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, USA2State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, China3The Institute 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”.

UnamendedAmended

X X XAmended for non-

polar organicsAmended for

ammonia

X X X

Amended for metals

X X X

Contaminated w/ non-polar organics

Matrix Choice

usgs.gov

Pore water

Sediment grain

Issues with pore water TIEs:

• Bioavailability

• Ingestion

• Water quality parameters

• Environmental Realistic?

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

Unamended Amended

U.S. EPA 2007 Whole sediment TIE guidelinesToxic Unit (TU) =

concentration of contaminantLC50 of that contaminant

• 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

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

• 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

1

4

2

3

5-78

10-11

12

13-15

169

17

1819

20

21 22

23

24

17

Sites Rivermile ( p )

Moore's Towhead (1) 76 Spring Lake Wildlife Area (2) 134 Pekin (3) 151 Mouth of Wesley Slough (4) 160 Peoria Dredge (5) 165 L Peoria Core 0-30 (6) 166 L Peoria Core 30-60 166 L Peoria Core 60-90 166 Upper Lower Peoria Lake (7) 166 Goose Lake (8) 179 Lacon (9) 187 Mudd Lake (10) 196 Sawmill Core 0-30 (11) 197 Sawmill Core 30-60 197 Sawmill Core 60-90 197 Down River of Hennepin (12) 205 Hennepin Power Plant (13) 212 Depue Lake (14) 212 Depue Core 0-30 (15) 212 Dupue Core 30-60 212 Dupue Core 60-90 212 Marseilles (16) 248 DuPage River (17) 277 Calmut 305 (18) 305 SS308 NC (19) 308 Stony Creek (20) 309 SS315 (21) 315 SS317 (22) 317 SR Cal RR (23) 318 Halstead Bridge (24) 320

1

4

2

3

5-78

10-11

12

13-15

169

17

1819

20

21 22

23

24

17

X

Carbondale

St. Louis

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

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 Toxicity Tests

Sites that were significantly different from controls (p<0.05) and were chosen for seasonal analysis.

0

20

40

60

80

100

120

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

% S

urvi

val

Increasing Rivermile

Touc

h of

Nat

ure

Moo

re’s

Tow

head

Spr

ing

Lake

Wild

life

Are

a

Pek

in

Upp

er L

ower

Peo

ria L

ake

Goo

se

Laco

n

Mud

d

Hen

nepi

n D

own

Riv

er

Hen

nenp

in P

ower

Pla

nt

DuP

ue

Mar

seille

s

DuP

age

CS

305

Sto

ny C

reek

SS

315

SR

CA

LRR

SS

317

Hal

stea

d

SS

308

LPL

Dre

dge

Wes

ley

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

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

Summer 2007 Results: Phase IUnamended (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.

TON LPL SS308 Halstead CS305 Stny Crk SRCALRR SS315 DuPage

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

Nonpolar Organic ToxicantsPAHs: 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]pyrenePCBs: 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 MetalsCu2+, Ni2+, Cr6+, Pb2+, Zn2+, Cd2+

AmmoniaNH4

+, NH3

Phase II: Identification

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

LPL SS308 Halstead CS305 StonyCreek SRCALRR SS315

∑Metals (µg/g dry) 6.39 37.7 26.5 27.6 50.4 23.8 17.9

Pore water total ammonia (mg N/L)

6.48 36.6 26.2 13.7 19.4 21.7 541

∑Pesticides (µg/g OC) BRL 0.447 0.208 0.414 2.14 1.12 0.405

∑PCBs (µg/g OC) 4.45 11.5 15.7 21.1 37.2 34.5 7.6

∑PAHs (µg/g OC) 586.8 1934 1328 1198 1021 1267 4112

Summer 2007 Phase II: Identification

BRL – 1 µg/kg

Toxic Units LPL SS308 Halstead CS305StonyCreek SRCALRR SS315

∑Metals (µg/g dry) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1Pore water total ammonia (mg N/L) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.4

PCBs (µg/g oc) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1Pesticides(µg/g oc) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

PAHs (µg/g oc) 0.7 2.8 1.9 1.8 1.4 1.6 4.6

Low TU = Low ToxicityHigh 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?

Is PCC always effective?

SUMMER 07’

Unamended (sand)

Organics (PCC)

SUMMER 08’

• 46% of sites (in all seasons) were characterized with PCC

0

0.2

0.4

0.6

0.8

1

1.2

SS315 SS308 CS305 SRCALRR Halstead StonyCreek

DuPage LPL

Toxic Sites

% D

iese

l Ran

ge O

rgan

ics

• Affect on PCC binding capability?

• Organics higher affinity for UCM?

• Causes toxicity itself?

% U

nres

olve

d C

ompl

ex M

atrix

(UC

M)

0

25

50

0

50

100

150

200

400600800

Phase II: Spatial and temporal variationC

once

ntra

tion

of C

onta

min

ant

Summer 2007Fall 2007Winter 2007-2008Spring 2008Summer 2008

mg

N/L

µg/g

dry

wt

mg/

g O

C

SS315 SS308 LPLCS305 SRCALRR Halstead

3.0

6.0

Total Pore Water Ammonia

Total Cationic Metals

Total PAHs

Calumet Sag Channel

Chicago Sanitary and Shipping Canal

Stony Creek

Spatial Trends: Ammonia

Rivermile on the Illinois River

50 100 150 200 250 300 350

Tota

l Por

e W

ater

Am

mon

ia C

once

ntra

tion

(mg

N/L

)

0

25

50

75500

550

600

Y = 0.1314x – 16.633 r2 = 0.608 p < 0.001

Rivermile

308 310 312 314 316 318

Tota

l Por

e W

ater

Am

mon

ia (m

g N

/L)

0

250

500

750

1000

SS315Total Ammonia

>400 mg N/L

Municipal Waste Plant

Courtesy of www.flashearth.com

Spatial Trends: Ammonia

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)

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 concentrationsSS308 – highest PAH concentrations

VS VS

Phase I: Pore Water Characterization

Zeolite

Unamended

5 H. azteca

10 C. dubia

8 reps per treatment

2-d

stat

ic

test

Diluted by 50%

SPE C18

1-d

stat

ic

test

Phase I: Whole Sediment Characterization

Zeolite

Unamended

10 H. azteca

10 C. dubia

8 reps per treatment

4-d

stat

ic

test

PCC

10-d

flow

-th

ru te

st

2-d

stat

ic

test

Zeolite

Unamended

PCC

Comparing Methodologies: AmmoniaPore Water TIE Whole Sediment TIE

359 mg N/L 37.9 mg N/L

0.272.56

SS315 Ammonia Concentrations (mg N/L)

Predicted TUs for H. azteca

PHASE I:

PHASE II:

Comparing Methodologies: Non-polar OrganicsPore Water TIE Whole-Sediment TIE

The affects of:

• UCM

• Black carbon

• ingestion, adsorption

• DOC

• Glassware binding

PHASE I:

SS308 ∑PAH Concentrations:

TUs for H. aztecaPHASE II:

1.810.52

1953 µg/L 4405 µg/g oc

Comparing Species Sensitivity/Susceptibility

H. azteca C. dubia

Species Sensitivity ≠ Species Susceptibility

• Body Size /Age (Life Stage)

• Physiology/Feeding Behavior

• Niche

≈ 47.25 mg N/L (2-d)bLC50 Total Ammonia:≈ 140 mg N/L (4-d)a

a – Ankley et al. 1995

b – extrapolated from Bailey et al. 2001

c – Suedel and Rodgers, Jr. 1996

LC50 Fluoranthene (PAH): C. dubia ≈ 102.6 µg/L (10-d)cH. azteca ≈ 30.6 µg/L (10-d)c

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

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

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)

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

Un-ionized ammonia – 11.2 mg/L (TU = 5.19)

SS315 pore water

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

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

?

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?