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At least 19 records

Scripts and data associated with a manuscript linking soil and sediment elemental composition with dissolved organic matter chemistry across CONUS

This data package provides scripts and geochemical data for a manuscript titled “Linkages between mineral element composition of soils and sediments with hyporheic zone dissolved organic matter chemistry across the contiguous United States” (preprint: doi: 10.22541/essoar.169447343.31694990/v1). This data is associated with the Worldwide Hydrobiogeochemistry Observation Network for Dynamic River Systems (WHONDRS, https://whondrs.pnnl.gov) and is an extension of the Summer 2019 Sampling campaign which crowdsourced samples from rivers and sediment across the continental United States. Data from this study can be found at https://data.ess-dive.lbl.gov/datasets/doi:10.15485/1603775 and https://data.ess-dive.lbl.gov/datasets/doi:10.15485/1729719. The main objective of this manuscript was to couple sediment water extractable dissolved organic matter chemistry, defined by ultra-high resolution mass spectrometry, with localized sediment elemental composition and watershed scale soil elemental characteristics. This data package contains one main folder with four subfolders. The main data folder contains (1) readme; (2) data dictionary (dd); (3) file-level metadata (flmd); (4) an R markdown to reproduce manuscript figures and analyses; (5) a pdf of instructions to reproduce NGS interpolations with ArcGIS software; and (6) a python script to reproduce NGS extrapolations with python. The four subfolders contain files required to reproduce NGS extrapolations include (1) ‘CONUS_boundaries’ containing boundary layers (.shp) for the Continental United States; (2) ‘ngs_project’ containing files (.shp) with point level NGS soil elemental data (Grossman et al., 2004); (3) ‘raster_outputs’ containing the interpolated raster output files for various soil elements; and (4) ‘NGS_Chemistry_Final’ contain final extracted soil elemental data.

54 ENVIRONMENTAL SCIENCES↗

Linkages Between Mineral Element Composition of Soils and Sediments With Hyporheic Zone Dissolved Organic Matter Chemistry Across the Contiguous United States

The hyporheic zone is a hotspot for biogeochemical cycling where interactions with mineral metals preserve the release and biodegradation of organic matter (OM). A small fraction of OM can still be exchanged between localized sediments and the overlying water column, and recent evidence suggests there exists a longitudinal structuring in sediment dissolved OM (DOM) chemistry across the continental United States (CONUS). In this study, we tested a hypothesis that water extractable sediment DOM chemistry could be explained by sediment metal contents and integrative watershed scale features at the CONUS scale. Crowdsourced samples were characterized for high resolution mass spectrometry and coupled with sediment metals determined via x-ray fluorescence as well as with land cover and soil elemental information obtained from national databases. Our results highlight weak relationships between DOM chemistry and elemental composition at the CONUS scale indicating limited transferability of organo-metal linkages into multi-scale hydrobiogeochemical models.

58 GEOSCIENCES↗

Global Maps of Lunar Neutron Fluxes from the LEND Instrument

The latest neutron spectrometer measurements with the Lunar Exploration Neutron Detector (LEND) onboard the Lunar Reconnaissance Orbiter (LRO) are presented. It covers more than 1 year of mapping phase starting on 15 September 2009. In our analyses we have created global maps showing regional variations in the flux of thermal (energy range < 0.015 eV) and fast neutrons (>0.5 MeV), and compared these fluxes to variances in soil elemental composition, and with previous results obtained by the Lunar Prospector Neutron Spectrometer (LPNS). We also processed data from LEND collimated detectors and derived a value for the collimated signal of epithermal neutrons based on the comparative analysis with the LEND omnidirectional detectors. Finally, we have compared our final (after the data reduction) global epithermal neutron map with LPNS data.

Epithermal neutrons↗

Mineralogy and Elemental Composition of Wind Drift Soil at Rocknest, Gale Crater

The Mars Science Laboratory rover Curiosity has been exploring Mars since August 5, 2012, conducting engineering and first-time activities with its mobility system, arm, sample acquisition and processing system (SA/SPaH-CHIMRA) and science instruments. Curiosity spent 54 sols at a location named "Rocknest," collecting and processing five scoops of loose, unconsolidated materials ("soil") acquired from an aeolian bedform (Fig. 1). The Chemistry and Mineralogy (CheMin) instrument analyzed portions of scoops 3, 4, and 5, to obtain the first quantitative mineralogical analysis of Mars soil, and to provide context for Sample Analysis at Mars (SAM) measurements of volatiles, isotopes and possible organic materials.

Blake, D. F.↗

Solar Ion Processing of Major Element Surface Compositions of Mature Mare Soils: Insights from Combined XPS and Analytical TEM Observations

Solar wind ions are capable of altering the sur-face chemistry of the lunar regolith by a number of mechanisms including preferential sputtering, radiation-enhanced diffusion and sputter erosion of space weathered surfaces containing pre-existing compositional profiles. We have previously reported in-situ ion irradiation experiments supported by X-ray photoelectron spectroscopy (XPS) and analytical TEM that show how solar ions potentially drive Fe and Ti reduction at the monolayer scale as well as the 10-100 nm depth scale in lunar soils [1]. Here we report experimental data on the effect of ion irradiation on the major element surface composition in a mature mare soil.

Christoffersen, R.↗

An integrated view of the chemistry and mineralogy of martian soils

The mineralogical and elemental compositions of the martian soil are indicators of chemical and physical weathering processes. Using data from the Mars Exploration Rovers, we show that bright dust deposits on opposite sides of the planet are part of a global unit and not dominated by the composition of local rocks. Dark soil deposits at both sites have similar basaltic mineralogies, and could reflect either a global component or the general similarity in the compositions of the rocks from which they were derived. Increased levels of bromine are consistent with mobilization of soluble salts by thin films of liquid water, but the presence of olivine in analysed soil samples indicates that the extent of aqueous alteration of soils has been limited. Nickel abundances are enhanced at the immediate surface and indicate that the upper few millimetres of soil could contain up to one per cent meteoritic material.

Geologic Sediments/chemistry↗

An integrated view of the chemistry and mineralogy of Martian soils.

The mineralogical and elemental compositions of the martian soil are indicators of chemical and physical weathering processes. Using data from the Mars Exploration Rovers, we show that bright dust deposits on opposite sides of the planet are part of a global unit and not dominated by the composition of local rocks. Dark soil deposits at both sites have similar basaltic mineralogies, and could reflect either a global component or the general similarity in the compositions of the rocks from which they were derived. Increased levels of bromine are consistent with mobilization of soluble salts by thin films of liquid water, but the presence of olivine in analysed soil samples indicates that the extent of aqueous alteration of soils has been limited. Nickel abundances are enhanced at the immediate surface and indicate that the upper few millimetres of soil could contain up to one per cent meteoritic material.

Zipfel, Jutta↗

Consistent Controls on Trace Metal Micronutrient Speciation in Wetland Soils and Stream Sediments

Trace metal are essential for microbially-mediated biogeochemical processes occurring in anoxic wetland soils and stream bed sediments, but low availability of these elements may inhibit anaerobic element cycling and transformations. Solid-phase speciation is likely a critical control on trace metal availability but has seen limited study in anoxic systems having concentrations similar to geological background levels, where metal limitations may be most prevalent. We have investigated trace metal concentrations and solid-phase speciation in three freshwater subsurface aquatic systems: marsh wetland soils, riparian wetland soils, and the sediments of a streambed. These systems displayed low solid-phase trace metal concentrations, generally at or below geological background levels, which generally followed the trend Zn > Cu ≈ Ni > Co and showed no correlation with major element compositions. All soils and sediments were dominated by quartz but varied in clay mineralogy as well as the organic matter, total sulfur, and total iron contents. X-ray absorption near-edge structure (XANES) spectroscopy shows that sulfur speciation in both wetlands is dominated by organic sulfur. Elemental sulfur and iron sulfides together made up <25% of the sulfur in the wetland soils, but the distribution between inorganic and organic forms was reversed in the stream sediments. Ferrous and ferric iron in clay minerals were common species identified by both XANES and extended X-ray absorption fine structure (EXAFS) spectroscopies at all sites. Iron(III) oxides were substantial components in all but the marsh wetland soils. Quantitative analysis of copper, nickel, and zinc XANES spectra revealed similar metal speciation across all sites. Copper speciation was dominated by sulfides, adsorbed species, and minor amounts of copper bound to organic matter; no metallic copper was detected. Nickel speciation also varied little and was dominated by nickel in clay mineral octahedral sheets and nickel sulfide, with adsorbed species also present. Zinc speciation was slightly more varied, with the marsh wetland soils and stream bed sediments containing adsorbed species, zinc associated with clay mineral structures, and zinc bound to reduced sulfur groups on organic matter, whereas the riparian wetland soils lacked clay-associated zinc but contained zinc sulfide. Trace metals bound to reduced sulfur occurred at every site, with a greater sulfur-bound fraction for copper. The fractional abundance of sulfur-bound species showed no relationship with soil or sediment total sulfur content, which varied by two orders of magnitude. More broadly, the observations in this study suggest that trace metal speciation in freshwater wetland soils and stream sediments is consistently dominated by a small set of recurring components which are distinct for each metal. Furthermore, this may represent a general geochemical phenomenon in anoxic soils and sediments containing trace metals at background concentrations (as low as 3 µg g -1 ) that was not predicted from systems that are contaminated with or naturally-enriched in copper, nickel, or zinc.

54 ENVIRONMENTAL SCIENCES↗

Synchrotron resolved microscale mineralogy and elemental composition of individual plinthic and manganiferous nodules from agricultural soils

Iron and manganese oxides are strong sorbents and elemental scavengers in the environment that can form macroscopic nodules in soils. Despite their importance in the geochemical cycling of nutrients and contaminants, nodules are rarely characterized. When analyzed, they are often combined into bulk samples, obscuring individual characteristics. This study investigates the composition and mineralogy of individual plinthic and manganiferous nodules in soil from cropping systems in the Farming Systems Project in Beltsville, Maryland. Elemental composition indicates the accumulation of contaminants and nutrients, including copper in all nodules and high levels of phosphorus in select nodules. Sequential extractions determine that highly crystalline minerals comprise the nodules, locking away these nutrients and contaminants. Bulk X-ray diffraction (XRD) demonstrated distinct mineralogies in the plinthic and manganiferous nodules, with the former comprised of quartz, goethite, and kaolinite, and the latter consisting of quartz, Mn 2 O 3 , and hematite. Synchrotron and laboratory-based X-ray fluorescence (XRF) mapping gives critical insight into the elemental distribution within the nodules and elucidates spatial elemental associations, including the coupling of manganese and iron in the manganiferous nodules. XRF maps paired with µXRD provide microscale spatial resolution in mineralogy, which resolved several phases not apparent in bulk XRD, manganese’s association with goethite, and minerals indicative of redox transformations, including magnetite and maghemite. These novel results provide critical insight into the microscale mineralogy and individual elemental composition of plinthic and manganiferous nodules, as well as how they alter bulk soil geochemistry in ways largely unaccounted for in research on soil systems.

36 MATERIALS SCIENCE↗

Major element composition of glasses in three Apollo 15 soils.

Approximately 180 glasses in each of three Apollo 15 soils have been analyzed for nine elements. Cluster analysis techniques allow the recognition of preferred glass compositions that are equated with parent rock compositions. Green glass rich in Fe and Mg, poor in Al and Ti may be derived from deep-seated pyroxenitic material now present at the Apennine Front. Fra Mauro basalt (KREEP) is most abundant in the LM soil and is tentatively identified as ray material from the Aristillus-Autolycus area. Highland basalt (anorthositic gabbro), believed to be derived from the lunar highlands, has the same composition as at other landing sites, but is less abundant. The Apennine Front is probably not true highland material but may contain a substantial amount of material with the composition of Fra Mauro basalt, but lacking the high-K content.

Reid, A. M.↗

The chemistry and mineralogy of Mars soil and dust

A single geological unit consisting of fine, apparently weathered soil material is covering large portions of the surface of Mars. This soil material has been thoroughly homogenized by global dust storms and it is plausible to assume that Mars dust is strongly correlated with it. The chemical-elemental composition of the soil was directly measured by the Viking Landers. Positive detection of Si, Al, Fe, Mg, Ca, Ti, S, Cl, and Br was achieved. Analyses of the SNC meteorites, a group of meteorites that has been suggested to be ejected Martian rocks, supply additional elemental-concentration data, broadening considerably the chemical data-base on the surface materials. A composition model for Mars soil, giving selected average elemental concentrations of major and trace elements, was recently suggested. It was constructed by combining the Viking Lander data, the SNC meteorite analyses, and other analyses. The mineralogy of the surface materials on Mars has not been directly measured yet. By use of various indirect approaches, including chemical correspondence to the surface analyses, spectral analogies, simulations of Viking Lander experiments, analyses of the SNC meteorites and various modeling efforts, the mineralogical composition was constrained to some extent. No direct analyses of soil reactivity have been done yet. Indirect evidence, mostly from the Viking biology experimental results, suggests that the soil probably has a slightly acidic reaction and is generally oxidized. Unambiguous identification of the Mars soil minerals by direct mineralogical analyses, and non-disturbed or in-situ measurements of the soil's reactivity, are of primary importance in future Mars research.

Banin, A.↗

Space Weathering in the Fine Size Fractions of Lunar Soils: Soil Maturity Effects

The effects of space weathering on the optical properties of lunar materials have been well documented. These effects include a reddened continuum slope, lowered albedo, and attenuated absorption features in reflectance spectra of lunar soils as compared to finely comminuted rocks from the same Apollo sites. However, the regolith processes that cause these effects are not well known, nor is the petrographic setting of the products of these processes fully understood. A Lunar Soil Characterization Consortium has been formed with the purpose of systematically integrating chemical and mineralogical data with the optical properties of lunar soils. Understanding space-weathering effects is critical in order to fully integrate the lunar sample collection with remotely-sensed data from recent robotic missions (e.g., Lunar Prospector, Clementine, and Galileo) We have shown that depositional processes (condensation of impact-derived vapors, sputter deposits, accreted impact material, e.g., splash glass, spherules, etc.) are a major factor in the modification of the optical surfaces of lunar regolith materials. In mature soils, it is the size and distribution of the nanophase metal in the soil grains that has the major effect on optical properties. In this report, we compare and contrast the space-weathering effects in an immature and a mature soil with similar elemental compositions. For this study, we analyzed <10 micron sieve fractions of two Apollo 17 soils, 79221 (mature, Is/FeO = 81) and 71061 (immature, Is/FeO = 14). Details of the sieving procedures and allocation scheme are given else where. The results of other detailed chemical, mineralogical, and spectroscopic analyses of these soil samples are reported elsewhere. A representative sample of each soil was embedded in low-viscosity epoxy, and thin sections (about 70nm thick) were obtained through ultra microtomy. The thin sections used for these analyses typically contained cross sections of up to 500 individual grains. The thin sections were studied using a JEOL 2010 transmission electron microscope (TEM) equipped with a thin window energy-dispersive X-ray (EDX) spectrometer. An individual thin section was selected from each soil, and for each grain in the section we determined (1) the elemental composition by EDX; (2) whether the grain was crystalline or glassy using electron diffraction and darkfield imaging; (3) the presence or absence of rims and accreted material; and (4) the distribution of nanophase Fe where present. Most of the categories are self-evident; however, we divide the agglutinate derived material into agglutinitic glass (glass with approximately the same composition as the bulk soil that contains nanophase Fe with or without vesicles) and agglutinate fragments, which are composed of crystalline grains and agglutinitic glass. Lithic fragments are defined as polymineralic grains with no glass. Pyroxene grains have been divided into high- and low-Ca groups. As expected, there are a number of differences in the petrography of the <10-microns fractions of 79221 and 71061 given the great difference in their respective maturities, but we focus here on two major distinctions: agglutinate content and the number of grains with micropatina. Slightly over 50% of the particles in 79221 consist of agglutinitic glass and agglutinate fragments, while the remainder are predominantly crystalline mineral grains. The agglutinic glass particles contain abundant nanophase Fe and vesicles. Angular particles are rare, with most showing smooth, rounded exteriors, Of the mineral grains analyzed thus far, over 90% of the grains have amorphous rims that contain nanophase Fe (these rims are believed to have formed by vapor deposition and irradiation effects). The nanophase Fe in these rims probably accounts for a significant fraction of the increase in Is/FeO measured in these size fractions. In addition to the rims, the majority of particles also show abundant accreted material in the form of glass splashes and spherules that also contain nanophase Fe. In stark contrast, the surfaces of the mineral grains in the 71061 sample are relatively prisitine, as only about 14% of the mineral grains in the sample exhibited amorphous rims. Furthermore, the mineral particles are more angular and show greater surface roughness than in the mature sample. Accreted material on particle surfaces is rare. Agglutinitic material is a major component of the 71061 sample; however, nanophase Fe and vesicles are not as well developed as in the 79221 sample. It is now recognized that nanophase Fe is probably the main agent in modifying the optical properties of lunar soil grains. The most important result of this study is the observation that in the fine size fractions of mature soils, nearly every grain has nanophase Fe within 100 run of the particle surface. (Additional Information contained in original)

Keller, L. P.↗

Fungal elemental profiling unleashed through rapid laser-induced breakdown spectroscopy (LIBS)

ABSTRACT Elemental profiling of fungal species as a phenotyping tool is an understudied topic and is typically performed to examine plant tissue or non-biological materials. Traditional analytical techniques such as inductively coupled plasma–optical emission spectroscopy (ICP-OES) and inductively coupled plasma–mass spectrometry (ICP-MS) have been used to identify elemental profiles of fungi; however, these techniques can be cumbersome due to the difficulty of preparing samples. Additionally, the instruments used for these techniques can be expensive to procure and operate. Laser-induced breakdown spectroscopy (LIBS) is an alternative elemental analytical technique—one that is sensitive across the periodic table, easy to use on various sample types, and is cost-effective in both procurement and operation. LIBS has not been used on axenic filamentous fungal isolates grown in substrate media. In this work, as a proof of concept, we used LIBS on two genetically distinct fungal species grown on a nutrient-rich and nutrient-poor substrate media to determine whether robust elemental profiles can be detected and whether differences between the fungal isolates can be identified. Our results demonstrate a distinct correlation between fungal species and their elemental profile, regardless of the substrate media, as the same strains shared a similar uptake of carbon, zinc, phosphorus, manganese, and magnesium, which could play a vital role in their survival and propagation. Independently, each fungal species exhibited a unique elemental profile. This work demonstrates a unique and valuable approach to rapidly phenotype fungi through optical spectroscopy, and this approach can be critical in understanding these fungi's behavior and interactions with the environment. IMPORTANCE Historically, ionomics, the elemental profiling of an organism or materials, has been used to understand the elemental composition in waste materials to identify and recycle heavy metals or rare earth elements, identify the soil composition in space exploration on the moon or Mars, or understand human disorders or disease. To our knowledge, ionomic profiling of microbes, particularly fungi, has not been investigated to answer applied and fundamental biological questions. The reason is that current ionomic analytical techniques can be laborious in sample preparation, fail to measure all potential elements accurately, are cost-prohibitive, or provide inconsistent results across replications. In our previous efforts, we explored whether laser-induced breakdown spectroscopy (LIBS) could be used in determining the elemental profiles of poplar tissue, which was successful. In this proof-of-concept endeavor, we undertook a transdisciplinary effort between applied and fundamental mycology and elemental analytical techniques to address the biological question of how LIBS can used for fungi grown axenically in a nutrient-rich and nutrient-poor environment.

59 BASIC BIOLOGICAL SCIENCES↗

Ion microprobe analyses of aluminous lunar glasses - A test of the 'rock type' hypothesis

Previous soil survey investigations found that there are natural groupings of glass compositions in lunar soils and that the average major element composition of some of these groupings is the same at widely separated lunar landing sites. This led soil survey enthusiasts to promote the hypothesis that the average composition of glass groupings represents the composition of primary lunar 'rock types'. In this investigation the trace element composition of numerous aluminous glass particles was determined by the ion microprobe method as a test of the above mentioned 'rock type' hypothesis. It was found that within any grouping of aluminous lunar glasses by major element content, there is considerable scatter in the refractory trace element content. In addition, aluminous glasses grouped by major elements were found to have different average trace element contents at different sites (Apollo 15, 16 and Luna 20). This evidence argues that natural groupings in glass compositions are determined by regolith processes and may not represent the composition of primary lunar 'rock types'.

Meyer, C., Jr.↗

Soil Components in Heterogeneous Impact Glass in Martian Meteorite EETA79001

Martian soil composition can illuminate past and ongoing near-surface processes such as impact gardening [2] and hydrothermal and volcanic activity [3,4]. Though the Mars Exploration Rovers (MER) have analyzed the major-element composition of Martian soils, no soil samples have been returned to Earth for detailed chemical analysis. Rao et al. [1] suggested that Martian meteorite EETA79001 contains melted Martian soil in its impact glass (Lithology C) based on sulfur enrichment of Lithology C relative to the meteorite s basaltic lithologies (A and B) [1,2]. If true, it may be possible to extract detailed soil chemical analyses using this meteoritic sample. We conducted high-resolution (~0.3 m/pixel) element mapping of Lithology C in thin section EETA79001,18 by energy dispersive spectrometry (EDS). We use these data for principal component analysis (PCA).

Schrader, C. M.↗