Atmospheric Measurements of Sub-20 nm Diameter Particle Chemical Composition by Thermal Desorption Chemical Ionization Mass Spectrometry

Smith, James N.; Moore, Katharine F.; McMurry, Peter H.; Eisele, F. L.

doi:10.1080/02786820490249036

Cited by 178 publications

(190 citation statements)

References 25 publications

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“…For example, aliphatic amines contributed 23% to the NPF events at a remote forested site in Hyytiala, Finland in March, 2006 and 47% to that at an urban site in Tecamac, Mexico in April, 2007. 12 Amines observed in Marshall Field Site, Colorado (2007), 13 North Boulder, Colorado (2009), and Atlanta, Georgia (2009) 14 have also been confirmed to play the same role in NPF events. 12 In laboratory studies, NPF was observed when amines were added into a smog chamber or flow tube reactor containing a certain concentration of nitric acid, 15 sulfuric acid, 16 or methanesulfonic acid (MSA).…”

Section: ■ Introductionmentioning

confidence: 90%

Ozonolysis of Trimethylamine Exchanged with Typical Ammonium Salts in the Particle Phase

Chu

et al. 2016

Environ. Sci. Technol.

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Alkylamines contribute to both new particle formation and brown carbon. The toxicity of particle-phase amines is of great concern in the atmospheric chemistry community. Degradation of particulate amines may lead to secondary products in the particle phase, which are associated with changes in the adverse health impacts of aerosols. In this study, O 3 oxidation of particulate trimethylamine (TMA) formed via heterogeneous uptake of TMA by (NH 4 ) 2 SO 4 , NH 4 HSO 4 , NH 4 NO 3 and NH 4 Cl, was investigated with in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and proton transfer reaction mass spectrometry (PTR-MS). HCOOH, HCHO, CH 3 NCH 2 , (CH 3 ) 2 NCHO, CH 3 NO 2 , CH 3 N(OH)CHO, CH 3 NHOH and H 2 O were identified as products on all the substrates based upon IR (one-dimensional IR and two-dimensional correlation infrared spectroscopy), quantum chemical calculation and PTR-MS results. A reaction mechanism was proposed to explain the observed products. This work demonstrates that oxidation might be a degradation pathway of particulate amines in the atmosphere. This will aid in understanding the fate of particulate amines formed by nucleation and heterogeneous uptake and their potential health impacts during atmospheric aging.

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Section: ■ Introductionmentioning

confidence: 90%

Ozonolysis of Trimethylamine Exchanged with Typical Ammonium Salts in the Particle Phase

Chu

et al. 2016

Environ. Sci. Technol.

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“…According to the classical ternary homogeneous theory developed recently, the presence of ammonia in partsper-trillion levels significantly enhances nucleation rates (Yu et al, 2006). Many field measurements and laboratory simulations have corroborated the crucial role of ammonia in the growth of newly formed particles (Smith et al, 2004;Sakurai et al, 2005;Gaydos et al, 2005). Though experimental evidence seems very limited, nitrate has been reported as a crucial contributor to nanoparticle growth, especially for 10-30 nm particles where nitrate is dominant (Hildebrandt et al, 2012).…”

Section: Insights Into the Chemical Species Involvedmentioning

confidence: 99%

“…Gaseous sulfur has proved to play a vital role in the nucleation process (Petäjä et al, 2009;Kulmala et al, 2013). Atmospheric ammonia can effectively lower the surface pressure of gaseous sulfuric molecular and participates in homogeneous nucleation with gaseous sulfuric acid and water vapor (Smith et al, 2004;Sakurai et al, 2005;Gaydos et al, 2005). In addition, there are other species responsible for NPF such as amines (Yu et al, 2012;Benson et al, 2011), low-volatility organic vapors Paasonen et al, 2010;Riipinen et al, 2011;Ehn et al, 2014) and iodine compounds (O'Dowd et al, 2002;Vuollekoski et al, 2009).…”

Section: Introductionmentioning

confidence: 99%

Impacts of new particle formation on aerosol cloud condensation nuclei (CCN) activity in Shanghai: case study

et al. 2014

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Abstract. New particle formation (NPF) events and their impacts on cloud condensation nuclei (CCN) were investigated using continuous measurements collected in urban Shanghai from 1 to 30 April 2012. During the campaign, NPF occurred in 8 out of the 30 days and enhanced CCN number concentration (N CCN ) by a factor of 1.2-1.8, depending on supersaturation (SS). The NPF event on 3 April 2012 was chosen as an example to investigate the NPF influence on CCN activity. In this NPF event, secondary aerosols were produced continuously and increased PM 2.5 mass concentration at a rate of 4.33 µg cm −3 h −1 , and the growth rate (GR) and formation rate (FR) were on average 5 nm h −1 and 0.36 cm −3 s −1 , respectively. The newly formed particles grew quickly from nucleation mode (10-20 nm) into CCN size range. N CCN increased rapidly at SS of 0.4-1.0 % but weakly at SS of 0.2 %. Correspondingly, aerosol CCN activities (fractions of activated aerosol particles in total aerosols, N CCN /N CN ) were significantly enhanced from 0.24-0.60 to 0.30-0.91 at SS of 0.2-1.0 % due to the NPF. On the basis of the κ-Köhler theory, aerosol size distributions and chemical composition measured simultaneously were used to predict N CCN . There was a good agreement between the predicted and measured N CCN (R 2 = 0.96, N predicted /N measured = 1.04). This study reveals that NPF exerts large impacts on aerosol particle abundance and size spectra; thus, it significantly promotes N CCN and aerosol CCN activity in this urban environment. The GR of NPF is the key factor controlling the newly formed particles to become CCN at all SS levels, whereas the FR is an effective factor only under high SS (e.g., 1.0 %) conditions.

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“…As a sensitive, selective, and soft-ionization measurement technique, chemical ionization mass spectrometry (CIMS) has received significant use in the real-time in situ measurement of atmospheric trace species (Huey et al, 1995;Fortner et al, 2004;Hearn and Smith, 2004;Smith et al, 2004;Crounse et al, 2006;Huey, 2007;Veres et al, 2008;Kercher et al, 2009;Zhao et al, 2010). The recent coupling of chemical ionization to high-resolution time-of-flight mass spectrometers (HR-ToF-MS) enables the simultaneous determination of the abundance and molecular composition of a wide array of atmospheric inorganic and organic compounds with fast time response and high sensitivity (Junninen et al, 2010;Bertram et al, 2011;Yatavelli et al, 2012;Aljawhary et al, 2013;Lee et al, 2014;Lopez-Hilfiker et al, 2014, 2016aFarmer, 2015, 2016;Yuan et al, 2016).…”

Section: Introductionmentioning

confidence: 99%

An electrospray chemical ionization source for real-time measurement of atmospheric organic and inorganic vapors

et al. 2017

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Abstract. We present an electrospray ion source coupled to an orthogonal continuous-flow atmospheric pressure chemical ionization region. The source can generate intense and stable currents of several specific reagent ions using a range of salt solutions prepared in methanol, thereby providing both an alternative to more common radioactive ion sources and allowing for the generation of reagent ions that are not available in current chemical ionization mass spectrometry (CIMS) techniques, such as alkaline cations. We couple the orthogonal electrospray chemical ionization (ESCI) source to a high-resolution time-of-flight mass spectrometer (HRToF-MS), and assess instrument performance through calibrations using nitric acid (HNO 3 ), formic acid (HCOOH), and isoprene epoxydiol (trans-β-IEPOX) gas standards, and through measurements of oxidized organic compounds formed from ozonolysis of α-pinene in a continuous-flow reaction chamber. When using iodide as the reagent ion, the HR-ToF-ESCIMS prototype has a sensitivity of 11, 2.4, and 10 cps pptv −1 per million counts per second (cps) of reagent ions and a detection limit (3σ , 5 s averaging) of 4.9, 12.5, and 1.4 pptv to HNO 3 , HCOOH, and IEPOX, respectively. These values are comparable to those obtained using an iodide-adduct HR-ToF-CIMS with a radioactive ion source and low-pressure ion-molecule reaction region. Applications to the α-pinene ozonolysis system demonstrates that HRToF-ESCIMS can generate multiple reagent ions (e.g., I − , NO − 3 , acetate, Li + , Na + , K + , and NH + 4 ) having different selectivity to provide a comprehensive molecular description of a complex organic system.

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Atmospheric Measurements of Sub-20 nm Diameter Particle Chemical Composition by Thermal Desorption Chemical Ionization Mass Spectrometry

Cited by 178 publications

References 25 publications

Ozonolysis of Trimethylamine Exchanged with Typical Ammonium Salts in the Particle Phase

Ozonolysis of Trimethylamine Exchanged with Typical Ammonium Salts in the Particle Phase

Impacts of new particle formation on aerosol cloud condensation nuclei (CCN) activity in Shanghai: case study

An electrospray chemical ionization source for real-time measurement of atmospheric organic and inorganic vapors

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