Transcript Objectives - Illinois Sustainable Technology Center

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
2State
Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry,
Chinese Academy of Sciences, Guangzhou, China
3The
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”.
Contaminated w/
non-polar
organics
X
X
X
Unamended
X
Amended for nonpolar organics
Amended
X
Amended for
ammonia
X
X
X
X
Amended for metals
Matrix Choice
Pore
water
Sediment
grain
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)
STEP 4
Unamended
Amended
PHASE II: IDENTIFICATION
Ammonia (Ammonia Probe)
Cationic metals (NAD & FAAS)
Nonpolar Organics (ASE & GC/HPLC)
concentration of contaminant
U.S. EPA 2007 Whole sediment TIE guidelines
Toxic Unit (TU) =
LC50 of that contaminant
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
19
18
22
24
20
23
13-15
10-11
4
9
17
17
•
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
16
8 12
5-7
2
1
3
•
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’
Site Name
(Map Number)
Moore's Towhead (1)
Spring Lake Wildlife Area (2)
Pekin (3)
Mouth of Wesley Slough (4)
Peoria Dredge (5)
L Peoria Core 0-30 (6)
L Peoria Core 30-60
L Peoria Core 60-90
Upper Lower Peoria Lake (7)
Goose Lake (8)
Lacon (9)
Mudd Lake (10)
Sawmill Core 0-30 (11)
Sawmill Core 30-60
Sawmill Core 60-90
Down River of Hennepin (12)
Hennepin Power Plant (13)
Depue Lake (14)
Depue Core 0-30 (15)
Dupue Core 30-60
Dupue Core 60-90
Marseilles (16)
DuPage River (17)
Calmut 305 (18)
SS308 NC (19)
Stony Creek (20)
SS315 (21)
SS317 (22)
SR Cal RR (23)
Halstead Bridge (24)
Sites
21
19
18
22
24
20
13-15
10-11
4
9
16
8 12
5-7
2
1
3
St. Louis
Carbondale
X
17
17
23
River
Rivermile
Mile
76
134
151
160
165
166
166
166
166
179
187
196
197
197
197
205
212
212
212
212
212
248
277
305
308
309
315
317
318
320
Sc
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
Toxicity Tests
120
100
Spring Lake Wildlife Area
Pekin
Wesley
Upper Lower Peoria Lake
LPL Dredge
Goose
Lacon
Mudd
Hennepin Down River
Hennenpin Power Plant
DuPue
Marseilles
DuPage
CS305
SS308
Stony Creek
SS315
SS317
76
134
151
160
165
166
179
187
196
205
212
212
248
277
305
308
309
315
317
20
0
SRCALRR
40
Halstead
Moore’s Towhead
60
Touch of Nature
% Survival
80
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)
% Survival
100
80
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
Cu2+, Ni2+, Cr6+, Pb2+, Zn2+, Cd2+
Ammonia
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
SS308
Halstead
CS305
Creek
LPL SS308 Halstead CS305 Creek SRCALRR
6.39
37.7
26.5
27.6
50.4
23.8
LPL
Toxic Units
Metals (µg/g dry)
∑Metals (µg/g dry)
<0.1
Pore water total
Pore water
total
ammonia
(mg N/L)
6.48
ammonia (mg N/L)
BRL
PCBs (µg/g OC)
4.45
PCBs (µg/g oc)
Pesticides
PAHs
(µg/g(µg/g
oc) OC)
PAHs (µg/g oc)
36.6
<0.1
Pesticides (µg/g OC)
<0.1
<0.1
26.2
<0.1
<0.1
13.7
<0.1
<0.1
19.4
<0.1
<0.1
<0.1
21.7
541
<0.1
0.4
0.447
0.208
0.414
2.14
1.12
11.5
15.7
21.1
37.2
34.5
7.6
<0.1
1328
<0.1 1021
<0.1
1198
<0.1
1267
<0.1
4112
<0.1
<0.1
<0.1
586.8<0.11934
0.7
<0.1
SS315
SS315
17.9
2.8
<0.1
1.9
<0.1
1.8
<0.1
1.4
Low TU = Low Toxicity
High TU= High Toxicity
<0.1
1.6
0.405
<0.1
BRL – 1 µg/kg
4.6
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?
Matrix (UCM)
% Unresolved
% DieselComplex
Range Organics
SUMMER 07’
SUMMER 08’
• 46% of sites (in all seasons)
were characterized with PCC
Unamended (sand)
1.2
1
Organics (PCC)
0.8
• Affect on PCC binding capability?
0.6
• Organics higher affinity for UCM?
0.4
• Causes toxicity itself?
Is PCC always effective?
0.2
0
SS315
SS308
CS305
SRCALRR
Halstead
Toxic Sites
Stony
Creek
DuPage
LPL
Phase II: Spatial and temporal variation
mg N/L
800
600
400
Summer 2007
200
Winter 2007-2008
150
Spring 2008
Calumet Sag Channel
100
Summer 2008
Chicago Sanitary and
Shipping Canal
Fall 2007
50
0
µg/g dry wt
Total Cationic Metals
50
25
0
Total PAHs
mg/g OC
Concentration of Contaminant
Total Pore Water Ammonia
6.0
3.0
SS315
SS308
CS305
SRCALRR
Halstead
Stony
Creek
LPL
Total Pore Water Ammonia Concentration (mg N/L)
Spatial Trends: Ammonia
600
Y = 0.1314x – 16.633
r2 = 0.608
p < 0.001
550
500
75
50
25
0
50
100
150
200
250
Rivermile on the Illinois River
300
350
Total Pore Water Ammonia (mg N/L)
Spatial Trends: Ammonia
1000
750
500
Municipal Waste Plant
250
SS315
0
308
Courtesy of www.flashearth.com
Total Ammonia
>400 mg N/L
310
312
314
Rivermile
316
318
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%
1-d static
test
2-d static
test
Unamended
Zeolite
5 H. azteca
10 C. dubia
8 reps per treatment
SPE C18
4-d static
test
Phase I: Whole Sediment
Characterization
Zeolite
10-d flowthru test
Unamended
PCC
10 H. azteca
10 C. dubia
Unamended
PCC
8 reps per treatment
2-d static
test
Zeolite
Comparing Methodologies: Ammonia
Pore Water TIE
PHASE I:
Whole Sediment TIE
2.56
0.27
Predicted TUs for H. azteca
PHASE II:
359 mg N/L
SS315 Ammonia
Concentrations (mg N/L)
37.9 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?