Articles | Volume 18, issue 23
https://doi.org/10.5194/amt-18-7221-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/amt-18-7221-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
High-purity nitrous acid (HONO) generation and quantification using broadband cavity-enhanced absorption spectroscopy (BBCEAS)
Alexis P. Harper
Brigham Young University, Department of Chemistry and Biochemistry, Provo, UT 84602, USA
Callum E. Flowerday
Brigham Young University, Department of Chemistry and Biochemistry, Provo, UT 84602, USA
Zachary Giauque
Brigham Young University, Department of Chemistry and Biochemistry, Provo, UT 84602, USA
Kaitlyn Brewster
Brigham Young University, Department of Chemistry and Biochemistry, Provo, UT 84602, USA
Ryan Thalman
Snow College, Department of Chemistry, Richfield, UT 84701, USA
Jaron C. Hansen
CORRESPONDING AUTHOR
Brigham Young University, Department of Chemistry and Biochemistry, Provo, UT 84602, USA
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EGUsphere, https://doi.org/10.5194/egusphere-2025-4033, https://doi.org/10.5194/egusphere-2025-4033, 2025
This preprint is open for discussion and under review for Atmospheric Measurement Techniques (AMT).
Short summary
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We built and tested a low-cost instrument to measure sunlight that drives chemical reactions in the atmosphere. By comparing different designs, we found one that gives the most accurate results without needing complex corrections. Our tests in both the lab and outdoors show that this homemade tool works well for tracking sunlight and calculating how quickly key air pollutants break down, especially where expensive commercial instruments are unavailable.
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Atmos. Meas. Tech. Discuss., https://doi.org/10.5194/amt-2021-172, https://doi.org/10.5194/amt-2021-172, 2021
Revised manuscript not accepted
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Sulfur dioxide (SO2) is an important gas precursor for formation of atmospheric sulfate aerosol and acid rain. SO2 has direct human health effects through the respiratory system. A new instrument using Broad Band Cavity Enhanced Absorption Spectroscopy (BBCEAS) for the measurement of SO2 with a minimum limit of detection of 0.6 ppbv has been fabricated. The instrument provides a new technique for the measurement of SO2 over a wide range of atmospherically relevant concentrations.
Cited articles
Beine, H., Colussi, A. J., Amoroso, A., Esposito, G., Montagnoli, M., and Hoffmann, M. R.: HONO emissions from snow surfaces, Environ. Res. Lett., 3, 045005, https://doi.org/10.1088/1748-9326/3/4/045005, 2008.
Bongartz, A., Kames, J., Welter, F., and Schurath, U.: Near-UV absorption cross sections and trans/cis equilibrium of nitrous acid, J. Phys. Chem., 95, 1076–1082, https://doi.org/10.1021/j100156a012, 1991.
Bottorff, B., Reidy, E., Mielke, L., Dusanter, S., and Stevens, P. S.: Development of a laser-photofragmentation laser-induced fluorescence instrument for the detection of nitrous acid and hydroxyl radicals in the atmosphere, Atmos. Meas. Tech., 14, 6039–6056, https://doi.org/10.5194/amt-14-6039-2021, 2021.
Braman, R. S. and De la Cantera, M. A.: Sublimation sources for nitrous acid and other nitrogen compounds in air, Anal. Chem., 58, 1533–1537, https://doi.org/10.1021/ac00298a059, 1986.
Burkholder, J. B., Sander, S. P., Abbatt, J. P. D., Barker, J. R., Cappa, C., Crounse, J. D., Dibble, T. S., Huie, R. E., Kolb, C. E., Kurylo, M. J., Orkin, V. L., Percival, C. J., Wilmouth, D. M., and Wine, P. H.: Chemical kinetics and photochemical data for use in atmospheric studies, evaluation number 19, Jet Propulsion Laboratory, Pasadena, CA, NASA JPL Publication 19-5, https://jpldataeval.jpl.nasa.gov/pdf/NASA-JPL Evaluation%2019-5.pdf (last access: 26 November 2025), 2020.
Cox, R. A. and Derwent, R. G.: The ultraviolet absorption spectrum of gaseous nitrous acid, J. Photochem., 6, 23–34, https://doi.org/10.1016/0047-2670(76)87004-9, 1976b.
Cox, R. A., Derwent, R. G., and Holt, P. M.: Relative rate constants for the reactions of OH radicals with H2, CH4, CO, NO and HONO at atmospheric pressure and 296 K, J. Chem. Soc. Faraday Trans. 1, 72, 231–243, https://doi.org/10.1039/F19767202031, 1976a.
Dixneuf, S., Ruth, A. A., Häseler, R., Brauers, T., Rohrer, F., and Dorn, H.-P.: Detection of nitrous acid in the atmospheric simulation chamber SAPHIR using open-path incoherent broadband cavity-enhanced absorption spectroscopy and extractive long-path absorption photometry, Atmos. Meas. Tech., 15, 945–964, https://doi.org/10.5194/amt-15-945-2022, 2022.
Duan, J., Qin, M., Ouyang, B., Fang, W., Li, X., Lu, K., Tang, K., Liang, S., Meng, F., Hu, Z., Xie, P., Liu, W., and Häsler, R.: Development of an incoherent broadband cavity-enhanced absorption spectrometer for in situ measurements of HONO and NO2, Atmos. Meas. Tech., 11, 4531–4543, https://doi.org/10.5194/amt-11-4531-2018, 2018.
Dusanter, S., Vimal, D., Stevens, P. S., Volkamer, R., Molina, L. T., Baker, A., Meinardi, S., Blake, D., Sheehy, P., Merten, A., Zhang, R., Zheng, J., Fortner, E. C., Junkermann, W., Dubey, M., Rahn, T., Eichinger, B., Lewandowski, P., Prueger, J., and Holder, H.: Measurements of OH and HO2 concentrations during the MCMA-2006 field campaign – Part 2: Model comparison and radical budget, Atmos. Chem. Phys., 9, 6655–6675, https://doi.org/10.5194/acp-9-6655-2009, 2009.
Elshorbany, Y., Barnes, I., Becker, K. H., Kleffmann, J., and Wiesen, P.: Sources and cycling of tropospheric hydroxyl radicals – an overview, Z. Phys. Chem., 224, 967–987, https://doi.org/10.1524/zpch.2010.6136, 2010.
Febo, A., Perrino, C., Gherardi, M., and Sparapani, R.: Evaluation of a high-purity and high-stability continuous generation system for nitrous acid, Environ. Sci. Technol., 29, 2390–2395, https://doi.org/10.1021/es00009a035, 1995.
Finlayson-Pitts, B. J., Wingen, L. M., Sumner, A. L., Syomin, D., and Ramazan, K. A.: The heterogeneous hydrolysis of NO2 in laboratory systems and in outdoor and indoor atmospheres: an integrated mechanism, Phys. Chem. Chem. Phys., 5, 223–242, https://doi.org/10.1039/b208564j, 2003.
Flowerday, C. E., Bhardwaj, N., Thalman, R., Asplund, M. C., Sevy, E. T., and Hansen, J. C.: Absorption cross-sections for the 5th and 6th vibrational overtones in a series of short chained alcohols using incoherent broadband cavity enhanced-absorption spectroscopy (IBBCEAS), J. Mol. Spectrosc., 392, 111746, https://doi.org/10.1016/j.jms.2023.111746, 2023a.
Flowerday, C. E., Thalman, R., Asplund, M. C., and Hansen, J. C.: Broadband cavity-enhanced absorption spectroscopy (BBCEAS) coupled with an interferometer for on-band and off-band detection of glyoxal, Toxics, 12, 26, https://doi.org/10.3390/toxics12010026, 2023b.
Flowerday, C. E., Thalman, R., Asplund, M. C., Badstubner, S. A., Cook, A. K., Lundrigan, P., and Hansen, J. C.: Open path spectroscopic detection of hydroxyl radical: a comparison between broadband cavity-enhanced absorption spectroscopy (BBCEAS) and BBCEAS coupled with a Fabry–Pérot interferometer (BBCEAS-FP), Anal. Chem., 97, 11831–11839, https://doi.org/10.1021/acs.analchem.5c01515, 2025.
Gherman, T., Venables, D. S., Vaughan, S., Orphal, J., and Ruth, A. A.: Incoherent broadband cavity-enhanced absorption spectroscopy in the near-ultraviolet: application to HONO and NO2, Environ. Sci. Technol., 42, 890–895, https://doi.org/10.1021/es0716913, 2008.
Gingerysty, N. J. and Osthoff, H. D.: A compact, high-purity source of HONO validated by Fourier transform infrared and thermal-dissociation cavity ring-down spectroscopy, Atmos. Meas. Tech., 13, 4159–4167, https://doi.org/10.5194/amt-13-4159-2020, 2020.
Gutzwiller, L., Arens, F., Baltensperger, U., Gäggeler, H. W., and Ammann, M.: Significance of semivolatile diesel exhaust organics for secondary HONO formation, Environ. Sci. Technol., 36, 677–682, https://doi.org/10.1021/es015673b, 2002.
Harper, A. P., Flowerday, C. E., Giauque, Z., Brewster, K., Thalman, R., and Hansen, J. C.: High-purity nitrous acid (HONO) generation and quantification using broadband cavity-enhanced absorption spectroscopy (BBCEAS), BYU ScholarArchive [data set], https://scholarsarchive.byu.edu/data/93 (last access: 10 November 2025), 2025.
Heland, J., Kleffmann, J., Kurtenbach, R., and Wiesen, P.: A new instrument to measure gaseous nitrous acid (HONO) in the atmosphere, Environ. Sci. Technol., 35, 3207–3212, https://doi.org/10.1021/es000303t, 2001.
Honrath, R. E., Lu, Y., Peterson, M. C., Dibb, J. E., Arsenault, M. A., Cullen, N. J., and Steffen, K.: Vertical fluxes of NOx, HONO, and HNO3 above the snowpack at Summit, Greenland, Atmos. Environ., 36, 2629–2640, https://doi.org/10.1016/S1352-2310(02)00132-2, 2002.
Jordan, N. and Osthoff, H. D.: Quantification of nitrous acid (HONO) and nitrogen dioxide (NO2) in ambient air by broadband cavity-enhanced absorption spectroscopy (IBBCEAS) between 361 and 388 nm, Atmos. Meas. Tech., 13, 273–285, https://doi.org/10.5194/amt-13-273-2020, 2020.
Kanda, Y. and Taira, M.: Chemiluminescent method for continuous monitoring of nitrous acid in ambient air, Anal. Chem., 62, 2084–2087, https://doi.org/10.1021/ac00218a007, 1990.
King, G. W. and Moule, D.: The ultraviolet absorption spectrum of nitrous acid in the vapor state, Can. J. Chem., 40, 2057–2065, https://doi.org/10.1139/v62-316, 1962.
Kleffmann, J.: Daytime sources of nitrous acid (HONO) in the atmospheric boundary layer, Chem. Phys. Chem., 8, 1137–1144, https://doi.org/10.1002/cphc.200700016, 2007.
Kurtenbach, R., Becker, K. H., Gomes, J. A. G., Kleffman, J., Lörzer, J. C., Spittler, M., Wiesen, P., Ackermann, R., Geyer, A., and Platt, U.: Investigations of emissions and heterogeneous formation of HONO in a road traffic tunnel, Atmos. Environ., 35, 3385–3394, https://doi.org/10.1016/S1352-2310(01)00138-8, 2001.
Lamkaddam, H., Gratien, A., Ropion, M., Pangui, E., and Doussin, J. F.: Kinetic study of the temperature dependence of OH-initiated oxidation of n-dodecane, J. Phys. Chem. A, 123, 9462–9468, https://doi.org/10.1021/acs.jpca.9b07704, 2019.
Lao, M., Crilley, L. R., Salehpoor, L., Furlani, T. C., Bourgeois, I., Neuman, J. A., Rollins, A. W., Veres, P. R., Washenfelder, R. A., Womack, C. C., Young, C. J., and VandenBoer, T. C.: A portable, robust, stable, and tunable calibration source for gas-phase nitrous acid (HONO), Atmos. Meas. Tech., 13, 5873–5890, https://doi.org/10.5194/amt-13-5873-2020, 2020.
Michoud, V., Colomb, A., Borbon, A., Miet, K., Beekmann, M., Camredon, M., Aumont, B., Perrier, S., Zapf, P., Siour, G., Ait-Helal, W., Afif, C., Kukui, A., Furger, M., Dupont, J. C., Haeffelin, M., and Doussin, J. F.: Study of the unknown HONO daytime source at a European suburban site during the MEGAPOLI summer and winter field campaigns, Atmos. Chem. Phys., 14, 2805–2822, https://doi.org/10.5194/acp-14-2805-2014, 2014.
Ning, C. L. and Pfab, J.: Generation and 355 nm laser photodissociation of nitrous acid (HONO) and HONO–water clusters, J. Phys. Chem. A, 101, 6008–6014, https://doi.org/10.1021/jp9711712, 1997.
O'Neil, M. J., Heckelman, P. E., Dobbelaar, P. H., Roman, K. J., Kenny, C. M., and Karaffa, L. S.: The Merck Index: an encyclopedia of chemicals, drugs, and biologicals, 15th edn., The Royal Society of Chemistry, Cambridge, UK, ISBN 9781849736701, 2013.
Picquet-Varrault, B., Suarez-Bertoa, R., Duncianu, M., Cazaunau, M., Pangui, E., David, M., and Doussin, J.-F.: Photolysis and oxidation by OH radicals of two carbonyl nitrates: 4-nitrooxy-2-butanone and 5-nitrooxy-2-pentanone, Atmos. Chem. Phys., 20, 487–498, https://doi.org/10.5194/acp-20-487-2020, 2020.
Pitts, J. N., Biermann, H. W., Winer, A. M., and Tuazon, E. C.: Spectroscopic identification and measurement of gaseous nitrous acid in dilute auto exhaust, Atmos. Environ., 18, 847–854, https://doi.org/10.1016/0004-6981(84)90270-1, 1984.
Reed, C., Brumby, C. A., Crilley, L. R., Kramer, L. J., Bloss, W. J., Seakins, P. W., Lee, J. D., and Carpenter, L. J.: HONO measurement by differential photolysis, Atmos. Meas. Tech., 9, 2483–2495, https://doi.org/10.5194/amt-9-2483-2016, 2016.
Ren, X., Harder, H., Martinez, M., Lesher, R. L., Oliger, A., Simpas, J. B., Brune, W. H., Schwab, J. J., Demerjian, K., He, Y., Zhou, X. L., and Gao, H.: OH and HO2 chemistry in the urban atmosphere of New York City, Atmos. Environ., 37, 3639–3651, https://doi.org/10.1016/s1352-2310(03)00459-x, 2003.
Ren, X., Brune, W. H., Mao, J., Mitchell, M. J., Lesher, R. L., Simpas, J. B., Metcalf, A. R., Schwab, J. J., Cai, C., Ii, Y., Demerjian, K., Felton, D., Boynton, G., Adams, A., Perry, J., He, Y., Zhou, X., and Hou, J.: Behavior of OH and HO2 in the winter atmosphere in New York City, Atmos. Environ., 40, 252–263, https://doi.org/10.1016/j.atmosenv.2005.11.073, 2006.
Stockwell, W. R. and Calvert, J. G.: The near ultraviolet absorption spectrum of gaseous HONO and N2O3, J. Photochem., 8, 193–203, https://doi.org/10.1016/0047-2670(78)80019-7, 1978.
Stutz, J., Kim, E. S., Platt, U., Bruno, P., Perrino, C., and Febo, A.: UV-visible absorption cross sections of nitrous acid, J. Geophys. Res., 105, 14585–14592, https://doi.org/10.1029/2000JD900003, 2000.
Su, H., Cheng, Y., Oswald, R., Behrendt, T., Trebs, I., Meixner, F. X., Andreae, M. O., Cheng, P., Zhang, Y., and Pöschl, U.: Soil nitrite as a source of atmospheric HONO and OH radicals, Science, 333, 1616–1618, https://doi.org/10.1126/science.1207687, 2011.
Taira, M. and Kanda, Y.: Continuous generation system for low-concentration gaseous nitrous acid, Anal. Chem., 62, 630–633, https://doi.org/10.1021/ac00205a018, 1990.
Thalman, R. and Volkamer, R.: Inherent calibration of a blue LED-CE-DOAS instrument to measure iodine oxide, glyoxal, methyl glyoxal, nitrogen dioxide, water vapour and aerosol extinction in open cavity mode, Atmos. Meas. Tech., 3, 1797–1814, https://doi.org/10.5194/amt-3-1797-2010, 2010.
Thalman, R., Bhardwaj, N., Flowerday, C. E., and Hansen, J. C.: Detection of sulfur dioxide by broadband cavity-enhanced absorption spectroscopy (BBCEAS), Sensors, 22, 2626, https://doi.org/10.3390/s22072626, 2022.
Vandaele, A. C., Hermans, C., Simon, P. C., Carleer, M. R., Colin, R., Fally, S., Merienne, M. F., Jenouvrier, A., and Coquart, B.: Measurements of the NO2 absorption cross-section from 42 000 cm−1 to 10 000 cm−1 (238–1000 nm) at 220 K and 294 K, J. Quant. Spectrosc. Ra., 59, 171–184, https://doi.org/10.1016/s0022-4073(97)00168-4, 1998.
Villena, G. and Kleffmann, J.: A source for the continuous generation of pure and quantifiable HONO mixtures, Atmos. Meas. Tech., 15, 627–637, https://doi.org/10.5194/amt-15-627-2022, 2022.
von der Heyden, L., Wißdorf, W., Kurtenbach, R., and Kleffmann, J.: A relaxed eddy accumulation (REA) LOPAP system for flux measurements of nitrous acid (HONO), Atmos. Meas. Tech., 15, 1983–2000, https://doi.org/10.5194/amt-15-1983-2022, 2022.
Washenfelder, R. A., Attwood, A. R., Flores, J. M., Zarzana, K. J., Rudich, Y., and Brown, S. S.: Broadband cavity-enhanced absorption spectroscopy in the ultraviolet spectral region for measurements of nitrogen dioxide and formaldehyde, Atmos. Meas. Tech., 9, 41–52, https://doi.org/10.5194/amt-9-41-2016, 2016.
Wu, T., Chen, W., Fertein, E., Cazier, F., Dewaele, D., and Gao, X.: Development of an open-path incoherent broadband cavity-enhanced spectroscopy-based instrument for simultaneous measurement of HONO and NO2 in ambient air, Appl. Phys. B, 106, 501–509, https://doi.org/10.1007/s00340-011-4818-3, 2012.
Wu, T., Zha, Q., Chen, W., Xu, Z., Wang, T., and He, X.: Development and deployment of a cavity enhanced UV-LED spectrometer for measurements of atmospheric HONO and NO2 in Hong Kong, Atmos. Environ., 95, 544–551, https://doi.org/10.1016/j.atmosenv.2014.07.016, 2014.
Xu, Z., Wang, T., Wu, J., Xue, L., Chan, J., Zha, Q., Zhou, S., Louie, P. K. K., and Luk, C. W. Y.: Nitrous acid (HONO) in a polluted subtropical atmosphere: seasonal variability, direct vehicle emissions and heterogeneous production at ground surface, Atmos. Environ., 106, 100–109, https://doi.org/10.1016/j.atmosenv.2015.01.061, 2015.
Yi, H., Cazaunau, M., Gratien, A., Michoud, V., Pangui, E., Doussin, J.-F., and Chen, W.: Intercomparison of IBBCEAS, NitroMAC and FTIR analyses for HONO, NO2 and CH2O measurements during the reaction of NO2 with H2O vapour in the simulation chamber CESAM, Atmos. Meas. Tech., 14, 5701–5715, https://doi.org/10.5194/amt-14-5701-2021, 2021.
Short summary
In this study, we developed a new way to produce and measure nitrous acid, an important atmospheric gas that can be difficult to synthesize. By carefully controlling temperatures and reaction conditions, we created high-purity (<96 %) samples and showed how they can be stored and released when needed. This advance makes it easier to study how nitrous acid contributes to air pollution and atmospheric interactions, while also improving tools for laboratory experiments and instrument testing.
In this study, we developed a new way to produce and measure nitrous acid, an important...