Determination of PCB fluxes from Indiana Harbor and Ship Canal using dual-deployed air and water passive samplers.

We have developed a method for measuring fluxes of PCBs from natural waters using air and water passive samplers deployed simultaneously in the Indiana Harbor and Ship Canal (IHSC). Net volatilization of ƩPCBs was determined for 2017, and ranged from 1.4 to 2.8 μg m-2 d-1, with a median of 2.0 μg m-2 d-1. We confirm earlier findings that the IHSC experiences constant release of gas-phase PCBs. Gas-phase and freely-dissolved water ƩPCB samples median were 4.0 ng m-3 and 14 ng L-1, both exhibiting increasing concentrations over the year of study, and with a strong positive correlation between them (R2 = 0.93 for ƩPCBs). The relative concentrations of individual PCB congeners were very similar between air and water samples, and resemble Aroclor 1248, a mixture previously reported to contaminate the IHSC sediments. Monthly variability of the volatilization fluxes was primarily driven by the freely-dissolved water concentration changes (R2 = 0.87). Although different sampling methods were performed to estimate air-water fluxes between the month of August of 2006 and 2017, ƩPCB net fluxes have decreased by more than 60%, suggesting that either dredging at IHSC from 2012 to 2017 or reduction of upstream sources have decreased the freely-dissolved water concentrations of PCBs, thus reducing the air-water net volatilization in IHSC. Finally, we have shown that this passive sampling approach represents a simple and cost-effective method to assess the air-water exchange of PCBs, increase analytical sensitivity, enable measurements over time, and reduce uncertainties related to unexpected episodic events.