Portable Analytical Instrumentation for Instantaneous Real-Time Measurement of Chemical Elements in Raw Petroleum and Refinery Products
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Nitrogen-fixing cyanobacteria bind atmospheric nitrogen and carbon dioxide using sunlight. This experimental study focused on a laboratory-based model system, Anabaena sp., in nitrogen-depleted culture. When combined nitrogen is scarce, the filamentous prokaryotes reconcile photosynthesis and nitrogen fixation by cellular differentiation into heterocysts. To better understand the influence of micronutrients on cellular function, 2D and 3D synchrotron X-ray fluorescence mappings were acquired from whole biological cells in their frozen-hydrated state at the Bionanoprobe, Advanced Photon Source. To study elemental homeostasis within these chain-like organisms, biologically relevant elements were mapped using X-ray fluorescence spectroscopy and energy-dispersive X-ray microanalysis. Higher levels of cytosolic K + , Ca 2+ , and Fe 2+ were measured in the heterocyst than in adjacent vegetative cells, supporting the notion of elevated micronutrient demand. P-rich clusters, identified as polyphosphate bodies involved in nutrient storage, metal detoxification, and osmotic regulation, were consistently co-localized with K + and occasionally sequestered Mg 2+ , Ca 2+ , Fe 2+ , and Mn 2+ ions. Machine-learning-based k-mean clustering revealed that P/K clusters were associated with either Fe or Ca, with Fe and Ca clusters also occurring individually. In accordance with XRF nanotomography, distinct P/K-containing clusters close to the cellular envelope were surrounded by larger Ca-rich clusters. The transition metal Fe, which is a part of nitrogenase enzyme, was detected as irregularly shaped clusters. The elemental composition and cellular morphology of diazotrophic Anabaena sp. was visualized by multimodal imaging using atomic force microscopy, scanning electron microscopy, and fluorescence microscopy. This paper discusses the first experimental results obtained with a combined in-line optical and X-ray fluorescence microscope at the Bionanoprobe.
The present disclosure relates to a detector system for imaging an optical signal received by a graded index (GRIN) optical element to account for known variations in a graded index distribution of the GRIN optical element. The detector system incorporates a plurality of optical detector elements configured to receive optical rays received by the GRIN optical element at specific locations on a plane of the GRIN optical element. Ray tracing software is configured to receive and map the optical rays to a plurality of additional specific locations on the plane based on the known variations in the graded index distribution of the GRIN optical element. A processor uses algorithms for diagonalization of a linear system matrix to determine information on both an intensity and an angle of the received optical rays at each one of the plurality of specific locations on the plane.
Plume volcanism may sample mantle sources deeper than mid-ocean ridge and arc volcanism. Ocean island basalts (OIBs) are commonly related to plume volcanism, and their diverse isotopic and elemental compositions can be described using a limited number of mantle endmembers. However, the origins and depths of these mantle endmembers are highly debated. Here we show that the HIMU (high μ, μ = 238 U/ 204 Pb) endmember may reside in the transition zone. Specifically, we report the geochemical signature of a high-pressure multiphase diamond inclusion, entrapped at 420–440 km depth and 1450 ±50 K, which matches exactly the geochemical patterns of the HIMU-rich OIBs. Since the HIMU component is variably sampled by almost all OIBs, our finding implies that the transition zone causes a major overprint of the geochemical features of mantle plumes. Furthermore, some mantle plumes, like those feeding Bermuda, St Helena, Tubuai and Mangaia, appear to be dominated by this source. Furthermore, our finding highlights the importance of the transition zone in highly incompatible element budget of the mantle.
We report Ophiolite complexes represent fragments of ocean crust and mantle formed at spreading centers and emplaced on land. The setting of their origin, whether at mid-ocean ridges, back-arc basins, or forearc basins has been debated. Geochemical classification of many ophiolite extrusive rocks reflect an approach interpreting their tectonic environment as the same as rocks with similar compositions formed in various modern oceanic settings. This approach has pointed to the formation of many ophiolitic extrusive rocks in a supra-subduction zone (SSZ) environment. Paradoxically, structural and stratigraphic evidence suggests that many apparent SSZ-produced ophiolite complexes are more consistent with mid-ocean ridge settings. Compositions of lavas in the southeastern Indian Ocean resemble those of modern SSZ environments and SSZ ophiolites, although Indian Ocean lavas clearly formed in a mid-ocean ridge setting. These facts suggest that an interpretation of the tectonic environment of ophiolite formation based solely on their geochemistry may be unwarranted. New seismic images revealing extensive Mesozoic subduction zones beneath the southern Indian Ocean provide one mechanism to explain this apparent paradox. Cenozoic mid-ocean-ridge–derived ocean floor throughout the southern Indian Ocean apparently formed above former sites of subduction. Compositional remnants of previously subducted mantle in the upper mantle were involved in generation of mid-ocean ridge lavas. The concept of historical contingency may help resolve the ambiguity on understanding the environment of origin of ophiolites. Many ophiolites with “SSZ” compositions may have formed in a mid-ocean ridge setting such as the southeastern Indian Ocean.
The release of leachates from intact coal ash impoundments is a concern due to the enrichment and mobilization of toxic elements such as arsenic (As) and selenium (Se). This study aims to explore the intrinsic properties of coal fly ash that correlate with the relative leachability of As and Se. We performed leaching experiments with 52 fly ash samples collected from 15 different U.S. power plants and representing coal feedstocks from the three major domestic regions. We assessed the mobilization potential of As and Se in fly ash based on standardized leaching protocols and performed multivariate and lasso regression analyses to explore correlations of leachable As and Se contents with characteristics such as major element contents, loss on ignition, and pH. The results of regression models indicated that major elements (Fe, Ca, and Al) for a wide range of fly ashes can serve as predictor variables for the leaching potential of As but not for Se. LOI and pH were not important predictive variables in the models. Both regression approaches resulted in relatively strong fits for leachable As (correlation coefficient R 2 = 0.78 for both models) compared to models for leachable Se (R 2 = 0.49). Overall, these results suggest that correlation models combined with on-site elemental analysis with portable analyzers may enable a screening method for leachable As in coal ash.
Elemental ratios in biogenic marine calcium carbonates are widely used in geobiology, environmental science, and paleoenvironmental reconstructions. It is generally accepted that the elemental abundance of biogenic marine carbonates reflects a combination of the abundance of that ion in seawater, the physical properties of seawater, the mineralogy of the biomineral, and the pathways and mechanisms of biomineralization. Here we report measurements of a suite of nine elemental ratios (Li/Ca, B/Ca, Na/Ca, Mg/Ca, Zn/Ca, Sr/Ca, Cd/Ca, Ba/Ca, and U/Ca) in 18 species of benthic marine invertebrates spanning a range of biogenic carbonate polymorph mineralogies (low-Mg calcite, high-Mg calcite, aragonite, mixed mineralogy) and of phyla (including Mollusca, Echinodermata, Arthropoda, Annelida, Cnidaria, Chlorophyta, and Rhodophyta) cultured at a single temperature (25°C) and a range of p CO 2 treatments (ca. 409, 606, 903, and 2856 ppm). This dataset was used to explore various controls over elemental partitioning in biogenic marine carbonates, including species-level and biomineralization-pathway-level controls, the influence of internal pH regulation compared to external pH changes, and biocalcification responses to changes in seawater carbonate chemistry. The dataset also enables exploration of broad scale phylogenetic patterns of elemental partitioning across calcifying species, exhibiting high phylogenetic signals estimated from both uni- and multivariate analyses of the elemental ratio data (univariate: λ = 0–0.889; multivariate: λ = 0.895–0.99). Comparing partial R 2 values returned from non-phylogenetic and phylogenetic regression analyses echo the importance of and show that phylogeny explains the elemental ratio data 1.4–59 times better than mineralogy in five out of nine of the elements analyzed. Therefore, the strong associations between biomineral elemental chemistry and species relatedness suggests mechanistic controls over element incorporation rooted in the evolution of biomineralization mechanisms.
The purpose of this dataset is to support research aimed at understanding the coupling between hydrologic and biogeochemical processes at watershed scale, particularly the relationship between aboveground vegetation characteristics and subsurface soil properties. These data are intended to inform and calibrate models of catchment-scale biogeochemical fluxes, including rock-derived nutrient cycling, and they were procured to address the following questions: (1) What is the distribution of vegetation characteristics across the study catchments? (2) Are foliar concentrations of rock-derived nutrients related to underlying lithology and soil availability, or are these signals masked by biotic nutrient cycling and retention processes?This data package contains foliar elemental data collected during the 2018 National Ecological Observatory Networks (NEON) Airborne Observation Platform (AOP) imaging spectroscopy and lidar surveys in Gunnison County, Colorado. Folair samples were collected across the East River, Washington Gulch, Slate River, and Coal Creek watersheds and contain a mixture of vegetation including meadow, shrub, and tree foliar samples. The samples were processed using aqua regia digestion and analyzed for elemental determination on inductively coupled plasma optical emission spectrometry (ICP-OES).The data package includes: (1) raw foliar elemental data files in CSV and PDF formats, (2) quality control certificates in PDF format, and (3) an aggregated CSV file containing all elemental measurements compiled across samples. No specialized software is required to access or use these files.
Abstract Scanning X-ray fluorescence (XRF) tomography provides powerful characterization capabilities in evaluating elemental distribution and differentiating their inter- and intra-cellular interactions in a three-dimensional (3D) space. Scanning XRF tomography encounters practical challenges from the sample itself, where the range of rotation angles is limited by geometric constraints, involving sample substrates or nearby features either blocking or converging into the field of view. This study aims to develop a reliable and efficient workflow that can (1) expand the experimental window for nanoscale tomographic analysis of local areas of interest within a laterally extended specimen, and (2) bridge 3D analysis at micrometer and nanoscales on the same specimen. We demonstrate the workflow using a specimen of HeLa cells exposed to iron oxide core and titanium dioxide shell (Fe3O4/TiO2) nanocomposites. The workflow utilizes iterative and multiscale XRF data collection with intermediate sample processing by focused ion beam (FIB) sample preparation between measurements at different length scales. Initial assessment combined with precise sample manipulation via FIB allows direct removal of sample regions that are obstacles to both incident X-ray beam and outgoing XRF signals, which considerably improves the subsequent nanoscale tomography analysis. This multiscale analysis workflow has advanced bio-nanotechnology studies by providing deep insights into the interaction between nanocomposites and single cells at a subcellular level as well as statistical assessments from measuring a population of cells.
This data package includes processed and undiluted measurements for metal, sulfur and organic carbon concentrations from pore water (groundwater) samples from the Slate River floodplain of Crested Butte, CO, a focus field site for the SLAC Floodplain Hydro-Biogeochemistry SFA. The data was generated as part of the work targeting the overarching research question for the SLAC SFA: How do ubiquitous subsurface interfaces mediate molecular-scale biogeochemical processes and groundwater quality in floodplains and watersheds? Samples were collected between March and October of 2021. These measurements were all recorded at the Environmental Measurements Facility (EM-1) at Stanford University in Stanford, CA. Groundwater samples were extracted from a network of installed rhizon (Rhizosphere Research Products, part no. 19.60.21F, 0.6 micrometer mesh size) and piezometer wells within the river floodplain. All water samples were shaded from sun exposure during extraction from the subsurface and preserved at 2C until measured at EM-1.Analysis by ICP-MS:Measurements for total metals were performed on an inductively coupled plasma optical emission spectrometer (ICP-OES; iCAP 6300, Thermo Scientific, Cambridge, U.K.). Calibration standards were prepared from the mulit element stock solution (Sigma-Aldrich Multielement standard for ICP, St. Louis, MO) using matrix matched to sample solutions (2% HNO3). Calibration curves included 5 points with correlation coefficients of >0.99. The QC protocol includes a continuing calibration blank and quality control samples that are analyzed just after calibration and again every 20 samples and at the completion of the run. Acceptable QC responses must be between 90-110% of the certified value. Analysis by Total Organic Carbon:Dissolved organic carbon concentrations were quantified on a total organic carbon (TOC) analyzer (TOC-L, Shimadzu, Kyoto, Japan) running the NPOC method. Standard curves were developed using an Organic Carbon Standard from RICCA Chemical Company (Arlington,TX). A series of 4 to 6 standards were automatically diluted by the instrument in a concentration range that spans that of the samples. A blank sample was run just after the calibration curve and at the end of the run. A QC sample was run every 25 samples. Acceptable QC responses must be between 90-110% of the certified value.All files are in csv format.
Mercury (Hg) is a ubiquitous environmental contaminant known to bioaccumulate in biota and biomagnify in food webs. Parasites occur in nearly every ecosystem and often interact in complex ways with other stressors that their hosts experience. Hepatozoon spp. are intraerythrocytic parasites common in snakes. The Florida green watersnake (Nerodia floridana) and the banded watersnake (Nerodia fasciata) occur syntopically in certain aquatic habitats in the Southeastern United States. The purpose of this study was to investigate relationships among total mercury (THg) concentrations, body size, species,habitat type and prevalence and parasitemia of Hepatozoon spp. infections in snakes. In the present study, we sampled N. floridana and N. fasciata from former nuclear cooling reservoirs and isolated wetlands of the Savannah River Site in South Carolina. We used snake tail clips to quantify THg and collected blood samples for hemoparasite counts. Our results indicate a significant, positive relationship between THg and snake body size in N. floridana and N. fasciata in both habitats. Average THg was significantly higher for N. fasciata compared to N. floridana in bays (0.22 ± 0.02 and 0.08 ± 0.006 mg/kg, respectively; p < 0.01), but not in reservoirs (0.17 ± 0.02 and 0.17 ± 0.03 mg/kg, respectively; p = 0.29). Sex did not appear to be related to THg concentration or Hepatozoon spp. infections in either species. In conclusion, we found no association between Hg and Hepatozoon spp. prevalence or parasitemia; however, our results suggest that species and habitat type play a role in susceptibility to Hepatozoon spp. infection.
Impurity ion and isotope partitioning into carbonate minerals provide a window into the molecular processes occurring at the fluid-mineral interface during crystal growth. Here, we employ calcium isotope fractionation together with process-based modeling to elucidate the mechanisms by which two divalent cations with starkly contrasting compatibility, magnesium and manganese, inhibit calcite growth and incorporate into the mineral lattice. Calcite growth inhibition by Mg 2+ is log-linear and K Mg is on the order of 0.02–0.03 throughout the range of {Mg 2+ }/{Ca 2+ } studied here (0.01–2.6). Mn 2+ exhibits much stronger log-linear growth rate inhibition at low Mn 2+ concentrations (fluid {Mn 2+ }/{Ca 2+ } = 0.001–0.02). Mn 2+ is readily incorporated into the calcite lattice to form a calcite-rhodochrosite solid solution, with large partition coefficients (K Mn 4.6–15.6) inversely correlated to growth rate. For both Mn 2+ and Mg 2+ , calcium isotope fractionation is found to be invariant with {Me 2+ }/{Ca 2+ } despite more than an order of magnitude decline in growth rate. This invariant Δ 44/40 Ca suggests that the presence of Mn 2 + or Mg 2+ does not significantly change the relative rates of Ca 2+ attachment and detachment at kink sites during growth, indicative of a dominantly kink blocking inhibition mechanism. Because the partitioning behavior dictates that Mn 2+ must attach to the surface significantly faster than Ca 2+ , attachment of Mn 2+ is likely to be as a non-monomer species such as an ion pair or possibly a larger polynuclear cluster. We propose that calcite growth rate inhibition by Mn is determined by the kinetics of carbonate attachment at Mn-occupied kink sites, potentially due to slow re-orientation kinetics of carbonate ions that have formed an inner-sphere complex with Mn 2+ at the surface but must reorient to incorporate into the lattice. We demonstrate that patterns in Mg 2+ partitioning and inhibition behavior are broadly consistent with growth inhibition driven by slow Mg 2+ -aquo complex dehydration relative to Ca 2+ but argue that this mechanism likely represents one endmember scenario, seen in Mg-calcite growth at low supersaturations and net precipitation rates. During growth at faster net precipitation rates, some portion of Mg 2+ is likely incorporated as a partially hydrated or otherwise complexed species, but calcite growth remains significantly inhibited by the kinetics of CO 3 2- attachment at Mg 2+ kink sites. These findings suggest a hybrid classical/nonclassical growth mechanism whereby Ca 2+ incorporates largely as a free ion at kink sites while Mn 2+ and some portion of Mg 2+ are incorporated via non-monomer attachment. This pattern may be generalizable; trace constituent cations with aquo-complex desolvation rates significantly slower than the mineral growth rate preferentially incorporate as a non-monomer species during otherwise classical crystal growth.
Mapping of leaves of hyperaccumulators can provide insights into the mechanisms these species utilize to accumulate high metal concentrations. We used synchrotron-based X-ray fluorescence (SXRF) to perform Zn and Ni imaging in leaves of different ages of Noccaea caerulescens. A mature leaf of the related non-hyperaccumulator Thlaspi arvense was also imaged. The concentrations of Zn, Ni, Co, and Cr in N. caerulescens grown on an ultramafic soil were 9-, 10-, 12-, and 3-fold higher than T. arvense. N. caerulescens showed an exceptional ability to accumulate Zn from the soil, posing a bioconcentration factor of 6.7. T. arvense had Zn and Ni distributed uniformly in the leaf blade with doubling fluorescence counts in the tip and margins, suggesting a strategy to excrete metals and avoid toxicity. On the other hand, N. caerulescens displayed distinctly different Zn and Ni accumulation patterns, regardless of the age or metal concentration in the leaves. Zinc was mainly distributed in the cells surrounding the central and secondary veins. Nickel accumulated in the margins and tips of the leaf blade. Finally, given the time required to image large leaves in synchrotron facilities, small leaves can be used to represent the leaf distribution of Zn and Ni in N. caerulescens.
Sulfate wastes are produced in large quantities and contain toxic heavy metals such as lead (Pb), posing environmental risks. Because of favorable solubility differences, these wastes can be repurposed for engineered carbon dioxide (CO 2 ) sequestration. Understanding the fate and mobility of heavy metals during this process is important. This study focuses on Pb and the effect of zinc (Zn) on Pb in carbon mineralization. Synthesized gypsum was treated with a carbonate-rich solution at pH 11.5 to convert the sulfates to carbonates. Aqueous solutions and mineral solids were analyzed. Synchrotron-based micro-X-ray fluorescence and a novel application of Pb M3-edge X-ray absorption near-edge structure provided detailed insights into Pb distribution and mineral forms. Results showed significant reductions in aqueous Pb and Zn concentrations, indicating effective metal sequestration. Carbon mineralization transformed Pb from soluble anglesite (PbSO 4 ) into insoluble cerussite (PbCO 3 ) and hydrocerussite (Pb 3 (CO 3 ) 2 (OH) 2 ). Pb primarily precipitated onto calcium carbonate surfaces through surface-mediated precipitation reactions. While the presence of Zn modified crystallization dynamics, it did not impede Pb sequestration and potentially enhanced surface reactivity, facilitating greater Pb immobilization. These findings highlight carbon mineralization as a sustainable approach to immobilize toxic metals in sulfate wastes while advancing CO 2 sequestration efforts.
Melt inclusions with large, positive Sr anomalies have been described in multiple tectonic settings, and the origins of this unusual geochemical feature are debated. Three origins have been proposed, all involving plagioclase as the source of the elevated Sr: (i) direct assimilation of plagioclase-rich lithologies, (ii) recycled lower oceanic gabbro in the mantle source, and (iii) shallow-level diffusive interaction between present day lower oceanic crust (i.e., plagioclase-bearing lithologies) and the percolating melt. A “ghost plagioclase” signature (i.e., a large, positive Sr anomaly without associated high Al 2 O 3 ) is present in melt inclusions from Mauna Loa. Here, we present new 87 Sr/ 86 Sr measurements of individual olivine-hosted melt inclusions from three Hawaiian volcanoes, Mauna Loa, Loihi, and Koolau. The data set includes a Mauna Loa melt inclusion with the highest reported Sr anomaly (or highest (Sr/Ce) N , which is 7.2) for Hawai'i. All melt inclusions have 87 Sr/ 86 Sr values within the range reported previously for the lavas from each volcano. Critically, the 87 Sr/ 86 Sr of the high (Sr/Ce) N melt inclusion lies within the narrow range of 87 Sr/ 86 Sr for Mauna Loa melts that lack high (Sr/Ce) N signatures. Therefore, to explain the high (Sr/Ce) N ratio of the ghost plagioclase signature using an ancient recycled gabbro, the gabbro-infused mantle source would have had to evolve, by chance, to have the same 87 Sr/ 86 Sr as the source of the Mauna Loa melts that lack a recycled gabbro (ghost plagioclase) signature. Alternatively, shallow-level diffusive interactions between Mauna Loa plagioclase-rich cumulates and a percolating mantle-derived melt provides a simpler explanation for the presence of the high (Sr/Ce) N Mauna Loa melts.
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The formation and transport of methylmercury (MeHg), a neurotoxin, in aquatic environments is a global concern for human health as MeHg can bioaccumulate and biomagnify to high concentrations in aquatic food webs. MeHg is formed by conversion from inorganic mercury through microbial mediated methylation. Sulfate-reducing bacteria have been identified as the primary organisms responsible for MeHg production. Pure-culture studies suggest that low availability of cobalt and copper may inhibit mercury methylation, but whether such limitations occur in the environment is unclear. To explore the possible interaction between trace metal availability and mercury methylation, sediments from the East Fork Poplar Creek in Oak Ridge, Tennessee were sampled and then incubated in the presence and absence of added dissolved cobalt and copper. Three types of data are provided in this package. The first reports the uptake of dissolved cobalt and copper by these stream sediments on short time scales (24 hours) in the form of final dissolved and adsorbed concentrations. The second data component consists of a time series of dissolved concentrations and pH values for stream sediments incubated with artificial stream water containing different addition levels of dissolved cobalt or copper. The dissolved concentrations reported include total iron, manganese, sulfur, phosphorus, nickel, zinc and cobalt, dissolved concentrations of sulfate and orthophosphate, and the amount of cobalt or copper adsorbed by the sediment. The third data component reports data at 0 and 72 hours of incubation time for stream sediments to which cobalt was added. These data include concentrations of methylmercury with isotope labeling to enable determination of methylation and demethylation rates as well as dissolved concentrations of sulfate, phosphate, chloride, iron, cobalt, and organic carbon. All data are provided in text-based CSV format with header sections indicating the data contained in each file and the corresponding units. Note that "u" is used in place of Greek lower-case mu to indicate the micro prefix on units. A Table of Contents file (Data_package_TableofContents.txt) provides an index for the data contained in the individual files.
This dataset contains the chemistry data of surface water and porewater samples collected from a wetland, referred to as The Cove, at Old Woman Creek Estuarine Research Reserve in Huron, OH. Surface and pore water samples were taken to analyze what nutrient and/or metal constituents were present at different depths in the wetland at different times and to compare to redox potential values. Porewater was collected by constructed sippers and deployed into the underlying soil of the wetland, and they were samples approximately every 2 weeks (when groundwater was present) in 2023. Surface water was collected approximately 1 inch below the surface of the water column (if available) via a syringe. Unfiltered and 0.45 micron filtered samples were collected. Samples were analyzed for various chemistry and is reported in the SWChem (surface water chemistry) and PWChem (porewater chemistry) .csv datafiles. Collection information about the samples can be found within the PWChem_SWChem_SampleMetdata.csv file. All files associated with this dataset are listed in the PWChem_SWChem_FLMD.csv file.