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Peer-reviewedCC BYEnvironmental science & technology

Optical and Photochemical Properties of Suwannee River Natural Organic Matter Fractions Generated by Preparative Free Flow Electrophoresis.

  • Garrett McKay1
  • Kai Cheng1
  • András Gáspár2
  • Mourad Harir2,3
  • Philippe Schmitt-Kopplin2,3
  • Norbert Hertkorn2,4
  • Ronald Benner5
  • Karl Kaiser6,7
7 affiliations
  1. 1Zachry Department of Civil & Environmental Engineering, Texas A&M University, College Station, Texas77843, United States.
  2. 2Research Unit Analytical Biogeochemistry, Helmholtz Munich , Neuherberg85764, Germany.
  3. 3Technical University of Munich, Chair of Analytical Food Chemistry, Freising85354, Germany.
  4. 4Department of Thematic Studies-Environmental Change, Linköping University, LinköpingSE 581 83, Sweden.
  5. 5Department of Biological Sciences, University of South Carolina, Columbia, South Carolina29208, United States.
  6. 6Department of Marine and Coastal Environmental Sciences, Texas A&M University, Galveston, Texas77554, United States.
  7. 7Department of Oceanography, Texas A&M University, College Station, Texas77843, United States.
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Abstract

Fractionation of dissolved organic matter (DOM) has been used for decades to simplify the challenging task of bulk sample characterization and to gain insight into the structural features governing DOM reactivity. Here, we used preparative free-flow electrophoresis (PFFE), which separates molecules based on their charge-to-size ratio, to separate Suwannee River natural organic matter (SRNOM) into fractions with varying electrophoretic mobility. Optical and photochemical data of the fractions were paired with extensive analytical characterization. The least electrophoretically mobile fraction had the lowest number-average molecular weight (Mn), aromaticity, and specific ultraviolet absorbance (SUVA254), while showing the largest quantum yields of fluorescence as well as singlet oxygen and hydroxyl radical formation. Structure-activity relationships for the fractions, which exhibited substantial differences in mobility, aromaticity, and Mn did not follow the conventional trends observed in size-based DOM fractionation studies (e.g., SUVA254 ∝ aromaticity). These findings highlight the role of charge and structural differences in driving optical and photochemical properties apart from bulk aromaticity and Mn. The distribution of absorbance, the sum of vanillyl and syringyl phenols, and DIOHBA (3,5-dihydroxybenzoic acid) indicates that the most electrophoretically mobile fractions with the highest absorbance are dominated by DIOHBA, a phenol monomer derived from tannins and flavonoids, rather than lignin. DIOHBA was inversely related to the fluorescence index and β/α. Overall, these results provide insight into SRNOM photophysics and highlight the utility of PFFE as a tool for resolving DOM structure-reactivity relationships.

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Cite

BibTeXRIS
BibTeX
@article{mckay2026optical,
  title = {{Optical and Photochemical Properties of Suwannee River Natural Organic Matter Fractions Generated by Preparative Free Flow Electrophoresis.}},
  author = {Garrett McKay and Kai Cheng and András Gáspár and Mourad Harir and Philippe Schmitt-Kopplin and Norbert Hertkorn and Ronald Benner and Karl Kaiser},
  journal = {Environmental science \& technology},
  year = {2026},
  month = oct,
  doi = {10.1021/acs.est.6c07200},
  url = {https://europepmc.org/article/MED/42917027},
  note = {CC BY},
}
RIS
TY  - JOUR
TI  - Optical and Photochemical Properties of Suwannee River Natural Organic Matter Fractions Generated by Preparative Free Flow Electrophoresis.
AU  - Garrett McKay
AU  - Kai Cheng
AU  - András Gáspár
AU  - Mourad Harir
AU  - Philippe Schmitt-Kopplin
AU  - Norbert Hertkorn
AU  - Ronald Benner
AU  - Karl Kaiser
PY  - 2026
DA  - 2026/10/01
JO  - Environmental science & technology
DO  - 10.1021/acs.est.6c07200
UR  - https://europepmc.org/article/MED/42917027
AB  - Fractionation of dissolved organic matter (DOM) has been used for decades to simplify the challenging task of bulk sample characterization and to gain insight into the structural features governing DOM reactivity. Here, we used preparative free-flow electrophoresis (PFFE), which separates molecules based on their charge-to-size ratio, to separate Suwannee River natural organic matter (SRNOM) into fractions with varying electrophoretic mobility. Optical and photochemical data of the fractions were paired with extensive analytical characterization. The least electrophoretically mobile fraction had the lowest number-average molecular weight (Mn), aromaticity, and specific ultraviolet absorbance (SUVA254), while showing the largest quantum yields of fluorescence as well as singlet oxygen and hydroxyl radical formation. Structure-activity relationships for the fractions, which exhibited substantial differences in mobility, aromaticity, and Mn did not follow the conventional trends observed in size-based DOM fractionation studies (e.g., SUVA254 ∝ aromaticity). These findings highlight the role of charge and structural differences in driving optical and photochemical properties apart from bulk aromaticity and Mn. The distribution of absorbance, the sum of vanillyl and syringyl phenols, and DIOHBA (3,5-dihydroxybenzoic acid) indicates that the most electrophoretically mobile fractions with the highest absorbance are dominated by DIOHBA, a phenol monomer derived from tannins and flavonoids, rather than lignin. DIOHBA was inversely related to the fluorescence index and β/α. Overall, these results provide insight into SRNOM photophysics and highlight the utility of PFFE as a tool for resolving DOM structure-reactivity relationships.
SN  - 0013-936X
SN  - 1520-5851
ER  -