Measurement of Nitrate Concentration in Aqueous Media Using an Electrochemical Nanosensor Based on Silver Nanoparticles-Nanocellulose/Graphene Oxide

Document Type : Research Paper


1 MSc in Analytical Chemistry, Department of Chemistry, Yadegar Imam Khomeini (RAH) Shahre Rey Branch, Islamic Azad University, Tehran, Iran

2 Assoc. Prof. in Analytical Chemistry, Department of Chemistry, Yadegar Imam Khomeini (RAH) Shahre Rey Branch, Islamic Azad University, Tehran, Iran


Nitrate pollution is at the forefront of groundwater contamination which poses serious environmental and public health hazards.  Nitrate is usually released in solution from agricultural activities and finds its way into groundwater resources. The objective of the present study was to determine, accurately concentrations of nitrate ions in water samples from the environment using sensitive electrochemical methods. For this purpose, a modified glassy carbon electrode modified with a nanocomposite consisting of silver nanoparticles, nanocellulose, and graphene oxide (Ag/NC/GO-GCE) was used. The characterization of the nanocomposite was investigated using scanning electron microscope (SEM), X-Ray diffraction (XRD), and electrochemical impedance spectroscopy (EIS). The modified Ag/NC/GO-GCE electrode was used as nanosensor for the electrocatalytic determination of nitrate using the voltammetric method. The effects of the parameters of scan rate, pH, and different nitrate concentrations were studied and the optimum conditions were obtained. A limit of detection of 0.016 µM (S/N=3) was found in the linear range of 0.005 to 10 mM nitrate. The Ag/NC/GO-GCE electrode exhibited a synergistic effect toward voltammetric determination of nitrate in the presence of graphene oxide, nanocellulose, and silver nanocatalyst. The nanosensor developed here showed excellent sensitivity, selectivity, and stability toward nitrate determination in aqueous solutions without any significant interference.


Main Subjects

Badeenejad, A., Gholami, M., Joneydi Jafari, A. & Ameri, A., 2012, "Investigation of effective parameters in nitrate concentration of Shiraz groundwater with geographical information system", Journal of Tolooe Behdasht, 2, 47-56. (In Persian)
Bonyani, M., Mirzaei, A., Leonardi, S.G. & Neri, G., 2016, "Silver nanoparticles/polymethacrylic acid (AgNPs/PMA) hybrid nanocomposites-modified electrodes for the electrochemical detection of nitrate ions", Meas, 84, 83-90.
Bourgeois, W., Burgess, J. E. & Stuetz, R. M., 2001, "On-line monitoring of wastewater quality: A review", Chemical Technology and Biotechnology, 76, 337-348.
Casella, I. & Contursi, M., 2014, "Highly dispersed rhodium particles on multi-walled carbonnanotubes for the electrochemical reduction of nitrate and nitrite ions in acid medium", Electrochimical Acta, 138, 447-453.
Chen, M., Li, X. & Ma, X., 2012, "Selective determination of catechol in wastewater at silver doped polyglycine modified film electrode", International Journal of Electrochemical Science, 7, 2616-2622.
De, D., Englehardt, J.D. & Kalu, E.E., 2000, "Cyclic voltammetric studies of nitrate and nitrite ion reduction at the surface of iridium‐modified carbon fiber electrode", Journal of Electrochemical Society, 147, 4224-4228.
Duca, G., Gonta, M., Matveevici, V. & Iambartev, V., 2002, "The mechanism of nitrate transformation on the processes of electrochemical treatment of natural waters", Environmental Engineering and Management Journal, 1, 341-346.
Ghanbari, K., 2013, "Silver nanoparticles dispersed in polypyrrole matrixes coated on glassy carbon electrode as a nitrate sensor", Analytical and Bioanalytical Electrochemistry, 5, 46-58.
Golabi, M., 2005, Introduction to electrochemistry analysis, principles and applications, Entesharate Sutude, Tabriz, Iran. (In Persian)
Korostynska, O. & Mason, A., 2012, "Monitoring of nitrate and phosphates in wastewater: Current technologies and further challenges", Smart Sensing and Intelligent Systems, 5, 149-176.
Keyvani, M., Aghaeai, M., Zare, K., Aghaeai, H. & Ansari, R., 2009, "Synthesis of electroactive nanopolymers and nanocomposites based on polyaniline and investigation of their mechanical, electrical conductivity and thermal stability properties", J. Basic Sci. Islamic Azad Univ., 72, 1-16. (In Persian)
Mattarozzi, L., Cattarin, S., Comisso, N., Guerriero, P., Musiani, M., Vazquez-Gomez, L. & Verlato, E., 2013, "Electrochemical reduction of nitrate and nitrite in alkaline media at CuNi alloy electrodes", Electrochimical Acta, 89, 488-498.
Mir Moghtadaeai, L. Mirza Nasiri, N. & Kadivar, M., 2013, "Measurement of folic acid in foods using a biosensor based on DNA", Journal of Nutritional Science and Food Technology, 4,189-198.
Mnsur, F. & Betondi, M., 2012, "Synthesis of silver nanoparticles by controlling its particle size", Iranian Journal of Physics Research, 1, 77-83.
Motahar, H., Kou, N., Toshikazu, K. & Katsuaki, S., 2013, "Reduction of nitrate on electrochemically pre-reduced tin-modified palladium electrodes", Journal of Electroanalytical Chemistry, 707, 59-65.
Qin, Y., Vu, A., Smyl, W. & Stein, A., 2012, "Facile preparation and electrochemical properties of V2O5-graphene composite films as free-standing cathodes for rechargeable lithium batteries", Journal of Electrochemical Society, 159, 1135-1140.
Remes, A., Manea, F., Sonea, D., Burtica, G., Picken, S.J. & Schoonman, J., 2009, "Electrochemical determination of nitrate from water sample using Ag-doped zeolite-modified", Ovidius University Anal. Chem. 20(1),61-65.
Saleem, M., Chakrabarti, H.M. & Basheer Hassn, D., 2011, "Electrochemical removal of nitrite in simulated aquaculture wastewater", African Journal of Bioethanology, 10(73), 16566-16576.
Stortini, A.M., Moretto, L.M., Mardegan, A., Ongaro, M. & Ugo, P., 2015, "Arrays of copper nanowire electrodes: Preparation, characterizationand application as nitrate sensor", Sens. Actuators B, 207,186-192.
Sun, F., Li, L., Liu, P. & Lian,Y., 2011, "Nonenzymatic electrochemical glucose sensor based on novel copper film", Electroanalysis, 23, 359-401.
Thinh, N.V., Thoa, N.T.P. & Hung, L.Q., 2007, "Cyclic voltammetry study on the reduction of nitrate and nitrite on a copper electrod", Journal of Chemistry, 45, 213-218.
Velusamy, V. & Arshak, K., 2010, "An overview of foodborne pathogen detection: In the perspective of biosensors", Biotechnology Advances, 28, 232-254.
Wang, S., Zhang, Y., Abidi, N. & Cabrales, L., 2009, "Wettability and surface free energy of graphene films", Langmuir, 25 (18), 11078-11081.
Yang, Y., Peng, Y., Zhao, F. & Zang, B., 2003, “Voltammetric determination of prochlorperazine and ethopropazine using a gold electrode modified with decanethiol SAM", Sensors, 3, 524-533.
Zapata, E.P., Ruiz, R.L., Harter, T., Ramirez, A.I. & Mahlknecht, J., 2014, "Assessment of sources and fate of nitrate in shallow groundwater of an agricultural area by using a multi-tracer approach", Science of the Total Environment, 470-471, 855-864.