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Pedro A. Palomino and *Treavor H. Boyer
AEESP 2011 Research and Education Conference                                                       University of Florida, Department of Environmental Engineering Sciences
         Tampa, FL July 12th, 2011                                                               *PO Box 116450, Gainesville, FL 32611 ~ (352)846-3351 ~ thboyer@ufl.edu


                           Drive                                                                                      Peak Location                                                          DOC vs. Intensity                                                                                                                                    SUVA vs. FI

                                                                                                                                                                                 3                                                                                                     10000                                         3.5                                            8
o Detailed monitoring is important in drinking water treatment,
                                                                                                                       Microbial            FI = 2.1                                                             Microbial                                                                                                                 FI
  especially for new processes like magnetic ion exchange (MIEX).                                                                                                                                                                                                                                                                                                                   7
                                                                                                                        Peaks                                                                                    Terrestrial                                                                                                           3   SUVA
o Dissolved organic carbon (DOC) and specific ultraviolet                                                                                                                       2.5
                                                                                                                                                                                                                                                                                       1000
                                                                                                                                                                                                                 DOC




                                                                                                Ichnetucknee Spring
  absorbance at 254 nm (SUVA) are measured to determine MIEX                                                                                                                                                                                                                                                                                                                        6
                                                                                                                                                                                                                                                                                                                                     2.5




                                                                                                                                                                                                                                                                                                                Fluorescence Index




                                                                                                                                                                                                                                                                                                                                                                                          SUVA (nm*L/mg C)
  treatment efficiency.                                                                                                                                                          2




                                                                                                                                                               Intensity (nm)
                                                                                                                                                                                                                                                                                                                                                                                    5




                                                                                                                                                                                                                                                                                               DOC (mg/L)
o Fluorescence spectroscopy has been shown to be an effective                                                                                                                                                                                                                          100                                             2
  technique to characterize dissolved organic matter (DOM) in                                                                                                                   1.5                                                                                                                                                                                                 4
  natural systems, but its use in drinking water applications is an
                                                                                                                                                                                                                                                                                       10                                            1.5
  active area of research.                                                                                                                                                                                                                                                                                                                                                          3
o The goal of this work is to develop improved monitoring techniques                                                                                                             1
                                                                                                                                                                                                                                                                                                                                       1
  for MIEX treatment.                                                                                                                                                                                                                                                                                                                                                               2
                                                                                                                                                                                                                                                                                       1
   1) Understand the shift in fluorescence peak location.                                                                                                                       0.5
                                                                                                                                                                                                                                                                                                                                     0.5                                            1
   2) Compare DOC to fluorescence intensity.
   3) Compare the SUVA to fluorescence index (FI).                                                                                                                               0                                                                                                     0.1                                             0                                            0




                                                                                                                                                                                                       Syn 1
                                                                                                                                                                                                                Syn 2
                                                                                                                                                                                                                          Syn 3
                                                                                                                                                                                                                                    Syn 4
                                                                                                                                                                                       SW 1
                                                                                                                                                                                               SW 2




                                                                                                                                                                                                                                              GW 1
                                                                                                                                                                                                                                                      L1
                                                                                                                                                                                                                                                            L2
                                                                                                                                                                                                                                                                  L3
                                                                                                                                                                                                                                                                        L4
                                                                                                                                                                                                                                                                              L5
                                                                                                                                                          (a)                                                           Raw Source Waters
                                                                                                                                                                                                                                                                            M: R2 = 0.54                      (a)                                       Raw Source Waters
                                                                                                                      FI = 1.6     Terrestrial Peak                                                                                                                         T: R2 = 0.15                                                                                     R2 = 0.88
                                                                                       from Suwannee River
                                                                                       IHSS Isolate of NOM




                                                                                                                                                                                 3                                                                                                 10000                                             3.5                                            9
                                                                                                                                                                                                Microbial                                                                                                                                          FI
                                                                                                                                                                                                                                                                                                                                                                                    8
                                                                                                                                                                           2.5                  Terrestrial                                                                                                                           3            SUVA
                                                                                                                                                                                                                                                                                   1000
                                                                                                                                                                                                DOC                                                                                                                                                                                 7
                                                                                                                                                                                                                                                                                                                                     2.5




                                                                                                                                                                                                                                                                                                              Fluorescence Index




                                                                                                                                                                                                                                                                                                                                                                                        SUVA (nm*L/mg C)
                                                                                                                                                                                 2                                                                                                                                                                                                  6




                                                                                                                                                                                                                                                                                              DOC (mg/L)
                                                                                                                                                       Intensity (nm)
                                                                                                                                                                                                                                                                                   100
                                                                                                                                                                                                                                                                                                                                      2                                             5
                                                                                                                                                                           1.5
                                                                                                                                                                                                                                                                                   10                                                1.5                                            4
                                                                                                                                                                                 1                                                                                                                                                                                                  3
                                                                                                                                                                                                                                                                                                                                      1
                                                                                                                                                                                                                                                                                   1                                                                                                2
                                                                                                                                                                           0.5
                                                                                                                                                                                                                                                                                                                                     0.5
 Figure 1 – Fluorescence peak location shift after MIEX treatment                           Figure 4 – Contour EEMs of fluorescence standards                                                                                                                                                                                                                                       1
                                                                                                                                                                                 0                                                                                                 0.1                                                0                                             0




                                                                                                                                                                                                      Syn 1
                                                                                                                                                                                                               Syn 2
                                                                                                                                                                                                                        Syn 3
                                                                                                                                                                                                                                  Syn 4
                                                                                                                                                                                                                                            GW 1
                                                                                                                                                                                      SW 1
                                                                                                                                                                                              SW 2




                                                                                                                                                                                                                                                     L1
                                                                                                                                                                                                                                                           L2
                                                                                                                                                                                                                                                                 L3
                                                                                                                                                                                                                                                                       L4
                                                                                                                                                                                                                                                                             L5
                                             Sampling and Analysis                                                                                       (b)                                           Treated Source Waters
                                                                                                                                                                                                                                                                        M: R2 = 0.74
                                                                                                                                                                                                                                                                        T: R2 = 0.69
                                                                                                                                                                                                                                                                                                                  (b)                              Treated Source Waters    R2 = 0.64

                                                                                                                                                       Figure 5 – DOC and fluorescence peak intensity for microbial and                                                                                       Figure 6 – SUVA and FI of both raw (a) and treated (b) samples
                                                                                                                                                       terrestrial regions of both raw (a) and treated (b) samples
                                        Syn2-4
                          Syn1         L4             o Samples collected between
                            L1            L5            February 2009 and
                                                        January 2010.
                                                                                                                                                                                                                                                                                             Impact
                        GW1               SW2
                                                      o Sample sources include
                                            SW1         landfills, surface water
    SW1: Lake Jesup                                     bodies and a groundwater                                                                       Peak Location
    SW2: St. Johns River        L2-3
                                                        aquifer. (Figure 2)                                                                                                                                                                                                                                 Fluorescence measurements could be a
    Syn1: Santa Fe River                                                                                                                               o MIEX treatment alters DOM chemistry
    Syn2-4: St. Mary’s River
                                                      o Analytical measurements
                                                                                                                                                       DOC vs. Intensity
                                                                                                                                                                                                                                                                                                            better alternative for monitoring MIEX
                                                        include: UV254, DOC, and                                                                                                                                                                                                                            treatment efficiency.
    GW1: Cedar Key GW                                   fluorescence EEM.                                                                              o Raw
    L1: Alachua SW Landfill                           o Fluorescence is the                                                                               o DOC: Synthetic < Ground < Surface < Waste
    L2-3: Polk Landfill                                                                                                                                                                                                                                                                                     Models for predicting MIEX treatment efficiency
    L4: New River Landfill
                                                        emission of light only                                                                            o Terrestrial peaks’ intensity > Microbial peaks’ intensity
                                                        during the absorption of the                                                                                                                                                                                                                        with fluorescence spectroscopy
    L5: Putnam Landfill                                                                                                                                o Treated
                                                        excitation light. (Figure 3)                                                                                                                                                                                                                        o DOC % Removal =
                                                                                                                                                          o Microbial peak intensity is better correlated to DOC
                                                                                                                                                                                                                                                                                                                     (1.24  Peak A Intensity % Removal) – 0.25
  Figure 2 – Florida Sampling Map                                                                                                                         o MIEX preferentially removes the terrestrial component
                                                                                                                                                                                                                                                                                                                  R2 = 0.93
                                                                                         Figure 3 – Jablonski Energy Diagram
                                                                                                                                                       SUVA vs. FI
                                                                                                                                                                                                                                                                                                            o SUVA % Removal =
                                                                                         (Johnson, Ian and Davidson, Michael. “Jablonski Energy        o Raw SUVA: Synthetic < Surface < Ground < Waste
                                Acknowledgements                                                                                                                                                                                                                                                                     (- 2.24 * FI % Removal) + 0.06
                                                                                         Diagram.” Microscopy Resource Center. Olympus                 o SUVA and FI are negatively correlated
      Thanks to Jennifer Apell, Troy Chasteen, Sarah Deavenport, Katherine
                                                                                         http://www.olympusmicro.com/primer/java/jablonski/jabintro/                                                                                                                                                              R2 = 0.61
      Graf, Katie Indarawis, Stephanie Ishii, Christopher Rokicki, Paul
                                                                                         index.html)
      Stevenson, and Krystal Walker for sample and data collection.

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Fluorescence as a Surrogate Measurement of MIEX Treatment Efficiency

  • 1. Pedro A. Palomino and *Treavor H. Boyer AEESP 2011 Research and Education Conference University of Florida, Department of Environmental Engineering Sciences Tampa, FL July 12th, 2011 *PO Box 116450, Gainesville, FL 32611 ~ (352)846-3351 ~ thboyer@ufl.edu Drive Peak Location DOC vs. Intensity SUVA vs. FI 3 10000 3.5 8 o Detailed monitoring is important in drinking water treatment, Microbial FI = 2.1 Microbial FI especially for new processes like magnetic ion exchange (MIEX). 7 Peaks Terrestrial 3 SUVA o Dissolved organic carbon (DOC) and specific ultraviolet 2.5 1000 DOC Ichnetucknee Spring absorbance at 254 nm (SUVA) are measured to determine MIEX 6 2.5 Fluorescence Index SUVA (nm*L/mg C) treatment efficiency. 2 Intensity (nm) 5 DOC (mg/L) o Fluorescence spectroscopy has been shown to be an effective 100 2 technique to characterize dissolved organic matter (DOM) in 1.5 4 natural systems, but its use in drinking water applications is an 10 1.5 active area of research. 3 o The goal of this work is to develop improved monitoring techniques 1 1 for MIEX treatment. 2 1 1) Understand the shift in fluorescence peak location. 0.5 0.5 1 2) Compare DOC to fluorescence intensity. 3) Compare the SUVA to fluorescence index (FI). 0 0.1 0 0 Syn 1 Syn 2 Syn 3 Syn 4 SW 1 SW 2 GW 1 L1 L2 L3 L4 L5 (a) Raw Source Waters M: R2 = 0.54 (a) Raw Source Waters FI = 1.6 Terrestrial Peak T: R2 = 0.15 R2 = 0.88 from Suwannee River IHSS Isolate of NOM 3 10000 3.5 9 Microbial FI 8 2.5 Terrestrial 3 SUVA 1000 DOC 7 2.5 Fluorescence Index SUVA (nm*L/mg C) 2 6 DOC (mg/L) Intensity (nm) 100 2 5 1.5 10 1.5 4 1 3 1 1 2 0.5 0.5 Figure 1 – Fluorescence peak location shift after MIEX treatment Figure 4 – Contour EEMs of fluorescence standards 1 0 0.1 0 0 Syn 1 Syn 2 Syn 3 Syn 4 GW 1 SW 1 SW 2 L1 L2 L3 L4 L5 Sampling and Analysis (b) Treated Source Waters M: R2 = 0.74 T: R2 = 0.69 (b) Treated Source Waters R2 = 0.64 Figure 5 – DOC and fluorescence peak intensity for microbial and Figure 6 – SUVA and FI of both raw (a) and treated (b) samples terrestrial regions of both raw (a) and treated (b) samples Syn2-4 Syn1 L4 o Samples collected between L1 L5 February 2009 and January 2010. Impact GW1 SW2 o Sample sources include SW1 landfills, surface water SW1: Lake Jesup bodies and a groundwater Peak Location SW2: St. Johns River L2-3 aquifer. (Figure 2) Fluorescence measurements could be a Syn1: Santa Fe River o MIEX treatment alters DOM chemistry Syn2-4: St. Mary’s River o Analytical measurements DOC vs. Intensity better alternative for monitoring MIEX include: UV254, DOC, and treatment efficiency. GW1: Cedar Key GW fluorescence EEM. o Raw L1: Alachua SW Landfill o Fluorescence is the o DOC: Synthetic < Ground < Surface < Waste L2-3: Polk Landfill Models for predicting MIEX treatment efficiency L4: New River Landfill emission of light only o Terrestrial peaks’ intensity > Microbial peaks’ intensity during the absorption of the with fluorescence spectroscopy L5: Putnam Landfill o Treated excitation light. (Figure 3) o DOC % Removal = o Microbial peak intensity is better correlated to DOC (1.24  Peak A Intensity % Removal) – 0.25 Figure 2 – Florida Sampling Map o MIEX preferentially removes the terrestrial component R2 = 0.93 Figure 3 – Jablonski Energy Diagram SUVA vs. FI o SUVA % Removal = (Johnson, Ian and Davidson, Michael. “Jablonski Energy o Raw SUVA: Synthetic < Surface < Ground < Waste Acknowledgements (- 2.24 * FI % Removal) + 0.06 Diagram.” Microscopy Resource Center. Olympus o SUVA and FI are negatively correlated Thanks to Jennifer Apell, Troy Chasteen, Sarah Deavenport, Katherine http://www.olympusmicro.com/primer/java/jablonski/jabintro/ R2 = 0.61 Graf, Katie Indarawis, Stephanie Ishii, Christopher Rokicki, Paul index.html) Stevenson, and Krystal Walker for sample and data collection.