Office Indoor PM and BC Level in Lithuania: The Role of a Long-Range Smoke Transport Event

While the impacts of climate change on wildfires and resulting air pollution levels have been observed, little is known about how indoor air filtering systems are performing under intensive smoke conditions. For this aim, particle number size distribution and concentration in a size range 0.5–18 μm and equivalent black carbon (eBC) mass concentration were measured in a modern office with a mechanical ventilation system. Measurements took place from 30 September to 6 October 2020 in the Center for Physical Sciences and Technology (FTMC) campus located in the urban background environment in Lithuania. During the measurement campaign, an intensive pollution episode, related to long-range transport wildfire smoke, was observed. The results indicated that the smoke event increased both indoor and outdoor eBC mass concentrations twice. Filters were non-selective for different eBC sources (biomass burning versus traffic) or chemical composition of carbonaceous aerosol particles (eBC versus brown carbon (BrC)). Air filtering efficiency was found to be highly dependent on particle size. During the smoke event the highest particle number concentration was observed at 2.1 μm and 1.0 μm size particles in outdoor and indoor air, respectively. Differences of indoor to outdoor ratio between event and non-event days were not significant. Because of lower removal rate for small particles, eBC had higher contribution to total PM2.5 mass concentration in indoor air than in outdoor air. The results gained are crucial for decision-making bodies in order to implement higher-quality air-filtering systems in office buildings and, as a result, minimize potential health impacts. © 2021 by the authors

Shipborne measurements of Antarctic submicron organic aerosols: an NMR perspective linking multiple sources and bioregions

Abstract. The concentrations of submicron aerosol particles in maritime regions around Antarctica are influenced by the extent of sea ice. This effect is two ways: on one side, sea ice regulates the production of particles by sea spray (primary aerosols); on the other side, it hosts complex communities of organisms emitting precursors for secondary particles. Past studies documenting the chemical composition of fine aerosols in Antarctica indicate various potential primary and secondary sources active in coastal areas, in offshore marine regions, and in the sea ice itself. In particular, beside the well-known sources of organic and sulfur material originating from the oxidation of dimethylsulfide (DMS) produced by microalgae, recent findings obtained during the 2015 PEGASO cruise suggest that nitrogen-containing organic compounds are also produced by the microbiota colonizing the marginal ice zone. To complement the aerosol source apportionment performed using online mass spectrometric techniques, here we discuss the outcomes of offline spectroscopic analysis performed by nuclear magnetic resonance (NMR) spectroscopy. In this study we (i) present the composition of ambient aerosols over open-ocean waters across bioregions, and compare it to the composition of (ii) seawater samples and (iii) bubble-bursting aerosols produced in a sea-spray chamber onboard the ship. Our results show that the process of aerosolization in the tank enriches primary marine particles with lipids and sugars while depleting them of free amino acids, providing an explanation for why amino acids occurred only at trace concentrations in the marine aerosol samples analyzed. The analysis of water-soluble organic carbon (WSOC) in ambient submicron aerosol samples shows distinct NMR fingerprints for three bioregions: (1) the open Southern Ocean pelagic environments, in which aerosols are enriched with primary marine particles containing lipids and sugars; (2) sympagic areas in the Weddell Sea, where secondary organic compounds, including methanesulfonic acid and semivolatile amines abound in the aerosol composition; and (3) terrestrial coastal areas, traced by sugars such as sucrose, emitted by land vegetation. Finally, a new biogenic chemical marker, creatinine, was identified in the samples from the Weddell Sea, providing another confirmation of the importance of nitrogen-containing metabolites in Antarctic polar aerosols

Response of the Aerodyne Aerosol Mass Spectrometer to Inorganic Sulfates and Organosulfur Compounds: Applications in Field and Laboratory Measurements

Organosulfur compounds are important components of secondary organic aerosols (SOA). While the Aerodyne high-resolution time-of-flight aerosol mass spectrometer (AMS) has been extensively used in aerosol studies, the response of the AMS to organosulfur compounds is not well-understood. Here, we investigated the fragmentation patterns of organosulfurs and inorganic sulfates in the AMS, developed a method to deconvolve total sulfate into components of inorganic and organic origins, and applied this method in both laboratory and field measurements. Apportionment results from laboratory isoprene photooxidation experiment showed that with inorganic sulfate seed, sulfate functionality of organic origins can contribute ∼7% of SOA mass at peak growth. Results from measurements in the Southeastern U.S. showed that 4% of measured sulfate is from organosulfur compounds. Methanesulfonic acid was estimated for measurements in the coastal and remote marine boundary layer. We explored the application of this method to unit mass-resolution data, where it performed less well due to interferences. Our apportionment results demonstrate that organosulfur compounds could be a non-negligible source of sulfate fragments in AMS laboratory and field data sets. A reevaluation of previous AMS measurements over the full range of atmospheric conditions using this method could provide a global estimate/constraint on the contribution of organosulfur compounds

Effects of NH3 and alkaline metals on the formation of particulate sulfate and nitrate in wintertime Beijing

Sulfate and nitrate from secondary reactions remain as the most abundant inorganic species in atmospheric particle matter (PM). Their formation is initiated by oxidation (either in gas phase or particle phase), followed by neutralization reaction primarily by NH3, or by other alkaline species such as alkaline metal ions if available. The different roles of NH3 and metal ions in neutralizing H2SO4 or HNO3, however, are seldom investigated. Here we conducted semi-continuous measurements of SO4 2−, NO3 −, NH4 +, and their gaseous precursors, as well as alkaline metal ions (Na+, K+, Ca2+, and Mg2+) in wintertime Beijing. Analysis of aerosol acidity (estimated from a thermodynamic model) indicated that preferable sulfate formation was related to low pH conditions, while high pH conditions promote nitrate formation. Data in different mass fraction ranges of alkaline metal ions showed that in some ranges the role of NH3 was replaced by alkaline metal ions in the neutralization reaction of H2SO4 and HNO3 to form particulate SO4 2− and NO3 −. The relationships between mass fractions of SO4 2− and NO3 − in those ranges of different alkaline metal ion content also suggested that alkaline metal ions participate in the competing neutralization reaction of sulfate and nitrate. The implication of the current study is that in some regions the chemistry to incorporate sulfur and nitrogen into particle phase might be largely affected by desert/fugitive dust and sea salt, besides NH3. This implication is particularly relevant in coastal China and those areas with strong influence of dust storm in the North China Plain (NCP), both of which host a number of megacities with deteriorating air quality

Response of the Aerodyne Aerosol Mass Spectrometer to Inorganic Sulfates and Organosulfur Compounds: Applications in Field and Laboratory Measurements

Organosulfur compounds are important components of secondary organic aerosols (SOA). While the Aerodyne high-resolution time-of-flight aerosol mass spectrometer (AMS) has been extensively used in aerosol studies, the response of the AMS to organosulfur compounds is not well-understood. Here, we investigated the fragmentation patterns of organosulfurs and inorganic sulfates in the AMS, developed a method to deconvolve total sulfate into components of inorganic and organic origins, and applied this method in both laboratory and field measurements. Apportionment results from laboratory isoprene photooxidation experiment showed that with inorganic sulfate seed, sulfate functionality of organic origins can contribute ∼7% of SOA mass at peak growth. Results from measurements in the Southeastern U.S. showed that 4% of measured sulfate is from organosulfur compounds. Methanesulfonic acid was estimated for measurements in the coastal and remote marine boundary layer. We explored the application of this method to unit mass-resolution data, where it performed less well due to interferences. Our apportionment results demonstrate that organosulfur compounds could be a non-negligible source of sulfate fragments in AMS laboratory and field data sets. A reevaluation of previous AMS measurements over the full range of atmospheric conditions using this method could provide a global estimate/constraint on the contribution of organosulfur compounds

Direct field evidence of autocatalytic iodine release from atmospheric aerosol

Reactive iodine plays a key role in determining the oxidation capacity, or cleansing capacity, of the atmosphere in addition to being implicated in the formation of new particles in the marine boundary layer. The postulation that heterogeneous cycling of reactive iodine on aerosols may significantly influence the lifetime of ozone in the troposphere not only remains poorly understood but also heretofore has never been observed or quantified in the field. Here, we report direct ambient observations of hypoiodous acid (HOI) and heterogeneous recycling of interhalogen product species (i.e., iodine monochloride [ICI] and iodine monobromide [IBr]) in a midlatitude coastal environment. Significant levels of ICI and IBr with mean daily maxima of 4.3 and 3.0 parts per trillion by volume (1-min average), respectively, have been observed throughout the campaign. We show that the heterogeneous reaction of HOI on marine aerosol and subsequent production of iodine interhalogens are much faster than previously thought. These results indicate that the fast formation of iodine interhalogens, together with their rapid photolysis, results in more efficient recycling of atomic iodine than currently considered in models. Photolysis of the observed ICI and IBr leads to a 32% increase in the daytime average of atomic iodine production rate, thereby enhancing the average daytime iodine-catalyzed ozone loss rate by 10 to 20%. Our findings provide direct field evidence that the autocatalytic mechanism of iodine release from marine aerosol is important in the atmosphere and can have significant impacts on atmospheric oxidation capacity.Peer reviewe

Data Descriptor : Collocated observations of cloud condensation nuclei, particle size distributions, and chemical composition

Cloud condensation nuclei (CCN) number concentrations alongside with submicrometer particle number size distributions and particle chemical composition have been measured at atmospheric observatories of the Aerosols, Clouds, and Trace gases Research InfraStructure (ACTRIS) as well as other international sites over multiple years. Here, harmonized data records from 11 observatories are summarized, spanning 98,677 instrument hours for CCN data, 157,880 for particle number size distributions, and 70,817 for chemical composition data. The observatories represent nine different environments, e.g., Arctic, Atlantic, Pacific and Mediterranean maritime, boreal forest, or high alpine atmospheric conditions. This is a unique collection of aerosol particle properties most relevant for studying aerosol-cloud interactions which constitute the largest uncertainty in anthropogenic radiative forcing of the climate. The dataset is appropriate for comprehensive aerosol characterization (e.g., closure studies of CCN), model-measurement intercomparison and satellite retrieval method evaluation, among others. Data have been acquired and processed following international recommendations for quality assurance and have undergone multiple stages of quality assessment.Peer reviewe

European aerosol phenomenology - 8 : Harmonised source apportionment of organic aerosol using 22 Year-long ACSM/AMS datasets

Organic aerosol (OA) is a key component of total submicron particulate matter (PM1), and comprehensive knowledge of OA sources across Europe is crucial to mitigate PM1 levels. Europe has a well-established air quality research infrastructure from which yearlong datasets using 21 aerosol chemical speciation monitors (ACSMs) and 1 aerosol mass spectrometer (AMS) were gathered during 2013-2019. It includes 9 non-urban and 13 urban sites. This study developed a state-of-the-art source apportionment protocol to analyse long-term OA mass spectrum data by applying the most advanced source apportionment strategies (i.e., rolling PMF, ME-2, and bootstrap). This harmonised protocol was followed strictly for all 22 datasets, making the source apportionment results more comparable. In addition, it enables quantification of the most common OA components such as hydrocarbon-like OA (HOA), biomass burning OA (BBOA), cooking-like OA (COA), more oxidised-oxygenated OA (MO-OOA), and less oxidised-oxygenated OA (LO-OOA). Other components such as coal combustion OA (CCOA), solid fuel OA (SFOA: mainly mixture of coal and peat combustion), cigarette smoke OA (CSOA), sea salt (mostly inorganic but part of the OA mass spectrum), coffee OA, and ship industry OA could also be separated at a few specific sites. Oxygenated OA (OOA) components make up most of the submicron OA mass (average = 71.1%, range from 43.7 to 100%). Solid fuel combustion-related OA components (i.e., BBOA, CCOA, and SFOA) are still considerable with in total 16.0% yearly contribution to the OA, yet mainly during winter months (21.4%). Overall, this comprehensive protocol works effectively across all sites governed by different sources and generates robust and consistent source apportionment results. Our work presents a comprehensive overview of OA sources in Europe with a unique combination of high time resolution (30-240 min) and long-term data coverage (9-36 months), providing essential information to improve/validate air quality, health impact, and climate models.Peer reviewe