MODIFIED CARBON PASTE ELECTRODE AS A SENSOR FOR POTENTIOMETRIC DETECTION OF NITRATES
DOI: https://doi.org/10.17721/1728-2209.2023.1(58).1
Keywords:
potentiometric sensor, quaternary ammonium salt – modified silica gel, modified carbon paste electrode, nitrate determinationAbstract
Background. Nitrate is one of the common contaminants in food. Potentiometry has a short response time and low requirement of sample preparation, high selectivity and sensitivity, ease of operation, and miniaturization. So, it is a promising method for the rapid detection of nitrates in various environmental matrices. An all-solid-state ion-selective electrodes based on modified carbon paste possess advantages such as ease of preparation and regeneration, stable response, and low Ohmic resistance. makes it a suitable anion exchanger. Therefore, a carbon paste electrode modified with such quaternary ammonium salt adsorbed onto silica gel could show a good response to nitrates.
Methods. The properties of the prepared electrode were studied by the potentiometric method according to the IUPAC recommendations. The potential of the investigated electrode, measured relative to the 3,5 M silver chloride reference electrode, was used as an analytical signal.
Results. The electrode proposed was fully characterized in terms of composition, response time, ionic strange, and usable pH range. The electrode with mass ratio carbon: modifier 1: 5 exhibits linear response to nitrate species in the range of 1,5⋅10-1 to 1⋅10-5 mol/l with Nernstian slope of 0,062 ± 0,007 V per decade of nitrate concentration and detection limit of 1 ⋅10-5 mol/l. The analytical response of the electrode to nitrate remains constant in the pH range of 2,5 to 9,8 and in the presence of 1 ⋅ 10-3 to 0,2 mol/l KCl. The response of the electrode reaches its equilibrium value within 25 s after immersing the electrode in nitrate solution with a concentration of 1⋅10-7 to 1⋅10-5 mol/l and 15 s in the solution of 1⋅10-3 to 1 ⋅10-1 mol/l. Selectivity coefficients showed chloride anions have minimal interfere with the electrode function. The electrode was used for the determination of nitrate in vegetables using the direct potentiometry method. The validation of results was proved by the reference method and satisfactory results were obtained.
Conclusions. A nitrate-selective electrode based on carbon paste with the addition of quaternary ammonium salt immobilized on the surface of silica gel is proposed. It was established that the modifier gives the electrode an anionic function. Given the high selectivity, sensitivity, and speed of response, the developed electrode is suitable for the determination of nitrates in drinking water of various mineralization and vegetable products after minimal sample preparation.
References
Chunbo, Jiang, Yinghe, He, Yang, Liu (2020). Recent advances in sensors for electrochemical analysis of nitrate in food and environmental matrices. Analyst, 145, 5400–5413. DOI: 10.1039/D0AN00823K (Critical Review)
Cuartero, M. and Crespo, G. A. (2018). All-solid-state potentiometric sensors: A new wave for in situ. Current Opinion in Electrochemistry, 10, 98–106. https://doi.org/10.1016/j.coelec.2018.04.004
DSTU 4948:2008 (2008). Fruits, vegetables and their processing products. Methods of determination of nitrate content. With correction. (Order of the Ministry of Health of Ukraine from 26.03.2008 № 101 On approval of national standards, amendments to national standards, cancellation of normative documents and amendments to the orders of Derzhspozhivstandart from 18.05.2007 № 104 and from 05.07.2007 № 144). http://online.budstandart.com/ua/catalog/doc-page?id_doc=83097
Gulbault, G. G. (1981). Recommendations for publishing Manuscripts on Ion-selective Electrodes. Pure & Appl. Chem., 53, l907–l9l2. https://publications.iupac.org/pac-2007/1981/pdf/5310x1907.pdf
Hord, N. G., Tang, Y., Bryan, N. S. (2009). Food sources of nitrates and nitrites: the physiologic context for potential health benefits. The American Journal of Clinical Nutrition, 90 (1), 1–10. DOI: 10.3945/ajcn.2008.27131
Jaksyn, P., Gonsalez, C. A. (2006). Nitrosamine and related food intake and gastric and oesophageal cancer risk: A systematic review of the epidemiological evidence. World J. Gastroenterol, 12(27), 4296-4303. https://doi.org/10.3748/wjg.v12.i27.4296
Kalcher, K., Kauffmann, J. M., Wang, J., Svancara, I., Vytras, K., Neuhold, C., Vaild, Z. (1995). Sensors Based on Carbon Paste in Electrochemical Analysis: A Review with Particular Emphasis on the Period 1990–1993. Electroanalysis, 7(1), 5–22. DOI:10.1002/elan.11400070103
Kong, Thoo Lin P., Araujo, A. N., Montenegro, M. S. B. S. M., Peres-Olmos, R. (2005). New PVC Nitrate-Selective Electrode: Application to Vegetables and Mineral Waters. J. Agric. Food Chem., 53 (2), 211–215. DOI: 10.1021/jf049227u
Nadzhafova, O. Yu., Zaporozhets, O. A., Rachinska, I. V., Fedorenko, L. L. and Yusupov, N. (2005). Silica gel modified with lumogallion for aluminum determination by spectroscopic methods. Talanta, 67 (4), 767–772. DOI:10.1016/j.talanta.2005.04.002
Nezamzadeh-Ejhieh, A., Nermatollahi, Z. (2011). Surfactant modified zeolite carbon paste electrode (SMZ-CPE) as a nitrate selective electrode. Electrochimica Acta, 56, 8334–8341. DOI: 10.1016/j.electacta.2011.07.013
Passport GRBA.4184.015 PS. Electrode ionselective ЭЛИС-121NO3 LLC "Measuring equipment". https://www.izmteh.ru/upload/Instr(electrod)/ES-1 /elis_121NO3.pdf
Schwarz, J., Enseleit, U., Trommer, K., Mertig, M. (2019). All-Solid-State Ion-Selective ElectrodesBased on Graphite Paste for Determination of Calcium(II) and Nitrate, International Journal of Chemistry, 11(2), 156–163.
Stani, Z. and Girousi, S. (2011). Carbon Paste Electrodes in Potentiometry: The State of the Art and Applications in Modern Electroanalysis (A Review). Sensing in Electroanalysis, 6, 89–128. URI: http://hdl.handle.net/10195/42535
State hygienic rules and norms (2013, 2020). Regulation of maximum levels of certain pollutants in food products (order №368 from 13.05.2013). With changes. (Order of the Ministry of Health of Ukraine from 22.05.2020 № 1238). https://zakononline.com.ua/documents/show/347397___656916
State sanitary norms and rules (2010). Hygienic requirements for drinking water intended for human consumption (ДСанПіН 2.2.4-171-10). (Order of the Ministry of Health of Ukraine from 01.07.2010 № 452/7747). https://zakon.rada.gov.ua/laws/show/z0452-10#Text
Svancara, I., Vytˇras, K., Barek, J., Zima, J. (2001). Carbon Paste Electrodes in Modern Electroanalysis. Critical Reviews in Analytical Chemistry, 31(4), 311–345. DOI: 10.1080/20014091076785 Corpus ID: 95843094
Zaporozhets, O. A., Kachan, I. A., Zinko, L. S., Bas, J. P. and Davydov, V. I. (2011). Interaction of Molybdo-Phosphoric and Molybdo-Antimono-Phosphoric Heteropoly Acids with Silica Gels Modified with Aliphatic and Heterocyclic Quaternary Ammonium Salts. Adsorption Science & Technology, 2011, 29 (3), 319–330. DOI: 10.1260/0263-6174.29.3.319
Zaporozhets, O. A., Nadzhafova, O. Yu., Verba, V. V., Dolenko, S. A., Keda, T. Ye., Sukhan, V. V. (1998). Solid phase reagents for the determination of anionic surfactants in water. Analyst, 123, 1583–1586. DOI: 10.1039/a708811f
Zaporozhets, O. A., Nadzhafova, O. Yu., Zubenko, O. I., Ischenko, V. B., Trachevskyj, V. V., Sukhan, V. V. (1995). Application of quaternary ammonium salt for concentration of heavy metals in the form of acid complexes. Ukr. khim. zhurn., 61, 64–69 [in Ukrainian].
Zaporozhets, O. A., Shulga, O. V., Nadzhafova, O. Yu., Turov, V. V., Sukhan, V. V. (2000). The nature of the binding of high-molecular weight aminoammonium and quaternary ammonium salts with the amorphous silica surface. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 168(2), 103–108. DOI: 10.1016/S0927-7757(99)00492-6
Zaporozhets, O. A., Zinko, L. S., Kachan, I. A. (2007). The solid-phase reagents for the determination of the phosphorus and organic reductants in water. Zhurn. analit. khimii, 62, 1271–1275 [in Russian].
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