<?xml version="1.0" encoding="utf-8" standalone="no"?>
<!DOCTYPE article SYSTEM "http://www.atmos-meas-tech.net/inc/amt/copernicus.dtd">
<article language="en">
	<journal>
		<journal_title>Atmospheric Measurement Techniques</journal_title>
		<journal_url>www.atmos-meas-tech.net</journal_url>
		<issn>1867-1381</issn>
		<eissn>1867-8548</eissn>
		<volume_number>3</volume_number>
		<issue_number>4</issue_number>
		<publication_year>2010</publication_year>
	</journal>
	<doi>10.5194/amt-3-1055-2010</doi>
	<article_url>http://www.atmos-meas-tech.net/3/1055/2010/</article_url>
	<abstract_html>http://www.atmos-meas-tech.net/3/1055/2010/amt-3-1055-2010.html</abstract_html>
	<fulltext_pdf>http://www.atmos-meas-tech.net/3/1055/2010/amt-3-1055-2010.pdf</fulltext_pdf>
	<start_page>1055</start_page>
	<end_page>1062</end_page>
	<publication_date>2010-08-17</publication_date>
	<article_title content_type="html">Formaldehyde measurements by Proton transfer reaction â€“ Mass Spectrometry (PTR-MS): correction for humidity effects</article_title>
	<authors>
		<author numeration="1" affiliations="1,2,3">
			<name>A. Vlasenko</name>
			<email>alexander.vlasenko@ec.gc.ca</email>
		</author>
		<author numeration="2" affiliations="2">
			<name>A .M. Macdonald</name>
		</author>
		<author numeration="3" affiliations="1,2">
			<name>S. J. Sjostedt</name>
		</author>
		<author numeration="4" affiliations="1">
			<name>J. P. D. Abbatt</name>
		</author>
	</authors>
	<affiliations>
		<affiliation numeration="1" content_type="html">Department of Chemistry, University of Toronto, Toronto, Canada</affiliation>
		<affiliation numeration="2" content_type="html">Science and Technology Branch, Environment Canada, Toronto, Canada</affiliation>
		<affiliation numeration="3" content_type="html">now at: Science and Technology Branch, Environment Canada, Toronto, Canada</affiliation>
	</affiliations>
	<abstract content_type="html">Formaldehyde measurements can provide useful information about photochemical
activity in ambient air, given that HCHO is formed via numerous oxidation
processes. Proton transfer reaction mass spectrometry (PTR-MS) is an online
technique that allows measurement of VOCs at the sub-ppbv level with good
time resolution. PTR-MS quantification of HCHO is hampered by the humidity
dependence of the instrument sensitivity, with higher humidity leading to
loss of PTR-MS signal. In this study we present an analytical, first
principles approach to correct the PTR-MS HCHO signal according to the
concentration of water vapor in sampled air. The results of the correction
are validated by comparison of the PTR-MS results to those from a Hantzsch
fluorescence monitor which does not have the same humidity dependence.
Results are presented for an intercomparison made during a field campaign in
rural Ontario at Environment Canada&apos;s Centre for Atmospheric Research
Experiments.</abstract>
	<references>
		<reference numeration="1" content_type="text"> Ammann, C., Spirig, C., Neftel, A., Steinbacher, M., Komenda, M., and Schaub, A.: Application of PTR-MS fro measurements of biogenic VOC in a deciduous forest, Int. J. Mass Spectrom., 239, 87â€“101, 2004. </reference>
		<reference numeration="2" content_type="text"> Ammann, C., Brunner, A., Spirig, C., and Neftel, A.: Technical note: Water vapour concentration and flux measurements with PTR-MS, Atmos. Chem. Phys., 6, 4643-4651, doi:10.5194/acp-6-4643-2006, 2006. </reference>
		<reference numeration="3" content_type="text"> Christian, T. J., Kleiss, B., Yokelson, R. J., Holzinger, R., Crutzen, P. J., Hao, W. M., Shirai, T., and Blake, D. R.: Comprehensive laboratory measurements of biomass-burning emissions: 2. First intercomparison of open-path FTIR, PTR-MS, and GC- MS/FID/ECD, J. Geophys. Res., 109, doi:10.1029/2003JD003874, 2004. </reference>
		<reference numeration="4" content_type="text"> Dasgupta, P. K., Li, J. Z., Zhang, G. F., Luke, W. T., McClenny, W. A., Stutz, J., and Fried, A.: Summertime ambient formaldehyde in five US metropolitan areas: Nashville, Atlanta, Houston, Philadelphia, and Tampa, Environ. Sci. Technol., 39, 4767â€“4783, 2005. </reference>
		<reference numeration="5" content_type="text"> de Gouw, J. and Warneke, C.: Measurements of volatile organic compounds in the earths atmosphere using proton-transfer-reaction mass spectrometry, Mass Spectrom. Rev., 26, 223â€“257, 2007. </reference>
		<reference numeration="6" content_type="text"> Frey, M. M., Hutterli, M. A., Chen, G., Sjostedt, S. J., Burkhart, J. F., Friel, D. K., and Bales, R. C.: Contrasting atmospheric boundary layer chemistry of methylhydroperoxide (CH3OOH) and hydrogen peroxide (H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt;) above polar snow, Atmos. Chem. Phys., 9, 3261â€“3276, doi:10.5194/acp-9-3261-2009, 2009. </reference>
		<reference numeration="7" content_type="text"> Fried, A., Henry, B., Wert, B., Sewell, S., and Drummond, J. R.: Laboratory, ground-based, and airborne tunable diode laser systems: performance characteristics and applications in atmospheric studies, Appl. Phys. B-Lasers Opt., 67, 317â€“330, 1998. </reference>
		<reference numeration="8" content_type="text"> Garcia, A. R., Volkamer, R., Molina, L. T., Molina, M. J., Samuelson, J., Mellqvist, J., Galle, B., Herndon, S. C., and Kolb, C. E.: Separation of emitted and photochemical formaldehyde in Mexico City using a statistical analysis and a new pair of gas-phase tracers, Atmos. Chem. Phys., 6, 4545â€“4557, doi:10.5194/acp-6-4545-2006, 2006. </reference>
		<reference numeration="9" content_type="text"> Grosjean, D. and Fung, K.: Collection efficiencies of cartridges and microimpingers for sampling of aldehydes in air as 2,4-dinitrophenylhydrazones, Anal. Chem., 54, 1221â€“1224, 1982. </reference>
		<reference numeration="10" content_type="text"> Grosjean, D.: Ambient levels of formaldehyde, acetaldehyde, and formic acid in Southern California: Results of a one-year base-line study, Environ. Sci. Technol., 25, 710â€“715, 1991. </reference>
		<reference numeration="11" content_type="text"> Haar, L., Gallagher, J. S., and Kell, G. S.: NBS/NRC Steam Tables, Hemisphere Publishing Corp., New York, 1984. </reference>
		<reference numeration="12" content_type="text"> Hansel, A., Singer, W., Wisthaler, A., Schwarzmann, M., and Lindinger, W.: Energy dependencies of the proton transfer reactions H&lt;sub&gt;3&lt;/sub&gt;O$^+$+CH&lt;sub&gt;2&lt;/sub&gt;O $\leftrightarrow $ CH&lt;sub&gt;2&lt;/sub&gt;OH$^+$+H&lt;sub&gt;2&lt;/sub&gt;O, Int. J. Mass Spectrom., 167, 697â€“703, 1997. </reference>
		<reference numeration="13" content_type="text"> Harris, G. W., Mackay, G. I., Iguchi, T., Mayne, L. K., and Schiff, H. I.: Measurements of Formaldehyde in the Troposphere by Tunable Diode-Laser Absorption-Spectroscopy, J. Atmos. Chem., 8, 119â€“137, 1989. </reference>
		<reference numeration="14" content_type="text"> Heckel, A., Richter, A., Tarsu, T., Wittrock, F., Hak, C., Pundt, I., Junkermann, W., and Burrows, J. P.: MAX-DOAS measurements of formaldehyde in the Po-Valley, Atmos. Chem. Phys., 5, 909â€“918, doi:10.5194/acp-5-909-2005, 2005. </reference>
		<reference numeration="15" content_type="text"> Herndon, S. C., Zahniser, M. S., Nelson, D. D., Jr., Shorter, J., McManus, J. B., JimÃ©nez, R., Warneke, C., and de Gouw, J. A.: Airborne measurements of HCHO and HCOOH during the New England Air Quality Study 2004 using a pulsed quantum cascade laser spectrometer, J. Geophys. Res., 112, doi:10.1029/2006JD007600, 2007. </reference>
		<reference numeration="16" content_type="text"> Hong, S. B., Kim, G. S., Kang, C. H., and Lee, J. H.: Measurement of ambient hydroperoxides using an automated HPLC system and various factors which affect variations of their concentrations in Korea, Environ. Monit. Assess., 147, 23â€“34, 2008. </reference>
		<reference numeration="17" content_type="text"> Hunter, E. P. and Lias, S. G.: Proton Affinity Evaluation, in: NIST Chemistry WebBook, NIST Standard Reference Database Number 69, edited by: Mallard, P. J. L. a. W. G., National Institute of Standards and Technology, Gaithersburg MD, 20899 (http://webbook.nist.gov), 2005. </reference>
		<reference numeration="18" content_type="text"> Hutterli, M. A., Rothlisberger, R., and Bales, R. C.: Atmosphere-to-snow-to-firn transfer studies of HCHO at Summit, Greenland, Geophys. Res. Lett., 26, 1691â€“1694, 1999. </reference>
		<reference numeration="19" content_type="text"> Inomata, S., Tanimoto, H., Kameyama, S., Tsunogai, U., Irie, H., Kanaya, Y., and Wang, Z.: Technical Note: Determination of formaldehyde mixing ratios in air with PTR-MS: laboratory experiments and field measurements, Atmos. Chem. Phys., 8, 273â€“284, doi:10.5194/acp-8-273-2008, 2008. </reference>
		<reference numeration="20" content_type="text"> Jobson, B. T. and McCoskey, J. K.: Sample drying to improve HCHO measurements by PTR-MS instruments: laboratory and field measurements, Atmos. Chem. Phys., 10, 1821â€“1835, doi:10.5194/acp-10-1821-2010, 2010. </reference>
		<reference numeration="21" content_type="text"> Karl, T., Jobson, T., Kuster, W. C., Williams, E., Stutz, J., Shetter, R., Hall, S. R., Goldan, P., Fehsenfeld, F., and Lindinger, W.: Use of proton-transfer-reaction mass spectrometry to characterize volatile organic compound sources at the La Porte super site during the Texas Air Quality Study 2000, J. Geophys. Res., 108, doi:10.1029/2002JD003333, 2003. </reference>
		<reference numeration="22" content_type="text"> Kelly, T. J. and Fortune, C. R.: Continuous Monitoring of Gaseous Formaldehyde Using an Improved Fluorescence Approach, Int. J. Environ. Anal. Chem., 54, 249â€“263, 1994. </reference>
		<reference numeration="23" content_type="text"> Knighton, W. B., Fortner, E. C., Midey, A. J., Viggiano, A. A., Herndon, S. C., Wood, E. C., and Kolb, C. E.: HCN detection with a proton transfer reaction mass spectrometer, Int. J. Mass Spectrom., 283, 112â€“121, 2009. </reference>
		<reference numeration="24" content_type="text"> Lawson, D. R., Biermann, H. W., Tuazon, E. C., Winer Mackay, A. M. G. I., Schiff, H. I., Kok, G. L., Dasgupta, P. K., and Fung, K.: Formaldehyde measurement methods evaluation and ambient concentrations during the Carbonaceous Species Methods Comparison Study, Aerosol Sci. Technol., 12, 64â€“76, 1990. </reference>
		<reference numeration="25" content_type="text"> Lindinger, W., Hansel, A., and Jordan, A.: On-line monitoring of volatile organic compounds at pptv levels by means of proton-transfer-reaction mass spectrometry (PTR-MS) - Medical applications, food control and environmental research, Int. J. Mass Spectrom., 173, 191â€“241, 1998. </reference>
		<reference numeration="26" content_type="text"> Macdonald, A. M., Wiebe, H. A., Li, S. M., Dryfhout-Clark, H., Asalian, K., Lu, G., Wang, D., Schiller, C. L., Harris, G. W., Sumner, A. L., and Shepson, P. B.: Results of a Formaldehyde Intercomparison Study in Ontario, Atmospheric Environment Service, Environment Canada, Toronto, ACSD-99-001, 1999. </reference>
		<reference numeration="27" content_type="text"> Macdonald, A. M., Makar, P. A., Anlauf, K. G., Hayden, K. L., Bottenheim, J. W., Wang, D., and Dann, T.: Summertime formaldehyde at a high-elevation site in Quebec, J. Geophys. Res., 106, 32361â€“32374, 2001. </reference>
		<reference numeration="28" content_type="text"> Midey, A. J., Arnold, S. T., and Viggiano, A. A.: Reactions of H3O+(H2O)(n) with formaldehyde and acetaldehyde, J. Phys. Chem. A, 104, 2706â€“2709, 2000. </reference>
		<reference numeration="29" content_type="text"> Riedel, K., Weller, R., and Schrems, O.: Variability of formaldehyde in the Antarctic troposphere, Phys. Chem. Chem. Phys., 1, 5523â€“5527, 1999. </reference>
		<reference numeration="30" content_type="text"> Å panÃªl, P., Wang, T., and Smith, D.: Quantification of hydrogen cyanide in humid air by selected ion flow tube mass spectrometry, Rapid Commun. Mass Spectrom., 18, 1869â€“1873, 2004. </reference>
		<reference numeration="31" content_type="text"> Steinbacher, M.: Volatile Organic Compounds and Their Oxidation Products in the Atmospheric Boundary Layer: Laboratory and Field Measurements, PhD Thesis Nr. 15557, Naturwissenschaften, ETH, ZÃ¼rich, 151 pp., 2004. </reference>
		<reference numeration="32" content_type="text"> Steinbacher, M., Dommen, J., Ammann, C., Spirig, C., Neftel, A., and Prevot, A. S. H.: Performance characteristics of a proton-transfer-reaction mass spectrometer (PTR-MS) derived from laboratory and field measurements, Int. J. Mass Spectrom., 239, 117â€“128, 2004. </reference>
		<reference numeration="33" content_type="text"> Sumner, A. L., Shepson, P. B., Grannas, A. M., Bottenheim, J. W., Anlauf, K. G., Worthy, D., Schroeder, W. H., Steffen, A., DominÃ©, F., Perrier, S., and Houdier, S.: Atmospheric chemistry of formaldehyde in the Arctic troposphere at Polar Sunrise, and the influence of the snowpack, Atmos. Environ., 36, 2553â€“2562, 2002. </reference>
		<reference numeration="34" content_type="text"> Tuazon, E. C., Winer, A. M., Graham, R. A., and Pitts, Jr., J. N.: Atmospheric measurements of trace pollutants by kilometer-pathlength FT-IR spectroscopy, Adv. Environ. Sci. Technol., 10, 259â€“300, 1980. </reference>
		<reference numeration="35" content_type="text"> Vlasenko, A., Slowik, J. G., Bottenheim, J. W., Brickell, P. C., Chang, R. Y. W., Macdonald, A. M., Shantz, N. C., Sjostedt, S. J., Wiebe, H. A., Leaitch, W. R., and Abbatt, J. P. D.: Measurements of VOCs by proton transfer reaction mass spectrometry at a rural Ontario site: Sources and correlation to aerosol composition, J. Geophys. Res., 114, doi:10.1029/2009JD012025, 2009. </reference>
		<reference numeration="36" content_type="text"> Warneke, C., van der Veen, C., Luxembourg, S., de Gouw, J. A., and Kok, A.: Measurements of benzene and toluene in ambient air using proton-transfer-reaction mass spectrometry: calibration, humidity dependence, and field intercomparison, Int. J. Mass Spectrom., 207, 167â€“182, 2001. </reference>
		<reference numeration="37" content_type="text"> Wisthaler, A., Apel, E. C., Bossmeyer, J., Hansel, A., Junkermann, W., Koppmann, R., Meier, R., Müller, K., Solomon, S. J., Steinbrecher, R., Tillmann, R., and Brauers, T.: Technical Note: Intercomparison of formaldehyde measurements at the atmosphere simulation chamber SAPHIR, Atmos. Chem. Phys., 8, 2189â€“2200, doi:10.5194/acp-8-2189-2008, 2008. </reference>
	</references>
</article>

