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

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.

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.

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.

Standard TIE Procedures

Initial Acute or Chronic Dilution Toxicity Test Baseline Toxicity Test EDTA SIR SIR Thiosulfate Aeration 3 EDTA SIR-300 Filtration C 18 SPE Ambersorb 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

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.

Alligator Bayou: Effective Acute TIE Treatments Test DateTest Type/StationOrganismTreatment(s) Porewater/10643C. dubiaAeration + EDTA, C Porewater/10643C. dubia S300, EDTA, Aeration + EDTA Sediment/10643H. aztecaNone Porewater/14410C. dubia Filt, S300, Porewater/10643C. dubia C18, Filt,

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 porewater) where appropriate.

Metal Chemistry of Alligator Bayou Sediment Porewater TIE 1 48-hour C. dubia test Metal Sed (mg/kg) 100%Base Aeration SIR 300 SIR Aeration Al Al As 8130ND ND ND ND As 8130ND ND ND ND Cd 636ND ND ND ND Cd 636ND ND ND ND Cr ND NDND Cr ND NDND Cu 42500ND ND NDND Cu 42500ND ND NDND Fe Fe Pb Pb Ni NDND Ni NDND Zn ND11.8 Zn ND % porewater dilutions

Metal Toxic Units of Alligator Bayou Sediment Porewater TIE 1 48-hour C. dubia test Metal 25%Base Aeration SIR 300 SIR Aeration Metal 25%Base Aeration SIR 300 SIR Aeration Al 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 Fe Pb Pb Ni NDND Ni NDND Zn ND2.95 Zn ND % porewater dilutions

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.

Finfeather Lake: Effective Chronic TIE Treatments Test DateTest Type/StationOrganismTreatment(s) Porewater/11798C. dubiaNone Porewater/11798C. dubiaSIR-300, SIR Porewater/11798C. dubiaSIR-300, SIR Sediment/11798H. aztecaSIR Porewater11798C. dubiaEDTA, SIR Porewater/11800C. dubiaEDTA

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 As Ba Cd Cr Cu Fe Pb Hg Ni Se Ag Zn Reconstituted 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; 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

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?!

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?