Determination of acaricides in honeys from different botanical origins by gas chromatography-mass spectrometry.

An analytical method has been proposed and validated to determine seven acaricides (atrazine, chlorpyrifos, chlorfenvinphos, α-endosulfan, bromopropylate, coumaphos, and τ-fluvalinate) in honeys from different botanical origins (multifloral, heather and rosemary) by means of gas chromatography-mass spectrometry. An efficient and simple sample treatment was proposed that involved a solvent extraction with an ethyl acetate and cyclohexane (50:50, v/v) mixture. Chromatographic analysis (<25 min) was performed in a DB-5MS column under programmed temperature conditions.

Residual Tau-Fluvalinate in Honey Bee Colonies Is Coupled with Evidence for Selection for Resistance to Pyrethroids.

is considered one of the most devastating parasites of the honey bee, , and a major problem for the beekeeping industry. Currently, the main method to control mites is the application of drugs that contain different acaricides as active ingredients. The pyrethroid tau-fluvalinate is one of the acaricides most widely used in beekeeping due to its efficacy and low toxicity to bees.

Simultaneous determination of carvacrol and thymol in bee pollen by using a simple and efficient solvent extraction method and gas chromatography-mass spectrometry.

A novel method is proposed to determine residues of carvacrol and thymol in bee pollen by means of gas chromatography coupled to mass spectrometry. This is an efficient and simple sample treatment (with average analyte recoveries between 90% and 104%) involving solvent extraction with hexane followed by evaporation. There is no need for any additional clean-up step, as the matrix did not affect determination of mass spectrometry for either compound.

Development and validation of ultra high performance-liquid chromatography-tandem mass spectrometry based methods for the determination of neonicotinoid insecticides in honey.

In this study, the feasibility of two sample treatments has been evaluated for the determination of seven neonicotinoid insecticides in honey from different botanical origins using ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). A solid phase extraction with a polymeric sorbent (Strata® X) is proposed for analyzing dark honeys, while a QuEChERS (quick, easy, cheap, effective, rugged and safe) approach is recommended for light honeys. Chromatographic analysis (6 min) was performed on a core-shell column (Kinetex® EVO C).

Extraction and determination of bioactive compounds from bee pollen.

Since ancient times bee pollen has been considered a good source of bioactive substances and energy. Taking into account the current demand for healthy and natural foods, it is not surprising that bee pollen has been attracting commercial interest in recent years, making it one of the most widely consumed food supplements. It has been extensively reported that bee pollen contains several health-promoting compounds, such as proteins, amino acids, lipids, phenolic compounds, vitamins or minerals.

Determination of flubendiamide in honey at trace levels by using solid phase extraction and liquid chromatography coupled to quadrupole time-of-flight mass spectrometry.

In this study, a new method has been developed to determine flubendiamide in honey using liquid chromatography coupled to a selective mass spectrometry detector (quadrupole-time-of-flight). An efficient sample treatment involving a solid phase extraction with a C sorbent was proposed (average analyte recoveries were between 94 and 104%). Chromatographic analysis (9min) was performed on a C column (Gemini C, 50×2.

Simultaneous determination of thiamethoxam, clothianidin, and metazachlor residues in soil by ultrahigh performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry.

A rapid pioneering method has been developed to simultaneously determine residues of three pesticides (thiamethoxam, clothianidin, and metazachlor) in soil by ultrahigh performance liquid chromatography coupled to a mass spectrometry detector (quadrupole time-of-flight). An efficient extraction procedure (90-105% average analyte recoveries) has also been proposed, involving solid-liquid extraction by a mixture of water and methanol (60:40, v/v), centrifugation, and concentration. A chromatographic analysis of the compounds was achieved in 5.

Fast determination of neonicotinoid insecticides in bee pollen using QuEChERS and ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry.

In this study, a new method has been developed to determine seven neonicotinoid insecticides (acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam) in bee pollen using ultra-high performance liquid chromatography coupled to a selective MS detector (qTOF). An efficient sample treatment involving an optimized quick, easy, cheap, effective, rugged and safe method was proposed. In all cases, average analyte recoveries were between 91 and 105%, and no matrix effect was observed.

An alternative method based on enzymatic fat hydrolysis to quantify volatile compounds in wheat bread crumb.

An alternative method to quantify 40 volatile compounds in wheat bread crumb is proposed. It consists of a Soxhlet extraction with a mixture of dichloromethane and diethyl ether containing lipases and a subsequent concentration with Vigreux column. It is the first time that lipases are added to transform the fat into free fatty acids and glycerol, which elute at the end of the chromatogram after the analytes, avoiding problems in the chromatography due to fat residues, such as dirtiness in the injector, column clogging or overlapping peaks.

Trace analysis of sulforaphane in bee pollen and royal jelly by liquid chromatography-tandem mass spectrometry.

In this study, we investigate for the first time the presence of sulforaphane (SFN) residues in two of the most currently consumed food/dietary supplements, royal jelly and bee pollen. Chromatography-tandem mass spectrometry (LC-MS/MS) was the method employed, the mass spectrometer consisting of an ion-trap mass analyzer used with electrospray ionization (ESI) in positive ion mode. An efficient sample treatment involving a solvent extraction with methanol, centrifugation, and concentration in a rotary evaporator was proposed.

Simultaneous determination of neonicotinoid insecticides in sunflower-treated seeds (hull and kernel) by LC-MS/MS.

A validated analytical method to determine seven neonicotinoids (dinotefuran, nitenpyram, thiamethoxam, clothianidin, imidacloprid, acetamiprid and thiacloprid) in sunflower seeds (hull and kernel) using HPLC coupled to electrospray ionisation mass spectrometry (ESI-MS) is presented. Sample clean-up based on a solid-liquid extraction, and the removal of lipid fraction, in the case of kernels, is proposed and optimised. Low limits of detection and quantification were obtained, ranging from 0.

Residues of neonicotinoids and their metabolites in honey and pollen from sunflower and maize seed dressing crops.

A study was carried out to evaluate the possible presence of thiamethoxam, clothianidin and imidacloprid, as well as the metabolic breakdown products of these three neonicotinoids in pollen and honey obtained from brood chamber combs of honeybee colonies located next to sunflower and maize crops from coated seeds. Samples were analyzed by liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry detector, in combination with accurate mass tools such as diagnostic ions by exact mass, chlorine mass filters, and MS/MS experiments. The presence of thiamethoxam and clothianidin was confirmed in some of the pollen samples analyzed.

Fast determination of intact glucosinolates in broccoli leaf by pressurized liquid extraction and ultra high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry.

In this study, we investigate for the first time the efficiency of an environmentally sustainable extraction technique (pressurized liquid extraction, PLE) in conjunction with a fast separation technique (ultra-high performance liquid chromatography, UHPLC) coupled to a selective mass spectrometry (MS) detector (quadrupole time-of-flight, qTOF) to extract, separate and quantify fifteen intact-glucosinolates (GLSs) in broccoli leaves. Firstly, we have developed and optimized by means of an experimental design an efficient extraction procedure based on PLE (using ethanol/water as a solvent), giving complete extraction within 15min; meanwhile, the average analyte recoveries were between 85% and 96% in all cases. Chromatography was performed on a UHPLC BEH Shield RP18 1.

Development and validation of a liquid chromatography-tandem mass spectrometry method to determine intact glucosinolates in bee pollen.

A new method was developed to determine twelve intact-glucosinolates (GLSs) (glucoiberin, GIB; glucoraphanin, GRA; glucoerucin GER; gluconapin, GNA; glucotropaeolin, GTL; glucobrassicin, GBC; gluconasturtiin, NAS; glucoalyssin, ALY; 4-hydroxyglucobrassicin, 4OH; 4-methoxyglucobrassicin, 4ME; neoglucobrassicin, NEO; sinigrin, SIN) in bee pollen, by means of liquid chromatography tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI). An efficient extraction procedure was proposed (average analyte recoveries were between 85% and 96%); this involved a solid-liquid extraction (SLE) with heated water, followed by a solid phase extraction (SPE) with a weak anion exchange (NH2) sorbent. Chromatography was performed on a Gemini(®) C18 analytical column with a mobile phase of formic acid in water (0.

Development and validation of a LC-MS/MS method to determine sulforaphane in honey.

A new method was developed to determine sulforaphane (SFN) in honey using liquid chromatography tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI). An efficient extraction procedure was proposed (average analyte recoveries were between 92% and 99%); this involved a solid phase extraction (SPE) with a polymeric sorbent. Chromatography was performed on a Synergi™ Hydro analytical column with a mobile phase of 0.

Development and validation of a liquid chromatography with mass spectrometry method to determine resveratrol and piceid isomers in beeswax.

This paper represents the first report of a liquid chromatography coupled to electrospray ionization mass spectrometry method for simultaneously analyzing resveratrol and piceid isomers (cis and trans) in beeswax. An efficient extraction procedure has been proposed (average analyte recoveries were between 89 and 95%); this involved a solid-liquid extraction using a mixture of ethanol and water (80:20, v/v) and a concentration step in a rotary evaporator. The separation of all the compounds was achieved using a C18 column and a mobile phase composed of ammonium formate 0.

Holistic screening of collapsing honey bee colonies in Spain: a case study.

Background: Here we present a holistic screening of collapsing colonies from three professional apiaries in Spain. Colonies with typical honey bee depopulation symptoms were selected for multiple possible factors to reveal the causes of collapse.

Results: Omnipresent were Nosema ceranae and Lake Sinai Virus.

Optimized extraction, separation and quantification of twelve intact glucosinolates in broccoli leaves.

A new method has been developed and validated to determine twelve intact glucosinolates (glucoiberin, GIB; glucoraphanin, GRA; glucoerucin GER; gluconapin, GNA; glucotropaeolin, GTL; glucobrassicin, GBC; gluconasturtiin, GST; glucoalyssin, ALY; 4-hydroxyglucobrassicin, 4-OH; 4-metoxyglucobrassicin, 4ME; neoglucobrassicin, NEO; sinigrin, SIN) in broccoli leaves using liquid chromatography (LC) coupled to diode array (DAD) and electrospray ionization mass spectrometry (ESI-MS) detection. An extraction procedure has also been proposed and optimized by means of statistical analysis (the Box-Behnken design and analysis of variance); this is based on the deactivation of myrosinase using a microwave and heated water. Low limits of detection and quantification were obtained, ranging from 10 to 72 μg/g with DAD and 0.

Comprehensive two-dimensional gas chromatography coupled with static headspace sampling to analyze volatile compounds: application to almonds.

The hyphenation of static headspace sampling with comprehensive 2D GC equipped with a modulator based on capillary flow technology and a flame ionization detector was used to separate and identify 43 representative target volatile compounds (light hydrocarbons, carbonyls, pyrazines, alcohols, furans, and benzenes) frequently detected in the roasting process of nuts. Five column combinations with differing degrees of orthogonality (one conventional and four inverted phase sets) were tested in order to obtain the best conditions for analyzing these volatile compounds. Optimization of the working conditions for each of the different column combinations was performed by means of a central composite design.

Determination of spinosad at trace levels in bee pollen and beeswax with solid-liquid extraction and LC-ESI-MS.

This paper reports the use of a new LC method with a fused-core analytical column coupled to ESI-MS to determine residues of the biopesticide spinosad in bee pollen and beeswax. The method analyzes the active ingredients, spinosyns A and D, with a simple and efficient sample treatment (recovery between 90 and 105%) consisting of a solid-liquid extraction with acetone (bee pollen) or acetonitrile (beeswax). The method was validated in terms of selectivity, LOD, LOQ, linearity, and precision.

Effects of organic modifier and temperature on the enantiomeric separation of several azole drugs using supercritical fluid chromatography and the Chiralpak AD column.

The effects of organic modifier and temperature on the enantioseparation of 10 triazoles and eight imidazoles, using supercritical fluid chromatography with the Chiralpak AD column, have been investigated in this work. For this purpose four different organic modifiers (methanol, ethanol, 2-propanol and acetonitrile) were evaluated. Only in the case of two compounds could the enantiomeric separation not be achieved with any of the modifiers tested; the rest of compounds were baseline or partially resolved with at least one of the modifiers.

Extraction, chemical characterization and biological activity determination of broccoli health promoting compounds.

Broccoli (Brassica oleracea L. var. Italica) contains substantial amount of health-promoting compounds such as vitamins, glucosinolates, phenolic compounds, and dietary essential minerals; thus, it benefits health beyond providing just basic nutrition, and consumption of broccoli has been increasing over the years.

Simultaneous determination of nine anticoagulant rodenticides in soil and water by LC-ESI-MS.

A new and sensitive analytical method is presented to determine nine anticoagulant rodenticide (chlorophacinone, bromadiolone, pindone, diphacinone, warfarin, coumatetralyl, brodifacoum, floucomafen, and difenacoum) residues in water and soil samples by LC-ESI-MS. Rodenticides were extracted from soil using a methanol and ammonium formate 30 mM mixture, while ethyl acetate was employed in the water samples. A Gemini 5 μm C18 column was employed, and a mobile phase comprising a mixture of ammonium formate 30 mM and di-n-butylamine 30 mM in water (pH 3.

Analysis of anticoagulant rodenticide residues in Microtus arvalis tissues by liquid chromatography with diode array, fluorescence and mass spectrometry detection.

We describe here a fast and selective analytical method to determine the levels of four anticoagulant rodenticides (chlorophacinone, bromadiolone, brodifacoum and difenacoum) in animal tissues by liquid chromatography (LC) using different detection methods: fluorescence (FLD), diode array (DAD) and electrospray ionization-mass spectrometry (ESI-MS). Rodenticides were extracted from freeze-dried and homogenized tissue samples (liver, intestine and muscle) that had been obtained from the common vole (Microtus arvalis). These samples were diluted in 5 mL of methanol, the solution was shaken and centrifuged, and the supernatant was removed and evaporated to dryness.

Determination of seven neonicotinoid insecticides in beeswax by liquid chromatography coupled to electrospray-mass spectrometry using a fused-core column.

A new method has been developed to measure seven neonicotinoid insecticides (acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam) in beeswax using liquid chromatography (LC) coupled to electrospray ionization mass spectrometry (ESI-MS) detection. Beeswax was melted and diluted in an n-hexane/isopropanol (8:2, v/v) mixture. After this, liquid extraction with water was performed followed by a clean-up on diatomaceous material based cartridges.