The binding of Cu2+ to soil-derived fulvic acid (SFA) measured by fluorescence quenching titration is much stronger than Co2+ and Mn2+ which are similar. The conditional stability constants from curve fitting at pH 6 are 1.1 × 105 for Cu2+, 5.1 × 103 for Co2+, and 4.2 × 103 for Mn2+. The slight advantage in strength for Co2+ over Mn2+ is also demonstrated by the binding curves at pH 6 and 7. These two metal ions not only tend to bind more weakly but also bind to fewer sites, giving complexing capacity values of about 1.5 × 10−6 M compared to 2.0 × 10−5 for Cu2+ at pH 6. This lower binding capacity may be due to outer sphere complexation that does not allow access to some sites complexed by inner sphere binding Cu2+. Scattering experiments demonstrate that Cu2+ is more effective at precipitating and aggregating SFA than Co2+ and Mn2+. Cu2+ probably neutralizes the negative charges on SFA molecules allowing larger hydrophobic aggregates to form and precipitate.
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