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Nitrogen geochemistry of a Cretaceous-Tertiary boundary site in New Zealand

Nitrogen in the basal layer of the K-T boundary clay at Woodside Creek, New Zealand, has an abundance of 1100 ppm, a 20-fold enrichment over Cretaceous and Tertiary values. The enrichment parallels that for Ir and elemental carbon (soot); all decrease over the next 6 mm of the boundary clay. The C/N ratio, assuming the nitrogen to be associated with organic rather than elemental carbon, is approximately 5 for the basal layer compared to 20 to 30 for the remainder of the boundary clay. The correlation between N and Ir abundances appears to persist above the boundary, implying that the N is intimately associated with the primary fallout and remained with it during the secondary redeposition processes that kept the Ir abundance relatively high into the lowermost Tertiary. Apparently the basal layer of the boundary clay represents the accumulation of a substantial quantity of N with an isotopic composition approximately 10 percent heavier than background delta value of N-15 values. If the boundary clay represents an altered impact glass from a meteorite impact than it probably denotes a time period of less than 1 year. Therefore, the changes in nitrogen geochemistry apparently occurred over a very short period of time. The high abundance of N and the correspondingly low C/N ratio may reflect enhanced preservation of organic material as a result of the rapid sweepout and burial of plankton by impact ejecta, with little or no bacterial degradation. It is conceivable that the shift in delta value of N-15 may represent an influx of nitrogen from a different source deposited contemporaneously with the impact ejecta. An interesting possibility is that it may be derived from nitrate, produced from the combustion of atmospheric nitrogen.

Gilmour, Iain

Trace element and isotope geochemistry of Cretaceous-Tertiary boundary sediments: identification of extra-terrestrial and volcanic components

Trace element and stable isotope analyses were performed on a series of sediment samples crossing the Cretaceous-Tertiary (K-T) boundary from critical sections at Aumaya and Sopelano, Spain. The aim is to possibly distinguish extraterrestrial vs. volcanic or authigenic concentration of platinum group and other elements in K-T boundary transitional sediments. These sediments also have been shown to contain evidence for step-wise extinction of several groups of marine invertebrates, associated with negative oxygen and carbon isotope excursions occurring during the last million years of the Cretaceous. These isotope excursions have been interpreted to indicate major changes in ocean thermal regime, circulation, and ecosystems that may be related to multiple events during latest Cretaceous time. Results to date on the petrographic and geochemical analyses of the Late Cretaceous and Early Paleocene sediments indicate that diagenesis has obviously affected the trace element geochemistry and stable isotope compositions at Zumaya. Mineralogical and geochemical analysis of K-T boundary sediments at Zumaya suggest that a substantial fraction of anomalous trace elements in the boundary marl are present in specific mineral phases. Platinum and nickel grains perhaps represent the first direct evidence of siderophile-rich minerals at the boundary. The presence of spinels and Ni-rich particles as inclusions in aluminosilicate spherules from Zumaya suggests an original, non-diagenetic origin for the spherules. Similar spherules from southern Spain (Caravaca), show a strong marine authigenic overprint. This research represents a new approach in trying to directly identify the sedimentary mineral components that are responsible for the trace element concentrations associated with the K-T boundary.

Margolis, S. V.

Geochemistry of Precambrian carbonates. IV - Early Paleoproterozoic (2.25 +/- 0.25 Ga) seawater

The mineralogy, chemistry, and isotopic composition of the Malmani Dolomite, Duck Creek Dolomite, and Bruce 'Limestone' Member of the Espanola Formation are studied in an effort to restrict the first- and second-order variations in isotopic composition of Early Paleoproterozoic seawater. The diagenetic rank is found to increase in the order Duck Creek less than Bruce less than Malmani. The interpolation of alteration trends to 'best' value yields an estimate of 0.70550 for Sr-87/Sr-86. For delta C-13, the measured range of 0 +/- 1.5 percent PDB is similar to that observed for Phanerozoic marine carbonates, while the 'best' delta O-18 value for dolostones is -5 percent PDB, depleted in O-18 relative to Phanerozoic counterparts but comparable to estimates obtained for Archean facies. The isotope geochemistry and mineralogy of Bruce 'Limestone' Member is consistent with the proposition that the sequence was deposited in a lacustrine environment.

Veizer, Jan

Geochemistry of lunar crustal rocks from breccia 67016 and the composition of the moon

The geochemistry of anorthositic clasts from an Apollo 16 breccia 67016 is studied in order to investigate the role of these rock types in lunar crustal evolution. The samples have aluminous, alkali-poor compositions and varied FeO and MgO contents. Three compositional groups are recognized. One group is poor in mafic constituents with low abundances of lithophile trace elements typical of lunar anorthosites, while the other two groups are more mafic and are distinguished from each other by FeO/MgO ratios greater than one in the case of ferroan noritic and less than one in the case of magnesian troctolitic. These mafic-enriched varieties have considerably higher lithophile element concentrations, at levels similar to that of the bulk lunar crust. The ferroan noritic clasts may represent a fundamental type of igneous rock in the lunar crust which has not been widely recognized.

Norman, Marc D.

Application of fuzzy set and Dempster-Shafer theory to organic geochemistry interpretation

An application of fuzzy sets and Dempster Shafter Theory (DST) in modeling the interpretational process of organic geochemistry data for predicting the level of maturities of oil and source rock samples is presented. This was accomplished by (1) representing linguistic imprecision and imprecision associated with experience by a fuzzy set theory, (2) capturing the probabilistic nature of imperfect evidences by a DST, and (3) combining multiple evidences by utilizing John Yen's generalized Dempster-Shafter Theory (GDST), which allows DST to deal with fuzzy information. The current prototype provides collective beliefs on the predicted levels of maturity by combining multiple evidences through GDST's rule of combination.

Kim, C. S.

Geochemistry and petrology of primitive achondrite meteorites LEW 88280, MAC 88177, ALHA 81187, EET 84302, and LEW 88663

Primitive achondrites are meteorites that have mineral and bulk chemical compositions similar to the most primitive meteorites (chondrites) but have textures similar to more evolved meteorites (achondrites). The unique geochemistry and texture of the primitive achondrites suggest these meteorites may be genetic intermediates between chondrites and achondrites and may preserve evidence of processes occurring in the early solar system. Five primitive achondrites LEW 88280, MAC 88177, ALHA 81187, EET 84302, and LEW 88663 were examined in this study in order to classify the meteorites and to determine processes that have affected them. Bulk chemical analyses of Nap, K2O, CaO, FeO, Cr, Co, Ni, Sc, Ir, Au, As, Sb, Se, Br, Cs, Ba, La, Ce, Nd, Sm, Eu, Tb, Yb, and Lu were determined for each meteorite by Instrumental Neutron Activation Analysis (INAA). Concentrations of Hf, U, and Th were determined for some meteorites. Polished thin sections of the five meteorites were examined in transmitted and reflected light microscopy to identify minerals and examine petrographic relationships. Minerals found in the meteorites include olivine, orthopyroxene, clinopyroxene, plagioclase, Cr-spinel, phosphates, troilite, kamecite, and taenite along with other minor phases. Mineral compositions were determined with an electron microprobe. The initial study suggests that the meteorites have been altered by metamorphic processes although igneous processes may also have played a role in the evolution of these rocks. Further studies of isotope and bulk chemistry are planned for these meteorites.

Field, Stephen W.

Euromet Ureilite Consortium: A preliminary report on carbon and nitrogen geochemistry

The first Euromet expedition to the Frontier Mountain in Antarctica in December 1990 recovered two ureilites, FRO 90036 (34.6g) and FRO 90054 (17.5g). Preliminary classification indicated that the specimens had very different textures and mineral chemistries, and hence were not paired. A third ureilite, Acfer 277 (41.0 g), has also recently been returned from the Sahara. Due to the small sample sizes of the meteorites, and the unusual mineralogy of FRO 90054, a consortium was established to ensure the most effective study of these samples; this abstract reports on the carbon and nitrogen stable isotope geochemistry of two of the three ureilites issued to the consortium.

Grady, Monica M.

Discovery Venera surface: Atmosphere geochemistry experiments mission concept

The phenomenal increase in our understanding of Venus provided by the Magellan Mission has raised a series of focused, fundamental scientific questions about the geochemistry of the surface of Venus, the nature of the lower atmosphere, and the relationship of the lower atmosphere and surface. First, surface geochemical measurements from the Venera/Vega spacecraft showed that widely spaced regions of the venusian plains are made of basalts; thus basalts are significant and may be the only component of the venusian crust. But we lack information on the composition of several key elements of Venus geology: (1) Tessera terrain (which may be outcrops of continental-like non-basaltic crustal material) and steep-sided domes/festoons are promising candidates for non-basaltic geochemically evolved material. The composition of the lower part of the Venusian crust is unknown: however, ejecta from large venusian craters provides us with the possibility of sampling this material on the surface; (2) bulk chemistry (structure and dynamics) of the venusian atmosphere are known. The altitude profiles of water vapor content and minor admixtures relevant to redox conditions in the lower atmosphere (less than 20 km altitude) remain uncertain. Lack of that knowledge means that we do not understand the fine chemical structure of the main mass of the Venusian atmosphere; and (3) thermodynamic models predict that igneous materials on the surface of Venus should react with gases of the venusian atmosphere. But because the water vapor content and redox conditions in the lower atmosphere are not well known, we do not understand the nature of venusian weathering: oxidation, sulfatization, carbonatization, and hydration. The answers to these questions are critical to the understanding of Venus, the most Earth-like of the terrestrial planets.

Surkov, Yuri A.

Volatile transport on Venus and implications for surface geochemistry and geology

The high vapor pressure of volatile metal halides and chalcogenides (e.g., of Cu, Zn, Sn, Pb, As, Sb, Bi) at typical Venus surface temperatures, coupled with the altitude-dependent temperature gradient of approximately 8.5 K/km, is calculated to transport volatile metal vapors to the highlands of Venus, where condensation and accumulation will occur. The predicted geochemistry of volatile metals on Venus is supported by observations of CuCl in volcanic gases at Kilauea and Nyiragongo, and large enrichments of these and other volatile elements in terrestrial volcanic aerosols. A one-dimensional finite difference vapor transport model shows the diffusive migration of a thickness of 0.01 to greater than 10 microns/yr of moderately to highly volatile phases (e.g., metal halides and chalcogenides) from the hot lowlands (740 K) to the cold highlands (660 K) on Venus. The diffusive transport of volatile phases on Venus may explain the observed low emissivity of the Venusian highlands, hazes at 6-km altitude observed by two Pioneer Venus entry probes, and the Pioneer Venus entry probe anomalies at 12.5 km.

Brackett, Robert A.

Petrology and Geochemistry of a Mg- and Al-Rich Orthopyroxenite Xenolith in the EETA79001 Shergottite: Implications for Mars Crustal Evolution

EETA79001 is a Mars meteorite (SNC) consisting of multiple rock types, including two basalt types, olivine and pyroxene xenocrysts, and ultramafic xenoliths. This study is focused on the petrology and geochemistry of one orthopyroxenite xenolith in PTS 68, designated X-1. It consists of chemically homogeneous orthopyroxene cores with exceptionally high Mg/Fe (mg#=85) and Al. Cores are permeated by minute high-Si+Al glassy inclusions, some with augite microlites. Magnesian core areas are mantled by more Fe-rich orthopyroxene rims grading to pigeonite away from cores. The xenolith is transected by cross-cutting shear planes, some of pre-incorporation origin. Major and minor element composition and variation suggest that core areas are primarily igneous, crystallized from a high temperature mafic melt. However, nearly constant mg# across cores suggest metamorphic equilibration. Si+Al inclusions may result from, among other processes, exsolution of feldspathic material during subsolidus cooling, or may be solid materials (alkali feldspar) poikilitically enclosed by growing igneous orthopyroxene crystals. Late reaction with more fractionated melts produced Fe-rich mantles, the whole assemblage later cut by tectonic micro-shear planes. Raw electron microprobe data produced during this study are available on request from the author.

Berkley, John L.

MESSENGER, MErcury: Surface, Space ENvironment, GEochemistry, and Ranging; A Mission to Orbit and Explore the Planet Mercury

MESSENGER is a scientific mission to Mercury. Understanding this extraordinary planet and the forces that have shaped it is fundamental to understanding the processes that have governed the formation, evolution, and dynamics of the terrestrial planets. MESSENGER is a MErcury Surface, Space ENvironment, GEochemistry and Ranging mission to orbit Mercury for one Earth year after completing two flybys of that planet following two flybys of Venus. The necessary flybys return significant new data early in the mission, while the orbital phase, guided by the flyby data, enables a focused scientific investigation of this least-studied terrestrial planet. Answers to key questions about Mercury's high density, crustal composition and structure, volcanic history, core structure, magnetic field generation, polar deposits, exosphere, overall volatile inventory, and magnetosphere are provided by an optimized set of miniaturized space instruments. Our goal is to gain new insight into the formation and evolution of the solar system, including Earth. By traveling to the inner edge of the solar system and exploring a poorly known world, MESSENGER fulfills this quest.

Source record

The Apollo 16 Mare Component: Petrography, Geochemistry, and Provenance

The A16 (Apollo16) site in the lunar nearside highlands is 220 km from the nearest mare. Thus it is no surprise that mare basalt samples are uncommon at the site. Here, we present the petrography and geochemistry of 5 new mare basalt samples found at the A16 site. We also discuss possible provenances of all A16 mare basalt samples using high-resolution global data for the distribution of Fe and Ti on the lunar surface derived from Clementine UV-VIS data [1-2].

Zeigler, R. A.

Geochemistry of approximately 1.9 Ga sedimentary rocks from northeastern Labrador, Canada

Fifty-eight rock chips from fifteen samples of sedimentary rocks from the Ramah Group (approximately 1.9 Ga) in northeastern Labrador, Canada, were analyzed for major and minor elements, including C and S, to elucidate weathering processes on the Earth's surface about 1.9 Ga ago. The samples come from the Rowsell Harbour, Reddick Bight, and Nullataktok Formations. Two rock series, graywackes-gray shales of the Rowsell Harbour, Reddick Bight and Nullataktok Formations, and black shales of the Nullataktok Formation, are distinguishable on the basis of lithology, mineralogy, and major and trace element chemistry. The black shales show lower concentrations than the graywackes-gray shales in TiO2 (0.3-0.7 wt% vs. 0.7-1.8 wt%), Al2O3 (9.5-20.1 wt% vs. 13.0-25.0 wt%), and sigma Fe (<1 wt% vs. 3.8-13.9 wt% as FeO). Contents of Zr, Th, U, Nb, Ce, Y, Rb, Y, Co, and Ni are also lower in the black shales. The source rocks for the Ramah Group sediments were probably Archean gneisses with compositions similar to those in Labrador and western Greenland. The major element chemistry of source rocks for the Ramah Group sedimentary rocks was estimated from the Al2O3/TiO2 ratios of the sedimentary rocks and the relationship between the major element contents (e.g., SiO2 wt%) and Al2O3/TiO2 ratios of the Archean gneisses. This approach is justified, because the Al/Ti ratios of shales generally retain their source rock values; however, the Zr/Al, Zr/Ti, and Cr/Ni ratios fractionate during the transport of sediments. The measured SiO2 contents of shales in the Ramah Group are generally higher than the estimated SiO2 contents of source rocks by approximately 5 wt%. This correction may also have to be applied when estimating average crustal compositions from shales. Two provenances were recognized for the Ramah Group sediments. Provenance I was comprised mostly of rocks of bimodal compositions, one with SiO2 contents approximately 45 wt% and the other approximately 65 wt%, and was the source for most sedimentary rocks of the Ramah Group, except for black shales of the Nullataktok Formation. The black shales were apparently derived from Provenance II that was comprised mostly of felsic rocks with SiO2 contents approximately 65 wt%. Comparing the compositions of the Ramah Group sedimentary rocks and their source rocks, we have recognized that several major elements, especially Ca and Mg, were lost almost entirely from the source rocks during weathering and sedimentation. Sodium and potassium were also leached almost entirely during the weathering of the source rocks. However, significant amounts of Na were added to the black shales and K to all the rock types during diagenesis and/or regional metamorphism. The intensity of weathering of source rocks for the Ramah Group sediments was much higher than that of typical Phanerozoic sediments, possibly because of a higher PCO2 in the Proterozoic atmosphere. Compared to the source rock values, the Fe3+/Ti ratios of many of the graywackes and gray shales of the Ramah Group are higher, the Fe2+/Ti ratios are lower, and the sigma Fe/Ti ratios are the same. Such characteristics of the Fe geochemistry indicate that these sedimentary rocks are comprised of soils formed by weathering of source rocks under an oxygen-rich atmosphere. The atmosphere about 1.9 Ga was, therefore, oxygen rich. Typical black shales of Phanerozoic age exhibit positive correlations between the organic C contents and the concentrations of S, U, and Mo, because these elements are enriched in oxygenated seawater and are removed from seawater by organic matter in sediments. However, such correlations are not found in the Ramah Group sediments. Black shales of the Ramah Group contain 1.7-2.8 wt% organic C, but are extremely depleted in sigma Fe (<1 wt% as FeO), S (<0.3 wt%), U (approximately l ppm), Mo (<5 ppm), Ni (<2 ppm), and Co (approximately 0 ppm). This lack of correlation, however, does not imply that the approximately 1.9 Ga atmosphere-ocean system was anoxic. Depletion of these elements from the Ramah Group sediments may have occurred during diagenesis.

Non-NASA Center

The combined application of organic sulphur and isotope geochemistry to assess multiple sources of palaeobiochemicals with identical carbon skeletons

Five immature sediments from a Messinian evaporitic basin, representing one evaporitic cycle, were studied using molecular organic sulphur and isotope geochemistry. It is shown that a specific carbon skeleton which is present in different "modes of occurrence" ("free" hydrocarbon, alkylthiophene, alkylthiolane, alkyldithiane, alkylthiane, and sulphur-bound in macromolecules) may have different biosynthetic precursors which are possibly derived from different biota. It is demonstrated that the mode of occurrence and the carbon isotopic composition of a sedimentary lipid can be used to "reconstruct" its biochemical precursor. This novel approach of recognition of the suite of palaeobiochemicals present during the time of deposition allows for identification of the biological sources with an unprecedented specificity.

Non-NASA Center

Petrology, Geochemistry and Genesis of Ureilites

Ureilites are enigmatic achondrites that have some characteristics resulting from high temperature igneous processing, yet retain other characteristics inherited from the solar nebula. They are basalt-depleted ultramafic rocks containing 7-66 mg/g elemental C. They are rich in noble gases and display a correlation between mg# and Delta (17)O. This mishmash of properties has engendered various models for ureilite genesis, from those in which nebular processes dominate to those in which parent body igneous processes dominate. Characterization of new ureilites, especially of new subtypes, is an important part of attempts to unravel the history of the ureilite parent body or bodies. Here we report on the petrology and geochemistry of a suite of ureilites, mostly from Antarctica, and use these data to discuss ureilite petrogenesis. Additional information is included in the original extended abstract.

Mittlefehldt, D. W.

Applicability of Electrical and Electroanalytical Techniques to Detect Water and Characterize the Geochemistry of Undisturbed Planetary Soils

The search for life is a primary goal of NASA s planetary exploration program. The search is, of necessity, tiered in both the detection approach (looking for evidence of microbial fossils or the presence of water in the geological history of a planetary body and/or looking for evidence of water, energy sources, precursors to life, signatures of life and/or life itself in the present day planetary environment) and in the survey method (scale, range, specificity) employed. Terrestrial investigations suggests that life as we know it requires water. Thus, the search for extant microbial life and habitats requires identifying water-bearing soils. Determining Reduction-Oxidation (REDOX) couples present in water, once it is found, provides information on soil geochemistry and identifies potential chemical energy sources for life. Mars offers a near-term target for conducting this search. The identification of gully formation [1], layered deposits [2] and elemental ratios of bromine and chlorine [3] present indirect evidence that water was abundant locally in the Martian past. Additionally, Viking images of polar ice and frost formation on the surface of Mars demonstrate that water can exist in at least some near-surface regions of present-day Mars. Atmospheric pressure data further suggest that liquid water may be stable for short periods of time in the mid-latitudes of the Martian surface. [4] Measurements of the global distribution of hydrogen in the Martian regolith offer tantalizing indirect evidence that water may at least exist in near-surface soils. [5] Evidently, any water to be found is likely to exist as soil mixtures at levels ranging between approx.0.5% and approx.5 %.

Seshadri, S.