UNT Institute of Applied Sciences, Parsons Engineering Sciences, Inc, &

Tx CEQ

SETAC 2002

TIE and TMDL Approaches for TIE and TMDL Approaches for Legacy Sediment Contaminants: Legacy Sediment Contaminants: Arsenic and Petrochemical Case Arsenic and Petrochemical Case

StudiesStudies

BW Brooks, PK Turner, JK Stanley, BW Brooks, PK Turner, JK Stanley, WT Waller, TW La Point, R Palachek WT Waller, TW La Point, R Palachek

& JA Sullivan& JA Sullivan

Background to StudyBackground to Study

Study purpose: to assess presence and Study purpose: to assess presence and causes of aqueous and sediment toxicity in causes of aqueous and sediment toxicity in Texas rivers;Texas rivers;

Develop approaches to sediment toxicity Develop approaches to sediment toxicity identification evaluations;identification evaluations;

Focus on complex sites: Alligator Bayou Focus on complex sites: Alligator Bayou and Finfeather Lake.and Finfeather Lake.

Alligator Bayou Study SiteAlligator Bayou Study Site

A freshwater tributary upstream of a salt A freshwater tributary upstream of a salt water barrier, near Port Arthur, TX. water barrier, near Port Arthur, TX.

Alligator Bayou receives discharges from Alligator Bayou receives discharges from municipal and industrial facilities, plus municipal and industrial facilities, plus smaller amount of agricultural runoff. smaller amount of agricultural runoff.

An urban, industrial river.An urban, industrial river.

Finfeather Lake Study SiteFinfeather Lake Study Site

A small municipal waterbody located in A small municipal waterbody located in Bryan, TX, upstream of Bryan Municipal Bryan, TX, upstream of Bryan Municipal Lake. Lake.

Historically, arsenic has been the parameter Historically, arsenic has been the parameter of concern due to surface and groundwater of concern due to surface and groundwater contaminationcontamination..

Standard TIE ProceduresStandard TIE Procedures

Initial Acute or Chronic Dilution Toxicity Test

Baseline Toxicity Test

EDTA SIR-3001 SIR-9002 Thiosulfate Aeration3

EDTA SIR-300

Filtration

C18 SPE Ambersorb 5634

Does TIE Treatment Statistically Improve ToxicityRelative 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

TIE Procedures in this StudyTIE Procedures in this Study

Treatment Chemical(s) Identified

Filtration Particulates/Sorptive chemicals

Ambersorb 563/C18 columns Nonpolar organics (PAH)

SIR-300, -900/EDTA chelation

Metals

Oxidant reduction w/thiosulfate

Halides/Metals

Aeration

Volatile organics/Surfactants

SIR-300 Resin SIR-300 Resin Used as a parallel TIE treatment to EDTA.Used as a parallel TIE treatment to EDTA.

A cation exchange resin, styrene & A cation exchange resin, styrene & divinylbenzene copolymer with iminodiacetic divinylbenzene copolymer with iminodiacetic functional group in the sodium form, chelates functional group in the sodium form, chelates divalent metal cations.divalent metal cations.

Reported affinity for metals: HgReported affinity for metals: Hg2+2+>Cu>Cu2+ 2+ > > VV2+2+>Pb>Pb2+2+>Ni>Ni2+2+>Zn>Zn2+2+>Co>Co2+2+>Cd>Cd2+2+>Fe>Fe2+2+>Be>Be2+2+ = = MnMn2+2+>Mg>Mg2+2+ = Ca = Ca2+2+> Sr> Sr2+2+>Ba>Ba2+2+>Na>Na2+2+. .

We found MgWe found Mg2+2+ and Ca and Ca2+ 2+ to be taken out.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 Sediment/10643 H. azteca None06-200207-2002 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 BayouStation 10643, Porewater Acute Toxic Units.

Metal Acute Criterion1 Source

 Al 991 TCEQAs 360 TCEQCd 104 TCEQCr 1000 USEPACu 48.6 TCEQFe 1000 USEPAPb 269 TCEQNi 3348 TCEQZn 274 TCEQ

1Acute criterion (µg/L) based on water hardness of 280 mg/L (25% station 10643 porewater) where appropriate.

Metal Chemistry of Alligator Bayou Sediment Porewater TIEMetal Chemistry of Alligator Bayou Sediment Porewater TIE11 48-hour 48-hour C. dubiaC. dubia test test

Metal Sed (mg/kg) 100%Base Aeration SIR 300 SIR 300 + Metal Sed (mg/kg) 100%Base Aeration SIR 300 SIR 300 +

AerationAeration

AlAl 2370000023700000 718718 179 179 340 340 266266 AsAs 8130 8130 ND ND ND ND ND ND NDND CdCd 636 636 ND ND ND ND ND ND NDND CrCr33 45400 45400 11.611.6 ND ND ND ND NDND Cu Cu 42500 42500 ND ND ND ND ND ND NDND FeFe 2180000021800000 581581 395 395 218 218 188188 PbPb 211000 211000 75 75 31.4 31.4 29 29 25.325.3 NiNi 17200 17200 12.412.4 11.1 11.1 ND ND NDND ZnZn 218000 218000 16.316.3 13.2 13.2 ND ND 11.811.8  1125% porewater dilutions25% porewater dilutions

Metal Toxic Units of Alligator Bayou Sediment Porewater TIEMetal Toxic Units of Alligator Bayou Sediment Porewater TIE11 48-hour 48-hour C. dubiaC. dubia test test

Metal 25%Base Aeration SIR 300 SIR 300 + AerationMetal 25%Base Aeration SIR 300 SIR 300 + Aeration

AlAl 180 180 44.744.7 85 85 66.566.5 AsAs ND ND ND ND ND ND NDND CdCd ND ND ND ND ND ND 0.680.68 CrCr33 2.9 2.9 NDND ND ND ND ND Cu Cu ND ND ND ND ND ND NDND FeFe 145.2 145.2 98.898.8 7.25 7.25 47 47 PbPb 18.8 18.8 7.8 7.8 31.4 31.4 6.36.3 NiNi 3.1 3.1 2.8 2.8 ND ND NDND ZnZn 4.1 4.1 3.3 3.3 ND ND 2.952.95  1125% porewater dilutions25% porewater dilutions

Alligator Bayou: ResultsAlligator Bayou: Results

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

Toxicity reduction with these treatments suggests Toxicity reduction with these treatments suggests that metals are causative toxicants to that metals are causative toxicants to Ceriodaphnia dubiaCeriodaphnia dubia..

Chemical analysis on baseline porewater, Chemical analysis on baseline porewater, Aeration, SIR-300 and Aeration + SIR-300 Aeration, SIR-300 and Aeration + SIR-300 samples indicates that SIR-300 reduced or samples indicates that SIR-300 reduced or removed Al, Cr, Fe, Pb, Ni, & Zn.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 60 mg/L1 80 mg/L 120 mg/L 128 mg/L

 Al NL NL NL NLAs 190 190 190 190Ba 1000 1000 1000 1000Cd 0.7 0.9 1.2 1.25Cr 100 100 100 100Cu 7.9 10.6 14.3 15.17Fe 1000 1000 1000 1000Pb 1.3 2.02 3.2 3.45 Hg 1.3 1.3 1.3 1.3Ni 102 136 183 194Se 5.0 5.0 5.0 5.0Ag 1.7 3.01 5.5 6.20Zn 67.8 90.1 122 129

1Reconstituted moderately hard water after treatment with SIR 300 and calcium and magnesium reintroduced.

Finfeather Lake: ResultsFinfeather Lake: Results

Consistent sediment toxicity to Consistent sediment toxicity to C. tentans C. tentans and and H. aztecaH. azteca;;

SIR-300 and SIR-900 significantly SIR-300 and SIR-900 significantly increased increased C. dubiaC. dubia reproduction and reproduction and H. H. aztecaazteca growth; growth;

Cu, Zn and Pb (Cu, Zn and Pb (not not As) are the major As) are the major players;players;

Phase III TIEPhase III TIE

Study ConclusionsStudy Conclusions

Currently, TSWQS do not include applicable promulgated Currently, TSWQS do not include applicable promulgated sediment criteria. sediment criteria.

There are insufficient procedures or methods to manage There are insufficient procedures or methods to manage Alligator Bayou sediment issues under the existing TMDL Alligator Bayou sediment issues under the existing TMDL program. program.

Alligator Bayou will require an innovative approach to Alligator Bayou will require an innovative approach to solving the sediment toxicity issue. solving the sediment toxicity issue.

Real Issue: how to deal with “legacy” toxicants?!Real Issue: how to deal with “legacy” toxicants?!

Overall RecommendationsOverall Recommendations

TIE and Resins/Adsorbent MediaTIE and Resins/Adsorbent Media

Look promising: Research needed for porewaters Look promising: Research needed for porewaters and whole sedimentsand whole sediments

TMDL approach to historical contamination: a TMDL approach to historical contamination: a valid approach?valid approach?

How to link TIE and Sediment Triad?How to link TIE and Sediment Triad?