A batch study of adsorption equilibrium and kinetic for methylene blue onto synthesized zeolite

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1 Journal of marials and Environmnal Scincs ISSN : 8-58 Copyrigh 7, Univrsiy of Mohammd Prmir Oujda Morocco JMES, 7 Volum 8, Issu, Pag hp:// A bach sudy of adsorpion uilibrium and kinic for mhyln blu ono synhsizd zoli Z. Bnmaamar *, H. Hamiouch, H. Bououmi, H. Bnmaamar 3, S. Ould Baba Ali 3, A. Bnmaamar 3, A. Aggoun Laboraoir d Applicaion Enrgéiu d l'hydrogèn, Univrsiy of Blida, Algria. Laboraoir d Géni Chimiu, Univrsiy of Blida, Algria. 3 Déparmn d Géni ds Procédés, Univrsiy of Blida, Algria. Rcivd 6 Apr 6, Rvisd 4 Nov 6, Accpd 8 Dc 6 Kywords Synhsizd zoli (ZS), Mhyln blu (MB), Linar, Non-linar rgrssion, Kinic adsorpion, Error simaion, Rgrssion cofficin (R ) Z. Bnmaamar bnmaamarzoubir@yahoo.fr Tl.: Absrac Synhsizd zoli (SZ) was characrizd by nirogn adsorpion dsorpion xprimns (spcific surfac ara masurmns by h BET mhod), by XRD, and usd for h mhyln blu (MB) adsorpion in synhsizd war. Th BET surfac ara (S BET ) was m /g. Th XRD indicad h formaion of zoli Y. Kinic adsorpion of mhyln blu (MB) ono synhsizd zoli (SZ) was sudid in a bach sysm. Th ffcs of ph and conac im wr xamind. Th maximum adsorpion occurrd a ph 7. Th plaau of h uilibrium sa was obaind afr 6 min. In ordr o drmin h bs-fi-kinic adsorpion, h xprimnal daa wr analyzd using psudo-firs-ordr, psudo-scond-ordr, psudo-hird-ordr, suivl, and lovich modls. Linar rgrssiv and non-linar rgrssiv mhods wr usd o obain h rlaiv paramrs. Th rror analysis was ulad o find which mhod was br o fi h xprimnal daa. Th non-linar psudo-scond ordr modl was bs o fi h uilibrium daa. Th valu of fr nrgy (ΔG) was also drmind. Th prsn work showd ha SZ can b usd as a low cos adsorbn for h MB rmoval from war.. Inroducion Th xil indusry is on of indusrial was war sourc. This conaminad war is vry oxic for h human and animals []. Mhyln blu (MB) is usd in coloring papr, dying coons, wools, silk, lahr and coaing for papr sock. Alhough mhyln blu is no srongly hazardous, i can caus som harmful ffcs, such as harba incras, vomiing, shock, cyanosis, jaundic, uadriplgia, and issu ncrosis in humans []. Th s, applicaion and dvlopmn of many ramn mhods wr h ssnial subjcs of many aricls such as: physical, chmical, biological [3]. Chmical coagulaion flocculaion [4] diffrn yp of oxidaion procsss [5] biological procss [6], mmbran-basd sparaion procsss [7] and adsorpion [8] wr h ramns usd in h purificaion of wars. Th bs fficin mhod usd for h uickly rmoval of dys from h auous soluion is h physical adsorpion [9]. In his cas, acivad carbon has bn provn o b widly usd adsorbn for lowring h concnraion of dys in was war, bu i prsns som disadvanags such as: flammabiliy [], lss rgnrabiliy a low mpraur [-], wak hydrophobociy [3] Acually, h bs alrnaiv o carbon adsorbn is zoli []. Rcnly, commrcial zolis hav bn usd o rmov h dissolvd polluans in war and/or waswar [4]. Howvr, hr ar rlaivly limid sudis don on h caionic dys adsorpion by synhsizd zolis [5]. In his work, w ar inrsing o h ponial of SZ for h MB dy rmoval from simulad was war using bach mhod. To opimiz xprimnal variabls (such as: ph and conac im), h adsorpion kinic fficincy of MB was sudid. Linar and non- JMES, 7, 8 (), pp

2 linar mhods wr usd o obain h rlaiv paramrs. Th rror analysis was ulad o find which mhod was br o fi h xprimnal daa.. Exprimnal.. Adsorbn Sodium silica Na SiO 3.5H O (PANREAC QUIMICA), sodium alumina NaAlO (PANREAC QUIMICA) and sodium hydroxid NaOH (98% puriy; PANREAC QUIMICA) wr usd o mak h SZ. SZ was synhsizd from sd gl (.g NaOH,.55g NaAlO, 4.98g H O, 5.68g Na SiO 3.5H O) and fd sock gl (.35g NaOH, 3.8g NaAlO, 3.7g H O, 35.6g Na SiO 3.5H O). Th sd gl was prpard as follows:. g of sodium hydroxid (NaOH) and.5 g of sodium alumina (NaAlO ) wr dissolvd in 4.98 g of disilld war. Afr dissoluion, 5.68 g of sodium masilica (Na SiO 3.5H O) ar addd o h mixur. Th gl was agd during 4 hours a room mpraur, undr agiaion, in closd polyhyln bol. Th fd sock gl was prpard in h following way:.35 g of sodium hydroxid NaOH and 3.8g of sodium alumina (NaAlO ) wr dissolvd in 3.7g of disilld war. Afr dissoluion, 35.6g of sodium masilica (Na SiO 3.5H O) wr vry gradually addd undr srong agiaion. Th gl was pu mauring during wo hours afr h nd of h addiion. Afr mauraion of h fd sock gl, h sd gl is addd undr srong agiaion a room mpraur. Th rsuling mixur is immdialy addd in a racor and kp in ovn a C for 4 hours. Afr complion of h synhsis im, h marials was filrd, washd and drid ovrnigh a C... Adsorba MB (3,7-bis (Dimhylamino)-phnazahionium chlorid ramhylhionin chlorid) in h prsn sudy was slcd from h lis of dys usd in Algria (such as: in h xil indusry, coloring papr, ) (Tabl. ), was purchasd from Mrck (Grmany). Dy Srucur Tabl : Slcd Propris of MB [6] MB Chmical formula Mass wigh C 6 H 8 N 3 SCl. 3H O g/mol.3. Characrizaion of synhsizd zoli SZ was characrizd by nirogn adsorpion a 77K, XDR and MB adsorpion kinic..4. N adsorpion dsorpion a 77 K Nirogn physisorpion daa wr obaind by N adsorpion a 77 K, in a Micromriics ASAP insrumn. Prior o masurmn, h sampls wr dgassd a 393 K for h. Th spcific surfac ara was ulad by h BET uaion; h oal por volum was drminad from N adsorpion a a rlaiv prssur of.98. Th micropor volums and micropor spcific surfac of sampls wr valuad by h -plo mhod. Th xrnal Surfac Ara was h dducion of BET Surfac Ara and Micropor Ara..5. X-ray diffracion (XRD) characrizaion Powdr X-ray diffracion parns wr collcd on a Brukr D8 Advanc diffracomr wih Cu Kα radiaion..6. Adsorpion of MB Adsorpion kinic of MB ono SZ was sudid in a bach sysm. Th ffcs of ph and uilibrium im wr xamind. Th adsorpion paramrs wr opimizd. In ach xprimn prwighd amoun of adsorbn (5 JMES, 7, 8 (), pp

3 mg) was addd o 5 ml of dy soluion (5 mg/l) akn in a 5 ml of conical flask and. M NaOH or. M HCl wr addd o adjus h ph. This soluion was agiad a 3 rpm and cnrifugd. Th BM concnraion in soluion was drmind a λmax = 665 nm by spcrophoomr UV-7 PHARMA SPEC SHIMADZU. Th MB adsorbd amoun pr mass uni of adsorbn (SZ) a im, (mg/g), was ulad as: = (C -C )*(V/M) () whr C is h iniial MB concnraion (mg/l), C is h MB dy concnraion a im (mg/l), V is h soluion volum (in L) and M is h adsorbn mass (in g) [7]. 3. Rsuls and discussion 3.. Synhsizd zoli characrizaion 3.. Physical characrizaion Th daa in Tabl. indicad h surfac aras, por volums, and por sizs of h SZ. Tabl : Main physical propris of h Synhsizd zoli SZ SZ Surfac Ara (m /g) Singl poin surfac ara a P/P = BET Surfac Ara S BET (m /g) Plo Micropor Ara Plo Exrnal Surfac Ara BJH Adsorpion cumulaiv surfac ara of pors bwn 7. Ǻ and Ǻ diamr BJH Dsorpion cumulaiv surfac ara of pors bwn 7. Ǻ and Ǻ diamr Por Volum (cm 3 /g) Singl poin dsorpion oal por volum of pors lss han 8.5 Ǻ diamr a P/P = Plo Micropor Volum.375 BJH Adsorpion cumulaiv volum of pors bwn 7. Ǻ and 3. Ǻ.46 diamr BJH Dsorpion cumulaiv volum of pors bwn 7. Ǻ and 3. Ǻ.547 diamr Por Siz (Ǻ) Dsorpion avrag por widh (4V/A by BET) 8.74 BJH Adsorpion avrag por diamr (4V/A) BJH Dsorpion avrag por diamr (4V/A) XRD characrizaion From Figur, h XRD of h synhsizd zoli xhibid som significan paks of rflcions a of abou 6.3,.3,., 5.9, 9.,.67, 8.6, 3.6, 33.66, 35.9, and 38.57, which wr indicaiv of h formaion of zoli-y [8]. 3.. Adsorpion sudis To sudy h ffc of vry paramr, i is ncssary o fix h valus of ohrs ph ffc Th liminaion of polluans from waswar by adsorpion is xrmly influncd by h soluion ph which affcs h naur of h adsorbn surfac charg, h ionizaion xn, h auous adsorba spcis spciaion and h adsorpion ra. Th adsorpiv procss hrough funcional groups dissociaion on h adsorba and adsorbn wr affcd by a ph chang [9]. JMES, 7, 8 (), pp

4 Posiion [ Tha] Figur : Synhsizd zoli XRD parn Th ffc of ph was conducd by mixing 5 mg of adsorbn wih 5 ml of MB synhic soluion 5 mg/l. Th soluion ph was varid from o, by adding.m NaOH or.m HCl soluions. Th suspnsion was shakn for 4 h a 5 C. Th adsorpion capaciy of MB incrass wih h incras of ph of h soluion. Figur shows h iniial ph ffc on h SZ uilibrium adsorpion capaciy. Th soluion ph affcd h valus of. Whn h valu of ph was from 5 o, h adsorpion uaniy was approximaly consan SZ 5 5 Figur : Th iniial ph ffc on h SZ uilibrium adsorpion capaciy. From h Figur, h MB maximum adsorpion occurrd a ph 7 and h lows adsorpion occurrd a ph. From his sudy, i is clar ha in h basic mdium h ngaivly chargd spcis nds dominaing and h surfac sars o acuir a ngaiv charg. In his cas h adsorbn surfac is ngaivly chargd, h MB adsorpion incrasd, du o h incrasing of lcrosaic aracion bwn h ngaivly chargd zoli paricls and h posiivly chargd MB spcis Conac im ffc Kinic xprimns wr prformd by mixing 5 ml of dy soluion (5 mg/l) wih 5 mg of adsorbn. Th iniial ph for ach dy soluion was s a 7. Th suspnsions wr pu undr agiaion during 4 hours for crain im inrvals, and MB concnraions in h suprnaans wr analyzd o ula h adsorbd dys on h zoli. Ths xprimns wr ralizd agains im (5,,, 3, 4, 5, 6,, 8, 4, 3, and, 36 min) (Figur 3). JMES, 7, 8 (), pp

5 SZ 3 4 Figur 3: MB adsorpion kinic on SZ. Th plo of synhic sampl could b dividd in hr zons: (i) -3 min, which indicad h fas adsorpion of MB, suggsing rapid xrnal diffusion and surfac adsorpion; (ii) 3-6 min, showd a gradual uilibrium, and (iii) 6-39 min, indicad h plaau of h uilibrium sa. Th adsorpion was rapid a h iniial sag of h conac, bu i gradually slowd down unil h uilibrium. Th fas adsorpion a h iniial sag can b aribud o h fac ha a larg numbr of surfac sis ar availabl for adsorpion. Afr a laps of im, h rmaining surfac sis ar difficul o b occupid. This is bcaus of h rpulsion bwn h solu molculs of h solid and bulk phass which mak i aking long im o rach uilibrium [] Adsorpion kinics modling and mchanism Adsorpion is a complx procss which is influncd by svral paramrs rlad o adsorbn and o h physicochmical condiions undr which h procss is carrid ou []. In ordr o undrsand h mchanism of h adsorpion procss, h following uaions: psudo-firs ordr (Lagrgrn Modl) [], psudo-scond ordr (Ho modl) [], suivl [3], psudo-hird ordr [4], and lovich [5] wr slcd o fi h xprimnal kinic daa. Euaions of hs modls wr illusrad in Tabl. 3. Tabl 3: Adsorpion kinic modls and hir linar and non linar forms. Isohrm Non Linar form Linar form Rfrnc Psudo-firs ordr Psudo-firs ordr log( ) log( ) [6] (yp) (.33 Psudo-firs ordr ) ln( ) ln( ) k [7] (yp) Psudo-firs ordr k C C C ln( ) k (yp3) C [8] Psudo-firs ordr C C (yp4) Hlfrich ln k C C [9] Psudo-scond ordr Psudo-scond ordr yp k [3] JMES, 7, 8 (), pp

6 Psudo-scond ordr yp Psudo-scond ordr yp 3 Psudo-scond ordr yp 4 Psudo-scond ordr yp 5 Psudo-scond ordr yp 6 Psudo-scond ordr yp 7 Psudo-scond ordr yp 8 Psudo-scond ordr yp 9 k ( [] k ) [3] k k [3] ( k ) [33] k k [34] k [35] k k k [36] [37] Psudo-scond ordr yp k [38] Psudo-scond ordr yp Psudo-scond ordr yp Psudo-scond ordr yp 3 k C C [39] k [33] C C C C k b [4] Esuivl modl (yp ) Esuivl modl (yp ) Psudo-hird ordr K E K E ( k 3 ) Elovich (yp) d k k ) Elovich (Roginsky- Zldovich) (yp ) K E [3] ( ) K E [3] k 4 xp( 5 k5 ln( k5k4) k5 ln( ) d d k 7 xp( k 6 ) ( / k6)ln( k6k7) (/ k6)ln( ) d 3 [4] [5] [4] whr k is psudo-firs ordr ra consan (min - ), k is psudo-scond ordr ra consan (g/(mg min)), k 3 is psudo-hird ordr ra consan (g /(mg min)), K E is suivl ra consan (min), k 4 is lovich ra consan (mg/(g min)), k 5 is xn of surfac covrag and acivaion nrgy of h procss mg/g min, k 6 xn of surfac covrag and acivaion nrgy of h procss (g/mg), k 7 lovich ra consan (mg/(g min)), is amoun of adsorpion a uilibrium (mg/g), and dimnsionlss paramr (=/ ). A non-linar and linar fiing procdur using Excl and Origin sofwar wr usd rspcivly. Th consans of all modls wr givn in Tabl. 4. JMES, 7, 8 (), pp

7 Tabl 4: Linar and non-linar psudo-firs ordr, psudo-scond ordr, suivl, and lovich kinic isohrms consans rlad o h adsorpion of MB ono SZ. Modl Linar Mhod Non-linar Mhod Psudo-firs ordr (yp ) (mg/g) k (min - ).3.38 R Euaion log( ) log( ) Psudo-firs ordr (yp ) (mg/g) 4.93 k (min - ).3 R.663 Euaion ln( ) ln( ). 3 Psudo-firs ordr (yp 3) C (mg/l) 5 5 k (min - ).6.6 R <.957 Euaion C ln( ).6 C C Psudo-scond ordr (yp ) (mg/g) k (g/(mg min)) R.996 Euaion Psudo-scond ordr (yp ) (mg/g) 4.9 k (g/(mg min)).47 R.946 Euaion.8 Psudo-scond ordr (yp 3) (mg/g) k (g/(mg min)).47 R.946 Euaion Psudo-scond ordr (yp 4) (mg/g) 4.9 k (g/(mg min)).45 R.93 Euaion Psudo-scond ordr (yp 5) (mg/g) 4.97 k (g/(mg min)).43 R.93 Euaion JMES, 7, 8 (), pp

8 Psudo-scond ordr (yp 6) (mg/g) 4.9 k (g/(mg min)).34 R.93 Euaion Psudo-scond ordr (yp 7) (mg/g) k (g/(mg min)).93 R.948 Euaion.97 Psudo-scond ordr (yp 8) (mg/g) 4.99 k (g/(mg min)).39 R.946 Euaion Psudo-scond ordr (yp 9) (mg/g) k (g/(mg min)).467 R.948 Euaion.467 Psudo-scond ordr (yp ) (mg/g) k (g/(mg.465 min)) R.948 Euaion.465 Psudo-scond ordr (yp ) C (mg/l) 5 k (g/(mg min)).44 R.88 Euaion.44 C C Esuivl Modl (yp ) (mg/g) k (g/(mg min)) R Euaion Esuivl Modl (yp ) (mg/g) k (g/(mg min)).39 R.946 Euaion JMES, 7, 8 (), pp

9 Elovich (yp ) k 5 (mg/(g min)). k 4 (g/mg) 9469 R.845 Euaion.* ln( ) Elovich (yp ) k 6 (mg/(g min) 4.55 k 7 (g/mg) R.845 Euaion.* ln( ) Error simaion using h wll-known spcial funcions In his par, h bs-fiing uaion is drmind using h wll-known spcial funcions o ula h rror dviaion bwn xprimnal and prdicd daa. Th mahmaical uaions of hs rror funcions wr illusrad in Tabl. 5. Tabl 5: Mahmaical uaions of rror funcions. Error funcions Euaions Rfrncs ARED ARE SAE = EABS ARS MPSD Δ(%)=*ARS n xp ARED i n xp i ARE SAE EABS n i xp ) / xp n [4] ( [43] xp [44] xp / xp ARS [45] ( n ) MPSD (%) xp xp n p xp ( n ) SSE MPSED / xp [46] [47] MPSED xp SSE [48] xp ( n p) / xp [49] HYBRID n xp HYBRID i ( n P) xp i [5] Whr n is h numbr of xprimnal daa poins, is h prdicd (ulad) uaniy of MB adsorbd ono zoli, xp is h xprimnal daa, p is h numbr of paramrs in ach kinic modl, ARED is avrag rlaiv rror dviaion (dimnsionlss paramr), ARE is avrag rlaiv rror (dimnsionlss paramr), ARS is avrag rlaiv sandard rror (dimnsionlss paramr), HYBRID is hybrid fracional rror funcion (dimnsionlss paramr), MPSD Maruard s is prcn sandard dviaion (dimnsionlss paramr), MPSED Maruard s is prcn sandard dviaion (dimnsionlss paramr), SAE=EABS is sum of absolu rror (mg/g), SSE is sum of h suars of h rrors (mg/g), and Δ(%) is normalizd sandard dviaion (mg/g). Th consans of all rror analysis wr rprsnd in Tabl. 6. JMES, 7, 8 (), pp

10 Tabl 6: Error dviaion daa rlad o h MB adsorpion ono SZ using mos commonly usd funcions. Error funcions ARED SAE=EABS MPSED SSE HYBRID ARE ARS Δ(%)=*ARS MPSD Non linar psudofirs ordr yp Non linar psudofirs ordr yp 3 Linar Psudo-nd ordr yp Linar psudo-nd ordr yp Linar psudo nd ordr yp 3 4 Linar psudo nd ordr yp 4 Linar psudo nd ordr yp 5 6 Linar psudo nd ordr yp 6 8 Linar psudo nd ordr yp 7 5 Linar psudo nd ordr yp 8 4 Linar psudo nd ordr yp 9 Linar psudo nd ordr yp Non linar psudo- nd ordr yp Linar suivl modl yp 4 36 Linar suivl modl yp 6 47 Whr from, according o h Tabl 6, is smd ha h non-linar psudo-scond ordr modl is h modl h mos suid o dscrib in a saisfacory way h phnomnon adsorpion sudid. Indd, h highs R valu and h lows ARED, ARE, SAE, ARS, MPSD, Δ, SSE, MSPED, and HYBRID valus wr found whn modling h daa of uilibrium using h non-linar psudo-scond ordr modl and linar psudo-scond ordr modl (yp 9 and yp ) (cf. Tabl. 6). By h way, a brif comparison bwn non-linar and linar analysis was carrid ou o invsiga, among hs rror funcions, h mos accpabl on(s) for ach rgrssion approach, aking h adua fiing modl (i.. psudo-scond ordr) as a sudy cas. Th rsuls showd ha, for h linar analysis, h rgrssion cofficin (R ) is h highs (i.. psudo-scond ordr yp ), which maks i mor adua as rror simaion ool o find h prfc isohrm fi for linar xprssion. For non-linar analysis, h rs of h rror funcions (i.. ARED, ARE, SAE, ARS, MPSD, Δ, SSE, MSPED, and HYBRID) sm o b h bs and h mos appropria. Rally, h non-linar ransformaion o linar rgrssion mhods disors h xprimnal rror, craing hrfor an inhrn rror simaion problm which limis h sudid ools validiy. Morovr, h linar analysis mhod assums h poins scar around h lin follows a Gaussian disprsion and rror simaion is h sam a h uilibrium liuid-phas rsidual concnraion valu (i.. X-axis). Nvrhlss, such bhaviour is impossibl wih uilibrium isohrm modls (sinc isohrm modls had non-linar shap) as h rror disribuion gs changd afr ransforming h daa o linar [49]. Improbably, non-linar rgrssion mhod would avoid such rrors, making his analyzing chniu h mos suiabl o obain mor ralisic isohrm paramrs [49]. JMES, 7, 8 (), pp

11 3..6. Acivaion paramrs assssmn To ula h acivaion paramrs such as nropy (ΔS), fr nrgy (ΔG) and nhalpy (ΔH), h Eyring xprssion was applid [5], k kb S H ln ln T h P R RT () H TS ( b a) RT (3) k k ln a and B ln b T h P whr k B is h consan of Bolzmann ( J.K -, h P is h consan of Plank (J.s) and, k is h psudo-scond ordr consan. Th Gibbs nrgy of acivaion may b wrin in rms of nropy and nhalpy of acivaion [5]: ΔG = ΔH - T*ΔS = (b a)* R*T (4) ΔG = (kj.mol - ) a T = 98 K Th posiiv ΔG valu proposs ha adsorpion racions nd nrgy o ransform soluion spcis o adsorbd spcis [53]. Conclusions Synhsizd zoli (SZ) was characrizd and usd for h mhyln blu adsorpion in synhsizd war. Th adsorpion dsorpion isohrms of N indica ha h BET surfac ara is ual o m g. Th XRD spcrum indicas ha is zoli Y yp. In bach sudis, h adsorpion was highly dpndn on various opraing paramrs, such as: conac im, and ph. Th rsuls suggs ha h MB adsorpion ono his SZ incrasd progrssivly ovr h firs 38 min and hn sayd unchangd wih furhr incrasing uilibrium im. Th apparn uilibrium was rachd afr 6 min for SZ. Surfac adsorpion mchanism was prdominan in h iniial sag of conac im, hr afr diffusion bcam ra-limiing procss. Th adsorpion kinic of MB ono SZ can b br fid by h non-linar psudo-scond-ordr modl han by h linar psudo-scond-ordr modl (yp 9 and ) as compard o h psudo firs ordr, psudo hird ordr, suivl, and lovich modls. Th valu of fr nrgy (ΔG) indicad ha h adsorpion racion was no a sponanous procss and ha h sysm ruirs nrgy gain from an xrnal sourc. On h whol, h xprimnal rsuls showd ha SZ is suiabl adsorbn for rmoval of MB dys. Rfrncs. Bgum R.A., Zaman M.W., Mondol A.T.M.A.I., Islam M.S., Hossain K.M.F, Bangladsh J. Agril. Rs., 36() () 39.. Kushwaha A.K., Gupa N., Chaopadhyaya M.C., J. Saudi. Chm. Soc., 8 (4). 3. Blaid K.D., J. Environ. Chm. Eng,. (3) Prakash N.B., Sockan V., Jayakaran P., In. J. Eng. Sci. Inno. Tch. (IJESIT), 3 () (4) Provic M., Rarjnovic J., Barclo D., Th Holisic Approach o Environ., () Csaro A., Naddo V., Blgiorno V., J. Biormd Biodg., 4 (8) (3) Wnn I.G., Khoiruddin, Aryani P.T.P., Hakim A.N., J. Mmbran Sci. Rs., (6) Admiluyi F.T., Amadi S.A., Amakama, Jacob Nimisingha J., J. Appl. Sci. Environ. Manag., (3) (9) Alln S. J., Koumanova B., J. Univ. Chm. Tchnol. Mall., 4(3) (5) 75.. Bnmaamar Z., Bnguddach A., J. Appl. Sci. Environ. Sani., () (7) 43.. El-Sharkawy E.A., Soliman A.Y., Al-Amr K.M., J. Colloid Inrf. Sci., 3 (7) Blocki S.W., Environ. Prog., (993) Tsai W.T., Hsin K.J., Hsu H.C., J. Hazard. Mar., 66 (9) Amin M.T., Alazba A.A., Manzoor U., Adv. Mar. Sci. Eng., (4). 5. Ms A., Kovacvic D., Vujvic D., Papic D., War Rs., 38 (4) JMES, 7, 8 (), pp

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