Experimental and Theoretical Study on the Enhancement of Alkanolamines on Sulfuric Acid Nucleation

Fomete, Sandra K.W.; Johnson, Jack S.; Myllys, Nanna; Jen, Coty N.

doi:10.1021/acs.jpca.2c01672

Cited by 4 publications

(7 citation statements)

References 95 publications

(205 reference statements)

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“…The important flows and voltage parameters used in the custom-built inlet of the PCC were chosen in order to result in a 25 ms chemical ionization reaction time . The systematic uncertainty of the PCC is estimated to be a factor of 2 . In addition, a versatile water condensation particle counter (vWCPC, TSI 3789) was connected through one of the side ports in the nucleation region of the reactor to detect the total particle number concentration of freshly nucleated particles .…”

Section: Methodsmentioning

confidence: 99%

“…44 A previously described custom-built transverse chemical ionization inlet, coupled to an atmospheric pressure, long timeof-flight mass spectrometer (Tofwerk AG), called the Pittsburgh Cluster CIMS (PCC), was attached in-line with the malonic acid flow reactor to measure concentrations of gases and freshly formed clusters. 58 Malonic and sulfuric acid concentrations, as well as the neutral clusters formed in the flow reactor, were measured in negative ion mode with the PCC using acetate as the chemical ionization reagent ion. Acetate ion, compared to nitrate, was chosen to ensure efficient ionization of malonic acid.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Limited Role of Malonic Acid in Sulfuric Acid–Dimethylamine New Particle Formation

et al. 2023

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Aerosols play an important role in climate and air quality; however, the mechanisms behind aerosol particle formation in the atmosphere are poorly understood. Studies have identified sulfuric acid, water, oxidized organics, and ammonia/amines as key precursors for forming aerosol particles in the atmosphere. Theoretical and experimental investigations have indicated that other species, such as organic acids, may be involved in atmospheric nucleation and growth of freshly formed aerosol particles. Organic acids, such as dicarboxylic acids, which are abundant in the atmosphere, have been measured in ultrafine aerosol particles. These observations suggest that organic acids may contribute to new particle formation in the atmosphere but their role remains ambiguous. This study examines how malonic acid interacts with sulfuric acid and dimethylamine to form new particles at warm boundary layer conditions using experimental observations from a laminar flow reactor and quantum chemical calculations coupled with cluster dynamics simulations. Observations reveal that malonic acid does not contribute to the initial steps (formation of <1 nm diameter particle) of nucleation with sulfuric acid-dimethylamine. In addition, malonic acid was found to not participate in the subsequent growth of the freshly nucleated 1 nm particles from sulfuric acid-dimethylamine reactions to diameters of 2 nm.

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Section: Methodsmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Limited Role of Malonic Acid in Sulfuric Acid–Dimethylamine New Particle Formation

et al. 2023

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“…11,13 The PCC and MCC were each connected in-line with a sulfuric acid flow reactor to minimize sampling losses. 13,55 For both the PCC and MCC, reagent ions were produced by passing nitrogen over liquid acetic acid (≥99.7% Millipor-eSigma, diluted to 60% v/v in HPLC-grade water) or nitric acid (69.3% Fisher Chemical) and then over 210 Po (model 1U200, NRD). The holder containing the 210 Po strip was shielded with a stainless-steel plate to prevent alpha particles from escaping into the reactor's flow and ionizing sulfuric acid.…”

Section: ■ Experimental Methodsmentioning

confidence: 99%

“…Two chemical ionization mass spectrometers (CIMS) were used to measure sulfuric acid. The Pittsburgh Cluster CIMS (PCC) contains a custom-built transverse atmospheric pressure chemical ionization inlet with two quadrupoles to focus the ion beam and a long time-of-flight mass filter . The Minnesota Cluster CIMS (MCC) includes another custom-built transverse atmospheric pressure chemical ionization inlet with dimensions and geometries that vary from PCC.…”

Section: Experimental Methodsmentioning

confidence: 99%

“…To evaluate this assumption, the relative rate constant for acetate reaction with sulfuric acid was measured relative to the known nitrate rate constant with sulfuric acid. Two identical, clean sulfuric acid flow reactors with highly reproducible conditions were each connected in-line with custom-built nitrate/acetate atmospheric pressure chemical ionization (1) long time-of-flight mass spectrometer (Pittsburgh Cluster CIMS, PCC) and (2) quadrupole mass spectrometer (Minnesota Cluster CIMS, MCC). ,, The measured acetate rate constant obtained from the PCC and MCC was compared with the rate constant calculated from ion–molecule collision theory. Note, temperature effects were not examined, and the relative ion–molecule rate constants presented in this study only apply at 303 K. The presented acetate ionization rate constant will enable more accurate measurements of sulfuric acid clusters using a CIMS and improve current models used to predict the rate of ion-induced nucleation in the atmosphere.…”

Section: Introductionmentioning

confidence: 99%

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Ion–Molecule Rate Constants for Reactions of Sulfuric Acid with Acetate and Nitrate Ions

et al. 2022

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Atmospheric nucleation from precursor gases is a significant source of cloud condensation nuclei in the troposphere and thus can affect the Earth’s radiative balance. Sulfuric acid, ammonia, and amines have been identified as key nucleation precursors in the atmosphere. Studies have also shown that atmospheric ions can react with sulfuric acid to form stable clusters in a process referred to as ion-induced nucleation (IIN). IIN follows similar reaction pathways as chemical ionization, which is used to detect and measure nucleation precursors via atmospheric pressure chemical ionization mass spectrometers. The rate at which ions form clusters depends on the ion–molecule rate constant. However, the rate constant varies based on the ion composition, which is often not known in the atmosphere. Previous studies have examined ion–molecule rate constants for sulfuric acid and nitrate ions but not for other atmospherically relevant ions like acetate. We report the relative rate constants of ion–molecule reactions between nitrate and acetate ions reacting with sulfuric acid. The ion–molecule rate constant for acetate and sulfuric acid is estimated to be a factor of 1.9–2.4 times higher than that of the known rate constant for nitrate and sulfuric acid. Using quantum chemistry, we find that acetate has a higher dipole moment and polarizability than nitrate. This may contribute to an increase in the collision cross-sectional area between acetate and sulfuric acid and lead to a greater reaction rate constant than nitrate. The ion–molecule rate constant for acetate with sulfuric acid will help quantify the contribution of acetate ions to atmospheric ion-induced new particle formation.

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Sulfuric Acid Nucleation Potential Model Applied to Complex Reacting Systems in the Atmosphere

Johnson,

Jen

2023

JGR Atmospheres

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Atmospheric aerosol particles impact Earth's radiation balance by acting as seeds for cloud droplet formation. Over half of global cloud seed particles are formed by nucleation, a process where gas‐phase compounds react to form stable particles. Reactions of sulfuric acid (SA) with a wide variety of atmospheric compounds have been previously shown to drive nucleation in the lower troposphere. However, global climate models poorly predict particle nucleation rates since current nucleation models do not describe nucleation for systems containing tens to hundreds of precursor compounds. The nucleation potential model (NPM) was recently developed to model SA nucleation of complex mixtures by measuring an effective base concentration using a 1‐nm condensation particle counter. This technique for estimating particle nucleation rates can be deployed at a much higher spatial and temporal resolution than current methods which require detailed knowledge of all nucleation reactions and measurements, typically using a mass spectrometer, of all nucleation precursor gases. This work expands NPM by showing that this model can capture enhancement and suppression of SA nucleation rates within a complex mixture of organic and inorganic acids, ambient air, and across a range of atmospherically relevant relative humidities. In addition, an expression for calculating atmospheric nucleation rates was also derived from the NPM. Ultimately, NPM provides a simple way to measure and model the extent compounds in a complex mixture enhance SA nucleation rates using a condensation particle counter.

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Experimental and Theoretical Study on the Enhancement of Alkanolamines on Sulfuric Acid Nucleation

Cited by 4 publications

References 95 publications

Limited Role of Malonic Acid in Sulfuric Acid–Dimethylamine New Particle Formation

Limited Role of Malonic Acid in Sulfuric Acid–Dimethylamine New Particle Formation

Ion–Molecule Rate Constants for Reactions of Sulfuric Acid with Acetate and Nitrate Ions

Sulfuric Acid Nucleation Potential Model Applied to Complex Reacting Systems in the Atmosphere

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