Determination of neonicotinoids in Estonian honey by liquid chromatography–electrospray mass spectrometry

The aim of the study was to provide a comprehensive overview of neonicotinoid pesticide residues in honey samples for a single country and compare the results with the import data for neonicotinoid pesticides. The levels of four neonicotinoid pesticides, namely thiamethoxam, imidacloprid, acetamiprid, and thiacloprid, were determined in 294 honey samples harvested from 2005 to 2013 from more than 200 locations in Estonia. For the analyzed honey samples, 27% contained thiacloprid, and its levels in all cases were below the maximum residue level set by the European Union. The other neonicotinoids were not detected. The proportion of thiacloprid-positive samples for different years correlates well with the data on thiacloprid imports into Estonia, indicating that honey contamination with neonicotinoids can be estimated based on the import data.     

Determination of Heavy Metals in Honey in Kahramanmaraş City, Turkey

Heavy metals in honey are of interest not only for quality control, but also for determination environmental contamination. The objective of this work was to determine distribution of the levels of selected heavy metals. Levels of copper (Cu), cadmium (Cd), manganese (Mn), Iron (Fe), magnesium (Mg) and nickel (Ni) in honey samples (21) in Kahramanmaraş region were determined by atomic absorption spectrometer (AAS). The mean values for Cu, Cd, Mn, Fe, and Mg were 0.01, 0.32, 0.03, 0.36 and 10.45 ppm, respectively. Nickel was not detected in honey samples. Kahramanmaraş honey samples were not free of heavy metals but the levels of them were found well below the permitted levels. The results suggested that honey may be useful for assessing the presence of environmental contaminants.     

Antiradical activity of natural honeys and antifungal effect against Penicillium genera

The purpose of the study was to examine the antiradical activity of 11 natural honeys and to evaluate the antifungal properties of honey. Honey samples (10) were collected from different locations of Slovak Republic. Honeys were native to different plant species of Robinia pseudoacaccia, Brassica napus subs. napus, Castanea sativa Mill. Thymus serpyllum vulgaris and the other samples had multifloral origin. The low antiradical activitity in honey samples was determined. The best results were found in thyme honey from Rhodos (11.84 %) and Castanea honey from Nitra (10.61 %). The lowest antiradical activity was found in Acacia honey and determined to be 7.62 %. Statistically significant differences (P< 0.001) were found among thyme/Rhodos and Castanea/Nitra. The antifungal activities of honey samples were tested by 10 %, 25 % and 50 % (by mass per volume) concentration against fungi Penicillium crustosum, P. expansum, P. griseofulvum, P. raistrickii and P. verrucosum and by the agar well diffusion method. The solutions containing 10 % (by mass per volume) of honey did not have any effect on the growth of fungi. The strongest antifungal effect was shown by 50 % honey concentration against P. raistrickii.     

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

A 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.     

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

In 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.     

The transfer of active ingredients of insecticides and fungicides from an orchard to beehives

This investigation was undertaken to determine whether active ingredients (AIs) of currently recommended plant protection products (PPPs) could be transferred to beehives from apple and pear trees. A field trial was carried out with apple trees of Ligol and Idared variety, and pear trees of Conference variety. For pest and diseases control of fungal origin, recommended PPPs were applied. Samples of flowers from the above-mentioned varieties of fruit trees, of bees, brood and honey from beehives located in their direct neighborhood were collected regularly and analyzed for the presence of lambda-cyhalothrin (an insecticide) and cyprodinil, captan, fluopyram, kresoxim-methyl, penthiopyrad and trifloxystrobin (fungicides). In samples of flowers of Ligol variety, fluopyram residues (on average 0.621 µg single flower^?1) were at the highest levels, whereas in samples of pear flowers of Conference variety, and in flowers of Idared variety, captan residues (on average, respectively, 0.705 and 165.7 µg single flower^?1). In samples of bees and honey, residues of five AIs were detected, and in brood six AIs, whereby in each case captan residues prevailed, respectively, up to 585.2, 51.52 and 126.5 µg kg^?1 bees and honey. In the honey, significantly larger residues of captan were found out than maximum residue level (MRL) for this AI – 103.04% MRL. In the case of any AI, the daily intake did not exceed 0.002% acceptable daily intake (ADI).     

Tualang honey supplementation improves oxidative stress status among chronic smokers

Free radicals induced by cigarette smoking have been linked to an increase in oxidative stress resulting in smoking-related cardiovascular diseases. However, the possible effect of honey that has antioxidant property in improving oxidative stress status among smokers has not yet been reported. Hence, this study was to determine the effects of 12-week Tualang honey supplementation on F₂-isoprostanes, superoxide dismutase, glutathione peroxidase, catalase, and total antioxidant status among chronic smokers. A total of 32 non-smokers and 64 chronic smokers were recruited from Quit Smoking Clinic and Health Campus, Universiti Sains, Malaysia. Smokers were randomized into two groups (n = 32/group) namely smokers without supplementation and smokers with honey supplementation (20 g/day) for 12 weeks. Blood was obtained from non-smokers and smokers at pre-intervention and from smokers at post-intervention. During pre-intervention, the levels/activity of F₂-isoprostanes, total antioxidant status, and catalase were significantly higher while superoxide dismutase and glutathione peroxidase were lower in smokers than non-smokers. During post-intervention, in supplemented smokers, there were significant decrease in F₂-isoprostanes and increase in total antioxidant status, glutathione peroxidase and catalase levels/activities compared with pre-intervention. This study indicates that honey supplementation improves oxidative stress status suggesting a beneficial role of honey in reducing the risk of cardiovascular diseases.     

Quality of Meliponinae honey: Pesticides residues,pollen identity,and microbiological profiles

This study aims at evaluating the quality of honey of Melipona quadrifasciata quadrifasciata Tetragonisca angustula and Scaptotrigona depilis. Pollen analysis was performed to identify the floral resources used for the production of honey, and 19 pollen types were identified. Microbiological analyses identified the presence of coliforms, molds, and yeasts, but Clostridium botulinum was not found. Using the modified “Quick, Easy, Cheap, Effective, Rugged, and Safe” method followed by ultra‐high performance liquid chromatography‐tandem mass spectrometry determination, eight pesticides were detected in the honey of T. angustula and only two in the honey from S. depilis. The honey of M. q. quadrifasciata did not present pesticide residues. The data pointed out the relevance of good practices to avoid the contamination of honey with sources of microbiological contaminants, which may impair the product's safety for human consumption.     

蜂蜜中氯霉素残留的检测及净化方法研究

建立了反相高效液相色谱-离子阱质谱法检测蜂蜜中氯霉素残留的方法.前处理采用改良的QuEChERS方法进行快速提取和净化.采用初级次级胺进行固相分散净化,可有效吸附蜂蜜中的糖类及有机色素等杂质.提取物在流动相甲醇:水(0.2%乙酸胺)=45:55(体积比)中,用整体色谱柱进行快速分离和质谱检测.并对MS检测中2种离子化方式(电喷雾ESI及大气压化学APCI)、各种离子化方式下正负离子模式及离子检测方法(总离子检测TIC和选择性离子监测MRM)进行了综合比较,最终确定采用电喷雾电离法(ESI)负离子模式、多反应离子监测(MRM)对氯霉素进行定性定量分析.在0.2～200μg/kgg添加浓度下,添加回收率水平在78%～93%间,变异系数在3.9%以下.该方法的检出限为0.1μg/kg,在0.1～100 μg/L浓度范围内,线性方程为y=58.753x 34867,相关系数R2=0.999 5.     

Different policing rates of eggs laid by queenright and queenless anarchistic honey-bee workers (<Emphasis Type="Italic">Apis mellifera</Emphasis> L.)

Worker-reproduction is rare in queenright honey-bee colonies. When workers do lay eggs, their eggs are normally eaten by other workers presumably because they lack the queen's egg-marking signal. Workers use the absence of this queen signal to enforce the queen's reproductive monopoly by policing any worker-laid eggs. In contrast, in anarchistic colonies, the majority of the males arise from worker-laid eggs. Anarchistic worker-laid eggs escape policing because workers perceive anarchistic eggs as queen-laid. However, in this study, we show that eggs laid by queenless anarchistic workers do not escape policing and have very similar removal rates to worker-laid eggs from queenless wild-type (i.e. non-anarchistic) colonies. This suggests that, under queenless conditions, eggs laid by anarchistic workers lose their chemical protection and are therefore no longer perceived as queen-laid. Hence, the egg-marking signal seems to be only applied to eggs when queen and brood are present. This suggests that in the absence of queen and brood, the biosynthetic pathway that produces the egg-marking signal is switched off.Communicated by L. Keller