Pesticides In Honey Research Articles

Rapid detection of pesticides in honey by solid-phase micro-extraction coupled with electrospray ionization mass spectrometry.

Detection of pesticide residues in food samples is important for safeguarding food quality and safety. Conventional approaches for detection of pesticides in food samples typically involve labour-intensive and time-consuming sample pretreatment and chromatographic separation. In this study, solid phase micro-extraction fibres were used to rapidly extract and enrich pesticides in honey, a popular agricultural product with complex matrix, and then directly coupled with electrospray ionization mass spectrometry for qualitative and quantitative analysis. Three pesticides, ie, atrazine, benalaxyl, and pirimicarb, were investigated using the technique and their analytical performances were evaluated. The limits of detection and limits of quantitation of all the three pesticides could fulfil the cut-off values of the international standard. Linear calibration curves were constructed with good R2 coefficients, and the accuracy and precision were in acceptable ranges for all the pesticides. The analysis time is much reduced, with only minimum sample preparation and no chromatographic separation involved. The technique is simple and easy to set up, and can be extended for analysis of other analytes and sample systems.

Pesticide and trace element residues in honey and beeswax combs from Israel in association with human risk assessment and honey adulteration

Beehive products are considered sentinels for environmental pollutants. The presence of trace elements and pesticides in honey and beeswax may pose a health hazard to consumers. The study’s aim was to determine the profile of pesticides and trace elements in Israeli honey and beeswax samples in relation to human risk assessment. At least two pesticides contaminated the honey and beeswax samples simultaneously, in which, amitraz metabolites and coumaphos were frequently detected. The neonicotinoid insecticides and 2,4-dichlorophenoxyacetic acid, were found only in honey samples, whereas the more lipophilic pesticides were predominantly found in beeswax. In honey, chromium displayed the highest mean concentration, followed by zinc, whereas lead and molybdene occurred only in beeswax. Our findings indicate that the daily consumption of honey and beeswax together may compromise children’s health. Sucrose-syrup fed honey could not be distinguished from floral honey based on sugar profile, rather by its trace elements levels.

Synthesis of a green high density deep eutectic solvent and its application in microextraction of seven widely used pesticides from honey

A green dispersive liquid–liquid microextraction using a new high density deep eutectic solvent (as an extraction solvent) has been developed and utilized in the simultaneous preconcentration and extraction of seven pesticides in honey followed by gas chromatography–flame ionization detection. The deep eutectic solvent is synthesized using menthol (as a hydrogen bond acceptor) and dichloroacetic acid (as a hydrogen bond donor) at a molar ratio of 1:2. Initially the analytes are extracted into acetone from the sample. After centrifuging, the synthesized deep eutectic solvent is added to the extract obtained from the previous step. Then this mixture is quickly injected into deionized water by a syringe for more concentration. A cloudy solution is formed by dispersion of fine droplets of the deep eutectic solvent by acetone into the aqueous solution and the pesticides are transferred into the extraction solvent. After extraction, phase separation is performed by centrifugation and the enriched analytes in the sedimented phase are determined. The influence of different parameters affecting the extraction efficiency was investigated and optimized. Under the optimized extraction conditions, enrichment factor for the analytes was obtained in the range of 279–428 with extraction recovery of 56–86%. Limits of detection and quantification were obtained in the ranges of 0.32–1.2 and 1.1–4.0 ng g−1, respectively. Relative standard deviations were ≤ 7% for intra– (n = 6) and inter–day (n = 5) precisions calculated at two concentrations of 10 and 50 ng g−1 of each analyte. Finally, some honey samples were effectively analyzed by the proposed method and diazinon was determined at ng g−1 concentration in one sample.

Pesticide distribution and depletion kinetic determination in honey and beeswax: Model for pesticide occurrence and distribution in beehive products.

Beehive products such as honey, beeswax and recently pollen have been regarded for many years as appropriate sentinels for environmental pesticide pollutions. However, despite yearly application of hundreds of approved pesticides in agricultural fields, only a minor fraction of these organic compounds were actually detected in honey and beeswax samples. This observation has led us to question the general suitability of beehive products as a sentinel for synthetic organic pesticides applied in the field. The aim of the present study was to experimentally determine the distribution (logarithmic ratio of beeswax to honey pesticide concentration, LogD) and depletion kinetics (half-life) of selected pesticides in honey and beeswax as a measure of the latter matrixes to serve as a pesticide sentinel. The obtained parameters were used to extrapolate to pesticide burden in honey and beeswax samples collected from German and Israeli apiaries. In addition, we aimed to establish a mathematical model, enabling us to predict distribution of selected pesticides between honey to beeswax, by utilizing simple substance descriptors, namely, octanol/water partitioning coefficient, molar weight and Henry coefficient. Based on the present results, it appears that pesticides with LogD values > 1 and half-life in beeswax > 1 day, were likely to accumulate and detected in beeswax samples, and less likely to be found in honey. On the other hand, pesticides with negative LogD values were highly likely to be found in honey and less so in beeswax samples. Finally, pesticides with LogD values between 0–1 were expected to be found in both matrixes. The developed model was successfully applied to predict LogD values, thereby identifying octanol/water partitioning and molar weight as the most prominent substance descriptors, which affect pesticide distribution between honey and beeswax.

Comparison of Two Methods for the Determination of Selected Pesticides in Honey and Honeybee Samples.

Developed and validated analytical methods for the determination of a wide spectrum of pesticide residues in honey and honeybee samples after the modification of QuEChERS extraction in combination with gas chromatography–tandem quadrupole mass spectrometry (GC-MS/MS) and liquid chromatography–tandem quadrupole mass spectrometry (LC-MS/MS) were discussed and compared. The developed methods were evaluated regarding the utilized equipment and reagents using Eco-Scale and compared in terms of extraction time, accuracy, precision, sensitivity and versatility, with similar procedures. The results proved that the QuEChERS protocol in combination with LC and GC techniques fulfills the requirements of green analytical chemistry, so it can be used as a tool in environmental monitoring. The recovery was 85–116% for honey and 85.5–103.5% for honeybee samples. The developed methods were successfully applied in monitoring real samples collected from three districts of Pomerania in Poland. Analysis of real samples revealed the presence of the following pesticides: bifenthrin, fenpyroximate, methidathione, spinosad, thiamethoxam, triazophos, metconazole and cypermethrin at levels higher than the MRLs established by the EU.

Organochlorine Pesticides in Honey and Pollen Samples from Managed Colonies of the Honey Bee Apis mellifera Linnaeus and the Stingless Bee Scaptotrigona mexicana Guérin from Southern, Mexico.

In this paper, we show the results of investigating the presence of organochlorine pesticides in honey and pollen samples from managed colonies of the honey bee, Apis mellifera L. and of the stingless bee Scaptotrigona mexicana Guérin. Three colonies of each species were moved into each of two sites. Three samples of pollen and three samples of honey were collected from each colony: the first collection occurred at the beginning of the study and the following ones at every six months during a year. Thus the total number of samples collected was 36 for honey (18 for A. mellifera and 18 for S. mexicana) and 36 for pollen (18 for A. mellifera and 18 for S. mexicana). We found that 88.44% and 93.33% of honey samples, and 22.22% and 100% of pollen samples of S. mexicana and A. mellifera, respectively, resulted positive to at least one organochlorine. The most abundant pesticides were Heptaclor (44% of the samples), γ-HCH (36%), DDT (19%), Endrin (18%) and DDE (11%). Despite the short foraging range of S. mexicana, the number of pesticides quantified in the honey samples was similar to that of A. mellifera. Paradoxically we found a small number of organochlorines in pollen samples of S. mexicana in comparison to A. mellifera, perhaps indicating a low abundance of pollen sources within the foraging range of this species.

Human dietary intake and hazard characterization for residues of neonicotinoides and organophosphorus pesticides in Egyptian honey

ABSTRACTIn two recently published reports, hazards posed by dietary exposure to organophosphate and neonicotinoid plant protection products on the European honey bee (Apis mellifera L.) in Egypt were investigated. Using concentrations reported in those studies, an assessment of hazards posed by these two classes of insecticides to humans due to consumption of Egyptian honey from the Nile Delta during both spring and summer was performed. Twenty-eight compounds including metabolites were assessed for exposure of adult Egyptians based on the best- and worst-case scenarios. Even for the worst-case scenario, exposure to these two classes of pesticides in honey was 15-fold less than hazard index value of 1.0 for adverse effects on humans. Based upon this analysis, people exposed to these insecticides through consumption of honey products would be unlikely to exhibit adverse health outcomes.

Direct detection of multiple pesticides in honey by neutral desorption-extractive electrospray ionization mass spectrometry

An analytical method was developed and validated for the simultaneous determination of residues of three kinds of organophosphorus insecticides and two kinds of carbamate insecticides in honey using neutral desorption-extractive electrospray ionization mass spectrometry (ND-EESI–MS) without any sample pretreatment. The detection limits of the assay ranged from 1.16 to 4.18ng/g for the studied pesticides. The developed assay was linear over the concentration range of 20.00–1000.00ng/mL, with correlation coefficients of more than 0.996, and the recoveries ranged between 87.00% and 114.98%, with RSD lower than 6.22% for all pesticides. The matrix effect for all of the pesticides showed signal suppression except for chlorpyrifos-methyl. This ND-EESI–MS method was proved to be effective for the detection of pesticide residues by analyzing eighteen kinds of commercial honey in this study.

From bees to honey

Neonicotinoids Neonicotinoid pesticides are applied globally. Concern about their impacts has been increasing as evidence for negative effects on bee health and persistence has accumulated. Mitchell et al. looked at the prevalence of these pesticides in honey from across the world and found traces in the majority of samples tested (see the Perspective by Connolly). The neonicotinoid compounds occurred at levels considered safe for human consumption, but the contamination confirms the inundation of bees and their environments with these pesticides, despite some recent efforts to decrease their use. Science , this issue p. [109][1]; see also p. [38][2] [1]: /lookup/doi/10.1126/science.aan3684 [2]: /lookup/doi/10.1126/science.aao6000

A worldwide survey of neonicotinoids in honey.

Growing evidence for global pollinator decline is causing concern for biodiversity conservation and ecosystem services maintenance. Neonicotinoid pesticides have been identified or suspected as a key factor responsible for this decline. We assessed the global exposure of pollinators to neonicotinoids by analyzing 198 honey samples from across the world. We found at least one of five tested compounds (acetamiprid, clothianidin, imidacloprid, thiacloprid, and thiamethoxam) in 75% of all samples, 45% of samples contained two or more of these compounds, and 10% contained four or five. Our results confirm the exposure of bees to neonicotinoids in their food throughout the world. The coexistence of neonicotinoids and other pesticides may increase harm to pollinators. However, the concentrations detected are below the maximum residue level authorized for human consumption (average ± standard error for positive samples: 1.8 ± 0.56 nanograms per gram).

Comparative Evaluation of Extraction Procedures and Chromatographic Techniques for Analysis of Multiresidue Pesticides in Honey

Comparative Evaluation of Extraction Procedures and Chromatographic Techniques for Analysis of Multiresidue Pesticides in Honey

Multiclass method for pesticides quantification in honey by means of modified QuEChERS and UHPLC–MS/MS

Bee products can be produced in an environment contaminated by pesticides that can be transported by honey bees to the hive and incorporated into the honey. Therefore, rapid and modern methods to determine pesticide residues in honey samples are essential to guarantee consumers’ health. In this study, a simple multiresidue method for the quantification of 116 pesticides in honey is proposed. It involves the use of a modified QuEChERS procedure followed by UHPLC–MS/MS analysis. The method was validated according to the European Union SANCO/12571/2013 guidelines. Acceptable values were obtained for the following parameters: linearity, limit of detection (0.005mg/kg) and limit of quantification (0.010 and 0.025mg/kg), trueness (for the four tested levels the recovery assays values were between 70 and 120%), intermediate precision (RSD<20.0%) and measurement uncertainty tests (<50.0%). The validated method was applied for determination of 100 honey samples from five states of Brazil.

Proficiency Testing Scheme for Pesticides in Honey

Proficiency Testing Scheme for Pesticides in Honey

Rapid determination of residues of pesticides in honey by µGC-ECD and GC-MS/MS: Method validation and estimation of measurement uncertainty according to document No. SANCO/12571/2013

ABSTRACTA simple and straightforward method for simultaneous determination of residues of 13 pesticides in honey samples (acrinathrin, bifenthrin, bromopropylate, cyhalothrin-lambda, cypermethrin, chlorfenvinphos, chlorpyrifos, coumaphos, deltamethrin, fluvalinate-tau, malathion, permethrin and tetradifon) from different pesticide classes has been developed and validated. The analytical method provides dissolution of honey in water and an extraction of pesticide residues by n-Hexane followed by clean-up on a Florisil SPE column. The extract was evaporated and taken up by a solution of an injection internal standard (I-IS), ethion, and finally analyzed by capillary gas chromatography with electron capture detection (GC-µECD). Identification for qualitative purpose was conducted by gas chromatography with triple quadrupole mass spectrometer (GC-MS/MS). A matrix-matched calibration curve was performed for quantitative purposes by plotting the area ratio (analyte/I-IS) against concentration using a GC-µECD instrument. According to document No. SANCO/12571/2013, the method was validated by testing the following parameters: linearity, matrix effect, specificity, precision, trueness (bias) and measurement uncertainty. The analytical process was validated analyzing blank honey samples spiked at levels equal to and greater than 0.010 mg/kg (limit of quantification). All parameters were satisfactorily compared with the values established by document No. SANCO/12571/2013. The analytical performance was verified by participating in eight multi-residue proficiency tests organized by BIPEA, obtaining satisfactory z-scores in all 70 determinations. Measurement uncertainty was estimated according to the top-down approaches described in Appendix C of the SANCO document using the within-laboratory reproducibility relative standard deviation combined with laboratory bias using the proficiency test data.

Simultaneous determination of 200 pesticide residues in honey using gas chromatography–tandem mass spectrometry in conjunction with streamlined quantification approach

A sensitive, accurate and reliable multi-class GC–MS/MS assay protocol for quantification and confirmation of 200 common agricultural pesticides in honey was developed and validated according to EU guidelines. A modified extraction procedure, based on QuEChERS method (quick, easy, cheap, effective, rugged and safe) was employed. Mass spectrophotometric conditions were individually optimized for each analyte to achieve maximum sensitivity and selectivity in MRM mode. The use of at least two reactions for each compound allowed simultaneous identification and quantification in a single run. The pesticides under investigation were separated in less than 31min using the ultra-inert capillary column (DB-35MS). For all analytes, neat standard calibration curves in conjunction with correction for matrix effect were successfully employed. The detection limits of the assay ranged from 1.00 to 3.00ngmL−1 for the studied pesticides. The developed assay was linear over concentration range of 10.00–500.00ngmL−1, with correlation coefficient of more than 0.996. At the LOQ, 81% of the studied pesticides were efficiently recovered in the range of 70.00–120.00%, with CV% less than 15.00% while 99.3% compounds had mean percentage recovery of 60.00–140.00%, with CV% less than 21.00% (N=18, over three different days). The proposed assay was successfully applied for the analysis of the studied pesticide residues in one PT sample and 64 commercial honey samples collected over 1year from different districts around Egypt. Results revealed that only one honey sample out of the 64 analyzed samples was contaminated with tau-Fluvalinate (10.00μgkg−1). This wide scope assay protocol is applicable for monitoring pesticide residues in honey by national regulatory authorities and accredited labs; that should help ensure safety of such widely used product.

Determination of triazine pesticides in honey by ultra high performance liquid chromatography-high resolution isotope dilution mass spectrometry combined with dispersive micro-solid phase extraction

An effective DMSPE procedure with PCX sorbent has been developed for the rapid analysis of triazine pesticides in honey.

Extraction and enrichment of triazole and triazine pesticides from honey using air-assisted liquid-liquid microextraction.

In the present work, an easy, fast, and effective approach is developed for the extraction and enrichment of triazole and triazine pesticides in honey by air-assisted liquid-liquid microextraction coupled with gas chromatography-flame ionization detection. Initially, honey is dissolved in an acetonitrile: water mixture and after that a few microliter of a less soluble organic solvent in aqueous phase is added. In order to form a cloudy solution, the extractant mixed with aqueous phase is repeatedly sucked and expelled by a syringe needle into a glass tube. After centrifugation, the sedimented phase (1 mL) is removed with a syringe and injected into de-ionized water. By this action, the settled phase volume is reduced to 10 μL and the analytes are concentrated, too. Under optimum extraction conditions, limits of detection and quantitation for the studied pesticides are in the ranges of 2 to 5 and 6 to 17 ng/g, respectively. Extraction recoveries and enrichment factors are from 61% to 95% and 61 to 95, respectively. The proposed approach can be applied for determination of pesticide in honey and may be developed to other complex matrices.

Residues of organochlorine and synthetic pyrethroid pesticides in honey, an indicator of ambient environment, a pilot study

Samples of honey were screened to monitor residues of organochlorine and pyrethroid pesticides. The study meant to examine the quality of honey, and to use honey as a bioindicator of environmental contamination. Residue levels were determined by gas chromatography (GC-μECD). Samples had a wide spectrum of organochlorine and synthetic pyrethroids pesticides, with hexachlorobenzene (HCB) as the most frequently detected organochlorine, followed by permethrin, heptachlor epoxide. Only one sample had a concentration of γ-HCH higher than maximum residue limit of honey (0.01mgkg−1). Residues of organochlorines detected, indicate the presence of some fresh supplies, despite the ban imposed on their use. The study confirmed that honey bee and beehive matrices could be used as gauge for monitoring environment contamination. From public health point of view, the observed levels of pesticide residues in honey do not pose a serious health risk to the consumers, but raises questions of the source of organochlorines.

Risk Assessment of Heavy Metals and Pesticides in Honey From Sicily (Italy)

&lt;p&gt;Honey, obtained by the honeybee (&lt;em&gt;Apis mellifera&lt;/em&gt;) from nectar plants, with different composition according to floral sources, regional and climatic conditions, is widely consumed for its nutritional value and various properties. It could be considered a bio-indicator of environmental pollution to assess the presence of metals, naturally present in soil, and pesticides, widely used in agricultural practices. Actually no specific legislation on honey’s metals and pesticides content exists. The aim of this study was to evaluate the presence of toxic metals (Pb and Cd) and insecticides (organochlorines, organophosphates, pyrethrins and pyrethroids) in carob, chestnut and eucalyptus honey samples from Sicily and carried out a risk assessment to dietary intake of these contaminants. The results obtained showed low residual levels of Pb (0.1709 ± 0.078 mg kg&lt;sup&gt;-1&lt;/sup&gt;) and Cd (0.0153 ± 0.004 mg kg&lt;sup&gt;-1&lt;/sup&gt;) while the concentrations of all pesticides analyzed were under the LOD (&amp;lt; 0.01 mg kg&lt;sup&gt;-1&lt;/sup&gt;). To explain the source of metals contamination in honey, the analytical investigation was conducted also in carob (&lt;em&gt;Ceratonia siliqua &lt;/em&gt;L.), chestnut (&lt;em&gt;Castanea sativa&lt;/em&gt;) and eucalyptus (&lt;em&gt;Eucalyptus globules &lt;/em&gt;Labill.) powders, from which nectar honey is produced, confirming the presence of Pb and Cd concentrations with statistically significant differences (P &amp;lt; 0.05 and P &amp;lt; 0.01) in all three types. The risk assessment, evaluated through the Target Hazard Quotient (THQ) and confirmed also by EFSA Provisional Tolerable Weekly Intake (PTWI), showed that metals daily intake through Sicilian honey consumption is not likely to cause deleterious effect for consumers.&lt;/p&gt;

Sensitive analytical methods for 22 relevant insecticides of 3 chemical families in honey by GC-MS/MS and LC-MS/MS

Several methods for analyzing pesticides in honey have been developed. However, they do not always reach the sufficiently low limits of quantification (LOQ) needed to quantify pesticides toxic to honey bees at low doses. To properly evaluate the toxicity of pesticides, LOQ have to reach at least 1 ng/g. In this context, we developed extraction and analytical methods for the simultaneous detection of 22 relevant insecticides belonging to three chemical families (neonicotinoids, pyrethroids, and pyrazoles) in honey. The insecticides were extracted with the QuEChERS method that consists in an extraction and a purification with mixtures of salts adapted to the matrix and the substances to be extracted. Analyses were performed by gas chromatography coupled with tandem mass spectrometry (GC-MS/MS) for the pyrazoles and the pyrethroids and by high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS) for the neonicotinoids and ethiprole. Calibration curves were built from various honey types fortified at different concentrations. Linear responses were obtained between 0.2 and 5 ng/g. Limits of detection (LOD) ranged between 0.07 and 0.2 ng/g, and LOQ ranged between 0.2 and 0.5 ng/g. The mean extraction yields ranged between 63 % and 139 % with RSD <25 %. A complete validation of the methods also examined recovery rates and specificity. These methods were applied to 90 honey samples collected during a 2009-2010 field study in two apiaries placed in different anthropic contexts.