Abstract
Three fulvic acids (fua) extracted from a Portuguese pinewood soil (dry pine needles, fual, leaf litter, fua2, and lower soil horizon, fua3) have been studied by synchronous molecular fluorescence spectroscopy (SyF) at variable pH and by potentiometric pH titrations. The number of macroscopic acid-base systems and their p K a s were calculated by analysis of the SyF-pH hyphenated data with a self-modeling curve resolution technique (evolving factor analysis, EFA). Four macroscopic acid-base systems were detected in the fulvic acid samples (with p K a s around 3.0, 4.5, 7.0 and 9.0). The concentrations of the groups responsible for the acid-base systems were calculated by a standard non-linear least squares adjustment of pH potentiometric titration curves using the p K a values obtained by EFA. The procedure detected differences between the three fua: the concentration of carboxylic groups increased from fual to fua3 but, in contrast, the concentration of the phenolic groups decreased. These results correlate well with the expected extent of humification of the samples.
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