-

-

Use of Activated Carbon Amendment as an In situ Sediment Remedy at the Lower Duwamish Waterway

EPA Region 10 Sponsored Technical workshop 14 15 Feb 2012, Seattle, WA

Grasse River, NY Activated Carbon Pilot Study

Marc S. Greenberg, Ph.D. U.S. EPA – Office Of Superfund Remediation And Technology Innovation

Environmental Response Team 2890 Woodbridge Ave.

Edison, NJ 08837 732-452-6413

greenberg.marc@epa.gov

Grasse River, New York, USA

2006 Activated Carbon

Pilot Study Area

Massena, NY

Historic use & release of PCBs

Near Saint Regis Mohawk Tribe

Fish consumption advisory

Managed land sources at plant site

Past remedial action includes sediments—1995 NTCRA

2

Stanford Lab Bioaccumulation Study

95%86%

67%

Reduction from Untreated Grasse

River sediment

0.2

0.4

0.6

0.8

1.0

1.2

1.4

Corb

icu

la P

CB

con

cen

trati

on

(u

g/g

dry

Untreated 0.7% 1.3% 2.5%

AC AC AC

3

DELIVERY DEVICES USED AT GRASSE RIVER, NY

Tine injection system

Designed and built by Brennan

with inputs from collaborators

Injection and mixing in an enclosed rototiller Designed and built by Brennan with inputs from collaborators 4

4

.. , .. l

&. Ill- • .... II A l:l!

e N A C)' '-• A04 • • 7 II A • ... ~ 0!1 v. OJ ,.,.

• • ,.,li:. ... b.

~ ... , • u ~ •

0 VA • tl .. .. •

.... ., .. • ·:.

6.,,

UT.l t1

• A •111/i:. •

I •. I

• A ~ I I ___ J

5

\ \

Unmixed Initial Tine Sled

Tiller (50’ x 100’) (50’ x 60’)

(50’ x 50’) Mixed Tiller (75’ x 100’)

Target dose of activated carbon = 0.5x TOC in surficial sediments (+50% safety factor)

Grasse River ACPS

Baseline & Long-Term Monitoring

Parameter

Baseline

(Aug/Sep

‘06)

After

Placement

(Oct ‘06)

Year 1

(Fall ‘07)

Year 2

(Fall ‘08)

Year 3

(Fall ‘09)

Carbon in sediment

cores (BC)

Field PCB biouptake

Lab PCB biouptake

Equilibrium

Desorption

Benthic community

Erosion potential

Impact of AC on

aquatic plant growth

6

Fall 2006 Water Quality

Monitoring Results

• Water column PCB monitoring during construction

– No measurable changes in water column PCB concentrations

observed downstream of the study area during application

Data from Alcoa 7

Post-Application Core Sampling

8

c 2.0 0 -e ('0 1.8 (.,)

I • Measured AC dose ~ -

(.,) ·- 1.6 c ('0 C) ....

1.4 0

- --• Target AC dose of 0.5xTOC + '- t-

!"'"'- safety factor of 50% -- - - 1- -

(1)

> 1.2 ·-...., ('0

- -

c It- 1.0 0

f-

!"'"'-!"'"'-

c 0 0.8 :.c (.,)

!"'"'- r--1- 1- 1- I~ - -- - ~ - . I - I• - I ~ - • - ~ ~ -. - - - . I -I• - -

('0 .... 0.6 It-

('0

1- I~ 1~ - I~ 1-~

tn 0.4 ('0 ~ r-- 1- - - 1- 1-

"C (1)

0.2 "C - I- 1- - - 1- I~ . -

"C ('0

() 0.0 ~

< M1 M2 M3 1\114 M5 M3 UTA3 UTAS UTA9 UTA 14 UTA 15 UTA 17

• Measured AC addition achieved at sampling sites compared to the target dose of half of native TOC plus safety factor of 50°/o

Dose of AC achieved in sediment

2007 sampling data

Data from Alcoa 9

Carbon Profile with Time

Native TOC Avg. 6.13%

10

--------

tl

------------------------------------iD

~ • ~ ·Z;. ·Z;.

~ ~ ~ ·Z;.

-·Z;.

' ·Z;. ·Z;.

~ ~ ~ ~ I ~ ~ I ~ ~ ~ ~ i ~ ·Z;.

I ·Z;.

·Z;. ·Z;.

~ ~ ~ i ~

ii ~ ~r ~ ·Z;. ., ·Z;.

r---- r----

I I I I I I I I I

-

I . I I

Aqueous Equilibrium

0

200

400

600

800

1000

1200

BG1

BG2

BG3

Mixed

Tiller

(M1)

Mixed

Tiller

(M2)

Mixed

Tiller

(M3)

Mixed

Tiller

(M4)

Mixed

Tiller

(M5)

Mixed

Tiller

(M6)

Tine

Sled

(UTA

3)

Tine

Sled

(UTA

5)

Tine

Sled

(UTA

9)

Unm

ixed

Tiller

(UTA

14)

Unm

ixed

Tiller

(UTA

15)

Unm

ixed

Tiller

(UTA

17)

PC

B c

on

ce

ntr

ati

on

in

wa

ter

(ng

/L)

2006 (baseline)

2007 (1-year post)

2008 (2-year post)

11

H

eig

ht

abo

ve s

ed

ime

nt

(cm

) PCB IN WATER BASED

ON IN-SITU PASSIVE

SAMPLERS

Reduced aqueous PCB on

sediment surface at AC treated

sites compared to overlying water

Data from UMBC, Beckham & Ghosh 12

Pore water – Surface water PCB Gradient in Grasse River, 2009

13

0 20 40 60 80 100 120 140

Total freely-dissolved aqueous PCBs (ng/L)

Untreated

AC Treated

Surface water

Pore water at

the interface

Pore water in

deeper sediment

+ 1.6 µg/m2d

– 0.4 µg/m2d

Flux (µg/m2d) = kf(C – C )pw sw

Data from UMBC, Beckham & Ghosh 13

-4.5

- 4.0 i

• 2006 (baseline pre-amendment)

• 2007 (1 -year post) -Q) 3.5 ~ C) -

o 2008 (2-yrs post)

o 2009 (3-yrs post) C) 3.0 ::1. -tn Q)

2.5 :::J tn tn :;:.

E 2.0 L..

0 ~ 1.5 s::::::

tn m 1.0 u a.. n:s -~ 0.5

0.0 BG1 BG2 BG3 M1 M2 M3 M4 M5 M6 UTA 3 UTA 5 UTA 9 UTA 14UTA 15UTA 17

Background II ~--------M __ ix_ed __ T_ill_e_r ________ ~l~l ____ ln~j_ec_t_ed ____ ~II~ ___ L_a~ye_r_ed ____ ~ Site and Treatment Area

14

Laboratory Bioaccumulation in L. variegatus

Data from UMBC, Beckham & Ghosh 14

IN-SITU PCB MONITORING STUDIES

In-river deployment of field exposure cages with L.

variegatus for baseline study (method adapted from

Burton et al. 2005)

L. variegatus 15

Data from UMBC,

Beckham & Ghosh PCB IN L. VARIEGATUS IN-SITU EXPOSURE

0

1

2

3

4

BG1 BG2 BG3 M1 M2 M3 M4 M5 M6

PC

Bs

in w

orm

s (u

g/g

wet

wt.

)

In situ Bioaccumulation 2006-20092006 (pre-amendment)

2007 (1-yr post)

2008 (2-yrs post)

2009 (3-yrs post)

Background sites Mixed treatment sites

• % reduction over 3 years: 46% in BG sites and 92% for Mixed Tiller sites 16

0.5

1.0

1.5

2.0

2.5

3.0

PCB IN WORMS AND WATER VS. CARBON DOSE 3.0

2.5

PC

Bs

in w

orm

s (

mg/

kg t

issu

e)

PC

Bs

in e

qu

ilib

rate

d w

ate

r (n

g/L)

P

CB

s in

wo

rms

(mg/

kg t

issu

e)

Background Background Background Background

Mixed Mixed Mixed Mixed

Injected Injected Injected Injected

Layered Layered Layered Layered

1-year after AC (2007)

2-years after AC (2008)

3-years after AC (2009)

63-99% reduction from background each year

A. Bioaccumulation—laboratory exposures

Before AC (2006)

62-93% reduction from background each year

B. Bioaccumulation—caged worms in river

0 2 4 6 8 10 12 14 16

2.0

1.5

1.0

0.5

0.0

Activated carbon (% dry wt.)

• Reduced uptake in field plots with

increasing AC dose

• > 90% reduction for all treatment

sites by 2009 for AC dose >4%

• Little incremental benefit above 5%AC

• Tighter range in aqueous PCBs

compared to worms

Data from UMBC, Beckham & Ghosh

0.0

1,100

1,000

900

800

700

600

500

400

300

200

100

0 0

C. Aqueous equilibrium

95-100% reduction from background each year

2 4 6 8 10 12 14 16

Activated carbon (% dry wt.)

17

Benthic Invertebrate Monitoring

Benthic communities continue to utilize amended areas

Slight community shifts in benthic order distributions

(dipterans to oligochaetes)

Similar trends at background and treatments, correlated with

temporal variability in grain size

Possible 2008 benthic community effect in Unmixed Tiller area Data from Alcoa 18

Moving forward

Carbon amendments appear to be promising enough for

serious consideration in remedies

AC can be applied to sediment at the field scale

AC remained in place 3 years after placement

Reductions in porewater PCB levels & desorption

Reductions in tissue PCB levels

No major changes to benthic community due to

amendment

Over time, the AC-amended sediment is covered with

new sediment deposits

Successful pilot scale demonstration of reduction in

bioavailable PCBs in the sediments 19

Acknowledgements

Young Chang, EPA Region 2,

Grasse River Study Area RPM

Larry McShea, Alcoa Project Manager

Drs. Upal Ghosh and Barbara Beckingham University of Maryland, Baltimore County

THANK YOU FOR YOUR ATTENTION TODAY

20