Review of stable mercury isotopes in ecology and biogeochemistry

Due to the advent of cold vapor-multicollector-inductively coupled plasma mass spectrometry (CV-MC-ICP-MS) in the past two decades, many research groups studying mercury (Hg) biogeochemistry have integrated stable Hg isotopes into their research. Currently, >200 studies using this technique have been published and this has greatly enhanced our understanding of the Hg biogeochemical cycle beyond what Hg concentration and speciation analyses alone can provide. These studies are largely divided into two groups: (i) controlled experiments investigating fractionation of Hg isotopes and refining tools of isotopic analyses, and (ii) studies of natural variations of Hg isotopes. It is now known that Hg isotopes undergo both mass dependent fractionation (MDF; reported as the ratio of mass ²⁰²Hg to ¹⁹⁸Hg) and mass independent fractionation (MIF), with MIF occurring at odd masses (¹⁹⁹Hg, ²⁰¹Hg) to a larger magnitude and at even masses (²⁰⁰Hg, ²⁰⁴Hg) to a much smaller magnitude. The two types of MIF are controlled by different photochemical processes. The range of isotopic variations of MDF, odd-MIF, and even-MIF are now well documented in a diverse set of environmental samples, and researchers are continuing to explore how the field of Hg isotope biogeochemistry can be further developed and taken to the next level of understanding. One application that has received considerable attention is the use of Hg isotopes to examine the environmental controls on the production and degradation of methylmercury (MeHg), the most toxic and bioaccumulative form of Hg. Since MeHg is efficiently assimilated and biomagnified along food chains, MeHg has the potential to be a robust ecological tracer. In this review, we give an updated overview of the field of Hg isotopes and focus on how Hg isotopes of MeHg can be used to address fundamental ecological questions, including energy transfer across ecosystem interfaces and as a tracer for animal movements.