The determination of ClNO<sub>2</sub> via thermal dissociation–tunable infrared laser direct absorption spectroscopy
<p>Nitryl chloride (ClNO<span class="inline-formula"><sub>2</sub></span>) is a reservoir species of chlorine atoms and nitrogen oxides, both of which play important roles in atmospheric chemistry. To date, all ambient ClNO<span class="inline-formula&qu...
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Copernicus Publications
2025-08-01
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| Series: | Atmospheric Measurement Techniques |
| Online Access: | https://amt.copernicus.org/articles/18/3799/2025/amt-18-3799-2025.pdf |
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| author | J. W. Halfacre L. Marden M. D. Shaw L. J. Carpenter E. Matthews T. J. Bannan H. Coe H. Coe S. C. Herndon J. R. Roscioli C. Dyroff T. I. Yacovitch P. R. Veres P. R. Veres M. A. Robinson M. A. Robinson S. S. Brown S. S. Brown P. M. Edwards P. M. Edwards |
| author_facet | J. W. Halfacre L. Marden M. D. Shaw L. J. Carpenter E. Matthews T. J. Bannan H. Coe H. Coe S. C. Herndon J. R. Roscioli C. Dyroff T. I. Yacovitch P. R. Veres P. R. Veres M. A. Robinson M. A. Robinson S. S. Brown S. S. Brown P. M. Edwards P. M. Edwards |
| author_sort | J. W. Halfacre |
| collection | DOAJ |
| description | <p>Nitryl chloride (ClNO<span class="inline-formula"><sub>2</sub></span>) is a reservoir species of chlorine atoms and nitrogen oxides, both of which play important roles in atmospheric chemistry. To date, all ambient ClNO<span class="inline-formula"><sub>2</sub></span> observations have been obtained by chemical ionization mass spectrometry (CIMS). In this work, thermal dissociation–tunable infrared laser direct absorption spectrometry (TD-TILDAS) is shown to be a viable method for quantifying ClNO<span class="inline-formula"><sub>2</sub></span> in laboratory and field settings. This technique relies on the thermal dissociation of ClNO<span class="inline-formula"><sub>2</sub></span> to create chlorine radicals, which undergo fast reactions with hydrocarbons to produce hydrogen chloride (HCl) that is detectable by the TILDAS instrument. Complete quantitative conversion of ClNO<span class="inline-formula"><sub>2</sub></span> to HCl was achieved at temperatures <span class="inline-formula">></span> 400 °C, achieving 1 Hz measurement precision of 11 <span class="inline-formula">±</span> 1 pptv (3<span class="inline-formula"><i>σ</i></span> limits of detection of 34 <span class="inline-formula">±</span> 2 pptv) during laboratory comparisons with other ClNO<span class="inline-formula"><sub>2</sub></span> detection methods. After blank and line loss corrections, method accuracy is estimated to be within <span class="inline-formula">±</span> 5 %. Performance metrics of TD-TILDAS during ambient sampling were a 1 Hz precision of 19 <span class="inline-formula">±</span> 1 pptv and 3<span class="inline-formula"><i>σ</i></span> limits of detection of 57 <span class="inline-formula">±</span> 3 pptv, which is directly comparable to previously reported ClNO<span class="inline-formula"><sub>2</sub></span> detection by quadrupole CIMS. Thus, TD-TILDAS can provide an alternative analytical approach for a direct measurement of ClNO<span class="inline-formula"><sub>2</sub></span> that can complement existing datasets and future studies. The quantitative nature of TD-TILDAS also makes it a potentially useful tool for the calibration of CIMS instruments. However, interpretation of ambient data may be complicated by potential interferences from unaccounted-for sources of thermolabile chlorine, such as ClNO, chloramines, and organochlorides.</p> |
| format | Article |
| id | doaj-art-88e1e64e5f164f768bc1050e7f54eaf2 |
| institution | Kabale University |
| issn | 1867-1381 1867-8548 |
| language | English |
| publishDate | 2025-08-01 |
| publisher | Copernicus Publications |
| record_format | Article |
| series | Atmospheric Measurement Techniques |
| spelling | doaj-art-88e1e64e5f164f768bc1050e7f54eaf22025-08-20T04:02:28ZengCopernicus PublicationsAtmospheric Measurement Techniques1867-13811867-85482025-08-01183799381810.5194/amt-18-3799-2025The determination of ClNO<sub>2</sub> via thermal dissociation–tunable infrared laser direct absorption spectroscopyJ. W. Halfacre0L. Marden1M. D. Shaw2L. J. Carpenter3E. Matthews4T. J. Bannan5H. Coe6H. Coe7S. C. Herndon8J. R. Roscioli9C. Dyroff10T. I. Yacovitch11P. R. Veres12P. R. Veres13M. A. Robinson14M. A. Robinson15S. S. Brown16S. S. Brown17P. M. Edwards18P. M. Edwards19Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UKWolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UKWolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UKWolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UKDepartment of Earth and Environmental Science, Centre for Atmospheric Science, School of Natural Sciences, The University of Manchester, Manchester, M13 9PL, UKDepartment of Earth and Environmental Science, Centre for Atmospheric Science, School of Natural Sciences, The University of Manchester, Manchester, M13 9PL, UKDepartment of Earth and Environmental Science, Centre for Atmospheric Science, School of Natural Sciences, The University of Manchester, Manchester, M13 9PL, UKNational Centre for Atmospheric Science, University of Manchester, Manchester, M13 9PL, UKAerodyne Research, Inc., Billerica, MA 01821, USAAerodyne Research, Inc., Billerica, MA 01821, USAAerodyne Research, Inc., Billerica, MA 01821, USAAerodyne Research, Inc., Billerica, MA 01821, USAChemical Sciences Laboratory, National Oceanic and Atmospheric Administration, Boulder, CO 80305, USAnow at: National Science Foundation, National Center for Atmospheric Research, Boulder, CO 80301, USAChemical Sciences Laboratory, National Oceanic and Atmospheric Administration, Boulder, CO 80305, USACooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80305, USAChemical Sciences Laboratory, National Oceanic and Atmospheric Administration, Boulder, CO 80305, USADepartment of Chemistry, University of Colorado, Boulder, CO 80309, USAWolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UKNational Centre for Atmospheric Science, University of York, York, YO10 5DD, UK<p>Nitryl chloride (ClNO<span class="inline-formula"><sub>2</sub></span>) is a reservoir species of chlorine atoms and nitrogen oxides, both of which play important roles in atmospheric chemistry. To date, all ambient ClNO<span class="inline-formula"><sub>2</sub></span> observations have been obtained by chemical ionization mass spectrometry (CIMS). In this work, thermal dissociation–tunable infrared laser direct absorption spectrometry (TD-TILDAS) is shown to be a viable method for quantifying ClNO<span class="inline-formula"><sub>2</sub></span> in laboratory and field settings. This technique relies on the thermal dissociation of ClNO<span class="inline-formula"><sub>2</sub></span> to create chlorine radicals, which undergo fast reactions with hydrocarbons to produce hydrogen chloride (HCl) that is detectable by the TILDAS instrument. Complete quantitative conversion of ClNO<span class="inline-formula"><sub>2</sub></span> to HCl was achieved at temperatures <span class="inline-formula">></span> 400 °C, achieving 1 Hz measurement precision of 11 <span class="inline-formula">±</span> 1 pptv (3<span class="inline-formula"><i>σ</i></span> limits of detection of 34 <span class="inline-formula">±</span> 2 pptv) during laboratory comparisons with other ClNO<span class="inline-formula"><sub>2</sub></span> detection methods. After blank and line loss corrections, method accuracy is estimated to be within <span class="inline-formula">±</span> 5 %. Performance metrics of TD-TILDAS during ambient sampling were a 1 Hz precision of 19 <span class="inline-formula">±</span> 1 pptv and 3<span class="inline-formula"><i>σ</i></span> limits of detection of 57 <span class="inline-formula">±</span> 3 pptv, which is directly comparable to previously reported ClNO<span class="inline-formula"><sub>2</sub></span> detection by quadrupole CIMS. Thus, TD-TILDAS can provide an alternative analytical approach for a direct measurement of ClNO<span class="inline-formula"><sub>2</sub></span> that can complement existing datasets and future studies. The quantitative nature of TD-TILDAS also makes it a potentially useful tool for the calibration of CIMS instruments. However, interpretation of ambient data may be complicated by potential interferences from unaccounted-for sources of thermolabile chlorine, such as ClNO, chloramines, and organochlorides.</p>https://amt.copernicus.org/articles/18/3799/2025/amt-18-3799-2025.pdf |
| spellingShingle | J. W. Halfacre L. Marden M. D. Shaw L. J. Carpenter E. Matthews T. J. Bannan H. Coe H. Coe S. C. Herndon J. R. Roscioli C. Dyroff T. I. Yacovitch P. R. Veres P. R. Veres M. A. Robinson M. A. Robinson S. S. Brown S. S. Brown P. M. Edwards P. M. Edwards The determination of ClNO<sub>2</sub> via thermal dissociation–tunable infrared laser direct absorption spectroscopy Atmospheric Measurement Techniques |
| title | The determination of ClNO<sub>2</sub> via thermal dissociation–tunable infrared laser direct absorption spectroscopy |
| title_full | The determination of ClNO<sub>2</sub> via thermal dissociation–tunable infrared laser direct absorption spectroscopy |
| title_fullStr | The determination of ClNO<sub>2</sub> via thermal dissociation–tunable infrared laser direct absorption spectroscopy |
| title_full_unstemmed | The determination of ClNO<sub>2</sub> via thermal dissociation–tunable infrared laser direct absorption spectroscopy |
| title_short | The determination of ClNO<sub>2</sub> via thermal dissociation–tunable infrared laser direct absorption spectroscopy |
| title_sort | determination of clno sub 2 sub via thermal dissociation tunable infrared laser direct absorption spectroscopy |
| url | https://amt.copernicus.org/articles/18/3799/2025/amt-18-3799-2025.pdf |
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