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Tyler Mehler 1, Jing You 2, Jon Maul 3 and Michael Lydy 1 1 Fisheries and Illinois Aquaculture and Department of Zoology, Southern Illinois University,

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Presentation on theme: "Tyler Mehler 1, Jing You 2, Jon Maul 3 and Michael Lydy 1 1 Fisheries and Illinois Aquaculture and Department of Zoology, Southern Illinois University,"— Presentation transcript:

1 Tyler Mehler 1, Jing You 2, Jon Maul 3 and Michael Lydy 1 1 Fisheries and Illinois Aquaculture and Department of Zoology, Southern Illinois University, Carbondale, Illinois, USA 2 2 State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, China 3 The Institute of Environmental and Human Health, Department of Toxicology, Box 41163, Texas Tech University, Lubbock, Texas, USA ISTC seminar: 9/9/09

2 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”. Unamended Amended X X X Amended for non- polar organics Amended for ammonia X X X Amended for metals X X X Contaminated w/ non-polar organics

3 Matrix Choice usgs.go v Pore water Sediment grain Issues with pore water TIEs: Bioavailability Ingestion Water quality parameters Environmental Realistic?

4 SITE SAMPLING SCREENING TOXICITY TEST PHASE I: CHARACTERIZATION Ammonia (Zeolite) Cationic Metals (Resin-Tech SIR 300) Nonpolar Organics (PCC) Conducting a Toxicity Identification Evaluation (TIE) PHASE II: IDENTIFICATION Ammonia (Ammonia Probe) Cationic metals (NAD & FAAS) Nonpolar Organics (ASE & GC/HPLC) STEP 1 STEP 2 STEP 3 STEP 4 X UnamendedAmended U.S. EPA 2007 Whole sediment TIE guidelines Toxic Unit (TU) = concentration of contaminant LC 50 of that contaminant

5 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 Objectives

6 SITE SAMPLING SCREENING TOXICITY TEST PHASE I: CHARACTERIZATION Ammonia (Zeolite) Cationic Metals (Resin-Tech SIR 300) Nonpolar Organics (PCC) Conducting a Toxicity Identification Evaluation (TIE) PHASE II: IDENTIFICATION Ammonia (Ammonia Probe) Cationic metals (NAD & FAAS) Nonpolar Organics (ASE & GC/HPLC) STEP 1 STEP 2 STEP 3 STEP 4 SITE SAMPLING

7 24 sites chosen with consultation of ISTC 2.5 kg was collected from each site Water samples from each site were also retrieved and water quality measurements for each site taken Hardness emulated Total pore water ammonia was 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’ Sampling Methods 17

8 SitesRivermile 17 X Carbondale St. Louis

9 SITE SAMPLING SCREENING TOXICITY TEST PHASE I: CHARACTERIZATION Ammonia (Zeolite) Cationic Metals (Resin-Tech SIR 300) Nonpolar Organics (PCC) Conducting a Toxicity Identification Evaluation (TIE) PHASE II: IDENTIFICATION Ammonia (Ammonia Probe) Cationic metals (NAD & FAAS) Nonpolar Organics (ASE & GC/HPLC) STEP 1 STEP 2 STEP 3 STEP 4 SCREENING TOXICITY TEST

10 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

11 Summer 07’ Results: Screening Toxicity Tests Sites that were significantly different from controls (p<0.05) and were chosen for seasonal analysis. Touch of NatureMoore’s TowheadSpring Lake Wildlife AreaPekinUpper Lower Peoria LakeGooseLaconMuddHennepin Down RiverHennenpin Power PlantDuPueMarseillesDuPageCS305Stony CreekSS315 SRCALRR SS317 Halstead SS308LPL DredgeWesley

12 SITE SAMPLING SCREENING TOXICITY TEST PHASE I: CHARACTERIZATION Ammonia (Zeolite) Cationic Metals (Resin-Tech SIR 300) Nonpolar Organics (PCC) Conducting a Toxicity Identification Evaluation (TIE) PHASE II: IDENTIFICATION Ammonia (Ammonia Probe) Cationic metals (NAD & FAAS) Nonpolar Organics (ASE & GC/HPLC) STEP 1 STEP 2 STEP 3 STEP 4 PHASE I: CHARACTERIZATION

13 Phase I: Characterization RT SIR 300 HP PCC Unamended (sand) 20% (12 g) 25% (15 g) 15% (9 g) 25% (15 g) Zeolite Unamended (sand) 20% (12 g) 10 H. azteca 6 reps per treatment 4 -d static test 10-d flow-thru test

14 Summer 2007 Results: Phase I Unamended (sand)Organics (PCC) TOXIC SITES The addition of zeolite (ammonia) and Resin-Tech SIR 300 (metals) showed no significant differences in comparison to the unamended sediment. TONLPLSS308HalsteadCS305Stny CrkSRCALRRSS315DuPage

15 SITE SAMPLING SCREENING TOXICITY TEST PHASE I: CHARACTERIZATION Ammonia (Zeolite) Cationic Metals (Resin-Tech SIR 300) Nonpolar Organics (PCC) Conducting a Toxicity Identification Evaluation (TIE) PHASE II: IDENTIFICATION Ammonia (Ammonia Probe) Cationic metals (NAD & FAAS) Nonpolar Organics (ASE & GC/HPLC) STEP 1 STEP 2 STEP 3 STEP 4 PHASE II: IDENTIFICATION

16 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 Cu 2+, Ni 2+, Cr 6+, Pb 2+, Zn 2+, Cd 2+ Ammonia NH 4 +, NH 3 Phase II: Identification

17 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

18 LPLSS308HalsteadCS305 Stony Creek SRCALRRSS315  Metals (µg/g dry) Pore water total ammonia (mg N/L)  Pesticides (µg/g OC) BRL  PCBs (µg/g OC)  PAHs (µg/g OC) Summer 2007 Phase II: Identification BRL – 1 µg/kg Toxic UnitsLPLSS308HalsteadCS305 Stony CreekSRCALRRSS315 ∑Metals (µg/g dry) <0.1 Pore water total ammonia (mg N/L) < PCBs (µg/g oc)<0.1 Pesticides (µg/g oc) <0.1 PAHs (µg/g oc) Low TU = Low Toxicity High TU= High Toxicity

19 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?

20 Is PCC always effective? SUMMER 07’ Unamended (sand) Organics (PCC) SUMMER 08’ 46% of sites (in all seasons) were characterized with PCC Affect on PCC binding capability? Organics higher affinity for UCM? Causes toxicity itself? % Unresolved Complex Matrix (UCM)

21 Phase II: Spatial and temporal variation Concentration of Contaminant Summer 2007 Fall 2007 Winter Spring 2008 Summer 2008 mg N/L µg/g dry wt mg/g OC SS315SS308 LPL CS305 SRCALRR Halstead Total Pore Water Ammonia Total Cationic Metals Total PAHs Calumet Sag Channel Chicago Sanitary and Shipping Canal Stony Creek

22 Spatial Trends: Ammonia

23 SS315 Total Ammonia >400 mg N/L Municipal Waste Plant Courtesy of Spatial Trends: Ammonia

24  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 Sparks and Ross (1992)

25 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 Two sites being evaluated: SS315 – highest ammonia concentrations SS308 – highest PAH concentrations VS

26 Phase I: Pore Water Characterization Zeolite Unamended 5 H. azteca 10 C. dubia 8 reps per treatment 2-d static test Diluted by 50% SPE C 18 1-d static test

27 Phase I: Whole Sediment Characterization Zeolite Unamended 10 H. azteca 10 C. dubia 8 reps per treatment 4-d static test PCC 10-d flow- thru test 2-d static test Zeolite Unamended PCC

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

29 Comparing Methodologies: Non-polar Organics Pore Water TIE Whole-Sediment TIE The affects of: UCM Black carbon ingestion, adsorption DOC Glassware binding PHASE I: SS308 ∑PAH Concentrations: TUs for H. azteca PHASE II: µg/L 4405 µg/g oc

30 Comparing Species Sensitivity/Susceptibility H. azteca C. dubia Species Sensitivity ≠ Species Susceptibility Body Size /Age (Life Stage) Physiology/Feeding Behavior Niche  mg N/L (2-d) b LC 50 Total Ammonia:  140 mg N/L (4-d) a a – Ankley et al b – extrapolated from Bailey et al c – Suedel and Rodgers, Jr LC 50 Fluoranthene (PAH): C. dubia  µg/L (10-d) c H. azteca  30.6 µg/L (10-d) c

31 Conclusions Toxic sites were identified on the IRC for future risk assessment & mitigation Rm 277 (DuPage) Calumet Sag Channel, Chicago Sanitary and Shipping Canal

32 Conclusions PAHs and the associated oils and grease were identified as the sources of the noted toxicity, however ammonia was elevated at SS315

33 Conclusions Little temporal variation was noted in toxicity and in concentrations However, spatial trends were found in toxicity especially concerning ammonia

34 Conclusions Which TIE approach is better and where are TIEs headed? Is the IRC a healthy system ?

35 Acknowledgements 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: Sampling Crew: Ed Workman, Mandy Rothert, Liz Tripp, Heather Foslund

36 For more information: Mehler WT, Maul JD, You J, and MJ Lydy 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 Comparative analysis of whole sediment and pore water Toxicity Identification Evaluation (TIE) techniques for ammonia and non-polar organic contaminants. Chemosphere. In Review.

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40 Questions?

41 Evaluating Ammonia SS315 overlying water Total ammonia – 37.9 mg N/L (TU = 0.29) Un-ionized ammonia – mg/L (TU = 0.27) Total ammonia – 359 mg N/L (TU = 2.56) Un-ionized ammonia – 11.2 mg/L (TU = 5.19) SS315 pore water

42 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

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44  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 beginning of a general recovery of the Illinois River Complex Sparks and Ross 1992?

45 Questions?

46 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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