Evaluation of Postharvest Washing on Removal of Silver Nanoparticles (AgNPs) from Spinach Leaves

There is increasing use of silver nanoparticles (AgNPs) as pesticides for fruits and vegetables due to the particles' unique antimicrobial and insecticidal properties. However, residual AgNPs in harvested produce may transfer through the food chain and pose a potential risk to public health. The objective of this study is to determine whether postharvest washing can effectively remove AgNPs that had accumulated on fresh produce. Ten microliters of commercially available 40 nm citrate coated AgNPs (0.4 mg/L) was dropped to a (1 × 1 cm(2)) spot on spinach leaves, followed by washing with deionized water (DI water), Tsunami 100 (80 mg/L), or Clorox bleach (200 mg/L). Then, the AgNP removal efficiency of the three treatments was evaluated by surface-enhanced Raman spectroscopy (SERS), scanning electron microscopy (SEM)-energy dispersive spectrometry (EDS), and inductively coupled plasma mass spectrometry (ICP-MS). ICP-MS results showed that deionized water removed statistically insignificant amounts of total Ag (5%), whereas Tsunami 100 and Clorox bleach yielded 21 and 10% decreases in total Ag, respectively (P < 0.05). The increased removal efficiency resulted from AgNP dissolution and Ag(+) release upon contact with the oxidizing agents in Tsunami 100 (peroxyacetic acid, hydrogen peroxide) and Clorox bleach (sodium hypochlorite). According to the SERS results, the deionized water and Tsunami 100 treatments removed nonsignificant amounts of AgNPs. Clorox bleach decreased Ag NPs by >90% (P < 0.05); however, SEM-EDS images revealed the formation of large silver chloride (AgCl) crystals (162 ± 51 nm) on the leaf, which explained the low total Ag removal from ICP-MS. This study indicates current factory washing methods for fresh produce may not be effective in reducing AgNPs (by water and Tsunami 100) and total Ag (by all three means). This highlights the necessity to develop an efficient washing method for NP removal from food surfaces in the future.