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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Refined views of ancient ocean chemistry: Tracking trace element incorporation in pyrite framboids using atom probe tomography

The trace element chemistry of pyrite can be used to determine the origin, timing, and conditions of formation of ore deposits; as a vectoring tool for mineral exploration; and to determine the evolution of the Earth’s oceanic and atmospheric chemistry. However, little is known about whether trace elements are held with the pyrite structure or within nano-inclusions of other phases. This distinction is important for two primary reasons. First, trace element incorporation into the pyrite structure can affect the partitioning of other trace elements. Second, if trace elements are held within nano-inclusions, the partition coefficient of the mineral phases that make up the nano-inclusion, rather than pyrite, are the critical consideration in related interpretations. Previous studies addressing this topic have used laser ablation inductively coupled plasma mass spectrometry; however, the resulting data do not provide sufficient spatial resolution to delineate trace element distributions unless the inclusions are large. Further, they use these flat element profiles in time resolved laser ablation output graphs to argue that pyrite trace element content provides a direct relationship between trace element content of seawater and pyrite trace element content. To improve resolution, we have used atom probe tomography to characterize trace element distributions in pyrite framboids from the Cariaco Basin and Demerara Rise in three-dimensions at sub-nanometer resolution. Manganese was found to be concentrated in the pyrite nanocrystal part of the original framboid structure. In contrast, Ni was mostly found along the grain boundary, though it still appeared to be contained within the pyrite structure. Copper was concentrated in later pyrite overgrowths, and As varied in its location. These observations suggest that some important trace elements are incorporated into pyrite during early diagenesis, even in euxinic settings dominated by water-column pyrite formation. Statistical analysis was used to determine whether trace elements were incorporated in the lattice or within nanoscale inclusions (referred to here are nano-inclusions). We found that As, Ni, Cu, and Mn were commonly held within the pyrite structure, but As, Ni, and Cu can also be held as nano-inclusions or within grain interfaces. Incorporation of As is known to enhance the incorporation of other trace elements and in this case appears to correlated to elevated Ni and Cu concentrations in the Cariaco Basin samples. Furthermore, understanding these relationships strongly impacts our ability to utilize pyrite trace metal concentrations to analyze and quantify early ocean chemistry and its evolution through time.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Exploring the Impact of N Solubility and Trace Elements on the Creep Properties of P92 Steel

Trace elements can have major consequences on the properties of creep resistant martensitic steels. To better understand the changes in microstructure and mechanical performance associated with the variation of trace elements and enable design of steels operating at more demanding conditions, we formulated three versions of P92 within the specified allowable N, B, C and Si ranges. Different service conditions were explored, and >80% decrease in creep life was observed at 625°C 155MPa for the highest B and N containing alloy. Multiscale characterization (OM, SEM, TEM) revealed key changes due to the trace element variation. The high trace content alloy formed deleterious BN precipitates with morphology that would promote crack nucleation, but also formed higher fractions of beneficial MX precipitates. The alloy with the lowest trace content showed the best creep performance – a result of the refined precipitate populations and the absence of large-scale inclusions and BN precipitates.

Antonov, Stoichko↗
DOE OSTI2025

Trace elements and their isotopes in streams and rivers

The occurrence and speciation of trace elements in streams and rivers are controlled by interconnected hydrogeological, biogeochemical, and anthropogenic factors that include rock weathering, climate, vegetation, and land use within the watershed. This chapter provides a broad overview of trace element abundance, speciation, and mobility in streams and rivers, including an assessment of how trace elements are partitioned into dissolved, colloidal, and particulate phases. We also discuss how trace elements are mobilized into stream networks and transformed during transport. Select isotopic systems are reviewed to provide examples of how isotopic analyses can be used to understand geochemical and anthropogenic processes.

Herndon, Elizabeth [ORNL] (ORCID:0000000291945493)↗
DOE OSTI2023

Trace Element Sampling and Partitioning Modeling to Estimate Wastewater Composition and Treatment Performance at Coal Generators

The coal combusted at coal-fired power plants (CFPPs) contains several trace elements that impact human heath if released to the environment. Effective combinations of air pollution control devices (APCDs) and water pollution control devices (WPCDs) are critical to reducing these impacts. This work sampled pulverized CFPPs owned and operated by Louisville Gas & Electricity – Kentucky Utilities (LGE-KU) during baseload and cycling conditions. Next, an open-source and easy-to-implement trace element partitioning model was developed using publicly available datasets, literature studies of trace element partitioning, and sampling data to estimate trace element partitioning in APCDs to the gas, liquid, and solid phases exiting CFPPs. These estimates of the liquid phase trace element concentration in FGD wastewater were then used to estimate trace element behavior in WPCDs and evaluate treated wastewater effluent concentrations for compliance with the Effluent Limitation Guidelines (ELG) for the Steam Electric Generating Sector. Finally, cost estimates were developed for established and emerging wastewater treatment trains to identify the most cost-effective approaches for ELG compliance.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2020

Trace Elemental Analysis of Bulk Thorium Using an Automated Separation–Inductively Coupled Plasma Optical Emission Spectroscopy Methodology

Presented here is a novel automated method for determining the trace element composition of bulk thorium by inductively coupled plasma–optical emission spectroscopy (ICP-OES). ICP-OES is a universal approach for measuring the trace elemental impurities present in actinide-rich materials; however, due to the emission rich spectrum of the actinide, a separation from the trace elements is warranted for spectrochemical analysis. Here, AG MP-1 ion exchange resin was utilized for retention of the Th matrix, while allowing the trace element impurities to be separated prior to subsequent analysis using ICP-OES. After demonstrating the separation on traditional gravity-driven columns, the methodology was transitioned to an automated platform for comparison. This automated platform utilizes syringe-driven sample and solvent flow and can collect the trace element and thorium fractions in separate locations. Finally, while reducing the sample size (500 µL, 1.5 mg of Th), maintaining the overall separation efficiency (recoveries >95%), and illustrating the sample throughput ability (n = 10+), this automated methodology could be readily adopted to nuclear facilities in which the determination of trace elemental impurities in Th samples is warranted.

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

Gas-mediated trace element incorporation into rhyolite-hosted topaz: A synchrotron microbeam XAS study

Magmatic gas exsolving during late-stage cooling of shallow magmas has been considered an important facilitator of low-pressure alteration and metal transport. However, the chemical properties of such gas, particularly its metal transport mechanisms and capacity, remain elusive. Trace elements in minerals produced by gas-mediated surface reaction or precipitation from gas capture details of gas composition and reaction pathways. However, interpretation of mineral trace element contents is dependent on understanding crystallographic controls on gas/mineral partitioning. Here, this work investigates the structural accommodation of As, Mn, Ga, Ge, Fe, and Ti in vapor-deposited topaz of vesicular topaz rhyolite from the Thomas Range, Utah, through single-crystal synchrotron microbeam X-ray techniques on picogram quantities of those trace elements. X-ray absorption near edge structure (XANES) data indicates that these elements are incorporated into topaz as As 5+ , Fe 3+ , Mn 3+ , Ti 4+ , Ga 3+ , and Ge 4+ . Extended X-ray absorption fine structure (EXAFS) analysis for these trace elements, compared to EXAFS of structural Al and Si, reveals that As 5+ and Ge 4+ are incorporated directly into the tetrahedral site of the topaz structure, with the octahedral site accommodating Mn 3+ , Fe 3+ , Ga 3+ , and Ti 4+ . For As 5+ and Fe 3+ , the structural impact of substitution extends to at least second neighbors (other elements were only resolvable to first neighbors). Further interpretation of the EXAFS results suggests that the substitution of Ti 4+ results in increased distortion of the octahedral site, while the other trace elements induce more uniform expansion correlating in magnitude to their ionic radius. Comparison of quantified X-ray fluorescence (XRF) data for two topaz crystals from this rhyolite reveals variable trace element concentrations for As 5+ , Fe 3+ , Ga 3+ , and Ti 4+ , reflective of a source gas undersaturated in these trace elements changing in concentration over the period of topaz deposition. The identical Ge 4+ content of the two topaz crystals suggests that Ge 4+ in the gas was buffered by the growth of another Ge 4+ -bearing phase, such as quartz. The very low Mn 3+ content in the topaz crystals does not reflect the abundance of Mn 3+ in the gas (saturation of Mn is evidenced by coexisting bixbyite). Instead, it suggests a strong Jahn-Teller inhibitory effect to the substitution of Mn 3+ for Al 3+ in the distorted octahedral site of topaz. It is proposed that exsolution of an HF-enriched gas from cooling rhyolitic magma led to local scouring of Al, Si, and trace metals from the magma. Once topaz crystals nucleated, self-catalyzed reactions that recycle HF led to continued growth of topaz.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Characterizing major and trace element compositions in fallout melt glass from a near-surface nuclear test

We report the chemical and isotopic compositions of fallout melt glasses from nuclear tests contain a range of information constraining the physical conditions within the fireball and the mechanisms of fallout formation but historic studies tended to exclude the behavior of stable major and trace elements. Here, we present a large study specifically focused on major and trace element relationships within a population of macroscale fallout samples from a single event. We interpret these data to better constrain how fallout melt glass formation in near surface environments is influenced by that environment and demonstrate how major and trace element abundances can provide useful insights into chemical processes within the fireball. Data confirm that the uranium in the fallout glass population derives from two isotopically distinct endmembers: isotopically enriched uranium (presumably from the weapon), and natural composition uranium that may be a combination of anthropogenic and environmental materials from within the blast zone. The similarity between major and trace element concentrations in fallout and corresponding local soils from the event site confirm the local soils as the most probable source of entrained material into the fireball and the source of carrier material into which the bomb vapor was incorporated. The lack of correlation between major and trace element abundances with size indicates that volatility driven processes, such as condensation from the fireball, do not control the composition of macroscale fallout melt glass. Although the fallout has major and trace element chemical characteristics broadly similar to those of the local, associated soils, some systematic differences are observed between the two populations. Fallout melt glass is depleted in volatile elements such as K, Na, Tl and Pb, consistent with heating to temperatures above ~1000 °C for 3-10 s. This is supported by the results of laser heating experiments performed on rhyolitic soil at temperatures (1600-2200 °C) and timescales (1-120 s) that are broadly relevant to fallout formation conditions. Relative enrichments of metals such as Cu and Co do not correlate with the abundance of uranium, suggesting that fallout also records input of near field anthropogenic materials. Our observations suggest that major chemical features can be related to processing in the fireball and used to inform the thermal-chemical evolution of the system. Ultimately, these data are consistent with a fallout formation mechanism that involves rapid melting of surface materials to form carrier material melts with minor incorporation of bomb vapor and a degree of volumetric volatile loss due to heating.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Trace element geochemistry of coarse-grained angrites from Northwest Africa: Implications for their petrogenesis on the angrite parent body

The angrites are a class of achondrites that encompass a wide range of igneous textures from quenched, volcanic, and subvolcanic stones to slowly cooled, plutonic rocks. The compositions of the various geochemical reservoirs generating this variety of rocks have not been investigated fully because historically the numbers and masses of angrites available for study have been quite small. However, the rapid increase in meteorites from Northwest Africa (NWA) has enabled a renewed opportunity for such an investigation. In particular, three samples, NWA 2999, 4590, and 4801, have provided a new window into our understanding of the origin and petrogenesis of the coarse-grained (plutonic) angrites. We report here the trace element abundances in individual mineral grains of pyroxene, plagioclase, olivine/kirschsteinite, and phosphate and in the whole-rock samples. We utilize these data to constrain the petrogenetic history of each of these samples on the angrite parent body (e.g., parental melt compositions and oxygen fugacity conditions) and assess genetic relationships to previously investigated angrites. The trace element abundances in each of the three coarse-grained angrites studied here indicate a unique history for each. The observed trace element abundances and patterns in NWA 2999 show similarities with previously studied fine-grained, volcanic angrites and potentially indicate a common geochemical source reservoir, even though NWA 2999 is temporally distinct from the volcanic angrites. In contrast, NWA 4590 has trace element characteristics analogous to other coarse-grained angrites (e.g., Lewis Cliff [LEW] 86010), suggesting that these samples originated from geochemically similar source reservoirs. The third angrite, NWA 4801, exhibits geochemical characteristics most similar to the plutonic, coarse-grained angrites, but also appears to have some affinities in its trace element characteristics to the volcanic, fine-grained angrites. This suggests that NWA 4801 may represent a petrogenetic link between two distinct geochemical reservoirs on the angrite parent body. In aggregate, the trace element distributions in these three plutonic angrites suggest that while they may have originated up to several million years after the fine-grained angrites, they sampled a range of source reservoirs on the angrite parent body. Here, some of these source reservoirs were likely similar to those of the fine-grained angrites, but others had distinct geochemical characteristics.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Rapid quantitative analysis of trace elements in plutonium alloys using a handheld laser-induced breakdown spectroscopy (LIBS) device coupled with chemometrics and machine learning

Here, we present the first reported quantification of trace elements in plutonium via a portable laser-induced breakdown spectroscopy (LIBS) device and demonstrate the use of chemometric analysis to enhance the handheld device's sensitivity and precision. Quantification of trace elements such as iron and nickel in plutonium metal via LIBS is a challenging problem due to the complex nature of the plutonium optical emission spectra. While rapid analysis of plutonium alloys has been demonstrated using portable LIBS devices, such as the SciAps Z300, their detection limits for trace elements are severely constrained by their achievable pulse power and length, light collection optics, and detectors. In this paper, analytical methods are evaluated as a means to circumvent the detection constraints. Three chemometric methods often used in analytical spectroscopy are evaluated; principal component regression, partial least-squares regression, and artificial neural networks. These models are evaluated based on goodness-of-fit metrics, root mean-squared error, and their achievable limits of detection (LoDs). Partial least squares proved superior for determining content of iron and nickel in plutonium metal, yielding LoDs of 15 and 20 ppm, respectively. These results of identifying the undesirable trace elements in plutonium components are critical for applications such as fabricating radioisotope thermoelectric generators or nuclear fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Quantifying fish otolith mineralogy for trace-element chemistry studies

Otoliths are frequently used to infer environmental conditions or fish life history events based on trace-element concentrations. However, otoliths can be comprised of any one or combination of the three most common polymorphs of calcium carbonate - aragonite, calcite, and vaterite - which can affect the ecological interpretation of otolith trace-element results. Previous studies have reported heterogeneous calcium carbonate compositions between left and right otoliths but did not provide quantitative assessments of polymorph abundances. In this study, neutron diffraction and Raman spectroscopy were used to identify and quantify mineralogical compositions of Chinook salmon Oncorhynchus tshawytscha otolith pairs. We found mineralogical compositions frequently differed between otoliths in a pair and accurate calcium carbonate polymorph identification was rarely possible by visual inspection alone. The prevalence of multiple polymorphs in otoliths is not well-understood, and future research should focus on identifying otolith compositions and investigate how variations in mineralogy affect trace-element incorporation and potentially bias environmental interpretations.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2019

Stepwise chemical abrasion–isotope dilution–thermal ionization mass spectrometry with trace element analysis of microfractured Hadean zircon

Abstract. The Hadean Jack Hills zircons represent the oldest known terrestrial material, providing a unique and truly direct record of Hadean Earth history. This zircon population has been extensively studied via high-spatial-resolution high-throughput in situ isotopic and elemental analysis techniques, such as secondary ionization mass spectrometry (SIMS), but not by comparatively destructive, high-temporal-precision (<0.05 % two-sigma) thermal ionization mass spectrometry (TIMS). In order to better understand the lead loss and alteration history of terrestrial Hadean zircons, we conduct stepwise chemical abrasion–isotope dilution–thermal ionization mass spectrometry with trace element analysis (CA-ID-TIMS-TEA) on manually microfractured Hadean Jack Hills zircon fragments previously dated by SIMS. We conducted three successive HF leaching steps on each individual zircon fragment, followed by column chromatography to isolate U–Pb and trace element fractions. Following isotopic and elemental analysis, the result is an independent age and trace element composition for each leachate of each zircon fragment. We observe ~50 Myr of age heterogeneity in concordant residues from a single zircon grain, along with a protracted history of post-Hadean Pb loss with at least two modes circa ~0 and 2–4 Ga. Meanwhile, stepwise leachate trace element chemistry reveals enrichments of light rare earth elements, uranium, thorium, and radiogenic lead in early leached domains relative to the zircon residue. In addition to confirming the efficacy of the LREE-I alteration index and providing new insight into the mechanism of chemical abrasion, the interpretation and reconciliation of these results suggest that Pb loss is largely driven by low-temperature aqueous recrystallization and that regional thermal events may act to halt – not initiate – Pb loss from metamict domains in the Hadean Jack Hills zircons.

Brenhin Keller, C. (ORCID:0000000174009428)↗
DOE OSTI2024

Trace elements and heavy metals in black vultures ( Coragyps atratus ) and turkey vultures ( Cathartes aura ) in the southeastern United States

Many vulture species worldwide are declining at alarming rates due to a variety of anthropogenic causes, including exposure to pollutants and pharmaceuticals through consumption of contaminated carrion. However, little is known about the extent to which vultures are exposed to various contaminants as well as toxicity thresholds for trace elements and heavy metals. Our objective was to quantify levels of trace elements and heavy metals within black vulture (Coragyps atratus) and turkey vulture (Cathartes aura) tissues to determine the extent to which populations in the southeastern United States are exposed to carrion that contains high levels of contaminants. We collected black vulture liver samples and examined differences in trace element and heavy metal concentrations between sexes and age classes (adult and juvenile). Further, we collected 81 blood and 42 feather samples from additional black and turkey vultures and compared differences between species and age classes. We found similar element concentrations between juvenile and adult black vultures with the exception of Cu, where levels 40 were higher in juveniles compared to adults. However, we did observe substantial differences in element concentrations between species for both blood and feather samples, with black vultures generally having higher concentrations of most elements. Our data revealed higher element levels in both species compared to toxicity thresholds found in other bird of prey species, such as blood and liver toxicity threshold suggestions for Pb poisoning in Falconiformes. Further, while average contaminant levels were generally low, extreme outliers were observed for some elements, including Pb, suggesting some individuals were exposed to high levels of potentially toxic elements. In conclusion, more research is needed to better understand contaminant exposure in black and turkey vultures across a broader geographic region, as well as elucidate toxicity thresholds and non-lethal impacts of contaminant exposure in these species.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗
DOE OSTI2024

Electrophoretic deposition for improved trace element homogeneity in silica reference materials

Spatially-resolved analysis requires homogeneous reference materials (RMs) to make reliable quantitative measurements. Here we previously developed an electrophoretic deposition (EPD) method for fabrication of glassy microanalytical RMs with superior platinum-group element homogeneity **[1], and now include further dopants. For 39 trace elements, we analyzed dopant homogeneity in sintered silica (SiO 2 ) samples consolidated either mechanically by die-pressing (DP) or by EPD. A set of EPD and DP samples was made from each of two nanoparticle feedstocks produced by variations of the Stöber process **[2]. Spatially-resolved dopant distribution was characterized in all samples by laser-ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS). In both sample sets, homogeneity of most trace elements was substantially improved by EPD relative to their DP counterpart.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Rapid and automated separation of uranium ore concentrates for trace element analysis by inductively coupled plasma – optical emission spectroscopy/triple quadrupole mass spectrometry

The present study documents an automated approach to performing elemental analysis on a large group uranium ore concentrate (UOC) samples. In this work, 17 UOC samples, 2 quality control samples, and 26 process blanks were purified sequentially through a single 500 μL Uranium and TEtra Valent Actinides (UTEVA®) column. For each sample, the trace elemental impurities were separated from its dissolved uranium matrix on the UTEVA column and collected for analysis by inductively coupled plasma – optical emission spectroscopy / triple quadrupole mass spectrometry (ICP-OES/TQMS). The UTEVA column was subsequently regenerated prior to separation of the following sample. The column was efficiently regenerated, for each UOC, even after processing ~50 mg of uranium, cumulatively. The validity of the method was established by determining the trace impurities of two quality control uranium reference samples (CRM 124–1 and CUP-2). The current trace element measurements from the 17 UOC samples were compared to previously reported values from an interlaboratory comparison exercise, when available. The methodology employed here produces trace elemental analysis with excellent correlation to the previously reported data for many of the elements / samples, particularly when viewed through the context of existing geochemical comparisons tools (e.g. chondrite normalized variation plots).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Evaluation of Compton suppression for enhancing trace element identification in neutron activation analysis of reference materials

Neutron activation analysis (NAA) is a powerful technique for identifying and quantifying trace elements in materials. However, challenges such as high dead times, spectral interferences, and high Compton continuum often arise. This study employs a Compton suppression system (CSS) to enhance NAA sensitivity by reducing the Compton continuum, thereby improving the peak-to-Compton ratio. National Institute of Standards and Technology certified reference materials 1632d, 1633c, and Canadian National Research Council TORT-1 were irradiated in a thermal and epithermal neutron flux under various irradiation, decay and counting times and analyzed using high-resolution gamma-ray spectroscopy with and without Compton suppression. The reduction factor was calculated to evaluate the effectiveness of the CSS, demonstrating significant background reduction and improved detection limits for trace elements. Additional experiments with a 137Cs point source demonstrated the impact of detector-source geometry on system performance, showing a decrease in the reduction factor as the source was moved further from the NaI detector. An optimum distance between the source and HPGe detector was observed, yielding the highest peak-to-Compton ratio. The results highlight the CSS's ability to minimize spectral interference and enhance elemental identification.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

Collaborative Study for Certification of Trace Elements in Uranium Ore Concentrate CRMs UCLO-1, UCHI-1, and UPER-1

Trace impurity patterns are important nuclear forensic signatures in uranium ore concentrates (UOCs) and Certified Reference Materials (CRMs) are used to validate the analysis methods employed by end users. Herein, we discuss the certification campaign for three new UOC CRMs from the National Research Council Canada: UCLO-1 (https://doi.org/10.4224/crm.2020.uclo-1), UCHI-1 (https://doi.org/10.4224/crm.2020.uchi-1), and UPER-1 (https://doi.org/10.4224/crm.2020.uper-1). This study involved 15 laboratories from 10 countries, using sector-field and (triple) quadrupole inductively-coupled plasma mass spectrometry to analyze 64 trace element impurities. We discuss the importance of the acids used for sample digestion, difficulties analyzing in a high uranium matrix, and data combination and uncertainty evaluation for this large dataset.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

Patterns of Trace Element Accumulation in Waterfowl Restricted to Impoundments Holding Coal Combustion Waste

Waterfowl are often exposed to and readily accumulate anthropogenic contaminants when foraging in polluted environments. Settling impoundments containing coal combustion waste (CCW) enriched in trace elements such as arsenic (As), selenium (Se), and mercury (Hg) are often used by free-ranging migratory and resident waterfowl and represent potential sources for contaminant uptake. To assess accumulation of CCW contaminants, we experimentally restricted waterfowl to a CCW-contaminated impoundment and quantified trace element burdens in blood, muscle, and liver tissues over known periods of exposure (between 3 and 92 d). From these data we developed models 1) to predict elemental bioaccumulation with increased exposure time, and 2) to predict muscle/liver burdens based on concentrations in blood as a nondestructive sampling method. Although Hg and As did not bioaccumulate in our waterfowl, we observed an increase in Se concentrations in muscle, liver, and blood tissues over the duration of our experiment. Furthermore, we found that blood may be used as an effective nondestructive sampling alternative to predict muscle and liver tissue concentrations in birds contaminated with Se and As through dietary exposure. These data provide unique insights into accumulation rates of contaminants for waterfowl utilizing habitats contaminated with CCW and demonstrate the efficacy of nonlethal sampling of waterfowl to quantify contaminant exposure. Environ Toxicol Chem 2020;39:1052–1059.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Nanoscale trace-element zoning in pyrite framboids and implications for paleoproxy applications

Pyrite framboids (spherical masses of nanoscale pyrite) are among the earliest textures of pyrite to form in sediments. It has been proposed that their trace-element (TE) contents can be used to track the TE composition of the water column in which they formed. However, it is not clear how these TEs are associated with the framboidal pyrite grains. For instance, it is important to know whether they are incorporated uniformly or are enriched in different regions of the framboid. Here, we used high-resolution scanning transmission electron microscopy to identify chemical zoning within pyrite framboids. We found that initial, nanoscale pyrite euhedral crystals, which make up the volumetric majority of the framboids, are covered/infilled by later pyrite that templates on the earlier pyrite. Further, this later pyrite is enriched in TEs, suggesting that many TEs are incorporated in pyrite relatively late (during early diagenesis; not in the water column). This observation suggests that although chemical analyses of pyrite framboids may provide ocean-water chemistry trends through time, the details are complex. Specifically, the TEs found in pyrite may be linked to adsorption onto organic matter, detrital material, and authigenic minerals such as Fe- and Mn-oxide phases followed by desorption in the sediments or release via dissolution and incorporation into pyrite as overgrowths on the initial nanoscale euhedral crystals that make up framboids. While the use of pyrite chemistry to understand past ocean conditions remains promising, and even diagenetic additions may not preclude the utility of pyrite for reconstructing ancient ocean conditions, care must be taken in interpretations because the end concentration may be influenced by diagenesis.

58 GEOSCIENCES↗