Carbon-Based Electrochemical Detection of Pharmaceuticals from Water
The presence of pharmaceuticals in the environment and especially in water has gained increasing attention. They are included in emerging class of pollutants, and for most of them, legal limits have not been set-up due to their impact on human health and ecosystem was not determined and/or there is not the advanced analytical method for their quantification. In this context, the development of various advanced analytical methods for the quantification of pharmaceuticals in water is required. The electrochemical methods are known to exhibit the great potential for high-performance analytical methods but their performance is in direct relation to the electrode material and the operating techniques. In this study, two types of carbon-based electrodes materials, i.e., boron-doped diamond (BDD) and carbon nanofiber (CNF)-epoxy composite electrodes have been investigated through voltammetric techniques for the detection of naproxen in water. The comparative electrochemical behavior of naproxen (NPX) on both BDD and CNF electrodes was studied by cyclic voltammetry, and the well-defined peak corresponding to NPX oxidation was found for each electrode. NPX oxidation occurred on BDD electrode at the potential value of about +1.4 V/SCE (saturated calomel electrode) and at about +1.2 V/SCE for CNF electrode. The sensitivities for NPX detection were similar for both carbon-based electrode and thus, CNF electrode exhibited superiority in relation to the detection potential. Differential-pulsed voltammetry (DPV) and square-wave voltammetry (SWV) techniques were exploited to improve the electroanalytical performance for the NPX detection, and the best results related to the sensitivity of 9.959 µA·µM-1 were achieved using DPV. In addition, the simultaneous detection of NPX and fluoxetine -a very common antidepressive drug, also present in water, was studied using CNF electrode and very good results were obtained. The detection potential values that allowed a good separation of the detection signals together with the good sensitivities were appropriate for the simultaneous detection of both tested pharmaceuticals. These results reclaim CNF electrode as a valuable tool for the individual/simultaneous detection of pharmaceuticals in water.
Digital Object Identifier (DOI): doi.org/10.5281/zenodo.1127078Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 941
 National Center for Biotechnology Information. PubChem Compound Database; CID=156391, (accessed Sept. 9, 2016) https://pubchem.ncbi.nlm.nih.gov/compound/156391
 DrugBank: Showing Naproxen (DB00788)." DrugBank: Home. N.p., n.d. Web. 9 Sept. 2016 DrugBank website, http://www.drugbank.ca/drugs/DB00788
 P. Norouzi, F. Dousty, M. R. Ganjali, R. Daneshgar, “Dysprosium nanowire modified carbon paste electrode for the simultaneous detection of naproxen and paracetamol: applications in pharmaceuticals formulations and biological fluids”, Int. J. Electrochem. Sci., vol. 4, pp. 1371-1386, Nov. 2009.
 N. Adhoum, L. Monser, M. Toumi, K. Boujlel, “Determination of naproxen in pharmaceuticals by differential pulse voltammetry at a platinium electrode”, Anal. Chim. Acta, vol. 495, pp. 69-75, Oct. 2003.
 S. Zorita, L. Martensson, L. Mathiasson, „Occurrence and removal of pharmaceuticals in a municipal sewage treatment system in the south of Sweden”, Sci.Total. Environ., vol. 407, pp. 2760-2770, Apr. 2009.
 L. H. Santos, A. N. Araujo, A. Fachini, A. Pena, C. Deleure-Matos, M.C.B.S.M. Montenegro, “Ecotoxicological aspects related to the presence of pharmaceuticals in the aquatic environment”, J. Hazard. Materials, vol.175, pp. 45-95, Mar. 2010.
 C. D. Metcalfe, X. S. Miao, B. G. Koening, J. Struger, „Distribution of acidic and neutral drugs in surface waters near sewage treatment plants in the lower Great Lakes, Canada”, Environ. Toxicol. Chem., vol. 22, no. 12, pp. 2881-2889, Dec. 2003.
 K. Fent, A. A. Weston, D. Caminada, “Ecotoxicology of human pharmaceuticals”, Aquat. Toxicol., vol. 76, pp. 122-129, Feb. 2006.
 B. Petrie, R. Barden, B. Kasprzyk-Hordern, „A review on emerging contaminants in wastewaters and the environment: Current knowledge, understudied areas and recommendations for future monitoring”, Water Res., vol. 72, pp. 3-27, Apr. 2015.
 D. D. Snow, S.L., Bartelt-Hunt, D. L. Brawn, J. Sangster, D. A. Cassada, „Detection, occurrence and fate of pharmaceuticals and steroid hormones in agricultural environments”, Water Environ. Res., vol. 82, no. 10, pp. 869-882, Jan. 2010.
 G.R. Boyd, H. Reemtsma, D.A. Grimm, S. Mitra, “Pharmaceuticals and personal care products (PPCPs) in the surface and treated waters of Louisiana, USA and Ontario, Canada”, Sci. Total Environ., vol. 311, pp.135-149, Jul. 2003.
 K.P. Singh, P. Rai, A.K. Singh, P. Verma, S. Gupta, “Occurrence of pharmaceuticals in urban wastewater of north Indian cities and risk assessment”, Environ. Monit. Assess. vol. 186, pp. 6663-6682, Oct. 2014.
 R.H. Lindberd, M. Ostman, U. Olofsson, R. Grabic, J. Fick, “Occurrence and behaviour of 105 pharmaceutical ingredients in sewage waters of municipal sewer collection data”, Water Res., vol. 58, pp. 221-229, Jul. 2014
 Y. Vystavna, F. Huneau, V. Grynenko, Y. Vergels, H. Celle-Jeanetot, “Pharmaceuticals in rivers of two regions with contrasted socio-economic conditions: occurrence, accumulation and comparison for Ukraine and France”, Wat.Air Soil Poll., vol. 223, pp. 2111-2124, Jun. 2012.
 J. S. Stefano, A. P de Lima, R. H. O. Montes, E. M. Richter, R. A. A. Muñoz, “Fast determination of naproxen in pharmaceutical formulations by batch injection analysis with pulsed amperometric detection”, J. Braz. Chem. Soc., vol. 23, no. 10, pp. 1834-1838, Oct. 2012.
 J. Tashkhourian, B. Hemmateenejad, H. Beigizadeh, M. Hoseini-Sarvari, Z. Razmi, “ZnO nanoparticles and multiwalled carbon nanotubes modified carbon paste electrode for determination of naproxen using electrochemical techniques”, J. Electroanal. Chem., vol. 714-715, pp. 103-108, Feb. 2014.
 V. Suryanarayanan, Y. Zhang, S. Yolshihara, T. Shirakashi, “Voltammetric assay of naproxen in pharmaceutical formulations using boron doped diamond electrode”, Electroanal., vol. 17, no. 11, pp. 925-932, Jun. 2005.
 M. Ardelean, F. Manea, N. Vaszilcsin, R. Pode, “Electrochemical determination of sulphide in water/seawater using nanostructured carbon-epoxy composite electrode”, Anal. Methods, vol.6, pp. 4775-4782, Jul. 2014.
 A. Baciu, F. Manea, A. remes, S. Motoc, G. Burtica, R. Pode, “Anodic determination of pentachlorophenol from water using carbon nanofiber-based composite electrode”, EEMJ, vol. 9, pp. 1555-1562, Nov. 2010.
 M. Ardelean, F. Manea, R. Pode, “Electrochemical detection of fluoxetine on a boron-doped diamond electrode”, Int. J. Pharm. Pharm. Sci, vol. 5, pp.318-322, 2013.