Measurement of trace atmospheric species by chemical ionization mass spectrometry: Speciation of reactive nitrogen and future directions

Huey, L. G.

doi:10.1002/mas.20118

Cited by 190 publications

(162 citation statements)

References 128 publications

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“…Whereas H 2 SO 4 -CIMS operates at atmospheric pressure with negative ion chemistry (reaction (R1)), NH 3 -CIMS operates at low pressure (2670-3330 Pa) with the following positive chemical ionization (CIMS) reaction [Huey, 2007;Nowak et al, 2007]:…”

Section: Nh 3 -Cimsmentioning

confidence: 99%

Correlation of aerosol nucleation rate with sulfuric acid and ammonia in Kent, Ohio: An atmospheric observation

Erupe¹,

Benson²,

Li³

et al. 2010

J. Geophys. Res.

115

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[1] New particle formation (NPF) occurs in various atmospheric environments, and these newly formed particles have the potential to grow to cloud condensation nuclei. But at present it is unclear which chemical species are involved in aerosol nucleation and growth, in part because there are only a limited number of simultaneous measurements of aerosol precursors and aerosol size distributions. Observations of ambient aerosol size distributions, sulfuric acid, and ammonia were made for over a year in Kent, Ohio, a relatively less polluted continental environment. Particle sizes in the diameter range from 3 to 1000 nm were measured continuously through the whole year, while sulfuric acid and ammonia were measured seasonally with two chemical ionization mass spectrometers. Strong NPF events were more frequently found during the spring and fall and less frequently during the summer and winter. The median of measured sulfuric acid was higher in spring (5.2 × 10 6 cm −3 ) and summer (2.9 × 10 6 cm −3 ) than in winter (6 × 10 5 cm −3 ) and fall (5 × 10 5 cm −3 ). We have used the inverse model Particle Growth and Nucleation to derive aerosol nucleation and growth rates from the measured aerosol size distributions. Nucleation rates derived during the NPF events ranged from 1.4 to 12.9 cm −3 s −1 and were proportional to the measured sulfuric acid concentration with a power of 0.6-2.3. Our results show that sulfuric acid is an important aerosol nucleation precursor, but only a small fraction of the aerosol growth rates could be explained by the condensation of sulfuric acid alone. Ammonia mixing ratios did not have a diurnal trend but had some seasonal variations, higher in spring than in fall and winter, typically at sub-ppbv level; aerosol nucleation rates did not show a clear correlation with ammonia at least at this sub-ppbv level, mostly because the ammonia mixing ratios were nearly constant. Our observations also indicate that the role that ammonia plays in aerosol nucleation is more complicated than is currently understood by the aerosol nucleation theories.Citation: Erupe, M. E., et al. (2010), Correlation of aerosol nucleation rate with sulfuric acid and ammonia in Kent, Ohio: An atmospheric observation,

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Section: Nh 3 -Cimsmentioning

confidence: 99%

Correlation of aerosol nucleation rate with sulfuric acid and ammonia in Kent, Ohio: An atmospheric observation

Erupe¹,

Benson²,

Li³

et al. 2010

J. Geophys. Res.

115

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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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“…A general review of such analytical methods has been compiled by Clemitshaw (2004). Rapid ion-molecule reactions have recently been exploited in specific chemical ionization mass spectrometric (CIMS) methods for acids and related species (Huey, 2007;Crounse et al, 2006;Spanel et al, 1995;Custer et al, 2000;Hirokawa et al, 2009;Kim et al, 2008) that have been developed in recent years and involve ion chemistry that is selective and unique to the compounds of interest. Desirable features of CIMS methods are that they can be very sensitive and selective, and permit rapid (<1 s) measurements without requiring elaborate collection and separation steps.…”

Section: Introductionmentioning

confidence: 99%

Measurement of HONO, HNCO, and other inorganic acids by negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS): application to biomass burning emissions

et al. 2010

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Abstract. A negative-ion proton-transfer chemical ionization mass spectrometric technique (NI-PT-CIMS), using acetate as the reagent ion, was applied to the measurement of volatile inorganic acids of atmospheric interest: hydrochloric (HCl), nitrous (HONO), nitric (HNO 3 ), and isocyanic (HNCO) acids. Gas phase calibrations through the sampling inlet showed the method to be intrinsically sensitive (6-16 cts/pptv), but prone to inlet effects for HNO 3 and HCl. The ion chemistry was found to be insensitive to water vapor concentrations, in agreement with previous studies of carboxylic acids. The inlet equilibration times for HNCO and HONO were 2 to 4 s, allowing for measurement in biomass burning studies. Several potential interferences in HONO measurements were examined: decomposition of HNO 3 ·NO − 3 clusters within the CIMS, and NO 2 -water production on inlet surfaces, and were quite minor (≤1%, 3.3%, respectively). The detection limits of the method were limited by the instrument backgrounds in the ion source and flow tube, and were estimated to range between 16 and 50 pptv (parts per trillion by volume) for a 1 min average. The comparison of HONO measured by CIMS and by in situ FTIR showed good correlation and agreement to within 17%. The method provided rapid and accurate measurements of HNCO and HONO in controlled biomass burning studies, in which both acids were seen to be important products.

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Measurement of trace atmospheric species by chemical ionization mass spectrometry: Speciation of reactive nitrogen and future directions

Cited by 190 publications

References 128 publications

Correlation of aerosol nucleation rate with sulfuric acid and ammonia in Kent, Ohio: An atmospheric observation

Correlation of aerosol nucleation rate with sulfuric acid and ammonia in Kent, Ohio: An atmospheric observation

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

Measurement of HONO, HNCO, and other inorganic acids by negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS): application to biomass burning emissions

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