Recent advances in understanding and measurement of Hg in the environment: Surface-atmosphere exchange of gaseous elemental mercury (Hg0).

The atmosphere is the major transport pathway for distribution of mercury (Hg) globally. Gaseous elemental mercury (GEM, hereafter Hg0) is the predominant form in both anthropogenic and natural emissions. Evaluation of the efficacy of reductions in emissions set by the UN's Minamata Convention (UN-MC) is critically dependent on the knowledge of the dynamics of the global Hg cycle. Of these dynamics including e.g. red-ox reactions, methylation-demethylation and dry-wet deposition, poorly constrained atmosphere-surface Hg0 fluxes especially limit predictability of the timescales of its global biogeochemical cycle. This review focuses on Hg0 flux field observational studies, namely the theory, applications, strengths, and limitations of the various experimental methodologies applied to gauge the exchange flux and decipher active sub-processes. We present an in-depth review, a comprehensive literature synthesis, and methodological and instrumentation advances for terrestrial and marine Hg0 flux studies in recent years. In particular, we outline the theory of a wide range of measurement techniques and detail the operational protocols. Today, the most frequently used measurement techniques to determine the net Hg0 flux (>95% of the published flux data) are dynamic flux chambers for small-scale and micrometeorological approaches for large-scale measurements. Furthermore, top-down approaches based on Hg0 concentration measurements have been applied as tools to better constrain Hg emissions as an independent way to e.g. challenge emission inventories. This review is an up-dated, thoroughly revised edition of Sommar et al. 2013 (DOI: 10.1080/10643389.2012.671733). To the tabulation of >100 cited flux studies 1988-2009 given in the former publication, we have here listed corresponding studies published during the last decade with a few exceptions (2008-2019). During that decade, Hg stable isotope ratios of samples involved in atmosphere-terrestrial interaction is at hand and provide in combination with concentration and/or flux measurements novel constraints to quantitatively and qualitatively assess the bi-directional Hg0 flux. Recent efforts in the development of relaxed eddy accumulation and eddy covariance Hg0 flux methods bear the potential to facilitate long-term, ecosystem-scale flux measurements to reduce the prevailing large uncertainties in Hg0 flux estimates. Standardization of methods for Hg0 flux measurements is crucial to investigate how land-use change and how climate warming impact ecosystem-specific Hg0 sink-source characteristics and to validate frequently applied model parameterizations describing the regional and global scale Hg cycle.