Critical Observations of Gaseous Elemental Mercury Air-Sea Exchange

Air-sea exchange of gaseous elemental mercury (Hg-0) is not well constrained, even though it is a major component of the global Hg cycle. Lack of Hg-0 flux measurements to validate parameterizations of the Hg-0 transfer velocity contributes to this uncertainty. We measured the Hg-0 flux on the Baltic Sea coast using micrometeorological methods (gradient-based and relaxed eddy accumulation [REA]) and also simulated the flux with a gas exchange model. The coastal waters were typically supersaturated with Hg-0 (mean +/- 1 sigma = 13.5 +/- 3.5 ng m(-3); ca. 10% of total Hg) compared to the atmosphere (1.3 +/- 0.2 ng m(-3)). The Hg-0 flux calculated using the gas exchange model ranged from 0.1-1.3 ng m(-2) h(-1) (10th and 90th percentile) over the course of the campaign (May 10-June 20, 2017) and showed a distinct diel fluctuation. The mean coastal Hg-0 fluxes determined with the two gradient-based approaches and REA were 0.3, 0.5, and 0.6 ng m(-2) h(-1), respectively. In contrast, the mean open sea Hg-0 flux measured with REA was larger (6.3 ng m(-2) h(-1)). The open sea Hg-0 flux indicated a stronger wind speed dependence for the Hg-0 transfer velocity compared to commonly used parameterizations. Although based on a limited data set, we suggest that the wind speed dependence of the Hg-0 transfer velocity is more consistent with gases that have less water solubility than CO2 (e.g., O-2). These pioneering flux measurements using micrometeorological techniques show that more such measurements would improve our understanding of air-sea Hg exchange.