Beyond the tropopause hypothesis: Drivers of even mercury isotope fractionation unraveled by 3D modeling.

Song, Zhengcheng; Huang, Shaojian; Zhang, Peng; Yuan, Tengfei; Miao, Xin; Tang, Kaihui; Sun, Guangyi; Fu, Xuewu et al. · Sci Adv · 2025

basic_science · Level V

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Abstract

Mercury (Hg) is a globally persistent contaminant with substantial health impact. The mass-independent fractionation of even mercury isotopes (even-MIF, denoted as Δ<sup>200</sup>Hg) is widely used to trace atmospheric Hg sources and fluxes. However, the chemical processes inducing even-MIF remain largely unknown. Here, we develop a three-dimensional atmospheric Hg isotope model linking Hg redox processes with even-MIF. The results show that the previous hypothesis of even-MIF occurring exclusively at the tropopause may not fully explain the global Δ<sup>200</sup>Hg patterns. We speculate OH-initiated reactions and photoreduction of Hg<sup>II</sup>(p) as likely dominant drivers. Simulations show that even-MIF primarily originates in the free troposphere and propagates downward to surface air. Our results reveal distinct spatial Δ<sup>200</sup>Hg variations that were previously unaccounted for in tracing Hg sources. This study provides critical insights into even-MIF drivers and serves as a reference for using Δ<sup>200</sup>Hg to trace atmospheric Hg sources.