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

Indiana Harbor

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

Aromatic Hydrocarbons

CH3

CH3

CH3

CH3

CH3

Resins

N

CH3

H

CH3

CH3

O

CH3

S

CH2CH2

CH2CH2

CH2CHCH3

CH3

OH

CH2

CH2

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

Acknowledgements

• Funding provided by U.S. EPA and Department of Fisheries and Oceans Canada