Removal of Ciprofloxazin and Carbamazepine by Adsorption on Functionalized Mesoporous Silicates

Ciprofloxacin (CIP) and Carbamazepine (CBZ), nonbiodegradable pharmaceutical residues, were become emerging pollutants in several aquatic environments. The objectives of this research were to study the possibility to recover these pharmaceuticals residues from pharmaceutical wastewater by increasing the selective adsorption on synthesized functionalized porous silicate, comparing with powdered activated carbon (PAC). Hexagonal mesoporous silicate (HMS), functionalized HMSs (3- aminopropyltriethoxy, 3- mercaptopropyltrimethoxy and noctyldimethyl) were synthesized and characterized physico-chemical characteristics. Obtained adsorption kinetics and isotherms showed that 3-mercaptopropyltrimethoxy functional groups grafted on HMS provided highest CIP and CBZ adsorption capacities; however, it was still lower than that of PAC. The kinetic results were compatible with pseudo-second order. The hydrophobicity and hydrogen bonding might play a key role on the adsorption. Furthermore, the capacities were affected by varying pH values due to the strength of hydrogen bonding between targeted compounds and adsorbents. Electrostatic interaction might not affect the adsorption capacities.

• Patiparn Punyapalakul
• Thitikamon Sitthisorn

• Adsorption
• Carbamazepine
• Ciprofloxazin
• Mesoporous Silicates
• Surface functional groups

[1] E.M. Golet, A.C. Alder, A. Hartmann, T.A. Ternes and W.Giger, "Trace
Determination of Fluoroquinolone Antibacterial Agents in Urban
Wastewater by Solid-Phase Extraction and Liquid Chromatography with
Fluorescence Detection" in Analytical Chemistry, vol. 73, no. 15, 2001,
pp 3632-3638.
[2] P. Jarnheimer , J. Ottoson, R. Lindberg, T. Stenström, M. Johanssan, M.
Tysklind, M. Winner and B. Olsen, "Fluoroquinolone Antibiotics in a
Hospital Sewage Line; Occurrence, Distribution and Impact on Bacterial
Resistance" in Scandinavian Journal of Infectious Diseases, vol. 36 ,
2004, pp 752-755.
[3] J.E. Renew and C.H. Huang, "Simultaneous determination of
fluoroquinolone, sulfonamide, and trimethoprim antibiotics in
wastewater using tandem solid phase extraction and liquid
chromatography-electrospray mass spectrometry" in Journal of
Chromatography A., vol. 1042 (1-2), 2004, pp 113-121.
[4] D.G.J. Larsson, C.de Pedro and N. Paxeus, "Effluent from drug
manufactures contains extremely high levels of pharmaceuticals" in
Journal of Hazardous Materials, vol. 148, no. 3, 2007, pp 751-755.
[5] A.L. Cordova-Kreylos and K.M. Scow, "Effects of ciprofloxacin on salt
marsh sediment microbial communities" in ISME J., vol. 1, no. 7, 2007,
pp 585-595.
[6] Brain, R.A., Johnson, D.J., Richards, S.M., Sanderson, H., Sibley,
P.K., and Solomon, K.R. 2004. Effects of 25 pharmaceutical compounds
to Lemna gibba using a seven-day static-renewal test. Environmental
toxicology and chemistry. 23 (2): 371-382.
[7] B. Halling-S├©rensen, H.-C. Holten L├╝tzholf, H.R.Andersen and F.
Ingerslev, "Environmental risk assessment of antibiotics: comparison of
mecillinam, trimethoprim and ciprofloxacin" in J Antimicrob
Chemother, vol. 46, 2000, pp 53-58.
[8] B. Sternebring, A. Liden, K. Andersson, and A. Melander,
"Carbamazepine kinetics and adverse effects during and after ethanol
exposure in alcoholics and in healthy volunteers" in European Journal
of Clinical Pharmacology, vol. 43, no. 4, 1992, pp 393-397.
[9] S.A. Montgomery, A.F. Schatzberg, J.D. Guelfi, C. Nemeroff, A.
Swann, and J. Zaiecka, "Pharmacotherapy of depression and mixed
states in bipolar disorder" in Journal of Affective Disorders, vol. 59, no.
1, 2000, pp S39-S56.
[10] G. Bertschy, Ch. Bryois, G. Bondolfi, A. Velardi, Ph. Burdy, D. Dascal,
C. Martinet, D. Baetting, and P. Baumann, "The Association
Carbamazepine-Mianserin in opiate withdrawal: A Double Blind Pilot
Study Versus Clonidine" in Pharmacological Research, vol. 35, no. 5,
1997, pp 451-456.
[11] C. Tixier, H.P. Singer, S. Oellers and S.R. Muller, "Occurrence and Fate
of Carbamazepine, Clofibric Acid, Diclofenac, Ibuprofen, Ketoprofen,
and Naproxen in Surface Waters" in Environmental Science &
Technology, vol. 37, no. 6, 2003, pp 1061-1068.
[12] T.J. Scheytt, P. Mersmann and T. Heberer, "Mobility of pharmaceuticals
carbamazepine, diclofenac, ibuprofen, and propyphenazone in miscibledisplacement
experiments" in Journal of Contaminant Hydrology, vol.
83, no. 1-2, 2006, pp 53-69.
[13] T.A. Ternes, "Occurrence of drugs in German sewage treatment plants
and rivers" in Water Research, vol. 32, no. 11, 1998, pp 3245-3260.
[14] T. Heberer, K. Reddersen and A. Mechlinski, "From municipal sewage
to drinking water: fate and removal of pharmaceutical residues in the
aquatic environment in urban areas" in Water Science and Technology,
vol. 46, no. 3, 2002, pp 81-88.
[15] M. Oetken, G. Nentwig, D. Loffler, T. Ternes and J. Oehlmann, "Effects
of Pharmaceuticals on Aquatic Invertebrates. Part I. The Antiepileptic
Drug Carbamazepine" in Archives of Environmental Contamination and
Toxicology, vol. 49, no. 3, 2005, pp 353-361.
[16] P. Punyapalakul, and S.Takizawa, "Effect of organic grafting
modification of hexagonal mesoporous silicate on haloacetic acid
removal" in Environ. Eng. Forum, vol. 44, 2004, pp 247-256.
[17] P. Punyapalakul and S.Takizawa, "Selective adsorption of nonionic
surfactant on hexagonal mesoporous silicates (HMSs) in the presence of
ionic dyes" in Water Research, vol. 40, no.17, 2006, pp 3177-3184.
[18] C. Gu and K.G. Karthikeyan, "Sorption of the Antimicrobial
Ciprofloxacin To Aluminum and Iron Hydrous Oxides" in
Environmental Science & Technology, vol. 39, no. 23, 2005, pp 9166-
9173.
[19] S.A. Breda, A.F. Jimenez-Kairuz, R.H. Manzo and M.E. Olivera,
"Solubility behavior and biopharmaceutical classification of novel highsolubility
ciprofloxacin and norfloxacin pharmaceutical derivatives" in
International Journal of Pharmaceutics, vol. 371, 2009, pp 106-113.