Global Observations and Modeling of Atmosphere-Surface Exchange of Elemental Mercury – A Critical Review
Abstract. Reliable quantification of air-surfaces flux of elemental Hg vapor (Hg0) is crucial for understanding mercury (Hg) global biogeochemical cycles. There have been extensive measurements and modeling efforts devoting to estimating the exchange fluxes between the atmosphere and various surfaces (e.g., soil, canopies, water, snow, etc.) in past three decades. However, large uncertainty remains due to the complexity of Hg0 bi-directional exchange, limitations of flux quantification techniques and challenges in model parameterization. In this study, we provide a comprehensive review on the state of science in the atmosphere-surface exchange of Hg0. Specifically, the advancement of flux quantification techniques, mechanisms in driving the air-surfaces Hg exchange, and modeling efforts are presented. Due to the semi-volatile nature of Hg0 and redox transformation of Hg in environmental media, Hg deposition and evasion are influenced by multiple environmental variables including seasonality, vegetative coverage and its life cycle, temperature, light, moisture, atmospheric turbulence, presence of reactants (e.g., O3, radicals, etc.) that drives the physicochemical process of Hg in the media where Hg0 exchange occurs. However, effects of these processes on flux have not been fundamentally and quantitatively determined, which limits the accuracy of flux modeling. In this study, we compile an up-to-date global observational flux database and discuss the implication of flux data on global Hg budget. Mean Hg0 flux obtained by micrometeorological measurement did not appear to be significantly greater than the flux measured by dynamic flux chamber methods over unpolluted surfaces (p=0.16, one-tailed, Mann-Whitney U test). The spatio-temporal coverage of existing Hg0 flux measurements is highly heterogeneous with large data gaps existing in multiple continents (Africa, South Asia, Middle East, South America and Australia). The magnitude of evasion flux is strongly enhanced by human activities, particularly at contaminated sites. Hg0 flux observations in East Asia are comparatively larger in magnitude than the rest of the world, suggesting substantial reemission of previously deposited mercury from anthropogenic sources. Hg0 exchange over pristine surfaces (e.g., background soil and water) and vegetation need better constrains for global analysis of atmospheric Hg budget. The existing knowledge gap and the associated research needs for future measurements and modeling efforts for the air-surface exchange of Hg0 are discussed.