. This study demonstrates that diacids and related compounds are largely produced in the northern vicinity of Beijing via photochemical processing of organic precursors emitted from urban center and forest areas. (C) 2014 Elsevier B.V. All rights reserved.

Biomass burning is a major source of greenhouse gases and influences regional to global climate. Pre-industrial fire-history records from black carbon, charcoal and other proxies provide baseline estimates of biomass burning at local to global scales spanning millennia, and are thus useful to examine the role of fire in the carbon cycle and climate system. Here we use the specific biomarker levoglucosan together with black carbon and ammonium concentrations from the North Greenland Eemian (NEEM) ice cores (77.49° N, 51.2° W; 2480 m a.s.l) over the past 2000 years to infer changes in boreal fire activity. Increases in boreal fire activity over the periods 1000–1300 CE and decreases during 700–900 CE coincide with high-latitude NH temperature changes. Levoglucosan concentrations in the NEEM ice cores peak between 1500 and 1700 CE, and most levoglucosan spikes coincide with the most extensive central and northern Asian droughts of the past millennium. Many of these multi-annual droughts are caused by Asian monsoon failures, thus suggesting a connection between low- and high-latitude climate processes. North America is a primary source of biomass burning aerosols due to its relative proximity to the Greenland Ice Cap. During major fire events, however, isotopic analyses of dust, back trajectories and links with levoglucosan peaks and regional drought reconstructions suggest that Siberia is also an important source of pyrogenic aerosols to Greenland.

Black carbon aerosols (BC) at a London urban site were characterised in both winter- and summertime 2012 during the Clean Air for London (ClearfLo) project. Positive matrix factorisation (PMF) factors of organic aerosol mass spectra measured by a high-resolution aerosol mass spectrometer (HR-AMS) showed traffic-dominant sources in summer but in winter the influence of additional non-traffic sources became more important, mainly from solid fuel sources (SF). Measurements using a single particle soot photometer (SP2, DMT), showed the traffic-dominant BC exhibited an almost uniform BC core size (Dc) distribution with very thin coating thickness throughout the detectable range of Dc. However, the size distribution of Dc (project average mass median Dc = 149 ± 22 nm in winter, and 120 ± 6 nm in summer) and BC coating thickness varied significantly in winter. A novel methodology was developed to attribute the BC number concentrations and mass abundances from traffic (BCtr) and from SF (BCsf), by using a 2-D histogram of the particle optical properties as a function of BC core size, as measured by the SP2. The BCtr and BCsf showed distinctly different Dc distributions and coating thicknesses, with BCsf displaying larger Dc and larger coating thickness compared to BCtr. BC particles from different sources were also apportioned by applying a multiple linear regression between the total BC mass and each AMS-PMF factor (BC–AMS–PMF method), and also attributed by applying the absorption spectral dependence of carbonaceous aerosols to 7-wavelength Aethalometer measurements (Aethalometer method). Air masses that originated from westerly (W), southeasterly (SE), and easterly (E) sectors showed BCsf fractions that ranged from low to high, and whose mass median Dc values were 137 ± 10 nm, 143 ± 11 nm and 169 ± 29 nm, respectively. The corresponding bulk relative coating thickness of BC (coated particle size/BC core – Dp/Dc) for these same sectors was 1.28 ± 0.07, 1.45 ± 0.16 and 1.65 ± 0.19. For W, SE and E air masses, the number fraction of BCsf ranged from 6 ± 2% to 11 ± 5% to 18 ± 10%, respectively, but importantly the larger BC core sizes lead to an increased fraction of BCsf in terms of mass than number (for W, SE and E air masses, the BCsf mass fractions ranged from 16 ± 6%, 24 ± 10% and 39 ± 14%, respectively). An increased fraction of non-BC particles (particles that did not contain a BC core) was also observed when SF sources were more significant. The BC mass attribution by the SP2 method agreed well with the BC–AMS–PMF multiple linear regression method (BC–AMS–PMF : SP2 ratio = 1.05, r2 = 0.80) over the entire experimental period. Good agreement was found between BCsf attributed with the Aethalometer model and the SP2. However, the assumed absorption Ångström exponent (αwb) had to be changed according to the different air mass sectors to yield the best comparison with the SP2. This could be due to influences of fuel type or burn phase., Atmospheric Chemistry and Physics, 14 (18), ISSN:1680-7375, ISSN:1680-7367

Organic aerosols (OA) are universally regarded as an important component of the atmosphere that have far-ranging impacts on climate forcing and human health. Many of these impacts are related to OA molecular characteristics. Despite the acknowledged importance, current uncertainties related to the source apportionment of molecular properties and environmental impacts make it difficult to confidently predict the net impacts of OA. Here we evaluate the specific molecular compounds as well as bulk structural properties of total suspended particulates in ambient OA collected from key emission sources (marine, biomass burning, and urban) using ultrahigh resolution mass spectrometry (UHR-MS) and proton nuclear magnetic resonance spectroscopy (1H NMR). UHR-MS and 1H NMR show that OA within each source is structurally diverse, and the molecular characteristics are described in detail. Principal component analysis (PCA) revealed that (1) aromatic nitrogen species are distinguishing components for these biomass burning aerosols; (2) these urban aerosols are distinguished by having formulas with high O/C ratios and lesser aromatic and condensed aromatic formulas; and (3) these marine aerosols are distinguished by lipid-like compounds of likely marine biological origin. This study provides a unique qualitative approach for enhancing the chemical characterization of OA necessary for molecular source apportionment.

Bisphenol A (BPA) is a suspected endocrine disruptor in the environment. However, little is known about its distribution and transport in the atmosphere. Here, the concentrations of BPA in the atmospheric aerosols from urban, rural, marine, and the polar regions were measured using solvent extraction/derivatization and gas chromatography/mass spectrometry technique. The concentrations of BRA (1-17,400 pg m^[-3]) ranged over 4 orders of magnitude in the world with a declining trend from the continent (except for the Antarctica) to remote sites. A positive correlation was found between BPA and 1,3,5-triphenylbenzene, a tracer for plastic burning, in urban regions, indicating that the open burning of plastics in domestic waste should be a significant emission source of atmospheric BRA. Our results suggest that the ubiquity of BRA in the atmosphere may raise a requirement for the evaluation of health effects of BRA in order to control its emission sources, for example, from plastic burning.

A case study of atmospheric aerosol measurements exploring the impact of the vertical distribution of aerosol chemical composition upon the radiative budget in North-Western Europe is presented. Sub-micron aerosol chemical composition was measured by an Aerodyne Aerosol Mass Spectrometer (AMS) on both an airborne platform and a ground-based site at Cabauw in the Netherlands. The examined period in May 2008 was characterised by enhanced pollution loadings in North-Western Europe and was dominated by ammonium nitrate and Organic Matter (OM). Both ammonium nitrate and OM were observed to increase with altitude in the atmospheric boundary layer. This is primarily attributed to partitioning of semi-volatile gas phase species to the particle phase at reduced temperature and enhanced relative humidity. Increased ammonium nitrate concentrations in particular were found to strongly increase the ambient scattering potential of the aerosol burden, which was a consequence of the large amount of associated water as well as the enhanced mass. During particularly polluted conditions, increases in aerosol optical depth of 50–100% were estimated to occur due to the observed increase in secondary aerosol mass and associated water uptake. Furthermore, the single scattering albedo was also shown to increase with height in the boundary layer. These enhancements combined to increase the negative direct aerosol radiative forcing by close to a factor of two at the median percentile level. Such increases have major ramifications for regional climate predictions as semi-volatile components are often not included in aerosol models. The results presented here provide an ideal opportunity to test regional and global representations of both the aerosol vertical distribution and subsequent impacts in North-Western Europe. North-Western Europe can be viewed as an analogue for the possible future air quality over other polluted regions of the Northern Hemisphere, where substantial reductions in sulphur dioxide emissions have yet to occur. Anticipated reductions in sulphur dioxide in polluted regions will result in an increase in the availability of ammonia to form ammonium nitrate as opposed to ammonium sulphate. This will be most important where intensive agricultural practises occur. Our observations over North-Western Europe, a region where sulphur dioxide emissions have already been reduced, indicate that failure to include the semi-volatile behaviour of ammonium nitrate will result in significant errors in predicted aerosol direct radiative forcing. Such errors will be particularly significant on regional scales.

Aerosol particles (PM2.5) were collected during the day (n=6) and nighttime (n=9) from a tropical pasture site in Rondônia, Brazil during an intensive biomass burning period (16-26 September, 2002). Higher normalized (by K+, levoglucosan, or apparent elemental carbon, ECa) mass concentrations of SO4^[2-] and CH3SO3- in daytime suggest their photochemical production, while the opposite trend for NO3- suggests its transfer to the aerosol phase at lower temperatures and higher humidities, as well as possibly production through hydrolysis of N2O5 on aqueous aerosol particles. About 4.2-7.5% of OC (5-13% of water-soluble organic carbon (WSOC)) could be characterized at the molecular level using GC-MS and GC-FID. Among the detected organic compound classes, the relative abundances of anhydrosugars and aromatics were higher in night samples, but sugars/sugar alcohols, diacids, oxoacids and α-dicarbonyls were more abundant in day samples. Consecutive day and night samples showed that δ13C values of total carbon (TC) were lower in daytime samples, which can be interpreted as resulting from higher contributions of refractory TC depleted in 13C due to predominantly flaming combustion. The δ15N values of total nitrogen (TN) ranged from +23.5‰ to +25.7‰, however, there was no trend in day and night samples. Higher values of δ13C and δ15N for biomass burning particles than those of unburned vegetation reflect positive isotopic enrichment either during the formation of particles or after the emission of particles in the atmosphere.

9 pages, 3 figures, 1 table, supporting information http://pubs.acs.org/doi/suppl/10.1021/acs.est.5b02922, A number of field observations employing aerosol mass spectrometers (AMS) have demonstrated that organic matter rich in monocarboxylic acids and aliphatic carbonyls originating from cooking activities (the COA factor) contributes significantly to ambient organic matter (OM) in urban environments. Little is known about the contribution and nature of COA in rural localities. We studied the correlation of COA with chemical tracers at a rural site in the Po Valley, Italy. Our statistical approach, based on positive matrix factorization (PMF) shows that the COA factor was clearly linked to local emissions of chloride and methanesulfonic acid (MSA), chemical tracers not associated with cooking emissions, or with combustion sources. While the association with Cl is not understood at this stage, the emission of reduced sulfur compounds, aliphatic carbonyls and monocarboxylic acids is consistent with several agricultural practices (e.g., manure storage) and waste disposal systems (e.g., landfills) which characterize the suburban and rural areas of the Po Valley and of other many populated environments. It is concluded that the nature and origins of the AMS COA factor measured at a rural site are complex and include far more than the emissions from food cooking, This work was funded by European integrated project on aerosol cloud climate and air quality interactions (no. 036833-2, EUCAARI). Manuel Dall’Osto and Roy M. Harrison thank the UK National Centre for Atmospheric Science for financial support. We acknowledge funding from the EU FP7-ENV-2013 programme “impact of Biogenic vs. Anthropogenic emissions on Clouds and Climate: towards a Holistic UnderStanding” (BACCHUS), project no. 603445. Programme Ramon y Cajal (RYC-2012-11922) also provided financial support

Trace element measurements in PM10–2.5, PM2.5–1.0 and PM1.0–0.3 aerosol were performed with 2 h time resolution at kerbside, urban background and rural sites during the ClearfLo winter 2012 campaign in London. The environment-dependent variability of emissions was characterized using the Multilinear Engine implementation of the positive matrix factorization model, conducted on data sets comprising all three sites but segregated by size. Combining the sites enabled separation of sources with high temporal covariance but significant spatial variability. Separation of sizes improved source resolution by preventing sources occurring in only a single size fraction from having too small a contribution for the model to resolve. Anchor profiles were retrieved internally by analysing data subsets, and these profiles were used in the analyses of the complete data sets of all sites for enhanced source apportionment. A total of nine different factors were resolved (notable elements in brackets): in PM10–2.5, brake wear (Cu, Zr, Sb, Ba), other traffic-related (Fe), resuspended dust (Si, Ca), sea/road salt (Cl), aged sea salt (Na, Mg) and industrial (Cr, Ni); in PM2.5–1.0, brake wear, other traffic-related, resuspended dust, sea/road salt, aged sea salt and S-rich (S); and in PM1.0–0.3, traffic-related (Fe, Cu, Zr, Sb, Ba), resuspended dust, sea/road salt, aged sea salt, reacted Cl (Cl), S-rich and solid fuel (K, Pb). Human activities enhance the kerb-to-rural concentration gradients of coarse aged sea salt, typically considered to have a natural source, by 1.7–2.2. These site-dependent concentration differences reflect the effect of local resuspension processes in London. The anthropogenically influenced factors traffic (brake wear and other traffic-related processes), dust and sea/road salt provide further kerb-to-rural concentration enhancements by direct source emissions by a factor of 3.5–12.7. The traffic and dust factors are mainly emitted in PM10–2.5 and show strong diurnal variations with concentrations up to 4 times higher during rush hour than during night-time. Regionally influenced S-rich and solid fuel factors, occurring primarily in PM1.0–0.3, have negligible resuspension influences, and concentrations are similar throughout the day and across the regions.

Understanding sources, concentrations, and transformations of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere is important because of their potent mutagenicity and carcinogenicity. The measurement of particle-bound PAHs by three different methods during the Mexico City Metropolitan Area field campaign in April 2003 presents a unique opportunity for characterization of these compounds and intercomparison of the methods. The three methods are ( 1) collection and analysis of bulk samples for time-integrated gas- and particle-phase speciation by gas chromatography/ mass spectrometry; ( 2) aerosol photoionization for fast detection of PAHs on particles' surfaces; and ( 3) aerosol mass spectrometry for fast analysis of size and chemical composition. This research represents the first time aerosol mass spectrometry has been used to measure ambient PAH concentrations and the first time that fast, real-time methods have been used to quantify PAHs alongside traditional filter-based measurements in an extended field campaign. Speciated PAH measurements suggest that motor vehicles and garbage and wood burning are important sources in Mexico City. The diurnal concentration patterns captured by aerosol photoionization and aerosol mass spectrometry are generally consistent. Ambient concentrations of particle-phase PAHs typically peak at similar to 110 ng m(-3) during the morning rush hour and rapidly decay due to changes in source activity patterns and dilution as the boundary layer rises, although surface-bound PAH concentrations decay faster. The more rapid decrease in surface versus bulk PAH concentrations during the late morning suggests that freshly emitted combustion-related particles are quickly coated by secondary aerosol material in Mexico City's atmosphere and may also be transformed by heterogeneous reactions. NSF Atmospheric Chemistry Program, Grants ATM-0308748, ATM-0528634 DOE Atmospheric Sciences Program, Grant DE-FG02-05ER63981

Tropical aerosols of PM 2.5 and PM 10 were collected at a rural site in Morogoro, Tanzania (East Africa), and analysed for stable carbon isotopic composition (δ 13 C) of dicarboxylic acids (C 2 –C 9 ), glyoxylic acid (ωC 2 ) and glyoxal (Gly) using gas chromatography/isotope ratio mass spectrometer. PM 2.5 samples showed that δ 13 C of oxalic (C 2 ) acid are largest (mean, −18.3±1.7‰) followed by malonic (C 3 , −19.6±1.0‰) and succinic (C 4 , −21.8±2.2‰) acids, whereas those in PM 10 are a little smaller: −19.9±3.1‰ (C 2 ), −20.2±2.7‰ (C 3 ) and −23.3±3.2‰ (C 4 ). The δ 13 C of C 2 –C 4 diacids showed a decreasing trend with an increase in carbon numbers. The higher δ 13 C values of oxalic acid can be explained by isotopic enrichment of 13 C in the remaining C 2 due to the atmospheric decomposition of oxalic acid or its precursors. δ 13 C of ωC 2 and Gly that are precursors of oxalic acid also showed larger values (mean, −22.5‰ and −20.2‰, respectively) in PM 2.5 than those (−26.7‰ and −23.7‰) in PM 10 . The δ 13 C values of ωC 2 and Gly are smaller than those of C 2 in both PM 2.5 and PM 10 . On the other hand, azelaic acid (C 9 ; mean, −28.5‰) is more depleted in 13 C, which is consistent with the previous knowledge; that is, C 9 is produced by the oxidation of unsaturated fatty acids emitted from terrestrial higher plants. A significant enrichment of 13 C in oxalic acid together with its negative correlations with relative abundance of C 2 in total diacids and ratios of water-soluble organic carbon and organic carbon further support that a photochemical degradation of oxalic acid occurs during long-range transport from source regions. Keywords: PM 2.5 and PM 10 , stable carbon isotope ratios, oxalic acid, diacids, glyoxylic acid, glyoxal, organic aerosols, Tanzania, East Africa (Published: 1 October 2014) Citation: Tellus B 2014, 66 , 23702, http://dx.doi.org/10.3402/tellusb.v66.23702

Ambient wintertime background urban aerosol in Cork city, Ireland, was characterized using aerosol mass spectrometry. During the three-week measurement study in 2009, 93% of the ca. 1 350 000 single particles characterized by an Aerosol Time-of-Flight Mass Spectrometer (TSI ATOFMS) were classified into five organic-rich particle types, internally mixed to different proportions with elemental carbon (EC), sulphate and nitrate, while the remaining 7% was predominantly inorganic in nature. Non-refractory PM1 aerosol was characterized using a High Resolution Time-of-Flight Aerosol Mass Spectrometer (Aerodyne HR-ToF-AMS) and was also found to comprise organic aerosol as the most abundant species (62 %), followed by nitrate (15 %), sulphate (9 %) and ammonium (9 %), and chloride (5 %). Positive matrix factorization (PMF) was applied to the HR-ToF-AMS organic matrix, and a five-factor solution was found to describe the variance in the data well. Specifically, "hydrocarbon-like" organic aerosol (HOA) comprised 20% of the mass, "low-volatility" oxygenated organic aerosol (LV-OOA) comprised 18 %, "biomass burning" organic aerosol (BBOA) comprised 23 %, non-wood solid-fuel combustion "peat and coal" organic aerosol (PCOA) comprised 21 %, and finally a species type characterized by primary m/z peaks at 41 and 55, similar to previously reported "cooking" organic aerosol (COA), but possessing different diurnal variations to what would be expected for cooking activities, contributed 18 %. Correlations between the different particle types obtained by the two aerosol mass spectrometers are also discussed. Despite wood, coal and peat being minor fuel types used for domestic space heating in urban areas, their relatively low combustion efficiencies result in a significant contribution to PM1 aerosol mass (44% and 28% of the total organic aerosol mass and non-refractory total PM1, respectively).Ambient wintertime background urban aerosol in Cork city, Ireland, was characterized using aerosol mass spectrometry. During the three-week measurement study in 2009, 93% of the ca. 1 350 000 single particles characterized by an Aerosol Time-of-Flight Mass Spectrometer (TSI ATOFMS) were classified into five organic-rich particle types, internally mixed to different proportions with elemental carbon (EC), sulphate and nitrate, while the remaining 7% was predominantly inorganic in nature. Non-refractory PM1 aerosol was characterized using a High Resolution Time-of-Flight Aerosol Mass Spectrometer (Aerodyne HR-ToF-AMS) and was also found to comprise organic aerosol as the most abundant species (62 %), followed by nitrate (15 %), sulphate (9 %) and ammonium (9 %), and chloride (5 %). Positive matrix factorization (PMF) was applied to the HR-ToF-AMS organic matrix, and a five-factor solution was found to describe the variance in the data well. Specifically, "hydrocarbon-like" organic aerosol (HOA) comprised 20% of the mass, "low-volatility" oxygenated organic aerosol (LV-OOA) comprised 18 %, "biomass burning" organic aerosol (BBOA) comprised 23 %, non-wood solid-fuel combustion "peat and coal" organic aerosol (PCOA) comprised 21 %, and finally a species type characterized by primary m/z peaks at 41 and 55, similar to previously reported "cooking" organic aerosol (COA), but possessing different diurnal variations to what would be expected for cooking activities, contributed 18 %. Correlations between the different particle types obtained by the two aerosol mass spectrometers are also discussed. Despite wood, coal and peat being minor fuel types used for domestic space heating in urban areas, their relatively low combustion efficiencies result in a significant contribution to PM1 aerosol mass (44% and 28% of the total organic aerosol mass and non-refractory total PM1, respectively).

The role of surfactants in governing water interactions of atmospheric aerosols has been a recurring topic in cloud microphysics for more than two decades. Studies of detailed surface thermodynamics are limited by the availability of aerosol samples for experimental analysis and incomplete validation of various proposed Köhler model frameworks for complex mixtures representative of atmospheric aerosol. Pollenkitt is a viscous material that coats grains of pollen and plays important roles in pollen dispersion and plant reproduction. Previous work suggests that it may also be an important contributor to pollen water uptake and cloud condensation nuclei (CCN) activity. The chemical composition of pollenkitt varies between species but has been found to comprise complex organic mixtures including oxygenated, lipid, and aliphatic functionalities. This mix of functionalities suggests that pollenkitt may display aqueous surface activity, which could significantly impact pollen interactions with atmospheric water. Here, we study the surface activity of pollenkitt from six different species and its influence on pollenkitt hygroscopicity. We measure cloud droplet activation and concentration-dependent surface tension of pollenkitt and its mixtures with ammonium sulfate salt. Experiments are compared to predictions from several thermodynamic models, taking aqueous surface tension reduction and surfactant surface partitioning into account in various ways. We find a clear reduction of surface tension by pollenkitt in aqueous solution and evidence for impact of both surface tension and surface partitioning mechanisms on cloud droplet activation potential and hygroscopicity of pollenkitt particles. In addition, we find indications of complex nonideal solution effects in a systematic and consistent dependency of pollenkitt hygroscopicity on particle size. The impact of pollenkitt surface activity on cloud microphysics is different from what is observed in previous work for simple atmospheric surfactants and more resembles recent observations for complex primary and secondary organic aerosol, adding new insight to our understanding of the multifaceted role of surfactants in governing aerosol–water interactions. We illustrate how the explicit characterization of pollenkitt contributions provides the basis for modeling water uptake and cloud formation of pollen and their fragments over a wide range of atmospheric conditions.

Observations during the 2006 dry season of highly elevated concentrations of cyanides in the atmosphere above Mexico City (MC) and the surrounding plains, demonstrate that biomass burning (BB) significantly impacted air quality in the region. We find that during the period of our measurements, fires contribute more than half of the organic aerosol mass and submicron aerosol scattering, and one third of the enhancement in benzene, reactive nitrogen, and carbon monoxide in the outflow from the plateau. The combination of biomass burning and anthropogenic emissions will affect ozone chemistry in the MC outflow.