Pyrolysis of humic acids from digested and composted sewage sludge

Humic acids (HAs) were extracted from four digested sewage sludge samples composted for four months, one, two and four years. HAs were pyrolyzed at three different temperatures applying both conventional and in situ methylation (ISM) pyrolysis. The pyrolysates were analyzed using gas chromatography-mass spectrometry (GC/MS). Derivatization (ISM) and pyrolysis temperature had dramatic effects on the composition and relative amounts of the pyrolysates. Among the derivatized HA fragments aliphatic compounds prevailed under all the pyrolysis conditions tested. Aromatic substances consisting mainly of guaiacyl-type compounds were detected in higher abundances only at elevated temperatures. Without ISM the contribution of aromatic structures to the total pyrogram was considerably greater than that of the aliphatics. Increase of the pyrolysis temperature from 450 degrees C to 600 degrees C had smaller effect on the proportions and composition of the compounds studied than increase from 350 degrees C to 450 degrees C.

Pyrolysis-GC-MS and CuO-oxidation-HPLC in the characterization of HMMs from sediments and surface waters downstream of a pulp mill.

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.

Characterization of the humic material formed by composting of domestic and industrial biowastes. Part 1. HPLC of the cupric oxide oxidation products from humic acids.

The changes induced by humification of anaerobically digested sewage sludge, source separated biowaste, and pulp mill biosludge were determined by extracting the fractions of bitumen and humic and fulvic acids from the samples of fresh and humified composts. In all cases, a distinct decrease in the amount of bitumen could be detected during humification. The amount of humic acids increased in sewage sludge and biowaste samples, but decreased in pulp mill biosludge sample during humification. The humic acids were degraded by CuO oxidation and the phenolic degradation products were analysed by reversed-phase high-performance liquid chromatography. The yield of these aromatic degradation products was in the range 0.9-2.0% for each sample. The main phenolic degradation products were 4-hydroxybenzoic acid, vanillic acid, 4-hydroxybenzaldehyde, vanillin, syringaldehyde, and acetovanillone. Two lignin dimers, dehydrodivanillin and dehydrodiacetovanillone, were also identified.