Geology topics

Brett Poulin

Publications and source records attributed to Brett Poulin.

10 recordsLinked to original sources

USGS2021

Effect of nanoparticle size and natural organic matter composition on the bioavailability of polyvinylpyrrolidone- coated platinum nanoparticles to a model freshwater invertebrate

The bioavailability of dissolved Pt(IV) and polyvinylpyrrolidone-coated platinum nanoparticles (PtNPs) of five different nominal hydrodynamic diameters (20, 30, 50, 75, and 95 nm) was characterized in laboratory experiments using the model freshwater snail Lymnaea stagnalis . Dissolved Pt(IV) and all nanoparticle sizes were bioavailable to L. stagnalis . Platinum bioavailability, inferred from conditional uptake rate constants, was greater for nanoparticulate than dissolved forms and increased with increasing nanoparticle hydrodynamic diameter. The effect of natural organic matter (NOM) composition on PtNP bioavailability was evaluated using six NOM samples at two nanoparticle sizes (20 and 95 nm). NOM suppressed the bioavailability of 95 nm PtNPs in all cases, and DOM reduced sulfur content exhibited a positive correlation with 95 nm PtNP bioavailability. The bioavailability of 20 nm PtNPs was only suppressed by NOM with a low reduced sulfur content. The physiological elimination of Pt accumulated after dissolved Pt(IV) exposure was slow and constant. In contrast, the elimination of Pt accumulated after PtNP exposures exhibited a triphasic pattern likely involving in vivo PtNP dissolution. This work highlights the importance of PtNP size and interfacial interactions with NOM on Pt bioavailability and suggests that in vivo PtNP transformations could yield unexpectedly higher adverse effects to organisms than dissolved exposure alone.

Environ. Sci. Technol.↗

USGS2020

Seasonal dynamics and interannual variability in mercury concentrations and loads through a three-reservoir complex

The Hells Canyon Complex (HCC) along the Snake River (Idaho-Oregon border, USA) encompasses three successive reservoirs that seasonally stratify, creating anoxic conditions in the hypolimnion that promote methylmercury (MeHg) production. This study quantified seasonal dynamics and interannual variability in mercury concentrations (inorganic divalent mercury (IHg) and MeHg) and loads at four reservoir inflow and outflow locations through the HCC (2014-2017). We observed (1) that the HCC is a net sink for both IHg and MeHg, (2) interannual variability in IHg and MeHg loads largely reflecting streamflow conditions, and (3) seasonal variability in particulate IHg loading at the inflow (greatest from February to April) and MeHg export from the outflow (greatest from September to December) of the HCC. Seasonal export of MeHg was evidenced by increases in monthly mean concentrations of unfiltered MeHg (approximately twofold) and the percentage of total mercury (THg) as MeHg (≥ fourfold) coincident with reservoir destratification. Despite evidence of seasonal export of MeHg from the HCC, annual loads indicate a 42% decrease in unfiltered MeHg from HCC inflow to outflow. Results from this study improve the understanding of seasonal variability in mercury transport through and transformation within a reservoir complex.

Idaho, Oregon↗

USGS2019

Aquatic cycling of mercury

This chapter examines crucial processes in the aquatic cycling of mercury (Hg) that may lead to microbial production of neurotoxic and bioaccumulative methylmercury (MeHg), and highlights environmental conditions in the Everglades that make it ideal for MeHg production and bioaccumulation. The role of complexation of Hg 2+ in surface water, especially by dissolved organic matter (DOM), in the transport of mercury to sites of microbial methylation are discussed. Photochemical reactions important in Hg cycling in surface water are also discussed. A principal focus of the chapter is on the environmental conditions that promote MeHg production, especially the role of sulfide and DOM in transport of inorganic Hg into bacteria for methylation, and the types of bacteria that have the ability to methylate Hg. Finally, perturbations to the ecosystem (e.g., fire and drought) that have important effects on Hg cycling are discussed.

Book chapter↗

USGS2019

Sulfur contamination in the Everglades, a major control on mercury methylation

In this chapter sulfur contamination of the Everglades and its role as a major control on methylmercury (MeHg) production is examined. Sulfate concentrations over large portions of the Everglades (60% of the ecosystem) are elevated or greatly elevated compared to background conditions of <1 mg/L. Land and water management practices in south Florida are the primary reason for the high levels of sulfate loading to the Everglades. Marshes in the northern Everglades that are highly enriched in sulfate have average concentrations of 60 mg/L, but water in canals in the Everglades Agricultural Area (EAA) contain the highest concentrations of sulfate averaging 60–70 mg/L. Studies that examined the mass balance of sulfur to the Everglades have determined that the primary sources of sulfate include: sulfur currently used in agriculture, and natural and legacy agricultural sulfur released by oxidation of organic soil within the EAA. The extensive loading of sulfate to the ecosystem increases microbial sulfate reduction, the dominant microbial process driving mercury methylation and MeHg production. The biogeochemical processes linking sulfate loading and MeHg production, however, are complex. MeHg production increases as sulfate levels rise from levels <1 mg/L up to about 20 mg/L. However, production of sulfide (a byproduct of microbial sulfate reduction) starts to inhibit MeHg production above 20 mg/L. Sulfate loading to canals in the EAA has impacted the northern Everglades the most, but the Everglades canal system can transport sulfate as far as Everglades National Park (ENP), 80 km further south. Plans to deliver more water to ENP as part of restoration may increase overall sulfate loads to the southern Everglades. Reduction of sulfate loading should be a major goal of Everglades restoration because of the many negative effects of sulfate on the ecosystem. The ecosystem has been shown to respond quickly to reductions in sulfate loading, and strategies for reducing sulfate loading may produce positive outcomes for the Everglades in the near-term. Strategies for reducing sulfate loading will need to include: best management practices for agricultural use of sulfate, approaches to minimize soil oxidation in the EAA, and modifications to stormwater treatment areas to improve sulfate retention.

Florida↗

USGS2019

Permafrost hydrology drives the assimilation of old carbon by stream food webs in the Arctic

Permafrost thaw in the Arctic is mobilizing old carbon (C) from soils to aquatic ecosystems and the atmosphere. Little is known, however, about the assimilation of old C by aquatic food webs in Arctic watersheds. Here, we used C isotopes (δ 13 C, Δ 14 C) to quantify C assimilation by biota across 12 streams in arctic Alaska. Streams spanned watersheds with varying permafrost hydrology, from ice-poor bedrock to ice-rich loess (that is, yedoma). We measured isotopic content of (1) C sources including dissolved organic C (DOC), dissolved inorganic C (DIC), and soil C, and (2) stream biota, including benthic biofilm and macroinvertebrates, and resident fish species (Arctic Grayling ( Thymallus arcticus ) and Dolly Varden ( Salvelinus malma )). Findings document the assimilation of old C by stream biota, with depleted Δ 14 C values observed at multiple trophic levels, including benthic biofilm ( 14 C ages = 5255 to 265 years before present (y BP)), macroinvertebrates (4490 y BP to modern), and fish (3195 y BP to modern). Mixing model results indicate that DOC and DIC contribute to benthic biofilm composition, with relative contributions differing across streams draining ice-poor and ice-rich terrain. DOC originates primarily from old terrestrial C sources, including deep peat horizons (39–47%; 530 y BP) and near-surface permafrost (12–19%; 5490 y BP). DOC also accounts for approximately half of fish isotopic composition. Analyses suggest that as the contribution of old C to fish increases, fish growth and nutritional status decline. We anticipate increases in old DOC delivery to streams under projected warming, which may further alter food web function in Arctic watersheds.

Alaska↗

USGS2019

Geochemical factors controlling dissolved elemental mercury and methylmercury formation in Alaskan wetlands of varying trophic status

Transformations of aqueous inorganic divalent mercury (Hg(II)i) to volatile dissolved gaseous mercury (Hg(0)(aq)) and toxic methylmercury (MeHg) governs mercury bioavailability and fate in northern ecosystems. This study quantified concentrations of aqueous mercury species (Hg(II)i, Hg(0)(aq), MeHg) and relevant geochemical constituents in pore waters of eight Alaskan wetlands that differ in trophic status (i.e., bog-to-fen gradient) to gain insight on processes controlling dark Hg(II)i reduction and Hg(II)i methylation. Regardless of wetland trophic status, positive correlations were observed between pore water Hg(II)i and dissolved organic carbon (DOC) concentrations. The concentration ratio of Hg(0)(aq) to Hg(II)i exhibited an inverse relationship to Hg(II)i concentration. A ubiquitous pathway for Hg(0)(aq) formation was not identified based on geochemical data, but we surmise that dissolved organic matter (DOM) influences mercury retention in wetland pore waters by complexing Hg(II)i and decreasing the concentration of volatile Hg(0)(aq) relative to Hg(II)i. There was no evidence of Hg(0)(aq) abundance directly limiting mercury methylation. The concentration of MeHg relative to Hg(II)i was greatest in wetlands of intermediate trophic status, and geochemical data suggest mercury methylation pathways vary between wetlands. Our insights on geochemical factors influencing aqueous mercury speciation should be considered in context of the long-term fate of mercury in northern wetlands.

Environmental Science & Technology↗

USGS2017

Effects of sulfide concentration and dissolved organic matter characteristics on the structure of nanocolloidal metacinnabar

Understanding the speciation of divalent mercury (Hg(II)) in aquatic systems containing dissolved organic matter (DOM) and sulfide is necessary to predict the conversion of Hg(II) to bioavailable methylmercury. We used X-ray absorption spectroscopy to characterize the structural order of mercury in Hg(II)–DOM–sulfide systems for a range of sulfide concentration (1–100 μM), DOM aromaticity (specific ultraviolet absorbance (SUVA 254 )), and Hg(II)–DOM and Hg(II)–DOM–sulfide equilibration times (4–142 h). In all systems, Hg(II) was present as structurally disordered nanocolloidal metacinnabar (β-HgS). β-HgS nanocolloids were significantly smaller or less ordered at lower sulfide concentration, as indicated by under-coordination of Hg(II) in β-HgS. The size or structural order of β-HgS nanocolloids increased with increasing sulfide abundance and decreased with increasing SUVA 254 of the DOM. The Hg(II)–DOM or Hg(II)–DOM–sulfide equilibration times did not significantly influence the extent of structural order in nanocolloidal β-HgS. Geochemical factors that control the structural order of nanocolloidal β-HgS, which are expected to influence nanocolloid surface reactivity and solubility, should be considered in the context of mercury bioavailability.

Environmental Science & Technology↗

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↗

USGS2014

Effects of iron on optical properties of dissolved organic matter

Iron is a source of interference in the spectroscopic analysis of dissolved organic matter (DOM); however, its effects on commonly employed ultraviolet and visible (UV–vis) light adsorption and fluorescence measurements are poorly defined. Here, we describe the effects of iron(II) and iron(III) on the UV–vis absorption and fluorescence of solutions containing two DOM fractions and two surface water samples. In each case, regardless of DOM composition, UV–vis absorption increased linearly with increasing iron(III). Correction factors were derived using iron(III) absorption coefficients determined at wavelengths commonly used to characterize DOM. Iron(III) addition increased specific UV absorbances (SUVA) and decreased the absorption ratios ( E 2 : E 3 ) and spectral slope ratios ( S R ) of DOM samples. Both iron(II) and iron(III) quenched DOM fluorescence at pH 6.7. The degree and region of fluorescence quenching varied with the iron:DOC concentration ratio, DOM composition, and pH. Regions of the fluorescence spectra associated with greater DOM conjugation were more susceptible to iron quenching, and DOM fluorescence indices were sensitive to the presence of both forms of iron. Analyses of the excitation–emission matrices using a 7- and 13-component parallel factor analysis (PARAFAC) model showed low PARAFAC sensitivity to iron addition.

Environmental Science & Technology↗