Geology topics

Paco Bustamante

Publications and source records attributed to Paco Bustamante.

7 recordsLinked to original sources

USGS2025

Mercury speciation and stable isotopes in emperor penguins: First evidence for biochemical demethylation of methylmercury to mercury-dithiolate and mercury-tetraselenolate complexes

Apex marine predators, such as toothed whales and large petrels and albatrosses, ingest mercury (Hg) primarily in the form of methylmercury (MeHg) via prey consumption, which they detoxify as tiemannite (HgSe). One of the most intriguing current questions in Hg research is how more abundant lower trophic level predators detoxify MeHg, particularly in marine environments where tissue Hg burdens can be elevated. To address this need, we used high energy-resolution X-ray absorption near edge structure spectroscopy paired with nitrogen (N) and Hg stable isotopes to identify the chemical forms of Hg, Hg source, and species-specific δ 202 Hg isotopic values in emperor penguin, a mesopredator feeding primarily on Antarctic silverfish. The penguin liver contains variable proportions of MeHg and two inorganic Hg species (IHg), Hg-dithiolate (Hg(SR) 2 ) and Hg-tetraselenolate (Hg(Sec) 4 ) complexes, each characterized by a specific isotopic value (δ 202 MeHg = 0.3 ± 0.2‰, δ 202 Hg(SR) 2 = −1.6 ± 0.2‰, δ 202 Hg(Sec) 4 = −2.0 ± 0.1‰). Using δ 15 N as tracer of food source, we show that Hg(SR) 2 is not dietary but a biochemical demethylation product of MeHg metabolism. Penguin females transfer Hg to the egg as MeHg in the egg albumen, 89% MeHg and 11% IHg in the membrane, and 32% MeHg and 68% Hg(Sec) 4 in the yolk, on average (n = 15). Despite IHg species in eggs, MeHg is the main species quantitatively transferred by the mother to the chick because of the disproportionate mass of the MeHg-rich albumen compared to the yolk (n = 18). Further research is needed to elucidate the MeHg to Hg(SR) 2 demethylation pathway firmly documented here for the first time in multicellular organisms, and to understand why the thiolate ligands are not exchanged for Se ligands to form Hg(Sec) 4 , as the liver does not suffer from Se deficiency.

Adelie Land↗

USGS2024

Global mercury concentrations in biota: Their use as a basis for a global biomonitoring framework

An important provision of the Minamata Convention on Mercury is to monitor and evaluate the effectiveness of the adopted measures and its implementation. Here, we describe for the first time currently available biotic mercury (Hg) data on a global scale to improve the understanding of global efforts to reduce the impact of Hg pollution on people and the environment. Data from the peer-reviewed literature were compiled in the Global Biotic Mercury Synthesis (GBMS) database (>550,000 data points). These data provide a foundation for establishing a biomonitoring framework needed to track Hg concentrations in biota globally. We describe Hg exposure in the taxa identified by the Minamata Convention: fish, sea turtles, birds, and marine mammals. Based on the GBMS database, Hg concentrations are presented at relevant geographic scales for continents and oceanic basins. We identify some effective regional templates for monitoring methylmercury (MeHg) availability in the environment, but overall illustrate that there is a general lack of regional biomonitoring initiatives around the world, especially in Africa, Australia, Indo-Pacific, Middle East, and South Atlantic and Pacific Oceans. Temporal trend data for Hg in biota are generally limited. Ecologically sensitive sites (where biota have above average MeHg tissue concentrations) have been identified throughout the world. Efforts to model and quantify ecosystem sensitivity locally, regionally, and globally could help establish effective and efficient biomonitoring programs. We present a framework for a global Hg biomonitoring network that includes a three-step continental and oceanic approach to integrate existing biomonitoring efforts and prioritize filling regional data gaps linked with key Hg sources. We describe a standardized approach that builds on an evidence-based evaluation to assess the Minamata Convention’s progress to reduce the impact of global Hg pollution on people and the environment.

Ecotoxicology↗

USGS2022

Quantitative meta-analysis reveals no association between mercury contamination and body condition in birds

Mercury contamination is a major threat to the global environment, and is still increasing in some regions despite international regulations. The methylated form of mercury is hazardous to biota, yet its sublethal effects are difficult to detect in wildlife. Body condition can vary in response to stressors, but previous studies have shown mixed effects of mercury on body condition in wildlife. Using birds as study organisms, we provide the first quantitative synthesis of the effect of mercury on body condition in animals. In addition, we explored the influence of intrinsic, extrinsic and methodological factors potentially explaining cross-study heterogeneity in results. We considered experimental and correlative studies carried out in adult birds and chicks, and mercury exposure inferred from blood and feathers. Most experimental investigations (90%) showed a significant relationship between mercury concentrations and body condition. Experimental exposure to mercury disrupted nutrient (fat) metabolism, metabolic rates, and food intake, resulting in either positive or negative associations with body condition. Correlative studies also showed either positive or negative associations, of which only 14% were statistically significant. Therefore, the overall effect of mercury concentrations on body condition was null in both experimental (estimate ± SE = 0.262 ± 0.309, 20 effect sizes, five species) and correlative studies (−0.011 ± 0.020, 315 effect sizes, 145 species). The single and interactive effects of age class and tissue type were accounted for in meta-analytic models of the correlative data set, since chicks and adults, as well as blood and feathers, are known to behave differently in terms of mercury accumulation and health effects. Of the 15 moderators tested, only wintering status explained cross-study heterogeneity in the correlative data set: free-ranging wintering birds were more likely to show a negative association between mercury and body condition. However, wintering effect sizes were limited to passerines, further studies should thus confirm this trend in other taxa. Collectively, our results suggest that ( i ) effects of mercury on body condition are weak and mostly detectable under controlled conditions, and ( ii ) body condition indices are unreliable indicators of mercury sublethal effects in the wild. Food availability, feeding rates and other sources of variation that are challenging to quantify likely confound the association between mercury and body condition in natura . Future studies could explore the metabolic effects of mercury further using designs that allow for the estimation and/or manipulation of food intake in both wild and captive birds, especially in under-represented life-history stages such as migration and overwintering.

Biological Reviews↗

USGS2022

Mercury contamination and potential health risks to Arctic seabirds and shorebirds

Since the last Arctic Monitoring and Assessment Programme (AMAP) effort to review biological effects of mercury (Hg) on Arctic biota in 2011 and 2018, there has been a considerable number of new Arctic bird studies. This review article provides contemporary Hg exposure and potential health risk for 36 Arctic seabird and shorebird species, representing a larger portion of the Arctic than during previous AMAP assessments now also including parts of the Russian Arctic. To assess risk to birds, we used Hg toxicity benchmarks established for blood and converted to egg, liver, and feather tissues. Several Arctic seabird populations showed Hg concentrations that exceeded toxicity benchmarks, with 50 % of individual birds exceeding the “no adverse health effect” level. In particular, 5 % of all studied birds were considered to be at moderate or higher risk to Hg toxicity. However, most seabirds (95 %) were generally at lower risk to Hg toxicity. The highest Hg contamination was observed in seabirds breeding in the western Atlantic and Pacific Oceans. Most Arctic shorebirds exhibited low Hg concentrations, with approximately 45 % of individuals categorized at no risk, 2.5 % at high risk category, and no individual at severe risk. Although the majority Arctic-breeding seabirds and shorebirds appeared at lower risk to Hg toxicity, recent studies have reported deleterious effects of Hg on some pituitary hormones, genotoxicity, and reproductive performance. Adult survival appeared unaffected by Hg exposure, although long-term banding studies incorporating Hg are still limited. Although Hg contamination across the Arctic is considered low for most bird species, Hg in combination with other stressors, including other contaminants, diseases, parasites, and climate change, may still cause adverse effects. Future investigations on the global impact of Hg on Arctic birds should be conducted within a multi-stressor framework. This information helps to address Article 22 (Effectiveness Evaluation) of the Minamata Convention on Mercury as a global pollutant.

Science of the Total Environment↗

USGS2021

Mercury isotope fractionation by internal demethylation and biomineralization reactions in seabirds: Implications for environmental mercury science

A prerequisite for environmental and toxicological applications of mercury (Hg) stable isotopes in wildlife and humans is quantifying the isotopic fractionation of biological reactions. Here, we measured stable Hg isotope values of relevant tissues of giant petrels ( Macronectes spp.). Isotopic data were interpreted with published HR-XANES spectroscopic data that document a stepwise transformation of methylmercury (MeHg) to Hg-tetraselenolate (Hg(Sec) 4 ) and mercury selenide (HgSe) (Sec = selenocysteine). By mathematical inversion of isotopic and spectroscopic data, identical δ 202 Hg values for MeHg (2.69 ± 0.04‰), Hg(Sec) 4 (−1.37 ± 0.06‰), and HgSe (0.18 ± 0.02‰) were determined in 23 tissues of eight birds from the Kerguelen Islands and Adélie Land (Antarctica). Isotopic differences in δ 202 Hg between MeHg and Hg(Sec) 4 (−4.1 ± 0.1‰) reflect mass-dependent fractionation from a kinetic isotope effect due to the MeHg → Hg(Sec) 4 demethylation reaction. Surprisingly, Hg(Sec) 4 and HgSe differed isotopically in δ 202 Hg (+1.6 ± 0.1‰) and mass-independent anomalies (i.e., changes in Δ 199 Hg of ≤0.3‰), consistent with equilibrium isotope effects of mass-dependent and nuclear volume fractionation from Hg(Sec) 4 → HgSe biomineralization. The invariance of species-specific δ 202 Hg values across tissues and individual birds reflects the kinetic lability of Hg-ligand bonds and tissue-specific redistribution of MeHg and inorganic Hg, likely as Hg(Sec) 4 . These observations provide fundamental information necessary to improve the interpretation of stable Hg isotope data and provoke a revisitation of processes governing isotopic fractionation in biota and toxicological risk assessment in wildlife.

Environmental Science and Technology↗

USGS2021

Demethylation of methylmercury in bird, fish, and earthworm

Toxicity of methylmercury (MeHg) to wildlife and humans results from its binding to cysteine residues of proteins, forming MeHg-cysteinate (MeHgCys) complexes that hinder biological functions. MeHgCys complexes can be detoxified in vivo, yet how this occurs is unknown. We report that MeHgCys complexes are transformed into selenocysteinate (Hg(Sec)4) complexes in multiple animals from two phyla (a waterbird, freshwater fish, and earthworms) sampled in different geographical areas and contaminated by different Hg sources. In addition, high energy-resolution X-ray absorption spectroscopy and chromatography-ICP mass spectrometry of the waterbird liver support the binding of Hg(Sec)4 to selenoprotein P and biomineralization of Hg(Sec)4 to chemically inert nanoparticulate mercury selenide (HgSe). The results provide a foundation for understanding mercury detoxification in higher organisms, and suggest that the identified MeHgCys to Hg(Sec)4 demethylation pathway is common in nature.

Environmental Science & Technology↗

USGS2018

Modulators of mercury risk to wildlife and humans in the context of rapid global change

Environmental mercury (Hg) contamination is an urgent global health threat. The complexity of Hg in the environment can hinder accurate determination of ecological and human health risks, particularly within the context of the rapid global changes that are altering many ecological processes, socioeconomic patterns, and other factors like infectious disease incidence, which can affect Hg exposures and health outcomes. However, the success of global Hg-reduction efforts depends on accurate assessments of their effectiveness in reducing health risks. In this paper, we examine the role that key extrinsic and intrinsic drivers play on several aspects of Hg risk to humans and organisms in the environment. We do so within three key domains of ecological and human health risk. First, we examine how extrinsic global change drivers influence pathways of Hg bioaccumulation and biomagnification through food webs. Next, we describe how extrinsic socioeconomic drivers at a global scale, and intrinsic individual-level drivers, influence human Hg exposure. Finally, we address how the adverse health effects of Hg in humans and wildlife are modulated by a range of extrinsic and intrinsic drivers within the context of rapid global change. Incorporating components of these three domains into research and monitoring will facilitate a more holistic understanding of how ecological and societal drivers interact to influence Hg health risks.

Ambio↗