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Biosorption of nickel (II) and copper (II) ions from aqueous solution using novel biomass derived from Nannorrhops ritchiana (Mazri Palm)

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Biosorption of nickel (II) and copper (II) ions from aqueous solution using novel biomass derived from Nannorrhops ritchiana (Mazri Palm)
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  This article was downloaded by: [University Technology Petronas]On: 14 December 2014, At: 18:51Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,37-41 Mortimer Street, London W1T 3JH, UK Click for updates Desalination and Water Treatment Publication details, including instructions for authors and subscription information:http://www.tandfonline.com/loi/tdwt20 Biosorption of nickel (II) and copper (II) ions fromaqueous solution using novel biomass derived fromNannorrhops ritchiana (Mazri Palm) Sefath Ullah Khan a , Farman Ullah Khan a , Ihsan Ullah Khan b , Nawshad Muhammad c , SyedBadshah d , Adnan Khan e , Asim Ullah a , Amir Sada Khan af , Hazrat Bilal a  & Asma Nasrullah aa  Department of Chemistry, University of Science and Technology, Bannu 28100, Pakistan,Tel. +923339730250, Tel. +923348480892, Tel. +923009392396, Tel. +00601116473142, Tel.+923339731300, Tel. +923349720250 b  Department of Fundamental and Applied Sciences, Universiti Teknologi PETRONAS (UTP),31750 Tronoh, Perak, Malaysia, Tel. +0060163091782 c  Interdisciplinary Research Center in Biomedical Materials COMSATS, Institute ofInformation Technology, Lahore, Pakistan, Tel. +923339223834 d  Department of Chemistry, Gomal University D.I. Khan, D.I. Khan, Pakistan e  Institute of Chemical Sciences, University of Peshawar, Peshawar, Pakistan, Tel.+923009890269 f  PETRONAS Ionic Liquid Centre, Department of Chemical Engineering, Universiti TeknologiPETRONAS (UTP), 31750 Tronoh, Perak, MalaysiaPublished online: 10 Dec 2014. To cite this article:  Sefath Ullah Khan, Farman Ullah Khan, Ihsan Ullah Khan, Nawshad Muhammad, Syed Badshah, AdnanKhan, Asim Ullah, Amir Sada Khan, Hazrat Bilal & Asma Nasrullah (2014): Biosorption of nickel (II) and copper (II) ions fromaqueous solution using novel biomass derived from Nannorrhops ritchiana (Mazri Palm), Desalination and Water Treatment,DOI: 10.1080/19443994.2014.989268 To link to this article: http://dx.doi.org/10.1080/19443994.2014.989268 PLEASE SCROLL DOWN FOR ARTICLETaylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) containedin the publications on our platform. However, Taylor & Francis, our agents, and our licensors make norepresentations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of theContent. Any opinions and views expressed in this publication are the opinions and views of the authors, andare not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon andshould be independently verified with primary sources of information. Taylor and Francis shall not be liable forany losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoeveror howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use ofthe Content.This article may be used for research, teaching, and private study purposes. Any substantial or systematicreproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in anyform to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http:// www.tandfonline.com/page/terms-and-conditions  Biosorption of nickel (II) and copper (II) ions from aqueous solution usingnovel biomass derived from  Nannorrhops ritchiana  (Mazri Palm) Sefath Ullah Khan a , Farman Ullah Khan a, *, Ihsan Ullah Khan  b ,Nawshad Muhammad c, *, Syed Badshah d , Adnan Khan e , Asim Ullah a ,Amir Sada Khan a,f  , Hazrat Bilal a , Asma Nasrullah a a Department of Chemistry, University of Science and Technology, Bannu 28100, Pakistan, Tel. +923339730250;email: safe5754@gmail.com (S.U. Khan), Tel. +923348480892; email: farmandphil@yahoo.com (F.U. Khan), Tel. +923009392396; email: dawarasim@yahoo.com (A. Ullah), Tel. +00601116473142; email: aamirsada_khan@yahoo.com (A.S. Khan), Tel. +923339731300; email: bilalmphil2013@gmail.com (H. Bilal), Tel. +923349720250; email: Nasrullahadvent_chemis@yahoo.com (A. Nasrullah) b Department of Fundamental and Applied Sciences, Universiti Teknologi PETRONAS (UTP), 31750 Tronoh, Perak, Malaysia,Tel. +0060163091782; email: ihsan_sagar@yahoo.com c  Interdisciplinary Research Center in Biomedical Materials COMSATS, Institute of Information Technology, Lahore, Pakistan,Tel. +923339223834; email: nawshadchemist@yahoo.com d Department of Chemistry, Gomal University D.I. Khan, D.I. Khan, Pakistan e  Institute of Chemical Sciences, University of Peshawar, Peshawar, Pakistan, Tel. +923009890269; email: adnanics@yahoo.com  f  PETRONAS Ionic Liquid Centre, Department of Chemical Engineering, Universiti Teknologi PETRONAS (UTP), 31750 Tronoh,Perak, Malaysia Received 6 February 2014; Accepted 11 November 2014 ABSTRACT In the present research work,  Nannorrhops ritchiana  (Mazri Palm) was used as an effective biosorbent for removal of Cu 2+ and Ni 2+ ions from aqueous solution.  Nannorrhops ritchiana (Mazri Palm), a dead biomass powder, was used as a low-cost adsorbent without any chem-ical treatment. In order to estimate the equilibrium parameters, the equilibrium adsorptiondata were analyzed using Freundlich, Langmuir, and Temkin isotherms. Freundlich iso-therms indicated that the sorption capacities on the biomass surfaces increased with increas-ing initial concentrations of both metals. The adsorption isotherms were correlated with acomparison of linear and non-linear regression analysis. The squares of the errors (SSE) andchi-square test (  χ  2 ) along with the coefficient of determination ( R 2 ) were used to determinethe best fit isotherm. Langmuir type I was found the best fitting isotherm for adsorption of  both Cu 2+ and Ni 2+ ions as compared to the other three Langmuir linear isotherms on the basis of the values for  R 2 and other error functions like SSE and  χ  2 obtained from Lang-muir-type I linear equation. The present study revealed that  Nannorrhops ritchiana  proved to be an effective, inexpensive, alternative, and environmentally friendly biosorbent for theremoval of Cu 2+ and Ni 2+ ions from aqueous solution.*Corresponding authors.1944-3994/1944-3986    2014 Balaban Desalination Publications. All rights reserved. Desalination and Water Treatment   (2014) 1–11 www.deswater.com doi: 10.1080/19443994.2014.989268    D  o  w  n   l  o  a   d  e   d   b  y   [   U  n   i  v  e  r  s   i   t  y   T  e  c   h  n  o   l  o  g  y   P  e   t  r  o  n  a  s   ]  a   t   1   8  :   5   1   1   4   D  e  c  e  m   b  e  r   2   0   1   4  Keywords: Nannorrhops ritchiana ; Biosorption; Cu and Ni; Adsorption isotherm 1. Introduction Environmental pollution is a key challenging prob-lem for the globe and it is increasing day by day dueto the fast growth in population, science, technology,and industries [1,2]. It has been estimated that the sur- face of earth consists of approximately 70% water.That is the mainly precious source for life present onearth globe. Devoid of this important resource, thepossibility of life on planet earth would not survive.Even if this reality is generally accepted, however, thesrcin of water from where contaminations occur is acommon problem which we are facing day today. Theeffluents coming out from various industries contain-ing both inorganic and organic toxic substances whichare being discharged into the surface water severelyaffect biodiversity and aquatic life. Contamination of drinking water occurs by direct or indirect method. Indirect method, sewage elution is from refineries, facto-ries, and from devastatingly handling vegetation; andin indirect method, the pollutants pierce the watersupply from two sources i.e. soil and ground watersystems and also from the environment through rain[3,4]. Modern engineering and technology is also to a huge extent accountable for contamination of ourclean environment [5]. Among these pollutants, metals ions are considered to be the most common and toxicwater pollutants. Metals are released into the environ-ment as a result of activities such as industrial, miningpigment and paint industries, and agricultural activi-ties [6,7]. The heavy metals such as lead, copper, cad- mium, zinc, and nickel are among the most commonpollutants found in industrial effluents. Even at lowconcentrations, these metals can be toxic to organisms,including humans [8]. Among these metals, copper (Cu 2+ ) and nickel(Ni 2+ ) ions are metals of major concern because of their widespread uses in developing countries andtheir toxic nature. Ni(II) concentrations varies from 0to 40 and 0.25 to 67 with an average concentration of  ∼ 22mg/L. The Ni(II) concentration of these levels areseriously dangerous for human beings and other live-stock due to the intrinsic carcinogenic nature. Cu(II),in particular, are among the most widely used metalions in industries, they are highly toxic and can causea variety of negative effects on human health, forexample, neurotoxicity, jaundice, liver toxicity, ane-mia, encephalopathy, hepatitis, and nephritic syn-drome [9]. The permissible limit of copper in drinking water as set by the World Health Organization is10 μ  gL –1 is 1.5mgL –1 [10]. The EPA requires lead, copper, cadmium, zinc, and nickel in drinking waternot to exceed 0.015, 1.3, 0.005, 5, and 0.04mgL –1 ,respectively [8]. Due to the aforementioned reasons, in recent years, there is great interest generated forremoving these metal ions from aqueous solution dueto their supreme toxicity to human health and ecologi-cal systems [4].There are various methods used for removal of metals ions from aqueous media such as chemicalredox reaction, chemical precipitation, evaporativerecovery, filtration, electrochemical treatment, reverseosmosis (membrane technologies), solvent extraction,and ion-exchange. However, most of these methodshave some major shortcoming, such as applicablewhere the concentration of metals is relatively high,costly, insufficient metals removal, production of toxicslush, and high energy required. Presently, the sorp-tion technique is proved to be quite simple, affective,economic, attractive, and most easily available tech-nique for the dyes removal from the metals-bearingwastewater [11]. Thus, there is a great demand forsuch type of adsorbents which are made from low costmaterial, environmentally benign, and have greatpotential for adsorption without any additional expen-sive pretreatment [12,13]. Thus, there is a great demand for such type of adsorbent which are cheaperand still have high adsorption capability toward pollu-tants and metals without any additional expensivepretreatment. Presently, cellulose and lignocellulosic biomass have got considerable attraction because of itsabundance in nature, effectiveness, low cost, and envi-ronmentally friendly nature of biopolymers. Thus, bio-sorption has been proved to be the most effectivetechnique for the removal of Cu and Ni from theaqueous solution [4, 13–17].Adsorption isotherm is very useful to describe theadsorption phenomenon and mobility of adsorbatefrom aqueous media to the solid phase adsorbent.These equilibrium models are very important in termsof describing the adsorption mechanism and also thesurface properties of adsorbent. Linear regression is animportant technique used for the determination of theadsorption isotherm parameters. In this research work, Nannorrhops ritchiana  (Mazri Palm) was collected fromhilly areas of North Waziristan Agency, KhyberPakhtunkhawa, Pakistan, and used as an effective bio-sorbent without any chemical treatment for removal of Cu 2+ and Ni 2+ ions from aqueous solution. The 2  S.U. Khan et al. / Desalination and Water Treatment    D  o  w  n   l  o  a   d  e   d   b  y   [   U  n   i  v  e  r  s   i   t  y   T  e  c   h  n  o   l  o  g  y   P  e   t  r  o  n  a  s   ]  a   t   1   8  :   5   1   1   4   D  e  c  e  m   b  e  r   2   0   1   4  utilization of this alternative, abundantly available andenvironmentally benign biosorbent, will solve bothwaste discarding problems as well as give access to aninexpensive material for wastewater decontamination.The main aim of this study to investigate the potentialof   Nannorrhops ritchiana  for Cu 2+ and Ni 2+ ions fromaqueous solution. Langmuir, Freundlich, and Temkinisotherms models were used for adsorption of Cu 2+ and Ni 2+ ions from aqueous solution. In addition, lin-ear and non-linear regression methods, in selecting theoptimum adsorption isotherm, were applied on theexperimental data. 2. Experimental 2.1. Collection of plant material (biosorbent) The plant  Nannorrhops ritchiana  (Mazri Palm), usedas a biosorbent, was collected from the hilly areas of North Waziristan Agency, KPK, Pakistan, in June2012. The plant leaves were dried and grounded intopowder form with the help of electrical grinder. Theground  Nannorrhops ritchiana  (Mazri Palm) leaves weresieved to smaller particle size in order to get highersurface area to permit the adsorbate to accumulatedeeply into the sewage in an elevated rate of adsorp-tion. To avoid the color leaching effect, the groundedpowder was soaked in water for 72 h, followed by fil-tration, and subsequent drying before subjecting to theadsorption process. 2.2. Biosorption batch experiments The 0.1-M solutions of copper (II) and nickel (II)were prepared by dissolving 24.97-g of copper sulfate(CuSO 4  5H 2 O) and 23.77-g of nickel chloride (NiCl 2 6H 2 O) in distilled water, respectively. The variousrequired concentration solutions were prepared fromthe stock solutions using the dilution formulaC 1 V 1 =C 2 V 2 . In typical batch experiment, 100-mLcapacity flasks were filled with 30 mL of the varyingconcentration of metal ions solutions and 20-mg  Nan-norrhops ritchiana  (Mazri Palm) powder was added toeach flask containing metal ions solutions. The flaskswere potted to reduce evaporation and were shakenin wise bath water bath shaker at 180 rpm. The experi-ments were carried out at natural pH and at roomtemperature. After specific interval of time, sample ali-quots were withdrawn and filtered to separate themetal-loaded biosorbent from metal ion-containingsolution. The remaining concentration of metal ionswas determined by Atomic Absorption Spectropho-tometer.Quantity of metal ions removed by the biomass of  Nannorrhops ritchiana  powder was determined usingthe Eq. (1) N   f   ¼ð C i  C s Þ V m  (1)where  N   f   is theconc. of metal ions adsorbed (mmol/g), V   is the volume of metal ions solutions (L),  C i  is the ini-tial conc. of metal ions (mmol/g),  C s  is the final conc. of metal ions in aqueous phase (mmol/g), and  m  is themass (g) of   Nannorrhops ritchiana  (Mazri Palm). 2.3. Analytical analysis of metal ions in solution The concentration of each Cu(II) and Ni(II) in eachsample after adsorption were analyzed with AA-7000atomic absorption spectrophotometer. Firstly, theinstrument was calibrated with standard solutions inthe range covering the expected concentrations indiluted samples and then, the samples were analyzedin triplicate. 2.4. Biomass characterization The chemical structure and nature of functionalgroups of biomass was studied using FTIR transmis-sion spectra on a Perkin–Elmer Spectrum One. FTIRspectrum was recorded in the wave number rangefrom 4,000 to 450 cm –1 with a resolution of 5 cm –1 . 2.5. Methods2.5.1. Adsorption isotherm The equilibrium relationship among the adsorbentand adsorbate is responsible for the studies of adsorp-tions procedure. Such separation processes have athermodynamic background and easily find out theamount of material, which is capable of beingadsorbed onto specific surfaces. To describe equilib-rium relationships, two factor isotherms of Langmuir,Freundlich, and Temkin have been developed. Never-theless, no single model is generally valid, all havingsome postulation that may or may not be applicablein a meticulous case. 2.5.2. Error functions In order to assess the fit of an isotherm to the equi-librium data, an error function evaluation is necessary.For this purpose, various error functions, such asHYBRID, fractional error function, sum of absoluteerror, sum of the square of errors, average relativeerrors, chi-square test, and standard deviation of  S.U. Khan et al. / Desalination and Water Treatment  3    D  o  w  n   l  o  a   d  e   d   b  y   [   U  n   i  v  e  r  s   i   t  y   T  e  c   h  n  o   l  o  g  y   P  e   t  r  o  n  a  s   ]  a   t   1   8  :   5   1   1   4   D  e  c  e  m   b  e  r   2   0   1   4  relative error have been adopted to conclude the best-fitting isotherm, among which the coefficient of determination ( R 2 ) is possibly the most commonlyapplicable error function to forecast the optimum iso-therm; and for the determination of the coefficient, theisotherm having  R 2 value closest to unity is believedto be the best-fit isotherm.The Origin 6.1 version of software was used for the experimental data analysis.The equations used for linear and non-linear fitting of isotherm models has been given in Table 1. 3. Results and discussion 3.1. Characterization of adsorbent The surface functional groups in biomass weredetermined using FTIR spectroscopy. The FTIR spec-trum in Fig. 1 shows the functional groups in biomass.The peak at 3,443 cm –1 is assigned to the presence of –OH stretching vibration. It represents the presence of –0H group on the surface of biomass and chemisorbedwater. The peak at 2,910 cm –1 showed the symmetricand unsymmetrical C–H stretching, due to the exis-tence of –CH and C–H groups which are present incellulose and lignin. The peak appeared at 2,834shows CH stretch. The presence of adsorption peaksin region from 1,300 to 900 cm –1 represents the variouscarbonyl components such as alcohols, esters, carbox-ylic acid, or ethers. The peak at position 1,637 cm –1 isassigned to C=C. Additional peak at 1,227 cm –1 showsthe C–O–C stretching. The peak associated at1,016 cm –1 is assigned to C–N stretch. The absorptionpeak at 874.69 cm –1 is a prominent peak for the  β  -glu-cosidic linkage of cellulose in biosorbent [18]. Thepresence of these various nucleophilic groups repre-sents that the biosorbent have potential to adsorb themetal ions effectively. 3.2. Linear method for adsorption isotherms3.2.1. Langmuir linear adsorption isotherm For the determination of isotherm parameters, thelinear forms of the adsorption isotherms having bestfit of an experimental data with various error func-tions were generally used. While analyzing the experi-mental data for the goodness of the Langmuir model,the equilibrium data were evaluated using the fourlinear forms of the Langmuir isotherm. To study theexperimental data, Langmuir type (I) isotherm is themost commonly used linear expression and has beenused by numerous researchers [19–22]. For one to fourtype linear form, Langmuir constants (sorption equi-librium constant)  b , and the saturated monolayer sorp-tion capacity  N  s ,  the sorption of Cu 2+ and Ni 2+ onto Nannorrhops ritchiana  (Mazri Palm) powder weredetermined from the slope and intercept of the plot between  C s  and  C s / N   f  , 1/ N   f   and 1/ C s ,  N   f   and  N   f  / C s ,and  N   f  / C s  and  N   f  , respectively as shown in Table 2. Itis confirmed from the Table 2 that the calculated val-ues for the Langmuir parameters for each type of lin-ear Langmuir equation are different along with thedifferent values for the co-efficient of determination( R 2 ) for each type of linear Langmuir equation. On the basis of the values for ( R 2 , Fig. 2(a) and (b)) and othererror functions like squares of the errors and Table 1Equations for linear and non-linear of Langmuir, Freundlich, and Temkin isothermsIsotherms Linear form Non-linear PlotLangmuir-1  c e q e ¼  1 bQ e þ C e Q o q e  ¼  Q e bC e 1 þ bC e C e q e vs : C e Langmuir-2  1 q e ¼  1 Q 0 þ  1 bC e Q o 1 q e vs :  1 C e Langmuir-3  q e  ¼ Q   q e bC e q e  vs :  q e C e Langmuir-4  q e c e ¼ bQ 0 þ qb eq e c e vs :  q e Freundlich  log q e  ¼ log K   f   þ 1 n log C e  q e  ¼ K   f  q 1 = ne  log q e  vs :  log C e Temkin  q e  ¼ RT b T  ln  A T  þ RT b T  ln C e q e  ¼ RT b T  ln  A T  C e  q e  vs :  C e 4000 3500 3000 2500 2000 1500 1000 500151821242730333639 10166051227163720482834 29153443    %    A   b  s  o  r   b  a  n  c  e Wavelength (nm) Fig. 1. FTIR spectrum of   Nannorrhops ritchiana  (MazriPalm).4  S.U. Khan et al. / Desalination and Water Treatment    D  o  w  n   l  o  a   d  e   d   b  y   [   U  n   i  v  e  r  s   i   t  y   T  e  c   h  n  o   l  o  g  y   P  e   t  r  o  n  a  s   ]  a   t   1   8  :   5   1   1   4   D  e  c  e  m   b  e  r   2   0   1   4
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