Occurrence of pesticides and environmental contaminants in vineyards: Case study of Portuguese grapevine canes

Abstract

Every year, after grape harvesting, high quantities of vine-canes are generated. Due to the high amount of bioactive compounds present in this woody material, several studies reported their potential to be used in different sustainable applications. However, before employing vine-canes in this kind of products, their safety needs to be assessed. A robust method for identification and quantification of 30 environmental contaminants (12 organochloride pesticides (OCPs), 6 organophosphorus pesticides (OPPs), 5 polychlorinated biphenyls (PCBs) and 7 brominated flame retardants (BFRs)) in vine-canes was developed. For that, the extraction and clean-up procedures were optimized, namely the vine-canes size, the QuEChERS (quick, easy, cheap, effective, rugged and safe) composition and the amount of carbon used in the dispersive-solid phase extraction (d-SPE). Suitable analytical parameters were obtained: linearity (r2) >0.99 for all the studied compounds and for the solvent and matrix-matched standards; relative standard deviation (RSD) below 14%; and mean recoveries for two spiking levels (10 and 20 μg/kg) between 75 and 103%, excepting for the PCBs that ranged between 59 and 105%. The limit of detection (LOD) and quantification (LOQ) ranged between 0.38 and 1.09 and 1.26 to 3.64 μg/kg, respectively. Regarding the analysis of 19 vine-cane samples, corresponding to four different varieties (Touriga Nacional, Tinta Roriz, Alvarinho, and Loureiro) collected in four different years in the North of Portugal, five contaminants (aldrin, 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (p,p′-DDE), α-hexachlorocyclohexane (α-HCH), 2,4,4′-trichlorobiphenyl (PCB28), and 2,2′,4,5,5′-pentachlorobiphenyl (PCB101)) were detected. However, only α-HCH (5.85 ± 0.32 to 5.99 ± 0.25 μg/kg) and aldrin (2.44 ± 0.15 μg/kg) were quantified above the LOQ. The screening of environmental contaminants in vine-canes is essential to waste valorization, especially if the goal is to apply them in products for human consumption.