Vertical profile measurements of soil air suggest immobilization of gaseous elemental mercury in mineral soil.

Evasion of gaseous elemental Hg (Hg(0)g) from soil surfaces is an important source of atmospheric Hg, but the volatility and solid-gas phase partitioning of Hg(0) within soils is poorly understood. We developed a novel system to continuously measure Hg(0)g concentrations in soil pores at multiple depths and locations, and present a total of 297 days of measurements spanning 14 months in two forests in the Sierra Nevada mountains, California, U.S. Temporal patterns showed consistent pore Hg(0)g concentrations below levels measured in the atmosphere (termed Hg(0)g immobilization), ranging from 66 to 94% below atmospheric concentrations throughout multiple seasons. The lowest pore Hg(0)g concentrations were observed in the deepest soil layers (40 cm), but significant immobilization was already present in the top 7 cm. In the absence of sinks or sources, pore Hg(0)g levels would be in equilibrium with atmospheric concentrations due to the porous nature of the soil matrix and gas diffusion. Therefore, we explain decreases in pore Hg(0)g in mineral soils below atmospheric concentrations--or below levels found in upper soils as observed in previous studies--with the presence of an Hg(0)g sink in mineral soils possibly related to Hg(0)g oxidation or other processes such as sorption or dissolution in soil water. Surface chamber measurements showing daytime Hg(0)g emissions and nighttime Hg(0)g deposition indicate that near-surface layers likely dominate net atmospheric Hg(0)g exchange resulting in typical diurnal cycles due to photochemcial reduction at the surface and possibly Hg(0)g evasion from litter layers. In contrast, mineral soils seem to be decoupled from this surface exchange, showing consistent Hg(0)g uptake and downward redistribution--although our calculations indicate these fluxes to be minor compared to other mass fluxes. A major implication is that once Hg is incorporated into mineral soils, it may be unlikely subjected to renewed Hg(0)g re-emission from undisturbed, background soils emphasizing the important role of soils in sequestering past and current Hg pollution loads.