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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)