Effects of anthropogenic emissions on aerosol formation from isoprene and monoterpenes in the southeastern United States.

Secondary organic aerosol (SOA) constitutes a substantial fraction of fine particulate matter and has important impacts on climate and human health. The extent to which human activities alter SOA formation from biogenic emissions in the atmosphere is largely undetermined. Here, we present direct observational evidence on the magnitude of anthropogenic influence on biogenic SOA formation based on comprehensive ambient measurements in the southeastern United States (US). Multiple high-time-resolution mass spectrometry organic aerosol measurements were made during different seasons at various locations, including urban and rural sites in the greater Atlanta area and Centreville in rural Alabama. Our results provide a quantitative understanding of the roles of anthropogenic SO2 and NOx in ambient SOA formation. We show that isoprene-derived SOA is directly mediated by the abundance of sulfate, instead of the particle water content and/or particle acidity as suggested by prior laboratory studies. Anthropogenic NOx is shown to enhance nighttime SOA formation via nitrate radical oxidation of monoterpenes, resulting in the formation of condensable organic nitrates. Together, anthropogenic sulfate and NOx can mediate 43-70% of total measured organic aerosol (29-49% of submicron particulate matter, PM1) in the southeastern US during summer. These measurements imply that future reduction in SO2 and NOx emissions can considerably reduce the SOA burden in the southeastern US. Updating current modeling frameworks with these observational constraints will also lead to more accurate treatment of aerosol formation for regions with substantial anthropogenic-biogenic interactions and consequently improve air quality and climate simulations.

Worldwide data sets constrain the water vapor uptake coefficient in cloud formation.

Cloud droplet formation depends on the condensation of water vapor on ambient aerosols, the rate of which is strongly affected by the kinetics of water uptake as expressed by the condensation (or mass accommodation) coefficient, αc. Estimates of αc for droplet growth from activation of ambient particles vary considerably and represent a critical source of uncertainty in estimates of global cloud droplet distributions and the aerosol indirect forcing of climate. We present an analysis of 10 globally relevant data sets of cloud condensation nuclei to constrain the value of αc for ambient aerosol. We find that rapid activation kinetics (αc > 0.1) is uniformly prevalent. This finding resolves a long-standing issue in cloud physics, as the uncertainty in water vapor accommodation on droplets is considerably less than previously thought.

Source apportionment of fine and ultrafine particle number concentrations in a major city of the Eastern Mediterranean.

Ultrafine particles (UFP) are recognized as an emerging pollutant able to induce serious health effects. However, quantitative information regarding the contributions of UFP sources is generally limited. This study evaluates statistical (k-means clustering) and receptor models (Positive Matrix Factorization - PMF) using particle number size distributions (PNSD), along with chemical speciation data, measured at an urban background supersite in Athens, Greece, aiming to characterize their sources. PNSD measurements (10-487 nm) were performed during three distinct periods (warm, cold, and lockdown cold). Traffic and residential biomass burning (BB) produced high UFP number concentrations (NUFP) in the cold period (+107 % compared to summer), while the lockdown restrictions reduced NUFP (-42 %). The five groups produced by cluster analysis that were common among periods were linked to high- and low-traffic, new particle formation (NPF), urban background and regional aerosols. PMF source apportionment identified 5 and 6 factors during warm and cold periods, respectively, indicating that traffic particles dominated NUFP (64-78 % in all periods), while accumulation-mode particles and volume concentrations were controlled by processed aerosol, and especially in the cold periods by BB emissions. A nucleation factor linked to NPF contributed 7-11 % to NUFP. Comparing the two cold periods (business-as-usual, lockdown), important lockdown reductions (-46 %) were seen for fresh traffic contributions to total number concentration (Ntotal). The impact of the source attributed to NPF also eroded (-41 % for Ntotal). Due to the large reduction (-47 % for Ntotal) observed also for the BB source during the lockdown (reduced wood usage due to a milder winter), the relative contributions of all sources did not change considerably (fractional reductions <7 % for Ntotal). The quantitative results, bolstered by source apportionment combining PNSD and online chemical composition measurements, indicate the potential to constrain UFP levels by regulating traffic and residential emissions, with a large upside for population exposure control.

Spatiotemporal Gradients of PAH Concentrations in Greek Cities and Associated Exposure Impacts.

To study the spatiotemporal variability of particle-bound polycyclic aromatic hydrocarbons (PAHs) and assess their carcinogenic potential in six contrasting urban environments in Greece, a total of 305 filter samples were collected and analyzed. Sampling sites included a variety of urban background, traffic (Athens, Ioannina and Heraklion), rural (Xanthi) and near-port locations (Piraeus and Volos). When considering the sum of 16 U.S. EPA priority PAHs, as well as that of the six EU-proposed members, average concentrations observed across locations during summer varied moderately (0.4-2.2 ng m-3) and independently of the population of each site, with the highest values observed in the areas of Piraeus and Volos that are affected by port and industrial activities. Winter levels were significantly higher and more spatially variable compared to summer, with the seasonal enhancement ranging from 7 times in Piraeus to 98 times in Ioannina, indicating the large impact of PAH emissions from residential wood burning. Regarding benzo(a)pyrene (BaP), an IARC Group 1 carcinogen and the only EU-regulated PAH, the winter/summer ratios were 24-33 in Athens, Volos, Heraklion and Xanthi; 60 in Piraeus; and 480 in Ioannina, which is afflicted by severe wood-burning pollution events. An excellent correlation was observed between organic carbon (OC) and benzo(a)pyrene (BaP) during the cold period at all urban sites (r2 > 0.8) with stable BaP/OC slopes (0.09-0.14 × 10-3), highlighting the potential use of OC as a proxy for the estimation of BaP in winter conditions. The identified spatiotemporal contrasts, which were explored for the first time for PAHs at such a scale in the Eastern Mediterranean, provide important insights into sources and controlling atmospheric conditions and reveal large deviations in exposure risks among cities that raise the issue of environmental injustice on a national level.

Emission of volatile organic compounds from residential biomass burning and their rapid chemical transformations.

Biomass combustion releases a complex array of Volatile Organic Compounds (VOCs) that pose significant challenges to air quality and human health. Although biomass burning has been extensively studied at ecosystem levels, understanding the atmospheric transformation and impact on air quality of emissions in urban environments remains challenging due to complex sources and burning materials. In this study, we investigate the VOC emission rates and atmospheric chemical processing of predominantly wood burning emissions in a small urban centre in Greece. Ioannina is situated in a valley within the Dinaric Alps and experiences intense atmospheric pollution accumulation during winter due to its topography and high wood burning activity. During pollution event days, the ambient mixing ratios of key VOC species were found to be similar to those reported for major urban centres worldwide. Positive matrix factorisation (PMF) analysis revealed that biomass burning was the dominant emission source (>50 %), representing two thirds of OH reactivity, which indicates a highly reactive atmospheric mixture. Calculated OH reactivity ranges from 5 s-1 to an unprecedented 278 s-1, and averages at 93 ± 66 s-1 at 9 PM, indicating the presence of exceptionally reactive VOCs. The highly pronounced photochemical formation of organic acids coincided with the formation of ozone, highlighting the significance of secondary formation of pollutants in poorly ventilated urban areas. Our findings underscore the pressing need to transition from wood burning to environmentally friendly sources of energy in poorly ventilated urban areas, in order to improve air quality and safeguard public health.

Impact of COVID-19 Lockdown on Oxidative Potential of Particulate Matter: Case of Athens (Greece).

This work evaluates the aerosol oxidative potential (OP) and its changes from modified air pollution emissions during the COVID-19 lockdown period in 2020, with the intent of elucidating the contribution of aerosol sources and related components to aerosol OP. For this, daily particulate matter (PM) samples at an urban background site were collected and analyzed with a chemical (acellular) assay based on Dithiothreitol (DTT) during the COVID-19 restriction period in Athens (Greece). The obtained time-series of OP, PM2.5, organic matter (OM) and SO42- of the pre-, post- and lockdown periods were also compared to the data of the same time periods during the years 2017-2019. Even though all traffic-related emissions have been significantly reduced during the lockdown period (by 30%), there is no reduction in water-soluble OP, organics and sulfate concentrations of aerosol during 2020. The results reveal that the decrease in traffic was not sufficient to drive any measurable change on OP, suggesting that other sources-such as biomass burning and secondary aerosol from long-range transport, which remained unchanged during the COVID lockdown-are the main contributors to OP in Athens, Greece.

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.

Corrigendum: Collocated observations of cloud condensation nuclei, particle size distributions, and chemical composition.

This corrects the article DOI: 10.1038/sdata.2017.3.

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.