TIE and TMDL Approaches for
Legacy Sediment Contaminants:
Arsenic and Petrochemical Case
Studies
BW Brooks, PK Turner, JK Stanley,
WT Waller, TW La Point, R Palachek
& JA Sullivan
UNT Institute of Applied Sciences,
Parsons Engineering Sciences, Inc, &
Tx CEQ
SETAC 2002
Background to Study
Study purpose: to assess presence and
causes of aqueous and sediment toxicity in
Texas rivers;
Develop approaches to sediment toxicity
identification evaluations;
Focus on complex sites: Alligator Bayou
and Finfeather Lake.
Alligator Bayou Study Site
A freshwater tributary upstream of a salt
water barrier, near Port Arthur, TX.
Alligator Bayou receives discharges from
municipal and industrial facilities, plus
smaller amount of agricultural runoff.
An urban, industrial river.
Finfeather Lake Study Site
A small municipal waterbody located in
Bryan, TX, upstream of Bryan Municipal
Lake.
Historically, arsenic has been the parameter
of concern due to surface and groundwater
contamination.
Standard TIE Procedures
TIE Procedures in this Study
Initial Acute or Chronic Dilution Toxicity Test
Phase I TIE Treatments at Appropriate Dilution Level
Thiosulfate
EDTA
SIR-3001
SIR-9002
Baseline
Toxicity Test
Aeration3
EDTA
SIR-300
Does TIE Treatment Statistically Improve Toxicity
Relative to Corresponding Baseline Dilution Level?
Yes
Phase II Procedures Including Analytical Measures of Effective
TIE Treatments to Screen for Suspected Toxicants
Phase III Confirmation Procedures
Filtration
C18 SPE
5634
Ambersorb
TIE Procedures in this Study
Treatment
Chemical(s) Identified
Filtration
Particulates/Sorptive
chemicals
Nonpolar organics (PAH)
Ambersorb 563/C18 columns
SIR-300, -900/EDTA
chelation
Metals
Oxidant reduction
w/thiosulfate
Halides/Metals
Aeration
Volatile organics/Surfactants
SIR-300 Resin
Used as a parallel TIE treatment to EDTA.
A cation exchange resin, styrene &
divinylbenzene copolymer with iminodiacetic
functional group in the sodium form, chelates
divalent metal cations.
Reported affinity for metals: Hg2+>Cu2+ >
V2+>Pb2+>Ni2+>Zn2+>Co2+>Cd2+>Fe2+>Be2+ =
Mn2+>Mg2+ = Ca2+> Sr2+>Ba2+>Na2+.
We found Mg2+ and Ca2+ to be taken out.
Alligator Bayou: Effective Acute TIE Treatments
Test Date
Test Type/Station
Organism
Treatment(s)
08-2001
Porewater/10643
C. dubia
Aeration + EDTA,
C18
12-2001
Porewater/10643
C. dubia
S300, EDTA,
Aeration + EDTA
05-2001
06-2002
07-2002
Sediment/10643
H. azteca
None
Porewater/14410
C. dubia
C18 @48h; Filt,
S300, A563@24hr
08-2002
Porewater/10643
C. dubia
C18, A563 @48h;
Filt, S300 @24hr
Water Quality Criteria Used To Calculate Alligator Bayou
Station 10643, Porewater Acute Toxic Units.
Metal
Al
As
Cd
Cr
Cu
Fe
Pb
Ni
Zn
1Acute
Acute Criterion1
991
360
104
1000
48.6
1000
269
3348
274
Source
TCEQ
TCEQ
TCEQ
USEPA
TCEQ
USEPA
TCEQ
TCEQ
TCEQ
criterion (µg/L) based on water hardness of 280 mg/L (25% station 10643
porewater) where appropriate.
Metal Chemistry of Alligator Bayou Sediment Porewater TIE1
48-hour C. dubia test
Metal Sed (mg/kg) 100%Base Aeration
Al
As
Cd
Cr3
Cu
Fe
Pb
Ni
Zn
125%
23700000
8130
636
45400
42500
21800000
211000
17200
218000
porewater dilutions
718
ND
ND
11.6
ND
581
75
12.4
16.3
179
ND
ND
ND
ND
395
31.4
11.1
13.2
SIR 300 SIR 300 +
Aeration
340
ND
ND
ND
ND
218
29
ND
ND
266
ND
ND
ND
ND
188
25.3
ND
11.8
Metal Toxic Units of Alligator Bayou Sediment Porewater TIE1
48-hour C. dubia test
Metal 25%Base
Al
As
Cd
Cr3
Cu
Fe
Pb
Ni
Zn
125%
Aeration
180
ND
ND
2.9
ND
145.2
18.8
3.1
4.1
porewater dilutions
44.7
ND
ND
ND
ND
98.8
7.8
2.8
3.3
SIR 300
85
ND
ND
ND
ND
7.25
31.4
ND
ND
SIR 300 + Aeration
66.5
ND
0.68
ND
ND
47
6.3
ND
2.95
Alligator Bayou: Results
TIE identified significant toxicity reduction at 25%
porewater dilution using EDTA, SIR-300 and
Aeration + EDTA, but not by Aeration treatments.
Toxicity reduction with these treatments suggests
that metals are causative toxicants to
Ceriodaphnia dubia.
Chemical analysis on baseline porewater, Aeration,
SIR-300 and Aeration + SIR-300 samples
indicates that SIR-300 reduced or removed Al, Cr,
Fe, Pb, Ni, & Zn.
Finfeather Lake: Effective Chronic TIE Treatments
Test Date
Test Type/Station
Organism
Treatment(s)
07-2001
Porewater/11798
C. dubia
None
09-2001
Porewater/11798
C. dubia
SIR-300, SIR-900
02-2002
Porewater/11798
C. dubia
SIR-300, SIR-900
03-2002
Sediment/11798
H. azteca
SIR-900
06-2002
Porewater11798
C. dubia
EDTA, SIR-300
06-2002
Porewater/11800
C. dubia
EDTA
Water Quality Criteria Used to Calculate Finfeather Lake,
Station 11798, Porewater Chronic Toxic Units
Hardness (mg/L as CaCO3)
Metal
Al
As
Ba
Cd
Cr
Cu
Fe
Pb
Hg
Ni
Se
Ag
Zn
1Reconstituted
60 mg/L1
NL
190
1000
0.7
100
7.9
1000
1.3
1.3
102
5.0
1.7
67.8
80 mg/L
NL
190
1000
0.9
100
10.6
1000
2.02
1.3
136
5.0
3.01
90.1
120 mg/L
NL
190
1000
1.2
100
14.3
1000
3.2
1.3
183
5.0
5.5
122
128 mg/L
NL
190
1000
1.25
100
15.17
1000
3.45
1.3
194
5.0
6.20
129
moderately hard water after treatment with SIR 300 and calcium and magnesium reintroduced.
Finfeather Lake: Results
Consistent sediment toxicity to C. tentans
and H. azteca;
SIR-300 and SIR-900 significantly
increased C. dubia reproduction and H.
azteca growth;
Cu, Zn and Pb (not As) are the major
players;
Phase III TIE
Study Conclusions
Currently, TSWQS do not include applicable promulgated
sediment criteria.
There are insufficient procedures or methods to manage
Alligator Bayou sediment issues under the existing TMDL
program.
Alligator Bayou will require an innovative approach to
solving the sediment toxicity issue.
Real Issue: how to deal with “legacy” toxicants?!
Overall Recommendations
TIE and Resins/Adsorbent Media
Look promising: Research needed for porewaters
and whole sediments
TMDL approach to historical contamination: a
valid approach?
How to link TIE and Sediment Triad?