Characterization of marine and terrestrial DOM in seawater using excitation emission matrix spectroscopy

High-resolution fluorescence spectroscopy was used to characterize dissolved organic matter (DOM) in concentrated and unconcentrated water samples from a wide variety of freshwater, coastal and marine environments. Several types of fluorescent signals were observed, including humic-like, tyrosine-like, and tryptophan-like. Humic-like fluorescence consisted of two peaks, one stimulated by UV excitation (peak A) and one by visible excitation (peak C). For all samples, the positions of both excitation and emission maxima for peak C were dependent upon wavelength of observation, with a shift towards longer wavelength emission maximum at longer excitation wavelength and longer wavelength excitation maximum at longer emission wavelength. A trend was observed in the position of wavelength-independent maximum fluorescence (Ex(max)/Em(max)) for peak C, with maximum at shorter excitation and emission wavelengths for marine samples than for freshwater samples. Mean positions of these maxima were: rivers Ex(max)/Em(max) = 340/448 nm; coastal water Ex(max)/Em(max) = 342/442 nm; marine shallow transitional Ex(max)/Em(max) = 310/423 nm; marine shallow eutrophic Ex(max)/Em(max) = 299/389 nm; and marine deep Ex(max)/Em(max) = 340/438 nm. Differences suggest that the humic material in marine surface waters is chemically different from humic material in the other environments sampled. These results explain previous conflicting reports regarding fluorescence properties of DOM from natural waters and also provide a means of distinguishing between water mass sources in the ocean.