Abstract
In this work, voltammetric methods were applied using a boron-doped diamond electrode (BDD) to detect Picloram (PCR), a very toxic and persistent herbicide. The method was applied to investigate environmental waters in the Amazon. In this context, an environmental-friendly method was developed using a miniaturized BDD electrode, and a compact electrochemical cell manufactured by a 3D printer using a polylactic acid biodegradable polymer to reduce the generated residue, leading to more sustainable research procedures with potential to be applied in field analysis. In addition, studies were carried out to establish the rate-limiting step of the reaction and the number of electrons and protons involved, being three protons and three electrons suggested for PCR electrochemical oxidation. For analytical purposes, the optimization of the square wave voltammetry (SWV) parameters and tests of precision, accuracy and sensitivity were performed. Thus, a low detection limit of 390 nmol L−1 and values for the intra-day and inter-day repeatability tests of 8.65% and 4.64%, respectively, were obtained. Due to its biodiversity abundance, environmental waters in the Amazon should be better monitored and this method can contribute to this task quite efficiently.
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References
Asmus CIRF, Camara VM, Landrigan PJ, Claudio L (2016) A systematic review of children’s environmental health in Brazil. Ann Glob Health 82:132–148. https://doi.org/10.1016/j.aogh.2016.02.007
Bard AJ, Faulkner LR (2001) Electrochemical methods: fundamentals and applications, 2nda edn. Wiley, New York
Brett CMA, Brett AMO (1994) Electrochemistry: principles, methods, and applications. Oxford University Press, Oxford
Cassal VB, de Azevedo LF, Ferreira RP, da Silva DG, Simão RS (2014) Agrotóxicos: Uma revisão de suasconsequências para a saúdepública. RevistaEletrônica em Gestão, Educação e TecnologiaAmbiental 18:437–445. https://doi.org/10.5902/2236117012498
Castello L, McGrath DG, Hess LL, Coe MT, Lefebvre PA, Petry P, Macedo MN, Renó VF, Arantes CC (2013) The vulnerability of Amazon freshwater ecosystems. Conserv Lett 6:217–229. https://doi.org/10.1111/conl.12008
Chaplin BP, Hubler DK, Farrell J (2013) Understanding anodic wear at boron doped diamond film electrodes. Electrochim Acta 89:122–131. https://doi.org/10.1016/j.electacta.2012.10.166
CONAMA, Conselho Nacional do Meio Ambiente (2005) Resolução N°357. https://www2.mma.gov.br/port/conama/legiabre.cfm?codlegi=459. Accessed 12 June 2020
D’Antonino L, França AC, Silva AA, Ferreira LR, Silva GR (2012) Crescimento de plantas de café em solos com resíduos de picloram. Planta Daninha 30:193–200. https://doi.org/10.1590/S0100-83582012000100022
da Luz LM, Rodrigues JEC, da Ponte FC, da Silva CN (2013) Atlas geográfico escolar do Estado do Pará. Belém: GAPTA/UFPA, p 64. https://livroaberto.ufpa.br/jspui/handle/prefix/127. Accessed 2 June 2020
de Alcântara Mendes R, da Costa Lopes AS, de Souza LC, de Oliveira Lima M, da Silva Santos L (2016) DDT concentration in fish from the Tapajós River in the Amazon region, Brazil. Chemosphere 153:340–345. https://doi.org/10.1016/j.chemosphere.2016.03.054
de Figueiredo-Filho LCS, dos Santos VB, Janegitz BC, Guerreiro TB, Fatibello-Filho O, Faria RC, Marcolino-Junior LH (2010) Differential pulse voltammetric determination of paraquat using a bismuth-film electrode. Electroanalysis 22:1260–1266. https://doi.org/10.1002/elan.200900553
de Oliveira A, Pereira SFP, Silva TMe, Rocha RM, da Costa HC, Silva CSe, Nogueira DP, dos Santos DC, Santos LP (2020a) Evaluation and geostatistical study of toxicological risk by water ingestion with Al, Ba, Fe and Pb in communities close to industrial areas in the Brazilian Amazon. J Braz Chem Soc 31:1492–1508. https://doi.org/10.21577/0103-5053.20200036
de Oliveira LMA, dos Santos VB, da Silva EKN, Lopes AS, Dantas-Filho HA (2020b) An environment-friendly spot test method with digital imaging for the micro-titration of citric fruits. Talanta 206:120219. https://doi.org/10.1016/j.talanta.2019.120219
de Souza D, Machado SAS, Avaca LA (2003) Voltametria de ondaquadrada. Primeira parte: aspectosteóricos. Quí Nova 26:81–89. https://doi.org/10.1590/S0100-40422003000100015
dos Santos LBO, Masini JC (2007) Determination of picloram in natural waters employing sequential injection square wave voltammetry using the hanging mercury drop electrode. Talanta 72:1023–1029. https://doi.org/10.1016/j.talanta.2006.12.030
dos Santos LBO, Masini JC (2015) Sequential injection analysis with square wave voltammetry (SI-SWV) detection for investigation of adsorption of picloram on a clay soil. J Braz Chem Soc 26:2063–2068. https://doi.org/10.5935/0103-5053.20150187
dos Santos VB, Guerreiro TB, Faria RC, Fatibello-Filho O, Suarez WT (2012) Construction and application of a portable microcontrolled turbidimeter for the in situ determination of sulfate. Quim Nova 35:802–807. https://doi.org/10.1590/S0100-40422012000400027
dos Santos VB, Fava EL, de Miranda Curi NS, Faria RC, Guerreiro TB, Fatibello-Filho O (2015) An electrochemical analyzer for in situ flow determination of Pb(ii) and Cd(ii) in lake water with on-line data transmission and a global positioning system. Anal Methods 7:3105–3112. https://doi.org/10.1039/C5AY00012B
Hadi M, Bayat M, Mostaanzadeh H, Ehsani A, Yeganeh-Faal A (2018) Sensitive electrochemical detection of picloram utilising a multi-walled carbon nanotube/Cr-based metal-organic framework composite-modified glassy carbon electrode. Int J Environ Anal Chem 98:197–214. https://doi.org/10.1080/03067319.2018.1441838
Janíková-Bandžuchová L, Švorc L, Sochr J, Svítková J, Chýlková J (2013) Voltammetric method for sensitive determination of herbicide picloram in environmental and biological samples using boron-doped diamond film electrode. Electrochim Acta 111:242–249. https://doi.org/10.1016/j.electacta.2013.08.071
Janíková-Bandžuchová L, Švorc L, Vojs M, Marton M, Michniak P, Chýlková J (2014) Self-assembled sensor based on boron-doped diamond and its application in voltammetric analysis of picloram. Int J Environ Anal Chem 94:943–953. https://doi.org/10.1080/03067319.2013.879300
Janíková-Bandžuchová L, Šelešovská R, Chýlková J, Nesnídalová V (2016) Voltammetric analysis of herbicide picloram on the silver solid amalgam electrode. Anal Lett 49:19–36. https://doi.org/10.1080/00032719.2014.979294
Juan-García A, Font G, Juan C, Picó Y (2010) Pressurised liquid extraction and capillary electrophoresis–mass spectrometry for the analysis of pesticide residues in fruits from Valencian markets. Spain Food Chem 120:1242–1249. https://doi.org/10.1016/j.foodchem.2009.11.071
Karise R, Raimets R, Bartkevics V, Pugajeva I, Pihlik P, Keres I, Williams IH, Viinalass H, Mänd M (2017) Are pesticide residues in honey related to oilseed rape treatments? Chemosphere 188:389–396. https://doi.org/10.1016/j.chemosphere.2017.09.013
Katseli V, Thomaidis N, Economou A, Kokkinos C (2020) Miniature 3D-printed integrated electrochemical cell for trace voltammetric Hg(II) determination. Sens Actuators B Chem 308:127715. https://doi.org/10.1016/j.snb.2020.127715
Kenfack IT, Ngameni E (2011) Chapter 19 - voltammetric analysis of pesticides. In: Stoytcheva M (ed) Pesticides in the modern world - trends in pesticides analysis. University of Baja California, Mexico, pp 465–488. https://doi.org/10.5772/18623
Massaroppi MRC, Machado SAS, Avaca LA (2003) Electroanalytical determination of the herbicide picloram in natural waters by square wave voltammetry. J Braz Chem Soc 14:113–119. https://doi.org/10.1590/S0103-50532003000100018
Mellado JMR, Pintado S, Montoya MR (2008) On the adsorption and reduction of the herbicide picloram on mercury and carbon electrodes. HelvChim Acta 91:1443–1452. https://doi.org/10.1002/hlca.200890157
O'Neil GD, Ahmed S, Halloran K, Janusz JN, Rodríguez A, Rodríguez IMT (2019) Single-step fabrication of electrochemical flow cells utilizing multi-material 3D printing. ElectrochemCommun 99:56–60. https://doi.org/10.1016/j.elecom.2018.12.006
Pawar RP, Tekale SU, Shisodia SU, Totre JT, Domb AJ (2014) Biomedical applications of poly(lactic acid). Recent Pat Regen Med 4:40–51. https://doi.org/10.2174/2210296504666140402235024
Pignati MT, de Souza LC, RdeA M, MdeO L, Pignati WA, Pezzuti JCB (2018) Levels of organochlorine pesticides in Amazon turtle (Podocnemis unifilis) in the Xingu River, Brazil. J Environ Sci Health Part B 53:810–816. https://doi.org/10.1080/03601234.2018.1505077
Primel EG, Zanella R, Kurz MHS, Gonçalves FF, SdeO M, Marchezan E (2005) Poluição das águasporherbicidasutilizados no cultivo do arroz irrigado na região central do estado do Rio Grande do Sul, Brasil: prediçãoteórica e monitoramento. Quím Nova 28:605–609. https://doi.org/10.1590/S0100-40422005000400010
Silva LP, Lourenção BC, Fatibello-Filho O (2015) Determinaçãovoltamétricasimultânea de besilato de anlodipino e hidroclorotiazida em amostras de urinasintéticautilizando um eletrodo de diamante dopado com boro. Quím Nova 38:801–806. https://doi.org/10.5935/0100-4042.20150077
Siqueira GW, Aprile F (2013) Avaliação de riscoambientalporcontaminaçãometálica e material orgânico em sedimentos da bacia do Rio Aurá, regiãometropolitana de Belém-PA. Acta Amazon 43:51–62. https://doi.org/10.1590/S0044-59672013000100007
Skoog DA, Holler FJ, West DM (2014) Fundamentos de QuímicaAnalítica, 9tha edn. Cengage learning, São Paulo
Sonter LJ, Herrera D, Barrett DJ, Galford GL, Moran CJ, Soares-Filho BS (2017) Mining drives extensive deforestation in the Brazilian Amazon. Nat Commun 8:1013. https://doi.org/10.1038/s41467-017-00557-w
Švorc Ľ, Rievaj M, Bustin D (2013) Green electrochemical sensor for environmental monitoring of pesticides: determination of atrazine in river waters using a boron-doped diamond electrode. Sens Actuators B Chem 181:294–300. https://doi.org/10.1016/j.snb.2013.02.036
Swathi R, Ramachandra B, Naidu NV, Rambabu K (2015) Spectrophotometric determination of picloram. Int J Sci Eng Res 6:1541–1556
Tang L, Zeng G, Shen G, Li Y, Zhang Y, Huang D (2008) Rapid detection of picloram in agricultural field samples using a disposable immunomembrane-based electrochemical sensor. Environ Sci Technol 42:1207–1212. https://doi.org/10.1021/es7024593
The Guardian (2018) Illegal mining in Amazon rainforest has become an 'epidemic'. Publishing theguardian.com. https://www.theguardian.com/world/2018/dec/10/illegal-mining-in-brazils-rainforests-has-become-an-epidemic. Accessed 1 June 2020
Torres JPM, Lailson-Brito J, Saldanha GC, Dorneles P, e Silva CEA, Malm O, Guimarães JR, Azeredo A, Bastos WR, da Silva VMF, Martin AR, Cláudio L, Markowitz S (2009) Persistent toxic substances in the Brazilian Amazon: contamination of man and the environment. J Braz Chem Soc 20(6):1175–1179. https://doi.org/10.1590/S0103-50532009000600024
USEPA, United States Environmental Protection Agency (2009) National primary drinking water regulations. https://www.epa.gov/ground-water-and-drinking-water/national-primary-drinking-water-regulations. Accessed 8 Mar 2018
Vega CM, Orellana JDY, Oliveira MW, Hacon SS, Basta PC (2018) Human mercury exposure in Yanomami indigenous villages from the Brazilian Amazon. Int J Environ Res Public Health 15:1051. https://doi.org/10.3390/ijerph15061051
Waichman AV, Römbke J, Ribeiro MOA, Nina NCS (2002) Use and fate of pesticides in the Amazon State, Brazil. Environ Sci Pollut Res 9:423–428. https://doi.org/10.1007/BF02987596
Wells MJM, Michael JL, Neary DG (1984) Determination of picloram in soil and water by reversed-phase liquid chromatography. Arch Environ ContamToxicol 13:231–235. https://doi.org/10.1007/BF01055881
Zhao P, Wang L, Chen L, Pan C (2011) Residue dynamics of clopyralid and picloram in rape plant rapeseed and field soil. Bull Environ ContamToxicol 86:78–82. https://doi.org/10.1007/s00128-010-0184-9
Acknowledgements
This work was supported by CNPq (Grant 421147/2018-0) and the authors are grateful for the CNPq and CAPES fellowship provided, we thank the GEAAP group for their support during the development of this work.
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da Silva, J.I.L., dos Santos, V.B., Neves, C.A. et al. An ecologically correct electroanalytical method to determine the herbicide Picloram in Amazon waters using a miniaturized boron-doped diamond electrode and a 3D compact electrochemical cell. Chem. Pap. 75, 1055–1067 (2021). https://doi.org/10.1007/s11696-020-01357-1
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DOI: https://doi.org/10.1007/s11696-020-01357-1