Comparison of Mn2+, Co2+, and Cu2+ binding to fulvic acid as measured by fluorescence quenching

1983 ◽  
Vol 61 (7) ◽  
pp. 1505-1509 ◽  
Author(s):  
David K. Ryan ◽  
Carl P. Thompson ◽  
James H. Weber

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.

2012 ◽  
Vol 2012 ◽  
pp. 1-9 ◽  
Author(s):  
Fengsong Zhang ◽  
Yanxia Li ◽  
Xiong Xiong ◽  
Ming Yang ◽  
Wei Li

The agricultural application of raw animal manure introduces large amounts of dissolved organic matter (DOM) into soil and would increase transport of heavy metals such as Cu which are widely present in animal manure. The purpose of this research was to evaluate the evolution of DOM from pig and cattle manures during composting through excitation-emission matrix (EEM) fluorescence spectroscopy and the binding ability of DOM toward copper (Cu) ions with the aid of fluorescence quenching titration. The excitation-emission matrix spectra indicated that tyrosine-like, tryptophan-like, and soluble microbial byproduct-like fluorescence decreased significantly, while humic-like and fulvic-like fluorescence increased and became the main peaks in composted manure DOM. Fluorescence quenching titration showed that the complexing capacities of pig and cattle manure DOM decreased after composting. Correlation analysis confirmed that complexing capacity of DOM positively and significantly correlates with tyrosine-like and soluble microbial byproduct-like materials which mostly degraded after composting. These results would suggest that the ability of manure DOM to complex with Cu is inhibited as a result of reduced protein-like materials after composting.


1974 ◽  
Vol 54 (4) ◽  
pp. 413-417 ◽  
Author(s):  
VENGHUOT CHEAM ◽  
DONALD S. GAMBLE

Conditional stability constants of some metal fulvate complexes have been determined at 25 C using specific ion electrodes. In aqueous 0.1 M NaNO3, solution, the log K values are: 4.86 and 5.08 at pH 3 and 4 for mercury complexes; 3.04 and 3.64 at pH 4.9 and 5.95 for cadmium complexes; and 3.22, 3.72, and 4.35 at pH 3, 4, and 5 for copper complexes. In 0.04 M NaNO3 solution, the log K value for mercury–fulvic acid system is 5.12 at pH 3.1. The order of metal affinity toward fulvic acid Hg > Cu > Cd is in general agreement with the literature for complexing of these metals with similar type donors.


2003 ◽  
Vol 57 (4) ◽  
pp. 454-460 ◽  
Author(s):  
Michael D. Hays ◽  
David K. Ryan ◽  
Stephen Pennell

In this work, a multi-wavelength model (MWM) is developed. It uses fluorescence bands in the fulvic acid (FA) spectrum that quench upon binding of inorganic Cu2+ to FA. Quenching data at pH values of 5, 6, and 7 are placed in sets, containing fluorescence measures at select wavelengths versus added copper ( CM). Intensity data of wavelength set 1 are obtained from 25 nm constant offset synchronous fluorescence spectra (SyF), in which are observed distinct peaks (λex = 415 nm, λem = 440 nm; and λex = 471 nm, λem = 496 nm). Wavelength set 2 intensity data are obtained from the FA fluorescence excitation and emission maxima (λex = 335 nm, λem = 450 nm; and λex = 471 nm, λem = 496 nm). Application of MWM shows that the multi-wavelength data sets characterize ligands of different binding strength (log Kx) and concentration ( CLx). Corresponding to pH values of 5, 6, and 7, mean and standard deviation values for wavelength set 1 are log K415/440 = 4.66 (0.12), 5.03 (0.12), and 5.05 (0.08), log K471/496 = 4.93 (0.06), 5.27 (0.11), and 5.39 (0.09), C415/440 = 3.1 (1.5), 10.9 (4.5), and 7.9 (3.9) μM, C471/496 = 14.3 (3.0), 1.7 (0.6), and 1.4 (0.5) μM. And for wavelength set 2, log K335/450 = 4.50 (0.03), 4.96 (0.27), and 5.22 (0.08), log K471/496 = 5.02 (0.04), 5.42 (0.32), and 5.71 (0.09), C335/450 = 8.8 (0.5), 21.9 (7.9), and 18.7 (0.3) μM, C471/496 = 21.0 (2.5), 7.17 (1.2), and 7.09 (0.3) μM. The ability of the 415/440 nm SyF transect to characterize the main excitation and emission maximum of FA at 335/440 nm is evaluated. Relatively low concentration values returned by the model for this transect (415/440 nm) suggest that it is not entirely illustrative of the maximum. The model predictive capability is verified at pH 6 with two fluorescing Cu2+ chelating organic compounds, L-tyrosine and salicylic acid. This test confirms that the model is capable of providing good estimates of equilibrium binding parameters from multi-wavelength measurements of a mixed ligand system.


1978 ◽  
Vol 56 (17) ◽  
pp. 2331-2336 ◽  
Author(s):  
Bill Brady ◽  
Gordon K. Pagenkopf

A soil fulvic acid bas been characterized and the complexation stability constants with cadmium have been evaluated. The average gram formula weight of the fulvic acid is 2775. Three complexes of stoichiometry CdFA, Cd2FA, and Cd3FA have been observed. The respective conditional stability constants at pH 5.7 are 105.3, 109.8, and 1014.0; at pH 6.7 they are 105.6, 1010.6, and 1015.5; and at pH 7.7 they are 106.0, 1010.7, and 1015.4.


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