64 American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) ISSN (Print) 2313-4410, ISSN (Online) 2313-4402 © Global Society of Scientific Research and Researchers http://asrjetsjournal.org/ Adsorption Studies of Cu2+ from Aqueous Solutions Using Unmodified and Citric Acid – Modified Plantain (Musa paradisiaca) Peels Abiodun Aderibigbea*, Oluwafemi Ogunlalub ,Oluwasegun Wahabc, Olugbenga Oluwasinad, Isiaka Amooe a,b,c,d,eDepartment of Chemistry, Federal University of Technology Akure, Ondo State, Nigeria aEmail: adaderibigbe@futa.edu.ng Abstract Natural plantain peel biomass and the citric-acid-modified form were used to study the adsorption of Cu2+ from a simulated aqueous solution in a batch adsorption system. The adsorption was strongly pH-dependent as maximum adsorption was recorded at a pH of 5 for the modified biomass and pH of 4 for the unmodified. The kinetics of the adsorption processes was studied with Pseudo-first-order, Pseudo-second-order, Intra-particle diffusion, Elovich and Fractional power kinetic models and the results were best fitted by the pseudo-second- order model. The experimental data were also subjected to Langmuir, Freundlich and Temkin isotherms for adsorption studies and the unmodified biomass was best fitted by the Temkin adsorption isotherm while the modified biomass, on the other hand was best fitted by the Freundlich isotherm. Thermodynamic studies revealed that the heat of adsorption of the unmodified biomass was higher than the modified. The maximum adsorption capacity obtained was 48.31 mg/g. Keywords: Adsorption; citric acid; copper (II); plantain peels. 1. Introduction Heavy metals, which are non-biodegradable substances that can constitute adverse health effects to man and livestock remains one of the main causes of pollution of water bodies. One of these is copper which when inadequately controlled as an industrial effluent has been responsible for notable havocs around the world. ------------------------------------------------------------------------ * Corresponding author. http://asrjetsjournal.org/ American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 32, No 1, pp 64-78 65 For instance, several incidences of copper poisoning in sheep were reported in the United Kingdom in summer, 2015 [1]; over 3,000 birds and 19,000 tons of fish died from water polluted by sewage leak from copper mines in Montana, United States and Fuijian, China respectively [2,3]. Ingesting contaminated foods and water exposes human to the risk of copper pollution as well [4].The limited access to safe water has therefore encouraged search for efficient ways of purifying available ones for better applications. To this end, a lot of attention has been channeled towards research bothering on efficient and sustainable ways of removing Cu2+ from aqueous systems. Notable conventional methods that have been employed include chemical precipitation, biodegradation, membrane filtration, chemical coagulation, electrolysis, ion exchange, chemical degradation, electro-coagulation and adsorption [4-6]. However, adsorption has been the most desired process because of its high efficiency. The vast abundance of different carbonaceous materials that have high adsorption capacity has also contributed in the versatility of this method of remediation. Adsorbents like activated carbon, biopolymers, metal oxides and biochars have been exploited. Recent studies have employed the use of hazelnut shell powder, raw pomegranate peel [7]. In some other studies, the various naturally occurring adsorbents used were first modified in order to increase their sorption performance [8,9] This could be achieved by physical (heating), chemical (acid / alkali treatment or impregnation of catalytic materials) or biological approach (incorporating species like bacteria for additional bioadsorption) [9]. Acid treatment has been established to contribute to acidic functional groups on adsorption sites and improves chelation with metal species [9]. Thus, Polyacrylonitrile, carboxylic acids and tetraethylene pentamine have been used in this regard [10-12]. Reactions like a ‘click reaction’ between 1,3-dipolar cycloaddition of azide and propargyl have also been used for modification [13]. In contribution to the discovery of cheap materials whose adsorption properties can be exploited to remediate Cu2+ in aqueous systems, the ability of plantain peels to adsorb these ions was investigated in this study. Plantain has a wide array of applications and it is abundantly cultivated in Africa [14] where only the fruit is sufficiently consumed and the peels are discarded as wastes while being allowed to degrade naturally. These peels constitute more than 40% of the total weight of the plantain [15] and thereby represent a cheap and easily- accessible raw material. This comparative advantage (in comparison with other adsorbents) coupled with the potentials of achieving chemical modification of the plantain peel biomass with an environment-friendly modifier like citric acid serves as the key motivation of this research work. 2. Materials and Methods 2.1 Materials and Instrumentation CuSO4, citric acid, HNO3, NaOH used were of analytical grade. Laboratory test sieve (Endecotts Ltd London, England, Serial No: 6085504) was used to sieve biomass used. Atomic Absorption Spectrophotometer (Buck Scientific). Fourier transform-Infra spectrophotometer (Shimadzu Corporation) was used for functional group identification. Whatman filter paper (No. 1) filter paper was used to separate metal laden biomass from aqueous solution. 2.2 Methods American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 32, No 1, pp 64-78 66 2.2.1 Preparation of plaintain peels adsorbent – unmodified and modified Peels plantain peels were collected from small scale local plantain roasters in Akure, Ondo state, Nigeria. Two roasters were from around the Federal University of Technology Akure (FUTA) area, one from Akure main market and the last from Akure-Ilesa road, Akure, Ondo state. The peels were thoroughly washed with deionized water and dried. After complete drying, they were ground and sieved to particle sizes between 300 – 1100 µm. Peels were treated with HNO3 and NaOH. Following the method of [12] with slight modification, 500 g of ground plantain peels (GPP) were treated with 5 litres 0.1 M HNO3 for 2 h in order to demineralise peels. Peels were then washed with 5 litres of deionized water and dried. Next, 350 g of acid treated-ground plantain peels (AT-GPP) were treated with 7 litres, 0.1 M NaOH by soaking for 2 h, filtered and rinsed thrice with a total of 10 litres of deionized water and dried. Base treated ground plantain peel (BT-GPP) was modified with citric acid. Ground Plantain peel obtained after both acid and base treatment (AT-GPP and BT-GPP) will be referred to as Unmodified Ground Plantain Peels (Un-GPP). Ninety grams of Un-GPP was treated with 900 ml, 0.6 M citric acid at 80 C for 1.5 h in order to introduce carboxylate groups on its surface referred to as citric-acid modified ground plantain peels (CA-GPP). CA-GPP was washed thrice with a total of 2 L of deionized water. Finally, it was dried at 60° C. Fourier transform – Infrared Spectroscopy (FT-IR) was employed for the characterization of Un-GPP and CA-GPP. 2.2.2 Preparation of synthetic Cu2+ aqueous solution All synthetic Cu2+ aqueous solution used for this study were prepared from a 1000 mg/L stock solution. Typically, the 1000 mg/L stock solution was prepared by dissolving 2.5118 g of CuSO4 in 1 L deionized water. 2.2.3 Batch adsorption studies All batch adsorption studies were undertaken at room temperature except otherwise stated. 0.5 g of adsorbent was contacted with 50 ml, 50 mg/L synthetic Cu2+ aqueous solution without shaking. pH studies were undertaken by varying pH of Cu2+ solution from 3 – 8. Contact time studies were undertaken by varying time from 30 - 180 min at pH 7 for Un-GPP and pH 5 for CA-GPP. For Un-GPP, time studies was extended to 10 and 20 mins after obtaining maximum adsorption at 30 mins. Adsorbent dose was varied from 30 - 70 mg at same pH used in contact time study but for 30 min (using Un-GPP) and 120 min (with CA-GPP). Temperature and adsorbate concentration studies were co-undertaken by variation of temperature from 308 – 328 K and adsorbate concentration from 25 - 100 mg/L. In this study, adsorbent dose was 0.4 g for Un-GPP and 0.5 g for CA-GPP. Percentage Cu2+ adsorbed was calculated using the equation below: 𝐶𝐶𝐶𝐶−𝐶𝐶𝐶𝐶 𝐶𝐶𝐶𝐶 × 100 (1) where Ci = initial Cu2+ concentration Cf = final Cu2+ concentration after adsorption 2.2.4 Kinetic, isotherm and thermodynamic studies American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 32, No 1, pp 64-78 67 2.2.4.1 Adsorption Kinetics The adsorption kinetics of Cu2+ on the natural plantain peel biomass and the citric-acid modified form was studied using the following models: The pseudo-first-order model: This model assumes that the amount of adsorbate that is adsorbed by an adsorbent is directly proportional to the difference in concentration saturation level [16]. Mathematically, the non-linear and linear forms of the model are represented by equations (2) and (3) respectively: 𝑑𝑑𝑑𝑑𝑡𝑡 𝑑𝑑𝑡𝑡 = 𝑘𝑘₁(𝑞𝑞𝑒𝑒 − 𝑞𝑞𝑡𝑡) (2) 𝑙𝑙𝑙𝑙𝑙𝑙(𝑞𝑞𝑒𝑒 − 𝑞𝑞𝑡𝑡) = 𝑙𝑙𝑙𝑙𝑙𝑙 𝑞𝑞𝑒𝑒 − � 𝑘𝑘1 2.303 � 𝑡𝑡 (3) where: k1 (min-1) is the rate constant of the pseudo-first-order reaction; qe denotes the adsorption amount (mg g- 1) and qt represents adsorption amount at a specific time, t. The pseudo-second-order-model: This kinetic model states that there is a chemical interaction between the adsorbate and the surface of the adsorbent leading to the formation of a chemical bond [17]. Equations (4) and (5) show the non-linear and linear forms of the model respectively: 𝑑𝑑𝑑𝑑𝑡𝑡 𝑑𝑑𝑡𝑡 = 𝑘𝑘₂(𝑞𝑞𝑒𝑒 − 𝑞𝑞𝑡𝑡)² (4) 𝑡𝑡 𝑑𝑑𝑡𝑡 = 1 𝑘𝑘2𝑑𝑑𝑒𝑒2 + 1 𝑑𝑑𝑒𝑒 𝑡𝑡 (5) where: k2 (g mg-1 min-1) is the rate constant of the pseudo-second-order reaction; qe denotes the adsorption amount (mg g-1) and qt represents adsorption amount at a specific time, t. The Weber-Morris equation or intra-particle diffusion model: This model states that adsorption occur in stages and these include transportation of adsorbate from the loaded solution, film diffusion, intra-particle diffusion into pores consequently followed by adsorption on the active centres. The model is represented by Equation (6): qt = Kp t1/2 + C (6) where: Kp is the intra-particle rate constant (g/mg.min -0.5) Elovich Kinetic model: This model has been applied for kinetic studies of Cu2+ in heterogeneous systems. The non-linear and linear forms represented mathematically by Equation (7) and (8) respectively: 𝑞𝑞𝑡𝑡 = 𝛽𝛽 ln(𝛼𝛼𝛽𝛽𝑡𝑡) (7) American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 32, No 1, pp 64-78 68 𝑞𝑞𝑡𝑡 = 1 𝛽𝛽 𝑙𝑙𝑙𝑙(αβ) + 1 𝛽𝛽 𝑙𝑙𝑙𝑙(t) (8) where: qt is the quantity of adsorbate adsorbed at time, t (mg/g); α is a constant related to chemisorptions rate and β is a constant that shows extent of surface coverage. Fractional power kinetic model: This model shows the amount of metal ions sorbed at a specific time [13]. Mathematically, the non-linear and linear forms are shown by Equations (9) and (10): 𝑞𝑞𝑡𝑡 = Ktv (9) log 𝑞𝑞𝑡𝑡 = log𝐾𝐾 + 𝑣𝑣𝑙𝑙𝑙𝑙𝑙𝑙𝑡𝑡 (10) where: qt is the amount of Cu2+ sorbed at a given time; k and v are constants with v < 1. 2.2.4.1 Adsorption Isotherms Langmuir isotherm: Langmuir isotherm defines a mono-molecular layer arrangement of adsorbate on the surface of the adsorbent and it states that there is no interaction between the adsorbed molecules [22]. The non- linear and linear forms are shown in Equations (11) and (12) respectively: 𝑞𝑞𝑒𝑒 = 𝑑𝑑𝑚𝑚 𝐾𝐾𝐿𝐿𝐶𝐶𝑒𝑒 1+ 𝐾𝐾𝐿𝐿𝐶𝐶𝑒𝑒 (11) 1 𝑑𝑑𝑒𝑒 = 1 𝐾𝐾𝐿𝐿𝑑𝑑𝑚𝑚 � 1 𝐶𝐶𝑒𝑒 � + 1 𝑑𝑑𝑚𝑚 (12) where qe is the amount of Cu2+ adsorbed per unit mass at equilibrium (mg/g); qm is the maximum adsorbate that can be adsorbed per unit mass of adsorbent (mg/g); KL is the adsorption equilibrium constant and Ce is the concentration of adsorbent (mg/L). To obtain a suitable graph, a plot of 1/qe against 1/Ce was made to yield values for the constants. Freundlich isotherm: This model suggests that adsorption occurs in form of a mono molecular layer or multilayer on heterogeneous adsorbent surfaces and that there is an interaction between the adsorbed molecules [18]. The non-linear and linear forms of the isotherm are mathematically represented by Equations (13) and (14) respectively: 𝑞𝑞𝑒𝑒 = 𝐾𝐾𝐹𝐹 Ce 1/n (13) log 𝑞𝑞𝑒𝑒 = log𝐾𝐾𝐹𝐹 + 1 𝑛𝑛 log𝐶𝐶𝑒𝑒 (14) where Ce (mg/L) and qe (mg/g) are the equilibrium concentration of adsorbent in the solution and the amount of adsorbent adsorbed at equilibrium respectively; n represents adsorption intensity and KF (mg1-1/nL1/ng-1) denotes the adsorption capacity for the adsorbent. The values of the constants were obtained by plotting log qe American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 32, No 1, pp 64-78 69 against log Ce. Temkin Isotherm: This model suggests that there is an indirect interaction between an adsorbate and the adsorbent and this occurs by a decrease in the heats of adsorption of molecules for the first layers and consequently followed by an increase in coverage [19]. The non-linear forms of the isotherm are mathematically represented by Equations (15) and (16) respectively: qe = BLn (ATCe) (15) qe = BLnAT + BLnCe (16) where Ce is the equilibrium concentration of Cu2+ in the solution (mg/L); qe is the equilibrium concentration of copper on the adsorbent (mg/g); AT is known as Temkin binding constant (L/g); B is a constant that is related to heat of adsorption and it is represented mathematically by Equation (17): 𝐵𝐵 = 𝑅𝑅𝑅𝑅 𝑏𝑏 (17) where b is the Temkin constant; T is the temperature (Kelvin) and R is the molar gas constant (8.314J.mol-1.K-1) 3. Results and Discussion 3.1 Modification and Characterization of plantain peels The citric acid modification was undertaken to provide potentially additional binding sites in the form of carboxylic groups on the surface of Un-GPP. Fig. 1a and Fig. 1b show FT-IR spectra of unmodified and modified plantain peels. Prominent among the peaks in Fig. 1a are those at 3417, 3350, 3308, 2924, 2359, 1641, 1076 and 1024 cm-1. The peaks from 3417 to 3308 cm-1 represent OH stretch (alcohol and carboxylic acid). This assignment is confirmed by the presence of a peak at 2924 cm-1 which also represents OH from carboxylic acid. Tannins (e.g. gallic acid), present in plantain peels may be responsible for the observed carboxylic functional group [19]. Also, cellulose and hemicelluloses which have appreciable amount of OH groups may be responsible for some of the OH signals observed [20]. The peak at 1641 cm-1 represents a C=C stretch. Unsaturated carbon-carbon bonds are found in some polyphenols. Last, the peak at 1024 cm-1 refers to =C-O-C symmetric and asymmetric stretch. Ether linkages of this type are again found in some polyphenols like tannin [19]. Fig. 1b presents IR spectrum of modified plantain peels. It is observed that two new sharp peaks at 1716 and 1541 cm-1 appear. Peak at 1716 cm-1 hints at a C=O stretch in carboxylic acids. It can also depict C=O stretch in esters. This assignment can be confirmed by the equally present peak at 1238 cm-1 (C=O for esters), 1157 cm-1 (for aliphatic carboxylates) and 1317 cm-1 (for aromatic carboxylates). It is very likely that free carboxylic groups remain on the surface of modified biomass since not all are esterified by OH groups in the biomass (Figure 5). Consequently, the peak at 1716 cm-1 hints at the fact that the plantain was modified with citric acid. American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 32, No 1, pp 64-78 70 O HOO OH OH O O O OH OHOH HO OH O HO OH O HO HO OH Cellulose Gallic acid (Polyphenol) OO OH OH O O O OH OH HO OH O HO O OHOH O OH OHO H2O, 80oC, 90 min O OH OH HO O O O OH O HO HO O OH OH O O OH O O OH OH O O OH O Figure 5: Proposed/suggested scheme for citric acid modification of plantain peels. Figure 1a: FT-IR spectra of unmodified plantain peels Figure 1b: FT-IR spectrum of citric acid-modified plantain peel American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 32, No 1, pp 64-78 71 3.2 Effect of pH Adsorption is a pH-dependent process and the effect of pH on the removal of Cu2+ was investigated at a range of 3.0 – 8.0 for both the unmodified and modified biomass. Maximum adsorption was recorded at pH values of 4 and 8 for the unmodified and modified biomass respectively. At low pH values, there is a large availability of H+ ions and these compete with the Cu2+ for active sites on the adsorbent consequently causing lower adsorption; this was observed in adsorption capacity of the biomass at low pH. It has been observed that at pH values greater than 6, adsorption is not the only process responsible for the removal of Cu2+ [7] as precipitation occurs and hydroxides like Cu(OH)+, Cu(OH)2, Cu2(OH)2 2+ and Cu(OH)3 - are produced. This perhaps may be the reason why the highest adsorption for the modified biomass was noticed at pH 8; the remaining concentration of Cu2+ in the reaction vessel at this pH is not due to the action of adsorption only but in addition, precipitation. Therefore, maximum adsorption before pH 6 will be considered; meaning that pH 5 produced maximum adsorption of Cu2+ and started experiencing a drop in value as the pH approached 6. This was consistent with results obtained in [7,25]. Figure 2: Effect of pH on the adsorption of copper from aqueous solution using Un-modified (Un-GPP) and Citric acid modified ground plantain peels (CA-GPP) 3.3 Effect of contact time This study was carried out at different contact times between 30-240mins at an interval of 30mins. There was a steady decrease in amount of Cu2+ adsorbed from 30-120mins as equilibrium was experienced between 60 and 90mins followed by a steady increase in amount of Cu2+ adsorbed from 150-240min. However, a different twist was observed for the modified biomass: there was a steady increase in the amount of Cu2+ adsorbed from 30- 180mins followed by a decrease between 210 and 240mins. This two-stage adsorption mechanism was reported in [28,34] and it suggests that the availability of active sites at initial contact times led to a sorption of more amount of Cu2+ than at final contact times when a repulsive force occurs between the Cu2+ in the solution and the ones already adsorbed [7]. American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 32, No 1, pp 64-78 72 Figure 3: Effect of contact time on the adsorption of copper from 50mg/l aqueous solution using Un-modified (Un-GPP) and Citric acid modified ground plantain peels (CA-GPP) 3.4 Effect of adsorbent dosage The dependence of varying adsorbent dose on the adsorption of Cu2+ was studied at a dose range of 0.1-0.7g of plantain peel biomass. For the unmodified biomass, the percentage removal of Cu2+ increased from 92.20% to 96.20% when adsorbent dosage was increased from 0.1-0.2g. This is as a result of the additional active sites that were introduced due to increase in area of adsorbent. However, there was a steady decrease afterwards in the percentage amount of Cu2+ that was adsorbed when adsorbent dose was increased sequentially. This suggests that an adsorbent dose of 0.2g can produce enough active sites sufficient for Cu2+ removal and further increase in dose will perhaps result into increase in adsorption density which causes an aggregation of adsorption sites hence limiting the capacity for effective adsorption. Therefore, a high removal efficiency is observed for the adsorbent. At dose value of 0.1g, the modified biomass adsorbed 97.40% as against the 92.20% observed for the unmodified and it continued this trend until a maximum adsorption of 99.43% was obtained at dose value of 0.3g. This indicates the effect of the citric acid modification on the biomass as it increased sorption capacity rapidly. Further increase beyond dose value of 0.3g for the modified biomass led to a consistent decrease in the amount of adsorbed ions. Figure 4: Effect of adsorbent dosage on the % copper removed from 50mg/l aqueous solution using Un- modified (Un-GPP) and Citric acid modified ground plantain peels (CA-GPP) American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 32, No 1, pp 64-78 73 3.5 Kinetic Studies Different adsorption kinetic models were applied to the experimental data to study the mechanism of adsorption. The values of the constants were obtained by making necessary plots as guided by the kinetic models and the results are shown in TABLE 1: Table 1: Values of constants obtained when experimental data was fitted to kinetic models. Pseudo-first-order kinetic model qe K1 R2 Unmodified 5.9786 0.0028 0.5966 Modified 2.4221 0.0018 0.2569 Pseudo-second-order kinetic model qe K2 R2 Unmodified 47.62 0.0048 0.9984 Modified 48.31 0.0809 0.9997 Intra-particle diffusion model Ki C R2 Unmodified 0.1955 43.6130 0.4687 Modified 0.0868 47.0840 0.3884 Elovich kinetic model β α R2 Unmodified 1.2140 1.0199 × 10²² 0.3477 Modified 2.1706 0.8128 × 1043 0.4566 Fractional power kinetic model K v R2 Unmodified 42.0920 0.0178 0.3450 Modified 45.9198 0.0096 0.4598 The correlation values obtained show that the pseudo-second-order kinetic model fitted the data for both the unmodified and modified biomass suggesting a chemisorption process [17] with the modified biomass showing American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 32, No 1, pp 64-78 74 an higher adsorption capacity. The intra-particle diffusion model gave a multi-linear plot which shows that more than one step is involved in the adsorption process [21]. These steps can include external surface adsorption, gradual adsorption, external diffusion and intra-particle diffusion. If a linear graph is obtained and the plot passes through the origin, then intra-particle diffusion is said to be the only rate-limiting step. In the case of this study, the plot did not pass through the origin. The Elovich kinetic model showed that the extent of surface coverage of the Cu2+ was higher for the modified biomass, perhaps as a result of the multiple available bonding sites leading to the attraction of the Cu2+in different directions. The chemisorption rate of the modified biomass was also discovered to be about twice the value of that of the unmodified biomass. The fractional power model shows that the amount of Cu2+ sorbed at unit time i.e. t=1 will be higher for the modified biomass than the unmodified because the former has a higher value of K. Table 2: Maximum copper adsorption capacities of previous studies in comparison with data obtained from this research work. Adsorbent qe (mg/g) References Sawdust 1.79 Yu and his colleagues [27] Pomegranate peel 1.32 El-Ashtoukhy and his colleagues [28] Rice shells 2.95 Ayidin and his colleagues [29] Lentil shells 9.52 Ayidin and his colleagues [29] Kolubara lignite 4.05 Milicevic and his colleagues [32] Litchi pericarp 8.83 Kong and his colleagues [33] Phosphoric-acid-modified-activated carbon from olive stones 17.66 Bohli and his colleagues [31] Sodium-hydroxide-modified loquat leaves 28.33 Awwad and his colleagues [30] Plantain peel biomass 47.62 This research work Citric-acid-modified plantain peel biomass 48.31 This research work 3.6 Adsorption Isotherms To understand the mechanism that governed the adsorption process of Cu2+ unto Un-GPP and CA-GPP, the experimental data obtained from this study were fitted into Langmuir, Freundlich and Temkin isotherms and results obtained are displayed in TABLE 3. The correlation values show that the experimental data for the unmodified biomass were better described by the Temkin isotherm which suggests that there must have been an indirect interaction between the adsorbate and adsorbent unlike a Langmuir situation where there is a dominant monolayer adsorption and no interaction American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 32, No 1, pp 64-78 75 between the molecules of the adsorbate. On the other hand, the modified biomass were better fitted by the Freundlich isotherm; signifying a heterogeneous adsorption. This was consistent with results obtained in [25] and [26]. This can be traced to the effect of the modifying agent (citric acid) which brings in additional surface sites-causing an interaction between the adsorbate molecules and the adsorbent surface. The value of KL for modified biomass was close to 5 times larger than that of the unmodified; thereby signifying that the adsorption of the Cu2+ was stronger for the modified biomass. The Temkin model also shows that the value of B which indicated heat of adsorption was higher for the unmodified than the modified biomass. Table 3: Values of constants obtained when experimental data for the unmodified and modified biomass were fitted to Langmuir, Freundlich and Temkin isotherm models. Langmuir isotherm model qm KL R2 Unmodified 0.0040 1.2114 0.0498 Modified 0.0049 5.8936 0.1866 Freundlich isotherm model n KF R2 Unmodified 3.2906 0.0053 0.0135 Modified 2.9878 0.0079 0.2088 Temkin isotherm model B AT R2 Unmodified 0.01 0.9324 0.1415 Modified 0.0023 0.0147 0.0877 4. Conclusion Citric acid was sufficiently capable of modifying natural plantain peel biomass; thereby increasing the adsorption capacity of the biomass to remove Cu2+ from an aqueous solution. Various parameters such as pH, dosage and contact times were used to study the behavior of the biomass and the effects of modification. The sorption process was largely a pseudo-second-order process and fitting of the experimental data into some kinetic models showed that the Temkin model fitted the unmodified form and best fitting for the citric-acid-form was achieved by the Freundlich isotherm model which suggests that the latter involved an heterogeneous adsorption. This study has also shown and increased the suitability of plantain peel as an excellent biosorbent for the American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 32, No 1, pp 64-78 76 remediation of Cu2+ in a simulated aqueous system as the maximum adsorption obtained was higher than what was derived in various adsorption studies of Cu2+. References [1] Animal and Plant Health Agency, United Kingdom. “Chemical Food Safety Quarterly Report”. Internet: www.gov.uk/government/uploads/system/uploads/attachment_data/file/477132/pub- chemfood0715.pdf, 2015 [Mar. 12, 2017]. [2] Fox News. “Thousands of bird deaths draw focus on brimming toxic pit in Montana”. Internet: http://www.foxnews.com/us/2017/01/23/thousands-bird-deaths-draw-focus-on-brimming-toxic-pit-in- montana.html, Jan. 23, 2017 [Mar. 12, 2017] [3] China Daily. “Sewage leakage kills slew of fish in East China”. Internet: http://www.chinadaily.com.cn/china/2010-07/13/content_10096687.htm, Jul. 13, 2010 [Mar. 12, 2017] [4] S. Mahdavi, “Nano-TiO2 modified with natural and chemical compounds as efficient adsorbents for the removal of Cd2+, Cu2+ and Ni2+ from water”, Clean Techn. Environ.Policy, 18, 81-94, 1898. [5] J. Komkiene and E. Baltrenaite, “Biochar as adsorbent for removal of heavy metal ions [Cadmium (II), Copper (II), Lead (II), Zinc (II)] from aqueous phase”, Int. J. Environ. Sci. Technol., 13, 471-482, 2016. [6] L. Linlin, J. Xiaojun, J. Lian and W. Hang, “Kinetic and Thermodynamic Studies on Adsorption of Cu2+, Pb2+, methylene blue and malachite green from aqueous solution using AMPS-modified hazelnut shell powder”, Chem. Res. Chin. Univ., 33, 112-118, 2017. [7] S. Ben-Ali, I. Jaouali, S. Souissi-Najar and A. Ouederni, “Characterization and adsorption capacity of raw pomegranate peel biosorbent for copper removal”, Journal of Cleaner Production, 142, 3809-3821, 2017. [8] R.K. Gautam, A. Mudhoo, G. Lofrano, M.C. Chattopadhyaya, “Biomass-derived biosorbents for metal ions sequestration: Adsorbent modification and activation methods and adsorbent regeneration”, Journal of Environmental Chemical Engineering, 2, 239–259, 2014. [9] X. Li, Y. Tang, Z. Xuan, Y. Liu, F. Luo, “Study on the preparation of orange peel cellulose adsorbents and biosorption of Cd2 + from aqueous solution”, Separation and Purification Technology, 55, 69–75, 2007. [10] Z. Du, T. Zheng, P. Wang, L. Hao and Y. Wang, “Fast microwave-assisted preparation of a low-cost and recyclable carboxyl modified lignocelluloses-biomass jute fiber for enhanced heavy metal removal from water”, Bioresource technology, 201, 41-49, 2016. American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 32, No 1, pp 64-78 77 [11] Y. Chang, C. Shen, P. Li, L. Fang, Z. Tong, M. Min and C. Xiong, “Optimization of polyacrylonitrile- cysteine resin synthesis and its selective removal of Cu(II) in aqueous solutions”, Chinese Chemical Letters, 28, 319-323, 2017. [12] L. Bingjie, C. Wei, P. Xiaoning, C. Qiqi, W. Qianrui, W. Dongfeng, M. Xianghong and Y. Guangli, “Biosorption of lead from aqueous solutions by ion-imprinted tetraethylene pentamine modified chitosan beads”, International Journal of Biological Macromolecules, 86, 562-569, 2016. [13] S. Lapwanit, T. Trakulsujaritchok and P. Nongkhai, “Chelating magnetic copolymer composite modified by click reaction for removal of heavy metal ions from aqueous solution”, Chemical Engineering Journal, 289, 286-295, 2016. [14] E. Umukoro, J. Oyekunle, O. Owoyomi, A. Ogunfowokan and I. Oke, “Adsorption characteristics and mechanisms of plantain peel charcoal in removal of Cu (II) and Zn(II) ions from wastewaters”, Ife Journal of Science, 16 , 365, 2014. [15] L. Eun-Hye, Y. Hye-Jung, H. Mi-Sun and B. Dong-Ho, “Development of banana peel jelly and its antioxidant and textural properties”, Food Sci. Biotechnol., 19, 449-455, 2010. [16] S. Lagergren, About the theory of so-called adsorption of soluble substances, 1898. [17] E. Bernard, A. Jimoh and J. Odigwe, “Heavy metals removal from industrial wastewater by activated carbon prepared from coconut shells”, Res. J. Chem. Sci., 3, 3-9, 2013. [18] Y. Ho and G. McKay, “Application of kinetic models to the sorption of Copper (II) onto peat”, Adsorption Science and Technology, 8, 800, 2002. [19] K. Adegboyega, “Chemical Composition of Unripe (Green) and Ripe Plantain (Musa paradisiaca)”, J. Sci. Fd Agric., 24, 703-707, 1973. [20] E. Agama-Acevedo, J. Sanuco-Barajas, R. Velez De La Rocha, G. Gonzalez-Agullar and L. Bello- Perez, “Potential of plantain peels flour (Musa paradisiaca L.) as a source of dietary fiber and antioxidant compound”, CyTA Journal of Food,14, 117-123, 2015. [21] L. Yang, W. Zhong, J. Cui, Z. Wei and W. Wei, “Enhanced removal of Cu (II) ions from aqueous solution by poorly crystalline hydroxyapatite nanoparticles”, Journal of Dispersion Science and Technology, 37, 956-968, 2016. [22] I. Langmuir, “The Adsorption of gases on plane surfaces of glass, mica and platinum”, J. Am. Chem. Soc., 40, 1361-1403, 1918. [23] H. Freundlich, “Ueber thixotropie”, Colloid & Polym. Sci., 46, 289-299, 1928. American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 32, No 1, pp 64-78 78 [24] M. Tempkin and V. Pyzchev, “Kinetics of ammonia synthesis on promoted iron catalyst”, Acta Phys. Chim. USSR, 12, 327, 1940. [25] A. Rais and H. Shaziya, “Absorptive removal of Pb2+, Cu2+ and Ni2+ from the aqueous solution by using groundnut husk modified with Guar Gum (GG): Kinetic and thermodynamic studies”, Groundwater for Sustainable Development, 1, 41-49, 2015. [26] F. Rashidi, R. Sarabi, Z. Ghasemi and A. Seif, “Kinetic, equilibrium and thermodynamic studies for the removal of lead (II) and copper (II) ions from aqueous solutions by nanocrystalline TiO2”, Superlattices and Microstructures, 48, 577-591, 2010. [27] B. Yu, Y. Zhang, A. Shukla, S. Shukla and K. Dorris, “The removal of heavy metal from aqueous solutions by sawdust adsorption removal of copper”, J. Hazard. Mater., 80, 33-42, 2000. [28] E. El-Ashtoukhy, N. Amin and O. Abdelwahab, “Removal of lead (II) and copper (II) from aqueous solution using pomegranate peel as a new adsorbent”, Desalination, 223, 162-173, 2008. [29] H. Ayidin, Y. Bulut and C. Yerlikaya, “Removal of copper (II) from aqueous solution by adsorption onto low-cost adsorbents”, J. Environ. Manag., 87, 37-45, 2008. [30] A. Awwad and M. Salem, “Biosorption of copper (II) and lead (II) ions from aqueous solutions by modified loquat (Eribotrya japonica) leaves (mll).”, J. Chem. Eng. Mater. Sci., 3, 7-17, 2012. [31] T. Bohli, A. Ouederni, N. Fiol and I. Villaescusa, “Evaluation of an activated carbon from olive stones used as an adsorbent for heavy metal removal from aqueous phases”, Comptes Rendus Chim., 18, 88- 99, 2015. [32] S. Milicevic, T. Boljanac, S. Mertinovic, M. Vlahovic, V. Milosevic and B. Babic, “Removal of copper from aqueous solutions by low-cost adsorbent-kolubara lignite”, Fuel Process. Technol., 95, 1-7, 2012. [33] Z. Kong, X. Li, J. Tian, Y. Yang and S. Sun, “Comparative study on the adsorption capacity of raw and modified litchi pericarp for removing Cu(II) from solutions”, J. Environ. Manag., 134, 109-116, 2014. [34] N. Fiol, L. Villaescusca, M. Martinez, N. Miralles, J. Poch and J. Serarols, “Sorption of Pb(II), Ni(II), Cu(II) and Cd(II) from aqueous solution by olive stone waste”, Sep. Purif. Technol., 50, 132-140, 2006.