Abstract
An automated technique for measuring SO2 in ambient air has been developed. Air is passed through a gas/liquid exchange coil with an aqueous absorber solution containing 10 µM formaldehyde and 0.84 mM Na2EDTA. The SO2 rapidly equilibrates with bisulfite (HSO −3 ) and sulfite (SO 2−3 ) in the aqueous solution. The aqueous S(IV) is subsequently reacted with o-phthaladehyde in the presence of excess ethanolamine to form a fluorescent isoindole in a continuous flow stream. This derivative is then separated using reversed phase HPLC and detected via fluorescence with excitation and emission wavelengths at 330 and 380 nm, respectively. The lower limit of detection is 7 pptv (S/N=3), with a measurement period of eight minutes per sample. The instrument response is linear over several orders of magnitude.
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Allison, L. A., Mayer, G. S., and Shoup, R. E., 1984,o-Phthalaldehyde derivatives of amines for high speed liquid chromatography/electrochemistry,Anal. Chem. 56, 1089.
Andreae, M. O., Berresheim, H., Andreae, T. W., Kritz, M. A., Bates, T. S., and Merrill, J. T., 1988, Vertical distribution of dimethylsulfide, sulfur dioxide, aerosol ions, and radon over the northeast Pacific Ocean,J. Atmos. Chem. 6, 149–173.
Ammons, J. M., 1980, Preconcentration methods for the determination of gaseous sulfur compounds in air, PhD Dissertation, University of South Florida.
Bates, T. S., Johnson, J. E., Quinn, P. K., Goldan, P. D., Kuster, W. C., Covert, D. C., and Hahn, C. J., 1990, The biogeochemical sulfur cycle in the marine boundary layer over the northeast Pacific Ocean,J. Atmos. Chem. 10, 59–81.
Berresheim, H., 1987, Biogenic sulfur emissions from the Subantarctic and Antarctic Oceans,J. Geophys. Res. 92, 13,245–13,262.
Boyce, S. D. and Hoffmann, M. R., 1984, Kinetics and mechanism of the formation of hydroxymethanesulfonic acid at low pH,J. Phys. Chem. 88, 4740–4746.
Cronin, J. R., Pizzarello, S., and Gandy, W. E., 1979, Amino acid analysis with o-phthalaldehyde detection: Effects of reaction temperature and thiol on fluorescence yields,Anal. Biochem. 93, 174–179.
Dasgupta, P. K., DeCesare, K., and Ullrey, J. C., 1980, Determination of atmospheric sulfur dioxide without tetrachloromercurate (II) and the mechanism of the Schiff reaction,Anal. Chem. 52, 1912–1922.
Driedger, A. R. III, Thornton, D. C., Lalevic, M., and Bandy, A. R., 1987, Determination of parts-pertrillion levels of atmospheric sulfur dioxide by isotope dilution gas chromatography/mass spectrometry,Anal. Chem. 59, 1196–1200.
Farhataziz and Ross, A. B., 1975, Selected specific rates of reactions of transients from water in aqueous solution. III. Hydroxyl radical and perhydroxyl radical and their radical ions. United States Department of Commerce/National Bureau of Standards Report, NSRDS-NBS 59.
Ferek, R. J., Hegg, D. A., Herring, J. A., and Hobbs, P. V., 1991, An improved filter pack technique for airborne measurement of low concentrations of SO2,J. Geophys. Res. 96, 22,373–22,378.
Genfa, Z., Dong, S., and Dasgupta, P. K., 1989, Measurement of atmospheric ammonia,Environ. Sci. Technol. 23, 1467–1474.
Gregory, G. L., Davis, D. D., Belz, N., Bandy, A. R., Ferek, R. J., and Thornton, D., 1992, An intercomparison of aircraft instrumentation for tropospheric measurements of sulfur dioxide,J. Geophys. Res., in press.
Jacobs, W. A., 1987,o-Phthalaldehyde-sulfite derivatization of primary amines for liquid chromatography-electrochemistry,J. Chromatogr. 392, 435.
Jacobs, W. A., Leburg, M. W., and Madaj, E. J., 1986, Stability ofo-phthalaldehyde-derived isoindoles,Anal. Biochem. 156, 334.
Klemm, O. and Talbot, R. W., 1991, A sensitive method for measuring atmospheric concentrations of sulfur dioxide,J. Atmos. Chem. 13, 325–342.
Kok, G. L., Holler, T. P., Lopez, M. B., Nachtrieb, H. A., and Yuan, M., 1978, Chemiluminescent method of determination of hydrogen peroxide in the ambient atmosphere,Environ. Sci. Technol. 12, 1072–1076.
Kunen, S. M., Lazarus, A. L., Kok G. L., and Heikes, B. G., 1986, Aqueous oxidation of SO2 by hydrogen peroxide,J. Geophys. Res. 88, 3671–3674.
Maahs, H. G., 1982, Sulfur dioxide/water equilibria between 0° and 50°C, an examination of data at low concentrations, in D. R. Schryer (ed.),Heterogeneous Atmospheric Chemistry, Am. Geophys. Union, Washington DC, pp. 187–195.
Meixner, F. X. and Jaeschke, W. A., 1981, The detection of low atmospheric SO2 concentrations with a chemiluminescence technique,Int. J. Environ. Anal. Chem. 10, 51–67.
Millero, F. J., Hubinger, S., Fernandez, M., and Garnett, S., 1987, Oxidation of H2S in seawater as a function of temperature, pH, and ionic strength,Environ. Sci. Technol. 21, 439–443.
Mopper, K. and Delmas, D., 1984, Trace analysis of biological thiols by liquid chromatography and precolumn fluorometric labeling witho-phthalaldeyde,Anal. Chem. 56, 2557–2560.
Munger, J. W., Jacob, D. J., and Hoffman, M. R., 1984, The occurrence of bisulfite-aldehyde addition products in fog- and cloudwater,J. Atmos. Chem. 1, 337–350.
Nakamura, H. and Tamura, Z., 1981, Fluorometric determination of thiols by liquid chromatography with post column derivatization,Anal. Chem. 53, 2190.
Nakamura, H., Matsumoto, A., and Tamura, Z., 1982, On the stability of isoindole-type fluorophores derived fromo-phthalaldehyde,Anal. Lett. 15, 1393–1410.
Olson, T. M. and Hoffman, M. R., 1986, Kinetics and mechanism of S(IV)-aldehyde adduct formation, Presented before the Div. of Environ. Chem., ACS, Anaheim, Ca.
Rubinson, K. A., 1987,Chemical Analysis, Little, Brown, Boston, MA.
Rapsomanikis, S., Wake, M., Kitto, A. M. N., and Harrison, R. M., 1990, Analysis of atmospheric ammonia and particulate ammonium by a sensitive fluorescence method,Environ. Sci. Technol. 22, 948–952.
Stobaugh, J. F., Repta, A. J., Sternson, L. A., and Garren, K. W., 1983, Factors affecting the stability of fluorescent isoindoles derived from reaction ofo-phthalaldehyde and hydroxyaldythiols with primary amines,Anal. Biochem. 135, 495–504.
Thornton, D. C., Bandy, A. R., and Driedger, A. R., 1988, Sulfur dioxide over the western Atlantic Ocean,Global Biogeochem. Cycles 1, 317–328.
Thornton, D. C., Driedger, A. R. III, and Bandy, A. R., 1986, Determination of part-per-trillion levels of sulfur dioxide in humid air,Anal. Chem. 58, 2688–2691.
Wong, O. S., Sternson, L. A., and Schowen, R. L., 1985, Reaction ofo-phthalaldehyde with alanine and thiols: Kinetics and mechanism,J. Am. Chem. Soc. 107, 6421–6422.
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Saltzman, E.S., Yvon, S.A. & Matrai, P.A. Low-level atmospheric sulfur dioxide measurement using HPLC/fluorescence detection. J Atmos Chem 17, 73–90 (1993). https://doi.org/10.1007/BF00699115
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DOI: https://doi.org/10.1007/BF00699115