Insights into Kinetics and Isotherms studies of Cadmium (II) adsorption behavior onto wood biochar from aqueous solution

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Lalhruaitluanga, Lalremruata Hauhnar This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3062902/v2 This work is licensed under a CC BY 4.0 License Status: Posted Version 2 posted You are reading this latest preprint version Show more versions Abstract Objectives: This study aims to investigate the Cd(II) adsorption from aqueous solutions via wood biochar (BC) as an adsorbent, using different parameters, adsorption isotherms, and kinetic models. Methods: Experimental tests were conducted to study the Cd(II) adsorption on a batch mode system. The study evaluated parameters such as pH, contact time, and Cd(II) concentration. To analyze the adsorption mechanism, various isotherms were utilized including Freundlich, Langmuir, Temkin, Redlich-Peterson, Sips, Flory-Huggins, Fowler-Guggenheim, and Harkin-Jura were used. Additionally, Pseudo-first-order and Pseudo-second-order were used to study the kinetics of adsorption. Findings: The Langmuir isotherm suggests that the maximum adsorption capacity ( q max ) is 28.57 mg/g. According to this model, the metal ions are adsorbed by forming a monolayer and do not interact or compete with each other. Based on the Temkin isotherm, it can be concluded that the adsorption of Cd(II) onto BC is mainly physical in nature, as the value of heat of adsorption is less than 1.0 kcal/mol. The Redlich-Peterson and Sips isotherms indicate that the adsorption process follows the Langmuir form and further supports the predominance of monolayer adsorption pattern. The negative value of Gibbs free energy (ΔG o ) suggests that the adsorption process is thermodynamically spontaneous and feasible. The Flory-Huggins and Fowler-Guggenheim isotherms indicate that the active zone of the adsorbent is occupied by adsorbate and also suggest the presence of repulsion between the adsorbate. The kinetics of the adsorption system followed a pseudo-second-order reaction rather than a pseudo-first-order reaction with an R 2 of 0.999 and 0.979, respectively. Novelty and applications: The results of various analyses indicate that the process of wood biochar adsorption is efficient and can be scaled up for the heavy metals removal from contaminated water. Environmental Engineering Adsorption Biochar Cadmium Isotherms Kinetics Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 1 Introduction Anthropogenic activities, such as electroplating, mining operations, battery, and paper manufacturing, disperse heavy metal pollution in water bodies, posing a serious environmental and health risk [1] . Domestic, commercial, and Agricultural sectors will suffer from clean water scarcity due to surface and groundwater contamination by toxic heavy metals [2] . Among all of the heavy metals that are knowingly or unknowingly being discharged into the environment, cadmium is one of the most important ones. Because of the high toxicity and persistence of Cd(II) in natural water and farmland, it has become an increasing concern over the past decades [3] . The recommended Cd(II) level in water is 0.003 mg/L/day [4] . Cadmium is considered the seventh-most hazardous chemical by the US Department of Health and Human Services [5] . Cadmium has harmful effects on the human body and causes hypertension, lung damage, hepatic injury, and renal dysfunction [6] . Long-term exposure to low concentrations of Cd(II) compounds will cause anemia, emphysema, neuralgia, stomach pain, osteoporosis, and other emergencies [7,8] . High levels of cadmium in the environment can have a detrimental impact on soil properties, pH levels, and the composition of microorganisms [9] . Due to its extreme toxicity, Cd(II) must be removed from contaminated water to ensure accessibility of safe and pure water. Hence, Cd(II) must be eliminated from wastewater before it is discharged into the environment. Various physical and chemical techniques have been employed to lower the Cd(II) concentration to meet environmental standards, including chemical precipitation, ionic exchange, adsorption, electrochemical deposition, reverse osmosis, electro-dialysis, electrochemical reduction, ultrafiltration, solvent extraction, evaporation [10] . Although these methods perform well at removing Cd(II) from wastewater, they still have significant disadvantages such as expensive, high sludge production and sometimes ineffective when metal ions present in sewage are at very low concentrations [11] . Considering the efficiencies and costs of various heavy metal removal methods, adsorption is recommended as a fast and universal treatment technology [12,13] . Therefore, identifying an affordable and efficient adsorbent for removing Cd(II) is crucial to ensuring the safety of drinking water and food. Various adsorbents are available, biochar (BC), an effective, low-cost, and eco-friendly adsorbent, has been recommended for heavy metal immobilization in wastewater and contaminated soils [14] . BC is a carbonaceous solid product, it is produced by the pyrolysis of biomass residuals under an oxygen-limited environment [15] . Carbon materials have been reported to perform the best owing to their numerous advantages, such as high stability, excellent removal efficiency, and large surface area [16] . Recently, various types of biochar materials such as banana peel biochar [17] , Clostridium thiosulfatireducens [18] , Ficus virens [19] , grape stalk [20] , Oyster shell [21] , sugar cane bagasse [22] , etc. have been used for Cd(II) adsorption. In Mizoram, wood BC was used for many purposes such as domestic fuels, pit latrines, water filters, etc. Wood BC was obtained by thermal decomposition of wood at a high temperature in the charcoal kiln. For the production of wood BC, the most preferred species were Quercus spp., Mesua ferrea , Anogeissus acuminate , and Vitex peduncularis due to their abundant availability in the area and showed the highest wood density [23] . The aim of this study was to assess the effectiveness of wood BC as an adsorbent in removing Cd (II) from aqueous solutions by analyzing various factors such as pH levels, contact time, and Cd(II) concentration. To explore the adsorption mechanism, we used several isotherms, including Freundlich, Langmuir, Temkin, Redlich-Peterson, Sips, Flory-Huggins, Fowler-Guggenheim, and Harkin-Jura. Additionally, we used Pseudo-first order, and Pseudo-second order models to investigate the kinetics of adsorption. We evaluated the adsorption using an MP-AES Element Analyser. 2 Materials and Methods 2.1 Wood BC as an adsorbent The wood BC was produced by the thermal decomposition of wood at a temperature of 700-800 o C under a reduced oxygen supply inside the charcoal kiln. The charring operation can take about 4-5 h. After the charring operation was completed, the wood BC was milled with a blender and sieved to particles of 100 mesh screens. 2.2 Preparation of stock solution of metal All the chemicals used in this study were analytical grade. A stock solution of cadmium (1000 mg/L) was prepared with miliQ water by weighing 2.036 g of CdCl 2. Different desired concentrations of Cd(II) were prepared by diluting 1000 mg/L of the stock solution. Acid and base solution (1 N HCl and 1 N KOH) were used for pH adjustment. The standard solution of Cd(II) (1000 mg/L) was obtained from SRL. 2.3 Batch mode adsorption studies The adsorption of Cd(II) ions using wood BC was investigated in a batch mode adsorption equilibrium experiment. All batch experiments were carried out in 250 mL conical Erlenmeyer flasks containing 100 mL of each metal solution. The effect of pH on the sorption capacity of wood BC for Cd(II) removal was evaluated in the range of pH 3.0 – 7.0. The pH of each metal solution was adjusted to the required pH value by using 1 N HCl or 1 N NaOH. Then 0.1 g of dried biosorbent was added to the metal solution. The reaction mixture was shaken on an orbital shaker for at 150 rpm, 29 o C for 6 h. which was enough to attain adsorption equilibrium. Similarly, contact time (15-360 min) and Cd(II) concentration (10-50 mg/L) were also conducted. At the end of the experiment, the solutions were separated from the biomass by centrifuging at 10,000 rpm for 8 min. The concentrations of metal in different solutions were analyzed using MP-AES element analysis. The instrument was calibrated with a standard solution. In order to obtain the result, the experiment was conducted in triplicate and the average values were used in this data analysis. The amount of Cd(II) adsorbed onto biochar at equilibrium, q e (mg/g), was calculated by the following Equation 1: 𝑞 𝑒 = (C 0 − C 𝑒 ) ×V/W (1) where C 0 and C e are the initial and equilibrium liquid-phase concentrations of Cd(II), respectively (mg/L), V is the volume of the solution (L), and W is the weight of the adsorbent used (g) 2.4 Adsorbent and its characters The samples were gold sputter coated and the scanning electron microscope (SEM) micrographs were taken by using an XL30 ESEM, Philips, USA to understand the surface morphology of the BC. 3 Results and discussion 3.1 Effect of pH The adsorption of cadmium was found maximum at pH 6 (81.21%) out of the different values of pH viz . 3, 4, 5, and 7. It was however found to be lowest at pH 3 (2.7%) as shown in Fig. 1(a). At pH 6 and 7 there are no significant changes, on the other hand, there is a drastic significant change between pH 3 and 4 for the adsorption capacity of Cd(II). At low pH, there was a high H + ions concentration, which competed with Cd(II) for a binding site at the surface of the negatively charged adsorbent, resulting in the decrease of Cd(II) adsorption. As the pH increases, metal adsorption also increase since ion exchange is more effective when fewer H + ions are available to compete with the metal ions for binding sites onto the BC surface and reached equilibrium at pH 6. At higher pH, the divalent cationic forms decrease, and more soluble or insoluble hydroxylated forms of cadmium increase [24] . The formation of hydroxylated complexes of the metal would also compete with metal ions for the binding sites; as a result the retention decrease again. 3.2 Effect of initial metal concentration The effect of initial metal concentration was studied in the range of 10 – 50 mg/L at 29 o C and pH 6. Cd(II) removal range from 86.53% to 43.46 % as shown in Fig. 1(b). The percentage of Cd(II) adsorption decreased with an increase in Cd(II) ions concentration and showed little decrease in percentage (%) of adsorption at higher concentration. This can be explained that all the adsorbents have a limited number of active sites for Cd(II) to bind, which would become saturated at a certain concentration. So, an increase in initial metal concentration does not increase the sorption process. 3.3 Effect of time Contact time study is also one of the important parameters of adsorption. The effect of contact time was determined at an initial Cd(II) concentration of 20 mg/L and at pH 6. The rate of adsorption was rapid initially and then gradually diminished to attain an equilibrium state at 360 min as shown in Fig. 1(c). The initial fast adsorption is due to the availability of abundant vacant active sites on the adsorbent, as uptake of Cd(II) is normally controlled by physical adsorption from the bulk to the surface of the adsorbent since adsorption phenomenon characteristically tends to attain instantaneous equilibrium [25] . The number of active sites in the system is fixed and each active site can absorb only one ion, therefore metal uptake by the sorbent surface is rapid initially and then decreases as the availability of active sites decreases. 3.4 Adsorption isotherm studies The Cd(II) uptake capacity on the wood BC at different concentrations (10-50 mg/L) on a fixed amount of adsorbent at pH 6.0 has been evaluated using different adsorption isotherm models. 3.4.1 Freundlich isotherm The Freundlich isotherm [26] assumes that monolayer sorption with a heterogeneous energetic distribution of active sites, accompanied by an interaction between adsorbed molecules. It is represented by the following Equation 2: logq e = log K f + (1/n) logC e (2) where C e (mg/L) is the equilibrium concentration, q e (mg/g) is the amount of metal ions adsorbed per specified amount of adsorbent at equilibrium, K f (mg/g) and ‘ n’ are constants which are adsorption capacity and intensity of adsorption, respectively. A graph was plotted log q e versus logC e . The graph gives a straight line with a correlation coefficient (R 2 ) of 0.907 as shown in Fig. 2(a). The slopes and intercepts of the graph were used to calculate the n and K f values. The n value gives information about the favorability of an adsorption process. If n = 0 to 10, which indicates that the sorption process is favorable [27] . In our experiments, the obtained values of n and K f are 2.98 and 9.2 mg/g respectively (Table 1). 3.4.2 Langmuir isotherm The Langmuir isotherm [28] assumes that a solid surface has a finite number of identical sites which are energetically uniform. According to this model, there is no interaction between adsorbed species, which means that the amount adsorbed has no influence on the rate of adsorption. A monolayer was formed when the equilibrium was attained. Its linear mathematical form is as follows: C e / q e = 1/ q max b + C e / q max (3) where C e (mg/L) is the concentration of Cd(II) in solution at equilibrium, q max (mg/g) is the maximum adsorption capacity corresponding to complete monolayer coverage, and b (/mg) is a parameter related to the energy of adsorption. A graph was plotted C e / q e versus C e giving a straight line with a correlation coefficient (R 2 ) of 0.993 as shown in Fig. 2(b). The slopes and intercepts of the graph were used to calculate the q max and b . The values of q max and b were 28.57 mg/g and 0.34, respectively. These values agree well with the theoretical q e value as shown in Table 1. The fitness of the adsorption data of Cd(II) ions to the Langmuir isotherm implies that the adsorbed metal ions do not interact or compete with each other and that they are adsorbed by forming a monolayer. 3.4.3 Temkin Isotherm The Temkin isotherm assumes linear rather than logarithm. The isotherm is used for the determination of physical or chemical sorption [29] . Its linear mathematical form is given as follows: q e = BlnA T + BlnC e (4) where q e is the amount of adsorbate adsorbed at equilibrium (mg/g); C e is the adsorbate concentration in solution at equilibrium (mg/L). B is defined by the expression B=RT/b T , T is the absolute temperature in Kelvin (K); R is the gas constant (8.314 J/mol K); b T is the Temkin constant related to the heat of sorption (J/mol); and A T is the Temkin isotherm constant (L/g). From the plot of q e vs lnC e , b T and A T can be calculated (b T = 461.8 J/mol) and intercepts (A T = 4.69) respectively as shown in Fig. 3(a). According to the Tempkin isotherm, physical adsorption occurs if the heat of the adsorption value is less than 1.0 kcal/mol. Furthermore, with a value of 20–50 kcal/mol, chemisorption occurs. If the heat of adsorption value is between the two (1–20 kcal/mol), both physisorption and chemisorption are involved in the adsorption [30] . The Cd(II) adsorption onto BC is predominantly physical adsorption since the heat of adsorption value is less than 1.0 kcal/mol. 3.4.4 Redlich - Peterson (R-P) Isotherm The R-P equation contains three parameters and incorporates the features of the Langmuir and Freundlich isotherms [31] . The R-P isotherm can be described as follows: q e = K RP C e /1 + a RP C e β (5) where K RP , a RP , and β are the R-P parameters. A non-linear graph was plotted C e versus q e as shown in Fig. 3(b) and the three parameters of R-P isotherm were calculated to describe the adsorption of Cd(II) ions and are shown in Table 1. β lies between 0 and 1. For β =1, the R-P equation converts to Langmuir form. The calculated β value is 1.01 with a high regression coefficient (R 2 ) of 0.999 which is very close to unity than “0”. This indicates that the adsorption process follows the Langmuir form and further supports the predominance of monolayer adsorption. 3.4.5 Sips Isotherm The Sips isotherm also called the Langmuir-Freundlich isotherm equation is characterized by the heterogeneity factor, “n” and is employed to describe the heterogeneity of sorbent surface if 0 < n < 1. The isotherm can be expressed as: q e = q m K LF C e n /1 + K LF C e n (6) where C e is the equilibrium concentration of the adsorbate (mg/L), q m and K LF are the Sips maximum adsorption capacity (mg/g) and Sips equilibrium constant (L/mg), respectively. The value of n is the heterogeneity factor, employed to describe the system’s heterogeneity when n is between 0 and 1. When 𝑛 = 1, the Sips equation reduces to the Langmuir equation and implies a homogeneous adsorption process [32] . A non-linear graph was plotted C e versus q e as shown in Fig. 3(c). The parameters of Sips isotherm were calculated, and the value of n is calculated as 1.05 i.e. ≈1 with an R 2 of 0.991. This indicated that the adsorption pattern follows Langmuir isotherm and the estimated q m value is also very close to the q m value obtained according to Langmuir isotherm (Table 1). 3.4.6 Flory-Huggins Isotherm The Flory-Huggins isotherm [33] was used to evaluate the degree of surface coverage characteristics of adsorbate on the adsorbent and is expressed in its linear form by the following Equation 7: ln(θ/Ci) = lnK FH + n FH ln(1-θ) (7) where θ = (1 - Ce/Ci) is the degree of surface coverage, K FH (L/mol) and n FH represent the Flory-Huggins equilibrium isotherm constant and model exponent, respectively. A linear plot of ln (θ/Ci) versus ln (1 – θ), K FH and n FH can be calculated (n FH = -1.48) and intercepts (K FH = 0.0039 L/mol) with an R 2 of 0.986 as shown in Fig. 4(a). In addition, the K FH value is used to calculate spontaneity Gibbs free energy (ΔG o ) [34] . The negative value of ΔG o = -13.86 kJ/mol (Table 1) indicates that the adsorption process is thermodynamically spontaneous and feasible [35] . If n FH >1, indicates multilayer adsorption of molecules on the adsorbent surface, if n FH < 1, indicates an active zone of the adsorbent would be occupied by adsorbate [36] . Therefore, the value of n FH is less than one, indicating that the adsorbent's active zone has been occupied by the adsorbate. 3.4.7 Fowler-Guggenheim isotherm The Fowler and Guggenheim [37] explain whether the lateral interaction between adsorbed molecules in the solid phase existed or not. The linearized form of this model is expressed by: lnC e (1-θ)/θ = -lnK FG + 2Wθ/RT (8) where K FG is the Fowler-Guggenheim equilibrium constant (L/mg), θ = (1-C e /C o ) is the degree of surface coverage, W is the interaction energy between adsorbed molecules (kJ/mol), R is the universal gas constant, 8.314 J/kmol and T is the absolute temperature (K). From a linear plot of lnC e (1-θ)/θ versus θ as shown in Fig. 4(b), W and K FH can be calculated (W = -12.04 kJ/mol), and intercepts (K FG = 4.02x10 -4 L/mg), respectively with R 2 of 0.99 (Table. 1). If W value is positive, the interaction between the adsorbed molecules is attractive. On the other hand, if W is negative, the interaction among adsorbed molecules is repulsive. If W is equal to 0, there is no interaction between adsorbed molecules. Therefore, the calculated value of W is negative, which indicates the presence of repulsion between the adsorbed molecules and R 2 = 0.99 which also implies the existence of a monolayer on the surface of the adsorbent [38] . 3.4.8 Harkin-Jura Isotherm The Harkin-Jura isotherm model [39] assumes the possibility of multilayer adsorption on the surface of absorbents having heterogeneous pore distribution. This model is expressed as follows: 1/q e 2 = B/A− (1/A ) log C e (9) The plot of 1/q e 2 versus logC e gave a correlation coefficient of 0.761 as shown in Fig. 4(c) with the values of A = 142.85 and B = 1.57 respectively, as Harkin-Jura Isotherm model constants (Table 1). The R 2 value was only 0.761, lesser than that of monolayer adsorption models of Langmuir and could not be the best fit for the adsorption. This indicates that the multilayer adsorption process is not followed. 3.5 Sorption kinetics studies To explain the mechanism of Cd(II) adsorption kinetics and the potential rate-controlling steps, Pseudo-first-order, and Pseudo-second-order kinetics models are used. 3.5.1 Pseudo-first-order reaction The Pseudo-first-order model [40] for solid/liquid systems of adsorption stated that the rate is proportional to the number of unoccupied sites. It is expressed as: log( q e – q t ) = log q e – k 1 t /2.303 (10) where q e and q t are the amounts of cadmium adsorbed on the adsorbent at equilibrium and at any time t, respectively, and k 1 is the rate constant of pseudo-first-order sorption. The slopes and intercepts of a plot of log ( q e – q t ) versus t (Fig. 5a) were used to calculate the first-order rate constant k 1 = 39.15x10 -3 /min and equilibrium adsorption capacity q e . = 13.03 mg/g. 3.5.2 Pseudo-second-order reaction The Pseudo-second-order [41] assumes that the rate of sorption is proportional to the square of the number of unoccupied sites. It is expressed as: t/ q t = 1/k 2 q e 2 + t/ q e (11) where k 2 is the equilibrium rate constant. The slopes and intercepts of plots t/ q t versus t (Fig. 5b) were used to calculate the pseudo-second-order rate constants k 2 = 6.42x10 -3 g/mg/min and q e = 16.66 mg/g. The correlation coefficient (R 2 ) of the pseudo-second-order kinetics model is 0.999. The experimental q e value of 16.18 mg/g was also agreed well with the calculated q e value of 16.66 mg/g. On the other hand, the correlation coefficients of a pseudo-first-order kinetics model were lower than the pseudo-second-order kinetics model as shown in Table 2. Therefore, it can be concluded that this adsorption system followed a pseudo-second-order reaction rather than a pseudo-first-order reaction. This suggests that the sorption of the metal ions involves two species, in this case, the metal ion and the biomass. 3.6 Adsorbant and its characters An SEM micrograph indicates that the adsorbent surface has multiple pores. These pores vary in size, with the smaller ones measuring 1.36 μm in diameter, while the larger ones have a diameter of 16.3 μm (Fig. 6). The presence of different pore sizes on the adsorbent can enhance the adsorption process by increasing the surface area available for adsorption. 4 Conclusions The purpose of this study was to evaluate the effectiveness of wood-based biochar as an adsorbent for removing Cd(II) from an aqueous solution. It was found that the maximum adsorption of Cd(II) occurred at a pH of 6. After 120 minutes, the adsorption of Cd(II) did not significantly increase. 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[24] Goswami M, Phukan P. Enhanced adsorption of cationic dyes using sulfonic acid modified activated carbon. Journal of Environmental Chemical Engineering . 2017;5(4):3508–3517. Available from: https://doi.org/10.1016/j.jece.2017.07.016. [25] Das B, Mondal NK. Calcareous soil as new adsorbent to remove lead from aqueous solution: equilibrium, kinetic and thermodynamic study. Environmental Research and Technology. 2011;1:515-530. [26] Freundlich H. Ueber die adsorption in loesungen. Zeitschrift fr Physikalische Chemie. 1907;57:385-470. [27] Ahmadi S, Mohammadi L, Rahdar A, Rahdar S, Dehghani R, Igwegbe CA, Kyzas GZ. Acid Dye Removal from Aqueous Solution by Using Neodymium(III) Oxide Nanoadsorbents. Nanomaterials. 2020;10:556. Available from: https://doi.org/10.3390/nano10030556. [28] Langmuir I. The constitution and fundamental properties of solids and liquids. Journal of The American Chemical Society. 1916;38:2221-2295. [29] Temkin MI, Pyzhev V. Kinetics of ammonia synthesis on promoted iron catalyst. Acta USSR. 1940;12:327–356. [30] Ettish MN, Gharieb E, Mohamed EA, Osama A. Preparation and characterization of new adsorbent from Cinnamon waste by physical activation for removal of Chlorpyrifos. Environmental Challenge. 2021;5:100208. Available from: http://dx.doi.org/10.1016/j.envc.2021.100208. [31] Redlich OJ, Peterson DL. Useful adsorption isotherm. Journal of Physical Chemistry. 1959;63:1024. Available from: http://dx.doi.org/10.1021/j150576a611. [32] Allen SJ, Mckay G, Porter JF. Adsorption isotherm models for basic dye adsorption by peat in single and binary component systems. Journal of Colloid Interface Science. 2004;280:322–333. Available from: https://doi.org/10.1016/j.jcis.2004.08.078. [33] Chaba JM, Nomngongo PN. Effective adsorptive removal of amoxicillin from aqueous solutions and wastewater samples using zinc oxide coated carbon nanofiber composite. Emerging Contaminants. 2019;5:143-149. Available from: https://doi.org/10.1016/j.emcon.2019.04.001. [34] Foo KY, Hameed BH. 2010 Insights into the modeling of adsorption isotherm systems. Chemical Engineering Journal . 2010;156 :2-10. Available from: https://doi.org/10.1016/j.cej.2009.09.013. [35] Rangabhashiyam S, Anu N, Giri Nandagopal MS, Selvaraju N. Relevance of isotherm models in biosorption of pollutants by agricultural byproducts. Journal of Environmental Chemical Engineering . 2014;2:398 – 414. Available from: https://doi.org/10.1016/j.jece.2014.01.014. [36] Cesaro A, Naddeo V, Belgiorno V. Wastewater Treatment by Combination of Advanced Oxidation Processes and Conventional Biological Systems. Journal of Bioremediation & Biodegradation . 2013;4:208. Available from: http://doi.org/10.4172/2155-6199.1000208. [37] Fowler RH, Guggenheim EA. Statistical Thermodynamics, Cambridge University Press, London, 1939. 431-450 p. [38] Ragadhita R, Nandiyanto A. How to Calculate Adsorption Isotherms of Particles Using Two-Parameter Monolayer Adsorption Models and Equations. Indonesian Journal of Science and Technology. 2021;6: 205-234. Available from: http://dx.doi.org/10.17509/ijost.v6i1.32354 . [39] Harkins WD. Jura G. Surfaces of Solids. XI. Determination of the Decrease (π) of Free Surface Energy of a Solid by an Adsorbed Film. Journal of the American Chemical Society. 1944;67:1356-1362. Available from: http://dx.doi.org/10.1021/ja01236a046 . [40] Lagergren S. About the theory of so-called adsorption of soluble substances. Kungliga Suenska Vetenskapsakademiens Handlingar 1898;241:1-39. [41] Ho YS, McKay G. Pseudo-second order model for sorption process. Process Biochemtry. 1999;34:451-465. Available from: https://doi.org/10.1016/S0032-9592(98)00112-5 . Declarations Acknowledgements The author gracefully acknowledged the Department of Chemistry, Mizoram University for allowing us to utilize instrument facilities. Author contributions This work was furnished out in collaboration between both authors. HLT designed the study, wrote the protocol, data collection, and analysis. LRH helps in literature search, evaluation, and participated in writing the manuscript. Competing Interest The authors have no relevant financial or non-financial interests to declare Funding The authors declare that no funds, grants, or other support were received during the preparation of this manuscript. Ethical Approval No experimental animal and/or human are used in this research. Therefore, not applicable in this section. Availability of data and materials The authors declare that the data supporting the findings of this study are available within the paper. Should any raw data files be needed in another format they are available from the corresponding author upon reasonable request. Tables Table 1 Different adsorption isotherm models with their Parameters for the adsorption of Cd(II) onto biochar Table 2 Different adsorption Kinetic models with their Parameters for the adsorption of Cd(II) onto biochar Additional Declarations The authors declare no competing interests. Cite Share Download PDF Status: Posted Version 2 posted You are reading this latest preprint version Show more versions Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-3062902","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":213390622,"identity":"b883bfa3-0302-4304-8348-897e96037a5f","order_by":0,"name":"H. Lalhruaitluanga","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA6UlEQVRIiWNgGAWjYFACHhAhwcDG3n7wAYjLR7QWPp4zyQYgLhuRWhgY5CQSzCRADIJadNvPHvvMU2Mhz8aQkFb5NcdOho2B+eGjG3i0mJ3JS57Nc0zCsI3h4LHbstuSgQ5jMzbOwaflQI4xMw+bBGMbY0PabcltQDbQO9J4tZx/A9TyT8K+jZnBrFhyWz0RWm4AbeFtk0hsY2MwY/y47TAxWt4YM87tk0hu4+FJlmbcdpyHjZmQX87nGDO8+VZnO3/+84Mff26rtudnb374GJ8WFMAMjiNmYpWDAOMPUlSPglEwCkbBiAEAExI/5vYeoqMAAAAASUVORK5CYII=","orcid":"","institution":"Mizoram University Aizawl","correspondingAuthor":true,"prefix":"","firstName":"H.","middleName":"","lastName":"Lalhruaitluanga","suffix":""},{"id":213390623,"identity":"adba1a5d-c69b-4374-aacc-abf2fb962012","order_by":1,"name":"Lalremruata Hauhnar","email":"","orcid":"","institution":"Government Champhai College Champhai","correspondingAuthor":false,"prefix":"","firstName":"Lalremruata","middleName":"","lastName":"Hauhnar","suffix":""}],"badges":[],"createdAt":"2023-06-14 12:14:26","currentVersionCode":2,"declarations":{"humanSubjects":false,"vertebrateSubjects":false,"conflictsOfInterestStatement":false,"humanSubjectEthicalGuidelines":false,"humanSubjectConsent":false,"humanSubjectClinicalTrial":false,"humanSubjectCaseReport":false,"vertebrateSubjectEthicalGuidelines":false},"doi":"10.21203/rs.3.rs-3062902/v2","doiUrl":"https://doi.org/10.21203/rs.3.rs-3062902/v2","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":54456696,"identity":"5f43b1e3-7ee4-441a-98cb-887af1814cff","added_by":"auto","created_at":"2024-04-10 19:44:11","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":112716,"visible":true,"origin":"","legend":"\u003cp\u003eEffect of (a) pH;(b) Initial metal concentration; (c) Contact time for the Cd(II) adsorption.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-3062902/v2/c327d024fa638648fe87a79d.png"},{"id":54456698,"identity":"3e36b693-77d1-487f-bb83-941be0c40db4","added_by":"auto","created_at":"2024-04-10 19:44:11","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":66118,"visible":true,"origin":"","legend":"\u003cp\u003eIsotherms studies: (a) Freundlich isotherm; (b) Langmuir isotherm model for the sorption of Cd(II).\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-3062902/v2/248002219f5e61eb235cadbd.png"},{"id":54457073,"identity":"4580810d-cf00-48db-97a6-24782e61c000","added_by":"auto","created_at":"2024-04-10 19:52:12","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":108062,"visible":true,"origin":"","legend":"\u003cp\u003eIsotherms studies: (a) Temkin isotherm; (b) Redlich - Peterson isotherm; (c) Sips isotherm.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-3062902/v2/b6960fae242cc87affc47cb9.png"},{"id":54456695,"identity":"a2abfc5b-06d9-411c-88c8-cd41fa754e0d","added_by":"auto","created_at":"2024-04-10 19:44:11","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":96820,"visible":true,"origin":"","legend":"\u003cp\u003eIsotherms studies: (a) Flory-Huggins isotherm; (b) Fowler–Guggenheim isotherm; (c) Harkin-Jura isotherm for Cd(II) adsorption.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-3062902/v2/551e460ae37927ec7280c6c4.png"},{"id":54456700,"identity":"ba8c11b8-9b55-455b-b68b-c907eb8e36f0","added_by":"auto","created_at":"2024-04-10 19:44:11","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":69172,"visible":true,"origin":"","legend":"\u003cp\u003ea) Pseudo-First-Order reaction; and b) Pseudo-Second-Order reaction for Cd(II) onto wood biochar.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-3062902/v2/24dfa3cfedaf3ecca68e0444.png"},{"id":54456699,"identity":"033ea3d9-6e83-4556-8d17-f3197ce250e0","added_by":"auto","created_at":"2024-04-10 19:44:11","extension":"jpg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":44778,"visible":true,"origin":"","legend":"\u003cp\u003eSEM micrograph revealing the present of different pores on the surface of wood biochar adsorbent.\u003c/p\u003e","description":"","filename":"Fig6.jpg","url":"https://assets-eu.researchsquare.com/files/rs-3062902/v2/e431552d57c1d760706c768e.jpg"},{"id":54457394,"identity":"e9bdca7e-6f4a-43da-8ba9-7d2ea0ec3988","added_by":"auto","created_at":"2024-04-10 20:00:12","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":600018,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3062902/v2/b243b325-5f41-464e-9a8e-8bb73943522c.pdf"}],"financialInterests":"The authors declare no competing interests.","formattedTitle":"\u003cp\u003e\u003cstrong\u003eInsights into Kinetics and Isotherms studies of Cadmium (II) adsorption behavior onto wood biochar from aqueous solution\u003c/strong\u003e\u003c/p\u003e","fulltext":[{"header":"1 Introduction","content":"\u003cp\u003eAnthropogenic activities, such as electroplating, mining operations, battery, and paper manufacturing, disperse heavy metal pollution in water bodies, posing a serious environmental and health risk\u003csup\u003e\u0026nbsp;[1]\u003c/sup\u003e. Domestic, commercial, and Agricultural sectors will suffer from clean water scarcity due to surface and groundwater contamination by toxic heavy metals \u003csup\u003e[2]\u003c/sup\u003e.\u0026nbsp;Among all of the heavy metals that are knowingly or unknowingly being discharged into the environment, cadmium is one of the most important ones. Because of the high toxicity and persistence of Cd(II) in natural water and farmland, it has become an increasing concern over the past decades \u003csup\u003e[3]\u003c/sup\u003e.\u0026nbsp;The recommended\u0026nbsp;Cd(II) level in water is 0.003 mg/L/day \u003csup\u003e[4]\u003c/sup\u003e.\u0026nbsp;Cadmium is considered the seventh-most hazardous chemical by the US Department of Health and Human Services \u003csup\u003e[5]\u003c/sup\u003e. Cadmium has harmful effects on the human body and causes hypertension, lung damage, hepatic injury, and renal dysfunction \u003csup\u003e[6]\u003c/sup\u003e.\u0026nbsp;Long-term exposure to low concentrations of Cd(II) compounds will cause anemia, emphysema, neuralgia, stomach pain, osteoporosis, and other emergencies \u003csup\u003e[7,8]\u003c/sup\u003e. High levels of cadmium in the environment can have a detrimental impact on soil properties, pH levels, and the composition of microorganisms\u003csup\u003e\u0026nbsp;[9]\u003c/sup\u003e.\u0026nbsp;\u0026nbsp;Due to its extreme toxicity, Cd(II) must be removed from contaminated water to ensure accessibility of safe and pure water. Hence, Cd(II) must be eliminated from wastewater before it is discharged into the environment. Various physical and chemical techniques have been employed to lower the Cd(II) concentration to meet environmental standards, including chemical precipitation, ionic exchange, adsorption, electrochemical deposition, reverse osmosis, electro-dialysis, electrochemical reduction, ultrafiltration, solvent extraction, evaporation \u003csup\u003e[10]\u003c/sup\u003e. Although these methods perform well at removing Cd(II) from wastewater, they still have significant disadvantages such as expensive, high sludge production and sometimes ineffective when metal ions present in sewage are at very low concentrations \u003csup\u003e[11]\u003c/sup\u003e.\u0026nbsp;Considering the efficiencies and costs of various heavy metal removal methods, adsorption is recommended as a fast and universal treatment technology \u003csup\u003e[12,13]\u003c/sup\u003e.\u0026nbsp;Therefore, identifying an affordable and efficient adsorbent for removing Cd(II) is crucial to ensuring the safety of drinking water and food. Various adsorbents are available,\u0026nbsp;biochar (BC), an effective, low-cost, and eco-friendly adsorbent, has been recommended for heavy metal immobilization in wastewater and contaminated soils\u0026nbsp;\u003csup\u003e[14]\u003c/sup\u003e. BC is a carbonaceous solid product, it \u0026nbsp;is produced by the pyrolysis of biomass residuals under an oxygen-limited environment \u003csup\u003e[15]\u003c/sup\u003e.\u0026nbsp;Carbon materials have been reported to perform the best owing to their numerous advantages, such as high stability, excellent removal efficiency, and large surface area \u003csup\u003e[16]\u003c/sup\u003e.\u0026nbsp;Recently, various types of biochar materials such as banana peel biochar \u003csup\u003e[17]\u003c/sup\u003e,\u0026nbsp;\u003cem\u003eClostridium thiosulfatireducens\u0026nbsp;\u003c/em\u003e\u003csup\u003e[18]\u003c/sup\u003e,\u0026nbsp;\u003cem\u003eFicus virens\u0026nbsp;\u003c/em\u003e\u003csup\u003e[19]\u003c/sup\u003e,\u0026nbsp;grape stalk \u003csup\u003e[20]\u003c/sup\u003e, Oyster shell \u003csup\u003e[21]\u003c/sup\u003e, sugar cane bagasse \u003csup\u003e[22]\u003c/sup\u003e,\u0026nbsp;etc. have been used for Cd(II) adsorption.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eIn Mizoram, wood BC was used for many purposes such as domestic fuels, pit latrines, water filters, etc. Wood BC was obtained by thermal decomposition of wood at a high temperature in the charcoal kiln. For the production of wood BC, the most preferred species were Quercus spp., \u003cem\u003eMesua ferrea\u003c/em\u003e, \u003cem\u003eAnogeissus acuminate\u003c/em\u003e, and \u003cem\u003eVitex peduncularis\u003c/em\u003e due to their abundant availability in the area and showed the highest wood density \u003csup\u003e[23]\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eThe aim of this study was to assess the effectiveness of wood BC as an adsorbent in removing Cd (II) from aqueous solutions by analyzing various factors such as pH levels, contact time, and Cd(II) concentration. To explore the adsorption mechanism, we used several isotherms, including Freundlich, Langmuir, Temkin, Redlich-Peterson, Sips, Flory-Huggins, Fowler-Guggenheim, and Harkin-Jura. Additionally, we used Pseudo-first order, and Pseudo-second order models to investigate the kinetics of adsorption. We evaluated the adsorption using an MP-AES Element Analyser.\u003c/p\u003e"},{"header":"2 Materials and Methods","content":"\u003cp\u003e\u003cstrong\u003e2.1 Wood BC as an adsorbent\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe wood BC was produced by the thermal decomposition of wood at a temperature of\u0026nbsp;700-800\u003csup\u003eo\u003c/sup\u003eC under a reduced oxygen supply inside the charcoal kiln. The charring operation can take about 4-5 h. After the charring operation was completed, the wood BC was milled with a blender and sieved to particles of 100 mesh screens.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e2.2 Preparation of stock solution of metal\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll the chemicals used in this study were analytical grade. A stock solution of cadmium (1000 mg/L) was prepared with miliQ water by weighing 2.036 g of CdCl\u003csub\u003e2.\u0026nbsp;\u003c/sub\u003eDifferent desired concentrations of Cd(II) were prepared by diluting 1000 mg/L of the stock solution. Acid and base solution (1 N HCl and 1 N KOH) were used for pH adjustment. The standard solution of Cd(II) (1000 mg/L) was obtained from\u0026nbsp;SRL.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e2.3 Batch mode adsorption studies\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe adsorption of Cd(II) ions using wood BC was investigated in a batch mode adsorption equilibrium experiment. All batch experiments were carried out in 250 mL conical Erlenmeyer flasks containing 100 mL of each metal solution. The effect of pH on the sorption capacity of wood BC for Cd(II) removal was evaluated in the range of pH 3.0 \u0026ndash; 7.0. The pH of each metal solution was adjusted to the required pH value by using 1 N HCl or 1 N NaOH. \u0026nbsp;Then 0.1 g of dried biosorbent was added to the metal solution. The reaction mixture was shaken on an orbital shaker for at 150 rpm, 29 \u003csup\u003eo\u003c/sup\u003eC for 6 h. which was enough to attain adsorption equilibrium. Similarly, contact time (15-360 min) and Cd(II) concentration (10-50 mg/L) were also conducted. At the end of the experiment, the solutions were separated from the biomass by centrifuging at 10,000 rpm for 8 min. The concentrations of metal in different solutions were analyzed using MP-AES element analysis. The instrument was calibrated with a standard solution. In order to obtain the result, the experiment was conducted in triplicate and the average values were used in this data analysis. The amount of Cd(II) adsorbed onto biochar at equilibrium, q\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e (mg/g), was calculated by the following Equation 1:\u003c/p\u003e\n\u003cp\u003e𝑞\u003cem\u003e\u003csub\u003e𝑒\u003c/sub\u003e\u003c/em\u003e = (C\u003cem\u003e\u003csub\u003e0\u003c/sub\u003e\u003c/em\u003e \u0026minus;\u0026nbsp;C\u003cem\u003e\u003csub\u003e𝑒\u003c/sub\u003e\u003c/em\u003e) \u0026times;V/W\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;(1)\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003ewhere C\u003cem\u003e\u003csub\u003e0\u0026nbsp;\u003c/sub\u003e\u003c/em\u003eand C\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u0026nbsp;\u003c/em\u003eare the initial and equilibrium liquid-phase concentrations of Cd(II), respectively (mg/L), V\u003cem\u003e\u0026nbsp;\u003c/em\u003eis the volume of the solution (L), and W\u003cem\u003e\u0026nbsp;\u003c/em\u003eis the weight of the adsorbent used (g)\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e2.4 Adsorbent and its characters\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe samples were gold sputter coated and the scanning electron microscope (SEM) micrographs were taken by using an XL30 ESEM, Philips, USA to understand the surface morphology of the BC.\u003c/p\u003e"},{"header":"3 Results and discussion","content":"\u003cp\u003e\u003cstrong\u003e3.1 Effect of pH\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe adsorption of cadmium was found maximum at pH 6 (81.21%) out of the different values of pH \u003cem\u003eviz\u003c/em\u003e. 3, 4, 5, and 7. It was however found to be lowest at pH 3 (2.7%) as shown in Fig. 1(a). At pH 6 and 7 there are no significant changes, on the other hand, there is a drastic significant change between pH 3 and 4 for the adsorption capacity of Cd(II). At low pH, there was a high H\u003csup\u003e+\u003c/sup\u003e ions concentration, which competed with Cd(II) for a binding site at the surface of the negatively charged adsorbent, resulting in the decrease of Cd(II) adsorption. As the pH increases, metal adsorption also increase since ion exchange is more effective when fewer H\u003csup\u003e+\u003c/sup\u003e ions are available to compete with the metal ions for binding sites onto the BC surface and reached equilibrium at pH 6. At higher pH, the divalent cationic forms decrease, and more soluble or insoluble hydroxylated forms of cadmium increase \u003csup\u003e[24]\u003c/sup\u003e. The formation of hydroxylated complexes of the metal would also compete with metal ions for the binding sites; as a result the retention decrease again.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.2 Effect of initial metal concentration\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe effect of initial metal concentration was studied in the range of 10 \u0026ndash; 50 mg/L at 29\u003csup\u003eo\u003c/sup\u003eC and pH 6. Cd(II) removal range from 86.53% to 43.46 % as shown in Fig. 1(b). The percentage of Cd(II) adsorption decreased with an increase in Cd(II) ions concentration and showed little decrease in percentage (%) of adsorption at higher concentration. This can be explained that all the adsorbents have a limited number of active sites for Cd(II) to bind, which would become saturated at a certain concentration. So, an increase in initial metal concentration does not increase the sorption process.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.3 Effect of time\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eContact time study is also one of the important parameters of adsorption. The effect of contact time was determined at an initial Cd(II) concentration of 20 mg/L and at pH 6.\u0026nbsp;The rate of\u0026nbsp;adsorption was rapid initially\u0026nbsp;and\u0026nbsp;then gradually diminished to attain an equilibrium state at 360 min as shown in Fig. 1(c).\u0026nbsp;The initial fast adsorption is due to\u0026nbsp;the availability of abundant vacant active sites on the adsorbent, as\u0026nbsp;uptake of Cd(II)\u0026nbsp;is normally controlled by\u0026nbsp;physical adsorption\u0026nbsp;from the bulk to the surface of the adsorbent\u0026nbsp;since adsorption phenomenon characteristically tends to attain instantaneous equilibrium \u003csup\u003e[25]\u003c/sup\u003e.\u0026nbsp;The number of active sites in the system is fixed and each active site can absorb only one ion, therefore metal uptake by the sorbent surface is rapid initially and then decreases as the availability of active sites decreases.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.4 Adsorption isotherm studies\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe Cd(II) uptake capacity on the wood BC at different concentrations (10-50 mg/L) on a fixed amount of adsorbent at pH 6.0 has been evaluated using different adsorption isotherm models.\u003c/p\u003e\n\u003cp\u003e3.4.1 Freundlich isotherm\u003c/p\u003e\n\u003cp\u003eThe Freundlich isotherm\u003csup\u003e\u0026nbsp;[26]\u003c/sup\u003e assumes that monolayer sorption with a heterogeneous energetic distribution of active sites, accompanied by an interaction between adsorbed molecules. It is represented by the following Equation 2:\u003c/p\u003e\n\u003cp\u003elogq\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u0026nbsp;\u003c/em\u003e= log K\u003cem\u003e\u003csub\u003ef\u003c/sub\u003e\u003c/em\u003e + (1/n) logC\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;(2)\u003c/p\u003e\n\u003cp\u003ewhere C\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e (mg/L) is the equilibrium concentration, \u003cem\u003eq\u003csub\u003ee\u0026nbsp;\u003c/sub\u003e\u003c/em\u003e(mg/g) is the amount of metal ions adsorbed per specified amount of adsorbent at equilibrium, K\u003cem\u003e\u003csub\u003ef\u003c/sub\u003e\u003c/em\u003e\u0026nbsp; (mg/g) and \u0026lsquo;\u003cem\u003en\u0026rsquo;\u003c/em\u003e are constants which are adsorption capacity and intensity of adsorption, respectively. A graph was plotted log\u003cem\u003eq\u003csub\u003ee\u0026nbsp;\u003c/sub\u003e\u003c/em\u003eversus logC\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e. The graph gives a straight line with a correlation coefficient (R\u003csup\u003e2\u003c/sup\u003e) of 0.907 as shown in Fig. 2(a). The slopes and intercepts of the graph were used to calculate the \u003cem\u003en\u0026nbsp;\u003c/em\u003eand K\u003cem\u003e\u003csub\u003ef\u003c/sub\u003e\u003c/em\u003e values. \u0026nbsp;The \u003cem\u003en\u003c/em\u003e value gives information about the favorability of an adsorption\u0026nbsp;process. If n = 0 to 10, which indicates that the sorption process is favorable \u003csup\u003e[27]\u003c/sup\u003e.\u0026nbsp;In our experiments, the obtained values of \u003cem\u003en\u0026nbsp;\u003c/em\u003eand K\u003cem\u003e\u003csub\u003ef\u003c/sub\u003e\u003c/em\u003e are\u0026nbsp;2.98 and 9.2\u0026nbsp;mg/g\u0026nbsp;respectively (Table 1).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e3.4.2 Langmuir isotherm\u003c/p\u003e\n\u003cp\u003eThe Langmuir isotherm\u003csup\u003e\u0026nbsp;[28]\u003c/sup\u003e assumes that a solid surface has a finite number of identical sites which are energetically uniform. According to this model, there is no interaction between adsorbed species, which means that the amount adsorbed has no influence on the rate of adsorption. A monolayer was formed when the equilibrium was attained. Its linear mathematical form is as follows:\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eC\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e/\u003cem\u003eq\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e = 1/\u003cem\u003eq\u003c/em\u003e\u003csub\u003emax\u003c/sub\u003e\u003cem\u003eb\u003c/em\u003e + C\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e/\u003cem\u003eq\u003c/em\u003e\u003csub\u003emax\u003c/sub\u003e\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;(3)\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003ewhere C\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e (mg/L) is the concentration of Cd(II) in solution at equilibrium, \u003cem\u003eq\u003c/em\u003e\u003csub\u003emax\u003c/sub\u003e (mg/g) is the maximum adsorption capacity corresponding to complete monolayer coverage, and \u003cem\u003eb\u003c/em\u003e (/mg) is a parameter related to the energy of adsorption. A graph was plotted C\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e/\u003cem\u003eq\u003c/em\u003e\u003csub\u003ee\u003c/sub\u003e versus C\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e giving a straight line with a correlation coefficient (R\u003csup\u003e2\u003c/sup\u003e) of 0.993 as shown in Fig. 2(b). The slopes and intercepts of the graph were used to calculate the \u003cem\u003eq\u003c/em\u003e\u003csub\u003emax\u0026nbsp;\u003c/sub\u003eand \u003cem\u003eb\u003c/em\u003e. The values of \u003cem\u003eq\u003c/em\u003e\u003csub\u003emax\u003c/sub\u003e and b were 28.57 mg/g and 0.34, respectively. These values agree well with the theoretical \u003cem\u003eq\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e value as shown in Table 1. The fitness of the adsorption data of Cd(II) ions to the Langmuir isotherm implies that the adsorbed metal ions do not interact or compete with each other and that they are adsorbed by forming a monolayer.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e3.4.3 Temkin Isotherm\u003c/p\u003e\n\u003cp\u003e\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;The Temkin isotherm assumes linear rather than logarithm. The isotherm is used for the determination of physical or chemical sorption \u003csup\u003e[29]\u003c/sup\u003e. Its linear mathematical form is given as follows:\u003c/p\u003e\n\u003cp\u003eq\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u0026nbsp;\u003c/em\u003e= BlnA\u003cem\u003e\u003csub\u003eT\u003c/sub\u003e\u003c/em\u003e + BlnC\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;(4)\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003ewhere q\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e is the amount of adsorbate adsorbed at equilibrium (mg/g); C\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e is the adsorbate concentration in solution at equilibrium (mg/L). B is defined by the expression B=RT/b\u003cem\u003e\u003csub\u003eT\u003c/sub\u003e\u003c/em\u003e, T is the absolute temperature in Kelvin (K); R is the gas constant (8.314 J/mol K); b\u003cem\u003e\u003csub\u003eT\u003c/sub\u003e\u003c/em\u003e is the Temkin constant related to the heat of sorption (J/mol); and A\u003cem\u003e\u003csub\u003eT\u003c/sub\u003e\u003c/em\u003e is the Temkin isotherm constant (L/g). From the plot of q\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e vs lnC\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e, b\u003cem\u003e\u003csub\u003eT\u003c/sub\u003e\u003c/em\u003e and A\u003cem\u003e\u003csub\u003eT\u003c/sub\u003e\u0026nbsp;\u003c/em\u003ecan be calculated (b\u003cem\u003e\u003csub\u003eT\u003c/sub\u003e\u003c/em\u003e = 461.8 J/mol) and intercepts (A\u003cem\u003e\u003csub\u003eT\u003c/sub\u003e\u003c/em\u003e = 4.69) respectively as shown in Fig. 3(a).\u003c/p\u003e\n\u003cp\u003eAccording to the Tempkin isotherm, physical adsorption occurs if the heat of the adsorption value is less than 1.0 kcal/mol. Furthermore, with a value of 20\u0026ndash;50 kcal/mol, chemisorption occurs. If the heat of adsorption value is between the two (1\u0026ndash;20 kcal/mol), both physisorption and chemisorption are involved in the adsorption\u0026nbsp;\u003csup\u003e[30]\u003c/sup\u003e. The Cd(II) adsorption onto BC is predominantly physical adsorption since the heat of adsorption value is less than 1.0 kcal/mol.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e3.4.4 Redlich - Peterson (R-P) Isotherm\u003c/p\u003e\n\u003cp\u003eThe R-P equation contains three parameters and incorporates the features of the Langmuir and Freundlich isotherms\u003csup\u003e[31]\u003c/sup\u003e. The R-P isotherm can be described as follows:\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;\u003cem\u003eq\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e = K\u003csub\u003eRP\u003c/sub\u003eC\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e/1 + a\u003csub\u003eRP\u003c/sub\u003eC\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003csup\u003e\u0026beta;\u003c/sup\u003e\u0026nbsp;\u003c/em\u003e\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;(5)\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003ewhere K\u003csub\u003eRP\u003c/sub\u003e, a\u003csub\u003eRP\u003c/sub\u003e, and \u003cem\u003e\u0026beta;\u003c/em\u003e are the R-P parameters. A non-linear graph was plotted C\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e versus q\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e as shown in Fig. 3(b) and the three parameters of R-P isotherm were calculated to describe the adsorption of Cd(II) ions and are shown in Table 1. \u003cem\u003e\u0026beta;\u003c/em\u003e lies between 0 and 1. For \u003cem\u003e\u0026beta;\u003c/em\u003e=1, the R-P equation converts to Langmuir form. The calculated \u003cem\u003e\u0026beta;\u003c/em\u003e value is 1.01 with a high regression coefficient (R\u003csup\u003e2\u003c/sup\u003e) of 0.999 which is very close to unity than \u0026ldquo;0\u0026rdquo;. This indicates that the adsorption process follows the Langmuir form and further supports the predominance of monolayer adsorption.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e3.4.5 Sips Isotherm\u003c/p\u003e\n\u003cp\u003eThe Sips isotherm also called the Langmuir-Freundlich isotherm equation is characterized by the heterogeneity factor, \u0026ldquo;n\u0026rdquo; and is employed to describe the heterogeneity of sorbent surface if \u0026nbsp;0 \u0026lt; \u003cem\u003en\u003c/em\u003e \u0026lt; 1. The isotherm can be expressed as:\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cem\u003eq\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e = \u0026nbsp;q\u003cem\u003e\u003csub\u003em\u003c/sub\u003e\u003c/em\u003eK\u003csub\u003eLF\u003c/sub\u003eC\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003csup\u003en\u003c/sup\u003e\u003c/em\u003e/1 + K\u003csub\u003eLF\u003c/sub\u003eC\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003csup\u003en\u003c/sup\u003e\u003c/em\u003e\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;(6)\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003ewhere C\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e is the equilibrium concentration of the adsorbate (mg/L), q\u003cem\u003e\u003csub\u003em\u003c/sub\u003e\u003c/em\u003e and \u0026nbsp;K\u003cem\u003e\u003csub\u003eLF\u003c/sub\u003e\u003c/em\u003e are the Sips maximum adsorption capacity (mg/g) and Sips equilibrium constant (L/mg), respectively. The value of\u0026nbsp;\u003cem\u003en\u0026nbsp;\u003c/em\u003eis the heterogeneity factor,\u0026nbsp;employed to describe the system\u0026rsquo;s heterogeneity when n is between 0 and 1. When\u0026nbsp;𝑛\u0026nbsp;= 1, the Sips equation reduces to the Langmuir equation and implies a homogeneous adsorption process \u003csup\u003e[32]\u003c/sup\u003e. A non-linear graph was plotted C\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e versus q\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e as shown in Fig. 3(c). The parameters of Sips isotherm were calculated, and the value of n is calculated as 1.05 i.e. \u0026asymp;1 with an R\u003csup\u003e2\u003c/sup\u003e of 0.991. This indicated that the adsorption pattern follows Langmuir isotherm and the estimated q\u003cem\u003e\u003csub\u003em\u003c/sub\u003e\u003c/em\u003e value is also very close to the q\u003cem\u003e\u003csub\u003em\u003c/sub\u003e\u003c/em\u003e value obtained according to Langmuir isotherm (Table 1).\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e3.4.6 Flory-Huggins Isotherm\u003c/p\u003e\n\u003cp\u003eThe Flory-Huggins isotherm\u003csup\u003e[33]\u003c/sup\u003e was used to evaluate the degree of surface coverage characteristics of adsorbate on the adsorbent and is expressed in its linear form by the following Equation 7:\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eln(\u0026theta;/Ci) = lnK\u003cem\u003e\u003csub\u003eFH\u003c/sub\u003e\u003c/em\u003e + n\u003cem\u003e\u003csub\u003eFH\u003c/sub\u003e\u003c/em\u003eln(1-\u0026theta;)\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;(7)\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003ewhere \u0026theta; = (1 - Ce/Ci) is the degree of surface coverage, K\u003cem\u003e\u003csub\u003eFH\u003c/sub\u003e\u003c/em\u003e (L/mol) and n\u003cem\u003e\u003csub\u003eFH\u003c/sub\u003e\u003c/em\u003e represent the Flory-Huggins equilibrium isotherm constant and model exponent, respectively. A linear plot of ln (\u0026theta;/Ci) versus ln (1 \u0026ndash; \u0026theta;),\u0026nbsp;K\u003cem\u003e\u003csub\u003eFH\u003c/sub\u003e\u003c/em\u003e and n\u003cem\u003e\u003csub\u003eFH\u0026nbsp;\u003c/sub\u003e\u003c/em\u003ecan be calculated (n\u003cem\u003e\u003csub\u003eFH\u0026nbsp;\u003c/sub\u003e\u003c/em\u003e= -1.48) and intercepts (K\u003cem\u003e\u003csub\u003eFH\u003c/sub\u003e\u003c/em\u003e = 0.0039 L/mol) with an R\u003csup\u003e2\u003c/sup\u003e of 0.986 as shown in Fig. 4(a).\u0026nbsp;In addition, the\u0026nbsp;K\u003cem\u003e\u003csub\u003eFH\u003c/sub\u003e\u003c/em\u003e value is used to calculate spontaneity Gibbs free energy (\u0026Delta;G\u003csup\u003eo\u003c/sup\u003e) \u003csup\u003e[34]\u003c/sup\u003e. The negative value of \u0026Delta;G\u003csup\u003eo\u003c/sup\u003e = -13.86 kJ/mol (Table 1) indicates that the adsorption process is thermodynamically spontaneous and feasible \u003csup\u003e[35]\u003c/sup\u003e.\u0026nbsp;If n\u003cem\u003e\u003csub\u003eFH\u003c/sub\u003e\u003c/em\u003e \u0026gt;1, indicates multilayer adsorption of molecules on the adsorbent surface, if n\u003cem\u003e\u003csub\u003eFH\u0026nbsp;\u003c/sub\u003e\u003c/em\u003e\u0026lt; 1, indicates an active zone of the adsorbent would be occupied by adsorbate \u003csup\u003e[36]\u003c/sup\u003e. Therefore, the value of n\u003cem\u003e\u003csub\u003eFH\u003c/sub\u003e\u003c/em\u003e is less than one, indicating that the adsorbent\u0026apos;s active zone has been occupied by the adsorbate.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e3.4.7\u0026nbsp;Fowler-Guggenheim isotherm\u003c/p\u003e\n\u003cp\u003eThe Fowler and Guggenheim \u003csup\u003e[37]\u003c/sup\u003e explain whether the lateral interaction between adsorbed molecules in the solid phase existed or not. The linearized form of this model is expressed by:\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003elnC\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e(1-\u0026theta;)/\u0026theta; = -lnK\u003cem\u003e\u003csub\u003eFG\u003c/sub\u003e\u003c/em\u003e + 2W\u0026theta;/RT\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;(8)\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003ewhere K\u003cem\u003e\u003csub\u003eFG\u003c/sub\u003e\u003c/em\u003e is the Fowler-Guggenheim equilibrium constant (L/mg), \u0026theta; = (1-C\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e/C\u003cem\u003e\u003csub\u003eo\u003c/sub\u003e\u003c/em\u003e) is the degree of surface coverage, W is the interaction energy between adsorbed molecules (kJ/mol), R is the universal gas constant, 8.314 J/kmol \u0026nbsp;and T is the absolute temperature (K). From a linear plot of lnC\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e(1-\u0026theta;)/\u0026theta; versus \u0026theta; as shown in Fig. 4(b), W and\u0026nbsp;K\u003cem\u003e\u003csub\u003eFH\u003c/sub\u003e\u003c/em\u003e can be calculated (W\u003cem\u003e\u003csub\u003e\u0026nbsp;\u003c/sub\u003e\u003c/em\u003e= -12.04 kJ/mol), and intercepts (K\u003cem\u003e\u003csub\u003eFG\u003c/sub\u003e\u003c/em\u003e = 4.02x10\u003csup\u003e-4\u003c/sup\u003e L/mg), respectively with R\u003csup\u003e2\u0026nbsp;\u003c/sup\u003eof 0.99 (Table. 1). If W value is positive, the interaction between the adsorbed molecules is attractive. On the other hand, if W is negative, the interaction among adsorbed molecules is repulsive. If W is equal to 0, there is no interaction between adsorbed molecules. Therefore, the calculated value of W is negative, which indicates the presence of repulsion between the adsorbed molecules and R\u003csup\u003e2\u0026nbsp;\u003c/sup\u003e= 0.99 which also implies the existence of a monolayer on the surface of the adsorbent \u003csup\u003e[38]\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e3.4.8 Harkin-Jura Isotherm\u003cem\u003e\u0026nbsp;\u003c/em\u003e\u003c/p\u003e\n\u003cp\u003eThe Harkin-Jura isotherm model\u003csup\u003e[39]\u003c/sup\u003e assumes the possibility of multilayer adsorption on the surface of absorbents having heterogeneous pore distribution. This model is expressed as follows:\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e1/q\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e\u003csup\u003e2\u003c/sup\u003e\u0026nbsp; = B/A\u0026minus; (1/A ) log C\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;(9)\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe plot of 1/q\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e\u003csup\u003e2\u003c/sup\u003e versus logC\u003cem\u003e\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e gave a correlation coefficient of 0.761 as shown in Fig. 4(c) with the values of A = 142.85 and B = 1.57 respectively, as Harkin-Jura Isotherm model constants (Table 1). The R\u003csup\u003e2\u003c/sup\u003e value was only 0.761, lesser than that of monolayer adsorption models of Langmuir and could not be the best fit for the adsorption. This indicates that the multilayer adsorption process is not followed.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.5 Sorption kinetics studies\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTo explain the mechanism of Cd(II) \u0026nbsp;adsorption kinetics and the potential rate-controlling steps, Pseudo-first-order, and Pseudo-second-order kinetics models are used.\u003c/p\u003e\n\u003cp\u003e3.5.1 Pseudo-first-order reaction\u003c/p\u003e\n\u003cp\u003eThe Pseudo-first-order model \u003csup\u003e[40]\u003c/sup\u003e for solid/liquid systems of adsorption stated that the rate is proportional to the number of unoccupied sites. It is expressed as:\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003elog(\u003cem\u003eq\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e\u0026ndash; \u003cem\u003eq\u003csub\u003et\u003c/sub\u003e\u003c/em\u003e) = log\u003cem\u003eq\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e \u0026ndash; k\u003csub\u003e1\u003c/sub\u003e\u003cem\u003e\u0026nbsp;t\u003c/em\u003e/2.303\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;(10)\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003ewhere \u003cem\u003eq\u003c/em\u003e\u003csub\u003ee\u003c/sub\u003e and \u003cem\u003eq\u003csub\u003et\u0026nbsp;\u003c/sub\u003e\u003c/em\u003eare the amounts of cadmium adsorbed on the adsorbent at equilibrium and at any time t, respectively, and k\u003csub\u003e1\u003c/sub\u003e is the rate constant of pseudo-first-order sorption. The slopes and intercepts of a plot of log (\u003cem\u003eq\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e\u0026ndash; \u003cem\u003eq\u003csub\u003et\u003c/sub\u003e\u003c/em\u003e) versus \u003cem\u003et\u0026nbsp;\u003c/em\u003e(Fig. 5a) were used to calculate the first-order rate constant k\u003csub\u003e1\u003c/sub\u003e = 39.15x10\u003csup\u003e-3\u003c/sup\u003e /min and equilibrium adsorption capacity \u003cem\u003eq\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e\u003csub\u003e.\u003c/sub\u003e= 13.03 mg/g.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e3.5.2 Pseudo-second-order reaction\u003c/p\u003e\n\u003cp\u003eThe Pseudo-second-order \u003csup\u003e[41]\u003c/sup\u003e assumes that the rate of sorption is proportional to the square of the number of unoccupied sites. It is expressed as:\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003et/\u003cem\u003e\u0026nbsp;q\u003csub\u003et\u003c/sub\u003e\u003c/em\u003e\u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;= 1/k\u003csub\u003e2\u003c/sub\u003e\u003cem\u003eq\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e\u003csup\u003e2\u003c/sup\u003e\u003csub\u003e+ \u0026nbsp;\u003c/sub\u003et/\u003cem\u003eq\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026nbsp;(11)\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003ewhere k\u003csub\u003e2\u003c/sub\u003e is the equilibrium rate constant. The slopes and intercepts of plots t/\u003cem\u003eq\u003csub\u003et\u0026nbsp;\u003c/sub\u003e\u003c/em\u003eversus t (Fig. 5b) were used to calculate the pseudo-second-order rate constants k\u003csub\u003e2\u003c/sub\u003e = 6.42x10\u003csup\u003e-3\u003c/sup\u003e g/mg/min and \u003cem\u003eq\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e = 16.66 mg/g.\u003c/p\u003e\n\u003cp\u003eThe correlation coefficient (R\u003csup\u003e2\u003c/sup\u003e) of the pseudo-second-order kinetics model is 0.999. The experimental \u003cem\u003eq\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e value of 16.18 mg/g was also agreed well with the calculated \u003cem\u003eq\u003csub\u003ee\u003c/sub\u003e\u003c/em\u003e value of 16.66 mg/g. On the other hand, the correlation coefficients of a pseudo-first-order kinetics model were lower than the pseudo-second-order kinetics model as shown in Table 2. Therefore, it can be concluded that this adsorption system followed a pseudo-second-order reaction rather than a pseudo-first-order reaction. This suggests that the sorption of the metal ions involves two species, in this case, the metal ion and the biomass.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.6 Adsorbant and its characters\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAn SEM micrograph indicates that the adsorbent surface has multiple pores. These pores vary in size, with the smaller ones measuring 1.36 \u0026mu;m in diameter, while the larger ones have a diameter of 16.3 \u0026mu;m (Fig. 6). The presence of different pore sizes on the adsorbent can enhance the adsorption process by increasing the surface area available for adsorption.\u003c/p\u003e"},{"header":"4 Conclusions","content":"\u003cp\u003eThe purpose of this study was to evaluate the effectiveness of wood-based biochar as an adsorbent for removing Cd(II) from an aqueous solution. It was found that the maximum adsorption of Cd(II) occurred at a pH of 6. After 120 minutes, the adsorption of Cd(II) did not significantly increase. The rate of adsorption was best described by the Pseudo-second-order reaction. Various adsorption isotherms were utilized to explain the mechanism of adsorption. Based on the results, it can be concluded that wood-based biochar is a highly efficient adsorbent for removing Cd(II) from an aqueous solution and could be scaled up to remove heavy metals from contaminated water. \u0026nbsp; \u003c/p\u003e"},{"header":"References","content":"\u003cp\u003e[1] Sabrina AS, Hemlata KB. 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Available from: \u003ca href=\"https://doi.org/10.1016/S0032-9592(98)00112-5\"\u003ehttps://doi.org/10.1016/S0032-9592(98)00112-5\u003c/a\u003e.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe author gracefully acknowledged the Department of Chemistry, Mizoram University for allowing us to utilize instrument facilities.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was furnished out in collaboration between both authors. HLT designed the study, wrote the protocol, data collection, and analysis. LRH helps in literature search, evaluation, and participated in writing the manuscript. \u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting Interest\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors have no relevant financial or non-financial interests to declare\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare that no funds, grants, or other support were received during the preparation of this manuscript.\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthical Approval\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNo experimental animal and/or human are used in this research. Therefore, not applicable in this section.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAvailability of data and materials\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare that the data supporting the findings of this study are available within the paper. Should any raw data files be needed in another format they are available from the corresponding author upon reasonable request.\u003c/p\u003e"},{"header":"Tables","content":"\u003cp\u003eTable 1 Different adsorption isotherm models with their Parameters for the adsorption of Cd(II) onto biochar\u003c/p\u003e\n\u003cp\u003e\u003cimg 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tm0jCAJ0u13e77HHbNuG67qmDFxfX+eyt5Ypy2ekg5fuwuv3+3MtIHbRbUjVl/MRfVQ2nxEKOYxc1zXL4ziu8CipSkIIBcDkLsouXzWfkVJqaZ6s4qXh9DHMZ0RERJVjNx0REVWOwYiIiCrHYERERJVjMCIiosoxGBERUeUYjIiIqHIMRkREVDkGIyIiqhyDERERVY7BiIiIKsdgRERElWMwIiKiyjEYERFR5RiMiIiocgxGRERUOQYjIiKqHIMRERFVjsGIiIgqx2BERESVYzAiIqLKMRgREVHlGIyIiKhyKwUjx3FgWZZ5bCPf9+H7ftWHQUTfJIoiU2eV/fazdVqSJEv35fu+2bbZbJrlzWYztx/LshBF0cY/S5nBYPAt7/NdVgpGs9kMQRDAdV0opb76mL7EcDjEcDis+jCI6BukaYrpdAqlFKSUGI1Gucq72WzC8zwopRDHMer1+tJ9HR4eQikFpRQeHh7M8l6vZ5YrpeC6Lg4ODr788+0idtMR0c75+/evOfm0bRtBEODx8dGsn81mODk5AQD8+vULwFtwKXN/f49Op1O6rlarmf+naYrZbJZb9lWiKMLx8fGXv8932mgwyjZVs2chjuMgiiLTpC02mYvNXMdxALw1Q5vNZq65DfzTZNbN5SRJ5l5XfJ9ms2mOSW+vt9u15u6+yZaPJEnYHUtzAeH379+5541GA71eDwDw/PwMz/Ng23bpvm5ubua65wDMbX9/f4/Ly8vSfaRpCsuyzL+6O0/XRXqdll1e1tX4+vpqPmN2n2VdiVtDrSgIAuW67tL1nucppZQKw1DpXbuuqwAoACqOYxXHsQKgpJRmfRAEZh9CiNw+AJj9CiGUEEKFYaiklGafenv9WqWU8jzPvM7zPAVABUFgXqef03bT5UlzXdd870RaEAQqDMPcMiFErn5ZRNdVevtFXNc19VGRrnP063Vdp+vUYrnN1m1lZTpbd+k6Uam3um5ZPf2Tbaxl1Ol0TLM422f68PAAIQTCMEStVjNNYm02m5mzlrOzM0gpAQCtVsuMU+n9Oo6Dy8tLtFqthWcxZYbDIVzXBfB2NhPHsTlm2m79fh9hGJrn65QL2h83NzdotVq5ZY1GAwAwGo0WdtEB/5Sp2WwGz/NKe1Le66LT9Zr+V9d5evwpW271sei68uLiInd8xS46KaWpc8/PzzGbzRZ+lp9s42NGvu8vHQwsury8xHQ6BfDWzyuE2PQh0Q5b9MPTXRe6Cy/b3asrE91t7DiO6bJtNptm+bIKiraH7/tz5cT3fZycnEApBc/zVq53zs/Pc2NP2rIuunXZtg3XdfH8/AzgrUsuG6ym02ku6Hmeh6enJwDAnz9/zHDFtvl0MNL9mPqHfnJyYloeq+h0OhiNRrAsC/V6HZPJ5LOHRGQGrdvtNpRSmM1mmE6nkFLi8fERaZrCtm1zdWin00EQBLBtG6enp1BKsZW1AwaDgblQIWs0GpnWxHA4hBDi3cu7tdPT07llj4+PG72goNfrod1uw7Is3Nzc5K4EPjw8zG17dXWFbrcLy7LQbrdNa2vbfCoYZa+nv729RRAEc03h9zSbTUgpzaWRH60ADg4OTBMYeCtsxcs5afdcXl6i3W6b58UfarYL7+rqyvzftm1cXV3BsixTbjqdztzraXvp+knXSUmSmIAjhMDd3R2At1a0lHJuCKHMxcXFXPf+V1xFd3FxYerEbKsuiiKcnZ3ltm00GrnLy7fWKgNLeuCu7KEHzrIXHGS3z17AkN0G/7mIQV9ckH3owcbsPrLb6cE//VwP9GWXZS9gyB7D//zP/8wNJtJ2K5ZP/b1nB62FEEpKqaSUynXd3AUv+t8gCHIP2l5l9Ur2AqfshUzZeiz7WqX+uUAmW2cVrVJeiu+VPaYgCEov1ioefxzHpRdbZOu3ss+zLSqvjcv+aKwI6KP0SUi2EtGVi+u6uSuoyk6u4jg2P26WQ6rKOvXirtSh//pEo+rToijC7e1trmuPg8a0CbVaLddlUTb7xqIZOba1z512g+/7c93Fi25yHQwGeHl5ydWhSZLM3Ve1FaqOhsUmZrYpTbSOsu4Oom2EQot9WXkudult631GllLbPOJFRES7gHPTERFR5RiMiIiocgxGtLXKJpP87pwy9LPpXGzvTRyqZ+BYVnb0rB70NRiMaGvpK+b03IfqPzf9xXGMdrvNgLTnfN/H5eUllFI4PT1dOJu7LifZslN2VS9ng/9avICBtp7jOOj3+7nLW3XFwYSK+ylNUwghzOX9xefFbbMzv1iWNbednsml2+1u9ywHPxhbRrRz0jTFaDQqnZOM9sPz87OZqR94m/5p0fxz2UDk+35uCingn3sfdy2Z3U9T6U2vRJvSbrdzc9RJKTnR6R57fX0tXf7nz5/S5brlBMzPb3h9fY3hcLjyRKr0MWwZ0U7IjhmFYQghBPv4aWV6BvcwDNHtdk3gGQwGOD8/r/jo9gODEe2cVqsFz/PeTZpGu2vRdDjZxJ9lWq0WXNc1+YFubm5Qr9dNihsAJr09bRaDEe0kpoLYb0dHRxiPx+a5ThOxSpoH27ZNMJvNZrmrNIG3q+42mS6C3jAY0c5JkgTdbheu63LcaE/pbKn6su3r62t4nvfu6/TFL+vmZaPP46XdtLWSJFmY4t51Xc6+TXAcB1LKufLgOA4cx8HDwwN838doNDLrFlWJuryxyvwaDEZERFQ5dtMREVHlGIyIiKhyDEZERFQ5BiMiIqocgxEREVWOwYj2wqp5bYioGgxGtLWWJdfLTgMURREmkwmUUpjNZpzKZY+sehKSLUvFOQ11Ur2y/SxbR+thMKKttSi5nuu6ZgZm4G2+MT0TQ6PRqOpw6ZutmlwvTVNzM6tSCpPJxOQvAgAhBKSU5mbX7H4ajYZ53Ww2y72O1sNgRDvn4uICABZOksp5xXafntan0+kAAM7OznKzLGTd398jCALzvN/v4+bmBsBbq9rzPHMy0+v1zH7SNMVsNjOvazQaCydopfcxGNHOabfbpfPSDQYDXF1dVXRU9J3WSa738vKSe350dAQpJdI0ncuLpE9kkiTJla8kSZCmKee0+wQGI9oJ7Xbb9N1LKefmpdMTZtq2za6UPbBucr1iQMp6Lw1Js9lEvV7PtZJofQxGtBPCMDRdLX///s2tGwwGaLfb6Ha7sCyLXSmUc3JygtFoZFpNuvzYto3j42OMx2NzMqMD069fv8zrHx4eoJSClJIJHT+BwYh2RqfTgeu6Zswou1wPMiul2JWyB9ZJrqeTMWaT6Ol0E7VaDUEQmJa3EGJhapIwDDGZTDb7QfYIgxHtlOFwCCklu+L23LrJ9YbDoTlZEUJgOByaddmTGdd1c+uyDg4O4DjOZj/IHmEwop1i2zaCIEC32zVdK7R/PpJcT98ztKh1Y1kWer3ewoSN/X5/rlVOa1BEWyqOYwXAPDzPM+tc1zXL4ziu8CipSkIIBUC5rju3XC8LgkABUEKIudeHYWjKUVGx/IVh+DUfYk8wuR4REVWO3XRERFQ5BiMiIqocgxEREVWOwYiIiCrHYERERJVjMCIiosoxGBERUeUYjIiIqHIMRkREVDkGIyIiqhyDERERVY7BiIiIKsdgRERElWMwIiKiyjEYERFR5RiMiIiocgxGRERUOQYjIiKqHIMRERFVjsGIiIgqx2BERESVYzAiIqLKrRSMBoMBLMta+NikZrOJwWCwcL1lWUiSZKPvSbvDcRxEUVT1YdAPY1kW0jR9d7soiubqtTRNzbJms1n6uiRJcnWi7/vvvs8qx7NPVm4ZxXEMpRTCMIQQAkopKKXguu7G/qi+72M8Hi/dRimFWq22kfej3ZIkCaSUuL29rfpQ6Ad5LzBozWYT7Xbb1G2aEAJSSrOsbH+1Wg1KKQghEIYhhsPh0vd6fX2FbdtrfIrdt3IwWhQALi4uNnYww+EQrutubH+0X+7u7hCGIcbjMc86CcBbC+Tw8PDd7XRvTDYI6dd7nmcCR6/Xw2g0+tQxsWyWWykYdTqdhetarZb5orLdedmzB9110mw2c+v0tou6VfT2juMA+Ke5rL9M3/fh+755X70d7a9WqwUAeH5+rvhI6CeYTqc4Oztbuk2apuh2uzg9PTV1kq5jXl9fc9vqk/LPDBU8Pz/njslxnC8d+tgWG7uAIUkSvLy8mCbuaDRCkiRoNpuQUqLdbqPX6yGOY4xGIziOA6UUgiBAr9cr3ed4PIaUErPZDMBbc1kbDAYYjUbmLEUpBSklxwv2VBRFOD8/BwB4nlfaVef7/tyPftUuHNo+vu+/210GvAUHXbfooYdsudh0SybbRef7PhqNhhkC0cewjzYWjO7u7jAajXKR/enpCQ8PD6YftVar4devXwCAyWQCAPj9+/fcvl5eXmBZFpRSuX5VKaX5f6fTged58DzPtNyywYr2y3Q6NWet5+fnC7vqdL++lBJSShPAaLdEUYSTk5OVtp1Op2g0GqYe6fV6pvwcHx9jPB6bk1xdpnQ9tq5imUzT1HQj6lb9vnbjbSwYpWmKIAhMy0gptbR7bxnd2uFVc7SKNE1zJ0L1eh3AfFfdcDg0P3R9ksOLYXbT7e0t2u02LMsyJ6lCiJV6TrKBplarIQiC3L5c1/3wxQf39/e5LrqLiws8Pj4CwFzZ3DcbC0a2bePl5WUj+wqCAGEYmkqFaJn7+3tztZN+LOqqe35+xuXlJYD9/dHvg4eHB1MWdI+KlNK0PrJOTk5MT02WLh+dTid39fAqXX9ZaZrmblfJlrtWq4XZbGYCXRzHa+17l2wsGJ2cnJhxImD+C1hXq9Wa67slKvP4+DgXWK6urjAej+da17e3tzg+Pv7Ow6MfrtVq5cabr6+vEQTB3HaWZaHX6619EuP7Po6Pj5Gm6dywhO/7uL29NcFur1vqag2u6yoA5iGlzK0PgiC3vviaMAxz67PPhRDK8zzzPAiC3Gv//e9/516bfS/P8+beh3ZfHMe5MpCVLSvZdWsWedoBUsq5+koIoVzXndsGQG55to5aJlsWyx5KvdWP79WZZWV5X1hK7emlG7RXoihCu90G8Ha13bpdLURfIYqiua7DwWDw4fH2bcZgRERUgSRJcHFxYW5d0Va9JH3X/KvqAyAi2ke1Wg2NRmPuJtd9bR+wZURERJVjCgkiIqocgxEREVWOwYi2WhRFnCCX3rUsn9GiCZsdx1npPsfsXIfLZo0pzo2Y3fYr8hu9lxvup2Ewoq2VJIm5XJtokUUBRSfSC8MQSqncJdaWZeXmwlyk2WzC8zwopRDH8dJZY4bDYS4fXPYG103nN1olN9xPw2BEW6tWq5mZjonKLMpnlKYp2u32wimC1H+mlHrPbDYzE7LqOe3WbeF8xcSo25gbjsGIdkI2XfS+znpM8xblM/J9H0EQQAgBy7I+3J3VaDRMCpzn5+dcIr5VZfMbLcrRVswFpy3KIbeNGIxo60kpMZ1Ozdlso9Ew68oSlzHn1X5YdvPoeDzG4+OjySPU7XY/dBKj929ZFqbT6YduVtVddItytDmOk8sFp49zMBiYz6D+k0NumwMSgxFtPSGEqQSurq4gpUSapkjTFJeXl5BSmn76MAxLu2VotyzLZ6QvHHh4eADwNlGqEAL39/cfei998pMNFKvKbr8oR1u/38/lgtNubm5wcXFhnodh+OmU6FViMKKdku0isW0bnU4Hz8/PpsI4Ojqq6tDoG62bz+ijV2T6vo+TkxPTKl83wWcxv9E6pJQ4ODgwz7P/30YMRrRTyhKUTadTk9GVOYz2w7J8RvoqtuJl2GVZp98zGo1MEBgOhxBCrJ0U9KNlUgiBp6enuWXbisGItp7ulgPKc9GMRqP9zhNDczzPQ7/fB/AWlGaz2Ye6b4UQuLu7A/B2IiSlfDcluW6ll+U3Wsfl5WVurOvu7s4kjtxK35uxgmjzsjlngiDIrYvjOJefhvZPWT4jpfK51orrhBCl+Y10/iG9fTYPEpbkUtPvJYTI7Sv7vu/laMu+j35dNgdcNg/SNuZ344rPZo4AACAASURBVESptLN83zcDurxwgehnYzAiIqLKccyIiIgqx2BERESVYzAiIqLKMRgREVHlGIxoL+g56prNZtWHQkQlGIxoayVJMjcJatnM3VEUYTKZQCmF2Wy29h3ytL1WPQnJlqWyyUazifGK+1o1uR4tx2BEW6tWq0EpBSGESZCmlILrurlpUVqtlplyJTujN+023/dxeXkJpRROT08Xzmidpinq9bopP5PJJJdSIk1THB4emvV6glVgveR6tByDEe0cPZPxohmUOTXQ7kvTFKPRyMx+fXZ2tnBG6/v7+9wUUv1+Hzc3N7n1ej9Fm0iuR28YjGjntNttuK47NwHlYDDA1dVVRUdF3+n5+TmX6dS27YWTmL68vOSeHx0d5eY7vLm5WdjVt4nkevSGwYh2gk4XYFkWpJS5rhQAJnWATmJGu+319bV0+Z8/f0qXFwNSVna80bKs3LpNJNejNwxGtBPCMDRdLX///s2tGwwGaLfb6Ha7sCzrUzMl0+45OTnBaDQyrSZdfnQLR/87m83ged7cycxnkuvRPxiMaGd0Oh24rpvLfqmX68FnpRQnTN0Di044yhLQtVoteJ6Her0Oy7JQr9fheV7p68/Pz/H4+Giefza5Hv2DwYh2ynA4hJSSXXF77ujoCOPx2DzXuYYWXbwyHA7NyUo2jX2Z09NT8/9NJNejNwxGtFNs20YQBOh2uwtTTNPus20bruuaMnB9fb2wtaOlaQrLsjCZTBZuc3Fxkbuy7iPJ9WiBb82eRLRBcRznEo4tSi4Wx3GFR0lV0knyigkWhRBmmU5ql018pxXLWDEJ36rJ9eh9zGdERESVYzcdERFVjsGIiIgqx2BERESVYzAiIqLKMRgREVHlGIyIiKhyDEZERFQ5BiMiIqocgxEREVWOwYiIiCrHYERERJVjMCIiosoxGBERUeUYjIiIqHIMRkREVDkGIyIiqhyDERERVY7BiIiIKsdgRERElWMwIiKiyjEYERFR5RiMiIiocisFI8dxYFnW3GMwGHzoTaMoguM4C58nSQLLst7dj+/78H3/Q8dQPJ6yzxdF0af3/VM4jgPf90s/Z7PZXPpa/X0s+v6TJNnI97Cu4nHpY8iW1yqOi34OXQ6y9UuZbB1Q3DZN05V/K/QJakVBECjXdc3zMAwVABWG4aq7UEopFcexAqCEEKXP1zkeAMrzvLVetwwAFcdxbv+rfL4gCJSUcmPHsUlSSpX9mvXfu7h+lb+jEML8PfT3HwSBUmq+fHyn7HFp2e+S9pMQwpQBz/MWlk/9G8hum/09ADC/b9d1N1rn0D8+3E3XarUAAK+vr2u9rlarIQzDhc9X1el04Hne2q9bZ/8AMJ1O39222+1+2XF8VqPRgJRy4XrbtuG6LtI0XWu/rVYLQgg8Pj4CePt7nZ6efri1vEmO40BKiVqtVvWhUEWSJIHjOKYMXF1dYTwel5bzv3//AoDZ9vDw0GwXRRE8z4Nt2wCAXq+H0Wj0HR9h73w4GOnuj7Ozs9zyZrNZ2s2Vbeq+F8CK3XbZ15Z13w0Gg5Wa4usSQuSeFz+bPi69rf6bZJv82WZ9s9k0x6pfp/cZRVGuIs9ul+1q0l1T2b9JkiSlxx9FERqNhvkhLdpmPB7j4uJizb8O5v7enU6n0sCs/yaTyWTpZ6bd9+fPn9xz27YhhMDz8/PctjoI6d/f4+Mjer0egPmTbb3tot8cfdxawWg8HpsK8PDwEEqp3I9+MBjg4uICSinEcYx2u23WCSEQxzGUUri5uVn4HkmS5F6nXyulhFIKQohcpa3PUpRSkFJurJAMBgNIKXFycrLws9m2bVodUkoMh0OkaYrb21sopaCUwmw2QxRF8H0f4/EY3W7XrEuSBKenp1BK4fb2Nvfej4+PZrvRaATf95GmKer1OoC3Fo9SCp7nod/vl36G29tbc/xF+nvUx6pbuqvSQez09DS33HXdSsbaptOp+ZssCkTZAJ89WSqOpf2E1h193mw2W3nbOI7R7XZhWRZ6vV6uVb1urwF90Kr9eXpMYNkYgxBCAcg94jhWQRDktg/DMDdGtOx5GIYL+3qLfbtlYwfrKB67Hg9Z9tn030P3KeuxpuxDH6Prurl9FsdvFn0OPT5T9pplYzXZPvOy9xRCrDVWV/wblJWB4nfyHfTnwApjj7oMx3Gc+7sJIcx3uMbPgn4o/bvM/t6A5eOIulxny4X+vejfY/H3TpuzdjedbdsIwxCj0WiuFSKlNK0f/ajVanh5eVn3bYzX19dPd7kUr5Zb1nrKHr8eNwIWf7ail5cXeJ6X2244HJa+V61Wg+d55rj0GZiUEgcHB2a77P/XsWysCAAmkwmklHMtgWx3ZLErLgzDdz9XFfr9vmkdv3clpm3beHp6MuUqTVM4jgPbtpEkyVz3LG0fXU/p1o5lWRBCLBxHtCzLlOvxeGy6xmu1GoIgQLvdNvtwXZfdwF/gQ2NGrVYLruvOjTMIIeb6arWPNnV///6NyWTyoddqrVbr3SDynmWfLSs7+LmK4XBoutsajYZ5r6enp7n3X9d7r7FtG0EQoNvt5o754eEh1824TdR/unKzwV3TXYuWZeHl5cUE0/v7e7O8Xq9/urzRz5D93Xuel+sKz4qiKPdbieM4VwY6nY7Zj+u6P+okbJd8+AKG4XAIKWVugL7RaOTGe6IoQpIkOD8/x3g8Nn300+l07rWLHB0dQUqZG4eo4t6RRZ+teIZ0fHyc+6zA4uNNksS0Sq6urszyy8vLXIC4u7vD5eXlh475vQDa6XQghNhYayBN04XjVN9lNpuZz5RtBU+nU4RhCNd1cX5+bpY/Pj6aMUm1ZMyJtpPjODg5OVl4EnpwcJAbb356eiq9GEqPJ7F8fJFV+vKKYwWaHstAYVwEJX2v2bEU13VzY0LZ5cXnSv3Tb6sfehwq+97Z91133Cj7nij0M2ct+mx6uV5W3J+UUnmeN7d/PW6R/Vxadnv9t9X91dnPWXY82c+VXZ7dZ/b9svstG3Mp/v2XjQmtWKQ2YtFxFT+nXq6PLQzD3N903Xvc6OfLlo2y8R0hxML6aVEdR1/LUkqpDcQ0+qEcx8Ht7e233HOjW3nZsbafIE1T0/ILggCdTmduXCkMw7WvKCSizWEw2nG6IpZSfmn3QhRF6PV6WzfGREQ/AydK3XG2bUMpZS6O+ApJkuD29paBiIg+jC0jIiKqHFtGRERUOQYjIiKqHIMREe0sndvqvXsas/MWFudWzM7gwnkLvw6DERHtJN/3cXl5CaUUTk9PF958roOPykyCrG84T5IE0+nUTDXV7XY5Y/cX4QUMRLRz9C0NunorPi9um73tQc9TV7bOcRymKPkibBnRVivmutqlVPH0cc/Pz3Bd1zzX+YzKWjXZwOL7fi7ZZzFFzuXlJQPRF2Ewoq12fX2NIAiglEIQBCYpGsD8RftsUQLPZRM5W5aF0WhU+lrLstDtdj+VgYCWYzCirTYcDs30Q79//86t63Q6cF3XpP/QszYPh8NcwsafnDaevoe+OVynnSi2oPR40mg0Yuv7izAY0U5oNptzGYI15i/aP8UTE+293GA6PU4xhQvwT/6x6XS6kWOkPAYj2mq6K67X6+X6+gHmL9pnR0dHGI/H5nmappBSrjRhsG3bC4PZ4eEhDg8PN3ac9A8GI9pqNzc3CMOwtJJh/qL9Zds2XNc1XWrX19fwPO/d16VpitFotHAG9263i7Ozs40eK/3HtyasINqwbB4anXdL5ycC8xftPV0mivm+svmMivmvsop5jspyI9Fm8D4j2jnMX0S0fRiMiIiochwzIiKiyjEYERFR5RiMiIiocgxGRERUOQYjIiKqHIMRbb1s8jPHcao+HPpBkiSBZVnv5iDKzv5eNnGuLmM6zxFtHoMRbbU0TdFut82MCo1GY2ESNdovURShXq+vtG2j0UAcx1BK4fHxMTcZ6mAwWDjvIW0OgxFttefnZwghzJQ+JycnPHslAG+Tnq5yG2UURXAcx0wpdXFxYWZ4B95mf5dSftlx0hsGI9opr6+vOD09rfowaItMp9NcmSlOskrfg8GIdoLu0395eTH5jYhWsaglzRb292Iwop2gu2ROTk54EQPRFmIwop3SarUgpXz36ikibVEKEaYW+V4MRkS0105OTvD4+GiePz8/w3XdCo9oPzEY0daTUpr+/SiKIIRYKaMnEfDWmh6Px6YM9Xo9XFxcVHxU+4fBiLaeEAKNRgOWZaHdbjONOAH454ZXAKjX67l7hxzHQbPZNM+llBBCwLIsXF5e5nJd6RMc4K2ssQv4azCfEW21KIpwe3uLh4eHqg+FiD6BLSMiIqocgxFttdfXV171RLQD2E1HRESVY8uIiIgqx2BEe8FxHFiWlbuCioh+DgYj2lr60t2yR3ZesSiKMJlMoJTCbDbjpbl7ZNWTkGxZKqYgyeY6KtuPfg99GTl9DIMRba1arQalFIQQCMMQSikopeC6rrkvBHi7qVFf5NBoNKo6XPpmvu/j8vISSimcnp4uzHOVpinq9bopP5PJJJdgTwhh8mXp/WrNZhP9fh9KKQRBwHkRP0MRbTkhhArD0DwPw1ABUFLKuW09z/vOQ6OKSClVtnorPs8KgkAFQWCeh2GohBDm/9kyE8ex2Y+U0mynAVBxHG/sc+wTtoxo57TbbbiuO3fJ92AwwNXVVUVHRd+pOL+cbdsLZ094eXnJPT86OjJTTL2+vubW6WmmkiTB379/5/blui6enp428RH2DoMR7YR2u2367aWUczMy6KlgbNvOdcHQbioGEe3Pnz+ly4sBKWtZXiNmgN0cBiPaCWEYIggCAJg7Yx0MBmi32+h2u7AsC79//67iEOmHOjk5wWg0Mq0mXX5s28bx8THG47E5mdGB6devX6aVlB1Dms1mLF8fVXU/IdFnZceMXNed68en/ROGoXJdN7dMCLFwPMfzPAXAPLLjREEQ5NZl96vHkLIP+hjOwEBbz3Ec9Pt9tFotpGkKIQSCIGD68T2my4Gu3orPl3EcB7PZrHRds9nEcDgsnYJqMBjg9+/fuRm/aXXspqOdYts2giBAt9vNpQyg/WLbNlzXNWXg+voanuctfY2+n2hRChLLstDr9UoDkb7/iIHoE6ptmBF9XLGLJNu14rquWc5LbfeXEGKua00v18t0N1xZ966+TaCsqtSXi7OMbQa76YiIqHLspiMiosoxGBERUeUYjIiIqHIMRkREVDkGIyIiqhyDERERVY7BiIiIKsdgRERElWMwIiKiyjEYERFR5RiMiIiocgxGRERUOQYjIiKqHIMRERFVjsGIiIgqx2BERESVYzAiIqLKMRgREVHlGIyIiKhyDEZERFQ5BiMiIqocgxEREVVu5WCUpiksy4JlWWg2m0jTFIPBwKyPogiO43zJQRIRrSuKIlNn+b6fW9dsNs06/YiiaOG+Fu0ny3EcJEmyseN/T7b+3QUrB6NGo4EwDKGUQq/XgxAit77VamE2m238AImI1pWmKabTKZRSkFJiNBqZyjtNU/R6PSilzMN1XRwcHJTuq9lsmroPKA8Cg8EAUsqv+0B7YKVglKYppJQ4OjoCANRqNf7hiejH+vv3L4bDIQDAtm0EQYDHx0ezvlarmf+naYrZbJZbpiVJgtlshlarBQA4Pz/Hzc3N3DbfLYoiHB8ff/v7fqWVgpFt2xBCoNFo5JZ1Oh3zfDAYoNlsmueWZSFJEtO8zZ5N+L5vmsXLmr1Eq8h2xyRJwjJFc4Hl9+/f5v+2befW3d/f4/LysnQ/T09PuXpPn4inaWqW3d3d5erCMnqYIzvcEUVRro7M7jO7vKyL8PX11XzG7D6zQynbZuVuuslkAillab9pFEXodrvmuR47qtfrUEohjmN0u10kSWL+4EopTKfTTXwG2mNJkqDdbpvuln6/X/Uh0Q/0+vqKi4uL0nWPj48LWxkvLy+ly//+/Qvg7ST86urq3ffXwxpCCCilEAQBer0e+v2+6Sa8vr4229frdcRxbNZ5nmdaekXZIRTP8+C6Lh4eHt49pp9m5WBk27b5sKPRyJyFAm/jRUEQmG312FEcxwDeziZc18XT0xMAYDQaIU1TDIfDhX9golX0+32EYWieF896iQDg5ubGdLVlLeuie4+u/1Ypc3pYQ/+rW2o6aGT3oU/Yf/36BQC4uLjItZqKXXRSSjPedX5+vrVj92tf2j0cDk20XnSmUUb/sXX/rRAiF9CIPmLZD8/3fTSbTdONB+Ddq6Zo9/i+v7CcLOuiA4DDw8PS5b9+/cLd3R263a7pGgPeWjSfvcrNtm24rovn52cAb626bLCaTqe54Ol5njnR//Pnz9Ze1bxyMCp2zfV6vbUuYkjT1JwNdDod01St1+sr74NoHcPhELZtYzqdwnVdc1XU6+tr1YdG32QwGODk5GTh+mVddABwfHyMyWRinidJAiEEbNs2J+b6Abz1Br03frSKXq+HdrsNy7Jwc3OT60EqBsirqysTFNvt9lZ20QFrBKPRaJQ7o7y7u4Pruktfo6N1mqYYj8dotVpI09QEtk18abTfLi8v0W63zfPsDzWKIkwmEwyHQ8xmM/R6PUynU5ydnVVxqPTNdH2lu+eSJMn1xKzSRafX6df1+/2lLalNubi4MEEu26qLomiu/DYajbmguJXUioIgUJ7nKQAKgBJC5Nbp5Z7nKfX2F1Gu65rlcRwrpZSSUuaWh2G46iEQlRJCmPKULYOe5ykppQrD0CxzXbfKQ6Vvkq2ryuospd7qrSAIFr42q1i2ymTrubJ12Tove0xl9WexTOt9l71/tj7d5np15WC09o6XfDFEX8XzvLnAo4NSHMfvVihEP0FZMCkLnOtu+5P960ubXUQV0n3n2Zsf1TZ3Y9Be8H1/blxo0U2ug8EALy8vuSsFkyTJ3Ve1LSz1Bb9Ox3HMxQ1xHH/oskmidQ0GA3O/27L7Moh+On11nrasPGfrWwBbe5/RlwQjIiKidTCFBBERVY7BiIiIKsdgRFurOJmkvn/NcZyV8s/Q7tNl4b2JQweDwcK8RsVcbvQ1GIxoa9VqNSilIIRAGIZmgDc7NyIvYthfvu/j8vISSimcnp4uPDHRwUf9Z1LndrudmwtOCAEppbkSkyc4X4MXMNDWcxwH/X7fXN7qOA4mkwknTd1jaZqaGbLLnhe3zZYVy7LMdlEUYTqdmpOaJElMNgLaLLaMaGfo7hQGInp+fs5NV6ZzspVNzJwtK77v52aBL85jWJweiDaHwYh2wnQ6NXN0LQpEOqljdrb4siRm2zrrMf1j0WS4f/78KV2uT2RGo9Hca7NddvR1GIxoJ+jkj8sCyXA4NP3/+gy3VqshCAKTnEwplcvsSftBz84RhqFJBAq8zdo9Ho/NuFIx1xBtDoMR7QSdMVNnIy6Tpikcx5lrOT0+PqLVamEwGJikj7TdFk2Ho5PQLdJqtXKJQPXJik7nIISA67rsBv4CDEa0U/TVdZZlzXWvPD8/4/T0NLdMpzfReWNYyeyGo6MjjMdj8zxN01yLeBnbtnPBTOdfU/9JKsqTla/BYEQ7ZzabQQgxN2B9e3s7N9nk8/MzgiCAUupb8tTQ99DZUnX32vX1NTzPe/d1aZpiNBqVpii3LAu9Xo8nLF/l+yYIJ9osnRICJXmMypYXc3Dp3FpMdbK7dF6gYh4rIUQuxUi2vGRlcw/R1+J9RrTzoijKZYMF3mY21t042zrLMdEuYTAiIqLKccyIiIgqx2BERESVYzAiIqLKMRgREVHlGIyIiKhyDEZEtLP0RLjvzbKdTaA3GAzm1mcn2WWCva/BYEREOymKItTr9ZW2bTQaiOMYSik8Pj7msr2maYrDw0MzJRDvSfsaDEZEtJNardZKSfCiKILjOGbeuouLC9ze3pr19/f36HQ6X3ac9IbBiLaarkiyeYmYf4bWMZ1OcxPoFidZvbm5YffcN2Awoq2VJAna7TaklCaFhOu6uL6+rvrQaIssOnnRyyeTCZRSmM1mC9OT0OcxGNHWqtVqCMMQQgjTj88ZlWnTdJmazWbwPK/0Agf6PAYjItpri05gypafn5/j8fHxqw9pLzEYEdFeOzk5yQWY5+dnuK67cPtigkbajH9VfQBERFVqtVpot9tI0xS2baPX66Hf75due3Fxgdls9s1HuCeqSqRE9FnZ5HpCCBUEwVxCPdpfxeSLYRiaddnkekopJaU02wVBsHAfUspv/Qz7hPmMiIiochwzIiKiyjEYERFR5RiMiIiocgxGRERUOQYj2guO43B+MaIfjMGItlZ2ctTiIzvfWBRFufnF3sttQ7tj1ZOQbFnyfT+3LpvrqGw/en027QStj8GItlatVoNSCkIIhGFo8s24rgshhNmu1WqZqV0ajUZVh0vfzPd9XF5eQimF09PTuSCjpWmKer1uys9kMsnNPyeEgJTSpKPI7idJklxZo49jMKKdc3FxAWDxbMw6bw3trjRNMRqNTB6is7MzjEaj0m3v7+8RBIF53u/3cXNzA+CtVe15njmZ6fV6uf1kT4jocxiMaOe02224rjs30eVgMMDV1VVFR0XfqTi/nG3bEEKUdtG+vLzknh8dHUFKiTRN8fr6mlunT2TY1bt5DEa0E9rttunXl1LOpYbW/fm2bTMFwB4oBhHtz58/pcuLASmLyRq/B4MR7YQwDE1Xy9+/f3PrBoMB2u02ut0uLMvC79+/qzhE+qFOTk4wGo1Ma0eXH9u2cXx8jPF4bE5mdGD69etXNQe7wxiMaGd0Oh24rmvGjLLL9eC0UgqtVquiI6TvsuiE4+DgYG5Zq9WC53mo1+uwLAv1eh2e5wF465YLgsC0vIUQpV3A9HkMRrRThsMhpJTsittzR0dHGI/H5nmappBSLrx4ZTgcmpMVIQSGw6FZlz2ZcV03t442h8GIdopt2wiCAN1ul/d97DHbtuG6rikD19fXprWziL5faDKZlK63LAu9Xo+toq/y3TkriDalmGsmm8PIdV2zPI7jCo+SqiSEUAByuYv0cr1M58ESQsy9PgxDU47KZPMgoZALidbDfEZERFQ5dtMREVHlGIyIiKhyDEZERFQ5BiMiIqocgxEREVWOwYiIiCrHYERERJVjMCIiosoxGBERUeUYjIiIqHIMRkREVDkGIyIiqhyDERERVY7BiIiIKsdgRERElWMwIiKiyjEYERFR5RiMiIiocgxGRERUOQYjIiKqHIMRERFVjsGIiIgqt1IwchwHlmWVPtI0BQAMBgM0m80vPVgt+/6O4wAA0jTNLf/qY2k2mxgMBl/6HrRckiS579z3fQD58qqX0X7SZeG9+iBbf5T9rheVp+zryt6j2WzO1ZWLjlE/3rPpeuc76+6l1IqCIFCu6+aWhWGo4jhWYRgqAHPrv5LnecrzvLnlQggVhuG3HQdVr+w7B6DiOK7oiOgn8DxPBUGglHqrv8rqC00IYcqL67q58pR9nt2nfl32/9l12W11HblIWf1aJgxDJaV8d7tVVVF3L/KpbrpWq4VarYZWq4UgCDYRG4k+zXEcSClRq9WqPhSqSJqmGI1G6HQ6AICzszOMRqPSbaMoguM4prxcXFzg9vYWwFvrezabodVqAQDOz89xc3Nj3mM2m5n9NBoN/P792zzPvn+r1YIQAlEUfepzTadT2Lb9qX1k/aS6+8PBaJXuj7LuPOCtshgMBnNdfnqfvu/DsqxPf3G6iaz3s+hYisdRfH3Z53Acx+xXF+Zst1HZe0RR9OnPRIvpLpPJZLLRHyxtn+fnZ7iua57btg0hBJIkmdt2Op3i9PTUPD86OsJ4PAYAPD09odFomHW1Wg1SSqRpmitjSZIgTVMTtMq65BqNBqbT6ac+1+HhoXk/Xc/oOidJEkRRVNrdVxzG+InWCkbj8dh8mMlksnRby7IQxzGUUgiCAEIIpGmKZrMJKSVubm6glDIPABgOhwCAq6srBEFgvthFRqPRXLCQUpr1Dw8PEEKY59l1wFvQazQaUEohDEMAMMei+2WVUojj2Lzetm3zGYC3QtFutyGlRL/fh1IKruvi+voawFug0st7vd7Sz0MfN51OzXe5KBAtOgEq9utnn9N2en19LV3+58+fuWWLxnLSNMXLy0vpur9//5r/N5tN1Ov1XCvpvX1/RBRFODs7Q5qmqNfrAGDKvOd5uLi4wHQ6hVIKQghTh6VpCiEEpJRm259YttcKRq7rmuChLxwoE0URhBCm2dvpdCCEwP39vQkQ/X4/9xrP80yr4f7+HmdnZ+8ej+d5uYCmv4RVpWlqzjSKZzQvLy+mUqvVahBCmAKYDXK1Wg1hGEIIgYeHBwCYqwx1EMo292mzJpMJpJRLy2Wn04HruuZHKaXE4eGh+d50IBsOhxBCmBMTomUeHh5MedK9O7ollu1BytY3H6G76GzbNifIOgAeHh7CcRxzQp/9Hdzf38N1XVMv6W1+Wi/Nh7vp9A+4zOvr61ylsKySAN5aQ7rSzgaC4tnsJs80Li4u8Pj4COCfIKTf9/z8PNf6k1Li169fa79Hq9XKdQXS19CtTynlu39n27bh+z5s20an00GSJPA8z6x/fn7G5eXlVx8yfaHs2E3WwcHB3LJFLWnbthcGj7K6IAzDXJ0xmUxyvUnj8Xilk+wynwlk2fpUW+ek/bt8yX1Gv3//Nn2uxeWL2LZtxmFOTk7M8k6nk2v5bHrwbjabwbIsCCHM2Qbw1uLJBpEwDD/83vrMyXXdn3EJ5Q7TreOyE5coikzlkPX09JTr8m232zg+Pv7Ow6YNy477AG+V+aKLWk5OTsxJKZAfbzo+Ps4FmCRJIIQorQsODg5yJ922bZt6KwxDBEGwdh2iW1bPz88fDmSHh4elwyplgblKXxKMdFeU/kOmaYrxePxuF9XFxQXa7TaOjo42diyO45j+4/v7ewD/nBX4vo/b21tTYLIFdTAY4OLiwqz7aPda9qIFjhl9j9lsBiHE3ID1dDpFHMeQUuZODcZwrQAAIABJREFUeG5ubkzXne6a45V42822bbiua35719fXudZvVqvVwng8NicvvV4PFxcXAP4pB7oc9fv9ha3mfr9vXpfl+z6m06m5sm5V2W6019fXD58Mn52dQUppxpD0Z/lxZXyV67+FEAqAeRQFQWDW6Wv5pZS51+hr413XNcvK7gdadi+Alt2vvs6/+H76unl9Hb0+tuyxZI+7ePzZ1xX3mf17/O///m/uWIp/izAMc595k/cI7Ls4jku/O/09F5eXlV0pZe4eiziOVyqDtB30b7V4H40QIrcsW39k7xXSimVJqfnyV3av26J6ruwYyx76vqLsMRXrumxd5bpurvzr1xWPVSuru6uy8k2v30HfQPtdyt4re5Na2fYMJtsn+0PM/qizP+I4jnM/TH7PRN/LUurnXDLk+7650uOrJUmCi4uLucsxfd/H1dVV6dVU33l8RET75F9VHwAAM6Cs7/X5DrVaDY1GY24wWwegIAjm1hXvUyIios34US0jIiLaT0whQURElWMwIiKiyjEYERFR5RiMiGivOY6zVhJGPUN/cZmeweOnzfm2LX7E1XRERFVYd77IwWBQOvu/4ziYzWZmhuyjoyOmMVkTW0ZEtLfUf1IqrKIsFxLwNt2ZzoekA1A2xQSthsGIttp7iQ2JNuXu7q50frnT01N0u10AbwHLdd2fN+/bFmAwoq31XmJDoDxbbzYbpp5lWT/nrOpUZjAY4OrqqnSdzpNlWRb6/f7S9Dq0GIMRba1VEhvqRIgqM5X/wcEB4jiG67pmOqgwDOF5HisSmqO755aNAeluuvF4vLA7j5ZjMKKdliSJmfLf9320Wi3UajU8PT3lpvufTqc4Pz+v6jDpi2Wvdlu39Xt3d4dut5tLkFmv101KBv2vUgpBEKBer7Or+AMYjGinZSuSbA6jx8dHtNttU8GMRiP28++w2WxmWsfrtn6Hw2EuwScAxHFsxo9ubm5M4lDdZff8/LzZD7AHGIxop00mE9M9p5M2pmmaq5x0lx3RRziOg9vbW/N8PB7/uCyq24D3GdHW0hcwAG8VwuXlJUajkVl/fn5uLlDIZup9fn7OZessdtnR/nAcx9w3lKapaTUNBgN0u11IKd+9X+jh4SHXhRcEAVvZH8BZu2kn6coEeOtS0ZWD7/smYCml0Gw2MR6PIYSYy21FRN+HwYiIiCrHMSMiIqocgxEREVWOwYiIiCrHYER7Qd/0yOl+iH4mBiPaWtnJUYuP7B3wURSZ+41msxmna9kjq56EZMtSMbdRsZwtwnxGn8NgRFurVqtBKQUhBMIwNDexuq4LIYTZrtVqmXtFGo1GVYdL38z3fVxeXkIphdPT04UJ9NI0Rb1eN+VnMpmYKX6At6l/dPkKgmAusOmJd/U22XvaaHUMRrRz9A2si+YH4w2Juy9NU4xGIzNlz9nZWe6G6Kz7+3sEQWCe9/t93NzcmP0AMLN3/P79O3c/WpqmZuZ4BqHPYTCindNut+G67tyd88vSANBueX5+zk3xZNs2hBClXbQvLy+550dHR5BSIk1T8zqdlmQ6naLf75ttfd9HEAQQQsCyrFyLitbDYEQ7ITvpqZRybjJM3Y9v2zYrjD3w+vpauvzPnz+ly4sBKWsymWA0GpnJdrMtoPF4jMfHRzP/Ybfb5YzdH8RgRDshDEPT1VJM+TwYDNBut83s3XqGZSIAODk5wWg0Mq0mXX50y1q3jgCg1+uZ1+nt9YlPq9WCEAL39/ffduy7hMGIdoaevr846Wmn08mlAGDf/u5bdMJRNpt2q9WC53mo1+uwLAv1eh2e55n1juOYqzEBLL0yT0/MS+tjMKKdMhwOIaVkV9yeOzo6wng8Ns/TNIWUcuHFK9mcRUIIDIdDAG+tn+zM3ZPJxOxX76s4DsWW98cwGNFOsW0bQRCg2+3yfo89Zts2XNc1ZeD6+jrX2imTpiksy8JkMjHLfv36BeCfMcfn5+fcbQOe55kLGpIkwWw2Y8v7oxTRlorjWAEwD8/zzDrXdc3yOI4rPEqqkhBCAVCu684t18uCIFAAlBCidB9hGObKmZQytz5b1orraHVMIUFERJVjNx0REVWOwYiIiCrHYERERJVjMCIiosoxGBERUeUYjIiIqHIMRrQz0jRdmLNGr88mSRsMBkiShMn29sxgMChNkrcswV6RzmFkWdbCKYCy+yubPDWKoqXTBzWbzaUJIzc9IavjOJXeKM5gRDvj/v5+Yc6aJEnmkvABb4nTsjM564pqUQVC2833fXS73bnlaZqi3++bsjEajRZWzDqHURzHUEqh0WjMBS/f91Gv1yGlhFJqLp1JkiRot9tLj/Xh4QFBEMB13bl9vL6+zu3zM5rNJqSUG9vfRzAY0c54fHwEgNJKpF6vIwiC3FQtnU4HcRybdANpmubSAbx3dkzbZzgcIo7j0nXZtCOu65ZOqgr8M6u3npvu8PBwYZr7RQGjVqshDMMPfYavOEl6eHjITXNUBQYj2glRFKHX68HzPNze3s6tA96yfRbVajWTDfT5+dlUHkdHR7mMnrTbskEjiiLYtr1wUlW9XE/G+/j4mEst0W63cXl5aVrYq3QDZ7v93tv++fnZlGXf9+H7vmnR624/3cVXPKHKtvx/2skWgxHthNvbW9RqNZyfn2M8HufOHqfTKQC8261xcHBguvn+/v3LdAB7yHEctNvtd1sfcRyb/Fi9Xq90Bm+lFDzPm0tpUmY6nSIIAiilFgZBTXfRDQYDjEYjU2aVUpBSwnEc9Ho9xHGM0WhkPstgMDAtf90V+ZMCEoMRbb0kScwPvlar5dJEL+M4jjlLbDabqNVq8DzP5LTRaQRof8xmM0gpMR6Pl6YhyQaMbBryp6cnuK5rWttXV1eQUi5t7TSbTZycnJjXLJMNkp1OB57nwfM881ohBPr9Pmq1mplxXLu5uckFxjAMF46xVoHBiLZev9/PjQX1+/3cj+zw8BDAfN6Z2Wxmfsx6vCCb12aTA8T0vbLdUetejKLTkOgxyDKWZZlyMh6PF7Yw3itDOvDp1vt77u/vS7ubVyGlzI2DLRoTqwqDEW21NE1xenqaW6YDkx4r0meN2TNY2m3F7L7rnlj8/v174WuiKMoN9sdxbHIgHR8f55L6acVWiiaEePfqvaKPniQJIfD09DS37KdgMKKtdn19XXqmWLyQIQxDjMfjpSmjibRer4fz8/PSdQcHB7mut6enJzO+qLuJdRffYDCA53nvBpAwDBde6q1PttI0/VQW2cvLS3S7XdNKvLu7w+Xl5Yf3t3HflzqJaLOklLmkZ2WPYmK9Vbah3aUT6aGQDK+YQK9YJrLJ+Mr2U6SXL0rYl00MKYTIvX8QBKVJAYMgyCXvyx6D53m5JH+LEgJ6nleajFK/X5W/BybXIyKiyrGbjoiIKsdgRERElWMwIiKiyjEYERFR5RiMiIiocgxGRERUOQYjIiKqHIMRERFVjsGIiIgqx2BERESVYzAiIqLKMRgREVHlGIyIiKhyDEZERFQ5BiMiIqocgxEREVWOwYiIiCrHYERERJVjMCIiosoxGBERUeUYjIiIqHIMRkREP9xgMMBgMKj6ML7USsHIcRxYllX6SNN0owdkWRaSJNnoPn3fzx0zgB/7xSZJYo5xHWmafsn38ZPpv5V++L4PIF9e9TLab+/9NvTvx7KsubphMBgsXLfqe5e9LrvfZceWJAm63W7pumazuVZ9/FPrPWDFYDSbzRAEAVzXhVLKPMIwxN+/fzd2MI7jbGxfWrPZxGQyyR23ZVm4ubnZ+Ht9VpqmqNfrH3qtbdtQSsG27Q0f1c9Vq9WglIL4/9u7f93ElTYM4A/SdxWr1WrF+BpSrAg6J0XMBaSA7FekimTqCBpKGltpT5CoUoGLXACmyDmKrRS5BsZaRdHexnxFvpkzNuZPEhIDeX4S2sU2xoTB78zr8YwQGI/HuLq6AvBcXgEgjmOzjD6vdSokx8fHiOMYSinc3t4iDEMAMBVjpRTiOEa32zXrVtEBrkiSJBgOh1BKQUoJIcTC/YxGI/i+X7huMplgPB5DCLHy958kCX78+LHWsZfhTWm6ZrOJWq22qWMxJ5FNCYIAURTN7Vcp9S6B762q1SriOC77MHae4ziQUm60bNJuCsMQ379/X7mN4zimvJydneH6+tqs73Q6AJ4rP57n4e7ubq331hVE13Xn1vX7ffT7fbOd67qFQa7dbuPi4mKt91tlNBpt9W/i1cGoqLZR1FzUzchGo5HZRj/XKbRFqTm7Gaq/LF3j0M3cRTWf4XAIz/MK100mk8y+dA0mDMPM8dnL7Idu7tqvz3+2RX8TXfjtNFO+eW3v1/7b2Mdiv08+vddoNBAEgfn76m11Cmubm+uvpf9m0+n0U7UQabG7uzucnJys3Obo6Mg8Pzg4QBRFADB38rYDm31uSpLE/NbW+W1FUYSDgwPz/OjoyAQ5vc///ve/GAwGEEKg2+2+qFVWRB+7ndK3z62Lzkf5dPi7pb/VmnzfVwDMQwiRWQ9AxXGc2VZKqZRSynVds04ppYQQ5rmUUo3H44X70eviOFb6cPUxeJ638HillAqA8n1/5Wez963f13XdzH70ZxFCZPYphDDH6HmeeZ3+3Pp1ep/6vQCYbV3XNZ9Fr9d/X8/zzDopZWb/+r31MerP4HmeeW6vF0KYv/cLvvqtJ4RQnufNlcm8fBm2y5D+m+gys6xs0W6wfzf2bzjPdd3Mb3rZ9p7nZc5ldrmL47jwfLPO/u1zThHf9xeey8bj8cqyH8exOW67/Ot9CyEKz0d6e/3a/LpNelHLyL5mZKe5wjCEEMLUIjqdDoQQuLm5AfAc9UejkdleSon7+3sAwM3NDZrNZuH7DYdDtFotVCoVcy0lSRJIKQHgVc3XfCtnVWcJfU1M17TPz8/x69evzGf5+vUrAOD09NSkBNM0RRRFEEKgUqmg2+0iiiLUajWT49Wts6JavN7P9+/fTS3l5uYGURSZY5dS4u7ubi69d3V1Bdd14fs+ms2m2f/19TWq1ao53n0ynU4hpVyafu10OnBdF1JKk6v//v07giBAr9czZZt2XxiGqNfrG91nmqZI0zTTWtLXJBuNBvr9vknpbRs7RafPn/rfb9++AUDh+Uife758+QLgOYX5Xp2kXp2m0wcOAI+Pj3MnAfv5yckJptMpgOdCMh6P1+pAIKU0FxX1Y1HO0+5B1Wg0zB/09vY2s12z2cx8GatyqLVaDUIIE7R+/fqVaap7nmcC69PTk/ncOojZx/7WE92vX7/geV5mf7xA/6zf75sAs6o3YrVaRbvdRrVaxcnJCbrdbua6YqfT4d91x11fX5uKrO4cIIQoTHMtSunml19eXmbOe9psNkMURZlU3zLrvp+t0+mUEuj09ayHhwcAz+f690qBb+Q+o2/fvpkca3458O8fOU1TPD4+moCwKsIKIfD09LTWMcxmM3OC1gXG931EUfTmruL9fh+Hh4cml2oXiouLC3S7XVQqFbRaLfPeuiaxyVqE3UqiYur/veuKrsOFYWhaltrDw0PmuqJ9HYB/6901mUzM+cCufBZlYer1eqbS+vDwMNfpoN1u4/T0tPC9HMcxPe3WPdfYJ3jgudK86Zacvq6TJMnCY19Hr9czgX04HL5bRW0jwUh/wfrD6xSV/cUfHx/j8vLSBCjP83B5ebm0q+Hx8TFarZZ5ri+yrUunCw8PD5e+Lh84hsMhoihCu91Gmqa4vr6eC3T2MRa1fKrVKoQQmQt9b73o9+PHD0RRlKnd8T6aebPZDEKITIsWeL5QHccxpJTmh//4+Jhp6U4mEwghIKVkJ4hPotlsIooi8/vv9Xo4Ozsz64MgQL1eN1mUMAwzHbSm06lJvx8eHq5VibF77CVJMne+fKskScxx3N/fv6kX3dnZmTm/bbrHc8Y6F5aEEHMXvfLsi+gouPiXv2hedBG96PWu685d8F/2PkWKLlznLxba75PviJB/7aLj0498hwz98H0/04FBd4bQz3/+/Dm3n/zx2sv0ceT3aXdg0Bcni/a55te/tezPrb83pbIdOOzlRZ8333lFSrnyYjDtlqIOA/YFe3sb/ZvRin7f+nW6nOnti84PReVQs3/765zHihQdX/5z5N930Tkmfz7Sr8uf/2F1aNik3T4bfRA7uGj6i162jraDHbSKvpt8gOb3R/SvjzrHcWy6Fex7ebQgCHBycoIgCOZugEuSxKQiaTvokRqUUoUXgZvNZibVuq09oog+WrvdxuPjY2ZZGIbvMpJDRSn2ZV0mTdO5oTp83zcnLH23v+a6bmGPGyKiXZTvnep53rt0YmAwIiKi0jFNR0REpWMwIiKi0jEY0c7KD+CYpmnmplW784keoWMbR2unj6UHWM6zhwpbdf/esvmP8tssogdMXmTZXEX2vU6b4jjOmwZifbON988j+kC627Z934PruoX3Ci0biJI+B/seNJuUcm5g1WXdl+3Bnl3XLez+rO8BKpIfEHmRRQOobrprtT7Wos/xUdgyop2mxw60h406OzvL9HAEnmup644dRvvr6uqqcM6w379/mx5i1WoVvu/PjWuprZr/CHhufS0rb3rEhtd4j2Gq9MgjZWIwop13fHycORnoYVXslMPNzc3KeW3o88oPl7PsXsFl8x8B/waLl9yLY6cIVw159vDwYMpyu91Gu902qUed9tMpvny60Z7qfNuGEmMwop13enqaORnoH3P+hmSONUfrenx8zIxPZ1vUMtHLLy8vX3zj9N3dHXzfXzozgX1s1WoVQRBgMBhgMBgAgBkU1nEc9Ho9xHGMwWBgjisIAtze3pqbuweDwVYFJAYj2nn2AJbA89wt4/HY/Eg5+ja91HA4fNXApUEQvHiE7EajgXq9vlYAs8typ9OB53nwPM+8VgiBfr+PWq1mBoDWhsNhJsDav5FtwGBEe8HzvExLSE/pnCRJJq1Bn4OdjnrpdCDtdnvp6NTL5iMaDodmuhk9Ieiy1JuUElEUzbXiF3lLutmeCBTA1k2yyWBEe6Fer2MwGCBJEtTrdTMp2Gg0MrPh0ufR6XQy4w2u+/3r6SKWWTb/kT2vmu4osSz1JoQwKbN1u1W/tiwLIcxEoPaybcFgRHtBp1QODw/N/4+OjjAYDDLzFREtooOBLj9JkhS2aFbNf/Qa4/E4M3ebTXeWSNP0TYMwn5+fo9vtmuMejUY4Pz9/9f42rqQu5UQb57puZu4Wfb/Ie8y9QrspP7eZnkcoPwcWcvcArTv/kS0/V1bROv0+9jQm9hxk9nv6vp+Z9yg/95A9t1HRvGf5z2n/Vuw5i8r6vXCgVCIiKh3TdEREVDoGIyIiKh2DERERlY7BiIiISsdgREREpWMwok9Bz2dkz3FERNuDwYh2Vn5yvWUTkU2nUyilMJvNVo6KTPtj3UqIXZbyg4faE+mxMvN+GIxoZ9VqNSilIITAeDw2w7C4rpsZ5qTZbJohVI6Pj8s6XPpg7XYb5+fnUErh6Oho4QjVaZri8PDQlJ/pdJqZvVUIASkl9C2Z2zTS9T5hMKK9o4dmWTQ45qoh+mn3pWmKwWBgRrM+OTlZOEL1zc0NfN83z/v9PobDIYDnVrXneaYy0+v1tmqk633CYER7p9VqwXXduQElgyDAxcVFSUdFH8kevBR4HlxUCFGYov3161fm+cHBAaSUSNMUj4+PmXW6IsNU7+YxGNFeaLVaJq8vpcRkMsms14Ng6knJaL/lg4hmT09vywckG+fD+hgMRrQXxuOxSbX8/v07sy4IArRaLXS7XVQqlTeNfEz7x55+BPi3/FSrVfz48QNRFJnKjA5M+Ynr6O0YjGhvdDoduK47N5x/fm6b18zgSbtlUYWjaEK5ZrMJz/Myk+J5ngfgOS3n+75peQshClPA9HYctZt2nuM46Pf7aDabSNMUQgj4vr/WNM60n3Q50Ke3/PNlHMdZONNro9HA1dUVg9E7YMuI9kq1WoXv++h2u2vPnEn7R8/0q8vA5eWlae0sou8nmk6nhesrlQp6vR4D0Xv58BmUiDbEnqAMucnC7InGOLne51U0SZ1erpfpSersyfQ0e5I6el9M0xERUemYpiMiotIxGBERUekYjIiIqHQMRkREVDoGIyIiKh2DERERlY7BiIiISsdgREREpWMwIiKi0jEYERFR6RiMiIiodAxGRERUOgYjIiIqHYMRERGVjsGIiIhKx2BERESlYzAiIqLSMRgREVHpGIyIiKh0DEZERFQ6BiMiIiodgxEREZVurWDkOA4qlYp5aPYyx3Fe/OZBEKDRaCxc32g0EATBi/erLTpu2l+O4yAMw7IPg7ZEkiSoVCpIkmThNo7jzK1/yXnD3ja/H/3++pGm6es+yCewVjCazWbwfR+u60IpZZYrpeC6Lnzfx2w2e9Ebh2GIbre7dJvJZIJOp/Oi/dpmsxk8z4PneZnjpv2UJAmklLi+vi77UGgLhGGIw8PDpdsEQQApZWZZo9GAUsqc35ZVtBuNhjm/xHE8936j0cjsSymFarX6+g+050pL0zWbTfi+X9bb0x4ajUYYj8eIoog1UEKz2VxaCV3UWur1eub/V1dXkFIuLE+z2Qz1eh0A8OXLFwAw26ZpatbRahsPRmEYFjZLdXM1CALzr00vt19jp1zCMDTN6dc2eRuNBiqVitlnfj/tdhvtdtuk99I0RbvdflMqkj5Ws9kEADw8PJR8JLTtRqNRYealVquZ/69qyRwfH5vg9fDwAM/zzGtubm7QarWYnlvTi4JRFEWZQFOpVBBFUWabXq+HOI5NE/fy8hJpmmaar0qpuUJwe3uL8XhsmrKNRsM0n5MkQavVgpQS/X4/s++XmEwmEEKY53bzPAgCDAYDDAYDTKdTU6MaDAamiS2l5PWILRWGIU5PTwEAnucxVUdLBUGAi4uLldulaQrXdRcGpaurKwDPFdu7uzvzHABOTk6glILv+xBC8NyxwouCkb5mZD9c181sM5vNTM1Cf4HVahVxHANAYU3EcRz0ej1TqwWygaNWq2E8HkMIgclkktn3pnQ6HXN9yT5uu5lvBzLaLnd3d6bcnZ6eMlVHC+n03DrnkMvLy0zarsjx8TGA54qrXeb0/judDuI4Xrmfz+7drhlVKhUMBoOV20VRBCkl7u/vX/1eOv32Xqk0nRrMX+ik7ZCmKQaDgSkDuhXOVB0VGY1G6Ha7md5yh4eHc5cOkiRBvV7PpO3y2u026vU6lFLwPG9hhVXvgxWkxTYejHRg0F/OKq7rQkqJbre7tPvlMpPJxLTUXtqrb5VKpWJSg2wZbaebmxtIKTMtdqbqaJGrq6tMWQGAOI4zWZs0TdHv9zPZmiKDwQBfv341+xVCLDyPOY7D3nRLbDQYpWlqWjovUa1W4fs+zs7ONnk4ht2jxXEcPD4+Ang+iQGL029hGGZSg7Sdbm9v537kFxcXiKLo1RUc+tyOj48zv/tF9zsKITAajQA8n/+klKZXnS0Ignc7v+0NtQYhhAJgHpq9TAihlFLKdd3MMgDq58+fc68fj8fmueu6yvd983w8Hmfe86+//srs097W87zCY1603n5fz/MUACWlXLjP/GfUx0fli+N44fdsf2+LygjtN7t8LPvdAlBxHBe+Rj/0en2ekFIqpZSSUi58D/sc5vv+O3/a3VdRineDEhFRuTg2HRERlY7BiIiISsdgREREpWMwIiKi0jEYERFR6RiMaGfl54qxHxwHjID15jPS7JFc2u22WV5UvjiSwuYxGNHOqtVqZmQMPciu+v+8Mq1WiwHpk1tnPiMtSRKcnZ2ZMqQHPA3DcG48TmDzY2MSgxHtoVqtBs/zcHd3V/ahUIlWzWdku7+/Lxz65+DgIPM8DMO1hjmjl2Mwor2jB07lxGa0Lj1wqp2eA+ZbQNfX12aqEtosjsBAO89xnLnxEKWUTKUQgOdrPnEcLxx9O01TU1YqlQqEEAsHXNaDQNPmsWVEe8G+ZqTnvsrXcomK2JUWpVRmhmkbU3Tvi8GI9k6z2YTneXOTnRGt4+zsrPB6I1N074vBiPbS9+/fyz4E2mFF1xujKFo60R69zX/KPgCiTUuSBN1uF67r8roRvViv15u7ZsQU3ftjy4h2lj0dfKvVykw77rouJ0X85HT5AJ6nFbevAzmOg0ajAeA50Ng3tBZ1XmCK7v2xNx0REZWOLSMiIiodgxEREZWOwYiIiErHYERERKVjMCIiotIxGBERUekYjGhnLZtcLz8MkL2tvr+E9p/jOCu/8zRNC8tQnl2G7PKlX8/5s96GwYh21qLJ9VzXhRAis22/3zfroyjiIKqfQLvdxvn5OZRSODo6WvidPzw8ZCbPk1LOlZ92u43Dw0NIKaGUMiN7JEkyty29DoMR7Z2zszMAMLXXJEkyozGMx2NMp9NSjo0+hp7TqtPpAABOTk4wGAwKt81PoHdzc4Pz83PzPAxDTKfTTBDS7AoRvQ2DEe2dVquVGZcuP7jl169fyzgs+kAPDw9wXdc8r1arEEIgSZK5bfMBZjgc4uTkxDxvtVo4Pz83KbqifdDbMRjRXrDHppNSLh2X7unpKVPzpf3z+PhYuPzp6Wnp63Rr2k7DaUopeJ5nWt60WQxGtBfG4zF83wcA/P79e+m2vV7PpG+IbPkU3f39PVzXNeXl4uICUkq2jt4BgxHtjU6nA9d1l9ZcgyDg9aJP4Nu3b4XLV6Vo8ym6PE5J8n4YjGivXF1dQUqJIAjm1umutzyh7L+DgwNEUWSep2kKKeXSyfHyKToA+PHjR2Y/2pcvXzZ4tAQwGNGeqVar8H0f3W43c99HkiS4u7sz6ZY0TXlfyB6rVqtwXdd8x5eXlysnx8un6IDnzi9CCFO5CYIAnuexQvMeFNGOiuNYATAPz/PMOtd1M8vt7fSD9p8QQgFQruvOLS9aJqUs3I8uM0KIzHIpZaZM+b6/2Q/wiXByPSIiKh3TdEREVDoGIyIiKt1/ihb++eef+Od/MAbEAAAAMklEQVSffz76WIiIaMf98ccf+Pvvv1/8Ol4zIiKi0jFNR0REpWMwIiKi0jEYERFR6f4H38DRe1f2dVwAAAAASUVORK5CYII=\" width=\"419\" height=\"601\"\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cp\u003eTable 2 Different adsorption Kinetic models with their Parameters for the adsorption of Cd(II) onto biochar\u003c/p\u003e\n\u003cp\u003e\u003cimg 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\" width=\"472\" height=\"295\"\u003e\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Adsorption, Biochar, Cadmium, Isotherms, Kinetics","lastPublishedDoi":"10.21203/rs.3.rs-3062902/v2","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3062902/v2","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003e\u003cstrong\u003eObjectives:\u003c/strong\u003e This study aims to investigate the Cd(II) adsorption from aqueous solutions via wood biochar (BC) as an adsorbent, using different parameters, adsorption isotherms, and kinetic models.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMethods:\u003c/strong\u003e Experimental tests were conducted to study the Cd(II) adsorption on a batch mode system. The study evaluated parameters such as pH, contact time, and Cd(II) concentration. To analyze the adsorption mechanism, various isotherms were utilized including Freundlich, Langmuir, Temkin, Redlich-Peterson, Sips, Flory-Huggins, Fowler-Guggenheim, and Harkin-Jura were used. Additionally, Pseudo-first-order and Pseudo-second-order were used to study the kinetics of adsorption.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFindings: \u003c/strong\u003eThe Langmuir isotherm suggests that the maximum adsorption capacity (\u003cem\u003eq\u003c/em\u003e\u003csub\u003emax\u003c/sub\u003e) is 28.57 mg/g. According to this model, the metal ions are adsorbed by forming a monolayer and do not interact or compete with each other. Based on the Temkin isotherm, it can be concluded that the adsorption of Cd(II) onto BC is mainly physical in nature, as the value of heat of adsorption is less than 1.0 kcal/mol. The Redlich-Peterson and Sips isotherms indicate that the adsorption process follows the Langmuir form and further supports the predominance of monolayer adsorption pattern. The negative value of Gibbs free energy (ΔG\u003csup\u003eo\u003c/sup\u003e) suggests that the adsorption process is thermodynamically spontaneous and feasible. The Flory-Huggins and Fowler-Guggenheim isotherms indicate that the active zone of the adsorbent is occupied by adsorbate and also suggest the presence of repulsion between the adsorbate. The kinetics of the adsorption system followed a pseudo-second-order reaction rather than a pseudo-first-order reaction with an R\u003csup\u003e2\u003c/sup\u003e of 0.999 and 0.979, respectively.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eNovelty and applications: \u003c/strong\u003eThe results of various analyses indicate that the process of wood biochar adsorption is efficient and can be scaled up for the heavy metals removal from contaminated water.\u003c/p\u003e","manuscriptTitle":"Insights into Kinetics and Isotherms studies of Cadmium (II) adsorption behavior onto wood biochar from aqueous solution","msid":"","msnumber":"","nonDraftVersions":[{"code":2,"date":"2024-04-10 19:44:06","doi":"10.21203/rs.3.rs-3062902/v2","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}},{"code":1,"date":"2023-06-26 17:46:40","doi":"10.21203/rs.3.rs-3062902/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"e9374238-b954-4031-9628-c62a0476fe26","owner":[],"postedDate":"April 10th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":30486247,"name":"Environmental Engineering"}],"tags":[],"updatedAt":"2023-09-27T20:14:21+00:00","versionOfRecord":[],"versionCreatedAt":"2024-04-10 19:44:06","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v2","identity":"rs-3062902","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3062902","identity":"rs-3062902","version":["v2"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}