Interspecific Variations in the Internal Mercury Isotope Dynamics of Antarctic Penguins: Implications for Biomonitoring.

Mercury (Hg) biomonitoring requires a precise understanding of the internal processes contributing to disparities between the Hg sources in the environment and the Hg measured in the biota. In this study, we investigated the use of Hg stable isotopes to trace Hg accumulation in Adélie and emperor penguin chicks from four breeding colonies in Antarctica. Interspecific variation of Δ199Hg in penguin chicks reflects the distinct foraging habitats and Hg exposures in adults. Chicks at breeding sites where adult penguins predominantly consumed mesopelagic prey showed relatively lower Δ199Hg values than chicks that were primarily fed epipelagic krill. Substantial δ202Hg variations in chick tissues were observed in both species (Adélie: -0.11 to 1.13‰, emperor: -0.27 to 1.15‰), whereas only emperor penguins exhibited the lowest δ202Hg in the liver and the highest in the feathers. Our results indicate that tissue-specific δ202Hg variations and their positive correlations with % MeHg resulted from MeHg demethylation in the liver and kidneys of emperor penguin chicks, whereas Adélie penguin chicks showed different internal responses depending on their exposure to dietary MeHg. This study highlights the importance of considering intra- and interspecific variations in adult foraging ecology and MeHg demethylation when selecting penguin chicks for Hg biomonitoring.

Elucidating sources of mercury in the west coast of Korea and the Chinese marginal seas using mercury stable isotopes.

Nearshore systems play an important role as mercury (Hg) sources to the open ocean and to human health via fish consumption. The nearshore system along East Asia is of particular concern given the rapid industrialization, which contributes to significant anthropogenic Hg emissions and releases. We used Hg stable isotopes to characterize Hg sources in the sediment and fish along the west coast of Korea, located at the northeast of the East China Sea. The Hg isotope ratios of the west coast sediments (δ202Hg; -0.89 to -0.27‰, Δ199Hg; -0.04 to 0.14‰) were statistically similar with other nearshore sediments (δ202Hg; -0.99 to -0.30‰, Δ199Hg; -0.04 to 0.19‰) and overlapped with the industrial Hg source end-member (δ202Hg; -0.5‰, Δ199Hg; 0.01‰) estimated from the Chinese marginal seas. Using a ternary mixing model, we estimated that industrial Hg sources contribute 83-97% in the west coast of Korea, and riverine and atmospheric Hg sources play minor roles in the Korean west coast and the Chinese marginal seas. The comparison between Hg isotope ratios of the sediment and nearshore fish revealed that the fish in the most west coast sites are exposed to MeHg produced in the sediment. At a few southwest coast sites, external MeHg produced in rivers and the open ocean water column appears to be more important as a source in fish. This is supported by much higher δ202Hg (0.74‰; similar to oceanic fish) and lower δ202Hg (-0.71‰; similar to riverine sources) compared to fish collected from other west coast sites influenced by sedimentary MeHg. The substantial Hg contributions from industrial activities suggest the national policies regulating anthropogenic Hg releases can directly mitigate human Hg exposure originating via local fish consumption. This study contributes to the growing regional and global inventories of Hg fluxes and sources exported into coastal oceans.

Isotope investigation of mercury sources in a creek impacted by multiple anthropogenic activities.

To investigate mercury (Hg) sources responsible for contamination at Gumu Creek in South Korea, Hg concentration (THg) and Hg isotope ratios were measured in the soil and sediment of Gumu Creek and the samples from a hazardous waste landfill (HWL). The THg ranged between 0.29-327 mg kg-1 and 9.5-414 mg kg-1 in the soil and sediment, respectively, reflecting heterogeneous distribution and elevated levels across the entire Gumu Creek. Without the soil with the lowest THg (0.30 ± 0.01 mg kg-1, n = 3), the δ202Hg (-0.83 to -0.18‰) and Δ199Hg (-0.24 to 0.01‰) of the sediment and soil of Gumu Creek were within the ranges of the HWL samples (δ202Hg; -1.29 to -0.38‰, Δ199Hg; -0.31 to 0.01‰). The comparison with the literature reporting sediment Hg isotope ratios impacted by various anthropogenic Hg sources revealed a presence of diverse Hg sources at Gumu Creek, including commercial liquid Hg, phenyl-Hg, and fly ash, consistent with the types of waste deposited within the HWL. Using commercial liquid Hg, fly ash, and the soil with the lowest THg as end-members, the ternary mixing model yielded 25-88% and 12-57% contributions from commercial liquid Hg and fly ash to the Gumu Creek sediment, respectively. The results of our study suggest that Hg isotope ratios are an effective tool for screening potential Hg sources at sites where the distribution of Hg is heterogeneous and multiple anthropogenic activities exist.

Internal dynamics of inorganic and methylmercury in a marine fish: Insights from mercury stable isotopes.

Mercury isotope ratios in fish tissues have been used to infer sources and biogeochemical processes of mercury in aquatic ecosystems. More experimental studies are however needed to understand the internal dynamics of mercury isotopes and to further assess the feasibility of using fish mercury isotope ratios as a monitoring tool. We exposed Olive flounder (Paralichthys olivaceus) to food pellets spiked with varying concentrations (400, 1600 ng/g) of methylmercury (MeHg) and inorganic mercury (IHg) for 10 weeks. Total mercury (THg), MeHg concentrations, and mercury isotope ratios (δ202Hg, Δ199Hg, Δ200Hg) were measured in the muscle, liver, kidney, and intestine of fish. Fish fed mercury unamended food pellets and MeHg amended food pellets showed absence of internal δ202Hg and Δ199Hg fractionation in all tissue type. For fish fed IHg food pellets, the δ202Hg and Δ199Hg values of intestine equilibrated to those of the IHg food pellets. Kidney, muscle, and liver exhibited varying degrees of isotopic mixing toward the IHg food pellets, consistent with the degree of IHg bioaccumulation. Liver showed additional positive δ202Hg shifts (∼0.63‰) from the binary mixing line between the unamended food pellets and IHg food pellets, which we attribute to redistribution or biliary excretion of liver IHg with a lower δ202Hg to other tissues. Significant δ202Hg fractionation in the liver and incomplete isotopic equilibration in the muscle indicate that these tissues may not be suitable for source monitoring at sites heavily polluted by IHg. Instead, fish intestine appears to be a more suitable proxy for identifying IHg sources. The results from our study are essential for determining the appropriate fish tissues for monitoring environmental sources of IHg and MeHg.