MODIFIED INDIGO METHOD FOR GASEOUS AND AQUEOUS OZONE ANALYSES

The indigo method developed by Bader and Hoigne for aqueous ozone analysis was modified to allow for both gaseous and aqueous ozone determination. Gas or water samples were extracted with a gas-tight syringe containing a known volume of indigo reagent. The modified procedure provided a more consistent basis for gaseous and aqueous ozone determination allowing for more accurate ozone mass balance calculations. Direct gaseous ozone UV absorbance with molar absorptivity of 3,000 M(-1)cm(-1) at 258 nm was used as primary standard to determine the molar absorptivity of the indigo reagent. The molar absorptivity of indigo reagent, assuming a 1:1 stoichiometric ratio for the reaction between indigo and ozone, was determined to be 23,150 +/- 80 M(-1)cm(-1), or approximately 16 percent higher than that of 20,000 M(-1)cm(-1) suggested by Bader and Hoigne. An independently calibrated membrane-electrode ozone monitor showed good correlation with indigo method results using the molar absorptivity value determined in this study. The apparent molar absorptivity of aqueous ozone at the wavelength of 258 nm measured by the modified indigo method increased from 2,400 to 3,600 M(-1)cm(-1) in the investigated ozone concentration range of 0.4 to 11.0 mg/L. This variation might have been caused by the inherent interference of unidentified ozone byproducts, which presence was supported with scanning spectra in the wavelength range of 200 to 300 nm.