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Field Testing of Activated Carbon MixingAnd In Situ Stabilization of PCBs in Sediment

ER - 0510

Richard G. LuthyStanford University

In-Progress Review Meeting

November 6, 2006

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Stanford University: R. Luthy, Y-M. Cho J. Tomazewski

Eng. Res. & Dev. Cen., WES: T. Bridges, A. Kennedy

Univ. of Maryland, Balt. Co.: U. Ghosh

US Navy, NAVFAC San Diego: R. Ahlersmeyer, Tetra Tech; Keith Foreman, BRAC Env. Coor.

Aquatic Environments, Inc.: Lance Dohman

Compass Environmental, Inc.: Mark Fleri

Project Team

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TECHNICAL OBJECTIVES

Demonstrate and compare the effectiveness of AC application and use of two available, large-scale mixing technologies.

Demonstrate that AC treatment reduces PCB bioaccumulation in field tests.

Demonstrate no significant sediment resuspension and PCB release after large-scale mixing technologies are used.

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TECHNICAL APROACH

BackgroundLab Findings for AC Treatment of PCB-contaminated Sediment

28-day exposure; 3.4 wt.% AC treatment

• PCBs are transferred from sediment to AC• AC - treatment reduces

1. PCB bioaccumulation: clam, worm, amphipod2. Aqueous PCB concentration3. PCB uptake in SPMD4. PCB flux from sediment

• If ingested, PCBs on AC are not absorbed• AC is not eroded out of sediment• Important ‘weight of evidence’

28-day contact time

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Demonstration Site Location

• PCB hot spot, 1-10 ppm• Inter-tidal zone• Cohesive sediment with low erosion rates• Site managers amenable to AC technology

Hunters Point Naval Shipyard, San Francisco, CA

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Demonstration Site Location

• ESTCP; Southwest Div. NAVFAC; US EPA Region IX; US Fish & Wildlife Ser.; US Geo. Survey; Calif. Dept. of Toxic Substance Control; Calif. Dept. of Fish & Game; SF Bay Regional Water Quality Control Bd.; City of San Francisco, Dept. of Public Health & Public Utilities Comm.

Hunters Point Naval Shipyard, San Francisco, CA

Active Superfund Site undergoing cleanup

Work Plan Approval: Federal, state & local groups

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Equipment for Mixing Carbon & Sediment

Injection system(Compass Environmental, Inc., Stone Mountain,GA)

Aquamog with rototiller arm(Aquatic Environments, Inc., Concord, CA)

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Demonstration Design Plots, Sampling, and Equipment

Five sampling locations

Four test plots

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TECHNICAL PROGRESS

06/200718 Month Post-Treatment Assessments

07/2006 -08/2006

--06/20066 Month Post-Treatment Assessments

01/2006--01/2006Deployment of Activated Carbon Treatments

12/2005 -01/2006

--11/20051 Month Pre-Treatment Assessments:(Sediment/PCB Resuspension, Biological Monitoring, Physicochemical Monitoring)

12/2005--10/2005Complete Final Draft of Demonstration Plan and Submit for ESTCP Approval

09/200508/200507/2005Complete Second Draft of Demonstration Plan and Submit to Regulatory Agencies and ESTCP for Review

11/200511/200506/2005Complete Regenerated Activated Carbon Studies to Compare Effectiveness to Virgin Activated Carbon

07/200507/200506/2005Submit First Draft of Demonstration Plan to ESTCP for Review

ActualDate

RevisedDate

PlanDate

Milestones for ESTCP ER-0510

06/200718 Month Post-Treatment Assessments

07/2006 -08/2006

--06/20066 Month Post-Treatment Assessments

01/2006--01/2006Deployment of Activated Carbon Treatments

12/2005 -01/2006

--11/20051 Month Pre-Treatment Assessments:(Sediment/PCB Resuspension, Biological Monitoring, Physicochemical Monitoring)

12/2005--10/2005Complete Final Draft of Demonstration Plan and Submit for ESTCP Approval

09/200508/200507/2005Complete Second Draft of Demonstration Plan and Submit to Regulatory Agencies and ESTCP for Review

11/200511/200506/2005Complete Regenerated Activated Carbon Studies to Compare Effectiveness to Virgin Activated Carbon

07/200507/200506/2005Submit First Draft of Demonstration Plan to ESTCP for Review

ActualDate

RevisedDate

PlanDate

Milestones for ESTCP ER-0510

6 Month Post-Treatment Assessments

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For each plot:5 tubes (6 clams + 1 SPMD)5 sediment cores5 amphipod samples5 sediment quadrats (indigenous benthic community)2 overlying water samples

Pre-Treatment Assessments, 12/2005

Clams SPMDs Cores

Quadrats

Amphipods

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Field Water Sampling

• Measure PCB in water column before and after carbon deployment• Sample water 6” above sediment at the centre of the plot• Duplicate water samples 20 L each• Trap suspended particles in glass fiber filters• Trap dissolved PCBs in XAD columns• Soxhlet extraction and PCB analysis

In-line pressure filters

XAD traps

Teflon tube inlet 0.5 ft above center of plot

Plot CAEI mix

Plot DAEI GAC-mix

Plot EControl

Plot FCEI AC-mix

Plot GCEI mix

PHC

PHD

Pum

p-he

ads

C &

DO

n pu

mp

# 1

C-c C-d

PHE

Pum

p-he

ad E

On

pum

p #

2

C-e

PHF

PHG

Pum

p-he

ads

F &

GO

n pu

mp

# 3

C-f C-gcarbuoys

F-e F-f F-gF-c F-dfilters

XAD

C

XAD

D

XAD

F

XAD

G

XAD

EXAD columns

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Water Sampling Data (1):Dissolved PCBs above Treatment Plots

Clams

•PCB homologs with 4-6 chlorines most dominant in dissolved fraction

•No significant difference in aqueous PCBs over treatment plots compared to control

•No significant increase in dissolved PCBs after treatment

XAD-1

0.0

0.2

0.4

0.6

0.8

1.0

1.2

Plot C Plot D Plot E(control)

Plot F Plot G

Dis

solv

ed P

CB

Con

c (n

g/L)

XAD-0

0.0

0.2

0.4

0.6

0.8

1.0

1.2

Plot C Plot D Plot E(control)

Plot F Plot G

Dis

solv

ed P

CB

Con

c (n

g/L)

Di Tri Tetra Penta Hexa Hepta Octa

Before Treatment

One day after treatment

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Water Sampling Data (2): Particle-associated PCBs above Treatment Plots

Clams

•PCB homologs with 6-7 chlorines most dominant in particle-associated fraction

•No significant difference in particle-associated PCBs over treatment plots compared to control

•Uniform increase in particulate load for both control and treatment plots the day after treatment likely due to wind conditions

Filter-0

0.0

0.5

1.0

1.5

2.0

2.5

Plot C Plot D Plot E(control)

Plot F Plot GPar

ticle

-ass

ocia

ted

PC

B (n

g/L) Tri Tetra Penta Hexa Hepta Octa

Before Treatment

Filter-1

0123456789

Plot C Plot D Plot E(control)

Plot F Plot G

Par

ticle

-ass

ocia

ted

PC

B (

ng/L

)One day after treatment

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Baseline Data : Sediment TOC

Reanalyzing some plotF samples

1.091.150.550.360.620.56

0.580.490.650.360.40

1.051.130.380.400.460.42

0.940.350.530.360.280.45

1.471.030.370.550.370.36

12 in

.

Plot C0.63±0.32

Core 2

Core 1

Core 3

Core 5Core 4

1.091.150.550.360.620.56

1.091.150.550.360.620.56

0.580.490.650.360.40

0.580.490.650.360.40

1.051.130.380.400.460.42

1.051.130.380.400.460.42

0.940.350.530.360.280.45

1.471.030.370.550.370.36

1.471.030.370.550.370.36

12 in

.

Plot C0.63±0.32

Core 2

Core 1

Core 3

Core 5Core 4

0.820.850.550.410.300.34

0.780.590.540.280.250.29

0.740.390.300.270.310.50

12 in

.

Plot D0.53±0.23

Core 2

Core 1

Core 3

0.800.950.740.430.370.43

Core 5Core 4

1.030.910.340.520.340.39 0.82

0.850.550.410.300.34

0.820.850.550.410.300.34

0.780.590.540.280.250.29

0.740.390.300.270.310.50

0.740.390.300.270.310.50

12 in

.

Plot D0.53±0.23

Core 2

Core 1

Core 3

0.800.950.740.430.370.43

Core 5

0.800.950.740.430.370.43

Core 5Core 4

1.030.910.340.520.340.39

1.030.910.340.520.340.39

0.820.850.550.410.300.34

0.780.590.54

0.280.250.29

0.740.390.300.270.310.50

12 in

.

Plot E0.60±0.20

Core 2Core 1

Core 3

0.800.950.740.430.370.43

Core 5

Core 4

1.030.910.340.520.340.39

0.820.850.550.410.300.34

0.820.850.550.410.300.34

0.780.590.54

0.280.250.29

0.740.390.300.270.310.50

0.740.390.300.270.310.50

12 in

.

Plot E0.60±0.20

Core 2Core 1

Core 3

0.800.950.740.430.370.43

Core 5

0.800.950.740.430.370.43

Core 5

Core 4

1.030.910.340.520.340.39

1.030.910.340.520.340.39

0.950.590.270.260.280.30

0.410.290.40

0.800.770.330.260.240.34

12 in

.

Plot F0.46±0.23

Core 2

Core 1

Core 3

Core 5

Core 4

0.950.590.270.260.280.30

0.950.590.270.260.280.30

0.410.290.40

0.800.770.330.260.240.34

0.800.770.330.260.240.34

12 in

.

Plot F0.46±0.23

Core 2

Core 1

Core 3

Core 5Core 5

Core 4

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Baseline Data : Sediment PCB Conc. & SPMD uptake

• Top six inch sediment cores analyzed for sediment PCBs

• Concentrations : 1.0~1.2 ppm

• No significant difference over the test plots

• SPMD uptake : No significance difference over four test plots

Sediment PCB Concentration:Baseline Data (Dec 05)

0.0

0.4

0.8

1.2

1.6

2.0

C: Mix only D: AEI(AC/mix)

E: No AC,No Mix

F: CEI(AC/Mix)

mg

PCB

s/kg

dry

sed

imen

t

SPMD uptake:Baseline Data (Dec 05)

0.00

0.05

0.10

0.15

0.20

0.25

C: Mix only D: AEI(AC/mix)

E: No AC,No Mix

F: CEI(AC/Mix)

m g P

CB

s

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Baseline Data : Aqueous Equilibrium Concentration

•14 day contact on a roller

•No significance difference over four test plots

Aqueous Equilibirum PCBConcentration:

Baseline Data (Dec 05)

0.0

5.0

10.0

15.0

20.0

C: Mix only D: AEI(AC/mix)

E: No AC,No Mix

F: CEI(AC/Mix)

ng/L

PC

Bs

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Laboratory Method:Bioaccumulation Studies : Deployed Clams

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Laboratory Method:Bioaccumulation Studies: Indigenous Amphipods

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Clams

Baseline Data : Macoma & Amphipods Bioaccumulation

• Similar uptake across test plots prior to treatment

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Clams

Laboratory Method : Benthic Community Survey

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Clams

Arthropod:Amphipod

SegmentedWormsAnnelid:CapitellidaeNematode

Mollusca:Clam

Cnidaria:Sea Anemone

Mean total abundance for six major phyla

UnsegmentedWorms

Nemertea

Baseline Data : Benthic Community Survey

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6 Month Post-Treatment Assessments, 07/2005

Clams

Sampling location remarking

Core sampling

Clam cage & clam deployment

Quardrat sampling

Amphipod sampling

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6 Month Post-Treatment Assessments, 08/2005

Clams

SPMD retrieval

Clam retrieval

Clam cage retrieval

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6 mo. Post Assessment Data : SPMD uptake

• Plot D showed significant reduction of SPMD uptake (66%) compare to Plot C (mix only).

• Plot F also showed significance reduction (63%) of uptake compare to Plot C (mix only).

• Mix only plot C showed increased SPMD uptake due to enhanced contact between sediment and SPMDs and possibly enhanced sediment concentration.

SPMD uptake:6 mo. Post-treatment Data (Jul 05)

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

C: Mix only D: AEI(AC/mix)

E: No AC,No Mix

F: CEI(AC/Mix)

mg

PCB

s

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6 mo. Post Assessment Data : Particle Size Analyses

% Sand % Fine

Coarse Medium Fine Silt Clay

• AC was found on No. 60 and No. 120 sieves for plot D and F.• Layered structures disappeared for mixed plots (Plots C, D, and F). Median particle size 0.2-1 mm• Plot E (unmixed control) retained layered structure.

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Clams

Status of Sample Analysis

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Measures of Success

Field measures:•Homogeneous AC mixing•Reduced PCB uptake by Macoma nasuta •Reduced PCB uptake by resident Corophium spp. •No detriment to indigenous community structure due to AC application•Reduced PCB uptake by SPMDs•Minimal sediment resuspension & PCB release

Lab measures: •Reduced Caq

•Reduced sediment PCB desorption rate

Macoma nasuta retrieved from clam cages

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ACTION ITEMS

Action Item: Provide a white paper (due 8 May 2006) that provides a discussion of the best possible uses for the plot that was unable to be tested with the Injection System (Plot G), while staying within the already budgeted resources.

Response: The white paper was submitted via email to Andrea Leeson on 5/4/06.In this white paper, we have proposed analyzing the THg and CH3Hg+ bioaccumulation in the clam sample splits obtained from Plots C, D, and E, in addition to the planned analyses of PCB bioaccumulation. In this way, we will be able to assess the efficacy of using AC as a multifunctional amendment for reducing the chemical and biological availability of both Hg species and PCBs.

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ER-0510 Web Pagehttp://www.stanford.edu/group/luthygroup/ESTCP.htm

TECHNOLOGY TRANSFER

AC Treatment Technology is under evaluation as an alternative option in the Hunters Point Shipyard Parcel F Feasibility Study.

Feasibility Study

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BACKUP MATERIAL

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PROJECT PLAN

Demonstration Plan

• ESTCP Office approved.

• Local regulatory agencies reviewed and commented.(U.S. EPA Region IX, DTSC, San Francisco Water QC Board, U.S. Fish and Wildlife, USGS, San Francisco PUC and Dept. of Pub. Health and others)

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OBLIGATIONS/EXPENDITURESFY05/FY06 FUNDS

expected

0

100

200

300

400

500

600

700

800

Mar-05 May-05 Jul-05 Sep-05 Nov-05 Jan-06 Mar-06 May-06 Jul-06 Sep-06 Nov-06

Dol

lars

($K

)

Planned-ObgActual-ObgPlanned-ExpActual-Exp

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FUTURE PROJECT FUNDING

102182Total10218218 mo. Post-AC Assessments

FY2007100343Total

087AC Deployments 1002566 mo. Post-AC Assessments

FY200693216Total054AC Deployments (Preparation)

72122Pre-AC Assessments2030RAC Studies110Demo Plan

$K$KFY2005ERDCStanfordMilestone

102182Total10218218 mo. Post-AC Assessments

FY2007100343Total

087AC Deployments 1002566 mo. Post-AC Assessments

FY200693216Total054AC Deployments (Preparation)

72122Pre-AC Assessments2030RAC Studies110Demo Plan

$K$KFY2005ERDCStanfordMilestone

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PUBLICATIONS

• Application of Activated Carbon Amendment for In-situ Stabilization of PCBs in Sediment: Field-Scale StudiesYeo-Myoung Cho, Dennis W. Smithenry, Upal Ghosh, Alan J. Kennedy, Rod N. Millward, Todd S. Bridges, Richard G. LuthyCALFED Bay-Delta Program Science Conference, Abstract for Oral Presentation, Oct 25 2006

• Field Testing of Activated Carbon Mixing and In Situ Stabilization of PCBsin Sediment Yeo-Myoung Cho, Dennis W. Smithenry, Upal Ghosh, Alan J. Kennedy, Rod N. Millward, Todd S. Bridges, Richard G. LuthyPartners in Environmental Technology Technical Symposium & Workshop, Abstract for Poster Presentation, Nov 28-30 2006

• Field methods for amending marine sediment with activated carbon and assessing treatment effectivenessYeo-Myoung Cho, Dennis W. Smithenry, Upal Ghosh, Alan J. Kennedy, Rod N. Millward, Todd S. Bridges, Richard G. LuthyMarine Environmental Research, Journal Paper (Submitted Aug 2006)