Volatile markers as a reliable alternative for the correct classification of citrus monofloral honey.

The pollen analysis to classify monofloral honey is an unresolved challenge specially when the pollen is under-represented as the case of citrus honey. Thus, this study assesses the validity of the volatile fraction to differentiate types of honey, with special attention to markers compounds of citrus honey that could permit their distinction. Unsupervised analysis (PCA and HCA) showed that the volatile fraction of honey containing Citrus sp. pollen, undoubtedly differentiates it from other types of honey. An OPLS model focused on citrus honey selected 5 volatile compounds (of the 123 found in all samples by GC-MS) as significant predictors of the currently used value of methyl anthranilate obtained by HPLC. The joint detection of 4 lilac-aldehydes and the volatile methyl-anthranilate has the advantage of providing more precise information. Therefore, it could be proposed as a consistent marker to ensure the correct classification of citrus honey, fostering its labelling reliability.

High Fundamental Frequency (HFF) Monolithic Quartz Crystal Microbalance with Dissipation Array for the Simultaneous Detection of Pesticides and Antibiotics in Complex Food.

As in the case of the food industry in general, there is a global concern about safety and quality in complex food matrices, such as honey, which is driving the demand for fast, sensitive and affordable analytical techniques across the honey-packaging industry. Although excellent techniques such as liquid chromatography-tandem mass spectrometry (LC-MS/MS) are available, these are located in centralized laboratories and are still lacking in speed, simplicity and cost-effectiveness. Here, a new approach is presented where a competitive immunoassay is combined with a novel High Fundamental Frequency Quartz Crystal Microbalance with Dissipation (HFF-QCMD) array biosensor for the simultaneous detection of antibiotics and pesticides in honey. Concretely, thiabendazole and sulfathiazole residues were monitored in spiked honey samples. Results revealed that HFF-QCMD arrays provide a complementary and reliable tool to LC-MS/MS for the analysis of contaminants in these kinds of complex matrices, while avoiding elaborate sample pre-treatment. The good sensitivity achieved (I50 values in the 70-720 µg/kg range) and the short analysis time (60 min for 24 individual assays), together with the ability for multiple analyte detection (24 sensor array) and its cost-effectiveness, pave the way for the implementation of a fast on-line, in situ routine control of potentially hazardous chemical residues in honey.

Monofloral honey authentication by voltammetric electronic tongue: A comparison with 1H NMR spectroscopy.

Proton-nuclear-magnetic-resonance-spectroscopy (1H NMR) is the widely accepted reference method for monitoring honey adulteration; however, the need to find cheaper, faster, and more environmentally friendly methodologies makes the voltammetric-electronic-tongue (VET) a good alternative. The present study aims to demonstrate the ability of VET (in comparison with 1H NMR) to predict the adulteration of honey with syrups. Samples of monofloral honeys (citrus, sunflower and heather, assessed by pollen analysis) simulating different levels of adulteration by adding syrups (barley, rice and corn) from 2.5 to 40% (w/w) were analyzed using both techniques. According to the indicators (slope, intercept, regression coefficient-R2, root mean square error of prediction-RMSEP) of the partial-least-squares (PLS) regression models, in general terms, the performance of these models obtained by both techniques was good, with an average error lower than 5% in both cases. These results support the use of VET as a screening technique to easily detect honey adulteration with syrups.

Quality parameters, pollen and volatile profiles of honey from North and Central Mozambique.

Honey from different provinces of North and Central Mozambique was characterised considering their physicochemical quality parameters, colour, sugars, total antioxidants, pollen analysis and volatile profile. Flora that surrounds the hives, and the apicultural practices also influence in their characteristics. According to a similar pollen spectrum, eight types of honey were found. In these, the predominant pollens were: I-Astragalus type; II-Acanthus sp; III-Celastraceae; IV-Brassicaceae; V-Anacardiaceae and Astragalus type; VI-Astragalus type and Myrtaceae; VII-Asteraceae family and VIII-unknown. Group I (from Nampula), especially distanced itself from the others mainly due to the special abundance of certain compounds (alcohols, aldehydes, esters, acids and terpenes). The presence of furan compounds largely identified in Sofala and Manica honeys could be due to inadequate beekeeping practices or storage conditions. A discriminant analysis correctly classified 96.7% of the groups, being electrical conductivity and moisture followed by the volatile-compound 3-Methylbutan-1-ol and the free acidity, the variables that most contributed.

Standardizing the analysis of phenolic profile in propolis.

The analysis of propolis is controversial, hampering the comparison of its biological properties and estimation of its commercial value. This work evaluates the effectiveness of combining maceration and ultrasonication extraction techniques on the yield, total phenol content (Folin-Ciocalteau) and the specific phenolic compounds (HPLC-UV), on propolis from different origins. The extraction method was not significant in any case; therefore ultrasonication is recommended (time-saving) but only when a double extraction is performed. Propolis yield varies significantly between samples, as it includes impurities, consequently the results should be expressed considering the yield (as balsam) instead of raw propolis. Of the 13 quantified phenolic compounds, CAPE and pinocembrin (803 and 701 mg/g balsam) stand out. The phenolic profile of a propolis must be fixed using both total phenol content (with a consensus reference compound) and the specific phenolic compounds, since the latter provides information about compounds that can play a significant antioxidant role.

Volatile profile in the accurate labelling of monofloral honey. The case of lavender and thyme honey.

The proliferation of hybrid plant varieties without pollen, such as lavender, has complicated the classification of specific types of honey. This study evaluated the correlation between the proclaimed type of monofloral honey (lavender or thyme) as appears on the label with the actual percentage of pollen. In addition, physicochemical parameters, colour, olfacto-gustatory profile, and volatile compounds were tested. All of the samples labelled as lavender were wrongly classified according to the usual commercial criteria (minimum 10% of pollen Lavandula spp.). In the case of lavender honey, there was significant agreement between commercial labelling and classification through organoleptic perception (81.8%), and above all between the commercial labelling and the volatile compounds (90.9%). For thyme honey, agreement for both parameters was 90.0%. These results offer compelling evidence that the volatile compounds are useful for the classification of lavender honey with low levels of pollen since this technique agrees well with the organoleptic analysis.

Antioxidant activity and physico-chemical parameters for the differentiation of honey using a potentiometric electronic tongue.

BACKGROUND: This work evaluates the capacity of a potentiometric electronic tongue to differentiate between types of honey (orange blossom, rosemary, thyme, sunflower, winter savory and honeydew honey) according to their antioxidant level. The classical procedures used to evaluate the antioxidant potential of honey are inappropriate for in situ monitoring on reception of batches of raw honey in the packaging industry. They are also destructive, time-consuming and very tedious, requiring highly expert analysts and specialised equipment. RESULTS: The electronic tongue system made with Ag, Ni, Co, Cu and Au was able to not only differentiate between types of honey but also to predict their total antioxidant capacity. The discrimination ability of the system was proved by means of a fuzzy ARTMAP type ANN, with 100% classification success. A prediction multiple linear regression model showed that the best correlation coefficient was for antioxidant activity (0.9666), then for electrical conductivity (0.8959) and to a lesser extent for aw , moisture and colour. CONCLUSION: The proposed measurement system could be a quick, easy option for the honey packaging sector to provide continuous in-line information about a characteristic as important as the antioxidant level. © 2016 Society of Chemical Industry.

Suitability of antioxidant capacity, flavonoids and phenolic acids for floral authentication of honey. Impact of industrial thermal treatment.

Total antioxidant activity, physicochemical parameters, and the profile of flavonoids and phenolic acid compounds were evaluated for: their ability to distinguish between the botanical origins of four types of Spanish honey, the impact of industrial thermal treatment, and the effect of the year of collection. Citrus honey had the lowest levels of all the analysed variables, then rosemary and polyfloral, and honeydew the highest ones. Botanical origin affects the profile of flavonoids and phenolic compounds sufficiently to permit discrimination thanks to the predominance of particular compounds such as: hesperetin (in citrus honey); kaempferol, chrysin, pinocembrin, caffeic acid and naringenin (in rosemary honey) and myricetin, quercetin, galangin and particularly p-coumaric acid (in honeydew honey). The impact of industrial thermal treatments is lower than the expected variability as a consequence of the year of collection, though neither factor has enough influence to alter these constituent compounds to the point of affecting the discrimination of honey by botanical origin.

Volatile fraction composition and physicochemical parameters as tools for the differentiation of lemon blossom honey and orange blossom honey.

BACKGROUND: Volatile fraction profile and physicochemical parameters were studied with the aim of evaluating their effectiveness for the differentiation between lemon blossom honey (Citrus limon L.) and orange blossom honey (Citrus spp.). They would be useful complementary tools to the traditional analysis based on the percentage of pollen. RESULTS: A stepwise discriminant analysis constructed using 37 volatile compounds (extracted by purge and trap and analysed by gas chromatography-mass spectrometry), and physicochemical and colour parameters (diastase, conductivity, Pfund colour and CIE L a b) together provided a model that permitted the correct classification of 98.3% of the original and 96.6% of the cross-validated cases, indicating its efficiency and robustness. This model proved its effectiveness in the differentiation of both types of honey with another set of batches from the following year. CONCLUSION: This model, developed from the volatile compounds, physicochemical and colour parameters, has been useful for the differentiation of lemon and orange blossom honeys. Furthermore, it may be of particular interest for the attainment of a suitable classification of orange honey in which the pollen count is very low. These capabilities imply an evident marketing advantage for the beekeeping sector, since lemon blossom honey could be commercialized as unifloral honey and not as generic citrus honey and orange blossom honey could be correctly characterized.