Method for the differentiation of leaf litter extracts and study of their interaction with Cu(II) by molecular fluorescence

Abstract

Six leaf litter extracts (LLE) (eucalyptus (Eucaliptus globulus), fern (Pteridium aquilinium), oak (Quercus robur), chestnut (Castanea sátiva), laurel (Laurus nobilis), and ulex (Ulex europoeus) canopies) were isolated following an extraction procedure similar to that used for fulvic acids (FA) and were characterized by elemental analysis and UV-Vis, FT-IR, and synchronous molecular fluorescence (SyF) spectroscopies. Moreover, information about their interaction with the Cu(II) ion in aqueous solution (100 mg yL of LLE in 0.1 M KNO3 at pH = 6) was obtained from the measurement of SyF spectra at increasing concentrations of Cu(II). These spectral sets were treated by a self-modeling mixture analysis method (SIMPLISMA) to obtain improved quenching profiles to be used in the estimation by the method of Ryan and Weber of the conditional stability constants (Kc), concentration of binding sites, and percentage of fluorescent binding sites accessible for complexation. For comparison purposes, two samples of FA extracted from two horizons of an oak forest soil (0-5 cm and 5-15 cm) were also studied. The spectroscopic data obtained for LLE and FA were different. The results suggest that LLE are characterized by relatively high concentrations of individualized simple molecules and include reactive structures (alkene and protein residues). The ratio of aliphatic yaromatic structures was higher in LLE than for FA. Both LLE and soil FA form stable complexes with Cu(II), but the logarithm of the conditional stability constant of the 1:1 complexes is larger for LLE (about 5) than for the soil FA (about 4.5).Key words: leaf litter extracts, soil fulvic acids, synchronous fluorescence, Cu(II) complexation, SIMPLISMA, spectral pattern recognition.

Study of the acid–base properties of fulvic acid-like substances extracted from senescent leaves of eucalyptus and oak

“…This is consistent with the findings of Esteves da Silva et al [20] in a similar study. The carboxylic group content of each sample was lower than the normal values for soil fulvic acids and corresponded to the upper limit of the range of values usually assigned to humic acids [21].…”

“…The infrared spectra of the OEFA and EEFA show a characteristic band at 1512 cm -1 which does not appear in the soil sample. The same band was found by Wershaw and Kennedy [6] and Esteves da Silva et al [20] for other FA extracted from senescent leaves, and is considered to provide evidence for the presence of parasubstituted phenyl rings, such as those in gallotannins. The charge-pH curves obtained for both samples are parallel throughout the pH range (Fig.…”