Chemosphere 46 (2002) 49±57

www.elsevier.com/locate/chemosphere

Treatment system for solid matrix contaminated with

¯uoranthene. II±±Recirculating photodegradation 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 solar reactor and photodegradation technique were developed to enhance the degradation
process of ¯uoranthene. Fluoranthene was used in this study to represent toxic polycyclic aromatic hydrocarbons
(PAHs) that are persistent in the environment. The extracted ¯uoranthene from soil in organic solvent (EFOS) and
hydrogen peroxide (H2 O2 ) were pumped from a 100 ml vessel into a solar glass cell coated with titanium dioxide …TiO2 †
at 80 ll min 1 . This work compares the eciency of the developed photocatalytic degradation technique with the
conventional batch process. The degradation eciency of the developed technique was assessed at di€erent initial
concentrations of ¯uoranthene and percentages of H2 O2 in the extract using di€erent ¯ow rates. Preliminary results
indicated that the developed technique degraded 99% of ¯uoranthene from EFOS in the presence of H2 O2 and 83%
without H2 O2 . There was no signi®cant di€erence between ¯uoranthene degradation rates by the developed technique
and the batch method. The developed technique however, treated double the volume of solution that was treated by the
batch reactor method which was time consuming and required continuous attention. Ó 2001 Published by Elsevier
Science Ltd.

Keywords: Soil; Titanium dioxide; Hydrogen peroxide; Solar degradation; PAH; Fluoranthene

1. Introduction marine prey species contaminated with ¯uoranthene to

Polycyclic aromatic hydrocarbons (PAHs) adsorp-
tion onto organic particles of sediments can cause car-
cinogenic PAHs to reach much higher concentrations
in the bottom±sediment compartment than in the upper
water column (Vigan, 2000). PAHs are introduced to
animals and humans from the food chain through the
digestion system (Boese et al., 1998; Nilsen et al., 1999;
Sram et al., 1999; Wang et al., 1999). Clarke et al. (2000)
determined high risk posed by consumption of seafood/
*
Corresponding author. Tel.: +81-298-61-8265; fax: +81-
298-61-8258.
E-mail address: rababah@mail2.nire.go.jp (A. Rababah).
humans and to the Chinese White Dolphin (Sousa
Chinensis). Such toxicity was enhanced with UV expo-
sure (Hatch and Burton, 1999; Monson et al., 1999). For
example, Cole et al. (2000) reported that the toxicity
of ¯uoranthene, at concentration below 50 lg g 1 (dry
weight) in sediments to marine infaunal amphipod
Rhepoxynius abronius was enhanced by UV irradiation
during 27±83 days of exposure. Monson et al. (1999)
correlated an increase in death of Rana pipiens larvae
(96±118 h old frogs) with ¯uoranthene concentration
and light exposure duration. Other researchers (Driscoll
et al., 1998; Lotufo, 1998; Raszyk et al., 1998; Clement
et al., 1999; Hellou et al., 1999) reported that ¯uo-
ranthene accumulated in the environment at concen-
tration of potential risk on aquatic and land life along
with risk on human health.

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 9 0 - X
50 A. Rababah, S. Matsuzawa / Chemosphere 46 (2002) 49±57
The identi®cation of ¯uoranthene as a priority pol-
lutant of potential carcinogenic risks, by the United
States Environmental Protection Agency (USEPA, 1985)
and the European Communities (European Commu-
nities, 1996) plan to regulate environmental levels for
PAH, necessitate the need for developing new degrada-
tion techniques and improving existing methods.
Di€erent degradation techniques may be used for the
remediation of PAH-contaminated matrices. Suitable
degradation technique however, depends on many fac-
tors, such as required duration of treatment, cost, type
of environmental matrix, site sensitivity, climate, PAH
molecular weight and concentration. The most com-
mon degradation techniques that have been widely
investigated are hydrothermal, biodegradation, phyto-
remediation and photodegradation. In hydrothermal
treatment, the contaminated matrix is treated with
water or CO2 under supercritical (>350°C) conditions.
Shanableh (2000) has shown that hydrothermal tech-
nique removed more than 95% of sewage sludge organic
matter. This technique however, may be limited by the
high cost of maintaining supercritical conditions and
reactor's material that must withstand the high pressure
and temperature. Phytoremediation technique utilizes
plants for contaminants removal. Liste and Alexander
(2000) have shown that plants promoted the removal of
74% of pyrene from vegetated soil within eight weeks
compared to less than 40% removal from unplanted soil.
It is generally accepted that marine sediments and
soils contain microorganisms able to biodegrade a wide
range of contaminants by using these contaminants as
a source of carbon and energy, therefore preventing
accumulation of pollutants in the environment. Biode-
gradation may be achieved under aerobic or/and an-
aerobic conditions. Aerobic biodegradation is more
favorable, because it is faster than anaerobic biode-
gradation. Joshi and Lee (1996) have shown that Aci-
netobacter sp. biodegraded more than 80% of PAHs
form contaminated soil aerobically, after seven days in
controlled laboratory conditions. Rockne and Strand
(1998) reported ecient anaerobic biodegradation of
naphthalene, phenanthrene, and biphenyl in a ¯uidized
bed reactor (FBR) enrichment after 100±200 days.
Nonetheless, microorganisms may be at risk from the
high levels of PAHs in soils and sediments under certain
environmental conditions (e.g., UV exposure). More-
over, PAHs are quite resistant to degradation. Their
half-lives in soils may reach 28 years depending on the
compound (Trapido, 1999). The fact that ¯uoranthene is
a high molecular weight PAH which is dominant and
persistent in sediments and soils (Zhou et al., 1998;
Hellou et al., 1999; Trapido, 1999) indicates that biode-
gradation may not be an ideal treatment option in some
cases.
Titanium dioxide …TiO2 † has been demonstrated to
be photocatalytically active in the presence of sunlight
for a large variety of chemicals. Moreover, TiO2 is stable
in acidic and basic media and non-toxic. Therefore, it is
the most widely used photocatalyst for organic photo-
destruction despite the fact that it utilizes only 3±4% of
the energy in the solar UV spectrum (300±400 nm)
(Vidal, 1998). Das et al. (1994) have shown ecient
photocatalytic oxidation of acenaphthene, anthracene,
¯uorene and naphthalene in aqueous suspensions of
TiO2 on irradiation with a 500 W superhigh pressure
mercury lamp in one experiment and sunlight in another
experiment. Nogueira and Jardim (1996) irradiated
dichloroacetic acid-contaminated water (5 mmol l 1 )
¯owing on an inclined TiO2 -coated glass plates at 2±6 l
h 1 with solar light and achieved 2 mmol min 1 degra-
dation rate. Processes combining UV radiation and hy-
drogen peroxide show in most cases high ecacy to
eliminate the parent compound and to form simpler
oxygenated molecules that are easier to degrade because
of the generation of the non-selective hydroxyl radical,
the principal oxidizing agent in this type of treatment
(Rivas et al., 2000). Furthermore, advanced oxidation
processes based on hydroxyl radical chemistry and
photocatalysis, can eciently oxidize many organic com-
pounds (Engwall et al., 1999). Hydrogen peroxide has the
ability to vigorously oxidize organic compounds, even
those with an aromatic moiety. The basic oxidation re-
action is described in Eq. (1) (Kawahara et al., 1995).
H2 O2 ‡ Cn Hx ! xH2 O ‡ nCO2 …1†
Hence, this work focuses on developing recirculating-
type photocatalytic technique assisted by the oxidizing
agent H2 O2 for solar light utilization in ¯uoranthene
degradation at low operational costs. The degradation
eciency of the developed technique at di€erent opera-
tional conditions was evaluated here in comparison to
the batch reactor method.
2. Experimental
2.1. Standards and reagents
Fluoranthene standard solutions were prepared by
diluting ¯uoranthene crystals (98%) (Aldrich, USA) in
acetonitrile (99.8%) (Wako Pure Industries, Japan).
Nitric acid solution 61%, (speci®c gravity (d) ˆ 1.38;
Wako Pure Industries, Japan) was used for dispensing
and coating glass with titanium dioxide. Ethanol 99.5%
and cyclohexane 99.7% (Wako Pure Industries, Japan).
Cyclohexane:ethanol (3:1) (CH:ETOH) mixture was used
for extraction. The reasons for selecting CH:ETOH mix-
ture are outlined in an accompanying paper (Rababah
and Matsuzawa, 2001). Titanium dioxide (TiO2 ) (P-25,
Japan Aerosil) was used as a photocatalyst. Aqueous
 A. Rababah, S. Matsuzawa / Chemosphere 46 (2002) 49±57 51

solution of H2 O2 30% (Wako Pure Industries, Japan) Water at 20°C was recirculating around the solar cell to
which yields OH radicals by photolysis was used to minimize heat e€ect (Fig. 2).
accelerate the photocatalytic degradation process. The ¯ow rate of the Roller pump (Furue Science,
Japan) ranges between 0.018 and 25 ml min 1 . The
pump was selected so that the extract mix does not come
2.2. Extract preparation
in contact with its mechanical parts. The Te¯on tubes
delivered the solvent from the extraction chamber to the
Soil sample extracts were prepared and treated as
bu€er tank, solar cell and recirculating tank.
described in (Rababah and Matsuzawa, 2001). Brie¯y,
the collected soil was cleaned then spiked with ¯uo-
ranthene 19:4 lg g 1 dry weight. About 200 mg of this
spiked soil sample, 22.5 ml of cyclohexane and 7.5 ml of 2.4. Operational principles of the photodegradation reac-
ethanol were mixed and ultrasonicated at 40°C for 20 tor
min by a 200 W/20 kHz Branson Soni®er in the ex-
traction chamber. Then, the extract was collected into a 2.4.1. Sample preparations for irradiation trials
100 ml glass container (bu€er tank) after 10 min of The extracted ¯uoranthene from soil in organic sol-
vent (EFOS) was transferred into two groups of vials.
settling. This procedure was repeated three times.
The EFOS samples in one group of the vials were mixed
with 30% H2 O2 . The ®nal solution contained 3% H2 O2 .
2.3. Recirculating-type photodegradation reactor The EFOS samples in the second group of the vials were
not mixed with H2 O2 .
The photodegradation system consists of bu€er tank,
solar cell, solar reactor, pump, Te¯on tubes and a re-
circulating tank as can be seen in Fig. 1. 2.4.2. Irradiation trials
The 50 mm in diameter solar cell was made from The two prepared EFOS samples were irradiated on
transparent Pyrex. The inner surfaces of the bottom and a TiO2 -coated solar cell in one experiment and on a not
the wall of the cell were mechanically roughened and
dried at 400°C for 2 h to clean the roughened sur-
faces. The dispensed TiO2 in 0.01% nitric acid solution
(10 mg ml 1 ) was pipetted on the rough surfaces of the
cell. The coated surfaces were annealed at 400°C for 2 h.
This procedure was repeated three times. The coated
solar cell was left to cool down to room temperature.
Cyclohexane, ethanol, dichloromethane, methanol, me-
thyl ethyl ketone, n-propyl acetate and toluene were
pumped over the coated TiO2 layer each at time for 2 h.
The TiO2 layer was not washed by the dynamic solvents
and was well ®xed onto the rough glass surfaces.
The solar reactor (Bunko Keiki, Japan) is equipped
with a 300 W xenon lamp (98 mW cm 2 ). The solar cell
was placed inside the solar cell chamber where the in-
coming light intensity of AM 1.5 is ®ltered by a water
cell situated between the xenon lamp and the solar cell.

Fig. 1. Experimental recirculating-type photodegradation sys- Fig. 2. Solar cell and solar cell chamber inside the developed
tem (not to scale). solar reactor (not to scale).
52 A. Rababah, S. Matsuzawa / Chemosphere 46 (2002) 49±57
coated solar cell in another experiment for comparison.
The irradiation trials were conducted in the solar reactor
using batch and continuous techniques as follows:
1. Batch technique. The xenon lamp of the solar reactor
was switched on and stabilized while the solar cell
was loaded with one of the prepared EFOS samples.
Each loaded cell was placed in the cell chamber (Fig.
2) of the solar reactor and irradiated for 6 h. The
depth of the 10 ml mixture inside the cell varied be-
tween 2 and 3 mm. The percentage degraded from
¯uoranthene was calculated using the concentration
in solution before and after irradiation.
2. Recirculating technique. The xenon lamp of the solar
reactor was switched on and stabilized. Each of the
prepared EFOS samples was recirculated through
the solar glass cell at 80 ll min 1 for 6 h. The cell
was located in the cell chamber of the reactor as in
the batch technique. The selected depth for the ¯ow
inside the solar cell ranged between 2 and 3 mm. In
this developed technique, the contact between ¯uo-
ranthene molecules and the TiO2 layer was optimized
by the shallow depths inside the solar cell. The per-
centage of degraded ¯uoranthene was calculated
based on ¯uoranthene concentration in solution be-
fore and after irradiation.
2.4.3. Fluoranthene measurement by HPLC
Fluoranthene concentrations were measured as de-
scribed in Rababah and Matsuzawa (2001). Following
standards solution injection, 2 ll of the irradiated sam-
ples was injected. Each sample was injected ®ve times.
Fig. 3. Fluoranthene degradation eciencies by the developed recirculating solar reactor and batch reactor in the EFOS under dif-
ferent conditions (n ˆ 5, error bar ˆ 1 standard deviation).
3. Results and discussion
Fig. 3 shows degradation eciencies of ¯uoranthene
obtained by using the recirculating-type solar degrada-
tion system under di€ered operational conditions.
Based on the null hypothesis test (Student's t-test,
Miller and Miller, 1993) there was no signi®cant di€er-
ence (P ˆ 0:05) between ¯uoranthene degradation e-
ciencies of the batch and recirculating techniques under
similar H2 O2 and/or TiO2 -utilization conditions (Fig. 3).
The recirculating-type solar system however, treated 20
ml of the EFOS while the batch-type solar system
treated 10 ml during 6 h of irradiation.
The single factor ANOVA test (Miller and Miller,
1993) showed that the photodegradation eciencies of
¯uoranthene in the presence of TiO2 , H2 O2 , TiO2 =H2 O2
and without adding any agent di€ered signi®cantly (P ˆ
0:05). There was no signi®cant di€erence (P ˆ 0:05)
between ¯uoranthene degradation eciencies for the
TiO2 -coated solar cell and the non-coated cell, when the
H2 O2 -EFOS mix was irradiated. The photodegradation
eciency in the presence of H2 O2 however, was signi®-
cantly (P ˆ 0:05) higher than the photodegradation ef-
®ciency when H2 O2 was not mixed with the EFOS.
H2 O2 poorly absorbs light of wavelength …k† > 300
nm compared to light of shorter wavelength (Vidal,
1998). Nonetheless, this study showed 99% ¯uoranthene
degradation eciency when irradiated with light of
k > 290 nm in the presence TiO2 and H2 O2 , 97% in the
presence H2 O2 and 83% in the presence of TiO2 (Fig. 3).
Fluoranthene did not degrade when mixed with H2 O2
(3% in the ®nal solution) and kept in the dark for 10
 A. Rababah, S. Matsuzawa / Chemosphere 46 (2002) 49±57 53

days. It can be concluded from these results that ir-

radiation is necessary for ¯uoranthene degradation.
However, the mechanism of ¯uoranthene photodegra-
dation under the laboratory conditions of this study is
not clear.
A charge separation process takes place when irra-
diating TiO2 with solar light as described in Eq. (2)
(Vidal, 1998).

TiO2 ! h‡
vb ‡ ecb ; …2†

where h‡ vb and ecb are valence band holes and conduction

band electrons, respectively. The h‡ vb can be used to
oxidize H2 O molecules to hydroxyl radicals (OH)
which are short lived, extremely potent, very reactive
and non-speci®c oxidizing agents capable of oxidizing
organic compounds (Kawahara et al., 1995; Vidal,
1998). Furthermore, direct photolysis of H2 O2 by UV
irradiation (254 nm) produces hydroxyl radicals (OH)
and hydroperoxy radicals (HO2 ) according to the fol-
lowing Eqs. (3)±(5) (Rivas et al., 2000):

H2 O2 ‡ hm ! 2  OH …3† Fig. 4. Variation in concentrations of ¯uoranthene and by-

H2 O2 ‡ OH ! HO2  ‡ H2 O …4† products with time. Fluoranthene initial concentration ˆ 10 5
M. HPLC chromatograms were measured at 288 and 462 nm
HO2 ‡ OH ! HO2  ‡ OH …5† excitation and emission wavelengths, respectively.

The generation of radicals (OH or/and HO2 ) in suf-

®cient quantities enhances ¯uoranthene degradation.
3.1. By-products of ¯uoranthene degradation
The eciency of the xenon lamp utilized in this work
to generate radicals may be low, because the wavelength
Fig. 4 shows chromatographic peaks of ¯uoranthene
of the emitted light was >290 nm. Nonetheless, there is
along with those of unidenti®ed by-products before and
clear evidence that reaction of hydrogen peroxide and
throughout the irradiation process.
ferrous ions under solar light or >300 nm irradiation
The peak intensities of the detected by-products at
(photo±Fenton reaction) plays an important role in the
1.5 h irradiation time gradually decreased throughout
degradation of toxic chemicals (Kong et al., 1998;
the degradation process as can be seen in Fig. 4. This
Fukushima et al., 2000). The average concentration of
decrease in the intensities indicates that the by-products
iron in the model soil used here was 57 mg g 1 and most
were being removed from the irradiated solution. They
likely in the form of Fe3‡ because soil's pH is more than
may have been photodegraded or transformed into
6 (Kawahara et al., 1995). Iron in soils may react with
gaseous products. It was dicult to collect gaseous prod-
H2 O2 to form ferrous ion (Fe2‡ ) according to Eq. (6)
ucts using the utilized solar reactor.
(Fukushima et al., 2000).

Fe3‡ ‡ H2 O2 ! Fe2‡ ‡ HO2  ‡ H‡ …6†

2‡
The Fe ions interact with hydrogen peroxide to gen-
erate hydroxyl radicals according to the Fenton reaction
that is described by Eq. (7) (Kawahara et al., 1995).
Fe2‡ ‡ H2 O2 ! Fe3‡ ‡ OH ‡ HO …7†
In addition to the above reactions, a complex set of
further interactions may have taken place in the modi-
®ed solar reactor to generate active species that may
have contributed to the enhancement of ¯uoranthene
photocatalytic degradation, including the partial degra-
dation without adding H2 O2 or TiO2 .
3.2. E€ect of ¯uoranthene initial concentration on degra-
dation
Fig. 5 shows the e€ect of the initial concentration of
¯uoranthene in the EFOS on the photodegradation ef-
®ciency of the developed technique.
There was no signi®cant di€erence (P ˆ 0:05) among
the degradation eciencies of the samples after 6 h of
irradiation in the developed recirculating type reactor
as can be seen in Fig. 5. This agrees with the results
obtained by Vidal (1998) where almost all ethylbenzene
photodegraded after 40 min of UV irradiation regardless
of ethylbenzene initial concentration in water.
54 A. Rababah, S. Matsuzawa / Chemosphere 46 (2002) 49±57

Fig. 5. Fluoranthene degradation eciencies at di€erent initial concentrations by the developed recirculating-type solar reactor.

Fig. 6. The eciencies of ¯uoranthene degradation in the developed recirculating-type solar reactor with di€erent percentages of H2 O2
in the EFOS.

3.3. E€ect of H2 O2 concentration on ¯uoranthene degra-
dation
Fig. 6 shows the e€ect of H2 O2 percentage in the
EFOS on ¯uoranthene degradation eciency. Fluo-
ranthene degradation eciencies when 3% and 6% of
H2 O2 dissolved in the EFOS were signi®cantly (P ˆ
0:05) higher than the degradation eciencies when the
percentage of H2 O2 was 1.5% or 9% (Fig. 6). There was
no signi®cant (P ˆ 0:05) di€erence between the degra-
dation eciencies of 3% and 6%. Hence 3% of H2 O2 in
the EFOS was employed for the developed technique.
Fig. 7 shows e€ect of irradiation time on ¯uoranth-
ene degradation eciency. Rate of ¯uoranthene degra-
dation eciency increased signi®cantly (P ˆ 0:05) after
3 h of irradiation as can be seen in Fig. 7. This tendency
is applied to batch and recirculating techniques.
Fig. 8 shows the e€ect of the EFOS ¯ow rate in the
developed recirculating-type solar reactor on ¯uoranth-
ene photodegradation eciency.
 A. Rababah, S. Matsuzawa / Chemosphere 46 (2002) 49±57 55

Fig. 7. E€ect of irradiation time on degradation eciencies of ¯uoranthene.

Fig. 8. Fluoranthene degradation eciencies of the developed recirculating-type solar reactor at di€erent ¯ow rates of the EFOS.

About 55% of ¯uoranthene was degraded when the 4. Conclusions

extract was recirculating at a relatively low rate through
the developed solar reactor for 6 h (Fig. 8). The low
degradation eciency at a slow ¯ow rate may be due to
the relatively long retention time inside the pipe system
where the solution was not exposed to solar radiation.
Fluoranthene degradation percentage however, reached
more than 99% when the ¯ow rate increased to 80
ll min 1 . There was no signi®cant di€erence (P ˆ 0:05)
between the ¯uoranthene degradation eciencies at 80
and 100 ll min 1 .
A recirculating-type photocatalytic technique was
developed and its eciency to degrade ¯uoranthene
from EFOS was evaluated as compared to batch solar
methods. The mass of ¯uoranthene degraded by the
developed recirculating-type system was larger than that
degraded by the batch system for the same size of solar
cell and irradiation duration. The batch technique nee-
ded continuous labor attention. The optimum operation
conditions for the laboratory-scale recirculating-type
56 A. Rababah, S. Matsuzawa / Chemosphere 46 (2002) 49±57
solar system were observed at 80 ll min 1 ¯ow rate and
3% of H2 O2 in the EFOS. Nonetheless, the degradation
eciency was not signi®cantly (P ˆ 0:05) a€ected by the
initial concentration of ¯uoranthene when the EFOS
was irradiated for 6 h. H2 O2 enhanced the ¯uoranthene
degradation eciency (99%) when the EFOS ¯owed
gently over a rough glass surface coated with TiO2 . The
developed technique would be automated for ®eld
applications to photodegrade ¯uoranthene without ex-
tensive labor attention. Further investigations are con-
tinuing to examine the application of the developed
method for the detoxi®cation of PAHs in contaminated
soils and sediments.
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