Combining Mass Spectrometry of Picoliter Samples with a Multicompartment Electrodynamic Trap for Probing the Chemistry of Droplet Arrays

Willis, Megan D.; Rovelli, Grazia; Wilson, Kevin R.

doi:10.1021/acs.analchem.0c02343

Cited by 17 publications

(30 citation statements)

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“…confines charged droplets along the axis of the quadrupole trapping electrodes, and is described in Willis et al, 50 and Jacobs et al 51 Aqueous micron-sized droplets are generated with a piezoelectric droplet with the aid of a humidity-controlled gas flow (Fig. S1).…”

Section: Quadrupole Electrodynamic Trap the Branched Quadrupole Elect...mentioning

confidence: 99%

“…Two complementary ionization sources are used in these experiments: paper spray ionization 50,54,55 and thermal desorption coupled to helium glow discharge ionization. 50,56 Development and use of these ion sources for detection of single micron-sized droplets is described in detail in Jacbos et al, 51 Kohli & Davies 54,55 and Willis et al 50 Their operation is summarized below.…”

Section: Single Droplet Ambient Ionization Mass Spectrometry All Meas...mentioning

confidence: 99%

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Coupled interfacial and bulk kinetics govern the timescales of multiphase ozonolysis reactions

Willis

Wilson

2022

Preprint

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Chemical transformations in aerosol impact the lifetime of particle-phase species, the fate of atmospheric pollutants, and both climate and health-relevant aerosol properties. Timescales for multiphase reactions of ozone in atmospheric aqueous phases are governed by coupled kinetic processes between the gas-phase, the particle interface and its bulk, which respond dynamically to reactive consumption of O3. However, models of atmospheric aerosol reactivity often do not account for the coupled nature of multiphase processes. To examine these dynamics, we use new and prior experimental observations of aqueous droplet reaction kinetics, including three systems with a range of surface affinities and ozonolysis rate coefficients (trans-aconitic acid (C6H6O6), maleic acid (C4H4O4) and sodium nitrite (NaNO2)). Using literature rate coefficients and thermodynamic properties, we constrain a simple two-compartment stochastic kinetic model, which resolves the interface from the particle bulk and represents O3 partitioning, diffusion and reaction as a coupled kinetic system. Our kinetic model accurately predicts decay kinetics across all three systems, demonstrating that both the thermodynamic properties of O3 and the coupled kinetic and diffusion processes are key to making accurate predictions. An enhanced concentration of adsorbed O3, compared to gas and bulk phases, is rapidly maintained and remains constant even as O3 is consumed by reaction. Multiphase systems dynamically seek to achieve equilibrium in response to reactive O3 loss, but this is hampered at solute concentrations relevant to aqueous aerosol by the rate of O3 arrival in the bulk by diffusion. As a result, bulk-phase O3 becomes depleted from its Henry’s Law solubility. This bulk-phase O3 depletion limits reaction timescales for relatively slow-reacting organic solutes with low interfacial affinity (i.e., trans-aconitic and maleic acids, with krxn ~ 10^3 - 104 M-1 s-1), which is in contrast to fast-reacting solutes with higher surface affinity (i.e., nitrite, with krxn ~ 10^5 M-1 s-1) where surface reactions strongly impact observed decay kinetics.

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Section: Quadrupole Electrodynamic Trap the Branched Quadrupole Elect...mentioning

confidence: 99%

Section: Single Droplet Ambient Ionization Mass Spectrometry All Meas...mentioning

confidence: 99%

Coupled interfacial and bulk kinetics govern the timescales of multiphase ozonolysis reactions

Willis

Wilson

2022

Preprint

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“…Vibrational sum frequency generation spectroscopy (SFG), Fourier transform infrared spectroscopy (FTIR), and fluorescence spectroscopy, which are also non-destructive, could be complementary to Raman in probing the chemical composition of single particles. Recently, novel combination of EDB and mass spectrometry was reported, which can directly introduce the trapped particle for mass spectrometry analysis (Jacobs et al, 2017;Birdsall et al, 2018;Willis et al, 2020). Adoption of this technique with Raman to form an EDB-Raman system with subsequent MS analysis is relatively straightforward.…”

Section: Future Directionsmentioning

confidence: 99%

Single-particle Raman spectroscopy for studying physical and chemical processes of atmospheric particles

et al. 2022

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Abstract. Atmospheric particles experience various physical and chemical processes and change their properties during their lifetime. Most studies on atmospheric particles, both in laboratory and field measurements, rely on analyzing an ensemble of particles. Because of different mixing states of individual particles, only average properties can be obtained from studies using ensembles of particles. To better understand the fate and environmental impacts of atmospheric particles, investigations on their properties and processes at a single-particle level are valuable. Among a wealth of analytic techniques, single-particle Raman spectroscopy provides an unambiguous characterization of individual particles under atmospheric pressure in a non-destructive and in situ manner. This paper comprehensively reviews the application of such a technique in the studies of atmospheric particles, including particle hygroscopicity, phase transition and separation, and solute–water interactions, particle pH, and multiphase reactions. Investigations on enhanced Raman spectroscopy and bioaerosols on a single-particle basis are also reviewed. For each application, we describe the principle and representative examples of studies. Finally, we present our views on future directions on both technique development and further applications of single-particle Raman spectroscopy in studying atmospheric particles.

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“…Recently, novel combination of EDB and mass spectrometry was reported, which can directly introduce the trapped particle for mass spectrometry analysis. (Birdsall et al, 2018;Willis et al, 2020;Jacobs et al, 2017) suggested. (Li et al, 2010;Anema et al, 2011) l Multiphase reaction studies based on single-particle Raman spectroscopy.…”

Section: Bioaerosolsmentioning

confidence: 99%

Single-particle Raman spectroscopy for studying physical and chemical processes of atmospheric particles

Liang

Chu

Gen

et al. 2021

Preprint

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Abstract. Atmospheric particles experience various physical and chemical processes and change their properties during their lifetime. Most studies on atmospheric particles, both in laboratory and field measurements, rely on analyzing an ensemble of particles. Because of different mixing state of individual particles, only average properties can be obtained from studies using ensembles of particles. To better understand the fate and environmental impacts of atmospheric particles, investigations on their properties and processes at a single-particle level are valuable. Among a wealth of analytic techniques, single-particle Raman spectroscopy provides an unambiguous characterization of individual particles under atmospheric pressure in a non-destructive and in-situ manner. This paper comprehensively reviews the application of such a technique in the studies of atmospheric particles, including particle hygroscopicity, phase transition and separation, and solute-water interactions, particle pH, and multiphase reactions. Investigations on enhanced Raman spectroscopy and bioaerosols on a single-particle basis are also reviewed. For each application, we describe the principle and representative examples of studies. Finally, we present our views on future directions on both technique development and further applications of single-particle Raman spectroscopy in studying atmospheric particles.

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Combining Mass Spectrometry of Picoliter Samples with a Multicompartment Electrodynamic Trap for Probing the Chemistry of Droplet Arrays

Cited by 17 publications

References 77 publications

Coupled interfacial and bulk kinetics govern the timescales of multiphase ozonolysis reactions

Coupled interfacial and bulk kinetics govern the timescales of multiphase ozonolysis reactions

Single-particle Raman spectroscopy for studying physical and chemical processes of atmospheric particles

Single-particle Raman spectroscopy for studying physical and chemical processes of atmospheric particles

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