Highly sensitive and selective FIA flow injection analysis procedures for the determination of sulfite/hydrogen sultite/sulfur dioxide were developed on the basis of an in situ-generated o-phthalaldehyde (OPA)/ammonium reagent and fluorescence detection. The highest sensitivity was achieved at an excitation wavelength of 330 nm, an emission wavelength of 390 nm, and at pH 6.5. Sulfite concentrations between 2.5 nM and 5 muM can be determined with relative standard deviations between 10.5 and 1.0% (n = 5, confidence level alpha = 0.05) by utilization of a reagent that contains 0.2 mM OPA and 0.4 M NH4Cl in 50 mM potassium phosphate buffer. A concentration of 0.1 mM sulfite can be selectively detected in the presence of thiosulfate, thioglycolate, tetrathionate, cysteine, and ascorbate, The fluorometric sulfite detection was combined with a membrane gas diffusion step to improve the selectivity with respect to nonvolatile fluorescing substances. The total sulfite content can be quantitatively separated as sulfur dioxide into an acceptor solution before its now detection. Between 40 nM and 0.1 mM sulfite can be determined. After 1000-fold dilution, the total sulfite content can be determined in white and red wines.
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