Analytical Method Development and Chemometric Approach for Evidencing Presence of Plasticizer Residues in Nectar Honey Samples

Abstract

Over the years, anthropogenic sources have increasingly affected food quality. One of the most sensitive and nutritional matrices affected by chemical contamination is honey, due to the use of acaricides. Recently, the attention has moved to the presence of phthalates (PAEs) and bisphenol A (BP-A), molecules present in plastic materials used both in the production phase and in the conservation of honey. In this study, an analytical method for the simultaneous determination of PAEs (dimethyl phthalate DMP, diethyl phthalate DEP, diisobutyl phthalate DiBP, dibutyl phthalate DBP, bis(2-ethylhexyl) phthalate DEHP, and di-n-octyl-phthalate DnOP) and BP-A was developed. The extraction technique is the ultrasound-vortex-assisted dispersive liquid–liquid microextraction (UVA-DLLME), using 150 µL of toluene as an extraction solvent, followed by the gas chromatography coupled with ion trap mass spectrometry analysis (GC–IT/MS). The developed method is sensitive, reliable, and reproducible: it shows high correlation coefficients (R > 0.999); limits of detection (LODs) less than 11 ng·g−1; limits of quantification (LOQs) less than 16 ng·g−1; repeatability below 3.6%, except BP-A (11.6%); and accuracy below 4.8%, except BP-A (17.6%). The method was applied to 47 nectar honey samples for evidencing similarities among them. The chemometric approach based on Hierarchical Cluster Analysis and Principal Component Analysis evidenced some similitudes about sample origin as well as marked differences between PAE and BP-A sources.

Critical Review on the Presence of Phthalates in Food and Evidence of Their Biological Impact

“…Considering the steady growth of consumption of bottled water and the toxicological effect of PAEs in the field of drinking water, the WHO and EPA set a maximum concentration level (MCL) for DEHP at 6/8 µg L −1 [ 211 ]. According to these guidelines, exposure to DBP, DEHP, and BBP via consumption of bottled water under condition of common use is well below the MCL stated by WHO and EPA [ 203 ] and, in particular, PAE exposure through water intake has been evaluated extremely low for children (0.002–1.1% TDI) [ 16 ].…”

“…In summary, different conditions such as pH [ 203 , 212 ], storage time [ 17 , 207 ], storage temperature (30–60 °C) [ 16 , 213 , 214 ], and exposure to sunlight [ 214 ] may influence the PAE concentration of PET bottled mineral water. Luo et al, analyzing the frequency of the five targeted phthalates in bottled water of twenty-one countries and more than three hundred different brands, found that the highest concentration of DEHP are detected in bottled water from Thailand, Croatia, the Czech Republic, Saudi Arabia, and China.…”

“…Recently, the importance of determining the presence of PAE in food, beverages, and in their packaging has become increasingly evident. Thus, different analytical methods have been developed to determine PAEs in different matrices [ 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 ] and many studies have been carried out in order to determine the risk correlated to phthalate contamination in foodstuffs, even though their association with the onset of several diseases is still controversial [ 17 , 18 , 19 ].…”

Comprehensive Insight from Phthalates Occurrence: From Health Outcomes to Emerging Analytical Approaches

“…The lowest concentration was obtained for DnOP with 5.1 ng/g, while the highest was for bisphenol A (BP-A) with 996.8 ng/g. Using honey samples, Notardonato et al [ 87 ] also developed and validated a UVA-DLLME combined with GC-MS to determine PAEs in six honey samples. The highest amount was obtained for DEP with 5.05 µg/g while the lowest for di-isobutyl phthalate (DiBP) with 0.01 µg/g.…”

Human Erythrocytes Exposed to Phthalates and Their Metabolites Alter Antioxidant Enzyme Activity and Hemoglobin Oxidation

“…Phthalates do not form covalent bonds with the substances they are being added to and thus they may migrate easily and enter food, water, air, cosmetics, and various products of everyday use [ 5 , 6 , 7 ]. These compounds enter the human body mainly via the enteral pathway (food, water, drugs) at about 7–10 µg/kg of body weight (BW)/day but also by inhalation (concentration in the air: BBP 0.058–3.97mg/m 3 , DBP 1.5–270 ng/m 3 ) or through dermal contact with cosmetics (DBP max 0.594 ppm and BBP max 186.770 ppm) [ 7 , 8 , 9 , 10 ]. After entering the organism, DBP and BBP are decomposed by lipases and esterases to monoesters, such as mono-n-butyl phthalate (MBP) and mono-benzyl phthalate (MBzP) ( Figure 1 ) [ 11 , 12 ].…”