Polymeric Nanofiber-Carbon Nanotube Composite Mats as Fast-Equilibrium Passive Samplers for Polar Organic Contaminants

Abstract

To improve the performance of polymeric electrospun nanofiber mats (ENMs) for equilibrium passive sampling applications in water, we integrated two types of multiwalled carbon nanotubes (CNTs; with and without surface carboxyl groups) into polyacrylonitrile (PAN) and polystyrene (PS) ENMs. For 11 polar and moderately hydrophobic compounds (-0.07 ≤ logKOW ≤ 3.13), 90% of equilibrium uptake was achieved in under 0.8 days (t90% values) in nonmixed ENM-CNT systems. Sorption capacity of ENM-CNTs was between 2-and 50-fold greater than pure polymer ENMs, with equilibrium partition coefficients (KENM-W values) ranging from 1.4 to 3.1 log units (L/kg) depending on polymer type (hydrophilic PAN or hydrophobic PS), CNT loading (i.e., values increased with weight percent (wt %) of CNTs), and CNT type (i.e., greater uptake with carboxylated CNTs composites). During field deployment at Muddy Creek in North Liberty, Iowa, optimal ENM-CNTs (PAN with 20 wt % carboxylated CNTs) yielded atrazine concentrations in surface water with a 40% difference relative to analysis of a same-day grab sample. We also observed a mean percent difference of 30 (±20)% when comparing ENM-CNT sampler results to grab sample data collected within 1 week of deployment. With their rapid, high capacity uptake and small material footprint, ENM-CNT equilibrium passive samplers represent a promising alternative to complement traditional integrative passive samplers while offering convenience over large volume grab sampling.