Article

Residues of organic contaminants in beeswax

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Abstract

Residues of the varroacides amitraz, chlordimeform, chlorfenvinphos, bromopropylate, coumaphos, tetradifon, acrinathrin, and fluvalinate, the organic microcontaminants 4,4'-DDE, 4,4'-TDE, PCB 153 and PCB 180, and the lipophilic pesticides lindane, chlorpyrifos and endosulfan have been determined by GC/MS in 52 beeswax samples. Recoveries on spiked samples ranged from 93 to 108% and determination limits varied from 4 to 65 µg/kg. Lindane (0.042–0.29 mg/kg), chlorfenvinphos (0.16–7.62 mg/kg), 4,4'-TDE (0.20 mg/kg), bromopropylate (0.041–0.12 mg/kg), tetradifon (0.032–0.58 mg/kg), acrinathrin (0.058–0.59 mg/kg), coumaphos (0.27–0.38 mg/kg), fluvalinate (0.064–5.10 mg/kg), endosulfan sulfate (0.12–0.37 mg/kg) and 3-phenoxybenzaldehyde, a degradation product of fluvalinate and acrinathrin (0.080–1.47 mg/kg), were the compounds detected in beeswax. Foundation beeswax sheets contained higher contaminant concentrations and a greater diversity of compounds in relation to comb beeswaxes. Repeated melting in boiling water of purified beeswax spiked with the contaminants did not substantially modify the content of most of the contaminants in beeswax, except for amitraz and chlordimeform, showing that the contaminants are stable and remain practically unchanged in the purified beeswax.

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... Indeed, the European Commission has since 2018 encouraged investigation into the decline of pollinators, including the causes and consequences [5,[13][14][15][16][17][18][19][20][21][22][23], with the aim of preventing it. However, it should be mentioned that pesticide residues in bee products, especially beeswax, were documented in several publications [24][25][26][27][28][29], in which amitraz, coumaphos, chlorfenvinphos, and tau-fluvalinate were detected in many of the analyzed samples. This confirms the significance of acaricide residues as the group of pesticides that are most frequently found in this matrix, including virgin beeswax. ...
... The current trend is the use of hybrid techniques combining chromatography with mass spectrometry in its different modalities [31]. Different solvents have been employed to extract pesticides from beeswax, such as hexane [10,22,[24][25][26]32,33], acetone [34], or mixtures of acetone with hexane [35] or water [36], although in several studies, a water and acetonitrile mixture was selected [10,20,27,[37][38][39]. To minimize potential matrix interferences, various clean-up procedures have been proposed, including solidphase extraction with C 18 and/or florisil-based cartridges [10,25,26,32,34], filtration [40], gel permeation chromatography [41], or matrix solid dispersion combined with clean-up on C 18 or florisil [42]. ...
... It can also be concluded that tau-fluvalinate was present in most of the samples, followed by coumaphos and chlorfenvinphos. As it was previously stated in the Introduction, the presence of those compounds in beeswax was previously reported in several publications [24][25][26][27][28][29]. In particular, the concentrations of detected coumaphos were quite high in some samples and were also much higher than those reported in 2010 [27]. ...
Article
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Pesticides can be found in beehives for several reasons, including contamination from surrounding cultivars; yet one of the most pertinent is related to the fact that beekeepers employ acaricides to control various types of mites, which may accumulate in beeswax due to their lipophilic nature. In the present study, foundation sheets of different origins, collected over a period of three years, were analyzed to detect the residues of seven acaricides (atrazine, chlorpyrifos, chlorfenvinphos, alpha-endosulfan, bromopropylate, coumaphos, tau-fluvalinate) by gas chromatography with mass spectrometric detection. An efficient sample treatment (recoveries between 90% and 108%) is proposed, involving solvent extraction with 1% acetic acid in acetonitrile mixture followed by dispersive solid-phase extraction (enhanced matrix removal lipid) and a polishing step. An evaluation was made of the analytical performance of the proposed method. It was shown to be selective, linear from a limit of quantification to 5000 µg/kg, precise (relative standard deviation values were below 6%), and with a goo sensitivity (limit of quantification ranging from 5 to 10 µg/kg). Finally, results showed that a large majority of the sheets analyzed (>90%) contained residues of at least one of these compounds. Coumaphos and tau-fluvalinate residues were the most common, with chlorpyrifos and chlorfenvinphos detected to a lesser extent.
... Different chromatographic procedures have been reported for pesticide analysis in beeswax [3][4][5][6][7][8][9][10][11][12][13][14][15]. In general, gas chromatography coupled to mass spectrometry has prevailed for pesticide separation and detection [4][5][6][8][9][10][11][12][15][16][17]. ...
... Different chromatographic procedures have been reported for pesticide analysis in beeswax [3][4][5][6][7][8][9][10][11][12][13][14][15]. In general, gas chromatography coupled to mass spectrometry has prevailed for pesticide separation and detection [4][5][6][8][9][10][11][12][15][16][17]. Moreover, there are some reports where liquid chromatography was used with diode array detector or mass spectrometry [2,3,[11][12][13]18]. ...
... In general, the first step is the solubilisation of beeswax in organic solvent, such as hexane [2,3,5,9,10,14,21]. Then, most of the approaches include freeze/centrifugation steps (few minutes or overnight) to eliminate the excess of high-molecular-weight compounds that could be coextracted with pesticides [2][3][4][8][9][10][11]14,16,18]. ...
Article
Beeswax is a complex mixture of lipophilic compounds and other components such as aliphatic alcohols and carotenoids. Then, extraction and clean-up for pesticide analysis in beeswax is a challenge. In this work, a multiresidue method for the analysis of dichlorvos (DCV), diazinon, malathion, methyl parathion and coumaphos (CMF) in beeswax was developed. The proposed approach is based on matrix solid-phase dispersion extraction. The adsorbent for sample clean-up was studied and a simplex-centroid cubic statistical design was applied to evaluate pure solvents and their binary and ternary mixtures to elute the analytes. Finally, Florisil and ethyl acetate were chosen as solid support and eluting solvent, respectively. After extraction, pesticides were separated and detected by gas chromatography/mass spectrometry. The method achieved acceptable recoveries (70–85%; except for DCV, 24–38%) with relative standard deviations below 5%. The repeatability of the method was lower than 8% and interday variability was below 12%. The limit of detection (LOD) for the analytes varies between 0.2 and 2.6 µg⋅kg⁻¹ and limit of quantification from 0.93 to 8.8 µg⋅kg⁻¹. LOD reached for CMF was below the maximum residue limit allowed by the legislation of the United States and Canada.
... Since 2007, Checkmite® (with coumaphos active substance) has been one of the authorized products against varroa mite and its residues have been found at high levels in Spanish beeswax foundation: 340 ng·g − 1 (Jimenez et al., 2005), 67.9 ng·g − 1 (Serra-Bonvehi and Orantes-Bermejo, 2010), and 9486 ng·g −1 (present study, 2016). Coumaphos residues had a frequency of 100% and reached the highest mean concentration of all pesticides in R, F, C and B. Capping wax showed significant differences in coumaphos levels compared to foundation (F) and old combs (R) ( Table 3). ...
... However, levels detected in this work suggest an illegal use of this organophosphate acaricide against varroosis according to the current legislation (EU regulation 1107/2009). Previous works of Spanish and Italian beeswax have also supported results found in the present study where chlorfenvinphos was one of the most frequently detected pesticides, and the unauthorized use of this compound was proved (Jimenez et al., 2005;Lodesani et al., 2008;Orantes-Bermejo et al., 2010;Serra-Bonvehi and Orantes-Bermejo, 2010). ...
... Residues were also found in wax cappings (58%) and its mean concentration reached 626 ng·g −1 .Concentrations of this acaricide in the samples analyzed could indicate an irregular use of this pyrethroid against varroa mite. Previous works have also detected acrinathrin in Spanish beeswax, supporting our results (Jimenez et al., 2005;Serra-Bonvehi and Orantes-Bermejo, 2010). ...
Article
Beeswax from Spain was collected during 2016 to determine pesticide residues incidence. The 35 samples were divided in foundation, old combs, cappings or virgin beeswax to compare pesticide content between groups. Wax was screened for 58 pesticides or their degradation products by QuEChERS extraction and liquid chromatography mass spectrometry (LC-MS/MS). Beeswax was uniformly contaminated with acaricides and, to a much lesser extent, with insecticide and fungicide residues. Virgin followed by cappings were less contaminated than foundation and old combs beeswax. The miticides applied in-hive had a contribution to average pesticide load higher than 95%. Compounds widely used as acaricides, as coumaphos (100%), fluvalinate (86%) and amitraz (83%), were the pesticides most frequently detected with maximum concentrations of 26,858, 3593 and 6884 ng·g− 1, respectively. Chlorfenvinphos, acrinathrin and flumethrin, also acaricides, were detected in 77, 71 and 54%, respectively. Frequencies of pesticides used in crops were 40% for chlorpyrifos, 29% for dichlofenthion, 9% for malathion, 6% for fenthion-sulfoxide and 3% for azinphos-methyl, carbendazim, ethion, hexythiazox, imazalil and pyriproxyfen. Pesticide assessment in beeswax could be an excellent monitoring tool to establish veterinary treatments applied by beekeepers and environmental contaminants exposure of honey bees.
... However, they are found in honey, producing an unwanted taste (Wallner 1999). Residues of fat-soluble and stable pesticides have been found in surveys in many countries: Greece (Thrasyvoulou and Pappas 1988), Italy (Lodesani et al. 1992(Lodesani et al. , 2008Russo and Neri 2002), Switzerland (Bogdanov et al. 1998(Bogdanov et al. , 2003, France (Martel et al. 2007;Chauzat and Faucon 2007), Germany (Wallner 1999), Spain (Fernandez-Muiño et al. 1995García et al. 1996;Jiménez et al. 2005), Portugal (Rial-Otero et al. 2007), North America (Nasr and Wallner 2003;Mullin et al. 2010) and Saudi Arabia (Kamel and Al-Ghamdi 2006). Experiments designed to assess the persistence, fate and metabolism of various pesticide compounds have been performed over periods of up to 2 years using experimental hives (van Buren et al. 1992;Bogdanov and Kilchenmann 1995;Fries et al. 1998;Tsigouri et al. 2001Tsigouri et al. , 2004Waliszewski et al. 2003;Tremolada et al. 2004;Martel et al. 2007). ...
... Passive distribution Varroa. τ-fluvalinate data are taken from: Lodesani et al. (1992Lodesani et al. ( , 2003, Wallner (1997Wallner ( , 1999, Russo and Neri (2002), Waliszewski et al. (2003), Kamel and Al-Ghamdi (2006), Tsigouri et al. (2004), Bogdanov and Kilchenmann (1995), Bogdanov (2006), Merle (1989, 1990), Jiménez et al. (2005), Faucon (2007), Friés et al. (1998), Nasr and Wallner (2003), Martel et al. (2007) and Mullin et al. (2010). Bromopropylate data are taken from: Lodesani et al. (1992), Wallner (1999), Jiménez et al. (2005) and Bogdanov (2006). ...
... τ-fluvalinate data are taken from: Lodesani et al. (1992Lodesani et al. ( , 2003, Wallner (1997Wallner ( , 1999, Russo and Neri (2002), Waliszewski et al. (2003), Kamel and Al-Ghamdi (2006), Tsigouri et al. (2004), Bogdanov and Kilchenmann (1995), Bogdanov (2006), Merle (1989, 1990), Jiménez et al. (2005), Faucon (2007), Friés et al. (1998), Nasr and Wallner (2003), Martel et al. (2007) and Mullin et al. (2010). Bromopropylate data are taken from: Lodesani et al. (1992), Wallner (1999), Jiménez et al. (2005) and Bogdanov (2006). Coumaphos data are taken from: Thrasyvoulou and Pappas (1988), van Buren et al. (1992), Wallner (1997Wallner ( , 1999, Kamel and Al-Ghamdi (2006), Jiménez et al. (2005), Chauzat and Faucon (2007), Bogdanov andKilchenmann (1995), Friés et al. (1998), Tremolada et al. (2004), Martel et al. (2007), Bogdanov (2006), Nasr and Wallner (2003), Ghini et al. (2004), Westcott and Winston (1999) and Mullin et al. (2010). ...
Article
Full-text available
τ-Fluvalinate residues in bees, honey and wax were measured in two experimental hives treated with Apistan to test a multi-compartmental predictive model. Pesticide residues were monitored for 30days after treatment in bees and for up to 180days in honey and wax. Concentrations ranged between 14 and 160ngg−1 f.w. in bees and between 98 and 1630ngg−1 in wax, while no residues were detected above the analytical limit (2.5ngg−1) in honey. τ-Fluvalinate residues are discussed in the context of a survey of data from the literature on other pesticides (bromopropylate, coumaphos, malathion and amitraz). This data review shows that residues of the same compound exhibit extremely high variability within the same matrix. This finding underlines the importance of developing predictive tools for both post-treatment analysis and a priori evaluation of the possible contamination effects of pesticides depending on the mode of application. Keywordsfluvalinate–pesticide residue–wax contamination–honey contamination–bee health
... Therefore, beeswax could represent an interesting matrix to assess the exposure of bees to pesticides and to evaluate the potentially negative ecotoxicological effects of pesticides on bees [2]. Different chromatographic procedures have been reported for pesticide analysis in beeswax [3][4][5][6][7][8][9][10][11][12][13][14][15]. In general, gas chromatography coupled to mass spectrometry has prevailed for pesticide separation and detection [4][5][6][8][9][10][11][12][15][16][17]. ...
... Different chromatographic procedures have been reported for pesticide analysis in beeswax [3][4][5][6][7][8][9][10][11][12][13][14][15]. In general, gas chromatography coupled to mass spectrometry has prevailed for pesticide separation and detection [4][5][6][8][9][10][11][12][15][16][17]. Moreover, there are some reports where liquid chromatography was used with diode array detector or mass spectrometry [2,3,[11][12][13]18]. ...
... In general, the first step is the solubilisation of beeswax in organic solvent, such as hexane [2,3,5,9,10,14,21]. Then, most of the approaches include freeze/centrifugation steps (few minutes or overnight) to eliminate the excess of high-molecular-weight compounds that could be coextracted with pesticides [2][3][4][8][9][10][11]14,16,18]. ...
Article
Five organophosphorus pesticides (dichlorvos, diazinon, malathion, methyl parathion and coumaphos) were extracted from propolis by matrix solid-phase dispersion (MSPD) extraction using octadecylsilica (C18, 1.0 g) as dispersant material. The kind of solvent elution (acetonitrile or ethyl acetate), volume (8 mL and 15 mL), and adsorbent used to clean-up the extracts (graphitized carbon, florisil™ and silica) were optimized using fortified propolis samples (5.0 μg g(-1)). Recovery was determined by gas chromatography with mass spectrometric detection in selected ion monitoring mode (GC/MS-SIM) and statistical analysis was done to determine better extraction conditions. Relatively high recovery and lower relative standard deviation values (3.1-14.6%) were obtained when analytes were eluted with ethyl acetate from the MSPD column. Diazinon, malathion, methyl parathion, and coumaphos show recoveries of 72.7%, 84.6%, 62.6%, and 78.3%, respectively. In contrast, the recovery for dichlorvos was 53.8%. Additional adsorbents tested for clean-up and increase in solvent elution did not affect recoveries positively and caused a high background in chromatograms. Thus, final conditions were 1 mL of sample, 1 g C18 and 8 mL of ethyl acetate.
... Levels in brood and adult bees can be higher than in the food, with 14 ppm amitraz, 5.9 ppm fluvalinate (vanEngelsdorp et al., 2009b; Mullin et al., 2010), 2.8 ppm of coumaphos (Ghini et al., 2004), and 2.2 ppm bromopropylate (Lodesani et al., 1992 ) being reported. Nevertheless, wax remains the ultimate sink for these varroacides reaching 46, 94 and 204 ppm, respectively, of amitraz, coumaphos and fluvalinate (vanEngelsdorp et al., 2009b; Mullin et al., 2010), 135 ppm of bromopropylate (Bogdanov et al., 1998), and 7.6 and 0.6 ppm, respectively, of the miticides chlorfenvinophos and acrinathrin (Jimenez et al., 2005). Pesticide residues of agrochemicals acquired by foragers are equivalent or higher in pollen (stored and trapped at the hive entrance ), adult bees and occasionally honey, than in wax. ...
... Elevated levels of the acetylcholinesterase-inhibitors azinphos methyl (0.8 ppm), fenitrothion (0.5 ppm, Chauzat and Faucon, 2007), carbaryl (0.8 ppm), parathion methyl (3.1 ppm, Russell et al., 1998), and malathion (6 ppm, Thrasyvoulou and Pappas, 1988) have been reported. Bogdanov et al., (2004) detected up to 60 ppm of p-dichlorobenzene and Jimenez et al., (2005) up to 0.6 ppm of the miticide tetradifon in beeswax. ...
... = not detected. 1 Jimenez et al. (2005); 2 Bernal et al. (2000); 3 Estep et al. (1977); 4 Fernandez-Muino et al. (1995); 5 Rissato et al. (2007); 6 Ghini et al. (2004); 7 Chauzat and Faucon (2007); 8 Nguyen et al. (2009); 9 Walorczyk et al. (2009); 10 Blasco et al. (2008); 11 Bogdanov et al. (1998); 12 Lodesani et al. (1992); 13 Anderson and Wojtas (1986); 14 Kubik et al. (2000); 15 Chauzat et al. (2006); 16 Bailey et al. (2005); 17 Blasco et al. (2003); 18 Balayiannis and Balayiannis (2008); 19 Rissato et al. (2004) 30 Kubik et al. (1999); 31 Thrasyvoulou and Pappas (1988); 32 Russell et al. (1998); 33 Rhodes et al. (1979); 34 Taylor et al. (2007). from migratory and stationary beekeepers. ...
Article
Full-text available
Until 1985 discussions of pesticides and honey bee toxicity in the USA were focused on pesticides applied to crops and the unintentional exposure of foraging bees to them. The recent introduction of arthropod pests of honey bees, Acarapis woodi (1984), Varroa destructor (1987), and Aethina tumida (1997), to the USA have resulted in the intentional introduction of pesticides into beehives to suppress these pests. Both the unintentional and the intentional exposure of honey bees to pesticides have resulted in residues in hive products, especially beeswax. This review examines pesticides applied to crops, pesticides used in apiculture and pesticide residues in hive products. We discuss the role that pesticides and their residues in hive products may play in colony collapse disorder and other colony problems. Although no single pesticide has been shown to cause colony collapse disorder, the additive and synergistic effects of multiple pesticide exposures may contribute to declining honey bee health.
... Most contaminants are stable and remain practically unchanged in the purified beeswax. 1,14 However, many of the acaricides frequently used appear to be unstable, producing different breakdown products, and, as a consequence, both the active ingredient and its metabolites may contaminate honey bee products in the hive. 18 -20 Thus, the purpose of this research was to determine acaricide residues in recycled beeswax following the long-term use of acaricides (since 1985) using gas chromatography with electron capture and nitrogen-phosphorus detectors (GC-rmµECD/NPD) combined with GC-mass spectrometry detection (GC-MSD). ...
... The method employs relatively simple sample preparation involving a single extraction step and an SPE clean-up procedure using Florisil cartridges. 10,14 Validation and optimisation of the SPE procedure with GC-MS detection was obtained in terms of recoveries, precision and limits of detection (LOD) and quantification (LOQ). The precision and accuracy of the procedure were obtained by analysis of five spiked beeswax samples at five concentrations (0.1, 0.5, 1, 3 and 5 mg kg −1 for each acaricide). ...
... 13,26 The remainder of the acaricides cited in Table 2 have also been applied in Spain over the last 10 years, but have declined in use. 14 (Tables 2 and 3). Chlorfenvinphos was the most widely applied acaricide in beehives during the sampling period, whereas tau-fluvalinate appeared to be accumulating (in terms of concentration) in beeswax with years of treatment. ...
Article
The purpose of this work was to determine residues of acaricides in recycled Spanish beeswax. Chlorfenvinphos, fluvalinate, amitraz, bromopropylate, acrinathrin, flumethrin, coumaphos, chlorpyrifos, chlordimeform, endosulfan and malathion residues were determined by GC-µECD/NPD/MS detection. Owing to the extreme instability of amitraz, this analyte was transformed into the stable end-metabolite 2,4-dimethylaniline, later derivatised with heptafluorobutyric anhydride and determined by GC-µECD/MS. Recoveries from spiked samples ranged from 86 to 108%, while quantification limits varied from 0.10 to 0.30 mg kg(-1) using GC-µECD/NPD, and from 12 to 85 µg kg(-1) by GC-MSD. Of a total of 197 samples analysed, only eight samples (4%) were free of residues of chlorfenvinphos (0.019-10.6 mg kg(-1)), fluvalinate was present in 93.6% of samples analysed (0.027 -88.7 mg kg(-1)), while coumaphos was confirmed in only five of the 134 samples analysed at concentrations of less than 195 µg kg(-1). The remaining acaricides were identified with different levels of incidence at concentrations from 12 to 231 µg kg(-1). Residues of acaricides were found in an extensive number of beeswax samples. The contamination with chlorfenvinphos and tau-fluvalinate was very relevant, particularly as chlorfenvinphos is not legally authorised for use in beekeeping. The possible impacts of the main acaricides detected on larval and adult honey bees are discussed.
... Levels in brood and adult bees can be higher than in the food, with 14 ppm amitraz, 5.9 ppm fluvalinate (vanEngelsdorp et al., 2009b;Mullin et al., 2010), 2.8 ppm of coumaphos (Ghini et al., 2004), and 2.2 ppm bromopropylate (Lodesani et al., 1992) being reported. Nevertheless, wax remains the ultimate sink for these varroacides reaching 46, 94 and 204 ppm, respectively, of amitraz, coumaphos and fluvalinate (vanEngelsdorp et al., 2009b;Mullin et al., 2010), 135 ppm of bromopropylate (Bogdanov et al., 1998), and 7.6 and 0.6 ppm, respectively, of the miticides chlorfenvinophos and acrinathrin (Jimenez et al., 2005). ...
... Elevated levels of the acetylcholinesterase-inhibitors azinphos methyl (0.8 ppm), fenitrothion (0.5 ppm, Chauzat and Faucon, 2007), carbaryl (0.8 ppm), parathion methyl (3.1 ppm, Russell et al., 1998), and malathion (6 ppm, Thrasyvoulou and Pappas, 1988) have been reported. Bogdanov et al., (2004) detected up to 60 ppm of p-dichlorobenzene and Jimenez et al., (2005) up to 0.6 ppm of the miticide tetradifon in beeswax. ...
... Contamination of bee products with pesticides has been widely documented for many years. 1,2 Pollution can be divided into environmental and apicultural sources, although some products can occur from both origins as they are used in both activities. Since the introduction of Varroa destructor (Anderson & Trueman) (Acari: Mesostigmata) into European colonies of honey bee (Apis mellifera L.), beekeepers have had to control the number of mites to prevent colony losses. ...
... However, very few references concerning beeswax contamination related to crop treatments are available in the literature. 2 Results of surveys have shown how widely residues are present in beeswax and how they could potentially impact upon colony biology. 4 From an economic point of view, bee products should maintain the image of being natural, healthy and clean substances. ...
Article
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In 2002 a field survey was initiated in French apiaries in order to monitor the health of honey bee colonies (Apis mellifera L.). Studied apiaries were evenly distributed across five sites located in continental France. Beeswax samples were collected once a year over 2 years from a total of 125 honey bee colonies. Multiresidue analyses were performed on these samples in order to identify residues of 16 insecticides and acaricides and two fungicides. Residues of 14 of the searched-for compounds were found in samples. Tau-fluvalinate, coumaphos and endosulfan residues were the most frequently occurring residues (61.9, 52.2 and 23.4% of samples respectively). Coumaphos was found in the highest average quantities (792.6 microg kg(-1)). Residues of cypermethrin, lindane and deltamethrin were found in 21.9, 4.3 and 2.4% of samples respectively. Statistical tests showed no difference between years of sampling, with the exception of the frequency of pyrethroid residues. Beeswax contamination was the result of both in-hive acaricide treatments and, to a much lesser extent, environmental pollution.
... These acaricide residues present in treated combs are known to affect varroa mite population growth (Kraus and Page 1995). Acaricides also are retained in wax used to produce commercial wax foundations (Lodesani et al. 2003;Jiménez et al. 2005;Leníček et al. 2006). High contamination levels (100 ppm fluvalinate, and 10 and 100 ppm coumaphos) caused dramatic varroa mite mortality during the first brood cycle (Fries et al. 1998). ...
... Acaricide residues have been detected in commercial wax foundations (Lodesani et al. 2003;Jiménez et al. 2005;Leníček et al. 2006) and can have negative effects on varroa mites. Fries et al. (1998) documented that comb drawn from foundations treated with 100 ppm fluvalinate, and 10 and 100 ppm coumaphos caused dramatic varroa mortality during the first brood cycle. ...
Article
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Earlier studies showed that Russian honey bees support slow growth of varroa mite population. We studied whether or not comb type influenced varroa reproduction in both Russian and Italian honey bees, and whether Russian bees produced comb which inhibited varroa reproduction. The major differences found in this study concerned honey bee type. Overall, the Russian honey bees had lower (2.44 +/- 0.18%) levels of varroa infestation than Italian honey bees (7.20 +/- 0.60%). This decreased infestation resulted in part from a reduced number of viable female offspring per foundress in the Russian (0.85 +/- 0.04 female) compared to the Italian (1.23 +/- 0.04 females) honey bee colonies. In addition, there was an effect by the comb built by the Russian honey bee colonies that reduced varroa reproduction. When comparing combs having Russian or Italian colony origins, Russian honey bee colonies had more non-reproducing foundress mites and fewer viable female offspring in Russian honey bee comb. This difference did not occur in Italian colonies. The age of comb in this study had mixed effects. Older comb produced similar responses for six of the seven varroa infestation parameters measured. In colonies of Italian honey bees, the older comb (2001 dark) had fewer (1.13 +/- 0.07 females) viable female offspring per foundress than were found in the 2002 new (1.21 +/- 0.06 females) and 1980s new (1.36 +/- 0.08 females) combs. This difference did not occur with Russian honey bee colonies where the number of viable female offspring was low in all three types of combs. This study suggests that honey bee type largely influences growth of varroa mite population in a colony.
... In fact, RJ can be contaminated by varroacides used to control the parasitic mite Varroa destructor Anderson and Trueman 2000. Many studies have been published on pesticide residues in honey, wax, beebread and propolis (Blasco et al., 2003;Boi et al., 2016;Chauzat et al., 2006;Jim enez et al., 2005;Lozano et al., 2019;Ostiguy & Eitzer, 2014;Serra-Bonveh ı & Orantes-Bermejo, 2010).In contrast, only a few exist regarding RJ, most of which concern its contamination by antibiotics and insecticides (Calvarese et al., 2006;Ding et al., 2006;Giannetti et al., 2010;Matsuka & Nakamura, 1990;Reybroeck, 2003;Tananaki et al., 2009;Xie et al., 2005;Xu et al., 2008). To our knowledge, the research so far carried out to trace acaricide residues in RJ concerns the development and validation of methods for the determination of the synthetic acaricides coumaphos and tau-fluvalinate (Balayannis, 2001;Bogdanov, 2006;Bogdanov et al., 1998;Karazafiris et al., 2008aKarazafiris et al., , 2011Li et al., 2018). ...
Article
In this study, Royal Jelly was produced from colonies under chemical treatment of coumaphos (Perizin and Checkmite+) and tau-fluvalinate (Apistan), using artificial plastic queen cells. The contamination level was assessed 42 days after the application. The application of CheckMite + strips during the production led to higher levels of acaricide residues in the final product, in contrast to the residues from Perizin and Apistan. For this reason, the CheckMite + strips were further applied in order to assess the contamination of the product after a long period (292 days after the application). For the specific sampling, natural (center and adjacent) and plastic cells were used. The results showed that the contamination of Royal Jelly produced in plastic queen cells decreased with time; one month after removing the strips, residues were not detectable. On the contrary, the contamination of samples collected from natural queen cells was high, particularly from those adjacent to the strips, where even 292 days after the strips’ removal, coumaphos concentration was 2.25 ± 0.50 mg kg⁻¹. The maximum concentration (12.52 ± 2.24 mg kg⁻¹) was detected in natural queen cells. Τo our knowledge, this is the highest contamination that has ever been recorded in a food product. Our results suggest that coumaphos may be transferred from wax to Royal Jelly even in low concentrations. Also, the findings of this research provide data for setting safe intervals between acaricide treatment and Royal Jelly production, raising at the same time awareness about the impact of wax contamination on honey bees’ health.
... Our finding is significant also because other commonly used acaricides such as amitraz [23], coumaphos [24], tau fluvalinate [25], flumethrin [26], and thymol [27] affect the beeswax. ...
Article
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The biggest threat to beekeeping is varroosis caused by the mite Varroa destructor. Chemicals available to treat this fatal disease may present problems of resistance or inconsistent efficacy. Recently, lithium chloride has appeared as a potential alternative. To date, the amount of residue lithium treatments may leave in honeybee products is poorly understood. Honeybees were fed with 25 mM lithiated sugar syrup, which was used in earlier studies. The accumulation and elimination of the lithium were monitored in bees and their products for 22 days. Lithium concentration increased in the entire body of the bees to day 4 post-treatment and then recovered rapidly to the control level. Lithium exposure was found to affect uncapped honey in the short term (<16 days), but ripe (capped) honey measured at the end of the trial remained affected. On the other hand, lithium treatment left beeswax lithium-free. Based on these data, we propose that comprehensive research on harvested honey is needed to decide on the veterinary use of lithium.
... Our finding is significant also because other commonly used acaricides such as amitraz [23], coumaphos [24], tau fluvalinate [25], flumethrin [26], and thymol [27] affect the beeswax. ...
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Varroosis caused by the ectoparasitic mite Varroa destructor has been the biggest threat to managed bee colonies over recent decades. Chemicals available to treat the disease imply problems of resistance, inconsistent efficacy, and residues in bee products. Recently, alongside novel compounds to defeat the pest, lithium chloride has been found to be effective. In this study, we found that lithium treatments leave beeswax residue-free. The possibility of decontamination in adult bees, bee bread, and uncapped honey was revealed. On the other hand, ripe honey was found to be affected by lithium administered via feeding. Case studies are necessary to uncover the level of exposition in harvested honey to estimate its potential risk once it becomes a registered veterinary medicine. Abstract: The biggest threat to beekeeping is varroosis caused by the mite Varroa destructor. Chemicals available to treat this fatal disease may present problems of resistance or inconsistent efficacy. Recently, lithium chloride has appeared as a potential alternative. To date, the amount of residue lithium treatments may leave in honeybee products is poorly understood. Honeybees were fed with 25 mM lithiated sugar syrup, which was used in earlier studies. The accumulation and elimination of the lithium were monitored in bees and their products for 22 days. Lithium concentration increased in the entire body of the bees to day 4 post-treatment and then recovered rapidly to the control level. Lithium exposure was found to affect uncapped honey in the short term (<16 days), but ripe (capped) honey measured at the end of the trial remained affected. On the other hand, lithium treatment left beeswax lithium-free. Based on these data, we propose that comprehensive research on harvested honey is needed to decide on the veterinary use of lithium.
... In addition, hazardous waste and solvents used during extraction are known to cause concerns (Pico et al. 2007). The determination of POPs in propolis is usually done by gaschromatography mass spectrometry, with some hazardous solvents and additional sample purification processes (Jim enez et al. 2005;Choudhary and Sharma 2008;Chen et al. 2009). ...
Article
Bee products produced in environments with persistent organic pollutants (POPs) may be contaminated by these compounds. Propolis usually consists of beeswax, resins, water, inorganic and phenolic substances, and essential oils. Although there are some studies on the detection of POPs in honey and some bee products, these are quite limited. Because propolis is a botanical-based and highly complex matrix, and thus difficult to analyze, a reliable and selective method based on solid-phase extraction (SPE) combined with gas chromatography-mass spectrometry was developed for the determination of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in the propolis. All analytes were extracted with acetonitrile and centrifuged for 10 min at 4000 rpm and 6 °C in a refrigerated centrifuge. The samples were filtered using a homemade SPE cartridge containing C18, primary-secondary amine, and magnesium sulfate. The residue collected with acetonitrile was subsequently analyzed by gas chromatography – mass spectrometry (GC-MS). The proposed method was validated according to the Eurachem guidelines and applied directly to the collected propolis samples. The results show that the method may be used successfully in residue monitoring laboratories for the determination of OCPs, PCBs and PBDEs in propolis.
... As we previously reported, the moderate use of pesticides in agricultural localities can lead to low pesticide levels in bees (Erban et al., 2019c). However, one possible source of pesticides in hives can be due to allocation of hive material by the beekeepers including use of old hive material (Jimenez et al., 2005;Karazafiris et al., 2011). ...
Article
Honey bees are major pollinators of crops with high economic value. Thus, bees are considered to be the most important nontarget organisms exposed to adverse effects of plant protection product use. The side effects of pesticides are one of the major factors often linked to colony losses. Fewer studies have researched acute poisoning incidents in comparison to the study of the sublethal effects of pesticides. Here, we compared pesticides in dead/dying bees from suspected poisoning incidents and the suspected crop source according to government protocols. Additionally, we analyzed live bees and bee bread collected from the brood comb to determine recent in-hive contamination. We used sites with no reports of poisoning for reference. Our analysis confirmed that not all of the suspected poisonings correlated with the suspected crop. The most important pesticides related to the poisoning incidents were highly toxic chlorpyrifos, deltamethrin, cypermethrin and imidacloprid and slightly toxic prochloraz and thiacloprid. Importantly, poisoning was associated with pesticide cocktail application. Almost all poisoning incidents were investigated in relation to rapeseed. Some sites were found to be heavily contaminated with several pesticides, including a reference site. However, other sites were moderately contaminated despite agricultural use, including rapeseed cultivation sites, which can influence the extent of pesticide use, including tank mixes and other factors. We suggest that the analysis of pesticides in bee bread and in bees from the brood comb is a useful addition to dead bee and suspected crop analysis in poisoning incidents to inform the extent of recent in-hive contamination.
... Various antivarroatosis products are available but Bromopropylate has advantage of being officially authorized drug available and its common use in Europe. Contamination of bee products with pesticides has been widely documented for many years (Bogdanov et al., 1998, Jimenez et al., 2005and Chauzat and Faucon, 2007. ...
... On the other hand, beeswax is not only recycled almost continuously in the form of comb foundation, but it is also processed for pharmaceutical purposes or for cosmetics industries, and in the food industry as a glazing agent, for the surface treatment of certain fruits and as a carrier for flavour and colours (EFSA, 2007). Beeswax is often contaminated by persistent lipophilic acaricides (Bogdanov, 2006;Jim enez et al., 2005). Moreover, many substances can easily migrate from wax to honey (Tremolada et al., 2004;Wallner, 1999), hence pesticide residues even at trace levels are problematic. ...
Article
Due to its multifunctional and complex role in the honey bee colony functioning and health (construction material allowing food storage, brood rearing, thermoregulation, mediation in chemical and mechanical communication, substrate for pathogens, toxins and waste), Apis mellifera beeswax has been widely studied over the last five decades. This is supported by a comprehensive set of scientific reports covering different aspects of beeswax research. In this article, we present an overview of the methods for studying chemical, biological, constructional, and quality aspects of beeswax. We provide a detailed description of the methods for investigating wax scales, comb construction and growth pattern, cell properties, chemical composition of beeswax using different analytical tools, as well as the analytical procedures for provenancing beeswax and beeswax-derived compounds based on the hydrogen isotope ratio (IRMS). Along with classical physico-chemical and sensory analysis, we describe more precise and accurate methods for detection of adulterants in beeswax (GC-MS and FTIR-ATR). Moreover, we present methods for studying the influence of beeswax (comb foundation) adulteration on comb construction. Analytical protocols for determining the pesticide residues using different chromatographic and spectroscopic techniques are also described. As beeswax is an agent of high risk for the transmission of bee diseases, we present methods for detection of pathogens in beeswax. To ensure the reproducibility of experiments and results, we present best practice approaches and detailed protocols for all methods described, as well as their advantages and disadvantages.
... Beeswax sample preparation Analysis of acaricide residues was performed on bulk samples of beeswax formed after the melting of all sections of the combs collected from one apiary. This procedure was based on techniques developed by Jimenez et al. (2005) and Adamczyk et al. (2007). The pieces of combs were cut, placed into a 1L-glass jar and soaked for about 30 min in distilled water (about 500 ml) at 60°C. ...
Article
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The present studies are the second part of the research project dedicated to finding the causes for increased winter mortality of honey bee colonies. The aim of this task was to investigate incidents of overwintered colonies’ death with regard to the potential interrelation to the exposure to pesticides. The samples of winter stores of bee bread and sugar food (honey or syrup processed by bees), beeswax and bees collected from apiaries with low and high rates of winter colony mortality were searched for acaricides used to control V. destructor and plant protection pesticides. The presence of acaricides used in apiculture has been detected in the 51% beeswax samples. The most abundant acaricide was tau-fluvalinate. The stores of bee bread and sugar food had a similar frequency of plant protection pesticide occurrence, ranging between 50–60%, but the number of active substances and their concentrations were substantially lower in sugar food samples. The most prevalent pesticides in pollen were fungicides (carbendazim and boscalid) and insecticides (acetamiprid and thiacloprid). Only a few pesticides were found in the several dead honey bees. The level of pesticide contamination (frequency, concentration, toxicity) of hive products and bees originating from apiaries with both a high and low winter colony survival rates, was similar, which created a similar extent of risk. Although the multiple varroacides and pesticides were present in the hive environment we not found unequivocal links between their residues and high winter colony mortality.
... Efforts should also be made to study the metabolisation of molecules in this complex matrix particularly in the specific conditions of temperature within the hive. Interactions between different molecules contained in beeswax might have an effect on ingredient stability (Jimenez et al., 2005;Chauzat and Faucon, 2007;Serra-Bonvehía and Orantes-Bermejob, 2010). Similarly, little information about beebread was available; despite this matrix being a significant route of honey bee exposure to pesticide (AFSSA, 2008;Giroud et al., 2013). ...
Article
Losses of honey bees have been repeatedly reported from many places worldwide. The widespread use of synthetic pesticides has led to concerns regarding their environmental fate and their effects on pollinators. Based on a standardised review, we report the use of a wide variety of honey bee matrices and sampling methods in the scientific papers studying pesticide exposure. Matrices such as beeswax and beebread were very little analysed despite their capacities for long-term pesticide storage. Moreover, bioavailability and transfer between in-hive matrices were poorly understood and explored. Many pesticides were studied but interactions between molecules or with other stressors were lacking. Sampling methods, targeted matrices and units of measure should have been, to some extent, standardised between publications to ease comparison and cross checking. Data on honey bee exposure to pesticides would have also benefit from the use of commercial formulations in experiments instead of active ingredients, with a special assessment of co-formulants (quantitative exposure and effects). Finally, the air matrix within the colony must be explored in order to complete current knowledge on honey bee pesticide exposure.
... It is known that the most toxic insecticide against larvae is fenitrothion (Kanga & Somorin, 2012). However, these pesticides can leave residues; for example, treatment with coumaphos accumulates in the wax and honey, constituting a harmful residue to humans and the honey bees (Jiménez, Bernal, del Nozal, & Martín, 2005;Karazafiris, Tananaki, Menkissoglu-Spiroudi, & Thrasyvoulou, 2008). This paper proposes a simple trap for controlling SHB that uses boric acid (BA) with an attractant. ...
Article
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The small hive beetle (SHB), Aethina tumida Murray, is a parasite native to sub-Saharan Africa that does not cause further damage to African bees; in its spread to other countries with strains of bees that are vulnerable, this parasite has caused loss of hives and their products. There are few advances in obtaining SHB-resistant bee strains; hence, it is imperative to develop alternative control techniques to prevent economic losses. New apicultural practices, including periodic revisions and cultural controls for detecting and eliminating adult beetles and larvae, are only effective when they are adopted by many beekeepers within a region. In the search for a suitable treatment, this article discusses the effectiveness of an in-hive trap with boric acid (BA) and different attractants to control the spread of the SHB. Although BA is widely used as an insecticide, we observed that it is only effective when a mixture of live yeast, pineapple, and sugar is used; this attractant for adult beetles mimics the fermentation process caused by the yeast Kodamaea ohmeri associated with the beetle. Results of bioassays conducted in the city of Valladolid, Yucatan (Mexico) from June to July 2014 show that two of the proposed baits are effective for controlling SHB after 168 h as they achieve a mortality (mean ± SE) of 90 ± 3.9% and 81.67 ± 5%, respectively.
... Wax is the beehive product more likely to be contaminated by organochlorine insecticides because of its strong lipophilic character. Moreover, OCPs were proved to remain stable during the conversion of old combs into new (Jimenez et al., 2005). The problem is magnified by the import of wax from continents where the use of chlorinated hydrocarbons is still permitted like Asia and Africa. ...
Article
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The presence of residues in bee products results mainly from treatments of colonies with protection agents including acaricides and antibacterials. Lipophilic active ingredients are present in honey at very low amounts, but accumulate at ppm levels as residues in beeswax with years of treatments. Thus, beeswax could become over rime a source of residues for honey. A review of the residues found in honey and beeswax in Greece and other European countries is given and acaricides' stability in honey and wax is discussed. Also, results of the effect of different treatment procedures on the presence of fluvalinate residues in honey and wax are presented.
... Vinchlozoline, "-Cyhalothrine, Bifenthrine ont été fournis par la société LGC Promochem (Molsheim, France) et les solvants, acétone, acétonitrile, hexane de qualité Chromasolv ® ainsi que le florisil par la société Sigma-Aldrich (S t Quentin Fallavier, France). 1-Extraction de la cire L'extraction de la cire est inspirée des protocoles publiés par Korta et al. (2003) et Jimenez et al. (2005). Deux grammes de cires sont fondus dans 50 mL d'hexane puis extraits 2 fois en ampoule à décanter avec 50 mL d'acétonitrile. ...
... The most prevalent pesticide identified here was fluvalinate followed by chlorfenvinphos, probably as a consequence of the application of these acaricides by beekeepers in homemade formulae to control the Varroa mite. These compounds are persistent and cumulative compounds in beeswax (Jiménez et al., 2005), and Toxicity to bees classification based on the DL50s (mg bee -1 ) according to Johansen and Mayer (1990) † or in the Pesticide Manual (Tomlin, 1997): ‡ > 100 mg bee -1 : virtually non-toxic (VNT); 11-100 mg bee -1 : slightly toxic (ST); 2-10.99 mg bee -1 : moderately toxic (MT); ...
Article
In recent years, a worldwide decline in the Apis mellifera populations has been detected in many regions, including Spain. This decline is thought to be related to the effects of pathogens or pesticides, although to what extent these factors are implicated is still not clear. In this study, we estimated the prevalence of honey bee colony depopulation symptoms in a random selected sample (n = 61) and we explored the implication of different pathogens, pesticides and the flora visited in the area under study. The prevalence of colony depopulation symptoms in the professional apiaries studied was 67.2% [95% confidence interval (CI) = 54.6-79.8; P < 0.0001]. The most prevalent pathogen found in the worker honey bee samples was Nosema ceranae[65.6%; 95% CI = 52.8-78.3; P < 0.0001], followed by Varroa destructor[32.7%; 95% CI = 20.2-45.4; P < 0.0001] and 97.5% of the colonies infected by N. ceranae were unhealthy (depopulated). Co-infection by V. destructor and N. ceranae was evident in 22.9% (95% CI = 11.6-34.3; P < 0.0001) of the samples and only in unhealthy colonies. Of the 40 pesticides studied, only nine were detected in 49% of the stored pollen samples analysed. Fipronil was detected in only three of 61 stored pollen samples and imidacloprid was not detected in any. Acaricides like fluvalinate, and chlorfenvinphos used to control Varroa mite were the most predominant residues in the stored pollen, probably as a result of their application in homemade formulae. None of the pesticides identified were statistically associated to colony depopulated. This preliminary study of epidemiological factors suggests that N. ceranae is a key factor in the colony losses detected over recent years in Spain. However, more detailed studies that permit subgroup analyses will be necessary to contrast these findings.
... Even in a less extent, studies reporting the occurrence of several lipophilic pesticides from environmental pollution in beeswax were established. Not only acaricide contamination occurs, residues of the OC lindane, and the OCs metabolites p,p'-TDE, endosulfan sulphate and 3- phenoxybenzaldehide were found in beeswax from Spanish beehives (Jiménez et al., 2005). A wide variety of residues of OPs, synthetic pyrethroids and dicarboximide fungicides (procymidone and vinclozolin) were also detected in beeswax from France (Chauzat & Faucon 2007). ...
... Wax is the beehive product more likely to be contaminated by organochlorine insecticides because of its strong lipophilic character. Moreover, OCPs were proved to remain stable during the conversion of old combs into new (Jimenez et al., 2005). The problem is magnified by the import of wax from continents where the use of chlorinated hydrocarbons is still permitted like Asia and Africa. ...
... The most effective and widely used acaricides to control Varroa are with the pyrethroid class of insecticide tau-fluvaliniate and with the organophosphate coumaphos. However, coumaphos and fluvalinate have been detected in wax and honey (Cabras et al., 1994;Wallner, 1995;Jimenez et al., 2005), which is a threat to the food chain for humans and compromising food and cosmetic sources. Other chemical acaricides such as flumethrin, amitraz, cymiazole, and bromopropylate are also associated with toxic residues (Gamber, 1990;Wallner, 1995). ...
Article
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Serratia marcescens GEI strain was isolated from the gut of the workers of Chinese honey bee Apis cerana and evaluated in the laboratory for the control of Varroa destructor, a parasite of western honey bee A. mellifera. The supernatant and the collected proteins by ammonium sulfate from the bacterial cultures showed a strong miticidal effect on the female mites, with 100% mite mortality in 5days. Heat (100 degrees C for 10min) and proteinase K treatment of the collected proteins destroyed the miticidal activity. The improved miticial activity of this bacterial strain on chitin medium indicated the involvement of chitinases. The expressed chitinases ChiA, ChiB and ChiC1 from S. marcescens GEI by recombinant Escherichia coli showed pathogenicity against the mites in the laboratory. These chitinases were active in a broad pH range (5-9) and the optimum temperatures were between 60 and 75 degrees C. Synergistic effects of ChiA and ChiB on the miticidal activity against V. destructor were observed. The workers of both honey bee species were not sensitive to the spraying and feeding chitinases. These results provided alternative control strategies for Varroa mites, by formulating chitinase agents and by constructing transgenetic honey bees.
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To make beekeeping sustainable, the management of bee colonies to produce bee products financially viable without compromising the life of bees must implement acceptable practices such as the treatment of hives with appropriate products. Occasionally, the use of acaricides to treat the hives against varroosis is uncontrolled and can accumulate in the hives endangering the bee colonies. In this work, a screening of seven acaricides was carried out in different apiaries in Andalusia (Spain). Their distribution in beeswax, brood, honey, and bee, was evaluated in different times considering the influence of the environment (agricultural, urban and forest) surrounding the colonies. It was found that beeswax was highly polluted but honey, brood and bees had acceptable levels, below their respective MRL or LD50, past a certain period after varrocide treatments. The landscape management around the hives treated with products against Varroa does not influence the hive contamination. Acaricides banned for their use against Varroa, such as chlorfenvinphos, cypermethrin and especially acrinathrin, were found in the hives analysed.
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ÖZ Bal mumu arı kolonisinin yaşamsal faaliyetlerini üzerinde yürüttüğü peteğin ham maddesidir. Arıcılık işletmeleri için bal, polen, arı sütü ve arı ekmeği gibi bal mumu da bir arı ürünüdür. Bal mumu absorbe etme yeteneği kaynaklı kovan içi ve dışı kirleticileri bünyesinde biriktirebilmektedir. Bu şekilde kalıntı içeren peteklerden üretilen arı ürünleri insan ve arı sağlığı için risk oluşturmaktadır. Aynı zamanda eski petekler patojen mikroorganizmalar için konak işlevi görebilmektedir. Özellikle petek işleme tesisleri eski peteklerin hijyenik hale gelmesi açısından oldukça önemli bir sorumluluk taşımaktadır. Bal mumunun çok geniş bir kullanım alanı içermesi dikkatleri de üzerine çekmiştir. Gıda sektöründe kaplayıcı ajan olarak, kozmetikte sabun ve kremlerde geniş kullanımının yanısıra, tekstil, boya, kâğıt sanayinde ve sağlık sektöründe birçok alanda kullanılan bir üründür. Bal mumundan yapılan birçok süs eşyası da bulunmaktadır. Bu çalışmada bal mumu ile ilgili son çalışmalar ışığında ilgili sektörlerinde faydalanabilecekleri yeni bakış açıları sunulması amaçlanmıştır. Anahtar Kelimeler: Bal mumu, arı sağlığı, kalıntı, gıda kaplama, ABSTRACT Beeswax is the raw material of the honeycomb that the bee colony carries out in its vital activities. Beeswax is also a bee product, such as honey, pollen, royal jelly and bee bread for beekeeping. Because beeswax is an absorbent, it can collect pollutants inside and outside the hive. The bee products produced from this honeycomb pose a risk to human and bee health. Older combs can also provide shelter from pathogenic microorganisms. In particular, honeycomb processing equipments have a very important responsibility for the hygiene of old honeycombs. Beeswax attracts attention with its wide usage area. As a coating agent in the food industry, it is a product used in cosmetics, soap, candle, cream, textile, paint, paper industry, health and many other fields, such as wax sculptures. This study aims to present new perspectives that can be used in relevant fields in the light of recent studies.
Article
Marketing of adulterated beeswax foundation has recently become a major economic problem for beekeepers. Paraffin contamination leads to collapse of combs, and stearic acid has a negative influence on the development of bee brood. The quality of beeswax for beekeeping has not been standardized in EU regulations. Recently it was shown that FTIR‐ATR spectroscopy can be used to determine beeswax adulteration. B Differences in the IR spectra of authentic beeswax can be identified and calculated through comparison with authentic beeswax. In this study, the method was further validated by employing a high number of samples of authentic beeswax from different origins. Low quantification and detection limits were achieved for paraffin, stearic acid, tallow, carnauba wax and candelilla wax. Furthermore, the FTIR‐ATR analytical conditions were verified by analyzing 358 samples of commercial and beekeeper‐produced beeswax foundations. Multi‐adulterated samples with as many as five different additives in beeswax mixtures were identified with the same accuracy as single substances. Additionally, the spectra of a further 14 different natural and synthetic waxes and hardened fats were analyzed and were compared with beeswax. Finally, a spectral library was established that can be used for further studies. Practical applications: FTIR‐ATR is a fast and cost‐efficient tool in beeswax analysis for accurately monitoring a high sample volume. Analysis of 358 beeswax foundations showed an adulteration of 21.8% of the samples with paraffin, stearic acid, tallow and combinations. Based on the results of this study it is possible to detect beeswax adulteration of less than 3% of these adulterants and their combinations by FTIR‐ATR spectroscopy. This method can be used for monitoring beeswax foundations to identify adulterated materials, exclude these material from the recycling process, and produce a high quality beeswax, which is essential for bee health. This article is protected by copyright. All rights reserved
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Pesticides plays an important role in the development of agriculture, it can not only improve the security of agricultural products and increase the production, but also promote the quality of the products. However, the using of pesticides has brought a lot of serious pollutions on agricultural products and food safety issues as well. This paper summarized the physical techniques and their applications in degrading pesticide residues in agricultural products, including illumination, ultrasonic wave, ionizing radiation; low temperature plasma, high pressure, washing and heating, etc. evaluated their research progress, the influential factors of applied techniques, and the scopes of their application. It might provide some ideas or methods for the effective degradation of pesticide residues by physical techniques and ensure the security of agricultural products.
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Bees are important pollinators of both managed crops and wild flora. An overview of the interactions between pesticides and other factors in effects on bees considered: 1) The importance of the different exposure routes in relation to the overall exposure of bees to pesticides; 2) Multiple exposure to pesticides (including substances used in bee medication) and potential additive and cumulative effects; and 3) Interactions between diseases and susceptibility of bees to pesticides. Nectar foraging bees are likely to experienced highest exposure to both sprayed and systemic seed and soil treatments compounds followed by nurse and brood-attending bees. In both cases the major contribution to exposure was contaminated nectar with direct overspray playing a significant role in exposure. However, there are a variety of other routes (and other bee species) where there is currently insufficient data to fully total exposure: There are a large number of studies that have investigated the interactions between pesticides in bees. By far the majority have related to the interactions involving EBI fungicides and can be related to their inhibition of P450. The scale of the synergy is shown to be dose and season-dependent in acute exposures but there are few data relating to the effect of time between exposures, the effect of route of exposure or on chronic exposure effects at realistic exposure levels. There are a wide range of factors which affect the immunocompetence of bees including diet quality, pest and diseases. Although there are a limited number of laboratory based studies which suggest effects of a pesticide on disease susceptibility there is no clear evidence from field-based studies that exposure of colonies to pesticides results in increased susceptibility to disease or that there is a link between colony loss due to disease and pesticide residues in monitoring studies.
Technical Report
The PPR Panel was asked to deliver a scientific opinion on the science behind the development of a risk assessment of plant protection products on bees (Apis mellifera, Bombus spp. and solitary bees). Specific protection goals options were suggested based on the ecosystem services approach. The different routes of exposure were analysed in detail for different categories of bees. The existing test guidelines were evaluated and suggestions for improvement and further research needs were listed. A simple prioritisation tool to assess cumulative effects of single pesticides using mortality data is suggested. Effects from repeated and simultanous exposure and synergism are discussed. Proposals for separate risk assessment schemes, one for honey bees and one for bumble bees and solitary bees, were developed.
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We developed a method for the hydrolysis of amitraz, and its degradation products 2,4-dimethylphenyl-N'-methylformamidine (DMPF) and 2,4-dimethylformamide (DMF) into 2,4-dimethylaniline (DMA), directly from QuEChERS extracts. The hydrolysis product DMA was analysed using liquid chromatography-electrospray tandem mass spectrometry (LC-ESI-MS/MS) in the positive ion mode with DMA D6 as an internal standard. Validation of DMPF and amitraz via DMA, following hydrolysis directly from the QuEChERS raw extracts, was performed at 0.05mgkg(-1) and at 0.5mgkg(-1). Individual recoveries of amitraz and DMPF, determined as DMA, ranged between 100 and 120% and between 96 and 118% respectively and the relative standard deviations (RSDs) below 5.2% and below 9.5% respectively (n=5 at each spiked level). Successful validation for amitraz, and DMPF at 0.01mgkg(-1), was also conducted following fivefold pre-concentration of QuEChERS extracts prior to hydrolysis. Pear samples with a history of amitraz treatment, containing residues of the amitraz metabolite DMPF but no detectable residues of amitraz or its other metabolites, DMF and DMA, were extracted using the QuEChERS method. DMPF-results obtained using direct LC-MS/MS analysis were found to be comparable with DMA-results obtained when the same extracts were subjected to alkaline hydrolysis, suggesting that DMPF constituted virtually the only source of DMA in the analysed pears and that the determination of amitraz (sum) in pears does not necessarily require a cumbersome method involving cleavage to DMA.
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In the last decade, an increase in honey bee (Apis mellifera L.) colony losses has been reported in several countries. The causes of this decline are still not clear. This study was set out to evaluate the pesticide residues in stored pollen from honey bee colonies and their possible impact on honey bee losses in Spain. In total, 1,021 professional apiaries were randomly selected. All pollen samples were subjected to multiresidue analysis by gas chromatography-mass spectrometry (MS) and liquid chromatography-MS; moreover, specific methods were applied for neonicotinoids and fipronil. A palynological analysis also was carried out to confirm the type of foraging crop. Pesticide residues were detected in 42% of samples collected in spring, and only in 31% of samples collected in autumn. Fluvalinate and chlorfenvinphos were the most frequently detected pesticides in the analyzed samples. Fipronil was detected in 3.7% of all the spring samples but never in autumn samples, and neonicotinoid residues were not detected. More than 47.8% of stored pollen samples belonged to wild vegetation, and sunflower (Heliantus spp.) pollen was only detected in 10.4% of the samples. A direct relation between pesticide residues found in stored pollen samples and colony losses was not evident accordingly to the obtained results. Further studies are necessary to determine the possible role of the most frequent and abundant pesticides (such as acaricides) and the synergism among them and with other pathogens more prevalent in Spain.
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Acaricides are applied in agriculture as phytosanitary products against pests and in apiculture to control the bee parasite Varroa destructor. Poor apicultural practices could result in an accumulation of residues in honeybees, in the environment, and in beeswax and other bee products by migration from the wax comb into stored honey through a process of diffusion and consequently constitute a potential risk for humans. In this study, six different types of beeswax samples were analysed for the determination of residues of fluvalinate, coumaphos, and bromopropylate and its metabolite 4,4'-dibromobenzophenone, all of which are the most commonly acaricides used by Spanish beekeepers against V. destructor. The analytic method consists of solid-phase extraction on a SPE Florisil cartridge and high-performance liquid chromatography separation using a photo diode array detector. The results show that fluvalinate residues were detected in 36.3% of samples, ranging from 1.2 to 6.6 microg/g wax. Residues of coumaphos, bromopropylate, and 4,4'-dibromobenzophenone were not found to be greater than their detection limits. This study indicates that the analysis of these compounds in beeswax samples could be used as bioindicators of fluvalinate sanitary treatment and handling practices applied by beekeepers.
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36 honey samples collected from colonies of Apis mellifera in apiaries and from combs of the wild honey bees A. dorsata and A. florea were analysed by gas liquid chromatography for insecticide residues. More apiary honeys were contaminated with organochlorines and organophosphates, usually at higher concentrations, than were honeys produced by wild Apis species. The most common contaminants were HCH (hexachlorocyclohexane or benzenehexachloride (BHC), detected in 83.3% of samples), endosulfan (69.4%), aldrin (36.1%) and quinalphos (33.3%). Overall mean residue levels (ppb) in honey from all species and samples combined were: acephate (153.9), aldrin (1.4), chlorpyriphos (6.6), DDT (0.6), dimethoate (7.1), endosulfan (2.5), HCH (84.9), heptachlor (1.3), malathion (15.3), methyl-parathion (2.2) and quinalphos (66.3). Carbaryl (a carbamate group insecticide) was detected in one honey sample each of A mellifera (901.8 ppb) and A florea (800.0 ppb). The studies reflect the potential contamination of honey by agricultural chemicals.
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Para-dichlorobenzene (PDCB) is an insecticide used in beekeeping for wax moth control. Analysis of PDCB residues were carried out on Swiss retail market honey samples by the cantonal food control authorities in 1997, 1998, 2000, 2001 and 2002. 173 Swiss honeys and 287 imported samples were analysed. On average, 30% of the Swiss honeys contained PDCB, 13% of them being above the Swiss tolerance value of 10 mug/kg. On the other hand, only 7% of the imported honeys were contaminated. The minimum values were 2 mug/kg, the maximum ones 112 mug/kg. Long-term monitoring of Swiss beeswax, carried out from 1993 to 2000, showed that most of the comb foundation beeswax produced in Switzerland is contaminated by PDCB with values ranging from one to 60 mg/kg. The results show that the reason for this contamination is the use of PDCB for the control of wax moth. These residues can be avoided as wax moth can be controlled successfully with alternative methods, carried out according to good apicultural practice.
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In Switzerland the acaricides Folbex VA (bromopropylate, BP), Perizin (coumaphos, CM), Apistan (fluvalinate, FV) Bayvarol (flumethrin, FM) are used for varroa control. We studied the contamination level of BP, CM and FV in brood and honey combs, sugar feed and honey after field trials. In samples of recycled pure beeswax and propolis, gathered by beekeepers, we examined the level of all four acaricides. All samples were analysed by gas chromatography with ECD detection. After one normal acaricide treatment in autumn the brood comb was contaminated by BP, CM and FV with residues ranging from 1.8 to 48 mg/kg. The residue level in the honeycomb wax was on average 5 to 10 times lower than in the brood combs. The residues in the combs increased with increasing number (Folbex) or longer duration of treatment (Apistan). The residues in the sugar feed and honey were much lower than in the combs and were all below the Swiss MRL (maximum residue limit). In a laboratory experiment we examined the behaviour of the acaricides during the recycling of old combs into new beeswax. The acaricide concentration in the new recycled wax was on average 1.7 times higher than in old combs under all conditions (longer boiling times or higher temperatures). Since 1991 we have been studying the contamination level of the acaricides in all recycled Swiss beeswax. All commercial samples contain BP, CM and FV in varying amounts. Between the years 1993 and 1996 the residues varied between 2.4 and 4.3 for BP, 0.7 and 1.3 for CM and 1.9 and 2.9 for FV. No flumethrin (FM, a.i. in Bayvarol) above the detection limit of 0.25 mg/kg was found. All but one propolis sample (n = 27) gathered in 1996 contained FV (average 9.80 mg/kg), 10 contained BP (average 1.17 mg/kg) and two of them FM (average 2.54).
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This article concentrates on the main quality issues of Apis mellifera beeswax: production by bees and processing by beekeepers and manufacturers, overall chemical composition, as well as sensory and physicochemical characteristics. The main quality issues today are adulteration and contamination. Contamination from the environment being relatively small, the main contaminants are synthetic and persistent acaricides used in beekeeping. Measures for prevention of contamination are discussed. Information on beeswax economy, as well as on beeswax uses is given.
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A number of mite infestation control products (Amitraz, Bromopropylate, Fluvalinate, Thymol) were used over a 3-year period (1987-1989) to control Varroa jacobsoni infestation by means of colony treatment in autumn. Treatment was given to 171 hives located in the plains area of the Emilia Romagna region in northern Italy. The residual levels of each product were measured in the honey, wax and adult bees. The samples were taken from each hive in March, May, July and August in the year following treatment. Chemical analysis via gas chromatography showed that: 1), bromopropylate, thymol and fluvalinate persisted in wax samples; 2), bromopropylate and thymol were present in honey samples from the brood chamber. None of the products was found in honey from the supers.
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In general, the use of varroacides in bee colonies leaves residues in various bee products. Among the variety of available varroacides, three ingredients are commonly detectable in honey and beeswax: bromopropylate (Folbex VA Neu), coumaphos (Perizin, Asuntol) and fluvalinate (Apistan, Klartan, Mavrik). These chemicals are fat-soluble and non-volatile, and thus they accumulate in ppm levels as residues in beeswax with years of treatment. Through the process of diffusion, these ingredients migrate from the wax comb into the stored honey. In German honey, the most frequently found varroacide is coumaphos (28 %). Bromopropylate is detectable but with decreasing frequency (11 %). Because of its high binding strength in beeswax, fluvalinate detection is relatively rare in honey (1 %). All residues were found with low ppb levels. Other ingredients with similar chemical behaviour presently play an unimportant role as residues in honey, beeswax and propolis owing to the very low amount of ingredients used (acrinathrine, flumethrine) or instability (amitraz). © Inra/DIB/AGIB/Elsevier, Paris
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Contrast constancy across changes in mean luminance was reported to hold over a wide range of luminances in a few studies and to be limited to approximately 1 log unit in another. The studies reporting contrast constancy over a wide luminance range used extended grafting stimuli presented dichoptically (bright stimulus to one eye and dim stimulus to the other) with long adaptation periods. The study reporting only limited constancy used narrow (1-octave-wide) Gabor patches presented side by side to both eyes with only a short (up to 5 s) period of adaptation. The current study was designed to determine whether differences in stimulus bandwidth, presentation format, or adaptation time could account for the different results reported. It was found that increasing stimulus size had no effect on the results. Dichoptic presentation with either a filter in front of one eye or calibrated screen luminance could account for the differences between the studies. When dichoptic presentation was combined with short adaptation periods (of a few seconds) an intermediate deviation from constancy was demonstrated. This effect suggests that the deviations from constancy demonstrated under free viewing are due to a lack of fast local adaptation and not to long-distance interactions across the retina.
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A simple, rapid, and accurate method is described for the determination of residual fluvalinate in beeswax. The procedure consists of partitioning on a disposable column of diatomaceous earth (Extrelut), followed by chromatographic cleanup on a Florisil cartridge. The final extract is analyzed by capillary gas chromatography with electron-capture detection (GC-ECD). Briefly, wax samples were dissolved in n-hexane, and the solutions were sonicated and transferred to Extrelut columns. The fluvalinate was extracted with acetonitrile, and a portion of the extract was cleaned up on a Florisil cartridge. The fluvalinate was eluted with diethyl ether-n-hexane (1 + 1) and directly determined by GC-ECD. Recoveries from wax samples spiked at 5 fortification levels (100-1500 microg/kg) ranged from 77.4 to 87.3%, with coefficients of variation of 5.12-8.31%. The overall recovery of the method was 81.4 +/- 3.2%, and the limit of determination was 100 microg/kg.
Article
Since 1986 perizin has been used in many European countries to combat the mite Varma jacobsoni, a parasite of the honeybee. We have studied the long-term presence of coumaphos, the active ingredient of perizin, by analyzing honey and wax for residues. We distinguished between the direct transfer of coumaphos into wax by contamination during treabnent and the indirect transfer through wax production by bees. To study the indirect transfer, we treated colonies with perizin and removed the combs, thus forcing the bees to produce new wax. The newly produced wax and honey were analyzed for the presence of coumaphos. Wax from colonies that had not been treated with perizin for 6 mo and up to 18 mo still contained coumaphos (7 and 1 μg/g wax, respectively). Moreover, newly produced wax from the colonies that had not been treated with perizin for 6 mo also contained coumaphos (≍17% of the amount found in old wax). No residues were found in honey. Only small amounts of coumaphos (±l‰ of the amount administered) were found in newly produced wax when colonies were fed a perizin-sugar solution. The largest amounts of contamination were found in the first samples secreted; samples taken 3-4 d after application contained only 1-5% of the amount secreted on the 1st d. Coumaphos is transferred mainly into the wax directly as a consequence of the application of perizin to combs, and the acaricide is persistent in the wax.
Article
Multiple pesticides were simultaneously present in dead honey bees, Apis mellifera L., or in brood comb in 28 of 55 poisoned apiaries in Connecticut in 1983-85. Methyl parathion (Penncap-M), carbaryl, and endosulfan were each detected in 34, 33, and 13 of the apiaries, respectively. Less frequently detected pesticides were methomyl, chlordane, diazinon, captan, and malathion. Health of colonies poisoned with methyl parathion only or methyl parathion in combination with other insecticides was often severely affected (141 of 168 poisoned colonies were either killed or weakened), whereas colonies affected by carbaryl only or carbaryl plus insecticides other than methyl parathion often recovered (16 of 79 poisoned colonies were either killed or weakened). One-half of the poisonings occurred in July. Aroclor 1248 and 1260 (polychlorinated biphenyls) were detected in dead bees, brood comb, honey comb, or honey. Environmental sources of these chlorinated hydrocarbons are unknown. Detectable quantities of polychlorinated biphenyls ≥0.80 ppm were in 4 of 71 honey samples.
Article
A comparative study on several extraction/clean-up procedures to determine total amitraz residues in beeswax is presented. The procedures are tested on samples spiked with amitraz, N-(2,4-dimethylphenyl)-N′-methylformamidine (DPMF) and 2,4-dimethylaniline (DMA) at two concentration levels. The extraction with methanol followed by a partitioning with n-hexane seems to be the most adequate procedure in terms of recovery (about 80%) and precision (R.S.D. lower than 15%). The analytes in the extracts are determined by GC/ECD after their hydrolysis to DMA and subsequent formation of the heptafluoro-N-(2,4-dimethylbenzene)-butanamide.
Article
A method is reported for the first time for the determination in beeswax of several acaricides used for the control of the bee parasite Varroa destructor. The method was optimized and validated for amitraz residues in wax and was applied to the determination of other acaricides: bromopropylate (BP), chlordimeform, cymiazole and chlorfenvinphos. It consists of a methanol extraction step, cleanup by solid-phase extraction (SPE) with octadecylsilica and determination by capillary gas chromatography–mass spectrometry (GC–MS) using selected ion monitoring (SIM) detection. The limits of detection for the different substances were between 0.02 and 0.2 mg/kg, and the recoveries, between 40 and 95%.
Article
Several samples of commercial grade honey collected from different parts of tennessee during the summer of 1973 were analyzed for chlorinated hydrocarbon insecticide (CHI) residues. A "Modified Mill's Procedure" was used to cleanup the samples prior to gas chromatographic analysis using electron capture (EC) detection. The presence of CHI residues was confirmed by analysis on three different columns of widely varying polarity. Most of the samples contained CHI residues at 0.01-0.30 parts per billion (ppb) level. Beeswax produced during the same season contained several times higher levels of the residue than the honey samples. Recoveries of CHI residues varied from 81-95 percent by the procedure employed.
Article
Organochlorines are ranked among the class of prevalent and environmentally persistent synthetic chemicals. Honey bees, beeswax, and honey could be indicators for monitoring environmental pollution by organochlorines such as polychlorobiphenyls (PCBs) and organochloro pesticides. Scarcely any data were reported on the distribution of organochloro compounds between beeswax and honey. Physicochemical factors such as adsorption, volatilization, lipophilicity (octanol-water partition coefficient) and metabolic stability can influence the level of individual organochlorine compounds in beeswax and honey. During wax and honey formation metabolic attack by different enzymes can degrade pollutants. In the PCB and chlorobenzene (CBz) series, biodegradation decreases and bioconcentration increases with increasing degree of chlorine substitution. Regarding the composition of honey (sugars, water, and some organic material and particles such as pollen, organic acid and essential oils in traces), and of beeswax (esters, hydrocarbons, acids and some natural wax from plants as minor components), it is expected that beeswax is more lipophilic and organochlorines could be more enriched in beeswax. However, the presence of particulate matters (e.g., pollen) in honey can increase the level of nonpolar compounds in honey due to sorption processes. This effect has been demonstrated in a similar system where suspended particles can influence the partition coefficient. In this contribution (i) the partition between beeswax and honey of some organochlorine compounds (PCB and CBz isomers, DDE) and (ii) bioconcentration in beeswax and honey from a feeding experiment by administration to honey bees of feed fortified with these compounds is presented and discussed. 17 refs., 3 figs., 1 tab.
Article
A procedure involving an extraction step and further gas chromatographic analysis with flame ionization detection to determine residues of acrinathrine and its main metabolite, 3-phenoxybenzaldehyde, in honey is proposed. Residues can be isolated from the matrix by means of liquid-liquid extraction with a mixture of benzene-isopropanol, by solid-phase extraction with octadecylsilane cartridges or Florisil packed columns, the latter method giving higher recoveries. Assays on spiked honey samples are carried out to test the procedures that are afterwards applied to honey samples from treated beehives.
Article
A study on the possible degradation of amitraz, bromopropylate, coumaphos, chlordimeform, cymiazole, flumethrin, and tau-fluvalinate during the storage of honey was carried out by HPLC. Except amitraz, the other acaricides are stable in this medium for at least 9 months. Degradation studies of amitraz in honey and beeswax were carried out; the degradation products detected in both matrices were 2,4-dimethylphenylformamide (DMF) and N-(2,4-dimethylphenyl)-N'-methylformamidine (DPMF). The reaction rate constants and the half-lives of the amitraz degradation in honey and wax were calculated. Amitraz was nearly completely degraded within 1 day in beeswax and within 10 days in honey. When amitraz-spiked combs are recycled into new beeswax, DMF was found to be the principal degradation product left in pure wax.
Article
A study about the most adequate conditions for the determination of the amitraz total residues in honey by gas chromatography is presented. Solvent and solid phase extraction procedures as well as the influence of several parameters on the extraction, hydrolysis and derivatization steps are considered. Solid phase extraction on ODS cartridges was found to be not reliable for the determination of total residues, because recovery for 2,4-dimethylaniline (DMA) was poor. Liquid-liquid extraction with hexane was accomplished in a single step and was more reproducible. The pH of the aqueous solution had to be set at pH 11 to achieve extraction of DMA. The derivatization of DMA with heptafluorobutyric anhydride (HFBA) was practically instantaneous at room temperature.
Article
Analytical methods for the simultaneous analysis of lindane, chlorpyriphos, z-chlorfenvinphos, endosulfan A and B, 4,4'-DDE, 4,4'-TDE, acrinathrine, bromopropylate, tetradifon, coumaphos and fluvalinate in pure beeswax samples are studied. For the analysis of bleached beeswaxes, a liquid-liquid extraction with acetonitrile followed by a clean-up on polymeric cartridges is the best option in terms of recovery and precision. However, some interferences that hinder the identification and quantification of important varroacides are found when non-bleached beeswaxes are analyzed. The analysis of all compounds in the latter samples require a clean-up by coupling an ODS cartridge before the polymeric cartridge. Considerations about the influence of the matrix in the quantitative analysis by a classical external standard calibration are also made and the use of a matrix-matched calibration is advised. Recoveries resulted to be about 100% with coefficients of variation between 10% and 20% (n = 5) for concentrations of 0.5 and 5 mg/kg.
Vorwohl: Determina-tion of bromopropylate, 4,4-dibromobenzophenone, cou-maphos and fluvalinate in beeswax
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The actual beeswax quality in foundations in the market
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Acaricide residues in beewax and organic beekeeping
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M. Lodesani, C. Costa, M. Bigliardi, R. Colombo: Acaricide residues in beewax and organic beekeeping. Apiacta. 2003, 38, 31–33.
The effect of fluvalinate applications in bee colonies in populations levels of Varroa jacobsoni and honey bees (Apis mellifera L) and on residues in honey and wax. Bee Science
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Y. Slabezki, H. Gal, Y. Lensky: The effect of fluvalinate applications in bee colonies in populations levels of Varroa jacobsoni and honey bees (Apis mellifera L) and on residues in honey and wax. Bee Science. 1991, 1, 189–195.
Gas chromatographic determination of bromopropylate residue in honey, beeswax and propolis after treatment of bee colonies with Folbex VA NEU. Tierärztl Umsch
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Gas chromatographic determination of bromopropylate residue in honey, beeswax and propolis after treatment of bee colonies with Folbex VA NEU
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Acaricide residues in beewax and organic beekeeping
  • Lodesani M.
Bestimmung der Rückstände von Fluvalinat in belgischem Honig und Bienenwachs
  • De Greef M.
The effect of fluvalinate applications in bee colonies in populations levels of Varroa jacobsoni and honey bees (Apis mellifera L) and on residues in honey and wax
  • Slabezki Y.
Determination of bromopropylate, 4,4‐dibromobenzophenone, coumaphos and fluvalinate in beeswax
  • Zimmermann S.
Apitol‐Zulassung zwischen den Zeilen gelesen
  • Wallner K.
Acrinathrin, an effective varroacide and its residues in stores, honey and wax
  • Vesely V.
Rückstandsuntersuchungen von Bienenprodukten Wachs, Honig und Pollen
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Determination of bromfenvinphos in bee products. Part II. Beeswax and propolis
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