Determination of Dynamic Metal Complexes and their Diffusion Coefficients in the Presence of Different Humic Substances by Combining Two Analytical Techniques

Abstract

The combined use of a competing ligand exchange (CLE) method and a diffusive gradient in thin films (DGT) technique in a quasi-labile system provides a better understanding of dynamic metal (Cu and Ni) complexes in the presence of humic substances of different origins. The CLE and DGT techniques provide total labile (dynamic) metal complexes (Cu and Ni) and their dissociation rate constants in environmental systems. DGT was found to estimate lower concentrations of labile metal complexes than CLE. These discrepancies were caused by diffusion controlled metal flux (towards the binding resin gel) in the diffusive gel of DGT. The interactions of Cu and Ni with humic acids are stronger than their interactions with fulvic acid and natural organic matter. Changes in the lability of Ni and Cu complexes (complexed with humic substances of different origins) with the changing analytical detection window indicate that the complexes of these metals were formed with different binding sites with diverse binding energies in the humic substances. The combination of these two techniques was found to be very useful in determining diffusion coefficients of labile metal-humate complexes in quasi-labile systems. The values of diffusion coefficients of labile Ni and Cu complexes determined in this study are in good agreement with limited results from the literature. This finding is novel and can be very useful in further improving our understanding of the metal-humate interactions in natural environments.

Keywords:

• Cu speciation
• DGT and CLE
• Diffusion coefficient
• Humic substances
• Ni speciation

ACKNOWLEDGMENTS

P. Chakraborty is thankful to the Director, NIO, Goa for his encouragement and support.

Notes

SAHA, soil humic acid from Sigma Aldrich; NAHA, Nordic aquatic humic acid; NAFA, Nordic aquatic fulvic acid; SRNOM, Suwanee River natural organic matter.

All the speciation parameters are reported as their mean ± standard deviation.

SAHA, soil humic acid from Sigma Aldrich; NAHA, Nordic aquatic humic acid; NAFA, Nordic aquatic fulvic acid; SRNOM, Suwanee River natural organic matter.

All the speciation parameters are reported as their mean ± standard deviation.

SAHA, soil humic acid from Sigma Aldrich; NAHA, Nordic aquatic humic acid; NAFA, Nordic aquatic fulvic acid; SRNOM, Suwanee River natural organic matter.

Flow Field-Flow Fractionation (FlFFF); Fluorescence Correlation Spectroscopy (FCS); Pulsed Field Gradient-NMR (PFG-NMR); AUC, analytical ultracentrifugation; PCS, photon correlation spectroscopy; SAHA, soil humic acid from Sigma Aldrich; NAHA, Nordic aquatic humic acid; NAFA, Nordic aquatic fulvic acid; SRNOM, Suwanee River natural organic matter; HA, Humic Acid; FA, Fulvic Acid; NOM, Natural Organic Matter.