Fluorescence fingerprint of fulvic and humic acids from varied origins as viewed by single-scan and excitation/emission matrix techniques

Excitation/emission matrix (EEM), single-scan excitation and synchronous fluorescence spectra of a series of FA and HA from distinct environments are presented. The EEM plots show at least four spectral features whose corresponding Ex/Em pairs relate to the alpha', alpha, beta and gamma (or delta) fluorophores previously found in natural waters spectra. The alpha' and alpha peaks, which identify typical humic-like components, are present in all samples, independently of the organic matter (OM) source. In FA, their Ex/Em pairs are approximately 260 nm/460 nm and approximately 310 nm/440 nm, respectively. In HA their excitation and emission maxima are red-shifted, the corresponding Ex/Em pairs being located at approximately 265 nm/525 nm and approximately 360 nm/520 nm, respectively. The appearance of beta and gamma (or delta) peaks is dependent both on the OM origin and on HS aging. The former (Ex/Em approximately 320 nm/430 nm), that has been associated with the incidence of marine humic-like material, is present only in a few marine and estuarine HA. It emerges as a shoulder on the alpha peak and its detection is dependent on a balance between its magnitude and the magnitude and emission maxima location of the alpha peak. The gamma (or delta) peak (Ex/Em approximately 275 nm/315 nm in FA, and approximately 275 nm/330 nm in HA), on the other hand, is better visualized in FA than in HA diagrams. It has typical protein-, mainly tryptophan-like, fluorescence properties and appears with varied significance in a few marine and estuarine samples being hardly detected in samples from exclusively terrestrial environments. It is also shown in this study that with selected lambda(ex), lambda(em) and (delta)(lambda) values, regular emission, excitation and synchronous spectra can, together, provide a good picture of the OM sources and aging for extracted HS.