Advanced Gel Electrophoresis Techniques Reveal Heterogeneity of Humic Acids Based on Molecular Weight Distributions of Kinetically Inert Cu2+-Humate Complexes

Humic acids (HAs) play important roles for the fate of metal ions in the environment. Most chemical speciation models involving HAs assume heterogeneous metal ion binding. However, these models also assume that the binding affinities of metal ions with HAs are the same regardless of the molecular we...

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Bibliographic Details
Published in:Environmental science & technology 2019-12, Vol.53 (24), p.14507-14515
Main Authors: Marumo, Kazuki, Matsumoto, Atsumasa, Nakano, Sumika, Shibukawa, Masami, Saito, Takumi, Haraga, Tomoko, Saito, Shingo
Format: Article
Language:English
Subjects:
Affinity
Binding
Chemical speciation
Contaminants
Copper
Coupling (molecular)
Electrophoresis
Emission analysis
Environment models
Factor analysis
Fluorescence
Gel electrophoresis
Heterogeneity
Humic acids
Ions
Metal ions
Molecular weight
Organic chemistry
Polyacrylamide
Speciation
Spectrometry
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Summary:Humic acids (HAs) play important roles for the fate of metal ions in the environment. Most chemical speciation models involving HAs assume heterogeneous metal ion binding. However, these models also assume that the binding affinities of metal ions with HAs are the same regardless of the molecular weight (MW) ranges of the HAs involved. Here, we develop new polyacrylamide gel electrophoresis (PAGE) techniques to investigate the MW distributions of HAs with strongly complexed Cu2+ ions. By combining contaminant metal-free and high-resolution PAGE for HAs, this work was able to provide accurate MW distributions for the complexed metal ions. The MW distribution of Cu2+ binding ability per quantity of HA indicates that strong metal-binding moieties in HAs are heterogeneous in terms of MW. Coupling of the PAGE techniques with UV–vis and excitation–emission matrix (EEM) spectrometry-parallel factor analysis (PARAFAC) methods revealed new insights into kinetically inert interactions between HAs and Cu2+ ions. By this method, we found that the protein-like fluorescence components in the high- and low-MW regions cooperatively responded through Cu2+ binding. Thus, the advanced gel electrophoresis techniques developed herein are able to shed new light on the heterogeneity of metal binding affinities of HAs in terms of MW.
ISSN:0013-936X
1520-5851
DOI:10.1021/acs.est.9b05169