Molecular characterization of effluent organic matter identified by ultrahigh resolution mass spectrometry

Effluent dissolved organic matter (EfOM) collected from the secondary-treated wastewater of the Orange County Sanitation District (OCSD) located in Fountain Valley, California, USA was compared to natural organic matter collected from the Suwannee River (SRNOM), Florida using ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Furthermore, the two different treatment processes at OCSD, activated sludge and trickling filter, were separately investigated. The blend of these two effluents was further evaluated after it had passed through the microfiltration process of the Advanced Water Purification Facility (AWPF) at Orange County Water District (OCWD). EfOM contained 872 different m/z peaks that were unambiguously assigned to exact molecular formulae containing a single sulfur atom and carbon, hydrogen and oxygen atoms (CHOS formulae). In contrast, the SRNOM sample only contained 152 CHOS formulae. The trend in CHO molecular compositions was opposite with 2500 CHO formulae assigned for SRNOM but only about 1000 for EfOM. The CHOS-derived mass peaks with highest abundances in EfOM could be attributed to surfactants such as linear alkyl benzene sulfonates (LAS), their co-products dialkyl tetralin sulfonates (DATS) and their biodegraded metabolites such as sulfophenyl carboxylic acids (SPC). The differences between the treatments were found minor with greater differences between sampling dates than treatment methods used.

► For the first time, ultrahigh resolution mass spectrometry was used in conjunction with NMR to characterize the complex mixture of effluent organic matter.
► Ultrahigh resolution mass spectrometry showed the substantial differences between natural and effluent organic matter and demonstrated that effluent organic matter contained over 1000 different sulfur containing molecular formulae.
► Linear alkyl benzene sulfonates and its co-products and metabolites showed the highest abundances in the FT-MS data of effluent organic matter and this finding was also supported by 2-D NMR and MS-MS analyses.