The removal of chloramphenicol from water through adsorption on activated carbon

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1 E3S Wb of Confrncs 9, 0008 (07) EEMS 07 DOI: 0.05/3sconf/ Th rmoval of chloramphnicol from war hrough adsorpion on acivad carbon Joanna Lach,*, Agniszka Ocipa-Kubicka Czsochowa Univrsiy of Tchnology, Faculy of Infrasrucur and Environmn, ul. Brzźnicka 60a, 4-00 Częsochowa, Poland Czsochowa Univrsiy of Tchnology, Faculy of Managmn, Armii Krajowj 9 B, 4-00 Częsochowa, Poland Absrac. Th prsnd rsarch invsigad h rmoval of chloramphnicol from war soluions on slcd acivad carbon availabl in hr grads wih diffrn porous srucur and surfac chmical composiion. Two modls of adsorpion kinics wr xamind, i.. h psudo-firs ordr and h psudoscond ordr modls. For all xamind cass, h rsuls of ss wih highr valu of cofficin R wr dscribd by h uaion for psudo-scond ordr kinics. Th adsorpion kinics was also invsigad on h acivad carbons modifid wih ozon. Th masurmns wr akn from h soluions wih ph valus of and 7. Chloramphnicol was h mos fficinly adsorbd on h acivad carbon F-300 from h soluions wih ph=7, and on h acivad carbon ROW 08 Supra from h soluions wih ph=. Th adsorpion of his anibioic was in h majoriy of cass highr from h soluions wih ph= han ph=7. Th modificaion of h acivad carbons wih ozon nhancd hir adsorpion capaciis for chloramphnicol. Th adsorpion is influncd by h modificaion mhod of acivad carbon (i.. h duraion of ozonaion of h acivad carbon soluion and h soluion mpraur). Th rsuls wr dscribd wih h Frundlich and Langmuir adsorpion isohrm uaions. Boh modls wll dscribd h obaind rsuls (high R valus). Inroducion On of h nw yps of conaminans ha can b found in war and waswar ar pharmacuicals. Th prsnc of drugs in rad waswar was rpord as arly as in 976 (clofibric acid - USA) []. Sinc ha im, a wid rang of almos all pharmacuical yps hav bn found in unrad and rad waswar, surfac war and vn drinking war []. Th prsnc of pharmacuicals in waswar is du o hir common us in h prophylaxis and ramn of popl and animals as wll as in agriculur (including fish farming) [3] and hrfor, h pharmacuicals ar found in municipal waswar. Th highs concnraions of pharmacuicals ar obsrvd in waswar from hospials and pharmacuical manufacuring plans [4]. On of h major groups of pharmacuicals ar anibioics. Th invnion of pnicillin by Alxandr Flming in 98 markd a brakhrough in mdicin. I is considrd on of h gras invnions of h 0h cnury. Unforunaly, vry soon, a drug-rsisanc phnomnon was sard o b obsrvd (in h mid-30s of h 0h cnury for sulphonamids and in h scond half of h 40s for pnicillin and srpomycin). Currnly, drug rsisanc has bcom a global problm [5]. In Europ, i is simad ha of pains di bcaus of infcions causd by drug rsisan bacrial srains. In h USA, as many as 70% bacria involvd in hospial infcions ar rsisan o a las on anibioic [6, 7]. Th currnly obsrvd prsnc of anibioics in surfac war and, consunly, in drinking war is dangrous for h funcioning of h nvironmn and for human halh [8]. Prolongd xposur, vn o low anibioic concnraions can: rduc h human immuniy, hav carcinognic raognic or muagnic propris or, having an ffc similar o ha of hormons, disurb h propr funcioning of h human organism [9]. An unavoidabl and, probably, h ky rsul is h mrgnc of supr-bacria rsisan o all anibioics [0]. Rmoval of various conaminans hrough adsorpion on acivad carbon can b usd for a wid variy of applicaions. I allows h rmoval of boh inorganic and organic compounds from war and waswar []. Diffrn yps of anibioics can b ffcivly rmovd by his mhod [-4]. Th papr rpors h rsuls obaind from h sudy on h adsorpion ra of chloramphnicol on hr diffrn grads of acivad carbon ha ar widly usd in war ramn. Th sudy aimd o compar h slcd acivad carbons and o drmin h ffc of ph and mpraur on h adsorpion fficincy. Th papr also prsns h fficincy of chloramphnicol adsorpion on h acivad carbon modifid wih ozon. * Corrsponding auhor: jlach@is.pcz.czs.pl Th Auhors, publishd by EDP Scincs. This is an opn accss aricl disribud undr h rms of h Craiv Commons Aribuion Licns 4.0 (hp://craivcommons.org/licnss/by/4.0/).

2 E3S Wb of Confrncs 9, 0008 (07) EEMS 07 DOI: 0.05/3sconf/ Marials and mhods Th war adsorpion ss wr conducd undr saic condiions by adding g of acivad carbon o 50 cm 3 of h soluion, whil sirring i on a mchanical shakr a h roaing spd of 60 rpm. Th adsorpion kinics ss wr conducd for h iniial concnraion of 0.5 mmol/dm 3, whras h adsorpion isohrm ss for h concnraions of 0.05; 0.; 0.; 0.5 and.0 mmol/dm 3 from h soluions wih ph=; 4; 6; 8 and 0, rspcivly. Th ph valu was rgulad using h soluion of HCl or NaOH. Bcaus of high fficincis of adsorpion on h modifid carbons, h adsorpion fficincy ss wr carrid ou for h concnraion of.5 mmol/dm 3. Th influnc of mpraur on h adsorpion procss was drmind for h soluions a h mpraur of 0, 30 and 40 o C, rspcivly, using a shaking war bah. Th acivad carbons wr modifid wih ozon in a war soluion a diffrn mpraurs (0, 40 and 60 0 C). Th 50 g sampl of acivad carbon was ransfrrd ino ach Erlnmyr flask and 300 cm 3 of disilld war was addd. Thn h flask was placd in h war bah. This mixur was purgd wih ozon a h concnraion of 3 mg/dm 3 and h flow ra of 40 mg/dm 3. This modificaion procss was coninud for 60 and 0 minus, rspcivly. Th ss wr conducd for hr acivad carbon grads wih h characrisics givn in Tabl [3]. Tabl. Physical and chmical propris of acivad carbons (PN-83/C-97555) [5]. Paramr Acivad carbons ROW 08 F-300 WG- Bulk dnsiy,, g/dm Surfac ara, m /g War absorpion, cm 3 /g 0,97 0,7 0,6 Mchanical srngh, % ph of war xrac 8,6 6,8 6,8 Mhyln blu numbr, LM Iodin adsorpion, LI, mg/g Chloramphnicol (Chloromycin) usd in his sudy was manufacurd by Sigma-Aldrich (Fig. ). Fig.. Th srucural formula of chloramphnicol. Th molcular wigh is 33.4 g/mol and h chmical formula is C H Cl N O 5, pka=5.5. Th concnraion of chloramphnicol was drmind spcrophoomrically a h wavlngh of λ=78. Th adsorpion isohrms wr dscribd wih h Langmuir and Frundlich uaions (Tabl ). Langmuir Frundlich whr: Tabl. Isohrms and hir linar forms. Isohrm = mk LC + K C L Linar form n = ln Q = lnc + ln KF K F C is h amoun of mal ions adsorbd pr uni mass of adsorbn (mg/g), C - uilibrium concnraion of h solu in h bulk soluion (mg/dm 3 ), m h solid phas concnraion corrsponding o h compl monolayr covrag of adsorpion sis, K L - h consan rlad o h fr nrgy of adsorpion, K F - Frundlich isohrm consans, n - adsorpion innsiy. Various modls hav bn suggsd o dscrib h kinics of adsorpion of h solu molculs on h sorbn. Th Pb adsorpion kinics daa wr corrlad wih h adsorpion kinic modls [6]: n - h psudo-firs-ordr kinic modl k log( ) = log.303 () - h psudo-scond-ordr kinic modl = k whr: k is h ra consan for h psudo-firs-ordr kinic modl, k is h ra consan for h psudo-scond-ordr kinic modl, is h amoun of solu adsorbd uilibrium and is h amoun of solvn adsorbd a im. 3 Rsuls and discussion = KL + A h firs sing sag, h kinics of chloramphnicol adsorpion from h soluion wih h concnraion of 0.5 mmol/dm 3 on hr acivad carbon grads (WG-, F-300 and ROW 08 Supra) was xamind (Fig. ). Th uilibrium was firs rachd (afr 7 hrs) for h acivad carbon wih h grad ROW 08 Supra. For h rmaining wo acivad carbons h im o rach h uilibrium was much longr and amouning o 9.5 hrs. Th uilibrium consans of m C + () m

3 E3S Wb of Confrncs 9, 0008 (07) EEMS 07 DOI: 0.05/3sconf/ adsorpion kinics wr drmind and prsnd in Tabl 3. Th chloramphnicol adsorpion kinics followd h psudo-scond ordr modl, as indicad by highr valus of h corrlaion cofficins (Tabl 3). Th ffc of ph on h fficincy of chloramphnicol adsorpion on h acivad carbon WG- was xamind (Fig. 3). Th highs fficincis wr achivd for h procss procding from h soluion wih ph=, whil slighly poorr fficincis wr rpord for h soluion wih ph=4. Th ras of chloramphnicol adsorpion from h soluions wih ph= 6.8 and 0 wr similar, bu lowr han for ph= and 4. This is mos likly du o h fac ha chloramphnicol undrgos dissociaion a highr ph valus and nondissociad molculs (prdominaing a ph= and ph =4) ar mor fficinly adsorbd compard o dissociad ons. Th obaind isohrms wr dscribd wih h Langmuir and Frundlich modl (Tabl 4). Boh modl yps wih high valus of h corrlaion cofficin R dscribd h obaind s rsuls. Also, h ffc of h soluion mpraur (in h rang from 0 o 40 o C) on h fficincy of chloramphnicol adsorpion was drmind in his sudy (Fig. 4, Tabl 5). I was obsrvd ha h highr h adsorpion mpraur was, h highr h adsorpion fficincy was rpord. Th diffrncs wr no larg. Taking ino considraion unmodifid acivad carbons i was found ha chloramphnicol was bs adsorbd on h acivad carbon F-300 from h soluions wih ph=7, and on h acivad carbon ROW 08 Supra from h soluions wih ph=. Th fficincy of adsorpion on h carbons modifid wih ozon was xamind. In h cas of all invsigad acivad carbons wih diffrn grads, h fficincis of chloramphnicol adsorpion wr highr on modifid acivad carbons (Tabl 6). For h acivad carbons WG- and ROW 08 Supra i was nod ha h highr h mpraur and h longr h modificaion im, h mor fficin h adsorpion of chloramphnicol was. In h cas of h acivad carbon F-300, h opimal modificaion mpraur was 0 o C. Th obaind rsuls can b associad wih h incras in h spcific surfac ara of h acivad carbons du o h modificaion wih ozon [7]. Th modificaion of acivad carbon nabls also h chang of h chmical srucur of h acivad carbon surfac. I was found ha ozon ld o h incras in h numbr of acid groups (capabl of xchanging anions) as wll as basic groups (capabl of xchanging anions) [8]. Th highs adsorpion fficincy (94.7%) was obsrvd whn h procss procdd from h soluion wih ph = on h acivad carbon F-300 modifid wih ozon a 0 o C for 0 minus. Th mos significan diffrncs in h adsorpion fficincy wr obsrvd for h procss procding from h soluion wih ph=7. Th fficincy of adsorpion on h unmodifid acivad carbon WG- was 7%, whras on h acivad carbon modifid a 60 o C for 0 minus, i amound o 89.3%. concnraion, mmol/dm 3 0,40 0,35 0,30 0,0 0,5 0,0 0, Tim, h Fig.. Kinics of chloramphnicol adsorpion. Adsorpion capaciy, mmol/g 0, 0,5 0, F- 300 WG- ROW 08 ph= ph=4 ph=6 ph=8 ph= , 0,5 0, Eulibrium cocncnraion, mmol/dm 3 Fig. 3. Effc of h soluion ph on h adsorpion of chloramphnicol. Adsorpion capaciy, mmol/g 0, 0,5 0, 0 0 0, 0,5 Eulibrium concnraion, mmol/dm 3 Fig. 4. Effc of mpraur on h adsorpion of chloramphnicol: a 0 o C, b - 30 o C, c - 40 o C. a b c 3

4 E3S Wb of Confrncs 9, 0008 (07) EEMS 07 DOI: 0.05/3sconf/ Tabl 3. Psudo firs- and psudo scond-ordr ra consans for h adsorpion of chloramphnicol on h acivad carbons. Acivad carbon (xp) mg/g Firs-ordr kinic modl Scond-ordr kinic modl k R k /h g/(mmol h) ROW F WG R Tabl 4. Th valus of Frundlich and Langmuir consans for h adsorpion of chloramphnicol. Isohrm Consans ph of h soluion Frundlich K F, mmol/kg /n, R Langmuir m, mmol/g K l, dm 3 /mmol R Tabl 5. Th valus of Frundlich and Langmuir consans for h adsorpion of chloramphnicol. Isohrm Consan Procss mpraur, o C Frundlich K F, mmol/kg /n, R Langmuir m, mmol/g K l, dm 3 /mmol R Tabl 6. Th fficincy of chloramphnicol adsorpion from h soluions wih h concnraion of.5 mmol/dm 3, %. Acivad carbons ph soluion 7 Acivad carbon yp WG- WG WG- O 3-0 min 0 0 C WG- O 3-60 min 40 0 C WG- O 3-0 min 40 0 C WG- O 3-60 min 60 0 C WG- O 3-0 min 60 0 C Acivad carbon yp ROW 08 Supra ROW ROW 08 O 3-60 min 0 0 C ROW 08 O 3-0 min 0 0 C

5 E3S Wb of Confrncs 9, 0008 (07) EEMS 07 DOI: 0.05/3sconf/ Tabl 6 (con.) ROW 08 O 3-60 min 40 0 C ROW 08 O 3-0 min 40 0 C Acivad carbon yp F-300 F F-300 O 3-60 min 0 0 C F-300 O 3-0 min 0 0 C F-300 O 3-60 min 40 0 C F-300 O 3-0 min 40 0 C Conclusions Th adsorpion of chloramphnicol on h invsigad acivad carbons WG-, F-300 and ROW 0 followd h psudo-scond ordr kinics uaion. Considring h unmodifid acivad carbons i was found ha chloramphnicol was h mos fficinly adsorbd on h acivad carbon F-300 from h soluions wih ph=7, and on h acivad carbon ROW 08 Supra from h soluions wih ph=. Whn xamining h ffc of h soluion ph on h adsorpion ra i was found ha h lowr h soluion ph was, h largr h capaciy of h acivad carbon was rpord. This is h rsul of mor favorabl adsorpion of nondissociad molculs which prdominad in acid soluions. Highr adsorpion fficincy was obsrvd whn h procss procdd from h soluion a h mpraur of 40 o C, compard o 30 o C or 0 o C, bu h diffrncs wr no larg. Th modificaion of h acivad carbons wih ozon rsuld in h incras in hir adsorpion capaciis wih rspc o chloramphnicol. Th opimal modificaion mpraur and duraion dpndd on h acivad carbon yp. Acknowldgmns: This rsarch was financd from h sauory gran No. BS/PB 40/30/. 7. L. Bruon, J.S. Lazo, K.L. Parkr., Farmakologia Goodmana & Gilmana (Wyd. Czlj, Lublin, 007) 8. L. Wollnbrgr, B. Halling-Sørnsn, K. Kusk, Chmosphr 40, 73 (000) 9. O.A. Jons. J.N. Lsr, N. Voulvoulis Trnds Biochnol. 3, 63 (005) 0. J.L. Marínz, Environ. Pollu. 57, 893 (009). J. Lach, E. Okoniwska, L. Sępniak, A. Ocipa- Kubicka, Dsalin. and War Tra (04). E. Bocos, E. Alfaya, O. Iglsias, M. Pazos, M. Á. Sanromán, Sp. Purif. Tchnol. 5, 43 (05) 3. X. Zhang, W. Guo, H.H. Ngo, H. Wn, N. Li, W. Wu, J. Environ. Manag. 7, 93 (06) 4. L. Qin, Z. Zhou, J. Dai, P. Ma, H. Zhao, J. H, A. Xi, C. Li, Y. Yan, J. Taiwan Ins. Chm. E. 6, 8 (06) 5. J.Lach, E. Okoniwska, L. Sępniak, E. Ocipa, Ann. S Environ. Pro. 5/3, 4 (03) 6. L. Largi, R. Pasuir, Chm. Eng. Rs. Ds. 09, 495 (06) 7. J. Rivra-Urilla, M. Sánchz-Polo, Chmosphr 65, 3 (006) 8. M. Sa nchz-polo, U.von Gunn, J. Rivra- Urilla, War Rs. 39, 389 (005) Rfrncs. K. Sosnowska, K. Syszko-Grochowiak, J. Gołaś, Krakowska Konfrncja Młodych Uczonych, 395, (009). A. Szymonik, J. Lach, K. Malińska, Chm. Eng. S. 4/, 65 (07) 3. F. Yu, Y. Li, S. Hans, J. Ma, Chmosphr 53, 365 (06) 4. A. Koszowska, M. Ebisz, T. Krzyśko-Łupicka, Environmnal Mdicin 8/, 6 (05) 5. Z. Markiwicz, Z. A. Kwiakowski, Bakri, anybioyki, lkooporność. (Wyd. Naukow PWN, Warszawa, 0) 6. D. Żabicka, E. Liracka, K. Bojarska, Akualności NPOA 3, (0) 5