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Brown carbon is a type of strong light-absorbing carbonaceous aerosol associated with radiative forcing. Nevertheless, the difficulty in correlating the chemical composition of brown carbon with its light absorption properties impairs the proper elucidation of its role in radiative forcing. Here, we have used a time-dependent density functional theory (TD-DFT)-based procedure to revisit the “real-world” absorption spectra of polycyclic aromatic hydrocarbons (PAHs) over the city of Porto, in Portugal, while correcting the spectra for their quantity in PM10 particulate matter. Our aim is to, by comparing these new results with those obtained previously regarding PM2.5 data, evaluate the role of different groupings of particulate matter in the light absorption of brown carbon. The results indicate that irrespective of the absorption spectra corresponding to their PM10 or PM2.5 data, the studied PAHs should contribute to radiative forcing by light absorption at UVA and (sub)visible wavelengths. However, the identity of the individual PAH species that contribute the most for the considered wavelengths can be quite different. Thus, different groupings of particulate matter appear to provide distinct contributions to light absorption and radiative forcing over the same location, even when considering the same class of molecular compounds.

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.

Liu et al. found that the formation rate of particulate ammonium is slower in the atmosphere than that observed in the laboratory, while it is sped up due to an increase in aerosol acidity driven by an emission reduction of dust in North China Plain.Ammonium salt is an important component of particulate matter with aerodynamic diameter less than 2.5 mu m (PM2.5) and has significant impacts on air quality, climate, and natural ecosystems. However, a fundamental understanding of the conversion kinetics from ammonia to ammonium in unique environments of high aerosol loading is lacking. Here, we report the uptake coefficient of ammonia (gamma(NH3)) on ambient PM2.5 varying from 2.2 x 10(-4) to 6.0 x 10(-4) in the North China Plain. It is significantly lower than those on the model particles under simple conditions reported in the literature. The probability-weighted gamma(NH3) increases obviously, which is well explained by the annual decrease in aerosol pH due to the significant decline in alkali and alkali earth metal contents from the emission source of dust. Our results elaborate on the complex interactions between primary emissions and the secondary formation of aerosols and the important role of dust in atmospheric chemistry.

The Community Earth System Model version 2 (CESM2) includes three main atmospheric configurations: the Community Atmosphere Model version 6 (CAM6) with simplified chemistry and a simplified organic aerosol (OA) scheme, CAM6 with comprehensive tropospheric and stratospheric chemistry representation (CAM6‐chem), and the Whole Atmosphere Community Climate Model version 6 (WACCM6). Both, CAM6‐chem and WACCM6 include a more comprehensive secondary organic aerosols (SOA) approach using the Volatility Basis Set (VBS) scheme and prognostic stratospheric aerosols. This paper describes the different OA schemes available in the different atmospheric configurations of CESM2 and discusses differences in aerosol burden and resulting climate forcings. Derived OA burden and trends differ due to differences in OA formation using the different approaches. Regional differences in Aerosol Optical Depth with larger values using the comprehensive approach occur over SOA source regions. Stronger increasing SOA trends between 1960 and 2015 in WACCM6 compared to CAM6 are due to increasing biogenic emissions aligned with increasing surface temperatures. Using the comprehensive SOA approach further leads to improved comparisons to aircraft observations and SOA formation of ≈143 Tg/yr. We further use WACCM6 to identify source contributions of OA from biogenic, fossil fuel, and biomass burning emissions, to quantify SOA amounts and trends from these sources. Increasing SOA trends between 1960 and 2015 are the result of increasing biogenic emissions aligned with increasing surface temperatures. Biogenic emissions are at least two thirds of the total SOA burden. In addition, SOA source contributions from fossil fuel emissions become more important, with largest values over Southeast Asia. The estimated total anthropogenic forcing of OA in WACCM6 for 1995–2010 conditions is −0.43 W/m2, mostly from the aerosol direct effect.

The chemical composition of non-refractory submicron aerosol (NR-PM1) was characterized at the Villum Research Station (Villum) at Station Nord in North Greenland during spring-summer 2016 using a Time of Flight Aerosol Chemical Speciation Monitor (ToF-ACSM). The composition is dominated by sulfate (48%) and organic species (40%). Positive Matrix Factorization (PMF) identified three key factors corresponding to a primary hydrocarbon-like organic aerosol (HOA), and two types of secondary organic aerosol: oxygenated organic aerosol (OOA) and a marine organic aerosol (MOA). The HOA factor accounts for 5% of the organic aerosol mass, which is consistent with previous findings at Villum. The OOA factor accounts for 77% of the organic aerosol mass and correlates with accumulation mode particles, which supports previous findings indicating that oxidized organic aerosols are predominantly from long-range transport during winter and spring at Villum. The MOA factor was characterized by mass spectral fragments of methane sulfonic acid (MSA) from atmospheric oxidation of dimethyl sulfide, for which reason the MOA factor is considered to be of biogenic origin. MOA accounts for 18% of the organic aerosol mass and correlates with locally produced Aitken mode particles. This indicates that biogenic processes are not only a significant source of aerosols at Villum, but MOA also appears to be formed in the vicinity of the measurement site. This local geographical origin was confirmed through air mass back trajectory modelling and source-receptor analysis. During May, air masses frequently arrived from the east, with source regions for the MOA factor and therewith MSA located in the Barents Sea and Lincoln Sea with lesser contributions from the Greenland Sea. During June, air mass origin shifted to the west, with source regions for the MOA factor and MSA shifting correspondingly to Baffin Bay and the Canadian Arctic Archipelago. While shifting transport patterns between May and June lead to shifting source regions, sea ice likely played a role as well. During May, marginal ice zones were present in the Barents Sea between Svalbard and Franz Josef Land, while during June, sea ice in the northern part of Baffin Bay retreated and sea ice in the Canadian Arctic Archipelago decreased. Although May and June experienced different transport patterns and sea ice conditions, levels of the MOA factor and MSA were similar between the months. This is likely due to similarities between marine biological activities in the Barents Sea and Baffin Bay. This research highlights the complex relationship between transport patterns, sea ice conditions, and atmospheric particle concentrations. Multiyear aerosol chemical composition from several High Arctic sites is encouraged to determine the full effects of ocean-atmosphere interactions and transport patterns on atmospheric aerosol concentrations.

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.

To prevent the transmission of the novel coronavirus disease 2019 (COVID-19), China adopted nationwide lockdown measures on January 25, 2020, leading to an evident diminution in the observed air pollutants. To investigate the influence of the lockdown on atmospheric chemistry, the specific molecular composition, oxidative potential of organic aerosols (OAs) in PM2.5 were studied using a high-resolution orbitrap mass spectrometry at a typical coal-combustion city, Linfen, in the North China Plain (NCP). The major air pollutants including PM2.5, PM10, SO2, NO2, and CO were observed to be diminished by 28.6–45.4%, while O3 was augmented by 52.5% during the lockdown compared to those before the lockdown. A significant decrease of oxygen-containing (CHO) compounds (24.7%) associated with anthropogenic acids was observed during the lockdown, implying a reduction in fossil fuel combustion. The coal-burning related sulfur-containing organosulfates (CHOS-) and nitrooxy-sulfates (CHONS-) have also shown attenuated in both their relative abundances and anthropogenic/biogenic ratios. Amine/amide-like CHON + components have decreased by 27.6%, while nitro/nitrooxy-containing CHON- compounds have only decreased by 7.1%. Multi-source nitrogen-containing (CHN) compounds have shown a moderate elimination of 24.0%, while the identified high-condensed azaarenes have fallen from 17.7% to 14.7%, implying a potential reduction in the health risk of OAs during quarantine. The measurement of OAs’ oxidative potential through dithiothreitol (DTT) assay has confirmed that as it had dropped from 0.88 nmol min−1 m−3 to 0.80 nmol min−1 m−3. High correlations were observed between the abundance of OA subgroups with the concentration of PM2.5 after the execution of the lockdown, suggesting a potential elevation in the contribution of organic components to the total PM2.5 level. Our study provides insightful compositional and health-related information in the variation of OAs during the lockdown period and attests to the validity of joint-control strategy in controlling the level and health risks of numerous atmospheric pollutants.

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.

In order to assess the evolution of aerosol parameters affecting climate change, a long-term trend analysis of aerosol optical properties was performed on time series from 52 stations situated across five continents. The time series of measured scattering, backscattering and absorption coefficients as well as the derived single scattering albedo, backscattering fraction, scattering and absorption Ångström exponents covered at least 10 years and up to 40 years for some stations. The non-parametric seasonal Mann–Kendall (MK) statistical test associated with several pre-whitening methods and with Sen’s slope was used as the main trend analysis method. Comparisons with general least mean square associated with autoregressive bootstrap (GLS/ARB) and with standard least mean square analysis (LMS) enabled confirmation of the detected MK statistically significant trends and the assessment of advantages and limitations of each method. Currently, scattering and backscattering coefficient trends are mostly decreasing in Europe and North America and are not statistically significant in Asia, while polar stations exhibit a mix of increasing and decreasing trends. A few increasing trends are also found at some stations in North America and Australia. Absorption coefficient time series also exhibit primarily decreasing trends. For single scattering albedo, 52 % of the sites exhibit statistically significant positive trends, mostly in Asia, eastern/northern Europe and the Arctic, 22 % of sites exhibit statistically significant negative trends, mostly in central Europe and central North America, while the remaining 26 % of sites have trends which are not statistically significant. In addition to evaluating trends for the overall time series, the evolution of the trends in sequential 10-year segments was also analyzed. For scattering and backscattering, statistically significant increasing 10-year trends are primarily found for earlier periods (10-year trends ending in 2010–2015) for polar stations and Mauna Loa. For most of the stations, the present-day statistically significant decreasing 10-year trends of the single scattering albedo were preceded by not statistically significant and statistically significant increasing 10-year trends. The effect of air pollution abatement policies in continental North America is very obvious in the 10-year trends of the scattering coefficient – there is a shift to statistically significant negative trends in 2009–2012 for all stations in the eastern and central USA. This long-term trend analysis of aerosol radiative properties with a broad spatial coverage provides insight into potential aerosol effects on climate changes., European Union (EU) 654109, ACTRIS PPP project 739530, IMPROVE, Co-operative Programme for Monitoring and Evaluation of the Long-range Transmission of Air pollutants in Europe (EMEP) under UNECE, Korea Meteorological Administration Research and Development Program "Development of Monitoring and Analysis Techniques for Atmospheric Composition in Korea" KMA2018-00522, "Arctic Monitoring and Assessment Programme" (AMAP) under EU action "Black Carbon in the Arctic" 80026, Norwegian Environment Agency, Basic Science Research Program through the National Research Foundation of Korea 2017R1D1A1B06032548, European Union (EU) 262254, European Union's Horizon 2020 research and innovation programme under project ACTRIS-2 654109, European Union's Horizon 2020 research and innovation programme under project iCUPE 689443, Academy of Finland 307331 264242 268004 284536 287440, AEMET, Swiss State Secretariat for Education, Research and Innovation, SERI 15.0159-1, Taiwan Environmental Protection Administration, Ministry of Science and Technology, European Union's Horizon 2020 research and innovation programme 654109, MINECO (Spanish Ministry of Economy, Industry and Competitiveness), FEDER fund under the PRISMA project CGL2012-39623-C02/00, FEDER fund under the HOUSE project CGL2016-78594-R, Generalitat de Catalunya AGAUR 2014 SGR33 AGAUR 2017 SGR41, Business Finland 2634/31/2015, Ramon y Cajal Fellowship - Spanish Ministry of Economy and Competitiveness RYC-2013-14036, Department of Biotechnology (DBT) India 2634/31/2015, Academy of Finland 307331, National Oceanic Atmospheric Admin (NOAA) - USA, ACTRIS-France National Research infrastructure, CNRS-INSU long-term observing program, Spanish Ministry of Economy and Competitiveness CGL2016-81092-R CGL2017-90884-REDT RTI2018-101154-A-I00, National Natural Science Foundation of China (NSFC) 41675129, National Key Project of the Ministry of Science and Technology of the People's Republic of China 2016YFC0203305 2016YFC0203306, Basic Research Project of the Chinese Academy of Meteorological of Sciences 2017Z011, Knut-and-AliceWallenberg Foundation within the ACAS project (Arctic Climate Across Scales) 2016.0024, CPR: Para La Naturaleza and the nature reserve of Cabezas de San Juan and the support of grants AGS 0936879 and EAR1331841.

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.

Atmospheric aerosol deposition (wet and dry) is an important source of macro and micronutrients (N, P, C, Si, and Fe) to the oceans. Most of the mass flux of air particles is made of fine mineral particles emitted from arid or semi-arid areas (e.g., deserts) and transported over long distances until deposition to the oceans. However, this atmospheric deposition is affected by anthropogenic activities, which heavily impacts the content and composition of aerosol constituents, contributing to the presence of potentially toxic elements (e.g., Cu). Under this scenario, the deposition of natural and anthropogenic aerosols will impact the biogeochemical cycles of nutrients and toxic elements in the ocean, also affecting (positively or negatively) primary productivity and, ultimately, the marine biota. Given the importance of atmospheric aerosol deposition to the oceans, this paper reviews the existing knowledge on the impacts of aerosol deposition on the biogeochemistry of the upper ocean, and the different responses of marine biota to natural and anthropogenic aerosol input.

Water-soluble organic aerosols (OA) are an important component of air particles and one of the key drivers that impact both climate and human health. Understanding the processes involving water-soluble OA depends on how well the chemical composition of this aerosol component is decoded. Yet, obtaining detailed information faces several challenges, including water-soluble OA collection, extraction, and chemical complexity. This review highlights the multidimensional non-targeted analytical strategies that have been developed and employed for providing new insights into the structural and molecular features of water-soluble organic components present in air particles. First, the most prominent high-resolution mass spectrometric methods for near real-time measurements of water-soluble OA and their limitations are discussed. Afterward, a special emphasis is given to the degree of compositional information provided by offline multidimensional analytical techniques, namely excitation–emission (EEM) fluorescence spectroscopy, high-resolution mass spectrometry and two-dimensional nuclear magnetic resonance (NMR) spectroscopy and their hyphenation with chromatographic systems. The major challenges ahead on the application of these multidimensional analytical strategies for OA research are also addressed so that they can be used advantageously in future studies.

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.

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 flows from North America through 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, ~ 2400 m a.s.l. in Tenerife Island. This study was performed within the context of the projects AEROATLAN (CGL2015-66299-P; 15 MINECO/FEDER) and TEAPARTICLE (CGL2011-29621), supported by the Ministry of Economy and Competitiveness of Spain and the European Regional Development Fund (ERDF).

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).

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.

The numerical analysis of a dynamic constrained optimization problem is presented. It consists of a global minimization problem that is coupled with a system of ordinary differential equations. The activation and the deactivation of inequality constraints induce discontinuity points in the time evolution. A numerical method based on an operator splitting scheme and a fixed point algorithm is advocated. The ordinary differential equations are approximated by the Crank-Nicolson scheme, while a primal-dual interior-point method with warm-starts is used to solve the minimization problem. The computation of the discontinuity points is based on geometric arguments, extrapolation polynomials and sensitivity analysis. Second order convergence of the method is proved when an inequality constraint is activated. Numerical results for atmospheric particles confirm the theoretical investigations.

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

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

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 composition of the planetary boundary layer in regions of deep tropical convection has a profound impact on the Tropical Tropopause Layer (TTL). The Aerosol and Chemical Transport in tropical conVEction (ACTIVE) aircraft campaign was conducted from November 2005 to February 2006 from Darwin, Australia, to characterize the influence of both monsoonal and localized land-based deep convection on the composition of the TTL. This paper summarizes the composition of the potential inflow to such convection in terms of aerosol particle size and composition, carbon monoxide, and ozone, as measured in the lowest 4 km of the atmosphere by the NERC Domier-228 aircraft during 28 flights in different meteorological regimes over the course of ACTIVE. Six contrasting periods are identified in the boundary layer background as a result of the prevailing meteorology and sources of pollution. The campaign began with a relatively polluted and variable biomass burning season in November, followed by a transition to the monsoon season through December with much less burning. A clean maritime flow dominated the wet-active, and dry-inactive, monsoon period in January; it was followed by a monsoon break period in February, with a return to continental flow and a more premonsoon background state. Deep convective systems, capable of transporting boundary layer air to the TTL, were observed daily outside of the monsoon periods. The chemical composition of submicron aerosols in the premonsoon periods was dominated by a mix of fresh and aged organic material with significant black carbon, well-coffelated with carbon monoxide indicating a common burning source, while marine aerosol during the monsoon changed markedly between the wet and dry phases. High concentrations of coarse-mode aerosols were also observed in the monsoon: the clean, marine air masses and high surface winds imply that sea salt may be the dominant aerosol type under these conditions. The climatology presented here will provide a valuable data set for model simulation of chemical and aerosol transport by deep convection in the Darwin region. Copyright 2008 by the American Geophysical Union.

Current mass spectrometry techniques for the online measurement of organic aerosol (OA) composition are subjected to either thermal/ionization-induced artifacts or limited mass resolving power, hindering accurate molecular characterization. Here, we combined the soft ionization capability of extractive electrospray ionization (EESI) and the ultrahigh mass resolution of Orbitrap for real-time, near-molecular characterization of OAs. Detection limits as low as tens of ng m(-3) with linearity up to hundreds of mu g m(-3) at 0.2 Hz time resolution were observed for single- and mixed-component calibrations. The performance of the EESI-Orbitrap system was further evaluated with laboratorygenerated secondary OAs (SOAs) and filter extracts of ambient particulate matter. The high mass accuracy and resolution (140 000 at m/z 200) of the EESI-Orbitrap system enable unambiguous identification of the aerosol components' molecular composition and allow a clear separation between adjacent peaks, which would be significantly overlapping if a medium-resolution (20 000) mass analyzer was used. Furthermore, the tandem mass spectrometry (MS2) capability provides valuable insights into the compound structure. For instance, the MS2 analysis of ambient OA samples and lab-generated biogenic SOAs points to specific SOA precursors in ambient air among a range of possible isomers based on fingerprint fragment ions. Overall, this newly developed and characterized EESI-Orbitrap system will advance our understanding of the formation and evolution of atmospheric aerosols.

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.