Atmospheric Measurement Techniques Discussions
www.atmos-meas-tech-discuss.net
1867-8610
3
1
2010
10.5194/amtd-3-333-2010
http://www.atmos-meas-tech-discuss.net/3/333/2010/
http://www.atmos-meas-tech-discuss.net/3/333/2010/amtd-3-333-2010.html
http://www.atmos-meas-tech-discuss.net/3/333/2010/amtd-3-333-2010.pdf
333
357
2010-01-29
Development and validation of a portable gas phase standard generation and calibration system for volatile organic compounds
P. Veres
Patrick.veres@noaa.gov
J. B. Gilman
J. M. Roberts
W. C. Kuster
C. Warneke
I. R. Burling
J. de Gouw
Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USA
Chemical Sciences Division, Earth System Research Laboratory, National Oceanic and Atmospheric Administration, Boulder, CO 80305, USA
Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USA
University of Montana, Department of Chemistry, Missoula, USA
We report on the development of an accurate, portable, dynamic calibration
system for volatile organic compounds (VOCs). The Mobile Organic Carbon
Calibration System (MOCCS) combines the production of gas-phase VOC
standards using permeation or diffusion sources with quantitative total
organic carbon (TOC) conversion on a palladium surface to CO<sub>2</sub> in the
presence of oxygen, and the subsequent CO<sub>2</sub> measurement. MOCCS was
validated using three different comparisons: (1) TOC of high accuracy
methane standards compared well to expected concentrations (3% relative
error), (2) a gas-phase benzene standard was generated using a permeation
source and measured by TOC and gas chromatography mass spectrometry (GC-MS)
with excellent agreement (<4% relative difference), and (3) total
carbon measurement of 4 known gas phase mixtures were performed and compared
to a calculated carbon content to agreement within the stated uncertainties
of the standards. Measurements from laboratory biomass burning experiments
of formic acid by negative-ion proton-transfer chemical-ionization mass
spectrometry (NI-PT-CIMS) and formaldehyde by proton transfer reaction-mass
spectrometry (PTR-MS), both calibrated using MOCCS, were compared to open
path Fourier transform infrared spectroscopy (OP-FTIR) to validate the MOCCS
calibration and were found to compare well (<i>R</i><sup>2</sup> of 0.91 and 0.99 respectively).
Altshuller, A. P. and Cohen, I. R.: Application of diffusion cells to the production of known concentrations of gaseous hydrocarbons, Anal. Chem., 32, 802–810, 1960.
Apel, E. C., Calvert, J. G., and Fehsenfeld, F. C.: The nonmethane hydrocarbon intercomparison experiment (nomhice) – task 1 and task 2, J. Geophys. Res.-Atmos., 99, 16651–16664, 1994.
Apel, E. C., Calvert, J. G., Greenberg, J. P., Riemer, D., Zika, R., Kleindienst, T. E., Lonneman, W. A., Fung, K., and Fujita, E.: Generation and validation of oxygenated volatile organic carbon standards for the 1995 southern oxidants study nashville intensive, J. Geophys. Res.-Atmos., 103, 22281–22294, 1998.
Barratt, R. S.: The preparation of standard gas-mixtures – a review, Analyst, 106, 817–849, 1981.
de Gouw, J. A. and Warneke, C.: Measurements of volatile organic compounds in the earth's atmosphere using proton-transfer-reaction mass spectrometry, Mass Spec. Rev., 26, 223–257, 2007.
Dlugokencky, E. J., Myers, R. C., Lang, P. M., Masarie, K. A., Crotwell, A. M., Thoning, K. W., Hall, B. D., Elkins, J. W., and Steele, L. P.: Conversion of noaa atmospheric dry air CH<sub>4</sub> mole fractions to a gravimetrically prepared standard scale, J. Geophys. Res.-Atmos., 110, D18306, doi:10.1029/2005jd006035, 2005.
Griffith, D. W. T.: Synthetic calibration and quantitative analysis of gas-phase ft-ir spectra, Appl. Spectrosc., 50, 59–70, 1996.
Hansel, A., Singer, W., Wisthaler, A., Schwarzmann, M., and Lindinger, W.: Energy dependencies of the proton transfer reactions H<sub>3</sub>O$^(+)$+CH<sub>2</sub>O double left right arrow CH<sub>2</sub>OH$^+$+H<sub>2</sub>O, Int. J. Mass Spectrom., 167, 697–703, 1997.
Maris, C., Chung, M. Y., Lueb, R., Krischke, U., Meller, R., Fox, M. J., and Paulson, S. E.: Development of instrumentation for simultaneous analysis of total non-methane organic carbon and volatile organic compounds in ambient air, ISI:000185829200010, S149–S158, 2003.
Naganowska-Nowak, A., Konieczka, P., Przyjazny, A., and Namiesnik, J.: Development of techniques of generation of gaseous standard mixtures, CRC. Cr. Rev. Anal. Chem., 35, 31–55, doi:10.1080/10408340590947916, 2005.
Namiesnik, J., Torres, L., Kozlowski, E., and Mathieu, J.: Evaluation of the suitability of selected porous polymers for preconcentation of volatile organic-compounds, J. Chromatogr., 208, 239–252, 1981.
Namiesnik, J.: Generation of standard gaseous-mixtures, J. Chromatogr., 300, 79–108, 1984.
Okeeffe, A. E. and Ortman, G. C.: Primary standards for trace gas analysis, Anal. Chem., 38, 760–763, 1966.
Possanzini, M., Di Palo, V., Brancaleoni, E., Frattoni, M., and Ciccioli, P.: Dynamic system for the calibration of semi-volatile carbonyl compounds in air, J. Chromatogr. A, 883, 171–183, 2000.
Rappengluck, B., Apel, E., Bauerfeind, M., Bottenheim, J., Brickell, P., Cavolka, P., Cech, J., Gatti, L., Hakola, H., Honzak, J., Junek, R., Martin, D., Noone, C., Plass-Dulmer, C., Travers, D., and Wang, D.: The first voc intercomparison exercise within the global atmosphere watch (gaw), Atmos. Environ., 40, 7508–7527, doi:10.1016/j.atmosenv.2006.07.016, 2006.
Roberts, J. M., Bertman, S. B., Jobson, T., Niki, H., and Tanner, R.: Measurement of total nonmethane organic carbon (c-y): Development and application at chebogue point, nova scotia, during the 1993 north atlantic regional experiment campaign, J. Geophys. Res.-Atmos., 103, 13581–13592, 1998.
Thompson, J. M. and Perry, D. B.: A new system of refillable and uniquely identifiable diffusion tubes for dynamically generating voc and svoc standard atmospheres at ppm and ppb concentrations for calibration of field and laboratory measurements, J. Environ. Monit., 11, 1543–1544, doi:10.1039/b901954e, 2009.
Veres, P., Roberts, J. M., Warneke, C., Welsh-Bon, D., Zahniser, M., Herndon, S., Fall, R., and de Gouw, J.: Development of negative-ion proton-transfer chemical-ionization mass spectrometry (ni-pt-cims) for the measurement of gas-phase organic acids in the atmosphere, Int. J. Mass Spectrom., 274, 48–55, 2008.
Veres, P., Roberts, J. M., Burling, I. R., Warneke, C., Gouw, J. d., and Yokelson, R.: Measurement of gas-phase inorganic and organic acids from biomass fires by negatiove-ion proton-transfer chemical-ionization mass spectrometry (ni-pt-cims), J. Geophys. Res.-Atmos., submitted, 2010.
Williams, J., Roberts, J. M., Bertman, S. B., Stroud, C. A., Fehsenfeld, F. C., Baumann, K., Buhr, M. P., Knapp, K., Murphy, P. C., Nowick, M., and Williams, E. J.: A method for the airborne measurement of pan, ppn, and mpan, J. Geophys. Res.-Atmos., 105, 28943–28960, 2000.
Yokelson, R. J., Karl, T., Artaxo, P., Blake, D. R., Christian, T. J., Griffith, D. W. T., Guenther, A., and Hao, W. M.: The Tropical Forest and Fire Emissions Experiment: overview and airborne fire emission factor measurements, Atmos. Chem. Phys., 7, 5175–5196, 2007.