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108 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Iron Bonding with Light Elements: Implications for Planetary Cores Beyond the Binary System

Light element alloying in iron is required to explain density deficit and seismic wave velocities in Earth’s core. However, the light element composition of the Earth’s core seems hard to constrain as nearly all light element alloying would reduce the density and sound velocity (elastic moduli). The alloying light elements include oxidizing elements like oxygen and sulfur and reducing elements like hydrogen and carbon, yet their chemical effects in the alloy system are less discussed. Moreover, Fe-X-ray Absorption Near Edge Structure (Fe-XANES) fingerprints have been studied for silicate materials with ferrous and ferric ions, while not many X-ray absorption spectroscopy (XAS) studies have focused on iron alloys, especially at high pressures. To investigate the bonding nature of iron alloys in planetary interiors, we presented X-ray absorption spectroscopy of iron–nitrogen and iron–carbon alloys at high pressures up to 50 GPa. Together with existing literature on iron–carbon, –hydrogen alloys, we analyzed their edge positions and found no significant difference in the degree of oxidation among these alloys. Pressure effects on edge positions were also found negligible. Our theoretical simulation of the valence state of iron, alloyed with S, C, O, N, and P also showed nearly unchanged behavior under pressures up to 300 GPa. This finding indicates that the high pressure bonding of iron alloyed with light elements closely resembles bonding at the ambient conditions. We suggest that the chemical properties of light elements constrain which ones can coexist within iron alloys.

Advanced Photon Source↗
DOE OSTI2020

Iodine Co-Precipitation with Calcium Carbonate in the Presence of Silica Ions - 20360

Historical releases of I-129 to the subsurface at the U.S. Department of Energy Hanford Site have resulted in large dilute plumes that cover an area of over 50 km{sup 2}. The most concentrated I-129 plume is associated with the 200 West Area in the 200-UP-1 operable unit of the Hanford Central Plateau, where peak concentrations have been measured up to 30 times the drinking water standard of 1 pCi/L. The mobility of iodine depends on many factors, including chemical speciation, pH, redox conditions, as well as the presence of organic matter, calcium carbonate minerals and microbial activities. Speciation measurements estimate that the majority of the iodine (∼76%) in Hanford groundwater exists as iodate. Information on processes that affect iodate mobility in the Hanford subsurface support evaluation of environmental management options for the I-129 plumes. Iodate can be incorporated into calcium carbonate, which is a potential mechanism of naturally attenuating radioiodine in groundwater. However, the silica content in porewater may impact the contaminant-calcium carbonate incorporation process. Silica is one of the most abundant elements in nature and can have an impact on chemical weathering of alkaline-earth carbonates in the environment. Hence, this research aims to advances knowledge of the iodine co-precipitation process with calcium carbonate in the presence of silica. This information supports the technical basis evaluation of natural attenuation for I-129. Samples for these studies were prepared using calcium carbonate-forming solutions that included certified grade sodium meta-silicate nonahydrate (Na{sub 2}SiO{sub 3}), calcium chloride dehydrate (CaCl{sub 2}.2H{sub 2}O), sodium carbonate (NaCO{sub 2}), and sodium hydroxide (NaOH) solutions for pH adjustments. Triplicate samples were prepared with silica concentrations in the solution of 0 mM, 0.5 mM and 20 mM, mixed with an iodate standard (1000 ppm of IO{sub 3}{sup -} in H{sub 2}O) and sampled over a one-week period. Preliminary data analyses suggest that less iodine remains in solution in the presence of silica (average remaining aqueous fraction 0.23±0.03 at 20 mM of Si) relative to samples without silica (0.52±0.06); an indication that more iodine has been sorbed or incorporated into precipitates. However, the mechanisms for this behavior are still under investigation and need to be interpreted relative to pore water compositions that are representative of Hanford site-specific conditions. Scanning electron microscope equipped with energy dispersive spectroscopy (SEM-EDS) analyses were performed to observe the solid phase morphology in these experiments and showed rhombohedral calcite crystals covered with amorphous Si floccules. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Insights on the dissolution of water in an albite melt at high pressures and temperatures from a direct structural analysis

The water dissolution mechanism in silicate melts under high pressures is not well understood. Here we present the first direct structure investigation of a water-saturated albite melt to monitor the interactions between water and the network structure of silicate melt at the molecular level. In situ high-energy X-ray diffraction was carried out on the NaAlSi 3 O 8 -H 2 O system at 800 °C and 300 MPa, at the Advanced Photon Source synchrotron facility. The analysis of the X-ray diffraction data was augmented with classical Molecular Dynamics simulations of a hydrous albite melt, incorporating accurate water-based interactions. The results show that metal–oxygen bond breaking at the bridging sites occurs overwhelmingly at the Si site upon reaction with H 2 O, with subsequent Si–OH bond formation and negligible Al–OH formation. Furthermore, we see no evidence for the dissociation of the Al 3+ ion from the network structure upon breaking of the Si–O bond in the hydrous albite melt. The results also indicate that the Na + ion is an active participant in the modifications of the silicate network structure of the albite melt upon water dissolution at high P–T conditions. We do not find evidence for the Na + ion dissociating from the network structure upon depolymerization and subsequent formation of NaOH complexes. Instead, our results show that the Na + ion persists as a structure modifier with a shift away from Na–BO bonding to an increase in the extent of Na-NBO bonding, in parallel with pronounced depolymerization of the network. Our MD simulations show that the Si–O and Al–O bond lengths are expanded by about 6% in the hydrous albite melt compared to those of the dry melt at high P–T conditions. The changes in the network silicate structure of a hydrous albite melt at high pressure and temperature, as revealed in this study, must be considered in the advancement of water dissolution models of hydrous granitic (or alkali aluminosilicate) melts.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A genetic metasomatic link between eclogitic and peridotitic diamond inclusions

Diamond inclusions sample the otherwise inaccessible archive of Earth’s deep interior. The geochemical and petrological diversity of diamond inclusions reflects either pre-metasomatic upper mantle heterogeneity or metasomatism coeval with diamond formation. We focus on the origin of lithospheric garnet and clinopyroxene inclusions by simulating metasomatic reactions between eclogitic fluids and mantle peridotites at 5 GPa, 1000 °C, and across a range of redox conditions (logƒO 2 = -1 to -6 ΔFMQ). Our results demonstrate that fluid-rock interaction can result in the formation of eclogitic, websteritic, and peridotitic silicates from a single fluid during a single diamond-forming metasomatic event. Ergo, the petrogenesis of diamond and their inclusions can be syngenetic, and the petrological diversity of diamond inclusions can reflect metasomatism coeval with diamond formation. Furthermore, during the metasomatism, refractory peridotite can be converted to fertile websterite which could become a pyroxenitic mantle source for oceanic basalts.

58 GEOSCIENCES↗
DOE OSTI2022

Ultrahigh-pressure disordered eight-coordinated phase of Mg 2 GeO 4 : Analogue for super-Earth mantles

Mg 2 GeO 4 is important as an analog for the ultrahigh-pressure behavior of Mg 2 SiO 4 , a major component of planetary interiors. In this study, we have investigated magnesium germanate to 275 GPa and over 2,000 K using a laser-heated diamond anvil cell combined with in situ synchrotron X-ray diffraction and density functional theory (DFT) computations. The experimental results are consistent with the formation of a phase with disordered Mg and Ge, in which germanium adopts eightfold coordination with oxygen: the cubic, Th 3 P 4 -type structure. DFT computations suggest partial Mg-Ge order, resulting in a tetragonal $I\bar{4}2d$ structure indistinguishable from $I\bar{4}3d$ Th 3 P 4 in our experiments. If applicable to silicates, the formation of this highly coordinated and intrinsically disordered phase may have important implications for the interior mineralogy of large, rocky extrasolar planets.

58 GEOSCIENCES↗
DOE OSTI2023

Formation and evolution of carbonaceous asteroid Ryugu: Direct evidence from returned samples

Samples of the carbonaceous asteroid Ryugu were brought to Earth by the Hayabusa2 spacecraft. We analyzed 17 Ryugu samples measuring 1 to 8 millimeters. Carbon dioxide–bearing water inclusions are present within a pyrrhotite crystal, indicating that Ryugu’s parent asteroid formed in the outer Solar System. The samples contain low abundances of materials that formed at high temperatures, such as chondrules and calcium- and aluminum-rich inclusions. The samples are rich in phyllosilicates and carbonates, which formed through aqueous alteration reactions at low temperature, high pH, and water/rock ratios of <1 (by mass). Less altered fragments contain olivine, pyroxene, amorphous silicates, calcite, and phosphide. Numerical simulations, based on the mineralogical and physical properties of the samples, indicate that Ryugu’s parent body formed ~2 million years after the beginning of Solar System formation.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

High-Temperature Thermodynamics of Cerium Silicates, A-Ce 2 Si 2 O 7 , and Ce 4.67 (SiO 4 ) 3 O

Lanthanide disilicates and oxyapatites have potential roles in high temperature applications as thermal (TBC) and environmental barrier coatings (EBC), or possible alteration phases in geological nuclear waste repositories. However, those Ce 3+ -bearing silicates have only been limitedly studied. In this work, we performed detailed structural and thermodynamic investigations on A-Ce 2 Si 2 O 7 (tetragonal, P4 1 ) and Ce 4.67 (SiO 4 ) 3 O (hexagonal, P6 3 /m). The high temperature structural behaviors and coefficients of thermal expansion were determined by in situ high temperature synchrotron X-ray diffraction (HT-XRD) implemented with Rietveld analysis and thermogravimetric analysis coupled with differential scanning calorimetry (TGA-DSC). A-Ce 2 Si 2 O 7 was found to be stable in N 2 and air up to ~1483 K with anisotropic thermal expansion along the a and c axes (α a = 12.3 × 10 -6 K -1 and α c = 12.4 × 10 -6 K -1 ). Ce 4.67 (SiO 4 ) 3 O had a slow partial oxidation between 533 K and 873 K to a new nonstoichiometric phase Ce 3+ 1.67- xCe4 + x Ce 3+ 3 (SiO 4 ) 3 O 1+0.5x , followed by a thermal decomposition to CeO 2 and SiO 2 at ~1000 K in air. By using high temperature oxide melt solution calorimetry at 973 K with lead borate as the solvent, the standard enthalpy of formation was determined for A-Ce 2 Si 2 O 7 (-3825.1 ± 6.0 kJ/mol) and Ce 4.67 (SiO 4 ) 3 O (-7391.3 ± 9.5 kJ/mol). Finally, these thermodynamic parameters were compared with those of CeO 2 , CeSiO 4 , and other silicate oxyapatites for examining their chemical stability in high temperature environments relevant for aeronautical applications, mineral formation, and nuclear fuel cycle.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Global ocean dimethyl sulfide climatology estimated from observations and an artificial neural network

Marine dimethyl sulfide (DMS) is important to climate due to the ability of DMS to alter Earth's radiation budget. Knowledge of the global-scale distribution, seasonal variability, and sea-to-air flux of DMS is needed in order to improve understanding of atmospheric sulfur, aerosol/cloud dynamics, and albedo. Here we examine the use of an artificial neural network (ANN) to extrapolate available DMS measurements to the global ocean and produce a global climatology with monthly temporal resolution. A global database of 82 996 ship-based DMS measurements in surface waters was used along with a suite of environmental parameters consisting of latitude–longitude coordinates, time of day, time of year, solar radiation, mixed layer depth, sea surface temperature, salinity, nitrate, phosphate, and silicate. Linear regressions of DMS against the environmental parameters show that on a global-scale mixed layer depth and solar radiation are the strongest predictors of DMS. These parameters capture ~9 % and ~7 % of the raw DMS data variance, respectively. Multilinear regression can capture more of the raw data variance (~39 %) but strongly underestimates DMS in high-concentration regions. In contrast, the artificial neural network captures ~66 % of the raw data variance in our database. Like prior climatologies our results show a strong seasonal cycle in surface ocean DMS with the highest concentrations and sea-to-air fluxes in the high-latitude summertime oceans. We estimate a lower global sea-to-air DMS flux (20.12±0.43 Tg S yr –1 ) than the prior estimate based on a map interpolation method when the same gas transfer velocity parameterization is used. Our sensitivity test results show that DMS concentration does not change unidirectionally with each of the environmental parameters, which emphasizes the interactions among these parameters. The ANN model suggests that the flux of DMS from the ocean to the atmosphere will increase with global warming. Given that larger DMS fluxes induce greater cloud albedo, this corresponds to a negative climate feedback.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Engineering microstructure to improve coercivity of bulk MnBi magnet

MnBi is a candidate material for high-temperature magnets because of its increasing coercivity with increasing temperatures up to 255 °C. However, most efforts in fabricating bulk MnBi magnets have run into the problem of preserving the coercivity (H cj) of its feedstock powders. About 70% of powder’s H cj would be lost during the densification process. Our micromagnetic modeling shows that the coercivity mechanism of the MnBi bulk magnet is controlled by nucleation of the reversal magnetization domains, and the large H cj loss that occurred during the powder consolidation process can be attributed to the inter-grain magnetic coupling. To attain a high H cj , the grains in the MnBi bulk magnet must be separated with a non-magnetic grain boundary phase (GBP). To validate this GBP hypothesis, we engineered MnBi bulk magnets with two different types of GBP. The first type of GBP was created in-situ by precipitating excessive Bi from the grains; the second type was created ex-situ by coating silicates on the feedstock powders before the consolidation. While both GBP work, the ex-situ approach resulted in a better H cj due to a more uniform GBP distribution. We report the H cj loss was reduced from 70% to 15%, and the (BH)max of a warm sintered bulk magnet reached 8.9 MGOe.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Xenon compatibility in magmatic processes: Hadean to current contexts

Xenon (Xe) behaviour in petrological processes, albeit essential to constrain mantle ingassing and degassing models, is elusive due to its volatile nature, and lack of direct investigation at the pressures (P) and temperatures (T) relevant to magma formation and crystallisation at depth. Xenon stands out amongst noble gases due to its unique reactivity with silicates of the lower crust and upper mantle, which could at least partially explain that published mineral/melt partitioning coefficients span up to six orders of magnitude. We report partition coefficients of Xe using in situ X-ray fluorescence at high P and T, and mass spectrometry analyses. Xenon is found to be moderately incompatible in anorthite-clinopyroxene mix in equilibrium with basalt (partition coefficient value of 0.16 ± 0.06), and compatible in olivine in equilibrium with basalt (partition coefficients in the range 88 ± 22 to 302 ± 46). While Xe is, thus, concentrated in basaltic melts coexisting with crystallising pyroxenes and feldspars, it is strongly retained in olivine at depth. Consequently, Xe originally contained in solid Earth has been preferentially retained at depth throughout Earth’s history, from the magma ocean stages to present day partial mantle melting processes.

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

Structural drivers controlling sulfur solubility in alkali aluminoborosilicate glasses

Abstract If the direct feed approach to vitrify the Hanford's tank waste is implemented, the low activity waste (LAW) will comprise higher concentrations of alkali/alkaline‐earth sulfates than expected under the previously proposed vitrification scheme. To ensure a minimal impact of higher sulfate concentrations on the downstream operations and overall cost of vitrification, advanced glass formulations with enhanced sulfate loadings (solubility) are needed. While, the current sulfate solubility predictive models have been successful in designing LAW glasses with sulfate loadings <2 wt.%, it will be difficult for them to design glass compositions with enhanced loadings due to our limited understanding of the fundamental science governing these processes. In this pursuit, this article unearths the underlying compositional and structural drivers controlling the sulfate solubility in model LAW glasses. It has been shown that the preferentially removes non‐framework cations from the modifier sites in the silicate network, thus, leading to the polymerization in the glass network via the formation of ring‐structured borosilicate units. Furthermore, though the sulfate solubility slightly decreases with increasing Li + /Na + in the glasses, the prefers to be charge compensated by Na + , as it is easier for to break Na–O bonds instead of Li–O bonds.

Xu, Xinyi↗
DOE OSTI2020

Calcium nitrate: A chemical admixture to inhibit aggregate dissolution and mitigate expansion caused by alkali-silica reaction

Alkali-silica reaction (ASR) is a significant cause of the degradation of concrete structures. ASR results from the dissolution of reactive silicate aggregates and the subsequent formation of damaging, expansive ASR gels. Despite the prevalence of ASR, so far only lithium-based chemical admixtures have been shown to be successful in mitigating its deleterious effects. Herein, dissolved calcium nitrate (Ca(NO 3 ) 2 : CN) is demonstrated to reduce ASR-induced expansion caused by the use of sodium borosilicate (NBS) glass as a model reactive aggregate. The significance of reductions of NBS-glass dissolution and mortar-bar expansion rates is discussed, with special focus on highlighting the mechanism by which calcium nitrate mitigates ASR, i.e., by the inhibition of aggregate dissolution. This study reveals a new and cost-effective pathway to suppress aggregate dissolution and ASR in concrete based on the dosage of soluble alkaline-earth additives.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Microbially induced precipitation of silica by anaerobic methane-oxidizing consortia and implications for microbial fossil preservation

Authigenic carbonate minerals can preserve biosignatures of microbial anaerobic oxidation of methane (AOM) in the rock record. It is not currently known whether the microorganisms that mediate sulfate-coupled AOM—often occurring as multicelled consortia of anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB)—are preserved as microfossils. Electron microscopy of ANME-SRB consortia in methane seep sediments has shown that these microorganisms can be associated with silicate minerals such as clays [Chen et al., Sci. Rep. 4, 1–9 (2014)], but the biogenicity of these phases, their geochemical composition, and their potential preservation in the rock record is poorly constrained. Long-term laboratory AOM enrichment cultures in sediment-free artificial seawater [Yu et al., Appl. Environ. Microbiol. 88, e02109-21 (2022)] resulted in precipitation of amorphous silicate particles (~200 nm) within clusters of exopolymer-rich AOM consortia from media undersaturated with respect to silica, suggestive of a microbially mediated process. The use of techniques like correlative fluorescence in situ hybridization (FISH), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS), and nanoscale secondary ion mass spectrometry (nanoSIMS) on AOM consortia from methane seep authigenic carbonates and sediments further revealed that they are enveloped in a silica-rich phase similar to the mineral phase on ANME-SRB consortia in enrichment cultures. Like in cyanobacteria [Moore et al., Geology 48, 862–866 (2020)], the Si-rich phases on ANME-SRB consortia identified here may enhance their preservation as microfossils. Finally, the morphology of these silica-rich precipitates, consistent with amorphous-type clay-like spheroids formed within organic assemblages, provides an additional mineralogical signature that may assist in the search for structural remnants of microbial consortia in rocks which formed in methane-rich environments from Earth and other planetary bodies.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Short-Term Stable Isotope Probing of Proteins Reveals Taxa Incorporating Inorganic Carbon in a Hot Spring Microbial Mat

The upper green layer of the chlorophototrophic microbial mats associated with the alkaline siliceous hot springs of Yellowstone National Park consists of oxygenic cyanobacteria ( Synechococcus spp.), anoxygenic Roseiflexus spp., and several other anoxygenic chlorophototrophs. Synechococcus spp. are believed to be the main fixers of inorganic carbon (C i ), but some evidence indicates that Roseiflexus spp. also contribute to inorganic carbon fixation during low-light, anoxic morning periods. Contributions of other phototrophic taxa have not been investigated. In order to follow the pathway of C i incorporation into different taxa, mat samples were incubated with [ 13 C]bicarbonate for 3 h during the early-morning, low-light anoxic period. Extracted proteins were treated with trypsin and analyzed by mass spectrometry, leading to peptide identifications and peptide isotopic profile signatures containing evidence of 13 C label incorporation. A total of 25,483 peptides, corresponding to 7,221 proteins, were identified from spectral features and associated with mat taxa by comparison to metagenomic assembly sequences. A total of 1,417 peptides, derived from 720 proteins, were detectably labeled with 13 C. Most 13 C-labeled peptides were derived from proteins of Synechococcus spp. and Roseiflexus spp. Chaperones and proteins of carbohydrate metabolism were most abundantly labeled. Proteins associated with photosynthesis, C i fixation, and N 2 fixation were also labeled in Synechococcus spp. Importantly, most proteins of the 3-hydroxypropionate bi-cycle for C i fixation in Roseiflexus spp. were labeled, establishing that members of this taxocene contribute to C i fixation. Other taxa showed much lower [ 13 C]bicarbonate incorporation. IMPORTANCE Yellowstone hot spring mats have been studied as natural models for understanding microbial community ecology and as modern analogs of stromatolites, the earliest community fossils on Earth. Stable-isotope probing of proteins (Pro-SIP) permitted short-term interrogation of the taxa that are involved in the important process of light-driven C i fixation in this highly active community and will be useful in linking other metabolic processes to mat taxa. Here, evidence is presented that Roseiflexus spp., which use the 3-hydroxypropionate bi-cycle, are active in C i fixation. Because this pathway imparts a lower degree of selection of isotopically heavy C i than does the Calvin-Benson-Bassham cycle, the results suggest a mechanism to explain why the natural abundance of 13 C in mat biomass is greater than expected if only the latter pathway were involved. Understanding how mat community members influence the 13 C/ 12 C ratios of mat biomass will help geochemists interpret the 13 C/ 12 C ratios of organic carbon in the fossil record.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Stability of hydrides in sub-Neptune exoplanets with thick hydrogen-rich atmospheres

Many sub-Neptune exoplanets have been believed to be composed of a thick hydrogen-dominated atmosphere and a high-temperature heavier-element-dominant core. From an assumption that there is no chemical reaction between hydrogen and silicates/metals at the atmosphere–interior boundary, the cores of sub-Neptunes have been modeled with molten silicates and metals (magma) in previous studies. In large sub-Neptunes, pressure at the atmosphere–magma boundary can reach tens of gigapascals where hydrogen is a dense liquid. A recent experiment showed that hydrogen can induce the reduction of Fe 2+ in (Mg,Fe)O to Fe 0 metal at the pressure–temperature conditions relevant to the atmosphere–interior boundary. However, it is unclear whether Mg, one of the abundant heavy elements in the planetary interiors, remains oxidized or can be reduced by H. Our experiments in the laser-heated diamond-anvil cell found that heating of MgO + Fe to 3,500 to 4,900 K (close to or above their melting temperatures) in an H medium leads to the formation of Mg 2 FeH 6 and H 2 O at 8 to 13 GPa. At 26 to 29 GPa, the behavior of the system changes, and Mg–H in an H fluid and H 2 O were detected with separate FeH x . The observations indicate the dissociation of the Mg–O bond by H and subsequent production of hydride and water. Therefore, the atmosphere–magma interaction can lead to a fundamentally different mineralogy for sub-Neptune exoplanets compared with rocky planets. The change in the chemical reaction at the higher pressures can also affect the size demographics (i.e., “radius cliff”) and the atmosphere chemistry of sub-Neptune exoplanets.

58 GEOSCIENCES↗
DOE OSTI2023

Eu speciation in apatite at 1 bar: An experimental study of valence-state partitioning by XANES, lattice strain, and Eu/Eu* in basaltic systems

Abstract Partition coefficients for rare earth elements (REEs) between apatite and basaltic melt were determined as a function of oxygen fugacity (fO2; iron-wüstite to hematite-magnetite buffers) at 1 bar and between 1110 and 1175 °C. Apatite-melt partitioning data for REE3+ (La, Sm, Gd, Lu) show near constant values at all experimental conditions, while bulk Eu becomes more incompatible (with an increasing negative anomaly) with decreasing fO2. Experiments define three apatite calibrations that can theoretically be used as redox sensors. The first, a XANES calibration that directly measures Eu valence in apatite, requires saturation at similar temperature-composition conditions to experiments and is defined by: ( E u 3 + ∑ E u ) Apatite = 1 1 + 10 - 0.10 ± 0.01 × l o g ⁡ ( f o 2 ) - 1.63 ± 0.16 . The second technique involves analysis of Sm, Eu, and Gd in both apatite and coexisting basaltic melt (glass), and is defined by: ( Eu E u * ) D Sm × Gd = 1 1 + 10 - 0.15 ± 0.03 × l o g ⁡ ( f o 2 ) - 2.46 ± 0.41 . The third technique is based on the lattice strain model and also requires analysis of REE in both apatite and basalt. This calibration is defined by ( Eu E u * ) D lattice strain = 1 1 + 10 - 0.20 ± 0.03 × l o g ⁡ ( f o 2 ) - 3.03 ± 0.42 . The Eu valence-state partitioning techniques based on (Sm×Gd) and lattice strain are virtually indistinguishable, such that either methodology is valid. Application of any of these calibrations is best carried out in systems where both apatite and coexisting glass are present and in direct contact with one another. In holocrystalline rocks, whole rock analyses can be used as a guide to melt composition, but considerations and corrections must be made to either the lattice strain or Sm×Gd techniques to ensure that the effect of plagioclase crystallization either prior to or during apatite growth can be removed. Similarly, if the melt source has an inherited either a positive or negative Eu anomaly, appropriate corrections must also be made to lattice strain or Sm×Gd techniques that are based on whole rock analyses. This being the case, if apatite is primary and saturates from the parent melt early during the crystallization sequence, these corrections may be minimal. The partition coefficients for the REE between apatite and melt range from a maximum DEu3+ = 1.67 ± 0.25 (as determined by lattice strain) to DLu3+ = 0.69 ± 0.10. The REE partition coefficient pattern, as observed in the Onuma diagram, is in a fortuitous situation where the most compatible REE (Eu3+) is also the polyvalent element used to monitor fO2. These experiments provide a quantitative means of assessing Eu anomalies in apatite and how they be used to constrain the oxygen fugacity of silicate melts.

Geochemistry & Geophysics↗
DOE OSTI2026

Data for "Depth of nutrient uptake by deep-rooted plants is regulated by water availability"

The data set consists of strontium (Sr) isotope ratios (87Sr/86Sr), water isotopes, soil cation concentrations, soil water potential sensor data, and results of 87Sr/86Sr mixing model. The plant canopy size files include the dataset of canopy dimension of sagebrush, lupine, and sunflower. The soil and plant ICPMS (Inductively Coupled Plasma Mass Spectrometry) data file includes both of 87Sr/86Sr, and cation concentration dataset from soil exchangeable pool, apatite pool, silicate extract, atmospheric rain deposition, and plant leaf and stem tissues. The plant dendrochronology file includes the dendrochronogical ring width of several sagebrush, and dendrochemical sample data includes the 87Sr/86Sr for each separated growth ring. The modeling result gives the proportion of nutrient sources of each plants (based on their 87Sr/86Sr in leaf tissues and growth rings) from atmospheric deposition and mineral weathering. Soil water potential data includes continuous collection of soil water potential dataset at 2 depths (30 cm and 60 cm, from Nov 24 - Jun 25) of the sampling site. All the samples were collected from 2 sampling campaign June and July 2023, and rain water is a separate sampling from Aug - Sept 2023, at north-facing hillslope near pumphouse site. The data showed that the depth of cation nutrient acquisition is thus tightly coupled with, and likely determined by, water availability in soil, saprolite and bedrock. The enhanced uptake of cations and water from regions of mineral weathering could confer plant and ecosystem resilience during low water years and may impact the rate of bedrock weathering and watershed chemistry during drought. This dataset includes a file-level metadata (flmd.csv) file that lists each file contained in the dataset with associated metadata; a data dictionary (dd.csv) file that contains column/row headers used throughout the files along with a definition, units, and data type; a location metadata file (locations.csv); and a samples metadata file (samples.csv). All files are provided as comma-separated values (CSV) files (.csv). This work was supported by the Watershed Function Science Focus Area at Lawrence Berkeley National Laboratory funded by the US Department of Energy, Office of Science, Biological and Environmental Research under Contract No. DE-AC02-05CH11231.

54 ENVIRONMENTAL SCIENCES↗