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At least 1,765 records · Page 98Linked to original sources

USGS2003

Challenges to reestablishment of free-ranging populations of black-footed ferrets

The black-footed ferret ( Mustela nigripes ) of North America is critically endangered due in part to its extreme specialization on formerly stable and abundant prairie dogs ( Cynomys ). Its close relative, the Siberian polecat ( M. eversmannii ) seems to have been subjected to a varying environment that was not conducive to specialization. One source of environmental variation in Asian steppes was plague (caused by Yersina pestis ), which was absent from North America. Introduction of plague to North America presents serious challenges to ferret recovery. Partial solutions to other biological and political problems have been found, resulting in improved production in captivity, increased survival post-release, and thriving populations in plague-free South Dakota.

Comptes Rendus - Biologies↗

USGS2007

Chapter 7 Magmatic-hydrothermal fluid interaction and mineralization in alkali-syenite nodules from the Breccia Museo pyroclastic deposit, Naples, Italy

The Breccia Museo, a pyroclastic flow that crops out in the Campi Flegrei volcanic complex (Naples, Italy), contains alkali-syenite (trachyte) nodules with enrichment in Cl and incompatible elements (e.g., U, Zr, Th, and rare-earth elements). Zircon was dated at ≈52 ka, by U-Th isotope systematics using a SHRIMP. Scanning electron microscope and electron microprobe analysis of the constituent phases have documented the mineralogical and textural evolution of the nodules of feldspar and mafic accumulations on the magma chamber margins. Detailed electron microprobe data are given for alkali and plagioclase feldspar, salite to ferrosalite clinopyroxene, pargasite, ferrogargasite, magnesio-hastingsite hornblende amphibole, biotite mica, Cl-rich scapolite, and a member (probable davyne-type) of the cancrinite group. Detailed whole rock, major and minor element data are also presented for selected nodules. A wide variety of common and uncommon accessory minerals were identified such as zircon, baddeleyite, zirconolite, pollucite, sodalite, titanite, monazite, cheralite, apatite, titanomagnetite and its alteration products, scheelite, ferberite, uraninite/thorianite, uranpyrochlore, thorite, pyrite, chalcopyrite, and galena. Scanning electron microscope analysis of opened fluid inclusions identified halite, sylvite, anhydrite, tungstates, carbonates, silicates, sulfides, and phosphates; most are probably daughter minerals. Microthermometric determinations on secondary fluid inclusions hosted by alkali feldspar define a temperature regime dominated by hypersaline aqueous fluids. Fluid-inclusion temperature data and mineral-pair geothermometers for coexisting feldspars and hornblende and plagioclase were used to construct a pressure-temperature scenario for the development and evolution of the nodules. We have compared the environment of porphyry copper formation and the petrogenetic environment constructed for the studied nodules. The suite of ore minerals observed in the nodules supports a potential for mineralization, which is similar to that observed in the alkaline volcanic systems of southern Italy (Pantelleria, Pontine Archipelago, Mt. Somma-Vesuvius).

Campi Flegrei↗

USGS2004

Molecular markers and their use in environmental organic geochemistry

Molecular markers are organic substances that carry information about sources of organic matter or contamination. The source/marker relation can be used to indicate the presence of a given source material (qualitative), or, under appropriate conditions, to estimate the amount of a source material (quantitative source apportionment) in the environment. Assemblages of markers can also be used as process probes. In this instance, systematic differences and/or similarities in the physical-chemical properties of markers are coupled with compositional changes in marker composition to infer the operation of natural processes. This paper provides an overview of what molecular markers are, what types of markers are present in the environment, the requirements for the use of markers, and some common applications. To illustrate how molecular markers can answer specific environmental questions, three case studies are presented. The first case study examines the impact of municipal waste on a large urban harbor (Boston Harbor). Linear alkylbenzenes (unreacted residues of linear alkylbenzenesulfonate surfactants) and coprostanol (a fecal indicator) provide information on the sources and likely transport pathways of municipal wastes in a complex hydrologic system. The marker data are also used to estimate the proportion of sewage-derived poly chlorinated biphenyls (PCBs) in polluted harbor sediments. The second case study concerns a portion of the continental shelf off southern California (Palos Verdes) where discharge of municipal wastewaters has led to extensive contamination of sediments and biota. Long-chain alkylbenzenes (surfactant residues), PCBs and the pesticide, DDT (dichlorodiphenyltrichloroethane), are used to develop sedimentation rate estimates for several time periods by molecular stratigraphy. These results, when combined with other information, allow conclusions to be drawn about the most likely transport pathway of sediments at the study site and to predict the fate of historically deposited contaminants. Finally, an investigation of a crude-oil spill in Bemidji, MN illustrates how monoaromatic hydrocarbons can be exploited as process probes, providing insights into the relative importance of different attenuation processes in a contaminated aquifer. The results show that natural attenuation of the monoaromatic hydrocarbons is occurring at this site and is dominated, not by physical and/or chemical processes, but by biodegradation.

Book chapter↗

USGS2008

Living in Yellowstone's Caldera: A geochemical trophic cascade in elk

Though the geology of earth's rare geothermal environments and their associated microbial communities are intensely studied, less scientific attention has focused on their potential effects through the plant-herbivore-carnivore trophic chain. The west-central portion of Yellowstone National Park contains a 2000-km 2 volcanic caldera with 2- to 60-million-year-old, predominantly rhyolitic, rocks that produce relatively infertile soils. The caldera area contains one of the largest concentrations of active geothermal features in the world, including thousands of geysers, fumaroles , hot springs, and mud pots. In many other chapters of this book, we address the ecological impacts of this unique geology to the ecology of the large mammals that live within the caldera, primarily through the effects of geothermal heat on snow pack. In this chapter, we explore the unique geochemistry of the geothermal environments and the consequences of this geochemistry to elk and perhaps other herbivores that reside within the caldera. These studies were prompted by behavioral and demographic observations of elk during the initial years of our studies that we could not explain and, in turn, led us to formulate hypotheses about potential geochemical influences on elk ecology. Specifically, we contrast the concentrations of fluoride (F) and silica (SiO 2 ) found in the Madison headwaters area with areas on Yellowstone's northern range located approximately 50 km to the northwest, where geothermal features are rare or absent. We then trace the consequences of geochemical differences through abiotic and biotic linkages in the ecosystem.

Book↗

USGS2019

Phylogenetic techniques in geomicrobiology

Molecular biological techniques have revolutionized the field of geomicrobiology by providing researchers with robust techniques for identifying microorganisms and characterizing microbial communities in a wide variety of environments. These techniques have freed researchers from the constraints of classical culture-based microbiology and allowed the discovery of previously unknown phylogenetic diversity of microorganisms. In this chapter, we discuss the theory, methods, and workflow for applying molecular techniques to identify and characterize microbial populations. Our chapter focuses on SSU rRNA gene-based approaches, guiding the reader from sample collection and gene amplification through bioinformatics and statistical analysis. The workflow presented has been successfully used to identify microbial populations and community dynamics in a wide variety of habitats to understand the interactions between microbes and their environment.

Book chapter↗

USGS2010

Implications of estuarine transport for water quality

In this chapter, some implications of estuarine transport for water quality are discussed. This is not an exhaustive review of all physical processes potentially important to water quality in estuaries. Rather, the focus is on (1) some fundamental relationships, concepts, and helpful idealizations (e.g., evolution equations for reactive scalars, transport time scales, scaling and non-dimensional numbers), (2) some common and often dominant physical processes in terms of their influence on estuarine water quality (e.g., stratification and turbulent mixing), and (3) some less prevalently discussed but probably widely important issues regarding high-frequency (i.e., intradaily) processes and their influence on water quality. Here, “water quality” refers to the full range of suspended constituents (or “scalars”, i.e., non-vector quantities) in an estuarine water column. These constituents may be dissolved or particulate, mineral, chemical, or biological, or they may represent physical properties of the water (e.g., temperature). The spatial distribution of a water quality constituent is influenced by the hydrodynamic environment in which it is suspended, but it may be additionally subject to motility, positive buoyancy, or negative buoyancy (e.g., some phytoplankton or zooplankton). Water quality scalars may be conservative (i.e., non-reactive, such as salt) or non-conservative (i.e., reactive and thereby potentially changing in concentration or form during transit; e.g., nitrogen, phosphorus, or phytoplankton). Hydrodynamic and transport processes are important not only because they “move stuff around” but also because, in the case of reactive scalars, those processes may expose the scalars to a range of environments, each of which may be associated with distinct rates of scalar transformation.

Book chapter↗

USGS2014

The effects of spilled oil on coastal ecosystems: Lessons from the Exxon Valdez spill

Oil spilled from ships or other sources into the marine environment often occurs in close proximity to coastlines, and oil frequently accumulates in coastal habitats. As a consequence, a rich, albeit occasionally controversial, body of literature describes a broad range of effects of spilled oil across several habitats, communities, and species in coastal environments. This statement is not to imply that spilled oil has less of an effect in pelagic marine ecosystems, but rather that marine spills occurring offshore may be less likely to be detected, and associated effects are more difficult to monitor, evaluate, and quantify (Peterson et al ., 2012). As a result, we have a much greater awareness of coastal pollution, which speaks to our need to improve our capacities in understanding the ecology of the open oceans. Conservation of coastal ecosystems and assessment of risks associated with oil spills can be facilitated through a better understanding of processes leading to direct and indirect responses of species and systems to oil exposure. It is also important to recognize that oil spilled from ships represents only ~9% of the nearly 700 000 barrels of petroleum that enter waters of North America annually from anthropogenic sources (NRC, 2003). The immediate effects of large spills can be defined as acute, due to the obvious and dramatic effects that are observed. In contrast, the remaining 625 000 barrels that are released each year can be thought of as chronic non-point pollution, resulting from oil entering the coastal ocean as runoff in a more consistent but much less conspicuous rate. In this chapter, we primarily address the effects of large oil spills that occur near coastlines and consider their potential for both acute and chronic effects on coastal communities. As described below, in some instances, the effects from chronic exposure may meet or exceed the more evident acute effects from large spills. Consequently, although quantifying chronic effects from low exposure rates can be challenging and time-consuming, the results of such efforts provide insights into the understudied effects of chronic non-point oil pollution.

Alaska↗

USGS2015

Management and the conservation of freshwater ecosystems

Riparian areas are the terrestrial environment adjacent to water that both influences and is influenced by the aquatic feature (Gregory et al ., 1991; Naiman et al ., 2010). Riparian areas along streams provide shade, sources of wood and organic matter, contribute to bank stability, filter sediments, take up excess nutrients from groundwater inputs, and other key processes that protect freshwaters (e.g. Naiman et al ., 2010; Richardson & Danehy, 2007; Figure 9.1). Riparian areas also increase biodiversity through habitat complexity and close juxtaposition of aquatic and terrestrial environments (Quinn et al ., 2004; Naiman et al ., 2010). Alterations to riparian areas, despite their small area relative to the landscape, have disproportionate effects on habitats and fish communities (Naiman et al ., 2010; Wipfli & Baxter, 2010). Key habitat losses and alterations are derived from modification of riparian areas by reducing instream habitat complexity (Bilby & Ward, 1989; Fausch & Northcote, 1992; Naiman et al ., 2010), diminishing the productive basis of freshwater food webs (Belsky et al ., 1999; Quinn et al ., 2004), increasing nutrient, contaminant and sediment intrusion (Muscutt et al ., 1993; Daniels & Gilliam, 1996; Nguyen et al ., 1998; Waters, 1999). Riparian and freshwater ecosystems are typically tightly coupled, especially in their natural states, and the linkages that couple them frequently exert strong influence on their associated invertebrate and fish fauna (e.g. Gregory et al ., 1991; Naiman et al ., 2010). Riparian habitats, and the condition of these habitats, further plays a key role in the ecology of these fresh waters, influencing critical processes such as water, nutrient and sediment delivery and dynamics; prey resources for fish and other consumers, and other organic materials exchanged between aquatic and terrestrial habitats (Nakano et al ., 1999; Naiman et al ., 2010); light and water temperature dynamics that in turn affect food web processes and fish metabolism and growth; aquatic physical habitat (wood); and terrestrial consumers that prey upon fishes (Bisson & Bilby, 1998; Naiman et al ., 2010; Wipfli & Baxter, 2010). These processes in turn directly or indirectly influence fishes in freshwater systems (Wang et al ., 2001; Pusey & Arthington, 2003; Allan, 2004; Richardson et al ., 2010a).

Book chapter↗

USGS2016

Bivalves and gastropods from the middle Campanian Anacacho limestone, South Central Texas

The Anacacho Limestone was deposited during the Campanian and represents two depositional intervals, one of early Campanian and one of middle Campanian age. These two intervals correspond to periods of major eustatic sea level rise. This study focuses on the molluscan paleontology of the middle Campanian interval in the eastern part of the Anacacho exposure belt in Medina County, Texas. Molluscan assemblages in this area are indicative of inner to mid-shelf environments. No significant reef components are present. These eastern Anacacho deposits are interpreted to represent more offshore, deeper water environments than those to the southwest, where reef and lagoonal deposits have been reported.

Journal of Paleontology↗

USGS2016

Late Cretaceous-Cenozoic history of deciduousness and the terminal Cretaceous event.

Deciduousness in mesic, broad-leaved plants occurred in disturbed, middle-latitude environments during the Late Cretaceous. Only in polar environments in the Late Cretaceous was the deciduous element dominant, although of low diversity. The terminal Cretaceous event resulted in wide-spread selection for plants of deciduous habit and diversification of deciduous taxa, thus leaving a lasting imprint on Northern Hemisphere vegetation. Various environmental factors have played important roles in subsequent diversification of mesic, broad-leaved deciduous taxa and in origination and decline of broad-leaved deciduous forests. Low diversity and rarity of mesic deciduous plants in the post-Cretaceous of the Southern Hemisphere indicate that the inferred “impact winter” of the terminal Cretaceous event had little effect on Southern Hemisphere vegetation and climate.

Paleobiology↗

USGS2007

Isotopic analysis of N and O in nitrite and nitrate by sequential selective bacterial reduction to N2O

Nitrite is an important intermediate species in the biogeochemical cycling of nitrogen, but its role in natural aquatic systems is poorly understood. Isotopic data can be used to study the sources and transformations of NO 2 - in the environment, but methods for independent isotopic analyses of NO 2 - in the presence of other N species are still new and evolving. This study demonstrates that isotopic analyses of N and O in NO 2 - can be done by treating whole freshwater or saltwater samples with the denitrifying bacterium Stenotrophomonas nitritireducens , which selectively reduces NO 2 - to N 2 O for isotope ratio mass spectrometry. When calibrated with solutions containing NO 2 - with known isotopic compositions determined independently, reproducible δ 15 N and δ 18 O values were obtained at both natural-abundance levels (±0.2−0.5‰ for δ 15 N and ±0.4−1.0‰ for δ 18 O) and moderately enriched 15 N tracer levels (±20−50‰ for δ 15 N near 5000‰) for 5−20 nmol of NO 2 - (1−20 μmol/L in 1−5 mL aliquots). This method is highly selective for NO 2 - and was used for mixed samples containing both NO 2 - and NO 3 - with little or no measurable cross-contamination. In addition, mixed samples that were analyzed with S. nitritireducens were treated subsequently with Pseudomonas aureofaciens to reduce the NO 3 - in the absence of NO 2 - , providing isotopic analyses of NO 2 - and NO 3 - separately in the same aliquot. Sequential bacterial reduction methods like this one should be useful for a variety of isotopic studies aimed at understanding nitrogen cycling in aquatic environments. A test of these methods in an agricultural watershed in Indiana provides isotopic evidence for both nitrification and denitrification as sources of NO 2 - in a small stream.

Indiana↗

USGS2024

Perfluorohexanesulfonic acid (PFHxS) impairs lipid homeostasis in zebrafish larvae through activation of PPARα

Perfluorohexanesulfonic acid (PFHxS), an emerging short-chain per- and polyfluoroalkyl substance, has been frequently detected in aquatic environments. Adverse outcome pathway studies have shown that perfluorinated compounds impair lipid homeostasis through peroxisome proliferator activated receptors (PPARs). However, many of these studies were performed at high concentrations and may thus be a result of overt toxicity. To better characterize the molecular and key events of PFHxS to biota, early life-stage zebrafish ( Danio rerio ) were exposed to concentrations detected in the environment (0.01, 0.1, 1, and 10 μg/L). Lipidomic and transcriptomic evaluations were integrated to predict potential molecular targets. PFHxS significantly impaired lipid homeostasis by the dysregulation of glycerophospholipids, fatty acyls, glycerolipids, sphingolipids, prenol lipids, and sterol lipids. Informatic analyses of the lipidome and transcriptome indicated alterations of the PPAR signaling pathway, with downstream changes to retinol, linoleic acid, and glycerophospholipid metabolism. To assess the role of PPARs, potential binding of PFHxS to PPARs was predicted and animals were coexposed to a PPAR antagonist (GW6471). Molecular simulation indicated PFHxS had a 27.1% better binding affinity than oleic acid, an endogenous agonist of PPARα. Antagonist coexposures rescued impaired glycerophosphocholine concentrations altered by PFHxS. These data indicate PPARα activation may be an important molecular initiating event for PFHxS.

Environmental Science & Technology↗

USGS2024

A multidisciplinary approach that considers occurrence, geochemistry, bioavailability, and toxicity to prioritize critical minerals for environmental research

Critical minerals (or critical elements) are minerals or elements that are essential to global security and development and have supply chains vulnerable to disruption. In general, knowledge of the environmental behavior and health effects of critical elements is needed to support the development of safe and environmentally responsible supplies. This knowledge includes identifying potential consequences of increased critical element production and use, alternative critical element sources such as mine wastes, and adverse effects of critical elements on ecosystem condition and organismal health. Here we identify significant data gaps in the understanding of critical elements in surficial and aquatic environments, and the need, given the large number of commodities (50) identified on the 2022 critical minerals list for the United States, for an approach to prioritize them for study of their environmental fate and effects. We propose a multidisciplinary approach for this prioritization, considering measures of occurrence, geochemistry, bioavailability, and toxicity. We describe relatively easy-to-obtain metrics for each of these topic areas and demonstrate the utility of this integrated prioritization approach using indium and zinc as examples. This approach facilitates prioritizing research with a focus on those critical elements that are most mobile in the environment, bioavailable, toxic, or simply lacking data in these categories.

Environmental Science & Technology↗

USGS2025

Sulfate reduction drives elevated methylmercury formation in water column of eutrophic freshwater lake

Mercury (Hg) contamination of aquatic food webs is controlled in part by the formation and accumulation of toxic and bioaccumulative methylmercury (MeHg). MeHg production is mediated by metabolically diverse microorganisms carrying the hgcAB gene pair, while the demethylation reaction is mediated by several biotic and abiotic processes. However, the relative importance of these two processes on MeHg accumulation and the environmental factors that influence them are poorly characterized, especially in eutrophic environments. In this study, both Hg methylation and MeHg demethylation in a eutrophic freshwater lake were linked to ambient MeHg concentrations and hgcA abundance and expression. High methylation rate potentials indicated in situ MeHg formation was a key source of MeHg to the water column, driven by high hgcA abundance and transcription. Molybdate treatment decreased methylation rate potentials, highlighting the importance of sulfate reduction in driving MeHg formation. Sulfate-reducing bacteria accounted for over 50% of the hgcA gene transcription, despite representing less than 10% of the hgcA -carrying microbial community. An arsR -like transcriptional regulator preceded many hgcA sequences; these were transcriptionally active and linked to lower hgcA expression. Overall, this study elucidates the microbial and biogeochemical processes that influence the in situ formation of MeHg in understudied eutrophic freshwater environments.

Wisconsin↗

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↗

USGS2025

Selenium differentially influences methylmercury retention across mayfly life stages

Though high mercury and selenium concentrations are individually toxic to organisms, there is a hypothesized antagonistic relationship. This potential mercury–selenium interaction is under-studied in aquatic macroinvertebrates, particularly in relation to complex life histories. We examined the proposed effect of selenium on methylmercury accumulation between four life stages for a parthenogenetic mayfly ( Neocloeon triangulifer ). We exposed diatoms to elevated methylmercury concentrations and fed them to mayflies exposed to elevated aqueous selenomethionine. We found some support for the mercury–selenium antagonism hypothesis, but it was context-specific. Selenium reduced methylmercury accumulation in high but not low methylmercury environments. Though terrestrial adult life stages had higher mercury concentrations compared to aquatic larval life stages, cumulative life history transfer factor (LHTF; ratio of methylmercury in adult imago to late instar larvae) differed by treatment. LHTF was constant for all aqueous selenium exposure levels at high dietary methylmercury (selenium impacts on methylmercury uptake and loss) but increased with aqueous selenium exposures at low dietary methylmercury (selenium impacts on methylmercury uptake only), suggesting a synergistic enhancement of MeHg transfer between life stages with increased aqueous Se exposure levels. These results suggest that animals eating adult aquatic insects are exposed to higher concentrations of methylmercury than those feeding on larval insects across selenium and methylmercury levels, but interference of selenium on methylmercury accumulation is only present at high methylmercury environments.

Environmental Science and Technology↗

USGS2025

Perfluorodecanoic acid (PFDA) disrupts immune regulation via the toll-like receptor signaling pathway in zebrafish

As there are a growing number of per- and polyfluoroalkyl substances (PFAS) alternative substitutes applied globally, it remains paramount to characterize their potential health risks. Perfluorodecanoic acid (PFDA) is the most common alternative PFAS detected in the environment; however, its toxic effects and underlying mechanism of action to aquatic biota remains unclear. In this study, we present in vitro evidence of PFDA-induced immunotoxicity and gain insight into underlying molecular mechanisms. PFDA induced immune dysfunction in zebrafish primarily through immunosuppression, apoptosis, and inflammatory response which further cascaded to suppress innate and adaptive immunities, ultimately weaking the ability of larvae to defend against pathogenic infection. PFDA-induced immunotoxicity was driven by a dysregulation in the toll-like receptor (TLR) signaling pathway, which was validated through a cotreatment of PFDA with either a morpholino knockdown or inhibitor of myeloid differentiation factor 88. Comparative toxicity studies were carried out with a subset of other alternative PFAS (PFBA, PFOA, PFNA) and it was found that PFDA posed a greater immunotoxic response than other commonly identified PFAS in the environment. This work identified a major target of PFDA, disrupting immune function through the TLR signaling pathway, while inducing a greater toxic response among other tested PFAS, which provides novel insights into understanding the potential environmental risks of PFAS substitutes.

Environmental Science & Technology↗

USGS2022

Crystal chemistry of thallium in marine ferromanganese deposits

Our understanding of the up to 7 orders of magnitude partitioning of thallium (Tl) between seawater and ferromanganese (FeMn) deposits rests upon two foundations: (1) being able to quantify the Tl(I)/Tl(III) ratio that reflects the extent of the oxidative scavenging of Tl by vernadite (δ-MnO 2 ), the principle manganate mineral in oxic and suboxic environments, and (2) being able to determine the sorption sites and bonding environments of the Tl(I) and Tl(III) complexes on vernadite. We investigated these foundations by determining the oxidation state and chemical form of Tl in FeMn crusts and nodules from the global oceans at a Tl concentration ranging from several hundred ppm (mg/kg) down to the low ppm level. Seventeen hydrogenetic crusts and eleven nodules from the Pacific, Atlantic, Arctic, and Indian Oceans and Baltic Sea were characterized by chemical analysis, X-ray diffraction, Raman spectroscopy, Mn K-edge X-ray absorption near-edge structure (XANES) spectroscopy, Tl L 3 -edge high energy-resolution XANES (HR-XANES) spectroscopy, and extended X-ray absorption fine structure (EXAFS) spectroscopy. The Tl concentration increases linearly from 1.5 to 319 ppm with the Mn/Fe ratio in Fe-vernadite from hydrogenetic crusts, whereas the percentage of Tl(III) to total Tl varies between 62 and 100% independent of both the Mn/Fe and Mn(III)/Mn(IV) ratios. The data, complemented by molecular modeling of the Tl(III) coordination and by XANES calculations, suggest that the enrichment of Tl in Fe-vernadite is driven by (1) the oxidative uptake of octahedrally coordinated Tl(III) above the vacant Mn(IV) sites and on the layer edges of the vernadite layers, and (2) the sorption of Tl(I) on the crystallographic site of Ba at the surface of the vernadite layers, which is an analogue to the surface site of K. Thus, Tl has a high affinity for vernadite regardless of its oxidation state, and the lack of correlation between Tl(III) and the Mn/Fe ratio in FeMn crusts is explained by the affinity of Tl(I) for the Ba site. The Tl concentration varies between 2 and 112 ppm in surface and buried nodules independent of the Mn/Fe ratio, and the percentage of Tl(III) varies between 0 and 100%. Nodules subjected to sediment diagenesis with replacement of layered vernadite by tunneled todorokite are depleted in Tl and have more reduced thallium. Knowledge of the complex interplay of mineralogy, surface chemical processes, and crystallographic siting is required to understand the variability of Tl concentrations, redox state, and acquisition processes by marine FeMn deposits.

ACS Earth and Space Chemistry↗