This paper presents the first gaseous elemental mercury (GEM) air-surface exchange measurements obtained over naturally enriched and background (< 0.1 μg g<sup>−1</sup> Hg) terrestrial landscapes in Australia. Two pilot field studies were carried out during the Australian autumn and winter periods at a copper-gold-cobalt-arsenic-mercury mineral field near Pulganbar, NSW. GEM fluxes using a dynamic flux chamber approach were measured, along with controlling environmental parameters over three naturally enriched and three background substrates. The enriched sites results showed net emission to the atmosphere and a strong correlation between flux and substrate Hg concentration, with average fluxes ranging from 14 ± 1 ng m<sup>−2</sup> h<sup>−1</sup> to 113 ± 6 ng m<sup>−2</sup> h<sup>−1</sup>. Measurements at background sites showed both emission and deposition. The average Hg flux from all background sites showed an overall net emission of 0.36 ± 0.06 ng m<sup>−2</sup> h<sup>−1</sup>. Fluxes show strong relationships with temperature, radiation, and substrate parameters. A compensation point of 2.48, representative of bare soils was determined. Comparison of the Australian data to North American data confirmed the need for Australian specific mercury air-surface exchange data representative of Australia's unique climatic conditions, vegetation types, land use patterns, and soils.