Geology topics

Kathryn L. Nagy

Publications and source records attributed to Kathryn L. Nagy.

4 recordsLinked to original sources

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↗

USGS2017

Spatial dependence of reduced sulfur in Everglades dissolved organic matter controlled by sulfate enrichment

Sulfate inputs to the Florida Everglades stimulate sulfidic conditions in freshwater wetland sediments that affect ecological and biogeochemical processes. An unexplored implication of sulfate enrichment is alteration of the content and speciation of sulfur in dissolved organic matter (DOM), which influences the reactivity of DOM with trace metals. Here, we describe the vertical and lateral spatial dependence of sulfur chemistry in the hydrophobic organic acid fraction of DOM from unimpacted and sulfate-impacted Everglades wetlands using X-ray absorption spectroscopy and ultrahigh-resolution mass spectrometry. Spatial variation in DOM sulfur content and speciation reflects the degree of sulfate enrichment and resulting sulfide concentrations in sediment pore waters. Sulfur is incorporated into DOM predominantly as highly reduced species in sulfidic pore waters. Sulfur-enriched DOM in sediment pore waters exchanges with overlying surface waters and the sulfur likely undergoes oxidative transformations in the water column. Across all wetland sites and depths, the total sulfur content of DOM correlated with the relative abundance of highly reduced sulfur functionality. The results identify sulfate input as a primary determinant on DOM sulfur chemistry to be considered in the context of wetland restoration and sulfur and trace metal cycling.

Florida↗

USGS2016

Mercury transformation and release differs with depth and time in a contaminated riparian soil during simulated flooding

Riparian soils are an important environment in the transport of mercury in rivers and wetlands, but the biogeochemical factors controlling mercury dynamics under transient redox conditions in these soils are not well understood. Mercury release and transformations in the Oa and underlying A horizons of a contaminated riparian soil were characterized in microcosms and an intact soil core under saturation conditions. Pore water dynamics of total mercury (HgT), methylmercury (MeHg), and dissolved gaseous mercury (Hg0(aq)) along with selected anions, major elements, and trace metals were characterized across redox transitions during 36 d of flooding in microcosms. Next, HgT dynamics were characterized over successive flooding (17 d), drying (28 d), and flooding (36 d) periods in the intact core. The observed mercury dynamics exhibit depth and temporal variability. At the onset of flooding in microcosms (1–3 d), mercury in the Oa horizon soil, present as a combination of ionic mercury (Hg(II)) bound to thiol groups in the soil organic matter (SOM) and nanoparticulate metacinnabar (b-HgS), was mobilized with organic matter of high molecular weight. Subsequently, under anoxic conditions, pore water HgT declined coincident with sulfate (3–11 d) and the proportion of nanoparticulate b-HgS in the Oa horizon soil increased slightly. Redox oscillations in the intact Oa horizon soil exhausted the mobile mercury pool associated with organic matter. In contrast, mercury in the A horizon soil, present predominantly as nanoparticulate b-HgS, was mobilized primarily as Hg0(aq) under strongly reducing conditions (5–18 d). The concentration of Hg0(aq) under dark reducing conditions correlated positively with byproducts of dissimilatory metal reduction (P(Fe,Mn)). Mercury dynamics in intact A horizon soil were consistent over two periods of flooding, indicating that nanoparticulate b-HgS was an accessible pool of mobile mercury over recurrent reducing conditions. The concentration of MeHg increased with flooding time in both the Oa and A horizon pore waters. Temporal changes in pore water constituents (iron, manganese, sulfate, inorganic carbon, headspace methane) all implicate microbial control of redox transitions. The mobilization of mercury in multiple forms, including HgT associated with organic matter, MeHg, and Hg0(aq), to pore waters during periodic soil flooding may contribute to mercury releases to adjacent surface waters and the recycling of the legacy mercury to the atmosphere.

Tennessee↗

USGS2015

Formation of mercury sulfide from Hg(II)−thiolate complexes in natural organic matter

Methylmercury is the environmental form of neurotoxic mercury that is biomagnified in the food chain. Methylation rates are reduced when the metal is sequestered in crystalline mercury sulfides or bound to thiol groups in macromolecular natural organic matter. Mercury sulfide minerals are known to nucleate in anoxic zones, by reaction of the thiol-bound mercury with biogenic sulfide, but not in oxic environments. We present experimental evidence that mercury sulfide forms from thiol-bound mercury alone in aqueous dark systems in contact with air. The maximum amount of nanoparticulate mercury sulfide relative to thiol-bound mercury obtained by reacting dissolved mercury and soil organic matter matches that detected in the organic horizon of a contaminated soil situated downstream from Oak Ridge, TN, in the United States. The nearly identical ratios of the two forms of mercury in field and experimental systems suggest a common reaction mechanism for nucleating the mineral. We identified a chemical reaction mechanism that is thermodynamically favorable in which thiol-bound mercury polymerizes to mercury–sulfur clusters. The clusters form by elimination of sulfur from the thiol complexes via breaking of mercury–sulfur bonds as in an alkylation reaction. Addition of sulfide is not required. This nucleation mechanism provides one explanation for how mercury may be immobilized, and eventually sequestered, in oxygenated surface environments.

Environmental Science & Technology↗