Abstract
Glyphosate is a herbicide that has been widely used worldwide and is used in agricultural areas to control weeds and unwanted vegetation. Electrochemical sensors developed from different nanomaterials have high efficiency, excellent cost–benefit, and fast analysis time for detecting traces of environmental pollutants. This study aimed to produce an electrochemical sensor with disposable screen-printed electrodes based on carbon black modified with niobium nanoparticles to determine glyphosate in aqueous solutions. The morphology, structure and electrochemical performance of the sensor were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction and cyclic voltammetry. Differential pulse voltammetry in BR buffer solution at pH 5.0 allowed the generation of a method to quantify glyphosate concentration in a linear range of 5.90–172.30 µmol/L (1.00–29.13 µg/mL), with a limit of detection calculated at 3.07 µmol/L (0.52 µg/mL). The method efficiently quantified glyphosate in real water samples and showed no interference from K+, Na+, Ca2+, Mg2+ ions or thiamethoxam, imidacloprid and carbendazim pesticides.
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Data Availability
The data that support the findings of this study are available from the corresponding author, upon reasonable request.
References
Battisti L, Potrich M, Sampaio AR, de Castilhos GN, Costa-Maia FM, Abati R, Martinez CBR, Sofia SH. Is glyphosate toxic to bees? A meta-analytical review. Sci Total Environ. 2021;767:145397.
Benbrook CM. Trends in glyphosate herbicide use in the United States and globally. Environ Sci Eur. 2016;28(1):3.
Prasad BB, Jauhari D, Tiwari MP. Doubly imprinted polymer nanofilm-modified electrochemical sensor for ultra-trace simultaneous analysis of glyphosate and glufosinate. Biosens Bioelectron. 2014;59:81–8.
Muñoz R, Guevara-Lara A, Santos JLM, Miranda JM, Rodriguez JA. Determination of glyphosate in soil samples using CdTe/CdS quantum dots in capillary electrophoresis. Microchem J. 2019;146:582–7.
Amarante Junior OP, Santos TCR, Brito NM, Ribeiro ML. Glifosato: propriedades, toxicidade, usos e legislação. Quim Nova. 2002;25:589–93.
Guyton KZ, Loomis D, Grosse Y, El Ghissassi F, Benbrahim-Tallaa L, Guha N, Scoccianti C, Mattock H, Straif K. Carcinogenicity of tetrachlorvinphos, parathion, malathion, diazinon, and glyphosate. Lancet Oncol. 2015;16:490–1.
WHO. Guidelines for drinking water quality. 3rd ed. World Heal. Organ. Geneva: World Health Organization; 2004.
Ministry of Health. Ordinance nº 2,914 (Annex VII) - Provides for control and surveillance procedures for the quality of water for human consumption and its potability standard. 2011. https://bvsms.saude.gov.br/bvs/saudelegis/gm/2011/prt2914_12_12_2011.html.
United States Environmental Protection Agency - USEPA. Edition of the drinking water standards and health advisories. 2018.
European Safety Authority - EFSA. Conclusion on the peer review of the pesticide risk assessment of the active substance glyphosate. EFSA J. 2015.
Health Canada. Guidelines for canadian drinking water quality: Guideline technical document – Glyphosate. 1987.
Gandhi K, Khan S, Patrikar M, Markad A, Kumar N, Choudhari A, Sagar P. Exposure risk and environmental impacts of glyphosate: Highlights on the toxicity of herbicide co-formulants. Environ Challenges. 2021;4:100149.
Fang F, Wei R, Liu X. Novel pre-column derivatisation reagent for glyphosate by high-performance liquid chromatography and ultraviolet detection. Int J Environ Anal Chem. 2014;94:661–7.
Islas G, Rodriguez JA, Mendoza-Huizar LH, Pérez-Moreno F, Carrillo EG. Determination of glyphosate and aminomethylphosphonic acid in soils by hplc with pre-column derivatization using 1,2-naphthoquinone-4-sulfonate. J Liq Chromatogr Relat Technol. 2014;37:1298–309.
Qian K, Tang T, Shi T, Wang F, Li J, Cao Y. Residue determination of glyphosate in environmental water samples with high-performance liquid chromatography and UV detection after derivatization with 4-chloro-3,5-dinitrobenzotrifluoride. Anal Chim Acta. 2009;635:222–6.
Arkan T, Csámpai A, Molnár-Perl I. Alkylsilyl derivatization of glyphosate and aminomethylphosphonic acid followed by gas chromatography mass spectrometry. Microchem J. 2016;125:219–23.
Schütze A, Morales-Agudelo P, Vidal M, Calafat AM, Ospina M. Quantification of glyphosate and other organophosphorus compounds in human urine via ion chromatography isotope dilution tandem mass spectrometry. Chemosphere. 2021. https://doi.org/10.1016/j.chemosphere.2020.129427.
De Almeida LKS, Chigome S, Torto N, Frost CL, Pletschke BI. A novel colorimetric sensor strip for the detection of glyphosate in water. Sensors Actuators B Chem. 2015;206:357–63.
Wimmer B, Pattky M, Zada LG, Meixner M, Haderlein SB, Zimmermann H-P, Huhn C. Capillary electrophoresis-mass spectrometry for the direct analysis of glyphosate: method development and application to beer beverages and environmental studies. Anal Bioanal Chem. 2020;412:4967–83.
Zouaoui F, Bourouina-Bacha S, Bourouina M, Abroa-Nemeir I, Ben Halima H, Gallardo-Gonzalez J, Hassani NA, Alcacer A, Bausells J, Jaffrezic-Renault N, Zine N, Errachid A. Electrochemical impedance spectroscopy determination of glyphosate using a molecularly imprinted chitosan. Sensors Actuators B Chem. 2020;309: 127753.
Regiart M, Fernández-Baldo MA, Navarro P, Pereira SV, Raba J, Messina GA. Nanostructured electrode using CMK-8/CuNPs platform for herbicide detection in environmental samples. Microchem J. 2020;157:105014.
Moraes FC, Mascaro LH, Machado SAS, Brett CMA. Direct electrochemical determination of glyphosate at copper phthalocyanine/multiwalled carbon nanotube film electrodes. Electroanalysis. 2010;22:1586–91.
Gholivand M-B, Akbari A, Norouzi L. Development of a novel hollow fiber- pencil graphite modified electrochemical sensor for the ultra-trace analysis of glyphosate. Sensors Actuators B Chem. 2018;272:415–24.
Fernandes JO, Bernardino CAR, Braz BF, Mahler CF, Santelli RE, Cincotto FH. (Bio)Sensing materials: Quantum dots. Encycl Sensor Biosens. 2023;2:389–400.
Cincotto FH, Moraes FC, Machado SAS. Graphene nanosheets and quantum dots: A smart material for electrochemical applications. Eur J Chem A. 2014;20:4746–53.
Setznagl S, Cesarino I. Copper nanoparticles and reduced graphene oxide modified a glassy carbon electrode for the determination of glyphosate in water samples. Int J Environ Anal Chem. 2022;102:293–305.
Wong A, Lima DG, Ferreira PA, Khan S, Silva RAB, Faria JLB, Sotomayor MPT. Voltammetric sensing of glyphosate in different samples using carbon paste electrode modified with biochar and copper(II) hexadecafluoro-29H,31 phtalocyanine complex. J Appl Electrochem. 2021;51:761–8.
Cincotto FH, Carvalho DAS, Canevari TC, Toma HE, Fatibello-Filho O, Moraes FC. A nano-magnetic electrochemical sensor for the determination of mood disorder related substances. RSC Adv. 2018;8:14040–7.
Talarico D, Arduini F, Constantino A, Del Carlo M, Compagnone D, Moscone D, Palleschi G. CB as successful screen-printed electrode modifier for phenolic compound detection. Electrochem commun. 2015;60:78–82.
Sfragano PS, Laschi S, Palchetti I. Sustainable printed electrochemical platforms for greener analytics. Front Chem. 2020;8:644.
Hayat A, Marty J. Disposable screen printed electrochemicals sensors: Tools for environmental monitoring. Sensors. 2014;14:10432–53.
Khodabakhshi S, Fulvio PF, Andreoli E. Carbon black reborn: Structure and chemistry for renewable energy harnessing. Carbon N Y. 2020;162:604–49.
Ni Z, Wang X, Dong Y, Yang Y, Yin Y, Zhao L, Wang X. Aptasensor based on screen-printed carbon electrodes modified with CS/AuNPs for sensitive detection of okadaic acid in shellfish. J Anal Test. 2023;7:136–46.
Durai L, Badhulika S. One-Pot synthesis of rGO supported Nb2O5 nanospheres for ultra-selective sensing of bisphenol a and hydrazine in water samples. IEEE Sens J. 2021;21:4152–9.
Athar T, Hashmi A, Al-Hajry A, Ansari ZA, Ansari SG. One-pot synthesis and characterization of Nb2O5 nanopowder. J Nanosci Nanotechnol. 2012;12:7922–6.
Yang M, Zhao X, Zheng S, Liu X, Jin B, Li H, Gan Y. A new electrochemical platform for ultrasensitive detection of atrazine based on modified self-ordered Nb2O5 nanotube arrays. J Electroanal Chem. 2017;791:17–22.
Uekawa N, Kudo T, Mori F, Wu YJ, Kakegawa K. Low-temperature synthesis of niobium oxide nanoparticles from peroxo niobic acid sol. J Colloid Interface Sci. 2003;264:378–84.
Santos JS, Pontes MS, Santiago EF, Fiorucci AR, Arruda GJ. An efficient and simple method using a graphite oxide electrochemical sensor for the determination of glyphosate in environmental samples. Sci Total Environ. 2020;749: 142385.
IUPAC. Limit of detection in analysis. IUPAC Compend Chem Terminol. Research Triangle Park, NC: International Union of Pure and Applied Chemistry (IUPAC); 2014.
Bochkova O, Khrizanforov M, Gubaidullin A, Gerasimova T, Nizameev I, Kholin K, Laskin A, Budnikova Y, Sinyashin O, Mustafina A. Synthetic tuning of coii-doped silica nanoarchitecture towards electrochemical sensing ability. Nanomaterials. 2020;10:1338.
Mbokana JGY, Dedzo GK, Ngameni E. Grafting of organophilic silane in the interlayer space of acid-treated smectite: Application to the direct electrochemical detection of glyphosate. Appl Clay Sci. 2020;188: 105513.
Xu J, Zhang Y, Wu K, Zhang L, Ge S, Yu J. A molecularly imprinted polypyrrole for ultrasensitive voltammetric determination of glyphosate. Microchim Acta. 2017;184(7):1959–67.
Aguirre MC, Urreta SE, Gomez CG. A Cu2+-Cu/glassy carbon system for glyphosate determination. Sensors Actuators B Chem. 2019;284:675–83.
Vaghela C, Kulkarni M, Haram S, Aiyer R, Karve M. A novel inhibition based biosensor using urease nanoconjugate entrapped biocomposite membrane for potentiometric glyphosate detection. Int J Biol Macromol. 2018;108:32–40.
Acknowledgements
All the authors thank the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) and Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro (FAPERJ) (Cincotto Proc. E-26/202.696/2019, Proc. E-26/010.002267/2019 and E-26/210.304/2022) for the financial support.
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JOF: conceptualization, methodology, data curation, formal analysis, writing—original draft preparation. CARB: conceptualization, writing—review and editing, methodology. JSF: writing—review and editing, methodology. CFM: supervision, writing—review and editing. BFB: writing—review and editing. BSA: writing—review and editing, methodology. RES: writing—review and editing. LHCS: synthesis. RJC: synthesis. ESR: synthesis. FHC: conceptualization, supervision, writing—review and editing, methodology.
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Fernandes, J.O., Bernardino, C.A.R., dos Santos Fernandes, J. et al. Direct Electrochemical Determination of Glyphosate Herbicide Using a Screen-Printed Carbon Electrode Modified with Carbon Black and Niobium Nanoparticles. J. Anal. Test. 7, 425–434 (2023). https://doi.org/10.1007/s41664-023-00276-w
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DOI: https://doi.org/10.1007/s41664-023-00276-w