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II Treatment

II Treatment

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Treatment system for solid matrix contaminated with
\u00afuoranthene. II\u00b1\u00b1Recirculating 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

A laboratory-scale solar reactor and photodegradation technique were developed to enhance the degradation process of \u00afuoranthene. Fluoranthene was used in this study to represent toxic polycyclic aromatic hydrocarbons (PAHs) that are persistent in the environment. The extracted \u00afuoranthene from soil in organic solvent (EFOS) and hydrogen peroxide (H2O2) were pumped from a 100 ml vessel into a solar glass cell coated with titanium dioxide\u0085TiO2\u0086 at 80ll min\u00c01. This work compares the e\u0081ciency of the developed photocatalytic degradation technique with the conventional batch process. The degradation e\u0081ciency of the developed technique was assessed at di\u0080erent initial concentrations of \u00afuoranthene and percentages of H2O2in the extract using di\u0080erent \u00afow rates. Preliminary results indicated that the developed technique degraded 99% of \u00afuoranthene from EFOS in the presence of H2O2and 83% without H2O2. There was no signi\u00aecant di\u0080erence between \u00afuoranthene 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.\u00d3 2001 Published by Elsevier Science Ltd.

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

Polycyclic aromatic hydrocarbons (PAHs) adsorp- tion onto organic particles of sediments can cause car- cinogenic PAHs to reach much higher concentrations in the bottom\u00b1sediment 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/

marine prey species contaminated with \u00afuoranthene to
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 \u00afuoranthene, at concentration below 50lg g\u00c01(dry weight) in sediments to marine infaunal amphipod

Rhepoxynius abroniuswas enhanced by UV irradiation

during 27\u00b183 days of exposure. Monson et al. (1999) correlated an increase in death of Rana pipiens larvae (96\u00b1118 h old frogs) with \u00afuoranthene 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 \u00afuo- ranthene accumulated in the environment at concen- tration of potential risk on aquatic and land life along with risk on human health.

Chemosphere 46 (2002) 49\u00b157
*Corresponding author. Tel.: +81-298-61-8265; fax: +81-
E-mail address:rababah@mail2.nire.go.jp (A. Rababah).
0045-6535/02/$ - see front matter\u00d3 2001 Published by Elsevier Science Ltd.
PII: S0045-6535(01)00090-X

The identi\u00aecation of \u00afuoranthene 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\u0080erent 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 CO2under supercritical (>350\u00b0C) 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 thatAci-

netobactersp. biodegraded more than 80% of PAHs

form contaminated soil aerobically, after seven days in controlled laboratory conditions. Rockne and Strand (1998) reported e\u0081cient anaerobic biodegradation of naphthalene, phenanthrene, and biphenyl in a \u00afuidized bed reactor (FBR) enrichment after 100\u00b1200 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 \u00afuoranthene 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\u0085TiO2\u0086has been demonstrated to
be photocatalytically active in the presence of sunlight

for a large variety of chemicals. Moreover, TiO2is 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\u00b14% of the energy in the solar UV spectrum (300\u00b1400 nm) (Vidal, 1998). Das et al. (1994) have shown e\u0081cient photocatalytic oxidation of acenaphthene, anthracene, \u00afuorene and naphthalene in aqueous suspensions of TiO2on 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\u00c01) \u00afowing on an inclined TiO2-coated glass plates at 2\u00b16 l h\u00c01with solar light and achieved 2 mmol min\u00c01 degra- dation rate. Processes combining UV radiation and hy- drogen peroxide show in most cases high e\u0081cacy 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\u0081ciently 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).

H2O2\u0087CnHx 3xH2O\u0087nCO2

Hence, this work focuses on developing recirculating- type photocatalytic technique assisted by the oxidizing agent H2O2for solar light utilization in \u00afuoranthene degradation at low operational costs. The degradation e\u0081ciency of the developed technique at di\u0080erent 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 \u00afuoranthene crystals (98%) (Aldrich, USA) in acetonitrile (99.8%) (Wako Pure Industries, Japan). Nitric acid solution 61%, (speci\u00aec gravity (d)\u0088 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\u00b157

solution of H2O2 30% (Wako Pure Industries, Japan) which yields OH radicals by photolysis was used to accelerate the photocatalytic degradation process.

2.2. Extract preparation

Soil sample extracts were prepared and treated as described in (Rababah and Matsuzawa, 2001). Brie\u00afy, the collected soil was cleaned then spiked with \u00afuo- ranthene 19:4lg g\u00c01dry weight. About 200 mg of this spiked soil sample, 22.5 ml of cyclohexane and 7.5 ml of ethanol were mixed and ultrasonicated at 40\u00b0C for 20 min by a 200 W/20 kHz Branson Soni\u00aeer in the ex- traction chamber. Then, the extract was collected into a 100 ml glass container (bu\u0080er tank) after 10 min of settling. This procedure was repeated three times.

2.3. Recirculating-type photodegradation reactor

The photodegradation system consists of bu\u0080er tank, solar cell, solar reactor, pump, Te\u00afon tubes and a re- circulating tank as can be seen in Fig. 1.

The 50 mm in diameter solar cell was made from transparent Pyrex. The inner surfaces of the bottom and the wall of the cell were mechanically roughened and dried at 400\u00b0C for 2 h to clean the roughened sur- faces. The dispensed TiO2in 0.01% nitric acid solution (10 mg ml\u00c01) was pipetted on the rough surfaces of the cell. The coated surfaces were annealed at 400\u00b0C 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 TiO2layer each at time for 2 h. The TiO2layer was not washed by the dynamic solvents and was well \u00aexed onto the rough glass surfaces.

The solar reactor (Bunko Keiki, Japan) is equipped with a 300 W xenon lamp (98 mW cm\u00c02). The solar cell was placed inside the solar cell chamber where the in- coming light intensity of AM 1.5 is \u00aeltered by a water cell situated between the xenon lamp and the solar cell.

Water at 20\u00b0C was recirculating around the solar cell to
minimize heat e\u0080ect (Fig. 2).

The \u00afow rate of the Roller pump (Furue Science, Japan) ranges between 0.018 and 25 ml min\u00c01. The pump was selected so that the extract mix does not come in contact with its mechanical parts. The Te\u00afon tubes delivered the solvent from the extraction chamber to the bu\u0080er tank, solar cell and recirculating tank.

2.4. Operational principles of the photodegradation reac-
2.4.1. Sample preparations for irradiation trials

The extracted \u00afuoranthene from soil in organic sol- vent (EFOS) was transferred into two groups of vials. The EFOS samples in one group of the vials were mixed with 30% H2O2. The \u00aenal solution contained 3% H2O2. The EFOS samples in the second group of the vials were not mixed with H2O2.

2.4.2. Irradiation trials
The two prepared EFOS samples were irradiated on
a TiO2-coated solar cell in one experiment and on a not
Fig. 1. Experimental recirculating-type photodegradation sys-
tem (not to scale).
Fig. 2. Solar cell and solar cell chamber inside the developed
solar reactor (not to scale).
A. Rababah, S. Matsuzawa / Chemosphere 46 (2002) 49\u00b157

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