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Permanganase

Permanganase

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Permanganate oxidation of sorbed polycyclic
aromatic hydrocarbons
G.S. Browna,b,*, L.L. Bartonb, B.M. Thomsonc

aSandia National Laboratories, PO Box 5800, Albuquerque, NM 87185, USA
bDepartment of Biology, University of New Mexico, Albuquerque, NM 87131, USA
cDepartment 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 e\ufb00ectively 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, \ufb02uoranthene, 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 KMnO4concentration of 160 mM. Minimal reductions in \ufb02uoranthene 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> \ufb02uoranthene> chrysene towards perman- ganate ion was observed. Aromatic sextet theory was applied to the degradation results to explain the highly variable and com- pound-speci\ufb01c chemical reactivity order.

#2002 Elsevier Ltd. All rights reserved.
1. Introduction

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

include hydroxyl radical, ozone, and permanganate ion. Hydroxyl radicals produced by several methods, such as, Fenton\u2019s 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 (Kornmu\u00a8 ller and Wiesmann, 1999), and sorbed to soils has also been demonstrated (Masten and Davies, 1997). Permanganate ion, however, has received little attention in the scienti\ufb01c 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\u2013carbon 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

0956-053X/02/$ - see front matter# 2002 Elsevier Ltd. All rights reserved.
PII: S0956-053X(02)00119-8
Waste Management 23 (2003) 737\u2013740
www.elsevier.com/locate/wasman
* Corresponding author. Tel.: +1-505-845-8312; fax: +1-505-844-
8405.E-mail address:gbrown@sandia.gov (G.S. Brown).
cleavage in the organic synthesis of phthaldehydic acid
(Blatt, 1943).

The study, presented in this paper, evaluates the e\ufb00ectiveness 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, \ufb02uoranthene, phenanthrene, and pyrene are explored.

2. Methods and materials

Rio Grande \ufb02ood 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 \ufb01rst sieved (No. 10 mesh) and then oven dried at 105\ue000C for 24 h. An amendment solution was prepared by dissolving 2 g of anthracene, benzo(a)- pyrene, chrysene, \ufb02uoranthene, 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\u2014Ultrasonic 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. SupelcosilTMLC-PAH Reverse Phase 250\u00c22.6 mm i.d. stainless steel column with 5mm particles. The average measured baseline concentrations (n=40) for the selected PAHs were 167 (\u00c6 26.4) mg/kg anthracene, 63 (\u00c610.3) mg/kg benzo(a)pyrene, 65 (\u00c69.2) mg/kg chrysene, 164 (\u00c612.6) mg/kg \ufb02uoranthene, 64 (\u00c65.6) mg/kg phenan- threne, and 204 (\u00c6 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 KMnO4into 1000 ml of deionized water, was added. The soil\u2013permanganate 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 bisul\ufb01te solution, prepared by dissolving 16.64 g sodium bisul\ufb01te into 1000 ml of deionized water. The potaasium permanganate and sodium bisul\ufb01te were obtained from Fisher Scienti\ufb01c (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 te\ufb02on 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 speci\ufb01c. 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 \ufb02uoranthene 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 speci\ufb01c PAHs are presented inTable 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 coe\ufb03cient greater than 0.95 was calculated indicating an appropriate model to data \ufb01t. The calculated reduction rates fell into two broad categories, those near 2 mg kg\u00c01min\u00c01and those below 0.5 mg kg\u00c01min\u00c01. Four PAHs, anthracene at 1.79 mg kg\u00c01min\u00c01, benzo(a)pyrene at 2.40 mg kg\u00c01min\u00c01, phenanthrene at 1.87 mg kg\u00c01 min\u00c01, and pyrene at 2.14 mg kg\u00c01 min\u00c01, were in the \ufb01rst category, and two, chrysene at 0.26 mg kg\u00c01min\u00c01and \ufb02uoranthene at 0.45 mg kg\u00c01min\u00c01, were in the second. The calculated reduction rates and corresponding linear correlation coe\ufb03cients are presented inTable 2.

As seen from the data analysis, chemical reactivity or susceptibility to oxidation by permanganate ion varies between speci\ufb01c PAHs. The relative reactivity order of the sorbed PAHs towards permanganate ion

is:
benzo(a)pyrene> pyrene> phenanthrene> anthracene>
\ufb02uoranthene> 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 theKekule\u2019 structure, which contains three double bonds and correctly repre- sents the number of electrons in the system. However,

Structure. 1.
738
G.S. Brown et al. / Waste Management 23 (2003) 737\u2013740

the true structure of benzene is better represented by a delocalized cloud ofp-electrons, shared by all carbon atoms, producing a very stable compound. A more pre- cise representation ofbenzene is therefore,

The circle in the hexagon symbolizes the sharedp-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 byClar (1972). The Clar structure assignsp-electrons that can participate in aromatic sextets to particular rings in the PAH structure in such a way as to maximize the number ofp-electron sextets. Asp-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\u2013carbon 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 inTable 3.

The observed chemical reactivity of the selected PAHs
in the permanganate reaction, when compared to the

Clar model, suggests a chemical reactivity hierarchy with primary, secondary, and tertiary elements. The primary element is number of true carbon\u2013carbon 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\u2013carbon double bonds. An increase in stabilized bond number results in an increase in overall reactivity to double bond selective reagents.

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 (\u00c6 15.8)
100.0 (\u00c6 16.4)
100.0 (\u00c6 14.1)
100.0 (\u00c6 7.7)
100.0 (\u00c6 8.7)
100.0 (\u00c6 8.6)
10
69.0 (\u00c6 2.3)
64.1 (\u00c6 6.0)
97.4 (\u00c6 9.2)
91.8 (\u00c6 2.5)
77.4 (\u00c6 2.2)
75.9 (\u00c6 1.4)
20
53.8 (\u00c6 3.4)
39.6 (\u00c6 2.9)
95.6 (\u00c6 6.7)
90.4 (\u00c6 8.9)
61.1 (\u00c6 5.7)
68.6 (\u00c6 6.5)
30
46.2 (\u00c6 2.6)
27.9 (\u00c6 3.2)
92.2 (\u00c6 14.4)
86.6 (\u00c6 3.9)
43.8 (\u00c6 2.1)
35.8 (\u00c6 2.0)
Table 2
Calculated linear reduction rate and correlation coe\ufb03cient with 160
mM KMnO4 treatment for selected PAHs
PAH
Linear reduction rate
(mg kg\u00c01min\u00c01)
Linear correlation
coe\ufb03cient
Anthracene
1.79
0.96
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
Structure. 2.
Table 3
Clar structure showing number of true double bonds, stabilizing aro-
matic sextets, and shared double bonds for representative PAHs
PAH
Clar structure

True
double
bonds

Stabilizing
sextets

Shared
double
bonds

Benzo(a)pyrene
1
2
1
Pyrene
1
2
1
Phenanthrene
1
0
0
Anthracene
0
1
4
Fluoranthene
0
1
1
Chrysene
0
2
3
G.S. Brown et al. / Waste Management 23 (2003) 737\u2013740
739

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