Effect of Potassium Permanganate on the … of Potassium Permanganate on the Biodegradation of...
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Effect of Potassium Permanganate on the Biodegradation of Weathered
Crude Oil from Indiana Harbor Canal
Brian A. WrennWashington University
Xiaowei Ma, Thomas King, and Kenneth LeeFisheries and Oceans Canada
Albert D. VenosaU.S. Environmental Protection Agency
PAH Concentrations in IHC Sediments
2-ring 3-ring 4-ring 5-ring
conc
entr
atio
n (m
g/kg
)
0
250
500
750
1000
Comparison of IHC Oil to Weathered Medium Crude Oil (Mesa): Alkanes
C12
C14
C16
Prs
Phy
C20
C22
C24
C26
C28
C30
C32
C34
ratio
to p
rista
ne (g
/g)
0.0
0.5
1.0
1.5
2.0
2.5Mesa IHC
Comparison of IHC Oil to Weathered Medium Crude Oil (Mesa): Aromatics
ratio
to C
2-ch
ryse
ne (g
/g)
0
2
4
6
8
10
12
14
16
18
20
MesaIHC
3-ring2-ring 4-ringnaphthalene
C0 C1 C2 C3 C4 C0 C1 C2 C3 C0 C1 C2 C3 C0 C1 C2 C3 C0 C1 C2 C0 C1 C2
fluorene DBT phe pyrene chrysene
Summary of Indiana Harbor Canal Shoreline Sediment Characteristics
• The IHC sediments are heavily contaminatedthe sediments can be up to 40% oil by mass
• The IHC oil is highly weatheredthe concentrations of easily degradable contaminants (e.g., normal alkanes and low MW PAHs) are very low relative to their more recalcitrant analogs (e.g., branched alkanes and alkyl-substituted high MW PAHs)IHC oil contains high absolute concentrations of compounds of concern (e.g., 4- and 5-ring PAHs)
Proposed Method of Treatment:Use chemical oxidation by potassium permanganate (KMnO4) or hydrogen peroxide (H2O2) to increase the biodegradability and bioavailability of IHC contaminants
2.9 g H2O2/L9.0 g KMnO4/L
Proposed Mechanism:Oxidation will increase the bioavailability and biodegradability of contaminants by
decreasing molecule size inserting hydrophilic functional groups
Oil Mineralization: No Oxidant Control
time (days)0 10 20 30 40 50 60 70
cum
ulat
ive
CO
2 (m
g C
)
0
20
40
60
80
100
120
no oxidant /+bio
Oil Mineralization: +H2O2
time (days)0 10 20 30 40 50 60 70
cum
ulat
ive
CO
2 (m
g C
)
0
20
40
60
80
100
120
no oxidant /+bio+H2O2/-bio
Oil Mineralization: +H2O2
time (days)0 10 20 30 40 50 60 70
cum
ulat
ive
CO
2 (m
g C
)
0
20
40
60
80
100
120
no oxidant/+bio H2O2/+bio
Oil Mineralization: +KMnO4
time (days)0 10 20 30 40 50 60 70
cum
ulat
ive
CO
2 (m
g C
)
0
20
40
60
80
100
120
no oxidant/+bio KMnO4/-bio
Oil Mineralization: +KMnO4
time (days)0 10 20 30 40 50 60 70
cum
ulat
ive
CO
2 (m
g C
)
0
20
40
60
80
100
120
no oxidant/+bioKMnO4/+bio
Summary of IHC Oil Biodegradation Experiments
∴ Permanganate is a more effective oxidant for the IHC oil than hydrogen peroxide
effect of permanganate on components not measured by GC-MS is unknown
Next Step:Determine effects of permanganate on the biodegradability of oil components with different chemical characteristics
aliphatics, aromatics, resins, and asphaltenes
Aliphatic Hydrocarbons
CH3
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH3
CH3
CHCH2
CH2CH2
CHCH2
CH2CH2
CHCH2
CH2CH2
CHCH3
CH3 CH3 CH3CH3
CH3
CH3
H
CH3
CH3
CH3CH3
CH3 CH3
H
N
O
N
O
S
O
O
N
S
N
S
CH3
CH3CH3 CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3 CH3
CH3
CH3CH3
CH3
CH3
CH3
CH3
CH3CH3
CH3
OHO
CH3CH3
S
CH3
CH3
S
S
CH3
CH3
CH3
CH3
Asphaltenes
Separation of IHC Oil into Discrete Fractions
IHC sedimentsExtract with methylene chloride
whole IHC oilTransfer extract into hexanes
deasphaltened IHC oil(soluble)
asphaltenes(insoluble)
Alumina chromatography
elute with hexanes
elute with methylene chloride
elute with methanol1 2 3
aliphatics aromatics resins
Iatroscan Analysis of IHC Oil Fractions
Aliphatic:
Aromatic:
Resin:
Asphaltene:
0.50.40.30.20.10.0
retention time (min)
Experimental Approach: Chemical Oxidationremove NaOH
CO2
measure[KMnO4](t)
measure[IC]trap(t)
add NaOH
treat sediments with 9 g/L KMnO4
incubate quench excess KMnO4 with FeSO4
separate aqueous phase from sediments
Experimental Approach: Biodegradation
inoculate with oil-degrading bacteria
measure[IC]trap(t)
add NaOH
CO2
add fresh medium incubatesediments(KMnO4-treated or
untreated) measure[IC]trap(t)
add NaOH
inoculate with oil-degrading bacteria
CO2
measure[DOC](t)
aqueous phase from KMnO4-
treated sediments
incubate
time (days)0 2 4 6 8 10
[KM
nO4]
(mol
e/l)
0.000
0.025
0.050
0.075aliphatic aromatic resin asphaltene
Reaction of Permanganate with IHC Oil Fractions
Biodegradation of Aqueous-Phase Products
time (days)0 5 10 15 20 25 30
TOC
(mg
C/l)
0
100
200
300
400
500none aliphatic aromatic resin asphalt
Mineralization of Aqueous-Phase Products
time (days)0 5 10 15 20 25 30
CO
2 (m
g C
/l)
0
100
200
300
400none aliphaticaromaticresinasphaltene
Biodegradation of Aliphatic Fraction
time (days)0 5 10 15 20 25 30
cum
ulat
ive
CO
2 (m
g C
)
0
10
20
30
40
none -KMnO4 +KMnO4
Biodegradation of Aromatic Fraction
time (days)0 5 10 15 20 25 30
cum
ulat
ive
CO
2 (m
g C
)
0
10
20
30
40
none -KMnO4 +KMnO4
Biodegradation of Resin Fraction
time (days)0 5 10 15 20 25 30
cum
ulat
ive
CO
2 (m
g C
)
0
10
20
30
40
none -KMnO4 +KMnO4
Biodegradation of Asphaltene Fraction
time (days)0 5 10 15 20 25 30
cum
ulat
ive
CO
2 (m
g C
)
0
10
20
30
40
none -KMnO4 +KMnO4
Effect of Chemical Oxidation onBiodegradation of IHC Oil Fractions
fraction and treatment
CO
2 pro
duce
d (m
g C
)
0
10
20
30
40
50
60
aliphatic aromatic resin asphaltene
+KMnO
4-K
MnO4
+KMnO
4-K
MnO4
+KMnO
4-K
MnO4
+KMnO
4-K
MnO4
solidaqueousabiotic
Conclusions• Permanganate reacted slowly with the aliphatic and
asphaltene fractionsthe solid-phase products were not more biodegradable than the parent compounds
- treatment with permanganate reduced the biodegradability of the aliphatic fraction, probably by coating the oil-water interface with MnO2(s)
very low concentrations of water-soluble products were formed
• Permanganate reacted quickly with the aromatic and resin fractions
the solid-phase products were more biodegradable than the parent compoundsthe water-soluble products that were formed were easily biodegradable