reductive bio-modification of sediment contaminants: an in situ, molecular hydrogen formation...
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Reductive Bio-Modification of Sediment Reductive Bio-Modification of Sediment Contaminants: An Contaminants: An In SituIn Situ, Molecular Hydrogen , Molecular Hydrogen
Formation Approach.Formation Approach.
NATO/CCMS Pilot StudyPrevention and Remediation In Selected Industrial Sectors:
Sediments. Ljubljana, Slovenia. June 17-22, 2007
Guy W. Sewell, Ph.D.Guy W. Sewell, Ph.D.Professor of Environmental Health SciencesProfessor of Environmental Health Sciences
Robert S. Kerr Endowed ChairRobert S. Kerr Endowed Chair
Executive Director IESERExecutive Director IESER
East Central UniversityEast Central University
East Central UniversityAda, Oklahoma~4000 Students
Ada is Home to the US-EPAsGround Water Research Center
Assumption: Dredging may be necessary but it is not desirable.
• Efficacy Questions
• Ecological Impacts
• Sustainability Questions
Can we treat in situ effectively?
Sediments: System Management Factors
• Dynamic System Solution Transport Rate Particulate Transport Rate
Contaminant Transport Rate is a Function of BothPrediction of Contaminant Distribution DifficultControl of Treatment/Residence Time Difficult
• Mixture of ContaminantsSink for Multiple SourcesPoint and Non-Point linear source
• Concentration vs Mass Loading (mass flux)Descrete Receptor-More likely than most mediaDo we manage for the media or the receptor?
Redox gradients, flood plain, reversing hydraulic gradient, velocity profiles, baseflow, storm flow
Is in situ Biotreatment an Option?
Bioaugmentation: Addition of microbes• Sediments contain significant native populations• Challenges: GW-transport, Sediment-dispersal
Biostimulation: Addition of nutrients, electron donor/acceptors• Relatively organic rich• Often oxygen limited• Dispersal issue
Biodegradation Triangle
Active M
icroorganisms
Redox Couple
Activity
Reductive Bio-transformations
• Oxygen Limited Conditions• Fermentation
– substrate is both oxidized and reduced, (Ethanol, CO2)
• Anaerobic Oxidation– Discrete electron donor and acceptor (not O2)
• Hydrogen is the Energy Currency in Anaerobic Consortial Systems
• Applicable to a Wide Variety of Chlorinated Organics (PCBs, PCE, PCP, HCB, CT) , inorganics (Nitrate) and metals (CrVI).
Electron AcceptorsElectron Donors
OrganicCompound
H2
PartiallyOxidized
Compound(s)
CO2
NO3-
SO4=
Fe3+
HCO3-
R-Clx
N2(NH4+)
H2S
Fe2+CH4
R-Clx-1
ANAEROBIC OXIDATION-REDUCTION
SEWELL, '95
Reduced Electron Acceptors
sewell
[H2]
Reducing Equivalent Flow inAnaerobic Biotransformations
Complex Substrate
Organic Acids
Acetate
Nitrate Reduction
Metal Reduction
Sulfate Reduction
Methanogenesis
+CO2?
ReductiveDehalogenation
How do We Stimulate Reductive Biotransformations?
• Hydrogen limiting bio-reactant
• Metabolic Formation– Complex substrate addition (bio-stimulation)– HRC
• Direct Injection– Low solubility– Hazardous
Metal Surface
H+
SO4=S=
SRBFe2+
Feoelectrondelocalization
Fe2+ Fe[-]HHHH
Metal Surface
H+C2Cl4HC2Cl3
?Fe2+
e-Feoelectronrich
Fe2+ Fe[-]HHHH
Electrolytic ReductiveDechlorination
AnaerobicCorrosion
Figure 2. Bottom: Microbial consortia operating at the surface of corroding iron, transferring electrons from removed hydrogen, and reducing sulfate. Top: Microbial consortia operating at the surface of metal that is electrolytically generating hydrogen and transferring electrons to chlorinated hydrocarbons.
The story of The story of Postgate’s nailPostgate’s nail
0
2
4
6
8
10
12
0 50 100 150
Time (days)
FIGURE 1. Environmentally benign products production from PCE degradationand concurrent methane formation with cathodic hydrogen as electron donor(Ο control; l enrichment only; s iron B (5 g/L) only; Δ enrichment + iron B (5g/L))
Metal Surface
H+
SO4=S=
SRBFe2+
Feoelectrondelocalization
Fe2+ Fe[-]HHHH
Metal Surface
H+C2Cl4HC2Cl3
?Fe2+
e-Feoelectronrich
Fe2+ Fe[-]HHHH
Electrolytic ReductiveDechlorination
AnaerobicCorrosion
Figure 2. Bottom: Microbial consortia operating at the surface of corroding iron, transferring electrons from removed hydrogen, and reducing sulfate. Top: Microbial consortia operating at the surface of metal that is electrolytically generating hydrogen and transferring electrons to chlorinated hydrocarbons.
The story of The story of Postgate’s nailPostgate’s nail
Reducing Equivalent Flow inAnaerobic Biotransformations
Nitrate Reduction
Metal Reduction
Sulfate Reduction
Methanogenesis
[H2]+CO2
ReductiveDehalogenation
Complex Substrate
Organic Acids
Acetate
[>4nM]
[1-3nM]
[1nM]
[0.5nM]
Hydrogen Generation vs. Applied Potential
0
50
100
150
200
0 20 40 60
Time (min)
H2
(nM)
at 50 mV
at 100 mV
at 200 mV
at 300 mV
at 400 mV
Figure 7. Hydrogen production versus applied potential.
2H+ (aq) + 2e- (induced potential) -> 2H. (surface) <-> H2 (aq)
(Not electrolysis, proton reduction)
.
Hydrogen EvolutionExperimental conditions: 150 mL water, Na2SO4 3500mg/L, headspace150mL, mild steel electrode, 0.18 g each, diameter 0.83mm, 40mmlong, distance between cathode and anode 40mm, voltage 0.03 V
0
50
100
150
200
250
0 30 60 90 120 150 180 210 240
Time (min)
Hydrogen(ppm)
0
2
4
6
8
10
12Hydrogen
Control
Current
Current (µA)
Figure 6. Quantification of evolved hydrogen at a constant applied potential of 0.03V
CH4
Profiles for the Electrode Reversal Test
0
0.2
0.4
0.6
0.8
1
0 2 4 6 8
Time (day)
Methane (mM)
Control at 0 V (Protein content 7.5 micro-g/L)
Continuous electricity at 0.4 V
8 hr/day & 1 switching/10 min at 0.4 V
Figure 14. Methane concentration profiles for the systems tested at 0 V, 0.4 V continuous, and 0.4 V with reversal.
.
Injection Cathode,E3E-10'E3E-12'
E1 E2Anode
Row 1 Row 2 Row 3 Row 4 Row 5 Row 6
A
B
C
D E
A AB B
C C
D D
EWells
NWells are represented by
Wells are designated by Lane, Row, Letter (when applicable), and depth (when applicable).For example, E4A, E3E-12', etc. Distance between wells within rows ≈ 1 ft.Note: Row 3 wells C, D, and E are out of sequence with Row 4 and 5 wells.
Ground Water Flow Cathode to Anode Distance
5' 5' 2.7' 2.6' 2.7' 5' 5' 2.6'
5'
10'
15.3'
4.2'
30'
Figure 16. Lane E map showing the anode, cathode, installed monitoring wells and physical dimensions.
5 ft
(Row
1)
7.7 ft
(Row
2)
10.3 ft
(Row
3)
13 ft
(Row
4)
18 ft
(Row
5)
23 ft
(Row
6)
E
D
C
B
A
0
10
20
30
40
50
60
70
80
90
100
110
120
H2
(nM)
Row
Well
Hydrogen Concentration Profile in Lane E
(Fallon, NV, 10/29/98)
E D C B A
Figure 17. Fallon, NV, pilot test Lane E hydrogen profile on October 29, 1998.
5 ft
(Row
1)
7.7 ft
(Row
2)
10.3 ft
(Row
3)
13 ft
(Row
4)
18 ft
(Row
5)
23 ft
(Row
6)
E
D
C
B
A
0
20
40
60
80
100
120
H2
(nM)
Row
Well
Hydrogen Concentration Profile in Lane E
(Fallon, NV, 12/3/98)
E D C B A
Figure 19. Fallon, NV, pilot test Lane E hydrogen profile on December 3, 1998.
0
10
20
30
40
50
60
70
0 10 20 30 40 50 60
Time (day)
Influent Effluent-Enrichment only
Effluent-Enrichment+Electric Potential Effluent-Iron Only
Effluent-Iron+Enrichment
Column 3 Electric Potential: 0.8V 5.0V 0.0V 2.5V
Effluent
Influent
Syringe Pump
Anode
Cathode
Packings
-
+
Power
Supply
Solution
Reservoir
NO3- NO2
- N2
2NO3- + 5H2
N2 + 4H2O + 2OH-
Guy W. Sewell
QuickTime™ and aTIFF (Uncompressed) decompressor
are needed to see this picture.
QuickTime™ and aTIFF (Uncompressed) decompressor
are needed to see this picture.QuickTime™ and a
TIFF (Uncompressed) decompressorare needed to see this picture.
Great Eastern 1860’s
Cable laying is a proven technology
Line-Electrode Characteristics:
• Ferrous based• Maximize surface area• Nutrient-biomass delivery• Sample collection
Power Characteristics:
• Low power requirements• Solar panel• Battery
• Low Hazard
BioLance Application to Sediments
BioLance Advantages• In situ application• Ease of installation• Low cost installation and
operation • Can be easily applied
where needed to intercept the plume or source
BioLance Disadvantages• Requires electricity source• Hydrogen is potentially
hazardous• Electrodes may need
replacement• There is a lack of
performance data due: ROI, rates
• Attenuation rates may be very slow
Summary• BioLance may be applicable to sediments• Low cost in situ technology• Appropriate for ex situ applications also• Ecologically Benign• Enhances Native Processes• Applicable to a variety of bio-reducible
contaminants
Next Step: Field Trials