Residues In Honey Samples Research Articles

Synergy of iron-natural phenolic microparticles and hydrophobic ionic liquid for enrichment of tetracycline residues in honey prior to HPLC-UV detection

Iron-natural phenolic microparticles were developed as absorbents for dispersive micro solid phase extraction (D-μSPE) synergistic with hydrophobic ionic liquid (IL) for dispersive liquid–liquid microextraction (DLLME) to enrich tetracycline residues, including tetracycline, doxycycline, oxytetracycline and chlortetracycline. In situ iron microparticles synthesized from betel nut natural reagent were employed as an adsorbent for D-μSPE. The hydrophobic IL [Hmim][PF6] was synergistically utilized as an extraction solvent to extract and accumulate adsorbents bound with tetracyclines before quantitation by HPLC-UV. The synergistic combination of DLLME with D-μSPE provided excellent extraction recovery compared with individual extraction. The developed method was successfully applied to enrich and determine tetracycline residues in honey samples, with recoveries ranging from 80.0 to 121.5% and providing high enrichment factors ranging from 61 to 197. This alternative method is simple and rapid, with high extraction efficiency and a high enrichment factor and is also environmentally friendly for the analysis of tetracyclines.

An electrochemical sensor based on MnO2/ZnO composites for the detection of ciprofloxacin in honey

Long-term consumption of honey containing ciprofloxacin (CIP) residues may harm human health. It is important to establish a sensitive and rapid CIP detection method. This study reports for the first time the development of an electrochemical sensor for rapid determination of CIP in honey, utilizing a MnO2/ZnO composites. Two types of ZnO with different morphologies were prepared, characterized, and compared for their electrocatalytic properties for CIP. The findings indicated that the rod-like ZnO had a better catalytic effect on CIP and was thus selected to combine with MnO2 to form the composite material. Characterization of the resulting composite material was conducted, followed by an investigation of the electrochemical reaction of CIP on the electrode and optimization of the detection conditions of the sensors. The results indicate that the current value of CIP had a linear relationship with its concentration within the range of 0.5 to 120 µM, and the detection limit was 0.21 µM. The MnO2/ZnO/GCE sensor was applied to detect the CIP residues in honey samples, and the recoveries ranged from 95.3% to 97.2%. The results show that the composite material-modified sensor has good sensitivity and can enable rapid detection of CIP content in honey. Therefore, it has a potential application in detecting CIP residues in honey.

Determination of Pesticide Residues in Honey Samples from East Shewa and West Arsi Zones of Oromia, Ethiopia

Determination of Pesticide Residues in Honey Samples from East Shewa and West Arsi Zones of Oromia, Ethiopia

Carbon Black Integrated Polylactic Acid Electrodes Obtained by Fused Deposition Modeling: A Powerful Tool for Sensing of Sulfanilamide Residues in Honey Samples

Sulfanilamide (SFL) is used to prevent infections in honeybees. However, many regulatory agencies prohibit or establish maximum levels of SFL residues in honey samples. Hence, we developed a low-cost and portable electrochemical method for SFL detection using a disposable device produced through 3D printing technology. In the proposed approach, the working electrode was printed using a conductive filament based on carbon black and polylactic acid and it was associated with square wave voltammetry (SWV). Under optimized SWV parameters, linear concentration ranges (1-10 μmol L-1 and 12.5-35.0 μmol L-1), a detection limit of 0.26 μmol L-1 (0.05 mg L-1), and suitable RSD values (2.4% for inter-electrode; n = 3) were achieved. The developed method was selective in relation to other antibiotics applied in honey samples, requiring only dilution in the electrolyte. The recovery values (85-120%) obtained by SWV were statistically similar (95% confidence level) to those obtained by HPLC, attesting to the accuracy of the analysis and the absence of matrix interference.

Multiresidue chromatographic method for the determination of antibiotic residues in honey by high-performance liquid chromatography with DAD detection

Clandestinely, consumers may be exposed to antibiotic (ATB) residues in honey, which could pose a health concern. For the first time, the simultaneous determination of Florfenicol (FF), Penicillin G (PG), and Tetracycline is described in this paper. The multiresidual method was developed and optimized using high-performance liquid chromatography (HPLC) coupled to a diode array detector (DAD). These ATBs were separated on a C18 analytical column after a cleanup process followed by solid-phase extraction (SPE). For the first time, the chromatographic conditions were perfected. After the method validation process, the method was used to assess ATB residues in four Lebanese honey samples. ATBs were separated in less than 15 min with an isocratic elution using a mixture of 80 % potassium dihydrogen phosphate aqueous solution, and 20 % acetonitrile. The UV detection was performed at 350 nm for TC, 224 nm for FF, and 230 nm for PG. The proposed method was linear (R2 ≥ 0.996) within the concentration ranges of 0.7-17.5 mg.Kg 1 for the three compounds. Both intra- and inter-day precision, expressed as RSD, were ≤15 %. The method was subsequently successfully applied to analyze examined ATB residues in honey samples collected from Lebanese beekeeping. The method described could be a valuable tool to conduct a comprehensive survey of honey samples produced in Lebanon, especially in the lack of serious national oversight.

Simultaneous Screening of Nitrofuran Metabolites in Honey Using Biochip Array Technology: Validation Study According to the Decision 2002/657/EC of the European Union.

Although no authorization is available for antibiotics to treat bee diseases, some veterinary compounds are used by beekeepers, and each country sets its own thresholds. Inappropriate and excessive use of these drugs can cause allergic reactions and antibiotic resistance in humans who consume the remaining antibiotic residues in honey and its products. It is, therefore, relevant to monitor the presence of antibiotic residues in this matrix. A rapid method for the simultaneous screening of nitrofuran metabolite residues in honey was validated according to Commission Decision 2002/657/EC (C.D 657) and the European guideline for the validation of screening methods for veterinary medicines. This multi-analytical screening method enables the simultaneous determination of four nitrofuran metabolites [3-amino-2-oxazolidone (AOZ), 3-amino-5-morpholinomethyl-2-oxazolidinone (AMOZ), 1-Aminohydantoin HCl (ADH), and semicarbazide (SEC)] from a single honey sample. Thirty-five honey samples were collected randomly as real samples for screening from Tehran, IR Iran, Germany, and the Netherlands in 2018. For all four antibiotic residues, the positivity threshold T was higher than the cut-off value Fm, and no false-positive results were obtained for three antibiotics (AOZ, AMOZ, and SEC). Detection capabilities (CCβ) of all compounds were under the minimum required performance limit (MRPL) authorized by the European Commission (currently 1 μg/kg). The screening results of 15 domestic and 20 imported honey samples showed that the levels of AOZ in 6.66% and 10% of the samples, the level of AMOZ in 13.33% and 0% of the samples, and the level of SEC in 33.33% and 40% of the samples were less than the cut-off ([in relative light units (RLUs)], respectively. This study found that this technique is valid for detecting and quantifying three antibiotic residues in honey samples at the measured validation levels. This method was simple, rapid, and capable of simultaneously screening three nitrofuran metabolites from a single honey sample.

Rapid determination of nitrofuran metabolites residues in honey by ultrasonic assisted derivatization - QuEChERS - high performance liquid chromatography / tandem mass spectrometry

In this study, a method of ultrasonic assisted derivatization combined with improved QuEChERS scheme and high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) was developed for the analysis of nitrofuran metabolite residues in honey samples. The optimized conditions such as ultrasonic assisted derivatization conditions, extraction methods and purification materials quantitatively obtained by matrix standard curve external standard method had finally been proved to be effective in the determination of nitrofuran metabolite residues in honey samples. In order to make the results more accurate, the matrix matched standard for isotope-labeled internal standard method was used for methodological verification. The concentration of all target substances ranged from were 0.25–20 ng/mL, with good linearity, and the correlation coefficient were 0.9999. The LOD and LOQ of the target analyte were 0.15 and 0.5 μg/kg respectively. The average recoveries of the three standards were between 1.89 % and 107.9 %. The recoveries of inter-day and intra-day tests were 96.0–100.2 % and 93.2–98.7 % respectively. The precisions of inter-day(n = 6) and intra-day(n = 6) analysis were 3.56–5.29 % and 3.09–5.13 % respectively. 85 honey samples obtained from the market were analyzed by our optimized method, of which 4 SEM and 1 AOZ were detected in 5 samples.

Development of magnetic solid phase extraction using magnetic amphiphilic polymer for sensitive analysis of multi-pesticides residue in honey

A sensitive and time-saving method for the determination of multi-pesticide residues in honey was developed using magnetic solid phase extraction (MSPE) coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS). Magnetic polymer (N-vinyl pyrrolidone-divinyl benzene) (MVP-DB) was fabricated and employed as the adsorbent for extraction and enrichment of multi-pesticide residues in honey. MVP-DB contains lipophilic benzene ring, divinyl group, and hydrophilic pyrrolidone group. The good hydrophilic and hydrophobic structure of MVP-DB not only ensures sufficient dispersion in honey samples, but also enhances the ability to enrich target analytes. The predominant factors affecting the recoveries of analytes were systematically investigated, affording a rapid and highly efficient MSPE method. Under the optimal conditions, the method was verified, including the recovery, precision, linearity, sensitivity, and matrix effects. The results displayed that these pesticides showed good linearity in the range of 2–250 µg L−1. The MLOQs were 0.5 µg kg−1. The recoveries of pesticides in honey at the pre-spiked concentrations of 0.5–25 µg kg−1 were 61.6%–112% with RSDs less than 18.2%. Hence, the developed method displayed good application prospect for the determination of multi-pesticide residues in honey samples.

In-Situ Formation of Modified Nickel-Zinc-Layered Double Hydroxide Followed by HPLC Determination of Neonicotinoid Insecticide Residues.

A single-step preconcentration procedure using the in-situ formation of modified nickel–zinc-layered double hydroxides (LDHs) prior to high-performance liquid chromatography (HPLC) is investigated for the determination of neonicotinoid insecticide residues in honey samples. The LDHs could be prepared by the sequential addition of sodium hydroxide, sodium dodecyl sulfate, nickel nitrate 6-hydrate and zinc nitrate 6-hydrate, which were added to the sample solution. The co-precipitate phase and phase separation were obtained by centrifugation, and then the precipitate phase was dissolved in formic acid (concentrate) prior to HPLC analysis. Various analytical parameters affecting extraction efficiency were studied, and the characterization of the LDHs phase was performed using Fourier-transformed infrared spectroscopy and scanning electron microscopy. Under optimum conditions, the limit of detection of the studied neonicotinoids, in real samples, were 30 μg L−1, for all analytes, lower than the maximum residue limits established by the European Union (EU). The developed method provided high enrichment, by a factor of 35. The proposed method was utilized to determine the target insecticides in honey samples, and acceptable recoveries were obtained.

Application of β-Cyclodextrin metal-organic framework/titanium dioxide hybrid nanocomposite as dispersive solid-phase extraction adsorbent to organochlorine pesticide residues in honey samples

A simple and efficient dispersive solid-phase extraction (D-SPE) method combined with gas chromatography tandem mass spectrometry (GC-MS/MS) was developed to determine organochlorine pesticides (OCP) in honey. Firstly, a type of hybrid nanocomposite (CD-MOF/TiO2) was prepared by grafting a metal-organic framework material synthesized with cyclodextrin as an organic ligand onto titanium dioxide. Then, the CD-MOF/TiO2 was used as a D-SPE adsorbent to extract the OCP, and the effects of the amount of adsorbent, ultrasonic time, vortex time, pH, and salinity on the extraction were investigated using Plackett–Burman design and Box-Behnken Design. Under the optimized adsorption and desorption conditions, an analysis method that combined D-SPE with GC-MS/MS was established. The linear ranges of 14 OCP are 1–500 μg kg−1 and the correlation coefficients are between 0.9991 and 1.000. The limits of detection and quantification vary from 0.01 to 0.04 μg kg−1 and 0.04 to 0.12 μg kg−1, respectively. The intra-day and inter-day precision of this method are suitable (RSDs% less than 11.3%). The established CD-MOF/TiO2 / D-SPE method was used for the extraction of OCP in honey samples with recovery in the range of 76.4 to 114.3%. The results demonstrate that the CD-MOF/TiO2 has a good selective enrichment ability for OCP and is suitable for the D-SPE pretreat of honey sample analysis.

Determination of multi-pesticide residues in honey with a modified QuEChERS procedure followed by LC-MS/MS and GC-MS/MS

This paper presents a modified QuEChERS method to determine 346 pesticide residues in honey by LC/MS-MS and GC/MS-MS. Acetate buffered acetonitrile extraction followed by dispersive SPE clean-up with C18-E, PSA and MgSO4 sorbents were used for sample preparation. This method was validated according to the European Union SANTE/2019/12682 guidelines. Acceptable values were obtained for the linearity, the limit of detection (0.001–0.003 mg/kg), limit of quantification (0.002–0.008 mg/kg), trueness (for the four tested levels, the recovery assays values were between 76 and 112%), precision (RSD ≤20.0%) and measurement uncertainty tests (<50%). The method was used for the analysis of 100 honey samples from Northern Cyprus and residues of 4 pesticides (coumaphos, thiamethoxam, N-(2,4-dimethylphenyl)formamide, piperonyl butoxide) were quantified in 42 honey samples. Coumaphos (29%) and N-(2,4-dimethylphenyl)formamide (11%) were the residues frequently detected in the samples. N-(2,4-dimethylphenyl)formamide concentrations (0.56 and 0.84 mg/kg) were determined above the MRL limits (0.2 mg/kg) in two samples. This study shows that LC/MS-MS and GC/MS-MS in combination with modified QuEChERS can be used to routinely scan pesticide residues in honey samples and direct contamination with acaricides/veterinary drugs applied in the treatment of plagues in the hive during honey harvest is the main source of honey pollution in Northern Cyprus.

Enrichment of tetracycline residues from honey samples using carrier-mediated hollow fibre liquid-phase micro-extraction and quantification by LC-Q-TOF/MS.

In this study, development and validation of a simple, miniaturized and, environmentally friendly carrier-mediated three-phase hollow-fibre liquid-phase micro-extraction (HFLPME) technique was investigated for the enrichment of tetracycline residues in honey samples. The extracts were analysed using UV-visible spectrophotometry and liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-Q-TOF/MS). Parameters affecting the extraction efficiency of HFLPME such as pH of the donor and acceptor solutions, salt addition, agitation speed and extraction time were optimized. The calibration curves showed good linearity, in the range of 1-100 μg kg-1 with correlation coefficients ranging between 0.9943 and 0.9992, under the optimized conditions. Recoveries of blank honey samples at three spiking levels (1, 10 and 20 μg kg-1 ) ranged from 81.2% to 107.5%. Relative standard deviations for the precision of the method were less than 15.0%. Limits of detection and limits of quantification were in the range of 0.0861-0.2628 μg kg-1 and 0.2610-0.7964 μg kg-1 , respectively. Finally, the proposed method was successfully applied in the extraction of five tetracyclines from honey samples. Doxycycline residue detected in one of the commercial honey samples was below the limit of quantification. Because of the advantages offered by HFLPME, this method can be employed as an alternative to conventional extraction techniques for the clean-up and pre-concentration of antibiotics in complex matrices, including food samples. © 2021 Society of Chemical Industry.

Investigation and human health risk assessment of multi-class veterinary antibiotics in honey from South Korea

Antibiotic residues in honey constitute potential threats to human health. To ensure food safety, a total of 26 antibiotics method based on liquid chromatography-tandem mass spectrometry for the determination of antibiotics was validated in honey. Sample preparation consists in acid hydrolysis and dispersive-solid phase extract clean-up methods. The primary secondary amine sorbent yielded the highest recoveries. All antibiotics showed good linearity, with correlation coefficients of more than 0.993. The method yielded limits of detection of 0.1–6.8 μg L−1, limits of quantification (LOQ) of 0.3–20.7 μg L−1, and recoveries of 70.5–107.4 %. The concentrations of individual antibiotics except chlortetracycline and tetracycline were below 100 ng mL−1. The chlortetracycline (38.2 %) and tetracycline (31.3 %) accounted for the highest antibiotic residues in honey samples. The estimation of exposure and risk assessment revealed that the upper residue levels of tetracycline-class exceeded the acceptable daily intake by 24.3–381.5 times. In particular, chlortetracycline alone accounted for 70 % of the hazard index, which was 4.62 in children and 2.26 in adults. This study calls attention to the human health risk of tetracyclines in honey consumption.

Assessment of risk to honey bees and honey consumers resulting from the insect exposure to captan, thiacloprid, penthiopyrad, and λ-cyhalothrin used in a commercial apple orchard.

Samples of leaves, flowers, soil, pollen, bee workers, bee brood, honey, and beeswax were collected to assess the possibility of a transfer of captan, thiacloprid, penthiopyrad, and λ-cyhalothrin from apple trees of Idared variety to honey bee (Apis mellifera) hives. Chemical analyses were performed using the Agilent 7890 Gas Chromatograph equipped with the Micro-cell Electron Capture Detector. It was found that significant amounts of penthiopyrad, the active ingredient of Fontelis 200 SC, were present in leaves, flowers, pollen, bee workers, and beeswax. Simultaneously, captan was present in the brood, worker bees, and honey samples. Significant levels of the captan residues were also detected on the soil surface. In honey samples, captan residue levels exceeded the acceptable standard, reaching 160% of its maximum residue level. However, in no case the amounts of captan, thiacloprid, penthiopyrad, and λ-cyhalothrin ingested with honey by an adult consumer exceeded the level of 0.02% of the acceptable daily intake. Despite the trace amounts of pesticide residues in honey samples collected during the field trial, bee honey consumption can be considered safe. An adult consumer can safely consume about 16kg of honey.

Determination of Neonicotinoids in Honey Samples Originated from Poland and Other World Countries.

A method development for determination of neonicotinoid residues in honey samples was developed. The proposed methodology consisted in QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe). That was used for sample preparation and UHPLC/UV (ultra-performance liquid chromatography with ultraviolet detection) utilized for chromatographic analysis. The developed method proved to be sensitive, with LOD (Limit of detection) value in the range of 60.80 to 80.98 ng/g hence LOQ (Limit of quantification) value was in the range of 184.26 to 245.40 ng/g. The method has tested on Polish honey and applied to honey from various countries (Bulgaria, Czech Republic, France, Greece, Italy, Portugal, Romania, Australia, Brazil, Cameroon, Russia, USA and Turkey). Several honey types were tested, while physicochemical properties of all honeys and were investigated. The methodology for general characterization of pollen grains originated from selected plants, to confirm the type of honey was also presented. There was a total lack of the mentioned neonicotinoids in sunflower honey. Except of this, only two samples of rapeseed and two samples of acacia honey (from Poland and Romania) were neonicotinoids free. In 19 samples the targeted pesticides were detected above LOQ. In all other investigated samples, the neonicotinoids were found at least at the LOD or LOQ level.

Assessment of Heavy Metals and Pesticide Residues in Honey Samples Collected From Selected Villages in Five Local Government Areas of Adamawa State, Nigeria

Assessment of Heavy Metals and Pesticide Residues in Honey Samples Collected From Selected Villages in Five Local Government Areas of Adamawa State, Nigeria

Vortex and Ultrasound-Assisted Surfactant-Enhanced Emulsification Microextraction for the Determination of Pesticide Residues in Honey using Gas Chromatography–Mass Spectrometry

A novel sample pre-treatment technique based on vortex and ultrasound-assisted surfactant-enhanced emulsification microextraction followed by gas chromatographic–mass spectrometric detection has been developed to determine the selected pesticide residues in honey samples. The key parameters which have affected extraction efficiency were investigated and optimized. Under optimal conditions, the extraction recovery was 90–101% and the enrichment factors were 173–191. The concentration ranges of detection and quantification limits were from 0.03 to 0.9 ng/g and from 0.1 to 3 ng/g, respectively, in honey samples. The relative standard deviation was <5% for intra-day (n = 6) and <8% for inter-day precision (n = 4). Target pesticides were observed in 25% of the samples. The results of this study showed that the residues of such pesticides as bifenthrin, fenpyroximate and thiamethoxam were more than the maximum amount in some honey samples, which causes serious harm to human health.

Capillary liquid chromatography as an effective method for the determination of seven neonicotinoid residues in honey samples.

A new analytical method based on capillary liquid chromatography with diode array detection has been developed for the simultaneous quantification of seven neonicotinoid insecticides commercially available (imidacloprid, thiacloprid, clothianidin, thiamethoxam, acetamiprid, nitenpyram, and dinotefuran) in honey samples. The separation was achieved in a Zorbax XDB-C18 column (150×0.5mm id, 5μm), with a mobile phase consisting of ultrapure water (solvent A) and acetonitrile (solvent B) at a flow rate of 10 μL/min. Capillary column was thermostated at 25°C during the analysis and 254 or 270nm was established as detection wavelength, depending on the analyte. Furthermore, full loop injection mode (8 μL) was selected, using water as injection solvent. Finally, the optimized method was applied to the analysis of neonicotinoid residues in honey of different floral origins using dispersive liquid-liquid microextraction as sample treatment. Variables affecting the extraction efficiency were optimized, choosing methanol and dichloromethane as dispersive and extraction solvents, respectively. The method was characterized in terms of linearity ( ≥ 0.9948), repeatability, reproducibility (relative standard deviation below 4.5 and 6.3% respectively), and recoveries (≥80.5%). Detection and quantification limits were lower than 6.6 and 22.0μg/kg for the studied analytes, respectively.

Rapid determination of sulfonamide residues in honey samples using non‐targeted liquid chromatography‐high resolution mass spectrometry

AbstractHoney is one of the most widespread natural harvest consumed as food and medicine. Many antibacterial groups can be used to protect bees from some bacterial diseases and infections. Among them, sulfonamides are one of the most effective antibacterial drugs used for a long time. While sulfonamides are used by beekeepers, the residues of them may appear in honey with the different levels of residues. These residues in honey at the high level of concentration can be a potential risk to the human body. In this study, a non‐targeted liquid chromatography with high resolution mass spectrometry method was designed to discover known and unknown sulfonamide residues in 13 honey samples. This study includes both sample preparation with a modified Quick, Easy, Cheap, Effective, Rugged, and Safe extraction and liquid chromatography analysis. The influences of the chromatographic separation parameters such as flow rate were studied. The detection of sulfonamides was carried out by a reversed‐phase chromatographic separation column (a Hypersil Gold C18, 100 mm × 2.1 mm I.D., 1.9 µm), with gradient elution mode of mobile phase at a flow rate of 0.3 mL/min. Full MS/all‐ion fragmentation was used for mass spectrometry acquisition mode. The limit of detection of sulfonamides ranged from 0.02 to 0.12 µg/kg while the limit of quantification values was between 0.08 and 0.72 µg/kg. The developed non‐targeted analysis was successfully applied for sulfonamide residue determination in honey samples. This study also shows the analysis of the arylamine groups originated from sulfonamides that is a very relevant issue for the toxic side effect of these compounds.

Monitoring and risk assessment due to presence of metals and pesticides residues in honey samples from the major honey producing forest belts and different brands

Monitoring and risk assessment due to presence of metals and pesticides residues in honey samples from the major honey producing forest belts and different brands