Structural characterization of fulvic acids, extracted from sewage sludge during composting, by thermochemolysis–gas chromatography–mass spectrometry

Abstract

Thermochemolysis coupled with gas chromatography and mass spectrometry were applied to determine the chemical structure of fulvic acids (FA) extracted from a sewage sludge and straw mixture at different steps of composting. The FA starting structures were composed mainly of mono-, di- and tri-methoxy (alkyl) benzoic acids representing lignin derivatives in an advanced stage of oxidation, as well as of methylated polyphenols and a series of fatty acids saturated C15, C16, C18, unsaturated and branched C18:1. Besides, there are many unidentified structures suspected to be N-containing compounds. During the composting process, the fate of the three structural typical monomer units of lignin was followed. The p-hydroxyphenyl units showed a strong relative decrease especially at the beginning of composting. The guiaicyl units showed a steady increase in course of composting. A relative decrease of syringyl units was noted at the beginning of composting, but they then relatively increased towards the end of composting. These changes support the formation during composting of more oxidized units. All subunits composing the fulvic acid structures have been subdivided into main five groups of similar chemical structure. The lignin-like C6–C3 subunits showed a relative decrease during composting attributed to microbial oxidation, but there was a relative increase during the intermediate step of composting related probably of an enhancing of lignin solubility. The C6–C1 subunits were reduced at the beginning of composting, which mainly attributed to the oxidation of 4-methoxybenzaldehyde to hydroquinones derivatives under the composting conditions. Although, the relative increase of these subunits (C6–C1) at the end of composting originates from oxidation of C6–C3 lignin side-chains or could be partly attributed to microbial neosynthesis. The unidentified N-containing compounds increased strongly during course of composting. The rise in the level of fatty acids at the beginning of composting is attributed to an increase of branched-chain fatty acids such as C18:1 commonly used as bacterial biomarkers. Their amounts were greatly reduced at the end of composting. Both the Shannon–Weaver and similitude indices show a relative increase in structural diversity at the start of composting conditions following the appearance of hydroquinone derivatives and unidentified nitrogen compounds in the FA network. But, the produced FA structure reaches a certain level of homogeneity at the end of composting through self-polycondensation or recombination of C6–C1 subunits and hydroquinones derivatives with N-containing compounds.