▎ 摘 要
To further assess the human being's exposure to polycyclic aromatic hydrocarbons (PAHs) through the dietary pathway, understanding the partitioning of these chemicals co-existed with nanomaterials in edible vegetable systems deserves specific consideration. In this study, the fiber-optic fluorimetry was applied to in situ examine the effects of graphene (GNS) and graphene oxide (GO) nanosheets on the quantification and depuration of three-ringed phenanthrene (Phe) and four-ringed fluoranthene (Fla) adsorbed individually onto the living spinach (Spinacia oleracea L) surfaces. When the GNS and GO dosages separately increased to the maximum values: a respective red-shift of 4-5 nm and blue-shift of 2-3 nm occurred for the optimal detection emission wavelengths (lambda(em)) of the two PAHs, indicating that individual GNS and GO resulted in different changes to the epicuticular wax (ECW) polarity; GNS-inducing fluorescence quenching for the PAHs was about two times greater than GO, owing to the stronger pi-pi interactions between PAH molecules and GNS relative to GO; the volatilization coefficients (k(c1)) were reduced by 31.1% versus 26.7% for Phe, and 51.6% versus 34.4% for Fla, mainly via providing an additional adsorbent and promoting the accessibility of the leaf cuticle; respective photolysis coefficients (k(p2)) of Phe and Fla decreased by 42.9% and 50.0% with GNS, primarily owing to the enhancement of the ECW light-adsorption capacity, but increased by 33.3% and 40.0% with GO due to its photocatalytic activities; overall, total depuration coefficients (k(T1), k(T2)) of the two PAHs decreased by 11.1-55.6%. These findings demonstrate that GNS and GO significantly alter the depuration behavior of PAHs in vegetable systems, potentially posing a threat to the safety of edible vegetables. (C) 2017 Elsevier Ltd. All rights reserved.