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Kinetic, Equilibrium and Thermodynamic Studies of the Biosorption of Heay Metals by Ceratonia Siliqua Bark
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Biosorption of Zn(II), Ni(II), Cu(II) and Cd(II) ions from aqueous solutions onto Ceratonia siliqua (Carob tree) bark has been investigated in a batch biosorption process. The biosorption process was found to be dependent on pH of solution, initial metal ion concentration, biosorbent dose, contact time and temperature. The experimental equilibrium biosorption data were analyzed by Langmuir, Freundlich, Temkin and Dubinin-Radushkevic isotherm models. The Langmuir model gave a better fit than the other three models by higher correlation coefficient, R2. The maximum biosorption capacity calculated from the Langmuir isotherm was 42.19 mg/g, 31.35 mg/g, 21.65 mg/g and 14.27 mg/g for Ni(II), Zn(II), Cu(II) and Cd(II), respectively at optimum conditions. The kinetic studies indicated that the biosorption process of the metal ions followed well pseudo-second-order model. The negative values of ΔGo and the positive ΔHo revealed that the biosorption process was spontaneous and endothermic. According to the biosorption capacity, Ceratonia siliqua bark considered as an effective, low cost, and environmentally friendly biosorbent for the removal of metal ions ions from aqueous solutions.
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... Mango Nigeria Parkia spp. + Locust bean Nigeria Douce et al. [57] Acer + Maple UK Dubey and Gupta [58] Acacia nilotica Babool India Farhan et al. [59] Ceratonia siliqua Carob Jordan Fauzia et al. [60] Metroxylon sago Sago Indonesia Gharde [61] Tectona grandis Teak + India Ghodbane et al. [62] Eucalyptus spp. + Eucalyptus Algeria ...
... Tables 2 and 3 presents the preparation techniques and modification techniques respectively for plant bark adsorbents reported in open literature. The plants barks are sourced then washed with distilled [2,5,59,64,115,118], double distilled [58,101], deionised [44,66,69,79,91,105] or permuted water [53,62,109,110]. The purpose is to remove dust, dirt and other attached substances from the plant barks. ...
... Moisture is then removed from the barks by oven drying [2,5,90,109,110], sun drying [44,80,92,97] or drying in the shade at ambient air conditions [45,46,58,59,94]. Sun drying takes longer time because the process temperature is lower and vice versa for oven drying. ...
Plant barks are among the most widely applied low-cost biomass materials in the study of pollutant removal from aqueous media. This paper extensively reviews the experimental findings presented in open literature with much focus on the last 15 years. This study classified plant bark adsorbents into 5 broad groups (based on their preparation technique): unmodified biosorbent, pre-modified biosorbent, chemically modified biosorbent, physically modified biosorbent and bio-based activated carbon. It was observed that eucalyptus, pine, neem, acacia and mango are the most explored source species in tree bark adsorption studies. About two-third of target impurities reported on the subject in open literature have been on heavy metals. The review elucidated the excellent adsorption capacities of plant bark based adsorbents and biosorbents for the uptake of heavy metals, dyes, pesticides and other pollutants. Adsorption was majorly best-fit to either the Langmuir or Freundlich isotherm models and the pseudo-second order kinetic model. The thermodynamics findings revealed that the adsorption is highly spontaneous and is by a physical mechanism in most cases. It was also observed that plant barks have high reusability potential thereby underlying their usefulness for industrial application. Knowledge gaps in the research area were also discussed in line with future perspectives.
... It describes how the MB adsorps MGP kinetically [34]. The following equation represents the model [35]: ...
... Take integration of.Eq. (2), depending on the boundary conditions of qt = 0 at t = 0 and qt = qt at t = t, the equation becomes Eqn 6 [35]: ...
After synthesis of geopolymer based on metakaolin, nano magnetite/geopolymer composite (MGC) was produced using the chemical co-precipitation technique to demonstrate the impact of geopolymer modification by precipitating nano material on methylene blue removal. Characterize the structure and morphology of the composite that were created also in this study, they were subjected to Brunauer–Emmett–Teller (BET) ,X-ray powder diffraction (XRD), vibrator sample magnetometers (Vsm), Fourier infrared spectroscopy (FTIR),and field-emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS). Methylene blue adsorption on the MGC was investigated. The existence of Fe3O4 has a substantial impact on the geopolymer's surface area and pore structure. The specific surface area of the geopolymer and Fe3O4/geopolymer composite was determined to be 26.604 m²/g and 69.04 m²/g, respectively. It was revealed that a mixture of Fe3O4 and geopolymer with percent 10% magnetite to geopolymer had high adsorption performance on MB, with a removal rate of over 95%, which was much greater than that of separate mesoporous geopolymers. The synthesized nanocomposites as promising adsorbents have a potential application in the removal of dyes from aqueous solution. Langmuir and Frendulich isotherm models were used to analyze the equilibrium data, the Frendulich model revealing a strong correlation coefficient. The kinetic process's results were in accordance with the pseudo-second-order model. Fluidization of biomass was used to demonstrate dye breakthrough curves under the influence of various operating conditions, and the actual results fitted with the predicted data produced using an artificial neural network(ANN).
Keyward :- Geopolymer , Methylene blue, Fe3O4, adsorption capacity, kaolin, artificial neural network
... The maximum biosorption capacity for this biosorbent, calculated from the Langmuir equation, for Cd(II), Ni(II), Cu(II), and Zn(II) ions at optimum conditions (pH 5.0-6.0, biosorbent dose 5.0 g/L, and initial concentration of boron in the solution of 100 mg/L) was 14.3 mg/g, 42.2 mg/g, 21.7 mg/g, and 31.4 mg/g, respectively [47]. Furthermore, it was reported that phosphoric acid-activated locust bean (carob kibbles) may remove considerable quantities of Cr(VI) and Cd(II) ions. ...
The release of boron into the environment as a result of anthropogenic activity modifies sustainable natural conditions, thus affecting ecosystems. To meet water quality regulations, commercial and natural boron adsorbents are available to reduce its concentrations in industrial effluents, with the former being not only more expensive but also less sustainable. In the publication, the biosorption parameters of carob kibbles (Ceratonia siliqua L.) were optimized in order to remove boron from aqueous solutions using batch experiments. The biosorbent used in the present research was agro-waste biomass provided by the local locust-beam gum industry. Boron removal by carob kibbles was favored at high initial pH values, and this capacity was found to be a function of boron initial concentration, biosorbent content in the solution, and particle size. The change in temperature did not affect the potential of biomass to remove boron. The highest boron removal efficiency (55.1%) was achieved under the following optimal conditions: 50 g/L biosorbent dose (Cs), with particle size range 0.025–0.106 mm, for the initial concentration (C0) of boron in the solution of 100 mg/L, at an initial pH of 11.5, for 5 h at 25 °C. This investigation suggests that carob kibble agro-waste can be valorized as a biosorbent to remove boron from wastewater, and the boron-loaded residue may eventually be explored as a new boron-fertilizer.
... The experimental data were analysed with Langmuir and Freundlich as the two most commonly use isotherm models. Langmuir adsorption isotherm models the monolayer coverage of the adsorption surfaces and assumes that sorption take places on a structurally homogeneous surface of the adsorbent the linearized equation is given in equation (10). Freundlich and Langmuir isotherm model was used to describe the equilibrium data. ...
... Tables 4 and 5 list the calculated parameter values that were derived from using these models in accordance with Eqs. 5-8 [31]. ...
In this paper, two types of iron oxide nanomaterial (Fe3O4) and nanocomposite (T-Fe3O4) were created from the bio-waste mass of tangerine peel. These two materials were utilized for adsorption tests to remove cefixime (CFX) from an aqueous solution. Before the adsorption application, both adsorbents have been characterized by various characterizations such as XRD, FTIR, VSM, TEM, and FESEM. The mesoporous nano-crystalline structure of Fe3O4 and T-Fe3O4 nanocomposite with less than 100-nm diameter is confirmed. The adsorption of the obtained adsorbents was evaluated for CFX removal by adjusting several operation parameters to optimize the removal. The optimal conditions for CFX removal were found to be an initial concentration of 40 and 50 mg/L, a dosage of 0.25 mg/50 mL, a contact time of 120 min, and a pH of 5. These settings resulted in qe max values of 41.322 and 56.49 mg g⁻¹ onto Fe3O4 and T-Fe3O4, respectively.
... The entropy and energy factors are used to calculate spontaneity of the bioadsorption process [90]. The positive value of ∆S 0 suggested the increasing uncertainty at the solid/liquid interface, while negative value of ∆G 0 specifies the possibility and spontaneous nature of the adsorption; negative value of ∆H 0 indicates exothermic nature (positive value indicates adsorption practice is endothermic [91][92][93][94]. At high temperatures, the adsorption process is faster and looks promising because rising temperatures can move the driving force of dispersal through the external boundary layer and increase the amount of dispersal within the pores, making it easier for metal ions to enter the bioadsorbents' internal pores. ...
The effectiveness of natural low-cost plant-based biomass and agricultural waste in order to remove the iron, aluminum, copper, and other heavy metals is presented in this review paper along with the experimental, equilibrium conditions and their ability as a low-cost bioadsorbent and analytical techniques used for the bioadsorption. The recent research focuses on the usage of various parts of the plants like leaves, seeds, peels, roots, etc., and other bioadsorbents in the form of husks, shells, and fibers in their natural, pre-treated, and modified states. This review has taken into account the use of adsorption isotherm and kinetics models as well as the influence of experimental parameters made by researchers like initial concentration, contact time, bioadsorbent mass, speed of agitation, temperature, and pH on heavy metal elimination. The review of the pertinent literature shows that the maximum removal efficacies of copper, aluminum, and iron using the various natural low-cost adsorbents vary between 50 and 100% with optimal pH from 4–9 for copper, 2–8 for iron and aluminum, and contact time varying from 20 min–24 h for copper, 90–240 min for aluminum, and 15 min–24 h for iron. However, optimal value adsorbent dose is in the range of 0.1 to 10 g/l for copper and iron, 1.5–10 g/l for aluminum. Additionally, the pseudo-second-order kinetics and Langmuir isotherm are the ascendent models that superlatively defined the copper, aluminum, and iron equilibrium data. The thermodynamic factors indicate that the biosorption of copper, aluminum, and iron on the bioadsorbents was spontaneous and endothermic at temperatures ranging from 25 to 60 °C for copper, from 25 to 50 °C for aluminum, and from 30 to 70 °C for iron. The carboxyl, hydroxyl, esters, alkynes, ether or phenol, and amine groups are the primary functional groups associated in the removal of metal ions by the majority of the studied bioadsorbents, regardless of their sources. Plant origin biomass and agricultural waste-derived biomass have been discovered to be viable replacements for commercial activated carbons in the treatment of metal-contaminated water. However, gaps in applicability, regeneration, reuse, and safe disposal of laden adsorbents, as well as optimization and commercialization of appropriate adsorbents, have been identified. Finally, the prospects for future research on heavy metal ions biosorption are outlined.
... The negative value of ΔG° specifies the viability and random nature of the adsorption, while the negative value of (ΔH°) indicates the exothermic nature. (positive value specifies adsorption process is endothermic) where as positive value of ΔS 0 specifies the increasing uncertainty at the solid/liquid boundary [30,33]. At high temperatures, the adsorption is faster and more beneficial because temperature changes will travel along the driving force of diffusion through the external interface layer and increase the diffusion rate inside the pores, making it easier for metal ions to reach the inner pores of bioadsorbents [51]. ...
Current review paper presents the performance of natural low-cost (economical) bioadsorbent, i.e., plant biomass and agricultural waste used for the removal or extraction of copper and other heavy metals. The current study focuses on use of various leaves, seed, peel, root, bark, husk, shell, fiber, and other bioadsorbents in their raw, pretreated as well as modified forms. This review paper objects to evaluate the applicability of said biomass for single and multimetal removal from water/wastewater. Researchers’ variations in different experimental parameters such as contact time, initial concentration, adsorbent mass, speed of agitation, temperature and pH, etc., are considered along with isotherm, kinetics, thermodynamic, and desorption studies. Researchers using various instruments such as UV vis. spectrophotometer, transmitted electron microscope (TEM), atomic absorption spectroscopy (AAS), molecular absorption spectrophotometer, SEM–EDX analyses, XDR spectroscopy and FTIR analysis, etc., to obtain the characterization of bioadsorbent. In this review, an extensive summary of previous literature on plant biomass, agricultural waste, and other biomass were compiled to provide information on experimental and equilibrium conditions and their potential as a low-cost sorbent.KeywordsCopper removalPlant-based bioadsorbentsAgricultural wasteAdsorption mechanism
... Thus, the Ni measured in polluted areas showed that the highest values of Ni were obtained in M. nigra, P. orientalis, and R. pseudoacacia; thus, these species can be used as indicator for Ni monitoring in polluted areas. Fossil fuel combustion (coal and petroleum), atmospheric and roadside dust exhaust gasses, and municipal waste incineration are considered to be the major sources of Zn in polluted urban areas (Dogan et al. 2010;Farhan et al. 2012;Norouzi et al. 2015). ...
The main scope of this study is to evaluate the uptake and accumulation potential of heavy metals in unwashed and washed leaves and particulate matter (PM) in leaf surfaces plus waxes of different tree species in Isfahan city. The highest mean concentrations of Cd, Cr, and Ni in unwashed and washed leaves were detected in M. nigra, Zn and Cu in P. fraxinifolia, and Pb was related to P. orientalis. The highest and lowest mean total depositions of total particulate matter (sum of PM10, PM2.5, and PM0.2) were found in the leaf of M. nigra (190.23 ± 23.5) and S. alba (11.9 ± 4.42 μg/cm2), respectively. The maximum bio-concentration factor (BCF) of Cd, Pb, and Ni was observed in Morus nigra; Cu and Zn in Pterocarya fraxinifolia, with the BCF of Cr found in Acer negundo. Comprehensive bio-concentration index (CBCI) and metal accumulation index (MAI) were applied for comparing different tree species in HMs accumulation from soil and ambient air. The highest CBCI was measured for M. nigra (0.86), so this tree has the potential to remediate metals from the polluted soil. Higher MAI values in washed and unwashed leaves were found in S. alba (6.77 and 6.98) and M. nigra (5.93 and 5.62), demonstrating the high capability of these trees for controlling air born-metal pollution. Based on the AOM factor, M. nigra, P. fraxinifolia, U. umbraculifera, P. fraxinifolia, A. altissima, and M. alba trees had the highest ability to capture Cd, Zn, Cu, Ni, Pb, and Cr from air. So, planting these trees would be beneficial in sensitive and critical zones such as industrial and urban areas with such atmospheric pollutants.
... Several treatment processes have been suggested for the removal of heavy metals from aqueous waste streams, such as adsorption (Kyzas et al., 2009), biosorption (Farhan et al., 2012), ion exchange (Inglezakis et al., 2003), cathodic reduction (Formari and Abbruzzese, 1999), electrodialysis/ electrodeionization using membranes (Arar et al., 2014;Caprarescu et al., 2011;Ren et al., 2013) or electrostatic shielding (Dermentzis, 2010), chemical coagulation -precipitation and electrocoagulation (Dermentzis et al., 2011;Verma et al., 2013). ...
تضمن موضوع البحث دراسة أيزوثيرمات وحركية وثيرموديناميكية الامتزاز لصبغة الصفرانين على ثلاث أسطح محضرة من نبات الطلح وهي المسحوق الجاف ومسحوق الفحمالمنشط بالحرارة و المنشط بالحمض. تم استخدام جهاز مطياف الاشعة المرئية وفوق البنفسجية لتقدير تركيز الصبغة قبل وبعد الامتزاز. تم دراسة العوامل التي تؤثر على الامتزاز وهي: الزمن، الرقم الهيدروجيني، كمية المادة المازة، التركيز الابتدائي، و درجة الحرارة. تم أيضا دراسة آيزوثيرم الامتزاز حيث أوضحت النتائج أن أيزوثيرمات الامتزاز مشابهة لأيزوثيرمات فرويندلش، وغير متفقة مع معادلة لانجماير، بناء على معامل الارتباط للمعادلات الخطية. أيضا تم دراسة تأثير الزمن على الامتزاز و حركية الامتزاز حيث بينت النتائج أن عملية الامتزاز من الرتبة الثانية. كما تم أيضا دراسة تأثير درجة الحرارة على الامتزاز، حيث أوضحت النتائج أن الامتزاز يقل بزيادة درجة الحرارة أي أن التفاعل طارد للحرارة(Exothermic) . بينت نتائج تأثيرالرقم الهيدروجيني على نسبة الاستخلاص، أن أعلى نسبة كانت بين 4=pH، و 9=pH.
Lagenaria vulgaris (LV) shell was used as a biosorbent for the removal of heavy metal ions, Pb 2+ , Cd 2+ and Zn 2+ , from aque-ous solutions. Experiments were carried out under batch conditions. The effects of contact time, initial pH, temperature and stirring speed on removal efficiency are presented. Sorption of the investigated metals was fast, reaching equilibrium after about 5 to 10 min, depending on the metal. Biosorption was highly pH-dependent, and the optimal pH for investigated metals was in the range of 4.5 to 6.0. The effect of temperature demonstrated that biosorption of the metals is a chemical process. SEM analysis revealed interesting morphological changes after acid refinement of the raw biosorbent and metal uptake that is related to the chemical nature of the biosorption process. EDX analysis of Lagenaria vulgaris biosorbent (LVB) before and after metal sorption revealed that the ion exchange mechanism was the principal sorption process. Fourier transform infrared spectroscopy (FTIR) analysis has shown that major functional groups (carboxyl and hydroxyl) on the biosorbent surface took part in the metal ion uptake process as active sites. The results obtained showed that Lagenaria vulgaris based biosorbent could be used as an effective and low-cost pre-treatment step for removal of toxic metals from wastewaters.
The adsorption behavior of Zn2+ and Pb2+ ions on rice husk was investigated using Rice Husk to remove the metals ions in dairy wastewater. The removal of mentioned heavy metal ions from aqueous solutions was studied by batch method. The main parameters that influencing Zn 2+ and Pb2+ sorption on rice husk were: amount of adsorbent, contact time and pH value of wastewater. The influences of pH (2–9), contact time (5-70min) and adsorbent amount (0.5-3 g) have been studied. The percent adsorption of Zn 2+ and Pb2+ ions increased with an increase in contact time and dosage of rice husk. The binding process was strongly affected by pH and the optimum pH for Zn 2+ and Pb2+ ions were 7.0 and 9.0, respectively. The experimental data were analyzed by Langmuir isotherm. The maximum adsorption capacity of the adsorbent for Zn 2+ and Pb2+ ions was calculated from the Langmuir isotherm and found to be 19.617 and 0.6216 mg/g, respectively. Actually the percent of removing Zn 2+ and Pb 2+ ions reached maximum to 70% and 96.8%, respectively. @JASEMJ. Appl. Sci. Environ. Manage. December, 2010, Vol. 14 (4) 159 - 162
Biosorption of lead (II), copper (II) and cadmium (II) ions from aqueous solutions onto olive leaves powder has been investigated. The biosorption of lead (II), copper (II), and cadmium (II) was found to be dependent on solution pH, initial metal ion concentrations, biosorbent dose, contact time and temperature. The experimental equilibrium biosorption data were analyzed by two widely used two-parameters, Langmuir and Freundlich isotherm models. The Langmuir model gave a better fit than the Freundlich model. The kinetic studies indicated that the biosorption process of the metal ions followed well pseudo-second-order model. The thermodynamic parameters Gibbs free energy, ∆G • , enthalpy, ∆H • , and entropy, ∆S • were also calculated, and the values indicated that the biosorption process was endothermic and spontaneous in nature. It was concluded that olive leaves powder can be used as an effective, low cost, and environmentally friendly biosorbent for removal of Pb(II), Cu(II) and Cd(II) ions from aqueous solution.
Effective removal of heavy metals from aqueous solutions belongs to the most important issues for many industrialized countries. Removal of copper(II) and zinc(II) ions from leaching solution of industrial waste were studied using hazelnut, almond and walnut shells. Batch adsorption experiments were performed in function of pH, contact time and adsorbent dosage. Adsorption kinetics was investigated using the pseudo-first and pseudo-second order, Elovich equations and intraparticle diffusion models. The results indicate that the second order model best describes adsorption kinetic data and the agricultural by products investigated may be used for removal of copper(II) and zinc(II) ions from leaching solution of industrial waste.
Peanut husk has been used in this work for removing Pb(II), Cr(III) and Cu(II) from aqueous solution. Batch adsorption studies were carried out under different pH, initial concentration of metal ions, interfering metal ions, time and temperature. Adsorption was poor in strongly acidic solution but was improved in alkaline medium and continuously increased with rise in pH. The presence of one metal decreased the removal of the other metal ions. The adsorption processes were more akin towards second-order equation. The suitability of the adsorbent was tested by fitting the adsorption data with Langmuir and Freundlich isotherms, which gave good fits with both isotherms. For an adsorbent amount of 2 g/L and initial metal ions 10 mg/L, the maximum monolayer values of Pb(II), Cr(III) and Cu(II) was 4.59 mg/g, 3.34 mg/g and 2.96 mg/g. The adsorption was in the order Pb(II) > Cu(II) > Cr(III). The values of the thermodynamic parameters, ΔH, ΔS and ΔG, indicated the interactions to be thermodynamically favorable.
Lagenaria vulgaris (LV) shell was used as a biosorbent for the removal of heavy metal ions, Pb2+, Cd2+ and Zn2+, from aqueous solutions. Experiments were carried out under batch conditions. The effects of contact time, initial pH, temperature and stirring speed on removal efficiency are presented. Sorption of the investigated metals was fast, reaching equilibrium after about 5 to 10 min, depending on the metal. Biosorption was highly pH-dependent, and the optimal pH for investigated metals was in the range of 4.5 to 6.0. The effects of temperature demonstrated that biosorption of the metals is a chemical process. SEM analysis revealed interesting morphological changes after acid refinement of the raw biosorbent and metal uptake that is related to the chemical nature of the biosorption process. EDX analysis of Lagenaria vulgaris biosorbent (LVB) before and after metal sorption revealed that the ion exchange mechanism was the principal sorption process. Fourier transform infrared spectroscopy (FTIR) analysis has shown that major functional groups (carboxyl and hydroxyl) on the biosorbent surface took part in the metal ion uptake process as active sites. The results obtained showed that Lagenaria vulgaris based biosorbent could be used as an effective and low-cost pre-treatment step for removal of toxic metals from wastewaters.
In activated chemisorption the plot of the reciprocal of the rate Z = (dq/dt)-1 against the time t is convex towards the Z axis at low t and concave at high t. This condition is satisfied if both the energy of activation, Et and the number of available sites, Nt decrease with the coverage q and if d2Et/dq2 < 0. Two models are considered: (a) A homogeneous surface model in which Et decreases proportionally to log q and Nt proportionally to q. (b) A model based on a heterogeneous surface comprising regions of different activation energies E and different heats of adsorption H, with E proportional to H. The activation energy at any region decreases logarithmically with the local coverage in that region. The total number of available sites decreases mainly because the low energy sites attain equilibrium during the adsorption run.