ORCID Profile
0000-0002-9675-3271
Current Organisations
University of Helsinki
,
University of Washington
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Publisher: American Chemical Society (ACS)
Date: 09-06-2020
Publisher: Proceedings of the National Academy of Sciences
Date: 28-08-2018
Abstract: Aerosol particles can form and grow by gas-to-particle conversion and eventually act as seeds for cloud droplets, influencing global climate. Volatile organic compounds emitted from plants are oxidized in the atmosphere, and the resulting products drive particle growth. We measure particle growth by oxidized biogenic vapors with a well-controlled laboratory setup over a wide range of tropospheric temperatures. While higher temperatures lead to increased reaction rates and concentrations of highly oxidized molecules, lower temperatures allow additional, but less oxidized, species to condense. We measure rapid growth over the full temperature range of our study, indicating that organics play an important role in aerosol growth throughout the troposphere. Our finding will help to sharpen the predictions of global aerosol models.
Publisher: Copernicus GmbH
Date: 27-09-2021
DOI: 10.5194/ACP-21-14275-2021
Abstract: Abstract. New particle formation (NPF) is a significant source of atmospheric particles, affecting climate and air quality. Understanding the mechanisms involved in urban aerosols is important to develop effective mitigation strategies. However, NPF rates reported in the polluted boundary layer span more than 4 orders of magnitude, and the reasons behind this variability are the subject of intense scientific debate. Multiple atmospheric vapours have been postulated to participate in NPF, including sulfuric acid, ammonia, amines and organics, but their relative roles remain unclear. We investigated NPF in the CLOUD chamber using mixtures of anthropogenic vapours that simulate polluted boundary layer conditions. We demonstrate that NPF in polluted environments is largely driven by the formation of sulfuric acid–base clusters, stabilized by the presence of amines, high ammonia concentrations and lower temperatures. Aromatic oxidation products, despite their extremely low volatility, play a minor role in NPF in the chosen urban environment but can be important for particle growth and hence for the survival of newly formed particles. Our measurements quantitatively account for NPF in highly erse urban environments and explain its large observed variability. Such quantitative information obtained under controlled laboratory conditions will help the interpretation of future ambient observations of NPF rates in polluted atmospheres.
Publisher: American Association for the Advancement of Science (AAAS)
Date: 29-05-2020
Abstract: NO x is important for particle growth as it can participate in HOM formation and alter the HOM volatility distribution.
Publisher: Copernicus GmbH
Date: 20-01-2021
Publisher: Copernicus GmbH
Date: 15-05-2023
DOI: 10.5194/EGUSPHERE-EGU23-15768
Abstract: Aromatic compounds contribute significantly to the formation of secondary organic aerosol (SOA) that have implications on health and on climate. Toluene is the most abundant aromatic compound in the atmosphere and is emitted through anthropogenic activities such as incomplete combustion and industrial processes. To form SOA, participating vapors such as toluene need to have sufficiently low volatility, which in practice implies molecules with multiple oxygen containing polar functional groups called highly oxygenated organic molecules (HOMs). The oxidation of toluene by OH can lead first to bicyclic peroxy radicals (BPR), and then to HOM. While the formation of HOM has been shown to be efficient, the underlying molecular level mechanism has been challenging to accurately elucidate because of the sheer number of potential pathways. This leads to a major gap in the understanding of the formation of SOA from toluene in the atmosphere. In this work, we conclusively demonstrate for the first time that the toluene derived BPR is unstable under atmospheric conditions and undergoes spontaneous molecular rearrangement to lead to completely ring broken RO2s at rates competitive with bimolecular reactions with NO even under polluted conditions. Intriguingly, several of the closed shell products deriving from the BPR are likewise unstable and decompose in finite timescales. This is relevant for those aromatic compounds that lead to BPRs that are otherwise stable against rearrangement reactions, providing, e.g., a long-range transport vehicle for NOx similar to peroxyacyl nitrates (PAN). Using quantum chemical calculations and master equation simulations that account for energy non-accommodation, we elucidate the molecular level mechanism of the subsequent autoxidation of the ring broken RO2s that leads rapidly to the HOM O9-RO2. Furthermore, using targeted flow reactor experiments of the OH reaction of toluene and partially deuterated toluene with nitrate chemical ionization mass spectrometry (CIMS) detection, we corroborate the proposed new mechanism. This is the only unambiguous reaction pathway to toluene derived HOM reported to date, and it has implications on the aerosol and ozone forming potential of toluene.
Publisher: Springer Science and Business Media LLC
Date: 04-04-2017
DOI: 10.1038/SREP45707
Abstract: Solar eclipses provide unique possibilities to investigate atmospheric processes, such as new particle formation (NPF), important to the global aerosol load and radiative balance. The temporary absence of solar radiation gives particular insight into different oxidation and clustering processes leading to NPF. This is crucial because our mechanistic understanding on how NPF is related to photochemistry is still rather limited. During a partial solar eclipse over Finland in 2015, we found that this phenomenon had prominent effects on atmospheric on-going NPF. During the eclipse, the sources of aerosol precursor gases, such as sulphuric acid and nitrogen- containing highly oxidised organic compounds, decreased considerably, which was followed by a reduced formation of small clusters and nanoparticles and thus termination of NPF. After the eclipse, aerosol precursor molecule concentrations recovered and re-initiated NPF. Our results provide direct evidence on the key role of the photochemical production of sulphuric acid and highly oxidized organic compounds in maintaining atmospheric NPF. Our results also explain the rare occurrence of this phenomenon under dark conditions, as well as its seemingly weak connection with atmospheric ions.
Publisher: Copernicus GmbH
Date: 21-12-2017
DOI: 10.5194/ACP-17-15181-2017
Abstract: Abstract. The formation of secondary particles in the atmosphere accounts for more than half of global cloud condensation nuclei. Experiments at the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber have underlined the importance of ions for new particle formation, but quantifying their effect in the atmosphere remains challenging. By using a novel instrument setup consisting of two nanoparticle counters, one of them equipped with an ion filter, we were able to further investigate the ion-related mechanisms of new particle formation. In autumn 2015, we carried out experiments at CLOUD on four systems of different chemical compositions involving monoterpenes, sulfuric acid, nitrogen oxides, and ammonia. We measured the influence of ions on the nucleation rates under precisely controlled and atmospherically relevant conditions. Our results indicate that ions enhance the nucleation process when the charge is necessary to stabilize newly formed clusters, i.e., in conditions in which neutral clusters are unstable. For charged clusters that were formed by ion-induced nucleation, we were able to measure, for the first time, their progressive neutralization due to recombination with oppositely charged ions. A large fraction of the clusters carried a charge at 1.5 nm diameter. However, depending on particle growth rates and ion concentrations, charged clusters were largely neutralized by ion–ion recombination before they grew to 2.5 nm. At this size, more than 90 % of particles were neutral. In other words, particles may originate from ion-induced nucleation, although they are neutral upon detection at diameters larger than 2.5 nm. Observations at Hyytiälä, Finland, showed lower ion concentrations and a lower contribution of ion-induced nucleation than measured at CLOUD under similar conditions. Although this can be partly explained by the observation that ion-induced fractions decrease towards lower ion concentrations, further investigations are needed to resolve the origin of the discrepancy.
Publisher: American Association for the Advancement of Science (AAAS)
Date: 07-12-2018
Abstract: Atmospheric aerosol formation from biogenic vapors is strongly affected by air pollutants, like NO x , SO 2 , and NH 3 .
Publisher: Copernicus GmbH
Date: 04-01-2018
Abstract: Abstract. It was recently shown by the CERN CLOUD experiment that biogenic highly oxygenated molecules (HOMs) form particles under atmospheric conditions in the absence of sulfuric acid, where ions enhance the nucleation rate by 1–2 orders of magnitude. The biogenic HOMs were produced from ozonolysis of α-pinene at 5 ∘C. Here we extend this study to compare the molecular composition of positive and negative HOM clusters measured with atmospheric pressure interface time-of-flight mass spectrometers (APi-TOFs), at three different temperatures (25, 5 and −25 ∘C). Most negative HOM clusters include a nitrate (NO3-) ion, and the spectra are similar to those seen in the nighttime boreal forest. On the other hand, most positive HOM clusters include an ammonium (NH4+) ion, and the spectra are characterized by mass bands that differ in their molecular weight by ∼ 20 C atoms, corresponding to HOM dimers. At lower temperatures the average oxygen to carbon (O : C) ratio of the HOM clusters decreases for both polarities, reflecting an overall reduction of HOM formation with decreasing temperature. This indicates a decrease in the rate of autoxidation with temperature due to a rather high activation energy as has previously been determined by quantum chemical calculations. Furthermore, at the lowest temperature (−25 ∘C), the presence of C30 clusters shows that HOM monomers start to contribute to the nucleation of positive clusters. These experimental findings are supported by quantum chemical calculations of the binding energies of representative neutral and charged clusters.
Publisher: Copernicus GmbH
Date: 20-01-2021
Abstract: Abstract. New-particle formation (NPF) is a significant source of atmospheric particles, affecting climate and air quality. Understanding the mechanisms involved in urban aerosols is important to develop effective mitigation strategies. However, NPF rates reported in the polluted boundary layer span more than four orders of magnitude and the reasons behind this variability subject of intense scientific debate. Multiple atmospheric vapours have been postulated to participate in NPF, including sulfuric acid, ammonia, amines and organics, but their relative roles remain unclear. We investigated NPF in the CLOUD chamber using mixtures of anthropogenic vapours that simulate polluted boundary layer conditions. We demonstrate that NPF in polluted environments are largely driven by the formation of sulfuric acid-base clusters, stabilized by the presence of amines, high ammonia concentrations and lower temperatures. Aromatic oxidation products, despite their extremely low volatility, play a minor role in NPF in the chosen urban environment but can be important for particle growth and hence for the survival of newly formed particles. Our measurements quantitatively account for NPF in highly erse urban environments and explain its large observed variability. Such quantitative information obtained under controlled laboratory conditions will help the interpretation of future ambient observations of NPF rates in polluted atmospheres.
No related grants have been discovered for Olga Garmash.