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Journal of Environmental and Public Health
Volume 2009, Article ID 149034, 6 pages
http://dx.doi.org/10.1155/2009/149034
Research Article

Preliminary Feasibility Study of Benzo(a)Pyrene Oxidative Degradation by Fenton Treatment

LEPÆ, Departamento de Engenharia Química, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal

Received 16 May 2009; Accepted 20 July 2009

Academic Editor: Ivo Iavicoli

Copyright © 2009 Vera Homem et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

Polycyclic aromatic hydrocarbons (PAHs) are considered priority compounds due to their toxic and carcinogenic nature. The concern about water contamination and the consequent human exposure has encouraged the development of new methods for PAHs removal. The purpose of this work was to study the feasibility of a degradation process of benzo(a)pyrene (BaP) in aqueous matrices by oxidation with Fenton reagent. A laboratory unit was designed to optimize the factors which may influence the process: pH (3.5 to 6.0), temperature (30 to ), (20 to 150 mg ), concentration (2.75 to 5.50 mg ), and the initial concentration of the pollutant (10 to 100  g ). The pH did not influence significantly the results in the range studied. An increase in temperature from 30 to improved the removal efficiency from 90% to 100%. The same effect was observed for ferrous ion concentrations from 2.75 to 5.50 mg (increase from 78% to 100% removal). The concentration played a double role during the process: from 20 to 50 mg an increase in the removal efficiency was achieved, but for higher concentrations ( 50 mg ) the degradation is lower. This study proved that the degradation of benzo(a)pyrene by Fenton's reagent is a viable process.

1. Introduction

In these last years, an increasing concern about monitoring water quality has been reflected in many studies. The amount of freshwater on Earth is limited and its quality constantly threatened. Hence there is a demand for the protection of water resources, in order to prevent their contamination by toxic compounds and pathogenic agents. Nowadays, the major concern is focused on organic pollutants such as polycyclic aromatic hydrocarbons (PAHs).

PAHs are compounds with two or more fused aromatic rings, containing only carbon and hydrogen [1]. They may enter the environment by either natural or anthropogenic sources. The former includes volcanic eruptions and forest fires. However, the largest fraction is produced by the latter, namely, by incomplete combustion of fossil fuels, petrochemical processing, automobile exhausts, and tobacco smoke [24]. These compounds provoke adverse effects in the ecosystems, even at low concentrations (ng- g ). They are toxic and persistent, reveal bioaccumulation effects [5], and are endocrine disrupting as well as tumorigenic substances [6]. In addition, PAHs with four or more rings are carcinogenic and mutagenic as a result of their ability to suffer metabolic transformations [7].

The Water Framework Directive (2000/60/EC) outlined a strategy to combat water pollution and also demanded the establishment of a list of priority pollutants [8]. In the Decision 2455/2001/EC, thirty three substances or groups of substances have been selected to be monitored by the EU member states. Eight PAHs are included in that list: anthracene, fluoranthene, naphthalene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(g,h,i)perylene, and indeno(1,2,3-cd)pyrene) [9]. Sixteen PAHs are also listed by the Environmental Protection Agency (EPA) [10] due to their toxicity—the eight mentioned above and acenaphtalene, acenaphthylene, fluorene, phenanthrene, benzo(a)anthracene, chrysene, pyrene, and dibenzo(a,h)anthracene.

Benzo(a)pyrene ( ), one of the most toxic PAHs, is usually selected as an indicator of the presence of other compounds belonging to that group [11]. It has been detected in a diversity of aqueous matrices such as surface waters, seawaters, groundwater, drinking water, as well as in sediments [12]. Maximum limits of 0.010  for drinking waters [13] and 0.1 μg for water surfaces [14] have been set for

Given the risks posed by these compounds to public health, several methodologies for the decontamination of environmental matrices have been developed. Some authors suggest removal through volatilization, oxidation, adsorption to soil particles, and biodegradation [4]. As a result of the low biodegradability of PAHs, advanced oxidation processes (AOPs) have been studied as treatment methods [15, 16]. They should be applied as an alternative or a complement to the conventional treatments. Among the AOPs, the Fenton method is one of the most promising treatments, due to its high performance, technological simplicity, and moderate cost [1619].

There are few studies about the degradation of PAHs via Fenton oxidative process in aqueous matrices. Beltrán et al. [20] investigated the aqueous oxidation of three PAHs (fluorene, phenanthrene, and acenaphthene), determining the influence of the main process variables and the products resulting from oxidation. The authors achieved a degradation of 80%, 97%, and 73%, respectively, (10 minutes) with initial concentrations of 0.9, 0.4, and 2 mg , which are above the values commonly found in the environment. Nadarajah et al. [4] studied the potential use of Fenton’s reagent as a pretreatment process to improve microbial treatment of anthracene and in an aqueous system. The studies were conducted with an initial concentration of 100 mg for . The application of Fenton’s reagent, biodegradation, and the combination of both were tested. In the first case, about 15% of removal was reached after 48 hours. In the biotreatment, the removal percentage was higher, about 30% in seven days. However, using the combination of both approaches, 80% of the pollutant was removed. It is important to point out that concentrations used in this study were also far from those found in naturally contaminated matrices. Besides that and given the level of degradation reached, the reaction time was too long. Flotron et al. [16] also tested the use of Fenton’s reagent to degrade three PAHs (fluoranthene, benzo(b)fluoranthene, and ) in sewage sludges at an initial concentration of 80 μg . They concluded that was the most easily degraded PAH, through hydroxyl radical oxidation, resulting in a removal of 85% after three hours. As mentioned in the previous case, the reaction time was long.

There are several studies describing PAHs degradation in other matrices such as soils and sediments [16, 2125]. Lundstedt et al. [26] reviewed the sources, fate, and toxic hazards of PAH contaminated sites and mentioned several by-products formed during oxidation reactions. This topic is currently of major concern.

The present work pretends to evaluate the feasibility of degradation (at μg levels) in water matrices applying Fenton’s reagent. The effect of variables that influence the Fenton degradation (temperature, initial concentrations of ferrous salt and hydrogen peroxide, and initial concentration of the analyte) was determined.

2. Materials and Methods

2.1. Reagents and Standards

A commercial solution of benzo(a)pyrene (1000 μg m in acetone) was obtained from Supelco (Bellefonte, PA, USA). From it, a 10 mg stock solution in ethanol was prepared as a base to calibration standards with concentrations of 1, 10, 40, 60, and 100 μg prepared in deionised water. The ethanol absolute (p.a.) was purchased to Panreac (Barcelona, Spain). From the stock solution, two control standards (10 and 100 μg ) were prepared weekly.

Hydrogen peroxide in stable form (30% Perhydrol, p.a.) and iron (II) sulfate heptahydrate were purchased from Merck (Darmstadt, Germany). The pH of the PAH solutions was adjusted with 1 M (Merck). Acetonitrile HPLC grade was obtained from BDH Prolabo (Poole, UK).

2.2. Equipment
2.2.1. Experimental Procedure

The experiments were conducted in a 250 mL jacketed thermostatic batch reactor (inner diameter: 7.5 cm, height: 11.5 cm). The outside of the reactor was covered with aluminium foil to protect from light, and an inlet for temperature measuring was placed on the top of the reactor. Homogeneous mixing was provided using a magnetic stirring bar and the temperature was kept constant with a thermostatic bath (Figure 1).

149034.fig.001
Figure 1: Scheme of the experimental device.

In each experiment, 100 mL of solution at the desired initial concentration were inserted in the reactor. An aliquot was withdrawn for further analysis. After that, the pH was adjusted with a sulphuric acid solution and another aliquot was collected. Then, the required amount of iron (II) salt was added. When the salt was totally dissolved, a certain quantity of solution was introduced, in order to start the reaction. Table 1 shows the conditions applied to each experiment performed. Aliquots were taken from the reactor at selected time intervals and immediately analyzed. The arrest of Fenton’s reaction was achieved with the addition of some drops of concentrated sulphuric acid in order to decrease the pH to less than 1.0 [27]. The option for sulphuric acid instead of sodium sulphite may be discussed, but it is acceptable to consider that the reaction rate is sufficiently decreased in order to allow the subsequent analysis.

tab1
Table 1: Experimental conditions used in Fenton’s reaction.
2.2.2. Analytical Method

HPLC analyses were performed with a Merck Hitachi LaChrom Elite system (Darmstadt, Germany) equipped with an L-2130 pump, L-2200 autosampler, and a L-2480 fluorescence detector. Data were acquired and processed by EZChrom Elite software from Agilent (Santa Clara, CA, USA). For chromatographic separation, a reversed-phase RP-18 endcapped Purospher STAR (250 mm 4 mm, particle size 5 μm) was used, combined with a guard column (4 mm 4 mm i.d.) also Purospher STAR, at room temperature. The mobile phase consisted of acetonitrile (90%) and water (10%) running in isocratic conditions at a flow rate of 1.2 mL The injection volume was 50 μL, and the excitation and emission wavelengths were 297 nm and 405 nm, respectively. Total run time was 15 minutes, and quantification was performed by external standard method.

3. Results and Discussion

3.1. Validation of the Analytical Method

The method linearity was verified in the 1 to 100 μg range (five calibration points), obtaining a coefficient of determination ( ) of 0.9993 and a limit of detection (LOD) of 2.4 μg , calculated from the calibration curve. Other validation parameters were evaluated in the linearity range: precision varied between 3.5% and 13.9% and accuracy from 71.3% to 85.3%. The uncertainty associated to the analytical method was calculated according to the EURACHEM/CITAC guide [28]. The global uncertainty values obtained ranged from 2.4% to 59.1%.

3.2. Oxidation Studies

As mentioned above, Fenton’s reagent is a strong oxidant mixture consisting of hydrogen peroxide and iron (II) salt that acts as a catalyst. In this process, the hydroxyl radicals are formed in situ and depend on several factors such as pH, temperature, and the initial concentrations of hydrogen peroxide, ferrous ion, and , whose effects were investigated in this work.

The standards of were prepared in water (neutral pH). However, the Fenton’s reaction occurs in acidic conditions. For that reason, it was necessary to compare the fluorescence response before and after the addition of sulphuric acid, and it was verified that such responses remained practically unchanged. Another central issue is the arrest of Fenton’s reaction, which is usually done using sodium sulphite. Nevertheless, in this work the stop was achieved with the addition of some drops of concentrated sulphuric acid in order to decrease the pH to less than 1.0. At pH < 1 an inhibition in the production of hydroxyl radicals occurs, due to ions scavenging. Therefore, the amount of is strongly reduced and, consequently, the reaction rate is very slow. This methodology is valid once the analyses were performed in a short time interval after the addition of acid to the aliquots; otherwise slight variation of the concentration may occur.

Effect of pH
The Fenton’s reaction is pH dependent, because this value affects the hydroxyl radicals generation and, consequently, the oxidation efficiency. For this degradation process, the optimal pH range mentioned in literature is 3 to 6. Therefore, in this work the 3.5 and 6.0 pH values were studied and the results are shown in Figure 2. It can be observed that the removal efficiency was not significantly changed with the pH increase from 3.5 to 6. In subsequent experiments, pH = 3.5 was used in order to compare the results with those presented in most of the previous studies reported in literature.

149034.fig.002
Figure 2: Effect of pH on oxidation with Fenton’s reagent (10 μg , , 5.5 mg , 200 mg ).

Effect of Temperature
Experiments were conducted under the same conditions at four different temperatures between 30 and to investigate the effect of temperature on the degradation kinetics of aqueous solutions. The results are illustrated in Figure 3. An enhancement in the rate and even in the extent of degradation reaction was observed with the temperature increase. Despite this, at higher temperatures the thermal decomposition of hydrogen peroxide may be accelerated, resulting in a decrease of the concentration of hydroxyl radicals, with consequent reduction in the reaction extent. On the other hand, there was practically no difference between the experiments carried out at 40 and (removal of 90%). The economic aspect is often a limiting factor; thus the best option would be working at

149034.fig.003
Figure 3: Effect of temperature on degradation (10 μg , pH = 3.5, 5.5 mg , 200 mg ).

Effect of Hydrogen Peroxide Concentration
Experiments were performed to determine the effect of hydrogen peroxide concentration on the process (Figure 4). In all experiments, it was observed that the maximum degradation of concentration was reached after two minutes. On the other hand, from Figure 4 it can also be seen that the increase of hydrogen peroxide concentration from 20 to 50 mg yields rising removal efficiencies. However, higher concentrations lead to lower degradation rates. The recombination of hydroxyl radicals and the reaction between them and hydrogen peroxide may explain this fact.

149034.fig.004
Figure 4: Influence of hydrogen peroxide concentration on degradation (10 μg , pH = 3.5, , 3.75 mg ).

Effect of Ferrous Ion Concentration
Experiments were conducted in order to investigate the effect of ferrous ion concentration (catalytic agent) on the process. Figure 5 shows the relationship between the degradation extent and the initial concentration of ferrous ion. Comparing the results, it was noticed that there is an increasing degradation with the concentration (70% to 100% removal), although no significant differences were found between 2.75 and 3.75 mg .
In 1996, Béltran et al. [20] established the influence of in the fluorene degradation (0.9 mg ). The initial ferrous ion concentration ranged between 0.6 and 11 mg They showed that augmenting this concentration improved the degradation (40% to 100% removal) as well as the reaction rate. The same conclusion was obtained in this study.
The homogeneous Fenton process has the disadvantage of commonly using high concentrations of ferrous ion (50 to 80 mg ), which is beyond the legal limit of 2 mg for treated water to be released directly into the environment [29]. In this work, a maximum ferrous ion concentration of 5.50 mg was applied. Therefore, a dilution of the treated effluent may be sufficient to achieve legal conformity.

149034.fig.005
Figure 5: Effect of the initial concentration of ferrous ion on degradation (10 μg , pH = 3.5, , 100 mg ).

Effect of Initial Concentration
Thinking about a possible application of this method to naturally contaminated samples, it is important to study the dependence of the degradation efficiency on the initial concentration of the analyte. In wastewater treatment plants, the analyte concentration present in the effluent is usually unknown. Therefore, it is essential to determine the maximum amount of pollutant that would be degraded with a fixed reagent concentration. As seen in Figure 6, the reaction occurs quickly in the first 10 minutes and then stabilizes at the maximum degradation value, for all cases studied. After a period of 90 minutes a removal of 100%, 90%, 70%, and 57% was, respectively, achieved with 10, 20, 60, and 100 μg , plus 3.75 mg and 50 mg There are two main problems related to the micropollutants degradation by Fenton’s reagent: sludge production and generation of by-products. Normally the total mineralization of the compounds does not occur, and the process generates metabolites equally or even more toxic than the original compounds. To check the possibility of applying another type of treatment (e.g., biodegradation) or discharge the effluent, the identification of these metabolites becomes an important issue, to be investigated in a subsequent study.

149034.fig.006
Figure 6: Effect of initial concentration (pH = 3.5, , 50 mg 3.75 mg ).

4. Conclusions

The main conclusion of the present work is that Fenton’s reagent is an appropriate method for the total degradation of benzo(a)pyrene in water matrices, providing that the ferrous ion and hydrogen peroxide are present in suitable concentrations. These parameters as well as temperature are important variables for the process. It was shown that an increase in temperature from 30 to led to an increase in the removal efficiency from 90% to 100%. The same effect was verified with the increase of the ferrous ion concentration from 2.75 to 5.50 mg (removals from 78% to 100%). The hydrogen peroxide was the only reagent with a double role during the oxidation: despite the degradation of increased with the concentration, at high concentrations of oxidant the removal was reduced. With an initial concentration of 50 mg , 90% removal was achieved while with 150 mg only 80% was eliminated.

Future work will consider a scale-up optimization as well as the identification of the reaction by-products, if they appear.

Acknowledgment

The authors wish to thank the Fundação para a Ciência e a Tecnologia (FCT), Portugal, for financial support (SFRH/BD/38694/2007).

References

  1. Y. Liu, Y. Hashi, and J.-M. Lin, “Continuous-flow microextraction and gas chromatographic-mass spectrometric determination of polycyclic aromatic hydrocarbon compounds in water,” Analytica Chimica Acta, vol. 585, no. 2, pp. 294–299, 2007. View at Publisher · View at Google Scholar
  2. N. Ratola, S. Lacorte, D. Barceló, and A. Alves, “Microwave-assisted extraction and ultrasonic extraction to determine polycyclic aromatic hydrocarbons in needles and bark of Pinus pinaster Ait. and Pinus pinea L. by GC-MS,” Talanta, vol. 77, no. 3, pp. 1120–1128, 2009. View at Publisher · View at Google Scholar
  3. S. K. Samanta, O. V. Singh, and R. K. Jain, “Polycyclic aromatic hydrocarbons: environmental pollution and bioremediation,” Trends in Biotechnology, vol. 20, no. 6, pp. 243–248, 2002. View at Publisher · View at Google Scholar
  4. N. Nadarajah, J. Van Hamme, J. Pannu, and A. Singh, “Enhanced transformation of polycyclic aromatic hydrocarbons using a combined Fenton's reagent, microbial treatment and surfactants,” Applied Microbiology and Biotechnology, vol. 59, no. 4-5, pp. 540–544, 2002. View at Publisher · View at Google Scholar
  5. J. H. Sun, G. L. Wang, Y. Chai, G. Zhang, J. Li, and J. Feng, “Distribution of polycyclic aromatic hydrocarbons (PAHs) in Henan Reach of the Yellow River, Middle China,” Ecotoxicology and Environmental Safety, vol. 72, no. 5, pp. 1614–1624, 2008. View at Publisher · View at Google Scholar
  6. L. Li-Bin, L. Yan, L. Jin-Ming, T. Ning, H. Kazuichi, and M. Tsuneaki, “Development of analytical methods for polycyclic aromatic hydrocarbons (PAHs) in airborne particulates: a review,” Journal of Environmental Science and Health, vol. 19, pp. 1–11, 2007. View at Google Scholar
  7. X. Luo, B. Mai, Q. Yang, J. Fu, G. Sheng, and Z. Wang, “Polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides in water columns from the Pearl River and the Macao harbor in the Pearl River Delta in South China,” Marine Pollution Bulletin, vol. 48, pp. 1102–1115, 2004. View at Google Scholar
  8. European Union, “Directive 2000/60/EC of the European Parliament and of the Council,” Official Journal of European Union, vol. L327, pp. 1–72, 2000. View at Google Scholar
  9. European Union, “Decision 2455/2001/EC of the European Parliament and of the Council,” Official Journal of European Union, vol. L331, pp. 1–5, 2001. View at Google Scholar
  10. US Environmental Protection Agency (EPA), “Code of Federal Regulations,” 40 CFR 423, Appendix A, 1982.
  11. A. Valero-Navarro, J. F. Fernández-Sánchez, A. L. Medina-Castillo et al., “A rapid, sensitive screening test for polycyclic aromatic hydrocarbons applied to Antarctic water,” Chemosphere, vol. 67, no. 5, pp. 903–910, 2007. View at Publisher · View at Google Scholar
  12. E. Manoli and C. Samara, “Polycyclic aromatic hydrocarbons in natural waters: sources, occurrence and analysis,” Trends in Analytical Chemistry, vol. 18, no. 6, pp. 417–428, 1999. View at Publisher · View at Google Scholar
  13. European Union, “Council Directive 98/83/EC,” Official Journal of European Union, vol. L330, pp. 32–54, 1998. View at Google Scholar
  14. Commission of the European Communities, “Proposal for the Directive of the European Parliament and of the Council on environmental quality standards in the field of water policy and amending Directive 2000/60/EC,” COM 397, 2006.
  15. B.-D. Lee, M. Iso, and M. Hosomi, “Prediction of Fenton oxidation positions in polycyclic aromatic hydrocarbons by Frontier electron density,” Chemosphere, vol. 42, no. 4, pp. 431–435, 2001. View at Publisher · View at Google Scholar
  16. V. Flotron, C. Delteil, Y. Padellec, and V. Camel, “Removal of sorbed polycyclic aromatic hydrocarbons from soil, sludge and sediment samples using the Fenton's reagent process,” Chemosphere, vol. 59, no. 10, pp. 1427–1437, 2005. View at Publisher · View at Google Scholar
  17. R. Oliveira, M. F. Almeida, L. Santos, and L. M. Madeira, “Experimental design of 2,4-dichlorophenol oxidation by Fenton's reaction,” Industrial and Engineering Chemistry Research, vol. 45, no. 4, pp. 1266–1276, 2006. View at Publisher · View at Google Scholar
  18. H. Lee and M. Shoda, “Removal of COD and color from livestock wastewater by the Fenton method,” Journal of Hazardous Materials, vol. 153, no. 3, pp. 1314–1319, 2008. View at Publisher · View at Google Scholar
  19. S. Wang, “A comparative study of Fenton and Fenton-like reaction kinetics in decolourisation of wastewater,” Dyes and Pigments, vol. 76, no. 3, pp. 714–720, 2008. View at Publisher · View at Google Scholar
  20. F. J. Beltrán, M. González, F. J. Rivas, and P. Alvarez, “Fenton reagent advanced oxidation of polynuclear aromatic hydrocarbons in water,” Water, Air, and Soil Pollution, vol. 105, no. 3-4, pp. 685–700, 1998. View at Publisher · View at Google Scholar
  21. P. T. S. Silva, V. L. Silva, B. B. Neto, and M.-O. Simonnot, “Phenanthrene and pyrene oxidation in contaminated soils using Fenton's reagent,” Journal of Hazardous Materials, vol. 161, no. 2-3, pp. 967–973, 2009. View at Publisher · View at Google Scholar
  22. B. Chen, X. Xuan, L. Zhu et al., “Distributions of polycyclic aromatic hydrocarbons in surface waters, sediments and soils of Hangzhou City, China,” Water Research, vol. 38, no. 16, pp. 3558–3568, 2004. View at Publisher · View at Google Scholar
  23. H. Wischmann and H. Steinhart, “The formation of PAH oxidation products in soils and soil/compost mixtures,” Chemosphere, vol. 35, no. 8, pp. 1681–1698, 1997. View at Publisher · View at Google Scholar
  24. B.-D. Lee, M. Hosomi, and A. Murakami, “Fenton oxidation with ethanol to degrade anthracene into biodegradable 9, 10-anthraquinon: a pretreatment method for anthracene-contaminated soil,” Water Science and Technology, vol. 38, no. 7, pp. 91–97, 1998. View at Publisher · View at Google Scholar
  25. B. D. Lee and M. Hosomi, “A hybrid Fenton oxidation-microbial treatment for soil highly contaminated with benz(a)anthracene,” Chemosphere, vol. 43, pp. 1127–1132, 2001. View at Google Scholar
  26. S. Lundstedt, P. A. White, C. L. Lemieux et al., “Sources, fate, and toxic hazards of oxygenated polycyclic aromatic hydrocarbons (PAHs) at PAH-contaminated sites,” Ambio, vol. 36, pp. 475–485, 2007. View at Google Scholar
  27. B.-D. Lee and M. Hosomi, “Ethanol washing of PAH-contaminated soil and Fenton oxidation of washing solution,” Journal of Material Cycles and Waste Management, vol. 30, pp. 2–24, 2000. View at Google Scholar
  28. S. L. R. Ellisson, M. Rosslein, and A. Williams, EURACHEM/CITAC Guide, Quantifying Uncertainty in Analytical Measurement, Teddington, UK, 2nd edition, 2000.
  29. J. H. Ramirez, C. A. Costa, L. M. Madeira et al., “Fenton-like oxidation of Orange II solutions using heterogeneous catalysts based on saponite clay,” Applied Catalysis B, vol. 71, no. 1-2, pp. 44–56, 2007. View at Publisher · View at Google Scholar