Chemosphere 91 (2013) 406414

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Chemosphere
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PAH oxidation in aged and spiked soils investigated by column

experiments
Julien Lemaire a,b,c, Fabien Laurent d,e,f,g, Corinne Leyval d,e, Christophe Schwartz f,g, Michel Bus c,
Marie-Odile Simonnot a,b,
a
Universit de Lorraine, Laboratoire Ractions et Gnie des Procds, CNRS UPR3349, 1 rue Grandville, BP 20451, 54001 Nancy Cedex, France
b
CNRS, Laboratoire Ractions et Gnie des Procds, UPR3349, 1 rue Grandville, BP 20451, 54001 Nancy Cedex, France
c
Universit de Lorraine, Laboratoire Environnement, Gomcanique et Ouvrages, rue du Doyen Marcel Roubault, BP 40, 54501 Vanduvre-ls-Nancy, France
d
Universit de Lorraine, Laboratoire des Interactions Microorganismes, Minraux, Matire Organique dans les Sols, UMR 7137, 54506 Vanduvre-ls-Nancy, France
e
CNRS, Laboratoire des Interactions Microorganismes, Minraux, Matire Organique dans les Sols, UMR 7137, 54506 Vanduvre-ls-Nancy, France
f
Universit de Lorraine, Laboratoire Sols et Environnement, UMR 1120, 2 avenue de la Fort de Haye, BP 175, 54505 Vanduvre-ls-Nancy, France
g
INRA, Laboratoire Sols et Environnement, UMR 1120, 2 avenue de la Fort de Haye, BP 175, 54505 Vanduvre-ls-Nancy, France

h i g h l i g h t s

" Chemical oxidation was performed with 2 aged industrial soils and a spiked one.
" Modied Fenton reaction and activated persulfate led to PAH degradation.
" Degradation was limited due to low PAH availability (cyclodextrin extractability).
" pH was also a very important factor.

a r t i c l e i n f o a b s t r a c t

Article history: Soils of former steel-making or coking plants have been contaminated for decades by PAHs. These soils
Received 17 September 2012 could be cleaned up by In situ chemical oxidation (ISCO) but the low PAH availability may be a drawback.
Received in revised form 19 November 2012 The objective of the present contribution was to study the efciency of PAH oxidation in two aged soils
Accepted 1 December 2012
compared to a spiked soil in dynamic conditions. Column experiments were performed with two oxi-
Available online 3 January 2013
dants: hydrogen peroxide used in modied Fentons reaction and activated persulfate. The oxidant doses
were moderate to ensure the feasibility of process upscaling. Besides, the availability of PAHs in these
Keywords:
soils was measured by extraction with a cyclodextrin. Our results showed that oxidation was limited:
PAH oxidation
Modied Fentons reaction
the higher PAH degradation rate was 30% with the aged soils and 55% with the spiked one. PAH availabil-
Activated persulfate ity was a parameter explaining these results but no direct correlation was found between PAH extract-
Column ability by the cyclodextrin and oxidation efciency. Other parameters were also involved, such as the
Cyclodextrin organic carbon content, the calcite content and the pH. This study was a rst achievement before study-
ing the inuence of a number of parameters on the efciency of PAH oxidation in aged soils.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
Many soils of former industrial sites are contaminated by Poly-
cyclic aromatic hydrocarbons (PAHs). These pollutants have a well-
known negative impact on soil functions and potentially threaten
human health because of their carcinogenic and mutagenic poten-
tial (White and Claxton, 2004). Huge areas of industrial and urban
soils are concerned, with contamination reaching a few thousands
Corresponding author at: Universit de Lorraine, Laboratoire Ractions et Gnie
des Procds, CNRS UPR3349, 1 rue Grandville, BP 20451, 54001 Nancy Cedex,
France. Tel.: +33 0 383 175 260; fax: +33 0 383 322 975.
E-mail address: marie-odile.simonnot@univ-lorraine.fr (M.-O. Simonnot).
to a few tens of thousands ppm. They are most often left in moni-
tored natural attenuation or treated by thermal or biological tech-
nologies (Ouvrard et al., 2011). In situ chemical oxidation has been
investigated for more than a decade for the treatment of such soils
(Forsey, 2004; ITRC, 2005; Huling and Pivetz, 2006; Rivas, 2006; De
Souza e Silva et al., 2009a,b). This method consists in injecting an
oxidant (e.g. permanganate, hydrogen peroxide mainly used in
Fenton or modied Fentons reaction, ozone, activated persulfate,
percarbonate) to degrade PAHs in less toxic substances, the nal
products being carbon dioxide and water. ISCO has been widely
studied and has shown its interest for the clean-up of groundwater
contaminated by chlorinated volatile organic compounds and
monoaromatic hydrocarbons (Crimi and Taylor, 2007; Lemaire

0045-6535/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.chemosphere.2012.12.003
 J. Lemaire et al. / Chemosphere 91 (2013) 406414 407

et al., 2011; Siegrist et al., 2011). The treatment of soils contami- Table 1
nated by persistent organic pollutants is another challenge. ISCO Physicochemical characteristics of the two industrial soil samples TNM and TH and of
the agricultural soil sample TCh.
has potential advantages to treat these soils because of its relative
simplicity and efciency. It also has drawbacks, since remediation Units TNM TH TCh Regional referencea
may not be complete (Bogan and Trbovic, 2003; Jonsson et al., mean max
2006; Alderman et al., 2007; Andreottola et al., 2009). Huge quan- Sand wt.% 62.9 64.1 68.9
tities of oxidants may be needed, particularly because of the oxida- Silt wt.% 24.1 25.3 22.9
tion of natural soil organic carbon and soil functions (e.g. plant Clay wt.% 13.0 10.6 8.2
production and biodiversity) can be affected (Sirguey et al., 2008; pH water 7.4 8.4 4.7
Total CaCO3 g kg1 35.7 369.0 <1.0
Laurent et al., 2012). Moreover, the roles of all the parameters gov-
Total N g kg1 2.69 2.14 1.19
erning ISCO efciency in soils bearing aged contamination are not Organic C g kg1 71.5 101.0 8.8
totally elucidated. PAHs g kg1 1.1 0.9 nd
The present contribution aims at investigating PAH oxidation in Zn mg kg1 2680 361 33.1 120 500
Pb mg kg1 684 121 27.2 25 100
aged soils in dynamic conditions and at studying the inuence of
Cr mg kg1 325 55.5 19.4 80 500
their availability on oxidation efciency. Three contrasted soils Ni mg kg1 260 24.3 7.43 30 100
were selected: two soils sampled from former steel-making plants Cu mg kg1 110 28.5 8.62 15 50
differing by their organic carbon and carbonate contents and an Hg 3.88 12.0 nd 0.5 2.0
uncontaminated agricultural soil spiked with two PAHs. These soils a
Values taken from Darmendrail et al. (2000).
were treated in laboratory column experiments with two oxidants
(Lemaire, 2011): hydrogen peroxide activated by iron II by the
modied Fentons reaction and persulfate activated by hydrogen
peroxide. Besides, PAH availability was investigated. We dene pH was measured in water suspension at the ratio 1/5 (v/v) (NF ISO
PAH availability as their ability to be desorbed from the soil and re- 10390). Total carbonate (NF ISO 10693) was determined by mea-
act in the liquid phase. Availability has been assessed by different surement of the emitted volume of CO2 during sample acidication
approaches, such as solid phase extraction (Tenax) (Cornelissen with HCl. Total C (NF ISO 10694) was determined by dry combus-
et al., 2001; Subramaniam et al., 2004; You et al., 2006; Barnier, tion and quantication of the emitted volume of CO2. Organic car-
2009) or cyclodextrin extractability (Cho et al., 2004; Viglianti bon was calculated from the difference between total carbon and
et al., 2006a,b; Ran et al., 2009). In the present study, availability total carbonate.
was evaluated by PAH extraction from soil with hydroxypropyl- Trace metals were analyzed by ICP-OES (Cr, Cu, Ni and Zn) and
beta-cyclodextrin because of its ease of use. Our objective was to by ICP-MS (Pb) after lithium metaborate attack and acid digestion.
relate PAH availability and oxidation efciency. PAHs were analyzed as described in Section 2.5.
The three soils were sandy loamy soils (Table 1). Apart from
2. Materials and methods texture, the two industrial soils were very different from the agri-
cultural one. TNM and TH were slightly alkaline with high carbon-
2.1. Chemicals ate content (resp. 35.7 and 369 g kg1 for resp. TNM and TH). TCh
was an acid soil with a very low carbonate content (<1 g kg1).
A standard solution composed of the 16 US EPA PAHs PAHs TNM and TH had high organic carbon content due the coking plant
standard (1 mg L1 each), phenanthrene (PHE, 98% purity), pyrene activity (Table 1). Moreover, organic matter was mainly composed
(PYR, 98% purity) and sulfuric acid (9597%) were supplied by Al- of organic compounds deriving from coal tars (Biache et al., 2008;
drich. Acetonitrile, methylene chloride and chloroform (99.8% pur- Sirguey et al., 2008; Monsri et al., 2009; Benhabib et al., 2010;
ity) were purchased from Fischer Scientic, Hydroxypropyl Beta Laurent et al., 2012). Organic carbon content was 811 fold lower
Cyclodextrin (HPCD) from Molekula. Potassium persulfate in TCh soil and organic matter was expected to be natural. TNM
(>99%) was supplied by Acros Organics, ortho-phosphoric acid and TH were contaminated by heavy metals, mainly Zn and Pb
(85%) by Merck, potassium permanganate (>99%) by Fluka Chemi- but also Cr, Ni, Cu and Hg (Table 1). Metal concentrations in TCh
ka, hydrogen peroxide (50%) and ferrous sulfate heptahydrate were comparable to regional references.
Rectapur by VWR Prolabo. TCh samples were spiked the day before the treatment: 100 g of
TCh were mixed with chloroform solution in which 250 mg phen-
anthrene (PHE) and 250 mg pyrene (PYR) had been dissolved. After
2.2. Soil samples chloroform evaporation, this sample was mixed with 400 g of
uncontaminated TCh. The nal concentrations of PHE and PYR
Three contrasted soil samples were used: two industrial soil were 500 mg kg1 respectively.
samples with an aged contamination, called TNM and TH and a
spiked agricultural soil sample called TCh. TNM was collected from
a former steel-making plant (Neuves-Maisons, France) (Biache 2.3. Oxidant doses
et al., 2008; Monsri et al., 2009; Laurent et al., 2012). TH was ta-
ken from the upper horizon of a former coking plant (Homcourt, The calculation of the oxidant doses was based on the stoichi-
France) (Sirguey et al., 2008) and TCh from the Ap horizon of an ometric balances written for each PAH/oxidant couple. For radicals
agricultural Cambisol (Chenevires, France) (Sirguey et al., 2008; involving reactions, chemical mechanisms are not always known
de Souza e Silva et al., 2009a,b). For all the three samples, large and then we considered the reaction leading to CO2 and H2O. For
amounts of soils were excavated and homogenized by quartering. instance, PHE oxidation by H2O2 yields:
Sub-samples were taken, sieved at 2 mm and air-dried at 25 C.
In what follows, all the concentrations refer to dry soil. The main
33H2 O2 C14 H10 ! 14CO2 38H2 O 1
physico-chemical characteristics of these soils are given in Table 1.
Soil analyses were performed by the Laboratory of Soil Analyses Knowing the PAH concentrations for each soil, this approach en-
(Arras, France) according to French standards (AFNOR, 1999): par- abled us to calculate a stoichiometric coefcient for each pair soil/
ticle size distribution, pH, total carbonate, total organic carbon. Soil oxidant. We used to call this coefcient stoichiometric molar ratio
408 J. Lemaire et al. / Chemosphere 91 (2013) 406414

Table 2
Flow experiment design.

Sample 1st Reagent 2nd 1st Reagent 2nd Reagent Duration

Reagent (h)
Amount Volume Flow rate Amount Volume Flow rate
(g kg1soil) (mL) (mL h1) (g kg1soil) (mL) (mL h1)
TNM Field H2O2 FeSO4, 7H20 50 5  16.7 20.6 20.4 5  8.3 61.8 4.7
capacity  26.5 gwater kg1soil Na2S2O8 H2O2 56 5  12.5 53 40 512.5 17.7 4.7
Water soil retention  53 ml Water (control) 125 26.5 4.7
TH Field capacity  22.5 gwater kg1soil H2O2 FeSO4, 7H20 50 5  16.7 17.5 20.4 5  8.3 52.5 5.6
Na2S2O8 H2O2 56 5  12.5 45 40 512.5 15 5.6
Water soil retention  45 ml Water (control) 125 22.5 5.6
TCh Field capacity  15.8 gwater kg1soil H2O2 FeSO4, 7H20 50 5  16.7 12.3 20.4 5  8.3 36.9 7.9
Na2S2O8 H2O2 56 5  12.5 31.5 40 5  12.5 10.5 7.9
Water soil retention  31.6 ml Water (control) 125 15.8 7.9

(SMR) (de Souza e Silva et al., 2009a,b; Lemaire, 2011; Lemaire
et al., 2011). In the present case, SMR for a given pair soil/oxidant
was calculated by the following equation:
P16
j1 Si PAHi
SMR P16
j1 PAHi
where Si is the stoichiometric coefcient of PAHi in the reaction be-
tween the oxidant and PAHi and [PAH]i the concentration of PAHi in
the soil sample (molPAH,i (kgdry soil)1).
As explained above, SMR is analogous to a stoichiometric coef-
cient for one soil/one oxidant. Then, the oxidant dose was calcu-
lated as follows. The stoichiometric oxidant demand yields:
SOD SMR M ox
where SOD is expressed in g (kgdry soil)1, Mox is the molar mass of
the oxidant (g mol1) and SMR dened by Eq. (2)
For modied Fentons reaction, we obtained SODs of respec-
tively 7.3, 6.0 and 5.5 gH2O2 (kgdry soil)1 for TNM, TH and spiked
TCh soils. With activated persulfate, we obtained SODs of respec-
tively 6.1, 5.0 and 4.6 gH2O2 (kgdry soil)1 and 8.6, 7.0 and
6.4 gNa2S2O8 (kgdry soil)1 for TNM, TH and spiked TCh soils.
The natural organic demand of the soils could not be measured
since we had no uncontaminated soil samples of TNM and TH soils.
The oxidant doses chosen for our column experiments corre-
sponded to ca 69 fold SOD. The amounts of oxidant of each oxi-
dant/soil pair were calculated on this basis (Table 2). In this way,
oxidant was in stoichiometric excess compared to the target pollu-
tants, while remaining in reasonable amounts. The notion of
reasonable amount was largely discussed between the partners
of OXYSOL project. We chose to use preferentially oxidant amounts
lower than 10 SOD since at high concentrations (i) radicals may
vanish because of radical scavenging, (ii) the impacts on soil prop-
erties are expected to be higher (Sirguey et al., 2008; Laurent et al.,
2012) and (iii) treatment cost may be too high and prevent
feasibility.
2.4. 2.4.Column experiments
Column experiments were performed at room temperature in
two identical stainless steel columns (internal diameter:
63.5 mm, length: 160 mm) (Fig. 1) for each soil and for each treat-
ment: modied Fenton (Fenton), persulfate activated with
hydrogen peroxide (activated persulfate) and water (control).
Eighteen column experiments were performed: the columns were
lled with 200 g (dry mass) soil samples; soil moisture was ad-
justed to the eld capacity of each soil sample by adding an appro-
priate volume of ultrapure water. This volume was 53.0 mL for
TNM, 45.0 mL for TH and 31.6 mL for TCh. Then the columns were
fed by 125 mL of reactants sparkled from the top. The feed volume
ow rate was set between 16 and 27 mL h1 depending on the soil
sample so that the residence time in all the columns equaled 2 h.
For modied Fentons reagent, the columns were alternatively
fed by two solutions: heptahydrate iron sulfate (98.1 g L1) and
hydrogen peroxide (120 g L1), corresponding to a molar ratio
2
[H2O2]:[FeSO4] of 20:1. For activated persulfate, the solutions were
hydrogen peroxide (128 g L1) and sodium persulfate (179.2 g L1),
corresponding to a molar ratio [H2O2]:[Na2S2O8] of 5:1. Operating
conditions are listed in Table 2.
Column efuents were collected in polyethylene bottles. At the
end of each experiment (Table 2), efuent pH and residual oxidant
concentration were measured. Twelve hours after the end of injec-
tion, cylindrical soil sample cores were collected with a piston.
3 They were divided into two equal parts corresponding to the upper
and the bottom part, except for control experiments. Efuents
were stored at 4 C and soil samples at 18 C.
The 16 PAHs were measured in triplicate in each soil sample;
oxidation efciency was estimated by comparing the concentra-
tion of the 16 PAHs before and after treatment. The availability
of the 16 PAHs was estimated by measuring the amount of PAHs
that can be extracted by a concentrated hydroxypropyl-beta-cyclo-
dextrin solution (see Section 2.5).
2.5. Analytical methods
2.5.1. Analyses of the 16 PAHs in the soil samples
Frozen soil samples were freeze-dried (Christ Alpha 1-2 LD
lyophilizer). Then 10 g of each soil sample were ground in a ball
mill for 10 min at 25 Hz. PAHs were extracted from soil samples
using Accelerated Solvent Extraction (ASE Dionex 350 extraction
yield > 95%). Anhydrous sodium sulfate (1 g) and Florisil was
added to each sample (1 g) in the extraction cell to purify the ex-
tract. The extraction solvent was composed of 50 vol.% acetone
and 50 vol.% methylene chloride and extraction was run at 100 C
and 130 bars for 5 min (Ouvrard et al., 2011). After evaporation
of the solvent, samples were diluted in 8 mL of acetonitrile and
evaporated to obtain exclusive acetonitrile extracts. PAH analysis
of acetonitrile samples was run with a HPLC (Shimadzu system)
equipped with a UV diode array detector, a Prosphere column
C-18 (Alltech, 250 mm  46 mm, particle size 5 lm) and a pre-col-
umn (Alltech, 150 mm  4.6 mm). The mobile phase was 85% ace-
tonitrile and 15% ultrapure water (ow rate: 0.4 mL min1).
External calibrations were done with standard solutions of 16 US
EPA PAHs in acetonitrile (de Souza e Silva et al., 2009a,b).
2.5.2. Residual oxidant
Efuent aliquots of 5 mL were taken to measure the concentra-
tions of residual oxidant by conventional titration (Brumblay,
1971; Lemaire et al., 2011). Hydrogen peroxide titrated with a
8.04 g L1 permanganate potassium solution: the sample was
 J. Lemaire et al. / Chemosphere 91 (2013) 406414
Fig. 1. Experimental set-up.
placed in a 250 mL baker with 100 mL ultrapure water, acidied
with 400 lL sulfuric acid (9597%) and magnetically stirred. Equiv-
alence was reached as the pink solution turned to colorless. Persul-
fate concentration was measured by indirect titration: the sample
was placed in a 250 mL baker with 100 mL ultrapure water, acidi-
ed with 400 lL sulfuric acid (9597%) and orthophosphoric acid
(85%) and 1.543 g of ferrous sulfate heptahydrate (FeSO4, 7H2O).
The solution was stirred for 5 min and excess Fe2+ ions were ti-
trated with an 8.04 g L1 permanganate solution. Equivalence
was reached when solution turned to pink.
2.5.3. PAH extractability with a cyclodextrin
A concentrated solution of hydroxypropyl-beta-cyclodextrin
(HPCD) was used to measure PAH extractability (Reid et al.,
2000). Soils samples (2 g) were placed in Teon (Nalgene) tubes
with 25 mL HPCD solution (69.5 g L1) and stirred for 12 h in a
rotating stirrer at 24 C. After centrifugation (10 min 10000 g,
Sorvall RC 5B), 20 mL of supernatant were collected and placed
in 50 mL glass (Schott) vials. Then 20 mL of ultra-pure water were
added in the Teon tubes for a second extraction and stirred man-
ually for 10 s. After centrifugation, 20 mL of supernatant were col-
lected and placed in the previous 50 mL glass vial. Thus, 96% of PAH
containing cyclodextrin solution was recovered. Ten mL methylene
chloride were added into the glass vials to extract PAHs trapped in
cyclodextrin.
The glass vial contents (50 mL) were placed in 250 mL glass sep-
arating funnels. A sequence of 3 liquidliquid extractions was per-
formed with 10 mL methylene chloride each (3 min stirring
followed by 3 min demixtion). The organic phase containing PAHs
was collected in 20 mL glass vial and the solvent was evaporated
(TurboVap Evaporation Workstation). The residue was diluted
in 5 mL acetonitrile and analyzed.
2.5.4. Statistical analysis
First, One-Way ANOVA was performed for each soil sample. It
showed that PAHs content differences before treatment and after
both control experiments were not signicant with an alpha risk
of 5% for TNM and TCh samples and 1% for TH sample (p-values
were equal to 16.68%, 11.69% and 1.04% respectively). For TH sam-
ple, low p-value was due to higher PAHs content in one of control
experiments, which can be explained only by soil sample heteroge-
409
neity. Consequently, all initial and control PAHs contents were
used to estimate a reference mean value (obtained from nine anal-
yses for TNM and TH, and 15 for TCh).
Then, for each soil sample, Students t-tests were run to com-
pare mean PAHs content after each treatment to corresponding ref-
erence mean value. Besides, degradation ratio was calculated from
these both mean values.
3. Results
3.1. PAH oxidation
The results of PAH oxidation in the three soil samples are pre-
sented in Fig. 2. On each graph, we plotted the concentrations of
the 16 PAHs in the treated soil samples (left-hand side) and the
PAH degradation ratios (right-hand side), the soil cores being split
into an upper and a bottom part. These results account for the 18
experiments and the 112 PAH analysis. Degradation ratios were
calculated as follows:
PAHtreated soil
Degradation ratio % 1  4
PAH0
where [PAH]treated soil and [PAH]0 are the concentration of the 16
PAHs in the treated soil and the initial soil respectively.
For TNM soil, the concentration of the 16 PAHs decreased signif-
icantly (p-value = 4.2%) only with activated persulfate in the bot-
tom part compared to the reference value (Fig. 2a). Degradation
ratios were higher in the bottom part of the column: 18% in Fenton
oxidation (low signicant: p-value = 19.6%) and 23% with activated
persulfate (Fig. 2b). For TH soil, Fentons reagent had no signicant
effect (p-value > 50%) whilst activated persulfate led to a degrada-
tion of about 20% with borderline signicance (p-value = 6.0% in
the bottom part and 15.0% in the upper part). For spiked TCh,
Fentons reagent drastically decreased PHE and PYR concentration
(p-value < 0.1%), with a degradation ratio of 55% in the upper part
of the column whilst no degradation occurred in the lower part.
With activated persulfate, degradation ratios were signicant
(p-value < 1.3%): 18% in the upper part and 35% in the lower
part (Fig. 2c). Persulfate oxidation was signicantly more efcient
in the bottom part (p-value = 0.7%). Fig. 3 shows the degradation
ratio of the 23 cycle PAHs (naphthalene, acenaphthylene,
410 J. Lemaire et al. / Chemosphere 91 (2013) 406414

Fig. 2. PAH content in the upper and bottom parts of each soil column (a) TNM soil sample, (b) TH soil and (c) TCh soil (mean values and standard deviations were calculated
and expressed by error bars).

acenaphthene, uorene, phenanthrene and anthracene), the four benzo[k]uoranthene, dibenz(a,h)anthracene, benzo[ghi]perylene,
cycles (uoranthene, pyrene, benz[a]anthracene, chrysene) and indeno(1,2,3-cd)pyrene) in TNM and TH soils and of phenanthrene
the 56 cycles (benzo[a]pyrene, benzo[b]uoranthene, (PHE) and pyrene (PYR) in spiked TCh. For TNM we observed that
 J. Lemaire et al. / Chemosphere 91 (2013) 406414
Fig. 3. PAH content and degradation ratio as a function of PAH aromaticity for each soil sample (mean values and standard deviations were calculated and expressed by error
bars).
the 23 cycles PAHs were signicantly degraded in the bottom part
by both oxidants contrary to 4-cycles compounds, more recalci-
trant (p-value < 4%). Besides, the 56-cycles compounds gave
intermediate results since their degradation was only signicant
with persulfate (p-value = 0.8%) (Fig. 3a and b). Between PHE and
PYR in spiked TCh, no clear trend was observed, in some cases
PHE was more degraded than PYR and vice versa (Fig. 3c).
3.2. Reagent consumption and pH in the column efuents
Reagent consumption, calculated as the weight ratio of the con-
sumed reagent to the mass of reagent introduced into the column,
is shown in Fig. 4. Hydrogen peroxide used as oxidant for Fentons
reaction and as activator for persulfate was totally consumed in all
cases. Persulfate consumption was between 60% (spiked TCh) and
ca 70% (TNM and TH).
Efuent pH was not signicantly affected by the reactions for
the two industrial soils: pH did not drop below neutrality, which
was attributed to the buffering effects of calcium carbonate in
these soils. Conversely, with spiked TCh, efuent pH was 4.8 for
the control experiment, 3.8 for Fentons reaction and dropped to
one with activated persulfate. The low carbonate content in spiked
TCh allowed these variations.
3.3. PAH extractability by cyclodextrin
In Fig. 5 we plotted the concentrations of the 16 PAHs extracted
by HPCD before and after each treatment (in the rst column) for
the three soil samples. The very low concentrations attained for
TNM and TCh (lower than 0.2% of the 16 PAHs present in these
soils) clearly show the very poor extractability in these aged con-
411
taminated soils. The differences between the situation before and
after treatment were not signicant. In spiked TCh, 5% of the PAHs
were extracted by HPCD before treatment, with higher concentra-
tions for PHE than PYR. Oxidation made these concentrations de-
crease but with borderline signicance (5% < p-value < 10%).
4. Discussion
In all cases, oxidation by modied Fentons reaction and acti-
vated persulfate performed in laboratory column decreased the to-
tal PAH content in soils. But, this degradation was limited, which
can be explained by several reasons: oxidant doses, PAH availabil-
ity, PAH reactivity, soil composition, pH, etc.
4.1. Inuence of oxidant doses on PAH oxidation ratio
Oxidant doses were intentionally moderate to stay in feasible
conditions for in situ application (please see Section 2.3). As a mat-
ter of fact, in many contributions, the oxidant doses are so high (up
to 30,000 fold the SOD) that they are not realistic and transposable
to real eld cases. Moreover, with radicalar reactions, oxidant con-
centrations must not be too high to avoid radical scavenging
(ITRC, 2005; Huling and Pivetz, 2006; Lemaire et al., 2011). Indeed,
radicals are very reactive species that can react with each other,
leading to termination reactions, instead of reacting with the target
pollutants.
4.2. Inuence of PAH availability on oxidation efciency
With both oxidants, degradation rates were higher for the
spiked soil than for the industrial ones. PAHs in aged contaminated
412 J. Lemaire et al. / Chemosphere 91 (2013) 406414

Fig. 4. Residual oxidant concentration in the percolates after treatment of the different soil samples (mean values and standard deviations were calculated and expressed by
error bars).

Fig. 5. PAH amount extracted by a cyclodextrin (HPCD) solution from different soil sample before and after treatment (mean values and standard deviations were calculated
and expressed by error bars).

soils are difcult to extract or mobilize since they are very strongly
sorbed by the soil matrix and may be even sequestrated. PAH sorp-
tion depends on the content of organic carbon and of the nature of
the organic compounds. In the present case, both industrial soils
had a high content of organic carbon close to 10 wt.%. Moreover
in industrial residues from former steel-making plants, manufac-
tured gas and coking plants, organic compounds generally derive
from coal tar and are mainly aromatic and hydrophobic; their nat-
ure is very different from natural organic matter of natural soils
(Sirguey et al., 2008; Benhabib et al., 2010). This hydrophobicity
reinforces PAH sorption. This strong sorption and the possible
sequestration are responsible for a very small PAH availability, lim-
iting the reaction with the oxidant in the soil solution.
We used PAH extraction by HPCD to assess their availability.
Actually, this method was chosen for its relative simplicity and
preferred to Tenax extraction. As shown in the results, this avail-
ability was very low for the industrial soil and low for the spiked
soil. Other results showed that the fractions of PAHs extractable
from TH and TNM soils with Tenax resin were comprised between
0.7% and 6.5% (Barnier, 2009). But whatever the absolute value, no
direct correlation was recorded; only a trend was found between
PAH extractability and their degradation by oxidation.
4.3. Inuence of PAH structure on oxidation efciency
To a lesser extent, the number of cycles of the target molecules
also had an inuence as stated in Section 3.1. With the aged soils,
the 23 cycle PAHs and the 56 cycle PAHs were more degraded
than the four cycle ones. The same was observed with TCh since
pyrene was more degraded than phenanthrene. These results are
consistent with the ones obtained by Forsey et al. (2010) on the
oxidation of PAHs in water by permanganate: the degradation rate
increased with the number of cycles because of the decrease of the
energy of bonding of cycles (decrease in aromaticity). Nonetheless
different results had been previously found with TCh (de Souza e
Silva, 2009a,b): phenanthrene was more degraded than pyrene. Di-
rect comparison is difcult since the oxidant amounts were in very
different ranges.
 J. Lemaire et al. / Chemosphere 91 (2013) 406414
4.4. Inuence of soil organic matter on PAH oxidation efciency
The content and type of organic matter also play a signicant
role since oxidation is non-selective. Then oxidants are partially
consumed by their reaction with organic matter (Sirguey et al.,
2008; Laurent et al., 2012). Our results clearly showed that PAH
degradation ratio decreased as the organic carbon content of soil
increased: the higher degradation was obtained in TCh soil (con-
taining less than 1 g kg1 of organic carbon) followed by TNM
(71.5 g kg1 organic carbon) and TH (101.0 g kg1 of organic car-
bon). Thus the competition between PAH and organic matter oxi-
dation was highlighted. The decrease of organic matter content
was not measured in this experiment but data are available in
other references (Sirguey et al., 2008; Laurent et al., 2012).
However, apart the content of organic carbon, the type and oxi-
dability of organic matter should be considered as well (Bogan and
Trbovic, 2003). Both TH and TNM contained organic matter derived
from industrial activities (e.g. coal tar products) manly composed
of persistent aromatic compounds (Benhabib et al., 2010). On the
contrary, the natural organic matter of TCh should be much easier
to oxidize than coal tar products. Anyway, given the low content in
this last soil, the type of organic matter did not make difference
here but could be important in other situations.
4.5. Inuence of pH and carbonate content on PAH oxidation efciency
Soil pH and carbonate content are also signicant parameters.
Fentons reaction is known to be favored at low pH and oxidation
by activated persulfate at alkaline pH. In our results, no severe
pH decrease occurred with TNM and TH because of their high car-
bonate content (Table 1) responsible for buffering effect. These
slightly alkaline pHs were an advantage for persulfate action but
a drawback for Fentons reaction. On the contrary, a dramatic pH
decrease was recorded when the spiked soil TCh was treated with
persulfate. No signicant buffering effect prevented this pH drop,
which was a real problem for persulfate oxidation, explaining the
low degradation ratios that were obtained.
Apart from pH buffering, a high carbonate content in soils may
be a disadvantage since hydrogen carbonate and carbonate ions
behave as radical scavengers and then radicalar reactions may be
partly hindered in carbonated media (ITRC, 2005; Huling and Pi-
vetz, 2006; Lemaire et al., 2011). Then TH and TNM soils were
not the best candidates for oxidation by modied Fentons and
activated persulfate.
5. Conclusion
In this contribution, we presented dynamic oxidation experi-
ments performed with two aged and one spiked soil samples con-
taminated with PAHs. Oxidation was run by modied Fentons
reaction and activated persulfate. The highest removal rate was ob-
tained with the spiked soil sample treated by modied Fentons
reaction. We explain the limited PAH oxidation in aged soils by
the poor PAH availability as assessed by the results of cyclodextrin
extraction. Moreover, the aged soils had a high carbonate content
which was also a drawback for radical reactions. They were also
very rich in organic matter compared to the spiked soil and organic
matter oxidation was a signicant competing reaction. In the
spiked soil, the low pH induced by the treatment was an advantage
for Fentons reaction but a real drawback for persulfate oxidation.
These results clearly demonstrated that PAH availability had a
strong inuence on oxidation efciency but other parameters were
involved as well. Nonetheless, it was difcult to show if one
parameter was predominant. In some cases pH was of major
413
importance but the other ones (e.g. competitive oxidation of organ-
ic matter, etc.) had to be considered as well (Lemaire, 2011).
As a consequence, the main lesson was that ISCO performance is
highly dependent on the characteristics of the pollutants and the
soil. Then feasibility studies (oxidant selection, oxidant dose and
operating conditions) must be carefully performed at the labora-
tory scale with soils samples taken from the polluted site and
not with spiked samples. Oxidation performance could be a little
increased by other injection methods for instance but there is no
chance to attain complete degradation with such aged industrial
soils.
For application in the eld, given that huge areas are contami-
nated by PAHs (for instance in the French context but also more
generally), oxidation must be used in combination with other
treatments. The objective of OXYSOL project was to combine oxi-
dation, soil construction and re-vegetation. This combination was
investigated at the lysimeter scale and is on the verge of being
tested at the eld scale. Very encouraging results were recorded
with PAH degradation ratio higher than with single oxidation. Be-
sides a cost-effectiveness study showed that this approach was
comparable to others on the French market which is a major point
for further development.
Acknowledgements
This work was funded by the ANR-PRECODD OXYSOL project,
the French government and the Lorraine Region. It was achieved
by members of the GISFI, research group on soil pollution (http://
www.gis.fr). The authors thank Pr. J.L. Morel, Dr. P. Faure and
Pr. K. Hanna for fruitful discussions, P. Beaurain for column making
and S. Pontvianne for his technical help.
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