Characterization of spectral responses of humic substances upon UV irradiation using two-dimensional correlation spectroscopy

The spectral responses of a leaf litter derived humic substance (LLHS) and Suwannee River fulvic acid (SRFA) upon ultraviolet (UV) A irradiation were characterized using two-dimensional correlation spectroscopy (2D-COS) based on the absorption and the synchronous fluorescence spectra at different irradiation times. A 12 day irradiation on the humic substances (HS) resulted in higher reduction of the absorbance relative to the dissolved organic carbon concentration, suggesting that aromatic chromophores were preferentially oxidized and/or non UV-absorbing compounds were generated by the photobleaching. Synchronous fluorescence spectra revealed the preferential removal of fulvic-like and humiclike fluorophores and delayed response of protein-like fluorescence upon the irradiation. The spectral features at long wavelengths (>430 nm) appear to be affected by intra-molecular interactions of the individual chromophores associated with shorter wavelengths. Absorption-based 2D-COS demonstrated that there are three types of absorption bands for the two HS, which changed sequentially in the order of 290-400 nm 200-250 nm 250-290 nm. In addition, two or three distinctive fluorescence bands in response to the irradiation were identified from 2D-COS. The sequential orders and the associated wavelength bands were possibly explained by the irradiation wavelengths and the differences between direct and indirect photochemical reactions. The interpretation of the 2D-COS results was very consistent with the kinetic rate constants individually calculated at several discrete wavelengths. Our study demonstrated that 2D-COS could be used as a powerful tool in identifying distinctive bands of HS that have dissimilar behavior and the associated sequential orders by visualizing the spectral changes at continuous wavelengths. (C) 2011 Elsevier Ltd. All rights reserved.