Isotopic Characterization of Mercury Atmosphere-Foliage and Atmosphere-Soil Exchange in a Swiss Subalpine Coniferous Forest.

To understand the role of vegetation and soil in regulating atmospheric Hg0, exchange fluxes and isotope signatures of Hg were characterized using a dynamic flux bag/chamber at the atmosphere-foliage/soil interfaces at the Davos-Seehornwald forest, Switzerland. The foliage was a net Hg0 sink and took up preferentially the light Hg isotopes, consequently resulting in large shifts (-3.27‰) in δ202Hg values. The soil served mostly as net sources of atmospheric Hg0 with higher Hg0 emission from the moss-covered soils than from bare soils. The negative shift of δ202Hg and Δ199Hg values of the efflux air relative to ambient air and the Δ199Hg/Δ201Hg ratio among ambient air, efflux air, and soil pore gas highlight that Hg0 re-emission was strongly constrained by soil pore gas evasion together with microbial reduction. The isotopic mass balance model indicates 8.4 times higher Hg0 emission caused by pore gas evasion than surface soil photoreduction. Deposition of atmospheric Hg0 to soil was noticeably 3.2 times higher than that to foliage, reflecting the high significance of the soil to influence atmospheric Hg0 isotope signatures. This study improves our understanding of Hg atmosphere-foliage/soil exchange in subalpine coniferous forests, which is indispensable in the model assessment of forest Hg biogeochemical cycling.

Canopy-Level Flux and Vertical Gradients of Hg0 Stable Isotopes in Remote Evergreen Broadleaf Forest Show Year-Around Net Hg0 Deposition.

Vegetation uptake represents the dominant route of Hg input to terrestrial ecosystems. However, this plant-directed sink is poorly constrained due to the challenges in measuring the net Hg0 exchange on the ecosystem scale over a long period. Particularly important is the contribution in the subtropics/tropics, where the bulk (∼70%) of the Hg0 deposition is considered to occur. Using the relaxed eddy accumulation technique, this study presents for the first time a whole ecosystem Hg0 flux record over an evergreen hardwood forest. This tower-based micrometeorological method gauged a cumulated net Hg0 flux of -41.1 µg m-2 over 16 months, suggesting that the subtropical montane forest acts as a large and continuous sink of atmospheric Hg0. The monthly net fluxes were consistently negative (-7.3 to -1.0 µg m-2 month-1) throughout the year, with the smallest absolute values occurring during the mild and dry subseason in spring, which was also the annual lowest in vegetation activity. Colocated measurements of multilevel gradients of Hg0 concentration and its stable isotopic composition support the finding of year-round Hg0 deposition. The stable Hg isotope measurements also show that in-canopy bi-directional Hg0 exchange is prevalent.

Mercury isotope variations within the marine food web of Chinese Bohai Sea: Implications for mercury sources and biogeochemical cycling.

Mercury (Hg) speciation and isotopic compositions in a large-scale food web and seawater from Chinese Bohai Sea were analyzed to investigate methylmercury (MeHg) sources and Hg cycling. The biota showed ∼5‰ variation in mass dependent fractionation (MDF, -4.57 to 0.53‰ in δ202Hg) and mostly positive odd-isotope mass independent fractionation (odd-MIF, -0.01 to 1.21‰ in Δ199Hg). Both MDF and odd-MIF in coastal biota showed significant correlations with their trophic levels and MeHg fractions, likely reflecting a preferential trophic transfer of MeHg with higher δ202Hg and Δ199Hg than inorganic Hg. The MDF and odd-MIF of biota were largely affected by their feeding habits and living territories, and MeHg in pelagic food web was more photodegraded than in coastal food web (21-31% vs. 9-11%). From the Hg isotope signatures of pelagic biota and extrapolated coastal MeHg, we suggest that MeHg in the food webs was likely derived from sediments. Interestingly, we observed complementary even-MIF (mainly negative Δ200Hg of -0.36 to 0.08‰ and positive Δ204Hg of -0.05 to 0.82‰) in the biota and a significant linear slope of -0.5 for Δ200Hg/Δ204Hg. This leads us to speculate that atmospheric Hg0 is an important source to bioaccumulated MeHg, although the exact source-receptor relationships need further investigation.