ICES5 proceeding-PP. 1-3 Gaza, 4-5 november14 JOURNAL OF ENGINEERING RESEARCH AND TECHNOLOGY, VOLUME 2, ISSUE 1, MARCH 2015 87 Landfill leachate treatment by Low Cost Activated Carbon Prepared from Agriculture Waste 1 Nurshazwani Bt. Azmi, 2 Alexanderrayar Singarayah, 3 Mohammed J.K. Bashir*, 4 Sumathi Sethupathi 1,2,3,4 Department of Environmental Engineering, Faculty of Engineering and Green Technology (FEGT), University Tunku Abdul Rahman, 31900 Kampar, Perak, Malaysia. 1 shazwani103@gmail.com (N.B.Azmi) 2 alex_rxz89@yahoo.com (A.Singarayah) 3 jkbashir@utar.edu.my (M.J.K.Bashir) 4 sumathi@utar.edu.my (S.Sethupathi) Abstract—Adsorption via activated carbon (AC) is one of the superior treatments for stabilized landfill leachate, but expensive and limited resource of AC precursor (bituminous and lignite) limit application of this technique in landfill leachate treatment. Based on previous studies, agriculture waste performed as an excellence potential for AC precursor. Thus, present study evaluates the sugarcane bagasse derived activated carbon (SBAC) for adsorptive removal of ammonical nitrogen, COD, and color from old anaerobic landfill leachate located in Perak, Malaysia. The chemical and physical properties of adsorbent were examined by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM). The effects of AC dosage (g) on adsorption performance were investigated in a batch mode study. Equilibrium data were favorably described by Langmuir isotherm model, with a maximum monolayer adsorption capacity for NH3- N, COD and color at 14.62 mg/g, 126.58 mg/g and 555.56 Pt/Co, respectively. The results illustrated the potential usability of SBAC for treatment of anaerobic landfill leachate. Index Terms: Landfill, Landfill leachate, Sugarcane Bagasse, Adsorption, Activated Carbon. I. INTRODUCTION Landfill is a well-known municipal solid waste (MSW) disposal method as up to 95% of MSW collected worldwide is buried in the landfill [1]. Due to such advantages such as low cost, simple disposal procedure [2] and ability to deal with high amounts of waste [3], landfill still widly used op- tion for MSW disposal. However, the major draw- back of landfilling is due to the generation of haz- ardous landfill leachate which can cause a serious environmental and aesthetic problem. Landfill leachate generally define as a dark color liquid with a strong odor due to the percolation of excess water with mixture of organic and inorganic pollutant deposited within the waste layers of the landfill [4]. As the consequences, landfill leachate characterized with high concentration of pollutant includes the organic matter, BOD, COD, ammoni- acal-nitogen, heavy metal, and inorganic salt. Moreover, stabilized landfill leachate contain hu- mid and fulvic substances that simply hard to be treated by biological treatment. Thus, physico- chemical method such as activated carbon (AC) adsorption could be a considerable option for stabi- lized landfill leachate treatment. Due to its unique properties such as larger surface area, high mi- cropore volume, rapid adsorption, low acid-base reactivity, and favor pore size distribution [5], AC becomes as one of the best filtration media in the world. However, high manufacturing cost and ex- pensive carbonaceous material [6] limit AC ad- sorption method applications in stabilized landfill leachate treatment. Currently, there is a great inter- est in finding low-cost and effective alternative to the existing commercial activated carbon [7]. The cost production of AC from cellulose waste materi- al is very low compared to the cost of commercial AC. Furthermore, low-cost activated carbon may contribute to environmental sustainability and offer benefits for future commercial applications [8]. Thus, the present work focusing on production of Sugarcane bagasse derive activated carbon (SBAC) for adsorptive removal of ammoniacal-nitrogen, COD and color from stabilized landfill leachate. mailto:%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%20%201shazwani103@gmail.com mailto:2alex_rxz89@yahoo.com mailto:3jkbashir@utar.edu.my mailto:4sumathi@utar.edu.my N.B.Azmi,A.Singarayah,M.J.K.Bashir,S.Sethupathi/ Landfill leachate treatment by Low Cost Activated Carbon Prepared from Agriculture Waste 88 The structural, functional and surface chemistry of the prepared AC was evaluated. The adsorptive removals of pollutants were studied by adsorption equilibrium and isotherm model. II Material and Methods Landfill leachate sampling Landfill leachate was collected from an anaerobic landfill known as Sahom landfill located at Kam- par, Perak, Malaysia. The landfill is equipped with leachate collection system, However, there is no leachate treatment system prior to discharge. Leachate samples were collected from leachate collection pond and characterized according to standard Method of Water and Wastewater [9]. Preparation of Sugarcane bagasse derived acti- vated carbon (SBAC) Sugarcane bagasse (SB) was used as AC precursor in this study. SB was obtaind from the neighboring shop. The SB was cut into small pieces, boiled and washed exhaustively in order to eliminate the im- purities from the surface followed by drying at 105˚C overnight in order to remove the unwanted moisture content. Dried bagasse was ground using grinding machine (ZM2000, Germany) with 0.1 mm blade and sieved to retain the particle sized ranging from 1.4 mm to 0.5 mm. The prepared bagasse was used for the char production with per- formed by the carbonization unit. The prepared bagasse was placed into a muffle furnace and car- bonized at 700˚C. The char produced was mixed with potassium hydroxide (KOH) solution with (Char: KOH) impregnation ratio at 1: 2.73 (wt%) and the wet bagasse was dried at 105 o C for three days before activated in muffle furnace for 3 hours at 600 o C with a ramping rate at 10˚C/min [10]. The resultant activated carbon was washed with 0.1M HCI and rinsed repeatly with deionized water until the pH of the filtrate reach 6.5-7 for removing or- ganic matters residue and alkalis. Finally, the pre- pared SBAC was dried at 105 o C for 24 hours prior to leachate treatment process. Characterization of SBAC Textural morphology of SBAC and chemical char- acterization of surface functional group was carried out by Scanning Electron Microscope (FESEM- JEOL 6701-F) and Fourier Transform Infrared spectrometer (Perkin-Elmer Spectrum RXI). Chemical characterization of surface functional groups was detected using the pressed potassium bromide (KBr) pellets which containing 5% of carbon sample. The FTIR spectra were recorded between 4000-400 cm -1 . Batch Study This study was concentrated on the identification of the optimum operational conditions. The exper- iments were conducted in a series of 250 ml Er- lenmeyer flask containing mixture of 100 ml raw leachate and SBAC with agitation speed of 200 rpmand contact time of 180 min. After each run, the media were filtered and the filtrates were kept for adsorptive uptake analysis of color, COD and NH3-N. The color concentration was measured at 455 nm wavelength using Hach color method 8025, whereas COD concentration was measured using HR+ COD vials by DR 6000 spectrophotom- eter, while NH3-N was measured with spectropho- tometer DR6000 at wavelength 640nm. All tests were conducted in accordance with the standard methods for examination of water and wastewater [9]. Equilibrium study The performance of the experiment was studied using adsorption isotherm which describes the rela- tionship between the concentrations of adsorbate accumulated on the adsorbent and the concentra- tion of the dissolved adsorbate at equilibrium [11]. Amounts of adsorbate accumulate on the adsorbent were measured by the difference between the initial concentration of adsorbate with the concentration of adsorbate at equilibrium within the dissolve so- lution where it is expressed as following equation: 𝑞 = (𝐶𝑜 − 𝐶𝑒)𝑉 𝑚 (1) where qe is amount of adsorption at equilibrium, Co is initial concentration for the adsorbate while Ce is the amount of adsorbate at equilibrium. V (L) is the volume of the solution and m (g) is the mass of the dry sorbent used. The pollutant removal percentage is calculated by the following equation: N.B.Azmi,A.Singarayah,M.J.K.Bashir,S.Sethupathi/ Landfill leachate treatment by Low Cost Activated Carbon Prepared from Agriculture Waste 89 𝑅𝑒𝑚𝑜𝑣𝑎𝑙 (%) = (𝐶 − 𝐶 ) 𝐶 𝑥 100 (2) where Co and Ce are the initial and equilibrium stage liquid-phase concentration of adsorbate, in term of color, COD and NH3-N. III. RESULT AND DISCUSSION Leachate Characteristic Table 1 shows leachate characteristic of Sahom landfill located in Kampar, Perak, Malaysia. The leachate has high concentration of color, COD, and NH3-N, with lower value of BOD5: COD ratio (< 0.1). Thus Sahom landfill can be categorized as stabilized landfill leachate [12]. As stabilized land- fill leachate contains refractory organic compound [13], effectiveness of biological process decreases and physico-chemical processes in particular AC adsorption may become one of the appropriate op- tions. Table 1: Sahom Landfill Chractristics SBAC Characterization FTIR Analysis The FT-IR analyses of SBAC before and after treatment were illustrated in Figure 1. The spectra of adsorbents were plotted to determine the vibra- tion frequency changes in the functional group of the adsorbent. The absorption peaks around 3426 cm -1 indicates the free and intermolecular bonded hydroxyl groups [14]. The peak around 1562 cm -1 may be attributes to aromatic group of lignin com- pound. The peak observed at 1084 cm -1 can be as- signed to C-O band, due to OCH3 group also con- firm the presence of lignin structure of SBAC [15]. Meanwhile, peak at 1384cm -1 may involve C-H deformation. After adsorption treatment, it was found that oxygen containing –OH groups are af- fected after uptake process. This is judged from shifts of its position to the lower frequency (3426- 3423 cm -1 ). Other remarkable shift included the C- O band from 1084 to 1090 cm -1 . The results indi- cated that the participation of these groups via ox- ygen for pollutant binding in leachate to SBAC in agreement with Person principal for hard-soft acids and bases [16] . SEM Analysis Scanning electron microscope (SEM) analysis of SBAC was presented in Figure 2. Base on the fig- ure, it showed the development of micropore struc- ture on the SBAC. As the non-carbon elements such as hydrogen, oxygen and nitrogen released in the form of tars and gases during pyrolysis process, a rigid carbon skeleton with a rudimentary pore structure known as char formed from the aromatic compound [17] . Pretreatment of the char with de- hydrating agent (KOH) inhibit formation of tar and other undesired product [17]. Consequently, CO2 creates activated carbon with larger micropore vol- ume and narrower micropore size distribution [17] that bring to higher adsorption capacity of the pol- lutant. Experimental performance Adsorbent dosage The effect of AC dosage on percentage removal of color, COD and NH3-N was illustrated on Figure 3. The shaking speed (200 rpm) and contact time (180 minutes) were remained constant with varied AC dosages (0-9g) throughout the experiment. Based on Figure 3, it is apparent that adsorptive removal Parameters Unit Average Value Temperature o C 26.9-27.1 pH - 8.60-8.75 Conductivity ms 10.93-11.02 Resistivity Ω 90.04-90.08 Turbidity ntu 105.6-126.0 Color Pt/Co 3300-3500 COD mg/L 1490-1570 NH3-N mg/L 1860-1950 BOD5 mg/L 106-120 BOD5/COD - 0.071-0.076 Total Sus- pended Solids mg/L 203-227 N.B.Azmi,A.Singarayah,M.J.K.Bashir,S.Sethupathi/ Landfill leachate treatment by Low Cost Activated Carbon Prepared from Agriculture Waste 90 of color, COD and NH3-N increased considerably by increasing adsorbent dosage from 0g/100ml to 2g/100ml. However, further increase in adsorbent dosage up to 9g/100ml showed steadily increased of pollutant uptake. According to Moodley et al. (2011), further increase of adsorbent dosage lead to overlapping of surface site due to the overcrowding of adsorbent particles [18]. As the result, it will bring to the decrease of accessible surface area of adsorbent, thus lowering the pollutant removal per unit adsorbent. Besides, adsorbent dosage presents a profound effect on the adsorption process due to the reason that it predicts the cost of adsorbent per unit of pollutant to be treated [19]. Thus, the opti- mum SBAC dosage for pollutant removal is 7g/100ml with percentage removal of 94.7 % color, 83.6% COD and 46.6% NH3 –N. (A) (B) Figure 1: FTIR analysis of (A) SBAC before treatment and (B) SCAC after treatmen. N.B.Azmi,A.Singarayah,M.J.K.Bashir,S.Sethupathi/ Landfill leachate treatment by Low Cost Activated Carbon Prepared from Agriculture Waste 91 Figure 2: SEM micrograph of sugarcane bagasse derive activated carbon at 900X magnification Figure 3: Removal efficiency in terms of COD, NH3-N and colour vs activated carbon dosage 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 0 10 20 30 40 50 60 70 80 90 100 0 1 2 3 4 5 6 7 8 9 E ff lu e n t C o n c e n tr a ti o n R e m o v a l E ff ic ie n c y ( % ) AC Dosage (g) COD removal (%) NH3-N removal(%) Colour removal (%) COD effluent (mg/L) NH3-N effluent (mg/L) Colour effluent (PtCo) N.B.Azmi,A.Singarayah,M.J.K.Bashir,S.Sethupathi/ Landfill leachate treatment by Low Cost Activated Carbon Prepared from Agriculture Waste 92 Equilibrium Study Adsorption properties of SBAC was studied using Langmuir and Freundlich Isotherms, which are the most common models for describing the adsorption characteristic of adsorbents used in water and wastewater treatment [20] . Langmuir isotherm describes the monolayer adsorption of adsorbate on specific homogenous site of adsorbent meanwhile, Freundlich isotherm theory assumes multilayer coverage of adsorbate over a heterogenous adsor- bent surface. Equation of both isotherm were ex- pressed as below: Langmuir isotherm: 1 𝑞 = 1 𝑄𝑏𝐶 + 1 𝑄 (3) Freundlich isotherm: log𝑞 = log𝐾 + log𝐶 (4) where Ce is the equilibrium liquid-phase concentra- tion and qe is the equilibrium uptake capacity (mg/g), while Q (mg/g), b (L/mg), 1/n and K are the constant. Based on Table 2, the adsorption of colour, COD and NH3-N was rationally explained by Langmuir and Freundlich isotherm. The R 2 value of Langmuir isotherm model for colour, COD and NH3-N were 0.9818, 0.9653 and 0.9728 while for Freundlich isotherm model were at 0.9524, 0.9085 and 0.923. As Langmuir model yielded relatively high R 2 val- ue and close to unity, thus the adsorption of pollu- tant on SBAC took places as monolayer adsorp- tion, with the maximum adsorption capacity of 555.56 Pt/Co, 126.58 mg/L and 14.62 mg/L for color, COD and NH3-N removal. Table 2: Isotherm Equation Parameters for colour, COD and NH3-N Adsorption onto Ac- tivated Carbon Parameter Langmuir isotherm coefficient Freundlich isotherm coefficient Q b R 2 K 1/n R 2 mg/g (L/mg) mg/g ((L/mg)1/n) Colour 555.556 0.0005224 0.9818 0.678734617 0.8199 0.9524 COD 126.582 0.0005521 0.9653 0.002761849 1.5929 0.9085 NH3-N 14.6199 0.0004753 0.9728 0.000000037 2.847 0.923 (IV) RECOMMENDATION The present study determines the optimum treatment for stabilized landfill leachate in terms of adsorbent dosage as well as the best fitted isother- mal models for color, COD and NH3 –N removal. There are much more research gaps which are yet to be explored in terms of landfill leachate treat- ment. Following are suggestions on research area for future studies. N.B.Azmi,A.Singarayah,M.J.K.Bashir,S.Sethupathi/ Landfill leachate treatment by Low Cost Activated Carbon Prepared from Agriculture Waste 93  Comparison on treatment efficiency using various types of experimental conditions such as the shaking speed, contact time and pH of the adsorbate.  Removal of different types of pollutant such as heavy metal (manganese, zinc, chromium, lead, copper and cadmium), organic and inorganic compound.  Activated carbon derived from other source of agricultural waste such as from fruit peel, fruit seed and cellulosic waste material. (V) CONCLUSION The potential of Sugarcane Bagasse derived activated carbon (SBAC) for adsorptive removal of colour, COD and NH3-N collected from a stabi- lized landfill leachate was examined. 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