Pesticide residues in bee pollen - validation of the gas chromatography-mass spectrometry multiresidual method and a survey of bee pollens from Slovenia

Helena BAŠA ČESNIK

Abstract


A new analytical method for determining environmental pesticide residues in pollen was introduced and validated. The extraction was conducted using acetonitrile, the clean-up using Supelclean Ultra 2400 solid phase extraction cartridges, which contain Grapsphere, anion exchanger, C18 and zirconia-based sorbent, and the determination was conducted using gas chromatography coupled with mass spectrometry. The method was applied in practice. A total of 49 active substances (pesticides) were sought in 30 bee pollen samples gathered from Slovenian beekeepers from all 12 statistical regions of Slovenia. The fungicide azoxystrobin was the only active substance found and was found only in one sample with a concentration of < 0.05 mg kg-1. The active substances sought were not detected in 96.7 % of the samples analysed. The risk assessment revealed that the analysed pollen samples do not represent an unacceptable risk for consumers. The results were compared with those from the literature and the outcome was that bee pollen from Slovenia contained a lower number of active substances at mainly lower contents as compared pollen from some other European countries.

Keywords


bee pollen; GC-MS; pesticide residues; multiresidual method

Full Text:

PDF

References


Alder L., Hill A., Holland P.T., Lantos J., Lee S.M., MacNeil J.D., O'Rangers J., van Zoonen P., Ambrus A. (2000). Guidelines for single-laboratory validation of analytical methods for trace-level concentrations of organic chemicals, Principles and practices of method validation (ed.: A. Fajgelj, A. Ambrus). The Royal Society of Chemistry, pp. 179 – 252.

Anastassiades M., Lehotay S. J., Štajnbaher D., Schenck F. J. (2003). Fast and easy multiresidue method employing acetonitrile extraction/partitioning and »dispersive solid-phase extraction« for the determination of pesticide residues in produce. Journal of AOAC

International, 86, 412-431. https://doi.org/10.1093/jaoac/86.2.412

Cabrera de Oliveira R. C., Queiroz S. C. do N., da Luz C. F. P., Porto R. S., Rath S. (2016). Bee pollen as a bioindicator of environmental pesticide contamination. Chemosphere, 163,525-534. https://doi.org/10.1016/j.chemosphere.2016.08.022

Calatayud-Vernich P., Calatayud F., Simó E., Picó Y. (2018). Pesticide residues in honey bees, pollen and beeswax: Assessing beehive exposure. Environmental Pollution, 241, 106-114. https://doi.org/10.1016/j.envpol.2018.05.062

Crenna E., Jolliet O., Collina E., Sala S., Fantke P. (2020). Characterizing honey bee exposure and effects from pesticides for chemical prioritization and life cycle assessment. Environment International, 138, 105642. https://doi.org/10.1016/j.envint.2020.105642

David A., Botías C., Abdul-sada A., Nicholls E., Rotheray E. L., Hill E. M., Goulson D. (2016). Widespread contamination of wildflower and bee-collected pollen with complex mixtures of neonicotinoids and fungicides commonly applied to crops. Environment International, 88, 169-178. https://doi.org/10.1016/j.envint.2015.12.011

Eckert J.E. (1933). The flight range of the honeybee. Journal of Agricultural Research, 47, 257-285.

García-Valcárcel A. I., Martínez-Ferrer M. T., Campos-Rivela J. M., Guil M. D. H. (2019). Analysis of pesticide residues in honeybee Ž(Apis mellifera L.) and in corbicular pollen. Exposure in citrus orchard with an integrated pest management system. Talanta, 204, 153-162. https://doi.org/10.1016/j.talanta.2019.05.106

Hakme E., Lozano A., Gómez-Ramos M. M., Hernando M. D., Fernández-Alba A. R. (2017). Non-target evaluation of contaminants in honey bees and pollen samples by gas chromatography time-of-flight mass spectrometry. Chemosphere, 184, 1310-1319. https://doi.org/10.1016/j.chemosphere.2017.06.089.

ISO 5725. (1994). Accuracy (trueness and precision) of measurement methods and results - Part2: Basic method for the determination of repeatability and reproducibility of a standard measurement method, pp. 1-42.

Kasiotis K. M., Anagnostopoulos C., Anastasiadou P., Machera K. (2014). Pesticide residues in honeybees, honey and bee pollen by LC-MS/MS screening: Reported death incidents in honeybees. Sciience of the Total Environment, 485-486, 633-642. https://doi.org/10.1016/j.scitotenv.2014.03.042

Lehotay S. J. (2007). Determination of pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate: collaborative study. Journal of AOAC International, 90, 485-520. https://doi.org/10.1093/jaoac/90.2.485

Li Q.-Q., Wang K., Marcucci M. C., Sawaya A. C. H. F., Hu L., Xue X.-F., Wu L.-M. (2018). Nutrient-rich bee pollen: A treasure trove of active natural metabolites. Journal of Functional Foods, 49, 472-484. https://doi.org/10.1016/j.jff.2018.09.008

Li Y., Kelley R. A., Anderson T. D., Lydy M. J. (2015). Development and comparison of two multi-residue methods for the analysis of select pesticides in honey bees, pollen, and wax by gas chromatography-quadropole mass spectrometry. Talanta, 140, 81-87. https://doi.org/10.1016/j.talanta.2015.03.031

Lozano A., Rajski Ł., Uclés S., Belmonte-Valles N., Mezcua M., Fernández-Alba A. R. (2014). Evaluation of zirconium dioxide-based sorbents to decrease the matrix effect in avocado and almond multiresidue pesticide analysis followed by gas chromatography tandem mass spectrometry. Talanta, 118, 68-83. https://doi.org/10.1016/j.talanta.2013.09.053

Mullin C. A., Frazier M., Frazier J. L., Ashcraft S., Simonds R., vanEngelsdorp D., Pettis J. S. (2010). High levels of miticides and agrochemicals in North American Apiaries: implications for honey bee health. PLOS one, 5, e9754. https://doi.org/10.1371/journal.pone.0009754

Nakajima Y., Tsuruma K., Shimazawa M., Mishima S., Hara H. (2009). Comparison of bee products based on assays of antioxidant capacities. BioMed Central, 9, 4. https://doi.org/10.1186/1472-6882-9-4

Raimets R., Bontšutšnaja A., Bartkevics V., Pugajeva I., Kaart T., Puusepp L., Pihlik P., Keres I., Viinalass H., Mänd M., Karise R. (2020). Pesticide residues in beehive matrices are dependent on collection time and matrix type but independent of proportion of foraged oilseed rape and agricultural land in foraging territory. Chemosphere, 238, 124555. https://doi.org/10.1016/j.chemosphere.2019.124555

Salles J., Cardinault N., Patrae V., Berry A., Giraudet C., Collin M.-L., Chanet A., Tagliaferri C., Denis P., Pouyet C., Boirie Y., Walrand S. (2014). Bee pollen improves muscle protein and energy metabolism in malnourished old rats through interfering with the Mtor signaling pathway and mitochondrial activity. Nutrients, 6, 5500-5516. https://doi.org/10.3390/nu6125500

SANTE/11813/2017. Guidance document on analytical quality control and method validation procedures for pesticide residues analysis in food and feed. DG SANTE, European Comission, 2017.

Stenerson K. K, (2018). Analysis of pesticides in turmeric powder by LC-MS/MS and GC-MS/MS after cleanup with a novel dual-layer SPE cartridge. Supelco Analytical Products, Analytix reporter, 1, 2018.

Thakur M., Nanda V. (2020). Composition and functionality of bee pollen: A review. Trends in Food Science & Technology, 98, 82-106. https://doi.org/10.1016/j.tifs.2020.02.001

Tosi S., Costa C., Vesco U., Quaglia G., Guido G. (2018). A 3-year survey of Italian honey bee-collected pollen reveals widespread contamination by agricultural pesticides. Science of the Total Environment, 615, 208-218. https://doi.org/10.1016/j.scitotenv.2017.09.226

Vázquez P. P., Lozano A., Uclés S., Ramos M. M. G., Fernández-Alba A. R. (2015). A sensitive and efficient method for routine pesticide multiresidue analysis in bee pollen samples using gas and liquid chromatography coupled to tandem mass spectrometry. Journal of Chromatography A, 1426, 161-173. https://doi.org/10.1016/j.chroma.2015.11.081

Wang P.-C., Lee R.-J., Chen C.-Y., Chou C.-C., Lee M.-R. (2012). Determination of cyromazine and melamine in chiken eggs using quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction coupled with liquid chromatography-tandem mass spectrometry. Analytica Chimica Acta, 752, 78-86. https://doi.org/10.1016/j.aca.2012.09.029

Wiest L., Buleté A., Giroud B., Fratta C., Amic S., Lambert O., Pouliquen H., Arnaudguilhem C. (2011). Multi-residue analysis of 80 environmental contaminants in honeys, honeybees and pollens by one extractuion procedure followed by liquid and gas chromatography coupled with mass spectrometric detection. Journal of Chromatography A, 1218, 5743-5756. https://doi.org/10.1016/j.chroma.2011.06.079




DOI: http://dx.doi.org/10.14720/aas.2021.117.2.1822

Refbacks

  • There are currently no refbacks.


Copyright (c) 2021 Helena Baša Česnik

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

 

Acta agriculturae Slovenica is an Open Access journal published under the terms of the Creative Commons CC BY License.

                           


eISSN 1854-1941