Comparison of adsorption behaviour and kinetic modeling of bio-waste materials using basic dye as adsorbate

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1 Indian Journal of Chmical Tchnology Vol. 21, Spt-Nov 2014, pp Comparison of adsorption bhaviour and kintic modling of bio-wast matrials using basic dy as adsorbat Harmindr Singh* & Sonam Chodn Dpartmnt of Chmistry, Lovly Profssional Univrsity, Panjab , India Rcivd 8 April 2014; accptd 11 August 2014 Adsorption of basic dy Crystal Violt (CV) from aquous solution by two low cost adsorbnts Ground Nut shll powdr (GNSP) and Ground nut shll ash (GNSA) has bn invstigatd through batch mod adsorption procss. Th study involvs th rmoval of CV using oprational paramtrs; initial concntration ( mg/l), diffrnt contact tim, adsorbnt dos ( g/100ml) and ph (3-10). It has bn found that prcntag rmoval of dy improv with rduction in original concntration, intnsification in tim of contact and adsorbnt dos. Basic ph of th dy solution show bttr adsorption capacity as compard to acidic dy solution. FTIR analysis rvals th prsnc of favourabl alcoholic and carboxylic groups on th surfac of th adsorbnt. SEM analyss show irrgular morphology with particls in micromtr rang. Langmuir isothrm fit bttr than Frundlich adsorption isothrm and to Lagrgrn scond ordr kintic modl fittd bttr than first ordr for both th adsorbnts. Rsults show that GNSP prformd bttr than GNSA. It can b concludd from th study that GNSP can b usd as a low cost adsorbnt. Kywords: Crystal Violt, Ground nut shll powdr, Ground nut shll ash, Adsorption isothrm, Kintics. Watr is th primary ncssity of lif on arth. Watr is rquird in almost all sphrs of lif. It has significant part in fulfilling a numbr of domstic, industrial and agricultural dmands. Watr rsourcs ar not only xploitd but quality of th watr has also bn dtrioratd du to startling incras in population, industrial activitis and agricultural practics. Natural as wll as wast watr tratmnt systms ar bing pollutd with a numbr of dys which is bing rlasd from various sourcs lik papr and pulp industris, txtil industris, dy industris tc. Dys ar problmatic as ths ar toxic and non-biodgradabl bcaus of thir complx and stabl structurs, thus rmoval of dys from wast watr has bcom grat challng to all global scintists 1. Numrous mthods ar rportd in th litratur for th limination of dys lik chmical coagulation 2, ozonation 3,4 and adsorption. Among th various practics for th rmoval of dys, adsorption is prfrrd ovr othr mthods as it provids suprior outcoms. For this purpos activatd carbons ar xtnsivly usd bcaus of thir fficincy and rsourcfulnss, howvr thy arcostly. A numbr of studis hav bn concdd by diffrnt prsonnl on adsorption of colourd mixturs from solutions by th us of conomical and co-frindly adsorbnts 5-8. Svral low cost and co-frindly adsorbnts for xampl activatd carbon prpard from panut shlls 9, Phragmit australis tratd with 40% H 3 PO 4 (Rf 10), Gmlina arbora bark 11, bottom ash 12, soil nano-clays 13, sludg acquird from caustic industris 14, tamarind (Tamarindus indica) fruit shll powdr 15, Tndu (Diospyros mlanoxylon) lavs wast; a solid wast from bidi industry 16, powdrd myclial biomass of Criporialacrat (CLB) 17, Artocarpus htrophyllus (jackfruit) laf powdr (JLP) 18, raw baggas 19, grapfruit pl (GFP) 20, conifrous pinus bark powdr (CPBP) 21, activatd carbons prpard from mal flowrs of coconut tr 22, numrous fly ash sampls having divrs unburnt carbon mattrs 23, Syzygium cumini sd (SCSC) 24, Agricultural Wast Cocoa (Thobroma cacao) Shll 25, carbon prpard from wast prawn shlls 26, chitin obtaind from shrimp shll 27, mustard wast ash and buffalo dung ash 28 hav bn dscribd in th litratur. This study dscrib th fficincy of two low cost bio adsorbnt viz. ground nut shll powdr (GNSP) and ground nut shll ash (GNSA) for th rmoval of crystal violt dy from aquous solution. Exprimntal Sction Prparation of Adsorbnts Ground Nut shlls wr gathrd from nativ bazaar in Jalandhar, India. Th prcursor was

2 360 INDIAN J. CHEM. TECHNOL., SEPT-NOV 2014 splashd with distilld watr to gt rid of th dirt and othr contaminations, drid at 60 C for 12 h in hot air ovn. Half of th dhydratd Ground nut shll was crushd and sivd (70 µm) to obtain fin particls of Ground nut shll powdr (GNSP). Th rst half of drid Ground nut shlls wr turnd to into ash (i.. GNSA) by kping it in a muffl furnac st at 500 C for 2 h. Charactrization of th adsorbnt surfac Surfac charactristics of th adsorbnts wr xamind using scanning lctron microscopic (SEM) analysis, nrgy disprsiv X-ray spctroscopy (EDX) and Fourir transform infra-rd (FT-IR) spctroscopy. In ordr to gt th clar pictur of particl siz and xtrnal surfac of matrial th imags of adsorbnt wr takn by Scanning Elctron Microscopy (SEM) (modl: ZEISS EVO-40 sris Scanning Elctron Microscop (SEM): Carl Ziss SMT Ltd., Cambridg, England). Th imags of adsorbnts bfor as wll as aftr th intraction with dy wr rcordd. For Enrgy Disprsiv X-ray (EDX) dtctor systm with X-FlashSilicon Drift Dtctor-4010, 10 mm 2, typ 1106 Brukr AXS, Grmany was usd. FTIR spctra of GNSA and GNSP wr takn using a Fourir transform infrard spctrophotomtr (Shimadzu 8400s) to lucidat th functional group prsnt on th surfac of th adsorbnts. For masuring IR spctra, th powdrd sampls wr ncapsulatd in KBr pllt and a spctrum was obtaind in th sris of 400 to 4000 cm -1. Adsorption studis Standard solution of Crystal Violt (CV) wasarrangd by mixing 1 g of th dy in 1000 ml of th doubl distilld watr (1000 mg/l). This solution was usd to mak dsird concntrations using doubl distilld watr. Hydrochloric acid and sodium hydroxid solution wr usd to adjust th ph of th dy solution. Adsorption studis data was obtaind using batch tchniqu xprimnts. A pr-dcidd amount of th adsorbnt was takn in 100 ml oprational solution of various concntrations ( mg/l) in 250 ml conical flask with stopprs. Ths flasks wr rtaind in a thrmostatic shakr sustaind at a tmpratur of 25 C and 150±10 rotations pr minut for sufficint tim to accomplish quilibrium. Subsquntly, th adsorbnt matrial was alinatd by cntrifugation at 1800 ± 100 rpm. Rsidual aquous phas concntration of dy was xamind with UV-VIS spctrophotomtr (Shimadzu-1800) by obsrving optical dnsity at 591 nm. Th abov mntiond procss was rpatd to discovr th influnc of diffrnt adsorption paramtrs lik adsorbnt load ( g/1000ml), initial ph of th dy solution (3-10), tim of contact and initial concntration of dy. Variation was don in on of th abov mntiond paramtrs by kping all othr conditions at a constant valu. Adsorption Isothrms Adsorption isothrm is a plot btwn amount of th dy adsorbd pr gram of th adsorbnt (Q ) against concntration of th dy at quilibrium (C ). It is usd to dcid th practicability of using an adsorbnt matrial for a spcific purpos. Quantity of dy adsorbd pr gram of th adsorbnt (Q ) is computd according to following xprssion: C o C Q = ( )V m whr C o and C ar original as wll as concntrations of dys at quilibrium rspctivly, m corrsponds to th wight of adsorbnt in grams and V spcifis th volum in litrs of th dy solution 29. Most common isothrm for th adsorption is Langmuir isothrm. Th assumptions of Langmuir modl ar: i. Adsorption is a rvrsibl procss. ii. Th adsorbd molculs do not mov on th surfac of th adsorbnt iii. Th surfac of th adsorbnt has a prcisquantity of positions whr th adsorbatcan b adsorbd. iv. Only a monolayr is formd at th surfac of th adsorbnt. Langmuir adsorption isothrm in linar form is rprsntd as: = + Q Q bqc whr Q and b ar Langmuir constants indicats th Langmuir adsorption capacity (mg/g) and nrgy of adsorption (L/g) rspctivly. Q and b can b calculatd from th slop and intrcpt of th graph btwn 1/C vrsus 1/Q 30. Langmuir adsorption is also articulatd in rlation of a sparation factor R L which is a dimnsionlss ntity 30 and is xprssd as:

3 SINGH & CHODEN t al.: ADSORPTION BEHAVIOUR AND KINETIC MODELING OF BIO-WASTE MATERIALS 361 R L = 1 1+ bc o 1,ads Log(Q Q t ) = LogQ t k C o rprsnts maximum initial concntration of dy in mg/l and b signifis Langmuir isothrm constant. If R L is gratr than 1, thn procss is uncomplimntary, if R L is qual to 1 thn procss is linar, if R L lis btwn 0 to 1 thn procss is ncouraging and if R L is 0 thn th procss is irrvrsibl. Frundlich adsorption rprsnts a plot rlating th quilibrium concntration of an adsorbat prsnt on th surfac of th adsorbnt, to th quilibrium concntration of th adsorbat in th liquid phas 28. Linar form of th Frundlich Adsorption Isothrm may b rprsntd as: LogQ = LogK F + 1 n LogC whr; K F rprsnts Frundlich adsorption capacity and 1/n indicats adsorption intnsity. Valu of 1/n is gratr and 1 and high valu of 1/n mans adsorption procss is promising. Adsorption kintics Data was fittd to Lagrgrn psudo-first ordr and psudo-scond ordr kintic modls to valuat th influnc tim of contact. Th linarizd form of Lagrgrn psudo-first ordr modl is xprssd as and Lagrgrn psudo-scond ordr modl in linar form is givn by = + t Q h Q t whr, Q is th amount of dy adsorbd on th surfac of adsorbnt at quilibrium (mg/g), Q t is th amount of dy adsorbd at tim t (mg/g), k 1,ads is th raction rat constant for psudo first-ordr in minuts, h is k 2 Q 2 and k 2 = raction rat constant of adsorption th for psudo-scond-ordr in mg/g/min 31. Rsults and Discussion Fourir Transform Infrard (FT-IR) spctroscopy Figur 1(a) rprsnts th FTIR spctrum of GNSP. Th broad and intns bands locatd at cm - 1 may b attributd to O-H group. Th othr absorption at 2926 cm -1 is associatd to alkn strtching. Paks at 1649 and 1030 cm -1 corrsponds to C=O and C-H bnding. It can b dducd from th FTIR spctra of GNSA shown in Fig. 1(b) that absorption pak at cm -1 corrsponds to O-H strtching and absorption at cm -1 is attributd to alkn strtching. Pak at cm -1 is C=O, th pak at cm -1 rsmbls to C=C and pak at Fig. 1(a) FTIR spctra of GNSP

4 362 INDIAN J. CHEM. TECHNOL., SEPT-NOV cm -1 is C-O strtching vibrations. Th paks hr, in this spctrum appard to b lss intns compar to th paks of GNSP [Fig. 1(a)]. This could b du to th burning of GNSP into a GNSA. It is clar from th abov analysis that surfac of th adsorbnt contain groups lik hydroxyl and carboxylic which ar favourabl for th adsorption of cationic dys 32. Surfac charactrization using SEM imags Th surfac morphology of th GNSP consists of irrgular fibrs structur with small grains in btwn th fibrs as shown in th Fig. 2(a). Th lngth of th fibrs is 158 µm and width is 3.87 µm. Th siz of pors on th surfac is 3.87 µm. Th SEM imag of GNSP aftr th raction whr all th pors and void btwn th spacs hav covrd by th dy adsorbd on its surfac was shown in th Fig. 2(b). Th surfac of GNSA consists of long uniform fibrous structur with som channls and pors as shown in Fig. 2(c). Th lngth of fibrs is µm. Th width of fibrs is 7.8 µm with a channl siz of 4.87 µm. Th Fig. 2(d) shows th imag of GNSA aftr th raction in which all th spac of channl and pors ar covrd by dy molculs. Enrgy disprsiv X-ray spctroscopy Elmntal analysis of adsorbnt was conductd through using Enrgy disprsiv X-ray spctroscopy(edx) for th two adsorbnts and shown in Figs 3(a) and 3(b) for GNSP and GNSA Fig. 1(b) FTIR spctra of GNSA Fig. 2(a) SEM imag of GNSP bfor th raction Fig. 2(b) SEM imag of GNSP aftr th raction

5 SINGH & CHODEN t al.: ADSORPTION BEHAVIOUR AND KINETIC MODELING OF BIO-WASTE MATERIALS 363 Fig. 2(c) SEM imag of GNSA bfor th raction Fig. 2(d) SEM imag of GNSA aftr th raction Fig. 3(a) EDX spctra for GNSP Fig. 3(b) EDX spctra for GNSA

6 364 INDIAN J. CHEM. TECHNOL., SEPT-NOV 2014 rspctivly along with thir spctrums. Both th adsorbnts showd th high contnt of carbon and oxygn whil th othr lmnts such as magnsium, potassium, silicon, aluminum, calcium, iron, chlorin and sulphur ar prsnt in lowr concntration. Prsnc of high contnt of oxygn indicats that adsorption is favorabl for ths adsorbnts. Effct of contact tim Effct of contact tim on adsorption for th initial dy concntration 600 mg/l is dpictd in Fig. 4. Th figur indicatd that th adsorption of th CV was rapid initially and thr aftr it bcam slow whil raching quilibrium. Initially a numbr of adsorption sits wr availabl for th adsorbat but at latr stag ths sits wr rducd and rpulsiv forcs may hav startd btwn th adsorbat molculs on th solid and bulk phass 33. GNSP and GNSA prsntd a limitd numbr of adsorption sits. CV dy adsorption xhibitd a fullnss tndncy at 120 min for GNSP and 150 min for GNSA. It is also clar that out of th two adsorbnts GNSP has bttr prformanc than GNSA as in this xprimnt adsorbnt dos for GNSP was 0.1 g/100 ml as compard to 0.5 g/100 ml of GNSA, vn thn it has shown bttr prcntag rmoval. Morovr quilibrium tim obsrvd with GNSP is lss than th GNSA which indicat that rat of adsorption for GNSP is gratr than that of GNSA. This may b attributd to th highr amounts OH and CO groups xisting at th surfac of GNSP as indicatd by th intnsity of absorption paks in th FTIR spctra. Effct of adsorbnt dos Adsorbnt to adsorbat ratio gratly influnc th ovrall adsorption procss and optimization of adsorption is usually don with rgard to adsorbnt dos in a fixd volum of adsorbat solution. Influnc of adsorbnt dos for th rmoval of CV at initial CV concntration of 600 mg/l, by varying adsorbnt dos from 0.05 to 0.35 g was invstigatd. Fig. 5 rvald that th prcntag of dy rmoval improvd with ris in adsorbnt dos. Prcntag dy rmoval incrasd from to 84.99% for GNSP and from to 66.91% for GNSA. This is bcaus of th xtra numbr of adsorption sits accssibl with an incras in th adsorbnt dos. On th othr hand amount of dy adsorbd pr gram of th adsorbnt rducd from to mg/g for GNSP and from to mg/g for GNSA. This may b attributd to th fact that th adsorption sits ar fficintly usd at lowr adsorbnt dos. With an incras in th adsorbnt dos, it could b possibl that a substantial portion of accssibl adsorption sits rmains xposd, which lad to lss pr gram adsorption. Similar rsults hav bn statd for th rmoval of cationic dy on biowast matrial 34. Effct of initial ph of th solution Solution ph of dy solution gratly influncs charg at th surfac of th adsorbnts along with th xtnt of ionization of th solut particls. Th H + and OH - ions ar adsorbd powrfully and for this rason adsorption of additional ions ar influncd by ph of adsorbat solution 35. Th influnc of ph on th Crystal violt adsorption onto GNSP and GNSA is rprsntd in Fig. 6. Th adsorption of CV has incrasd for both th adsorbnts with ris in th ph of th dy solution from 3 to 10. As for th cationic dy, a nt ngativ charg on th surfac is xpctd to favour th adsorption which in turn can b maintaind by basic ph. It can b obsrvd from Fig. 6, that at ph valu of 3 a clar positiv charg bcaus of prsnc of hydronium ion dvlopd du to which Fig. 4 Effct of contact tim on th adsorption procss for CV onto GNSP and GNSA (Tmpratur= 25 C, RPM= 150±1, dos= 0.1 g/100ml of GNSP and 0.5 g/100ml of GNSA, ph=7.8, concntration of dy =600mg/L) Fig. 5 Effct of adsorbnt dos on th adsorption procss of CV onto GNSP and GNSA. (Tmpratur= 25 C, RPM= 150±1, concntration of dy =600 g/l, ph=7.8, quilibrium tim= 120 min for GNSP and 150 min for GNSA)

7 SINGH & CHODEN t al.: ADSORPTION BEHAVIOUR AND KINETIC MODELING OF BIO-WASTE MATERIALS 365 Fig. 6 Effct of ph on th adsorption procss of CV onto GNSP and GNSA (Tmpratur= 25 C, RPM= 150±1, dos= 0.1 g of GNSP and 0.5 g of GNSA, ph=7.8, concntration of dy = 600 mg/l, quilibrium tim = 120 min GNSP and 150 min for GNSA) minimum adsorption was obsrvd at ph 3. Thrfor as th ph was raisd, a ngativ charg on th surfac of th adsorbnt was dvlopd which incrasd with th furthr incras in ph. This nabld adsorbnts for gratr dy rmoval. Prcnt adsorption of dy was improvd from 39-88% for GNSP and 36-78% for GNSA whn ph was raisd from Effct of initial dy concntration Th xtnt of CV adsorbd pr unit mass of adsorbnt improvd with th ris in initial concntration and prcnt adsorption of CV from bulk phas dcrasd with th ris in original concntration (Fig. 7). Th quantity of CV adsorbd pr gram of th adsorbnt (Q ) incrasd from mg/g to mg/g for GNSA and it incrasd from gm/g to mg/g for GNSP whn th original concntration of dy was raisd from 100 to 600 mg/l. Ris in th original concntration of th dy adds to th implling caus to ovrcom th mass transfr opposition of dy molculs btwn th adsorbnt and adsorbat bulk phas which incrass th accptanc of dy molculs. Morovr, numbr of collisions btwn dy molculs and th adsorbnt also incrass which rsults in incras of th adsorption 36. Howvr, th CV prcntag rmoval dcrasd from 70.2 to 46.1% for GNSP and it dcrasd from 54.1 to 36.9 % for GNSA as th CV concntration was raisd from 100 to 600 mg/l. This could b bcaus of th rduction in numbr of activ sits rquird for high initial concntration of dy. At first, molculs of dy quickly touch th priphry of adsorbnt by mass transfr and thron thy gradually diffus from priphry to th adsorbnt du to th occupation of th activ sits. This lad to th diffusion of dy into th porous arrangmnt of th adsorbnt 37. Fig. 7 Effct of initial concntration of CV onto GNSP and GNSA (Tmpratur= 25 C, RPM= 150±1, dos= 0.1 g of GNSP and 0.5 g of GNSA, ph=7.8, quilibrium tim= 120 min for GNSP and 150 min for GNSA) Tabl 1 Langmuir and Frundlich Constants for MB using GNSP and GNSA Langmuir Constants Frundlich Constants Paramtr GNSP GNSA Paramtr GNSP GNSA Q (mg/g) K F b (L/mg) n R R SD SD R L Adsorption Isothrms Isothrms show an association among amounts of dy adsorbd pr gram of th adsorbnt sampl (Q ) and th concntration of dy at quilibrium (C ) of aquous phas. Adsorption isothrm for data obtaind was drawn which is similar to that of typ I adsorption isothrm which indicat that adsorbnt por sizs was approximatly qual to th molcul siz of adsorbat. Exprimntal data for batch adsorption studis was applid to th Langmuir and Frundlich modls. Th rsults obtaind from Langmuir and Frundlich isothrms indicatd strong adsorption capacity of GNSP and GNSA for crystal violt. Adsorption constant for Langmuir (b and Q) and Frundlich isothrm (K F and n) wr computd from slop and intrcpt and which ar prsntd in Tabl 1. Data was fittd wll to Langmuir isothrm than th Frundlich isothrm as indicatd by th R valus in Tabl 1. It is vidnt that GNSP prformd bttr than GNSA. A spcial paramtr R L was also calculatd and its valu for GNSP was found to b 0.34 and 0.73 GNSA which is btwn 0 and 1, and dircts that adsorption procss was favourabl.

8 366 INDIAN J. CHEM. TECHNOL., SEPT-NOV 2014 Adsorbnt Tabl 2 Constants for Lagrgrn psudo-first ordr and psudo-scond ordr adsorption kintic modl Psudo-first ordr kintic modl Psudo-scond ordr kintic modl Q (mg/g) k 1,ads (min -1 ) R 2 SD Q (mg/g) h (mg/g.min) k 2 (g/mg.min) R 2 SD GNSP GNSA Valus of Langmuir adsorption capacitis (Q) wr compard with th valus rportd in litratur for Crystal violt using low cost matrials 28 and it was found that GNSP and GNSA has comparabl or bttr adsorption capacitis than much of th low cost matrial alrady rportd. Adsorption kintics Adsorption data achivd aftr th variation in intraction tim was fittd in th Lagrgrn psudofirst ordr and psudo-scond ordr adsorption kintic modls. Corrlation cofficints (R 2 ) for th Lagrgrn psudo-first ordr and psudo-scond ordr kintic plots wr found to b and rspctivly. From ths linar plots valus of Q and rat constants wr calculatd and ar prsntd in Tabl 2. It can also b vrifid from Tabl 2 that corrlation cofficints (R 2 ) for psudo-scond ordr kintic modl ar highr that th psudo-first ordr kintic which indicat that psudo-scond ordr kintic modl fittd bttr on th adsorption data for both th adsorbnts. Conclusions This study highlights th potntial of ground nut shll powdr (GNSP) and ground nut shll ash (GNSP) for th rmoval of Crystal Violt dy from aquous solutions by batch adsorption studis. It can b concludd that: 1. FTIR spctrum show that alcoholic, carboxylic groups ar prsnt on th surfac of both th adsorbnt which favour th adsorption procss for cationic adsorbats. 2. GNSP and GNSA hav diffrnt morphology. GNSP has irrgular fibrous structur with small grain in btwn th fibrs whras GNSA consists of fibrs having channls and pors in btwn. Particl sizs for both th adsorbnts ar falling in th micromtr rang. 3. Th prcntag of dy rmoval incrass with th ris in adsorbnt dosag, and contact tim. Adsoprtion also incrass with ris in th ph of th CV dy solution. 4. Th adsorption data is fitting wll to Langmuir adsorption isothrm than Frundlich adsorption isothrm and to Lagrgrn scond ordr kintic modl than first ordr, for both th adsorbnts. 5. GNSP outprforms GNSA in trms of adsorption capacity which may b du to th gratr amount of ngativly chargd functional groups availabl on th surfac. 6. Th rsults indicat that both GNSP and GNSA hav similar adsorption capacity prtaining to othr low cost adsorbnts rportd in litratur. Thrfor ths could b ngagd as low cost substitut to commrcially availabl adsorbnts for th rmoval of basic dys. Acknowldgmnt Authors ar thankful to Dirctor, Wadia Institut of Himalyan Gology, Dhradun and othr staff mmbrs for providing us SEM-EDX facility for physico-chmical charactrization of th matrial. Rfrncs 1 Ali H, Watr Air Soil Pollut, 213 (2010) Choi J H, Shin W S, L, S H, Joo D J, L J D & Choi, S, Environ Tchnol, 22 (2001) Bnszdits S, Am Dyst Rp, 69 (1980) Wu, J & Wang T, Watr Rs, 35 (2001) Nawar S S & Doma H S, Sci Total Environ, 79 (1989) Wu F C, Tsng R L & Juang R S, J Hazard Matr, B69 (1999) Wu F C, Tsng R L & Juang R S, J Environ Sci Halth, A34 (1999) Kadirvlu K, Thamaraislvi K & Namasivayam C, Biors Tchnol, 76 (2000) Zhang J X & Ou L L, Watr Sci Tchnol, 67 (2012) Shouman M & Rashwan W E, Univrsal J Environ Rs Tchnol, 2 (2012) Jovr A I & Alvacion J W L, Intrnational Confrnc on Environmnt and Industrial Innovation IPCBE, 35 (2012) Nidhsh P V, Gandhimathi R, Ramsh S T & Singh T S A, J Urban Environ Eng, 6 (2012) Chn Y, Tsao T & Wang M, IPCBEE, 8 (2011) Martin D M P, Pandian G V, Jayaraj R, Srinivasan A P & Slvamathan S, Int J Rs Chm E, 2 (2012) Patl H & Vashi R T, E-J Chm, 7 (2010) Nagda G K & Ghol V S, Int J Environ Rs, 2 (2008), Lin Y, H X, Han G, Tian Q & Hu W, J Environ Sci, 23 (2011) Saha P D, Chakraborty S & Chowdhury S, Colloids Surf B Biointrfacs, 92 (2012) Mahsh S, Kumar G V & Agrawal P, J Environ Bio, 31 (2010) 277.

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