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Tetracyclines are widely used in Chinese apiculture. However, limited information is available on the presence of tetracycline residues in honey and the sources, degradation patterns, and associated health risks of these compounds. In this study, the presence of tetracyclines in honey samples across China was investigated over a four-year period. Additionally, the risks of dietary intake, as well as the sources and degradation patterns of tetracyclines in honey, were assessed. The three-dimensional spatial distributions (floral region, geographical region and entomological origin) of tetracyclines contamination varied significantly. Tetracycline residues in honey posed a moderate risk to children aged 3-10 years in Northwest China. Source analysis indicated that colony migration serves as the primary source of tetracyclines in honey. Based on the degradation patterns of tetracyclines in honey within colonies and during storage, oxytetracycline is more readily degraded than other tetracyclines. The main degradation products of tetracyclines are epimers and dehydration products, and the effects of these products on human health and the environment should be further evaluated in future studies. This comprehensive investigation provides valuable insights into the safe use and regulation of tetracyclines in Chinese apiculture., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A new idea and strategy for honey traceability and identification was provided by studying the carbon isotope fractionation of rape honey and its components in the different ripening process, as well as the fractionation from rape flowers, stamens, nectar to rape honey. The results showed the moisture content of rape honey continued to decrease, and the glucose and fructose content continued to increase during the ripening process. The δ 13 C of rape honey and its protein were less affected by honey ripeness, while the δ 13 C of sugars in rape honey were greatly affected by this. At the same time, the fractionation of carbon isotope from rape flowers to honey was significant. The δ 13 C of rape honey and its protein, disaccharide, fructose, and glucose had a strong correlation, and the δ 13 C of rape honey and its components were mainly related to rape flowers and its stamens., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

A comprehensive liquid chromatography-mass spectrometry (LC-MS)-based metabolomics approach was developed to discriminate honey harvested from Apis mellifera ligustica Spinola ( A. mellifera ) and Apis cerana cerana Fabricius ( A. cerana ). Based on an untargeted strategy, ultrahigh-performance liquid chromatography electrospray ionization quadrupole orbitrap high-resolution mass spectrometry (UPLC Q-Orbitrap) was combined with chemometrics techniques to screen and identify tentative markers from A. mellifera and A. cerana honey. In targeted metabolomics analysis, a sensitive method of solid-phase extraction followed by ultrahigh-performance liquid chromatography coupled with triple quadrupole tandem mass spectrometry (UPLC-MS/MS) was established for quantifying three markers, and the results showed that 3-amino-2-naphthoic acid and methyl indole-3-acetate could be considered markers of A. cerana honey, as they were present in higher amounts in A. cerana honey than in A. mellifera honey, whereas kynurenic acid was determined to be a marker of A. mellifera honey. This work highlights critical information for the authentication of A. cerana and A. mellifera honey.

An effective sample pretreatment method followed by liquid chromatography tandem mass spectrometry (LC-MS/MS) was first developed for simultaneous determination of five antiviral drug residues including ribavirin, moroxydine, amantadine, rimantadine and memantine in honey. To adsorb analytes with different binding properties and overcome the interference of sugars and uridine as endogenous ribavirin structural analogs in honey, the target drugs were extracted with 1% formic acid and then purified by a phenylboronic acid (PBA) solid phase extraction cartridge using two-step fraction capture prior to LC-MS/MS analysis. This method was validated by analyzing honey samples from nine floral origins including miscellaneous flowers, citrus, vitex, rape, acacia, sunflower, linden, buckwheat and jujube spiking at multiple levels, and the recoveries ranged from 82.46% to 116.34%, with relative standard deviations (RSDs) less than 14.58%. The limits of detection (LODs) and limits of quantitation (LOQs) of moroxydine, ribavirin, amantadine, rimantadine, and memantine were 0.1-2 µg/kg and 0.2-5 µg/kg, respectively. Depletion experiments of five antiviral drugs in honey at different storage and process temperatures demonstrated that moroxydine can potentially be used as a drug to cure sacbrood disease in honeybees., Competing Interests: Declaration of Competing Interest The authors declare that there are no conflicts of interest., (Copyright © 2021. Published by Elsevier B.V.)

The fascinating collection and evaluation of natural products with enormous structural and chemical diversity can contribute to ensure human health and inspire potential drug discovery. We reported the identification of 14-(R)-hydroxy-gelsenicine (HGE), a new component from poisonous honey, which has recently caused multiple serious intoxications and deaths up on consumption. The prevalence, toxicity, toxicokinetics and metabolic profile of HGE were evaluated through in vitro and in vivo analyses. HGE is a very toxic substance and shows significant gender difference with LD 50 of 0.125 mg kg -1 and 0.295 mg kg -1 for the female and male mice, respectively. Toxicokinetics test indicates that HGE has good bioavailability in rats, and is metabolized extensively, in which hydroxylation, reduction, N-demethyl ether and glucuronication are the major metabolic pathways. Additionally, HGE shows specific neurotoxicity by enhancing the binding of γ-aminobutyric acid (GABA) to its receptors. We found that flumazenil, a selective antagonist of GABA receptor, could effectively increase the survival of the tested animals, which provides a potential therapy for future clinical applications., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Fraudulent acts regarding honey authenticity that use Apis mellifera honey as a substitute for Apis cerana honey have garnered considerable concern in China and triggered a trust crisis from consumers. In this study, untargeted metabolomics analysis was carried out based on volatile fractions in honey from A. cerana and A. mellifera using headspace gas chromatography-ion mobility spectrometry (HS-GC-IMS). Honey from A. cerana and A. mellifera was discriminated by HS-GC-IMS profiling, principal component analysis, and orthogonal partial least-squares discrimination analysis. Tentative markers were identified from p -values and the variable importance in projection analysis and confirmed using the retention index, mass fragments, and reference standards by gas chromatography-mass spectrometry (GC-MS). A targeted method was established using the headspace solid phase coupled with microextraction GC-MS (HS-SPME-GC-MS) to quantitate the markers. The results demonstrated that the developed untargeted and targeted metabolomics approach performed well when discriminating honey from A. cerana and A. mellifera .

A simple and environmentally approach using untargeted imaging of volatile substances combined with chemometrics and markers response was proposed for discriminating different species of honey with headspace gas-chromatography-ion-mobility (HS-GC-IMS). The 3D HS-GC-IMS imaging and their response differences enabled the clear discrimination between winter honey and sapium honey. Principal component analysis (PCA) and partial least-squares discrimination analysis (PLS-DA) were employed to discriminate different honey. Markers of two kinds of honey were identified and confirmed with a user-built imaging database combined with multivariate analysis. Benzaldehyde dimer and phenylacetaldehyde dimer were found to be reliable markers of winter honey, and phenylethyl acetate dimer was of sapium honey. Adulteration identification of the honey samples with different adulteration ratios were subjected to this triple-locked strategy analysis. The results demonstrate that HS-GC-IMS imaging coupled with chemometrics and marker identification is a useful triple-locked strategy to discriminate honey from different floral origins and adulterated honey., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The aim of this study was to predict the geographical origin of acacia honey of China through analysis of physicochemical parameters combination with chemometrics. Samples from six different origins were investigated on parameters of δ 13 C value, oligosaccharides and polyphenols, using EA-IRMS/LC-IRMS, GC-MS and HPLC-MS, respectively. The results indicated that the δ 13 C value of honey from Gansu region were lower than those of other regions. Oligosaccharides of honey from Shanxi and Shaanxi regions were both higher than other four regions. Polyphenols of honey from Shandong region was the highest and were better parameters than both δ 13 C and oligosaccharides in discrimination of geographical origins. Partial Least Square Discriminant Analysis (PLS-DA) showed that when all 31 different parameters were combined, a correct classification rate of 94.12% could be achieved using external cross validation method. In conclusion, the method in discrimination of geographical can be used to provide reliable and useful reference information., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

A robust and sensitive method of solid-phase extraction followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) was established and performed for the simultaneous determination of eleven aminoglycosides (AGs) in royal jelly and honey. After sample extraction by a phosphate buffer containing trichloroacetic acid (TCA) and ethylenediaminetetracetic acid disodium salt (Na 2 EDTA), the extraction solution was subjected to a parallel solid-phase extraction for clean-up prior to the LC-MS/MS analysis. The same method was applied to analyze two completely different matrices, honey and royal jelly. Good sensitivity, repeatability, and recovery were obtained by using the mobile phase without an ion-pairing reagent such as heptafluorobutyric acid (HFBA) or sodium heptanesulfonate. The calibration curves of the honey and royal jelly samples exhibited a good linear response (R 2  > 0.99) at six concentrations in the range of 10-1000 μg/mL. The limit of quantification (LOQ) of the AGs ranged from 10 to 25 μg/kg in the honey and from 12.5 to 25 μg/kg in the royal jelly. The recoveries of the AGs for the honey and royal jelly samples were in the range of 79.48% to 108.95% and 74.61% to 113.70% respectively and the relative standard deviations (RSDs) were between 1.23% and 9.59%, and between 1.51% and 9.98%, respectively. The proposed approach has been allowed in China as a reference method for the simultaneous determination of eleven AGs in honey and royal jelly., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Honey discrimination based on floral and geographic origins is limited by the ability to determine reliable markers because developing hypothetical substances in advance considerably limits the throughput of metabolomics studies. Here, we present a novel approach to screen and elucidate honey markers based on comparative untargeted metabolomics using ultrahigh-performance liquid chromatography-hybrid quadrupole-orbitrap mass spectrometry (UHPLC-Q-Orbitrap). To reduce metabolite information losses during sample preparation, the honey samples were dissolved in water and centrifuged to remove insoluble particles prior to UHPLC-Q-Orbitrap analysis in positive and negative electrospray ionization modes. The data were pretreated using background subtraction, chromatographic peak extraction, normalization, transformation and scaling to remove interferences from unwanted biases and variance in the experimental data. The pretreated data were further processed using principal component analysis (PCA) and a three-stage approach (t-test, volcano plot and variable importance in projection (VIP) plot) to ensure marker authenticity. A correlation between the molecular and fragment ions with a mass accuracy of less than 1.0ppm was used to annotate and elucidate the marker structures, and the marker responses in real samples were used to confirm the effectiveness of the honey discrimination. Moreover, we evaluated the data quality using blank and quality control (QC) samples based on PCA clustering, retention times, normalized levels and peak areas. This strategy will help guide standardized, comparative untargeted metabolomics studies of honey and other agro-products from different floral and geographic origins., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The phenolic and proline content were determined in honey samples of different floral origins (rapeseed, sunflower, buckwheat and Codonopsis ) from five different regions of China. The phenolic and proline profile of these samples were used to construct a statistical model to distinguish honeys from different floral origins. Significant differences were identified among the studied honey samples from multivariate chemometric methods. The proline content varied among the four types of honeys, with the values decreasing in the order: buckwheat > Codonopsis > sunflower > rapeseed. Rapeseed honeys contained a high level of benzoic acid, while rutin, p -coumaric acid, p -hydroxybenzoic acid were present at relatively high levels in buckwheat honeys. Principal component analysis (PCA) revealed that rapeseed honey could be distinguished from the other three unifloral honeys, and benzoic acid, proline and kaempferol could serve as potential floral markers. Using 18 phenolic compounds and proline the honey samples were satisfactorily classified according to floral origin at 94% correct prediction by linear discriminant analysis (LDA). The results indicated that phenolic compounds and proline were useful for the identification of the floral origin of the four type honeys., Competing Interests: The authors declare no conflict of interest.

The aim of this study was to develop an analytical method for the analysis of a wide range of veterinary drugs in honey and royal jelly. A modified sample preparation procedure based on the quick, easy, cheap, effective, rugged and safe (QuEChERS) method was developed, followed by liquid chromatography tandem mass spectrometry determination. Use of the single sample preparation method for analysis of 42 veterinary drugs becomes more valuable because honey and royal jelly belong to completely different complex matrices. Another main advantage of the proposed method is its ability to identify and quantify 42 veterinary drugs with higher sensitivity than reference methods of China. This work has shown that the reported method was demonstrated to be convenient and reliable for the quick monitoring of veterinary drugs in honey and royal jelly samples., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

This study reports a rapid, automated screening and quantification method for the determination of multi-xenobiotic residues in honey using ultra-high performance liquid chromatography-hybrid quadrupole-Orbitrap mass spectrometry (UHPLC-Q-Orbitrap) with a user-built accurate-mass database plus parallel reaction monitoring (PRM). The database contains multi-xenobiotic information including formulas, adduct types, theoretical exact mass and retention time, characteristic fragment ions, ion ratios, and mass accuracies. A simple sample preparation method was developed to reduce xenobiotic loss in the honey samples. The screening method was validated based on retention time deviation, mass accuracy via full scan-data-dependent MS/MS (full scan-ddMS2), multi-isotope ratio, characteristic ion ratio, sensitivity, and positive/negative switching performance between the spiked sample and corresponding standard solution. The quantification method based on the PRM mode is a promising new quantitative tool which we validated in terms of selectivity, linearity, recovery (accuracy), repeatability (precision), decision limit (CCα), detection capability (CCβ), matrix effects, and carry-over. The optimized methods proposed in this study enable the automated screening and quantification of 157 compounds in less than 15 min in honey. The results of this study, as they represent a convenient protocol for large-scale screening and quantification, also provide a research approach for analysis of various contaminants in other matrices., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A simple, rapid, and reliable liquid-liquid extraction coupled to GC-MS method was developed and validated for the quantification of 22 phthalate esters (PAEs) in honey and royal jelly. Instrument parameters for GC-MS were tested to obtain the satisfactory separation between 22 PAEs with high sensitivity. The extraction procedure was optimized in order to achieve the best recovery. The following criteria were used to validate the developed method: linearity, LOD, lower LOQ, precision, accuracy, matrix effect and carry-over. Correlation coefficients were >0.999 by applying the linear regression model based on the least-squares method with a weighting factor (1/x). The intra- and interday precision were within 12.7% in terms of RSD, and the accuracy was within -11.8% in terms of relative error. The mean extraction recoveries ranged between 80.1 and 110.9% for honey and royal jelly. No significant matrix effect and carry-over for PAEs were observed for the analysis of honey and royal jelly samples. A total of 20 real samples were analyzed for a mini-survey using the developed method. Seven PAEs in honey samples and five PAEs in royal jelly samples were found, indicating potential contamination with several PAEs., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A high performance liquid chromatography-diode array detection-tandem mass spectrometry (HPLC-DAD-MS/MS) method for the floral origin traceability of chaste honey and rape honey samples was firstly presented in this study. Kaempferol, morin and ferulic acid were used as floral markers to distinguish chaste honey from rape honey. Chromatographic fingerprinting at 270 nm and 360 nm could be used to characterise chaste honey and rape honey according to the analytical profiles. Principal component analysis (PCA), partial least squares (PLS), partial least squares-discrimination analysis (PLS-DA) and soft independent modeling of class analogy (SIMCA) were applied to classify the honey samples according to their floral origins. The results showed that chaste honey and rape honey could be successfully classified by their floral sources with the analytical methods developed through this study and could be considered encouraging and promising for the honey traceability from unifloral or multifloral nectariferous sources., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

A rapid and sensitive high-performance liquid chromatography (LC) method was developed for the simultaneous determination of metronidazole (MNZ), dimetridazole (DMZ), ronidazole (RNZ), tinidazole (TNZ), and 2-hydroxymethyl-1-methyl-5-nitroimidazole (HMMNI) in honey. After extraction with ethyl acetate and evaporation, the residue containing the nitroimidazoles was dissolved in ethyl acetate-hexane and subjected to solid-phase extraction cleanup by amine extraction columns. The effluent was evaporated to dryness, and residues were dissolved and determined by LC with an ultraviolet detector set at 315 nm. The limits of detection were 1.0-2.0 ng/g for MNZ, DMZ, RNZ, TNZ, and HMMNI in honey. Average recoveries ranged from 71.5-101.4% in honey fortified at 10, 20, 50, and 100 ng/g. The method was validated for the analysis of real honey samples.

Honey, a natural healthy liquid bee product, is rich in amino acids, vitamins, and other essential nutrients. Different origin honeys also varied in organic acids. The objective of this study is to establish an efficient solid-phase extraction-gas chromatography–mass spectrometry (SPE-GC–MS) method to eliminate interference of sugar and other impurities for accurately estimating 22 organic acids in honey by optimizing extraction, purification, derivatization, and gas chromatography–mass spectrometry (GC–MS) analytical conditions. After being extracted, purified and derivatized, organic acids in honey were qualified and quantified by GC–MS. This method was evaluated experimentally, and the results showed that, within a certain concentration range, the standard curve linear relationship was satisfactory (R2 > 0.9942), and the target organic acid recovery rate was 86.74% ~ 118.68%. Besides, precision (relative standard deviation, RSD = 2.98% ~ 13.42%), detection limit (LOD = 0.002 ~ 0.2 mg kg−1), and quantification limit (LOQ = 0.008 ~ 0.5 mg kg−1) met the target requirements. Also, based on this analytical method, the organic acids in five types of honey (acacia, jujube, vitex, canola and linden honey) were estimated. Notably, they all contained 22 different kinds of organic acids, and significant differences (p < 0.05) in the organic acid content and composition among different honey varieties were observed. PCA analysis showed that the five honeys could be differentiated based on the content of 22 organic acids. [ABSTRACT FROM AUTHOR]

Abstract: We report the use of ultra performance liquid chromatography (UPLC) separation together with evaporative light scattering detection (ELSD) to effectively distinguish honey adulterated with maltooligosaccharides. UPLC separation utilizing a mobile phase with pure water and acetonitrile containing 0.2% triethylamine, resulted in enhanced separation and a running time of less than 6min. Also, only a simple liquid–liquid extraction was required for the sample pretreatment. This UPLC–ELSD method provides limits of quantifications (LOQs) from 0.30 to 0.60mg/g for the six maltooligosaccharides (maltose, maltotriose, maltotetraose, maltopentaose, maltohexaose and maltoheptaose) ranging from 15 to 2000μg/mL with excellent linearity(R2 ≥0.9914). This optimized method also offers a satisfactory intra-day precision of 2.4%–9.4%, inter-day precision of 5.5%–12.1% and accuracy of −7.7%–+11.4% at each level. We successfully applied this system for detecting maltooligosaccharide contamination in 290 honey samples collected from apiaries, supermarkets and traditional agri-product markets. Concentrations of the six maltooligosaccharides varied from undetectable to 14.1mg/mL. The lowest quantifiable concentration that could be detected by this established method was 0.132mg/mL. This study therefore demonstrates the reliability and potential use of the UPLC–ELSD technique in scrutinizing the authenticity of honey in the food processing industry. [Copyright &y& Elsevier]

To ensure that honey belongs to a very appreciated botanical class, the classical methodology is melissopalynology analysis to identify and count pollen grains. However, this method is time-consuming and laborious. In this work, four stable isotopes (δ13C h , δ13C p , δ18O and δ2H) and twelve elemental contents (Na, Mg, Ca, K, Fe, Cr, Mn, Co, Cu, Sr, Se, Mo) were used to build the dataset, and the Random Forest (RF) algorithm, Support Vector Machines (SVM), Classification and Regression Trees (CART) and Linear Discriminant Analysis (LDA) were investigated to classify six varieties of Chinese honey (linden, sunflower, vetch, rape, acacia, and jujube). The results showed the RF algorithm exhibits the highest training accuracy (99.4%) and testing accuracy (96.5%) of the four algorithms. Hence, the RF algorithm was selected to rank the 16 attributes according to their contribution, and δ2H, Sr, δ18O, Mn, Ca, and K were considered the most important factors for identifying six varieties of honey. Furthermore, the results of the RF algorithm were verified by the parallel coordinates plot. This suggests that the RF algorithm provides an effective and accurate approach for classifying Chinese honey according to stable isotopic and elemental composition, which theoretically can be used to classify more types of honey. • A simple and rapid random forest algorithm classification method was developed. • Six varieties of Chinese honey samples were analyzed. • δ2H, Sr, δ18O, Mn, Ca and K establish valuable contributions for classification. • The RF algorithm exhibits a higher classification accuracy (96.5%). [ABSTRACT FROM AUTHOR]