Geology topics

Robin Stewart

Publications and source records attributed to Robin Stewart.

5 recordsLinked to original sources

USGS2022

Using tissue cysteine to predict the trophic transfer of methylmercury and selenium in lake food webs

The biomagnification of toxic methylmercury (MeHg) and selenium (Se) through aquatic food webs using nitrogen stable isotopes (δ 15 N) varies among ecosystems but underlying mechanisms are yet unexplained. Given the strong links between MeHg and thiol-containing amino acids and proteins containing selenocysteine, our hypothesis was that cysteine content is a better predictor of MeHg and Se transfer through lake food webs than δ 15 N. Food web samples were collected from six lakes in Kejimkujik National Park, Nova Scotia, Canada, and the regression slopes of log MeHg or Se versus protein-bound cysteine or bulk δ 15 N were compared. Across all six lakes, MeHg varied by a factor of 10 among taxa and was significantly and positively related to both cysteine (R 2 = 0.65–0.80, p < 0.001) and δ 15 N (R 2 = 0.88–0.94, p < 0.001), with no among-system differences in these slopes. In contrast, total Se concentrations varied by less than a factor of 2 among taxa in four lakes and were significantly related to cysteine in only two food webs (R 2 = 0.20 & 0.37, p = 0.014 & < 0.001); however, δ 15 N was not a predictor of Se in any lake (p = 0.052–0.777). Overall, these novel results indicate that cysteine content predicts MeHg, and sometimes Se, across trophic levels, providing a potential mechanism for among-system differences in their biomagnification.

Environmental Pollution↗

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↗

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↗

USGS2019

Near-field receiving-water monitoring of trace metals and a benthic community near the Palo Alto Regional Water Quality Control Plant in south San Francisco Bay, California—2018

Trace-metal concentrations in sediment and in the clam Macoma petalum (formerly reported as Macoma balthica ), clam reproductive activity, and benthic macroinvertebrate community structure were investigated in a mudflat 1 kilometer south of the discharge of the Palo Alto Regional Water Quality Control Plant (PARWQCP) in south San Francisco Bay, Calif. This report includes the data collected by U.S. Geological Survey (USGS) scientists for the period January 2018 to December 2018. These append to long-term datasets extending back to 1974. A major focus of the report is an integrated description of the 2018 data within the context of the longer, multi-decadal dataset. This dataset supports the City of Palo Alto’s Near-Field Receiving-Water Monitoring Program, initiated in 1994. Significant reductions in silver and copper concentrations in both sediment and M. petalum occurred at the site in the 1980s following the implementation by PARWQCP of advanced wastewater treatment and source control measures. Since the 1990s, concentrations of these elements appear to have stabilized at concentrations somewhat above (silver [Ag]) or near (copper [Cu]) regional background concentrations. Data for other metals, including chromium (Cr), mercury (Hg), nickel (Ni), selenium (Se), and zinc (Zn), have been collected since 1994. Over this period, concentrations of these elements have remained relatively constant, aside from seasonal variation that is common to all elements. In 2018, concentrations of silver and copper in M. petalum varied seasonally in response to a combination of site-specific metal exposures and annual growth and reproduction, as reported previously. Seasonal patterns for other elements, including Cr, Ni, Zn, Hg, and Se, were generally similar in timing and magnitude as those for Ag and Cu. This record suggests that legacy contamination and regional-scale factors now largely control sedimentary and bioavailable concentrations of silver and copper, as well as other elements of regulatory interest, at the Palo Alto site.

California↗

USGS2008

Water quality

Sustainable water policy in California will require maintaining or improving water quality. The Delta is an important source of drinking water for Californians, but sustaining a quality sufficient for human and agricultural consumption presents a number of problems and challenges to water managers. Similarly, poor environmental water quality is recognized as one of the influential stressors contributing to the ecological problems of the Delta (Bennett 2005; Kimmerer 2004).

California↗