Application of low-density polyethylene (LDPE) passive samplers for monitoring PAHs in groundwater

Equilibrium passive sampling continues to find increasing use for performing in situ assessments and monitoring of hydrophobic organic compounds (HOCs). Although this method has been successfully used in several field studies including open surface waters and sediments, comparatively, their use in groundwater has been very limited. In this study, low-density polyethylene (LDPE) passive samplers were deployed for 80 days in three groundwater wells contaminated with polycyclic aromatic hydrocarbons (PAHs). Prior to deployment, LDPE was loaded with performance reference compounds (PRCs) consisting of deuterated PAHs and their release used to ascertain system equilibrium. Within the 80-day deployment period, LDPE-groundwater equilibrium was confirmed for PAHs with molecular weights (MWs) in the range of 178 to 228 (i.e. anthracene, chrysene). Measured freely dissolved concentrations (C_w) were between one to three orders of magnitude lower than the total filtered concentrations (C_total) in the studied wells. The sum of PAHs (ΣPAHs) measured based on C_w and C_total were 2.05, 0.07 and 29.2 μg L^-1 and 197, 59.7 and 1010 μg L^-1, at wells 1, 2 and 3, respectively. A separate dataset, comprising long-term (2010 to 2022) concentrations of PAHs in total (i.e., unfiltered) groundwater, is also presented to provide insight into PAH contamination levels at the assessed groundwater wells based on conventional measurement. Estimated in situ LDPE daily clearance volumes (2.34 to 27.56 Ld^-1) for the target analytes were far less than the daily turnover of ground water (144 to 348 Ld^-1) encountered in the wells eliminating the possibility of depletive sampling of the groundwater by the passive samplers. These results represent the first published study on the practical application of equilibrium passive sampling using LDPE for monitoring and quantitatively assessing PAHs in groundwater. Also, this work demonstrates that LDPEs are a useful tool for measuring the C_w of PAHs in groundwater, a critical contaminant in many ecological and human health risk assessments.