Presence, persistence and distribution of thymol in honeybees and beehive compartments by high resolution mass spectrometry

Sánchez, Lorena Manzano; Ramos, María José Gómez; Gómez-Ramos, María del Mar; Vázquez, P. Parrilla; Flores, José Manuel; Fernández‐Alba, Amadeo R.

doi:10.1016/j.envadv.2021.100085

Cited by 7 publications

(9 citation statements)

References 31 publications

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“…The effect of formic acid is faster, since formic acid acts on the phoretic mites as well as the mites in the cells, while thymol acts solely on phoretic mites. This development is in contrast to the beekeeping practices of some other countries with a growing interest in using thymol for the mite treatment of honeybee colonies [ 14 ]. Due to the regular treatment of the bee colonies, thymol can accumulate in the beeswax and subsequently diffuse from wax into honey.…”

Section: Discussionmentioning

confidence: 99%

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Quantitation of 1,4-Dichlorobenzene and Thymol in Beeswax Using Dynamic Headspace Vacuum Transfer in Trap Extraction Prior to Gas Chromatography-Mass Spectrometry

2022

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A method based on dynamic headspace vacuum transfer in trap extraction, followed by gas chromatography coupled with a mass spectrometer (DHS-VTT-GC-MS), was validated for the fast quantitation of 1,4-dichlorobenzene (p-dichlorobenzene; PDCB) and thymol residues in beeswax. The quantitation limits (LOQ) were 0.05 mg/kg (PDCB) and 0.25 mg/kg (thymol). Recoveries above 80% were obtained for PDCB concentrations between 0.05 and 10 mg/kg and for thymol concentrations between 0.25 and 200 mg/kg. Analysis of beeswax samples showed a good correlation between the results obtained by DHS-VTT-GC-MS analysis and those of a previous method based on SPE extraction followed by gas chromatography and triple- quadrupole mass spectrometry (GC-MS/MS) (R2 = 0.9770 for PDCB and 0.9666 for thymol). However, the sample preparation and chromatography were much shorter using the DHS-VTT-GC-MS method. Forty comb foundations samples produced in Switzerland in 2019 and 2021 were analysed using DHS-VTT-GC-MS. Fourteen samples contained PDCB above the LOQ of 0.05 mg/kg, ranging up to a maximum of 1.53 mg/kg. The mean concentration of the positive samples was 0.22 mg/kg. All samples contained thymol residues ranging between 3.9 and 84.4 mg/kg with mean and median concentrations of 22.7 mg/kg and 17.4 mg/kg. Residue levels of PCDB and thymol in Swiss beeswax were substantially below those measured 20 (PDCB) and 10 (thymol) years ago, respectively.

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Section: Discussionmentioning

confidence: 99%

“…However, this extraction procedure is time-consuming, since it is based on solid-phase extraction and includes several freezing steps. Other sample preparation methods described for the determination of thymol in beeswax use distillation [ 12 ] or extraction by QuEChERS [ 13 , 14 ].…”

Section: Introductionmentioning

confidence: 99%

Quantitation of 1,4-Dichlorobenzene and Thymol in Beeswax Using Dynamic Headspace Vacuum Transfer in Trap Extraction Prior to Gas Chromatography-Mass Spectrometry

2022

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“…Thymol was proved to interact with other substances acting at the GABA receptor and, similarly to organic acids and synthetic acaricides, can also reduce production of vitellogenin [ 51 ]. On the other hand, studies of thymol residues in beeswax showed that only a small proportion of thymol is transferred directly to the bee brood via contaminated wax inside the beehive during larval development [ 52 ]. This observation stands in contrast to most synthetic acaricides, in which beeswax plays a main role in the developing bees’ exposure to chemical residue [ 44 ].…”

Section: Vmps Residues In Propolismentioning

confidence: 99%

Propolis Contra Pharmacological Interventions in Bees

Wojtacka

2022

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In addition to wax, propolis is a mixture of resins, terpenes, and etheric and aromatic oils. This composition supports its very strong biochemical activity that affects bee health. Bee colonies are externally exposed to the activity of other different pharmacologically active substances and toxic agents used in beekeeping procedures, veterinary interventions, and the environment. Even if free form common diseases, they may suffer from parasites or toxins. In any such case the abundance and variety of honeyflow, besides proper therapy, is crucial for the maintenance of bee health. Propolis itself cannot be considered as food but can be considered as micro-nutrients for bees. This is due to the fact that some of its compounds may penetrate different bee products, and this way be consumed by bees and their larvae, while stored in the hive. This perspective shows propolis as natural agent reducing the toxicity of pyrethroid acaricides, stimulating production of detoxification enzymes, enhancing the action of antibiotics, and increasing expression of genes that encode proteins responsible for detoxication. The aim of this review is to summarize current data on the possible impact on veterinary public health of the introduction into propolis of residues of pharmacological agents approved in the EU for use in the treatment of bee colonies and their environment.

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“…Recently, beekeeping industry has focused on the use of naturally occurring chemicals for the control of V. destructor in attempt to find more “natural” and non-toxic substances [ 12 , 13 ]. Essential oils of several plants are used to control Varroa mites in honeybee colonies; among them, Thyme ( Thymus vulgaris ) oil, which is rich in thymol and carvacrol [ 13 – 16 ]. However, residues of thymol may be accumulated in bee products (beeswax, honey, and bee pollen) after its application [ 13 , 17 ].…”

Section: Introductionmentioning

confidence: 99%

“…Essential oils of several plants are used to control Varroa mites in honeybee colonies; among them, Thyme ( Thymus vulgaris ) oil, which is rich in thymol and carvacrol [ 13 – 16 ]. However, residues of thymol may be accumulated in bee products (beeswax, honey, and bee pollen) after its application [ 13 , 17 ]. Although they do not seem to be toxic for humans, their possible effects on the quality of the products could be a reason of important concern; it has been demonstrated a change in the taste of honey due to the presence of thymol [ 16 , 18 ].…”

Section: Introductionmentioning

confidence: 99%

Ion chromatography coupled to Q-Orbitrap for the analysis of formic and oxalic acid in beehive matrices: a field study

et al. 2022

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There is an increasing concern about the use of synthetic acaricides to fight the ectoparasitic mite Varroa destructor. Natural products such as formic acid (FA) and oxalic acid (OA) have emerged as a possible alternative control strategy. However, given the difficulty of analysing these highly polar compounds and the lack of robust and reliable methods, there are very few studies of the concentration and distribution of these natural acaricides in the beehive compartments. We present a reliable and simple analytical methodology, based on sample extraction with modified quick polar pesticide (QuPPe) methods followed by ion chromatography coupled to a quadrupole Orbitrap mass analyser for the analysis of FA and OA in honeybees, honey, beeswax, and beebread. The developed methods have been used in a field study for the evaluation of the presence and distribution of FA and OA in the beehive products, as well as in adult bees and bee brood samples, before, during, and up to 3 months after the application of the treatments by the beekeeper. Beebread and honey samples presented the highest concentration levels of OA and FA, respectively, mainly due to their natural presence. As expected, the organic acids showed low persistence in wax after the treatments. The natural acaricides were found in adult and developing bees at concentration levels below the reported LD50 in all the cases; however, residue levels of OA in larvae during the treatment application were very close to the reported LD50. Graphical abstract

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Presence, persistence and distribution of thymol in honeybees and beehive compartments by high resolution mass spectrometry

Cited by 7 publications

References 31 publications

Quantitation of 1,4-Dichlorobenzene and Thymol in Beeswax Using Dynamic Headspace Vacuum Transfer in Trap Extraction Prior to Gas Chromatography-Mass Spectrometry

Quantitation of 1,4-Dichlorobenzene and Thymol in Beeswax Using Dynamic Headspace Vacuum Transfer in Trap Extraction Prior to Gas Chromatography-Mass Spectrometry

Propolis Contra Pharmacological Interventions in Bees

Ion chromatography coupled to Q-Orbitrap for the analysis of formic and oxalic acid in beehive matrices: a field study

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