High molecular mass fractions of lignin and humic compounds in sediments and waters downstream of a pulp mill were characterized applying pyrolysis-gas chromatography-mass spectrometry. The results were compared to those obtained using reversed phase HPLC on the cupric oxide oxidation products. The chromatographic data of both pyrolysis and cupric oxide oxidation were also subjected to the principal component analysis (PCA). The sediment samples and fractions obtained by ultrafiltration of river water samples were freeze dried prior to characterization. The sediment samples were also extracted using 2 M sodium hydroxide solution. The extracts were ultrafiltrated, freeze dried and compared to the freeze dried original sediments using the procedures mentioned above. The amounts of HMMs obtained from the sediments ranged from 62 mg to 97 mg per one gram of sediment. Gel permeation chromatography was applied to samples obtained from sediments by extraction with tetrahydrofuran. The weight average molecular weights of these fractions were in the range of 1500-2300 amu.