Biosorptive Removal of Copper (II) ion from Aqueous Solution using Lawsonia Inermis Plant Leaf Biomass

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1 Biosorptiv Rmoval of Coppr (II) ion from Aquous Solution using Lawsonia Inrmis Plant Laf Biomass Amarprt Kour Bhatia Fahmida Khan * Dpartmnt of Chmistry, National Institut of Tchnology, Raipur, , CG, India Corrsponding author: fkhan.chy@nitrr.ac.in Abstract Th prsnt study invstigats th biosorptiv rmoval of Coppr (II) ion from aquous solution using plant laf biomass undr various conditions. Biosorption studis hav bn carrid out to dtrmin th ffct of ph, Cu (II) mtal concntration, contact tim, tmpratur and biomass dos on th biosorption capacity of Cu (II) ions by th biomass. Th procss was invstigatd using concntrations of Cu (II) ions ranging from mg/l in quilibrium batch tsts for Langmiur and Frundlich isothrm modls. Th biosorption data was bttr fittd to Langmuir isothrm modl, and th maximum biosorption capacity (q max ) was 6.06 mg/g. Th optimum ph for th rmoval of Cu (II) ions was around ph 5.0 and th rmoval of Cu (II) ions was 85.6%.Th biosorption kintics followd th psudo-scond ordr modl. FTIR clarly showd that OH, -CH and C=O group ar likly to participat in Cu (II) ion adsorption. Th rsults dmonstratd that plant laf biomass was a conomic and co-frindly biosorbnt possssd strong biosorption charactristics for Cu (II) ions. Kywords: Lawsonia Inrmis. Cu (II) rmoval, Biosorption, Isothrm. 1. INTRODUCTION: Coppr is on of th most common toxic mtals that finds its way to watr sourcs from various industris, i.. lctroplating, mining, lctrical and lctronics, iron and stl production, non-frrous mtal industry, printing and photographic industris. On th othr hand, Cu2+ is a minral that is naturally found in th human body and is a ncssary microlmnt. It participats in hmatopoitic functions, mainly th synthsis of hmoglobin [1]. Howvr, coppr concntrations in humans hav incrasd to toxic lvls causing various disass and disordrs, such as livr damag, gastrointstinal problms, and continud inhalation of coppr-containing sprays is linkd with an incras in lung cancr among xposd workrs[2][3]. According to U.S. Environmntal Protction Agncy (EPA) standards, th prmissibl limit of coppr discharg in industrial fflunts into watr bodis is limitd to 1.3 mg/l. World Halth Organization (WHO) dfins th Cu (II) prmissibl limit of 1.5 mg/l in drinking watr [4] A larg numbr of tchnologis hav bn usd to rmov Cu (II) from th nvironmnt. Th main tratmnt procsss for th rmoval of Cu (II) ions includ: chmical prcipitation, Chlation/complxation Rvrs osmosis, Elctrochmical tratmnts, mmbran sparation, and sorption/ion xchang [5]. Among th procsss usd for th rmoval of Cu (II) from wastwatr, adsorption is an ffctiv and co-frindly tratmnt mthod for mtal rmoval from aquous solutions. Th us of biomass is prfrrd bcaus it dos not rquir nutrints, it is not affctd by toxic pollutants, and may b rgnratd and rusd in a numbr of adsorptiondsorption cycls [6]. In this study, th Laf biomass of Lawsonia Inrmis adsorbnt for rmoval Cu (II) ion was usd to dtrmin adsorption fficincy as a function of ph, tmpratur, biomass dos, contact tim and initial mtal concntration and constants of th adsorption isothrm and invstigatd its adsorption kintics for rmoval of coppr ions from aquous solutions. FTIR analysis was carrid out to undrstand th functional group of biomass. 2. Matrial and mthods: 2.1. Lawsonia Inrmis Biomass: Lawsonia Inrmis biomass (LIB) usd in this work was collctd, procssd and stord as dscribd arlir [7] 2.2. Ragnts: All chmicals wr of an analytical grad. Solutions of 0.01 M NaOH and HCl (from Mrck) wr usd for ph adjustmnt. Stock solutions of Cu (II) containing 1,000 mg/l, wr prpard by dissolving appropriat mtal (chlorid) salts in Milli-Q ultrapur watr. Th stock solution was dilutd as rquird to obtain standard solutions with Milli-Q ultrapur watr whn ndd Analysis for mtal biosorption tsts: Th concntrations of Cu (II) in th solutions bfor and aftr quilibrium wr dtrmind by flam atomic absorption spctromtry (FAAS), using Atomic adsorption spctrophotomtr AAS4129D, ECIL India which oprats in flam mod and controlld by Intl prsonal computr Mtal Biosorption Studis: Batch biosorption xprimnts wr conductd in a st of conical flasks 21

2 containing 50 ml of solution to invstigat th ffcts of ph (2-7), biomass dos ( g/l), initial mtal ion concntration ( mg/l), tmpratur (303, 313 and 323 K) and contact tim ( min).th adsorbnt and solution wr sparatd by filtration through a mmbran filtr. Th mtal ion concntration in th original solution and lft in bulk solution wr dtrmind by th AAS tchniqu. Th optimum conditions for th biosorption of Cu (II) ion wr dtrmind, and biosorption kintics was invstigatd using 50 mg/l initial coppr concntration, 0.5g/L biomass dos at solution ph of 5 at 303 K tmpratur. Biosorption isothrms wr xamind by mixing a dosag of 0.5 g/l of biomass dos with Cu (II) solution at ph 5 at various initial concntrations in th rang of mg/l at thr diffrnt tmpraturs. Th diffrnc btwn initial and final Cu (II) concntrations in aquous solution was usd to calculat th bios orbd mtal concntrations. Cu (II) ions rmoval fficincy (% R) is dfind as CO C R = C o 100% Whr C o (mg L -1 ) is th initial and C (mg L -1 ) is th quilibrium concntration of mtal ions, rspctivly. Th amount of th mtal adsorbd (mg) pr unit mass of biomass was obtaind by using following quation: q = ( C C ) Whr q (mg g -1 ) is th adsorption capacity at quilibrium, C o (mg L -1 ) is th initial and C (mg L -1 ) is th quilibrium concntration of mtal ions, W (g) is th wight of adsorbnt usd and V (ml) is th volum of sampl. Control sampls with no addd biomass wr usd as blanks. Each xprimnt was rpatd for thr tims. o 2.5. Fourir transform infrard (FTIR): In ordr to idntify th functionalitis bing capabl of intracting with coppr ions in biomass, FTIR tchniqu was usd. FTIR spctrums of raw and mtal loadd biomass wr rcordd with a Thrmo Nicolt, Avatar 370 Modl FTIR spctromtr in th rang cm -1 having rsolution 4 cm -1 at th SAIF KOCHI, Cochin, Krala, India. 3. Rsult and Discussion: 3.1. Effct of ph: Th ph ffct not only on spciation of coppr ions, but also th chargs on th activ sits of biomass [8]. Whn th ph of mtal ions solution is changd, th hydroxyl group on th surfac of biomass is also changd [9]. Th ffct of solution ph on Cu (II) sorption was valuatd from th ph rangs of and rsults ar dpictd in Fig.1. As obsrvd from Fig.1, at lowr ph, th biosorption fficincy is low du to th prsnc of high concntration of H 3 O + ion which will compt with th Cu (II) prsnt in th solution. As th ph is incrasd from 2.0 to 5.0 th biosorption fficincy also incrass from 40.6% to 85.6%. By furthr incras in ph from 5.0 to 7.0 causs a dcras in th biosorption fficincy du to prcipitation of watr insolubl Cu (OH) 2. Basd on th high biosorption fficincy by th conjugat adsorbnt, th ph 5.0 was chosn for dtrmining th othr xprimntal paramtrs for subsqunt biosorption opration in this study Biosorption tim of Cu (II): Th biosorption of Cu (II) was studid in ordr to dtrmin th contact tim rquird to rach th quilibrium. Fig.2. shows th ffct of contact tim on th biosorption of Cu (II) ions onto biomass. From Fig.2, it can b sn that 50% adsorption was compltd within 60 min and quilibrium was achivd within 90 min and rmaind narly constant aftrwards. Thrfor, this tim valu was slctd as optimum contact tim for sufficint biosorption of th Cu (II) ions. w V 3.3. Effct of biomass dosag: Th ffct of biomass dosag on th biosorption of Cu (II) ions was studid using th biomass in th rang of gL 1 (Fig. 3). From Fig.3, it was obsrvd th biosorption of th mtal ions incrasd with incrasing biomass dosag and almost constant at highr than 0.5 g/l. This is bcaus an incras in biomass dosag causs an incras in surfac ara of th biosorbnt, which consquntly incrass th numbr of activ binding sits on th surfac of biomass [10]. Thrfor, th amount of biomass was slctd as 0.5 g/l for furthr xprimnts Effct of initial mtal concntration: In this th ffct of initial mtal concntration on biomass rmoval was carrid out in th rang mg L 1 whil kping th othr paramtrs constant. From Fig.4, it is shown that with incras in initial mtal concntration causs dcras in biosorption fficincy bcaus all th availabl sits prsnt in th solution gt saturat and no mor binding sits ar availabl for biosorption. Th biosorption fficincy of mtal was % for mg L -1 of Cu (II) solution. 22

3 Fig 5 shows th ffct of diffrnt mtal concntration onto biomass with rspct to tim, from this w can gt that maximum biosorption fficincy is achivd at th tim of quilibrium i.. 90 min Kintics modling: Th kintic data was analyzd using psudo-2nd-ordr quation (PSE) [11]: t q 1 = K q 1 + q 2 t 2 Whr, q t is th amount of mtal ion adsorbd at tim t (mg g -1 ) q is th amount of mtal ions adsorbd at quilibrium (mg g -1 ). K 2 is th rat constant of scond-ordr adsorption. (g mg -1 min -1 ) By fitting th xprimntal data to Eq. 1 th scond ordr rat constant (k 2 ) and q wr dtrmind. Th plots of t/q t vrsus t and valus of th constants of PSE kintic modls obtaind from th plots ar givn in Fig.6 and Tabl 1.Th linar plot concludd that PSE kintic modl is appropriat to dscrib this adsorption. Th Valu of K 2 can b dtrmind by th intrcpt of th plot Adsorption isothrms: Adsorption Isothrm studis provid information on th capacity of adsorbnt, which is th most important paramtr for a biosorption systm. Th quilibrium adsorption data was dscribd by most frquntly usd two isothrm modls: Langmuir [12] and Frundlich [13] isothrm modls: Langmuir quation: C q = 1 q K C + q m L m Whr, C is th concntration of th adsorbat at quilibrium in th solution (mg L -1 ), q is th amount adsorbd at quilibrium on th adsorbnt (mg g -1 ), q m is th monolayr adsorption capacity of th adsorbnt (mg g -1 ) and K L = nrgy of adsorption constant (L mg -1 ) or Langmuir constant. Frundlich quation: 1 log q = logkf + logc n Whr, K F is th constant rlatd to adsorbnt capacity (mgg -1 ) and 1/n= is an mpirical paramtr rlatd to sorption intnsity of th adsorbnt (n = 1-10). Tabl 2 lists th calculatd paramtrs and rgrssion cofficints (R 2 ). Th study found that th biosorption of Cu (II) on th biomass was fittd using both th Langmuir and Frundlich modls. Howvr, th Langmuir isothrm (R 2 >0.99) corrlatd bttr with th xprimntal data according to th r 2 valu. Similar rsults wr rportd in th litratur for biosorption of Cu (II) onto Solanum lycoprsicum [14]. Convninc of th xprimntal data with th Langmuir isothrm modl suggstd that thr is monolayr covrag of th adsorbat on th surfac of adsorbnt and that adsorption occurs at spcific homognous sits on th adsorbnt. By Comparing th maximum Cu (II) uptak capacity obtaind from Langmuir modl for biomass with othr biosorbnts shows that q m (mg/g) valu of th prsnt biomass was 6.06 mg/g whil Activatd carbon has 3.56 mg/g [15], Rd mud (5.34 mg/g) [16], Barly straw (BS) (4.64 mg/g) [17], Almond shll (3.62 mg/g) [18], Pycnoporus sanguinus (2.76 mg/g) [19]. From ths rsults, it is clar that th prsnt biomass can b usd as an adsorbnt as th adsorption capacity of this highr than th othr adsorbnt rportd by various scintists FTIR rsults: Fig.7. shows th FTIR spctra of biomass bfor and aftr adsorption and FTIR spctroscopic charactristics ar shown in Tabl 3. Th vibrating signals bfor and aftr adsorption of Cu (II) was diffrnt. Th adsorption band at cm -1 is du to bandd OH groups [20]. Th wak band at cm -1 could b assignd to th aliphatic C-H group [21]. Th adsorption band at cm -1 ar attributd to C=O strong strtching Vibration. Th trough at cm -1 ar charactristics of C=C in aromatic ring [22]. Th Pak obsrvd at 1033 cm -1 corrsponds to C-O strtching in carboxylic group prsnt in biomass containing aromatic ring. Whn compard th two spctra in Fig shows that thr was som pak that wr shiftd to anothr wavlngth. Th adsorption pak of bondd OH group gt shiftd from 3380 cm -1 to cm -1 in cas of FTIR spctra aftr adsorption which showd that Hydroxyl polymrization in biomass was dcrasd by th addition of Cu (II) ions. This shows that Cu (II) ions can b bondd to th hydroxyl groups. Th similar rsult was obsrvd by [23]. Th anothr chang in pak was obsrvd in C-H group whr th pak in cas of FTIR spctra aftr adsorption gt shiftd to lowr wavlngth i cm -1. Th pak at 1726 cm -1 which corrsponds to C=O strtching vibration bcom wak in cas of FTIR spctra aftr adsorption. This indicats that th fr t 23

4 carbonyl changs to coordinatd COO - group. This chang in pak shows that OH, -CH and C=O group ar likly to participat in Cu (II) ion adsorption. Th ion xchang procss may b th mchanism involvd in th biomass and Cu (II) intraction. 4. CONCLUSION In this study, th adsorption of Cu (II) ions from aquous solution by using Lawsonia Inrmis laf biomass as an adsorbing agnt was implmntd succssfully. Th biosorption charactristic has bn xamind at various ph, biomass dos, initial concntrations, tmpratur and contact tim and th following conclusions can b mad 1. It was found that maximum biosorption of Cu (II) ion was obtaind in ph 5 with 85.6% rmoval fficincy. Thus, mtal ion uptak was found as ph-dpndnt, with that th contact tim also affcts biosorption rsults. 2. Adsorption isothrm has bn carrid out using th Langmuir and Frundlich isothrm modls. Th Langmuir modl was dtrmind as th bst fit for th biosorption data and th isothrm constants wr usd to compar th adsorptiv capacity of Lawsonia inrmis biomass. 3. Th maximum biosorption capacity of th biomass was 6.06 mg g -1 which can b compard with othr biosorbnts. 4. Psudo-scond ordr kintic modls wr usd to tst th biosorption kintics. It was shown that th biosorption of Cu (II) ion onto biomass could provid th bst rsults by th psudo-scond ordr modl, showing that chmical sorption can control th biosorption. 5. Thus, th prsnt biosorbnts can b usd as an ffctiv and conomically fasibl biosorbnt to rmov Cu (II) ion from aquous solutions as is chap can b locally availabl and dos not produc any kind of wast. 5. REFERENCES 1. Kawasaki, N., Tominaga, H., Ogata, F., & Kakhi, K. (2010). Rmoval of cadmium and coppr by vgtabl biomass tratd with hydrochloric Acid. Chmical Enginring Journal, 157, Nuhoglu, Y. & Oguz, E. (2003). Rmoval of coppr (II) from aquous solutions by biosorption on th con biomass of Thuja orintalis. Procss Biochmistry, 38, Ertugay, N. & Bayhan, Y.K. (2010). Th rmoval of coppr (II) ion by using mushroom biomass (Agaricus bisporus) and its kintic modling. Dsalination, 255, Phlivan, E., Altun, T., & Parlayici, S. (2012). Modifid barly straw as a potntial biosorbnt for rmoval of coppr ions from aquous solution. Food Chmistry, 135, Bilal, M., Shah, J. A., Ashfaq, T., Gardazi, S., Tahir, A. A., Prvz, A., Haroon, H., & Mahmood, Q. (2013). Wast biomass adsorbnts for coppr rmoval from industrial wastwatr A rviw. Journal of Hazardous Matrials, 263, Kumara, R., Bishnoi, N.R., & Bishnoi, G.K. (2008). Biosorption of chromium (VI) from aquous solution and lctroplating wastwatr using fungal biomass. Chmical Enginring Journal, 135, Bhatia, A. K. & Khan, F. (2014). Kintic and Isothrmal Studis for Rmoval of Zn (II) Ions from Aquous Solutions by Using Lawsonia inrmisas a Novl Biosorbnt. Advancs in Rsarch, 2(12), Articl no. AIR Dng, Y., Gao, Z., Liu, B., Hu, X., Wi, Z., & Sun, C. (2013). Slctiv rmoval of lad from aquous solutions by thylndiamin modifid Attapulgit. Chmical Enginring Journal, 223, Farooq, U., Kozinski, J.A., Khan, M.A., & Athar, M. (2010). Biosorption of havy mtal ionsusing what basd biosorbnts a rviw. Biorsour Tchnology, Razmovski, R., & Sciban, M. (2008). Biosorption of Cr (VI) and Cu (II) by wast ta fungal biomass. Ecological nginring, 34, Ho, Y.S., & McKay, G. (1999). Psudo-scond ordr modl for sorption procss. Procss Biochmistry, 34, Altin, O., Ozblg, H.O., & Dogu, T. (1998). Us of gnral purpos adsorption isothrms for havy mtal clay minral intractions. Journal of Colloid & Intrfac Scinc, 198, Simsk, I., Karatas, M., & Basturk, E. (2013). Cu (II) rmoval from aquous solution by urolytic mixd cultur (UMC). Colloids and Surfacs B: Biointrfacs, 102, Yargıc, A.S., YarbaySahin, R.Z., Ozbay, N., & Onal, E. (2014). Assssmnt of toxic coppr (II) biosorption from aquous solution by chmically-tratd tomato wast (Solanum lycoprsicum). Journal of Clanr Production, Machida, M., Aikawa, M., & Tatsumoto, H. (2005). Prdiction of simultanous adsorption of Cu (II) and Pb (II) onto activatd carbon by convntional Langmuir typ quations. Journal of Hazardous Matrials, 120, Nadaroglu, H., Kalkan, E., & Dmir, N. (2013). Rmoval of coppr from aquous solutionusing rd mud. 24

5 Dsalination, 251, Phlivan, E., Altun, T., & Parlayıc, S. (2009). Utilization of barly straws as biosorbnts for Cu 2+ and Pb 2+ ions. Journal of Hazardous Matrials, 164, Altun, T. & Phlivan, E. (2007). Rmoval of coppr (II) ions from aquous solutions by walnut, hazlnut and almond-shlls. Clan-Soil Air Watr, 35(6), Yahaya, Y.A., Don, M.M., & Bhatia, S. (2009). Biosorption of coppr (II) onto immobilizd clls of Pycnoporus sanguinus from aquous solution: quilibrium and kintic studis. Journal of Hazardous Matrials, 161, Vin, D., Colthup, N. B., Fatly, W. G., & Grasslli, J. C. (1991). Th handbook of IR and Raman Charactrstics Frquncis of organic Moloculs, Acadmic Prss, San Digo, USA, 21. Pannrslvam, P., Morad, N., & Tan, K. (2011). Magntic nanoparticls (F 3 O 4 ) imprgnatd onto ta wast for th rmoval of Nickl (II) from aquous solution, Journal of hazardous matrials, 186, Rocha, C.G., Zaia, D.A.M., Alfaya, R.V.S. & Alfaya, A.A.S. (2009). Us of ric straw as biosorbnt for rmoval of Cu (II), Zn (II), Cd (II) and Hg (II) ions in industrial fflunts, Journal of hazardous matrials, 166, Chn, G., Zng, G., Tang, L., Du, C., Jiang, X., Huang, G., Liu, H., & Shn, G. (2008). Cadmium rmoval from simulatd wastwatr to biomass byproduct of Lntinusdods, Biorsourc Tchnology, 99, Fig. 1. Effct of ph on Cu (II) uptak onto biomass. (C 0 = 50 mg L 1 ; W = 0.5 g; T = 303 K; V = 50 ml, contact tim = 90 min.) 25

6 Fig. 2. Effct of Contact tim on Cu (II) uptak onto biomass. (C 0 = 50 mg L 1 ; W = 0.5 g; T = 303 K; V = 50 ml, ph = 5.0) Fig. 3. Effct of biomass dosag on Cu (II) uptak onto biomass. (C 0 = 50 mg L 1, T = 303 K, V = 50 ml, ph = 5.0, contact tim = 90 min.) 26

7 Fig. 4. Effct of initial mtal concntration on Cu (II) uptak onto biomass. (W= 0.5 g, T = 303 K, V = 50 ml, ph = 5.0, contact tim = 90 min.) Fig. 5. Th Effct of diffrnt mtal concntration onto biomass with rspct to contact tim Fig.6. Psudo-scond ordr kintic modl of Cu (II) uptak onto biomass. 27

8 Fig.7. FTIR spctrum of BTLP (a) bfor and (b) aftr adsorption. 28

9 Tabl.1. Valus of rat constant of adsorption Exprimntal Psudo scond ordr kintic modl q (mg g -1 ) K 2 (g mg -1 min -1 ) q (mg g -1 ) R Tabl.2. Th Valus of Constant paramtrs and corrlation cofficints for Langmuir and Frundlich adsorption modls at diffrnt tmpraturs. Isothrm Modls 303 K 313 K 323 K Langmuir q m (mg/g) K L (L/g) R Frundlich K F (mg g -1 ) n R Tabl.3. Th FTIR spctral charactristics of Biomass Frquncy (cm -1 ) Functional Group 3370 bondd OH group 2922 Aliphatic CH group 1720 Strtching C=O group 1626 Aromatic C=C group 1033 C-O strtching of Carboxylic group 29

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