UPTAKE OF METHYLENE BLUE DYE FROM AQUEOUS SOLUTIONS ONTO CHEMICAL ACTIVATED CARDOON (CYNARA CARDUNCULUS)

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1 Procdings of h 14 h Inrnaional Confrnc on Environmnal Scinc and Tchnology Rhods, Grc, 3-5 Spmbr 2015 UPTAKE OF METHYLENE BLUE DYE FROM AQUEOUS SOLUTIONS ONTO CHEMICAL ACTIVATED CARDOON (CYNARA CARDUNCULUS) PSARA E. 1, IOANNOU Z. 1 and DANALATOS N. 2 1 Dparmn of Food Scinc & Nuriion, Univrsiy of h Agan, 2 Miropolii Ioakim S., Myrina, Limnos, Grc, 2 Dparmn of Agriculur, Crop Producion & Rural Environmn, Univrsiy of Thssaly, Fyoko S., Volos, Magnsia, Grc zioan@mail.gr ABSTRACT A nw adsorpiv marial was prpard from h chmical modificaion of cardoon (Cynara cardunculus) appropria for dy rmoval. Cardoon was usd ihr as pll or powdr (300μm) form during h xprimns. I was acivad wih acid soluions of HCL or H 2SO 4 a diffrn iniial concnraions (1-5 M). Acivad cardoon adsorbns wr characrizd hrough FTIR analysis. Kinic and quilibrium sudis of dy upak ono h acivad cardoon wr also xamind. According o h rsuls, h FTIR analysis of h acivad cardoon has shown h prsnc of diffrn funcional groups such as C=O, -C-O, -C-H and OH. Dy adsorpion abiliy on acivad cardoon dpnds on h shap of cardoon and h yp of acid usd for acivaion and incrass according o h ordr: HCL, Powdr (300 μm) > H 2SO 4, Pll > HCL, Pll > H 2SO 4, Powdr (300 μm). Mhyln blu adsorpion prcnag ono h cardoon dpnds on h acid concnraion following h sam ordr (1Μ < 4Μ < 3Μ < 5Μ < 2Μ) for boh acids. Th rsuls hav shown ha h cardoon in powdr form acivad wih HCL 2M prsnd h highs MB adsorpion abiliy (97.9%) from h firs 60 min. Th kinic modls ha wr applid o MB adsorpion daa indicad ha h adsorpion procss follows psudo-scond ordr kinic modl and h ovrall ra is conrolld by chmisorpion. Equilibrium sudis of MB adsorpion on cardoon has shown ha dy soluion concnraion in quilibrium dcrasd by h incras in h dos of adsorbn du o h incras in h availabiliy of surfac aciv sis. In conclusion, acivad cardoon ihr in pll or powdr form, is a vry promising marial in war purificaion as filr, so i is usful o b invsigad horoughly in h fuur. Kywords: cardoon, pll, chmical acivaion, mhyln blu dy, kinic analysis 1. Inroducion Indusris, such as xil, papr and plasics, us a subsanial amoun of dys and war o color hir producs. Mhyln blu (MB) is a caionic dy ha is usd xrmly for dying coon, wool and silk. I is a dangrous polluan, bcaus i can b harmful for human and ohr living pics. Thrfor many mhods such as chmical coagulaion, ion xchang, lcrolysis, biological ramns and adsorpion (Gupa al., 2004) hav bn dvlopd for dy polluion rmoval from waswar bfor bing dischargd ino h nvironmn. Among hs mhods, adsorpion hrough acivad adsorbns is highly ffciv, chap and cofrindly for h rmoval of dys and pigmns as wll as ohr organic and inorganic pollurs (Acmioğlu, 2005). Th gnral procss o produc acivad lignocllulosic adsorbns is basd on h carbonizaion and acivaion procss of h raw marials of agriculural origin. Plan-basd marials such as cynara cardunculus, can b applid as raw marials for adsorpion purposs. Th procdur of carbonizaion aks plac in furnacs wih a gradual incras of mpraur undr a coninuous flow of an inr gas such as nirogn. An acivaion procss is an indpndn sag, which ihr follows h carbonizaion procss lading o acivad carbons or is applid dircly o h raw lignocllulosic marials lading o acivad adsorbns. In boh

2 cass h por volum and porosiy ar amliorad. Acivaion procss may b achivd ihr physically (hrmal procss) by using carbon dioxid, sam or chmically by using soluions of ZnCL 2, H 3PO 4, KOH (Ioannou al., 2015). Th purpos of h prsn papr is h dvlopmn of a novl yp of adsorbn for MB adsorpion. Spcifically, a chmical acivad cardoon (Cynara cardunculus) has bn succssfully synhsizd hrough a chmical mhod wih ihr HCL or H 2SO 4. Kinic and quilibrium sudis of dy upak ono h acivad cardoon wr also xamind using diffrn kinic modls. 2. Marials & mhods 2.1 Prparaion of chmical acivad adsorbns Cardoon was prpard in pll form using a hammr mill. In h xprimn, i was usd ihr as pll or was crushd and sivd up o 300 μm (powdr form). An amoun of 0.4 g of cardoon raw marial was addd o 20mL of hydrochloric acid (1-5M) or sulfuric acid (1-5M) ino 50mL falcon ubs. Thn, h sampls wr placd in an orbial shakr for 24 h in ordr o sablish compl conac bwn hydrochloric acid - biomass and sulfuric acid - biomass, a 24 o C. Thy wr filrd and washd svral ims wih disilld war, o rmov hydrochloric or sulfuric acid rsidus unil h filra ph rmaind nural (~7). Afr ha, h sampls wr drid in an ovn a 110 o C for 24 h (Hayashi al., 2000; Açikyildiz al., 2014) Prparaion of dy soluion An aquous mhyln blu (MB) soluion wih a concnraion of 0.03 g L -1 a 24 o C was prpard. An amoun of h chmical acivad adsorbn was placd in 14mL-plasic ubs in an adsorbn o ΜΒ soluion raio qual o 10 g L -1 undr coninuous sirring using an orbial shakr. A spcific im inrvals, an amoun of h soluion was cnrifugd for 2 min a 2,000 rpm and h rspciv MB concnraion was drmind by using a Prkin Elmr Lamda 25 UV-Vis spcrophoomr a 664nm. Th bach xprimns wr don wic. Th adsorbd amoun ( ) of MB was dducd from h diffrnc bwn h iniial amoun of adsorba ( o) in h soluion and h masurd amoun of h adsorba in vry soluion sampl. Equilibrium sudis of MB adsorpion ono h acivad cardoon wr also xamind Characrizaion of adsorbns Th infrard spcra (FTIR) of cardoon sampls in powdr form, which wr acivad wih HCL or H 2SO 4 in a concnraion of 5M, wr obaind using a Prkin Elmr spcrophoomr. Morovr, h FTIR spcra of acivad cardoon sampls afr MB adsorpion wr also obaind. All FTIR imags wr akn and collcd in ransmission mod in h rgion of cm -1 a a rsoluion of 4 cm Adsorpion kinic analysis Four diffrn kinic modls wr usd o invsiga h mchanism of adsorpion (McKay and Ho, 1999). Th psudo-firs-ordr kinic modl is givn by h following quaion: k1 log( ) log (1) whr and rfr o h amouns, of dy adsorbd pr uni mass of adsorbn (μmol g -1 ) a quilibrium and a im, rspcivly and k 1 is h quilibrium ra consan (min 1 ). Th slop and h inrcp of h plo of log( ) vrsus was usd o drmin k 1 and, which can b xprssd as h horical adsorbd dy a quilibrium, i..,hor. Th psudo scond ordr kinic modl can b xprssd as follows: 1 2 k2 (2)

3 whr k 2 (μmolg 1 min 1 ) is h quilibrium ra consan of psudo-scond-ordr adsorpion. Th slop and h inrcp of h plo of / vrsus was usd o drmin k 2 and. This modl prdics h bhavior ovr h whol rang of adsorpion if chmical adsorpion mchanism is h ra-conrolling sp. Kinic adsorpion daa wr furhr rad wih h Elovich quaion: ( 1/ ) ln( ) (1/ ) ln (3) In his cas h slop and h inrcp of h sraigh lin obaind by ploing vrsus ln, is usd o drmin 1/β, and h adsorpion quaniy, ln(αβ)/β. Anohr modl such as inraparicl diffusion modl can b dfind as: k id 0.5 C (4) whr is h amoun adsorbd a im, k id (μmolg -1 min -0.5 ) is h inraparicl diffusion ra consan and C is h inrcp. 3. Rsuls & discussion Cardoon consiss of cllulos, hmicllulos and lignin componns. Figur 1: FTIR spcra of acivad cardoon wih HCL or H 2SO 4 (5M) bfor and afr MB adsorpion. According o h FTIR analysis (Fig.1), h absorpion bands a 1244 and 1234 cm -1 indica h prsnc of MB in adsorbns du o h apparanc of C-N srching vibraions. Th bands a 1593 cm -1 rflc h aromaic ring vibraions plus h carbonyl group srching whil h bands a 1647 cm -1 rflc C=O srching vibraion. Acivad cardoon afr MB adsorpion prsns highr wavnumbrs a 1596 cm -1 insad of 1593 cm -1 and lowr valus 1633 cm -1 insad of 1647 cm -1 indicaing h craion of amid groups bwn MB and cardoon. Morovr, h wavnumbrs of 1106 and 1054 cm -1, which rfr o acivad cardoon ha adsorbd MB, corrspond o -C-O srching vibraions of alcohols and hrs and prsn a ransporaion o highr valus han h wavnumbrs of acivad cardoon bfor adsorpion, i or 1090 and 1051 or 1047 cm -1 for cardoon acivad wih HCL or H 2SO 4. Funcional groups such as OH and -C-H wr also prsnd a 3330 and 2930, 2890, 1450, 1425 cm -1, rspcivly. Th wavnumbrs of 1726, 1159, 1031, 890 cm -1 blong o C=O srching vibraions unconjugad, C-O-C- asymmrical srching, C-O srching vibraions and glycosidic linkags, rspcivly. Bnding vibraions of C-H and C-O groups wr also appard a 1360 and 1315 cm -1 (Bodîrlău and Tacă, 2009; Fior al., 2011).

4 (a) (b) (c) Figur 2: Upak of MB from aquous soluions ono chmical acivad cardoon ihr wih HCL acid in (a) pll and (b) powdr form or wih H 2SO 4 acid in (c) pll and (d) powdr form a diffrn concnraions (1-5 M) Acivad cardoon was usd as adsorbn in a bach opraion. As i is shown from Fig. 2a,b, h maximum MB adsorpion prcnag was qual o 87.65% and 97.92% a 60 min for h cardoon acivad wih HCL (2M) in pll and in powdr form, rspcivly whil h lows MB adsorpion was qual o 80.22% and 92.71% for h cardoon acivad wih HCL 1M in pll and in powdr form, rspcivly. Examining cardoon acivaion wih H 2SO 4 (Fig. 2c,d), i sms ha h maximum MB adsorpion prcnag was qual o 93.26% and 85.25% a 60 min for h cardoon acivad wih H 2SO 4 (2M) in pll and in powdr form, rspcivly whil h lows MB adsorpion was qual o 90.74% and 76.61% for h cardoon acivad wih H 2SO 4 1M in pll and in powdr form, rspcivly. All h ohr acivaions of h cardoon wih HCL or H 2SO 4 acid in concnraions qual o 3, 4 and 5 M prsnd inrmdia MB adsorpion prcnag valus. Th prcnag of MB adsorpion ono h cardoon dpnds on h HCL or H 2SO 4 acid concnraion, which acivad cardoon and incrass according o h ordr: 2M>5M>3M>4M>1M. During acivaion, h acid aacks o hmicllulos and lignin du o hir amorphous srucur and hn o crysallin cllulos. As a rsul, glycosidic linkags ar hydrolyzd in hmicllulos and cllulos and aryl-hr bonds in h lignin ar clavd. Th abov racions ld o molcular wigh rducion spcially of hmicllulos, i.. producion of glucos molculs and lignin, i.. formaion of kons. Ohr racions consiss of aliphaic chains clavag such as C=C- clavag of lignin (Marsh and Rodríguz-Rinoso, 2006). Th lack of C=C- and h inns prsnc of C=O and C-O- funcional groups xplaind also by h FTIR analysis of acivad cardoon. According o Pandy and Nair (1974), h dgr of cllulos polymrizaion dcrasd incrasing acid concnraion and mpraur. Acid inracs wih cllulos producing swlling in crysallin and inr-crysrallin rgions lading o a brakdown of cllulos chains (Marsh and Rodríguz-Rinoso, 2006; Pandy and Nair, 1974). (d)

5 Figur 3: Comparison of MB adsorpion bwn diffrn yps of acivad cardoon (in pll or powdr form), diffrn acid (HCL or H 2SO 4) for acivaion and diffrn concnraions (2 or 5 M). Figur 4: Sudy of MB soluion in quilibrium (C q) afr is adsorpion on chmical acivad cardoon wih HCL or H 2SO 4 (5M) a diffrn raios of adsorbn o adsorba, i.. 1.4, 2.4, 5.0, 10.0, 12.9 g/l. Figur 3 compars h diffrn cardoons ha wr acivad a wo acid concnraions, i.. 2 and 5 M, for hir adsorpion abiliy. According o h prvious rsuls (Fig.2), cardoons acivad wih ihr HCL or H 2SO 4 acid a 2 and 5 M prsnd h bs MB adsorpion prcnags. I sms ha h incras of MB adsorpion follows h ordr: cardoon acivad wih HCL (2M) in powdr form > cardoon acivad wih HCL (5M) in powdr form > cardoon acivad wih H 2SO 4 (2M) in pll form > cardoon acivad wih H 2SO 4 (5M) in pll form > cardoon acivad wih HCL (2M) in pll form > cardoon acivad wih HCL (5M) in pll form > cardoon acivad wih H 2SO 4 (2M) in powdr form > cardoon acivad wih H 2SO 4 (5M) in powdr form. Th highs MB adsorpion pr g of adsorbn was qual o 9.19 μmolg -1 a 120 min and was prsnd for h cardoon acivad wih HCL (2M) in powdr form whil h lows MB adsorpion pr g of adsorbn (8.00 μmolg -1 ) was prsnd for h cardoon acivad wih H 2SO 4 (5M) in powdr form. All h ohr acivaions and shaps of h cardoon wih HCL or H 2SO 4 prsnd inrmdia MB adsorpion valus. Equilibrium sudis of MB adsorpion ono chmical acivad cardoon in a concnraion of 5M a diffrn raios of adsorbn o adsorba wr also invsigad (Fig. 4). According o Fig.4, h gradual incras of h raio of adsorbn o adsorba from 1.4 o 12.9 g/l ld o gradual dcras of MB molculs in h soluion from o μmol/l for cardoon acivad wih HCL and from o μmol/l for cardoon acivad wih H 2SO 4. Th incras of h raio of adsorbn o adsorba soluion incrass h adsorpion sis of adsorbn lading o an incras in MB adsorbd molculs and a dcras o MB molculs in h soluion. Corncob acivad wih phosphoric acid (El-Sayd al., 2014), which was usd for mhyln blu rmoval, has shown ha h prcnag rmoval of h dy incrasd wih h incras in dos of adsorbn du o h incras in availabiliy of surfac aciv sis. According o MB adsorpion in quilibrium ihr xprimnal (,xp.) or horical (,hor.) and corrlaion cofficin facor (r 2 ) valus applid o kinic modls (Tabl 1), h psudo-scond ordr kinic modl fid vry wll h xprimnal MB adsorpion daa ono acivad cardoon ihr in pll or in powdr form. Sinc psudo-scond-ordr mchanism is prdominan, h ovrall ra of dy adsorpion would b conrolld by h chmisorpion procss (McKay al., 1999). Psudo-firs ordr, inraparicl diffusion and Elovich quaions prsnd rlaivly low r 2 valus showing hir inapproprianss for analyzing h xprimnal daa of h nir adsorpion procss. Similar sudis concrning h adsorpiv rmoval of mhyln blu from a was (Uddin al., 2009) and sasam hull (Fng al., 2011) has shown ha psudo scond ordr modl fid wll o h xprimnal MB adsorpion daa.

6 Tabl 1: Psudo-scond ordr kinic modl paramrs of mhyln blu adsorpion from aquous soluions on cardoon acivad wih diffrn acids (HCL, H 2SO 4) and diffrn concnraions (1-5M) Typ of adsorbn Acid Conc.,xp. (μmolg -1 ) k2 (μmolg -1 min -1 ),hor. (μmolg -1 ) R 2 1M Acivad cardoon 2M wih HCL, 3M Pll form 4M M Acivad cardoon wih HCL, Powdr form Acivad cardoon wih H2SO4, Pll form Acivad cardoon wih H2SO4, Powdr form 1M M M M M M M M M M M M M M M Conclusions Th following conclusions can b mniond from h prsn sudy: a) FTIR analysis of h acivad cardoons has shown h prsnc of funcional groups such as C=O, -C-O, -C-H and OH. Afr MB adsorpion, nw funcional groups such as C-N wr prsnd du o h craion of amids, b) MB adsorpion abiliy on acivad cardoon dpnds on h shap of cardoon and h yp of acid usd for acivaion and incrass according o h ordr: HCL, Powdr > H 2SO 4, Pll > HCL, Pll > H 2SO 4, Powdr, c) MB adsorpion prcnag from aquous soluions ono h cardoon dpnds on h acid concnraion, which acivad cardoon and incrass according o h ordr: 2M>5M>3M>4M>1M for boh acids, d) h cardoon in powdr form wih HCL a a concnraion of 2M prsnd h highs MB adsorpion abiliy from h firs 60 min, )diffrn kinic modls wr applid o MB adsorpion daa indicaing ha h adsorpion procss follows psudo-scond ordr kinic modl and is ovrall ra is conrolld by chmisorpion, f) quilibrium sudis of MB adsorpion on cardoon has shown ha dy soluion concnraion in quilibrium dcrasd wih h incras in h dos of adsorbn du o h incras in availabiliy of surfac aciv sis. Consqunly, Cynara cardunculus ihr in pll or powdr form, is a vry promising marial in war purificaion as filr, so i is usful o b invsigad horoughly in h fuur. REFERENCES 1. Gupa V. K., Mial A., Krishnan L., and Gajb V. (2004), Adsorpion kinics and column opraions for h rmoval and rcovry of malachi grn from waswar using boom ash, Sp. Purif. Tchnol., 40(1), Acmioğlu B. (2005), Bach kinic sudy of sorpion of mhyln blu by prli, Chm. Eng. J., 106(1), Ioannou Z., Kavvadias V. and Karasavvidis C. (2015), Rcycling of agriculural wass: Tramn and Uss, Agriculural Wass: Characrisics, Typs and Managmn, Chapr 1, Nova Publishrs, Nw York. 4. Hayashi J., Kazhaya A., Muroyanna K. and Wakinson A.P. (2000), Prparaion of acivad carbon from lignin by chmical acivaion, Carbon, 38,

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