Validity and limitations of simple reaction kinetics to calculate concentrations of organic compounds from ion counts in PTR-MS

Rupert Holzinger; W. F. Joe Acton; William W. Bloss; Martin Breitenlechner; Leigh L. Crilley; Sebastien Dusanter; Marc Gonin; Valerie Gros; Frank F. Keutsch; Astrid Kiendler-Scharr; Louisa L. Kramer; Jordan J. Krechmer; Baptiste Languille; Nadine Locoge; Felipe Lopez-Hilfiker; Dusan Materi; Sergi Moreno; Eiko Nemitz; Lauriane L. Quéléver; Roland Sarda Esteve; Stephane Sauvage; Simon Schallhart; Roberto Sommariva; Ralf Tillmann; Sergej Wedel; David D. Worton; Kangming Xu; Alexander Zaytsev

doi:10.5194/amt-12-6193-2019

Validity and limitations of simple reaction kinetics to calculate concentrations of organic compounds from ion counts in PTR-MS

Rupert Holzinger^*, W. F. Joe Acton, William W. Bloss, Martin Breitenlechner, Leigh L. Crilley, Sebastien Dusanter, Marc Gonin, Valerie Gros, Frank F. Keutsch, Astrid Kiendler-Scharr, Louisa L. Kramer, Jordan J. Krechmer, Baptiste Languille, Nadine Locoge, Felipe Lopez-Hilfiker, Dusan Materi, Sergi Moreno, Eiko Nemitz, Lauriane L. Quéléver, Roland Sarda EsteveStephane Sauvage, Simon Schallhart, Roberto Sommariva, Ralf Tillmann, Sergej Wedel, David D. Worton, Kangming Xu, Alexander Zaytsev

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

11 Citations (Scopus)

Abstract

In September 2017, we conducted a proton-transfer-reaction mass-spectrometry (PTR-MS) intercomparison campaign at the CESAR observatory, a rural site in the central Netherlands near the village of Cabauw. Nine research groups deployed a total of 11 instruments covering a wide range of instrument types and performance. We applied a new calibration method based on fast injection of a gas standard through a sample loop. This approach allows calibrations on timescales of seconds, and within a few minutes an automated sequence can be run allowing one to retrieve diagnostic parameters that indicate the performance status. We developed a method to retrieve the mass-dependent transmission from the fast calibrations, which is an essential characteristic of PTR-MS instruments, limiting the potential to calculate concentrations based on counting statistics and simple reaction kinetics in the reactor/drift tube. Our measurements show that PTR-MS instruments follow the simple reaction kinetics if operated in the standard range for pressures and temperature of the reaction chamber (i.e. 1-4 mbar, 30-120ĝ', respectively), as well as a reduced field strength Eĝ'•N in the range of 100-160 Td. If artefacts can be ruled out, it becomes possible to quantify the signals of uncalibrated organics with accuracies better than ±30 %. The simple reaction kinetics approach produces less accurate results at Eĝ'•N levels below 100 Td, because significant fractions of primary ions form water hydronium clusters. Deprotonation through reactive collisions of protonated organics with water molecules needs to be considered when the collision energy is a substantial fraction of the exoergicity of the proton transfer reaction and/or if protonated organics undergo many collisions with water molecules.

Original language	English
Pages (from-to)	6193-6208
Number of pages	16
Journal	Atmospheric Measurement Techniques
Volume	12
Issue number	11
DOIs	https://doi.org/10.5194/amt-12-6193-2019
Publication status	Published - 27 Nov 2019

Bibliographical note

Funding Information:
Acknowledgements. This project has received funding from the European Union’s Horizon 2020 research and innovation programme (ACTRIS-2) under grant agreement no. 654109 and by the Dutch NWO Earth and Life Science (ALW), project 824.14.002. W. Joe F. Acton, Martin Breitenlechner, Leigh R. Crilley, Louisa J. Kramer, Jordan E. Krechmer, Felipe Lopez-Hilfiker, Eiko Nemitz, Lauri-ane L. J. Quéléver, Simon Schallhart, Ralf Tillmann, Sergej Wedel, and Alexander Zaytsev acknowledge Transnational Access (TNA) travel funding from ACTRIS-2 (grant agreement no. 654109). Eiko Nemitz further acknowledges the support of the UK Natural Environment Research Council (NERC) through grants NE/P016502/1 for instrument funding and NE/R016429/1 as part of the UK-SCaPE programme delivering National Capability. Lauriane L. J. Quéléver and Simon Schallhart acknowledge the Finnish Centre of Excellence program (Project no 307331). Lauriane L. J. Quéléver thank the European Research Council (ERC grant no. 638703-COALA). W. Joe F. Acton has received funding from Natural Environment Research Council (UK) grant NE/N006976/1, Sources and Emissions of Air Pollutants in Beijing (AIRPOLL-Beijing).

Funding Information:
pean Commission (ACTRIS-2, grant no. 654109) and the Netherlands Organisation for Scientific Research (NWO) (grant no. 824.14.002).

Publisher Copyright:
© Author(s) 2019. This work is distributed under the Creative Commons Attribution 4.0 License.

Copyright:
Copyright 2019 Elsevier B.V., All rights reserved.

ASJC Scopus subject areas

Atmospheric Science

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10.5194/amt-12-6193-2019

Cite this

Holzinger, R., Joe Acton, W. F., Bloss, W. W., Breitenlechner, M., Crilley, L. L., Dusanter, S., Gonin, M., Gros, V., Keutsch, F. F., Kiendler-Scharr, A., Kramer, L. L., Krechmer, J. J., Languille, B., Locoge, N., Lopez-Hilfiker, F., Materi, D., Moreno, S., Nemitz, E., Quéléver, L. L., ... Zaytsev, A. (2019). Validity and limitations of simple reaction kinetics to calculate concentrations of organic compounds from ion counts in PTR-MS. Atmospheric Measurement Techniques, 12(11), 6193-6208. https://doi.org/10.5194/amt-12-6193-2019

@article{7da9ecd0bac749739015e6f620401aaa,

title = "Validity and limitations of simple reaction kinetics to calculate concentrations of organic compounds from ion counts in PTR-MS",

abstract = "In September 2017, we conducted a proton-transfer-reaction mass-spectrometry (PTR-MS) intercomparison campaign at the CESAR observatory, a rural site in the central Netherlands near the village of Cabauw. Nine research groups deployed a total of 11 instruments covering a wide range of instrument types and performance. We applied a new calibration method based on fast injection of a gas standard through a sample loop. This approach allows calibrations on timescales of seconds, and within a few minutes an automated sequence can be run allowing one to retrieve diagnostic parameters that indicate the performance status. We developed a method to retrieve the mass-dependent transmission from the fast calibrations, which is an essential characteristic of PTR-MS instruments, limiting the potential to calculate concentrations based on counting statistics and simple reaction kinetics in the reactor/drift tube. Our measurements show that PTR-MS instruments follow the simple reaction kinetics if operated in the standard range for pressures and temperature of the reaction chamber (i.e. 1-4 mbar, 30-120ĝ', respectively), as well as a reduced field strength Eĝ'•N in the range of 100-160 Td. If artefacts can be ruled out, it becomes possible to quantify the signals of uncalibrated organics with accuracies better than ±30 %. The simple reaction kinetics approach produces less accurate results at Eĝ'•N levels below 100 Td, because significant fractions of primary ions form water hydronium clusters. Deprotonation through reactive collisions of protonated organics with water molecules needs to be considered when the collision energy is a substantial fraction of the exoergicity of the proton transfer reaction and/or if protonated organics undergo many collisions with water molecules.",

author = "Rupert Holzinger and {Joe Acton}, {W. F.} and Bloss, {William W.} and Martin Breitenlechner and Crilley, {Leigh L.} and Sebastien Dusanter and Marc Gonin and Valerie Gros and Keutsch, {Frank F.} and Astrid Kiendler-Scharr and Kramer, {Louisa L.} and Krechmer, {Jordan J.} and Baptiste Languille and Nadine Locoge and Felipe Lopez-Hilfiker and Dusan Materi and Sergi Moreno and Eiko Nemitz and Qu{\'e}l{\'e}ver, {Lauriane L.} and {Sarda Esteve}, Roland and Stephane Sauvage and Simon Schallhart and Roberto Sommariva and Ralf Tillmann and Sergej Wedel and Worton, {David D.} and Kangming Xu and Alexander Zaytsev",

note = "Funding Information: Acknowledgements. This project has received funding from the European Union{\textquoteright}s Horizon 2020 research and innovation programme (ACTRIS-2) under grant agreement no. 654109 and by the Dutch NWO Earth and Life Science (ALW), project 824.14.002. W. Joe F. Acton, Martin Breitenlechner, Leigh R. Crilley, Louisa J. Kramer, Jordan E. Krechmer, Felipe Lopez-Hilfiker, Eiko Nemitz, Lauri-ane L. J. Qu{\'e}l{\'e}ver, Simon Schallhart, Ralf Tillmann, Sergej Wedel, and Alexander Zaytsev acknowledge Transnational Access (TNA) travel funding from ACTRIS-2 (grant agreement no. 654109). Eiko Nemitz further acknowledges the support of the UK Natural Environment Research Council (NERC) through grants NE/P016502/1 for instrument funding and NE/R016429/1 as part of the UK-SCaPE programme delivering National Capability. Lauriane L. J. Qu{\'e}l{\'e}ver and Simon Schallhart acknowledge the Finnish Centre of Excellence program (Project no 307331). Lauriane L. J. Qu{\'e}l{\'e}ver thank the European Research Council (ERC grant no. 638703-COALA). W. Joe F. Acton has received funding from Natural Environment Research Council (UK) grant NE/N006976/1, Sources and Emissions of Air Pollutants in Beijing (AIRPOLL-Beijing). Funding Information: pean Commission (ACTRIS-2, grant no. 654109) and the Netherlands Organisation for Scientific Research (NWO) (grant no. 824.14.002). Publisher Copyright: {\textcopyright} Author(s) 2019. This work is distributed under the Creative Commons Attribution 4.0 License. Copyright: Copyright 2019 Elsevier B.V., All rights reserved.",

year = "2019",

month = nov,

day = "27",

doi = "10.5194/amt-12-6193-2019",

language = "English",

volume = "12",

pages = "6193--6208",

journal = "Atmospheric Measurement Techniques",

issn = "1867-1381",

publisher = "European Geosciences Union",

number = "11",

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Holzinger, R, Joe Acton, WF, Bloss, WW, Breitenlechner, M, Crilley, LL, Dusanter, S, Gonin, M, Gros, V, Keutsch, FF, Kiendler-Scharr, A, Kramer, LL, Krechmer, JJ, Languille, B, Locoge, N, Lopez-Hilfiker, F, Materi, D, Moreno, S, Nemitz, E, Quéléver, LL, Sarda Esteve, R, Sauvage, S, Schallhart, S, Sommariva, R, Tillmann, R, Wedel, S, Worton, DD, Xu, K & Zaytsev, A 2019, 'Validity and limitations of simple reaction kinetics to calculate concentrations of organic compounds from ion counts in PTR-MS', Atmospheric Measurement Techniques, vol. 12, no. 11, pp. 6193-6208. https://doi.org/10.5194/amt-12-6193-2019

TY - JOUR

T1 - Validity and limitations of simple reaction kinetics to calculate concentrations of organic compounds from ion counts in PTR-MS

AU - Holzinger, Rupert

AU - Joe Acton, W. F.

AU - Bloss, William W.

AU - Breitenlechner, Martin

AU - Crilley, Leigh L.

AU - Dusanter, Sebastien

AU - Gonin, Marc

AU - Gros, Valerie

AU - Keutsch, Frank F.

AU - Kiendler-Scharr, Astrid

AU - Kramer, Louisa L.

AU - Krechmer, Jordan J.

AU - Languille, Baptiste

AU - Locoge, Nadine

AU - Lopez-Hilfiker, Felipe

AU - Materi, Dusan

AU - Moreno, Sergi

AU - Nemitz, Eiko

AU - Quéléver, Lauriane L.

AU - Sarda Esteve, Roland

AU - Sauvage, Stephane

AU - Schallhart, Simon

AU - Sommariva, Roberto

AU - Tillmann, Ralf

AU - Wedel, Sergej

AU - Worton, David D.

AU - Xu, Kangming

AU - Zaytsev, Alexander

N1 - Funding Information: Acknowledgements. This project has received funding from the European Union’s Horizon 2020 research and innovation programme (ACTRIS-2) under grant agreement no. 654109 and by the Dutch NWO Earth and Life Science (ALW), project 824.14.002. W. Joe F. Acton, Martin Breitenlechner, Leigh R. Crilley, Louisa J. Kramer, Jordan E. Krechmer, Felipe Lopez-Hilfiker, Eiko Nemitz, Lauri-ane L. J. Quéléver, Simon Schallhart, Ralf Tillmann, Sergej Wedel, and Alexander Zaytsev acknowledge Transnational Access (TNA) travel funding from ACTRIS-2 (grant agreement no. 654109). Eiko Nemitz further acknowledges the support of the UK Natural Environment Research Council (NERC) through grants NE/P016502/1 for instrument funding and NE/R016429/1 as part of the UK-SCaPE programme delivering National Capability. Lauriane L. J. Quéléver and Simon Schallhart acknowledge the Finnish Centre of Excellence program (Project no 307331). Lauriane L. J. Quéléver thank the European Research Council (ERC grant no. 638703-COALA). W. Joe F. Acton has received funding from Natural Environment Research Council (UK) grant NE/N006976/1, Sources and Emissions of Air Pollutants in Beijing (AIRPOLL-Beijing). Funding Information: pean Commission (ACTRIS-2, grant no. 654109) and the Netherlands Organisation for Scientific Research (NWO) (grant no. 824.14.002). Publisher Copyright: © Author(s) 2019. This work is distributed under the Creative Commons Attribution 4.0 License. Copyright: Copyright 2019 Elsevier B.V., All rights reserved.

PY - 2019/11/27

Y1 - 2019/11/27

N2 - In September 2017, we conducted a proton-transfer-reaction mass-spectrometry (PTR-MS) intercomparison campaign at the CESAR observatory, a rural site in the central Netherlands near the village of Cabauw. Nine research groups deployed a total of 11 instruments covering a wide range of instrument types and performance. We applied a new calibration method based on fast injection of a gas standard through a sample loop. This approach allows calibrations on timescales of seconds, and within a few minutes an automated sequence can be run allowing one to retrieve diagnostic parameters that indicate the performance status. We developed a method to retrieve the mass-dependent transmission from the fast calibrations, which is an essential characteristic of PTR-MS instruments, limiting the potential to calculate concentrations based on counting statistics and simple reaction kinetics in the reactor/drift tube. Our measurements show that PTR-MS instruments follow the simple reaction kinetics if operated in the standard range for pressures and temperature of the reaction chamber (i.e. 1-4 mbar, 30-120ĝ', respectively), as well as a reduced field strength Eĝ'•N in the range of 100-160 Td. If artefacts can be ruled out, it becomes possible to quantify the signals of uncalibrated organics with accuracies better than ±30 %. The simple reaction kinetics approach produces less accurate results at Eĝ'•N levels below 100 Td, because significant fractions of primary ions form water hydronium clusters. Deprotonation through reactive collisions of protonated organics with water molecules needs to be considered when the collision energy is a substantial fraction of the exoergicity of the proton transfer reaction and/or if protonated organics undergo many collisions with water molecules.

AB - In September 2017, we conducted a proton-transfer-reaction mass-spectrometry (PTR-MS) intercomparison campaign at the CESAR observatory, a rural site in the central Netherlands near the village of Cabauw. Nine research groups deployed a total of 11 instruments covering a wide range of instrument types and performance. We applied a new calibration method based on fast injection of a gas standard through a sample loop. This approach allows calibrations on timescales of seconds, and within a few minutes an automated sequence can be run allowing one to retrieve diagnostic parameters that indicate the performance status. We developed a method to retrieve the mass-dependent transmission from the fast calibrations, which is an essential characteristic of PTR-MS instruments, limiting the potential to calculate concentrations based on counting statistics and simple reaction kinetics in the reactor/drift tube. Our measurements show that PTR-MS instruments follow the simple reaction kinetics if operated in the standard range for pressures and temperature of the reaction chamber (i.e. 1-4 mbar, 30-120ĝ', respectively), as well as a reduced field strength Eĝ'•N in the range of 100-160 Td. If artefacts can be ruled out, it becomes possible to quantify the signals of uncalibrated organics with accuracies better than ±30 %. The simple reaction kinetics approach produces less accurate results at Eĝ'•N levels below 100 Td, because significant fractions of primary ions form water hydronium clusters. Deprotonation through reactive collisions of protonated organics with water molecules needs to be considered when the collision energy is a substantial fraction of the exoergicity of the proton transfer reaction and/or if protonated organics undergo many collisions with water molecules.

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U2 - 10.5194/amt-12-6193-2019

DO - 10.5194/amt-12-6193-2019

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SN - 1867-1381

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EP - 6208

JO - Atmospheric Measurement Techniques

JF - Atmospheric Measurement Techniques

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ER -

Validity and limitations of simple reaction kinetics to calculate concentrations of organic compounds from ion counts in PTR-MS

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