Batch Biosorption of Metanil Yellow from Aqueous Solution on Egg Membrane: Kinetics and Mechanism

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1 Inrnaional Journal of Chmical, Marial and Environmnal Rsarch 018, 5 (): Rsarch aricl INTERNATIONAL JOURNAL OF CHEMICAL, MATERIAL AND ENVIRONMENTAL RESEARCH An Inrnaional Opn Fr Accss, Pr Rviwd Rsarch Journal ISSN , Vol. 5, No. : pg Bach Biosorpion of Manil Yllow from Auous Soluion on Egg Mmbran: Kinics and Mchanism Bniah Obinna Isiuku *, Judih Onyinychi Onyokoro Dparmn of Chmisry, Imo Sa Univrsiy, Owrri, Imo Sa, Nigria (Rcivd: January 0, 018; Accpd: Fbruary 8, 018) Absrac Th rmoval of manil yllow (MY), a hazardous azo dy from auous soluion by bach biosorpion on hn gg mmbran (HEM) was carrid ou. Th ffcs of conac im, iniial soluion concnraion, iniial soluion ph, and biosorbn dosag wr valuad. Exprimnal daa wr analyzd wih h psudo-scond-ordr, Elovich, inra-paricl diffusion, liuid film diffusion, and Boyd modls. Rsuls show ha h opimum iniial concnraion, ph, and biosorbn dosag wr 50 mg/l, 3 and 0.01 g pr 5 ml soluion, rspcivly a 9 o C. Th highs xprimnal biosorpion capaciis, obaind wr 58.15, and 1.65mg/g, rspcivly for 5, 50 and 100 mg/l MY wihin h firs 60min. Th psudo-scond-ordr and Elovich kinic modls analyzd h xprimnal daa wll. Howvr, h psudo-scond-ordr modl fid br wih corrlaion cofficin valus, R, , and 0.846, for iniial concnraions of 5, 50 and 100mg/L, rspcivly. This was also confirmd by h sum of suar rrors (SSE) which wr 0.31, 1.41 and 0.81 for C o 5, 50 and 100 mg/l, rspcivly. Th Boyd modl confirmd ha h biosorpion procss was conrolld by boh h inra-paricl diffusion and h liuid film diffusion mchanisms. From h rsuls obaind, HEM has a high ponial for h rmoval of MY from auous soluion. I migh also hav h capaciy o rmov war-solubl anionic organic compounds if wll harnssd. Kywords: Biosorpion, kinics, mchanism, gg mmbran, manil yllow 1. Inroducion Th discharg of auous dy ffluns from xil and dysuff indusris ino h auaic cosysm has bn gnraing a lo of public concrn [1]. Ths ffluns cra ashic displasur, hindrs ligh pnraion ino h war body which is ncssary for phoosynhsis in auaic plans, lowrs war ualiy and causs harm gnrally o auaic lif []. Manil yllow (MY) is a synhic azo dy applid on wool, nylon, silk, papr, ink, aluminium, drgn, wood, fur, cosmics, and as a biological sain. I is hazardous whn ingsd and slighly hazardous whn inhald or conacs h ys [3]. Toxiciy daa rvals ha oral fding or inrapronal and inrasicular adminisraion of MY in animals producs sicular lsions, causing sminifrous ubuls o suffr damag, rducing h ra of sprmaognsis. On oral consumpion, i causs mhamoglobinamia [4] and cyanosis [5] in humans, whil skin conac rsuls ino allrgic drmaiis [6]. MY also has umour-producing ffcs and can also cra insinal [7] and nzymic [8] disordrs in h human body. I is no muagnic bu can alr h xprssion of gns [9]. Sris of mhods hav bn dvlopd for h rmoval of synhic dys from waswars. Thy includ mmbran filraion, adsorpion, coagulaion, advancd oxidaion procsss and ozonaion [10]. Among hs procsss, adsorpion is suprior du o is chapnss, flxibiliy, simpliciy of dsign, as of opraion and lack of snsiiviy o oxicans [11, 1]. * Corrsponding auhor: obinnabisiuku@yahoo.com Publishd onlin a Copyrigh 018 In. J. Chm. Mar. Environ. Rs. All Righs Rsrvd.

2 156 BO Isiuku & JO Onyokoro: Biosorpion of Manil Yllow on Egg Mmbran Adsorpion is a procss ha aks plac a h surfac du o h adhsion of paricls (aoms, ions or molculs) of on subsanc (adsorba) o h surfac of h ohr (adsorbn) [1]. Biosorpion is h binding of adsorba paricls on h surfac of an adsorbn. Th adsorbn is a naural subsanc of biological origin whhr aliv or non-living [13]. Du o incrasd ra of urbanizaion, hr is incras in h numbr of food manufacurrs, hachris, hols, rsaurans and homs ha us hn ggs. Larg uaniis of ggshll ar discardd as was. Hn gg mmbran (HEM) has good adsorpion propris. I conains polysaccharid fibrs and collagn which provid hydroxyl, amin and sulphonic funcional groups on which h adsorba paricls sick [14]. Pramanpol and Niayapa [15] usd ggshll and ggshll conaining h mmbran o rmov raciv yllow 05. Thir rsul showd a 10-7 fold incras in adsorpion capaciy du o h prsnc of h mmbran. Morovr, Hassan and Hassan [14] usd ggshll conaining h mmbran o ffcivly rmov mhyln blu, a caionic dy, from auous soluion. Thrfor, h bach biosorpion of MY, an anionic azo dy, on HEM was invsigad in his work wih a viw o sudy h kinics and procss mchanism.. Marials and Mhods.1. Prparaion of Dy Soluion Th MY also calld C.I. acid yllow 36, usd in his sudy, was supplid by Mrck, Swizrland and usd dircly wihou furhr ramn. Th srucur of MY is shown in Figur 1. Th sock soluion was prpard by dissolving 1.0 g MY dy pr lir soluion in 1 L volumric flask wih disilld war. Diffrn iniial MY concnraion (5-100 mg/l) usd in his work wr obaind by diluion of h sock soluion. A 0.1 M niric acid and 0.1 M sodium hydroxid soluions wr usd for ph adjusmns... Prparaion of HEM Figur 1. Srucur of Manil Yllow Hn ggshlls wr obaind from rsaurans and hachris in Owrri, Imo Sa, Nigria. Th ggshlls wr washd wih ho war and rinsd hric wih ho disilld war o rmov odour and dir. Th ggshlls wr boild for 30 min and coold. Whil soakd, h mmbrans wr pld off, packd in a laic and allowd for war o drain off. Th mmbran biomass was drid a 110 o C in a ho air ovn for 1 h and coold. Th drid mmbran biomass was ground wih a blndr and sivd o obain mm paricls and packd in an airigh plasic conainr...1 Analysis of h HEM Infra-rd spcrophoomric analysis of h HEM was carrid ou by FTIR-8400S spcrophoomr (M/s Shimadzu, Japan). Proxima analysis of h biosorbn was carrid ou using h Associaion of Official Analyical Chmiss (AOAC) 1990 mhods [16]..3. Bach Biosorpion Procss Bach biosorpion of MY from auous soluion was carrid ou by agiaing 0.01 g porions of h HEM wih 5 ml porions of diffrn MY concnraions in 50 ml volumric flasks. This was don by sing h sampls flasks in a warbah shakr and agiaing for 6 h a 9 o C and a spd of 175 rpm. Sampls wr collcd ach hour, filrd, and h filra analyzd using UV-Visibl spcrophoomr (Shimadzu, modl 75, M/s Shimadzu, Japan) a a wavlngh of 440 nm λ max o drmin h amoun of dy biosorbd on h biosorbn using Euaions 1 and. ( Co C)V m ( Co C) %Rmoval x 100 C o

3 In. J. Chm. Mar. Environ. Rs. 018; 5 (): whr, V (ml) is h volum of soluion, C (mg/l), h uilibrium concnraion of h dy rmaining in h soluion, and m (g) is h dry mass of h HEM. 3. Rsuls and Discussion 3.1. Analysis of h Biosorbn Tabl 1 shows h proin, carbohydra, fibr, and lipid conns of h biomass and Figur shows h infra-rd spcrum of h biosorbn. Th infra-rd paks a , , , , and cm -1 indica h prsnc of NH- and OH funcional groups, whil , , , and cm -1 show h prsnc of CO- funcional group. Th NH- and CO- funcional groups xis in proin and proin fibrs. Carbohydras furnish OH, and srs (lipids) conain CO and C-O- funcional groups [17, 18, ]. Figur. FTIR Spcrum of HEM Tabl 1. Proxima Analyical Daa for HEM Paramrs Valu (%) Crud proin.1 Carbohydra Fibr 7.59 Lipid Moisur 11.7 Ash Effcs of Iniial Dy Concnraion and Conac Tim Th ffcs of iniial MY concnraion and conac im ar shown in Figur 3, for 5, 50 and100 mg/l a 9 o C, agiaion spd of 175 rpm and ph 3. Maximum biosorpion was wihin h firs 60 min for all h concnraions. Howvr, xprimnal a maximum im of 360 min wr 5.83, 99.6 and mg/g for 5, 50 and 100 mg/l, rspcivly. Gnrally, h biosorpion capaciis wr high for all h MY concnraion. Howvr, hr was apprciabl dclin in biosorpion wih im, spcially for 100 mg/l. Rsuls show incras in wih incras in iniial concnraion. This agrs wih h work of Njoku and Hamd [19]. Th opimum im of biosorpion for iniial concnraion 5 and 50 mg/l was 10 min. For 100mg/L, uilibrium was no rachd a 360 min. Th apprciabl dcras in wih im for 100mg/L migh b as a rsul of h compiion of h biosorba anions for h availabl binding sis [0, 1]. Th incras in wih incras in MY iniial concnraion was as a rsul of h incras in h driving forc from h concnraion gradin. Th biosorpion was nhancd by h proonaion of h amino and carboxyla moiis in h proin fibrs and h oxo groups in h polysaccharid prsn in h HEM [, 3, 4]. A highr biosorba concnraions h aciv sis on h mmbran wr surroundd by many mor biosorba ions, lading o nhancd biosorpion [5] Effc of Sorbn Dosag Various masss ( g) of h HEM wr inracd wih 5 ml porions of h dy soluion (5 mg/l) a ph 3, 9 o C and agiaion spd of 175 rpm for 6 h in ordr o valua h ffc of biosorbn dosag. Th rsuls dpicd in Figur 4 show ha dcrasd wih incras in biosorbn dosag. This is in agrmn wih h work of Koumanova al. [6].

4 158 BO Isiuku & JO Onyokoro: Biosorpion of Manil Yllow on Egg Mmbran Figur 3. Effc of Iniial MY Concnraion on h Bach Biosorpion of Manil Yllow on HEM Figur 4. Effc of Biosorbn Dosag on h Bach Biosorpion of Manil Yllow on HEM A highr biosorbn dosag, hr was a vry fas suprficial biosorpion ono h biosorbn surfac ha producd a lowr solu concnraion in h soluion han whn biosorbn dosag was lowr. Thus, wih incrasing biosorbn dosag, h amoun of MY biosorbd pr uni mass of HEM rducd, hnc lading o a dcras in. This is in conformiy wih h rpor of Han al. [5]. Incrasing h biosorbn dosag from 0.01 o 0.3 g/5 ml of h soluion ld o a dcras in, from o 1.80 mg/g. Th opimum biosorbn dosag was found o b g pr 5 ml soluion Effc of Iniial Biosorba ph Soluion ph affcs h propris of boh biosorba and biosorbn and is hrfor a vry imporan paramr ha affcs biosorpion in auous soluions [19]. Th ffc of iniial soluion ph on h biosorpion of MY on HEM was invsigad wihin h ph rang -7 and h rsul is shown in Figur 5. Th figur shows ha h highs was 9.40 mg/g a ph 3, for 5 mg/l iniial MY concnraion, adsorbn dosag 0.0 g pr 5 ml, and mpraur of 9 o C. Thr was a dcras in wih incras in ph. A ph 7, hr was virually no biosorpion. Th ph valus -4 wr idal for h biosorpion of MY on HEM. Th, dcrasd from 9.40 mg/g a ph 3 o 6.45 mg/g a ph. Th rason for h dcras is aribud o h incras in H + concnraion lading o h formaion of aua complxs hrby rarding h biosorpion procss. This agrs wih h rpor of Mas Haris and Sahasivam [7]. Th ffc of ph is aribud o h lcrosaic inracion bwn h biosorba paricls and biosorbn surfac. A low ph, h carboxyla anion of h proin fibr prsn in h mmbran as par of h amino acid funcional group is proonad and h amino acid xiss primarily as h ammonium ion; h oxo funcional group prsn in h polysaccharid is also proonad. Ths condiions cra posiivly chargd surfac on h biosorbn, hnc a high biosorpion; if h ph is raisd, h ammonium ion si in h proin is dproonad, and h molcul xiss as h carboxyla anion; h

5 In. J. Chm. Mar. Environ. Rs. 018; 5 (): oxo funcional group is hydrad gnraing hydroxyl ions which rpl h MY anions [, 3]. Ths condiions wr rsponsibl for poor biosorpion a highr ph valus Biosorpion Kinics Figur 5. Effc of Iniial Soluion ph on h Bach Biosorpion of Manil Yllow on HEM Isohrms ar obaind undr uilibrium condiions, whras in mos biosorpion ramn applicaions h rnion im is oo shor for uilibrium o b aaind. Hnc, informaion mus b obaind on h im dpndnc of biosorpion procsss by carrying ou procss-orinad kinic sudis [4]. Th im dpndn xprimnal daa in his sudy wr analyzd using fiv kinic modls Psudo-scond-ordr Kinic Modl Th linarizd form of h psudo-scond-ordr modl [8] is xprssd as Euaion 3; 1 3 h o whr, (mg/g) is h biosorpion capaciy a im, h o (mg/g/min) h iniial biosorpion ra and (min) is im. h o is xprssd as Euaion 4. h o k 4 whr, k (g/mg/min) is h scond-ordr ra consan. A plo of / agains, yilds a sraigh lin wih slop 1/ and inrcp 1/h o (Figur 6). Th R valus show ha h psudo-scond-ordr modl simulad h xprimnal rsuls wll. Th calculad ra consans, xprimnal and prdicd wih corrsponding R valus ar shown in Tabl. Figur 6. Psudo-scond Ordr Kinic Plos for h Bach Biosorpion of Manil Yllow on HEM

6 160 BO Isiuku & JO Onyokoro: Biosorpion of Manil Yllow on Egg Mmbran Elovich Kinic Modl Tabl. Kinic Modls Paramrs for h Biosorpion of MY on HEM a 9 o C and ph 3 C o (mg/l) Modl/Paramr Psudo-scond-ordr xp. (mg/g) o (mg/g) k (g/mg/min) R SSE Elovich Α Β R Liuid film diffusion K id R Boyd B R Th linarizd form of h Elovich modl is mainly applicabl o chmisorpions kinics. Th uaion xprssd in Euaion 5 is ofn valid for sysms in which h biosorbing surfac is hrognous [9]. 1 1 ln( ) ln 5 A plo of agains In givs a sraigh lin wih slop 1/β and inrcp (1/β)ln(αβ), whr α is h iniial biosorpion ra (mg/g/min) and β is rlad o h xn of surfac covrag and h acivaion nrgy for chmisorpions (g/mg) (Figur 7). Th R valus porray h Elovich modl good for analyzing h xprimnal daa. Howvr, h psudo-scond-ordr modl was a br modl for h analysis han h Elovich modl. Tabl shows h R, α and β valus Liuid Film Diffusion Modl Figur 7. Elovich Kinic Plos for h Bach Biosorpion of Manil Yllow on HEM Whn h ranspor of h biosorba molculs from h liuid phas up o h solid phas boundary plays a major rol in biosorpion, h liuid film diffusion modl uaion is usd which is xprssd as Euaion 6. ln(1 F) K id 6 whr, F is h fracional aainmn of uilibrium (F = / ), K id, h biosorpion ra consan and, h im (min). A linar plo of In(1-F) agains wih zro inrcp suggss ha h kinics of h biosorpion procss is conrolld by

7 In. J. Chm. Mar. Environ. Rs. 018; 5 (): diffusion hrough h liuid surrounding h biosorbn [9]. Figur 8 shows h R valus and inrcps for iniial MY concnraions 5, 50 and 100mg/L. Non of h inrcps is zro hough h modl fis h xprimnal daa wll. Hnc h liuid film diffusion biosorpion mchanism was no h only ra-drmining sp in h biosorpion procss Inra-paricl Diffusion Modl Figur 8. Liuid Film Diffusion Plos for h Bach Biosorpion of Manil Yllow on HEM Th possibiliy of inra-paricl diffusion bing h ra drmining sp in h biosorpion procss can b ascraind using h inra-paricl diffusion modl [30]. Involvd in h procss ar h ranspor of h biosorba o h surfac of h sorbn which is usually a slow procss. Basd on his hory; 0.5 K id C 7 whr, K id is h inra-paricl diffusion ra consan (mg/g/min 0.5 ) and C is a consan ha givs ida abou h hicknss of h boundary layr, i.., h largr h valu of C h grar is h boundary layr ffc [31]. If a plo of agains 0.5 givs a sraigh lin, hn h biosorpion procss is conrolld by inra-paricl diffusion only and h slop givs h ra consan, K id. Howvr, if h daa show muli-layr plos, wo or mor sps conrolld h biosorpion procss. Figur 9 shows h analysis of xprimnal daa wih his modl. Figur 9. Inra-paricl Diffusion Plo for h Biosorpion of Manil Yllow on HEM Th figur shows ha h biosorpion procss was govrnd by h inra-paricl diffusion for iniial MY concnraion 5 mg/l.

8 16 BO Isiuku & JO Onyokoro: Biosorpion of Manil Yllow on Egg Mmbran Th Boyd Modl Th Boyd kinic uaion [19, 3] was applid o disinguish bwn film diffusion and inra-paricl diffusion and o drmin h ra drmining sp in h biosorpion. Th uaion is xprssd as Euaion F 1 xp( n ) B 8 n 1 n whr, B is a mahmaical funcion of F, h fracional aainmn of uilibrium a im. F is givn by Euaion 9. F 9 Euaion 8 can b simplifid wih approximaions o giv Euaions 10 and 11. B ln(1 F) ( for F 0.85) 10 F B ( for F 0.85) 3 A plo of B agains yilds a sraigh lin which can b usd o drmin h ra-drmining sp in h biosorpion procss. A sraigh lin which passs hrough h origin for a givn iniial concnraion shows ha inra-paricl or por diffusion is h ra-drmining sp in h biosorpion procss. If h plo is nonlinar or linar bu dos no pass hrough h origin hn h biosorpion procss is conrolld by liuid film diffusion. Figur 10 shows ha h biosorpion procss was conrolld by inra-paricl diffusion for 100 mg/l. For iniial concnraion 5 and 50 mg/l, h biosorpion procss was conrolld by liuid film diffusion. Th R valus 0.736, and for 5, 50 and 100 mg/l, rspcivly show ha h Boyd modl is a good fi for h xprimnal daa. 11 Figur 10. Boyd Modl Plos for h Bach Biosorpion of Manil Yllow on HEM Tabl 3. Comparison of Maximum Biosorpion Capaciy of HEM for MY wih ohr Biosorbns Sorbn Sorba % Rmoval Rfrncs Hn gg mmbran Manil yllow This work Immobilizd auaic wd Manil yllow 98.8 Sivashankar al. [35] H 3PO 4-acivad carbon Manil yllow 1.04 Isiuku al. [36] NaOH-acivad carbon Manil yllow 1.90 Egg mmbran, 4-DCP 48.; 71. Koumanova al. [4] A comparison of h biosorpion capaciy of HEM for MY wih ohr biosorbns in liraur is prsnd in Tabl 3. Sivashankar al. [35] usd immobilizd auaic wd o rmov MY from auous soluion and obaind 98.8% oal rmoval. Isiuku al. [36] usd H 3PO 4- and NaOH-acivad carbons o rmov h sam dy and obaind 1.04 and 1.90%

9 In. J. Chm. Mar. Environ. Rs. 018; 5 (): oal rmoval, rspcivly. Koumanova al. [4] usd HEM o rmov, 4-Dichlorophnol undr varying condiions and obaind 48. and 71.% oal rmoval, rspcivly. Th oal rmoval of MY from auous soluion wih HEM of 79.69% obaind in his work is comparaivly high Sponaniy of h of h Biosorpion Th sponaniy of h biosorpion procss was drmind by valuaing h Gibb s fr nrgy of biosorpion ΔG ads [33, 34] xprssd as Euaion 1. G RT ln K 1 ads D whr, R (8.314J/mol/K) is h univrsal gas consan, T (K) h absolu mpraur and K D h uilibrium disribuion consan. K D is drmind from Euaion 13. K D ( Co C ) 13 C Th ΔG ads valus wr -4.61, and.13 kj/mol for iniial MY concnraions 5, 50 and 100 mg/l, rspcivly. Th valus show ha h biosorpion was sponanous for 5 and 50 mg/l bu non-sponanous for 100 mg/l. 4. Conclusion Th highs xprimnal uilibrium biosorpion capaciis of 58.15, and 1.65 mg/g for iniial MY concnraion 5, 50 and 100 mg/l, rspcivly wr obaind wihin h firs 60 min a ph 3, sorbn dosag 0.01 g/5 ml soluion and 9 o C. Ho s psudo-scond-ordr kinic modl simulad xprimnal daa bs. Th Boyd modl confirmd ha for iniial MY concnraion 100 mg/l, h biosorpion procss was conrolld by inra-paricl diffusion whil for 5 and 50 mg/l, h biosorpion was conrolld by h liuid film diffusion. Th sudy shows ha HEM is a good biosorbn for MY rmoval from waswar. REFERENCES [1] Isiuku B.O., Nwosu C.N., 017. Fixd-bd adsorpion of manil yllow from auous soluion on HNO3-rad-H3PO4-acivad carbon from G. abora bark. Asian J. Chm., 9 (3), [] Isiuku B.O., Horsfall Jnr. M., Spiff A.I., 014. Colour rmoval from a simulad mhyl rd waswar by adsorpion on carbon in a fixd bd. Rs. J. Appl. Sci., 9 (4), [3] Isiuku B.O., 015. Adsorpion of manil yllow and mhyl rd from auous soluions using cassava (Maniho sculna) pls acivad carbon in a fixd-bd column. Ph D. Dissraion, Univrsiy of PorHarcour, PorHarcour, Nigria. [4] Sachdva S.M., Mani K.V., Adval S.K., Jolpoa V.P., Rasla K.C., Chadha D.S., 199. Acuird oxic mhamoglobinamia. J. Assoc. Physcians Ind., 40, [5] Chandro S.S., Nagaraja T., A food poisoning ou-brak wih chmical dy: An invsigaion rpor. Mdical J. Armd Forcs Ind., 43, [6] Hausn B.M., A cas of allrgic conac drmaiis du o manil yllow. Conac Drmaiis, 31, [7] Ramachandani S., Das M., Joshi A., Khanna S.K., Effc of oral and parnal adminisraion of manil yllow on som hpaic and insinal biochmical paramrs. J. Appl. Toxicol., 17, [8] Das M., Ramachandani S., Upri R.K., Khanna S.K., Manil yllow: a bifuncional inducr of hpaic phas I and phas II xnoblasic-mabolizing nzyms. Food Chm. Toxicol., 35, [9] Gupa S., Sundarrajan M., Rao K.V.K., 003. Tumor promoion by manil yllow and malachi grn during ra hpaocarcinognsis associad wih disrgulad xprssion of cll cycl rgulaory proins. Trogn. Carcin. Mu. (Suppl. 1), [10] Turhan K., Durukan I., Ozurcan S.A., Turgu Z., 01. Dcolorizaion of xil Basic Dy in auous soluion by ozon. Dys Pigm., 9, [11] Tong Z., Zhng P., Bai B., 016. Adsorpion prformanc of Mhyl Viol via α porous hollow carbonacous microsphrs and is ffciv rgnraion hrough a Fnon-lik racion. Caalyss, 6(4), p 58.

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