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In the period between 2014 mid-2017, more than 200 samples of honeybees were sent by authorities and individuals in Benaki Phytopathological Institute after incidents of unexpected deaths of bees in various parts of Greece. The samples were analyzed for pesticides and breakdown products, by two multi-residue methods based on an expanded HPLC-ESI-MS/MS and a newly developed GC-MS/MS method. Sample preparation was optimized and based on modified QuEChERS using for clean-up C18 and PSA. Until mid-2017, 293 detections were registered in a total of 205 honeybee samples, resulting in a 76% percent of positive samples, to at least one active substance. Concentrations’ range varied from 1 to 160000 ng/g bee body weight . In some cases, these levels surpassed LD 50 values indicating intoxication events. Predominant substances were clothianidin, coumaphos, imidacloprid, acetamiprid and dimethoate. In less extent, other acaricides such as amitraz (mostly its breakdown products DMF, DMPF), tau-fluvalinate and certain pyrethroids exemplified by cyhalothrin, cypermethrin and deltamethrin were also recorded. In several samples, more than one active substance was detected. Overall, this work aspires to provide valuable insight to pesticides and metabolites occurrence in honeybees in Greece between 2014-2017 and in parallel assist research community and apiculturists in this pivotal Mediterranean region that bee health and pollination services have prolific importance.

A human intoxication incident attributed to pesticide abuse was investigated using cutting-edge analytical methodologies. An LC-ESI-MS/MS method, based on a hybrid solid-phase extraction protocol (hybrid-SPE), was applied for the detection and quantification of several pesticides and metabolites in human biological fluids. Concomitantly, an UHPLC-HRMS method was applied to investigate potential metabolites, assisted by a complementary GC-MS method to elucidate the presence of plausible pesticides co-formulants. The LC-ESI-MS/MS method exhibited acceptable mean recoveries at the lower limit of quantification (LLOQ) and three additional levels, varying from 85 to 106% for all analytes and matrices. In serum, urine, and gastric fluid samples, the suspect compounds, namely chlorpyrifos and myclobutanil, predominated. Gastric fluid samples contained the highest concentrations of chlorpyrifos (39,800 ng/mL) and myclobutanil (18,800 ng/mL), while the neonicotinoid imidacloprid was also quantified, below 30 ng/mL. Notwithstanding, the UHPLC-HRMS analysis unveiled several metabolites of chlorpyrifos and myclobutanil. In parallel, GC-MS analysis, corroborated the presence of several co-formulants in gastric fluid samples, exemplified by m- and o-xylene, and cyclohexanone. Overall, three analytical methods were implemented to elucidate the chemical causality of a human intoxication incident. The presence of suspected active substances, one additional, and several metabolites and co-formulants were documented.

The monitoring of contaminants in fish species is pivotal for fishes' health and reproduction, as well as for human health. In the specific work, three major categories of contaminants, pesticides, pharmaceuticals, and macro and trace elements, were investigated in two major fish species, Dicentrarchus labrax and Solea solea, collected from Thermaikos Gulf, in Greece. To achieve this goal, three analytical methods using LC-MS/MS, GC-MS/MS, and ICP-MS were developed, validated, and applied to the collected fish samples. The results indicated a very low prevalence of caffeine and acetaminophen, both not exceeding 3.8 μg/kg fish. Similarly, thiabendazole, cypermethrin, and tricyclazole (pesticides) were found in a concentration range of 0.9 to 13.7 μg/kg fish, while in one D. labrax sample, traces of the metabolite of organochlorine pesticide DDT, o,p'-DDE were detected. Al, Mn, Fe, Zn, and Sr were the predominant trace elements in a concentration range of 500–20,000 μg/kg fish. Macro elements levels varied from 280 to 5405 mg/kg fish. Health risk assessment did not unveil an unacceptable risk for the human health of adults, apart from one sample presenting Hg above the regulatory levels. On the contrary, for children, the calculated hazard quotient values for Hg in all cases and for two As detections were higher than the threshold value of 1, indicating a potential risk. [ABSTRACT FROM AUTHOR]

Legumes provide nutritious floral resources for bees thus are commonly considered for use in schemes to enhance pollinators in agroecosystems. In particular, legume landraces are important elements in practices towards sustainable agriculture. Differences in flower morphology and nectar may affect the attraction of pollinators. The aim of the present study was to investigate possible differences in pollinator attraction between a Vicia faba L. landrace and a commercial variety and to indicate differences in floral characteristics and nectar quality traits which can be associated with bee visits. To assess this, floral morphological trait measurements and chemical analysis using high‐resolution mass spectrometry‐based non‐targeted screening of the flower nectar were carried out and bee visits on faba bean flowers were recorded. Floral traits that contributed to the separation of the two accessions were 'intensity of streaks' and 'extent of anthocyanin colouration' on standard petal which were more pronounced in the landrace. All nectar traits examined contributed to the separation of the two V. faba accessions. Chemical substances such as amino acids and sugars which are important for bee nutrition are differentially increased in the landrace compared with the commercial variety. The landrace attracted more bee genera (Apis, Anthophora, Eucera) and bee visits compared with the commercial variety (only Eucera) supporting that the floral and nectar differences between the accessions of the same plant species are important to bees. The well‐fitting interrelation of the landrace flowers and bee visits can have possible implications in agricultural practices such as crop breeding for pollinator friendly varieties through selecting floral traits, improvement of foraging resources for pollinators in agroecosystems and subsequently food production. Exploitation of the V. faba landrace in agroecological schemes to support conservation of flora and fauna genetic resources in situ should be considered also for the benefit of future food stability and security. [ABSTRACT FROM AUTHOR]

There is a principal need for more precise methodology with regard to the determination of occupational dermal exposure. The goal of the Systematic analysis of Dermal Exposure to hazardous chemical Agents at the workplace project was therefore to generate scientific knowledge to improve and standardize measurement methods for dermal exposure to chemicals at the workplace. In addition, the comparability of different measurement methods was investigated. Different methods (body sampling by means of coveralls and patches, hand sampling by means of gloves and washing, and head sampling by means of headbands and wiping) were compared. Volunteers repeatedly performed a selection of tasks under standardized conditions in test chambers to increase the reproducibility and decrease variability. The selected tasks were pouring, rolling, spraying, and handling of objects immersed in liquid formulations, as well as dumping and handling objects contaminated with powder. For the chemical analysis, the surrogate test substance Tinopal SWN was analyzed by means of a high-performance liquid chromatographic method using a fluorescence detector. Tinopal SWN was either applied as a solid product in its pure form, or as a low and high viscosity liquid containing Tinopal SWN in dissolved form. To compare the sampling methods with patches and coveralls, the exposure values as measured on the patches were extrapolated to the surface areas of the respective parts of the coverall. Based on this extrapolation approach, using the patch method resulted in somewhat higher exposure values compared to using a coverall for all exposure situations, but the differences were only statistically significant in case of the liquid exposure situations. Using gloves resulted in significantly higher exposure values compared to hand wash for handling immersed objects, rolling, and handling contaminated objects, and slightly higher (not significant) exposure values during pouring and spraying. In the same context, applying wipe sampling resulted in higher exposure values than using a headband, which was at least partly due to extrapolation of the wipe results to the surface area of the headband. No 'golden standard' with regard to a preferred measurement method for dermal exposure could be identified from the methods as investigated in the current study. [ABSTRACT FROM AUTHOR]