Characterization of organic matter in pristine and contaminated coastal marine sediments using solid-state ¹³C NMR, pyrolytic and thermochemolytic methods: A case study in the San Diego harbor area

Chemical composition of coastal marine sedimentary organic matter (S_DOM) is a function of natural and anthropogenic inputs to the system. In this study a combination of analytical techniques: ¹³C nuclear magnetic resonance (NMR), pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and tetramethylammonium hydroxide thermochemolysis-gas chromatography/mass spectrometry (TMAH thermochemolysis-GC/MS) were used to study the contribution of hydrophobic organic contaminants and terrestrial OM to the S_DOM. Sediments were collected from two sites in the San Diego Bay: Paleta Creek, which is contaminated, and Coronado Cayes, which is relatively pristine. Concentrations of polycyclic aromatic hydrocarbons (PAHs) at both sites, as determined by ultrasonically assisted lipid extraction are found to be higher in the surface layer, to generally decrease with depth, and to be present at about two orders of magnitude higher concentration at the contaminated site as compared to the pristine site. The sediment samples were partially deashed with HF/HC1 treatment before further analysis, ¹³C-NMR spectra of the Paleta Creek samples show a higher aromatic carbon content and a distinct phenolic carbon peak. This suggests a large input from terrestrial carbon (lignin). Data from both Py-GC/MS and TMAH thermochemolysis-GC/MS support this and indicate the presence of lignin-derived residues, primarily of the guaiacyl type at the contaminated site. In contrast, S_DOM at the Coronado Cayes site exhibits less terrestrial input. In general, the S_DOM resembles soil OM rather than typical marine S_DOM. Chemical analyses of the lipid-extracted, partially deashed sediments, does not reveal the presence of any PAHs.