▎ 摘　　要

An electrochemical method is presented for the determination of arsenic at subnanomolar levels. It is based on potentiometric stripping analysis (PSA) using a graphene paste electrode modified with the thiacrown 1,4,7-trithiacyclononane (TTCN) and gold nanoparticles (AuNPs). The electrode surface was characterized by means of cyclic voltammetry, electrochemical impedance spectroscopy, chronocoulometry and scanning electron microscopy. The modified electrode displays a 15-fold enhancement in the PSA signal (dt/dE) compared to a conventional graphene paste electrode. Under optimized conditions, the signal is proportional to the concentration of As(III) in the range from 25 pM to 34 nM (r(2) = 0.9977), and the detection limit (SD/s) is as low as 8 pM. The modified electrode was successfully applied to the determination of total arsenic [i.e., As(III) and As(V)] in pharmaceutical formulations, human hair, sea water, fruits, vegetables, soil, and wine samples.