Waste Management 23 (2003) 737–740

www.elsevier.com/locate/wasman

Permanganate oxidation of sorbed polycyclic

aromatic hydrocarbons
G.S. Browna,b,*, L.L. Bartonb, B.M. Thomsonc
a
Sandia National Laboratories, PO Box 5800, Albuquerque, NM 87185, USA
b
Department of Biology, University of New Mexico, Albuquerque, NM 87131, USA
c
Department of Civil Engineering, University of New Mexico, Albuquerque, NM 87131, USA

Accepted 16 July 2002

Abstract
The polycyclic aromatic hydrocarbons (PAH) that contaminate soils at many industrial and government sites are resistant to
natural biotic and abiotic degradation processes. The recalcitrant nature of these compounds may require aggressive chemical
treatment to effectively remediate these sites. This study was conducted to assess the viability of permanganate oxidative treatment as a
method to reduce PAH concentration in contaminated soils. Study results demonstrated a reduction in soil sorbed concentration for a
mixture of six PAHs that included anthracene, benzo(a)pyrene, chrysene, fluoranthene, phenanthrene, and pyrene by potassium per-
manganate (KMnO4) oxidative treatment. The greatest reduction in soil concentration was observed for benzo(a)pyrene, pyrene,
phenanthrene, and anthracene at 72.1, 64.2, 56.2, and 53.8%, respectively, in 30 min at a KMnO4 concentration of 160 mM. Minimal
reductions in fluoranthene and chrysene concentration were observed at 13.4 and 7.8%, respectively, under the same conditions. A
relative chemical reactivity order of benzo(a)pyrene>pyrene>phenanthrene> anthracene> fluoranthene> chrysene towards perman-
ganate ion was observed. Aromatic sextet theory was applied to the degradation results to explain the highly variable and com-
pound-specific chemical reactivity order.
# 2002 Elsevier Ltd. All rights reserved.

1. Introduction include hydroxyl radical, ozone, and permanganate ion.

Polycyclic aromatic hydrocarbons (PAHs) con-
taminate soils, sludges, and sediments as a result of
industrial operations associated with manufactured gas,
wood impregnation, hydrocarbon production, coke
production, and metal processing facilities (Mahmood,
1989; Sims and Overcash, 1983). PAHs are recalcitrant
to natural biotic and chemical degradation, and some
are known toxins, mutagens, and carcinogens (Keith
and Telliard, 1979). Because of the potential adverse
impact on human health, PAHs have long been the
subject of environmental research.
The recalcitrant nature of PAH molecules to natural
degradation mechanisms necessitates the need for a
more aggressive chemical approach to achieve remedia-
tion. Chemical agents with PAH oxidation potential
* Corresponding author. Tel.: +1-505-845-8312; fax: +1-505-844-
8405.
E-mail address: gbrown@sandia.gov (G.S. Brown).
0956-053X/02/$ - see front matter # 2002 Elsevier Ltd. All rights reserved.
PII: S0956-053X(02)00119-8
Hydroxyl radicals produced by several methods, such
as, Fenton’s reagent reaction (Martens and Franken-
berger, 1995), hydrogen peroxide/UV reaction (Mokrini
et al., 1997; Ghaly et al., 2001), and ultrasonic cavita-
tion (Wheat and Tumeo, 1997; Laughrey et al., 2001),
have been shown to oxidize aromatics and selected
PAHs. Ozone oxidation of PAHs dissolved in water
(Kornmüller and Wiesmann, 1999), and sorbed to soils
has also been demonstrated (Masten and Davies, 1997).
Permanganate ion, however, has received little attention
in the scientific community as a PAH oxidant, perhaps
because of its inability to oxidize benzene, the basic
building block of all PAHs.
However, permanganate ion is known to readily oxi-
dize alkene carbon–carbon double bonds (Wolfe and
Ingold, 1981; Walton et al., 1992) indicating a potential
for oxidation of aromatic double bonds under appro-
priate conditions. Evidence of that potential is found in
the permanganate oxidation of naphthalene to an
unstable dihydrodiol with subsequent aromatic ring
738 G.S. Brown et al. / Waste Management 23 (2003) 737–740
cleavage in the organic synthesis of phthaldehydic acid
(Blatt, 1943).
The study, presented in this paper, evaluates the
effectiveness of permanganate in the oxidation of PAHs
sorbed to a soil matrix. PAH-permanganate degrada-
tion rates and chemical reactivity for a sandy alkaline
soil, amended with six common PAHs, anthracene,
benzo(a)pyrene, chrysene, fluoranthene, phenanthrene,
and pyrene are explored.
2. Methods and materials
Rio Grande flood plain soil categorized as sandy with
1.3% total organic matter and a pH of 8.25 was used in
this study. The soil was first sieved (No. 10 mesh) and then
oven dried at 105  C for 24 h. An amendment solution
was prepared by dissolving 2 g of anthracene, benzo(a)-
pyrene, chrysene, fluoranthene, phenanthrene, and pyrene
into 4000 ml of methylene chloride. The PAH amendment
solution was then added to 10 kg of prepared soil, and
allowed to equilibrate for 72 h. After equilibration, the
soil was air dried for one week, and then homogenized,
and placed into clean, sealed, and labeled metal contain-
ers. The PAHs used to amend the soil were > 97% pure
and were obtained from Aldrich (St. Louis, MO).
The baseline PAH soil concentrations were deter-
mined by acetonitrile solvent extraction of the sorbed
PAHs by USEPA SW846 Method 3550A—Ultrasonic
Extraction (USEPA, 1996) with analysis by high pressure
liquid chromatography (HPLC). A Waters Corporation
HPLC system running under Millennium 2010 Software
version 2.0 was used for data acquisition and analysis.
PAH separation was accomplished using a Supelco Inc.
SupelcosilTM LC-PAH Reverse Phase 2502.6 mm i.d.
stainless steel column with 5 mm particles. The average
measured baseline concentrations (n=40) for the selected
PAHs were 167 ( 26.4) mg/kg anthracene, 63 ( 10.3)
mg/kg benzo(a)pyrene, 65 ( 9.2) mg/kg chrysene, 164
( 12.6) mg/kg fluoranthene, 64 ( 5.6) mg/kg phenan-
threne, and 204 ( 17.5) mg/kg pyrene.
The PAH-amended soil was transferred to three 250-
ml glass reaction vessels in 50 g dry weight quantities,
and 100 ml of 160 mM KMnO4, prepared by dissolving
25.28 g KMnO4 into 1000 ml of deionized water, was
added. The soil–permanganate solution slurries were
then continuously stirred for 10, 20, or 30 min intervals.
The oxidation reactions were quenched at the appro-
priate time interval by the addition of 100 ml of 160
mM sodium bisulfite solution, prepared by dissolving
16.64 g sodium bisulfite into 1000 ml of deionized water.
The potaasium permanganate and sodium bisulfite were
obtained from Fisher Scientific (Pittsburgh, PA).
Triplicate samples were processed for each reaction
period. After reaction quenching, all samples were
allowed to air dry in a fume hood for 1 week, and then
sealed in glass containers with teflon lined lids. Deter-
mination of the air-dried soils for PAH concentration
was performed by acetonitrile solvent extraction and
HPLC analysis.
3. Results and discussion
A reduction in soil PAH concentration with perman-
ganate treatment was observed for all selected PAHs at
room temperature and a pH of 8.2. However, the rate of
reduction between PAHs was highly variable, and PAH
specific. The greatest reduction in soil concentration was
observed for benzo(a)pyrene, pyrene, phenanthrene,
and anthracene with a reduction of 72.1, 64.2, 56.2, and
53.8%, respectively, at 30 min. Minimal reductions in
fluoranthene and chrysene concentration for the same
reaction time were observed at 13.4 and 7.8%, respec-
tively. The average relative residual fraction values
(n=3) with standard deviation as a function of time for
specific PAHs are presented in Table 1.
To determine PAH reduction rates, a linear regression
analysis was performed on the observed data to determine
the validity of a linear rate model. In all cases, a linear
correlation coefficient greater than 0.95 was calculated
indicating an appropriate model to data fit. The calculated
reduction rates fell into two broad categories, those near 2
mg kg 1 min 1 and those below 0.5 mg kg 1 min 1. Four
PAHs, anthracene at 1.79 mg kg 1 min 1, benzo(a)pyrene
at 2.40 mg kg 1 min 1, phenanthrene at 1.87 mg kg 1
min 1, and pyrene at 2.14 mg kg 1 min 1, were in the first
category, and two, chrysene at 0.26 mg kg 1 min 1 and
fluoranthene at 0.45 mg kg 1 min 1, were in the second.
The calculated reduction rates and corresponding linear
correlation coefficients are presented in Table 2.
As seen from the data analysis, chemical reactivity or
susceptibility to oxidation by permanganate ion varies
between specific PAHs. The relative reactivity order of the
sorbed PAHs towards permanganate ion is:
benzo(a)pyrene > pyrene > phenanthrene > anthracene>
fluoranthene > chrysene. The observed chemical
reactivities are best understood when compared to ben-
zene, which is totally non-reactive to permanganate.
The structure of benzene, the basic building block of
PAHs, is often represented by the Kekule’ structure,
which contains three double bonds and correctly repre-
sents the number of electrons in the system. However,
Structure. 1.
 G.S. Brown et al. / Waste Management 23 (2003) 737–740 739

Table 1
Average (n=3) relative residual PAH fraction with standard deviation after treatment with 160 mM KMnO4

Time (min) PAH Residual Fraction (%)

Anthracene Benzo(a)pyrene Chrysene Fluoranthene Phenanthrene Pyrene

0 100.0 ( 15.8) 100.0 ( 16.4) 100.0 ( 14.1) 100.0 ( 7.7) 100.0 ( 8.7) 100.0 ( 8.6)
10 69.0 ( 2.3) 64.1 ( 6.0) 97.4 ( 9.2) 91.8 ( 2.5) 77.4 ( 2.2) 75.9 ( 1.4)
20 53.8 ( 3.4) 39.6 ( 2.9) 95.6 ( 6.7) 90.4 ( 8.9) 61.1 ( 5.7) 68.6 ( 6.5)
30 46.2 ( 2.6) 27.9 ( 3.2) 92.2 ( 14.4) 86.6 ( 3.9) 43.8 ( 2.1) 35.8 ( 2.0)

Table 3
Table 2
Clar structure showing number of true double bonds, stabilizing aro-
Calculated linear reduction rate and correlation coefficient with 160
matic sextets, and shared double bonds for representative PAHs
mM KMnO4 treatment for selected PAHs
PAH Clar structure True Stabilizing Shared
PAH Linear reduction rate Linear correlation
double sextets double
(mg kg 1 min 1 ) coefficient
bonds bonds
Anthracene 1.79 0.96
Benzo(a)pyrene 1 2 1
Benzo(a)pyrene 2.40 0.98
Chrysene 0.26 0.99
Fluoranthene 0.45 0.95
Phenanthrene 1.87 1.00
Pyrene 2.14 0.97

Pyrene 1 2 1
the true structure of benzene is better represented by a
delocalized cloud of p-electrons, shared by all carbon
atoms, producing a very stable compound. A more pre-
cise representation of benzene is therefore,
Phenanthrene 1 0 0

Anthracene 0 1 4

Structure. 2.
The circle in the hexagon symbolizes the shared p-elec-
tron cloud or aromatic sextet of benzene.
The chemical reactivities of PAHs can best be under-
stood in terms of localization of aromatic sextets in PAH
molecules, as proposed by Clar (1972). The Clar structure
assigns p-electrons that can participate in aromatic sextets
to particular rings in the PAH structure in such a way as to
maximize the number of p-electron sextets. As p-electron
sextets monopolize electron pairs for increased stability,
the remaining ring structure double bonds exhibit proper-
ties more closely resembling the classic alkene double
bond. The Clar structure may be represented as the circle
in hexagon for aromatic sextets, as arrows to shared dou-
ble bonds, and as true alkene double bonds. The Clar
structure, number of true carbon–carbon double bonds,
number of stabilizing sextets, and number of shared dou-
ble bonds for the selected PAHs, arranged in decreasing
order of chemical reactivity, are presented in Table 3.
The observed chemical reactivity of the selected PAHs
in the permanganate reaction, when compared to the
Fluoranthene 0 1 1
Chrysene 0 2 3
Clar model, suggests a chemical reactivity hierarchy
with primary, secondary, and tertiary elements. The
primary element is number of true carbon–carbon dou-
ble bonds, with reactivity being proportional to the
number of bonds. The secondary element is the number
of stabilizing aromatic sextets. An increase in stabilizing
sextets decreases the reactivity of double bond selective
reactions as noted in benzene. The tertiary element of
the reactivity hierarchy is the number of sextet stabilized
or shared carbon–carbon double bonds. An increase in
stabilized bond number results in an increase in overall
reactivity to double bond selective reagents.
740 G.S. Brown et al. / Waste Management 23 (2003) 737–740
4. Conclusion
In the presence of permanganate ion, chemical oxida-
tion of polycyclic aromatic hydrocarbons can occur.
The extent and rate of PAH concentration reduction in
amended soils by permanganate oxidation reaction has
been demonstrated, and specific PAH–permanganate
chemical reactivity explained as a function of aromatic
structure. The Clar structural model, with an emphasis
on stabilizing aromatic sextets, was shown to be a
potentially effective tool for predicting chemical reac-
tivity of PAHs with permanganate ion.
The findings obtained from this research suggest that
soils and sediments contaminated with practically inso-
luble PAHs may be amenable to in situ and ex situ
remediation through permanganate oxidation reaction.
While PAHs are most likely not completely mineralized
by permanganate oxidation reactions, their structure is
altered by polar functional groups providing vast
improvements in aqueous solubility and availability for
natural biotic mineralization. The identity and char-
acteristics of the oxidation reaction products obtained
from permanganate treatment have not been deter-
mined, but potential oxidation products will include
aromatic diols and short chain alkanes. Further
research is required to identify the reaction intermediate
and final products before permanganate oxidation can
be applied as a PAH contaminated soil remediation
technology.
Acknowledgements
This work was supported, in part, by the US Depart-
ment of Energy through a grant from the Waste-man-
agement Education Research Consortium, and Sandia
National Laboratories.
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