Micro-diffuse reflectance Fourier transform infrared (DRIFT) and matrix isolation (MI) Fourier transform infrared spectra of the 22 tetrachlorodibenzodioxin (TCDD) isomers have been recorded. The DRIFT and MI techniques required about four minutes and one-half minute, respectively, of signal averaging to produce high signal-to-noise (S/N) spectra on low-nanogram-level samples. Spectral subtraction was employed to remove DRIFT solvent impurity interferences. The validity of the DRIFT subtraction technique was demonstrated by comparison of the corrected DRIFT, with the chromatographically pure, MI spectra. The reproducibility of DRIFT frequencies and intensities was tested by comparison of the 1,3,7,8-TCDD spectra from samples independently prepared by two analysts. The MI technique successfully identified 2,3,7,8 in environmental samples. MI spectral subtraction was applied to one sample to remove a coeluting impurity. The DRIFT and MI spectral techniques, used in conjunction with modern chromatographic separation and spectral subtraction, are very promising for the on-line or off-line differentiation of low-level toxic isomeric compounds.

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