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Balloon-borne winch system; stratospheric free radicals; stratospheric sounding; copper vapor lasers; ozone measurement; NO2 analysis; chlorine chemistry; trace elements; and ClO observations are discussed.
The distributions of Ga, In, Sn, and Te between copper-iron mattes and silica-saturated iron silicate slags over a wide range of matte grades 55 to 75 pct Cu were determined at 1300 °C using a gas-phase equilibration-quenching technique and direct phase composition analysis by Electron Probe X-ray Microanalysis and Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry. Alumina from aluminum, a typical minor element of electric and electronic copper scrap, and lime were adopted as slag modifiers for increasing the trace element recoveries. Gallium and tin were distributed predominantly in the slag, indium preferred sulfide matte at low matte grades and slag at high, whereas tellurium strongly favored the sulfide matte in particular in high matte grades. The slag modifiers alumina and lime had a minor impact on the distribution coefficients of gallium and tin, but for indium and tellurium the distribution coefficients were more strongly affected by the basic oxides. The strong tendencies of tin and tellurium to vaporize at the experimental temperature were confirmed.
Analyses of mineral REE and selected minor and trace elements were carried out on individual grains of pyroxenes, whitlockite, maskelynite, and olivine of the Antarctic shergottite ALHA77005, and the results are used to interpret its parent magma and crystallization history. The results of mineral compositions and textural observations suggest that ALHA77005 is a cumulate with about half cumulus material (olivine + chromite) and half postcumulus phases. Most of the REEs in ALHA77005 reside in whitlockite whose modal concentration is about 1 percent. Mineral REE data support previous suggestions that plagioclase and whitlockite crystallized late, and that low-Ca pyroxene initiated crystallization before high-Ca pyroxene. The REE patterns for the intercumulus liquid, calculated from distribution coefficients for ALHA77005 pyroxene, plagioclase, and whitlockite, are in very good agreement and are similar to that of Shergotty.
Major and minor element abundances in pyroxene, principally pigeonite, from Zagami meteorite samples were determined by electron microprobe; abundances of trace elements Ni, Cu, Zn, and Ga were obtained by synchrotron X-ray (SXRF) microprobe. Abundances of Ni and Cr in the magnesian zones and cores are partially decoupled from abundances of other compatible (Mg) and incompatible (Fe,Ti) elements. The textures, chemical zoning, and element decouplings in the pigeonites are consistent with igneous crystal growth at moderate cooling rates, not isothermally or near equilibrium. From element partitioning and mass balance, Zagami is estimated to contain 20 +/- 5 percent or less cumulus pyroxene (half augite and half pigeonite), half the proportion suggested by equilibrium distribution of Fe/Mg between pigeonite and melt. This inconsistency may be resolved if all pigeonite/melt element partitioning was affected by the rapid growth of the pigeonites. The inference that the pyroxene zoning patterns reflect only magmatic events is consistent with an igneous age of 180 m.y. for Zagami.
Apollo 12 lunar soils and igneous rocks from Ocean of Storms, determining major, minor and trace element composition with chemical, X ray fluorescence and spectrographic techniques
Phase equilibrium experiments on the most magnesian Apollo 15C green picritic glass composition indicate a multiple saturation point with olivine and orthopyroxene at 1520 C and 1.3 GPa (about 260 km depth in the moon). This composition has the highest Mg# of any lunar picritic glass and the shallowest multiple saturation point. Experiments on an Apollo 15A composition indicate a multiple saturation point with olivine and orthopyroxene at 1520 C and 2.2 GPa (about 440 km depth in the moon). The importance of the distinctive compositional trends of the Apollo 15 groups A, B, and C picritic glasses merits the reanalysis of NASA slide 15426,72 with modern electron microprobe techniques. We confirm the compositional trends reported by Delano (1979, 1986) in the major element oxides SiO2, TiO2, Al2O3, Cr2O3, FeO, MnO, MgO, and CaO, and we also obtained data for the trace elements P2O5, K2O, Na2O, NiO, S, Cu, Cl, Zn, and F. Petrogenetic modeling demonstrates that the Apollo 15 A-B-C glass trends could not have been formed by fractional crystallization or any continuous assimilation/fractional crystallization (AFC) process. The B and C glass compositional trends could not have been formed by batch or incremental melting of an olivine + orthopyroxene source or any other homogeneous source, though the A glasses may have been formed by congruent melting over a small pressure range at depth. The B compositional trend is well modeled by starting with an intermediate A composition and assimilating a shallower, melted cumulate, and the C compositional trend is well modeled by a second assimilation event. The assimilation process envisioned is one in which heat and mass transfer were separated in space and time. In an initial intrusive event, a picritic magma crystallized and provided heat to melt magma ocean cumulates. In a later replenishment event, the picritic magma incrementally mixed with the melted cumulate (creating the compositional trends in the green glass data set), ascended to the lunar surface, and erupted as a fire fountain. A barometer created from multiple saturation points provides a depth estimate of other glasses in the A-B-C trend and of the depths of assimilation. This barometer demonstrates that the Apollo 15 A-B-C trend originated over a depth range of approx.460 km to approx.260 km within the moon.
The Mars rover Curiosity has encountered silica-enriched bedrock (as strata and as veins and associated halos of alteration) in the largely basaltic Murray Fm. of Mt. Sharp in Gale Crater. Alpha Particle X-ray Spectrometer (APXS) investigations of the Murray Fm. revealed decreasing Mg, Ca, Mn, Fe, and Al, and higher S, as silica increased (Fig. 1). A positive correlation between SiO2 and TiO2 (up to 74.4 and 1.7 wt %, respectively) suggests that these two insoluble elements were retained while acidic fluids leached more soluble elements. Other evidence also supports a silica-retaining, acidic alteration model for the Murray Fm., including low trace element abundances consistent with leaching, and the presence of opaline silica and jarosite determined by CheMin. Phosphate stability is a key component of this model because PO4 3- is typically soluble in acidic water and is likely a mobile ion in diagenetic fluids (pH less than 5). However, the Murray rocks are not leached of P; they have variable P2O5 (Fig. 1) ranging from average Mars (0.9 wt%) up to the highest values in Gale Crater (2.5 wt%). Here we evaluate APXS measurements of Murray Fm. bedrock and veins with respect to phosphate stability in acidic fluids as a test of the acidic alteration model for the Lower Mt. Sharp rocks.
Soils regulate the environmental impacts of trace elements, but direct measurements of reaction mechanisms in these complex, multi-component systems can be challenging. The objective of this work was to develop approaches for assessing effects of co-localized geochemical matrix elements on the accumulation and chemical speciation of arsenate applied to a soil matrix. Synchrotron X-ray fluorescence microprobe (µ-XRF) images collected across 100 µm × 100 µm and 10 µm × 10 µm regions of a naturally weathered soil sand-grain coating before and after treatment with As(V) solution showed strong positive partial correlations ( r ' = 0.77 and 0.64, respectively) between accumulated As and soil Fe, with weaker partial correlations ( r ' > 0.1) between As and Ca, and As and Zn in the larger image. Spatial and non-spatial regression models revealed a dominant contribution of Fe and minor contributions of Ca and Ti in predicting accumulated As, depending on the size of the sample area analyzed. Time-of-flight secondary ion mass spectrometry analysis of an area of the sand grain showed a significant correlation ( r = 0.51) between Fe and Al, so effects of Fe versus Al (hydr)oxides on accumulated As could not be separated. Fitting results from 25 As K -edge microscale X-ray absorption near-edge structure (µ-XANES) spectra collected across a separate 10 µm × 10 µm region showed ~60% variation in proportions of Fe(III) and Al(III)-bound As(V) standards, and fits to µ-XANES spectra collected across the 100 µm × 100 µm region were more variable. We find that, consistent with insights from studies on model systems, the results obtained here indicate a dominance of Fe and possibly Al (hydr)oxides in controlling As(V) accumulation within microsites of the soil matrix analyzed, but the analyses inferred minor augmentation from co-localized Ti, Ca and possibly Zn.
Samples of anorthosite from Stillwater complex units AN-I and AN-II have been studied by instrumental neutron activation analysis for FeO, CaO, Na2O, REE, and other trace elements, and the results are discussed. No systematic variations of chemical composition with stratigraphic position were observed. The major and trace compositions of both units appear to be identical, with plagioclase compositions virtually constant throughout both. Thus, there is almost no evidence for evolution of parent magma composition during the genesis of these units. The bulk of the anorthosites appear to consist of cumulus-adcumulus plagioclase and pyroxene. Very little trapped liquid component was found. The chemical elements are not normally or lognormally distributed among samples taken from either anorthosite unit. The irregular distribution of pyroxene oikocrysts indicates that interstitial melt migrated substantially prior to final consolidation of the rock.
A two-parameter modeling formula is proposed for quadrupole ICP-MS (ICP-QMS) data, which corrects for nonlinearity with a “dead-time” function and makes subsequent weighted mass-bias corrections to normalize isotope ratio data to pertinent isotopic reference materials. The methodology improves the short-term and long-term precision as well as accuracy of the measurements. Applying the model to isotopes spanning a wide mass range revealed that values for the parameters describing nonlinearity and mass bias do not conform to expectations based on conventional interpretation. Within a single analysis run for a specific element, nonlinearity and mass-bias corrections can be evaluated to very tight tolerances and the model fits the data to within a few parts per thousand. However, in a different run or with a different element, the values of the parameters might change. A comprehensive strategy for conducting measurements of isotope ratios or trace-element concentrations is described, which takes advantage of the model’s strengths and accommodates the observed run-to-run variations. in conclusion, supporting data is presented to demonstrate improved precision and accuracy with the widely available ICP-QMS system.
The ionome represents elemental composition in plant tissues and can be an indicator of nutrient status as well as overall plant performance. Thus, identifying genetic determinants governing elemental uptake and storage is an important goal for breeding and engineering biomass feedstocks with improved performance. In this study, we coupled high-throughput ionome characterization of leaf tissues with high-resolution genome-wide association studies (GWAS) to uncover genetic loci that modulate ionomic composition in leaves of poplar ( Populus trichocarpa ). Significant agreement was observed across the three ionomic profiling platforms tested: inductively coupled plasma-mass spectrometry (ICP-MS), neutron activation analysis (NAA) and laser-induced breakdown spectroscopy (LIBS). Relative quantification of 20 elements using ICP-MS across a population of 584 genotypes, revealed larger variation in micro-nutrients and trace elements content than for macro-nutrients across genotypes. The GWAS performed using a set of high-density (>8.2 million) single nucleotide polymorphisms, identified over 600 loci significantly associated with variations in these mineral elements, pointing to numerous uncharacterized candidate genes. A significant enrichment for genes related to ion homeostasis and transport was observed, including several members of the cation-proton antiporters (CPA) family and MATE efflux transporters, previously reported to be critical for plant growth and fitness in other species. Our results also included a polymorphic copy of the high-affinity molybdenum transporter MOT1 found directly associated to molybdenum content. For the first time in a perennial plant, our results provide evidence of genetic control of mineral content in a model tree species.
Data are presented on ion microprobe measurements of REE and selected trace element abundances in individual grains of merrillite, fassaite, olivine, kirschsteinite, and plagioclase of Lewis Cliff 86010 (LEW 86010) meteorite and in merrillite and fassaite grains of Angra dos Reis (ADOR). Results show a close relationship between the two meteorites and support a magmatic origin for LEW 86010. However, the measurements indicate that, despite numerous common characteristics, the two meteorites must have been produced in separate magmatic events involving similar but distinct processes and parent melts.
There remains a lack of knowledge regarding ecosystem transfer, transport processes, and mechanisms, which influence the long-term mobility of Pu-239 and Cs-137 in natural environments. Monitoring the distribution and migration of trace radioisotopes as ecosystem tracers has the potential to provide insight into the underlying mechanisms of geochemical cycles. This study investigated the distribution of anthropogenic radionuclides Pu-239 and Cs-137 along with total organic carbon, iron, and trace element in contaminated sediments of Pond B at the Savannah River Site (SRS). Pond B received reactor cooling water from 1961 to 1964, and trace amounts of Pu-239 and Cs-137 during operations. Our study collected sediment cores to determine concentrations of Pu-239, Cs-137, and major and minor elements in solid phase, pore water and an electrochemical method was used on wet cores to determine dissolved elemental concentrations. More than 50 years after deposition, Pu-239 and Cs-137 in sediments are primarily located in the upper 5 cm in area where deposition of particulate-bound contaminants was prevalent and located between 5 and 10 cm in areas of high sedimentation, showing a limited migration of Pu-239 and Cs-137. A Factor analysis demonstrated different sediment facies across the pond resulting in a range of geochemical processes controlling accumulation of Pu and Cs. Highest concentrations appear to be controlled by particulate input from the influent canal, dominated by clay, silt, and sand minerals bearing Fe. Elevated Pu-239 in the sediments were observed in areas with high organic matter and higher deposition rate relative to the Pond B system near the outlet indicating strong association of Pu with OM and particulates. Therefore, organic matter cycling likely plays a role in Pu redistribution between sediment and overlying pond water, and deposition in organic rich sediments accumulating near the outlet. Though Pu appears to have been distributed throughout the pond, Cs-137 concentrations remained the highest near the influent canal.
Nakhlites are olivine-bearing clinopyroxene cumulates. Based on petrographic characteristics, they may be divided into groups that cooled at different rates and may have been formed at different depths in a single flow. The order of cooling rate from slowest to fastest is NWA998<Lafayette < Governador Valadares approx. Nakhla < Yamato000593 < NWA817 approx. MIL03346. Nakhlite cumulus pyroxene grains consist of large cores that are nearly homogeneous in major element composition surrounded by thin rims that are zoned to Fe-rich compositions. Detailed study of these pyroxenes is important because they retain a record of the crystallization history of the nakhlite magma. Moreover, because the composition of the nakhlite parent melt cannot be directly determined, inversion of the major and minor element composition of the cumulate pyroxene cores can be used to estimate the composition of that melt. Moreover, minor and trace element zoning of pyroxenes can provide information about the oxidation conditions under which these samples crystallized. Thus it is important to understand the major and minor element zoning in the cumulus pyroxenes. While major elements are nearly homogeneous, minor elements exhibit distinctive zoning patterns that vary from one nakhlite to another. This abstract reports unusual Cr zoning patterns in pyroxenes from MIL03346 (MIL) and contrast these with pyroxenes from Y593 and Nakhla.
The howardite meteorites consist of approximately 200 polymict breccias of eucrite (basaltic) and diogenite (orthopyroxenitic) material (collectively, the HED group) that originate from the asteroid belt. Infrared reflectance spectroscopy of asteroids and laboratory studies of HEDs have indicated that the asteroid 4-Vesta is the likely parent body, and the partially-demolished south pole may be the source region. Asteroid regolith formation processes may be responsible for a number of observed petrological features including impact melt clasts, reworked clasts and mosaisicm. We have identified such features in a study of 30 howardites and polymict eucrites, and developed a regolith grading scheme based on petrology. However, the true regolithic nature of the howardite suite is not well defined, and previous research has suggested correlations between Ni contents of 300 - 1200 micron / g, a minimal variation in Al2O3 content around 8-9 wt% and the presence of solar wind noble gases are key hallmarks of an ancient regolith on Vesta . Through combined petrological, compositional and noble gas research, we aim to better understand howardite petrological diversity, regolith formation processes on parent asteroids, and to establish what defines a truly "regolithic" howardite. Our research will play an integral part in the interpretation of data gathered by the Dawn mission. Here we report the preliminary results from our noble gas analyses of four howardites: LEW 85313, EET 99408, MET 96500 and PCA 02066. Bulk major element compositional data have been collected, further petrological data for the HED group are reported by our colleagues, whilst trace-element analyses are underway. Our work will investigate the extent of whether previously described Ni, Al2O3 and noble gas characteristics are in fact indicative of a "regolithic" howardite.
Coccolithophores produce vast quantities of stable calcium carbonate coccoliths, occupying the distinctive position as one of the most productive calcifying organisms on Earth. Gephyrocapsa huxleyi, the most abundant species of coccolithophores across modern oceans, plays an important role in the biological carbon pump and may serve as inspiration for nature-based carbon capture and sequestration technologies. Despite intensive study into G. huxleyi, the biological mechanisms of coccolith synthesis remain unclear. Here, we employ synchrotron X-ray fluorescence to quantitatively map elemental incorporation (calcium, Ca; strontium, Sr; sulfur, S; iron, Fe; and silicon, Si) into G. huxleyi coccoliths at 40-nanometer resolution. Trace elements play a role in determining the thermodynamic stability of coccolith carbonate sequestration and may provide insight into unknown mechanisms of coccolithogenesis. Although the coccolith Sr/Ca ratio has been widely applied as a paleoceanographic proxy, understanding of the Sr/Ca phenomena is limited. Our results confirm that Sr/Ca is temperature dependent but challenge the hypothesis that growth rate is a primary determinant. We find that increased light irradiance led to an ~30% decrease in calcium incorporated into the coccoliths. Surprisingly, X-ray fluorescence spectra and mapping revealed evidence of sulfur, at approximately three times the concentration of Sr, embedded in and around the calcite matrix, suggesting that G. huxleyi coccoliths may play an expanded role in the global sulfur cycle. Here, based on our elemental maps, we postulate that sulfur is active in the intracellular coccolith vesicle and plays a direct role in formation of G. huxleyi coccoliths.
The reported investigation is concerned with the resolution of a number of questions related to the ancient meteoritic component in Apollo 17 boulders. Numerical taxonomic methods have been adopted to objectively group the components. Only the nonvolatile siderophile elements have been used for the classification. Efforts were made to obtain data on the metal composition of breccias analyzed for trace elements, to determine if metal homogeneity was reflected in siderophile ratios. Thirty-one samples were analyzed of which twenty-eight have significant siderophile contents. It is concluded that highland breccias are largely the product of large basin-forming impacts. Highland soils are then produced by comminution of the breccias by small local impacts and micrometeorite bombardment. The long-lived component of bulk soils considered by Baedecker et al. (1974) is thought to contain a substantial micrometeorite contribution, plus assorted debris.
A 6 mm-diameter dark spherule, 15434,28, from the regolith on the Apennine Front at the Apollo 15 landing site has a homogeneous glass interior with a 200 microns-thick rind of devitrified or crystallized melt. The rind contains abundant small fragments of Apollo 15 olivine-normative mare basalt and rare volcanic Apollo 15 green glass. The glass interior of the spherule has the chemical composition, including a high FeO content and high CaO/Al2O3, of a mare basalt. Whereas the major element and Sc, Ni, and Co abundances are similar to those of low-Ti mare basalts, the incompatible elements and Sr abundances are similar to those of high-Ti mare basaits. The relative abundance patterns of the incompatible trace elements are distinct from any other lunar mare basalts or KREEP; among these distinctions are a much steeper slope of the heavy rare earth elements. The 15434,28 glass has abundances of the volatile element Zn consistent with both impact glasses and crystalline mare basalts, but much lower than in glasses of mare volcanic origin. The glass contains siderophile elements such as Ir in abundances only slightly higher than accepted lunar indigenous levels, and some, such as Au, are just below such upper limits. The age of the glass, determined by the Ar-40/Ar-39 laser incremental heating technique, is 1647 +/- 11 Ma (2 sigma); it is expressed as an age spectrum of seventeen steps over 96% of the Ar-38 released, unusual for an impact glass. Trapped argon is negligible. The undamaged nature of the sphere demonstrates that it must have spent most of its life buried in regolith; Ar-38 cosmic ray exposure data suggest that it was buried at less than 2m but more than a few centimeters if a single depth is appropriate. That the spherule solidified to a glass is surprising; for such a mare composition, cooling at about 50 C/s is required to avoid crystallization, and barely attainable in such a large spherule. The low volatile abundances, slightly high siderophile abundances, and the young age are perhaps all most consistent with an impact origin, but nonetheless not absolutely definitive.