Evaluation of novel techniques for measurement of air-water exchange of persistent bioaccumulative toxicants in Lake Superior

We report initial measurements of concentrations and net air-water exchange fluxes of target persistent bioaccumulative toxicants (PBTs) in Lake Superior utilizing techniques not previously applied for this purpose. Gaseous PBTs are collected in diffusion denuders containing sections of commercial chromatography columns and subsequently thermally extracted into the cooled injection inlet of a high-resolution gas chromatograph. The PBT sampling/analytical methods enable accurate determination of gas-phase PBT concentration and micrometeorological measurement of fluxes to be carried out. PBT fluxes are measured by the modified Bowen ratio technique in which sensible heat flux is related to PBT flux, with the assumption of identical transfer velocities of heat and PBTs between two heights in the atmospheric surface layer. Micrometeorological measurement of flux accounts for all sources of resistance to mass transfer, including atmospheric stability effects, surface films, waves, sea spray, and bubbles. The sensible heat flux, PBT concentration, and PBT flux measurements carried out in 14 2- or 3-h periods during seven sampling events in Lake Superior in summer and fall 2002 and spring 2003 demonstrate advantages under the constraints of the techniques. The uncertainty of the flux measurements was typically in the range from 1% to 160%. Gaseous concentrations of α-hexachlorocyclohexane (α-HCH) and hexachlorobenzene (HCB) over Lake Superior were in the range from 6 to 170 and 12-95 pg/m3, respectively. Fluxes out of Lake Superior were measurable in 75% of the cases in which a concentration gradient was measured, and were in the range from -0.17 to +0.064 ng/m 2·h for α-HCH and from -0.60 to -0.093 ng/m 2·h for HCB. © 2005 American Chemical Society