Mercury (Hg) stable isotopes have emerged as a powerful tracer to resolve the sources, transformations, and deposition pathways of atmospheric Hg. Beyond conventional mass-dependent fractionation (MDF), atmospheric reactions can induce unique Hg mass-independent fractionation (MIF). This review synthesizes current sampling strategies and pretreatment protocols for gaseous Hg(0) and reactive Hg(II) in particulates and precipitation, and compiles their isotope compositions (δ202Hg for MDF, Δ199Hg for odd-MIF and Δ200Hg for even-MIF) across terrestrial background, urban-industrial, marine boundary layer, and polar regions. Terrestrial background Hg(0) typically exhibits positive δ202Hg with negative Δ199Hg and Δ200Hg, whereas reactive Hg(II) shows negative δ202Hg with positive Δ199Hg and Δ200Hg. These complementary patterns reflect predominant roles of photoreduction of Hg(II) and vegetation uptake of Hg(0). Urban-industrial Hg(0) tends to have low δ202Hg and elevated Δ199Hg and Δ200Hg, consistent with anthropogenic influence. However, post-emission transformations frequently obscure primary isotope signatures of Hg(II), complicating source-receptor relationships. In polar regions, reactive Hg (II) bears strong imprints of photoredox reactions at the snow-atmosphere interface, typically exhibiting very negative Δ199Hg values. Integrating isotope observations with deposition pathways indicates that dry deposition of Hg(0) often dominates fluxes to both terrestrial and marine surfaces. Scenario analysis under Shared Socioeconomic Pathways project notable increases in δ202Hg and Δ199Hg under low-emission futures. To better implement the Minamata Convention in a changing climate, future research should prioritize species-specific Hg sampling, better mechanistic understanding of isotope fractionation, and expanded isotope monitoring in underrepresented regions.
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