Total Maximum Daily Load for Dioxin in the Houston Ship ... · Total Maximum Daily Load for Dioxin in the Houston Ship Channel University of Houston Parsons Water&Infrastructure PBS&J

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


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


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


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

1E-2

1E-1

1E+0

1E+1

-20-15-10-505101520253035404550

Distance from Morgan's Point (km)

Conc

entra

tions

(pg/

L)

Main channel San Jacinto River Tributaries Side Bays

1007 242110051006

Morgan's Point

Dioxin in sedimentDioxin in sediment--ococ profilesprofiles

1E+2

1E+3

1E+4

1E+5

-20-15-10-505101520253035404550


Conc

entra

tions

(ng/

kg-o

c)

Main channel San Jacinto River Side Bays Tributaries

1007 242110051006

Morgan's Point


Dioxin in catfish profilesDioxin in catfish profiles

1E-1

1E+0

1E+1

1E+2

-20-15-10-505101520253035404550


Conc

entra

tions

(ng/

kg-w

et w

t)


1007 242110051006

Morgan's Point


Texas TEQ health-based std: 0.47 ng/kg

Dioxin in crab profilesDioxin in crab profiles

1E-1

1E+0

1E+1

1E+2

-20-15-10-505101520253035404550


Conc

entra

tions

(ng/

kg-w

et w

t)


1007 242110051006

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

0.00

0.05

0.10

0.15

0.20

0.25

Aver

age C

once

ntra

tion

(pg/

L)

2378-TCDD TEQ

DissolvedDissolved

0.0

0.5

1.0

1.5

2.0

Aver

age C

once

ntra

tion

(pg/

L) SuspendedSuspended

2378-TCDD TEQ

Seasonal trends in sedimentSeasonal trends in sediment--ococ samplessamples


Error bars correspond to the 95 % confidence intervals

0

2000

4000

6000

8000

10000

12000

14000

Aver

age C

once

ntra

tion

(ng/

kg-o

c)

2378-TCDD TEQ

Seasonal trends in tissue samplesSeasonal trends in tissue samples


Error bars correspond to the 95 % confidence intervals 0

1

2

3

4

5

6

7

Aver

age C

once

ntra

tion

(ng/

kg-w

et w

t)

CrabsCrabs

2378-TCDD TEQ

0

2

4

6

8

10

12

14

16

Aver

age C

once

ntra

tion

(ng/

kg-w

et w

t)

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

0.01

0.1

1

10

100

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

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

Conc

entra

tion

in C

atfis

h (n

g/kg

)

0.01

0.1

1

10

100

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

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

Dissolved concentration (ng/L)

Conc

entra

tion

in C

rabs

(ng/

kg)

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

0.01

0.1

1

10

100

1000

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

median BSAF (0.01003)

ratio (avg catfish/avg sediment-oc)

Conc

entra

tion

in C

atfis

h (n

g/kg

)

0.01

0.1

1

10

100

1000

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

median BSAF (0.0042)

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

Conc

entra

tion

in C

rabs

(ng/

kg)

Sediment concentration (ng/kg-oc)

Deep and shallow sample resultsDeep and shallow sample results

0.001

0.01

0.1

1

10

100

1000

2378

-TCD

D

1237

8-Pe

CDD

1234

78-H

xCDD

1236

78-H

xCDD

1237

89-H

xCDD

1234

678-

HpCD

D

OCDD

2378

-TCD

F

1237

8-Pe

CDF

2347

8-Pe

CDF

1234

78-H

xCDF

1236

78-H

xCDF

2346

78-H

xCDF

1237

89-H

xCDF

1234

678-

HpCD

F

1234

789-

HpCD

F

OCDF

Conc

entra

tion

in W

ater

(pg/

L)

11193-Shallow11193-Deep

0.001

0.01

0.1

1

10

100

2378

-TCD

D

1237

8-Pe

CDD

1234

78-H

xCDD

1236

78-H

xCDD

1237

89-H

xCDD

1234

678-

HpCD

D

OCDD

2378

-TCD

F

1237

8-Pe

CDF

2347

8-Pe

CDF

1234

78-H

xCDF

1236

78-H

xCDF

2346

78-H

xCDF

1237

89-H

xCDF

1234

678-

HpCD

F

1234

789-

HpCD

F

OCDF

Conc

entra

tion

in W

ater

(pg/

L)

15979-Shallow15979-Deep

DissolvedDissolved--suspended fugacity ratiossuspended fugacity ratios

1.E-03

1.E-02

1.E-01

1.E+00

1.E+0123

78-T

CDD

1237

8-Pe

CDD

1234

78-H

xCDD

1236

78-H

xCDD

1237

89-H

xCDD

1234

678-

HpCD

D

OCDD

2378

-TCD

F

1237

8-Pe

CDF

2347

8-Pe

CDF

1234

78-H

xCDF

1236

78-H

xCDF

2346

78-H

xCDF

1237

89-H

xCDF

1234

678-

HpCD

F

1234

789-

HpCD

F

OCDF

Fuga

city R

atio

(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

78-T

CDD

1237

8-Pe

CDD

1234

78-H

xCDD

1236

78-H

xCDD

1237

89-H

xCDD

1234

678-

HpCD

D

OCDD

2378

-TCD

F

1237

8-Pe

CDF

2347

8-Pe

CDF

1234

78-H

xCDF

1236

78-H

xCDF

2346

78-H

xCDF

1237

89-H

xCDF

1234

678-

HpCD

F

1234

789-

HpCD

F

OCDF

Fuga

city R

atio

(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

0

1000

2000

3000

4000

5000

600011

280

1839

2

1127

1

1127

0

1839

1

1126

9

1598

0

1597

9

1126

8

1126

7

1119

7

1838

8

1838

9

1119

3

1839

0

TEQ

in S

edim

ent (

ng/kg

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

0

500

1000

1500

2000

2500

3000

350011

280

1839

2

1127

1

1127

0

1839

1

1126

9

1598

0

1597

9

1126

8

1126

7

1119

7

1838

8

1838

9

1119

3

1839

02378

-TCD

D in

Sed

imen

t (ng

/kg-o

c)

Main Channel (segments 1007-1006) San Jacinto River

Sediment concentrations along15979 transectSediment concentrations along15979 transect

0

500

1000

1500

2000

A B C D E

TEQ

in S

edim

ent (

ng/kg

-oc)

0200400600800

10001200

A B C D E2378

-TCD

D in

Sed

imen

t (ng

/kg-o

c)

Sediment core locationsSediment core locations

Sediment aging and deposition rate estimates underway

Dioxin concentrations in 11261 coreDioxin concentrations in 11261 core

05

1015202530354045

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

Dept

h (cm

)

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



0

10

20

30

40

500 5 10 15 20 25 30 35 40

Concentration (ng/kg-dry wt)

Dept

h (cm

)



05

1015202530354045

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

Dept

h (cm

)

Air monitoring locationsAir monitoring locations

Clinton Dr

Lang

Haden Rd

Bayland Park

Mont Belvieu

Dioxin in ambient airDioxin in ambient airTo

tal T

EQ in

Am

bien

t Air

(fg/m

3)

Tota

l TEQ

in A

mbi

ent A

ir (fg

/m3)

0

2

4

6

8

Sep Oct Nov Dec Jan Feb Mar Apr May Jun Jul

Haden Rd.

0

2

4

6

8


Clinton Dr.

0

2

4

6

8


Bayland Park

0

2

4

6

8


Lang

0

2

4

6

8


Mont Belvieu

Monthly average concentrations in airMonthly average concentrations in air

0

10

20

30

40

50

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

Conc

entra

tion

(fg/m

3 )

0

200

400

600

800

1000

1200

1,2,3,

4,6,7,

8-HpC

DD, O

CDD

(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

0

5

10

15

20

25

30

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

Conc

entra

tion

(fg/m

3 )

10

50

90

130

170

210

250

2,3,7,

8-HxC

DFs,

2,3,7,

8-HpC

DFs

OCDF

(fg/

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

0

50

100

150

200

250

300

350

400

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

PCDD

s & P

CDFs

conc

entra

tion

(fg/m

3 )

0

5

10

15

20

25

30

35

Parti

cle M

ass C

once

ntra

tion

(ug/

m3)

2378-PCDDs2378-PCDFsParticle mass conc

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

519

54228165530.9

125

8942 4 30

100

200

300

400

500

600

2,3,7,

8-TC

DD

1,2,3,

7,8-P

eCDD

1,2,3,

4,7,8-

HxCD

D

1,2,3,

6,7,8-

HxCD

D

1,2,3,

7,8,9-

HxCD

D

1,2,3,

4,6,7,

8-Hp

CDD

OCDD

2,3,7,

8-TC

DF

1,2,3,

7,8-P

eCDF

2,3,4,

7,8-P

eCDF

1,2,3,

4,7,8-

HxCD

F

1,2,3,

6,7,8-

HxCD

F

2,3,4,

6,7,8-

HxCD

F

1,2,3,

7,8,9-

HxCD

F

1,2,3,

4,6,7,

8-Hp

CDF

1,2,3,

4,7,8,

9-Hp

CDF

OCDF

Conc

entra

tions

(fg/

m3)

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


models




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

Stack emissions

Dispersion

Dry d

epos

ition

Wet

dep

ositi

on

Discharges from tributaries

Runoff

Equilibrium partitioning

Discharges from GW

Bottom sediments

Volat

ilizat

ion

BurialResuspension

Dissolved phase

BSAFBSAF

Suspended solids

IN

OUT

Photodegradation

Biodegradation

Point source effluent

BAF

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

0.01

0.1

1

10

0510152025303540


2378

-TCD

D (p

g/L)

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

0.001

0.01

0.1

1

0510152025303540


2378

-TCD

D (p

g/L)

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

Sensitivity analysisSensitivity analysis--suspendedsuspended

0.01

0.10

1.00

10.00

0510152025303540


2378

-TCD

D (n

g/kg

)

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


0.001

0.01

0.1

1

0510152025303540


2378

-TCD

D (n

g/kg

)

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


0.00

0.04

0.08

0.12

0.16

0.20

0510152025303540

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


0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0510152025303540


2378

-TCD

D (n

g/kg

)

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







models


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


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

1E-2

1E-1

1E+0

1E+1

1E+2

1E+3

1E+4

-20-15-10-505101520253035404550Distance from Morgan's Point (km)

Conc

entra

tions

(pg/

L)

Main channel San Jacinto River Side Bays

1007 242110051006

Morgan's Point

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

1E+0

1E+1

1E+2

1E+3

1E+4

1E+5

1E+6

1E+7

1E+8

-20-15-10-505101520253035404550


Conc

entra

tions

(ng/

kg-o

c)


1007 242110051006

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

1E-1

1E+0

1E+1

1E+2

1E+3

1E+4

1E+5

1E+6

1E+7

-20-15-10-505101520253035404550


Conc

entra

tions

(pg/

L)


1007 242110051006

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

1E-1

1E+0

1E+1

1E+2

1E+3

1E+4

1E+5

1E+6

1E+7

-20-15-10-505101520253035404550


Conc

entra

tions

(pg/

L)


1007 242110051006

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

33

45

45

45

69

45

87

115

117

108

75

47

In-stream water

Sediment

Catfish

Crab

Sludge

Effluent

28

17

28

28

-

-

71

68

53

47

-

-

MediaMedia Phase II#sites #samples

Phase III#sites #samples

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

-

10

5

-

-

-

-

-

11

87

-

-

-

-

Sediment cores

Runoff

Ambient air

Dry deposition

Wet deposition

Bulk deposition

Particulate

6

3

2

2

2

1

1

70

71

68

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MediaMedia Phase II#sites #samples

Phase III#sites #samples

Documents

Total Maximum Daily Load for Dioxin in the Houston Ship ... · Total Maximum Daily Load for Dioxin in the Houston Ship Channel University of Houston Parsons Water&Infrastructure PBS&J