Reactive Barriers for the Passive Remediation of Chlorinated - - PowerPoint PPT Presentation

Reactive Barriers for the Passive Remediation of Chlorinated Solvents in Sediments and Groundwater Discharge

Michelle M. Lorah USGS, Baltimore, Maryland

in cooperation with

DoD, Aberdeen Proving Ground USEPA, Region III NIEHS, Superfund Research Program

Conceptual model for chlorinated solvent contamination in wetland

(modified from Lorah et al., 2005)

dissolved plumes

DNAPL

Aerobic micro-zones around roots

Fe2+ S2- NH3 CH4

Stottmeister et al.(2003) Biotech.Advances

O2

Chlorinated VOCs at West Branch Canal Creek and their anaerobic degradation pathways

Ethane 112TCA 12DCA CA 1122- TeCA TCE 12DCE VC Ethene PCE CT CF MeCl

Methane

CO2 HCA PtCA Ethane 112TCA 12DCA CA 1122- TeCA TCE 12DCE VC Ethene PCE CT CF MeCl

Methane

CO2 HCA Parent VOCs in orange

Chlorinated ethanes: HCA= hexachloroethane PtCA= pentachloroethane 1122TeCA= 1,1,2,2-tetrachloroethane Chlorinated ethenes: PCE= tetrachloroethene TCE= trichloroethene Chlorinated methanes: CT= carbon tetrachloride CF= chloroform

Site Characterization

Chloroform

Tetrachloroethene West Branch Canal Creek, APG TIR Image PDB

Relative Abundances above 1% 100 liter

WBC-2 Dechlorinating Culture

Reactive Barrier Design and Monitoring

Single-hole multilevel diffusion samplers and multilevel wells

Hydraulic Gradient (Artesian) Re-amendment System Aquifer (~40 ft thick) Geotextile Wetland Sediment (10-15 ft thick) Sand, Peat, Compost, ZVI (option for CT) Sand, Peat, Compost, Chitin, WBC2 Pea Gravel

NOT T O SCAL E Se e p Ar e a

Below surface microwells Passive diffusion bags

Microcosms: Wetland Sediment- Compost Mixtures

• Different composts tested

for support of WBC-2 activity and VOC degradation

• Variable results with

different composts for degradation of both parent and daughter compounds

Bioaugmented microcosms, TeCA

APG Reactive Barrier: Upward Flow Columns

Contaminant k (day-1) t1/2 (hrs) 1122TeCA 3.4 4.8 Chloroform 2.3 7.2 Carbon tetrachloride 2.8 5.9 Tetrachloro- ethene 1.4 12 Trichloroethene 3.0 5.5

TeCA TCE ethene ethane VC

Salinity microcosms

20 40 60 80 100 120 10 20 30

Percent TeCA remaining

Days

TeCA Removal

10,000 20,000 30,000 40,000 50,000 10 20 30

Methane (ug/L)

Days

Methane

500 1,000 1,500 2,000 2,500 3,000 3,500 10 20 30

Sulfate, milligrams per literr

Days

Sulfate

Reactive Barrier- West Branch Canal Creek, APG

5 ft bls 1 ft bls

Standard Chlorine of Delaware,DNAPL Extent

CB, DCBs, TCBs DCBs, TCBs Not DNAPL

Aquifer Wetland porewater

Containment wall

• Chemical plant 1966-

2002; EPA Superfund 2002

• 1981- 5,000 gal CB
• 1986 storage tanks-

579,000 gal 14DCB and TCBs

• Abuts Red Lion Creek,

part of Delaware River watershed

• Treatment in uplands,

but not in wetlands

• Half of water flow to

Red Lion Creek is from Columbia Aquifer

Ethane 112TCA 12DCA CA 1122- TeCA TCE 12DCE VC Ethene PCE CT CF MeCl

Methane

CO2

M

135TCB,124TCB, 123TCB

Chlorobenzene*

14DCB, 13DCB, 12DCB

Benzene * CO2, CH4 ??

Biodegradation Pathways

Trichlorobenzenes* Dichlorobenzenes*

Aerobic CO2, HCl

* Parent contaminant

Anaerobic (reductive dechlorination)

• CB serves as terminal

electron acceptor

• Separate e- donor

required

• rate decreases with

decreasing number Cl

Aerobic (oxidation)

• O2 required as electron

acceptor

• CBs utilized as C and e-

donor

• rate increases with

decreasing number Cl

• Short-lived

intermediates

5 100 75 (14DCB) 70 (124TCB) Drinking Water MCL µg/L

Wetland Study Area, SCD

• Upward

flow at all sites

• Seepage

measured

• n

wetland surface and creek bottom

• Red Lion Creek
• 24-hr Seepage =

Conceptual model for contamination and dual-biofilm reactive barrier in wetland

dissolved plumes

DNAPL

Mixed anaerobic and aerobic conditions

Fe2+ S2- NH3 CH4

DNAPL

O2

Sand+Inoculated GAC+Chitin

sorbent and biofilm attach GAC

Approach to evaluate natural and enhanced biodegradation

• In situ microcosms with Bio-

Traps (Microbial Insights)

– Stable isotope probing (13C- labeled 14DCB, CB, B) – Microbial species and functional genes for biodegradation

• Evaluate biodegradation

processes in flow-through bioreactors

– Upflow fixed film bioreactors – Mimic growth in subsurface – Allows changing conditions

Bioreactor polypropylene support matrix for biofilms

0.0 5.0 10.0 15.0 20.0 25.0

8 102 131 132 133 134 135 11 138 139 140 141 142 143 144

Concentration, in milligrams per liter

Site Number

Northwest PDBs, October 2011

Methane Sulfide Ferrous iron Ammonia 0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0

106 107 108 109 110 6 112 113 114 14 116 117 118 119 120 122 123 15 125 126 127

Concentration, in milligrams per liter Site Number

Northeast PDBs, October 2011

Methane Sulfide Ferrous iron Ammonia

Bio-Traps:

13C-labeled

Chloro- benzene

• 500

500 1,000 1,500 2,000 2,500 3,000 Background MNA Lactate/Chitin WBC-2 DIC Del (‰)

13C Utilized for CO2, 13C Chlorobenzene

PDB-01 PDB-04 PDB-07 PDB-10 (2009)

• 40
• 20

20 40 60 80 Background MNA Lactate/Chitin WBC-2 PLFA Del (‰)

13C Utilized for Biomass, 13C Chlorobenzene

PDB-01 PDB-04 PDB-07 PDB-10 (2009) 8 (NW) 104 (NW) 107 (NE) 6 (NE)

8 (NW) 104 (NW) 107 (NE) 6 (NE)

QuantArray Microbial Analysis- Anaerobic

Reductive dechlorination:

DHC , Dehalococcoides spp. TCE, tceA reductase VCR, vinyl chloride reductase BV1 , vinyl chloride reductase DHBt, Dehalobacter spp. DHG, Dehalogenimonas spp.

J < < 1.0E+01 1.0E+02 1.0E+03 1.0E+04 1.0E+05 1.0E+06 1.0E+07 1.0E+08 DHC tceA vcr BVC DHBt DHG BCR bssA assA Cells/mL MNA LAC WBC-2

BTEX, PAHs and alkanes:

BCR, Benzoyl coenzyme A reductase bssA, benzylsuccinate synthase assA, alkylsuccinate synthase

• ------Reductive dechlorination-------

QuantArray Microbial Analysis- Aerobic

pMMO, particulate methane monooxygenase sMMO, soluble methane monooxygenase TCBO, trichlorobenzene dioxygenase RDEG, toluene monooxygenase 2 RMO, toluene monooxygenase

< < <

1.0E+02 1.0E+03 1.0E+04 1.0E+05 1.0E+06 1.0E+07 1.0E+08

pMMO sMMO TCBO RDEG RMO PHE EDO PM1 ALKB Cells/mL

MNA LAC WBC-2

NA

NA

PHE, phenol hydroxylase EDO, ethylbenzene/isopropyl- benzene dioxygenase PM1, Methylibium petroliphilum PM1 ALKB, alkane monooxygenase

500 1,000 1,500 2,000 2,500 3,000

3/12 3/22 4/1 4/11 4/21 5/1 5/11 5/21 5/31 6/10 6/20 6/30 7/10 7/20 7/30 8/9 8/19 8/29 9/8 9/18 9/28 10/8 10/18 10/28 11/7

Total CBs +Benzene , in µg/L

Native (C ) Bioreactor

aerobic 6/20-8/25

added buffer + nutrients 7/27/12

aerobic 10/10- 10/20

Inflow Tank Waste

500 1,000 1,500 2,000 2,500 3,000

3/12 3/22 4/1 4/11 4/21 5/1 5/11 5/21 5/31 6/10 6/20 6/30 7/10 7/20 7/30 8/9 8/19 8/29 9/8 9/18 9/28 10/8 10/18 10/28 11/7

Total CBs +Benzene , in µg/L

2012

WBC-2 (D) Bioreactor

aerobic 10/10- 10/20

Inflow Tank Waste

SCD Bioreactors

Aerobic Native Culture (15B)

2,000 4,000 6,000 8,000 20 40 60 Concnetration (ug/L) Time (hrs)

15BN-B

124TCB 12DCB Chlorobenzene

124TCB 12DCB CB k (per hr) 0.051 0.071 0.15 half life (hrs) 13.6 9.8 4.6 r2 .972 .999 .968

Sand Grains GAC – sorbent and biofilm support Anaerobic Biofilm Predominant Aerobic Biofilm Predominant Chitin – Slowly dissolving C source

GW flow

O2 diffusion from surface and dispersed throughout from plant roots

H2O CO2 HCl

Anaerobic zone Aerobic Zone

Reductive dechlorination Aerobic degradation

Reactive Barrier Concept

GAC with WBC-2: Classes >1% Abundance

20 40 60 80 100 Relative Abundance (%)

Bacilli Actinobacteria Mollicutes Bacteroidia Thermotogae Gammaproteobacteria Betaproteobacteria Deltaproteobacteria Synergistia Clostridia Dehalococcoidetes Anaerolineae

1 2 Chloroflexi

GAC with 15B: Proteobacteria, Order

• Significant increase in the Betaproteobacteria group Burkholderiales on GAC.

10 20 30 40 50 60 15B.1 15B.2 +GAC.1 +GAC.2 Relative Abundance (% ) Burkholderiales Rhizobiales Caulobacterales Order 1 2

Microcosm Results: Anaerobic WBC-2 Biofilm on GAC

20 40 60 80 100 120 5 10 15

Percent Remaining Days

Anaerobic WBC-2: 14DCB

W-DCB GAC-DCB W-GAC-DCB DIW-DCB-TECA

Bacteria GAC Biofilm-GAC DIW Control

20 40 60 80 100 120 5 10 15

Percent Remaining Days

Anaerobic WBC-2: 12DCB

W-DCB GAC-DCB W-GAC-DCB DIW-DCB-TECA

Bacteria GAC Biofilm-GAC DIW Control

• Slight decrease

in CBs with culture in mineral media compared to DIW

• Rapid sorption

to GAC with and without anaerobic biofilm

• Distinctly faster
• verall CB

removal in biofilm-GAC

Microcosm Results: Aerobic 15B Seeded on GAC

20 40 60 80 100 120 5 10 15

Percent Remaining Days

Aerobic: 14DCB

AB-DCB A-GAC-DCB AB-GAC-DCB A-DIW-DCB

Bacteria GAC Biofilm-GAC DIW Control

20 40 60 80 100 120 5 10 15

Percent Remaining

Days

Aerobic: 12DCB

AB-DCB A-GAC-DCB AB-GAC-DCB A-DIW-DCB

Bacteria GAC Biofilm-GAC DIW Control

• Delay in

sorption to GAC with aerobic biofilm

• Slightly faster
• verall CB

removal in biofilm-GAC

Column Testing

Sand Columns: Medium Sand+ 5 % GAC + 3 % Chitin Sediment Columns: in progress- no data yet 5 % GAC + 3 % Chitin

Sand Columns:

Medium Sand+ HRT= 0.45 day A= WBC2-GAC B= WBC2+15B-GAC

0.000 0.050 0.100 0.150 0.200 0.250 5 10 15 20 25 5 10 15 20 25 Outflow (A2,B2), mg/L Inflow (A1,B1), mg/L A1 12DCB B1 12DCB A2: 12DCB B2 12DCB 0.000 0.010 0.020 0.030 0.040 0.050 0.060 0.070 5 10 15 20 25 30 35 5 10 15 20 25 Outflow (A2,B2), mg/L Inflow (A1,B1), mg/L A1 CB B1 CB A2: CB B2 CB

28

• Outflow VOC

concentrations very low in both columns

• Greater CB

removal column with both the anaerobic and aerobic culture

Sand Columns:

Sediment methanol extract analysis A= WBC2-GAC B= WBC2+15B-GAC

50,000 100,000 150,000 0-2.5" 2.5-5.0" 5.0-7.5" 7.5-10" Concentration, mg/kg

12DCB, Sand Columns

A B 50,000 100,000 150,000 0-2.5" 2.5-5.0" 5.0-7.5" 7.5-10" Concentration, mg/kg

CB, Sand Columns

A B

Generally, less VOCs remaining in the columns that contained both the WBC-2 and 15B cultures

Depth from bottom of column

……lab testing ongoing but also

started small-scale field pilot tests

GM: GAC-chitin-sand mixed into top 10”

GAC seeded with WBC-2 and 15B aerobes

Two plots- sites 135 and 8 GC: GAC-chitin-sand placed as 3” cap (remove top root mat)

GAC seeded with WBC-2 and 15B aerobes

One plot- site 8 C: sand placed as 3” control cap (remove top root mat) One plot- site 135

TOTAL Sand Chitin GAC

pounds 783 30 43

Barrier Reactive Pilot Test Plots

31

GM GC C

10” 3” 3”

Site 135 test area with 3 plots and pre-installation sampling.

40 L of each culture

15B aerobes grown in lab in 5 days WBC-2 in anaerobic cylinder from Sirem Lab

(20L mixed with DI-H20 for GAC seeding)

Buckets of pre-measured sand-chitin-seeded GAC dumped in plot and mixed into sediment to depth of 10 inches with small auger or “egg-beater” attachments on drill.

Johns Hopkins University

• Dr. Ed Bouwer

Steven Chow, PhD student Site

characterization

Feasibility evaluation Technology development Pilot test remediation USGS MD-DE-DC Fate and Bioremediation Team

• Dr. Michelle Lorah

Jessica Teunis Mastin Mount Michael Brayton

• Dr. Charles Walker

Roberto Cruz Emily Majcher Anna Baker Luke Myers NRP Collaborators:

• Dr. Isabelle Cozzarelli
• Dr. Denise Akob

Geosyntec Consultants

• Dr. Neal Durant
• Dr. Amar Wadhawan

Acknowledgements