Fluorescence excitation–emission matrix combined with regional integration analysis to characterize the composition and transformation of humic and fulvic acids from landfill at different stabilization stages

Fluorescence excitation–emission matrix spectroscopy (EEMs) combined with fluorescence regional integration (FRI) analysis was used to investigate the composition and transformation of humic acid (HA) and fulvic acid (FA) from landfill. The EEMs of HAs at different landfill ages were characterized by two typical fluorescence chromophores with Ex/Em pairs at Ex = 420–470 nm/Em = 490–530 nm and Ex = 345–375 nm/Em = 450–465 nm. EEMs of FA were featured by other two distinctly different fluorophores with Ex/Em pairs at Ex = 315–335 nm/Em = 420–440 nm and Ex = 255–275 nm/Em = 425–455 nm. The results show that HA extracted from the refuse disposed in the year of 1989 was formed by connecting small-condensed aromatic structures with protein-like chains. Compared with HA extracted from the refuse disposed in the year of 1992, HA extracted from the refuse of 1996 had a higher fluorescence intensity and lower r(B,A) (the ratio of the fluorescence intensities of peak B and peak A) value. It contained low molar mass components, low aromatic condensation degree, and more easily oxidized substituents. This indicates that the landfill time strongly affects the EEMs characteristics of HA, and that the humification degree of HA increases with the landfill time. A red shift to a longer wavelength region and an increase of fluorescence intensity were observed when the concentration of HA was increased, suggesting that concentration had a great influence on the fluorescence characteristics of HAs. pH (2–12) also had significant effects on the fluorescence intensity, although it exerted no effect on the peak position of fluorescence of HA and FA. The results of FRI show that increasing concentration lead to more interactions among various structure components and that small molecular weight units tend to aggregate or be masked into more complicated and larger structures. The pH influence on the fluorescence intensity of HA seems mainly through molecular configuration, while the fluorescence intensity change with pH may be due to various substituents of FA.

► Concentration increase causes interaction between different components of HA and FA.
► pH influence the fluorescence intensity of HA mainly through molecular configuration.
► The fluorescence intensity change with pH may be due to various substituents of FA.
► The humification degree of HA increases with the landfill time.