Development of film-based passive samplers for in situ monitoring of trace levels of pyrethroids in sediment

Highlights: • Pyrethroids are widely used and sediment toxicity is of great concern. • We developed film-based samplers suitable for in situ ambient monitoring. • Both PE and SR samplers were capable of detecting all pyrethroids at ng/L. • The in situ values were validated by ex situ results and H. azteca toxicity test. • The developed samplers may be used for rapid and sensitive in situ monitoring. Residues of pyrethroid insecticides tend to accumulate in bed sediments due to their strong hydrophobicity. Rather than the total or bulk sediment concentration, it is the freely dissolved concentration (C_free) that drives toxicity to benthic invertebrates. In this study we developed thin film-based samplers for in situ ambient monitoring of pyrethroids at trace levels in sediment. Out of five common polymer materials, polyethylene (PE) and silicone rubber (SR), were identified to offer superior enrichment for pyrethroids from sediment. To circumvent the slow equilibrium process, ¹³C-permethrin and bifenthrin-d₅ were preloaded onto the films as performance reference compounds (PRCs). The PRC-preloaded film samplers were deployed at five sites in Southern California under field conditions for 7 d and retrieved for analysis. The sediment porewater C_free of eight pyrethroids derived from PRC-PE films ranged from 173 to 903 ng/L, accounting for 18.2–36.1% of the corresponding total porewater concentrations. The PRC-SR film samplers yielded C_free values closely mimicking those from the PRC-PE samplers, cross-validating the two sampling devices. Additionally, a significant positive association was found between the observed mortality from toxicity tests using Hyalella azteca and the C_free of bifenthrin (r = 0.628, p = 0.02). A significant linear correlation (R² = 0.99) between C_free derived from in situ monitoring and that of ex situ measurement under equilibrium conditions was also observed. Results from this study demonstrated that the film-based samplers may be used for in situ ambient monitoring to detect biologically relevant contamination of pyrethroids in bed sediments, which may contribute to improved risk assessment for this class of widely used insecticides.