Chemosphere 46 (2002) 39±47

www.elsevier.com/locate/chemosphere

Treatment system for solid matrix contaminated with

¯uoranthene. I±±Modi®ed extraction technique
Abdellah Rababah *, Sadao Matsuzawa
Atmospheric Environmental Protection Department, National Institute for Resources and Environment, 16-3 Onogawa, Tsukuba,
Ibaraki 305-8569, Japan
Received 11 December 2000; received in revised form 15 March 2001; accepted 15 March 2001

Abstract

A laboratory-scale ultrasonication technique was developed for ¯uoranthene extraction from soils and sediments
where the utilized organic solvent would be recovered after the extraction process. Therefore, the remedied soils and
sediments would be free from toxicant and trace of added chemicals. The developed ultrasonication technique outlined
here is an integrated part of a complete remediation system consisting of extraction and solar detoxi®cation reactors.
This paper investigates extraction eciencies under di€erent conditions, outlines solvent recovery technique and
compares extraction eciency of the developed ultrasonication technique with a commercially available laboratory-
scale sonication bath.
The spiked soil sample with ¯uoranthene (19.4 lg g 1 ) and organic solvent was ultrasonicated at 40°C for 20 min.
The sonicated mixture was allowed to settle for 10 min before the extract gravitated into the modi®ed solar reactor for
¯uoranthene detoxi®cation. The added solvents were removed from the remedied soil before it was released to site. The
mixture of cyclohexane and ethanol (CH:ETOH) (3:1) was the favorable solvent from among 10 organic solvents
because of its high extraction eciency, safety and low cost. Preliminary results indicated that the developed extraction
technique recovered more than 93% of ¯uoranthene from soil samples. Ó 2001 Published by Elsevier Science Ltd.

Keywords: PAH; Fluoranthene; Soil; Sediments; Remediation; Organic solvent; Extraction

1. Introduction mutagens and teratogens. Such acute toxicity of PAHs is

Polycyclic aromatic hydrocarbons (PAHs) were
found to induce tumorigenicity and were introduced to
animals and humans through the skin (Tokiwa and Sera,
2001). Bosset et al. (1998) found that Swiss cheese
manufactured using an open ®re with logs often con-
tained ¯uoranthene, ¯uorene and naphthalene. In ani-
mals, PAHs caused genetic e€ects and tumor incidences
(Wang et al., 1999). Fluoranthene penetrates into the
food chain and can operate as potential carcinogens,
*
Corresponding author. Tel.: +81-298-61-38262; fax: +81-
298-61-38258.
E-mail address: rababah@mail2.nire.go.jp (A. Rababah).
greatly enhanced under UV irradiations (Wang and
Brusseau, 1995).
PAHs are widely distributed in air, soil, waters, river
and ocean sediments, sludges and plants around the
world. Fluoranthene and pyrene are the predominant
organic toxicants in air at concentrations of 0.02±1.14
ng m 3 (Dimashki et al., 2000). Fluoranthene and py-
rene concentrations dominated pore water and solid
sediments of a small aquatic ecosystem in upper
Bavaria, Germany (Gao et al., 1998). Over 53,000 t of
PAHs (¯uoranthene is predominant) are estimated to
reside in the contemporary United Kingdom environ-
ment (Wild and Jones, 1995). Concentration of ¯uo-
ranthene in mussels and shore crabs at south Point
Molate and Lauritzen Canal (North California) was the

0045-6535/02/$ - see front matter Ó 2001 Published by Elsevier Science Ltd.

PII: S 0 0 4 5 - 6 5 3 5 ( 0 1 ) 0 0 0 8 9 - 3
40 A. Rababah, S. Matsuzawa / Chemosphere 46 (2002) 39±47
highest from among 34 PAHs (Miles and Roster, 1999).
Vanhattum et al. (1998) found PAHs in isopods of eight
di€erent water systems in Netherlands.
The concentrations of PAHs in natural samples are
small compared to interfering substances in laboratory
analyses. Furthermore, PAHs as a general class of com-
pounds di€er greatly in their physico-chemical proper-
ties from other organic matrices. Hence, di€erent
operation conditions were investigated in this paper to
extract and analyze ¯uoranthene.
Di€erent techniques may be used to extract PAHs
from solids. Common techniques include; Soxhlet tech-
nique, supercritical ¯uid extraction, accelerated solvent
extraction, focused microwave-assisted extraction and
ultrasound sonication. In the Soxhlet technique, the
solid sample is extracted in Soxhlet apparatus with sol-
vent at over 55°C for relatively long time (>7 h). In the
supercritical ¯uid extraction apparatus, high pressure
and temperature are applied to CO2 (or water) and the
contaminated solid sample in the presence of methanol
as a polar modi®er for PAH recovery. In the accelerated
solvent extraction technique, the sample is immersed
in solvent under high temperature and pressure. In the
focused microwave-assisted extraction, the immersed
solid sample in acetonitrile is irradiated with microwave
energy in a closed-vessel system to recover PAH. Ul-
trasound sonication achieved the highest extraction ef-
®ciency of ¯uoranthene compared to most extraction
methods (Dupeyron et al., 1999). Hence, the ultrasoni-
cation technique was modi®ed for ¯uoranthene extrac-
tion in this paper.
The worldwide occurrence of ¯uoranthene in the
environment raised concerns of its potential risk on
aquatic, land life and human health. Hence, this work
focuses on developing laboratory-scale extraction sys-
tem that may be scaled up for ®eld applications aiming
for soil and sediment remediation. Although the ana-
lytical techniques were adapted to suit the collected
samples and analytical instrumentation, this work does
not aim to develop or modify analytical techniques. The
modi®ed extraction system outlined in this paper is an
integrated part of a complete treatment system aiming
for the detoxi®cation of PAHs present in sludge, soil and
sediment. In addition to the extraction part, the com-
plete treatment system consists of a recirculating-type
photodegradation reactor. The photodegradation reac-
tor is described in an accompanying paper (Rababah
and Matsuzawa, 2001).
2. Experimental
2.1. Apparatus
Iuchi model VS 50R ultrasonic bath (Iuchi, Japan),
which has 320 W average power outlet and mean ope-
Table 1
Utilized solvents (Wako Pure Industries, Japan) for ¯uoranth-
ene extraction
Solvents Boiling
point °C
Cyclohexane:Ethanol (3:1) (CH:ETOH) 80
Dichloromethane (DCM) 40
Ethanol (ETOH) 78
Methanol (MEOH) 65
Methyl Ethyl Ketone (MEK) 80
N , N -Dimethylacetamide (DMA) 165
N , N -Dimethylformamide (DMF) 153
N -Butyl Acetate (BA) 125
N -Propyl acetate (PA) 102
Toluene (TOL) 110
rating frequency of 40 kHz was used for cleaning the
collected soil samples and as a conventional extraction
method for comparison with the modi®ed method.
Centrifuge, H-103 series (Kokusan, Japan), which has
revolution speed up to 5000 rpm was used for solvent
separation and partitioning at 3000 rpm. A high-pres-
sure liquid chromatograph (HPLC) equipped with a
photodiode array ultra-violet detector SPD M60A
(Shimazu, Japan) and a ¯uorescence detector FP-920S
(Jasco, Japan) was used for analysis of PAHs. The ¯uo-
rescence detector excitation and emission wavelengths
were set at 288 and 462 nm, respectively. PAHs were
separated on a C18 ODS column (4.6£, 250 mm) (G.L
Science, Japan) using a mixture of acetonitrile and dis-
tilled water (74%:26%) pumped through the system at 1
ml min 1 .
2.2. Standards and reagents
The utilized solvents (HPLC or analytical grade) for
laboratory trials extraction are listed in Table 1.
The solvents shown in Table 1 were evaluated be-
cause of their relatively high dipole moment and polarity
index values (Water-Associates, 1993) that indicate the
ability of solvent to solvate solutes. Furthermore, re-
searchers (Budzinski et al., 1996; Kaupp and Sklorz,
1996; Kiss et al., 1997; Noordkamp et al., 1997; Barcelo
et al., 1998; Guiteras et al., 1998; Dupeyron et al., 1999;
Mazzera et al., 1999; Roy et al., 1999) have reported
high recovery percentages of polycyclic aromatic com-
pounds from solid matrices by some of the listed
solvents. Roy et al. (1999) reported the highest mole
fraction solubility of ¯uoranthene in DMA from among
the wide range of organic solvents. Hence, DMA 1 was
added to Table 1.
1
N , N -Dimethylacetamide.
 A. Rababah, S. Matsuzawa / Chemosphere 46 (2002) 39±47 41

Fluoranthene crystals 98% (Aldrich, USA) was used

to spike-treated soil samples. Sodium Hydroxide crystals
99.5%, Acetone 99.5%, Cyclohexane 99.7% (Wako Pure
Industries, Japan), n-hexane 98% (Tokyo Kasei Kogyo)
and Silica cartridges (SEP±PAK, Water Associates,
USA) were used in cleaning up the extract prior to
HPLC analysis. The silica cartridge removed polar
compounds that would otherwise contaminate HPLC
column and interfere with analyses.

2.3. Soil sample preparation

About 500 g of soil was collected from di€erent

points along the side of a major road near Tsukuba City
center (Roadside soil) in Japan and another 500 g of
soil was collected from the local park of the National
Institute for Resources and Environment (NIRE soil).
The two soils were sandy clay loam.
After removal of stones and visible plant material,
the humus material was crumbled and the mineral Fig. 1. Schematic drawing of the extraction chamber (not to
soil was fractionated using a nylon mesh sieve of 1 mm. scale).
Fourteen grams of the sieved soil (particle size <1 mm)
were air dried for four days and divided into 28 portions
nected to vacuum distillation control unit (Shibata,
of about 500 mg each. Each portion was extracted to
Japan) was used to collect the utilized solvent for reuse.
remove any residual PAHs with 1:1 mixture of acetone
Other items used in the extraction system in addition
and dichloromethane for 10 min in Iuchi ultrasonic
to sonication and distillation include; a 200 ml conical
bath. The centrifuge was used for solid separation and
Pyrex glass container (extraction chamber) opened from
partitioning at 3000 rpm. Each portion was extracted
both ends, heating element was used to elevate the sol-
three times until ¯uoranthene was not detected in the
vent's temperature, digital temperature controller Pt-100
extract by the HPLC. The treated soil was air dried for
(Iuchi), valve at the bottom of the extraction chamber,
further four days and kept in the dark in an airtight
Te¯on cover sealing the top of the extraction chamber,
bottle for laboratory investigations.
the allowance for solvent and reagent bottles to be
About 10 g of the puri®ed soil by the above proce-
screwed to airtight joints at the Te¯on cover. The soni-
dure was mixed in a 50 ml beaker with 1000 ll of 10 3 M
cation-bar was inserted down into the extraction
of ¯uoranthene/acetonitrile solution to prepare a con-
chamber through elastic hole at the center of the Te¯on
taminated soil sample with known mass of ¯uoranth-
cover. The design of the cover and its ®ttings mini-
ene. The mixture was kept in the dark for four days to
mized solvent escapage. Te¯on joint was ®tted into the
completely evaporate the solvent under atmospheric
Te¯on cover to connect a Te¯on pipe for transferring
pressure. The ¯uoranthene percentage that has not been
the evaporated chemicals into a bu€er tank belonging to
adsorbed onto soil particles was estimated by measuring
the recirculating solar detoxi®cation system. Perforated
the remaining ¯uoranthene in the beaker. Results
¯oating ball with maximum whole size of 0.5 mm and
showed that 97% of the added ¯uoranthene was ad-
Te¯on elastic pipe were used to transfer the solvent from
sorbed on soil. Therefore, 19.4 lg of ¯uoranthene is
the extraction chamber into the bu€er tank. The elastic
assumed to be adsorbed onto the surface of 1 g of soil
pipe allowed the ball to remain ¯oating on the solvent
sample particles. This assumed concentration is within
surface as the volume of solvent changes while gravi-
the reported range for soils and sediments (Wild and
tating into the bu€er tank or being added from the
Jones, 1995; Spehar et al., 1999; Witt and Trost, 1999).
solvent bottles into the extraction chamber.
The spiked soil was transferred into a clean container
for storage (prepared sample).
2.5. Operation principles of the developed apparatus
2.4. Apparatus developed for the experimental trial
2.5.1. Extraction of ¯uoranthene
The extraction apparatus as can be seen in Fig. 1 was About 200 mg of the prepared sample, 30 ml of
designed and built for this study, which included an solvent were ultrasonicated at 40°C for 20 min in the
adapted commercially available 200 W/20 kHz Branson extraction chamber and allowed to settle for 10 min be-
Soni®er 250. A 100 V/60 Hz rotary evaporator con- fore the extract gravitated through the intake structure
42 A. Rababah, S. Matsuzawa / Chemosphere 46 (2002) 39±47
into the bu€er tank. This extraction procedure was re-
peated three times for each solvent listed in Table 1. The
total volume of each solvent collected in the bu€er tank
after each sonication trial was measured. Equivalent
volume of the same type of solvent was evaporated into
the distillation unit. The volume of distilled solvent was
measured to assess solvent recovery. Note that the sol-
vent recovery at this stage of treatment was conducted
for analytical purposes. The hypothetical ®eld applica-
tion system would be automated to continuously
transfer the solvent for solar treatment.
2.5.2. Soil remediation
The remedied soil was recovered from the extraction
chamber by opening the valve at the bottom of the
chamber (Fig. 1). The recovered soil contained signi®-
cant volume of solvent after being collected in the soil
recovery tank. Centrifuging the soil±solvent mixture
separated this volume of solvent before being trans-
ferred into the bu€er tank of the recirculating solar de-
gradation system. The remaining trace of solvent in the
remedied soil after the separation step was evaporated
and transferred into the bu€er tank through the con-
nection provided at the top of the soil recovery tank.
The evaporated solvent from the extraction chamber
was transferred to the bu€er tank. This is to ensure
complete solvent recovery and negligible volume of re-
siduals may be discharged into the environment.
It is recommended to develop a technique to inocu-
late the remedied soil with background microorganisms
and nutrients for the hypothetical full-scale solar de-
gradation system. This however, requires consulta-
tion with microbiologists, plant physiologists and soil
scientists.
2.5.3. Clean-up of extract prior to analyses
The utilized solvent for ¯uoranthene extraction was
centrifuged, separated and pippetted o€ into a separa-
tion funnel to be mixed with 20 ml of 5% NaOH solu-
tion. The mixture was allowed to settle so that the soil's
humic substances are separated at the bottom of the
funnel and discarded. The organic layer that is left in the
funnel was transferred into a conical ¯ask for rotary
evaporation down to 1 ml (evaporated extract). 5 ml of
n-hexane was injected through the SEP±PAK cartridge
to damp the silica gel. The 1 ml of the evaporated extract
followed by additional 2 ml of n-hexane were injected
through the cartridge. The fractions of aliphatics were
discarded with the ®rst 1 ml of the discharged mixture
out of the cartridge. Five ml of acetone and n-hexane
mix (5:95) were injected through the cartridge and col-
lected in a 10 ml graduated cylinder with joint cap. This
allows fractionation of PAHs. This mixture that con-
tains the fraction of PAH was evaporated under gentle
stream of nitrogen gas down to 1 ml. The treated sample
was diluted with 5 ml of acetonitrile and evaporated
down to 1 ml under gentle stream of nitrogen gas. Ad-
ditional 2 ml of acetonitrile were added and the ®nal
volume of the treated sample was adjusted to 2 ml (the
prepared extract).
2.5.4. PAH measurement by HPLC
Five ¯uoranthene standard solutions 10 6 ; 3  10 6 ;
5  10 6 ; 7  10 6 and 10 5 M were prepared. 2 ll of
each ¯uoranthene standard solution was injected into
the ODS column ®ve times for calibration. Following
standards solution injection, 2 ll of the prepared extract
was injected after the clean-up process. Each sample was
injected ®ve times.
3. Results and discussion
3.1. Extraction eciencies and solvent recovery
Extraction under elevated temperature improves the
solubility of analyte in the solvent and the di€usion
coecient, decreases the partition coecients of PAHs,
solvents viscosity and super®cial tension (Noordkamp
et al., 1997; Tanabe, 1997; Doong et al., 2000). Fur-
thermore, Tanabe (1997) reported that highest ultra-
sonic extraction eciency of PAHs was achieved by CH:
ETOH (3:1) at 40°C when investigating twelve di€erent
organic solvents. Hence, a mixture of soil sample and
the selected solvents was ultrasonicated for 20 min at
40°C (DCM at 25°C) in the developed soni®er for ¯uo-
ranthene extraction. Fig. 2 shows percentages of ¯uo-
ranthene recovered from spiked soil samples.
Fig. 2 shows that all the selected solvents extracted
more than 70% of ¯uoranthene from the model soil
sample. Based on the single factor ANOVA test (Miller
and Miller, 1993), the recovery percentages of ¯uo-
ranthene by the di€erent solvents di€ered signi®-
cantly (P ˆ 0:05). There was no signi®cant di€erence
(P ˆ 0:05) between the extraction eciencies of TOL
and MEOH. The null hypothesis tests (Student's t-test,
(Miller and Miller, 1993)) however, showed that the
extraction eciency of TOL was signi®cantly higher
(P ˆ 0:05) than the percentage recovered by any of
DCM, ETOH, PA or BA. The same t-test showed that
the recovery percentage of ¯uoranthene by CH:ETOH,
DMA or DMF was signi®cantly (P ˆ 0:05) higher than
the percentage recovered by any of DCM, ETOH,
MEOH, MEK, PA, BA or TOL. There was no signi®-
cant di€erence (P ˆ 0:05) between CH:ETOH, DMA
and DMF extraction eciencies.
Fig. 2 shows that the developed sonication technique
using CH:ETOH (3:1) recovered about 93% of ¯uo-
ranthene from soil samples. This extraction eciency
encourages to further investigate the possibility of scal-
ing up the developed technique aiming for the ®eld
 A. Rababah, S. Matsuzawa / Chemosphere 46 (2002) 39±47 43

Fig. 2. Eciency of ultra sound sonication in extracting ¯uoranthene from the Roadside soil using di€erent solvents at 40°C (DCM at
25°C) (n ˆ 5, error bar ˆ 1 standard deviation (S.D.)). Added ¯uoranthene was 19.4 lg g 1 . Type of soil was sandy clay loam.

applications in remediation of contaminated soils and
sediments.
The recovered volumes of the utilized solvents were
measured and compared with the initial volume used for
extraction to obtain solvent recovery eciencies (Fig. 3).
Fig. 3 shows that more than 70% of all of the selected
solvents were recovered after being used for extraction.
Based on the single factor ANOVA test (Miller and
Miller, 1993), the volume recovery percentages of the
di€erent solvents di€ered signi®cantly (P ˆ 0:05). There
was however, no signi®cant di€erence (P ˆ 0:05) be-
tween the recovered percentages of CH:ETOH, ETOH,
MEK MEOH, DMA, DMF, PA and TOL. The null
hypothesis tests (Student's t-test, (Miller and Miller,
1993)) showed that the recovery percentage of CH:
ETOH, ETOH, DMA or DMF was signi®cantly higher
(P ˆ 0:05) than the percentage of recovered solvent
volume for DCM or BA. The low boiling point of DCM

Fig. 3. Percentages of solvent volumes recovered after the extraction, separation and evaporation processes (n ˆ 5, error bar ˆ 1 S.D.).
44 A. Rababah, S. Matsuzawa / Chemosphere 46 (2002) 39±47

Fig. 4. Fluoranthene extraction eciencies (using CH:ETOH (3:1)) from two soil samples by a commercially available small-scale
soni®er and the soni®er developed in this work (n ˆ 5, error bar ˆ 1 S.D.).

may have caused solvent escape during the extraction, Table 2

separation and rotary evaporation processes. The low Elemental analyses of solvent-treated soils
percentage of the recovered volume for BA (boiling Element Concentration mg g 1

point ˆ 125°C) may have been caused by solvent loss,

most probably during rotary evaporation. Roadside soil NIRE soil
The organic solvent CH:ETOH (3:1) was selected for Silica (Si) 220.0 220.0
¯uoranthene extraction because it has high extraction Calcium (Ca) 9.9 7.9
eciency as can be seen in Fig. 2, it was recommended Magnesium (Mg) 8.2 5.5
by other researchers (Tanabe, 1997; Tanabe et al., 1999) Aluminum (Al) 92.0 92.0
as ecient and safe for PAH extraction, simple cleaning- Titanium (Ti) 6.1 5.5
up process prior to HPLC analyses is required as com- Iron (Fe) 62.0 52.0
Phosphorus (P) 0.9 0.9
pared to the cleaning-up process for other solvents,
Sodium (Na) 8.4 8.0
available at a relatively low cost and easy to recover and Potassium (K) 10.0 10.0
reuse after the extraction process. TOCa 4.6 wt% 3.6 wt%
a
TOC ˆ Total organic carbon.
3.1.1. E€ect of soil type on extraction eciency
Fig. 4 shows ¯uoranthene extraction eciencies of
the developed soni®er compared to the extraction e-
than NIRE soil. Nonetheless, the extraction eciencies
ciencies of the commercially available small-scale soni-
for the commercially available soni®er and the devel-
®er using CH:ETOH (3:1). Two soil samples (Roadside
oped soni®er did not di€er signi®cantly (P ˆ 0:05) for
and NIRE soils) were extracted to examine the e€ect of
the two soil samples as can be seen in Fig. 4. This means
soil constituents on extraction eciencies.
that the di€erence in humic substance concentrations
Table 2 shows the elemental composition of the two
between the two soils does not signi®cantly a€ect the
soils.
extraction eciencies in this study.
Roadside and NIRE soils contained almost equal
concentrations of elements (Table 2). The reported TOC
values in Table 2 indicate the level of the remained 3.1.2. E€ect of temperature on extraction eciency
humic substances in soil after solvent treatment. This Extraction of ¯uoranthene at elevated temperature
TOC value is not signi®cantly a€ected by spiking the soil involves extra cost for energy and safety precautions.
with low concentration 19.4 lg g 1 (0.002%) of ¯uo- Therefore, ¯uoranthene extraction eciencies were in-
ranthene. The TOC values indicate that the Roadside vestigated by the developed soni®er at di€erent CH:
soil contains higher levels of the humic substances ETOH (3:1) temperatures (Fig. 5).
 A. Rababah, S. Matsuzawa / Chemosphere 46 (2002) 39±47 45

Fig. 5. E€ect of temperature of CH:ETOH mixture (3:1) on extraction eciency.

Fig. 5 shows that elevating the temperature of CH:
ETOH to 40°C continued to enhance ¯uoranthene re-
covery from soil. The extraction eciency however, did
not signi®cantly (P ˆ 0:05) increase when solvent's
temperature increased from 40°C to 45°C. Therefore, it
is recommended to use 40°C as a suitable CH:ETOH
temperature for optimum sonication. Elevating the tem-
perature of the solvent in the modi®ed extraction tech-
nique up to 40°C would not require very high-energy
input for ®eld applications. Furthermore, material that
is capable of withstanding 40°C is readily accessible.
Nonetheless, it is necessary to train technicians to safely
operate ultrasonication systems and prevent solvents
escapage into the environment.
3.1.3. E€ect of sonication duration on extraction eciency
The e€ect of sonication time on extraction eciency
as can be seen in Fig. 6 was investigated to optimize
operational conditions.
Fig. 6 shows that extraction eciency increases with
sonication duration. The highest extraction eciency of
¯uoranthene was achieved when the soil sample was

Fig. 6. E€ect of sonication time on extraction eciency. Solvent temperature during extraction was 40°C.
46 A. Rababah, S. Matsuzawa / Chemosphere 46 (2002) 39±47
Fig. 7. E€ect of soil sample size on extraction eciency. Concentration of ¯uoranthene in soil (19.4 lg g 1 ) was constant.
extracted for 20 min. This result however, does not agree
with the result obtained by (Pensado et al., 2000) who
observed that microwave extraction eciency of
benzo(a)pyrene from wood samples decreased when
extraction time increased from 15 to 20 min. Nonethe-
less, Pensado et al. (2000) explained that his result may
have been a€ected by an experimental error from an
unidenti®ed source and adopted the longer extraction
time (20 min). Therefore, it is recommended to use
20 min as a suitable extraction time.
3.1.4. E€ect of soil sample size on extraction eciency
Soil sample size in¯uenced extraction eciency of
¯uoranthene from soil as can be seen in Fig. 7.
Fig. 7 shows that extraction eciency decreased sig-
ni®cantly when soil mass increased from 1000 to 5000
mg when extraction was carried out at equal volumes of
CH:ETOH (3:1). This extraction eciency is expected to
increase when larger volume of solvent is used.
4. Conclusions
A laboratory-scale ultrasonication apparatus was
developed for ¯uoranthene extraction and solvent reuse.
Optimum operational conditions for ¯uoranthene ex-
traction (about 93%) from soil were observed in this
work when CH:ETOH (3:1) was used at 40°C for 20
min. Fluoranthene recovery eciency decreased signi®-
cantly for large size soil samples. The collected data
from the developed laboratory-scale apparatus would be
used to design a hypothetical extraction system feasible
for ®eld applications where the utilized solvent would
be eciently recycled within the system. Therefore, the
remedied soils and sediments are free from toxicants and
added chemicals.
References
Barcelo, D., Oubina, A., Salau, J.S., Perez, S., 1998. Determi-
nation of PAHs in river water samples by ELISA. Analytica
Chimica Acta 376 (1), 49±53.
Bosset, J.O., Butikofer, U., Da‚on, O., Koch, H., Scheurer-
simonet, L., Sieber, R., 1998. Occurrence of polycyclic
aromatic hydrocarbons in cheese with and without a
smoked ¯avour. Sciences des Aliments 18 (4), 347±359.
Budzinski, H., Letellier, M., Baumard, P., Garrigues, P.,
1996. Focused microwave assisted extraction of polycyclic
aromatic hydrocarbons (PAHs) and polychlorobiphenlys
(PCPs) from environmental samples (sediments, soils and
biological tissues). The 47th Pittsburgh Conference in
Analytical Chemistry and Applied Spectroscopy, Chicago,
USA.
Dimashki, M., Harrad, S., Harrison, R.M., 2000. Measure-
ments of nitro-PAH in the atmosphere of two cities.
Atmospheric Environment 34, 2459±2469.
Doong, R., Chang, S., Sun, Y., 2000. Solid-phase microex-
traction for determining the distribution of sixteen US
Environmental Protection Agency polycyclic aromatic hy-
drocarbons in water samples. Journal of Chromatography
A 879, 177±188.
Dupeyron, S., Dudermel, P., Couturier, D., Guarini, P.,
Delattre, J., 1999. Extraction of polycyclic aromatic hydro-
carbons from soils: a comparison between focused micro-
wave assisted extraction, supercritical ¯uid extraction,
subcritical solvent extraction, sonication and Soxhlet tech-
niques. International Journal of Environmental Analytical
Chemistry 73 (3), 191±210.
 A. Rababah, S. Matsuzawa / Chemosphere 46 (2002) 39±47
Gao, J., Maguhn, J., Spitzauer, P., Kettrup, A., 1998. Distri-
bution of polycyclic aromatic hydrocarbons (PAHS) in pore
water and sediment of a small aquatic ecosystem. Interna-
tional Journal of Environmental Analytical Chemistry 69
(3), 227±242.
Guiteras, J.L., Beltran, J., Ferrer, R., 1998. Quantitative
multicomponent analysis of polycyclic aromatic hydrocar-
bons in water samples. Analytica Chimica Acta 361 (3),
233±240.
Kaupp, H., Sklorz, M., 1996. A method for analysing polycy-
clic aromatic hydrocarbons (PAHs) in plant samples.
Chemosphere 32 (5), 849±854.
Kiss, G., Gelencser, A., Krivacsy, Z., Hlavay, J., 1997.
Occurrence and determination of organic pollutants in
aerosol, precipitation, and sediment samples collected at
Lake Balaton. Journal of Chromatography 774 (1-1), 349±
361.
Mazzera, D., Hayes, T., Lowenthal, D., Zielinska, B., 1999.
Quanti®cation of polycyclic aromatic hydrocarbons in soil
at McMurdo Station, Antarctica. Science of the Total
Environment 229 (1-1), 65±71.
Miles, A.K., Roster, N., 1999. Enhancement of polycyclic
aromatic hydrocarbons in estuarine invertebrates by surface
runo€ at decommissioned military fuel depot. Marine
Environmental Research 47, 49±60.
Miller, J., Miller, J., 1993. Statistics for Analytical Chemistry.
Ellis Horwood, West Sussex, England.
Noordkamp, E., Grotenhuis, J., Rulkens, W., 1997. Selection of
an ecient extraction method for the determination of
polycyclic aromatic hydrocarbons in contaminated soil and
sediment. Chemosphere 35 (9), 1907±1917.
Pensado, L., Casais, C., Mejuto, C., Cela, R., 2000. Optimiza-
tion of the extraction of polycyclic aromatic hydrocarbons
from wood samples by the use of microwave energy. Journal
of Chromatography A 869 (1-2), 505±513.
Rababah, A., Matsuzawa, S., 2001. Treatment system for solid
matrix contaminated with ¯uoranthene (II) recirculating
photodegradation technique. Chemosphere.
Roy, L.E., Hernandez, C.E., Acree Jr., W.E., 1999. Ther-
modynamics of mobile order theory. part 3. comparison
of experimental and predicted solubilities for ¯uoranth-
ene and pyrene. Polycylic Aromatic Compounds 13, 205±
219.
47
Spehar, R.L., Poucher, S., Brooke, L.T., Hansen, D.J., Cham-
plin, D., Cox, D.A., 1999. Comparative toxicity of
¯uoranthene to freshwater and saltwater species under
¯uorescent and ultraviolet light. Archives of Environmental
Contamination and Toxicology 37, 496±502.
Tanabe, A., 1997. GC/MS determination of PAHs and n-
alkanes in airborne particulate matter: evaluation of solvent
for ultrasonic extraction and application to environmental
samples. Journal of Environmental Chemistry. Japan Soci-
ety for Environmental Chemistry 7 (4), 841±849.
Tanabe, A., Suzuki, S., Hanada, Y., 1999. Evaluation of
ultrasonic extraction method compared with the Soxhlet
extraction method for the determination of polycyclic
aromatic hydrocarbons and n-alkanes in airborne particu-
late matter. The Japan Society for Analytical Chemistry 48
(10), 939±944.
Tokiwa, H., Sera, N., 2001. Contribution of nitrated polycyclic
aromatic hydrocarbons in diesel particles to human cancer
induction. 17th International Symposium on Polycyclic
Aromatic Compounds. Bordeaux, France, 231±245.
Vanhattum, B., Pons, M., Montanes, J., 1998. Polycyclic
aromatic hydrocarbons in freshwater isopods and ®eld-
partitioning between abiotic phases. Archives of Environ-
mental Contamination & Toxicology 35 (2), 257±267.
Wang, J., He, X., Mulder, P., Boere, B., Cornelisse,
J., Lugtenburg, J., Busby, W., 1999. Comparative tu-
morigenicity of the cyclopenta-fused polycyclic aromatic
hydrocarbons aceanthrylene, dihydroaceanthrylene and
acephenanthrylene in preweanling CD-1 and BLU: Ha
mouse bioassays. Carcinogenesis 20 (6), 1137±1141.
Wang, X., Brusseau, M., 1995. Cyclopentanol-enhanced solu-
bilization of polycyclic aromatic hydrocarbons by cyclo-
dextrins. Environmental Science & Technology 29 (9),
2346±2351.
Water-Associates, 1993. Solvent Use Index. Water Associates,
USA.
Wild, S.R., Jones, K.J., 1995. Polycyclic aromatic hydrocar-
bons in the United Kingdom environment: a preliminary
source inventory and budget. Environmental Pollution 88,
91±108.
Witt, G., Trost, E., 1999. Polycyclic aromatic hydrocarbons
(PAHs) in sediments of the Baltic Sea and of the German
coastal waters. Chemosphere 38 (7), 1603±1614.