Multi-method characterization of DOM from the Turia river (Spain)

Water concentrates from Turia river (1.5 mg L⁻¹ total organic C) obtained by nanofiltration (membrane mass cut-off 90 Da) were fractioned by non-ionic Amberlite resins (DAX8 and XAD4) to afford three samples termed as hydrophobic acid (50%), transphilic acid (24%) and hydrophobic neutral (12%). If a nanofiltration membrane 270 Da mass cut-off is used then about 50% of dissolved organic matter is not retained. These three fractions were characterized by analytical and spectroscopic techniques (¹H NMR, MALDI–TOF-MS, ESI–API-MS, ESI–MS/MS). Overall, these data are compatible with the presence of oligosaccharides, oligopeptides and fatty acids as the main components of dissolved organic matter. Particularly revealing was the information from MALDI–TOF-MS and ESI–MS/MS where series of compounds differing in the number of hexose units were identified. The three fractions have many spectroscopic similarities and, particularly the hydrophobic and transphilic ones, are really almost identical. This similarity in the fraction composition shows that the conventional fractionation procedure is inefficient as a standard general method for separation of different compound types. The composition of dissolved organic matter was confirmed, and some individual organic compounds identified, by GC–MS analysis of the silylated derivatives obtained by reacting the fractions with a mixture of N,O-bis(trimethylsilyl)trifluoroacetamide with trimethylchlorosilane (10%). Thus, rather surprisingly, the dissolved organic matter of this natural raw water is predominantly composed of a relatively simple mixture of a few types of compounds with molecular weights well below 1100 Da (about six hexose units). These results, particularly the absence of detectable amounts of high molecular weight humic acids and low molecular weight phenolic compounds indicates that trihalomethanes formed in the water disinfection process by Cl₂ really derive from oligosaccharides and oligopeptides. Also, the data suggests alternative strategies to effect a more efficient fractionation of the dissolved organic matter.