Chemosphere 59 (2005) 1427–1437

www.elsevier.com/locate/chemosphere

Removal of sorbed polycyclic aromatic hydrocarbons

from soil, sludge and sediment samples using the
FentonÕs reagent process
Vanina Flotron, Corine Delteil, Yann Padellec, Valérie Camel *

Institut National Agronomique Paris-Grignon, Laboratoire de Chimie Analytique—UMR Environnement et Grandes

Cultures, 16 Rue Claude Bernard, 75231 Paris cedex 05, France

Received 19 May 2004; received in revised form 10 December 2004; accepted 24 December 2004

Abstract

The use of the FentonÕs reagent process has been investigated for the remediation of environmental matrices con-
taminated by polycyclic aromatic hydrocarbons (PAHs). Laboratory experiments were first conducted in aqueous solu-
tions, to study the kinetics of oxidation and adsorption of PAHs. Benzo[a]pyrene was more rapidly degraded than
adsorbed, while only partial oxidation of fluoranthene occurred. In the case of benzo[b]fluoranthene, its adsorption pre-
vented its oxidation. Besides competition effects between PAHs were found, with slower oxidation of mixtures as com-
pared to single PAH solutions. Apparition of some by-products was observed, and a di-hydroxylated derivative of
benzo[a]pyrene could be identified under our conditions. Consequently, application to solid environmental matrices
(soil, sludge and sediment samples) was performed using large amounts of reagents. The efficiency of the Fenton treat-
ment was dependent on the matrix characteristics (such as its organic carbon content) and the PAH availability (cor-
related to the date and level of contamination). However, no pH adjustment was required, as well as no iron addition
due to the presence of iron oxides in the solid matrices, suggesting the potential application of Fenton-like treatment for
the remediation of PAH-contaminated environmental solids.

2005 Elsevier Ltd. All rights reserved.

Keywords: AOP; Fenton; Oxidation; PAH; Remediation; Solid

1. Introduction cern due to the possible bioavailability of these toxic

Polycyclic aromatic hydrocarbons (PAHs) are ubiq-
uitous pollutants that occur in natural media such as
soil, sediment, water and air as a result of both natural
and anthropogenic processes (Henner et al., 1997). Their
presence in such environmental matrices is of great con-
*
Corresponding author. Tel.: +33 1 44 08 17 25; fax: +33 1 44
08 16 53.
E-mail address: camel@inapg.fr (V. Camel).
compounds. In some cases, remediation should be con-
sidered with a view of reducing the toxicity. Because of
the very low biodegradability of these organic pollu-
tants, a chemical oxidative treatment should be pre-
ferred. The FentonÕs reagent (Fe(II)–H2O2) seems very
attractive for such treatment for several reasons: (i) its
moderate cost, (ii) its simplicity of operation, (iii) its ad-
vanced oxidative potential due to the formation of hy-
droxyl radicals OH (Watts, 1992; Venkatadri and
Peters, 1993; Schulte et al., 1995; Neyens and Baeyens,
2003). Hydroxyl radicals are the most oxidative species

0045-6535/$ - see front matter
2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2004.12.065
1428 V. Flotron et al. / Chemosphere 59 (2005) 1427–1437
that can be formed in aqueous solutions, and they have
been shown to degrade many organic compounds
including PAHs, using different advanced oxidation pro-
cesses (AOPs).
Nowadays, the FentonÕs reagent is often used to treat
wastewaters from various industries (Kuo, 1992; Schulte
et al., 1995; Wanpeng et al., 1996; Lin and Lo, 1997;
Kang and Hwang, 2000). It can also be applied to the
remediation of contaminated solid matrices, such as
soils, sediments or sludges (Mustranta and Viikari,
1993; Kawahara et al., 1995; Martens and Frankenber-
ger, 1995; Watts and Dilly, 1996; EPA, 1998; Watts
et al., 1999; Nam et al., 2001; Lee et al., 2002; Neyens
et al., 2002; Watts et al., 2002; Neyens and Baeyens,
2003). Furthermore, Fenton oxidation is a process that
can be used in combination with bioremediation tech-
niques, either as a pre-treatment for the oxidation of
PAHs to more biodegradable compounds, or as a post-
treatment for residual PAHs (Kelley et al., 1991;
Martens and Frankenberger, 1995; Nam et al., 2001).
This process may be effective for the treatment of
PAHs in waters. The FentonÕs reaction is based on the
hydrogen peroxide decomposition in the presence of fer-
rous iron to produce a hydroxyl radical, which is the
main oxidizing species (reaction (1)).
Fe2þ þ H2 O2 ! Fe3þ þ OH þ  OH
k 1 ¼ 53–76 mol1 l s1
It is generally conducted in very acidic medium (pH
2–3) to prevent iron salts precipitation (Kuo, 1992).
The hydroxyl radicals formed degrade organic com-
pounds either by hydrogen abstraction (reaction (2))
or by hydroxyl addition (reaction (3)).
RH þ  OH !  R þ H O k ¼ 107 –1010 mol1 l s1
2 2
R þ  OH !  ROH
Usually the disappearance of the organic substrate
follows a pseudo-first order kinetic law, the OH concen-
tration being considered as a constant (due to their high
reactivity). Thus, the pseudo-first order rate constant for
PAH oxidation can be estimated experimentally (i.e.
kexp) by following the studied PAH disappearance over
time.
An optimal oxidation of the organic substrate can be
obtained if the consumption of the hydroxyl radicals by
other reactions, especially with the reagents themselves
(reactions (4) and (5)) is limited. Tang and Huang
(1996) have reported a 10:1 H2O2/Fe(II) molar ratio to
allow for the best degradation of 2,4-dichlorophenol.
Fe2þ þ  OH ! Fe3þ þ OH k 4 ¼ 3–4  108 mol1 l s1
H2 O2 þ  OH ! H2 O þ HO2
k 5 ¼ 1:2–4:5  107 mol1 l s1 ð5Þ
As the hydroxyl radicals are generated in aqueous
solution, a solid/solution suspension should be produced
in order to apply the FentonÕs reagent for the remedia-
tion of contaminated solid matrices. In such a system,
previous studies reported that pollutants should be first
desorbed from the solid phase in order to be able to
react with hydroxyl radicals generated in the solution
(Sedlak and Andren, 1994; Watts et al., 1999). More re-
cently, Watts et al. (2002) showed that the presence of
iron minerals in the solid matrix can allow the genera-
tion of the reactive species close to benzo[a]pyrene
adsorbed or present in non-aqueous phase liquid
(NAPL), enabling its degradation. In addition, the pres-
ence of iron minerals in the sludges could enable the
Fenton oxidation to proceed without any iron addition
in presence of large amounts of hydrogen peroxide (Ven-
katadri and Peters, 1993; Lin and Gurol, 1998; Watts
et al., 1999).
So, this study was undergone to investigate the feasi-
bility of using the FentonÕs reagent to degrade sorbed
PAHs in three different solid matrices: a sewage sludge,
an agricultural soil, and a marine sediment. Besides, as
Fenton oxidation has not been studied in sufficient detail
to provide substantial information on the efficiency of
ð1Þ this treatment to degrade PAHs, the behaviour of PAHs
in aqueous solutions containing OH has first been stud-
ied. Elevated PAH concentrations were chosen in order
to study adsorption and oxidation kinetics. Moreover,
efforts were done to determine kinetics of appearance
of by-products and to identify them.
2. Materials and methods
ð2Þ
2.1. Reagents and chemicals
ð3Þ
Individual standard solutions (10 mg l1 in acetoni-
trile) of the following PAHs were obtained from CIL
Cluzeau (Paris, France): fluoranthene (Fla, purity:
98.3%), benzo[b]fluoranthene (BbF, purity: 99.0%),
benzo[a]pyrene (BaP, purity: 98.7%). Their structure
and properties are reported in Table 1. Hydrogen per-
oxide (30% solution as weight) and iron (II) sulfate hep-
tahydrate (purity: 99.5%) were supplied by VWR
(France), as well as HPLC-grade methanol (purity:
99.8%), acetonitrile (purity: 99.8%), tetrahydrofuran
(purity: 99.7%), n-hexane (purity: 99.8%) and acetone
(purity: 99.8%). Deionized water was produced with a
Milli-Q system from Millipore (Saint-Quentin-en-Yve-
lines, France).
To avoid cross contamination, before use all vessels
were rinsed several times with acetone, and then rinsed
ð4Þ with milli-Q water.
 V. Flotron et al. / Chemosphere 59 (2005) 1427–1437 1429

Table 1 X31–147 (AFNOR, 1996); organic carbon content was

Structure and properties of the investigated PAHs estimated based on the modified Anne method (which
Compounds Structure Water Log Kowa consists in the oxidation of organic matter by potassium
solubility dichromate in sulfuric medium).
at 25 C All samples were frozen upon reception in the labora-
(mg l1)a tory for their storage. Before their use, samples (around
Fluoranthene 0.26 5.2 100 g) were taken, and carefully dried in an oven (40 C,
72 h) to avoid PAH losses (Berset et al., 1999), before
being homogenized with a mortar and the fraction greater
Benzo[b]fluoranthene 0.0015 6.6 than 2 mm removed through sieving.

2.3. Fenton oxidation

All experiments were done in triplicate.

Benzo[a]pyrene 0.0038 6.0

2.3.1. Oxidation of solubilized and sorbed PAHs in

aqueous solutions
a
Manoli and Samara (1999). Experiments were conducted at room temperature in
50 ml Teflon erlenmeyers, covered with aluminium foil to
avoid any photolytic degradation. Aqueous solutions of
2.2. Environmental solid samples PAHs (25 ml, 80 lg l1 each) were prepared upon dilu-
tion with milli-Q water of the stock PAH solutions.
Solid sewage sludge samples were obtained from the Initial pH was adjusted to 3 with H2SO4. The ferrous
municipal wastewater station of Achères near Paris, and iron and hydrogen peroxide solutions, freshly prepared
sampled at the end of the sludge treatment (according to every day in stock concentrations, were successively
a statistical sampling plan, the composite sample ob- added. Time zero was sampled just before the addition
tained being homogenized). The soil is an agricultural of hydrogen peroxide to the solution. The FentonÕs reac-
soil, which has received wastewaters from the municipal tion was then started upon addition of H2O2. At various
wastewater plant of Achères during several decades; sev- time intervals (after 45, 120 and 180 min), an aliquote
eral soil samples were taken from the 0–30 cm layer, and (1 ml) was withdrawn, mixed with 0.25 ml methanol (to
mixed together to produce the final soil sample. The quench radicals) before being neutralized with NaOH
sediment comes from the ‘‘Ria de Aveiro’’, a lagoon lo- (final pH around 6) and further injected in HPLC.
cated in the centre of Portugal that received industrial At the end of the oxidation experiment, the remain-
effluents; several sediment samples were taken from the ing solution was discarded, and the recipient walls as
15–16 cm layer, and mixed together to produce the final well as magnetic stir bar were rinsed with acetonitrile
sediment sample. The characteristics of these three (2 h contact time with continual mixing). This solution
matrices are summarized in Table 2. The pH was taken was then injected in the HPLC system, to analyse possi-
in a solid/water (1:2.5) suspension; total iron was ble retained PAHs.
determined according to the French norm NF
2.3.2. Oxidation of sorbed PAHs in solid matrix
Table 2 suspension
Characteristics of the sludge, sediment and soil samples Solid matrix suspensions were prepared in Teflon
Characteristics Sludge Soil Sediment recipients by adding 10 ml of milli-Q water to 2 g of
oven-dried matrix, followed by the Fe(II) solution (final
Fluoranthene 1.20 0.107 0.017
concentration of 102 mol l1). After stirring the suspen-
(mg kg1)
Benzo[b]fluoranthene 0.43 0.064 0.123
sion a few minutes, hydrogen peroxide (final concentra-
(mg kg1) tion of 4.9 mol l1) was slowly added with great care to
Benzo[a]pyrene 0.31 0.051 0.003 avoid excessive temperature increase. The suspension
(mg kg1) was then magnetically stirred during 24 h to allow Fen-
Organic carbon (%) 20.8 1.7 nd ton oxidation. Experiments have been carried out on
Organic matter (%) 36.1 3.0 10.4 non-spiked as well as spiked samples. In the latter case,
Total iron (mg g1) 94 nd 30 80 ll of each PAH standard (at 10 mg l1 in acetonitrile)
pH 8.8 7.1 4.4 were carefully added on the matrix surface without mix-
Type nd Fine sand 70% Sand ing to avoid PAH losses on the recipient walls. In addi-
Silt 17%
tion, blank experiments were carried out under the same
nd: not determined. conditions, except that no hydrogen peroxide was
1430 V. Flotron et al. / Chemosphere 59 (2005) 1427–1437
added, to study possible desorption or degradation of
the PAHs.
2.4. Extraction
After Fenton oxidation in solid/aqueous suspensions,
the solid matrix was separated from the aqueous phase
by centrifugation in Teflon tubes (15 min, 1397 g,
15 C). Then the aqueous supernatant was pre-concen-
trated using solid-phase extraction on styrene-divinyl-
benzene copolymer, after addition of methanol (4 ml)
to the solution to avoid PAH adsorption on recipient
walls. Cartridges (Bond Elut PPL, 0.2 g, Varian) were
conditioned successively with methanol/tetrahydrofuran
(10/90 v/v—2 · 2.5 ml), methanol (2 · 2.5 ml) and milli-
Q water (2 · 2.5 ml), and PAHs were eluted with meth-
anol/tetrahydrofuran (10/90 v/v—3 + 2 ml). The overall
extraction efficiency of the solid-phase extraction has
been evaluated: 92.6% (2.4), 67.1% (5.1) and 63.4%
(9.5) for fluoranthene, benzo[b]fluoranthene and ben-
zo[a]pyrene respectively (RSDs are given in italic and
in brackets). Then the obtained fractions were concen-
trated under a gentle stream of nitrogen to around
1 ml, filtered (nylon filters, 13 mm, 0.45 lm, CIL Clu-
zeau) before being injected in the HPLC system.
The solid residues were dried in an oven (40 C,
2 · 24 h) before being extracted using pressurized fluid
extraction (ASE 100 system, Dionex). The conditions
were as follows: 1 g dried matrix mixed with hydroma-
trix and alumina, hexane/acetone (50/50 v/v), 120 C,
5 min static time, solvent purge volume 6.8 ml, nitrogen
purge time 100 s, and two static cycles. The extraction
efficiency of this step has also been evaluated: 106.4%
(3.3), 103.0% (3.6) and 75.5% (4.7) for fluoranthene,
benzo[b]fluoranthene and benzo[a]pyrene respectively
(RSDs are given in italic and in brackets). The extracts
were further concentrated to dryness, and the solid res-
idue redissolved in 1 ml acetonitrile for HPLC analysis.
2.5. Liquid chromatography analysis
The HPLC system consisted of a Varian 9010
low-pressure gradient pump, a Rheodyne Model 7125
injection valve equipped with a 20 ll loop, a Thermo
Separation Science fluorimetric detector (FL3000), a
PE Nelson 900 Series interface, and a computer (Intel
Pentium, speed 90 MHz, hard disk 813 Mo, RAM 16
Mo, operating system Windows 3.11). Data analysis
was performed using the TurboChrom TC4 Navigator.
A Supelcosil LC-PAH column (250 · 4.6 mm i.d.,
C18-silica, 5 lm particle size, Supelco) was used, along
with a pre-column (Supelguard LC-18, Supelco). Sepa-
ration was performed using the following gradient:
acetonitrile/water (60:40 v/v) for 5 min, followed by a
25-min ramp to attain 100% acetonitrile, this solvent
being further maintained for 15 min. The total flow-rate
was 1.5 ml min1. Detection was performed at selected
excitation/emission wavelengths, respectively 230/410 nm
for fluoranthene, 250/420 nm for benzo[b]fluoranthene
and benzo[a]pyrene. Quantitation was performed using
external calibrations with standard solutions of PAHs
in acetonitrile/water (60/40 v/v) in the range 25–
200 lg l1.
2.6. Formation of oxidation by-products
For identification of by-products formed, due to the
low sensitivity of the detectors used, pre-concentration
of the aqueous solutions was performed by solid-phase
extraction onto styrene-divinylbenzene (as retention of
the initial PAH was also required). Cartridges (Bond Elut
PPL, 0.2 g, Varian) were conditioned successively with
methanol/tetrahydrofuran (50/50 v/v, 2 · 2.5 ml), metha-
nol (2 · 2.5 ml) and milli-Q water at pH 3 (2 · 2.5 ml),
and PAHs were eluted with methanol/tetrahydrofuran
(50/50 v/v, 5 · 1 ml). The obtained fractions were ana-
lysed using an HPLC system coupled with a diode-array
UV–visible detector (HPLC-DAD). It consisted of a
Waters 1525 high-pressure gradient pump, a Rheodyne
injection valve equipped with a 20 ll loop, a Waters
2996 DAD detector, and a computer (AMD K7, type
Athlon XP, speed 2 MHz, hard disk 9.54 Go, RAM
256 Mo, operating system Windows 2000). Data analysis
was performed using the Millenium software. A Supelco-
sil LC-PAH column (150 · 3.0 mm i.d., C18-silica, 5 lm
particle size, Supelco) was used, along with a pre-column
(Supelguard LC-18, Supelco). Separation was performed
using the following gradient: acetonitrile/water (40:60
v/v) for 4 min, followed by a 11-min ramp to attain
100% acetonitrile, this solvent being further maintained
for 10 min. The total flow-rate was 0.8 ml min1.
Some samples were also analysed using an HPLC
system coupled to a UV–visible detector (detection at
254 nm) and to a mass spectrometer (MS) equipped with
an atmospheric pressure chemical ionization (APCI)
interface. The HPLC system consisted of a Perkin–
Elmer 200LC high-pressure gradient pump, a Rheodyne
injection valve equipped with a 20 ll loop, an APCI
interface, a PE-Sciex API 100 simple quadrupole, a
channel electromultiplier and a computer. Data analysis
was performed using the MacDAD software. A Supelco-
sil LC-PAH column (150 · 3.0 mm i.d., C18-silica, 5 lm
particle size, Supelco) was used, along with a pre-column
(filled with C18-silica). Separation was performed using a
similar gradient as with the HPLC-DAD system, except
that the mobile phase was acidified (0.2% acetic acid):
acetonitrile/water/acetic acid (39.9:59.9:0.2 v/v/v) for
4 min, followed by a 11-min ramp to attain 100% aceto-
nitrile/acetic acid (99.8:0.2 v/v), this solvent being fur-
ther maintained for 10 min. The total flow-rate was
0.8 ml min1. Other conditions for the APCI interface
were: positive mode, source temperature 400 C, source
 V. Flotron et al. / Chemosphere 59 (2005) 1427–1437 1431

needle current 5 lA, orifice voltage 30 V, ring volt-
age 300 V, nebulizer gas 8 l min1, curtain gas (N2)
0.8 l min1.
3. Results and discussion
Experiments were first conducted in aqueous solu-
tions, due to the lack of data related to Fenton oxidation
of PAHs in water. As we were interested in studying oxi-
dation of both solubilized and sorbed PAHs, we used
experimental conditions that enabled partial adsorption
of the pollutants on the recipient walls (Flotron et al.,
2003). Mild Fenton conditions were used, due to the ab-
sence of natural organic matter that may consume OH.
Then, oxidation of PAHs sorbed onto solid samples was
investigated, using stronger Fenton conditions to take
into account the presence of large amounts of organic
matter and the subsequent radical scavenging.
3.1. Oxidation of sorbed and solubilized PAHs in
aqueous solutions
3.1.1. Kinetics of oxidation
Experiments were first conducted with PAH mixture
in aqueous solutions. The system was studied in presence
of an excess of hydrogen peroxide (i.e. [H2O2]0/
[Fe2+]0 = 2 or 10, this latter value being the theoretically
optimal ratio according to Tang and Huang (1996)). In
all cases, the reagents were in excess compared to the
substrates (see Table 3). Results obtained for the differ-
ent experiments are shown in Fig. 1, and compared to
control experiments (i.e. no reagent addition, enabling
the estimation of adsorption kineticsP on recipient walls).
For experiment no. 1 (i.e. [Fe2+]0/[ PAHs]0 = 10 and
[H2O2]0/[Fe2+]0 = 10), 60% of benzo[a]pyrene were de-
graded, the remaining benzo[a]pyrene being sorbed on
the recipient walls. By comparison with the experiment
without FentonÕs reagent, for which around 60% of this
PAH was solubilized, we assumed that only the solubi-
lized benzo[a]pyrene could be oxidized by the hydroxyl
radicals generated in the solution, suggesting that sorp-
tion prevents oxidation under our conditions. In the
same time, no degradation of either fluoranthene or
benzo[b]fluoranthene could be observed, despite the
large soluble content of the former compound. Thus, it
is evident that benzo[a]pyrene is more rapidly degraded
than these two compounds, probably due to its aromatic
structure, the presence of a five-atom ring in the PAH
structure leading to a lower oxidation. This efficient oxi-
dation of benzo[a]pyrene using the FentonÕs reagent has
already been reported (Kawahara et al., 1995; Nam
et al., 2001), and is of great interest due to its recalci-
trance to microbial degradation.

Table 3
Experimental pseudo-first order rate kinetic constants determined under different FentonÕs reagent concentrations (and related
correlation coefficients R2)
P
Experiment [Fe2+]0 [H2O2]0 [Fe2+]0/[ PAHs]0 [H2O2]0/[Fe2+]0 PAH k 1exp R21 k 2exp R22
(mol l1) (mol l1) (mol/mol) (mol/mol) (min1) (min1)
0a 0 0 0 0 Fla—mixture 0.001 0.971 – –
BbF—mixture 0.002 0.961 – –
BaP—mixture 0.004 0.964 – –
1 1.0 · 105 1.0 · 104 10 10 Fla—mixture – – – –
BaP—mixture 0.017 0.991 – –
2 8.2 · 105 1.7 · 104 80 2 Fla—mixture 0.020 0.997 – –
BaP—mixture 0.138 0.976 0.047 0.984
3 1.6 · 104 3.2 · 104 155 2 Fla—mixture 0.039 0.996 0.001 0.948
BaP—mixture 0.422 1.000 0.052 0.992
4 1.6 · 104 1.6 · 103 155 10 Fla—mixture 0.150 1.000 0.002 0.970
BaP—mixture 0.648 1.000 0.070 0.994
5 3.1 · 104 3.1 · 103 300 10 Fla—mixture 0.051 0.984 0.003 0.947
BaP—mixture 0.088 0.951 – –
6 1.6 · 104 3.2 · 104 155 2 Fla—mixture 0.033 0.973 0.001 0.861
(2-step BaP—mixture 0.170 0.944 0.006 0.921
addition)
7 3.1 · 104 3.1 · 103 300 10 Fla—single 0.303 1.000 0.006 0.999
BaP—single 0.539 1.000 0.058 0.975
k 1exp and k 2exp are the kinetic constants of PAH oxidation with the Fe2+/H2O2 or the Fe3+/H2O2 system respectively.
a
In this experiment, adsorption kinetic constants were estimated, while for the others only oxidation kinetics are presented.
1432 V. Flotron et al. / Chemosphere 59 (2005) 1427–1437

Solubilised Adsorbed Degraded prone to adsorption). Again, this suggests that adsorp-
140% tion prevents oxidation under these conditions. One
Percentage of BaP content (%)

120%
explanation lies in the moderate OH concentrations,
leading to the consumption of these species in the solu-
100%
tion before coming near the recipient walls where the
80% sorbed PAHs are present.
60% Adding hydrogen peroxide in two steps (at time 0
and 30 min) instead of one did not enhance the remo-
40%
vals, suggesting that the production of hydroxyl radicals
20% was limited by the ferrous iron concentration in the
0% solution. This was confirmed by the oxidation kinetics
0 1 2 3 4 5 6
(a) observed for fluoranthene and benzo[a]pyrene. A pseu-
do-first order reaction was noted with a change in the
Solubilised Adsorbed Degraded experimental kinetic rate constant after a certain time,
140%
leading to a slower degradation as indicated in Table
Percentage of Fla content (%)

120% 3. This could be explained by an initial rapid production

100%
of OH upon oxidation of Fe(II) into Fe(III) by hydro-
gen peroxide (leading to rapid substrate degradation
80%
and kinetic constant k 1exp ), followed by partial regenera-
60% tion of Fe(II) when an excess of hydrogen peroxide is
40% present, according to reaction (6).
20% Fe3þ þ H O ! Fe2þ þ Hþ þ HO
2 2 2

0% k 6 ¼ 0:01 mol1 l s1 ð6Þ

0 1 2 3 4 5 6
(b)
However, this reaction being considerably slower than
Solubilised Adsorbed Degraded the reaction (1), the rate constant will be decreased
160% (k 2exp  k 1exp ).
Percentage of BbF content (%)

140% Performing the same type of experiments on single

120% PAHs for the two previously degraded compounds re-
100%
vealed competition effects (see experiment no. 7). Hence,
the kinetic constants are obviously higher when organic
80%
compounds are sole in solution, as more OH are avail-
60%
able for the considered PAH oxidation. On the opposite,
40% when both organic compounds are present, competition
20% effects between the two solutes lead to a slower oxidation
0% of both compounds, especially for the more recalcitrant
0 1 2 3 4 5 6
(c) compound, fluoranthene. This suggests that higher re-
agent concentrations should be added in presence of dif-
Fig. 1. Effect of FentonÕs reagent concentrations on the
behaviour of PAHs in acidic aqueous solutions: (a) benzo[a]- ferent organic substrates to achieve significant PAH
pyrene, (b) fluoranthene and (c) benzo[b]fluoranthene. Vertical oxidation, especially with solid matrices that contain
bars represent the 95% confidence interval of the mean on natural organic matter. Experiments performed on sin-
triplicates. The X-axis represent the series of experiment gle benzo[b]fluoranthene confirmed the absence of oxi-
according to Table 3. Experimental conditions: [PAH]0 = dation under our conditions.
80 lg l1; pH 3; 3 h oxidation.

3.1.2. By-products formation

As the reagent concentrations were increased, almost
complete degradation of benzo[a]pyrene could be
achieved, indicating that this compound was more rap-
idly degraded than adsorbed. Significant degradation of
fluoranthene also occurred, but as its adsorption re-
mained constant, we assumed that only solubilized
fluoranthene could be oxidized under our conditions.
On the opposite, benzo[b]fluoranthene remained unde-
graded, being mainly adsorbed on the recipient walls (this
compound being the most hydophobic, it is the most
Efforts were made to follow the formation of some by-
products, and possibly identify some structures. Results
are presented in Fig. 2 for fluoranthene and benzo[a]pyr-
ene. A few compounds appeared on the chromatograms,
with much lower retention times than the parent com-
pounds, indicating more polar structures. Some com-
pounds further disappeared, being oxidized, while
others remained in the solution over time. However,
these compounds could be detected only at trace levels,
so that their identification could not be achieved. Yet,
 V. Flotron et al. / Chemosphere 59 (2005) 1427–1437 1433

Fig. 2. By-product formation during the FentonÕs oxidation in aqueous solution: (a) appearance of peaks on the chromatogram during
fluoranthene oxidation, (b) appearance of peaks on the chromatogram during benzo[a]pyrene oxidation and (c) APCI-HPLC-MS mass
spectrum of by-product P3. Experimental conditions: [BaP]0 = 80 lg l1; [Fe2+]0 = 3.1 · 104 mol l1; [H2O2]0 = 3.1 · 103 mol l1; pH
3. By-products of fluoranthene are noted P 0 ; by-products of benzo[a]pyrene are noted P.
1434 V. Flotron et al. / Chemosphere 59 (2005) 1427–1437

some structural information could be obtained in the
case of the more concentrated by-product for benzo[a]-
pyrene (i.e. P3) as shown in Fig. 2. The molecular mass
of this compound should be 284, assuming the m/z 285
being MH+ (which is produced in the APCI interface).
The other major fragments can be explained as follows:
m/z 286 is the fraction of MH+ corresponding to the nat-
ural isotopic 13C content of the molecule; m/z 267 is
formed upon the loss of water giving (MH  H2O)+;
m/z 257 is the result of the loss of CO leading to
(MH  CO)+. All these observed fragments are consis-
tent with a di-hydroxylated derivative of benzo[a]pyrene,
but they do not give information about the position of
the two hydroxylated groups on the molecule. Due to
possible high toxicity of such derivatives, efforts need
to be pursued to ascertain the structures of by-products
formed. In particular, we attributed the low levels of
by-products in our solutions to the fact that aqueous
samples were pre-concentrated on a PS-DVB copolymer
during solid-phase extraction, which should not effi-
ciently retain polar compounds. So, in order to achieve
higher sensitivity, samples should be pre-treated on a
more polar sorbent such as porous graphitized carbon
to achieve better extraction of by-products.
3.2. Oxidation of sorbed PAHs in solid matrices under
strong conditions without pH adjustment
Experiments for solid matrices were performed using
aqueous solid matrices suspensions, and upon large con-
centrations of FentonÕs reagent, to enable sufficient OH
to be available for PAH oxidation, as their consumption
by natural organic matter has to be taken into account.
No pH adjustment was performed, as previous studies
reported efficient oxidation of sorbed compounds under
such conditions (Watts et al., 2002). Preliminary experi-
ments conducted with PAHs solubilized in aqueous
solutions (at the 40 lg l1 level) under such conditions
showed that almost complete oxidation of the three sol-
utes could be achieved, with removals of 99.4%, 88.8%
and 99.3% for fluoranthene, benzo[b]fluoranthene and
benzo[a]pyrene respectively.
3.2.1. Removal of native PAHs
Blank experiments (conducted in the absence of
hydrogen peroxide) revealed no desorption of the native
PAHs. Therefore, oxidation of the pollutants should
occur in the sorbed form. Hence, it is interesting to note
that oxidation of the sorbed native PAHs could be ob-
served (see Table 4). Besides, a strong dependence on
the nature of the matrix was evident. Large removal of
the three tested PAHs could be obtained for the sludge
sample, while only benzo[b]fluoranthene was signifi-
cantly degraded for the sediment sample, and none of
these compounds could be efficiently oxidized in the case
of the soil sample under these conditions. The influence
of the matrix on PAH oxidation by the FentonÕs reagent
has already been observed (Nam et al., 2001).
Despite no clear correlation between the observed
percentages of removal and the natural organic matter

Table 4
Total PAH content (expressed as percentage of the total PAH content) removed from the matrix and recovered in the aqueous phase
after FentonÕs reagent application (24 h reaction) (RSDs are given in italic and in brackets)
Sample PAH Spiked content (%) Total removed (%) Total recovered in solution (%)
Native (no spike) Native + spiked
Sludge Fluoranthene 0.0 46.2 (0.0) – 0.2 (13.4)
25.0 – 38.0 (5.1) nd
Benzo[b]fluoranthene 0.0 36.2 (0.2) – 0.8 (20.2)
48.2 – 42.0 (5.5) nd
Benzo[a]pyrene 0.0 48.1 (0.2) – 0.4 (28.0)
56.3 – 67.0 (2.0) nd
Sediment Fluoranthene 0.0 9.7 (141.4) – nd
96.0 – 97.8 (0.2) nd
Benzo[b]fluoranthene 0.0 85.0 (4.4) – 5.4 (25.4)
76.5 – 97.6 (0.4) nd
Benzo[a]pyrene 0.0 16.9 (123.9) – nd
99.2 – 99.1 (0.5) nd
Soil Fluoranthene 0.0 0.0 – 1.5 (45.2)
78.9 – 85.7 (0.2) nd
Benzo[b]fluoranthene 0.0 8.0 (40.7) – 2.7 (47.3)
86.1 – 87.4 (0.5) 0.1 (141.4)
Benzo[a]pyrene 0.0 0.0 – 1.5 (36.8)
88.7 – 88.6 (0.8) 0.1 (20.7)
nd: not detected.
 V. Flotron et al. / Chemosphere 59 (2005) 1427–1437 1435

contents of the matrix, some assumptions can be made
to explain these results. Thus, the limited degradation
of the PAHs in the sludge sample could be due to two
effects. Firstly, insufficient OH concentrations could be
available for PAH oxidation, due to their consumption
with the sludge natural organic matter (benzo[a]pyrene
being slightly more degraded than the other two com-
pounds due to its easiest oxidation as observed previ-
ously), as natural organic matter is well-known to
inhibit PAH oxidation by the FentonÕs reagent (Lindsey
and Tarr, 2000).
Secondly, it seems that the fraction of undegraded
benzo[a]pyrene was related to the unavailable fraction
of this pollutant, as extraction of the sludge sample with
ethanol enabled only 50% benzo[a]pyrene removal
(while complete removal of the other two PAHs could
be achieved) (data not shown). The higher removal of
benzo[b]fluoranthene as well as the limited fluoranthene
and benzo[a]pyrene degradation in the sediment were
attributed to the low content of these native PAHs,
and thus to lower required OH content for oxidation
(in case of benzo[b]fluoranthene) or to their non-avail-
ability (for the latter two compounds). In case of the
soil, the absence of significant oxidation was attributed
to the low levels of both benzo[b]fluoranthene and ben-
zo[a]pyrene, as well as on the low organic matter of the
that spiked PAHs were quantitatively oxidized in each
case, while native PAH removals differed depending on
the compound and the matrix as already observed.
Nam et al. (2001) also reported more efficient degrada-
tion of spiked PAHs than native PAHs in soils.
3.2.3. Effect of the solid matrix iron oxides
In order to investigate possible effect of iron oxides
present in the solid matrix, experiments were conducted
upon the sole addition of hydrogen peroxide. The results
presented in Fig. 3 give evidence that the addition of fer-
rous iron to the solid suspension had no significant effect
as compared to the sole addition of hydrogen peroxide.
This observation suggests that iron oxides present in the
solid matrix may be involved in the oxidation process, as
already reported (Watts et al., 1999). Indeed, in presence
of a large excess of hydrogen peroxide, Lin and Gurol
(1998) assumed that this reagent reacts with iron oxides
Control Fe2+/H2O2 H2O2
140
120
100
Recovery (%)

soil. Hence, a recent study showed that for soils contain-

80
ing less than 5% organic matter, the pollutants were ad-
sorbed in the micropores, being less available than for 60
soils with higher organic matter content for which pollu-
tants are mainly sorbed onto the organic matter (Bogan 40
and Trbovic, 2003). This could explain the absence of 20
fluoranthene oxidation observed for our soil sample.
Consequently, it is obvious that the efficiency of the 0
(a) Fla BbF BaP
Fenton treatment is strongly dependent on the solid ma-
trix characteristics and the contaminant availability. In Control Fe2+/H2O2 H2O2
particular, in the case of low levels of contamination, 120
large amounts of hydrogen peroxide are required to en-
able oxidation of sorbed PAHs due to strong matrix- 100
PAH interactions, which may reduce the cost-efficiency
Recovery (%)

of this remediation process. So it seems that the Fenton 80

treatment would be more dedicated in practice to highly
contaminated environmental matrices, such as the reme- 60
diation of industrial sites (EPA, 1998).
40
3.2.2. Removal of spiked and native PAHs
Spiked PAHs (0.4 mg kg1 each) were added to the 20
investigated environmental matrices (sludge, soil and
sediment), as such compounds are expected to be less 0
(b) Fla BbF BaP
sorbed than the native pollutants, being more available
for OH oxidation. Results presented in Table 4 show
Fig. 3. Influence of the addition of reagents on the oxidation of
the total PAH content removed from the matrix and sorbed native PAHs from real solid matrices: (a) sediment and
recovered in solution after Fenton oxidation using (b) sludge. Vertical bars represent the 95% confidence interval
strong conditions without pH adjustment. In that case, of the mean on triplicates. Experimental conditions: [Fe2+]0 =
large removals of the three compounds were obtained, 102 mol l1; [H2O2]0 = 4.9 mol l1; no pH adjustment; 24 h
ranging from 38% to nearly 100%. So, we may assume oxidation.
1436 V. Flotron et al. / Chemosphere 59 (2005) 1427–1437
of the solid matrix, enabling the formation of hydroxyl
radicals at the surface of the solid, which can further oxi-
dize sorbed pollutants that are in their vinicity. They
proposed as the initial mechanism the formation of a
surface complex between hydrogen peroxide and iron
oxides. This step would be followed by an electron trans-
fer inside the complex, leading to Fe(II) and the radical
HO2 . This complex further dissociates, and due to the
high reactivity of the radical this dissociation should
be non-reversible. Then excess hydrogen peroxide fur-
ther reacts with Fe(II) with a mechanism similar to that
of the Fenton reaction, except that this is an heteroge-
neous reaction in that case, leading to the generation
of OH at the surface of the solid matrix. Due to their
high reactivity, such radicals would oxidize only pollu-
tants that are near their site of production.
4. Conclusion
The Fenton oxidation of sorbed PAHs from solid
environmental samples can be achieved, using large ex-
cess of hydrogen peroxide, without any pH adjustment.
Besides, the presence of iron oxides in the matrix may
avoid the addition of ferrous iron to the system. How-
ever, the level and nature of the contamination appear
as important factors for the success of the oxidation pro-
cess, as well as the organic matter content of the matrix.
In particular, experiments conducted with spiked sam-
ples are insufficient to assess the efficiency of an oxida-
tive remediation process. Also, reagent addition should
be optimized as competition between PAH and natural
organic matter for reaction with hydroxyl radicals was
evident, as well as competition between PAHs. In partic-
ular, benzo[a]pyrene was found more reactive towards
 Lin, S.-S., Gurol, M.D., 1998. Catalytic decomposition of
OH than PAHs containing a five-atom carbon cycle.
So, further studies should be conducted to assess the ex-
tent of oxidation, especially the nature and toxicity of
possible by-products formed.
Acknowledgement
The authors gratefully thank Dr. L. Debrauwer
(INRA, Toulouse, France) and Dr. J. Einhorn (INRA,
Versailles, France) for their precious advices and help
in conducting HPLC-MS experiments and proposing
identification of by-product P3.
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