Enhanced anaerobic dechlorination

Modified from lecture slides by

Poul L. Bjerg
DTU – Technical University of Denmark
 Background
Chlorinated aliphatic compounds are degradable under
certain conditions
Cometabolism: chlorinated ethenes are degraded by an
enzyme synthesized by the cell for metabolism of another
compound
Natural attenuation (NA) and enhanced natural attenuation
(ENA) of contaminants have obtained significant interest
lately.
NA doubtful due to long time frames and degradation
products (VC)
• ENA emerging
– Some skepticism exists due to long time frames, lack
of knowledge and failures
– Legislation (permission to inject, bioaugmentation)
Anaerobic dechlorination of PCE/TCE
Accumulation?

Halorespiring bacteria:
Dehalobacter
Dehalospirillum Only some bacteria of
Desulfitobacterium the genus
Desulfuromonas
Dehalococcoides
Dehalococcoides (Dhc)
 Dehalococcoides (Dhc)

Strain 195: Stephen Zinder, Cornell CBDB1:Adrian et al. 2000

BAV1: He, J. et al., (2003)
• Small organisms (<1m)  migration in
groundwater
• Slow growth in pure cultures; faster growth
rates in mixed bacteria consortia
• H2 is the electron donor
• Chlorinated aliphatic compounds are used as
electron acceptors (EA)

KB-1/VC: Edwards, U of Toronto

 ENA for PCE/TCE
Low H2 partial pressures provide a selective advantage to
dechlorinators over methanogens Methanogens

Electron donors that are slowly fermented, such as propionate and butyrate,
typically provide a steady source of electrons with corresponding low H2
partial pressures, whereas rapidly fermented substrates such as lactate
typically provide a quicker release of electrons with corresponding high H2
partial pressures.

Many possible substrates

Simple: lactate, glucose, ethanol, metanol, acetate
Complex: molasses, soya, organic matter
Complex process
Consortia of bacteria
Specific organisms, ”Dehalococciodes”, responsible for degradation of
cis-DCE to VC
Simulation of sequential reductive dechlorination of chlorinated ethenes in a
microcosm experiment. Lines are simulated values; symbols depict
observations. Dashed lines are the results from the modified model

days

Simulation with
constant degradation
rated
From VAN
BREUKELEN et al.,
2005

Distance from source (m)

 Identification of site specific conditions
• Geology
– Heterogeneity
• Hydrogeology
– Flow field
– Hydraulic conductivities
• Biogeochemistry
– Redox conditions
– Sorption, (volatilization)
– Degradation
• Characterization of contamination
– Distribution in the aquifer
– On-going degradation processes

• Infra structure, physical limitations

Dry cleaning facility
 Former dry cleaning facility,
Jægersborg Allé, 2001-2003
Jægersborg Allé 24

> 1000 µg PCE l

100 - 1000 µg PCE

l
Test area

Present dry cleaner

Trunnevangen 2
Pilot test: Monitoring net work

Injection wells

Pilot test

Flow direction
Geology and hydrogeology

Parking lot

0m
Top soil

5m
Groundwater table

Meltwater sand
10 m
Pore flow velocity
200 m/year
15 m
Till
NV
Redox conditions in the aquifer SØ

O2 M1 M2 P1 M5

FYLD

VSP 25-07-2000

3.77 mg/l 3.26 mg/l 4.15 mg/l 0.62 mg/l

Aerobic
0.07 mg/l 0.27 mg/l 0.32 mg/l SMELTEVANDSSAND 0.41 mg/l

Nitrate-
0.15 mg/l 0.21 mg/l 0.39 mg/l
reducing 0.23 mg/l

MORÆNELER

0 10 m
 PCE contamination in the aquifer
NV SØ

O2 M1 M2 P1 M5

FYLD

VSP 25-07-2000

340 310 310 180

660 310 300 SMELTEVANDSSAND 140

1.1
110 160 26

MORÆNELER

0 10 m
 Aerobic aquifer

Manipulation of redox conditions
Aerobic to Anaerobic

Stimulation of reductive
dechlorination
 Expected lactate demand
Background Lactate/yr Heron et al. (1994)
concent. (kg)
Oxygen 1 mg/l 5

Nitrate 75 mg/l 239

Iron (III), solid 0.5 g/kg 1,834

Oxidation capacity :
Sulfate 200 mg/l 658 5-20 eq/g

total -
2,736 Aerobic Danish aquifers:
30-60 eq/g
Injection of HRC/Primer
Injection of HRC/Primer
“Open tip” injection
NV Distribution of lactate after 5 months (mg/l) SØ

O2 M1 M2 P1 M5

FYLD

VSP 25-07-2000

0.67 mg/l 0 mg/l 0 mg/l 00mg/l

mg/l

0 mg/l 38 mg/l 0 mg/l SMELTEVANDSSAND 0 mg/l

30.2 mg/l
5100 mg/l 580 mg/l 76.6 mg/l

MORÆNELER

0 10 m
 Experiences with HRC injection
• Distribution of HRC - all substrate in the lower part of the aquifer
• Horizontally distribution of substrate is not ideal - high HRC content
upgradient injection points
• HRC flows in high conductivity zones

Reasons?
• Heterogeneities, high permeability zones
• Pressure during injection too high
• Injection method

Lessons learned
• test injection method
• Hydraulic characterization critical
• Multi level sampling!
NV SØ

O2 M1 M2 P1 M5

Before
FYLD
Iron(II)
VSP 25-07-2000

0 0 0 0.047
• Significant
0 0 0 SMELTEVANDSSAND 0.011
generation of
iron(II)
0 0 0
0.29
• Accordance
MORÆNELER
between lactate
0
NV

O2 M1
10 m

M2 P1 M5
SØ
addition and
After 5
FYLD
reduction of iron(II)
months • Iron reduction
capacity maintained
VSP 25-07-2000

0 mg/l 0.52 mg/l 0.011 mg/l 0.12 mg/l

for almost a year

0.076 mg/l 15 mg/l 5.5 mg/l SMELTEVANDSSAND 0.17 mg/l

2 mg/l
0.2 mg/l 7.6 mg/l 29 mg/l

MORÆNELER

0 10 m
NV SØ

O2 M1 M2 P1 M5

FYLDBefore
cis-DCE
• No indication of
VSP 25-07-2000

0.82 0.17 0.82 1.2

anaerobic
0.87 0.19 0.55 SMELTEVANDSSAND 3.9
dechlorination
before
0.3

• No indication of
0.75 0.47 0.38

MORÆNELER

0NV 10 m SØ
anaerobic
O2 M1 M2 P1 M5
dechlorination
After 5
FYLD

after
months
0.61 0.51 0.35
VSP 25-07-2000

2.4
• Overall a slight
reduction in PCE
0.72 0.33 0.26 SMELTEVANDSSAND 3 level due to
source treatment
1.5
0.55 1.6 0.52

MORÆNELER

0 10 m
Stimulation of reductive dechlorination
• Redox conditions changed from aerobic/nitrate reducing
conditions to anaerobic conditions in lower part of aquifer
• Significant iron reduction, sulfate reduction and
methanogenesis on-going
• No anaerobic dechlorination observed

Reasons?
• Microbes not present
• Long lag phase caused by low PCE levels
• toxicity/pH effects caused by high lactate conc.
• Redox conditions are not ideal – iron reduction – H2
levels - methanogenesis