Degradation of PAHs in Soils
Research Articles
Comparison of Fenton's Reagent and Ozone Oxidation of Polycyclic
Aromatic Hydrocarbons in Aged Contaminated Soils
Sofia Jonsson1*, Ylva Persson1, Sofia Frankki2, Staffan Lundstedt1,3, Bert van Bavel4, Peter Haglund1 and Mats Tysklind1
1 Environmental Chemistry, Department of Chemistry, Umeå University, 901 87 Umeå, Sweden
2 Department of Forest Ecology, Swedish University of Agricultural Sciences, 901 83 Umeå, Sweden
3 Present Address: Environmental Health Centre, Tunney's Pasture Ottawa, Ontario, K1A 0K9, Canada
4 Man-Technology- Environment Research Centre, Örebro University, 701 82 Örebro, Sweden
* Corresponding author (sofia.jonsson@chem.umu.se)
DOI: http://dx.doi.org/10.1065/jss2006.08.179
Abstract
Background. Polycyclic aromatic hydrocarbons (PAHs) are formed
as a result of incomplete combustion and are among the most fre-
quently occurring contaminants in soils and sediments. PAHs are
of great environmental concern due to their ubiquitous nature and
toxicological properties. Consequently, extensive research has been
conducted into the development of methods to remediate soils con-
taminated with PAHs. Fenton's reagent or ozone is the most com-
monly studied chemical oxidation methods. However, the majority
of remediation studies use soils that have been artificially contami-
nated with either one or a limited number of PAH compounds in
the laboratory. Hence, it is essential to extend such studies to soils
contaminated with multiple PAHs under field conditions.
Objectives. The objective of this study is to investigate the capac-
ity of Fenton's reagent and ozone to degrade PAHs in soils. The
soils have been collected from a number of different industrial sites
and, therefore, will have been exposed to different PAH compounds
in varying concentrations over a range of time periods. The capac-
ity of Fenton's reagent and ozone to degrade PAHs in industrially
contaminated soils is compared to results obtained in studies us-
ing soils artificially contaminated with PAHs in the laboratory.
Methods. Nine soil samples, contaminated with PAHs, were col-
lected from five different industrial sites in Sweden. For the
Fenton's reagent procedure, the pH of the soil slurry samples was
adjusted to pH 3 and they were kept at a constant temperature of
70ºC whilst H2O2 was added. For the ozone procedure, soil
samples were mixed with 50% water and 50% ethanol and kept
at a constant temperature of 45ºC. Ozone was then continually
introduced to each soil sample over a period of four hours. Fol-
lowing the Fenton's reagent and ozone oxidation procedures, the
samples were filtered to isolate the solid phase, which was then
extracted using pressurized liquid extraction (PLE). The sample
extracts were cleaned up using open columns and then analysed
by gas chromatography-mass spectrometry (GC-MS).
Results. The relative abundance of the detected PAHs varied be-
tween soils, associated with different industries. For example, low
molecular weight (LMW) PAHs were more abundant in soil
samples collected from wood impregnation sites and high overall
PAH degradation efficiencies were observed in soils originating
from these sites. In the contaminated soils studied, PAHs were
more effectively degraded using Fenton's reagent (PAH degrada-
tion efficiency of 40–86%) as opposed to ozone (PAH degrada-
tion efficiency of 10–70%). LMW PAHs were more efficiently
degraded, using ozone as the oxidizing agent, whereas the use of
Fenton's reagent resulted in a more even degradation pattern for
PAHs with two through six fused aromatic rings.
208
© 2006 ecomed publishers (Verlagsgruppe Hüthig Jehle Rehm GmbH), D-86899 Landsberg and Tokyo • Mumbai • Seoul • Melbourne • Paris
Research Articles
Discussion. The degradation efficiency for both methods was
largely dependent on the initial PAH concentration in the soil
sample, with higher degradation observed in highly polluted soils.
LMW PAHs are more susceptible to degradation than high mo-
lecular weight (HMW) PAHs. As a result of this the relative abun-
dance of large (often carcinogenic) PAHs increased after chemical
oxidation treatment, particularly after ozone treatment. Repeated
Fenton's reagent treatment did not result in any further degrada-
tion of soil PAHs, indicating that residual soil PAHs are strongly
sorbed. The effectiveness of the two oxidation treatment ap-
proaches differed between industrial sites, thus highlighting the
importance of further research into the influence of soil proper-
ties on the sorption capacity of PAHs.
Conclusions. This study demonstrates that the degree to which
chemical oxidation techniques can degrade soil bound PAHs
chemical degradation is highly dependent on both the concentra-
tion of PAHs in the soils and the compounds present, i.e. the vari-
ous PAH profiles. Therefore, similarities in the PAH degradation
efficiencies in the nine soil samples studied were observed with
the two chemical oxidation methods used. However, the degra-
dation performance of Fenton's reagent and ozone differed be-
tween the two methods. Overall, Fenton's reagent achieved the
highest total PAH degradation due to stronger oxidation condi-
tions. LMW PAHs showed higher susceptibility to oxidation,
whereas high molecular weight (HMW) PAHs appear to be
strongly sorbed to the soils and therefore less chemically avail-
able for oxidation. This study highlights the importance of in-
cluding soils collected from a range of contaminated sites in
remediation studies. Such soil samples will contain PAH contami-
nants of varying concentrations, chemical and physical proper-
ties, and have been aged under field conditions. In addition to the
chemical and physical properties of the soils, these factors will all
influence the chemical availability of PAHs to oxidation.
Recommendations and Perspectives. We recommend including
aged contaminated soils in chemical degradation studies. In fu-
ture chemical remediation work, we intend to investigate the po-
tential influence of the chemical and physical properties of PAHs
and soil parameters potential influence on the chemical oxidation
efficiency in aged contaminated soils.
Due to the vast number of contaminated sites there is a great need
of efficient remediation methods throughout the world. This study
shows the difficulties which may be experienced when applying
remediation methods to a variation of contaminated sites.
Keywords: Aged contaminated soils; chemical oxidation; coke
production; degradation; Fenton's reaction; gas works; ozone oxi-
dation; polycyclic aromatic hydrocarbons (PAHs); soil remedia-
tion; wood impregnation
J Soils Sediments 6 (4) 208 – 214 (2006)
Research Articles Degradation of PAHs in Soils

Introduction decreases as the chemical oxidation process proceeds to

Polycyclic aromatic hydrocarbons (PAHs), which consist of oxidise the organic constituents of the soils. The period of
two or more fused benzene rings, comprise one of the most time that has elapsed from when the soil was first contami-
frequently occurring groups of organic contaminants in soils nated with PAHs and when the soil is treated is also of great
importance as the contaminants will diffuse further into the
and sediments as a result of their extensive release into the
organic material of the soil over time. This process is often
environment. The physico-chemical properties of PAHs vary
referred to as aging and often results in a reduced suscepti-
greatly. For example, high molecular weight (HMW) PAHs
bility of the contaminants to remediation processes [16]. The
are more hydrophobic and have a greater affinity for soil
majority of soil remediation studies focus on bioremediation
organic matter than low molecular weight (LMW) PAHs.
[17], and the susceptibility of PAHs to chemical oxidation is
Sixteen PAHs, many of which are toxic, mutagenic, and car-
much less frequently investigated. Understanding of the un-
cinogenic, have been identified by the US Environmental
derlying mechanism of the sequestration phenomenon of
Protection Agency (US-EPA) and the Swedish EPA as prior-
contaminants in soils is essential for the development of ef-
ity pollutants [1]. In addition, the Swedish EPA has issued
ficient and cost-effective chemical remediation methods. To
recommended maximum residue levels of PAHs in soils af-
date, the majority of chemical optimisation studies have been
ter remediation treatment [2].
performed using soils that have been artificially contami-
Degrading PAHs by chemical oxidation is one of several nated with one or a limited number of individual PAHs in
approaches adopted in the remediation of contaminated soil. the laboratory. The degradation of a complex mixture of
Fenton's reagent (discovered in the 1890s by H.J.H. Fenton) PAH compounds in soils that have been contaminated for
and ozone treatment are two of the most frequently investi- many years is far more difficult [18,19]. In this study, nine
gated chemical oxidation techniques [3,4]. These reagents soil samples have been collected for investigation from five
form hydroxyl (OH) radicals, which are strong, non-spe- different industrial sites in Sweden. By their very nature, the
cific, oxidizing agents. Chemical oxidation using Fenton's soils will have been contaminated with a complex mixture
reagent is conducted under acidic conditions where OH radi- of PAHs at varying concentrations and over different peri-
cals are formed by using hydrogen peroxide with Fe2+ as a ods of time. The soil samples from these sites have been
catalyst. Chemical oxidation with ozone, introduced either subjected to Fenton's reagent and ozone treatments in order
in a gaseous or aqueous form, occurs when ozone decom- to investigate the techniques efficiency in degrading the vari-
poses to form OH radicals via a catalytic reaction at the ous PAH compounds and whether the type and concentra-
reactive site on soils [3]. Ozone has been proposed as a prom- tion of PAHs in the soils influences their susceptibility to
ising in situ remediation technique [5–9], as has a modified degradation by oxidation. The capacity of Fenton's reagent
Fenton's reaction in recent years (i.e. without the addition and ozone to degrade PAHs in aged contaminated soils is
of Fe2+ or at neutral pH) [10–15]. compared to results obtained in studies using soils artifi-
cially contaminated with PAHs in the laboratory.
Remediation of soils contaminated with PAHs via chemical
oxidation is hampered by the fact that sorbed contaminants 1 Materials and Methods
resist oxidative attack more effectively than contaminants
1.1 Soil sampling
in solution [12,15]. Sorbed contaminants are likely to re-
main unavailable to the chemical reactants that reside in the Nine soil samples, each 5–10 kg in weight, were collected
aqueous phase. In addition, the efficiency of oxidation also from five different industrial sites in Sweden (Table 1). The
Table 1: Sample site location, industry characteristics and soil types
Site Location Coordinates Industry Period of Sampling Soil Observations
operation depth
1 (W) Holmsund N 63º 42m 00s Wood 1943–1983 20–30 cm Sandy Till Black aggregated soil, strong smell of tar
E 20º 21m 00s preservation
2 (W) Holmsund N 63º 42m 00s Wood 1943–1983 10–20 cm Sandy Till Black aggregated soil, strong smell of tar
E 20º 21m 00s preservation
3 (W) Holmsund N 63º 42m 00s Wood 1943–1983 10–20 cm Sandy Till Smell of tar
E 20º 21m 00s preservation
a
4 (C) Luleå N 65º 35m 00s Coke Top soil Sediment Black waterlogged sediment, oily film on
E 22º 09m 00s production water surface
5 (W) Forsmo N 63º 16m 00s Wood 1933–1950 2–18 cm Fine sand Black aggregated well sorted sandy soil
E 17º 12m 00s preservation
6 (W) Forsmo N 63º 16m 00s Wood 1933–1950 0–10 cm Fine sand Black aggregated well sorted sandy soil
E 17º 12m 00s preservation
7 (W) Hässleholm N 65º 09m 00s Wood 1946–1965 40 cm Coarse Smell of tar
E 13º 46m 00s preservation sand
8 (W) Hässleholm N 65º 09m 00s Wood 1946–1965 40–60 cm Coarse Smell of tar
E 13º 46m 00s preservation sand
b
9 (G) Husarviken N 59º 21m 18s Gas work 1893–1972 Sand Smell of tar
E 18º 06m 12s
a
Facility still in use, start unknown
b
Not known

J Soils Sediments 6 (4) 2006 209

Degradation of PAHs in Soils
soil samples were transported back to the laboratory in un-
used, solvent-washed steel containers. The industrial sites
were carefully selected in order to obtain soil samples that
would contain multiple PAH compounds at varying con-
centrations. The soil samples were air dried at room tem-
perature, passed through a 2 mm sieve, and kept at constant
temperature (4ºC) prior to analysis. In the tables and figures
that follow, each soil sample has been assigned a code con-
sisting of the sample number followed by a letter referring
to the type of industry associated with the soil sample site
(i.e. W for wood impregnation, C for coke production and
G for gas works).
1.2 Chemicals
All solvents used were of analytical or glass distilled grade.
Glassware was of high quality, machine washed with alka-
line detergent and rinsed with solvent prior to usage. Hy-
drogen peroxide (30%) was purchased from J.T Baker
(Deventer, Holland). FeSO4x7H2O (p.a), sulphuric acid
(p.a,), silica gel 60 (0.063–0.20 mm), and sodium sulphate
(p.a.) were from Merck (Darmstadt, Germany). The silica
gel was activated at 130ºC for 24 hours and sodium sul-
phate at 550ºC for 48 hours. Silica gel was deactivated with
10% water (w/w) prior to use. Filter papers were purchased
from Munktell (Grycksbo, Sweden), and internal standards
(IS) and recovery standards (RS) were from Cambridge Iso-
tope Laboratories (Andover, MA, USA). The IS consisted of
2[H ]naphthalene, 2[H ]acenaphthylene, 2[H ]acenaphthene,
8 8 10
2[H ]fluorene, 2[H ]anthracene, 2[H ]pyrene, 2[H ]benz-
10 10 10 12
[a]anthracene, 2[H12]benzo[k]fluoanthene, 2[H12]benzo-
[ghi]perylene and the RS consisted of 2[H10]fluoranthene.
The compounds were quantified using a certified PAH ref-
erence standard mixture (SRM 2260, National Institute of
Standards & Technology, Gaithersburg, MD, USA).
1.3 Soil treatment
Soil samples were subjected to chemical oxidation using both
Fenton's reagent and ozone. Triplicate oxidation experiments
were performed for all samples except for samples 2 and 3,
which were only treated once. After treatment, all soil
samples were filtered and air-dried at room temperature prior
to further analysis.
1.3.1 Fenton's reagent procedure
The oxidation experiments were performed on slurries made
up of 20 g of soil, 10 ml of 4 mM iron sulphate and 40 ml of
hydrogen peroxide (30%) in 250 ml Erlenmeyer flasks, at a
temperature of 70°C. 5% sulphuric acid was added to ad-
just the slurry to a pH of 3 prior to oxidation. The soil mix-
ture was kept in suspension using a magnetic stirrer whilst
40 ml was added in increments (10 ml) within the first thirty
min in order to avoid a violent reaction. The reaction was
terminated after two hours with the addition of five drops
of concentrated H2SO4 (pH < 1).
1.3.2 Ozone oxidation procedure
For the ozone oxidation procedure, 20 g of soil was mixed
with 50 ml of 50% ethanol in water. The mixture was kept
210
Research Articles
at a constant temperature (45°C) and in suspension using a
combined magnetic stirrer and heater. The ozone was gener-
ated from pure oxygen through electric discharges using an
ozone generator (Anseros, Tübingen, Germany). Ozone was
continuously pumped into the mixture at a rate of 25 mg
per hour over a four hour period, with additional ethanol
added to compensate for ethanol evaporation during the
oxidation process. The amount of ozone produced was cal-
culated by measuring the amount of oxygen used. The ex-
cess ozone that was not consumed by the slurry was passed
through a catalyst and destroyed.
1.4 Extraction and sample clean-up
PAHs were extracted from the soil samples by pressurised
liquid extraction (PLE) using a Dionex ASE200 (Sunnyvale,
CA, USA) equipped with 11 ml stainless steel extraction cells.
All extractions were performed at 14 MPa and a tempera-
ture of 150ºC with seven min of dynamic extraction, two
static cycles of five min each, and with one cell volume used
for rinsing with a purge time of sixty seconds.
1.4.1 Soil extraction
The PLE extraction cells were fitted with a cellulose filter to
prevent clogging of the metal frit at the outlet of the cell.
The cells contained 1 g of soil mixed with 5 g of anhydrous
sodium sulphate, and were filled with anhydrous sodium
sulphate. PLE was performed using n hexane:acetone (1:1,
v/v) followed by methanol:acetic acid (99:1, v/v). 50 µL of
IS was added to 10% portions of each extract and then evapo-
rated to 1 ml and fractionated on open columns (15 mm in
diameter, containing 5 g of silica and 1 g of anhydrous sodium
sulphate). Each column was pre-rinsed with 20 ml n-hexane
and eluted with 5 ml n hexane (waste fraction) followed by
15 ml n-hexane/dichloromethane (3:1, v/v). The second frac-
tions were evaporated under a gentle stream of N2 and re-
constituted in 1 ml of toluene.
1.4.2 Liquid-liquid extraction
The PAHs in the slurry filtrates were extracted by liquid-liq-
uid extractions (1:1, v/v), performed in triplicate for each
sample. The extraction solvents used were n-hexane and
dichloromethane (for the Fenton's reagent and ozone treat-
ments, respectively). The extracts were combined and evapo-
rated under a gentle stream of N2 and reconstituted in 1 ml of
n-hexane and fractionated as described above for soil extracts.
1.5 PAH determination
50 µL of RS was added to each sample; which were then
transferred into 2 ml glass vials. The samples were analysed
using a Fisons GC 8000 Top gas chromatograph (GC) with
a 30 m (25 mm i.d.) DB-5 capillary column, film thickness
0.25 µM (J&W Scientific/Agilent Technologies, Folsom, CA,
USA), coupled to an electron impact (EI) Fisons MD800
low resolution mass spectrometer (LR-MS). The sample
aliquots (1 µL) were injected, split-less, into the GC. MS
data were collected in full scan mode for identification and
single ion monitoring (SIM) for quantification. Target com-
J Soils Sediments 6 (4) 2006
Research Articles Degradation of PAHs in Soils

Table 2: All Polycyclic aromatic hydrocarbon species analyzed in the soils of this study
2 Aromatic Rings 3 Aromatic Rings 4 Aromatic Rings 5 Aromatic Rings 6 Aromatic Rings
Naphthalene Phenanthrene Pyrene Benzo(e)pyrene Benzo(g,h,i)perylene
2-Methylnaphthalene 1-Methylphenanthrene Chrysene a Benzo(a)pyrene a
a
1-Methylnaphthalene Anthracene Benz(a)anthracene Perylene
2,6-Dimethylnaphthalene Fluoranthene Benzo(b)fluoranthene a Dibenz(a,c)anthracene
2,3,5-Trimethylnaphthalene Benzo(k)fluoranthene a Indeno(c,d)pyrene a
Biphenylene
Acenaphthylene
Acenaphthene
Fluorene
a
Carcinogenic PAH according to the Swedish EPA

pounds (Table 2) were identified by comparing their mass spec-

tra and relative retention times with those of reference stan-
dards and quantified using the isotope-dilution technique.

2 Results and Discussion

2.1 PAH profiles and concentrations in contaminated soils

The concentrations of PAHs in the soils studied are given in

Table 3, whilst Fig. 1 illustrates the PAH profiles (two
through six rings) present in each soil sample. Initial PAH
concentrations in the soils ranged from 100 to 9300 mg/kg,
a span of almost two orders of magnitude. The PAH pro-
files were less variable and, in general, PAHs with three or
four fused aromatic rings together accounted for over 60%
of the total. Nevertheless, the soil samples originating from
the former wood impregnation industrial sites generally con-
tained greater concentrations (>80%) of PAHs with two to
four fused aromatic rings (consistent with published values
[20]), whilst the soil sample from the former gas work in-
dustrial site contained higher concentrations of HMW PAHs.
This may relate to the fact that the gas site was contami-
nated with coal-tar instead of creosote. An alternative ex-
planation may be that the soil sample from the gas work site
was contaminated with PAHs much earlier, and over a longer
time period, than the soil samples collected from the wood
impregnation industrial sites and this may explain the dif-
fering PAH profiles of the soils. The relatively even distribu-
tion of two- to six-ringed PAHs exhibited in the soil sample
Fig. 1: Initial soil PAH profiles showing the relative abundance of two
through six aromatic ring PAHs. W (wood impregnation), C (coke produc-
tion) and G (gas work)
collected from the coke-producing industrial site (which was
still in use when the samples were collected) may indicate a
'young' PAH profile, since environmental processes such as
natural degradation and evaporation are known to cause a
reduction in the concentrations of LMW PAHs [21,22].
2.2 PAH degradation
As the concentration of PAHs in the aqueous phase was neg-
ligible (< 1%) following chemical oxidation treatment, the
relative effectiveness of the Fenton's reagent and ozone treat-
ments were assessed by calculating the residual concentra-
tions of PAHs in the solid phase. Overall, Fenton's reagent
was more effective than ozone in degrading PAHs, at the
conditions used in this study. The Fenton's reagent proce-

Table 3: Soil PAH concentrations and standard deviations (based on triplicate measurements) before and after Fenton's reagent and ozone treatment

Soil sample Start concentration After Fenton's reagent After Ozone

(mg/kg) (± stdev) (mg/kg) (± stdev) (mg/kg) (± stdev)
1 (W) 3400 ± 136 460 ± 23 1900 ± 152
a a
2 (W) 9300 1300 3000 a
a a
3 (W) 1500 310 1100 a
4 (C) 510 ± 77 270 ± 111 430 ± 4
5 (W) 1600 ± 256 580 ± 23 1200 ± 132
6 (W) 2800 ± 252 1400 ± 70 2200 ± 220
7 (W) 820 ± 33 490 ± 78 730 ± 131
8 (W) 1400 ± 70 590 ± 201 910 ± 27
9 (G) 140 ± 48 74 ± 9 91 ± 12
a
Single sample

J Soils Sediments 6 (4) 2006 211

Degradation of PAHs in Soils
Fig. 2: Graph of the PAH degradation efficiency of Fenton's reagent and Ozone for the nine soil samples. (* not statistically significant from start
concentration, p= 0.1, one-tailed t-test)
dure was performed under conditions of high temperature
and oxidant load and resulted in the removal of 40% to
86% of PAHs in the solid soil material. Oxidation using
ozone resulted in the removal of between 10% and 70% of
the PAHs in the solid soil material, despite the use of etha-
nol to enhance the desorption process (Fig. 2). The hetero-
genic nature of the soils necessitated a statistical assessment
of oxidation efficiency. The results demonstrate that, at the
0.10 significance level, significant degradation of PAHs in
the solid material of soil could not be proven for soil sample
(4C, and 9G) treated with ozone.
Soil LMW PAHs were degraded more effectively than HMW
PAHs using ozone as the oxidant (Fig. 3). This was consis-
tent with expectations because HMW PAHs are more
strongly sorbed to the soil matrix and soil-bound contami-
nants resist oxidation more effectively than contaminants in
solution [12,15]. However, the results of the present study
indicate that PAH size exerts little influence on the degree of
degradation achieved using Fenton's reagent (see Fig. 3). This
may be explained by the high oxidant load used in this study
[14,23]. Watts et al. [14] suggests that the use of a high oxi-
dant load results in the generation of (as yet) unidentified spe-
cies that are capable of oxidising sorbed contaminants. Since
milder oxidation methods are more dependent on the desorp-
tion of contaminants prior to degradation [12], attempts have
been made in many studies to increase the desorption of HMW
PAHs, in particular, from soils using vegetable oil or alcohol,
for example [17]. Since ozone was performed under milder
oxidation conditions than for Fenton's reagent, it is therefore
Fig. 3: Average degradation efficiencies of two through six ring PAHs with
Fenton's reagent (
) and Ozone (
) in all nine soil samples
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Research Articles
reasonable to assume that a greater difference in the degree
of degradation of LMW and HMW PAHs would have been
observed if ethanol had not been added during the ozone
treatment. Nevertheless, in this study an increase in the rela-
tive concentration of HMW PAHs was observed in the soil
samples after treatment with ozone, as HMW PAHs are less
susceptible to oxidation using this technique.
The effectiveness of PAH degradation was highly dependent
on the initial concentrations of PAHs in the soil, with greater
PAH degradation observed in soils that contained high ini-
tial concentrations of these contaminants (Fig. 4). This phe-
nomenon has been observed previously in sorption studies
performed on soils that contained PAHs introduced in the
laboratory in order to determine PAH bioavailability [22,
24,25]. However, there was no clear correlation between
the degradation efficiency of PAHs with two through to six
fused aromatic rings and their respective initial concentra-
tions. Organic compounds sorb on the soil matrix in a non-
linear fashion, suggesting that sorption sites can become
saturated when soil PAH concentrations are high [26]. The
saturation of soil sorption sites in soils with high initial PAH
concentrations suggests that greater quantities of PAHs
would become chemically available and therefore higher
degradation should be achieved. The data presented here
appear to support this hypothesis.
None of the soil samples in this study contained PAH con-
centrations at or below the current Swedish EPA regulatory
Fig. 4: Influence of initial PAH concentration on the degradation efficiency
of PAHs with Fenton's reagent (
) and Ozone (
). R2 values for Fenton's
reagent and ozone were 0.45 and 0.71, respectively
J Soils Sediments 6 (4) 2006
Research Articles
limit of 7 mg carcinogenic PAHs/kg soil [2] after treatment.
This is despite the fact that, in some cases, chemical oxida-
tion treatment reduced PAH concentrations by over 80%.
Soil samples one and seven, which exhibited the highest and
lowest degradation levels, respectively, were subjected to a
second oxidation cycle, using Fenton's reagent as the oxi-
dant. However, no significant further reduction in PAH con-
centrations was observed, indicating that the residual PAHs
are strongly sorbed to the soil. This demonstrates that a site-
specific risk assessment may be appropriate after contami-
nated soils have been chemically treated.
Fenton's reagent and ozone are often proposed as promis-
ing chemical oxidation methods with potential use as in situ
techniques. However, their use has been limited because of
technical uncertainties and regulatory barriers [4]. If such
obstacles could be removed it is likely that both ozone treat-
ment and treatment with Fenton's reagent would be most
suitable soil remediation techniques. The type of treatment
used would however depend on pollutant levels, soil char-
acteristic and time available for the remediation. The fastest
results would be obtained using ex situ or on site batch treat-
ment under harsh conditions, as those applied in the present
study. However, if time would be less critical than treatment
cost, it is reasonable to expect that the oxidant load may be
reduced (as would the treatment cost) by using in situ treat-
ment. Finally, it is worth pointing out that a thorough site
characterisation is crucial for an efficient and cost effective
remediation [27] and it is therefore surprising that few stud-
ies have been performed using soils collected from contami-
nated sites. In order to further investigate contaminant se-
questration and chemical availability, it is imperative to
include aged soils contaminated with multiple PAHs as well
as soil samples artificially contaminated in the laboratory,
in future remediation studies.
3 Conclusions
This study has demonstrated that the efficiency of degrada-
tion using Fenton's reagent and ozone is highly dependent
on the initial concentration of PAHs in soils and the particu-
lar compounds present. The highest degradation efficien-
cies were achieved in soil samples taken from wood im-
pregnation industrial sites, probably due to the relatively
high concentrations of LMW PAHs and high initial PAH
concentrations in the soils from these sites. Significant PAH
degradation efficiencies were observed in soils with rela-
tively high initial concentrations of PAHs and this is thought
to be a consequence of the saturation of sorption sites.
Overall, at the conditions used in this study Fenton's re-
agent was found to be more effective than ozone in degrad-
ing PAHs. In addition, Fenton's reagent degraded large
PAHs more effectively, probably because the desorption
dependency is lowered by the strong oxidation conditions.
Ozone treatment yielded a higher degradation of LMW
PAHs, but this resulted in the relative enrichment of HMW
PAHs in the residual soil. The remaining PAHs in soils af-
ter both Fenton's reagent and ozone treatment appear to
J Soils Sediments 6 (4) 2006
Degradation of PAHs in Soils
be strongly sorbed to the soil matrix and therefore chemi-
cally unavailable. Further, the low concentrations of PAHs
observed in the liquid phase indicated that desorbed PAHs
were either oxidised rapidly or resorbed in the soil matrix.
None of the soil samples in this study, either before or after
treatment, contained PAH concentrations at or below the
current Swedish EPA regulatory limit. This study has clearly
demonstrated the importance of including aged contami-
nated soils in chemical degradation studies. The degree of
PAH degradation varied greatly in the soils studied, which
can largely be explained by the multitude of differing PAH
compounds encountered in the soils from the different in-
dustrial sites and the large variation in initial soil PAH con-
centrations. In addition, some of this variability may be
due to the chemical and physical properties of the PAH
contaminants, and the characteristics of the soils studied, as
well as the time-period over which the PAHs have been as-
sociated with the soil. All of these factors will influence, to
some degree, the chemical availability of PAHs and, conse-
quently, the effectiveness of any remediation efforts. It is
therefore the intention to investigate these parameter and
their potential influence on the chemical oxidation efficiency
in future chemical remediation work.
4 Recommendations and Perspectives
Due to the vast number of contaminated sites there is a great
need of efficient remediation methods throughout the world.
This study shows the difficulties which may be experienced
when applying remediation methods to a variation of con-
taminated sites. Therefore, we recommend including aged
contaminated soils in chemical degradation studies. In fu-
ture chemical remediation work, we intend to investigate
the potential influence of the chemical and physical proper-
ties of PAHs and soil parameters potential influence on the
chemical oxidation efficiency in aged contaminated soils.
Acknowledgements. This study was supported by the northern Swe-
den Soil Remediation Centre (MCN), which is partially funded by the
European Union Regional Development Funds (ERDF), New Objective
1. Contract Numbers: 113-12534-00, 304-12732-2004, 304-12738-2004.
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Further Literature
Antiƒ MP, Jovanciceviƒ B, Iliƒ M, Vrviƒ MM, Schwarzbauer J
(2006): Petroleum pollutant degradation by surface water
microorganisms. Environ Sci Pollut Res 13 (5) 320–327
Booth L, Heppelthwaite V, O'Halloran K (2005): Effects-based
assays in the earthworm Aporrectodea caliginosa: Their utili-
sation for evaluation of contaminated sites before and after
remediation. J Soils Sediments 5 (2) 87–94
Chaudhry Q, Blom-Zandstra M, Gupta SK, Joner E (2005): Uti-
lising the synergy between plants and rhizosphere microorgan-
isms to enhance breakdown of organic pollutants in the envi-
ronment. Environ Sci Pollut Res 12 (1) 34–48
Jones R, Sun W, Tang C-S, Robert F (2004): Phytoremediation of
petroleum hydrocarbons in tropical coastal soils – II. Micro-
bial response to plant roots and contaminant. Environ Sci Pollut
Res 11 (5) 340–346
Jovanciceviƒ B, Antiƒ MP, Soleviƒ TM, Vrviƒ MM, Kronimus A,
Schwarzbauer J (2005): Investigation of interactions between
surface water and petroleum type pollutants. Environ Sci Pollut
Res 12 (4) 205–212
Kammann U (2006): PAH metabolites in bile fluids of Dab
(Limanda limanda) and Flounder (Platichthys flesus): Spatial
distribution and seasonal changes. Environ Sci Pollut Res
OnlineFirst <DOI: http://dx.doi.org/10.1065/espr2006.
05.308>
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on cadmium toxicity to soil enzymes and microbial growth.
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Sun W, Lo J, Robert F, Ray C, Tang C-S (2004): Phytoremediation
of petroleum hydrocarbons in tropical coastal soils – I. Selec-
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Trably E, Patureau D (2006): Successful Treatment of Low PAH-
Contaminated Sewage Sludge in Aerobic Bioreactors. Environ
Sci Pollut Res 13 (3) 170–176
Vaajasaari K, Joutti A (2006): Field-Scale assessment of phyto-
treatment of soil contaminated with weathered hydrocarbons
and Heavy Metals. J Soils Sediments 6 (3) 128–136
Zechmeister HG, Dullinger S, Hohenwallner D, Riss A, Hanus-
Illnar A, Scharf S (2006): Pilot study on road traffic emissions
(PAHs, heavy metals) measured by using mosses in a tunnel
experiment in Vienna, Austria. Environ Sci Pollut Res 13 (6)
398–405
Received: May 17th, 2006
Accepted: August 24th, 2006
OnlineFirst: August 25th, 2006
J Soils Sediments 6 (4) 2006