Assessing the trends and effects of environmental parameters on the behaviour of mercury in the lower atmosphere over cropped land over four seasons

Abstract. Mercury is released to the atmosphere from natural and anthropogenic sources. Due to its persistence in the atmosphere, mercury is subject to long range transport and is thus a pollutant of global concern. Mercury emitted to the atmosphere enters terrestrial and aquatic ecosystems which act as sinks but also as sources of previously emitted and deposited mercury when the accumulated mercury is emitted back to the atmosphere. Studying the factors and processes that influence the behaviour of mercury from terrestrial sources is thus important for a better understanding of the role of natural ecosystems in the mercury cycling and emission budget.

A study was conducted over ten months (November 2006 to August 2007) at Elora, Ontario, Canada to measure gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate bound mercury (Hg^P) as well as GEM fluxes over different ground cover spanning the four seasons typical of a temperate climate zone. GEM concentrations were measured using a mercury vapour analyzer (Tekran 2537A) while RGM and Hg^P were measured with the Tekran 1130/1135 speciation unit coupled to another mercury vapour analyzer. A micrometeorological approach was used for GEM flux determination using a continuous two-level sampling system for GEM concentration gradient measurement above the soil surface and crop canopy. The turbulent transfer coefficients were derived from meteorological parameters measured on site.

A net GEM volatilization (6.31 ± 33.98 ng mM⁻² hr⁻¹, study average) to the atmosphere was observed. Average GEM concentrations and GEM fluxes showed significant seasonal differences and distinct diurnal patterns while no trends were observed for Hg^P or RGM. Highest GEM concentrations, recorded in late spring and fall, were due to meteorological changes such as increases in net radiation and air temperature in spring and lower atmospheric mixing height in fall. Highest GEM fluxes (18.1 ng m⁻² hr⁻¹, monthly average) were recorded in late spring but also during specific events in winter and fall. The main factors influencing the GEM flux were soil moisture content, soil temperature, precipitation events and ground cover. These trends indicate that the soil surface could be a significant mercury source in spring and summer seasons but also under specific meteorological conditions during the winter and fall.