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Outline
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Using Fluorescence, Size Exclusion Chromatography, and Ultraviolet Spectrometry to Characterize Changes in Natural Organic Matter During Water Treatment
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Disinfection/Oxidation
  • Inactivates pathogenic microorganisms
  • As an oxidant
    • Taste/Odor control
    • Removal of color- Natural organic matter (NOM)
    • Oxidation of inorganic cpds
  • Disadvantages
    • Formation of disinfection by-products (DBPs) Human and ecological health concern
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Conventional Water Treatment
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Natural Organic Matter
  • Humic substances- produced within natural water and sediments by natural processes
  • Heterogeneous-Aromatics/Aliphatics
  • Nonhumic substances- carbohydrates, lipids, amino acids/proteins.
  • Location and climate drives NOM characteristics


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NOM Characterization
  • Total organic carbon (TOC)
  • Ultraviolet spectroscopy
  • Fluorescence
  • Size Exclusion Chromatography
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Fluorescence
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Size Exclusion Chromatography
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Problem Statement
  • The character of NOM is being changed with oxidant addition
    • DBPs
    • biofoulants
  • Each oxidant will possibly offer a unique fingerprint signature.
    • Relative to the oxidant demand.
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Study Objectives
  • Evaluate the use of SEC and fluorescence for characterizing NOM changes after oxidation
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Approach
  • Bench-scaled jar testing to simulate water treatment.
  • Coagulant
    • Alum- 100 mg/L
  • Four represented oxidants
  • KMnO4- 1.4 mg/L
  • Cl2- 3.0 mg/L
  • ClO2 – 3.5 mg/L
  • O3- 0.5:1 TOC
  •  2 water matrices


  • Rapid Mix:
    • 250 rpms for 3 min
  • Floccuation taper 1:
    • 30 rpms for 10 min.
  • Flocculation taper 2:
    • 20 rpms for 10 min
  • Flocculation taper 3:
    • 10 rpms for 10 min
  • Sedimentation:
    • 0 rpms for 90 min
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Mt. Orab Sample Matrix
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NOM Fluorescence
  • All EEMs revealed two fluorophores, characteristic of fulvic acids. Occurring within ~425-450 nm emission spectra (depending on oxidation)
  • According to literature review, microbial derived NOM has lower emission maxima than terrestrial.
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Mt. Orab Coagulation/Sedimentation
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Mt. Orab Summary
  • Discernable order in oxidative effects on fluorescence
    • Ozone-Best (‘Knocked the Snot out of it’)
    • ClO2- Very Good
    • Cl2- Good
    • KMnO4-Not as great as the rest
  • Coagulation/Sedimentation played substantial role in NOM removal.
  • Same order observed in Settled water samples
  • SEC is a less sensitive measure of oxidative effects.


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Tampa Bay Sample Matrix
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"What about Ultraviolet spectroscopy?"
  • What about Ultraviolet spectroscopy?
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Ultraviolet Spectrometry/TOC of TB
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TB Summary
  • Same patternized order of oxidation observed
  • Coagulation/Flocculation removed greater percentage of TOC in TB matrix
  • Small difference in fluorophore emission in KMnO4 sample compared to no oxidant
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Conclusions
  • Coagulation/Flocculation/Sedimentation removed a substantial amount of NOM seen in SEC, UV and Fluorescence results
  • Implication for moving point of disinfectant/oxidant in water treatment
    • NOM availability during treatment process
  • Dosing oxidants at post-sedimentation yielded enhanced oxidation of NOM
    • Greatest reduction fluorescence seen in ClO2 and O3
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Comparing Raw and Settled ClO2 Treated Waters
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"Preliminary data suggests that SEC..."
  • Preliminary data suggests that SEC may be problematic for correlation to Fluorescence EEM.
    • Eluent, mass balance, hydrophobic interactions, lag. (Mt. Orab)
  • Preliminary data also suggests that UV can serve a good oxidative monitoring instrument. Detects all doubles bonds, not as selective.
  • Pilot run



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Barely Scratching the Surface
  • Peak signatures are not fully understood and identified.
    • Need to differentiate b/w humic and nonhumic cpds.
  • The identification of functional groups of NOM can help better understand the transformation NOM oxidation undergoes.
  • Quantification of remaining NOM, transformed NOM/DPB yield needs to be addressed.