New Particle Formation and Growth from Dimethyl Sulfide Oxidation by Hydroxyl Radicals

Rosati, Bernadette; Christiansen, Sofus; Jonge, Robin Wollesen de; Roldin, Pontus; Jensen, Mads Mørk; Wang, Kai; Moosakutty, Shamjad P.; Thomsen, Ditte L.; Salomonsen, Camilla; Hyttinen, Noora; Elm, Jonas; Feilberg, Anders; Glasius, Marianne; Bilde, Merete

doi:10.1021/acsearthspacechem.0c00333

Cited by 23 publications

(32 citation statements)

References 100 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Oxidation of DMS leads to the concurrent formation of MSA and SA. Based on quantum chemical calculations, Rosati et al 77 recently demonstrated that cluster formation involving (SA) x (MSA) y (A) 1−4 (with x + y ≤ 4) consisted of different mixtures of both SA and MSA molecules. Hence, exchanging one MSA molecule with SA might alleviate the identified deficiencies in the MSA-base system, as this leads to an additional S−OH group, thus increasing the hydrogen-bonding capacity of the clusters.…”

Section: Discussionmentioning

confidence: 99%

Clusteromics II: Methanesulfonic Acid–Base Cluster Formation

Elm

2021

ACS Omega

Self Cite

View full text Add to dashboard Cite

The role of methanesulfonic acid (MSA) in atmospheric new particle formation remains highly uncertain. Using state-of-the-art computational methods, we study the electrically neutral (MSA) 0−2 (base) 0−2 clusters, with base = ammonia (A), methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), and ethylenediamine (EDA). The cluster configurations are obtained using the ABCluster program and the number of initial cluster configurations is reduced based on PM7 calculations. Thermochemical parameters are calculated using the quasi-harmonic approximation based on the ωB97X-D/6-31++G(d,p) cluster structures and vibrational frequencies. The single point energies are calculated at the DLPNO-CCSD(T 0 )/aug-cc-pVTZ level of theory. We find that MSA shows a different interaction pattern with the bases compared to sulfuric acid and does not simply follow the basicity of the bases for these small clusters. In all cases, we find that the MSA-base clusters show very low cluster formation potential, indicating that electrically neutral clusters consisting solely of MSA as the clustering acid are most likely not capable of forming and growing under realistic atmospheric conditions.

show abstract

Section: Discussionmentioning

confidence: 99%

Clusteromics II: Methanesulfonic Acid–Base Cluster Formation

Elm

2021

ACS Omega

Self Cite

View full text Add to dashboard Cite

show abstract

“…By photolysing H 2 O 2 , OH radicals were produced. The OH radical concentrations in the experiments are estimated to be in the range of typical tropospheric concentrations (4.64-5.71E+06 molecules cm −3 ; Seinfeld and Pandis, 2016) based on supplementary experiments investigating the decay of 1-butanol in the bag (Rosati et al, 2021a, b;Wollesen de Jonge et al, 2021). Either 200 or 400 ppb of DMS (Sigma Aldrich, anhydrous ≥99.0 %, 274380) were injected into the chamber by evaporating a known amount and guiding it into the chamber using 10 L min −1 of N 2 gas heated to 333 K. The sequential order of the procedure was: 1) setting the desired chamber temperature, 2) filling the chamber with purified air (Active Carbon, HEPA filter and zero-air generator (Aadco Model 737-14)), 3) injecting humidified air to reach the desired RH, 4) injecting H 2 O 2 , 5) switching the UV lights on, 6) injecting DMS.…”

Section: Methodsmentioning

confidence: 99%

“…This work focuses on the water uptake of the studied aerosol particles, thus Exp. 1, 5, 6, 7 and 9 are presented in terms of the hygroscopicity and CCN activity, which were not addressed in any of the previous studies (Rosati et al, 2021a;Wollesen de Jonge et al, 2021). Analytik, Innsbruck, Austria; e.g.…”

Section: Methodsmentioning

confidence: 99%

“…The experiments were designed to mimic a realistic marine atmosphere by simulating different relevant humidity and temperature conditions. For completeness, we also include in this work results from five experiments already presented by Rosati et al (2021a) and/or Wollesen de Jonge et al (2021) but not discussed with respect to hygroscopicity and CCN activation potential previously. Our extensive measurement setup covers the formation rates of particles larger than 1.7 nm, the growth rates of 10-20 nm particles, the water uptake of particles from 10-150 nm (dry size), and provides insight into the bulk chemical composition of the DMS derived aerosols.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Hygroscopicity and CCN potential of DMS derived aerosol particles

Rosati

Isokääntä

Christiansen

et al. 2022

Preprint

Self Cite

View full text Add to dashboard Cite

Abstract. Dimethyl sulphide (DMS) is emitted by phytoplankton species in the oceans and constitutes the largest source of naturally emitted sulphur to the atmosphere. The climate impact of secondary particles, formed through the oxidation of DMS by hydroxyl radicals, is still elusive. This study investigates the hygroscopicity and cloud condensation nuclei activity of such particles and discusses the results in relation to their chemical composition. We show that mean hygroscopicity parameters, κ, during an experiment for particles of 80 nm in diameter range from 0.46 to 0.52 as measured at both sub- and supersaturated water vapour conditions. Ageing of the particles leads to an increase in κ from for example 0.50–0.58 over the course of 3 hours (Exp. 7). Aerosol mass spectrometer measurements from this study indicate that this change most probably stems from a change in chemical composition leading to slightly higher fractions of ammonium sulphate compared to methanesulfonic acid (MSA) within the particles with ageing time. Lowering the temperature to 258 K increases κ slightly, particularly for small particles. These κ-values are well comparable to previously reported model values for MSA or mixtures between MSA and ammonium sulphate. Particle nucleation and growth rates suggest a clear temperature dependence, with slower rates at cold temperatures. Quantum chemical calculations show that gas-phase MSA clusters are predominantly not hydrated even at high humidity conditions indicating that their gas-phase chemistry should be independent of relative humidity.

show abstract

“…Recent DMS + OH oxidation experiments performed in the AURA chamber at Aarhus University show that MSA dominates the secondary aerosol mass formation . Aerosol dynamics model simulations which intended to replicate the observations during these AURA experiments, using the DMS gas-phase chemistry scheme from the Master Chemical Mechanism, MCMv3.3.1 (Jenkin et al, 1997(Jenkin et al, , 2015Saunders et al, 2003), substantially underestimate the particle mass and number concentrations and the MSA : SO 2− 4 ratio (Rosati et al, 2021;. Based on these findings, Wollesen de Jonge et al ( 2021) developed a new DMS multi-phase chemistry scheme based on MCM v3.3.1, CAPRAM DMS module 1.0 (DM1.0) (Hoffmann et al, 2016), a subset of the multiphase halogen chemistry mechanism CAPRAM Halogen Module 2.0 (HM2.0) (Bräuer et al, 2013), and new reactions leading to the formation of hydroperoxymethyl thioformate (HPMTF).…”

Section: Introductionmentioning

confidence: 98%

Secondary aerosol formation in marine Arctic environments: a model measurement comparison at Ny-Ålesund

et al. 2022

Self Cite

View full text Add to dashboard Cite

Abstract. In this study, we modeled the aerosol particle formation along air mass trajectories arriving at the remote Arctic research stations Gruvebadet (67 m a.s.l.) and Zeppelin (474 m a.s.l.), Ny-Ålesund, during May 2018. The aim of this study was to improve our understanding of processes governing secondary aerosol formation in remote Arctic marine environments. We run the Lagrangian chemistry transport model ADCHEM, along air mass trajectories generated with FLEXPART v10.4. The air masses arriving at Ny-Ålesund spent most of their time over the open ice-free ocean. In order to capture the secondary aerosol formation from the DMS emitted by phytoplankton from the ocean surface, we implemented a recently developed comprehensive DMS and halogen multi-phase oxidation chemistry scheme, coupled with the widely used Master Chemical Mechanism (MCM). The modeled median particle number size distributions are in close agreement with the observations in the marine-influenced boundary layer near-sea-surface Gruvebadet site. However, while the model reproduces the accumulation mode particle number concentrations at Zeppelin, it overestimates the Aitken mode particle number concentrations by a factor of ∼5.5. We attribute this to the deficiency of the model to capture the complex orographic effects on the boundary layer dynamics at Ny-Ålesund. However, the model reproduces the average vertical particle number concentration profiles within the boundary layer (0–600 m a.s.l.) above Gruvebadet, as measured with condensation particle counters (CPCs) on board an unmanned aircraft system (UAS). The model successfully reproduces the observed Hoppel minima, often seen in particle number size distributions at Ny-Ålesund. The model also supports the previous experimental findings that ion-mediated H2SO4–NH3 nucleation can explain the observed new particle formation in the marine Arctic boundary layer in the vicinity of Ny-Ålesund. Precursors resulting from gas- and aqueous-phase DMS chemistry contribute to the subsequent growth of the secondary aerosols. The growth of particles is primarily driven via H2SO4 condensation and formation of methane sulfonic acid (MSA) through the aqueous-phase ozonolysis of methane sulfinic acid (MSIA) in cloud and deliquescent droplets.

show abstract

New Particle Formation and Growth from Dimethyl Sulfide Oxidation by Hydroxyl Radicals

Cited by 23 publications

References 100 publications

Clusteromics II: Methanesulfonic Acid–Base Cluster Formation

Clusteromics II: Methanesulfonic Acid–Base Cluster Formation

Hygroscopicity and CCN potential of DMS derived aerosol particles

Secondary aerosol formation in marine Arctic environments: a model measurement comparison at Ny-Ålesund

Contact Info

Product

Resources

About