REMOVAL OF ANALGESIC PARACETAMOL FROM WASTEWATER USING DRIED OLIVE STONE

International Journal of Mechanical Engineering and Technology (IJMET) Volume 9, Issue 13, December 2018, pp. 293 299, Article ID: IJMET_09_13_032 Available online at http://www.ia aeme.com/ijmet/issues.asp?jtype=ijmet&vtype= =9&IType=13 ISSN Print: 0976-6340 and ISSN Online: 0976-6359 IAEME Publication Scopus Indexed REMOVAL OF ANALGESIC PARACETAMOL FROM WASTEWATER USING DRIED OLIVE STONE Zainab T. Al-Sharify Lecturer, Department of Environmental Engineering, College of Engineering, University of Al-Mustansiriya, Baghdad, Iraq Lahieb Faisal M.A Academic visitor, School of Chemical Engineering, University of Birmingham, Birmingham, UK Talib A. Al-Sharif Assit Professor, Al Rafidain University College, College of Engineering Sciences, Hay Al - Mustansiriya, Baghdad, Iraq Noor T. Al-Sharify Asst. Lecturer, Medical Instrumentation Engineering Department, Al-Issra University Collage, Baghdad, Iraq Farah Faisal M.A Department of Civil Engineering, College of Engineering, University of Al-Mustansiriya, Baghdad, Iraq ABSTRACT The utilizing of batch studies was focused on low cost natural waste materials as adsorbents like an olive stones to remove the pain relieving paracetamol from wastewater. Exploratory examinations were focused on studying its isothermal adsorption capacity where controlled by Freundlich and Langmuir, the suitable model was Langmuir model for paracetamol adsorption / biosorption on olive stones. As compare with the models of kinetic; pseudo-first orderr and pseudo-second order; Pseudo-secondd order was as the more fitted model to an experimental data. The adsorption was relatively subject to the impact of ph, contact time, biosorbent dose, and agitation speed. Also technique of Fourier Transformation Infrared (FTIR) utilized to characterize the quantification of paracetamol before and after equilibrium. The maximum percentage of paracetamol removal (approximately about 86.75%) was attained after about 2 h of shaking time with agitation speed 200 rpm. Keyword: Paracetamol, Olive Stones, Biosorption, FTIR, Adsorption, Wastewater. http://www.iaeme.com/ IJMET/index.asp 293 editor@iaeme.com

Removal of Analgesic Paracetamol From Wastewater Using Dried Olive Stone Cite this Article: Zainab T. Al-Sharify, Lahieb Faisal M.A, Talib A. Al-Sharify, Noor T. Al-Sharify and Farah Faisal M.A, Removal of Analgesic Paracetamol From Wastewater Using Dried Olive Stone, International Journal of Mechanical Engineering and Technology, 9(13), 2018, pp. 293 299. http://www.iaeme.com/ijmet/issues.asp?jtype=ijmet&vtype=9&itype=13 1. INTRODUCTION Recently, the release of emerging-pollutants was an environmental problem. This set chiefly consists from component utilized as large amount during our life, like medicines of human and veterinary, products of personal care, surfactants, and pesticides also various additives of industry. Elimination of some emerging-pollutants in wastewater treatment plants (WWTP) has been somewhat low because most of them are hard to degrade biologically [1]. The best method to reduce these materials may be to use the step of adsorption before discharging effluents from sewage treatment. The capacity of adsorption by activated carbon depends upon its characteristics (physical and chemical); like: surface area; size of pore; functional groups, and the nature of adsorbate as: size; molecular weight; hydrophobicity; polarity, and functional groups [1, 2]. Activated carbons are significantly used to adsorb organic compounds from gases or liquids. Because of it economically expensive; several researches try to find another material to utilize as sorbent to remove contaminants. These sorbent were found from residues of vegetables and fruits, etc. The release of pharmaceuticals in environment is as a result of various sources such as humans (get rid of medications that are not used, secretion of drugs or drugs metabolites which not absorbed by a body of human are disposed of by toilet), Agricultural field (aquaculture and veterinary medicines, fodder additives in cattle breeding by dung diffusion within ground as fertilizer can filtrate inside municipal currents and rivers), also manufacture (drugs industrialization remains) [3]. Heberer [1,4] and Halling-Sorensen et al. [5] suggested projects presenting potential sources and paths to release the residue of medicines into the aquatic environment. Origin of medicines material is non biodegradable; also not totally removed while using traditional wastewater treating [4, 6]. When the treatments are ineffective, these pollutants thrown into lakes and rivers those are popular supplies for drinking water sources. Paracetamol (acetaminophen, 4-hydroxyacetanilide) is type of medicinal drugs of widespread using in the world due to it activity in relieving pain and fever. Paracetamol adsorption by carbon was extensively examined by Terzyk and Rychlicki [7] and Terzyk [8]. Researchers detect relationship between the carbon surface layer composition and physic-chemical characteristics, whereas adsorbed of paracetamol at various ph and temperatures. Several researchers detect that paracetamol is not significant for silica alumina and PorapakP absorption [9] also on aquifer sand [10]. There are many studies related to performance of bio-sorption technology to passively eliminate metals from water media [11, 12]. The formula of Paracetamol (PC) and physic-chemical properties are described in Figure 1 [9]. http://www.iaeme.com/ IJMET/index.asp 294 editor@iaeme.com

Zainab T. Al-Sharify, Lahieb Faisal M.A, Talib A. Al-Sharify, Noor T. Al-Sharify and Farah Faisal M.A Figure 1 Physicochemical parameters of paracetamol Application of low cost sorbents from agricultural waste materials and the replacement of traditional low-cost methods to remove paracetamol from wastewater would be reviewed. This current research deals with the paracetamol sorption from aqueous solution on dried olive stones obtained from local natural resources. 2. MATERIALS AND METHODS 2.1. Sorbent Preparation Olive stone (sorbent) is prepared by grinding and sieving to obtain a grain size of range less than 0.6mm in diameter; then washed by distilled water, and dried by oven at 105 C o for 24hr and stored in a dryer until use. 2.2. Preparation of Paracetamol (PC) Solutions A PC solution has been prepared by dissolving a known weight of PC in distilled water. To adjust ph of solution to require value using 0.1 M (HCl) acid or (NaOH) solutions. 2.3. Procedure of Sorption At room temperature (25±2 C) experiments of batch were tested on a rotary shaker (SI-600R Lab. Companion) at 200rpm, using glass tapered tubes. In all experiments a certain mass of sorbent used with constant agitation with a solution of PC. At end of shaking, the sorbent was removed from solution by filtration using Filter paper (Whatman 70mm. The remaining PC concentration was found by calculating the difference between the initial (C i ) and final (C f ) concentration of PC. Calculate the specific uptake by the sorbent, q (mg g 1 of dry solid using equation below: q = ( C i C f ) V / w (1) Where: V (L) is the solution volume; and w(g) is a quantity of dry sorbent used. 3. RESULTS AND DISCUSSION 3.1. ph Effect The ratio of paracetamol sorption removal on dried olive stone as a key-function of initial ph is offered in Figure 2; various ph values ranged from 3 to 9 were tested. The paracetamol removal was higher at ph 7 with dried olive stone amount about 1g for 60min at room temperature. So ph 7 was chosen for other experiments. The result agrees with that obtained by (Valentina et.al 2017) [13] used various activated carbons with modified chemical surfaces to sorption of paracetamol; capacities of sorption at ph 7 were highest by using three types of activated carbon [13]. http://www.iaeme.com/ IJMET/index.asp 295 editor@iaeme.com

Removal of Analgesic Paracetamol From Wastewater Using Dried Olive Stone 3.2. Contact Time Effect An influence result of contact time was studied under conditions as: ph 7; agitation speed 200 rpm; amount of sorbent 1gm, and at room temperature. Figure 3 shown that the increase in removal at 1 st hour because of at beginning the surface area of dried olive stone is larger then become steady until equilibrium state which at 120 min. (after 3hr mixing). The result agrees with that obtained by (Ferreira et al. 2015) [14] was used activated carbon of dende coconut mesocarp to remove paracetamol water by adsorption [14]. Re % 80 70 60 50 40 30 20 10 0 0 2 4 6 8 10 ph Re% 100 80 60 40 20 0 0 50 100 150 200 Time (min) Figure 2: Effect of ph Figure 3: Effect of Contact Time. 3.4. Effect of Sorbent Amount At room temperature with different amount (0.5-3.0g) of dried olive stone and ph7; the effect of sorbent amount is tested as shown below Figure 4. It was found that Sorption of paracetamol was increased when the amount of sorbent increased. The result was expecting due to a concentration of paracetamol is fixed, by increasing the quantity of adsorbent a larger surface area or sorption site was provided [15]. So the better dose of biosorbent is chosen as 2.5 g/l. Re % 100 90 80 70 60 50 40 30 20 10 0 0 0.5 1 1.5 2 2.5 3 3.5 Dose (g) Figure 4: Effect of Sorbent Amount. 3.4. Adsorption Isotherm and Kinetics Studies Isotherms of adsorption are the equilibrium relationships between the paracetamol adsorbed concentrations and the paracetamol ion in the solution at a specific temperature. Langmuir and Freundlich isotherm models were used to investigate the adsorption equilibrium between the paracetamol solution and olive stones phase. The Langmuir adsorption isotherm equation, as shown, requires that the applicability has monolayer coverage on the surface of the adsorbed material [16]: http://www.iaeme.com/ IJMET/index.asp 296 editor@iaeme.com

Zainab T. Al-Sharify, Lahieb Faisal M.A, Talib A. Al-Sharify, Noor T. Al-Sharify and Farah Faisal M.A q mb C e qe = (1 + b C e ) (2) Where: q e is the sorbed metal ions on the biomass (mg/g), q m is the highest sorption ability of monolayer coverage (mg/g), b is the constant associated with attraction of binding site (L/mg), and C e is concentration of metal ions in solution at balance (mg /L). The Freundlich equation applies to multi-component adsorption; which is expressed by [17]: 1 logqe = log K + logc e (Linear form) (3) n Where: K = constant indicative of the proportional sorption ability of sorbent (mg/g), 1/n = constant expressive of strength of the sorption (K, and n: are being expressive of a range of sorption and the grade of non-linearity between solution and concentration, respectively). The results of both models are presented in Table 1. From this Table which appeared that equation Langmuir is suitable of the experiential data more than Freundlich model. Mechanism of paracetamol adsorption is clarified by the kinetics models of adsorption; these are pseudo-first-order and pseudo-second-order; which explain the behavior of paracetamol adsorption on olive stone. The pseudo-first-order and pseudo-second-order models, consecutively [18, 19]: ln ( q q ) = lnq k t eq t e 1 (3a) t 1 t = ( + ) q k q q 2 t 2 eq eq Where: q eq and q t (mg g 1 ) are the amount of dye adsorbed at equilibrium and at time correspondingly. K 1 (min 1 ) and K 2 (g mg 1 min 1 ) are the kinetics rate constants for the pseudo first- and second order models, correspondingly. Table 2 showed the results below: As shown from Table 2 that the theoretic values of q e (cal) corresponded with the values of experiential uptake, q e (exp) in the case of pseudo-second-order model. Moreover, the relation coefficient (R 2 ) was 0.995, suggesting that the procedure of this sorption possible to depicted as completely using pseudo-second-order process. Table 1 Parameters of Isotherm forms. Langmuir coefficients paracetamol Freundlich coefficients paracetamol R 2 0.973 R 2 0.883 q m 3.333 1/n 0.448 b 0.142 K 0.388 Table 2 Parameters of Kinetic Models. q e experimental Pseudo-first-order Pseudo-second-order k 1 1/min q e calculated R 2 k 2 q e calculated R 2 1.420-0.032 1.1984 0.940 0.0872 1.4663 0.995 3.4. FTIR FTIR spectra before and after sorption was plotted in Figure 5 in order to show the vibration frequency changes of the functional groups in the sorbents. The results appeared that paracetamol could be adsorbed by H and O atoms of hydroxyl and carboxylic bonds, which (4) http://www.iaeme.com/ IJMET/index.asp 297 editor@iaeme.com

Removal of Analgesic Paracetamol From Wastewater Using Dried Olive Stone transferred bands to lower frequencies. These changes could be the reason of these changes may be the cause of changes in the anti-hydroxyl antagonists, carboxylic acids, alcohol, carboxyl and carbonyl. The results indicate that groups of hydroxyl groups have shifted to a lower frequency. Total displacements of these functional groups were because of the biosorption of paracetamol onto the surface of biomass. Figure 5 FTIR result 4. CONCLUSION From this study we suggest that dried olive stone is efficient to remove paracetamol from wastewater by adsorption process. This olive stone is available and low costs. The highest ability of adsorption was at ph 7 by using dried olive stone. Modeling calculations indicated that Pseudo-second-order equation and Langmuir model were selected. ACKNOWLEDGMENTS The authors acknowledge the support of Mustansiriyah University, College of Engineering and their Laboratory staff for their for their support with the experiments. REFERENCES [1] Jordi L., Conxita L.L., B. Ruiz, E. Fuenteb, Montserrat S.S., Antonio D.D. (2015). Role of activated carbon properties in atrazine and paracetamol adsorption equilibrium and kinetics. Process Safety and Environmental Protection, Vol. 9 5, pp. 51 59. [2] Mohamed, E.F., Andriantsiferana, C., Wilhelm, A.M., Delmas, H. (2011). Competitive adsorption of phenolic compounds from aqueous solution using sludge-based activated carbon. Environ. Technol. 32, 1325 1336. [3] Isabel V., Núria F., Jordi P., Antonio B., Carla B. (2011). Mechanism of paracetamol removal by vegetable wastes: The contribution of π π. interactions, hydrogen bonding and hydrophobic effect. Desalination, Vol. 270, pp. 135 142. http://www.iaeme.com/ IJMET/index.asp 298 editor@iaeme.com

Zainab T. Al-Sharify, Lahieb Faisal M.A, Talib A. Al-Sharify, Noor T. Al-Sharify and Farah Faisal M.A [4] T. Heberer. (2002).Occurrence, fate, and removal of pharmaceutical residues in the aquatic environment: a review of recent research data. Toxicol. Lett. Vol. 131, pp. 5 17. [5] B. Halling-Sorensen, S. Nors Nielsen, P.F. Lanzky, F. Ingerslev, Lützhoft Holten, H.C. Holten, S.E. Jorgensen. (1998). Occurrence, fate and effects of pharmaceutical substances in the environment a review. Chemosphere. Vol. 36, No. 2, pp. 357 393. [6] O.A.H. Jones, N. Voulvoulis, J.N. Lester. (2007).The occurrence and removal of selected pharmaceutical compounds in sewage treatment works utilising activated sludge treatment. Environ. Pollut. Vol. 145, pp. 738 744. [7] A.P.Terzyk,G. Rychlicki. (2000). The influence of activated carbon surface chemical composition on the adsorption of acetaminophen (paracetamol) in vitro. The temperature dependence of adsorption at the neutral ph. Colloids Surf. Vol. 165, pp. 135 150. [8] A.P. Terzyk. (2003). Adsorption of biologically active compounds from aqueous solutions on to commercial unmodified activated carbons. Part IV. Do the properties of amphoteric carbon surface layers influence the adsorption of paracetamol at acidic ph levels. Adsorpt. Sci. Technol. Vol. 21, pp. 93 123. [9] O. Lorphensri, J. Intravijit, D.A. Sabatini, T.C.G. Kibbey, K. Osathaphan, C. Saiwan. (2006). Sorption of acetaminophen, 17α-ethynyl estraiol, nalidixic acid, and norfloxacin to silica, alumina, and a hydrophobic medium. Water Res. Vol. 40, pp. 1481 1491. [10] O.Lorphensri, D.A. Sabatini, T.C.g. Kibbey, K. Osathapahn, C. Saiwan. (2007). Sorption and transport of acetaminophen, 17α-ethynyl estradiol, nalidixic acid with low organic content aquifer sand. Water Res. Vol. 41, pp. 2180 2188. [11] V.M. Nurchi, G. Crisponi, I. Villaescusa. (2010). Chemical equilibria in wastewaters during toxic metal ion removal by agricultural biomass. Coord. Chem. Rev. Vol. 254, pp. 2181 2192. [12] V.M. Nurchi, I. Villaescusa. (2008). Agricultural biomasses as sorbents of some trace metals. Coord. Chem. Rev. Vol. 252, pp. 1178 1188. [13] Valentina B., Alessandro E., Liliana G. and Juan C.M. (2017). Effect of Solution ph on the Adsorption of Paracetamol on Chemically Modified Activated Carbons. Molecules. Vol. 22, pp. 1-14. [14] Ferreira R.C., Couto K.Q., Arroyo P.A., and BarrosM.A., (2015). Effect of Solution ph on the Removal of Paracetamol by Activated Carbon of Dende Coconut Mesocarp. Chem. Biochem. Eng. Q., 29 (1) 47 53. [15] Heidari, A., Younesi, H., Mehraban, Z. (2009). Removal of Ni (II), Cd (II), and Pb(II) from a ternary aqueous solution by amino functionalized mesoporous and nano mesoporous silica. Chem. Eng. J. Vol. 153, pp. 70 79. [16] Langmuir, I., The constitution and fundamental properties of solids and liquids. (1916). J. Am. Chem. Soc. Vol. 38, 2221. doi: http://dx.doi.org/10.1021/ja02268a002 [17] Ruthven, D. M. (1984). Principles of Adsorption and Adsorption Processes. John Wiley & Sons. New York. Pp. 1 464. [18] Giles, C. H., Macewan, T. H., Nakhwa, S. N., Smith, D. (1960). Studies in Adsorption. Part XI.* A System of Classification of Solution Adsorption Isotherms, and its Use in Diagnosis of Adsorption Mechanisms and in Measurement of Specific Surface Areas of Solids. J. Chem. Soc. 3973. doi: http://dx.doi.org/10.1039/jr9600003973. [19] Maryam Q. Al-Qaisi, Lahieb Faisal M.A., Zainab T. Al-Sharify and Talib A. Al-Sharify, Possibility of Utilizing from Lemon Peel as a Sorbent in Removing of Contaminant Such as Copper Ions from Simulated Aqueous Solution, International Journal of Civil Engineering and Technology (IJCIET) 9(11), 2018, pp. 571 579. http://www.iaeme.com/ IJMET/index.asp 299 editor@iaeme.com