Understanding the chemistry of atmospheric aerosol particle formation via observations of physical properties

It is widely accepted that the global climate is heating up due to human activities, such as burning of fossil fuels. Therefore we find ourselves forced to make decisions on what measures, if any, need to be taken to decrease our warming effect on the planet before any irrevocable damage occurs. Research is being conducted in a variety of fields to better understand all relevant processes governing Earth s climate, and to assess the relative roles of anthropogenic and biogenic emissions into the atmosphere. One of the least well quantified problems is the impact of small aerosol particles (both of anthropogenic and biogenic origin) on climate, through reflecting solar radiation and their ability to act as condensation nuclei for cloud droplets. In this thesis, the compounds driving the biogenic formation of new particles in the atmosphere have been examined through detailed measurements. As directly measuring the composition of these newly formed particles is extremely difficult, the approach was to indirectly study their different characteristics by measuring the hygroscopicity (water uptake) and volatility (evaporation) of particles between 10 and 50 nm. To study the first steps of the formation process in the sub-3 nm range, the nucleation of gaseous precursors to small clusters, the chemical composition of ambient naturally charged ions were measured. The ion measurements were performed with a newly developed mass spectrometer, which was first characterized in the laboratory before being deployed at a boreal forest measurement site. It was also successfully compared to similar, low-resolution instruments. The ambient measurements showed that sulfuric acid clusters dominate the negative ion spectrum during new particle formation events. Sulfuric acid/ammonia clusters were detected in ambient air for the first time in this work. Even though sulfuric acid is believed to be the most important gas phase precursor driving the initial cluster formation, measurements of the hygroscopicity and volatility of growing 10-50 nm particles in Hyytiälä showed an increasing role of organic vapors of a variety of oxidation levels. This work has provided additional insights into the compounds participating both in the initial formation and subsequent growth of atmospheric new aerosol particles. It will hopefully prove an important step in understanding atmospheric gas-to-particle conversion, which, by influencing cloud properties, can have important climate impacts. All available knowledge needs to be constantly updated, summarized, and brought to the attention of our decision-makers. Only by increasing our understanding of all the relevant processes can we build reliable models to predict the long-term effects of decisions made today.Brännandet av stora mängder fossila bränslen under de senaste århundraden har ökat koldioxidhalten i luften, vilket tros leda till en växthuseffekt som värmer vår planet. Atmosfären är dock ett oerhört komplicerat system där samarbete mellan en mängd olika forskningsgrenar krävs för att förstå alla relevanta processer. En ju mer komplett bild av atmosfären vi har, desto sannolikare kan vi göra de rätta besluten för att trygga vår framtid. En av de processer som anses vara av stor betydelse, men som har visat sig mycket svår att kvantifiera, är aerosolpartiklarnas inverkan på jordens strålningsbalans. Aerosolpartiklar är små luftburna partiklar i antingen fast form eller vätskeform som kan direkt reflektera solljus tillbaka ut i rymden eller fungera som kärnor för molndroppar. Höga halter partiklar leder till flera, men mindre, molndroppar, som i sin tur leder till ljusare och mer långlivade moln som effektivt reflekterar solens strålning och därmed ger upphov till en nedkylande effekt. Aerosolpartiklar produceras både i naturen och av människan, och för att förstå följderna av ökad eller minskad antropogen partikelproduktion måste vi först förstå den naturliga produktionen. Denna avhandling har fokuserat på att ge insikt i den kemiska sammansättningen av de allra minsta (pienempi kuin 50 nm i diameter) partiklarna i situationer där nya partiklar bildas genom nukleation och kondensation av gasmolekyler. P.g.a. de väldigt små massorna hos dessa partiklar, är det mycket svårt att direkt mäta deras kemiska sammansättning. I detta arbete har indirekta metoder använts för att få information om vad partiklarna kan innehålla. Partiklarnas hygroskopisitet, d.v.s. deras förmåga att uppta vatten, samt deras volatilitet, d.v.s. mängden material som förångas från partiklarna vid upphettning, uppmättes i ett barrskogsområde i södra Finland. Därtill studerades sammansättningen hos luftens joner under partikelformation på samma ställe. Resultaten av de indirekta mätningarna tyder på att nukleationsprocessen domineras av svavelsyra som bildar kluster, möjligen stabiliserade av baser såsom ammoniak, som senare växer genom kondensation. Kondensationen som leder till 10-50 nm stora partiklar är dock dominerad av oxiderade organiska föreningar. Dessa organiska föreningar härstammar sannolikt från kolväten som avgetts från de omkringliggande träden, medan svavelsyran, som produceras genom oxidering av svaveldioxid, kan vara influerad av människan. Denna avhandling är ett litet, men viktigt, steg framåt i vår strävan efter en kvantitativ förståelse över hur aerosolpartiklarna inverkar på jordens klimat. Den förståelsen kommer, i sin tur, att hjälpa oss att producera pålitligare klimatmodeller som kan förutspå framtida klimat på basen av olika utsläppsscenarier

Highly Oxygenated Molecules from Atmospheric Autoxidation of Hydrocarbons : A Prominent Challenge for Chemical Kinetics Studies

Recent advances in chemical ionization mass spectrometry have allowed the detection of a new group of compounds termed highly oxygenated molecules (HOM). These are atmospheric oxidation products of volatile organic compounds (VOC) retaining most of their carbon backbone, and with O/C ratios around unity. Owing to their surprisingly high yields and low vapor pressures, the importance of HOM for aerosol formation has been easy to verify. However, the opposite can be said concerning the exact formation pathways of HOM from major aerosol precursor VOC. While the role of peroxy radical autoxidation, i.e., consecutive intramolecular H-shifts followed by O-2 addition, has been recognized, the detailed formation mechanisms remain highly uncertain. A primary reason is that the autoxidation process occurs on sub-second timescales and is extremely sensitive to environmental conditions like gas composition, temperature, and pressure. This, in turn, poses a great challenge for chemical kinetics studies to be able to mimic the relevant atmospheric reaction pathways, while simultaneously using conditions suitable for studying the short-lived radical intermediates. In this perspective, we define six specific challenges for this community to directly observe the initial steps of atmospherically relevant autoxidation reactions and thereby facilitate vital improvements in the understanding of VOC degradation and organic aerosol formation. (C) 2017 Wiley Periodicals, Inc.Peer reviewe

Unwanted Indoor Air Quality Effects from Using Ultraviolet C Lamps for Disinfection

Ultraviolet germicidal irradiation (UVGI) is known to inactivate various viruses and bacteria, including SARS-CoV-2, and is widely applied especially in medical facilities. This inactivation results from the high photon energies causing molecular bonds to break, but when nonpathogen molecules are affected, unwanted effects may occur. Here, we explored the effect of a commercial high intensity (similar to 2 kW) UVC disinfection device on the composition and concentration of gases and particles in indoor air. We find that the UVC (254 nm) caused dramatic increases in particle number concentrations, and nearly all (similar to 1000) monitored gas phase species also increased. These responses were unsurprising when considering the typical impacts of UVC on atmospheric chemistry. High particle concentrations are associated with adverse health effects, suggesting that the impact of UVGI devices on indoor air quality (IAQ) should be studied in much more detail. The high-intensity device in this study was intended for short durations in unoccupied rooms, but lower-intensity devices for continuous use in occupied rooms are also widely applied. This makes further studies even more urgent, as the potential IAQ effects of these approaches remain largely unexplored.Peer reviewe

Formation of Highly Oxidized Radicals and Multifunctional Products from the Atmospheric Oxidation of Alkylbenzenes

Aromatic hydrocarbons contribute significantly to tropospheric ozone and secondary organic aerosols (SOA). Despite large efforts in elucidating the formation mechanism of aromatic-derived SOA, current models still substantially underestimate the SOA yields when comparing to field measurements. Here we present a new, up to now undiscovered pathway for the formation of highly oxidized products from the OH-initiated oxidation of alkyl benzenes based on theoretical and experimental investigations. We propose that unimolecular H-migration followed by O-2-addition, a so-called autoxidation step, can take place in bicyclic peroxy radicals (BPRs), which are important intermediates of the OH -initiated oxidation of aromatic compounds. These autoxidation steps lead to the formation of highly oxidized multifunctional compounds (HOMs), which are able to form SOA. Our theoretical calculations suggest that the intramolecular H-migration in BPRs of substituted benzenes could be fast enough to compete with bimolecular reactions with HO2 radicals or NO under atmospheric conditions. The theoretical findings are experimentally supported by flow tube studies using chemical ionization mass spectrometry to detect the highly oxidized peroxy radical intermediates and closed-shell products. This new unimolecular BPR route to form HOMs in the gas phase enhances our understanding of the aromatic oxidation mechanism, and contributes significantly to a better understanding of aromatic-derived SOA in urban areas.Peer reviewe

Experimental investigation into the volatilities of highly oxygenated organic molecules (HOMs)

Secondary organic aerosol (SOA) forms a major part of the tropospheric submicron aerosol. Still, the exact formation mechanisms of SOA have remained elusive. Recently, a newly discovered group of oxidation products of volatile organic compounds (VOCs), highly oxygenated organic molecules (HOMs), have been proposed to be responsible for a large fraction of SOA formation. To assess the potential of HOMs to form SOA and to even take part in new particle formation, knowledge of their exact volatilities is essential. However, due to their exotic, and partially unknown, structures, estimating their volatility is challenging. In this study, we performed a set of continuous flow chamber experiments, supported by box modelling, to study the volatilities of HOMs, along with some less oxygenated compounds, formed in the ozonolysis of α-pinene, an abundant VOC emitted by boreal forests. Along with gaseous precursors, we periodically injected inorganic seed aerosol into the chamber to vary the condensation sink (CS) of low-volatility vapours. We monitored the decrease of oxidation products in the gas phase in response to increasing CS, and were able to relate the responses to the volatilities of the compounds. We found that HOM monomers are mainly of low volatility, with a small fraction being semi-volatile. HOM dimers were all at least low volatility, but probably extremely low volatility; however, our method is not directly able to distinguish between the two. We were able to model the volatility of the oxidation products in terms of their carbon, hydrogen, oxygen and nitrogen numbers. We found that increasing levels of oxygenation correspond to lower volatilities, as expected, but that the decrease is less steep than would be expected based on many existing models for volatility, such as SIMPOL. The hydrogen number of a compound also predicted its volatility, independently of the carbon number, with higher hydrogen numbers corresponding to lower volatilities. This can be explained in terms of the functional groups making up a molecule: high hydrogen numbers are associated with, e.g. hydroxy groups, which lower volatility more than, e.g. carbonyls, which are associated with a lower hydrogen number. The method presented should be applicable to systems other than α-pinene ozonolysis, and with different organic loadings, in order to study different volatility ranges.Secondary organic aerosol (SOA) forms a major part of the tropospheric submicron aerosol. Still, the exact formation mechanisms of SOA have remained elusive. Recently, a newly discovered group of oxidation products of volatile organic compounds (VOCs), highly oxygenated organic molecules (HOMs), have been proposed to be responsible for a large fraction of SOA formation. To assess the potential of HOMs to form SOA and to even take part in new particle formation, knowledge of their exact volatilities is essential. However, due to their exotic, and partially unknown, structures, estimating their volatility is challenging. In this study, we performed a set of continuous flow chamber experiments, supported by box modelling, to study the volatilities of HOMs, along with some less oxygenated compounds, formed in the ozonolysis of alpha-pinene, an abundant VOC emitted by boreal forests. Along with gaseous precursors, we periodically injected inorganic seed aerosol into the chamber to vary the condensation sink (CS) of low-volatility vapours. We monitored the decrease of oxidation products in the gas phase in response to increasing CS, and were able to relate the responses to the volatilities of the compounds. We found that HOM monomers are mainly of low volatility, with a small fraction being semi-volatile. HOM dimers were all at least low volatility, but probably extremely low volatility; however, our method is not directly able to distinguish between the two. We were able to model the volatility of the oxidation products in terms of their carbon, hydrogen, oxygen and nitrogen numbers. We found that increasing levels of oxygenation correspond to lower volatilities, as expected, but that the decrease is less steep than would be expected based on many existing models for volatility, such as SIM-POL. The hydrogen number of a compound also predicted its volatility, independently of the carbon number, with higher hydrogen numbers corresponding to lower volatilities. This can be explained in terms of the functional groups making up a molecule: high hydrogen numbers are associated with, e.g. hydroxy groups, which lower volatility more than, e.g. carbonyls, which are associated with a lower hydrogen number. The method presented should be applicable to systems other than alpha-pinene ozonolysis, and with different organic loadings, in order to study different volatility ranges.Peer reviewe

Modeling the Charging of Highly Oxidized Cyclohexene Ozonolysis Products Using Nitrate-Based Chemical Ionization

Several extremely low volatility organic compounds (ELVOCs) formed in the ozonolysis of endocyclic alkenes have recently been detected in laboratory and field studies. These experiments have been carried out with chemical ionization atmospheric pressure interface time-of-flight mass spectrometers (CI-APi-TOP) with nitrate ions as reagent ions. The nitrate ion binds to the detected species through hydrogen bonds, but it also binds very strongly to one or two neutral nitric acid molecules. This makes the measurement highly selective when there is an excess amount of neutral nitric acid in the instrument. In this work, we used quantum-chemical methods to calculate the binding energies between a nitrate ion and several highly oxidized ozonolysis products of cydohexene. These were then compared with the binding energies of nitrate ion nitric acid clusters. Systematic configurational sampling of the molecules and clusters was carried out at the B3LYP/6-31+G* and omega B97xD/aug-cc-pVTZ levels, and the final single-point energies were calculated with DLPNO-CCSD(T)/def2-QZVPP. The binding energies were used in a kinetic simulation of the measurement system to determine the relative ratios of the detected signals. Our results indicate that at least two hydrogen bond donor functional groups (in this case, hydroperoxide, OOH) are needed for an ELVOC molecule to be detected in a nitrate ion CI-APi-TOP. Also, a double bond in the carbon backbone makes the nitrate cluster formation less favorable.Peer reviewe

Gas-to-Particle Partitioning of Cyclohexene- and alpha-Pinene-Derived Highly Oxygenated Dimers Evaluated Using COSMOtherm

Oxidized organic compounds are expected to contribute to secondary organic aerosol (SOA) if they have sufficiently low volatilities. We estimated saturation vapor pressures and activity coefficients (at infinite dilution in water and a model water-insoluble organic phase) of cyclohexene- and alpha-pinene-derived accretion products, "dimers", using the COSMOtherm19 program. We found that these two property estimates correlate with the number of hydrogen bond-donating functional groups and oxygen atoms in the compound. In contrast, when the number of H-bond donors is fixed, no clear differences are seen either between functional group types (e.g., OH or OOH as H-bond donors) or the formation mechanisms (e.g., gas-phase radical recombination vs liquid-phase closed-shell esterification). For the cyclohexene-derived dimers studied here, COSMOtherm19 predicts lower vapor pressures than the SIMPOL.1 group-contribution method in contrast to previous COSMOtherm estimates using older parameterizations and nonsystematic conformer sampling. The studied dimers can be classified as low, extremely low, or ultra-low-volatility organic compounds based on their estimated saturation mass concentrations. In the presence of aqueous and organic aerosol particles, all of the studied dimers are likely to partition into the particle phase and thereby contribute to SOA formation.Peer reviewe

Improving the Sensitivity of Fourier Transform Mass Spectrometer (Orbitrap) for Online Measurements of Atmospheric Vapors

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Improving the Sensitivity of Fourier Transform Mass Spectrometer (Orbitrap) for Online Measurements of Atmospheric Vapors

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