Journal of Hazardous Materials 174 (2010) 859863

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Journal of Hazardous Materials

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Investigation on the photocatalytic degradation of pyrene on soil surfaces using nanometer anatase TiO2 under UV irradiation
Dianbo Dong a,b , Peijun Li a, , Xiaojun Li a , Qing Zhao a,b , Yinqiu Zhang a,b , Chunyun Jia a , Peng Li b,c
a b c

Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang 110016, China Graduate University of Chinese Academy of Sciences, Beijing 100049, China Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China

a r t i c l e

i n f o

a b s t r a c t
Photocatalytic degradation of pyrene on soil surfaces was investigated in the presence of nanometer anatase TiO2 under a variety of conditions. After being spiked with pyrene, soil samples loaded with different amounts of TiO2 (0%, 1%, 2%, 3%, and 4%, w/w) were exposed to UV irradiation for 25 h. The results indicated that the photocatalytic degradation of pyrene followed pseudo-rst-order kinetics. TiO2 accelerated the degradation of pyrene generally as indicated by the half-life reduction from 45.90 to 31.36 h, corresponding to the TiO2 amounts from 0% to 4%, respectively. The effects of H2 O2 , light intensity and humic acids on the degradation of pyrene were also investigated. The degradation of pyrene increased along with increasing the concentration of H2 O2 , light intensity and the concentration of humic acids. All results indicated that the photocatalytic method in the presence of nanometer anatase TiO2 was an advisable choice for the treatments of PAHs polluted soil in the future. 2009 Elsevier B.V. All rights reserved.

Article history: Received 31 May 2009 Received in revised form 24 September 2009 Accepted 25 September 2009 Available online 2 October 2009 Keywords: Nanometer anatase TiO2 Photocatalytic degradation Pyrene Soil surfaces UV irradiation

1. Introduction Polycyclic aromatic hydrocarbons (PAHs) are a group of aromatic compounds containing two or more benzenoid rings in a linear, angular, or cluster structure. These compounds are mostly derived from the incomplete combustion of organic matter. Mineral production, combustion of fossil fuels in heat and power generation, refuse burning, coke oven, pyrolysis, and forest and agricultural res, all of them, can produce PAHs [1,2]. Because of hydrophobic, recalcitrant, and bioaccumulating characteristics, PAHs are adsorbed strongly on suspended particulates and biota, and accumulated in soil and sediment, resulting in serious soil contamination problems. Many of them are toxic and carcinogenic [35], and 16 PAHs are listed by the US EPA as priority pollutants [6]. While not as active a carcinogen as benzo[a]pyrene [7], pyrene is an important mutagen prevalent in contaminated soils [8]. Heterogeneous photocatalysis of organic pollutants using TiO2 under UV irradiation and/or solar light has demonstrated successful performance in various remediation systems of polluted soil. The addition of small amounts of TiO2 enhanced the photodegradation of p,p -DDT on soil surfaces signicantly [911]. The

Corresponding author. Tel.: +86 24 83970367; fax: +86 24 83970368. E-mail address: lipeijun@iae.ac.cn (P. Li). 0304-3894/$ see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.jhazmat.2009.09.132

photocatalytic treatment using TiO2 combined with solar light was very efcient in the destruction of pesticide Diuron in the top 4 cm of contaminated soils [12]. The organic contaminants were destroyed in a relatively short time when the contaminated soils containing atrazine, 2-chlorophenol, 2,7-dichlorodibenzodioxin were mixed with TiO2 and exposed to simulated solar radiation [13,14]. Photocatalytic degradation might be also an efcient way to eliminate PAHs. It is extensively reported that PAHs can be photocatalytically degraded in pure solid phase such as silica, alumina, Fe2 O3 and TiO2 [1519] and liquid phase [2022]. However, few studies investigated the photocatalytic degradation of PAHs in the presence of nanometer anatase TiO2 on soil surfaces. In China, the backgrounds of PAHs in arable soils vary between 10 and 20 ppb, while soil PAHs concentrations have been found to be as high as 102 to 104 ppb in some contaminated areas [23], which may pose great threats to the agricultural food quality, human health, and ecological security. Thus great attentions have been paid to the remediation of the contaminated soils [24]. In this paper, the result of the photocatalytic degradation of pyrene on soil surfaces with the addition of nanometer anatase TiO2 under UV irradiation is presented and the possibility of heterogeneous photocatalysis using nanometer anatase TiO2 in remediation of pyrene contaminated soils was discussed. The main inuencing factors, such as H2 O2 , the light intensity and the humic acids (HA) were taken into consideration.

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Table 1 Main elements and components of the experimental soil. Element As Ba Ce Cl Co Cr Cu Ga La Mn Concentration (mg kg1 ) 8.95 676.65 123.00 49.55 11.70 67.65 36.70 17.90 65.90 577.70 Element Ni P Pb Rb Sr Th Ti Zn Zr V Concentration (mg kg1 ) 26.70 630.30 37.00 109.75 189.75 13.00 4459.40 70.45 276.95 76.35 Component SiO2 Al2 O3 Fe2 O3 MgO CaO Na2 O K2 O Concentration (%) 68.22 13.41 4.19 1.13 1.16 1.78 2.43

2. Materials and methods 2.1. Reagents and materials Pyrene was purchased from Fluka, Germany, and used without further purication. Methanol (HPLC grade) was purchased from Shandong Yuwang Company, China. Hexane and dichloromethane (Analytical grade) were purchased from Tianjin Concord Technical Company, China. NaN3 was purchased from Zhejang Hailan Chemical Co., LTD, China. Nanometer anatase TiO2 (chemical purity) was obtained from the Hangzhou Wang Jing New Material Co., LTD, China. H2 O2 (AR, 30% content), was purchased from Shenyang Chemistry Reagent Corporation, China. Humic acid was purchased from Tianjin Jinke Company, China. Surface soil samples (010 cm) were collected from the Ecological Station of the Shenyang, Institute of Applied Ecology, Chinese Academy of Sciences. The soil samples were sterilized by soaking in NaN3 solution for about 48 h and then dried in an oven at 105 C. After drying, the soil samples were passed through a 1 mm sieve. The sieved soil samples were then stored in a dark chamber before use. Its characteristics are as follows: the contents of sand, silt, and clay are 21.4%, 46.5 %, and 32.1%, respectively; organic matter 1.78%; density 2.53 g cm3 ; pH 6.8. Mineral components of the experimental soil samples were analyzed by X-ray uorescence (XRF) and the results were listed in Table 1. For the individual experiments, the soil samples were treated with a methanol solution of pyrene, mixed thoroughly and then air-dried to evaporate the methanol. The concentration of pyrene in the resulting soil samples was 40 ppm. 2.2. Photolysis experiments The photolysis experiments were conducted in a photodegradation chamber with UV lamps xed at the top and separated by 60 mm as shown in Fig. 1. The UV lamps (Phillips ATLD 20W, Model UVA) had a wavelength of 253.7 nm. In all photolysis experiments, three replicates of 5.00 g of soil samples were evenly spread on Petri dishes and randomly located in the photodegradation chamber under the UV lamps. Light proof Petri dishes also containing 5.00 g of uniformly spread soil samples were used as controls for the measurement of non-photolytic pyrene loss for all experimental treatments. Petri dishes containing soil samples were placed on the shelves for UV irradiation. The height of the lamps above the soil samples was 100 mm. Temperature within the chamber was held constant at 25 C using a heater and fans throughout all experiments. Soil samples were taken at 5 h intervals from the Petri dishes exposed to UV light irradiation. Obtained soil samples were spiked with nanometer anatase TiO2 powder in a similar way as the method described by Higarashi and Jardim [12]. The catalyst load was made by adding desired amount of TiO2 to the pyrene spiked soil.

Effect of H2 O2 on the photocatalytic degradation was investigated by loading the desired amount of H2 O2 to the soil samples in the presence of 2 wt% TiO2 . The different number of UV lamps was adjusted accordingly to change the light intensity. Three different levels of light intensity were obtained corresponding to three different number of UV lamps, respectively. Effect of humic acids on the degradation of pyrene was also examined. Ten grams of HA was dissolved in 0.1 M NaOH solution, diluted with 1000 ml distilled water as storage solution. Different dosages of HA storage solution were added to contaminated soil samples. The addition concentration of HA in the soil samples were 0, 10, 20, 30 and 40 mg kg1 , respectively. After being air-dried, the soil samples were mixed with 2 wt% TiO2 .

2.3. Pyrene extraction procedure Concentrations of pyrene in the irradiated and non-irradiated soil samples were obtained by the following method: the soil samples were transferred into 100 ml Teon tubes and mixed 20 ml dichloromethane. Each sample was extracted for 2 h in an ultrasonic bath in which the water temperature was lower than 35 C. The mixtures were then centrifuged at 4000 rpm for 5 min to separate the supernatant from the soil samples. An aliquot of 0.5 ml of extraction was passed through a glass column containing 0.9 g of silica gel wetted with hexane. The extraction was eluted with 1 ml hexane:dichloromethane (1:1, v/v) four times. The eluate was completely dried under a gentle stream of nitrogen. The solid residue was re-dissolved in 1 ml of methanol for HPLC analysis.

Fig. 1. Schematic experimental device for photocatalytic degradation of pyrene on soil surfaces.

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Fig. 2. X-ray diffractometer (XRD) pattern of nanometer anatase TiO2 after calcined.

2.4. Analytical methods Quantication of pyrene in methanol solutions were conducted using an Agilent model 1200 HPLC with a variable wavelength detector set at 240 nm (Agilent Technologies, USA). The mobile phase used was methanol:water (90:10, v/v) at a ow rate of 0.7 ml min1 . Injection volume was 10 l. Three replicates were performed for analysis. The crystalline of TiO2 is determined by X-ray diffractometer (Rigaku, RINT2200, Japan). Transmission electron microscopy (TEM) which was operated using JEM 2010 electron microscope (JEOL company, Japan) at 200 kV. 3. Results and discussion 3.1. Description of nanometer anatase TiO2 particles after calcined It is well known that there are three naturally occurring phases of titania: rutile, anatase and brookite. The photocatalytic activity of TiO2 is related to their crystalline phase. In order to characterize the nanometer TiO2 which was calcined at 200 C, the crystalline phase of TiO2 was determined by X-ray diffractometry (XRD), and transmission electron microscopy was used to determine the size of the TiO2 particles. Fig. 2 shows the XRD patterns over a scan range from 10 to 70 for a calcined sample. The XRD data for the sample matched the standard anatase pattern (peaks at 25.36 , 37.92 , 48.18 , 54.04 , 55.03 , 62.8 and 68 ). There were no diffraction peaks at 27 or 31 , indicating that samples were free of rutile and brookite TiO2 [25,26]. Fig. 3 shows the TEM for a sample which indicates a crystal size of the sample of about 1525 nm. 3.2. Effect of TiO2 additional amount The amount of photocatalyst added to the sample is a major parameter affecting the photocatalytic oxidation rate. The photocatalytic degradation of pyrene in soils spiked with given amounts of TiO2 was carried out to investigate the photocatalytic activity of TiO2 toward degrading the pyrene on soil surfaces. Experimental results indicated that photocatalytic degradation of pyrene tted pseudo-rst-order kinetics. The pseudo-rst-order kinetics form is: ln Ct = kt C0 (1)
Fig. 3. Transmission electron microscopy (TEM) of nanometer anatase TiO2 after calcined.

Half-life t1/2 was calculated using Eq. (2) which was derived from Eq. (1) by replacing Ct with C0 /2: t1/2 = ln 2 0.6931 = k k (2)

The pseudo-rst-order rate constants (k) in the presence of 0%, 1%, 2%, 3% and 4% TiO2 in soils were 0.0151, 0.0171, 0.0185, 0.0202 and 0.0221 h1 , respectively, as listed in Table 2. It is suggested that the photocatalytic degradation rate of pyrene increases with the TiO2 additional amount. It is well established that conduction band electrons (e ) and valence band holes (h+ ) are generated when TiO2 is irradiated with light energy greater than its band gap energy (3.2 eV). The photogenerated electrons can reduce the organic compounds or react with electron acceptors such as O2 , reducing it to superoxide radical anion O2 . The photogenerated holes can oxidize the organic molecule directly. The O2 and photogenerated holes may be responsible for the TiO2 photocatalytic degradation of pyrene on soil surfaces.

Table 2 Kinetic parameters for the photocatalytic degradation of pyrene on soil surfaces at different TiO2 additional amount. TiO2 additional amount (wt%) 0 1 2 3 4 k (h1 ) S.D. 0.0151 0.0171 0.0185 0.0202 0.0221 0.00007 0.00014 0.00036 0.00042 0.00028 t1/2 (h) 45.90 40.53 37.46 34.62 31.36 R2 0.9907 0.9836 0.971 0.9948 0.9823

where C0 and Ct are the pyrene concentration at times zero and t, respectively, and k is the rate constant. Pseudo-rst-order degradation rate constants were determined by regression analysis.

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D. Dong et al. / Journal of Hazardous Materials 174 (2010) 859863 Table 3 Effect of humic acid on photocatalytic degradation of pyrene on soil surfaces with 2% TiO2 . Humic acid (mg kg1 ) 0 10 20 30 40 k (h1 ) S.D. 0.0185 0.019 0.0225 0.0236 0.0248 0.00036 0.00021 0.00014 0.00021 0.00049 t1/2 (h) 37.46 36.48 30.80 29.37 27.95 R2 0.971 0.9559 0.9662 0.9218 0.9302

Fig. 4. Effect of H2 O2 on pyrene degradation in the presence of 2 wt% TiO2 under 238 W cm2 light intensity: ( ) 0%, ( ) 10%, ( ) 20%, ( ) 30%.

3.3. Effect of H2 O2 Hydrogen peroxide has accelerated degradation of pyrene, depending on its concentration and nature of reductants [27]. The effect of H2 O2 in the range of 030% (w/w) on the degradation of pyrene was examined over 25 h. The results are shown in Fig. 4. As seen in Fig. 4, the degradation of pyrene increased when H2 O2 changed from 0% to 30% (w/w). The observed enhancement by H2 O2 of pyrene degradation was due to both the increase of soil moisture and the oxidative effect of hydroxyl radicals formed from the H2 O2 . The degradation of pyrene could increase with increasing soil moisture. Hilarides et al. [28], Shelton and Parkin [29], Frank et al. [30] and Graebing et al. [31] have reported that the photodegradation of organic pollution can increase with increasing soil moisture. There are two probable reasons contributing to this. Firstly, the superoxide radical anion (O2 ) and hole (h+ ) can react with water (H2 O) to produce hydroxyl radicals (OH ) which can enhance the degradation of pyrene on soil surfaces. Secondly, there is a direct radiation effect; water greatly increases the amount of radiation absorbed in the soil. H2 O2 could also increase the formation rate of hydroxyl radicals in two ways. Firstly, H2 O2 could enhance the degradation by providing additional hydroxyl radicals through trapping of photogenerated electrons as shown in Eq. (3) [32]. Secondly, the self-decomposition by photolysis would also produce hydroxyl radicals shown in Eq. (4) [32,33]. H2 O2 + e OH + OH H2 O2 + h 2OH 3.4. Effect of light intensity UV light intensity is an important factor in the process of photocatalytic degradation. The effect of the UV light intensity on the degradation of pyrene on soil surfaces is illustrated in (3) (4)

Fig. 5. The pseudo-rst-order rate constants with the increase of UV light intensity from 119 to 357 W cm2 were 0.013, 0.0185 and 0.0229 h1 , respectively. The results indicated that the degradation increased with UV light intensity. This phenomenon may be explained as following: under the higher light intensity, the enhancement was considerably higher because that the electronhole formation is predominant and, hence, electronhole recombination is negligible. However, at lower light intensity, electronhole pair separation competes with recombination which in turn decreases the formation of free radicals, thereby, causing less effect on the degradation of the pyrene on soil surfaces [34]. 3.5. Effect of humic acids (HA) Humic acids are complex organic molecules produced by the decomposition of plant and animals remained in soil, they can either enhance [3539] or inhibit photolysis [40,41]. The effect of the concentration of humic acids on the photocatalytic degradation of pyrene on soil surface was studied when the concentration increased from 0 to 40 mg kg1 . The pseudo-rst-order rate constants are listed in Table 3. It can be seen from Table 3, humic acids have accelerating effects on the photocatalytic degradation of pyrene in the presence of TiO2 . Humic acids can enhance the degradation of pyrene in several ways. On one hand, Zepp and Schlotzhauer [42] have found that the photosensitized reactions can be sensitized by humic substances (HS) only when the pollutants with triplet state energies are less than 250 kJ mol1 . Pyrene with triplet state energy is 201 kJ mol1 [43], the absorption of light by HA can lead to rapid photosensitized reactions of pyrene via energy transfer from molecules in its triplet state. On the other hand, ultraviolet irradiation also induces a variety of photochemical changes in HA and leads to production of reactive oxygen species in the presence of TiO2 (e.g., singlet oxygen, free radicals) [44]. These reactive oxygen species could also oxidize the pyrene on soil surfaces. Konstantinou and Albanis [45] and Lin and Lin [46] have reported that humic acid enhances the degradation of organic pollution in the presence of TiO2 due to increasing the concentration of reactive oxygen species. Thirdly, high humic acid concentrations were sufcient to enhance the diffusive mass transfer of the pyrene from lower soil layers to surface soil in the process of air drying. Similar results have been reported by Mayer et al. [47] in the liquid phase. 4. Conclusions The photocatalytic degradation of pyrene in the presence of nanometer anatase TiO2 on soil surfaces under UV light irradiation followed pseudo-rst-order kinetics. Photocatalytic degradation of pyrene was enhanced by TiO2 additional amount from 0 to 4 wt%. The increases of the addition of H2 O2 , the concentration of HA and irradiation intensity sped up the photocatalytic degradation of pyrene in the presence of nanometer anatase TiO2 on soil surfaces. The highest degradation achieved of pyrene on soil surfaces was 43.5 1.1%. The obtained result demonstrates that the pyrene on soil surfaces could be decomposed by the method of photocatalytic

Fig. 5. Degradation kinetics of pyrene on soil surfaces under different light intensity ( ) 119 W/cm2 , ( ) 238 W/cm2 , ( ) 357 W/cm2 .

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degradation in the presence of nanometer anatase TiO2 . Meanwhile, some important parameters (such as catalyst additional amount, the addition of H2 O2 , the concentration of HA and light intensity, etc.) needed to be monitored in order to control the degradation. In Shenyang city, the average magnitude of UV intensity was about 6669 W cm2 on the surface soils. Although the UV intensity of solar radiation is less than the intensity of these experiments, the catalytic technique in the presence of nanometer TiO2 using solar radiation will still be quite attractive in remediation of surface soils contaminated with persistent organic pollutants. Despite the fact that the light penetration into soils is very limited, it is worth mentioning that few efforts were made to turn over the soil to increase the degradation rate by exposing deeper fractions of the contaminated soil to light and TiO2 . Acknowledgements This work was supported by the National High Technology Research and Development Program of China (863 Program), No. 2008AA06Z331, Key Program of Knowledge Innovation, Chinese Academy of Sciences (kzcx1-yw-06-03), National High Technology Research and Development Program of China (863 Program), No. 2007AA061101, and Ministry of Environmental Protection of the Peoples Republic of China. The authors wish to thank Prof. Xiong for his help in revision of the manuscript. References
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