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Trace element geochemistry and the early lunar differentiation

The results are considered of experiments in which thermal neutron activation analysis was used to measure the halogens, U, Te, Ru, Os, and Hg in lunar samples. A calorimetric method was used for P2O5. Three Apollo 17 basalts, one Apollo 11 basalt, and one Apollo 15 basalt were used for the Ru-Os study. Os and Ru were measured in seven samples of breccia 14305 in a series of experiments to check an apparent anomaly in the isotopic composition of the Hg which it contains. A lunar model for Ru-Os partition is discussed. It is suggested that Ru and Os were partitioned and fractionated in the original differentiation of the lunar surface ocean. Fractionation among near-surface materials was less than a factor of 2 according to the lithic breccia data. Fractionations among basaltic sources were very large, exceeding 100, and primarily due to Ru. A clue to Ru and Os distributions at the depths from which mare basalts were derived may be provided by the relative ages of the basalts. These are interpreted as being related to partial melting in response to temperature increases at depth with time.

Jovanovic, S.

Chemical fractionations in meteorites. IX - C3 chondrites

Radiochemical neutron activation is applied to the analysis of four C3V chondrites and three C3O chondrites for 17 trace elements (U, Re, Ir, Ni, Au, Sb, Ge, Ag, Rb, Cs, Bi, Tl, Br, Se, Te, In, and Cd). It is shown that both classes exhibit a typical chondritic step pattern, reflecting loss of volatiles during chondrule formation. It appears that the H2S/H2 ratio is the key variable to account for the condensation of chalcophile elements as a function of H2S. C3O's seem to have condensed in a region where enough metallic Fe was present to buffer the H2S pressure, whereas C3V's condensed in a more oxidized region where H2S was in excess. Accretion temperatures for both subclasses is determined. Sb and Au show variable depletion, presumably reflecting variable loss during chondrule formation.

Anders, E.

A fundamental approach to adhesion: Synthesis, surface analysis, thermodynamics and mechanics

Several techniques were used to study pretreated Ti 6-4 surfaces including scanning electron microscopy (SEM), electron spectroscopy of chemical analysis (ESCA), and, reflectance visible spectroscopy. Each pretreatment type gave a characteristic surface morphology as seen by SEM. Elemental analysis of the Ti 6-4 surfaces was done using ESCA. Trace residual contaminants from particular chemical pretreatments were identified readily. Results indicate that reflectance visible spectroscopy using indicator dyes placed on Ti 6-4 surfaces appears to be a feasible approach to establish surface acidity. Differences in surface acidity were observed using bromthymol blue on Ti 6-4 surfaces pretreated by two different methods.

Beck, B.

Spectroscopic characterization of titanium 6-4 surfaces after chemical pretreatments

Several techniques have been used to study pretreated Ti 6-4 surfaces including scanning electron microscopy (SEM), electron spectroscopy of chemical analysis (ESCA), and, reflectance visibile spectroscopy. Each pretreatment type gives a characteristic surface morphology as seen by SEM. Elemental analysis of the Ti 6-4 surfaces was done using ESCA. Trace residual contaminants from particular chemical pretreatments are identified readily. Reflectance visible spectroscopy using indicator dyes placed on Ti 6-4 surfaces appears to be a feasible approach to establish surface acidity. Differences in surface acidity have been observed using bromthymol blue on Ti 6-4 surfaces pretreated by two different methods.

Chen, W.

Chemical fractionation in the solar system

The cosmochemical and geochemical history of planetary material is reflected in relative and absolute abundances of two groups of trace elements; siderophiles and volatiles. Many of these elements can be determined at the required levels only by radiochemical neutron activation analysis. The abundance patterns of elements in chondritic meteorites result from condensation processes in the solar nebula. The composition of planetisimals which bombarded the moon is characterized from trace elements in lunar breccias, and is also related to nebula processes. Trace elements in anorthosites and basalts from earth and moon suggest that the moon is refractory-rich and volatile-poor relative to the earth.

Morgan, J. W.

The measurement of trace elements in interplanetary dust and cometary particles by ultra-high sensitivity INAA

Today the major elemental composition of interplanetary dust particles (IDPs) is routinely determined in many laboratories. These and mineralogical studies have revealed the presence of at least two major types of IDPs, chondritic and refractory. Preliminary results of a successful attempt to determine abundances of a large suite of trace elements from both chondritic and refractory IDPs are reported. The analytical procedure can be used in the grain-by-grain analysis of returned cometary samples. Chondritic and refractory IDPs are characterized by standard scanning electron microscopy and energy dispersive x ray spectroscopy (SEM-EDX) techniques. With this system, detection limits for many elements are well below picogram levels, and some approach femtogram levels. This technique is non-destructive, although some sample handling is required, so particles can be analyzed by other techniques after instrument neutron activation analysis (INAA) is completed. Data is presently being reduced from the analyses of 7 IDPs. These are U2015E10, U2015F1, W7029-A2, W7029-A3, W7013A8, LACl (all chondritic) and 705 (refractory). So far, 17 different major and trace elements were detected and measured in these particles, including rare earths and some very volatile elements (Br and Zn).

Zolensky, M. E.

Nanoscale elemental and morphological imaging of nitrogen-fixing cyanobacteria

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.

Anabaena sp

Minor and trace elements in some meteoritic minerals.

Despite the information available (Mason, 1971) on trace elements in different types of meteorites, relatively little is known about the distribution of these elements among the individual mineral phases. The mineral phases including olivine, orthopyroxene, clinipyroxene, troilite, nickel-iron, plagioclase, chromite, and the phosphates were separated from several meteorites. The purified minerals were analyzed for trace and minor elements by spark source mass spectrometry and instrumental neutron activation analysis. The elements are classified as siderophile, lithophile, and chalcophile.

Allen, R. O., Jr.

Pontlyfni - A differentiated meteorite related to the group IAB irons

The abundances of 23 major and trace elements in the Pontlyfni meteorite have been measured by instrumental neutron activation analysis. The compositions of the metal and silicate fractions suggest a genetic relationship between Pontlyfni and the group IAB irons.

Davis, A. M.

Design and development of a trace contaminant removal canister for Spacelab

The paper describes the overall approach used by NASA-MSFC to design and develop a trace contaminant removal canister for Spacelab. The elements of this approach include the establishment of a trace contaminant load model, analysis and testing to define a preliminary design, development testing to verify the adequacy of the selected design, and testing to define a suitable canister location in the transfer tunnel ventilation system. The canister utilizes a catalyst material which is effective in removing carbon monoxide at room temperature, as well as plain and acid treated charcoal. The canister alone will control all contaminants in the load model below their maximum allowable concentration (MAC) levels without assistance from the baseline environmental control system (ECS) except for methyl alcohol and ammonia.

Ray, C. D.

Search for a meteoritic component at the Beaverhead impact structure, Montana

The Beaverhead impact structure, in southwestern Montana, was identified recently by the presence of shatter cones and impactites in outcrops of Proterozoic sandstones of the Belt Supergroup. The cones occur over an area greater than 100 sq km. Because the geologic and tectonic history of this region is long and complex, the outline of the original impact crater is no longer identifiable. The extent of the area over which shatter cones occur suggests, however, that the feature may have been at least 60 km in diameter. The absence of shatter cones in younger sedimentary units suggests that the impact event occurred in late Precambrian or early Paleozoic time. We have collected samples of shocked sandstone from the so-called 'Main Site' of dark-matrix breccias, and of impact breccias and melts from the south end of Island Butte. The melts, occurring often as veins through brecciated sandstone, exhibit a distinctive fluidal texture, a greenish color, and a cryptocrystalline matrix, with small inclusions of deformed sandstone. Samples of the same type, along with country rock, were analyzed previously for major- and trace-element abundances. It was found that, although the major-element composition as relatively uniform, trace-element composition showed variations between the melt material and the adjacent sandstone. These variations were attributed to extensive weathering and hydrothermal alteration. In a more specific search for a possible meteoritic signature in the breccia and the melt material we have conducted a new series of trace-element analyses on powders of our own samples by thermal neutron activation analysis. Our results indicate that Ir abundances in the breccia, the melts, and the adjacent sandstone clasts are no greater than about 0.1 ppb, suggesting no Ir enrichment of the breccia or the melts relative to the country rock. However, both the breccia and the melt material exhibit notable enrichments in Cr (8- and 10-fold), in U (9- and 5-fold), and in the heavy REE's (1.5- and 3-fold), respectively.

Lee, Pascal

Remote in-situ elemental analysis systems for underwater application

The systems approach, theoretical measurement calculations, and preliminary measurements to be used in monitoring and mapping pollutants (such as traces of heavy metals) in the Chesapeake Bay are discussed. A neutron gamma-ray method is under development for demonstrating the system. The excitation source to be used is a machine accelerator using a deuterium/tritium reaction to produce 14-MeV neutrons. The neutrons excite characteristic gamma ray emission from the neutron irradiated surface. The discrete line emission produced can be used to infer both qualitative and quantitative elemental composition. A data preprocessor will accumulate, digitize, store, format, and prepare the data for transmission which can be accomplished by telephone, microwave, and possibly satellite link to central processors.

Trombka, J. I.

Finding a needle in a haystack: quantitative HERFD-XRF imaging and HERFD-XANES characterization of trace platinum in gold solidi from the Late Roman and Byzantine Empires

High-Energy Resolution Fluorescence Detection X-Ray Fluorescence (HERFD-XRF) imaging and HERFD X-ray Absorption Near Edge Structure (XANES) spectroscopy are used to quantify and characterize trace platinum (Pt) in gold solidi from the Late Roman and Byzantine Empires. Historically, the elemental analysis of coins has been pivotal in distinguishing authentic artifacts from forgeries, elucidating minting practices, and understanding economic shifts. Notably, a new gold source with high platinum content appeared in the fourth century CE, transforming the Roman economy. Traditional methods struggled to detect platinum due to the overwhelming gold matrix. Here, this study demonstrates the effectiveness of HERFD techniques in resolving this challenge. Three gold solidi, minted between 654 and 659 CE, were analyzed alongside reference gold materials with known Pt concentrations. The HERFD-XRF imaging revealed spatial distributions of platinum, highlighting non-uniformities within the coins. Additionally, HERFD-XANES spectroscopy identified the oxidation states and chemical speciation of platinum. Results demonstrate that platinum in the solidi primarily exists as metallic Pt, with some surface oxidation. The findings align with previous measurements but reveal higher Pt concentrations and significant inhomogeneities. This research confirms the reliability of HERFD methods for quantifying trace elements and provides new insights into the raw material sources and minting techniques of ancient gold coins. The non-destructive nature of this approach allows for extensive analyses, offering valuable data for historical, economic, and archaeological studies. This innovative application of HERFD-XRF imaging and XANES in cultural heritage research underscores the potential for detailed material characterization and conservation, enhancing our understanding of ancient economies and trade patterns.

Van Loon, Lisa L.

Bulk, rare earth and other trace elements in Apollo 14 and 15 and Luna 16 samples

The chemical abundances were measured by instrumental and radiochemical neutron activation analysis in a variety of lunar specimens. Apollo 14 soils are characterized by significant enrichments of Al2O3, Na2O and K2O and depletions of TiO2, FeO, MnO and Cr2O3 relative to Apollo 11 and to most of Apollo 12 soils. The uniform abundances in 14230 core tube soils and three other Apollo 14 soils indicate that the regolith is uniform to at least 22 cm depth and within approximately 200 m from the lunar module. Two Luna 16 breccias are similar in composition to Luna 16 soils. Four Apollo 15 soils (LM, STA 4, 9, and 9a) have variable compositions. Interelement correlations between MnO-FeO, Sc-FeO, V-Cr2O3 and K2O-Hf negate the hypothesis that howardite achondrites may be primitive lunar matter, argue against the fission hypothesis for the origin of the moon, and precludes any selective large scale volatilization of alkalies during lunar magmatic events.

Laul, J. C.

Non-destructive trace element microanalysis of as-received cometary nucleus samples using synchrotron x ray fluorescence

The Synchrotron X ray Fluorescence (SXRF) microprobe at the National Synchrotron Light Source (NSLS), Brookhaven National Laboratory, will be an excellent instrument for non-destructive trace element analyses of cometary nucleus samples. Trace element analyses of as-received cometary nucleus material will also be possible with this technique. Bulk analysis of relatively volatile elements will be important in establishing comet formation conditions. However, as demonstrated for meteorites, microanalyses of individual phases in their petrographic context are crucial in defining the histories of particular components in unequilibrated specimens. Perhaps most informative in comparing cometary material with meteorites will be the halogens and trace metals. In-situ, high spatial resolution microanalyses will be essential in establishing host phases for these elements and identifying terrestrial (collection/processing) overprints. The present SXRF microprobe is a simple, yet powerful, instrument in which specimens are excited with filtered, continuum synchrotron radiation from a bending magnet on a 2.5 GeV electron storage ring. A refrigerated cell will be constructed to permit analyses at low temperatures. The cell will consist essentially of an air tight housing with a cold stage. Kapton windows will be used to allow the incident synchrotron beam to enter the cell and fluorescent x rays to exit it. The cell will be either under vacuum or continuous purge by ultrapure helium during analyses. Several other improvements of the NSLS microprobe will be made prior to the cometary nucleus sample return mission that will greatly enhance the sensitivity of the technique.

Sutton, S. R.

Soret diffusion: A possible cause of compositional heterogeneity within tektites

Although a terrestrial origin for tektites is well-established on geochemical evidence, the physical processes involved in tektite formation have been largely ignored by geochemists and petrologists. For example, two observations that potentially bear on the physics of their origin are the following: (1) The flange of an australite is often more heterogeneous than its core; and (2) microtektites are compositionally more diverse than tektites. The first observation contradicts the traditional view of flange formation since a second heating to super-liquidus temperatures during atmospheric re-entry should, by chemical diffusion and mixing, have tended to homogenize the melt as it flowed off the leading edge of the core to form the flange. Analyses of an australite flange have been performed by electron microprobe. The results of those analyses emphasize the magnitude of the heterogeneity, as well as the well-defined elemental correlations that may constrain the process responsible for it. The second observation that the bulk compositions of microtektites are more divers than the tektites within the same strewnfield is a well-known characteristic, for which no quantitative explanation has been offered. The current investigation has involved the analysis of 43 Australasian microtektites from the Wharton Basin by electron microprobe, as well as trace-element abundances on fifteen of these microtecktites by INAA.

Delano, J. W.

Antarctic and non-Antarctic meteorites form different populations

The trace element differences between Victoria Land H5 chondrites and non-Antarctic H5 chondrites are studied. The focus on common meteorites was stimulated by Antarctic and non-Antarctic differences in meteorite types and in the trace element contents of congeners of rare type. Thirteen elements were analyzed by neutron activation analysis with radiochemical separation, and eight differed significantly. Eliminating test biasing and the possibility of compositional difference due to Antarctic weathering of the 300,000 year-old (on the average) Victoria Land falls, it is concluded that the two sets of chondrites differ due to extraterrestrial causes. The three possibilities discussed, differences in sample population, physical properties, orbital characteristics, and meteoroid flux with time, are all seen as problematic.

Dennison, J. E.

Collection requirements for trace-element analyses of extraterrestrial samples

Trace-element abundances have proven important in understanding the evolution of and interrelationships between different meteorites. Preliminary investigations of the trace-element contents of interplanetary dust particles indicate that trace-element abundances will prove equally important in distinguishing between micrometeorites of different types, comparing the interplanetary dust to the meteorites, and assessing the degree of thermal alteration experienced either on the parent body or during the collection process. Sample collection, delivery, and curation must be accomplished in a manner to avoid contamination with even trace amounts of the elements to be analyzed. The present SXRF sensitivity for micrometeorite analysis is of order 1 femtogram, but anticipated improvements in sensitivity will require sample contamination substantially below this level. Sample collection and handling equipment should be constructed from materials selected for ultrahigh purity, and serious consideration should be given in selecting the particular set of elements from which the collection apparatus is composed so as not to compromise useful information.

Flynn, George J.