1. UNT Institute of Applied Sciences, Parsons Engineering Sciences, Inc, & Tx CEQ SETAC 2002 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

2. Background to Study Study purpose: to assess presence and causes of aqueous and sediment toxicity in Texas rivers; Study purpose: to assess presence and causes of aqueous and sediment toxicity in Texas rivers; Develop approaches to sediment toxicity identification evaluations; Develop approaches to sediment toxicity identification evaluations; Focus on complex sites: Alligator Bayou and Finfeather Lake. Focus on complex sites: Alligator Bayou and Finfeather Lake.

5. Alligator Bayou Study Site A freshwater tributary upstream of a salt water barrier, near Port Arthur, TX. 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. Alligator Bayou receives discharges from municipal and industrial facilities, plus smaller amount of agricultural runoff. An urban, industrial river. An urban, industrial river.

7. Finfeather Lake Study Site A small municipal waterbody located in Bryan, TX, upstream of Bryan Municipal Lake. 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. Historically, arsenic has been the parameter of concern due to surface and groundwater contamination.

8. Standard TIE Procedures

9. Initial Acute or Chronic Dilution Toxicity Test Baseline Toxicity Test EDTA SIR-300 1 SIR-900 2 Thiosulfate Aeration 3 EDTA SIR-300 Filtration C 18 SPE Ambersorb 563 4 Does TIE Treatment Statistically Improve Toxicity Relative to Corresponding Baseline Dilution Level? Phase I TIE Treatments at Appropriate Dilution Level Phase II Procedures Including Analytical Measures of Effective TIE Treatments to Screen for Suspected Toxicants Yes Phase III Confirmation Procedures TIE Procedures in this Study

11. SIR-300 Resin Used as a parallel TIE treatment to EDTA. 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. A cation exchange resin, styrene & divinylbenzene copolymer with iminodiacetic functional group in the sodium form, chelates divalent metal cations. Reported affinity for metals: Hg 2+ >Cu 2+ > V 2+ >Pb 2+ >Ni 2+ >Zn 2+ >Co 2+ >Cd 2+ >Fe 2+ >Be 2+ = Mn 2+ >Mg 2+ = Ca 2+ > Sr 2+ >Ba 2+ >Na 2+. Reported affinity for metals: Hg 2+ >Cu 2+ > V 2+ >Pb 2+ >Ni 2+ >Zn 2+ >Co 2+ >Cd 2+ >Fe 2+ >Be 2+ = Mn 2+ >Mg 2+ = Ca 2+ > Sr 2+ >Ba 2+ >Na 2+. We found Mg 2+ and Ca 2+ to be taken out. We found Mg 2+ and Ca 2+ to be taken out.

12. Alligator Bayou: Effective Acute TIE Treatments Test DateTest Type/StationOrganismTreatment(s) 08-2001Porewater/10643C. dubiaAeration + EDTA, C18 12-2001Porewater/10643C. dubia S300, EDTA, Aeration + EDTA 05-2001 Sediment/10643H. aztecaNone 06-2002 07-2002Porewater/14410C. dubia C18 @48h; Filt, S300, A563@24hr 08-2002Porewater/10643C. dubia C18, A563 @48h; Filt, S300 @24hr

13. Water Quality Criteria Used To Calculate Alligator Bayou Station 10643, Porewater Acute Toxic Units. MetalAcute Criterion 1 Source Al 991TCEQ As 360TCEQ Cd 104TCEQ Cr1000USEPA Cu 48.6TCEQ Fe1000USEPA Pb 269TCEQ Ni3348TCEQ Zn 274TCEQ 1 Acute criterion (µg/L) based on water hardness of 280 mg/L (25% station 10643 porewater) where appropriate.

14. Metal Chemistry of Alligator Bayou Sediment Porewater TIE 1 48-hour C. dubia test Metal Sed (mg/kg) 100%Base Aeration SIR 300 SIR 300 + Aeration Al23700000718 179 340266 Al23700000718 179 340266 As 8130ND ND ND ND As 8130ND ND ND ND Cd 636ND ND ND ND Cd 636ND ND ND ND Cr 3 4540011.6 ND NDND Cr 3 4540011.6 ND NDND Cu 42500ND ND NDND Cu 42500ND ND NDND Fe 21800000581 395 218188 Fe 21800000581 395 218188 Pb 21100075 31.4 2925.3 Pb 21100075 31.4 2925.3 Ni 1720012.4 11.1 NDND Ni 1720012.4 11.1 NDND Zn 21800016.3 13.2 ND11.8 Zn 21800016.3 13.2 ND11.8 1 25% porewater dilutions

15. Metal Toxic Units of Alligator Bayou Sediment Porewater TIE 1 48-hour C. dubia test Metal 25%Base Aeration SIR 300 SIR 300 + Aeration Metal 25%Base Aeration SIR 300 SIR 300 + Aeration Al 18044.7 85 66.5 As NDND ND ND As NDND ND ND Cd NDND ND 0.68 Cd NDND ND 0.68 Cr 3 2.9ND ND ND Cr 3 2.9ND ND ND Cu NDND ND ND Cu NDND ND ND Fe 145.298.8 7.25 47 Fe 145.298.8 7.25 47 Pb 18.8 7.8 31.46.3 Pb 18.8 7.8 31.46.3 Ni 3.1 2.8 NDND Ni 3.1 2.8 NDND Zn 4.1 3.3 ND2.95 Zn 4.1 3.3 ND2.95 1 25% porewater dilutions

18. Alligator Bayou: Results TIE identified significant toxicity reduction at 25% porewater dilution using EDTA, SIR-300 and Aeration + EDTA, but not by Aeration treatments. 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. 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. 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.

19. Finfeather Lake: Effective Chronic TIE Treatments Test DateTest Type/StationOrganismTreatment(s) 07-2001Porewater/11798C. dubiaNone 09-2001Porewater/11798C. dubiaSIR-300, SIR-900 02-2002Porewater/11798C. dubiaSIR-300, SIR-900 03-2002Sediment/11798H. aztecaSIR-900 06-2002Porewater11798C. dubiaEDTA, SIR-300 06-2002Porewater/11800C. dubiaEDTA

20. Water Quality Criteria Used to Calculate Finfeather Lake, Station 11798, Porewater Chronic Toxic Units Hardness (mg/L as CaCO 3 ) Metal 60 mg/L 1 80 mg/L 120 mg/L 128 mg/L AlNL NL NL NL As190 190 190 190 Ba1000 1000 1000 1000 Cd 0.7 0.9 1.2 1.25 Cr100 100 100 100 Cu7.9 10.6 14.3 15.17 Fe1000 1000 1000 1000 Pb1.3 2.02 3.2 3.45 Hg1.3 1.3 1.3 1.3 Ni 102136 183 194 Se5.0 5.0 5.0 5.0 Ag1.7 3.01 5.5 6.20 Zn67.8 90.1 122 129 1 Reconstituted moderately hard water after treatment with SIR 300 and calcium and magnesium reintroduced.

21. Finfeather Lake: Results Consistent sediment toxicity to C. tentans and H. azteca; Consistent sediment toxicity to C. tentans and H. azteca; SIR-300 and SIR-900 significantly increased C. dubia reproduction and H. azteca growth; SIR-300 and SIR-900 significantly increased C. dubia reproduction and H. azteca growth; Cu, Zn and Pb (not As) are the major players; Cu, Zn and Pb (not As) are the major players; Phase III TIE Phase III TIE

22. Study Conclusions Currently, TSWQS do not include applicable promulgated sediment criteria. 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. 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. Alligator Bayou will require an innovative approach to solving the sediment toxicity issue. Real Issue: how to deal with “legacy” toxicants?! Real Issue: how to deal with “legacy” toxicants?!

23. Overall Recommendations TIE and Resins/Adsorbent Media TIE and Resins/Adsorbent Media Look promising: Research needed for porewaters and whole sediments TMDL approach to historical contamination: a valid approach? TMDL approach to historical contamination: a valid approach? How to link TIE and Sediment Triad? How to link TIE and Sediment Triad?