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Micellar electrokinetic chromatography as efficient alternative for the multiresidue determination of seven neonicotinoids and 6-chloronicotinic acid in environmental samples

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Abstract

A simple, sensitive, and efficient method has been developed for the determination of the seven neonicotinoid insecticides commercially available (imidacloprid, thiacloprid, clothianidin, thiamethoxam, acetamiprid, nitenpyram, and dinotefuran) and the main metabolite 6-chloronicotinic acid. Micellar electrokinetic chromatography (MEKC) mode was applied, using 48.5 cm of total length capillary (50 μm i.d.) with an extended light-path capillary (150 μm). The running electrolyte consisted of 25 mM sodium tetraborate buffer (pH 9.2) containing 120 mM of sodium dodecyl sulfate and 15% of methanol (v/v). A voltage of 27 kV and a temperature of 25 °C were applied. Samples dissolved in deionized water were hydrodynamically injected at 50 mbar for 12 s, achieving the analysis in less than 12 min. Diode array detection (DAD) was performed at 220, 254, and 270 nm, depending on the analyte. Two different methodologies as sample treatments were developed; for water samples, solid-phase extraction was checked using different cartridges (C18, Oasis® HLB, Oasis® HLB Prime, and Strata-X), being the best option Oasis® HLB for preconcentration and cleanup. In the case of soil samples, a simple solid–liquid extraction was applied using a mixture of 1:3 (v/v) acetonitrile/dichloromethane. Satisfactory linearity, trueness, and precision were achieved, with detection limits in the range of 0.1–0.4 μg L−1 for river water and 1.0–2.9 μg kg−1 for soil samples. Recoveries in the range of 80–107% for all of the assayed neonicotinoids in water samples of different origin and 73–92% for soil samples were achieved.

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References

  1. Jeschke P, Nauen R, Beck ME. Nicotinic acetylcholine receptor agonists: a milestone for modern crop protection. Angew Chemie Int Ed. 2013;52:9464–95.

    Article  CAS  Google Scholar 

  2. Ihara M, Matsuda M. Neonicotinoids: molecular mechanisms of action, insights into resistance and impact on pollinators. Curr Opin Insect Sci. 2018;30:86–92.

    Article  Google Scholar 

  3. Simon-Delso N, Amaral-Rogers V, Belzunces LP, Bonmatin JM, Chagnon M, et al. Systemic insecticides (neonicotinoids and fipronil): trends, uses, mode of action and metabolites. Environ Sci Pollut Res. 2015;22:5–34.

    Article  CAS  Google Scholar 

  4. Han W, Tian Y, Shen X. Human exposure to neonicotinoid insecticides and the evaluation of their potential toxicity: An overview. Chemosphere. 2018;192:59–65.

    Article  CAS  Google Scholar 

  5. Zhang Q, Li Z, Chang C, Lou J, Zhao M, Lu C. Potential human exposures to neonicotinoid insecticides: A review. Environm Pollution. 2018;236:71–81.

    Article  CAS  Google Scholar 

  6. Kasiotis KM, Anagnostopoulos C, Anastasiadou P, Machera K. Pesticide residues in honeybees, honey and bee pollen by LC–MS/MS screening: Reported death incidents in honeybees. Sci Total Environ. 2014;485–486:633–42.

    Article  Google Scholar 

  7. Regulation (EC) No 396/2005 of the European Parliament and the Council of 23. on maximum residue levels of pesticides in or on food and feed of plant and animal origin and amending Council Directive 91/414/EEC. Off. J. EU. February 2005;L70:1–16.

    Google Scholar 

  8. Commission Directive 2007/11/EC of 21 February 2007. Amending certain Annexes to Council Directives 86/362/EEC, 86/363/EEC and 90/642/EEC as regards maximum residue levels of acetamiprid, thiacloprid, amazosulfuron, methoxyfenozide, S-metholachlor, milbemectin and tribenuron. Off. J. EU, L63, 26–37.

  9. Commission Regulation (EU) No 491/2014 of 5 May 2014 amending Annexes II and III to Regulation (EC) No 396/2005 of the European Parliament and of the Council as regards maximum residue levels for ametoctradin, azoxystrobin, cycloxydim, cyfluthrin, dinotefuran, fenbuconazole, fenvalerate, fludioxonil, fluopyram, flutriafol, fluxapyroxad, glufosinateammonium, imidacloprid, indoxacarb, MCPA, methoxyfenozide, penthiopyrad, spinetoram and trifloxystrobin in or on certain products. Off. J. EU, L146, 1-91.

  10. Commission Regulation (EU) 2017/671 Of 7 April 2017 amending Annex II to Regulation (EC) No 396/2005 of the European Parliament and of the Council as regards maximum residue levels for clothianidin and thiamethoxam in or on certain Products. Off. J. EU, L97, 9-23.

  11. Commission Implementing Regulation (EU) No 485/2013 of 24 May 2013 amending Implementing Regulation (EU) No 540/2011, as regards the conditions of approval of the active substances clothianidin, thiamethoxam and imidacloprid, and prohibiting the use and sale of seeds treated with plant protection products containing those active substances. Off. J. EU, L139, 12-26.

  12. https://ec.europa.eu/food/plant/pesticides/approval_active_substances/approval_renewal/ neonicotinoids_en.

  13. Van Der Sluijs JP, Amaral-Rogers V, Belzunces LP. Bijleveld Van Lexmond MF, Bonmatin JM, et al. Conclusions of the worldwide integrated assessment on the risks of neonicotinoids and fipronil to biodiversity and ecosystem functioning. Environ Sci Pollut Res. 2015;22:148–54.

    Google Scholar 

  14. Sánchez-Bayo. The trouble with neonicotinoids. Science. 2014;346(6211):806–7.

    Article  Google Scholar 

  15. Campillo N, Viñas P, Férez-Melgarejo G, Hernández-Córdoba M. Liquid chromatography with diode array detection and tandem mass spectrometry for the determination of neonicotinoid insecticides in honey samples using dispersive liquid-liquid microextraction. J Agric Food Chem. 2013;61:4799–805.

    Article  CAS  Google Scholar 

  16. Jovanov P, Guzsvány V, Lazić S, Franko M, Sakač M, Šarić L, et al. Development of HPLC-DAD method for determination of neonicotinoids in honey. J Food Compos Anal. 2015;40:106–13.

    Article  CAS  Google Scholar 

  17. Moyakao K, Santaladchaiyakit Y, Srijaranai S, Vichapong J. Preconcentration of trace neonicotinoid insecticide residues using vortex-assisted dispersive micro solid-phase extraction with montmorillonite as an efficient sorbent. Molecules. 2018;23:883.

    Article  Google Scholar 

  18. Kachangoon R, Vichapong J, Burakham R, Santaladchaiyakit Y, Srijaranai S. Ultrasonically modified amended-cloud point extraction for simultaneous pre-concentration of neonicotinoid insecticide residues. Molecules. 2018;23:1165.

    Article  Google Scholar 

  19. Abdel-Ghany MF, Hussein LA, El Azab NF. Multiresidue analysis of five neonicotinoid insecticides and their primary metabolite in cucumbers and soil using high-performance liquid chromatography with diode-array detection. J AOAC Int. 2017;100:176–88.

    Article  CAS  Google Scholar 

  20. Abdel-Ghany MF, Hussein LA, El Azab NF, El-Khatib AH, Linscheid MW. Simultaneous determination of eight neonicotinoid insecticide residues and two primary metabolites in cucumbers and soil by liquid chromatography–tandem mass spectrometry coupled with QuEChERS. J Chromatogr B. 2016;1031:15–28.

    Article  CAS  Google Scholar 

  21. Kamel A. Refined methodology for the determination of neonicotinoid pesticides and their metabolites in honey bees and bee products by liquid chromatography-tandem mass spectrometry (LC-MS/MS). J Agric Food Chem. 2010;58:5926–31.

    Article  CAS  Google Scholar 

  22. Xie W, Han C, Qian Y, Ding H, Chen X, Xi J. Determination of neonicotinoid pesticides residues in agricultural samples by solid-phase extraction combined with liquid chromatography–tandem mass spectrometry. J Chromatogr A. 2011;1218:4426–33.

    Article  CAS  Google Scholar 

  23. Martel AC, Lair C. Validation of a highly sensitive method for the determination of neonicotinoid insecticides residues in honeybees by liquid chromatography with electrospray tandem mass spectrometry. Int J Environ Anal Chem. 2011;91:978–88.

    Article  CAS  Google Scholar 

  24. Jovanov P, Guzsvány V, Franko M, Lazić S, Sakač M, Šarić B, et al. Multi-residue method for determination of selected neonicotinoid insecticides in honey using optimized dispersive liquid–liquid microextraction combined with liquid chromatography-tandem mass spectrometry. Talanta. 2013;111:125–33.

    Article  CAS  Google Scholar 

  25. Wang P, Yang X, Wang J, Cui J, Dong AJ, Zhao HT, et al. Multi-residue method for determination of seven neonicotinoid insecticides in grains using dispersive solid-phase extraction and dispersive liquid–liquid micro-extraction by high performance liquid chromatography. Food Chem. 2012;134:1691–8.

    Article  CAS  Google Scholar 

  26. Hao C, Morse D, Zhao X, Sui L. Liquid chromatography/tandem mass spectrometry analysis of neonicotinoids in environmental water. Rapid Commun Mass Spectrom. 2015;29:2225–32.

    Article  CAS  Google Scholar 

  27. Sánchez-Hernández L, Higes M, Martín MT, Nozal MJ, Bernal JL. Simultaneous determination of neonicotinoid insecticides in sunflower-treated seeds (hull and kernel) by LC-MS/MS. Food Addit Contam - Part A. 2016;33:442–51.

    Article  Google Scholar 

  28. Rodríguez-Cabo T, Casado J, Rodríguez I, Ramil M, Cela R. Selective extraction and determination of neonicotinoid insecticides in wine by liquid chromatography–tandem mass spectrometry. J Chromatogr A. 2016;1460:9–15.

    Article  Google Scholar 

  29. Pastor-Belda M, Garrido I, Campillo N, Viñas P, Hellín P, Flores P, et al. Determination of spirocyclic tetronic/tetramic acid derivatives and neonicotinoid insecticides in fruits and vegetables by liquid chromatography and mass spectrometry after dispersive liquid–liquid microextraction. Food Chem. 2016;202:389–95.

    Article  CAS  Google Scholar 

  30. Montiel-León JM, Duy SV, Muñoz G, Amyot M, Sauvé S. Evaluation of on-line concentration coupled to liquid chromatography tandem mass spectrometry for the quantification of neonicotinoids and fipronil in surface water and tap water. Anal Bioanal Chem. 2018;410:2765–79.

    Article  Google Scholar 

  31. Zhou Y, Lu X, Fu X, Yu B, Wang D, Zhao C, et al. Development of a fast and sensitive method for measuring multiple neonicotinoid insecticide residues in soil and the application in parks and residential areas. Anal Chim Acta. 2018;1016:19–28.

    Article  CAS  Google Scholar 

  32. Moreno-González D, Alcántara-Durán J, Gilbert-López B, Beneito-Cambra M, Cutillas VM, Rajski L, et al. Sensitive detection of neonicotinoid insecticides and other selected pesticides in pollen and nectar using nanoflow liquid chromatography orbitrap tandem mass spectrometry. J AOAC Int. 2018;101:367–73.

    Article  Google Scholar 

  33. Valverde S, Ares AM, Arribas M, Bernal JL, MJ MJN, Bernal J. Development and validation of UHPLC–MS/MS methods for determination of neonicotinoid insecticides in royal jelly-based products. J Food Compos Anal. 2018;70:105–13.

    Article  CAS  Google Scholar 

  34. Hou J, Xie W, Hong D, Zhang W, Li F, Qian Y, et al. Simultaneous determination of ten neonicotinoid insecticides and two metabolites in honey and Royal-jelly by solid−phase extraction and liquid chromatography−tandem mass spectrometry. Food Chem. 2019;270:204–13.

    Article  CAS  Google Scholar 

  35. Segura Carretero A, Cruces-Blanco C, Pérez Durán S, Fernández GA. Determination of imidacloprid and its metabolite 6-chloronicotinic acid in greenhouse air by application of micellar electrokinetic capillary chromatography with solid-phase extraction. J Chromatogr A. 2003;1003:189–95.

    Article  CAS  Google Scholar 

  36. Amelin VG, Bol’shakov DS, Tret’yakov AV. Dispersive liquid-liquid microextraction and solid-phase extraction of polar pesticides from natural water and their determination by micellar electrokinetic chromatography. J Anal Chem. 2013;68:386–97.

    Article  CAS  Google Scholar 

  37. Bol’shakov DS, Amelin VG, Tret’yakov AV. Determination of polar pesticides in soil by micellar electrokinetic chromatography using QuEChERS sample preparation. J Anal Chem. 2014;69:89–97.

    Article  Google Scholar 

  38. Zhang S, Yang X, Yin X, Wang C, Wang Z. Dispersive liquid–liquid microextraction combined with sweeping micellar electrokinetic chromatography for the determination of some neonicotinoid insecticides in cucumber samples. Food Chem. 2012;133:544–50.

    Article  CAS  Google Scholar 

  39. Ettiene G, Bauza R, Plata MR, Contento AM, Ríos A. Determination of neonicotinoid insecticides in environmental samples by micellar electrokinetic chromatography using solid-phase treatments. Electrophoresis. 2012;33:2969–77.

    Article  CAS  Google Scholar 

  40. Sánchez-Hernández L, Hernández-Domínguez D, Bernal J, Neusüß C, Martín MT, Bernal JL. Capillary electrophoresis-mass spectrometry as a new approach to analyze neonicotinoid insecticides. J Chromatogr A. 2014;1359:317–24.

    Article  Google Scholar 

  41. Chen GH, Sun J, Dai YJ, Dong M. Determination of nicotinyl pesticide residues in vegetables by micellar electrokinetic capillary chromatography with quantum dot indirect laser-induced fluorescence. Electrophoresis. 2012;33:2192–6.

    Article  CAS  Google Scholar 

  42. Vichapong J, Burakham R, Srijaranai S. Vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction with solidification of floating organic droplet combined with HPLC for the determination of neonicotinoid pesticides. Talanta. 2013;117:221–8.

    Article  CAS  Google Scholar 

  43. Farajzadeh MA, Bamorowat M, Mogaddam M.R.A. Ringer tablet-based ionic liquid phase microextraction: Application in extraction and preconcentration of neonicotinoid insecticides from fruit juice and vegetable samples. Talanta 2016;160:211–216.

  44. Seccia S, Fidente P, Attard D, Morrica P. Multiresidue determination of nicotinoid insecticide residues in drinking water by liquid chromatography with electrospray ionization mass spectrometry. Anal Chim Acta. 2005;553:21–6.

    Article  CAS  Google Scholar 

  45. Sunganthi A, Bhuvaneswari K, Ramya M. Determination of neonicotinoid insecticide residues in sugarcane juice using LCMSMS. Food Chem. 2018;241:275–80.

    Article  Google Scholar 

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Acknowledgments

LCR thanks the Youth Employment Operational Program co-funded by the Ministry of Science, Innovation and Universities of the Junta de Andalucía and the European Social Fund (ESF).

Funding

The authors received financial support from the Spanish Ministry of Economy and Competitiveness (project ref: AGL2015-70708-R). FJL received personal funding from the Special Research Program of the University of Granada.

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Authors and Affiliations

  1. Department of Analytical Chemistry, Faculty of Sciences, University of Granada, Campus Fuentenueva s/n, 18071, Granada, Spain

    Laura Carbonell-Rozas, Francisco J. Lara, Monsalud del Olmo Iruela & Ana M. García-Campaña

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  1. Laura Carbonell-Rozas
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  2. Francisco J. Lara
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  3. Monsalud del Olmo Iruela
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  4. Ana M. García-Campaña
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Correspondence to Ana M. García-Campaña.

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Analytes: NTP, nitenpyram; DNT, dinotefuran; CLT, clothianidin; THT, thiamethoxam; ACT, acetamiprid; IMD, imidacloprid; TCP, thiacloprid; 6-CNA, 6-chloronicotinic acid

CPE, cloud point extraction; DLLME, dispersive liquid–liquid microextraction; DSPE, dispersive solid-phase extraction; MSPD, matrix solid-phase dispersion; QuEChERS, quick, easy, cheap, effective, rugged, and safe; RTIL-LPME, ringer tablet-based ionic liquid-phase microextraction; SLE, solid–liquid extraction; VA-d-μ-SPE, vortex-assisted dispersive microsolid-phase extraction; VSLLME-SFO, vortex-assisted surfactant-enhanced emulsification liquid–liquid microextraction with solidification of floating organic droplet

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Carbonell-Rozas, L., Lara, F.J., del Olmo Iruela, M. et al. Micellar electrokinetic chromatography as efficient alternative for the multiresidue determination of seven neonicotinoids and 6-chloronicotinic acid in environmental samples. Anal Bioanal Chem 412, 6231–6240 (2020). https://doi.org/10.1007/s00216-019-02233-y

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