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					      Identification of the Causes of
    Sediment-Associated Toxicity in the
      Illinois River Complex Using a
           Sediment-TIE Approach

         Tyler Mehler1, Jing You2, Jon Maul3 and Michael Lydy1
1Fisheries and Illinois Aquaculture and Department of Zoology, Southern Illinois
University, Carbondale, Illinois, USA
2StateKey Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry,
Chinese Academy of Sciences, Guangzhou, China
3TheInstitute of Environmental and Human Health, Department of Toxicology, Box
41163, Texas Tech University, Lubbock, Texas, USA
                                 ISTC seminar: 9/9/09
                   What is a TIE?
As defined by the EPA (2007):
The Toxicity Identification Evaluation approach “is to
use physical/chemical manipulations of a sample to
isolate or change the potency of different groups of
toxicants potentially present in a sample”.

 Contaminated w/
    non-polar
    organics




    X    X   X                        X     X       X      X     X    X
                   Amended for non-   Amended for
   Unamended        polar organics     ammonia
                                                        Amended for metals
                           Amended
                           Matrix Choice
                    Sediment
    Pore
                      grain
    water




                      usgs.go
                            v



Issues with pore water TIEs:
      • Bioavailability
        • Ingestion
• Water quality parameters
• Environmental Realistic?
 Conducting a Toxicity Identification Evaluation (TIE)

STEP 1            SITE SAMPLING

STEP 2           SCREENING TOXICITY TEST

STEP 3          PHASE I: CHARACTERIZATION

                                Ammonia (Zeolite)

                                Cationic Metals (Resin-Tech SIR 300)
                                                                                   X

                                Nonpolar Organics (PCC)                       Unamended     Amended


STEP 4           PHASE II: IDENTIFICATION

                                 Ammonia (Ammonia Probe)

                                 Cationic metals (NAD & FAAS)

                                 Nonpolar Organics (ASE & GC/HPLC)

                                                                       concentration of contaminant
                                              Toxic Unit (TU) =          LC50 of that contaminant
U.S. EPA 2007 Whole sediment TIE guidelines
                     Objectives
• Identify toxic sites throughout the Illinois River
  Complex

• Identify the contaminant classes (ammonia, metals,
  non-polar organics) that attribute to the toxicity of
  those sites using a whole-sediment TIE test

• Evaluate the temporal and spatial trends in correlation
  to the toxicity of those sites

• Examine the difference between TIE methodologies
  and the test organisms used

• Compare past and present TIE research on the IRC
 Conducting a Toxicity Identification Evaluation (TIE)

STEP 1    SITE SAMPLING

STEP 2   SCREENING TOXICITY TEST

STEP 3   PHASE I: CHARACTERIZATION

                 Ammonia (Zeolite)

                 Cationic Metals (Resin-Tech SIR 300)

                 Nonpolar Organics (PCC)


STEP 4   PHASE II: IDENTIFICATION

                  Ammonia (Ammonia Probe)

                  Cationic metals (NAD & FAAS)

                  Nonpolar Organics (ASE & GC/HPLC)
                                           Sampling Methods
                       21        22
                     19           24   •   24 sites chosen with consultation of
                      18                   ISTC
                            20
                                 23    •   2.5 kg was collected from each site
        13-15         17
                     17                •   Water samples from each site were
    10-11
                                           also retrieved and water quality
                16
    4   9                                  measurements for each site taken
            8 12
             5-7
    2
                                            •   Hardness emulated
                                            •   Total pore water ammonia was
            3
1                                               analyzed upon arrival at SIUC
                                       •   Sediments and water samples were
                                           analyzed at SIUC Fisheries and
                                           Illinois Aquaculture Center

                                       •   Samples were taken in summer 07’,
                                           fall 07’, winter 07-08’, spring 08’ and
                                           again in summer 08’
                                                   Site Name                        River   Sc
                                                          Sites
                                                   (Map Number)                Rivermile
                                                                                   Mile
                                                    Moore's Towhead (1)              76
                                   21        22
                                                    Spring Lake Wildlife Area (2)   134
                                 19           24    Pekin (3)                       151
                                  18                Mouth of Wesley Slough (4)      160
                                                    Peoria Dredge (5)               165
                                        20          L Peoria Core 0-30 (6)          166
                                             23     L Peoria Core 30-60             166
            13-15                 17
                                                    L Peoria Core 60-90             166
                                 17
       10-11                                        Upper Lower Peoria Lake (7)     166
                                                    Goose Lake (8)                  179
                    16                              Lacon (9)                       187
       4    9
                8 12                                Mudd Lake (10)                  196
                 5-7                                Sawmill Core 0-30 (11)          197
      2                                             Sawmill Core 30-60              197
                                                    Sawmill Core 60-90              197
                3                                   Down River of Hennepin (12)     205
  1                                                 Hennepin Power Plant (13)       212
                                                    Depue Lake (14)                 212
                                                    Depue Core 0-30 (15)            212
                                                    Dupue Core 30-60                212
St. Louis                                           Dupue Core 60-90                212
                                                    Marseilles (16)                 248
                    Carbondale                      DuPage River (17)               277
                                                    Calmut 305 (18)                 305
                                                    SS308 NC (19)                   308
                 X                                  Stony Creek (20)                309
                                                    SS315 (21)                      315
                                                    SS317 (22)                      317
                                                    SR Cal RR (23)                  318
                                                    Halstead Bridge (24)            320
 Conducting a Toxicity Identification Evaluation (TIE)
STEP 1    SITE SAMPLING

STEP 2   SCREENING TOXICITY TEST

STEP 3   PHASE I: CHARACTERIZATION

                 Ammonia (Zeolite)

                 Cationic Metals (Resin-Tech SIR 300)

                 Nonpolar Organics (PCC)


STEP 4   PHASE II: IDENTIFICATION

                  Ammonia (Ammonia Probe)

                  Cationic metals (NAD & FAAS)

                  Nonpolar Organics (ASE & GC/HPLC)
 Screening Toxicity Tests
• 10-d bioassays (U.S. EPA) in flow-thru
  system with three water changes per day
  (100 ml per change)
• 10 H. azteca (14 to 21-d old) per 300 ml
  beaker, 6 replicates per site
• Control: Touch of Nature (TON) hydrated
  soil – Carbondale, IL
• Amendment Reference: Lower Peoria Lake
  (LPL)
• Statistical Analysis: Dunnett’s Multiple
  Comparison Test
                                    Summer 07’ Results: Screening
         120                               Toxicity Tests
         100




             80
% Survival




             60
                                                                                                   Upper Lower Peoria Lake
                                                      Spring Lake Wildlife Area




                                                                                                                                                                                       Hennenpin Power Plant
                                                                                                                                                                 Hennepin Down River
             40




                                                                                                                                                                                                                                                                                                     Halstead
                                    Moore’s Towhead
                  Touch of Nature




                                                                                                                                                                                                                                                             Stony Creek
                                                                                                                             LPL Dredge




                                                                                                                                                                                                                       Marseilles
             20




                                                                                                                                                                                                                                                                                           SRCALRR
                                                                                                                                                                                                                                    DuPage
                                                                                          Wesley




                                                                                                                                                                                                               DuPue




                                                                                                                                                                                                                                             CS305

                                                                                                                                                                                                                                                     SS308



                                                                                                                                                                                                                                                                           SS315
                                                                                                                                          Goose




                                                                                                                                                                                                                                                                                   SS317
                                                                                                                                                  Lacon
                                                                                  Pekin




                                                                                                                                                          Mudd




              0
                                    76                134                         151     160      165                       166          179     187     196    205                   212                     212     248          277      305     308     309           315     317     318       320


                                                                                                                                                  Increasing Rivermile

              Sites that were significantly different from controls (p<0.05) and were chosen for seasonal analysis.
 Conducting a Toxicity Identification Evaluation (TIE)
STEP 1    SITE SAMPLING

STEP 2   SCREENING TOXICITY TEST

STEP 3   PHASE I: CHARACTERIZATION

                 Ammonia (Zeolite)

                 Cationic Metals (Resin-Tech SIR 300)

                 Nonpolar Organics (PCC)


STEP 4   PHASE II: IDENTIFICATION

                  Ammonia (Ammonia Probe)

                  Cationic metals (NAD & FAAS)

                  Nonpolar Organics (ASE & GC/HPLC)
Phase I: Characterization
        20% (12 g)



         Zeolite
        20% (12 g)



       Unamended
         (sand)
                                             4 -d static test
                         10 H. azteca

        25% (15 g)    6 reps per treatment


                                             10-d flow-thru test

      RT SIR 300 HP
         15% (9 g)




          PCC
        25% (15 g)



       Unamended
         (sand)
              Summer 2007 Results: Phase I
             120                           Unamended (sand)          Organics (PCC)


             100

                  80
     % Survival




                  60

                  40

                  20

                  0
                       TON   LPL   SS308     Halstead   CS305   Stny Crk SRCALRR   SS315   DuPage

                                                    TOXIC SITES

• The addition of zeolite (ammonia) and Resin-Tech SIR 300 (metals) showed no significant differences
  in comparison to the unamended sediment.
 Conducting a Toxicity Identification Evaluation (TIE)
STEP 1    SITE SAMPLING

STEP 2   SCREENING TOXICITY TEST

STEP 3   PHASE I: CHARACTERIZATION

                 Ammonia (Zeolite)

                 Cationic Metals (Resin-Tech SIR 300)

                 Nonpolar Organics (PCC)


STEP 4   PHASE II: IDENTIFICATION

                  Ammonia (Ammonia Probe)

                  Cationic metals (NAD & FAAS)

                  Nonpolar Organics (ASE & GC/HPLC)
                Phase II: Identification
                          Nonpolar Organic Toxicants
PAHs: acenaphthene, acenapthylene, anthracene, chrysene, fluoranthene,
fluorene, naphthalene, phenanthrene, pyrene, benzo[a]anthracene,
benzo[b]fluoranthrene, benzo[k]fluoranthene, benzo[a]pyrene,
benzo[g,h,i]perylene, dibenzo[a,h]anthracene and indeno[1,2,3-cd]pyrene
PCBs: Congeners: 8, 18, 28, 31, 43, 44, 48, 49, 52, 66, 70, 86, 87, 95, 97, 99, 101,
105, 110, 114, 118, 123, 126, 128, 138, 153, 156, 157, 167, 169, 170, 174, 180, 183,
187, 189, 194, 195, 200, 201, 203 and 206.
OCPs: alpha-BHC, beta-BHC, gamma-BHC, delta-BHC, p,p’-DDE, p,p’-DDD, p,p’-
DDT, aldrin, gamma-chlordane, alpha-chlordane, diedrin, endrin, endrin aldehyde,
endrin ketone, endosulfan I, endosulfan II, endosulfan sulfate, heptachlor,
heptachlor epoxide and methoxychlor.
OP/Pyrethroids: chlorpyrifos, permethrin, lambda-cyhalothrin, cypermethrin,
esfenvalerate, deltamethrin, cyfluthrin, bifenthrin.

                Heavy Metals                            Ammonia
       Cu2+, Ni2+, Cr6+, Pb2+, Zn2+, Cd2+               NH4+, NH3
            The reasons we analyzed total ammonia:

1. It’s commonly performed in standard TIE methods


2. Allows comparisons in pore water ammonia concentrations between past and
   present studies (Sparks and Ross 1992 – Concentrations measured as total
   ammonia)


3. Allows comparisons in pore water ammonia concentrations among sites (since
   water quality characteristics differed among sites)


4. Difficult to account for drifting pHs or changing temperature throughout studies
         Summer 2007 Phase II: Identification


                                                     Stony
                                                       Stony SRCALRR
                        LPL     SS308 Halstead CS305                                SS315
        Toxic Units                                  Creek
                             LPL SS308 Halstead CS305 Creek SRCALRR                 SS315
Metals (µg/g dry)      6.39     37.7   26.5    27.6  50.4     23.8                  17.9
∑Metals (µg/g dry)             <0.1     <0.1     <0.1     <0.1    <0.1   <0.1        <0.1
Pore water total        6.48         36.6      26.2     13.7     19.4    21.7         541
 Pore water total
ammonia (mg N/L)
                               <0.1     <0.1     <0.1     <0.1    <0.1   <0.1         0.4
ammonia (mg N/L)
Pesticides (µg/g OC)   BRL          0.447     0.208    0.414    2.14    1.12        0.405
PCBs (µg/g oc)                 <0.1     <0.1     <0.1     <0.1    <0.1   <0.1        <0.1
PCBs (µg/g OC)         4.45          11.5     15.7     21.1     37.2    34.5          7.6
Pesticides
PAHs (µg/g OC)
(µg/g oc)
                                    <0.1
                        586.8<0.11934            <0.1
                                               1328       <0.1 1021
                                                        1198    <0.1     <0.1
                                                                         1267        <0.1
                                                                                     4112
                                                                                BRL – 1 µg/kg
PAHs (µg/g oc)                 0.7       2.8      1.9      1.8    1.4    1.6          4.6


                          Low TU = Low Toxicity
                          High TU= High Toxicity
        Summer 2007 Conclusions


• Phase I findings strongly suggests that
non-polar organics are the problem, with
Phase II findings further suggesting that
PAHs were at high concentrations to cause
the noted toxicity.

• What about the other seasons?
                                                     SUMMER 07’                                                      SUMMER 08’




                                    1.2           Unamended (sand)                             • 46% of sites (in all seasons)
% Unresolved Complex Matrix (UCM)




                                     1
                                                  Organics (PCC)                                 were characterized with PCC
     % Diesel Range Organics




                                    0.8                                                                  • Affect on PCC binding capability?
                                    0.6                                                                  • Organics higher affinity for UCM?
                                    0.4                                                                  • Causes toxicity itself?
                                    0.2
                                                          Is PCC always effective?
                                     0
                                          SS315   SS308   CS305   SRCALRR   Halstead   Stony   DuPage   LPL
                                                                                       Creek

                                                                    Toxic Sites
                                 Phase II: Spatial and temporal variation
                                                     Total Pore Water Ammonia
                                              800
                                              600                                        Summer 2007
                                              400
                                                                                         Fall 2007
                               mg N/L


                                              200                                        Winter 2007-2008
                                              150                                        Spring 2008                          Calumet Sag Channel
Concentration of Contaminant




                                                                                                                              Chicago Sanitary and
                                              100                                        Summer 2008                            Shipping Canal
                                               50

                                                0
                                                       Total Cationic Metals
                                µg/g dry wt




                                               50




                                               25




                                                0

                                                            Total PAHs
                                mg/g OC




                                               6.0




                                               3.0




                                                         SS315      SS308       CS305   SRCALRR      Halstead   Stony   LPL
                                                                                                                Creek
                                                  Spatial Trends: Ammonia
Total Pore Water Ammonia Concentration (mg N/L)


                                                  600
                                                             Y = 0.1314x – 16.633
                                                  550
                                                             r2 = 0.608
                                                  500        p < 0.001
                                                   75




                                                  50




                                                  25




                                                   0
                                                        50         100        150        200         250      300   350

                                                                            Rivermile on the Illinois River
  Total Pore Water Ammonia (mg N/L)
                                              Spatial Trends: Ammonia

                                      1000




                                      750




                                      500

                                               Municipal Waste Plant
                                      250


                                                         SS315
                                                        Total Ammonia
                                         0               >400 mg N/L
                                             308    310         312      314   316   318
Courtesy of www.flashearth.com
                                                                 Rivermile
       Sparks and Ross (1992)

 Gradient of increased toxicity associated
   with the total ammonia concentration
 Ammonia the primary source of toxicity
   in the Illinois River Complex
 Patches of toxicity occurring due to
   PAHs
A Comparison Study:
  – Determine differences between pore water TIE testing and
    whole-sediment TIE testing
  – Determine differences between test organisms (H. azteca
    and C. dubia)
  – While still comparing past and present research




         VS                              VS
  Two sites being evaluated:
  SS315 – highest ammonia concentrations
  SS308 – highest PAH concentrations
                 Phase I: Pore Water
                  Characterization


Diluted by 50%
                    Unamended




                                                   2-d static
                                                      test
                                                   1-d static
                                                      test
                     Zeolite


                                    5 H. azteca
                                    10 C. dubia
                                8 reps per treatment
                     SPE C18
Phase I: Whole Sediment
   Characterization




                                          4-d static
        Zeolite




                                             test
       Unamended




                                          10-d flow-
                                           thru test
          PCC


                      10 H. azteca
                       10 C. dubia

      Zeolite
                   8 reps per treatment




                                                       2-d static
     Unamended




                                                          test
       PCC
Comparing Methodologies: Ammonia
                                                 Whole Sediment TIE
 Pore Water TIE           PHASE I:




    2.56                                                0.27
                  Predicted TUs for H. azteca
                          PHASE II:
                          SS315 Ammonia
  359 mg N/L                                          37.9 mg N/L
                       Concentrations (mg N/L)
Comparing Methodologies: Non-polar Organics
   Pore Water TIE         PHASE I:               Whole-Sediment TIE



                         The affects of:
                             • UCM
                         • Black carbon
                     • ingestion, adsorption
                             • DOC
                      • Glassware binding


     0.52                                               1.81
                    TUs for H. azteca
                       PHASE II:
   1953 µg/L        SS308 ∑PAH Concentrations:       4405 µg/g oc
Comparing Species Sensitivity/Susceptibility




  H. azteca  140 mg N/L (4-d)a     LC50 Total Ammonia:      C. dubia  47.25 mg N/L (2-d)b
  H. azteca  30.6 µg/L (10-d)c   LC50 Fluoranthene (PAH):   C. dubia  102.6 µg/L (10-d)c

                                                                                   a – Ankley et al. 1995
                                                                 b – extrapolated from Bailey et al. 2001
                                                                      c – Suedel and Rodgers, Jr. 1996


                             Species Sensitivity ≠ Species Susceptibility
                             • Body Size /Age (Life Stage)
                             • Physiology/Feeding Behavior
                             • Niche
              Conclusions
• Toxic sites were identified on the IRC for
  future risk assessment & mitigation
• Rm 277 (DuPage) Calumet Sag Channel,
  Chicago Sanitary and Shipping Canal
              Conclusions
• PAHs and the associated oils and grease
  were identified as the sources of the noted
  toxicity, however ammonia was elevated
  at SS315
             Conclusions
• Little temporal variation was noted in
  toxicity and in concentrations
• However, spatial trends were found in
  toxicity especially concerning ammonia
             Conclusions
• Which TIE approach is better and where
  are TIEs headed?
• Is the IRC a healthy system ?
                 Acknowledgements
Sampling Crew:
Ed Workman, Mandy Rothert, Liz Tripp, Heather
Foslund

A special thanks goes to SETAC (Student
Exchange Program) and Teresa Norberg-King and
the rest of the EPA Duluth Lab.
Fisheries and Aquaculture Center and Dept. of
Zoology staff and students

Funding:
           For more information:
Mehler WT, Maul JD, You J, and MJ Lydy. 2009. Identifying the
  causes of sediment-associated contamination in the Illinois
  River using a whole-sediment Toxicity Identification
  Evaluation (TIE). Environmental Toxicology and Chemistry.
  In Press.
Mehler WT, You J, Maul JD, and MJ Lydy. 2009. Comparative
  analysis of whole sediment and pore water Toxicity
  Identification Evaluation (TIE) techniques for ammonia and
  non-polar organic contaminants. Chemosphere.
  In Review.
Questions?
 Evaluating Ammonia

       SS315 overlying water

Total ammonia – 37.9 mg N/L (TU = 0.29)

Un-ionized ammonia – 0.584 mg/L (TU = 0.27)




        SS315 pore water

  Total ammonia – 359 mg N/L (TU = 2.56)

Un-ionized ammonia – 11.2 mg/L (TU = 5.19)
       Sparks and Ross (1992)
 Gradient of increased toxicity associated
   with the total ammonia concentration
 Ammonia was the primary source of
   toxicity in the Illinois River Complex
 Patches of toxicity occurring due to
   PAHs
 The beginning of a general recovery of
   the Illinois River Complex
        Sparks and Ross 1992

 Gradient of increased toxicity associated
   with the total ammonia concentration
 Ammonia the primary source of toxicity
   in the Illinois River Complex
 Patches of toxicity occurring due to
   PAHs

? the Illinois River Complex
 The beginning of a general recovery of
Questions?
                      Conclusions:
• Differences in past and present TIE
  studies is attributed to the differences in
  methodologies and perhaps on a lesser
  note test organism choice.
• Which test organism is better?
  –   Realistic Test Organism?

  – Using Historic Test Organism?

• Which TIE is better and where are TIEs
  headed?

				
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