Unraveling atmospheric mercury dynamics at Mauna Loa through the isotopic analysis of total gaseous mercury

Our investigation seeks to uncover the intricate nature of mercury dynamics in the free troposphere through analysis of the isotopic composition of total gaseous elemental mercury (TGM) at the high altitude Mauna Loa Observatory (MLO, 3397 m) in Hawaii, USA. By focusing on this unique site, we aim to provide essential insights into the behavior and cycling of mercury, contributing valuable data to a deeper understanding of its global distribution and environmental impacts. Forty-eight hours of TGM sampling from January to September 2022 revealed significant variations in δ²⁰²Hg (-1.86 % to -0.32 %; mean = -1.17 ± 0.65 %, 2 SD, n = 34) and small variations in Δ¹⁹⁹Hg (-0.27 % to 0.04 %; mean = -0.13 ± 0.14 %, 2 SD, n = 34) and Δ²⁰⁰Hg (-0.20 % to 0.06 %; mean = -0.05 ± 0.13 %, 2 SD, n = 34). During the sampling period, GEM was negatively correlated with gaseous oxidized mercury (GOM). However, the GOM/GEM ratio was not -1, suggesting that GEM oxidation and subsequent scavenging occurred previously. The δ²⁰²Hg isotopic compositions of TGM at MLO were different from those of reported values of high-altitude mountains; the δ²⁰²Hg of TGM at MLO was lower than the isotopic ratios that were obtained from other mountain regions. The unique atmospheric conditions at Mauna Loa, with (upslope winds during the day and downslope winds at night, likely result in the) possibly mixing of GEMs from terrestrial (and possibly oceanic GEM emission) sources with and tropospheric sources, influencing and affect the isotopic composition. During the late summer to early fall (September 14-28), negative correlations were found between relative humidity and GOM and between particle number concentrations and Δ¹⁹⁹Hg, indicating the gas-to-particle partitioning of the atmospheric mercury during this period. This study will improve our understanding on mercury dynamics of marine origin and high altitudes and shed light on its complex interactions with environmental factors.