The majority of the aerosol particle number (condensation nuclei or CN) in the marine boundary layer (MBL) consists of sulfate and organic compounds that have been shown to provide a large fraction of the cloud condensation nuclei (CCN). Here we use submicron non-refractory Aerosol Mass Spectrometer (AMS) and filter measurements of organic and sulfate components of aerosol particles measured during four North Atlantic Aerosol and Marine Ecosystems Study (NAAMES) research cruises to assess the sources and contributions of submicron organic and sulfate components for CCN concentrations in the MBL during four different seasons. Submicron hydroxyl group organic mass (OM) correlated strongly to sodium concentrations during clean marine periods (R ¼ 0.9), indicating that hydroxyl group OM can serve as a proxy for sea-spray OM in ambient measurements. Sea-spray OM contributed 45% of the sum of sea-spray OM and sea salt during late spring (biomass climax phase) compared to <20% for other seasons, but the seasonal difference was not statistically significant. The contribution of noncombustion sources during clean marine periods to submicron OM was 47 to 88% and to non-sea-salt sulfate 31 to 86%, with likely sources being marine and biogenic. The remaining submicron OM and sulfate were likely associated with ship or continental sources, including biomass burning, even during clean marine periods. The seasonal contribution from secondary sulfate and OM components to submicron aerosol mass was highest during late spring (60%), when biogenic emissions are expected to be highest, and lowest during winter (18%). Removing submicron sea-spray OM decreased CCN concentrations by <10% because of competing effects from increased hygroscopicity and decreased particle size. During all seasons, adding biogenic secondary sulfate increased hygroscopicity, particle size, and CCN concentrations at 0.1-0.3% supersaturations by 5-66%. The largest change was during early spring when the fraction of hygroscopic sulfate components in the 0.1-0.2 μm size range was highest (80%). During continental periods, the increased contribution from low-hygroscopicity organic components to 0.1-0.2 μm diameter particles reduces the CCN/CN by 20-100% for three seasons despite the increased CN and mass concentrations. These results illustrate the important role of the chemical composition of particles with diameters 0.1-0.2 μm for controlling CCN in the MBL.

Abstract. Understanding sources and atmospheric processes that can influence the physiochemical properties of carbonaceous aerosols is essential to evaluate their impacts on air quality and climate. However, resolving the sources, emission characteristics, and aging processes of carbonaceous aerosols in complex urban environments remains challenging. In this work, a soot particle aerosol mass spectrometer (SP-AMS) was deployed to characterize organic aerosols (OAs), refractory black carbon (rBC), and trace metals in Singapore, a highly urbanized city with multiple local and regional air pollution sources in the tropical region. rBC (C1+–C9+) fragments and trace metal ions (K+, Na+, Ni+, V+, and Rb+) were integrated into our positive matrix factorization of OA. Two types of fossil fuel combustion-related OAs with different degrees of oxygenation were identified. This work provides evidence that over 90 % of rBC originated from local combustion sources with a major part related to traffic and ∼30 % associated with fresh secondary organic aerosol (SOA) produced under the influence of shipping and industrial emission activities (e.g., refineries and petrochemical plants) during daytime. The results also show that ∼43 % of the total rBC was emitted from local traffic, while the rest of the rBC fraction stemmed from multiple sources including vehicular sources, shipping, and industrial emissions, but was not fully resolved. There was only a weak association of the cooking-related OA component with rBC. Although there was no observable biomass burning episode during the sampling period, K+ and Rb+ were mainly associated with the more oxidized oxygenated OA component, indicating the potential contribution of regional biomass burning and/or coal combustion emissions to this aged OA component. Furthermore, the aerosol pollutants transported from the industrial area and shipping ports presented higher C1+/C3+ and V+/Ni+ ratios than those associated with traffic. The observed association between Na+ and rBC suggests that the contribution of anthropogenic emissions to total particulate sodium should not be ignored in coastal urban environments. Overall, this work demonstrates that rBC fragments and trace metal ions can improve our understanding of the sources, emission characteristics, and aging history of carbonaceous aerosol (OA and rBC) in this type of complex urban environment.

Atmospheric brown carbon (BrC) is a significant contributor to particulate light absorption. Reactions between small aldehydes and reduced nitrogen species have been shown to produce secondary BrC in atmospheric droplets. These reactions can be substantially accelerated upon droplet evaporation. Despite aqueous droplets undergoing continuous water evaporation and uptake in response to the surrounding relative humidity (RH), secondary BrC formation in these droplets under various RH conditions remains poorly understood. In this work, we investigate BrC formation from reactions of two aqueous-phase precursors, glyoxal and methylglyoxal, with ammonium sulfate or glycine in aqueous droplets after drying at a range of RH (30−90%). Our results illustrate, for the first time, that BrC production varies as a function of RH. For all four chemical reaction systems being investigated, mass absorption efficiencies (MAE, m 2 /g C) of aqueous aerosol products (from 270 to 512 nm wavelength range) generally increase with reducing RH to reach a maximum at ∼55−65% RH and subsequently decrease, caused by further drying. Chemical characterization using high-resolution aerosol mass spectrometry shows that the formation of nitrogen-containing organic species also follows a similar variation with RH. Our observations reveal that the acceleration of BrC production from evaporation of water may be diminished by other factors, such as limited particle-phase water content, phase transition, and volatility of reactants and products. Overall, our results highlight that intermediate RH conditions in the atmosphere may be more efficient in secondary BrC formation, indicating that the effect of RH needs to be included in atmospheric models for a more accurate representation of light-absorbing aerosol formation in aqueous droplets.

Brown carbon (BrC) has significant climatic impact, but its emission sources and formation processes remain under-represented in climate models. However, there are only limited field studies to quantify the light absorption properties of specific types of primary and secondary organic aerosols (POAs and SOAs) in different environments. This work investigates the light absorption properties of the major OA components in Singapore, a well-developed city in the tropical region, where air quality can be influenced by multiple local urban sources and regional biomass burning events. The source-specific mass absorption cross-section (MAC) and wavelength dependence of different BrC components were quantified based on highly time-resolved aerosol chemical composition and absorption measurements. In particular, the combustion-related emission sources were the primary contributors to BrC light absorption and they were moderately absorbing. The SOA materials, which were freshly formed under atmospheric conditions with industrial influences, were also moderately light absorptive. The aged SOA components that were composed of aged regional emissions, including biomass burning and coal combustion emissions from nearby regions, were weakly light absorbing, highlighting the possibility of photobleaching of BrC during their atmospheric aging and dispersion. Lastly, our estimations illustrate that typical urban POAs and SOAs can contribute up to approximately 36−58% of the BrC absorption, even in some urban locations that are influenced by biomass burning emissions.

Abstract. The present study offers the first chemical characterization of the submicron (PM 1 ) fraction in western Africa at a high time resolution, thanks to collocated measurements of nonrefractory (NR) species with an Aerosol Chemical Speciation Monitor (ACSM), black carbon and iron concentrations derived from absorption coefficient measurements with a 7-wavelength Aethalometer, and total PM 1 determined by a TEOM-FDMS (tapered element oscillating microbalance-filtered dynamic measurement system) for mass closure. The field campaign was carried out over 3 months (March to June 2015) as part of the SHADOW (SaHAran Dust Over West Africa) project at a coastal site located in the outskirts of the city of Mbour, Senegal. With an averaged mass concentration of 5.4 µg m −3 , levels of NR PM 1 in Mbour were 3 to 10 times lower than those generally measured in urban and suburban polluted environments. Nonetheless the first half of the observation period was marked by intense but short pollution events (NR PM 1 concentrations higher than 15 µg m −3 ), sea breeze phenomena and Saharan desert dust outbreaks (PM 10 up to 900 µg m −3 ). During the second half of the campaign, the sampling site was mainly under the influence of marine air masses. The air masses on days under continental and sea breeze influences were dominated by organics (36-40 %), whereas sulfate particles were predominant (40 %) for days under oceanic influence. Overall, measurements showed that about threequarters of the total PM 1 were explained by NR PM 1 , BC (black carbon) and Fe (a proxy for dust) concentrations, leaving approximately one-quarter for other refractory species. A mean value of 4.6 % for the Fe / PM 1 ratio was obtained. Source apportionment of the organic fraction, using positive matrix factorization (PMF), highlighted the impact of local combustion sources, such as traffic and residential activities, which contribute on average to 52 % of the total organic fraction. A new organic aerosol (OA) source, representing on average 3 % of the total OA fraction, showed similar variation to nonrefractory particulate chloride. Its rose plot and daily pattern pointed to local combustion processes, i.e., two open waste-burning areas located about 6 and 11 km away from the receptor site and to a lesser extent a traditional fish-smoking location. The remaining fraction was identified as oxygenated organic aerosols (OOA), a factor that prevailed regardless of the day type (45 %) and was representative of regional (approximately three-quarters) but also local (approximately one-quarter) sources due to enhanced photochemical processes.

The mixing state of black carbon (BC) affects its environmental fate and impacts. This work investigates particle diversity and mixing state for refractory BC (rBC) containing particles in an urban environment. The chemical compositions of individual rBC-containing particles were measured, from which a mixing state index and particle diversity were determined. The mixing state index() varied between 26 % and 69% with the average of 48% in this study, and was slightly enhanced with the photochemical age of air masses, indicating that most of the rBC-containing particles cannot be simply explained by fully externally and internally mixed model. Clustering of single particle measurements was used to investigate the potential effects of different primary emissions and atmospheric processes on rBC-containing particle diversity and mixing state. The average particle species diversity and the bulk population species diversity both increased with primary traffic emissions and elevated nitrate concentrations in the morning but gradually decreased with secondary organic aerosol (SOA) formation in the afternoon. The single particle clustering results illustrate that primary traffic emissions and entrainment of nitrate-containing rBC particles from the residual layer to the surface could lead to more heterogeneous aerosol compositions, whereas substantial fresh SOA formation near vehicular emissions made the rBC-containing particles more homogeneous. This work highlights the importance of considering particle diversity and mixing state for investigating the chemical evolution of rBC-containing particles and the potential effects of coating on BC absorption enhancement. TOC graphic

&lt;p&gt;&lt;strong&gt;Abstract.&lt;/strong&gt; Understanding sources and atmospheric processes that can influence the physio-chemical properties of carbonaceous aerosols are essential to evaluate their impacts on air quality and climate. However, resolving the sources, emission characteristics and aging processes of carbonaceous aerosols in complex urban environments remain challenging. In this work, a soot-particle aerosol mass spectrometer (SP-AMS) was deployed to characterize organic aerosols (OA), refractory BC (rBC) and trace metals in Singapore, a highly urbanized city with multiple local and regional air pollution sources in the tropical region. rBC (C&lt;sub&gt;1&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt;&amp;#8211;C&lt;sub&gt;9&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt;) fragments and trace metals ions (K&lt;sup&gt;+&lt;/sup&gt;, Na&lt;sup&gt;+&lt;/sup&gt;, Ni&lt;sup&gt;+&lt;/sup&gt;, V&lt;sup&gt;+&lt;/sup&gt; and Rb&lt;sup&gt;+&lt;/sup&gt;) were integrated into our positive matrix factorization of OA. Two types of fossil fuel combustion-related OA with different degree of oxygenation were identified. This work provides evidence that over 90&amp;#8201;% of rBC was originated from local combustion sources with ~&amp;#8201;30&amp;#8201;% of them associated with the fresh secondary organic aerosol (SOA) produced under the influences of industrial emissions during daytime. The results also show that ~&amp;#8201;43&amp;#8201;% of the total rBC was emitted from local traffic, and the rest of rBC fraction due to multiple sources, including vehicular, shipping and industrial emissions, being not fully resolved. There was only a weak association between the cooking-related OA component and rBC. Although there was no observable biomass burning episode during the sampling period, tracers for biomass burning, K&lt;sup&gt;+&lt;/sup&gt; and Rb&lt;sup&gt;+&lt;/sup&gt;, were mainly associated with the more-oxidized oxygenated OA component (~&amp;#8201;32&amp;#8201;% of the total OA), indicating significant contributions of regional biomass burning emissions to this aged OA component. Furthermore, the aerosol pollutants transported from the industrial area and shipping ports gave higher C&lt;sub&gt;1&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt;/C&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt; and V&lt;sup&gt;+&lt;/sup&gt;/Ni&lt;sup&gt;+&lt;/sup&gt; ratios than those associated with traffic and biomass burning. The observed association between Na+ and rBC suggests that the contribution of anthropogenic emissions to total particulate sodium should not be ignored in coastal urban environments. Overall, this work demonstrates that rBC fragments and trace metal ions can improve our understanding on the sources, emissions characteristics and aging history of carbonaceous aerosol (OA and rBC) in this type of complex urban environments.&lt;/p&gt;

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