Fractionation of Stable Isotope-Labeled Organic Pollutants as a Potential Tracer of Atmospheric Transport Processes

To test the potential for using stable isotope fractionation to examine the atmospheric transport of semivolatile organic compounds (SOCs), we conducted simplified distillation experiments in the laboratory and a tracer-release experiment using mixtures of stable isotope-labeled (D and 13C) and unlabeled SOCs. Perdeuterated phenanthrene and α-hexachlorocyclohexane were transported more slowly via air−water gas exchange in our laboratory experiments, resulting in significant isotope fractionation of perdeuterated/unlabeled compound mixtures. In contrast, isotope fractionation of 13C6-labeled SOCs was much lower. A field tracer-release study was then conducted by spiking a seawater retention pond with a mixture of D10-labeled, 13C2-labeled, and unlabeled phenanthrene and examining isotope fractionation of the mixture after air−water gas exchange. No preferential fractionation of D10- vs 13C2-labeled phenanthrene was observed in the pond water; however, greater fractionation of D10- vs 13C2-labeled phenanthrene was observed in air samples collected within a 1−100 m radius of the pond. Thus, stable isotope tracers may provide a means of examining the atmospheric transport and air−earth exchange rates of POPs in an environmental realistic setting.