Total Maximum Daily Load for Dioxin in the Houston Ship ... · Total Maximum Daily Load for Dioxin...

Total Total Maximum Maximum Daily Load Daily Load for Dioxin for Dioxin

in the in the Houston Houston

Ship Ship ChannelChannel

University of HoustonUniversity of HoustonParsons Water&InfrastructureParsons Water&Infrastructure

PBS&JPBS&J

Main tasks Phase III Main tasks Phase III –– (WO7)(WO7)

Develop a QAPP for additional data collection

Conduct dioxin monitoring and additional data collection in the HSC

Model fate and transport of dioxins in the HSC using sophisticated

models

Estimate TMDL allocationsEstimate TMDL allocations

Participate in stakeholder processParticipate in stakeholder process

Evaluate PCB data gathered to dateEvaluate PCB data gathered to date

models

Task 1 Task 1 –– Develop a QAPPDevelop a QAPP

QAPP approved on 01/27/2004Amendment 1, approved on 07/01/2004, developed to add:

vertical profiles of dioxin at 2 locationshigh-resolution sediment samplingboundary concentrations for model

Amendment 2, approved on 08/19/2004, developed toadd one set of runoff samplesmodify dry/wet and add bulk deposition samplingadd air sampling by particle size

Annual update, submitted on 01/20/2005add flow measurements

models

Task 2 Task 2 –– Monitoring and data collectionMonitoring and data collection

Assess current levels and trends in the project area:17 in-channel locations for water (dissolved and particulate matter), sediment, fish, and crab twice11 tributary locations for fish and crab 1 timesediment cores from 6-8 locations to gather data on the historical deposition of dioxins and furans as well as accumulation rates2 locations for deep&shallow water sampling once15 locations for high-resolution sediment sampling once2 locations in upper watershed for water sampling once

Task 2 Task 2 –– Monitoring and data collection Monitoring and data collection –– contcont’’dd

Assess major sources:• Ambient water at confluences with main tributaries (11

locations, 2 times)• Ambient air, wet/dry/bulk deposition, and particle size at 1

location• Runoff sampling at 10 locations once

Sampling locationsSampling locations

Water, sediment, and tissue (main channel)

Water and tissue (tribs)

Vertical profile (water)

Water, sediment, and tissue (main channel)

Water and tissue (tribs)

Vertical profile (water)

Dioxin in water profilesDioxin in water profiles

Texas WQS:0.093 pg/L

Open symbols: spring 2004Closed symbols average WO4

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Distance from Morgan's Point (km)

Main channel San Jacinto River Tributaries Side Bays

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Morgan's Point

Dioxin in sedimentDioxin in sediment--ococ profilesprofiles

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Main channel San Jacinto River Side Bays Tributaries

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Morgan's Point

Dioxin in catfish profilesDioxin in catfish profiles

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Morgan's Point

Texas TEQ health-based std: 0.47 ng/kg

Dioxin in crab profilesDioxin in crab profiles

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Morgan's Point

Texas TEQ health-based std: 0.47 ng/kg

Seasonal trends in water samplesSeasonal trends in water samples

Summer-02Fall-02Spring-03Spring-04

Error bars correspond to the 95 % confidence intervals

2378-TCDD TEQ

DissolvedDissolved

L) SuspendedSuspended

2378-TCDD TEQ

Seasonal trends in sedimentSeasonal trends in sediment--ococ samplessamples

Error bars correspond to the 95 % confidence intervals

2378-TCDD TEQ

Seasonal trends in tissue samplesSeasonal trends in tissue samples

Error bars correspond to the 95 % confidence intervals 0

CrabsCrabs

2378-TCDD TEQ

CatfishCatfish

2378-TCDD TEQ

Approach 1:Water concentration target, relying on hi-vol water sampling

Approach 2:Tissue-based WQS, using bioaccumulation factors to link water/sediment concentrations to tissue concentrations

Identifying WQ targetsIdentifying WQ targets

Approach 1:Use measures of central tendency of the Cb/Cw and Cb/Coc ratios

Approach 2:Calculate BAF and BSAF from average concentrations (EPA, 2003)

Calculating bioaccumulation factorsCalculating bioaccumulation factors

Cb=concentration in biota [pg/kg-wet wt]Cw=concentration in water [pg/L]Coc=organic-carbon normalized concentration [pg/kg-oc]

BAF = Cb / Cw BSAF = Cb / CsedOC

23782378--TCDD HSC siteTCDD HSC site--specific BAF (specific BAF (CCbb//CCww))

Resulting WQ targets for catfish:

App 1: 0.042 pg/L

App 2: 0.045 pg/L

Resulting WQ targets for catfishResulting WQ targets for catfish:

App 1: 0.042 pg/L

App 2: 0.045 pg/L

Resulting WQ targets for crab:

App 1: 0.059 pg/L

App 2: 0. 061 pg/L

Resulting WQ targets for crabResulting WQ targets for crab:

App 1: 0.059 pg/L

App 2: 0. 061 pg/L

Data from 4 events

1E-06 1E-05 1E-04 1E-03

avg log BAF (5.17)log (avg catfish/avg dissolved) (5.05)

1E-06 1E-05 1E-04 1E-03

avg log BAF (4.78)log (avg crab/avg dissolved) (4.73)

Dissolved concentration (ng/L)

23782378--TCDD HSC siteTCDD HSC site--specific BSAF (specific BSAF (CCbb//CsCsococ))

Resulting sediment targets from catfish:

App 1: 72 ng/kg-oc

App 2: 151 ng/kg-oc

Resulting sediment targets from Resulting sediment targets from catfishcatfish:

App 1: 72 ng/kg-oc

App 2: 151 ng/kg-oc

Resulting sediment targets from crab:

App 1: 126 ng/kg-oc

App 2: 253 ng/kg-oc

Resulting sediment targets from Resulting sediment targets from crabcrab:

App 1: 126 ng/kg-oc

App 2: 253 ng/kg-oc

Data from 4 events

1E+00 1E+01 1E+02 1E+03 1E+04 1E+05

median BSAF (0.01003)

ratio (avg catfish/avg sediment-oc)

1E+00 1E+01 1E+02 1E+03 1E+04 1E+05

median BSAF (0.0042)

ratio (avg crab/avg sediment-oc)(0 0021)

Sediment concentration (ng/kg-oc)

Deep and shallow sample resultsDeep and shallow sample results

11193-Shallow11193-Deep

15979-Shallow15979-Deep

DissolvedDissolved--suspended fugacity ratiossuspended fugacity ratios

1.E-03

1.E-02

1.E-01

1.E+00

1.E+0123

city R

(fs/fw

11193-sh11193-de15979-sh15979-de

Equilibrium

sh=shallow

de=deep

sediment water column flux

water column sediment flux

DissolvedDissolved--bottom sediment fugacity ratiosbottom sediment fugacity ratios

1.E-02

1.E-01

1.E+00

1.E+01

1.E+0223

city R

(fs/fw

11193-de15979-de

de=deep

Equilibriumsediment water column flux

water column sediment flux

HighHigh--resolution sediment samplingresolution sediment sampling

8.1-11.711.7-15.915.9-20.420.4-32.032.0-55.1

TEQ (ng/kg-dry wt)

HighHigh--resolution sediment sampling resultsresolution sediment sampling results

600011

-oc) Main Channel (segments 1007-1006) San Jacinto River

350011

Main Channel (segments 1007-1006) San Jacinto River

Sediment concentrations along15979 transectSediment concentrations along15979 transect

A B C D E

0200400600800

10001200

A B C D E2378

Sediment core locationsSediment core locations

Sediment aging and deposition rate estimates underway

Dioxin concentrations in 11261 coreDioxin concentrations in 11261 core

1015202530354045

0 5 10 15 20 25 30Concentration (ng/kg-dry wt)

2378-TCDD 2378-TCDF 12378-PeCDD 23478-PeCDF TEQOCDD/100

500 5 10 15 20 25 30 35 40

Concentration (ng/kg-dry wt)

1015202530354045

0 5 10 15 20 25 30 35 40 45Concentration (ng/kg-dry wt)

Air monitoring locationsAir monitoring locations

Clinton Dr

Haden Rd

Bayland Park

Mont Belvieu

Dioxin in ambient airDioxin in ambient airTo

ir (fg

Sep Oct Nov Dec Jan Feb Mar Apr May Jun Jul

Haden Rd.

Clinton Dr.

Bayland Park

Mont Belvieu

Monthly average concentrations in airMonthly average concentrations in air

sep oct nov dec jan feb mar apr may jun jul augMonth

1,2,3,

4,6,7,

(fg/m3 )

TEMP (°C) 2,3,7,8-TCDD 1,2,3,7,8-PeCDD2,3,7,8-HxCDDs 1,2,3,4,6,7,8-HpCDD OCDD

sep oct nov dec jan feb mar apr may jun jul augMonth

2,3,7,

m3 )TEMP (°C) 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF2,3,7,8-HxCDFs 2,3,7,8-HpCDFs OCDF

Dioxins by particle sizeDioxins by particle size

>7.2 um 7.2-3.0 3.0-1.5 1.5-0.95 0.95-0.49 <0.49 umCascade Impactor Stages

2378-PCDDs2378-PCDFsParticle mass conc

Dioxin in ambient air (SeptDioxin in ambient air (Sept--Oct, 2004)Oct, 2004)

54228165530.9

8942 4 30

2,3,7,

1,2,3,

4,7,8-

1,2,3,

6,7,8-

1,2,3,

7,8,9-

1,2,3,

4,6,7,

2,3,7,

1,2,3,

2,3,4,

1,2,3,

4,7,8-

1,2,3,

6,7,8-

2,3,4,

6,7,8-

1,2,3,

7,8,9-

1,2,3,

4,6,7,

1,2,3,

4,7,8,

Air deposition Air deposition –– sampling locationssampling locations

DryDry--deposition samplingdeposition sampling

Average deposition velocity (cm/sec)

2378-TCDD 4.2

OCDD 0.2

2378-TCDF 1.3

OCDF 0.3

Average deposition flux (fg/m2-hr)

2378-TCDD 43

OCDD 6,880

2378-TCDF 44

OCDF 410

Total TEQ in runoffTotal TEQ in runoff

2005 sampling site

2002 sampling site

candidate site

models

Conceptual model for dioxins in the HSCConceptual model for dioxins in the HSC

Stack emissions

Dispersion

Discharges from tributaries

Runoff

Equilibrium partitioning

Discharges from GW

Bottom sediments

ilizat

BurialResuspension

Dissolved phase

BSAFBSAF

Suspended solids

Photodegradation

Biodegradation

Point source effluent

Segmentation for simplified modelSegmentation for simplified model

Loading schematicLoading schematic

1 Main channel segment (14 in total)

1 Boundary segment (13 in total)

1 Loading segment (11 in total)

1 benthic segment (not shown)

PS for simplified modelPS for simplified model

Segment Total flow (m 3/s)

2378-TCDD load (kg/day)

TSS load (kg/day)

1 3.9E-04 5.7E-13 8.9E-032 2.5E+00 2.0E-09 17923 4.4E-01 2.9E-09 3104 1.4E+00 5.1E-11 9845 1.6E+00 1.6E-09 15936 9.0E-01 1.7E-09 6237 1.1E+00 1.3E-08 768

18 5.0E-01 2.7E-09 34719 1.1E-01 1.4E-09 7721 1.7E+00 3.3E-09 1173

NPS for simplified modelNPS for simplified model

Segment Area (km 2)

Avg. daily rainfall (in)

2378-TCDD load (kg/day)

TSS load (kg/day)

1 1244 0.13 3.1E-08 467282 339 0.13 1.2E-08 308523 242 0.14 7.3E-09 100264 62 0.13 2.0E-09 38785 91 0.16 2.7E-09 52136 585 0.14 1.4E-08 558607 14 0.14 3.6E-10 12428 98 0.17 2.2E-09 7618

18 1125 0.18 1.8E-08 6173522 85 0.17 2.1E-09 415123 50 0.14 1.2E-09 3980

Sensitivity analysisSensitivity analysis--dissolveddissolved

0510152025303540

Base case settling vel*10 settling vel*100 settling vel*1000settling vel/10 settling vel/100 settling vel/1000 no settling

Sensitivity analysisSensitivity analysis--dissolveddissolved

0510152025303540

Base case benthic exchange*100 benthic exchange/10benthic exchange/100 no benthic exchange

Sensitivity analysisSensitivity analysis--suspendedsuspended

0510152025303540

Base case settling vel*10 settling vel*100 settling vel*1000settling vel/10 settling vel/100 settling vel/1000 no settling

0510152025303540

Base case benthic exchange*100 benthic exchange/10benthic exchange/100 no benthic exchange

0510152025303540

Base case Sorption*10 Sorption*100 Sorption/10 Sorption/100

0510152025303540

Base case NPS no PS PS loads*2PS loads*5 PS loads/2 PS loads/5 NPS*2

models

Stakeholder process participationStakeholder process participation

Meeting at Port of Houston Authority on 05/17/2004Meeting at UH on 05/24/2004Responses to comments from stakeholdersTechnical presentations at

The Haden Road CAP on 03/22/2004Board Meeting of the GBEP on 04/22/2004The Baytown Area CAP on 05/17/2004

models

PCB assessmentPCB assessment

209 congeners (EPA 1668A) vs Aroclors (EPA 8082)

Texas WQS for total PCBs (based on Aroclors)1.3 ng/L in freshwater0.885 ng/L in saltwater

TDH screening value 47 ng/g (based on Aroclors)

PCB and dioxin in water profilesPCB and dioxin in water profiles

Texas PCB WQS: 885 pg/L

Texas dioxin WQS: 0.0933 pg/L

Open symbols: dioxin TEQClosed symbols total PCBsPlotted data are averages by station

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Main channel San Jacinto River Side Bays

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Morgan's Point

PCB and dioxin in sedimentPCB and dioxin in sediment--ococ profilesprofiles

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Morgan's Point

Open symbols dioxin TEQClosed symbols total PCBsPlotted data are averages by station

PCB and dioxin in catfish profilesPCB and dioxin in catfish profiles

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Morgan's Point

TDH PCB screening value: 47,000 ng/kg

TDH dioxin screening value: 0.47 ng/kg

PCB and dioxin in crab profilesPCB and dioxin in crab profiles

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Morgan's Point

TDH PCB screening value: 47,000 ng/kg

TDH dioxin screening value: 0.47 ng/kg

PCB assessmentPCB assessment

Water concentrations showed a Tier-1 primary concern based on congener analysis in segments 1006 and 1007. Aroclor data showed no concern.Tissue data confirms a concern for PCBs in catfish in segments 1001, 1006, and 1007 (congener data). Aroclor data showed concern in 1001 only.Congener data in catfish showed potential concerns in Sims Bayou, Vince Bayou, Patrick Bayou, Buffalo Bayou, and Whiteoak Bayou.Need to evaluate Aroclor and congener data and determine listings and define methodology to compare congener data and to establish criteria to assess use support.

Total number of dioxin samplesTotal number of dioxin samples

In-stream water

Sediment

Catfish

Sludge

Effluent

MediaMedia Phase II#sites #samples

Phase III#sites #samples

Total number of dioxin samplesTotal number of dioxin samples--contcont’’dd

Sediment cores

Runoff

Ambient air

Dry deposition

Wet deposition

Bulk deposition

Particulate

MediaMedia Phase II#sites #samples

Phase III#sites #samples

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