ABSTRACT
In this work, a novel analytical methodology for the extraction and determination of polycyclic aromatic hydrocarbon derivatives, nitrated (NPAH) and oxygenated (OPAH), in bee honey samples was developed. The extraction approach resulted in being straightforward, sustainable, and low-cost. It was based on a salting-out assisted liquid-liquid extraction followed by liquid chromatography-tandem mass spectrometry determination (SALLE-UHPLC-(+)APCI-MS/MS). The following figures of merit were obtained, linearity between 0.8 and 500 ng g-1 for NPAH and between 0.1 and 750 ng g-1 for OPAH compounds, coefficients of determination (r2) from 0.97 to 0.99. Limits of detection (LOD) were from 0.26 to 7.42 ng g-1 for NPAH compounds and from 0.04 to 9.77 ng g-1 for OPAH compounds. Recoveries ranged from 90.6% to 100.1%, and relative standard deviations (RSD) were lower than 8.9%. The green assessment of the method was calculated. Thus, the Green Certificate allowed a classification of 87 points. This methodology was reliable and suitable for application in honey samples. The results demonstrated that the levels of nitro- and oxy-PAHs were higher than those reported for unsubstituted PAHs. In this sense, the production chain sometimes transforms foods as direct carriers of contaminants to consumers, representing a concern and demonstrating the need for routine control.
ABSTRACT
In this study, a novel, simple, and highly sensitive analytical procedure for the quantitative evaluation of oxygenated and nitrated polycyclic aromatic hydrocarbons in volcanic ash samples based on dispersive solid-liquid microextraction (DSLME) coupled to ultra high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was developed. Diverse chemometric tools were applied to optimize DSLME working conditions. Thus, a linear calibration curve for all the target analytes in the concentration range from 0.01 to 100 µg g-1 (r2 > 0.994) was obtained. The limits of detection for all the compounds were between 14.6 and 56.0 pg g-1, with high reproducibility (relative standard deviation (RSD) was below 8.1% for all the analytes). Additionally, recoveries ranged from 94.2 to 100%. The applicability of the method was evaluated and the feasibility of the existence of nitrated and oxygenated-PAHs in volcanic ashes at ultra-trace levels was demonstrated, which reveals an unknown source of distribution of these pollutants to the environment. Graphical Abstract.
