In Situ Measurements of Atmospheric Nitrous Acid by Chemical Ionization Mass Spectrometry Using Chloride Ion Transfer Reactions

Hirokawa, Jun; Kato, Takehiro; Mafuné, Fumitaka

doi:10.1021/ac901117b

Cited by 18 publications

(22 citation statements)

References 33 publications

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“…Taking into consideration the important role of the HONO photodissociation in the atmosphere, various techniques have been developed and deployed for its atmospheric measurements, such as long path differential optical absorption spectroscopy (LP-DOAS) and chemical techniques (Febo et al 1996;Spindler et al 2003), long path absorption photometry (LOPAP) (Heland et al 2001;Kleffmann et al 2006) and ion-drift chemical ionization mass spectrometry (ID-CIMS) (Hirokawa et al 2009;Levy et al 2014). Time resolution, sensitivity, the absence of any artefact and the capability to perform measurements under diverse environmental conditions are paramount of importance in the performance of analytical instruments.…”

Section: Responsible Editor: Gerhard Lammelmentioning

confidence: 99%

Measurements of nitrous acid (HONO) in urban area of Shanghai, China

Bernard

Cazaunau

Grosselin

et al. 2015

Environ Sci Pollut Res

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Nitrous acid (HONO), as a precursor of the hydroxyl radical (OH), plays an important role in the photochemistry of the troposphere, especially in the polluted urban atmosphere. A field campaign was conducted to measure atmospheric HONO concentration and that of other pollutants (such as NO 2 and particle mass concentration) in the autumn of 2009 at Shanghai urban areas. HONO mixing ratios were simultaneously measured by three different techniques: long path absorption photometer (LOPAP), differential optical absorption spectroscopy (DOAS) and chemical ionization mass spectrometer (CIMS). The measurements showed that the mixing ratios of HONO were highly variable and depended strongly on meteorological parameters. The HONO levels ranged from 0.5 to 7 ppb with maximum values during early morning and minimum levels during late afternoon. The three instruments reproduced consistent diurnal pattern of HONO concentrations with higher concentration during the night compared to the daylight hours. Comparison of HONO LOPAP /HONO CIMS ratios during daytime and nighttime periods exhibited a non-systematic disagreement of 0.93 and 1.16, respectively. This would indicate different chemical compositions of sampled air for the LOPAP and the CIMS instruments during daytime and nighttime periods, which have possibly affected measurements. Mean HONO concentration reported by LOPAP was 33 % higher than by DOAS on the whole period with no significant difference between daytime and nighttime periods. This revealed a systematic deviation from both instruments. The present data provides complementary information of HONO ambient levels in the atmosphere of Shanghai urban areas.

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Section: Responsible Editor: Gerhard Lammelmentioning

confidence: 99%

Measurements of nitrous acid (HONO) in urban area of Shanghai, China

Bernard

Cazaunau

Grosselin

et al. 2015

Environ Sci Pollut Res

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“…Compared to I − , NO − 3 , and acetate, which are generally more sensitive to more oxygenated organic compounds than to less oxygenated ones (Aljawhary et al, 2013;Lee et al, 2014;Hyttinen et al, 2015;Iyer et al, 2016;Berndt et al, 2016), these metal cations are expected to be able to sensitively detect both less oxygenated (e.g., compounds containing only carbonyl groups) and highly oxygenated multi-functional organic species (Gao et al, 2010;Nguyen et al, 2010;Nizkorodov et al, 2011;Laskin et al, 2012;Witkowski and Gierczak, 2013;Zhao et al, 2015Zhao et al, , 2016Tu et al, 2016;Zhang et al, 2017), and to form more strongly bound ion adducts. In addition, at present most CIMS techniques use a radioactive ion source such as 210 Po to produce the reagent ions, although more recently some utilize X-ray radiation, electrical discharge (Hirokawa et al, 2009;Yuan et al, 2016), or electron impact (Inomata and Hirokawa, 2017). Safety regulations for the transport and use of radioactive materials may limit the deployment of the instrument with a radioactive ion source in the field, while other methods may be less intense or lead to higher backgrounds.…”

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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In Situ Measurements of Atmospheric Nitrous Acid by Chemical Ionization Mass Spectrometry Using Chloride Ion Transfer Reactions

Cited by 18 publications

References 33 publications

Measurements of nitrous acid (HONO) in urban area of Shanghai, China

Measurements of nitrous acid (HONO) in urban area of Shanghai, China

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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