Abstract
Neonicotinoids are systemic insecticides of great importance for agriculture due to their powerful activity against pests and insects. However, concerns regarding the side effects on health and the environment of this family of insecticides continue to increase, since these can then be transferred to the environment and the food chain, with potential adverse consequences for nontargeted organisms such as bees. In fact, exposure to neonicotinoids has been identified as one of the factors involved in the sudden decline in the bee population, and for this reason, numerous studies have been published relating to their extraction and determination in bee products (honey, beeswax, bee pollen, royal jelly, nectar, and bee bread). Therefore, the main goal of this chapter is to present an overview of the analytical methodologies generally employed to determine neonicotinoid insecticides and related compounds in bee products during the last 10 years (2010–2020), as this could help to facilitate their assessment. The layout of the chapter is in accordance with the different bee products, indicating and discussing the most common sample treatments and evaluation methods used to determine neonicotinoids in each of them. A list of some of the most relevant applications is provided for each bee product. The references included will provide the reader with a comprehensive overview of and insight into the analysis of neonicotinoid insecticides in bee products.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Abbreviations
- ACN:
-
Acetonitrile
- CIAME:
-
Cold-induced aggregation microextraction
- DAD:
-
Diode array detector
- DCM:
-
Dichloromethane
- DI:
-
Dilution
- DLLME:
-
Dispersive liquid–liquid microextraction
- DPX:
-
Disposable pipette extraction
- dSPE:
-
Dispersive solid-phase extraction
- EMR-lipid:
-
Enhanced matrix removal-lipid
- ESI:
-
Electrospray ionization
- EV:
-
Evaporation
- FLD:
-
Fluorescence detector
- GCB:
-
Graphitized carbon black
- HPLC:
-
High-performance liquid chromatography
- IL:
-
Ionic liquid
- IT:
-
Ion trap
- LOD:
-
Limit of detection
- LOQ:
-
Limit of quantification
- MS:
-
Mass spectrometry
- MS/MS:
-
Tandem mass spectrometry
- NEOs:
-
Neonicotinoids
- PDA:
-
Photodiode array
- PSA:
-
Primary secondary amine
- QqQ:
-
Triple quadrupole
- QTOF:
-
Quadrupole time-of-flight
- QTRAP:
-
Triple quadrupole linear ion trap mass spectrometer
- QuEChERS:
-
Quick, Easy, Cheap, Effective, Rugged and Safe
- RI:
-
Refractive index
- SFC:
-
Supercritical fluid chromatography
- SQ:
-
Single quadrupole
- SULLE:
-
Sugaring-out-assisted liquid–liquid extraction
- UHPLC:
-
Ultra-high-performance liquid chromatography
References
Sánchez-Bayo F, Goka K (2014) Pesticide residues and bees—a risk assessment. PLoS One 9:1–14
VanEngelsdorp D, Evans C, Evans JD, Saegerman C, Mullin C, Haubruge E, Nguyen BK, Frazier M, Frazier J, Cox-Foster D, Chen Y, Underwood R, Tarpy D, Pettis J (2009) Colony collapse disorder: a descriptive study. PLoS One 4:1–17
Fairbrother A, Purdy J, Anderson T, Fell R (2014) Risks of neonicotinoid insecticides to honeybees. Environ Toxicol Chem 33:719–731
Yamamoto I, Casida JE (2001) Neonicotenoid insecticides and the nicotinic acetycholine receptor. Pest Manag Sci 57:102–103
Pettis JS, Vanengelsdorp D, Johnson J, Dively G (2012) Pesticide exposure in honey bees results in increased levels of the gut pathogen Nosema. Naturwissenschaften 99:153–158
Commission Implementing Regulation (EU) No 485/2013. https://eur-lex.europa.eu/legalcontent/EN/TXT/PDF/?uri=CELEX:32013R0485&from=E. Accessed 19 Nov 2020
Lawal A, Wong RCS, Tan GH, Abdulra’uf LB, Alsharif AMA (2018) Recent modifications and validation of QuEChERS-dSPE coupled to LC–MS and GC–MS instruments for determination of pesticide/ agrochemical residues in fruits and vegetables: review. J Chromatogr Sci 56:656–669
Garrido-Frenich AG, Romero-González R, Aguilera-Luiz MM (2014) Comprehensive analysis of toxics (pesticides, veterinary drugs and mycotoxins) in food by UHPLC-MS. TRAC-Trend Anal Chem 63:158–169
Madej K, Kalenik TK, Piekoszewski W (2018) Sample preparation and determination of pesticides in fat-containing foods. Food Chem 269:527–541
Masiá A, Suarez-Varela MM, Llopis-Gonzalez PY (2016) Determination of pesticides and veterinary drug residues in food by liquid chromatography-mass spectrometry: a review. Anal Chim Acta 936:40–61
Jiménez-López J, Llorent-Martínez EJ, Ortega-Barrales P, Ruiz-Medina A (2020) Analysis of neonicotinoid pesticides in the Agri-food sector: a critical assessment of the state of the art. Appl Spectrosc Rev 58:613–646
Tu X, Chen W (2020) Overview of analytical methods for the determination of neonicotinoid pesticides in honeybee products and honeybee. Crit Rev Anal Chem 51(4):329–338. https://doi.org/10.1080/10408347.2020.1728516
Juan-Borrás M, Domenech E, Escriche I (2016) Mixture-risk assessment of pesticide residues in retail polyfloral honey. Food Control 67:127–134
Ares AM, Valverde S, Bernal JL, Toribio L, Nozal MJ, Bernal J (2017) Determination of flubendiamide in honey at trace levels by using solid phase extraction and liquid chromatography coupled to quadrupole time-of-flight mass spectrometry. Food Chem 232:169–176
Valverde S, Ibáñez M, Bernal JL, Nozal MJ, Hernández F, Bernal J (2018) Development and validation of ultra high performance-liquid chromatography–tandem mass spectrometry-based methods for the determination of neonicotinoid insecticides in honey. Food Chem 266:215–222
Kamel A (2010) 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 58:5926–5831
Tanner G, Czerwenka C (2011) LC-MS/MS analysis of neonicotinoid insecticides in honey: methodology and residue findings in Austrian honeys. J Agric Food Chem 59:12271–12277
Paradis D, Bérail G, Bonmatin JB, Belzunces (2014) Sensitive analytical methods for 22 relevant insecticides of 3 chemical families in honey by GC-MS/MS and LC-MS/MS. Anal Bioanal Chem 406:621–633
Kasiotis KM, 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. Sci Total Environ 485-486:633–642
Jovanov P, Guzsvány V, Franko M, Lazić S, Sakač M, Šarić B, Kos J (2015) Development of HPLC-DAD method for determination of neonicotinoids in honey. J Food Compos Anal 40:106–113
Chen Z, Dong F, Li S, Zheng Z, Xu Y, Xu J, Liu X, Zheng Y (2015) Response surface methodology for the enantioseparation of dinotefuran and its chiral metabolite in bee products and environmental samples by supercritical fluid chromatography/tandem mass spectrometry. J Chromatogr A 1410:181–189
Tette PA, da Silva Oliveira FA, Pereira EN, Silva G, de Abreu Glória MB, Fernandes C (2016) Multiclass method for pesticides quantification in honey by means of modified QuEChERS and UHPLC–MS/MS. Food Chem 211:130–139
Codling G, Al Naggar Y, Giesy JP, Robertson AJ (2016) Concentrations of neonicotinoid insecticides in honey, pollen and honey bees (Apis mellifera L.) in Central Saskatchewan, Canada. Chemosphere 144:2321–23288
Laaniste A, Leito I, Rebane R, Lõhmus R, Lõhmus A, Punga F, Kruve A (2016) Determination of neonicotinoids in Estonian honey by liquid chromatography-electrospray mass spectrometry. J Environ Sci Health B 51:455–464
Al Naggar Y, Codling G, Giesy JP (2017) Human dietary intake and hazard characterization for residues of neonicotinoids and organophosphorus pesticides in Egyptian honey. Toxicol Environ Chem 99:1397–1408
Amulen DR, Spanoghe P, Houbraken M, Tamale A, de Graaf DC, Cross P et al (2017) Environmental contaminants of honeybee products in Uganda detected using LC-MS/MS and GC-ECD. PLoS One 12:e0178546
Michlig MP, Merke J, Pacini A, Orellano E, Beldoménico HR, Repetti MR (2018) Determination of imidacloprid in beehive samples by UHPLC-MS/MS. Microchem J 143:72–81
Hrynko I, Łozowicka B, Kaczyński P (2018) Liquid chromatographic MS/MS analysis of a large group of insecticides in honey by modified QuEChERS. Food Anal Methods 11:2307–2319
Bridi R, Larena A, Pizarro PN, Giordano A, Montenegro G (2018) LC-MS/MS analysis of neonicotinoid insecticides in honey: residue findings in Chilean honeys. Cienc Agrotec 42:51–57
Bommuraj V, Chen Y, Klein H, Sperling R, Barel S, Shimshoni JA (2019) Pesticide and trace element residues in honey and beeswax combs from Israel in association with human risk assessment and honey adulteration. Food Chem 299:125123
Gaweł M, Kiljanek T, Niewiadowska A, Semeniuk S, Goliszek M, Burek O, Posyniak A (2019) Determination of neonicotinoids and 199 other pesticide residues in honey by liquid and gas chromatography coupled with tandem mass spectrometry. Food Chem 282:36–47
Mrzlikar M, Heath D, Heath E, Markelj, Borovšak AK, Prosen H (2019) Investigation of neonicotinoid pesticides in Slovenian honey by LC-MS/MS. LWT-Food Sci Technol 104:45–52
Mejias E, Gómez C, Garrido T, Godoy P, Gómez M, Montenegro G (2019) Natural attributes of Chilean honeys modified by the presence of neonicotinoids residues. Agrofor Syst 93:2257–2266
Kammoun S, Mulhauser B, Aebi A, Mitchell EAD, Glauser G (2019) Ultra-trace level determination of neonicotinoids in honey as a tool for assessing environmental contamination. Environ Pollut 247:964–972
Campillo N, Viñas P, Férez-Melgarejo G, Hernández-Córdoba M (2013) 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 61(20):4799–4805
Gbylik-Sikorska M, Sniegocki T, Posyniak A (2015) Determination of neonicotinoid insecticides and their metabolites in honey bee and honey by liquid chromatography tandem mass spectrometry. J Chromatogr B 990:132–140
Sánchez-Hernández L, Hernández D, Martín MT, Nozal MJ, Higes M, Bernal JL (2016) Residues of neonicotinoids and their metabolites in honey and pollen from sunflower and maize seed dressing crops. J Chromatogr A 1428:220–227
Hou J, Xie W, Hong D, Zhang W, Li F, Qian Y, Han C (2019) Simultaneous determination of neonicotinoid insecticides and two metabolites in royal-jelly by LC-MS/MS. Food Chem 270:204–213
Jovanov P, Guzsvány V, Franko M, Lazić S, Sakač M, Šarić B, Banjac V (2013) 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 111:125–133
Vichapong J, Burakham R, Srijaranai S (2015) In-coupled syringe assisted octanol-water partition microextraction coupled with high-performance liquid. Chromatography for simultaneous determination of neonicotinoid insecticide residues in honey. Talanta 139:21–26
Carbonell-Rozas L, Lara FJ, Iruela MO, García-Campaña AM (2020) Capillary liquid chromatography as an effective method for the determination of seven neonicotinoid residues in honey samples. J Sep Sci 43:3847–3855
Yang C, Ran L, Xu M, Ren D, Yi L (2019) In situ ionic liquid dispersive liquid-liquid microextraction combined with ultra high performance liquid chromatography for determination of neonicotinoid insecticides in honey samples. J Sep Sci 42:1930–1937
Vichapong J, Burakham R, Santaladchaiyakit Y, Srijaranai S (2016) A preconcentration method for analysis of neonicotinoids in honey samples by ionic liquid-based cold-induced aggregation microextraction. Talanta 155:216–221
Chen W, Wu S, Zhang J, Yu F, Hou J, Miao X, Tu X (2019) Matrix-induced sugaring-out: a simple and rapid sample preparation method for the determination of neonicotinoid pesticides in honey. Molecules 24:2761
Song S, Zhang C, Chen Z, He F, Wei J, Tan H, Li X (2018) Simultaneous determination of neonicotinoid insecticides and insect growth regulators residues in honey using LC-MS/MS with anion exchanger-disposable pipette extraction. J Chromatogr A 1557:51–61
Yáñez KP, Bernal JL, Nozal MJ, Martín MT, Bernal J (2013) Fast determination of Imidacloprid in beeswax by liquid chromatography coupled to electrospray-mass spectrometry. Curr Anal Chem 9:495–503
Yáñez KP, Bernal JL, Nozal MJ, Martín MT, Bernal J (2013) Determination of seven neonicotinoid insecticides in beeswax by liquid chromatography coupled to electrospray-mass spectrometry using a fused-core column. J Chromatogr A 1285:110–117
Sánchez-Hernández L, Hernández-Domínguez D, Bernal J, Neusüß C, Martín MT, Bernal JL (2014) Capillary electrophoresis-mass spectrometry as a new approach to analyze neonicotinoid insecticides. J Chromatogr A 1359:317–324
Valverde S, Ares AM, Bernal JL, Nozal MJ, Bernal J (2018) Fast determination of neonicotinoid insecticides in beeswax by ultra-high performance liquid chromatography-tandem mass spectrometry using an enhanced matrix removal-lipid sorbent for clean-up. Microchem J 142:70–77
Daniele G, Giroud B, Jabot C, Vulliet E (2018) Exposure assessment of honeybees through study of hive matrices: analysis of selected pesticide residues in honeybees, beebread, and beeswax from French beehives by LC-MS/MS. Environ Sci Pollut Res Int 25:6145–6153
Jabot C, Fieu M, Giroud B, Buleté A, Casablanca H, Vulliet E (2015) Trace-level determination of pyrethroid, neonicotinoid and carboxamide pesticides in beeswax using dispersive solid-phase extraction followed by ultra-high-performance liquid chromatography-tandem mass spectrometry. Int J Environ Anal Chem 95:240–257
Mullin CA, Frazier M, Frazier JL, Ashcraft S, Simonds R, Vanengelsdorp D, Pettis JS (2010) High levels of miticides and agrochemicals in north American apiaries: implications for honey bee health. PLoS One 5:e9754
Niell S, Cesio V, Hepperle J, Doerk D, Kirsch L, Kolberg D, Scherbaum E, Anastassiades M, Heinzen H (2014) QuEChERS-based method for the multiresidue analysis of pesticides in beeswax by LC-MS/MS and GC×GC-TOF. J Agric Food Chem 62:3675–3683
Harriet J, Campá JP, Grajales M, Lhéritier C, Gómez Pajuelo A, Mendoza-Spina Y, Carrasco-Letelier L (2017) Agricultural pesticides and veterinary substances in Uruguayan beeswax. Chemosphere 177:77–83
Herrera López S, Lozano A, Sosa A, Hernando MD, Fernández-Alba AR (2016) Screening of pesticide residues in honeybee wax comb by LC-ESI-MS/MS. A pilot study. Chemosphere 163:44–53
Lehotay SJ, Maštovská K, Lightfield R (2005) Use of buffering and other means to improve results of problematic pesticides in a fast and easy method for residue analysis of fruits and vegetables. J AOAC Int 88:615–629
Ares AM, Valverde S, Bernal JL, Nozal MJ, Bernal J (2018) Extraction and determination of bioactive compounds from bee pollen. J Pharm Biomed Anal 147:110–124
Chen M, Collins EM, Tao L, Lu C (2013) Simultaneous determination of residues in pollen and high-fructose corn syrup from eight neonicotinoid insecticides by liquid chromatography-tandem mass spectrometry. Anal Bioanal Chem 405:9251–9264
David A, Botías C, Abdul-Sada A, Goulson D, Hill EM (2015) Sensitive determination of mixtures of neonicotinoid and fungicide residues in pollen and single bumblebees using a scaled down QuEChERS method for exposure assessment. Anal Bioanal Chem 407:8151–8162
Valverde S, Bernal JL, Martín MT, Nozal MJ, Bernal J (2016) Fast determination of neonicotinoid insecticides in bee pollen using QuEChERS and ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry. Electrophoresis 37:2470–2477
Moreno-González D, Alcántara-Durán J, Gilbert-López B, Beneito-Cambra M, Cutillas VM, Rajski LR, Molina-Díaz A, García-Reyes AM (2019) Sensitive detection of neonicotinoid insecticides and other selected pesticides in pollen and nectar using nanoflow liquid chromatography orbitrap tandem mass spectrometry. J AOAC Int 101:367–373
Hall MJ, Dang V, Bradbury SP, Coats JR (2020) Optimization of QuEChERS method for simultaneous determination of neonicotinoid residues in pollinator forage. Molecules 25:2732
Yáñez KP, Martín MT, Bernal JL, Nozal MJ, Bernal J (2014) Trace analysis of seven neonicotinoid insecticides in bee pollen by solid–liquid extraction and liquid chromatography coupled to electrospray ionization mass spectrometry. Food Anal Methods 7:490–499
López-Fernández O, Rial-Otero R, Simal-Gándara J (2015) High-throughput HPLC–MS/MS determination of the persistence of neonicotinoid insecticide residues of regulatory interest in dietary bee pollen. Anal Bioanal Chem 407:7101–7110
Hou J, Xie W, Zhang W, Li F, Qian Y, Sheng T, Mao R, Yao X (2019) Simultaneous determination of neonicotinoid insecticides and two metabolites in royal-jelly by LC-MS/MS. J Chinese Mass Spectrom Soc 40:139–150
Giroud B, Bruckner S, Straub L, Neuman P, William GR, Vulliet E (2019) Trace-level determination of two neonicotinoid insecticide residues in honey bee royal jelly using ultra-sound assisted salting-out liquid liquid extraction followed by ultra-high-performance liquid chromatography-tandem mass spectrometry. Microchem J 151:104249
Valverde S, Ares AM, Arribas M, Bernal JL, Nozal MJ, Bernal J (2018) Development and validation of UHPLC–MS/MS methods for determination of neonicotinoid insecticides in royal jelly-based products. J Food Compos Anal 70:105–113
Bishop CA, Woundneh MB, Maisonneuve F, Common J, Elliott JE, Moran AJ (2020) Determination of neonicotinoids and butenolide residues in avian and insect pollinators and their ambient environment in Western Canada (2017, 2018). Sci Total Environ 737:139386
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2022 The Author(s), under exclusive license to Springer Science+Business Media, LLC, part of Springer Nature
About this protocol
Cite this protocol
Valverde, S., Ares, A.M., Nozal, M.J., Bernal, J. (2022). Analytical Methodologies for Neonicotinoid Determination in Bee Products. In: Gallardo, E., Barroso, M. (eds) Pesticide Toxicology. Methods in Pharmacology and Toxicology. Humana, New York, NY. https://doi.org/10.1007/978-1-0716-1928-5_4
Download citation
DOI: https://doi.org/10.1007/978-1-0716-1928-5_4
Published:
Publisher Name: Humana, New York, NY
Print ISBN: 978-1-0716-1927-8
Online ISBN: 978-1-0716-1928-5
eBook Packages: Springer Protocols