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REMOVAL OF IBUPROFEN FROM AQUEOUS SOLUTIONS BY ADSORPTION ON LENTIL AND RICE HUSK

REMOVAL OF IBUPROFEN FROM AQUEOUS SOLUTIONS BY ADSORPTION ON LENTIL AND RICE HUSK

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  • GRADUATION THESIS REMOVAL OF IBUPROFEN FROM AQUEOUS SOLUTIONS BY ADSORPTION ON LENTIL AND RICE HUSK Supervisor: Prof. Dr. Belma KIN ÖZBEK 10051042 Esra ALTUN 11051803 Ayşe ÇELİK
  • CONTENTS Materials and Methods Conclusions Results and Discussions Adsorption Industrial Wastewater Treatment Pharmaceuticals
  • PHARMACEUTICALS
  • These excreted wastes can easily metabolise by microorganisms in sewage treatment plants. Many human and veterinary pharmaceuticals aren’t completely metabolized and excreted unchanged via urine and feces. Pharmaceuticals are organic compounds that are signing anthropogenic origin, consumed, produced and/or excreted by humans and animals, or used in household products.
  • Consume of Pharmaceutical in Public 30% 153% 0 20 40 60 80 100 120 140 160 180 Years 1994-2002 2002-2012 %Change
  • IBUPROFEN
  • Acidic drugs are ionic in neutral pH, which makes them an interesting compound to study. Ibuprofen is a non-steroidal acidic anti-inflammatory drug which is largely used throughout the world (Lischman et al., 2006).
  • Melting Point; 77-78 °C Boiling Point ; 157 °C (4 mmHg) Storage T ; -20°C Freezer Water Solubulity; Insoluble UV Spectrum; 220nm Colourless, Crystalline Steam Pressure; 1.86.10-4(mm Hg) pKa; 4.9 Henry Laws Constant 1.50.10-7 (atm.m3/mole)
  • INDUSTRIAL WASTEWATER TREATMENT
  • Industrial wastewater treatment includes the mechanisms and processes used to treat waters which have been contaminated in some way by anthropogenic industrial or commercial activities prior to its release into the environment. In the developed world, recent trends have been to minimize or recycle waste inside the production process. Sources of Industrial Wastewater; Iron and steel industry Mines and quarries Food industry Complex organic chemicals industry
  • Solid removal • Most solids can be removed by using simple sedimentation techniques with the solids recovered as sludge or slurry. Oil and grease removal • Skimming devices can recover many oils from open water surfaces. Removal of biodegradable organics • Biodegradable organic materials can be removed using extended usual wastewater treatment processes such as trickling filter or activated sludge. Activated sludge process • Activated sludge is a biochemical process for treating sewage and industrial wastewater by air (or oxygen) and microorganisms.
  • Treatment of acids and alkalies • Alkalis and acids can usually be neutralized under controlled conditions. Neutralization frequently produces sediment that will require treatment as a solid residue that may also be toxic. Treatment of toxic materials • Toxic materials (many organic materials, metals, acids, alkalis and non-metallic elements) are generally resistant to biological processes unless very dilute. Metals can often be precipitated out by changing the pH or by treatment with other chemicals. Trickling filter process • A trickling filter consists of a bed of rocks, slag, gravel, plastic media or peat moss. The process involves adsorption of organic compounds in the wastewater by the microbial slime layer covering the bed media. Aerobic conditions are continued by forced air flowing through the bed.
  • ADSORPTION
  • Adsorption is the adhesion of molecules, atoms or ions from a dissolved solid, liquid or gas to a surface. Adsorption is the binding of molecules or particles to a surface. It must be distinguished from absorption by the filling of pores in a solid. The surface binding is generally weak and reversible. Types of Adsorption; Physical adsorption or physisorption Chemical adsorption or chemisorption
  • Physisorption Low heat of adsorption Van der Waal's forces Takes place at low temperature Its reversible Related to the ease of liquefaction of the gas Not very specific It forms multi-molecular layers No requirement of activation energy Chemisorption High heat of adsorption Chemical bond forces Takes place at high temperature It is irreversible Extent of adsorption is generally not related to liquefaction of the gas Highly specific Forms monomolecular layers Requires activation energy
  • • Schematic representation of the adsorption and possible subsequent reaction of carbon monoxide on various solid surfaces
  • Most Important Adsorbents Adsorbents are usually used in the form of rods, spherical pellets, monoliths or moldings, with hydrodynamic diameters between 10 and 0.5 mm. Adsorbents are mostly microporous and high specific surface materials (200 - 2000 m2/g) The adsorbent is the separating agent which is used to express the difference between molecules in a mixture: adsorption equilibrium or kinetics.
  • Activated carbon Silica gel Alumina Alumino silicates ZeoliteMordenite Clays Carbon nanotubes Red mud Adsorbents
  • Factors Affecting Adsorption • Surface area of adsorbent • Particle size of adsorbent • Contact time or residence time • Solubility of solute (adsorbate) in liquid (wastewater) • Affinity of the solute for the adsorbent (carbon) • Number of carbon atoms • Size of the molecule with respect to size of the pores • Degree of ionization of the adsorbate molecule • pH
  • Adsorption Isoterms NAME ISOTHERM EQUATION APPLICABILITY Langmuir 𝐪 = 𝐪 𝐦 𝐤 𝟏. 𝐂 𝟏 + 𝐤 𝟏 𝐂 Chemisorption and physical adsorption Freundlich 𝐪 = 𝐊 𝐅 𝐂 𝟏/𝐧 Chemisorption and physical adsorption at low coverages Temkin 𝐪 𝐞 = 𝐑𝐓 𝐛 𝐥𝐧 𝐀 𝐓 𝐂 𝐞 Chemisorption
  • Langmuir isotherm vs. Freundlich isotherm Theoretical justification Assumes reversible adsorbtion and desorption Represents well data for single components Represents an empirical model No assumption Used also for mixtures of compounds LANGMUIR FREUNDLICH
  • Temkin Isotherm Temkin isotherm comprises a factor that explicitly taking into the account of adsorbent– adsorbate interactions. The model assumes that heat of adsorption of all molecules in the layer would decrease linearly rather than logarithmic with coverage by ignoring the extremely low and large value of concentrations (Tempkin et al., 1940; Aharoni et al., 1977). As denoted in the equation, its derivation is characterized by a uniform distribution of binding energies.
  • Adsorption Kinetics Pseudo-first order rate model 𝐥𝐨𝐠 𝐪 𝐞 − 𝐪𝐭 = 𝐥𝐨𝐠𝐪 𝐞 − 𝐤 𝐩 𝟐. 𝟑𝟎𝟑 𝐭 Pseudo-second order rate model 𝐭 𝐪𝐭 = 𝟏 𝐤 𝟐 𝐪 𝐞 𝟐 + 𝐭 𝐪 𝐞 Intraparticle diffusion model 𝐪𝐭 = 𝐤 𝐩 𝐭 𝟏/𝟐 + 𝐂 Elovich kinetic model 𝐪𝐭 = 𝛃 𝐥𝐧 𝛂𝛃 + 𝐥𝐧 𝐭
  • MATERIALS and METHODS
  • MATERİALS Ibuprofen •The chosen pharmaceutical ibuprofen was supplied from a pharmaceutical factory and used as the single component adsorbate in the present study. The concentration of ibuprofen was used as 30 mg/L Rice Husk •Rice husk was supplied from Güven Rice Factory in Osmancık Çorum. Rice husk’s outer surface area is around 4000 m2/ m3. The moisture of rice husk was obtained 7% in the present study. Lentil Husk •Lentil husk was supplied from Arpacioglu lentil production factory in Şehitkamil in Gaziantep. The moisture of lentil husk was obtained 1%.
  • APARATUS IKA KS 4000 IC Shaker Scale SHIMADZU UV- 1800 spectrofotometer Eutech pH meter Syringe Filter
  • Experimental Methods Several amounts of adsorbent were poured to 100 mL water and taken to the shaker for a good mixing for an hour. 3 mg of ibuprofen was dissolved in 5 mL methanol and it was added into the solution. pH of the solutions were adjusted before the adsorption experiments. When the adsorption started, samples were taken in defined time intervals.
  • Experimental Methods During the adsorption experiments, the residual of the ibuprofen amounts were examined for a time interval. For determination ibuprofen amounts, the adsorbent solution was filtrated by using the syringe filter and absorbance values were measured. By using the calibration curve, the concentration values were calculated from absorbance values. In the meantime, adsorbent solution without ibuprofen was used as blank solution at defined pH and temperature values. The absorbance values of the blank solution were measured.
  • Calibration curve of ibuprofen σ=0.00384
  • RESULTS and DISCUSSIONS
  • pH Effect on Ibuprofen Adsorption Concentrations (mg/L) Time (h) pH 3 pH 4 pH 5 0 30.00 30.00 30.00 1 21.92 24.59 29.19 2 16.55 22.38 25.36 3 16.36 20.95 22.76 4 15.84 20.95 21.89 5 15.52 20.63 21.27 6 15.00 18.98 21.09 • The ibuprofen adsorption was examined at various pH values such as 3, 4 and 5, respectively. • The adsorbent concentration was 10 g/L and ibuprofen concentration was 30 mg/L at temperature of 25 0C. • The adsorption percentages for pH 3, 4 and 5 were obtained as 50.0 %, 36.7% and 29.7%, respectively.
  • pH Effects on Ibuprofen Adsorption 0 5 10 15 20 25 30 35 0 1 2 3 4 5 6 7 Concentration(mg/L) Time (h) pH 3 pH 4 pH 5
  • Rice Husk Concentration Effect on Ibuprofen Adsorption • The ibuprofen adsorption was examined at various adsorbent concentration values such as 5, 10, 20 and 40g/L, respectively. • The pH value was 3 and ibuprofen concentration was 30 mg/L at temperature of 25 0C. • The adsorption percentages for adsorbent concentrations 5, 10, 20 and 40g/L were obtained as 10.17 %, 50.00 %, 53.73 % and 51.99 %, respectively. Concentrations (mg/L) Time (h) 5 g/L 10 g/L 20 g/L 40 g/L 0 30.00 30.00 30.00 30.00 1 27.97 21.92 19.28 16.51 2 27.46 16.55 16.51 15.95 3 27.27 16.36 14.41 15.32 4 27.27 15.84 14.21 14.96 5 26.95 15.52 13.88 14.82 6 26.95 15.00 13.88 14.40
  • Rice Husk Concentration Effect on Ibuprofen Adsorption 0 5 10 15 20 25 30 35 0 1 2 3 4 5 6 7 Concentration(mg/L) Time (h) 5 g/L 10 g/L 20 g/L 40 g/L
  • Temperature Effect on Ibuprofen Adsorption Concentrations (mg/L) Time (h) 25 ºC 30 ºC 40 ºC 0 30.00 30.00 30.00 1 19.28 18.96 19.49 2 16.51 16.83 17.36 3 14.41 14.70 15.23 4 14.21 14.17 14.90 5 13.88 13.84 14.70 6 13.88 13.84 14.57 • Ibuprofen adsorption was examined for various temperatures such as 25, 30 and 40 ºC, respectively. • At pH 3, ibuprofen concentration was 30 mg/L and rice husk concentration was 20 g/L. • The adsorption percentages for temperatures 25, 30 and 40 ºC were obtained as 53.73%, 53.88% and 51.44%, respectively.
  • Temperature Effect on Ibuprofen Adsorption 0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 0 1 2 3 4 5 6 7 Concentration(mg/L) Time (h) 25 C 30 C 40 C
  • Ibuprofen Adsorption onto Lentil Husk for Optimum Conditions • The optimum conditions were 20 g/ L adsorbent, 30 mg/ L ibuprofen, pH 3 and room temperature. • The removal percentage of ibuprofen was 26.43%. Time (h) Concentration (mg/ L) 0 30.00 1 26.45 2 24.85 3 23.67 4 22.84 5 22.49 6 22.07 0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 0 1 2 3 4 5 6 7 Concentration(mg/L) Time (h)
  • Optimum data of adsorption onto rice husk • From 6 hours’ experiments, optimum conditions were; pH 3, room temperature (25 ± 2 ºC), 180 rpm shaking velocity and 20 g/L adsorbent concentration. Time (h) Adsorbed Concentration (mg/L) qt (mg/g) 0 0.00 0.00 1 10.72 0.54 2 13.49 0.67 3 15.59 0.78 4 15.79 0.79 5 16.12 0.81 6 16.12 0.81
  • Adsorption capacities (qe) of 20 g/L rice husk against time 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 0 1 2 3 4 5 6 7 qt(mg/g) Time (h)
  • Adsorption Isotherms
  • Langmuir Isotherm • Ce was adsorbed ibuprofen concentration and qe was removed ibuprofen per unit mass of adsorbent. Time (h) Ce = C1-C2 (mg /L) Ce/ qe (g/L) 1 10.72 13.31 2 13.49 16.73 3 15.59 19.35 4 15.79 19.59 5 16.12 19.90
  • Langmuir Isotherm y = 1.2322x + 0.1034 R² = 0.9998 13.00 14.00 15.00 16.00 17.00 18.00 19.00 20.00 10.50 11.50 12.50 13.50 14.50 15.50 16.50 Ce/q(g/L) Ce (mg/L)
  • Langmuir Isotherm • KL is the adsorption equilibrium constant which is related to the energy of adsorption (L/mg). • qmax (mg/g) is the maximum adsorption capacity. Langmuir Equation qmax (mg/g) KL (L/mg) R2 σ 𝐂 𝐞 𝐪 𝐞 = 𝟏. 𝟐𝟑𝟐𝟐 ∙ 𝐂 𝐞 + 𝟎. 𝟏𝟎𝟑𝟒 0.812 11.92 0.9998 0.0471
  • Freundlich Isotherm Time (h) Ln qt Ln Ce 1 -0.62 2.37 2 -0.39 2.60 3 -0.25 2.75 4 -0.24 2.76 5 -0.22 2.78
  • Freundlich Isotherm y = 1x - 2.9957 R² = 1 -0.70 -0.60 -0.50 -0.40 -0.30 -0.20 -0.10 0.00 2.35 2.40 2.45 2.50 2.55 2.60 2.65 2.70 2.75 2.80 2.85 lnqt ln Ce
  • Freundlich Isotherm • K (mg/g) (L/g)1/n is the Freundlich constant related to sorption capacity • n is the heterogeneity factor. Freundlich Equation KF (mg.L/g2) n R2 σ Ln qe= -2.9957+ln Ce 0.05 1 1 0.0029
  • Temkin Isotherm Time (h) qt (mg/g) Ln Ce 1 0.54 2.37 2 0.67 2.60 3 0.78 2.75 4 0.79 2.76 5 0.81 2.78
  • Temkin Isotherm y = 0.6617x - 1.0377 R² = 0.9976 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 2.35 2.40 2.45 2.50 2.55 2.60 2.65 2.70 2.75 2.80 2.85 qt(mg/g) ln Ce
  • Temkin Isotherm • q 𝑒 = 𝑅𝑇 𝑏 ln 𝐴 + 𝑅𝑇 𝑏 ln 𝐶𝑒 = 𝐵 ln 𝐴 + 𝐵 ln 𝐶𝑒 • R is Gas constant (J/moleK). • A and B are Temkin constants. • B is written instead of RT/b. Temkin Equation A B R2 σ 𝐪 𝐞 = −𝟏. 𝟎𝟑𝟕𝟕 + 𝟎. 𝟔𝟔𝟏𝟕 𝐥𝐧 𝐂 𝐞 0.208 0.6617 0.9976 0.0102
  • Adsorption Kinetics
  • Pseudo first order kinetic model • qe is the adsorbed ibuprofen onto unit adsorbent in equilibrium (mg/g). • qt is the adsorbed ibuprofen onto unit adsorbent at any time (mg/g). • K1,ad is the pseudo first order kinetic constant (h-1) Time (h) log(qe-qt) 0 -0.09 1 -0.57 2 -0.88 3 -1.58 4 -1.78
  • Pseudo first order kinetic model y = -0.4391x - 0.1032 R² = 0.9787 -2.00 -1.80 -1.60 -1.40 -1.20 -1.00 -0.80 -0.60 -0.40 -0.20 0.00 0 0.5 1 1.5 2 2.5 3 3.5 4 log(qe-qt) time (h) Pseudo First Order Kinetic Model Equation qe (mg/g) qe,h (mg/g) k1,ad(h-1) R2 σ Log(qe-qt)= -0.439t-0.1032 0.810 0.788 1.011 0.9787 0.1197
  • Pseudo second order kinetic model Time (h) t/qt (g.h/mg) 1 1.87 2 2.97 3 3.85 4 5.07 5 6.20 6 7.44 y = 1.1095x + 0.6825 R² = 0.9977 0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 t/qt(g.h/mg) time (h)
  • Pseudo second order kinetic model Pseudo Second Order Kinetic Model Equation qe (mg/g) qe,h (mg/g) k2,ad(h-1) R2 σ t/qt= 1.1095t+0.6825 0.810 0.901 1.803 0.9977 0.1119
  • Elovich kinetic model data • α is the adsorption kinetic at the beginning (mg/g.h) • β is the adsorption constant during the experiments (g/mg). qt (mg/g) ln t 0.54 0.00 0.67 0.69 0.78 1.10 0.79 1.39 0.81 1.61
  • Elovich kinetic model y = 0.1747x + 0.5498 R² = 0.9561 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60 1.80 qt(mg/g) ln t Elovich Kinetic Model Equation α (mg/g.h) β (g/mg) R2 σ qt= 0.1747 ln t+0.5498 4.065 5.724 0.9561 0.0257
  • Intraparticle diffusion kinetic model • ki is the intraparticle diffusion model kinetic constant (mg/g.h0.5) • Ci is a constant that gives information about the layer thickness between the adsorbent and adsorbate. qt (mg/g) t0.5 (h0.5) 0.54 1.00 0.67 1.41 0.78 1.73 0.79 2.00 0.81 2.24
  • Intraparticle diffusion kinetic model y = 0.2219x + 0.3451 R² = 0.904 0.5 0.6 0.7 0.8 0.9 1 1.5 2 qt(mg/g) t1/2 (h1/2) Intraparticle Diffusion Model Equation ki (mg/g.h0.5) Ci (mg/g) R2 σ qt= 0.2219 t0.5 +0.3451 0.2219 0.3451 0.904 0.0387
  • The comparison of studies about removal of Ibuprofen by adsorption Reference Adsorbent Parameters Adsorbent Cons.(g/L) Working Cons. (g/L) Time (hour) Temperature (°C) pH Isotherm Model % Adsorption The present study, 2014 Rice husk 20 0.03 2 25 3 Freundlich 53.8 % The present study, 2014 Lentil husk 20 0.03 2 25 3 26.32 % Guedidi et al. 2014 Activated carbon cloth 0.1 0.01 16 25, 40, 55 3, 7 Freundlich Langmuir 23 % Connors et al. 2013 Filtrasorb 200 GAC, PWA PAC, Purolite A530E, Amberlite XAD-4, Amberlite XAD-7, and Optipore L-493 0.0006 0.015 24 25 4, 5, 7 Freundlich Langmuir 96 % Behera et al. 2012 Kaolinite, montmorillonite, goethite, and activated carbon 1 0.06 6 25 3-11 AC (90 %) Diğerleri (10 %) Jodeh, 2012 Agriculture soil 20 0.05 2 25 1-4 Freundlich 88 % Staiti, 2012 Soil 0.05 (20-50).10-6 10,30,60,120,1 80 min 15,25,35 1.5-7 Freundlich Langmuir 92 %
  • The comparison of studies about removal of Ibuprofen by adsorption Reference Adsorbent Parameters Adsorbent Cons.(g/L) Working Cons. (g/L) Time (hour) Temperature (°C) pH Isotherm Model % Adsorption Almendra, 2011 Activated carbon F400 0.01 100.10-6 2-24 23 4,5-8 Langmuir Freundlich 80 % Deng, 2010 Powdered activated carbon 0.0005-0.07 100.10-6 2, 5, 10, 15, 30, 60 and 120 min 25 4-7 Freundlich 90 % Serrano et al. 2010 Activated sludge 0.01 0.1-1 48 25 2.5 Freundlich 90 % Bui et al. 2009 SBA-15 1-2 0.1 24 25 3 Langmuir Freundlich 94.3 % Xu et al. 2009 Agricultural soils 0.001g/kg (0.5,1,2.5,5, 10).10-3 24 20 Freundlich 98 % Säfström, 2008 Powdered activated carbon 0.05 25.10-6 2 25 2.6 92 % Kabak et al. 2008 Activated sludge 3 0.01-0.05 160min 25 7.5-8.3 Freundlich 79 %
  • CONCLUSIONS • In previous study, ibuprofen which is mostly used by human being was chosen as pollutant because of its common usage. • For removing ibuprofen, rice husk and lentil husk were chosen as bioadsorbent for the adsorption studies, since they were agricultural residues and they weren’t harmful to the environment and they are low-cost materials . • Adsorption capacity was dependent on adsorbent amount, contact time and pH value. • To achieve these goals, different concentration, pH and temperature values were studied. • As a result of 6 hours experiments, optimum conditions were; pH 3, room temperature (25 ± 2 ºC), 180 rpm shaking velocity and 20 g/L adsorbent concentration.
  • CONCLUSIONS • When ibuprofen adsorption was examined at various pH values (3, 4 and 5), the most efficient pH value was 3 for ibuprofen adsorption with a percentage of 50. • When ibuprofen adsorption was examined at various adsorbent concentrations (5, 10, 20 and 40g/L), the most efficient value was 20g/L with a percentage of 53.73. • When ibuprofen adsorption was examined at various temperatures (25, 30, 40 ºC), the adsorption percentages for temperatures were 53.73%, 53.88% and 51.44%, respectively. • For optimum conditions adsorption percentage of ibuprofen onto lentil husk was 26.43%. • For optimum conditions adsorption isotherms (Langmuir isotherm, Freundlich isotherm and Temkin isotherm) and adsorption kinetics (Pseudo first order kinetic model, Pseudo second order kinetic model, Elovich kinetic model and Intraparticle diffusion model) were studied.
  • CONCLUSIONS • Among all of the isotherm models Freundlich isotherm model was fitted best. • Pseudo second order kinetic model was fitted best than the other kinetic models applied. • Consequently, adsorption of ibuprofen onto rice husk gave better results than adsorption onto lentil husk. But, the result obtained needs still improvement.  Activated carbon can be produced from rice husk for more effective adsorption process.  Fresh rice husk can be obtained to removal of residual ibuprofen.  Adsorption onto rice husk can be done for different pharmaceuticals in the wastewater.
  • THANKS FOR LISTENING TO US
  • REFERENCES • Almendra, A. R. P., (2011), “The Effect of Water Inorganic Matrix in Ibuprofen Adsorption onto Activated Carbon for Water and Wastewater Treatment”, Faculdade de Ciencias e Tecnologia, Universidade Nova de Lisbqa. • Behera, S. K., Oh, S. Y., Park, H. S., (2012), “Sorptive Removal of Ibuprofen from Water Using Selected Soil Minerals and Activated Carbon”, DOI 10.1007/s13762-011-0020-8, South Korea. • Connors, S., Lanza, R., Sirocki, A., (2013), “Removal of Ibuprofen from Drinking Water Using Adsorption”, Worcester Polytechnic Institute, Worcester. • Gereli, G., Seki, Y., Kusoglu, I. M., Yurdakoc, K., (2006),"Equilibrium and Kinetics for the Sorption of Promethazine Hydrochloride onto K10 Montmorillonite", J. Colloid Interface Sci., vol. 299, p.155-162. • Guedidi, H., Reinert L., Soneda Y., Bellakhal N., Duclaux L., (2014), “Adsorption of Ibuprofen from Aqueous Solution on Chemically Surface-Modified Activated Carbon Cloths”, Saudi Arabia, http://dx.doi.org/10.1016/j.arabjc.2014.03.007. • Jodeh, S., (2012), “The Study of Kinetics and Thermodynamics of Selected Pharmaceuticals and Personal Care Products on Agriculture Soil”, Chemistry Department, An‐Najah National University, Nablus, Palestine. • Lischman, L., Smyth, S. A., Sarafin, K., Kleygwegt, S., Toito, J., Peart, T., Lee, B., Servos, M., Beland, M., Seto, P., (2006), “Occurence and Reductions of Pharmaceuticals and Personal Care Products and Estrogens by Municipal Wastewater Treatment Plants in Ontario, Canada”, Science of the Total Environment, Volume 367, pp. 544-558, Canada. • Roccaro, P., Sgroi, M., Vagliasindi, F. G. A., (2013), “Removal of Xenobiotic Compounds from Wastewater for Environment Protection: Treatment Processes and Costs”, Department of Civil and Environmental Engineering, University of Catania, Viale A. Doria 6, 95125, Vol.32: Pg.507, Catania, Italy. • Staiti, H. A. S., (2012), “Fate of Amoxicillin, Ibuprofen, and Caffeine in Soil and Ground Water Using Soil Columns”, An-Najah National University, Palastine. • http://www.saglik.gov.tr/TR/dosya/1-82968/h/faaliyetraporu2012.pdf • http://amrita.vlab.co.in/?sub=2&brch=190&sim=606&cnt=1