Geology topics

Tylor Rosera

Publications and source records attributed to Tylor Rosera.

7 recordsLinked to original sources

USGS2026

Comparing in vivo methylmercury detoxification in hunted duck: Implications for wildlife and human health

Great Salt Lake (GSL) waterfowl have elevated mercury (Hg) concentrations, and in vivo detoxification of neurotoxic and bioaccumulative methylmercury (MeHg) can occur through Hg-selenium (Se) complexation, influencing the suitability of Hg consumption advisories. Here, we present Hg chemical speciation and Hg stable isotope measurements of brain, breast muscle, liver, and kidney samples from two GSL duck species─northern shoveler ( Spatula clypeata ) and cinnamon teal (Spatula cyanoptera). Chemical and stable isotope measurements, along with high energy resolution fluorescence detected X-ray absorption near-edge structure (HERFD-XANES) spectroscopy, indicate the occurrence of in vivo MeHg demethylation in both bird species. The percentage of total Hg (THg) as MeHg (% MeHg) varied with tissue type (brain > breast muscle > kidney > liver), and differences between δ 202 THg and δ 202 MeHg were linearly correlated with % MeHg. Demethylated inorganic Hg was a mixture of Hg-dithiolate (Hg(SR) 2 ) and Hg-tetraselenolate (Hg(Sec) 4 ) in both bird species. Notably, liver THg concentrations were elevated in northern shoveler liver tissues relative to those of cinnamon teal (7.54 ± 4.69 mg/kg versus 2.19 ± 1.27 mg/kg, dry weight, respectively) and % MeHg liver values were significantly lower (40% ± 19% versus 68% ± 14%), indicating taxonomic differences in Hg detoxification and depuration. THg concentrations in waterfowl species from this study were comparable to previously reported levels, indicating that elevated Hg concentrations in northern shoveler and cinnamon teal at GSL have persisted over the past two decades. Due to in vivo demethylation, we show that THg is not an effective proxy for MeHg within duck species, carrying implications for current GSL waterfowl consumption advisories and assessments exposure risk. This study highlights important differences in MeHg detoxification between waterbird taxa and provides further insights into Hg toxicity risk to GSL waterbirds.

Utah↗

USGS2025

Seasonal stratification drives bioaccumulation of pelagic mercury sources in eutrophic lakes

Increased lake eutrophication, influenced by changing climate and land use, alters aquatic cycling and bioaccumulation of mercury (Hg). Additionally, seasonally dynamic lake circulation and plankton community composition can confound our ability to predict changes in biological Hg concentrations and sources. To assess temporal variation, we examined seasonal total Hg (THg) and methylmercury (MeHg) concentrations and stable isotope values in seston, waters, sediments, and fish from two adjacent urban eutrophic lakes in Madison, Wisconsin. In Lake Monona, surface sediment THg concentrations were elevated due to comparably higher urbanization and historical industrial inputs, whereas Lake Mendota sediments had lower concentrations corresponding with largely agricultural and suburban surrounding watershed. Surface water THg and MeHg were similar between lakes and seasonally dynamic, but water profiles exhibited elevated concentrations in the meta- and hypolimnion, highlighting water column MeHg production. Seston MeHg concentrations were often highest at shoulder seasons, possibly owing to metalimnetic MeHg delivery, but also differences in biomass and water clarity. The ∆199Hg and δ202Hg values in seston were similar between lakes, despite differing sediment THg concentrations and values, suggesting a shared bioaccumulated source of MeHg. Measurement of MeHg stable isotopes further elucidated that seston and fish predominantly bioaccumulated pelagic-sourced MeHg.

Wisconsin↗

USGS2022

Methylmercury stable isotopes: New insights on assessing aquatic food web bioaccumulation in legacy impacted regions

Through stable isotope measurements of total mercury (HgT), identification of crucial processes and transformations affecting different sources of mercury (Hg) has become possible. However, attempting to use HgT stable isotopes to track bioaccumulation of Hg sources among different food web compartments can be challenging, if not impossible, when tissues have varying methylmercury (MeHg) contents. We measured HgT and MeHg stable isotope ratios within the lower Fox River to examine how these values differed across the food web and if isotope values in biota were influenced by legacy contamination. We showed that seston, invertebrates, and fish had a large range of δ 202 HgT (−0.74 to 0.15 ‰, n = 11) due to varying MeHg contents in tissues but a commonly conserved MeHg isotope value (δ 202 MeHg ave = 0.01 ± 0.12 ‰, 1 standard deviation, n = 11). We also examined some mathematical approaches to estimate the MeHg isotope values, which were mostly comparable to measured MeHg isotope values in the Fox River, with some exceptions. In this study, we observed that the MeHg isotope values can elucidate links between different food web compartments and provide insight on aquatic Hg cycling that can be masked by the sole use of HgT isotopes in contaminated sites.

Wisconsin↗

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

Enhanced susceptibility of methylmercury bioaccumulation into seston of the Laurentian Great Lakes

Mercury concentrations in the Laurentian Great Lakes waters are among the lowest reported in the literature, while game fish concentrations approach consumption advisory limits, particularly in Lakes Superior, Huron, and Michigan, indicating efficient methylmercury transfer from water to game fish. To determine if increased transfer efficiency is evident within the lower food web, we measured (2010–2018) mercury and dissolved organic carbon (DOC) in water, and in size-sieved seston, dietary tracers (carbon and nitrogen isotope ratios), phytoplankton methylmercury bioaccumulation, and methylmercury biomagnification between increasing seston size fractions. We observed consistently low filter-passing methylmercury (<0.010 ng L –1 ) and comparatively variable DOC (1.1 to 3.4 mg L –1 ) concentrations. Methylmercury biomagnification factors between size-sieved seston were similar between lakes. Bioaccumulation factors in phytoplankton were among the highest in the literature (log 5.5 to 6.1), exceeding those in oceans, smaller lakes, and streams, and was influenced by DOC. Higher bioaccumulation rates increase the susceptibility of methylmercury accumulation into the food web. Because mercury is dominantly delivered to the Great Lakes through the atmosphere and the biota therein is highly susceptible to methylmercury uptake, we propose that the Laurentian Great Lakes are excellent sentinels to trace the success of efforts to decrease global mercury emissions (e.g., Minamata Treaty) in the future.

Environmental Science and Technology↗

USGS2021

Isotope fractionation from In Vivo methylmercury detoxification in waterbirds

The robust application of stable mercury (Hg) isotopes for mercury source apportionment and risk assessment necessitates the understanding of mass-dependent fractionation (MDF) due to internal transformations within organisms. Here, we used high energy-resolution XANES spectroscopy and isotope ratios of total mercury (δ202THg) and methylmercury (δ202MeHg) to elucidate the chemical speciation of Hg and the resultant MDF due to internal MeHg demethylation in waterbirds. In three waterbirds (Clark’s grebe, Forster’s tern, south polar skua), between 17-86% of the MeHg was demethylated to inorganic mercury (iHg) species primarily in the liver and kidneys as Hg-tetraselenolate (Hg(Sec)4) and minor Hg-dithiolate (Hg(SR)2) complexes. Tissular differences between δ202THg and δ202MeHg correlated linearly with %iHg (Hg(Sec)4 + Hg(SR)2), and were interpreted to reflect a kinetic isotope effect during in vivo MeHg demethylation. The product-reactant isotopic enrichment factor (εp/r) for the demethylation of MeHg  Hg(Sec)4 was −2.2 ± 0.1‰. δ202MeHg values were unvarying within each bird regardless of Hg(Sec)4 abundance, indicating fast internal cycling or replenishment of MeHg relative to demethylation. Our findings document a universal selenium-dependent demethylation reaction in birds, provide new insights on the internal transformations and cycling of MeHg and Hg(Sec)4, and allow for mathematical correction of δ202THg values due to the MeHg  Hg(Sec)4 reaction.

ACS Earth and Space Chemistry↗

USGS2019

Isolation of methylmercury using distillation and anion-exchange chromatography for isotopic analyses in natural matrices

The development of mercury (Hg) stable isotope measurements has enhanced the study of Hg sources and transformations in the environment. As a result of the mixing of inorganic Hg (iHg) and methylmercury (MeHg) species within organisms of the aquatic food web, understanding species-specific Hg stable isotopic compositions is of significant importance. The lack of MeHg isotope measurements is due to the analytical difficulty in the separation of the MeHg from the total Hg pool, with only a few methods having been tested over the past decade with varying degrees of success, and only a handful of environmentally relevant measurements. Here, we present a novel anion-exchange resin separation method using AG 1-X4 that further isolates MeHg from the sample matrix, following a distillation pretreatment, in order to obtain ambient MeHg stable isotopic compositions. This method avoids the use of organic reagents, does not require complex instrumentation, and is applicable across matrices. Separation tests across sediment, water, and biotic matrices showed acceptable recoveries (98 ± 5%, n = 54) and reproducible δ 202 Hg isotope results (2 SDs ≤ 0.15‰) down to 5 ng of MeHg. The measured MeHg pools in natural matrices, such as plankton and sediments, showed large deviations from the non-speciated total Hg measurement, indicating that there is an important isotopic shift during methylation that is not recorded by typical measurements, but is vital in order to assess sources of Hg during bioaccumulation.

Analytical and Bioanalytical Chemistry↗