Geology topics

Ryan F. Lepak

Publications and source records attributed to Ryan F. Lepak.

23 records · Page 2Linked to original sources

USGS2019

Rapid pre-concentration of mercury in solids and water for isotopic analysis

The precise quantification of mercury (Hg) stable isotope compositions in low concentration or dilute samples poses analytical challenges due to Hg mass limitations. Common Hg pre-concentration procedures require extended processing times, making rapid Hg stable isotope measurements challenging. Here we present a modified pre-concentration method that combines commonly used Hg reduction and gold trap amalgamation followed by semi-rapid thermal desorption (less than 1 h) and chemical trapping. This custom designed system was demonstrated to perform adequately on multiple trapping matrices including a new bromine monochloride (BrCl) wet oxidant trap (40% 3HNO 3 :BrCl), capable of trapping consistently in 2 mL volume over a wide range of Hg masses (5–200 ng). The procedure was also shown to work effectively on natural matrices, waters and sediments, producing comparable isotope results to the direct digestion analyses. Here, we present a method that can effectively triple sample throughput in comparison to traditional procedures, and also access lower concentration matrices without compromising the accuracy or precision of Hg isotope measurements.

Analytica Chimica Acta↗

USGS2018

Mercury isotopes reveal an ontogenetic shift in habitat use by walleye in lower Green Bay of Lake Michigan

In general, fish residing in rivers differ from fish residing in lakes in their mercury (Hg) isotope ratios. Specifically, fish residing in lakes typically show enriched values for the isotope ratios of δ 202 Hg (mass-dependent fractionation of isotope 202 Hg) and Δ 199 Hg (mass-independent fractionation of isotope 199 Hg) compared with fish residing in rivers, because photochemical effects acting on Hg isotope ratios are stronger in lakes than in rivers. Whole-fish determinations of Hg isotope ratios in age-0 and adult (ages 4–11) walleye ( Sander vitreus ) caught in the Fox River, the main tributary to lower Green Bay of Lake Michigan, were dissimilar. Age-0 fish exhibited a river signature for δ 202 Hg and Δ 199 Hg, with means equal to 0.00 and 0.26‰, respectively. Significantly elevated levels of δ 202 Hg and Δ 199 Hg were observed in adult fish, indicating that adult fish primarily resided in the bay. Our results implied that the Fox River serves as a nursery area for juvenile walleye in the Fox River–lower Green Bay ecosystem. Moreover, corrections for photochemical fractionation of δ 202 Hg revealed that age-0 and adult walleye shared the same source of Hg in this ecosystem. In addition, Hg isotope ratios did not significantly differ between the sexes of adult walleye, suggesting that these ratios did not fractionate during the Hg elimination process.

Environmental Science & Technology Letters↗

USGS2018

Factors affecting mercury stable isotopic distribution in piscivorous fish of the Laurentian Great Lakes

Identifying the sources of methylmercury (MeHg) and tracing the transformations of mercury (Hg) in the aquatic food web are important components of effective strategies for managing current and legacy Hg sources. In our previous work, we measured stable isotopes of Hg (δ 202 Hg, Δ 199 Hg, and Δ 200 Hg) in the Laurentian Great Lakes and estimated source contributions of Hg to bottom sediment. Here, we identify isotopically distinct Hg signatures for Great Lakes trout ( Salvelinus namaycush ) and walleye ( Sander vitreus ), driven by both food-web and water-quality characteristics. Fish contain high values for odd-isotope mass independent fractionation (MIF) with averages ranging from 2.50 (western Lake Erie) to 6.18‰ (Lake Superior) in Δ 199 Hg. The large range in odd-MIF reflects variability in the depth of the euphotic zone, where Hg is most likely incorporated into the food web. Even-isotope MIF (Δ 200 Hg), a potential tracer for Hg from precipitation, appears both disconnected from lake sedimentary sources and comparable in fish among the five lakes. We suggest that similar to the open ocean, water-column methylation also occurs in the Great Lakes, possibly transforming recently deposited atmospheric Hg deposition. We conclude that the degree of photochemical processing of Hg is controlled by phytoplankton uptake rather than by dissolved organic carbon quantity among lakes.

Environmental Science & Technology↗

USGS2016

Distribution and geochemical speciation of soil mercury in Wanshan Hg mine: Effects of cultivation

The distribution and speciation of mercury (Hg) were investigated in contaminated soils collected from two adjacent land use systems (arid land and rice paddy) near the Wanshan Mercury mine, SW China. In both sites, fine soil aggregate size fractions (<231μm) showed higher total Hg concentrations and higher soil organic matter contents than in larger aggregate size fractions (231 to 2000μm). Compared to arid land, paddy soils are characterized by higher proportions of fine soil aggregates, higher soil organic matter and higher total Hg content. Soil Hg speciation, based on X-ray absorption spectroscopy (XANES) analysis, indicated that the majority (64–81%) of Hg in soils under both land use systems was associated with metacinnabar (β-HgS), indicating the precipitation of β-HgS in soils. We also observed the presence of bioavailable HgCl 2 and Hg(0) in soils at both sites, which may represent a considerable environmental concern. Our study clearly showed that different cultivation practices can largely change the distribution and speciation of Hg in agriculture soils.

Guizhou Province↗

USGS2015

Use of stable isotope signatures to determine mercury sources in the Great Lakes

Sources of mercury (Hg) in Great Lakes sediments were assessed with stable Hg isotope ratios using multicollector inductively coupled plasma mass spectrometry. An isotopic mixing model based on mass-dependent (MDF) and mass-independent fractionation (MIF) (δ 202 Hg and Δ 199 Hg) identified three primary Hg sources for sediments: atmospheric, industrial, and watershed-derived. Results indicate atmospheric sources dominate in Lakes Huron, Superior, and Michigan sediments while watershed-derived and industrial sources dominate in Lakes Erie and Ontario sediments. Anomalous Δ 200 Hg signatures, also apparent in sediments, provided independent validation of the model. Comparison of Δ 200 Hg signatures in predatory fish from three lakes reveals that bioaccumulated Hg is more isotopically similar to atmospherically derived Hg than a lake’s sediment. Previous research suggests Δ 200 Hg is conserved during biogeochemical processing and odd mass-independent fractionation (MIF) is conserved during metabolic processing, so it is suspected even is similarly conserved. Given these assumptions, our data suggest that in some cases, atmospherically derived Hg may be a more important source of MeHg to higher trophic levels than legacy sediments in the Great Lakes.

Lake Erie, Lake Huron, Lake Michigan, Lake Ontario↗