Adsorption of anthracene using activated carbon and Posidonia oceanica

Mouhamed El Khames Saad; Ramzi Khiari; Elimame Elaloui; Younes Moussaoui

doi:10.1016/j.arabjc.2013.11.002

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SPECIAL ISSUE: ENVIRONMENTAL CHEMISTRY

7 (

); 109-113

doi:

10.1016/j.arabjc.2013.11.002

Adsorption of anthracene using activated carbon and Posidonia oceanica

Mouhamed El Khames Saad^{^a}, Ramzi Khiari^{^b}, Elimame Elaloui^{^a,^c}, Younes Moussaoui^{^c,^d,∗}

a Materials, Environment and Energy Laboratory (06/UR/12-01), Science Faculty of Gafsa, University of Gafsa, 2112 Gafsa, Tunisia

b LGP2 – Laboratory of Pulp and Paper Science, UMR CNRS 5518, 461, Rue de la Papeterie, BP 65, 38402 Saint Martin d’Hères Cedex, France

c Science Faculty of Gafsa, University of Gafsa, 2112 Gafsa, Tunisia

d Physical Organic Chemistry Laboratory (UR11ES74), Science Faculty of Sfax, University of Sfax, 3018 Sfax, Tunisia

∗Corresponding author at: Science Faculty of Gafsa, University of Gafsa, 2112 Gafsa, Tunisia. Tel.: +216 97623805 y.moussaoui2@gmx.fr (Younes Moussaoui) y.moussaoui2@gmail.com (Younes Moussaoui)

Received: 2013-7-2, Accepted: 2013-11-1, Published: 2013-01-01

Disclaimer:
This article was originally published by Elsevier and was migrated to Scientific Scholar after the change of Publisher.

Peer review under responsibility of King Saud University.

Available online 15 November 2013

Abstract

The aim of this work was to examine the static capacity of adsorption of anthracene by Posidonia oceanica and activated carbon. The effect of experimental parameters pH and contact time on the anthracene adsorption onto cited materials was investigated in detail. The results showed that the anthracene removal on both P. oceanica and activated carbon was unaffected in the pH range of 2–12. The equilibrium data fit well to the Langmuir model with a maximum adsorption capacity of 8.35 mg/g and 0.14 mg/g, respectively with activated carbon and P. oceanica.

Keywords

Anthracene

PAHs

Activated carbon

Adsorption isotherm

Posidonia oceanica

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1 Introduction

Polycyclic aromatic hydrocarbons (PAHs) are a group of chemical compounds consisting of carbon and hydrogen, arranged in the form of two or more aromatic rings. They are mainly originated from the incomplete combustion of fossil fuels, petrochemical industry and biomass burning. PAHs become ubiquitous contaminants in the environment (Jacques et al., 2008; Sartoros et al., 2005; Ye et al., 2011 ). Indeed, PAHs are stable and persistent in the environment due to their low aqueous solubility, low volatility and their slow response to biodegradation (Sartoros et al., 2005; Cheung et al., 2008; Nkansah et al., 2011 ). These compounds are considered as priority pollutants since they are harmful to organisms at low concentrations (Nkansah et al., 2011) and many of them have been classified as hazardous pollutants because of their potential to harm human health (Karim and Husain, 2010). Consequently, PAHs have raised great environmental concern all over the world to be an environmental potential problem. In addition, water resources management is a predominant problem for future development in the Arabian Gulf region, while water demand will continue to increase and the amount of available fresh water is limited. Thus the reuse of treated waste water effluents constitutes one of the solutions to solve this problem (Hamoda et al., 2004).

The removal of PAHs from wastewater is currently performed by physical, chemical and biological treatments (Yan and Urmila, 2004). In fact, the biological process usually requires a considerably long time to break down organic pollutants to an acceptable level of PAHs. The adsorption method is considered to be an effective method for the wastewater treatment due to its low cost, simplicity of design, ease of operation and insensitivity to toxic pollutants. Therefore, this last decade, there has been an increasing interest to find cheap and easily provided natural adsorbent. Posidonia oceanica (P. oceanica) an endemic marine magnoliophyta is found in the Mediterranean Sea (Demirak et al., 2011). It is a local biomass abundant on the coasts of Tunisia (Douissa et al., 2013; Khiari et al., 2011), has shown its effectiveness in removing organic and inorganic pollutants (Cengiz et al., 2012; Demirak et al., 2011; Douissa et al., 2013; Dridi et al., 2011; Dural et al., 2011 ).

The present work aims to present the usage of a sustainable environmental waste, P. oceanica, and activated carbon as promising precursors for the removal of anthracene from wastewaters. The effects of some parameters such as pH and contact time on the adsorption of the anthracene/P. oceanica or activated carbon system have been examined. Secondly a modeling of the isotherms of adsorption has been under taken by fitting the parameters of the Langmuir and Freundlich models.

2 Experimental

2.1

2.1 Materials

2.1.1

2.1.1 Anthracene

Anthracene (molecular weight 178.23 g mol⁻¹; melting point: 216–218 °C; boiling point: 340 °C) was purchased from Aldrich (Fig. 1).

2.1.2

2.1.2 Posidonia oceanica

The P. oceanica balls were collected from the Monastir beach (Tunisia). The collected material was washed with tap and distilled water to remove salt, impurities and epiphytes, and then dried at 60 °C for 3 days. The resulting material was crushed to produce homogeneous particles of size 50 μm.

2.1.3

2.1.3 Activated carbon

Commercial activated carbon was used in this study: a granular activated carbon (GAC) supplied by Merck Germany (2–8 mesh).

2.2

2.2 Methods

2.2.1

2.2.1 Effect of the initial pH

The adsorption of anthracene by the activated carbon or P. oceanica was studied over a pH range of 2–12 at 25 ± 1 °C. Initial concentration of anthracene was 4 mg/L. The influence of the initial solution pH was studied by shaking, in different brown flasks, 0.3 g of sorbent and 30 mL of the anthracene solution (4 mg/L) at different pHs. The flasks were agitated for 20 min with a constant stirring speed of 150 rpm. The solution pH was adjusted at the desired value by adding a small amount of HCl (0.1 M) or NaOH (0.1 M).

After the adsorption step, the solid phase was separated by filtration. The final concentration of anthracene in the solution was analyzed using a UV–Vis spectrometer (BECKMAN DU 800) at 252 nm wavelength. The adsorbed amount of anthracene at equilibrium, qe (mg/g) was calculated by the following expression:

(1)

q_{e} = \frac{(C_{0} - C_{e})}{m} \cdot V

Where C₀ and C_e (mg/L) are the initial and equilibrium concentration of anthracene solution, respectively. V (L) is the volume of the solution, and m (g) is the mass of adsorbent used.

2.2.2

2.2.2 Effect of contact time

In order to determine the contact time necessary for establishment of adsorption equilibrium, the adsorbed quantity of anthracene on activated carbon is measured as a function of the contact time corresponding to adsorption equilibrium. Adsorption studies were carried out by agitating 30 mL of anthracene solution (4 mg/L) with 0.3 g of adsorbent in a 50 mL brown flask at room temperature (25 ± 1 °C). The amount of adsorbed anthracene was determined at different time intervals (5–60 min).

2.2.3

2.2.3 Adsorption isotherms

The adsorption experiments were carried out at room temperature (25 ± 1 °C) and at natural pH. The brown flasks containing 30 mL of desired anthracene concentration (Table 1) with 0.3 g of adsorbent were mechanically agitated with a constant stirring rate of 150 rpm. After sharking, the samples were filtered and residual concentration of anthracene in the filtrate was estimated at λ_max = 252 nm using a UV–Vis spectrometer (BECKMAN DU 800).

Table 1 Anthracene concentration (mg/L).

Sample	1	2	3	4	5	6	7	8	9	10	11
Concentration (mg/L)	0.33	1.33	2	2.66	4	16.66	33.33	50	66.66	83.33	100

2.3

2.3 Theoretical

The equilibrium study on adsorption has provided information on the capacity of the adsorbent. The adsorption isotherms describe how solutes interact with adsorbents and express the surface properties and affinity of the adsorbent. The adsorption isotherm generally fits the Langmuir or Freundlich model (Cherifi et al., 2009; Freundlich, 1906; Hameed and Rahman, 2008; Langmuir, 1916; Montanher et al., 2005; Woodard, 2001 ).

2.3.1

2.3.1 Langmuir model

Langmuir model assumes that the maximum adsorption capacity consists of a monolayer adsorption, that the adsorption energy is distributed homogeneously over the adsorbent surface and that there are no interactions between adsorbed molecules. Langmuir equation is (Langmuir, 1916; Kobya, 2003)

(2)

q_{e} = \frac{q_{max} \cdot K_{L} \cdot C_{e}}{1 + K_{L} \cdot C_{e}}

Where q_e, q_max, K_L and C_e are the amount adsorbed at equilibrium (mg/g), maximum adsorption capacity (mg/g), Langmuir constant (L/mg) and the concentration of adsorbate at equilibrium (mg/L), respectively.

The linear form of the Langmuir isotherm can be represented by the following equation (Hameed and Rahman, 2008):

(3)

\frac{C_{e}}{q_{e}} = \frac{C_{e}}{q_{max}} + \frac{1}{q_{max} \cdot K_{L}}

The essential characteristics of Langmuir isotherm can be expressed in terms of a dimensionless constant called equilibrium parameter R_L as follows:

(4)

R_{L} = \frac{1}{1 + K_{L} \times C_{0}}

When C₀ is the highest initial solution concentration. The value of R_L indicates the type of isotherm to the reversible (R_L = 0), favorable (0 < R_L < 1), linear (R_L = 1) or unfavorable (R_L > 1).

2.3.2

2.3.2 Freundlich model

The Freundlich model assumes a heterogeneous surface with a non-uniform distribution of adsorption over the surface of adsorbent. The Freundlich model can be expressed by the equation (Freundlich, 1906; Kobya, 2003)

(5)

q_{e} = K_{F} \cdot C_{e}^{1 / n}

Where K_F and n are Freundlich constant. K_F and n values can be determined from a linear plot of log q_e versus log C_e.

(6)

\log q_{e} = \log K_{F} + (1 / n) \log C_{e}

3 Results and discussion

3.1

3.1 Effect of the initial pH

To study the influence of pH on the adsorption capacity of activated carbon and P. oceanica for anthracene, experiments were performed at room temperature and anthracene initial concentration of 4 mg/L using different initial solution pH values, varying from 2 to 12. The obtained results of anthracene removal at different pH solution values are shown in Fig. 2.

Effect of pH on anthracene adsorption onto activated carbon and Posidonia oceanica.

It is clear that anthracene was unaffected by varying pH of solution. A similar trend of pH effect was observed for the adsorption of anthracene on activated carbon and P. oceanica. Thus medium pH was used to study the adsorption isotherms.

3.2

3.2 Effect of contact time

The effect of the contact time on the removal of anthracene by activated carbon is shown in Fig. 3. It was observed that the adsorbed amount of anthracene increased with the increase of contact time. The removal of anthracene was rapid in the initial stage of the contact time and gradually decreased with lapse of time until equilibrium. The fast adsorption at initial stage may be due to the availability of uncovered surface area and the remaining active sites on the adsorbents. Optimum contact time was found to be 30 min. The equilibrium time considered for the further work has been taken as 30 min to ensure steady state.

Effect of contact time on anthracene adsorption.

3.3

3.3 Adsorption isotherms

The equilibrium of adsorption is one of the important physico-chemical aspects for the evaluation of the adsorption process as a unit operation. The adsorption isotherm studies were conducted by varying the initial concentration of anthracene from 0.33 to 100 mg/L (Table 1) while the adsorbent mass in each sample was kept constant. Figs. 4 and 5 depict the adsorption isotherm (q_e versus C_e) and show that the adsorption capacity increased with increasing equilibrium of anthracene concentrations and eventually attained a constant value before remounting.

Adsorption isotherm of anthracene onto activated carbon.

Adsorption isotherm of anthracene onto Posidonia oceanica.

3.3.1

3.3.1 Modeling of isotherms

In order to obtain information on the properties and mechanism of the adsorption process, the experimental results of anthracene adsorption on activated carbon and P. oceanica are commonly fitted to the Langmuir and Freundlich model (Eq. (2), Eq. (5), Figs. 6 and 7). The calculated constants using linear forms (Eqs. ()()()(3)–(5)), are given in Table 2 for the two materials. The value of R_L is found to be 0.036 and 0.077 for activated carbon and P. oceanica, respectively suggesting a favorable adsorption of anthracene on the used materials. Although correlation coefficients (R²) (Table 2) of both equations (Eqs. (2) and (5)) are considerably well obtained with two adsorbents (activated carbon and P. oceanica). The Langmuir model exhibited a better fit to the adsorption data than the Freundlich model. K_F and n of the Freundlich isotherm constants showed the tendency of anthracene uptake from the adsorption medium with the high capacity of the activated carbon. All n values were greater than unity, indicating that anthracene adsorption was favorably adsorbed by the activated carbon and P. oceanica.

Langmuir and Freundlich isotherms fitted to experimental sorption of anthracene onto activated carbon.

Langmuir and Freundlich isotherms fitted to experimental sorption of anthracene onto Posidonia oceanica.

Table 2 Isotherm constants for adsorption of anthracene onto Posidonia oceanica and activated carbon.

Sorbents	Langmuir constants			Freundlich constants
Sorbents	q_max (mg/g)	K_L (L/mg)	R²	n	K_F	R²
Posidonia oceanica	0.14	2.97	0.99	1.74	8.78	0.92
Activated carbon	8.35	0.26	0.99	1.20	1.37	0.98

Figs. 6 and 7 confirmed that the suitable isotherm for our experimental equilibrium curves was the Langmuir one. Thus we can notice that the better anthracene retention was achieved onto activated carbon.

The maximum capacity, q_max, defines the total capacity of the anthracene adsorbent. The maximum equilibrium adsorption capacity values were determined as 8.35 mg/g and 0.14 mg/g for activated carbon and P. oceanica, respectively.

4 Conclusions

On the basis of the described results a number of conclusions can be proposed:

The adsorption of anthracene on activated carbon and P. oceanica was not influenced by the initial pH variation.

Adsorption equilibrium was reached within short period (30 min).

The equilibrium data were fitted to Langmuir and Freundlich isotherms and the equilibrium data were best described by the Langmuir isotherm model.

Results showed that activated carbon can be effectively used as an adsorbent for the removal of anthracene. Adsorption capacity was 8.35 mg/g and 0.14 mg/g for activated carbon and P. oceanica, respectively.

Marine waste, P. oceanica, is a sustainable natural resource and eco-friendly material due to its large use as raw material for many applications such as waste water treatment. P. oceanica can be used as a precursor material for the preparation of activated carbon. The preparation of activated carbon from P. oceanica is an economically promising twofold. The endemic species in the Mediterranean Sea would be utilized and the production of activated carbon for the treatment of wastewaters would be achieved at low cost. The present study offers an alternative usage of P. oceanica accumulated on the beach in the industrial wastewater treatment.

Acknowledgements

We greatly acknowledge the financial support of the Ministry of Higher Education and Scientific Research of Tunisia (Ministère de l’Enseignement Supérieur et de la Recherche Scientifique de Tunisie).

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Introduction

Experimental

Materials
Methods
Theoretical

Results and discussion

Effect of the initial pH
Effect of contact time
Adsorption isotherms

Conclusions

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[1] Cherifi H., Hanini S., Bentahar F., . Adsorption of phenol from wastewater using vegetal cords as a new adsorbent. Desalination. 2009;244:177-187.
[Google Scholar]

[2] Cheung K.C., Zhang J.Y., Deng H.H., Ou Y.K., Leung H.M., Wu S.C., Wong M.H., . Interaction of higher plant (jute), electrofused bacteria and mycorrhiza on anthracene biodegradation. Bioresource Technology. 2008;99:2148-2155.
[Google Scholar]

[3] Cengiz S., Tanrikulu F., Aksu S., . An alternative source of adsorbent for the removal of dyes from textile waters: Posidonia oceanica (L.) Chemical Engineering Journal. 2012;189–190:32-40.
[Google Scholar]

[4] Demirak A., Dalman O., Tilkan E., Yildiz D., Yavuz E., Gökçe C., . Biosorption of 2,4 dichlorophenol (2,4-DCP) onto Posidonia oceanica (L.) seagrass in a batch system: Equilibrium and kinetic modelling. Microchemical Journal. 2011;99:97-102.
[Google Scholar]

[5] Douissa N., Bergaoui L., Mansouri S., Khiari R., Mhenni M.F., . Macroscopic and microscopic studies of methylene blue sorption onto extracted celluloses from Posidonia oceanica. Industrial Crops and Products. 2013;45:106-113.
[Google Scholar]

[6] Dridi S., Ben Douissa L.N., Mhenni M.F., . Removal of lead and Yellow 44 acid dye in single and binary component systems by raw Posidonia oceanica and the cellulose extracted from the raw biomass. Environmental Technology. 2011;32:325-340.
[Google Scholar]

[7] Dural M.U., Cavasa L., Papageorgiou S.K., Katsaros F.K., . Methylene blue adsorption on activated carbon prepared from Posidonia oceanica (L.) dead leaves: kinetics and equilibrium studies. Chemical Engineering Journal. 2011;168:77-85.
[Google Scholar]

[8] Freundlich H.M.F., . Uber die adsorption in losungen. Zeitschrift für Physikalische Chemie. 1906;57:385-470.
[Google Scholar]

[9] Hameed B.H., Rahman A.A., . Removal of phenol from aqueous solutions by adsorption onto activated carbon prepared from biomass material. Journal of Hazardous Materials. 2008;160:576-581.
[Google Scholar]

[10] Hamoda M.F., Al-Ghusain I., Al-Mutairi N.Z., . Sand filtration of wastewater for tertiary treatment and water reuse. Desalination. 2004;164:203-211.
[Google Scholar]

[11] Jacques R.J.S., Okeke B.C., Bento F.M., Teixeira A.S., Peralba M.C.R., Camargo F.A.O., . Microbial consortium bioaugmentation of a polycyclic aromatic hydrocarbons contaminated soil. Bioresource Technology. 2008;99:2637-2643.
[Google Scholar]

[12] Karim Z., Husain Q., . Removal of anthracene from model wastewater by immobilized peroxidase from Momordica charantia in batch process as well as in a continuous spiral-bed reactor. Journal of Molecular Catalysis B: Enzymatic. 2010;66:302-310.
[Google Scholar]

[13] Khiari R., Marrakchi Z., Belgacem M.N., Mauret E., Mhenni M.F., . New lignocellulosic fibres-reinforced composite materials: a step forward in the valorisation of the Posidonia oceanica balls. Composites Science and Technology. 2011;71:1867-1872.
[Google Scholar]

[14] Kobya M., . Adsorption, kinetic and equilibrium studies of Cr (VI) by Hazelnut shell activated carbon. Adsorption Science Technology. 2003;22:51-64.
[Google Scholar]

[15] Langmuir I., . The constitution and fundamental properties of solids and liquids. I. Solids. Journal of the American Chemical Society. 1916;38:2221-2295.
[Google Scholar]

[16] Montanher S.F., Oliveira E.A., Rollemberg M.C., . Removal of nickel onto alkali treated rice bran. Journal of Hazardous Materials. 2005;117:207-211.
[Google Scholar]

[17] Nkansah M.A., Christy A.A., Barth T., . The use of anthracene as a model compound in a comparative study of hydrous pyrolysis methods for industrial waste remediation. Chemosphere. 2011;84:403-408.
[Google Scholar]

[18] Sartoros C., Yerushalmi L., Beron P., Guiot S.R., . Effects of surfactant and temperature on biotransformation kinetics of anthracene and pyrene. Chemosphere. 2005;61:1042-1050.
[Google Scholar]

[19] Woodard F., . Industrial Waste Treatment Handbook. Boston: Butterworth-Heinemann; 2001.

[20] Yan F., Urmila M.D., . Cost effective environmental control technology for utilities. Advances in Environmental Research. 2004;8:173-196.
[Google Scholar]

[21] Ye J.S., Yin H., Qiang J., Peng H., Qin H.M., Zhang N., He B.Y., . Biodegradation of anthracene by Aspergillus fumigatus. Journal of Hazardous Materials. 2011;185:174-181.
[Google Scholar]

Adsorption of anthracene using activated carbon and Posidonia oceanica

Abstract

Keywords

Anthracene

PAHs

Activated carbon

Adsorption isotherm

Posidonia oceanica

1 Introduction

2 Experimental

2.1 Materials

2.1.1 Anthracene

2.1.2 Posidonia oceanica

2.1.3 Activated carbon

2.2 Methods

2.2.1 Effect of the initial pH

2.2.2 Effect of contact time

2.2.3 Adsorption isotherms

2.3 Theoretical

2.3.1 Langmuir model

2.3.2 Freundlich model

3 Results and discussion

3.1 Effect of the initial pH

3.2 Effect of contact time

3.3 Adsorption isotherms

3.3.1 Modeling of isotherms

4 Conclusions

Acknowledgements

References

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