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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Chemistry imaging and distribution analysis of rare earth elements in coal using LIBS and LA-ICP-MS instruments

Currently, demand for rare earth elements (REEs) increased significantly. Coal is actively evaluated as potential economic sources for extraction of REEs. Here, in this work, laser-induced breakdown spectroscopy (LIBS) was evaluated for rapid estimation of REEs content and their distribution in the natural coal samples. The results were compared with similar laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) measurements. Thirteen coal samples (nine standard samples and five natural samples) were used in this study. Powder samples were pressed into pellets while coal chunks were directly ablated for data recording. Pellets of the powder standard samples were used to optimize the data acquisition system and then data recorded with this optimized system was used to identify the proper data acquisition and analysis models. After establishing the proper data acquisition system and analysis model using the standard samples, natural coal samples in powder form and their chunks were utilized to record LIBS and LA-ICP-MS spectra. Multivariate calibration models were developed using four of the natural samples, which were evaluated by predicting the REE content in the fifth sample. Principal component analysis was performed on the LIBS data obtained from the natural samples and it classified all the samples with high accuracy. Two-dimensional (2D) elemental mapping on coal chunk samples was also performed using both LIBS and LA-ICP-MS to study the distribution of REEs in the samples. The resulting elemental images and their correlations can be used to infer mineral distributions.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

Laser Ablation-Capillary Absorption Spectroscopy: A novel approach for high throughput and increased spatial resolution measurements of δ 13 C in plant-soil systems

Spatial and temporal heterogeneity of nutrient exchange within the rhizosphere is a topic of increasing interest, although challenging to study due to limits in existing analytical capabilities. Here, we developed and demonstrated a new approach applying laser ablation sample introduction to capillary absorption spectroscopy (LA-CAS) to characterize carbon isotopic distribution within plant tissues, rhizosphere, and soil. We exposed switchgrass plants to 13 CO 2 to allow tracing of 13 C-labelled photosynthates within plant biomass and into the associated soil. The LA-CAS methods we describe leverage continuous measurements of a sample stream derived from laser ablation line scans (10-25 µm in width) over a sample surface which enables the user to produce an isotope map with a) higher data density or b) over larger spatial areas versus previously existing techniques. This versatility of LA-CAS is assessed through testing of a range of laser parameters (spot size, scan rates) on various materials (soil, plant biomass/tissues, and rhizosphere). Here, we demonstrate the ability of LA-CAS to provide near instantaneous $δ$ 13 C measurements over isotopically distinct surfaces to enable high spatially resolved mapping of 13 C-labelled material within the rhizosphere. Applying LA-CAS analysis to plant biomass, we observed higher $δ$ 13 C values concentrated within phloem structures, consistent with localized photosynthate transport. When mapping across the rhizosphere, 13 C-enriched soil was typically present within 5-10µm of root boundaries with a steep spatial increase in $δ$ 13 C when the scan approached the middle of the root. As with all LA approaches, care is required to ensure accurate results as phenomena linked to ablation, combustion, and isotopic measurement can impart artifacts if not carefully controlled. Still, taken as a whole, our demonstrations highlight the increased sample throughput, improved data density, and enhanced $δ$ 13 C capability of LA-CAS versus other LA techniques and emphasize the role this method can play in future plant and rhizosphere related studies.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2008

Genesis of Augite-Bearing Ureilites: Evidence From LA-ICP-MS Analyses of Pyroxenes and Olivine

Ureilites are ultramafic achondrites composed primarily of coarse-grained low-Ca pyroxene and olivine with interstitial carbonaceous material, but a number of them contain augite [1]. Ureilites are considered to be restites after partial melting of a chondritic precursor, although at least some augite-bearing ureilites may be partially cumulate [1, 2]. In this scenario, the augite is a cumulus phase derived from a melt that infiltrated a restite composed of typical ureilite material (olivine+low-Ca pyroxene) [2]. To test this hypothesis, we examined the major and trace element compositions of silicate minerals in select augite-bearing ureilites with differing mg#. Polished thick sections of the augite-bearing ureilites ALH 84136 , EET 87511, EET 96293, LEW 88201, and META78008 and augite-free typical ureilite EET 90019 were examined by EPMA for major and minor elements and laser ablation ICP-MS (LA-ICP-MS) for trace elements, REE in particular. Although EET 87511 is reported to contain augite, the polished section that we obtained did not.

Herrin, J. S.↗
NASA NTRS2012

In Situ Geochemical Analysis and Age Dating of Rocks Using Laser Ablation-Miniature Mass Spectrometer

A miniaturized instrument for performing chemical and isotopic analysis of rocks has been developed. The rock sample is ablated by a laser and the neutral species produced are analyzed using the JPL-invented miniature mass spectrometer. The direct sampling of neutral ablated material and the simultaneous measurement of all the elemental and isotopic species are the novelties of this method. In this laser ablation-miniature mass spectrometer (LA-MMS) method, the ablated neutral atoms are led into the electron impact ionization source of the MMS, where they are ionized by a 70-eV electron beam. This results in a secondary ion pulse typically 10-100 microsecond wide, compared to the original 5-10-nanosecond laser pulse duration. Ions of different masses are then spatially dispersed along the focal plane of the magnetic sector of the miniature mass spectrometer and measured in parallel by a modified CCD (charge-coupled device) array detector capable of detecting ions directly. Compared to conventional scanning techniques, simultaneous measurement of the ion pulse along the focal plane effectively offers a 100% duty cycle over a wide mass range. LAMMS offers a more quantitative assessment of elemental composition than techniques that detect laser-ionized species produced directly in the ablation process because the latter can be strongly influenced by matrix effects that vary with the structure and geometry of the surface, the laser beam, and the ionization energies of the elements. The measurement of high-precision isotopic ratios and elemental composition of different rock minerals by LAMMS method has been demonstrated. The LA-MMS can be applied for the absolute age determination of rocks. There is no such instrument available presently in a miniaturized version that can be used for NASA space missions. Work is in progress in the laboratory for geochronology of rocks using LA-MMS that is based on K-Ar radiogenic dating technique.

Sinha, Mahadeva P.↗
DOE OSTI2025

Comparison of atomized mass and crater volume in laser ablation

The extent and dynamics of laser ablation are typically studied using crater imaging or by invoking the relationship between atomic emission and the mass removed. The former is a static view of a dynamic process and requires the accumulation of multiple shots in one location. The latter is complex and not absolute without calibration of the optical system with a standard of spectral radiance. We measure the mass of the atomized plume by laser atomic-absorption spectroscopy at 2 µs without external mass calibration; mass uncertainty in laser-ablation atomic absorption spectroscopy (LA-AAS) results from uncertainties in line area fitting, tabulated oscillator strengths, and partition functions as well as a <10% underrepresentation of the mass due to treating the plasma as a single thermodynamic equilibrium. The LA-AAS-measured mass pertains to the atoms in the probed charge states and does not include condensed or molecular species. The ablation efficiency at 300 mbar of helium varies significantly between the two focusing conditions used. A comparison of crater-derived masses and LA-AAS masses suggests that more defocused ablation may result in significant redeposition of material in the crater, distorting the conclusions from drilling studies and crater imaging. More focused ablation conditions result in crater-derived masses that exceed those measured with LA-AAS and suggest melt expulsion or phase explosion.

Merten, Jonathan [Arkansas State University, Jones↗
NASA NTRS2018

The Contrast in Outgassing of Germanium Between Shergottites and Nakhlites

Final Paper and not the abstract is attached. Introduction: Germanium is generally thought to follow Si in its geochemical behavior, but little data has existed to rigorously understand the behavior of Ge in the Martian mantle. Germanium is known to be more siderophile than Si, and its partitioning into the martian core has been studied by. Typical abundances in igneous martian meteorites range from 0.5-3 ppm, a larger range than what is observed in terrestrial basalts (1.5 +/- 0.1 ppm). In situ measurements by the MER and MSL rovers have revealed a surprisingly large range in Ge abundances in surface rocks (30-650 ppm), but many igneous rocks and soils are shown to have greater than 30 ppm Ge (the detection limit of the APXS). Recently, reported that shergottite minerals showed a depletion of Ge with increasing fractionation, while nakhlites and chassignites exhibited Ge behavior compatible with closed system igneous differentiation. They interpreted their observations as tentatively indicating volcanic outgassing of Ge from shergottites (but not from nakhlite-chassignites) with recondensation of the Ge vapor into soils and breccias. Recent experimental studies show that Ge is significantly volatile from magmas. In this study, we followed up on those results by analyzing minerals in five nakhlites and five shergottites by laser ablation ICP-MS (LA-ICP-MS). See Attached

Yang, S.↗
DOE OSTI2021

Oak Ridge National Laboratory Official TM Cover: Development and Qualification of Tungsten Reference Materials for LA-ICP-MS

Reference materials have been developed to provide areal density measurements of tungsten that is deposited on graphite when using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Several reference materials of varying areal densities have been produced using a magnetron sputtering, thin film deposition technique. With multiple reference materials that have varying areal densities, a calibration curve has been developed for translating the detector response of an ICP-MS into a quantitative measurement. These results provide the opportunity to make calibrated comparisons across graphite samples that were exposed to tungsten transport experiments for nuclear fusion research. In addition, these methods may be applied to provide individual areal density measurements for the five unique isotopes of tungsten. It is found that areal density measurements via LA-ICP-MS agree with characterization for the same samples when using the more traditional Rutherford backscattering ion beam technique. Qualification of these reference materials was completed using ion beam laboratories at the University of Tennessee, Knoxville and Massachusetts Institute of Technology, and Sandia National Laboratory.

36 MATERIALS SCIENCE↗
NASA NTRS2019

Trace Element Abundances of Olivine-Hosted Melt Inclusions in Shergottites Northwest Africa 7397 and Robert Massif 04262

Olivine-hosted melt inclusions (MIs) may retain trapped parent magma compositions as well as record progressive differentiation while magmas crystallize and ascend towards the surface [1,2 and references therein]. Major element compositions of the MIs, especially Fe and Mg, can be affected by post-entrapment re-equilibration with their host olivine [1,2]. Therefore, Fe/Mg ratio correction is required to obtain MI bulk compositions following equilibrium with their host olivine. Partition coefficients of most of the trace elements in olivine are very low (i.e. DOL/melt<0.001). Thus, ratios of trace elements of olivine-hosted MIs are unlikely to be affected by post-entrapment re-equilibration and no correction is necessary [2]. Hence, tracking trace element behavior in MIs may constrain the composition of the parent magma and its evolution yielding insights on magma differentiation of shergottites. However, analyzing MIs for chemical compositions is a challenging task due to their low abundances and small sizes. Using a highly sensitive and precise micro-beam technique is essential to examine olivine-hosted MIs in order to measure trace element abundances. For this purpose, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is an excellent tool due to its wide range of laser spot sizes (1-150 μm), ability to obtain raster analysis (several mm2) and lower detection limits (0.1 ppb) [3].

Ferdous, J.↗
DOE OSTI2025

Evaluating the feasibility of LA-ICP-TOF-MS for the analysis of environmental particle collections

Laser ablation-inductively coupled plasma-time-of-flight-mass spectrometry (LA-ICP-TOF-MS) was employed to rapidly analyze environmental particle samples collected using aerosol contaminate extractors (ACE). The ACE particle collectors were placed at various distances (0.5, 1.3, and 4.5 km) from a source that released Ru-bearing particles. Samples for measurement were then generated (as sub-samples) from the ACE collection plates via particle “lift off” with gunshot residue (GSR) tabs. The LA-ICP-TOF-MS method was employed such that 10+ samples could be analyzed in a single unattended analytical session. A 3 × 1 mm area of individual GSR tab samples were analyzed in less than 30 minutes. This provided spatially resolved elemental and isotopic measurements of the particulate content and confirmed the presence of Ru-bearing particles within the complex background environmental particle loading. As anticipated, measurements showed collectors closest to the source had the highest concentration of the released Ru-bearing particles, while all collectors, regardless of distance, contained similar levels of background particles (e.g., Fe and Sr). Sequential scanning electron microscopy – automated particle analysis (SEM-APA) and LA-ICP-TOF-MS analysis was employed for method validation and a demonstration of the multi-modal approach. The same 2-dimensional region was analyzed by both methods and the particles identified via SEM-APA were also detected using LA-ICP-TOF-MS, with 100% accuracy. Overall, LA-ICP-TOF-MS demonstrated its utility for rapid elemental and isotopic particle analysis from environmental air samples.

Manard, Benjamin T. [Oak Ridge National Laboratory↗
DOE OSTI2024

Uranium Single Particle Analysis for Simultaneous Fluorine and Uranium Isotopic Determinations via Laser-Induced Breakdown Spectroscopy/Laser Ablation–Multicollector–Inductively Coupled Plasma–Mass Spectrometry

Uranyl fluoride (UO 2 F 2 ) particles (<20 μm) were subjected to first-of-its-kind analysis via simultaneous laser-induced breakdown spectroscopy (LIBS) and laser ablation multi-collector inductively coupled plasma–mass spectrometry (LA–MC–ICP–MS). Briefly, a nanosecond pulsed high-energy laser was focused onto the sample (particle) surface. In a single laser pulse, the UO 2 F 2 particle was excited/ionized within the microplasma volume, and the emission of light was collected via fiber optics such that emission spectroscopy could be employed for the detection of uranium (U) and fluorine (F). The ablated particle was simultaneously transported into the MC–ICP–MS for high precision isotopic (i.e., 234 U, 235 U, and 238 U) analysis. This method, LIBS/LA–MC–ICP–MS was optimized and employed to rapidly measure 80+ UO 2 F 2 particles, which were subjected to different calcination processes, which results in varying degrees of F loss from the individual particles. In measuring the particles, the average F/U ratios for the populations treated at 100 and 500 °C were 2.78 ± 1.28 and 1.01 ± 0.50, respectively, confirming loss of F through the calcination process. The average 235 U/ 238 U on the particle populations for the 100 and 500 °C were 0.007262 (22) and 0.007231 (23), which was determined to be <0.2% from the expected value. The 234 U/ 238 U ratios on the same particles were 0.000053 (11) and 0.000050 (10) for the 100 and 500 °C, respectively, <10% from the expected value. Notably, each population was analyzed in under 5 min, demonstrating the truly rapid analysis technique presented here in this paper.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2021

Plutonium Co-precipitation with Calcite

The mobility of plutonium (Pu) in the environment is affected by Pu–mineral interactions, such as adsorption–desorption and structural incorporation. Calcite (CaCO 3 ) is a common secondary phase in near surface environments and a major component of many rocks and soils and is expected to form as an alteration product of cement-based materials planned for use in geological repositories. The reactivity of the calcite surface and its ability to tolerate significant variations in its chemical composition through substitution of Ca for other cations make calcite a potentially important sink for environmental contaminants. Here, single crystals of calcite were synthesized from aqueous solutions in equilibrium with air containing Pu as either Pu(VI) or Pu(IV) and characterized using a combination of laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) and X-ray absorption spectroscopy (XAS). These data are used to assess the amount, structure, and oxidation state of Pu co-precipitated into calcite, providing insight into the potential for Pu sequestration in calcite precipitates. Overall, the XAS and LA–ICP–MS data support the co-precipitation of plutonyl [Pu(VI/V)] in the bulk calcite, although the exact nature of the co-precipitated Pu complex is difficult to elucidate in the synthesized material. Co-precipitated plutonyl could be incorporated in either distorted Ca lattice sites or defect sites, and we provide evidence to suggest that Pu(VI) is reduced mainly to Pu(V) in the precipitated solid. LA–ICP–MS additionally shows that the co-precipitation of Pu(VI/V) is favored over the co-precipitation of Pu(IV). Altogether, our results suggest that Pu sequestration in calcite under environmental conditions could immobilize Pu and isolate it from groundwater interactions in contaminated environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

Application of High-Spatial Resolution LA-MC-ICP-MS in Planetary Materials

High-precision stable and radiogenic isotopic measurements of planetary materials can help elucidate processes taking place during early Solar System formation, as well as during subsequent planetary differentiation. Laser Ablation Multi Collector Inductively Coupled Plasma Mass Spectrometry (LA-MC-ICP-MS) adds the valuable ability of preserving the spatial context of these isotopic measurements, by sampling small sample volumes (~10 – 60 um diameter) using a pulsed laser system. In the Center for Isotope Cosmochemistry and Geochronology (CICG) at NASA Johnson Space Center, these in-situ isotopic measurements are primarily made using the Applied SpectraTM iX-fs-Tandem LA-LIBS Instrument coupled to the Nu InstrumentsTM SP1700 MC-ICP-MS. The instrumental set-up also provides simultaneous Laser Induced Breakdown Spectroscopy (LIBS) measurements and the potential use of a low energy path with a collision/reaction cell for additional interference removal, though we focus here on the typical high-energy LA-MC-ICP-MS operation. We will provide examples of stable (e.g., Mg) and radiogenic (e.g., Lu-Hf) isotopic systems measured in planetary materials and their terrestrial analogs. The measurement of mass dependent Mg isotopic variations is an important tool for reconstructing processes such as evaporation and condensation of solids in the solar nebula. For early Solar System samples, Mg isotope measurements are also important for the short-lived (t1/2 = 0.7 Ma) Al-Mg chronometer. During laser ablation analyses, the measurement of the Al-Mg isotopic system is made in medium mass resolution (RP ~9500 at ~20% transmission) to limit interferences from 48Ti2+ and 48Ca2+ on 24Mg+, in addition to 52Cr2+ and 12C14N+ on 26Mg+. Measured in the mineral zircon, the 176Lu-176Hf decay system is often used for understanding the growth of continents on Earth, and is also a vital aid in deciphering early large-scale planetary differentiation processes, such as the crystallization of the lunar magma ocean, which is thought to be responsible for much of the Moon’s crust. Lu-Hf measurements are made in low resolution mode (RP <2000), with 10 ion masses (from 171Yb to 180Hf) measured simultaneously to facilitate corrections for isobaric interferences from 176Yb and 176Lu on 176Hf.

Jacob B Setera↗
NASA NTRS2010

Determining the Metal/Silicate Partition Coefficient of Germanium: Implications for Core and Mantle Differentiation.

Currently there are several hypotheses for the thermal state of the early Earth. Some hypothesize a shallow magma ocean, or deep magma ocean, or heterogeneous accretion which requires no magma ocean at all. Previous models are unable to account for Ge depletion in Earth's mantle relative to CI chondrites. In this study, the element Ge is used to observe the way siderophile elements partition into the metallic core. The purpose of this research is to provide new data for Ge and to further test these models for Earth's early stages. The partition coefficients (D(sub Ge) = c(sub metal)/c(sub silicate), where D = partition coefficient of Ge and c = concentration of Ge in the metal and silicate, respectively) of siderophile elements were studied by performing series of high pressure, high temperature experiments. They are also dependent on oxygen fugacity, and metal and silicate composition. Ge is a moderately siderophile element found in both the mantle and core, and has yet to be studied systematically at high temperatures. Moreover, previous work has been limited by the low solubility of Ge in silicate melts (less than 100 ppm and close to detection limits for electron microprobe analysis). Reported here are results from 14 experiments studying the partitioning of Ge between silicate and metallic liquids. The Ge concentrations were then analyzed using Laser Ablation Inductively Coupled Mass Spectrometry (LA-ICP-MS) which is sensitive enough to detect ppm levels of Ge in the silicate melt.

King, C.↗
NASA NTRS2017

Determination of Trace and Volatile Element Abundance Systematics of Lunar Pyroclastic Glasses 74220 and 15426 Using LA-ICP-MS

Since their recognition as pyroclastic glasses generated by volcanic fire fountaining on the Moon, 74220 and 15426 have garnered significant scientific interest. Early studies recognized that the glasses were particularly enriched in volatile elements on their surfaces. More recently, detailed analyses of the interiors of the glasses, as well as of melt inclusions within olivine grains associated with the 74220 glass beads, have determined high H2O, F, Cl and S contents. Such elevated volatile contents seem at odds with evidence from moderately volatile elements (MVE), such as Zn and K, for a volatile- depleted Moon. In this study, we present initial results from an analytical campaign to study trace element abundances within the pyroclastic glass beads. We report trace element data determined by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for 15426 and 74220.

McIntosh, E. Carrie↗
DOE OSTI2021

Absolute quantitation of propranolol from 200-μm regions of mouse brain and liver thin tissues using laser ablation-dropletProbe-mass spectrometry

Rationale: The ability to quantify drugs and metabolites in tissue with sub-mm resolution is a challenging but much needed capability in pharmaceutical research. To fill this void, a novel surface sampling approach combining laser ablation with the commercial dropletProbe automated liquid surface sampling system (LA-dropletProbe) was developed and presented here.Methods: Parylene C-coated 200 × 200 μm tissue regions of mouse brain and kidney thin tissue sections were analyzed for propranolol by laser ablation of tissue directly into a preformed liquid junction. Propranolol was detected by high performance liquid chromatography with positive ion mode electrospray ionization tandem mass spectrometry. Quantitation was achieved via application of a stable isotope-labeled internal standard and an external calibration curve.Results: Absolute concentration of propranolol determined from 200 × 200 µm tissue regions were compared to propranolol concentrations obtained from 2.3-mm-diameter tissue punches of adjacent, non-coated sections using standard bulk tissue extraction protocols followed by regular HPLC-MS/MS analysis. Average concentration of propranolol in both organs determined by the two employed methods agreed within ±12%. Furthermore, the relative abundance of phase II hydroxypropranolol glucuronide metabolites were recorded and found to be consistent with previous results.Conclusions: This work illustrates that depositing a thin parylene C layer onto thin tissue prior to analysis, which seals the surface and prevents direct liquid extraction of the drug from the tissue, coupled to the novel LA-dropletProbe surface sampling system is a viable approach for sub-mm resolution quantitative drug distribution analysis.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Advancing Elemental and Isotopic Analysis of Uranium Mineral Inclusions: Rapid Screening via Laser-Induced Breakdown Spectroscopy and High-Resolution Laser Ablation-ICP-MS Mapping

The work presented herein employs two laser-based analytical techniques (laser-induced breakdown spectroscopy (LIBS) and laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS)) to spatially determine the elemental and isotopic composition of uranium bearing minerals. Uniquely, this work leverages the high-speed applicability of LIBS to “screen” the sample(s) for their elemental constituents. After determining the location of the uranium inclusions (via LIBS), high-resolution LA-ICP-MS was employed to further characterize the inclusions. The high-resolution (sub-µm) capabilities of LA-ICP-MS were able to extract important information from the uranium minerals including discerning its chemical form (e.g., finchite from carnotite, Sr- and K-bearing uranyl vanadates, respectively) as well as their 235 U/ 238 U isotopic composition. This approach, LIBS followed by LA-ICP-MS, significantly reduces the analysis time (~95 %) in comparison to employing a LA-ICP-MS only approach. Furthermore, this work presented a novel approach to analyzing inclusions via a particle/inclusion analysis tool which is commercially available within the iolite 4 software. This tool allowed for a more accurate characterization of the isotopic distribution of the inclusions, as well as allowing for rapid sizing of the inclusions. Finally, this analytical approach could readily be applied to other sample types in which the target species (e.g., µm-sized inclusions) are embedded in complex matrices (e.g., cm-sized samples).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

Additional Trials & Tribulations in Synthesizing a Sulfide Standard

Well-characterized sulfide reference materials that can serve as matrix-matched calibrants for in-situ trace element analyses via laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remain elusive. Here, we describe the creation an in-house sulfide standard at NASA JSC that will be used to measure siderophile and chalcophile trace elements in low pressure experimental products, specifically pentlandite ([FeNi]9S8) and pyrrhotite ([FeNi]1-xS), as well as natural sulfides in terrestrial and meteoritic mineral assemblages. Recent methods in creating a homogenous sulfide standard include pressed pellets, synthesized chips, or fused glass [e.g. 1-3]. Other studies, however, have had success in forming homogenous FeS standards via synthesization methods [e.g. 4-6]. We present a variation of the method described in [4], in which we create a pyrrhotite standard doped with a variety of trace elements (Zn, As, Se, Mo, Ru, Rh, Pd, Sn, Sb, Te, W, Os, Ir, Pt, Au) at ~10-40 ppm and Cu at ~200 ppm. Sulfide compositions were constructed using Fe and Ni metal and elemental sulfur powders. Trace elements were added to elemental sulfur from Atomic Absorption Spectroscopy (AAS) elemental standards as either nitrate or chloride solutions to prevent oxidation of the metal powders. The dried sulfur mixture was mixed with Fe and Ni powders and mechanically mixed before two aliquots were placed in separate SiO2 tubes. Each tube was held under vacuum for ~30 minutes, sealed under vacuum, and then heated at 800C for 48 hours. Like [4], the synthesis products were composed of pourous sulfide crystals. Major element analyses of both experimental aliquots, collected using an Electron Probe Microanalyser (EPMA), yield indistinguishable major element compositions (uncertainties in 2SE & 2RSE[%]), with an average of 57.90  0.09 (0.16 %), 4.95  0.03 (0.55 %), and 39.70  0.14 (0.34 %), for Fe, Ni, and S, respectively. Trace element data were measured using a Photon Machines 193nm laser ablation system coupled to a Thermo-Scientific Element-XR ICP-MS. Spot sizes were limited to 50 μm due to the porous nature of the sulfide target material. Trace element abundances, normalized to Fe as an internal standard, were also found to be homogenous between the two aliquots, with weighted mean 2RSE (%) values of <3.0 for all trace elements. Synthesized products were re-powdered and absolute concentrations measured via solution ICP-MS. Although the sulfide appears to be homogenous, sintering experiments will be performed to more closely match the standard density to natural sulfides and minimize differences in ablation behavior. Improved density also allows for higher sensitivity (i.e. more compact target material) and larger spot sizes or traverses, as void space is eliminated. Additional major and trace element analyses on the products of the sintering experiments will be undertaken.

Jacob B Setera↗