The influence of carbon, sulfur, and silicon on trace element partitioning in iron alloys
NASA Astrophysics Data System (ADS)
Han, J.; Van Orman, J. A.; Crispin, K. L.; Ash, R. D.
2014-12-01
Non-metallic light elements are important constituents of planetary cores and have a strong influence on the partitioning behavior of trace elements. Planetary cores may contain a wide range of non-metallic light elements, including H, N, S, P, Si, and C. Under highly reducing conditions, such as those that are thought to have pertained during the formation of Mercury's core, Si and C, in addition to sulfur, may be particularly important constituents. Each of these elements may strongly effect and have a different impact on the partitioning behavior of trace elements but their combined effects on trace element partitioning have not been quantified. We investigated the partitioning behavior of more than 25 siderophile trace elements within the Fe-S-C-Si system with varying concentrations of C, S, and Si. The experiments were performed under pressures varying from 1 atm to 2 GPa and temperatures ranging from 1200˚C to 1450˚C. All experiments produced immiscible liquids, one enriched in Si and C, and the other predominantly FeS. We found some highly siderophile elements including Os, Ru, Ir, and Re are much more enriched in Fe-Si-C phase than in Fe-S phase, whereas other trace elements like V, Co, Ag, Hf, and Pb are enriched in S-rich phase. However, not all the trace elements enriched in Fe-Si-C phase are repelled by sulfur. Elements like Re and Ru could have different partitioning trends if sulfur concentration in S-rich phase rises. The partitioning behavior of these trace elements could enhance our understanding of the differentiation of Mercury's core under oxygen-poor conditions.
Trace element partitioning between ionic crystal and liquid
NASA Technical Reports Server (NTRS)
Tsang, T.; Philpotts, J. A.; Yin, L.
1978-01-01
The partitioning of trace elements between ionic crystals and the melt has been correlated with lattice energy of the host. The solid-liquid partition coefficient has been expressed in terms of the difference in relative ionic radius of the trace element and the homogeneous and heterogeneous strain of the host lattice. Predictions based on this model appear to be in general agreement with data for alkali nitrates and for rare-earth elements in natural garnet phenocrysts.
NASA Astrophysics Data System (ADS)
Prowatke, S.; Klemme, S.
2003-04-01
The aim of this study is to systematically investigate the influence of melt composition on the partitioning of trace elements between titanite and different silicate melts. Titanite was chosen because of its important role as an accessory mineral, particularly with regard to intermediate to silicic alkaline and calc-alkaline magmas [e.g. 1] and of its relative constant mineral composition over a wide range of bulk compositions. Experiments at atmospheric pressure were performed at temperatures between 1150°C and 1050°C. Bulk compositions were chosen to represent a basaltic andesite (SH3 - 53% SiO2), a dacite (SH2 - 65 SiO2) and a rhyolite (SH1 - 71% SiO2). Furthermore, two additional experimental series were conducted to investigate the effect of Al-Na and the Na-K ratio of melts on partitioning. Starting materials consisted of glasses that were doped with 23 trace elements including some selected rare earth elements (La, Ce, Pr, Sm, Gd, Lu), high field strength elements (Zr, Hf, Nb, Ta) and large ion lithophile elements (Cs, Rb, Ba) and Th and U. The experimental run products were analysed for trace elements using secondary ion mass spectrometry at Heidelberg University. Preliminary results indicate a strong effect of melt composition on trace element partition coefficients. Partition coefficients for rare-earth elements uniformly show a convex-upward shape [2, 3], since titanite accommodates the middle rare-earth elements more readily than the light rare-earth elements or the heavy rare-earth elements. Partition coefficients for the rare-earth elements follow a parabolic trend when plotted against ionic radius. The shape of the parabola is very similar for all studied bulk compositions, the position of the parabola, however, is strongly dependent on bulk composition. For example, isothermal rare-earth element partition coefficients (such as La) are incompatible (D<1) in alkali-rich silicate melts and strongly compatible (D>>1) in alkali-poor melt compositions. From our experimental data we present an model that combines the influence of the crystal lattice on partitioning with the effect of melt composition on trace element partition coefficients. [1] Nakada, S. (1991) Am. Mineral. 76: 548-560 [2] Green, T.H. and Pearson, N.J. (1986) Chem. Geol. 55: 105-119 [3] Tiepolo, M.; Oberti, R. and Vannucci, R. (2002) Chem. Geol. 191: 105-119
NASA Technical Reports Server (NTRS)
Colson, R. O.; Mckay, G. A.; Taylor, L. A.
1988-01-01
This paper presents a systematic thermodynamic analysis of the effects of temperature and composition on olivine/melt and low-Ca pyroxene/melt partitioning. Experiments were conducted in several synthetic basalts with a wide range of Fe/Mg, determining partition coefficients for Eu, Ca, Mn, Fe, Ni, Sm, Cd, Y, Yb, Sc, Al, Zr, and Ti and modeling accurately the changes in free energy for trace element exchange between crystal and melt as functions of the trace element size and charge. On the basis of this model, partition coefficients for olivine/melt and low-Ca pyroxene/melt can be predicted for a wide range of elements over a variety of basaltic bulk compositions and temperatures. Moreover, variations in partition coeffeicients during crystallization or melting can be modeled on the basis of changes in temperature and major element chemistry.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Saqib, Naeem, E-mail: naeem.saqib@oru.se; Bäckström, Mattias, E-mail: mattias.backstrom@oru.se
Highlights: • Different solids waste incineration is discussed in grate fired and fluidized bed boilers. • We explained waste composition, temperature and chlorine effects on metal partitioning. • Excessive chlorine content can change oxide to chloride equilibrium partitioning the trace elements in fly ash. • Volatility increases with temperature due to increase in vapor pressure of metals and compounds. • In Fluidized bed boiler, most metals find themselves in fly ash, especially for wood incineration. - Abstract: Trace element partitioning in solid waste (household waste, industrial waste, waste wood chips and waste mixtures) incineration residues was investigated. Samples of flymore » ash and bottom ash were collected from six incineration facilities across Sweden including two grate fired and four fluidized bed incinerators, to have a variation in the input fuel composition (from pure biofuel to mixture of waste) and different temperature boiler conditions. As trace element concentrations in the input waste at the same facilities have already been analyzed, the present study focuses on the concentration of trace elements in the waste fuel, their distribution in the incineration residues with respect to chlorine content of waste and combustion temperature. Results indicate that Zn, Cu and Pb are dominating trace elements in the waste fuel. Highly volatile elements mercury and cadmium are mainly found in fly ash in all cases; 2/3 of lead also end up in fly ash while Zn, As and Sb show a large variation in distribution with most of them residing in the fly ash. Lithophilic elements such as copper and chromium are mainly found in bottom ash from grate fired facilities while partition mostly into fly ash from fluidized bed incinerators, especially for plants fuelled by waste wood or ordinary wood chips. There is no specific correlation between input concentration of an element in the waste fuel and fraction partitioned to fly ash. Temperature and chlorine content have significant effects on partitioning characteristics by increasing the formation and vaporization of highly volatile metal chlorides. Zinc and cadmium concentrations in fly ash increase with the incineration temperature.« less
An in situ approach to study trace element partitioning in the laser heated diamond anvil cell
DOE Office of Scientific and Technical Information (OSTI.GOV)
Petitgirard, S.; Mezouar, M.; Borchert, M.
2012-01-15
Data on partitioning behavior of elements between different phases at in situ conditions are crucial for the understanding of element mobility especially for geochemical studies. Here, we present results of in situ partitioning of trace elements (Zr, Pd, and Ru) between silicate and iron melts, up to 50 GPa and 4200 K, using a modified laser heated diamond anvil cell (DAC). This new experimental set up allows simultaneous collection of x-ray fluorescence (XRF) and x-ray diffraction (XRD) data as a function of time using the high pressure beamline ID27 (ESRF, France). The technique enables the simultaneous detection of sample meltingmore » based to the appearance of diffuse scattering in the XRD pattern, characteristic of the structure factor of liquids, and measurements of elemental partitioning of the sample using XRF, before, during and after laser heating in the DAC. We were able to detect elements concentrations as low as a few ppm level (2-5 ppm) on standard solutions. In situ measurements are complimented by mapping of the chemical partitions of the trace elements after laser heating on the quenched samples to constrain the partitioning data. Our first results indicate a strong partitioning of Pd and Ru into the metallic phase, while Zr remains clearly incompatible with iron. This novel approach extends the pressure and temperature range of partitioning experiments derived from quenched samples from the large volume presses and could bring new insight to the early history of Earth.« less
NASA Technical Reports Server (NTRS)
Irving, A. J.; Frey, F. A.
1984-01-01
Rare earth and other trace element abundances are determined in megacrysts of clinopyroxene, orthopyroxene, amphibole, mica, anorthoclase, apatite and zircon, as well as their host basalts, in an effort to gather data on mineral/melt trace element partitioning during the high pressure petrogenesis of basic rocks. Phase equilibria, major element partitioning and isotopic ratio considerations indicate that while most of the pyroxene and amphibole megacrysts may have been in equilibrium with their host magmas at high pressures, mica, anorthoclase, apatite, and zircon megacrysts are unlikely to have formed in equilibrium with their host basalts. It is instead concluded that they were precipitated from more evolved magmas, and have been mixed into their present hosts.
Trace element partitioning during the retorting of Julia Creek oil shale
DOE Office of Scientific and Technical Information (OSTI.GOV)
Patterson, J.H.; Dale, L.S.; Chapman, J.f.
1987-05-01
A bulk sample of oil shale from the Julia Creek deposit in Queensland was retorted under Fischer assay conditions at temperatures ranging from 250 to 550 /sup 0/C. The distributions of the trace elements detected in the shale oil and retort water were determined at each temperature. Oil distillation commenced at 300 /sup 0/C and was essentially complete at 500 /sup 0/C. A number of trace elements were progressively mobilized with increasing retort temperature up to 450 /sup 0/C. The following trace elements partitioned mainly to the oil: vanadium, arsenic, selenium, iron, nickel, titanium, copper, cobalt, and aluminum. Elements thatmore » also partitioned to the retort waters included arsenic, selenium, chlorine, and bromine. Element mobilization is considered to be caused by the volatilization of organometallic compounds, sulfide minerals, and sodium halides present in the oil shale. The results have important implications for shale oil refining and for the disposal of retort waters. 22 references, 5 tables.« less
Saqib, Naeem; Bäckström, Mattias
2014-12-01
Trace element partitioning in solid waste (household waste, industrial waste, waste wood chips and waste mixtures) incineration residues was investigated. Samples of fly ash and bottom ash were collected from six incineration facilities across Sweden including two grate fired and four fluidized bed incinerators, to have a variation in the input fuel composition (from pure biofuel to mixture of waste) and different temperature boiler conditions. As trace element concentrations in the input waste at the same facilities have already been analyzed, the present study focuses on the concentration of trace elements in the waste fuel, their distribution in the incineration residues with respect to chlorine content of waste and combustion temperature. Results indicate that Zn, Cu and Pb are dominating trace elements in the waste fuel. Highly volatile elements mercury and cadmium are mainly found in fly ash in all cases; 2/3 of lead also end up in fly ash while Zn, As and Sb show a large variation in distribution with most of them residing in the fly ash. Lithophilic elements such as copper and chromium are mainly found in bottom ash from grate fired facilities while partition mostly into fly ash from fluidized bed incinerators, especially for plants fuelled by waste wood or ordinary wood chips. There is no specific correlation between input concentration of an element in the waste fuel and fraction partitioned to fly ash. Temperature and chlorine content have significant effects on partitioning characteristics by increasing the formation and vaporization of highly volatile metal chlorides. Zinc and cadmium concentrations in fly ash increase with the incineration temperature. Copyright © 2014 Elsevier Ltd. All rights reserved.
Two-lattice models of trace element behavior: A response
NASA Astrophysics Data System (ADS)
Ellison, Adam J. G.; Hess, Paul C.
1990-08-01
Two-lattice melt components of Bottinga and Weill (1972), Nielsen and Drake (1979), and Nielsen (1985) are applied to major and trace element partitioning between coexisting immiscible liquids studied by RYERSON and Hess (1978) and Watson (1976). The results show that (1) the set of components most successful in one system is not necessarily portable to another system; (2) solution non-ideality within a sublattice severely limits applicability of two-lattice models; (3) rigorous application of two-lattice melt components may yield effective partition coefficients for major element components with no physical interpretation; and (4) the distinction between network-forming and network-modifying components in the sense of the two-lattice models is not clear cut. The algebraic description of two-lattice models is such that they will most successfully limit the compositional dependence of major and trace element solution behavior when the effective partition coefficient of the component of interest is essentially the same as the bulk partition coefficient of all other components within its sublattice.
Insights into Igneous Geochemistry from Trace Element Partitioning
NASA Technical Reports Server (NTRS)
Jones, J. H.; Hanson, B. Z.
2001-01-01
Partitioning of trivalent elements into olivine are used to explore basic issues relevant to igneous geochemistry, such as Henry's law. Additional information is contained in the original extended abstract.
NASA Astrophysics Data System (ADS)
Bhattacharyya, S.; Donahoe, R. J.; Graham, E. Y.
2006-12-01
For much of the U.S., coal-fired power plants are the most important source of electricity for domestic and industrial use. Large quantities of fly ash and other coal combustion by-products are produced every year, the majority of which is impounded in lagoons and landfills located throughout the country. Many older fly ash disposal facilities are unlined and have been closed for decades. Fly ash often contains high concentrations of toxic trace elements such as arsenic, boron, chromium, molybdenum, nickel, selenium, lead, strontium and vanadium. Trace elements present in coal fly ash are of potential concern due to their toxicity, high mobility in the environment and low drinking water MCL values. Concern about the potential release of these toxic elements into the environment due to leaching of fly ash by acid rain, groundwater or acid mine drainage has prompted the EPA to develop national standards under the subtitle D of the Resource Conservation and Recovery Act (RCRA) to regulate ash disposal in landfills and surface impoundments. An attempt is made to predict the leaching of toxic elements into the environment by studying trace element partitioning in coal fly ash. A seven step sequential chemical extraction procedure (SCEP) modified from Filgueiras et al. (2002) is used to determine the trace element partitioning in seven coal fly ash samples collected directly from electric power plants. Five fly ash samples were derived from Eastern Bituminous coal, one derived from Western Sub-bituminous coal and the other derived from Northern Lignite. The sequential chemical extraction procedure gives valuable information on the association of trace elements: 1) soluble fraction, 2) exchangeable fraction, 3) acid soluble fraction, 4) easily reducible fraction, 5) moderately reducible fraction, 6) poorly reducible fraction and 7) oxidizable organics/sulfide fraction. The trace element partitioning varies with the composition of coal fly ash which is influenced by the type of coal burned. Preliminary studies show that in some fly ash samples, significant amounts of As, B, Mo, Se, Sr and V are associated with the soluble and exchangeable fraction, and thus would be highly mobile in the environment. Lead, on the other hand, is mainly associated with the amorphous Fe and Mn oxide fractions and would be highly immobile in oxidizing conditions, but mobile in reducing conditions. Ni and Cr show different associations in different fly ash samples. In most fly ash samples, significant amounts of the trace elements are associated with more stable fractions that do not threaten the environment. The study of trace element partitioning in coal fly ash thus helps us to predict their leaching behavior under various conditions.
NASA Technical Reports Server (NTRS)
Irving, A. J.; Merrill, R. B.; Singleton, D. E.
1978-01-01
An experimental study was carried out to measure partition coefficients for two rare-earth elements (Sm and Tm) and Sc among armalcolite, ilmenite, olivine and liquid coexisting in a system modeled on high-Ti mare basalt 74275. This 'primitive' sample was chosen for study because its major and trace element chemistry as well as its equilibrium phase relations at atmospheric pressure are known from previous studies. Beta-track analytical techniques were used so that partition coefficients could be measured in an environment whose bulk trace element composition is similar to that of the natural basalt. Partition coefficients for Cr and Mn were determined in the same experiments by microprobe analysis. The only equilibrium partial melting model appears to be one in which ilmenite is initially present in the source region but is consumed by melting before segregation of the high-Ti mare basalt liquid from the residue.
Trace elements as quantitative probes of differentiation processes in planetary interiors
NASA Technical Reports Server (NTRS)
Drake, M. J.
1980-01-01
The characteristic trace element signature that each mineral in the source region imparts on the magma constitutes the conceptual basis for trace element modeling. It is shown that abundances of trace elements in extrusive igneous rocks may be used as petrological and geochemical probes of the source regions of the rocks if differentiation processes, partition coefficients, phase equilibria, and initial concentrations in the source region are known. Although compatible and incompatible trace elements are useful in modeling, the present review focuses primarily on examples involving the rare-earth elements.
NASA Astrophysics Data System (ADS)
van Westrenen, W.; Allan, N. L.; Blundy, J. D.; Purton, J. A.; Wood, B. J.
2000-05-01
We have studied the energetics of trace element incorporation into pure almandine (Alm), grossular (Gros), pyrope (Py) and spessartine (Spes) garnets (X 3Al 2Si 3O 12, with X = Fe, Ca, Mg, Mn respectively), by means of computer simulations of perfect and defective lattices in the static limit. The simulations use a consistent set of interatomic potentials to describe the non-Coulombic interactions between the ions, and take explicit account of lattice relaxation associated with trace element incorporation. The calculated relaxation (strain) energies Urel are compared to those obtained using the Brice (1975) model of lattice relaxation, and the results compared to experimental garnet-melt trace element partitioning data interpreted using the same model. Simulated Urel associated with a wide range of homovalent (Ni, Mg, Co, Fe, Mn, Ca, Eu, Sr, Ba) and charge-compensated heterovalent (Sc, Lu, Yb, Ho, Gd, Eu, Nd, La, Li, Na, K, Rb) substitutions onto the garnet X-sites show a near-parabolic dependence on trace element radius, in agreement with the Brice model. From application of the Brice model we derived apparent X-site Young's moduli EX(1+, 2+, 3+) and the 'ideal' ionic radii r0(1+, 2+, 3+), corresponding to the minima in plots of Urel vs. radius. For both homovalent and heterovalent substitutions r0 increases in the order Py-Alm-Spes-Gros, consistent with crystallographic data on the size of garnet X-sites and with the results of garnet-melt partitioning studies. Each end-member also shows a marked increase in both the apparent EX and r0 with increasing trace element charge ( Zc). The increase in EX is consistent with values obtained by fitting to the Brice model of experimental garnet-melt partitioning data. However, the increase in r0 with increasing Zc is contrary to experimental observation. To estimate the influence of melt on the energetics of trace element incorporation, solution energies ( Usol) were calculated for appropriate exchange reactions between garnet and melt, using binary and other oxides to simulate cation co-ordination environment in the melt. Usol also shows a parabolic dependence on trace element radius, with inter-garnet trends in EX and r0 similar to those found for relaxation energies. However, r0( i+) obtained from minima in plots of Usol vs. radius are located at markedly different positions, especially for heterovalent substitutions ( i = 1, 3). For each end-member garnet, r0 now decreases with increasing Zc, consistent with experiment. Furthermore, although different assumptions for trace element environment in the melt, e.g., REE 3+ (VI) vs. REE 3+ (VIII), lead to parabolae with differing curvatures and minima, relative differences between end-members are always preserved. We conclude that: 1. The simulated variation in r0 and EX between garnets is largely governed by the solid phase. This stresses the overriding influence of crystal local environment on trace element partitioning. 2. Simulations suggest r0 in garnets varies with trace element charge, as experimentally observed. 3. Absolute values of r0 and EX can be influenced by the presence and structure of a coexisting melt. Thus, quantitative relations between r0, E and crystal chemistry should be derived from well-constrained systematic mineral-melt partitioning studies, and cannot be predicted from crystal-structural data alone.
Piper, David Z.; Skorupa, J.P.; Presser, T.S.; Hardy, M.A.; Hamilton, S.J.; Huebner, M.; Gulbrandsen, R.A.
2000-01-01
Major-element oxides and trace elements in the Phosphoria Formation at the Hot Springs Mine, Idaho were determined by a series of techniques. In this report, we examine the distribution of trace elements between the different solid components aluminosilicates, apatite, organic matter, opal, calcite, and dolomite that largely make up the rocks. High concentrations of several trace elements throughout the deposit, for example, As, Cd, Se, Tl, and U, at this and previously examined sites have raised concern about their introduction into the environment via weathering and the degree to which mining and the disposal of mined waste rock from this deposit might be accelerating that process. The question addressed here is how might the partitioning of trace elements between these solid host components influence the introduction of trace elements into ground water, surface water, and eventually biota, via weathering? In the case of Se, it is partitioned into components that are quite labile under the oxidizing conditions of subaerial weathering. As a result, it is widely distributed throughout the environment. Its concentration exceeds the level of concern for protection of wildlife at virtually every trophic level.
NASA Astrophysics Data System (ADS)
Chabot, N. L.
2017-12-01
As planetesimals were heated up in the early Solar System, the formation of Fe-Ni metallic melts was a common occurrence. During planetesimal differentiation, the denser Fe-Ni metallic melts separated from the less dense silicate components, though some meteorites suggest that their parent bodies only experienced partial differentiation. If the Fe-Ni metallic melts did form a central metallic core, the core eventually crystallized to a solid, some of which we sample as iron meteorites. In all of these planetesimal evolution processes, the composition of the Fe-Ni metallic melt influenced the process and the resulting trace element chemical signatures. In particular, the metallic melt's "light element" composition, those elements present in the metallic melt in a significant concentration but with lower atomic masses than Fe, can strongly affect trace element partitioning. Experimental studies have provided critical data to determine the effects of light elements in Fe-Ni metallic melts on trace element partitioning behavior. Here I focus on combining numerous experimental results to identify trace elements that provide unique insight into constraining the light element composition of early Solar System Fe-Ni metallic melts. Experimental studies have been conducted at 1 atm in a variety of Fe-Ni systems to investigate the effects of light elements on trace element partitioning behavior. A frequent experimental examination of the effects of light elements in metallic systems involves producing run products with coexisting solid metal and liquid metal phases. Such solid-metal-liquid-metal experiments have been conducted in the Fe-Ni binary system as well as Fe-Ni systems with S, P, and C. Experiments with O-bearing or Si-bearing Fe-Ni metallic melts do not lend themselves to experiments with coexisting solid metal and liquid metal phases, due to the phase diagrams of these elements, but experiments with two immiscible Fe-Ni metallic melts have provided insight into the qualitative effects of O and Si relative to the well-determined effects of S. Together, these experimental studies provide a robust dataset to identify key elements that are predicted to produce distinct chemical signatures as a function of different Fe-Ni metallic melt compositions during planetesimal evolution processes.
NASA Astrophysics Data System (ADS)
Nielsen, R. L.; Ghiorso, M. S.; Trischman, T.
2015-12-01
The database traceDs is designed to provide a transparent and accessible resource of experimental partitioning data. It now includes ~ 90% of all the experimental trace element partitioning data (~4000 experiments) produced over the past 45 years, and is accessible through a web based interface (using the portal lepr.ofm-research.org). We set a minimum standard for inclusion, with the threshold criteria being the inclusion of: Experimental conditions (temperature, pressure, device, container, time, etc.) Major element composition of the phases Trace element analyses of the phases Data sources that did not report these minimum components were not included. The rationale for not including such data is that the degree of equilibration is unknown, and more important, no rigorous approach to modeling the behavior of trace elements is possible without knowledge of composition of the phases, and the temperature and pressure of formation/equilibration. The data are stored using a schema derived from that of the Library of Experimental Phase Relations (LEPR), modified to account for additional metadata, and restructured to permit multiple analytical entries for various element/technique/standard combinations. In the process of populating the database, we have learned a number of things about the existing published experimental partitioning data. Most important are: ~ 20% of the papers do not satisfy one or more of the threshold criteria. The standard format for presenting data is the average. This was developed as the standard during the time where there were space constraints for publication in spite of fact that all the information can now be published as electronic supplements. The uncertainties that are published with the compositional data are often not adequately explained (e.g. 1 or 2 sigma, standard deviation of the average, etc.). We propose a new set of publication standards for experimental data that include the minimum criteria described above, the publication of all analyses with error based on peak count rates and background, plus information on the structural state of the mineral (e.g. orthopyroxene vs. pigeonite).
Effect of silicon on trace element partitioning in iron-bearing metallic melts
NASA Astrophysics Data System (ADS)
Chabot, Nancy L.; Safko, Trevor M.; McDonough, William F.
2010-08-01
Despite the fact that Si is considered a potentially important metalloid in planetary systems, little is known about the effect of Si in metallic melts on trace element partitioning behavior. Previous studies have established the effects of S, C, and P, nonmetals, through solid metal/liquid metal experiments in the corresponding Fe binary systems, but the Fe-Si system is not appropriate for similar experiments because of the high solubility of Si in solid metal. In this work, we present the results from 0.1MPa experiments with two coexisting immiscible metallic liquids in the Fe-S-Si system. By leveraging the extensive available knowledge about the effect of S on trace element partitioning behavior, we explore the effect of Si. Results for 22 trace elements are presented. Strong Si avoidance behavior is demonstrated by As, Au, Ga, Ge, Sb, Sn, and Zn. Iridium, Os, Pt, Re, Ru, and W exhibit weak Si avoidance tendencies. Silicon appears to have no significant effect on the partitioning behaviors of Ag, Co, Cu, Cr, Ni, Pd, and V, all of which had similar partition coefficients over a wide range of Si liquid concentrations from Si-free to 13 wt%. The only elements in our experiments to show evidence of a potentially weak attraction to Si were Mo and Rh. Applications of the newly determined effects of Si to problems in planetary science indicate that (1) The elements Ni, Co, Mo, and W, which are commonly used in planetary differentiation models, are minimally affected by the presence of Si in the metal, especially in comparison to other effects such as from oxygen fugacity. 2) Reduced enstatite-rich meteorites may record a chemical signature due to Si in the metallic melts during partial melting, and if so, elements identified by this study as having strong Si avoidance may offer unique insight into unraveling the history of these meteorites.
Yang, Zhenzhou; Chen, Yan; Sun, Yongqi; Liu, Lili; Zhang, Zuotai; Ge, Xinlei
2016-07-01
In the present study, the trace elements partitioning behavior during cement manufacture process were systemically investigated as well as their distribution behaviors in the soil surrounding a cement plant using hazardous waste as raw materials. In addition to the experimental analysis, the thermodynamic equilibrium calculations were simultaneously conducted. The results demonstrate that in the industrial-scale cement manufacture process, the trace elements can be classified into three groups according to their releasing behaviors. Hg is recognized as a highly volatile element, which almost totally partitions into the vapor phase. Co, Cu, Mn, V, and Cr are considered to be non-volatile elements, which are largely incorporated into the clinker. Meanwhile, Cd, Ba, As, Ni, Pb, and Zn can be classified into semi-volatile elements, as they are trapped into clinker to various degrees. Furthermore, the trace elements emitted into the flue gas can be adsorbed onto the fine particles, transport and deposit in the soil, and it is clarified here that the soil around the cement plant is moderately polluted by Cd, slightly polluted by As, Cr, Ba, Zn, yet rarely influenced by Co, Mn, Ni, Cu, Hg, and V elements. It was also estimated that the addition of wastes can efficiently reduce the consumption of raw materials and energy. The deciphered results can thus provide important insights for estimating the environmental impacts of the cement plant on its surroundings by utilizing wastes as raw materials.
NASA Astrophysics Data System (ADS)
Iveson, A. A.; Webster, J. D.; Rowe, M. C.; Neill, O. K.
2016-12-01
New experimental data for crystal-melt partitioning behaviour of a suite of trace-elements are presented. Hydrous rhyo-dacitic starting glasses from Mt. Usu, Japan, were doped with Li, Sc, Cr, Mn, Ni, Cu, Zn, Ga, Rb, Sr, Y, Nb, Mo, Ba, W, and Pb. Aqueous solutions were added such that the volatile phase(s) coexisting with amphibole, plagioclase, and clinopyroxene at run conditions buffered the S, F, and Cl contents of the melts. Internally-heated pressure vessel experiments were conducted at 750-850 °C, 1.0-4.0 Kbar, and ƒO2 ≈ NNO-NNO+2 log units. Major- and minor-element concentrations in the phenocrysts and glasses were analysed by EPMA, and trace-element contents by SIMS and/or LA-ICP-MS. The long run durations, homogeneous glasses, and minimal compositional zonation of crystals suggest that near-equilibrium conditions were achieved. Results of multiple phenocryst and glass analyses show that Nernst-type crystal-melt partition coefficients for these elements range from strongly incompatible e.g. Dmineral/melt ≈ 0 for Nb into plagioclase, to moderately incompatible e.g. Dmineral/melt ≈ 0.75 for Ga into amphibole, to strongly compatible e.g. Dmineral/melt > 50 for Ni into amphibole and clinopyroxene. Furthermore, unlike other elements investigated, partitioning of Li between phenocrysts and melt is similar for all three phases, with average DLicpx/melt ≈ 0.26 > DLiplag/melt ≈ 0.24 > DLiamph/melt ≈ 0.19. Relative to major-element composition of crystalline phases, the temperature, pressure, and ƒO2 conditions do not appear to strongly affect this behaviour. The incorporation of F and Cl into amphiboles is also consistent with the Fe-F and Mg-Cl crystallographic avoidance principles. Importantly, across two orders of magnitude in concentration, partitioning behaviours of all analysed trace-elements appear to obey Henry's Law. The experimental data are integrated with new amphibole, plagioclase, and pyroxene analyses from eruptive products of Augustine and Mt. St. Helens volcanoes. The results are applicable to understanding processes governing melt evolution during shallow magma storage and formation of economic metal deposits, where the crystallisation of porphyry-type magmas leads to fluid exsolution, and enrichment and transport of such trace- and ore-elements.
Atomistic simulation of mineral-melt trace-element partitioning
NASA Astrophysics Data System (ADS)
Allan, Neil L.; Du, Zhimei; Lavrentiev, Mikhail Yu.; Blundy, Jon D.; Purton, John A.; van Westrenen, Wim
2003-09-01
We discuss recent advances in computational approaches to trace-element incorporation in minerals and melts. It is crucial to take explicit account of the local structural environment of each ion in the solid and the change in this environment following the introduction of a foreign atom or atoms. Particular attention is paid to models using relaxation (strain) energies and solution energies, and the use of these different models for isovalent and heterovalent substitution in diopside and forsterite. Solution energies are also evaluated for pyrope and grossular garnets, and pyrope-grossular solid solutions. Unfavourable interactions between dodecahedral sites containing ions of the same size and connected by an intervening tetrahedron lead to larger solubilities of trace elements in the garnet solid solution than in either end member compound and to the failure of Goldschmidt's first rule. Our final two examples are the partitioning behaviour of noble gases, which behave as 'ions of zero charge' and the direct calculation of high-temperature partition coefficients between CaO solid and melt via Monte Carlo simulations.
NASA Astrophysics Data System (ADS)
Brenan, J. M.; Shaw, H. F.; Ryerson, F. J.; Phinney, D. L.
1995-10-01
In order to more fully establish a basis for quantifying the role of amphibole in trace-element fractionation processes, we have measured pargasite/silicate melt partitioning of a variety of trace elements (Rb, Ba, Nb, Ta, Hf, Zr, Ce, Nd, Sm, Yb), including the first published values for U, Th and Pb. Experiments conducted at 1000°C and 1.5 GPa yielded large crystals free of compositional zoning. Partition coefficients were found to be constant at total concentrations ranging from ˜ 1 to > 100 ppm, indicating Henry's Law is oparative over this interval. Comparison of partition coefficients measured in this study with previous determinations yields good agreement for similar compositions at comparable pressure and temperature. The compatibility of U, Th and Pb in amphibole decreases in the order Pb > Th > U. Partial melting or fractional crystallization of amphibole-bearing assemblages will therefore result in the generation of excesses in 238U activity relative to 230Th, similar in magnitude to that produced by clinopyroxene. The compatibility of Pb in amphibole relative to U or Th indicates that melt generation in the presence of residual amphibole will result in the long-term enrichment in Pb relative to U or Th in the residue. This process is therefore incapable of producing the depletion in Pb relative to U or Th inferred from the Pb isotopic composition of MORB and OIB. Comparison of partition coefficients measured in this study with previous values for clinopyroxene allows some distinction to be made between expected trace-element fractionations produced during dry (cpx present) and wet (cpx + amphibole present) melting. Rb, Ba, Nb and Ta are dramatically less compatible in clinopyroxene than in amphibole, whereas Th, U, Hf and Zr have similar compatibilities in both phases. Interelement fractionations, such as DNb/DBa are also different for clinopyroxene and amphibole. Changes in certain ratios, such as Ba/Nb, Ba/Th, and Nb/Th within comagmatic suites may therefore offer a means to discern the loss of amphibole from the melting assemblage. Elastic strain theory is applied to the partitioning data after the approaches of Beattie and Blundy and Wood and is used to predict amphibole/melt partition coefficients at conditions of P, T and composition other than those employed in this study. Given values of DCa, DTi and DK from previous partitioning studies, this approach yields amphibole/melt trace-element partition coefficients that reproduce measured values from the literature to within 40-45%. This degree of reproducibility is considered reasonable given that model parameters are derived from partitioning relations involving iron- and potassium-free amphibole.
A finite volume method for trace element diffusion and partitioning during crystal growth
NASA Astrophysics Data System (ADS)
Hesse, Marc A.
2012-09-01
A finite volume method on a uniform grid is presented to compute the polythermal diffusion and partitioning of a trace element during the growth of a porphyroblast crystal in a uniform matrix and in linear, cylindrical and spherical geometry. The motion of the crystal-matrix interface and the thermal evolution are prescribed functions of time. The motion of the interface is discretized and it advances from one cell boundary to next as the prescribed interface position passes the cell center. The appropriate conditions for the flux across the crystal-matrix interface are derived from discrete mass conservation. Numerical results are benchmarked against steady and transient analytic solutions for isothermal diffusion with partitioning and growth. Two applications illustrate the ability of the model to reproduce observed rare-earth element patterns in garnets (Skora et al., 2006) and water concentration profiles around spherulites in obsidian (Watkins et al., 2009). Simulations with diffusion inside the growing crystal show complex concentration evolutions for trace elements with high diffusion coefficients, such as argon or hydrogen, but demonstrate that rare-earth element concentrations in typical metamorphic garnets are not affected by intracrystalline diffusion.
NASA Technical Reports Server (NTRS)
Danielson, L. R.; Sharp, T. G.; Hervig, R. L.
2005-01-01
Siderophile elements in the Earth.s mantle are depleted relative to chondrites. This is most pronounced for the highly siderophile elements (HSEs), which are approximately 400x lower than chondrites. Also remarkable is the relative chondritic abundances of the HSEs. This signature has been interpreted as representing their sequestration into an iron-rich core during the separation of metal from silicate liquids early in the Earth's history, followed by a late addition of chondritic material. Alternative efforts to explain this trace element signature have centered on element partitioning experiments at varying pressures, temperatures, and compositions (P-T-X). However, first results from experiments conducted at 1 bar did not match the observed mantle abundances, which motivated the model described above, a "late veneer" of chondritic material deposited on the earth and mixed into the upper mantle. Alternatively, the mantle trace element signature could be the result of equilibrium partitioning between metal and silicate in the deep mantle, under P-T-X conditions which are not yet completely identified. An earlier model determined that equilibrium between metal and silicate liquids could occur at a depth of approximately 700 km, 27(plus or minus 6) GPa and approximately 2000 (plus or minus 200) C, based on an extrapolation of partitioning data for a variety of moderately siderophile elements obtained at lower pressures and temperatures. Based on Ni-Co partitioning, the magma ocean may have been as deep as 1450 km. At present, only a small range of possible P-T-X trace element partitioning conditions has been explored, necessitating large extrapolations from experimental to mantle conditions for tests of equilibrium models. Our primary objective was to reduce or remove the additional uncertainty introduced by extrapolation by testing the equilibrium core formation hypothesis at P-T-X conditions appropriate to the mantle.
NASA Astrophysics Data System (ADS)
Hadizadeh, Jafar; Foit, Franklin F.
2000-04-01
Cement phases such as calcite or quartz often incorporate trace elements from the parent fluids as they crystallize. Experimental sedimentary diagenesis indicates that trace element partition coefficients reflect rates of cementation. The applicability of these findings to fault zone cementation is examined as we make a preliminary attempt to estimate calcite cementation rate in a brittle fault zone directly from the fault-rock composition data. Samples for this study were collected from the Knoxville outcrop of the Saltville fault in Tennessee. The cementation rates for the fault rock samples range from 1×10 -12 to 3×10 -13 m3/ h per m, in agreement with some experimental rates and the rates reported for samples from the DSDP sites. When applied to a non-responsive pore-system model, these rates result in rapid precipitation sealing indicating the influence exerted by the surface-area/volume ratio of the pore network. We find it feasible to obtain a reasonable range of values for the cementation rate using the trace element partition method. However, the study also indicates the need for relatively accurate values for the trace/carrier element ratio in the fault zone syntectonic pore fluid, and exhumed cement.
NASA Astrophysics Data System (ADS)
Corrigan, Catherine M.; Chabot, Nancy L.; McCoy, Timothy J.; McDonough, William F.; Watson, Heather C.; Saslow, Sarah A.; Ash, Richard D.
2009-05-01
To better understand the partitioning behavior of elements during the formation and evolution of iron meteorites, two sets of experiments were conducted at 1 atm in the Fe-Ni-P system. The first set examined the effect of P on solid metal/liquid metal partitioning behavior of 22 elements, while the other set explored the effect of the crystal structures of body-centered cubic (α)- and face-centered cubic (γ)-solid Fe alloys on partitioning behavior. Overall, the effect of P on the partition coefficients for the majority of the elements was minimal. As, Au, Ga, Ge, Ir, Os, Pt, Re, and Sb showed slightly increasing partition coefficients with increasing P-content of the metallic liquid. Co, Cu, Pd, and Sn showed constant partition coefficients. Rh, Ru, W, and Mo showed phosphorophile (P-loving) tendencies. Parameterization models were applied to solid metal/liquid metal results for 12 elements. As, Au, Pt, and Re failed to match previous parameterization models, requiring the determination of separate parameters for the Fe-Ni-S and Fe-Ni-P systems. Experiments with coexisting α and γ Fe alloy solids produced partitioning ratios close to unity, indicating that an α versus γ Fe alloy crystal structure has only a minor influence on the partitioning behaviors of the trace element studied. A simple relationship between an element's natural crystal structure and its α/γ partitioning ratio was not observed. If an iron meteorite crystallizes from a single metallic liquid that contains both S and P, the effect of P on the distribution of elements between the crystallizing solids and the residual liquid will be minor in comparison to the effect of S. This indicates that to a first order, fractional crystallization models of the Fe-Ni-S-P system that do not take into account P are appropriate for interpreting the evolution of iron meteorites if the effects of S are appropriately included in the effort.
Experimental Study of the Partitioning of Siderophile Elements in a Crystallizing Lunar Magma Ocean
NASA Technical Reports Server (NTRS)
Galenas, M.; Righter, K.; Danielson, L.; Pando, K.; Walker, R. J.
2012-01-01
The distributions of trace elements between the lunar interior and pristine crustal rocks were controlled by the composition of starting materials, lunar core formation, and crystallization of the lunar magma ocean (LMO) [1]. This study focuses on the partitioning of highly siderophile elements (HSE) including Re, Os, Ir, Ru, Pt, Rh, Pd and Au as well as the moderately siderophile elements Mo and W, and the lithophile elements of Hf and Sr. Our experiments also include Ga, which can be slightly siderophile, but is mostly considered to be chalcophile. Partitioning of these elements is not well known at the conditions of a crystallizing LMO. Previous studies of HSE partitioning in silicate systems have yielded highly variable results for differing oxygen fugacity (fO2) and pressure [2-4]. For example, under certain conditions Pt is compatible in clinopy-roxene [2] and Rh and Ru are compatible in olivine [3]. The silicate compositions used for these experiments were nominally basaltic. Ruthenium, Rh, and Pd are incompatible in plagioclase under these conditions[4]. However, this latter study was done at extremely oxidizing conditions and at atmospheric pressure, possibly limiting the applicability for consideration of conditions of a crystallizing LMO. In this study we address the effects of pressure and oxygen fugacity on the crystal/liquid partition coefficients of these trace elements. We are especially interested in the plagioclase/melt partition coefficients so that it may be possible to use reverse modeling to constrain the concentrations of these elements in the lunar mantle through their abundances in pristine crustal rocks.
A simple model for closure temperature of a trace element in cooling bi-mineralic systems
NASA Astrophysics Data System (ADS)
Liang, Yan
2015-09-01
Closure temperature is defined as the lower temperature limit at which the element of interest effectively ceases diffusive exchange with its surrounding medium during cooling. Here we generalize the classic equation of Dodson (1973) for cooling mono-mineralic systems to cooling bi-mineralic aggregates by considering diffusive exchange of a trace element between the two minerals in a closed system. We present a simple analytical model that includes key parameters affecting the closure temperature of a trace element in cooling bi-mineralic systems: cooling rate, temperature-dependent diffusion coefficients for the trace element in the two minerals, temperature-dependent partition coefficient of the trace element between the two minerals, effective grain sizes of the two minerals, and volume proportions of the minerals in the system. We show that closure temperatures of a trace element in cooling bi-mineralic systems are bounded by the closure temperatures of the trace element in the two mono-mineralic systems and that our generalized model reduces to Dodson's equation when one of the mineral serves as "an effective infinite" reservoir to the other mineral. Application to closure temperatures of REE in orthopyroxene and clinopyroxene bi-mineralic systems highlights the importance of REE diffusion and partitioning in the pyroxenes as well as clinopyroxene modal abundance and grain size in the systems. Closure temperatures for REE in two-pyroxene bearing equigranular rocks are controlled primarily by diffusion in orthopyroxene unless the modal abundance of clinopyroxene is very small. This has important bearings on the interpretation of temperatures derived from the REE-in-two-pyroxene thermometer.
NASA Technical Reports Server (NTRS)
Jones, J. H.; Walker, D.
1993-01-01
Previously we have reported carbonate liq./silicate liq. partition coefficients (D) for a standard suite of trace elements (Nb, Mo, Ba, Ce, Pb, Th, and U) and Ra and Pa as well. In brief, we have found that immiscible liquid partitioning is a strong function of temperature. As the critical temperature of the carbonate-silicate solvus is approached, all partition coefficients approach unity. Additionally, for the overwhelming majority of the partitioning elements, InD is a linear function of 'ionic field strength,' z/r, where z is the charge of the partitioned cation and r is its ionic radius.
STRUCTURAL DYNAMICS OF METAL PARTITIONING TO MINERAL SURFACES
The conceptual understanding of surface complexation reactions that control trace element partitioning to mineral surfaces is limited by the assumption that the solid reactant possesses a finite, time-invariant population of surface functional groups. This assumption has limited...
Apatite/Melt Partitioning Experiments Reveal Redox Sensitivity to Cr, V, Mn, Ni, Eu, W, Th, and U
NASA Technical Reports Server (NTRS)
Righter, K.; Yang, S.; Humayun, M.
2016-01-01
Apatite is a common mineral in terrestrial, planetary, and asteroidal materials. It is commonly used for geochronology (U-Pb), sensing volatiles (H, F, Cl, S), and can concentrate rare earth elements (REE) during magmatic fractionation and in general. Some recent studies have shown that some kinds of phosphate may fractionate Hf and W and that Mn may be redox sensitive. Experimental studies have focused on REE and other lithophile elements and at simplified or not specified oxygen fugacities. There is a dearth of partitioning data for chalcophile, siderophile and other elements between apatite and melt. Here we carry out several experiments at variable fO2 to study the partitioning of a broad range of trace elements. We compare to existing data and then focus on several elements that exhibit redox dependent partitioning behavior.
NASA Technical Reports Server (NTRS)
Kennedy, A. K.; Lofgren, G. E.; Wasserburg, G. J.
1993-01-01
The presence of perovskite (CATiO3) and hibonite (Ca Al12O19) within different regions of Calcium-, Aluminum-rich Inclusions (CAI) and the trace element concentrations of these minerals in each circumstance, constrain models of precursor formation, nebular condensation, the thermal history of inclusions with relict perovskite and hibonite, and the formation of the Wark-Lovering rim. At present mineral/melt partition coefficient data for hibonite are limited to a few elements in simple experimental systems, or to those derived from hibonite-glass pairs in hibonite/glass microspherules. Similarly, there is only limited data on perovskite D that are applicable to meteorite compositions. Apart from the importance of partitioning studies to meteorite research, D values also are invaluable in the development of thermodynamic models, especially when data is available for a large number of elements that have different ionic charge and radii. In addition, study of the effect of rapid cooling on partitioning is crucial to our understanding of meteorite inclusions. To expand our knowledge of mineral/melt D for perovskite and hibonite, a study was instituted where D values are obtained in both equilibrium and dynamic cooling experiments. As an initial phase of this study mineral/melt D was measured for major elements (Ca, Mg, Al, Ti, and Si), 15 rare earth elements (La-Lu) and 8 other elements (Ba, Sr, U, Th, Nb, Zr, Hf, and Ge) in perovskite and hibonite grown under equilibrium conditions, in bulk compositions that are respectively similar to Compact Type A (CTA) CAI and to a hibonite/glass microspherule. Experimental mixes were doped with REE at 20-50x chondritic (ch) abundances, Ba at 50 ppm, Sr, Hf, Nb, and Zr at 100 ppm and, U and Th at 200 ppm. Trace element abundances were measured with the PANURGE ion microprobe. Major element compositions were obtained by electron microprobe analysis.
Usmani, Zeba; Kumar, Vipin
2017-06-01
Coal-based thermal power plants are the major source of power generation in India. Combustion of coal gives rise to by-products such as fly ash (FA) in huge quantities. The current study focuses on physico-chemical and mineralogical characterization and risk evaluation of FA, generated from five thermal power plants (TPPs) of India. The coal, and corresponding FA and bottom ash (BA) were further analyzed for trace elements in order to observe the enrichment and partitioning behavior of elements. The environmental risk assessment of trace elements in FA was performed in accordance with geoaccumulation index (I geo ) and potential ecological risk index (PERI). The results demonstrated that FA was enriched predominantly in SiO 2 , Al 2 O 3 , and Fe 2 O 3 along with small concentrations of CaO and MgO. The mineral phases identified in FA were quartz, mullite, hematite, and magnetite. Elemental characterization indicated that the metals were more enriched in FA as compared to coal and BA. The concentrations of trace elements, Cr, Pb, Hg, and As in FA (TPPs), varied from 12.59-24.28, 22.68-43.19, <0.0001-2.29, and 0.08-3.39 mg/kg, respectively. Maximum enrichment ratio (ER) was observed for Pb (5.21) in TPP3 FA. Hg in TPP1 showed the highest partition ratio (PR) value. I geo values for metals were mostly below zero. The PERI values indicated moderate risk from TPP4 FA and low risk from TPP1, TPP2, TPP3, and TPP5 FA to the environment, according to the threshold values provided.
NASA Technical Reports Server (NTRS)
Drake, Michael J.; Rubie, David C.; Mcfarlane, Elisabeth A.
1992-01-01
The partitioning of elements amongst lower mantle phases and silicate melts is of interest in unraveling the early thermal history of the Earth. Because of the technical difficulty in carrying out such measurements, only one direct set of measurements was reported previously, and these results as well as interpretations based on them have generated controversy. Here we report what are to our knowledge only the second set of directly measured trace element partition coefficients for a natural system (KLB-1).
Experimental geochemistry of Pu and Sm and the thermodynamics of trace element partitioning
NASA Technical Reports Server (NTRS)
Jones, John H.; Burnett, Donald S.
1987-01-01
An experimental study of the partitioning of Pu and Sm between diopside/liquid and whitlockite/liquid supports the hypothesis that Pu behaves as a light rare earth element during igneous processes in reducing environments. D-Pu/D-Sm is found to be about 2 for both diopsidic pyroxene and whitlockite, and the amount of fractionation would be decreased further if Pu were compared to Ce or Nd. Data indicate that temperature, rather than melt composition, is the most important control on elemental partitioning, and that P2O5 in aluminosilicate melts serves as a complexing agent for the actinides and lanthanides.
Trace Element Partitioning Between low-Ca Pyroxene and Ultracalcic Liquids.
NASA Astrophysics Data System (ADS)
Pertermann, M.; Schmidt, M. W.; Pettke, T.
2003-12-01
Low-Ca pyroxene or pigeonite ( ˜0.25-0.35 Ca per formula unit, pfu) is an important residual phase during high temperature melting of refractory mantle (e.g., ankaramite formation). High-Ca cpx (>0.6-0.7 Ca pfu) may be residual to relatively low temperature melting of fertile mantle (MOR and OI), but the opx-cpx solvus narrows considerably at higher temperatures (>1330-1350° C), leading to coexisting opx and low-Ca cpx. Little is known about the trace element partitioning of such low-Ca cpx at upper mantle conditions. Our new partitioning experiments investigate the role of low-Ca cpx during melting of depleted peridotite. Nominally anhydrous experiments with graphite-lined Pt-capsules were conducted at 1.4 GPa and 1360-1370° C. The synthetic starting material is close in composition to an ultracalcic liquid saturated in opx+pigeonite+olivine+spinel. The experiments yielded assemblages of glass, low-Ca cpx, ol, and minor Cr-spinel; opx is absent. The low-Ca clinopyroxenes have 0.20 and 0.32 Ca pfu at 1370 and 1360° C, respectively, and tetrahedral Al of 0.046 and 0.067 pfu. The liquids have ˜50 wt% SiO2, ˜12.5 wt% CaO and CaO/Al2O3 of 1.44-1.54. Pyroxenes and glasses were analyzed for trace elements (La, Ce, Nd, Sm, Eu, Gd, Dy, Er Yb, Lu, Sc, Y, Sr, Zr, Hf, V, Cr, Mn, Co, Zn) by LA-ICP-MS using a 193 nm ArF excimer laser coupled to an Elan 6100 mass spectrometer. Ablation occurred in He, and ablation spot sizes were 15-30 μ m for minerals and 50 μ m for glasses. Trace element concentrations in pyroxenes were low for most 3+ and 4+ cations. This resulted in small mineral/melt partition coefficients (D-values), approximately an order of magnitude lower than those for high-Ca cpx associated with peridotite melting, thus making the low-Ca cpx partitioning behavior rather similar to the behavior of peridotitic opx. Cpx with 0.32 Ca pfu has slightly elevated D-values for 3+ cations when compared to the 0.20 Ca pfu cpx: DSc = 0.45, DY = 0.11, DSm = 0.054 and DYb = 0.141, compared to values of 0.32, 0.065, 0.016 and 0.075, respectively. Regardless of Ca content, V, Mn, Co and Zn are mildly incompatible (Ds ˜0.5-0.9). Therefore, only Sc, V, Cr, Mn, Co, Ni and Zn are retained during partial mantle melting with a pigeonite+opx+ol residue. Most other elements partition strongly into the melt, and barring exotic residual minerals, the composition of ultracalcic liquids reflects the incompatible trace element budget of the depleted peridotite source.
NASA Astrophysics Data System (ADS)
Evans, G. N.; Tivey, M. K.; Seewald, J.; Rouxel, O. J.; Monteleone, B.
2016-12-01
Analyses of trace elements (Ag, As, Co, Mn, and Zn) hosted in the chalcopyrite linings of `black smoker' chimneys using secondary ion mass spectrometry (SIMS) have been combined with data for trace metal concentrations in corresponding vent fluids to investigate fluid-mineral partitioning of trace elements. Goals of this research include development of proxies for fluid chemistry based on mineral trace element content. The use of SIMS allows for the measurement of trace elements below the detection limits of electron microprobe and at the necessary spatial resolution (20 microns) to examine fine-grained and mixed-mineral samples. Results indicate that the chalcopyrite linings of many `black smoker' chimneys are homogeneous with respect to Ag, Mn, Co, and Zn. Minerals picked from samples exhibiting homogeneity with respect to specific elements were dissolved and analyzed by solution inductively coupled plasma mass spectrometry (ICP-MS) for use as working standards. Results also document a strong correlation between the Ag content of chalcopyrite and the Ag:Cu ratio of the corresponding hydrothermal fluid. This supports systematic partitioning of Ag into chalcopyrite as a substitute for Cu, providing a proxy for fluid Ag concentration. Additionally, the Ag content of chalcopyrite correlates with fluid pH, particularly at pH>3, and thus represents an effective proxy for fluid pH. Application of these proxies to chimney samples provides an opportunity to better identify hydrothermal conditions even when fluids have not been sampled, or not fully analyzed.
He, Mei; Ke, Cai-Huan; Wang, Wen-Xiong
2010-03-24
In current human health risk assessment, the maximum acceptable concentrations of contaminants in food are mostly based on the total concentrations. However, the total concentration of contaminants may not always reflect the available amount. Bioaccessibility determination is thus required to improve the risk assessment of contaminants. This study used an in vitro digestion model to assess the bioaccessibility of several trace elements (As, Cd, Cu, Fe, Se, and Zn) in the muscles of two farmed marine fish species (seabass Lateolabrax japonicus and red seabream Pagrosomus major ) of different body sizes. The total concentrations and subcellular distributions of these trace elements in fish muscles were also determined. Bioaccessibility of these trace elements was generally high (>45%), and the lowest bioaccessibility was observed for Fe. Cooking processes, including boiling, steaming, frying, and grilling, generally decreased the bioaccessibility of these trace elements, especially for Cu and Zn. The influences of frying and grilling were greater than those of boiling and steaming. The relationship of bioaccessibility and total concentration varied with the elements. A positive correlation was found for As and Cu and a negative correlation for Fe, whereas no correlation was found for Cd, Se, and Zn. A significant positive relationship was demonstrated between the bioaccessibility and the elemental partitioning in the heat stable protein fraction and in the trophically available fraction, and a negative correlation was observed between the bioaccessibility and the elemental partitioning in metal-rich granule fraction. Subcellular distribution may thus affect the bioaccessibility of metals and should be considered in the risk assessment for seafood safety.
NASA Astrophysics Data System (ADS)
Kavner, A.
2017-12-01
In a multicomponent multiphase geochemical system undergoing a chemical reaction such as precipitation and/or dissolution, the partitioning of species between phases is determined by a combination of thermodynamic properties and transport processes. The interpretation of the observed distribution of trace elements requires models integrating coupled chemistry and mechanical transport. Here, a framework is presented that predicts the kinetic effects on the distribution of species between two reacting phases. Based on a perturbation theory combining Navier-Stokes fluid flow and chemical reactivity, the framework predicts rate-dependent partition coefficients in a variety of different systems. We present the theoretical framework, with applications to two systems: 1. species- and isotope-dependent Soret diffusion of species in a multicomponent silicate melt subjected to a temperature gradient, and 2. Elemental partitioning and isotope fractionation during precipitation of a multicomponent solid from a multicomponent liquid phase. Predictions will be compared with results from experimental studies. The approach has applications for understanding chemical exchange in at boundary layers such as the Earth's surface magmatic systems and at the core/mantle boundary.
Laboratory actinide partitioning - Whitlockite/liquid and influence of actinide concentration levels
NASA Technical Reports Server (NTRS)
Benjamin, T. M.; Jones, J. H.; Heuser, W. R.; Burnett, D. S.
1983-01-01
The partition coefficients between synthetic whitlockite (beta Ca-phosphate) and coexisting silicate melts are determined for the actinide elements Th, U and Pu. Experiments were performed at 1 bar pressure and 1250 C at oxygen fugacities from 10 to the -8.5 to 10 to the -0.7 bars, and partitioning was determined from trace element radiography combined with conventional electron microprobe analysis. Results show Pu to be more readily incorporated into crystalline phases than U or Th under reducing conditions, which is attributed to the observation that Pu exists primarily in the trivalent state, while U and Th are tetravalent. Corrected partition coefficients for whitlockite of 3.6, less than or equal to 0.6, 1.2, 0.5 and less than or equal to 0.002 are estimated for Pu(+3), Pu(+4), Th(+4), U(+4) and U(+6), respectively. Experiments performed at trace levels and percent levels of UO2 indicate that Si is involved in U substitution in whitlockite, and show a reduced partition coefficient at higher concentrations of U that can be explained by effects on melt structure or the fraction of tetravalent U.
NASA Astrophysics Data System (ADS)
Reichart, G. J.; Nooijer, L. D.; Geerken, E.; Mezger, E.; van Dijk, I. V.; Daemmer, L. K.
2017-12-01
Reconstructions of past climate and environments are largely based on stable isotopes and trace element concentrations measured on fossil foraminiferal calcite. Their element and isotope composition roughly reflects seawater composition and physical conditions, which in turn, are related to paleoceanographic parameters. More recently, attempts are being made to infer ranges in environmental parameters using the observed differences in the composition within individual tests. Remarkably, inter-species differences in trace element incorporation are well-correlated over a wide range of environmental conditions. This is particularly remarkable knowing that different environmental factors influence incorporation of these elements at various magnitudes. Most likely the complex biomineralization of foraminifera potentially offsets trace elements similarly at all these scales and also between different species. This suggests that at least parts of the mechanisms underlying foraminiferal biomineralization are similar for all species, which in turn provides important clues on the cellular mechanisms operating during calcification. Moreover, the systematics in trace element partitioning between species could potentially provide important clues for unravelling past changes in trace element composition of the ancient ocean.
Trace elements in magnetite as petrogenetic indicators
NASA Astrophysics Data System (ADS)
Dare, Sarah A. S.; Barnes, Sarah-Jane; Beaudoin, Georges; Méric, Julien; Boutroy, Emilie; Potvin-Doucet, Christophe
2014-10-01
We have characterized the distribution of 25 trace elements in magnetite (Mg, Al, Si, P, Ca, Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Sn, Hf, Ta, W, and Pb), using laser ablation ICP-MS and electron microprobe, from a variety of magmatic and hydrothermal ore-forming environments and compared them with data from the literature. We propose a new multielement diagram, normalized to bulk continental crust, designed to emphasize the partitioning behavior of trace elements between magnetite, the melt/fluid, and co-crystallizing phases. The normalized pattern of magnetite reflects the composition of the melt/fluid, which in both magmatic and hydrothermal systems varies with temperature. Thus, it is possible to distinguish magnetite formed at different degrees of crystal fractionation in both silicate and sulfide melts. The crystallization of ilmenite or sulfide before magnetite is recorded as a marked depletion in Ti or Cu, respectively. The chemical signature of hydrothermal magnetite is distinct being depleted in elements that are relatively immobile during alteration and commonly enriched in elements that are highly incompatible into magnetite (e.g., Si and Ca). Magnetite formed from low-temperature fluids has the lowest overall abundance of trace elements due to their lower solubility. Chemical zonation of magnetite is rare but occurs in some hydrothermal deposits where laser mapping reveals oscillatory zoning, which records the changing conditions and composition of the fluid during magnetite growth. This new way of plotting all 25 trace elements on 1 diagram, normalized to bulk continental crust and elements in order of compatibility into magnetite, provides a tool to help understand the processes that control partitioning of a full suit of trace elements in magnetite and aid discrimination of magnetite formed in different environments. It has applications in both petrogenetic and provenance studies, such as in the exploration of ore deposits and in sedimentology.
NASA Astrophysics Data System (ADS)
Nielsen, Roger L.; Ustunisik, Gokce; Weinsteiger, Allison B.; Tepley, Frank J.; Johnston, A. Dana; Kent, Adam J. R.
2017-09-01
Quantitative models of petrologic processes require accurate partition coefficients. Our ability to obtain accurate partition coefficients is constrained by their dependence on pressure temperature and composition, and on the experimental and analytical techniques we apply. The source and magnitude of error in experimental studies of trace element partitioning may go unrecognized if one examines only the processed published data. The most important sources of error are relict crystals, and analyses of more than one phase in the analytical volume. Because we have typically published averaged data, identification of compromised data is difficult if not impossible. We addressed this problem by examining unprocessed data from plagioclase/melt partitioning experiments, by comparing models based on that data with existing partitioning models, and evaluated the degree to which the partitioning models are dependent on the calibration data. We found that partitioning models are dependent on the calibration data in ways that result in erroneous model values, and that the error will be systematic and dependent on the value of the partition coefficient. In effect, use of different calibration datasets will result in partitioning models whose results are systematically biased, and that one can arrive at different and conflicting conclusions depending on how a model is calibrated, defeating the purpose of applying the models. Ultimately this is an experimental data problem, which can be solved if we publish individual analyses (not averages) or use a projection method wherein we use an independent compositional constraint to identify and estimate the uncontaminated composition of each phase.
NASA Astrophysics Data System (ADS)
Yang, Panseok; Rivers, Toby
2000-04-01
Coexisting biotite and muscovite in ten metapelitic and quartzofeldspathic rocks from western Labrador have been analyzed by electron microprobe for major and minor elements and by a laser ablation microprobe coupled to ICP-MS (LAM-ICP-MS) for selected trace elements - Li, Sc, V, Cr, Mn, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Cs, Ba, REE, Hf and Ta. The samples have experienced a single prograde Grenvillian metamorphism ranging from 490 to 680°C and from 7 to 12 kbar. The trace element compositions of coexisting micas in the metamorphic rocks are used to assess the effects of crystal structure, major element composition and temperature on the partitioning of each element between biotite and muscovite. Overall, trace element distributions are systematic across the range of metamorphic grade and bulk composition, suggesting that chemical equilibrium was approached. Most distribution coefficients (biotite/muscovite) show good agreement with published data. However, distribution coefficients for Co and Sr are significantly different from previous determinations, probably because of contamination associated with older data obtained by bulk analysis techniques. The sequence of distribution coefficients is governed mainly by the ionic radii and charges of substituting cations compared to the optimum ionic radius of each crystallographic site in the micas. In particular, distribution coefficients exhibit the sequence Cr 3+ (0.615 Å) > V 3+ (0.64 Å) > Sc 3+ (0.745 Å) in VI-sites, and Ba 2+ (1.61 Å) > Sr 2+ (1.44 Å) and Cs + (1.88 Å) > K + (1.64 Å) > Rb + (1.72 Å) > Na + (1.39 Å) in XII-sites. The distributions of Li, Sc, Sr and Ba appear to be thermally sensitive but are also controlled by major element compositions of micas. V and Zr partitioning is dependent on T and may be used to cross-check thermometry calculations where the latter suffer from retrograde re-equilibration and/or high concentrations of Fe 3+. The ranges and dependence of distribution coefficients on major element compositions provide important constraints on the values that can be used in geochemical modeling.
Grotti, M; Soggia, F; Ardini, F; Magi, E
2011-09-01
In order to provide a new insight into the Antarctic snow chemistry, partitioning of major and trace elements between dissolved and particulate (i.e. insoluble particles, >0.45 μm) phases have been investigated in a number of coastal and inland snow samples, along with their total and acid-dissolvable (0.5% nitric acid) concentrations. Alkaline and alkaline-earth elements (Na, K, Ca, Mg, Sr) were mainly present in the dissolved phase, while Fe and Al were predominantly associated with the particulate matter, without any significant difference between inland and coastal samples. On the other hand, partitioning of trace elements depended on the sampling site position, showing a general decrease of the particulate fraction by moving from the coast to the plateau. Cd, Cu, Pb and Zn were for the most part in the dissolved phase, while Cr was mainly associated with the particulate fraction. Co, Mn and V were equally distributed between dissolved and particulate phases in the samples collected from the plateau and preferentially associated with the particulate in the coastal samples. The correlation between the elements and the inter-sample variability of their concentration significantly decreased for the plateau samples compared to the coastal ones, according to a change in the relative contribution of the metal sources and in good agreement with the estimated marine and crustal enrichment factors. In addition, samples from the plateau were characterised by higher enrichment factors of anthropogenic elements (Cd, Cr, Cu, Pb and Zn), compared to the coastal area. Finally, it was observed that the acid-dissolvable metal concentrations were generally lower than the total concentration values, showing that the acid treatment can dissolve only a given fraction of the metal associated with the particulate (<20% for iron and aluminium).
Trace and minor elements in sphalerite from metamorphosed sulphide deposits
NASA Astrophysics Data System (ADS)
Lockington, Julian A.; Cook, Nigel J.; Ciobanu, Cristiana L.
2014-12-01
Sphalerite is a common sulphide and is the dominant ore mineral in Zn-Pb sulphide deposits. Precise determination of minor and trace element concentrations in sulphides, including sphalerite, by Laser-Ablation Inductively-Coupled-Plasma Mass-Spectrometry (LA-ICP-MS) is a potentially valuable petrogenetic tool. In this study, LA-ICP-MS is used to analyse 19 sphalerite samples from metamorphosed, sphalerite-bearing volcanic-associated and sedimentary exhalative massive sulphide deposits in Norway and Australia. The distributions of Mn, Fe, Co, Cu, Ga, Se, Ag, Cd, In, Sn, Sb, Hg, Tl, Pb and Bi are addressed with emphasis on how concentrations of these elements vary with metamorphic grade of the deposit and the extent of sulphide recrystallization. Results show that the concentrations of a group of trace elements which are believed to be present in sphalerite as micro- to nano-scale inclusions (Pb, Bi, and to some degree Cu and Ag) diminish with increasing metamorphic grade. This is interpreted as due to release of these elements during sphalerite recrystallization and subsequent remobilization to form discrete minerals elsewhere. The concentrations of lattice-bound elements (Mn, Fe, Cd, In and Hg) show no correlation with metamorphic grade. Primary metal sources, physico-chemical conditions during initial deposition, and element partitioning between sphalerite and co-existing sulphides are dominant in defining the concentrations of these elements and they appear to be readily re-incorporated into recrystallized sphalerite, offering potential insights into ore genesis. Given that sphalerite accommodates a variety of trace elements that can be precisely determined by contemporary microanalytical techniques, the mineral has considerable potential as a geothermometer, providing that element partitioning between sphalerite and coexisting minerals (galena, chalcopyrite etc.) can be quantified in samples for which the crystallization temperature can be independently constrained.
Zhang, Yingyi; Nakano, Jinichiro; Liu, Lili; Wang, Xidong; Zhang, Zuotai
2015-10-01
Energy recovery is a promising method for coal gangue utilization, during which the prevention of secondary pollution, especially toxic metal emission, is a significant issue in the development of coal gangue utilization. In the present study, investigation into trace element partitioning behavior from a coal gangue-fired power plant in Shanxi province, China, has been conducted. Besides the experimental analysis, thermodynamic equilibrium calculation was also conducted to help the further understanding on the effect of different parameters. Results showed that Hg, As, Be, and Cd were highly volatile elements in the combustion of coal gangue, which were notably enriched in fly ash and may be emitted into the environment via the gas phase. Cr and Mn were mostly non-volatile and were enriched in the bottom ash. Pb, Co, Zn, Cu, and Ni were semi-volatile elements and were enriched in the fly ash to varying degrees. Equilibrium calculations show that the air/fuel ratio and the presence of Cl highly affect the element volatility. The presence of mineral phases, such as aluminosilicates, depresses the volatility of elements by chemical immobilization and competition in Cl. The coal gangue, fly ash, and bottom ash all passed the toxicity characteristic leaching procedure (TCLP), and their alkalinity buffers the acidity of the solution and contributes to the low solubility of the trace elements.
NASA Astrophysics Data System (ADS)
Thomas, J. B.; Bodnar, R. J.; Shimizu, N.; Sinha, A. K.
2002-09-01
Partition coefficients ( zircon/meltD M) for rare earth elements (REE) (La, Ce, Nd, Sm, Dy, Er and Yb) and other trace elements (Ba, Rb, B, Sr, Ti, Y and Nb) between zircon and melt have been calculated from secondary ion mass spectrometric (SIMS) analyses of zircon/melt inclusion pairs. The melt inclusion-mineral (MIM) technique shows that D REE increase in compatibility with increasing atomic number, similar to results of previous studies. However, D REE determined using the MIM technique are, in general, lower than previously reported values. Calculated D REE indicate that light REE with atomic numbers less than Sm are incompatible in zircon and become more incompatible with decreasing atomic number. This behavior is in contrast to most previously published results which indicate D > 1 and define a flat partitioning pattern for elements from La through Sm. The partition coefficients for the heavy REE determined using the MIM technique are lower than previously published results by factors of ≈15 to 20 but follow a similar trend. These differences are thought to reflect the effects of mineral and/or glass contaminants in samples from earlier studies which employed bulk analysis techniques. D REE determined using the MIM technique agree well with values predicted using the equations of Brice (1975), which are based on the size and elasticity of crystallographic sites. The presence of Ce 4+ in the melt results in elevated D Ce compared to neighboring REE due to the similar valence and size of Ce 4+ and Zr 4+. Predicted zircon/meltD values for Ce 4+ and Ce 3+ indicate that the Ce 4+/Ce 3+ ratios of the melt ranged from about 10 -3 to 10 -2. Partition coefficients for other trace elements determined in this study increase in compatibility in the order Ba < Rb < B < Sr < Ti < Y < Nb, with Ba, Rb, B and Sr showing incompatible behavior (D M < 1.0), and Ti, Y and Nb showing compatible behavior (D M > 1.0). The effect of partition coefficients on melt evolution during petrogenetic modeling was examined using partition coefficients determined in this study and compared to trends obtained using published partition coefficients. The lower D REE determined in this study result in smaller REE bulk distribution coefficients, for a given mineral assemblage, compared to those calculated using previously reported values. As an example, fractional crystallization of an assemblage composed of 35% hornblende, 64.5% plagioclase and 0.5% zircon produces a melt that becomes increasingly more enriched in Yb using the D Yb from this study. Using D Yb from Fujimaki (1986) results in a melt that becomes progressively depleted in Yb during crystallization.
NASA Astrophysics Data System (ADS)
Mollo, S.; Blundy, J. D.; Giacomoni, P.; Nazzari, M.; Scarlato, P.; Coltorti, M.; Langone, A.; Andronico, D.
2017-07-01
A peculiar characteristic of the paroxysmal sequence that occurred on March 16, 2013 at the New South East Crater of Mt. Etna volcano (eastern Sicily, Italy) was the eruption of siliceous crustal xenoliths representative of the sedimentary basement beneath the volcanic edifice. These xenoliths are quartzites that occur as subspherical bombs enclosed in a thin trachybasaltic lava envelope. At the quartzite-magma interface a reaction corona develops due to the interaction between the Etnean trachybasaltic magma and the partially melted quartzite. Three distinct domains are observed: (i) the trachybasaltic lava itself (Zone 1), including Al-rich clinopyroxene phenocrysts dispersed in a matrix glass, (ii) the hybrid melt (Zone 2), developing at the quartzite-magma interface and feeding the growth of newly-formed Al-poor clinopyroxenes, and (iii) the partially melted quartzite (Zone 3), producing abundant siliceous melt. These features makes it possible to quantify the effect of magma contamination by siliceous crust in terms of clinopyroxene-melt element partitioning. Major and trace element partition coefficients have been calculated using the compositions of clinopyroxene rims and glasses next to the crystal surface. Zone 1 and Zone 2 partition coefficients correspond to, respectively, the chemical analyses of Al-rich phenocrysts and matrix glasses, and the chemical analyses of newly-formed Al-poor crystals and hybrid glasses. For clinopyroxenes from both the hybrid layer and the lava flow expected relationships are observed between the partition coefficient, the valence of the element, and the ionic radius. However, with respect to Zone 1 partition coefficients, values of Zone 2 partition coefficients show a net decrease for transition metals (TE), high-field strength elements (HFSE) and rare earth elements including yttrium (REE + Y), and an increase for large ion lithophile elements (LILE). This variation is associated with coupled substitutions on the M1, M2 and T sites of the type M1(Al, Fe3 +) + TAl = M2(Mg, Fe2 +) + TSi. The different incorporation of trace elements into clinopyroxenes of hybrid origin is controlled by cation substitution reactions reflecting local charge-balance requirements. According to the lattice strain theory, simultaneous cation exchanges across the M1, M2, and T sites have profound effects on REE + Y and HFSE partitioning. Conversely, both temperature and melt composition have only a minor effect when the thermal path of magma is restricted to 70 °C and the value of non-bridging oxygens per tetrahedral cations (NBO/T) shifts moderately from 0.31 to 0.43. As a consequence, Zone 2 partition coefficients for REE + Y and HFSE diverge significantly from those derived for Zone 1, accounting for limited cation incorporation into the newly-formed clinopyroxenes at the quartzite-magma interface.
NASA Technical Reports Server (NTRS)
Grzybowski, J. M.; Allen, R. O.
1974-01-01
The factors that affect the preferred positions of cations in ionic solid solutions were investigated utilizing vibrational spectroscopy. Solid solutions of the sulfate and chromate ions codoped with La(+3) and Ca(+2) in a KBr host lattice were examined as a function of the polyvalent cation concentration. The cation-anion pairing process was found to be random for Ca(+2), whereas the formation of La(+3)-SO4(-2) ion pairs with a C2 sub v bonding geometry is highly preferential to any type of La(+3)-CrO4(-2) ion pair formation. The relative populations of ion pair site configurations are discussed in terms of an energy-entropy competition model which can be applied to the partition of trace elements during magmatic processes.
NASA Technical Reports Server (NTRS)
Kuehner, S. M.; Laughlin, J. R.; Grossman, L.; Johnson, M. L.; Burnett, D. S.
1989-01-01
The applicability of ion microprobe (IMP) for quantitative analysis of minor elements (Sr, Y, Zr, La, Sm, and Yb) in the major phases present in natural Ca-, Al-rich inclusions (CAIs) was investigated by comparing IMP results with those of an electron microprobe (EMP). Results on three trace-element-doped glasses indicated that it is not possible to obtain precise quantitative analysis by using IMP if there are large differences in SiO2 content between the standards used to derive the ion yields and the unknowns.
NASA Astrophysics Data System (ADS)
Edmonds, Marie
2015-02-01
An enigmatic record of light lithophile element (LLE) zoning in pyroxenes in basaltic shergottite meteorites, whereby LLE concentrations decrease dramatically from the cores to the rims, has been interpreted as being due to partitioning of LLE into a hydrous vapor during magma ascent to the surface on Mars. These trends are used as evidence that Martian basaltic melts are water-rich (McSween et al., 2001). Lithium and boron are light lithophile elements (LLE) that partition into volcanic minerals and into vapor from silicate melts, making them potential tracers of degassing processes during magma ascent to the surface of Earth and of other planets. While LLE degassing behavior is relatively well understood for silica-rich melts, where water and LLE concentrations are relatively high, very little data exists for LLE abundance, heterogeneity and degassing in basaltic melts. The lack of data hampers interpretation of the trends in the shergottite meteorites. Through a geochemical study of LLE, volatile and trace elements in olivine-hosted melt inclusions from Kilauea Volcano, Hawaii, it can be demonstrated that lithium behaves similarly to the light to middle rare Earth elements during melting, magma mixing and fractionation. Considerable heterogeneity in lithium and boron is inherited from mantle-derived primary melts, which is dominant over the fractionation and degassing signal. Lithium and boron are only very weakly volatile in basaltic melt erupted from Kilauea Volcano, with vapor-melt partition coefficients <0.1. Degassing of LLE is further inhibited at high temperatures. Pyroxene and associated melt inclusion LLE concentrations from a range of volcanoes are used to quantify lithium pyroxene-melt partition coefficients, which correlate negatively with melt H2O content, ranging from 0.13 at low water contents to <0.08 at H2O contents >4 wt%. The observed terrestrial LLE partitioning behavior is extrapolated to Martian primitive melts through modeling. The zoning observed in the shergottite pyroxenes is only consistent with degassing of LLE from a Martian melt near its liquidus temperature if the vapor-melt partition coefficient was an order of magnitude larger than observed on Earth. The range in LLE and trace elements observed in shergottite pyroxenes are instead consistent with concurrent mixing and fractionation of heterogeneous melts from the mantle.
NASA Astrophysics Data System (ADS)
Blundy, Jonathan D.; Wood, Bernard J.
1991-01-01
The isothermal (750°C) experiments of LAGACHE and DUJON (1987) reveal that the partitioning of Sr between plagioclase feldspar and hydrothermal solutions is a funtion of the anorthite (An) content of the plagioclase, indicating that crystal chemistry may exert a powerful influence on trace element partitioning. In order to compare these results with those on trace element partitioning between plagioclase and silicate melts we have compiled from the literature a large dataset of experimental and volcanic distribution coefficients ( D's) for Sr (and Ba). These data, which span a compositional range from lunar basalt to high silica rhyolite and a temperature range of over 650°C, show a relationship between DSr (and DBa) and mole fraction An ( XAn) which is similar to that exhibited by the hydrothermal results obtained at constant temperature. Plots of In DSr and In DBa versus XAn are linear with negative slope, indicating that both elements are more compatible in albite than anorthite. In terms of molar distribution coefficients ( D Sr∗) the hydrothermal and silicate melt data display an identical linear relationship between RT In D Sr∗ (where T is the absolute temperature in K and R is the gas constant, 8.314 JK -1 mol -1) and XAn. We conclude therefore that crystal chemistry provides the dominant control on partitioning of Sr and Ba into plagioclase and that the effects of temperature, pressure, and fluid composition are minor. Apparent relationships between DSr (and DBa) and the reciprocal temperature (1/ T) are artefacts of the linear relationships between XAn and 1/ T in the experimental studies. By defining a Henry's law standard state for the silicate melts and hydrothermal solutions, and considering plagioclases to be ternary regular solutions, we are able to relate the observed relationships between RT In D i∗ (where i is Ba or Sr) and XAn to the excess free energies of the trace element partitioning reactions between plagioclase and melt or hydrothermal solution. The interaction parameters are consistent with simple models in which the larger Ba or Sr cations are accommodated by lattice strain in the host plagioclase lattice, which is assumed to be perfectly elastic and isotropic. Thus D i∗ is a function of the Young's modulus of the host crystal and the size mismatch between trace and host cations. The greater elasticity of albite relative to anorthite accounts for the observed preference of Sr and Ba for sodic plagioclases over calcic plagioclases. For geochemical purposes the weight fraction partition coefficient Di is of more value than its molar counterpart. Regression of the Di data versus XAn yields the semi-empirical relationships RTIn DSr = 26,800 - 26,700 · XAnRTIn DBa = 10,200 - 38,200 · XAn. Thus measurement of the An and trace element (Ba, Sr) contents of a magmatic plagioclase enables calculation of the Ba and Sr contents of the coexisting liquid, which can be extremely important in the deciphering of igneous processes. By reference to plagioclase fractionation in the simple An-Ab binary we show that failure to take into account the compositional dependence of DSr can result in erroneous interpretations of geochemical trends. We also consider applications to three natural igneous suites: the Aden Volcanics; the layered Kiglapait Intrusion, Labrador; and the southern Actamello Massif, Italy.
Re-187-Os-187, Pt-190-Os-186 Isotopic and Highly Siderophile Element Systematics of Group IVA Irons
NASA Technical Reports Server (NTRS)
Walker, R. J.; McCoy, T. J.; Schulte, R. F.; McDonough, W. F.; Ash, R. D.
2005-01-01
We have recently completed Re-187-Os-187 and Pt-190-Os-186 isotopic and elemental studies of the two largest magmatic iron meteorite groups, IIAB and IIIAB [1]. These studies revealed closed-system behavior of both isotopic systems, but complex trace element behavior for Re, Pt and Os in group IIIAB. Here we examine isotopic and trace elemental systematics of group IVA irons. The IVA irons are not as extensively fractionated as IIAB and IIIAB and their apparently less complex crystallization history may make for more robust interpretation of the relative partitioning behavior of Re, Pt and Os, as well as the other highly siderophile elements (HSE) measured here; Pd, Ru and Ir [e.g. 2]. An additional goal of our continuing research plan for iron meteorites is to assess the possibility of relating certain ungrouped irons with major groups via trace element modeling. Here, the isotopic and trace element systematics of the ungrouped irons Nedagolla and EET 83230 are compared with the IVA irons.
Qian, Peng; Zheng, Xiang-min; Zhou, Li-min
2013-05-01
Atmospheric particulates were sampled from three sampling sites of Putuo, Minhang and Qingpu Districts in Shanghai between Oct. , 2009 and Oct. , 2010. In addition, particulate samples were also collected from Nantong, Zhengzhou, Xi'an, and Beijing city where dust storm dust transported along during spring. Element compositions of atmospheric particulates were determined by XRF and ICP-MS. The concentrations of major and trace elements in atmospheric particulates from Putuo, Minhang and Qingpu Districts were similar, indicating their common source. The UCC standardization distribution map showed that the major element composition of dust storm samples was similar to that of loess in northwestern China, indicating that the dust storm dust was mainly derived from Western desert and partly from local area. The REE partition patterns of dust storm dusts among different cities along dust transport route were similar to each other, as well as to those of northern loess, which indicates that the dust storm samples may have the same material source as loess, which mainly comes from crust material. However, the REE partition patterns of non-dust storm particulates were different among the studied cities, and different from those of loess, which suggests that the non-dust storm samples may be mixed with non-crust source material, which is different from dust storm dust and loess. The major element composition and REE partition pattern are effective indicators for source tracing of dust storm dust.
NASA Astrophysics Data System (ADS)
Lammers, L. N.
2014-12-01
The dependence of the isotopic and trace element composition of calcium carbonate minerals on growth conditions including temperature, pH, and salinity is widely used to infer paleoclimate conditions. These inferences rely heavily on phenomenological observations of biogenic and inorganic precipitation both in and ex situ, where only limited variability in solution conditions can be explored. Ionic fluxes between the mineral surface and aqueous growth solution govern the net uptake of both stoichiometric and trace species during calcification, so developing a mechanistic understanding of the reactions governing these fluxes is critical to refine existing proxies and to develop new ones. The micro-scale mechanisms of calcite precipitation from aqueous solution have been extensively studied, and net ionic uptake post-nucleation is known to occur primarily at monomolecular kink sites along step edges at the mineral surface. In this talk, I will present a theoretical framework that uses the quasi-elementary ion attachment and detachment reactions governing ion uptake at kink sites to simultaneously model bulk mineral growth kinetics and tracer partitioning during calcite precipitation. Several distinct processes occur during ion uptake at kink sites that can influence the distribution of trace species, directly impacting the composition of various carbonate paleoproxies including δ44Ca, δ18O, Sr/Ca and Mg/Ca. The distribution of these trace species will be shown to depend on (1) the relative rates of ion desolvation during attachment to kink sites, (2) the relative rates of bond breaking during detachment from kink sites, and (3) the equilibrium partitioning of trace aqueous species. This model accounts for the impact of solution conditions on net ion fluxes and surface speciation, which in turn controls the population of kink sites available for direct ion exchange with the aqueous phase. The impacts of solution variables including pH, temperature and salinity can be treated independently, which unlike traditional partitioning studies allows the impacts of these parameters to be deconvolved. The type of theoretical framework discussed here can be readily extended to explicitly account for each of the major solution composition variables that are implicated in paleoproxy composition.
Hayzoun, H; Garnier, C; Durrieu, G; Lenoble, V; Le Poupon, C; Angeletti, B; Ouammou, A; Mounier, S
2015-01-01
An annual-basis study of the impacts of the anthropogenic inputs from Fez urban area on the water geochemistry of the Sebou and Fez Rivers was conducted mostly focusing on base flow conditions, in addition to the sampling of industrial wastewater characteristic of the various pressures in the studied environment. The measured trace metals dissolved/particulate partitioning was compared to the ones predicted using the WHAM-VII chemical speciation code. The Sebou River, upstream from Fez city, showed a weakly polluted status. Contrarily, high levels of major ions, organic carbon and trace metals were encountered in the Fez River and the Sebou River downstream the Fez inputs, due to the discharge of urban and industrial untreated and hugely polluted wastewaters. Trace metals were especially enriched in particles with levels even exceeding those recorded in surface sediments. The first group of elements (Al, Fe, Mn, Ti, U and V) showed strong inter-relationships, impoverishment in Fez particles/sediments and stable partition coefficient (Kd), linked to their lithogenic origin from Sebou watershed erosion. Conversely, most of the studied trace metals/metalloids, originated from anthropogenic sources, underwent significant changes of Kd and behaved non-conservatively in the Sebou/Fez water mixing. Dissolved/particulate partitioning was correctly assessed by WHAM-VII modeling for Cu, Pb and Zn, depicting significant differences in chemical speciation in the Fez River when compared to that in the Sebou River. The results of this study demonstrated that a lack of compliance in environmental regulations certainly explained this poor status. Copyright © 2014 Elsevier B.V. All rights reserved.
NASA Technical Reports Server (NTRS)
Nickodem, K.; Righter, K.; Danielson, L.; Pando, K.; Lee, C.
2012-01-01
There are currently several hypotheses on the origin of volatile siderophile elements in the Earth. One hypothesis is that they were added during Earth s accretion and core formation and mobilized into the metallic core [1], others claim multiple stage origin [2], while some hypothesize that volatiles were added after the core already formed [3]. Several volatile siderophile elements are depleted in Earth s mantle relative to the chondrites, something which continues to puzzle many scientists. This depletion is likely due to a combination of volatility and core formation. The Earth s core is composed of Fe and some lighter constituents, although the abundances of these lighter elements are unknown [4]. Si is one of these potential light elements [5] although few studies have analyzed the effect of Si on metal-silicate partitioning, in particular the volatile elements. As, In, Ge, and Sb are trace volatile siderophile elements which are depleted in the mantle but have yet to be extensively studied. The metal-silicate partition coefficients of these elements will be measured to determine the effect of Si. Partition coefficients depend on temperature, pressure, oxygen fugacity, and metal and silicate composition and can constrain the concentrations of volatile, siderophile elements found in the mantle. Reported here are the results from 13 experiments examining the partitioning of As, In, Ge, and Sb between metallic and silicate liquid. These experiments will examine the effect of temperature, and metal-composition (i.e., Si content) on these elements in or-der to gain a greater understanding of the core-mantle separation which occurred during the Earth s early stages. The data can then be applied to the origin of volatile elements in the Earth.
NASA Astrophysics Data System (ADS)
Dasgupta, R.; Jego, S.; Ding, S.; Li, Y.; Lee, C. T.
2015-12-01
The behavior of chalcophile elements during mantle melting, melt extraction, and basalt differentiation is critical for formation of ore deposits and geochemical model and evolution of crust-mantle system. While chalcophile elements are strongly partitioned into sulfides, their behavior with different extent of melting, in particular, in the absence of sulfides, can only be modeled with complete knowledge of the partitioning behavior of these elements between dominant mantle minerals and basaltic melt with or without dissolved sulfide (S2-). However, experimental data on mineral-melt partitioning are lacking for many chalcophile elements. Crystallization experiments were conducted at 3 GPa and 1450-1600 °C using a piston cylinder and synthetic silicate melt compositions similar to low-degree partial melt of peridotite. Starting silicate mixes doped with 100-300 ppm of each of various chalcophile elements were loaded into Pt/graphite double capsules. To test the effect of dissolved sulfur in silicate melt on mineral-melt partitioning of chalcophile elements, experiments were conducted on both sulfur-free and sulfur-bearing (1100-1400 ppm S in melt) systems. Experimental phases were analyzed by EPMA (for major elements and S) and LA-ICP-MS (for trace elements). All experiments produced an assemblage of cpx + melt ± garnet ± olivine ± spinel and yielded new partition coefficients (D) for Sn, Zn, Mo, Sb, Bi, Pb, and Se for cpx/melt, olivine/melt, and garnet/melt pairs. Derived Ds (mineral/basalt) reveal little effect of S2- in the melt on mineral-melt partition coefficients of the measured chalcophile elements, with Ds for Zn, Mo, Bi, Pb decreasing by less than a factor of 2 from S-free to S-bearing melt systems or remaining similar, within error, between S-free and S-bearing melt systems. By combining our data with existing partitioning data between sulfide phases and silicate melt we model the fractionation of these elements during mantle melting and basalt crystallization. The model results are compared with the chalcophile element abundance in oceanic basalts. We will discuss the implications of our new partitioning data and model results on sulfur and chalcophile element geochemistry of mantle source regions of ocean floor basalts and the fate of sulfides during mantle melting.
Trace element profiles of the sea anemone Anemonia viridis living nearby a natural CO2 vent
Borell, Esther M.; Fine, Maoz; Shaked, Yeala
2014-01-01
Ocean acidification (OA) is not an isolated threat, but acts in concert with other impacts on ecosystems and species. Coastal marine invertebrates will have to face the synergistic interactions of OA with other global and local stressors. One local factor, common in coastal environments, is trace element contamination. CO2 vent sites are extensively studied in the context of OA and are often considered analogous to the oceans in the next few decades. The CO2 vent found at Levante Bay (Vulcano, NE Sicily, Italy) also releases high concentrations of trace elements to its surrounding seawater, and is therefore a unique site to examine the effects of long-term exposure of nearby organisms to high pCO2 and trace element enrichment in situ. The sea anemone Anemonia viridis is prevalent next to the Vulcano vent and does not show signs of trace element poisoning/stress. The aim of our study was to compare A. viridis trace element profiles and compartmentalization between high pCO2 and control environments. Rather than examining whole anemone tissue, we analyzed two different body compartments—the pedal disc and the tentacles, and also examined the distribution of trace elements in the tentacles between the animal and the symbiotic algae. We found dramatic changes in trace element tissue concentrations between the high pCO2/high trace element and control sites, with strong accumulation of iron, lead, copper and cobalt, but decreased concentrations of cadmium, zinc and arsenic proximate to the vent. The pedal disc contained substantially more trace elements than the anemone’s tentacles, suggesting the pedal disc may serve as a detoxification/storage site for excess trace elements. Within the tentacles, the various trace elements displayed different partitioning patterns between animal tissue and algal symbionts. At both sites iron was found primarily in the algae, whereas cadmium, zinc and arsenic were primarily found in the animal tissue. Our data suggests that A. viridis regulates its internal trace element concentrations by compartmentalization and excretion and that these features contribute to its resilience and potential success at the trace element-rich high pCO2 vent. PMID:25250210
The Influence of Oxygen and Sulfur on Uranium Partitioning Into the Core
NASA Astrophysics Data System (ADS)
Moore, R. D., Jr.; Van Orman, J. A.; Hauck, S. A., II
2017-12-01
Uranium, along with K and Th, may provide substantial long-term heating in planetary cores, depending on the magnitude of their partitioning into the metal during differentiation. In general, non-metallic light elements are known to have a large influence on the partitioning of trace elements, and the presence of sulfur is known to enhance the partitioning of uranium into the metal. Data from the steelmaking literature indicate that oxygen also enhances the solubility of oxygen in liquid iron alloys. Here we present experimental data on the partitioning of U between immiscible liquids in the Fe-S-O system, and use these data along with published metal-silicate partitioning data to calibrate a quantitative activity model for U in the metal. We also determined partition coefficients for Th, K, Nb, Nd, Sm, and Yb, but were unable to fully constrain activity models for these elements with available data. A Monte Carlo fitting routine was used to calculate U-S, U-O, and U-S-O interaction coefficients, and their associated uncertainties. We find that the combined interaction of uranium with sulfur and oxygen is predominant, with S and O together enhancing the solubility of uranium to a far greater degree than either element in isolation. This suggests that uranium complexes with sulfite or sulfate species in the metal. For a model Mars core composition containing 14 at% S and 5 at% O, the metal/silicate partition coefficient for U is predicted to be an order of magnitude larger than for a pure Fe-Ni core.
Tin in granitic melts: The role of melting temperature and protolith composition
NASA Astrophysics Data System (ADS)
Wolf, Mathias; Romer, Rolf L.; Franz, Leander; López-Moro, Francisco Javier
2018-06-01
Granite bound tin mineralization typically is seen as the result of extreme magmatic fractionation and late exsolution of magmatic fluids. Mineralization, however, also could be obtained at considerably less fractionation if initial melts already had enhanced Sn contents. We present chemical data and results from phase diagram modeling that illustrate the dominant roles of protolith composition, melting conditions, and melt extraction/evolution for the distribution of Sn between melt and restite and, thus, the Sn content of melts. We compare the element partitioning between leucosome and restite of low-temperature and high-temperature migmatites. During low-temperature melting, trace elements partition preferentially into the restite with the possible exception of Sr, Cd, Bi, and Pb, that may be enriched in the melt. In high-temperature melts, Ga, Y, Cd, Sn, REE, Pb, Bi, and U partition preferentially into the melt whereas Sc, V, Cr, Co, Ni, Mo, and Ba stay in the restite. This contrasting behavior is attributed to the stability of trace element sequestering minerals during melt generation. In particular muscovite, biotite, titanite, and rutile act as host phases for Sn and, therefore prevent Sn enrichment in the melt as long as they are stable phases in the restite. As protolith composition controls both the mineral assemblage and modal contents of the various minerals, protolith composition eventually also controls the fertility of a rock during anatexis, restite mineralogy, and partitioning behavior of trace metals. If a particular trace element is sequestered in a phase that is stable during partial melting, the resulting melt is depleted in this element whereas the restite becomes enriched. Melt generation at high temperature may release Sn when Sn-hosts become unstable. If melt has not been lost before the breakdown of Sn-hosts, Sn contents in the melt will increase but never will be high. In contrast, if melt has been lost before the decomposition of Sn-hosts, the small volume of the high-temperature melt will not be diluted by low-temperature, low-Sn melts and, therefore, could have high Sn-contents. The combination of multiple melt extractions and Sn-mobilization at high temperature results in strong Sn enrichment in late, high-temperature melts. Metal enrichment during partial melting becomes particularly efficient, if the sedimentary protolith had experienced intense chemical alteration as the loss of Na and Ca together with a relative enrichment of K favors muscovite-rich metamorphic mineral assemblages that produce large amounts of melt during muscovite dehydration melting.
Evidence for a high temperature differentiation in a molten earth: A preliminary appraisal
NASA Technical Reports Server (NTRS)
Murthy, V. Rama
1992-01-01
If the earth were molten during its later stages of accretion as indicated by the present understanding of planetary accretion process, the differentiation that led to the formation of the core and mantle must have occurred at high temperatures in the range of 3000-5000 K because of the effect of pressure on the temperature of melting in the interior of the earth. This calls into question the use of low-temperature laboratory measurements of partition coefficients of trace elements to make inferences about earth accretion and differentiation. The low temperature partition coefficients cannot be directly applied to high temperature fractionations because partition coefficients refer to an equilibrium specific to a temperature for a given reaction, and must change in some proportion to exp 1/RT. There are no laboratory data on partition coefficients at the high temperatures relevant to differentiation in the interior of the earth, and an attempt to estimate high temperature distribution coefficients of siderophile elements was made by considering the chemical potential of a given element at equilibrium and how this potential changes with temperature, under some specific assumptions.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Shearer, C.K.; Papike, J.J.; Simon, S.B.
1989-05-01
To study the effects of crystallization sequence and rate on trace element zoning characteristics of pyroxenes, the authors used combined electron microprobe-ion microprobe techniques on four nearly isochemical Apollo 12 and 15 pigeonite basalts with different cooling rates and crystallization histories. Major and minor element zoning characteristics are nearly identical to those reported in the literature. All the pyroxenes have similar chondrite-normalized REE patterns: negative Eu anomalies, positive slopes as defined by Yb/Ce, and slopes of REE patterns from Ce to Sm much steeper than from Gd to Yb. These trace element zoning characteristics in pyroxene and the partitioning ofmore » trace elements between pyroxene and the melt are intimately related to the interplay among the efficiency of the crystallization process, the kinetics at the crystal-melt interface, the kinetics of plagioclase nucleation and the characteristics of the crystal chemical substitutions within both the pyroxene and the associated crystallizing phases (i.e. plagioclase).« less
NASA Technical Reports Server (NTRS)
Snyder, Gregory A.; Taylor, Lawrence A.; Crozaz, Ghislaine
1993-01-01
Results are presented of trace-element analyses of three lunar zircons. The major-element and REE compositions were determined using electron microprobes, and a correction was made for zircon for Zr-Si-O molecular interferences in the La to Pr mass region. The three zircons were found to exhibit similar REE abundances and patterns. Results of the analyses confirm earlier studies (Hess et al., 1975; Watson, 1976; Neal and Taylor, 1989) on the partitioning behavior of trace elements in immiscible liquid-liquid pairs. The results also support the postulated importance of silicate liquid immiscibility in the differentiation of the upper mantle and crust of the moon.
Saravanabhavan, Gurusankar; Werry, Kate; Walker, Mike; Haines, Douglas; Malowany, Morie; Khoury, Cheryl
2017-03-01
Human biomonitoring reference values are statistical estimates that indicate the upper margin of background exposure to a given chemical at a given time. Nationally representative human biomonitoring data on 176 chemicals, including several metals and trace elements, are available in Canada from 2007 to 2013 through the Canadian Health Measures Survey (CHMS). In this work, we used a systematic approach based on the reference interval concept proposed by the International Federation of Clinical Chemistry and Laboratory Medicine and the International Union of Pure and Applied Chemistry to derive reference values (RV 95 s) for metals and trace elements. These RV 95 s were derived for blood and urine matrices in the general Canadian population based on the latest biomonitoring data from the CHMS. Biomarkers were chosen based on specific selection criteria, including widespread detection in Canadians (≥66% detection rate). Reference populations were created for each biomarker by applying appropriate exclusion criteria. Age and sex were evaluated as possible partitioning criteria and separate RV 95 s were derived for the sub-populations in cases where partitioning was deemed necessary. The RV 95 s for metals and trace elements in blood ranged from 0.18μg/L for cadmium in young children aged 3-5 years to 7900μg/L for zinc in males aged 20-79 years. In the case of urinary biomarkers, the RV 95 s ranged from 0.17μg/L for antimony in the total population aged 3-79 years to 1400mg/L for fluoride in adults aged 20-79 years. These RV 95 s represent the first set of reference values for metals and trace elements in the general Canadian population. We compare the RV 95 s from other countries where available and discuss factors that could influence such comparisons. Copyright © 2016 The Authors. Published by Elsevier GmbH.. All rights reserved.
Trace element release from estuarine sediments of South Mosquito Lagoon near Kennedy Space Center
NASA Technical Reports Server (NTRS)
Menon, M. P.; Ghuman, G. S.; Emeh, C. O.
1979-01-01
Analytical partitioning of four trace metals in estuarine sediments collected from eight sites in South Mosquito Lagoon near Kennedy Space Center, in terms of four different categories was accomplished using four different extraction techniques. The concentrations of the four trace metals, Zn, Mn, Cd, and Cu, released in interstitial water extract, 1 N ammonium acetate extract, conc. HCl extract and fusion extract of sediments as well as their concentrations in water samples collected from the same location were determined using flame atomic absorption technique. From the analytical results the percentages of total amount of each metal distributed among four different categories, interstitial water phase, acetate extractable, acid extractable and detrital crystalline material, were determined. Our results suggest that analytical partitioning of trace metals in estuarine sediments may be used to study the mechanism of incorporation of trace metals with sediments from natural waters. A correlation between the seasonal variation in the concentration of acetate extractable trace metals in the sediment and similar variation in their concentration in water was observed. A mechanism for the release of trace metals from estuarine sediments to natural water is also suggested.
Tourrette, T.Z.L.; Burnett, D.S.; Bacon, C.R.
1991-01-01
Crystal-liquid partitioning in Fe-Ti oxides and zircon was studied in partially melted granodiorite blocks ejected during the climactic eruption of Mt. Mazama (Crater Lake), Oregon. The blocks, which contain up to 33% rhyolite glass (75 wt% SiO2), are interpreted to be portions of the magma chamber walls that were torn off during eruption. The glass is clear and well homogenized for all measured elements except Zr. Results for Fe-Ti oxides give DUoxide/liq ??? 0.1. Partitioning of Mg, Mn, Al, Si, V, and Cr in Fe-Ti oxides indicates that grains surrounded by glass are moderately well equilibrated with the melt for many of the minor elements, while those that are inclusions in relict plagioclase are not. Uranium and ytterbium inhomogeneities in zircons indicate that the zircons have only partially equilibrated with the melt and that uranium appears to have been diffusing out of the zircons faster than the zircons were dissolving. Minimum U, Y, and P concentrations in zircons give maximum DUzrc/liq = 13,DYzrc/liq = 23, and DPzrc/liq = 1, but these are considerably lower than reported by other workers for U and Y. Based on our measurements and given their low abundances in most rocks, Fe-Ti oxides probably do not play a major role in U-Th fractionation during partial melting. The partial melts were undersaturated with zircon and apatite, but both phases are present in our samples. This demonstrates an actual case of non-equilibrium source retention of accessory phases, which in general could be an important trace-element fractionation mechanism. Our results do not support the hypothesis that liquid structure is the dominant factor controlling trace-element partitioning in high-silica rhyolites. Rough calculations based on Zr gradients in the glass indicate that the samples could have been partially molten for 800 to 8000 years. ?? 1991.
Geochemical Constraints on the Size of the Moon — Forming Giant Impact
NASA Astrophysics Data System (ADS)
Piet, H.; Badro, J.; Gillet, P.
2018-05-01
We use the partitioning of siderophile trace elements to model the geochemical influence of the Moon-forming giant impact on Earth’s mantle during core formation. We find the size of the impactor to be 15% of Earth mass or smaller.
The effect of tissue structure and soil chemistry on trace element uptake in fossils
NASA Astrophysics Data System (ADS)
Hinz, Emily A.; Kohn, Matthew J.
2010-06-01
Trace element profiles for common divalent cations (Sr, Zn, Ba), rare-earth elements (REE), Y, U, and Th were measured in fossil bones and teeth from the c. 25 ka Merrell locality, Montana, USA, by using laser-ablation ICP-MS. Multiple traverses in teeth were transformed into 2-D trace element maps for visualizing structural influences on trace element uptake. Trace element compositions of different soils from the fossil site were also analyzed by solution ICP-MS, employing progressive leaches that included distilled H 2O, 0.1 M acetic acid, and microwave digestion in concentrated HCl-HNO 3. In teeth, trace element uptake in enamel is 2-4 orders of magnitude slower than in dentine, forming an effective trace element barrier. Uptake in dentine parallel to the dentine-enamel interface is enhanced by at least 2 orders of magnitude compared to transverse, causing trace element "plumes" down the tooth core. In bone, U, Ba and Sr are nearly homogeneous, implying diffusivities ˜5 orders of magnitude faster than in enamel and virtually complete equilibration with host soils. In contrast all REE show strong depletions inward, with stepwise linear segments in log-normal or inverse complementary error function plots; these data require a multi-medium diffusion model, with about 2 orders of magnitude difference in slowest vs. fastest diffusivities. Differences in REE diffusivities in bone (slow) vs. dentine (fast) reflect different partition coefficients ( Kd's). Although acid leaches and bulk digestion of soils yield comparable fossil-soil Kd's among different elements, natural solutions are expected to be neutral to slightly basic. Distilled H 2O leachates instead reveal radically different Kd's in bone for REE than for U-Sr-Ba, suggest orders of magnitude lower effective diffusivities for REE, and readily explain steep vs. flat profiles for REE vs. U-Sr-Ba, respectively. Differences among REE Kd's and diffusivities may explain inward changes in Ce anomalies. Acid washes and bulk soil compositions yield misleading Kd's for many trace elements, especially the REE, and H 2O-leaches are preferred. Patterns of trace element distributions indicate diagenetic alteration at all scales, including enamel, and challenge the use of trace elements in paleodietary studies.
NASA Astrophysics Data System (ADS)
Gao, Wenyuan; Ciobanu, Cristiana L.; Cook, Nigel J.; Huang, Fei; Meng, Lin; Gao, Shang
2017-12-01
Permian mafic-ultramafic layered intrusions in the central part of the Emeishan Large Igneous Province (ELIP), Southwestern China, host Fe-Ti-V-oxide ores that have features which distinguish them from other large layered intrusion-hosted deposits. The origin of these ores is highly debated. Careful petrographic examination, whole rock analysis, electron probe microanalysis, and measurement and mapping of trace element concentrations by laser ablation inductively coupled plasma mass spectrometry in all major and minor minerals (clinopyroxene, plagioclase, olivine, amphibole, titanomagnetite, ilmenite, pleonaste and pyrrhotite) has been undertaken on samples from the Lanjiahuoshan deposit, representing the Middle, Lower and Marginal Zone of the Panzhihua intrusion. Features are documented that impact on interpretation of intrusion petrology and with implications for genesis of the Fe-Ti-V-oxide ores. Firstly, there is evidence, as symplectites between clinopyroxene and plagioclase, for introduction of complex secondary melts. Secondly, reaction between a late hydrothermal fluid and clinopyroxene is recognized, which has led to formation of hydrated minerals (pargasite, phlogopite), as well as a potassium metasomatic event, postdating intrusion solidification, which led to formation of K-feldspar. Lastly, partitioning of trace elements between titanomagnetite and silicates needs to consider scavenging of metals by ilmenite (Mn, Sc, Zr, Nb, Sn, Hf and Ta) and sulfides, as well as the marked partitioning of Co, Ni, Zn, Ga, As and Sb into spinels exsolved from titanomagnetite. The role of these less abundant phases may have been understated in previous studies, highlighting the importance of petrographic examination of complex silicate-oxide-sulfide assemblages, as well as the need for a holistic approach to trace element analysis, acknowledging all minerals within the assemblage.
NASA Astrophysics Data System (ADS)
Ayers, John C.; Peters, Timothy J.
2018-02-01
Hydrothermal zircon grains have trace element characteristics such as low Th/U, high U, and high rare earth element (REE) concentrations that distinguish them from magmatic, metamorphic, and altered zircon grains, but it is unclear whether these characteristics result from distinctive fluid compositions or zircon/fluid fractionation effects. New experiments aimed at measuring zircon/fluid trace element partition coefficients Dz/f involved recrystallizing natural Mud Tank zircon with low trace element concentrations in the presence of H2O, 1 m NaOH, or 1 m HCl doped with ∼1000 ppm of rare earth elements (REE), Y, U and Th and ∼500 ppm of Li, B, P, Nb, Ba, Hf, and Ta. Experiments were run for 168 h at 1.5 GPa, 800-1000 °C, and fO2 = NNO in a piston cylinder apparatus using the double capsule method. LA-ICP-MS analysis shows that run product zircon crystals have much higher trace element concentrations than in Mud Tank zircon starting material. Dz/f values were estimated from run product zircon analyses and bulk composition using mass balance. Most elements behave incompatibly, with median Dz/f being highest for Hf = 8 and lowest for B = 0.02. Addition of NaOH or HCl had little influence on Dz/f values. Dz/f for LREE are anomalously high, likely due to contamination of run product zircon with quenched solutes enriched in incompatible elements, so DLREE were estimated using lattice strain theory. Brice curves for +3 ions yield zircon/fluid DLu/DLa of ∼800-5000. A Brice curve fit to +4 ions yielded DCe4+ values. Estimated concentrations of Ce3+ and Ce4+ show that the average Ce4+/Ce3+ in zircon of 27 is much higher than in fluid of 0.02. Th and U show little fractionation, with median DTh/DU = 0.7, indicating that the low Th/U in natural hydrothermal zircon is inherited from the fluid. Natural fluid compositions estimated from measured Dz/f and published compositions of hydrothermal zircon grains from aplite and eclogite reflect the mineralogy of the host rock, e.g., fluid in equilibrium with eclogite garnet is depleted in heavy REE relative to middle REE, and has low Th/U.
NASA Astrophysics Data System (ADS)
Xiong, Z.; Tsuchiya, T.
2017-12-01
Element partitioning is an important property in recording geochemical processes during the core-mantle differentiation. However, experimental measurements of element partitioning coefficients under extreme temperature and pressure condition are still challenging. Theoretical modeling is also not easy, because it requires estimation of high temperature Gibbs free energy, which is not directly accessible by the standard molecular dynamics method. We recently developed an original technique to simulate Gibbs free energy based on the thermodynamics integration method[1]. We apply it to element partitioning of geochemical intriguing trace elements between molten silicate and liquid iron such as potassium, helium and argon as starting examples. Radiogenic potassium in the core can provide energy for Earth's magnetic field, convection in the mantle and outer core[2]. However, its partitioning behavior between silicate and iron remains unclear under high pressure[3,4]. Our calculations suggest that a clear positive temperature dependence of the partitioning coefficient but an insignificant pressure effect. Unlike sulfur and silicon, oxygen dissolved in the metals considerably enhances potassium solubility. Calculated electronic structures reveal alkali-metallic feature of potassium in liquid iron, favoring oxygen with strong electron affinity. Our results suggest that 40K could serve as a potential radiogenic heat source in the outer core if oxygen is the major light element therein. We now further extend our technique to partitioning behaviors of other elements, helium and argon, to get insides into the `helium paradox' and `missing argon' problems. References [1] T. Taniuchi, and T. Tsuchiya, Phys.Rev.B. In press [2] B.A. Buffett, H.E. Huppert, J.R. Lister, and A.W. Woods, Geophys.Res.Lett. 29 (1996) 7989-8006. [3] V.R. Murthy, W. Westrenen, and Y. Fei, Nature. 426 (2003) 163-165. [4] A. Corgne, S.Keshav, Y. Fei, and W.F. McDonough, Earth.Planet.Sci.Lett. 256 (2007) 567-576
NASA Technical Reports Server (NTRS)
Pun, A.; Papike, J. J.
1994-01-01
We are evaluating the trace-element concentrations in the pyroxenes of Pasamonte. Pasamonte is a characteristic member of the main group eucrites, and has recently been redescribed as a polymict eucrite. Our Pasamonte sample contained eucritic clasts with textures ranging from subophitic to moderately coarse-grained. This study concentrates on pyroxenes from an unequilibrated, coarse-grained eucrite clast. Major-, minor-, and trace-element analyses were measured for zoned pyroxenes in the eucritic clast of Pasamonte. The major- and minor-element zoning traverses were measured using the JEOL 733 electron probe with an Oxford-Link imaging/analysis system. Complemenatry trace elements were then measured for the core and rim of each of the grains by SIMS. The trace elements analyzed consisted of eight REE, Sr, Y, and Zr. These analyses were performed on a Cameca 4f ion probe. The results of the CI chondrite normalized (average CI trace-element analyses for several grains and the major- and minor-element zoning patterns from a single pyroxene grain are given. The Eu abundance in the cores of the pyroxenes represents the detection limit and therefore the (-Eu) anomaly is a minimum. Major- and minor-element patterns are typical for igneous zoning. Pyroxene cores are Mg enriched, whereas the rims are enriched in Fe and Ca. Also, Ti and Mn are found to increase, while Cr and Al generally decrease in core-to-rim traverses. The cores of the pyroxenes are more depleted in the Rare Earth Elements (REE) than the rims. Using the minor- and trace-element concentrations of bulk Pasamonte and the minor- and trace-element concentrations from the cores of the pyroxenes in Pasamonte measured in this study, we calculated partition coefficients between pyroxene and melt. This calculation assumes that bulk Pasamonte is representative of a melt composition.
Siderophile Element Profile Measurements in Iron Meteorites Using Laser Ablation ICP-MS
NASA Technical Reports Server (NTRS)
Watson, H. C.; Watson, E. B.; McDonough, W. F.
2005-01-01
Understanding the behaviour of siderophile elements during cooling of iron meteorites can lead to insight into the general thermal histories of the meteorites as well as their respective parent bodies. Traditionally trace element analyses in meteorites have been done using techniques that only measure the average concentration in each phase. With these methods, all of the spatial information with respect to the distribution of an element within one phase is lost. Measuring concentration profiles of trace elements in meteorites is now possible, with the advent of high-resolution analytical techniques such as laser ablation, inductively coupled plasma mass spectrometry (LA-ICP-MS) with spatial resolution <20 microns. [e.g. 1,2] and secondary ion mass spectrometry [3]. These profiles can give more insight into both the partitioning and diffusive behavior of siderophile elements in metal systems relevant to iron meteorites, as well as parent body cooling rates.
Budakoglu, Murat; Karaman, Muhittin; Kumral, Mustafa; Zeytuncu, Bihter; Doner, Zeynep; Yildirim, Demet Kiran; Taşdelen, Suat; Bülbül, Ali; Gumus, Lokman
2018-02-23
The major and trace element component of 48 recent sediment samples in three distinct intervals (0-10, 10-20, and 20-30 cm) from Lake Acıgöl is described to present the current contamination levels and grift structure of detrital and evaporate mineral patterns of these sediments in this extreme saline environment. The spatial and vertical concentrations of major oxides were not uniform in the each subsurface interval. However, similar spatial distribution patterns were observed for some major element couples, due mainly to the detrital and evaporate origin of these elements. A sequential extraction procedure including five distinct steps was also performed to determine the different bonds of trace elements in the < 60-μ particulate size of recent sediments. Eleven trace elements (Ni, Fe, Cd, Pb, Cu, Zn, As, Co, Cr, Al and Mn) in nine surface and subsurface sediment samples were analyzed with chemical partitioning procedures to determine the trace element percentage loads in these different sequential extraction phases. The obtained accuracy values via comparison of the bulk trace metal loads with the total loads of five extraction steps were satisfying for the Ni, Fe, Cd, Zn, and Co. While, bulk analysis results of the Cu, Ni, and V elements have good correlation with total organic matter, organic fraction of sequential extraction characterized by Cu, As, Cd, and Pb. Shallow Lake Acıgöl sediment is characteristic with two different redox layer a) oxic upper level sediments, where trace metals are mobilized, b) reduced subsurface level, where the trace metals are precipitated.
Majorite-Garnet Partitioning of the Highly Siderophile Elements: New Results and Application to Mars
NASA Technical Reports Server (NTRS)
Danielson, L. R.; Righter, K.; Waeselmann, N.; Humayun, M.
2015-01-01
HSE and Os isotopes are used to constrain processes such as accretion, mantle evolution, crustal recycling, and core-mantle mixing, and to constrain the timing and depth of differentiation of Mars. Although showed that the HSE contents of the martian mantle could have been established by metal-silicate equilibrium in early Mars, the role of a cooling magma ocean and associated crystallization in further fractionating the HSEs is unclear. Garnet is thought to have played an important role in controlling trace element concentrations in the martian mantle reservoirs. However, testing these models, including Os isotopes, has been hindered by a dearth of partitioning data for the HSE in deep mantle phases - majorite, wadsleyite, ringwoodite, akimotoite - that may be present in the martian mantle. We examine the partitioning behavior of HSEs between majorite garnet (gt), olivine (oliv), and silicate liquid (melt).
NASA Astrophysics Data System (ADS)
Evans, Thomas M.; O'Neill, Hugh St. C.; Tuff, James
2008-12-01
Partition coefficients for a range of Rare Earth Elements (REEs), Y, Sc, Al and Zr were determined between forsteritic olivine (nearly end-member Mg 2SiO 4) and ten melt compositions in the system CaO-MgO-Al 2O 3-SiO 2 (CMAS) at 1 bar and 1400 °C, with concentrations of the trace elements in the olivine and the melt measured by laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The REEs and Sc were added at levels sufficient to ensure that concentrations in the olivine were well above the detection limits. The REE partition coefficients (DREEol/melt) decrease with increasing silica in the melt, indicating strong bonding between REEO 1.5 and SiO 2 in the melt. The variation of DREEol/melt as a function of ionic radius is well described by the Brice equation for each composition, although a small proportion of this variation is due to the increase in the strength of the REEO 1.5-SiO 2 interactions in the melt with ionic radius. Scandium behaves very similarly to the REEs, but a global fit of the data from all ten melt compositions suggests that DScol/melt deviates somewhat from the parabolas established by the REE and Y, implying that Sc may substitute into olivine differently to that of the REEs. In contrast to the behaviour of the large trivalent cations, the concentration of Al in olivine is proportional to the square root of its concentration in the melt, indicating a coupled substitution in olivine with a high degree of short-range order. The lack of any correlation of REE partition coefficients with Al in olivine or melt suggests that the REE substitution in olivine is charge-balanced by cation vacancies. The partition coefficient of the tetravalent trace element Zr, which is highly incompatible in olivine, depends on the CaO content of the melt.
Experimental and Analytical Studies of Solar System Chemistry
NASA Technical Reports Server (NTRS)
Burnett, Donald S.
2003-01-01
The cosmochemistry research funded by this grant resulted in the publications given in the attached Publication List. The research focused in three areas: (1) Experimental studies of trace element partitioning. (2) Studies of the minor element chemistry and O isotopic compositions of MgAlO4 spinels from Ca-Al-Rich Inclusions in carbonaceous chondrite meteorites, and (3) The abundances and chemical fractionations of Th and U in chondritic meteorites.
Jephcoat, Andrew P; Bouhifd, M Ali; Porcelli, Don
2008-11-28
The present state of the Earth evolved from energetic events that were determined early in the history of the Solar System. A key process in reconciling this state and the observable mantle composition with models of the original formation relies on understanding the planetary processing that has taken place over the past 4.5Ga. Planetary size plays a key role and ultimately determines the pressure and temperature conditions at which the materials of the early solar nebular segregated. We summarize recent developments with the laser-heated diamond anvil cell that have made possible extension of the conventional pressure limit for partitioning experiments as well as the study of volatile trace elements. In particular, we discuss liquid-liquid, metal-silicate (M-Sil) partitioning results for several elements in a synthetic chondritic mixture, spanning a wide range of atomic number-helium to iodine. We examine the role of the core as a possible host of both siderophile and trace elements and the implications that early segregation processes at deep magma ocean conditions have for current mantle signatures, both compositional and isotopic. The results provide some of the first experimental evidence that the core is the obvious replacement for the long-sought, deep mantle reservoir. If so, they also indicate the need to understand the detailed nature and scale of core-mantle exchange processes, from atomic to macroscopic, throughout the age of the Earth to the present day.
Application of New Partition Coefficients to Modeling Plagioclase
NASA Technical Reports Server (NTRS)
Fagan, A. L.; Neal, C. R.; Rapp, J. F.; Draper, D. S.; Lapen, T. J.
2017-01-01
Previously, studies that determined the partition coefficient for an element, i, between plagioclase and the residual basaltic melt (Di plag) have been conducted using experimental conditions dissimilar from the Moon, and thus these values are not ideal for modeling plagioclase fractionation in a lunar system. However, recent work [1] has determined partition coefficients for plagioclase at lunar oxygen fugacities, and resulted in plagioclase with Anorthite contents =An90; these are significantly more calcic than plagioclase in previous studies, and the An content has a profound effect on partition coefficient values [2,3]. Plagioclase D-values, which are dependent on the An content of the crystal [e.g., 2-6], can be determined using published experimental data and the correlative An contents. Here, we examine new experimental data from [1] to ascertain their effect on the calculation of equilibrium liquids from Apollo 16 sample 60635,2. This sample is a coarse grained, subophitic impact melt composed of 55% plagioclase laths with An94.4-98.7 [7,8], distinctly more calcic than of previous partition coefficient studies (e.g., [3-6, 9-10]). Sample 60635,2 is notable as having several plagioclase trace element analyses containing a negative Europium anomaly (-Eu) in the rare-earth element (REE) profile, rather than the typical positive Eu anomaly (+Eu) [7-8] (Fig. 1). The expected +Eu is due to the similarity in size and charge with Ca2+, thereby allowing Eu2+ to be easily taken up by the plagioclase crystal structure, in contrast to the remaining REE3+. Some 60635,2 plagioclase crystals only have +Eu REE profiles, some only have -Eu REE profiles, and some +Eu and -Eu analyses in different areas on a single crystal [7, 8]. Moreover, there does not seem to be any core-rim association with the +Eu or -Eu analyses, nor does there appear to be a correlation between the size, shape, or location of a particular crystal within the sample and the sign of its Eu anomaly, which suggests a complex evolution. In order to investigate this sample further, we can calculate the equilibrium liquids, but with An contents distinct from previous experimental studies, we must calculate the appropriate partition coefficients for each trace element analysis.
A SIMS study of lunar 'komatiitic glasses' - Trace element characteristics and possible origin
NASA Technical Reports Server (NTRS)
Shearer, C. K.; Papike, J. J.; Galbreath, K. C.; Wentworth, S. J.; Shimizu, N.
1990-01-01
In Apollo 16 regolith breccias, Wentworth and McKay (1988) identified a suite of minute (less than 120 microns) 'komatiitic glass beads'. The wide major element compositional range, and ultra-Mg-prime character of the glasses suggest a variety of possible origins from complex impact processes to complex volcanic processes involving rather unusual and primitive magmatism. The extent of trace element depletion or enrichment in these glasses appears to be correlated to the siderophile character of the element (ionization potential or experimentally determined silicate melt/Fe metal partition coefficients. The ultra-Mg-prime glasses are depleted in Co relative to a bulk Moon Mg/Co exhibited by many lunar samples (volcanic glasses, basalts, regolith breccia, estimated upper mantle). The low Co and high incompatible element concentrations diminish the possibility that these glasses are a product of lunar komatiitic volcanism or impact, excavation, and melting of a very high Mg-prime plutonic unit.
NASA Astrophysics Data System (ADS)
Kawamoto, T.; Mibe, K.
2014-12-01
Chemical fractionation of slab-derived supercritical fluids can play an important role in elemental transfer from subducting slab to the mantle wedge and arc magmatism [1]. Recent findings of saline fluids from sub-arc mantle peridotite indicate that aqueous fluids in mantle wedge can contain 3.7 wt% NaCl in Ichinomageta, Northeast Japan arc [2] to 5.1 wt% NaCl in Pinatubo, Luzon arc [3]. It is, therefore, important to determine the effect of Cl on the trace element partitioning between aqueous fluids and melts. Synchrotron radiation X-ray fluorescence (XRF) analysis is conducted to know Rb, Sr, and Pb partitioning between aqueous fluids and melts [4]. There is a positive correlation between partition coefficients and pressure, as well as salinity. Two slab-derived components, melt and fluid components, are suggested to explain trace element characteristics of arc-basalts in the Mariana arc [5]. The fluid component is characterized by enrichment of alkali and alkali earth elements. Such features can be explained if the fluid component is a saline fluid, because alkali earth elements and Pb are much less mobile with Cl-free fluids than Cl-rich fluids [4]. We suggest that slab-derived components have compositional features consistent with a saline fluid and a melt, which can be formed through a separation of a slab-derived supercritical fluid [1]. Slab derived supercritical fluids contain Cl, and aqueous fluids inherit much of the Cl and some of the large-ion lithophile elements. [1] Kawamoto et al. 2012, Separation of supercritical slab-fluids to form aqueous fluid and melt components in subduction zone magmatism. PNAS, pnas.org/content/109/46/18695 [2] Kumagai et al. Evolution of carbon dioxide bearing saline fluids in the mantle wedge beneath the Northeast Japan arc, CMP [3] Kawamoto et al. 2013, Mantle wedge infiltrated with saline fluids from dehydration and decarbonation of subducting slab. PNAS, pnas.org/content/110/24/9663 [4] Kawamoto et al. 2014, Large ion lithophile elements delivered by saline fluids to the sub-arc mantle, EPS, earth-planets-space.com/content/66/1/61 [5] Pearce et al. 2005, Geochemical mapping of the Mariana arc-basin system: Implications for the nature and distribution of subduction components. G-cubed, onlinelibrary.wiley.com/doi/10.1029/2004GC000895/full
Apollo 15 green glass - Compositional distribution and petrogenesis
NASA Technical Reports Server (NTRS)
Steele, Alison M.; Colson, Russell O.; Korotev, Randy L.; Haskin, Larry A.
1992-01-01
We have characterized a comprehensive suite of individual green-glass beads from Apollo 15 soil to determine interelement behavior and to constrain petrogenetic relationships. We analyzed 365 particles for trace elements by instrumental neutron activation analysis and analyzed 52 of them, selected to cover the compositional ranges observed for trace elements, for major elements by electron microprobe analysis. We confirm the observation of Delano (1979) that the beads comprise discrete compositional groups, although two of the groups he defined are further split on the basis of trace-element compositions. Each of the resulting seven groups has distinct average rare-earth abundances. The coherence between major- and trace-element data was masked in previous studies by imprecision, correlated error, and nonrepresentative sampling of the different groups. Most of the compositional characteristics of the green glasses can be explained by a model for batch equilibrium melting of a nearly homogeneous, ultramafic source region, when the complicating effects of high pressure and low oxygen fugacity are taken into account. The previously puzzling behavior of Ni and Co as apparently incompatible elements may arise from partial reduction of those elements to the zero oxidation state, resulting in low mineral/melt partition coefficients. The model also offers explanations for why the green glasses form boomerang-shaped trends on many two-element variation diagrams and why certain compositions (Groups A and D) are more abundant than glasses with other compositions.
Dehydration and melting experiments constrain the fate of subducted sediments
NASA Astrophysics Data System (ADS)
Johnson, Marie C.; Plank, Terry
1999-12-01
Geochemical tracers demonstrate that elements are cycled from subducted sediments into the arc melting regime at subduction zones, although the transfer mechanism is poorly understood. Are key elements (Th, Be, Rb) lost during sediment dehydration or is sediment melting required? To investigate this question, we conducted phase equilibria and trace element partitioning experiments on a pelagic red clay for conditions appropriate to the slab beneath arc volcanoes (2-4 GPa, 600°-1000°C). Using both piston cylinders and multianvils, we determined the solidus, phase stabilities, and major element compositions of coexisting phases. The solidus (H2O + Cl fluid-saturated) was located at 775 +/- 25°C at 2 GPa, 810 +/- 15°C at 3 GPa, and 1025 +/- 25°C at 4 GPa with noevidence for complete miscibility between melt and fluid. This sediment composition produces a profusion of phases both above and below the solidus: garnet, jadeitic pyroxene, alkali-rich amphibole, phengite, biotite, magnetite, coesite, kyanite, apatite, zircon, Cl-rich fluids, and peraluminous to peralkaline granitic melts. At 2 GPa the phengite dehydration solidus is at 800°-825°C, while biotite breaks down between 850° and 900°C. To explore trace element partitioning across the solidus at 2 GPa, we used diamonds to trap fluids and melts. Both the bulk sediment residues and diamond traps were analyzed postexperiment by inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) for 40 elements for which we calculated bulk partition coefficients (D = Csolid/Cfluid). Below the solidus, Rb, Sr, Ba, and Pb showed the greatest mobility (D ~ 0.5-1.0), while at the solidus, Th and Be became notably partitioned into the melt (D values changing from >2.0 to <1.0). K and Rb D values fall below 1.0 when the micas breakdown. Only at the solidus do Th and Rb attain similar partition coefficients, a condition required by arc data. Taken together, the experimental results indicate that critical elements (Th and Be) require sediment melting to be efficiently transferred to the arc. This conclusion is at odds with most thermal models for subduction zones, which predict slab temperatures more than 100°C lower than sediment solidi. Thus the condition of sediment melting (with oceanic crust dehydration) may provide new constraints on the next generation of thermal/geodynamical models of subduction zones.
Dehydration and melting experiments constrain the fate of subducted sediments
NASA Astrophysics Data System (ADS)
Johnson, Marie C.; Plank, Terry
2000-12-01
Geochemical tracers demonstrate that elements are cycled from subducted sediments into the arc melting regime at subduction zones, although the transfer mechanism is poorly understood. Are key elements (Th, Be, Rb) lost during sediment dehydration or is sediment melting required? To investigate this question, we conducted phase equilibria and trace element partitioning experiments on a pelagic red clay for conditions appropriate to the slab beneath arc volcanoes (2-4 GPa, 600°-1000°C). Using both piston cylinders and multianvils, we determined the solidus, phase stabilities, and major element compositions of coexisting phases. The solidus (H2O + Cl fluid-saturated) was located at 775 ± 25°C at 2 GPa, 810 ± 15°C at 3 GPa, and 1025 ± 25°C at 4 GPa with noevidence for complete miscibility between melt and fluid. This sediment composition produces a profusion of phases both above and below the solidus: garnet, jadeitic pyroxene, alkali-rich amphibole, phengite, biotite, magnetite, coesite, kyanite, apatite, zircon, Cl-rich fluids, and peraluminous to peralkaline granitic melts. At 2 GPa the phengite dehydration solidus is at 800°-825°C, while biotite breaks down between 850° and 900°C. To explore trace element partitioning across the solidus at 2 GPa, we used diamonds to trap fluids and melts. Both the bulk sediment residues and diamond traps were analyzed postexperiment by inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) for 40 elements for which we calculated bulk partition coefficients (D = Csolid/Cfluid). Below the solidus, Rb, Sr, Ba, and Pb showed the greatest mobility (D ˜ 0.5-1.0), while at the solidus, Th and Be became notably partitioned into the melt (D values changing from >2.0 to <1.0). K and Rb D values fall below 1.0 when the micas breakdown. Only at the solidus do Th and Rb attain similar partition coefficients, a condition required by arc data. Taken together, the experimental results indicate that critical elements (Th and Be) require sediment melting to be efficiently transferred to the arc. This conclusion is at odds with most thermal models for subduction zones, which predict slab temperatures more than 100°C lower than sediment solidi. Thus the condition of sediment melting (with oceanic crust dehydration) may provide new constraints on the next generation of thermal/geodynamical models of subduction zones.
NASA Astrophysics Data System (ADS)
Guzmics, Tibor; Zajacz, Zoltán; Mitchell, Roger H.; Szabó, Csaba; Wälle, Markus
2015-02-01
We have reconstructed the compositional evolution of the silicate and carbonate melt, and various crystalline phases in the subvolcanic reservoir of Kerimasi Volcano in the East African Rift. Trace element concentrations of silicate and carbonate melt inclusions trapped in nepheline, apatite and magnetite from plutonic afrikandite (clinopyroxene-nepheline-perovskite-magnetite-melilite rock) and calciocarbonatite (calcite-apatite-magnetite-perovskite-monticellite-phlogopite rock) show that liquid immiscibility occurred during the generation of carbonatite magmas from a CO2-rich melilite-nephelinite magma formed at relatively high temperatures (1,100 °C). This carbonatite magma is notably more calcic and less alkaline than that occurring at Oldoinyo Lengai. The CaO-rich (32-41 wt%) nature and alkali-"poor" (at least 7-10 wt% Na2O + K2O) nature of these high-temperature (>1,000 °C) carbonate melts result from strong partitioning of Ca (relative to Mg, Fe and Mn) in the immiscible carbonate and the CaO-rich nature (12-17 wt%) of its silicate parent (e.g., melilite-nephelinite). Evolution of the Kerimasi carbonate magma can result in the formation of natrocarbonatite melts with similar composition to those of Oldoinyo Lengai, but with pronounced depletion in REE and HFSE elements. We suggest that this compositional difference results from the different initial parental magmas, e.g., melilite-nephelinite at Kerimasi and a nephelinite at Oldoinyo Lengai. The difference in parental magma composition led to a significant difference in the fractionating mineral phase assemblage and the element partitioning systematics upon silicate-carbonate melt immiscibility. LA-ICP-MS analysis of coeval silicate and carbonate melt inclusions provides an opportunity to infer carbonate melt/silicate melt partition coefficients for a wide range of elements. These data show that Li, Na, Pb, Ca, Sr, Ba, B, all REE (except Sc), U, V, Nb, Ta, P, Mo, W and S are partitioned into the carbonate melt, whereas Mg, Mn, Fe, Co, Cu, Zn, Al, Sc, Ti, Hf and Zr are partitioned into the silicate melt. Potassium and Rb show no preferential partitioning. Kerimasi melt inclusions show that the immiscible calcic carbonate melt is strongly enriched in Sr, Ba, Pb, LREE, P, W, Mo and S relative to other trace elements. Comparison of our data with experimental results indicates that preferential partitioning of oxidized sulfur (as SO4 2-), Ca and P (as PO4 3-) into the carbonate melt may promote the partitioning of Nb, Ta, Pb and all REE, excluding Sc, into this phase. Therefore, it is suggested that P and S enrichment in calcic carbonate magmas promotes the genesis of REE-rich carbonatites by liquid immiscibility. Our study shows that changes in the partition coefficients of elements between minerals and the coexisting melts along the liquid line of descent are rather significant at Kerimasi. This is why, in addition to the REE, Nb, Ta and Zr are also enriched in Kerimasi calciocarbonatites. We consider significant amounts of apatite and perovskite precipitated from melilite-nephelinite-derived carbonate melt as igneous minerals can have high LREE, Nb and Zr contents relative to other carbonatite minerals.
Modelling the petrogenesis of high Rb/Sr silicic magmas
Halliday, A.N.; Davidson, J.P.; Hildreth, W.; Holden, P.
1991-01-01
Rhyolites can be highly evolved with Sr contents as low as 0.1 ppm and Rb Sr > 2,000. In contrast, granite batholiths are commonly comprised of rocks with Rb Sr 100. Mass-balance modelling of source compositions, differentiation and contamination using the trace-element geochemistry of granites are therefore commonly in error because of the failure to account for evolved differentiates that may have been erupted from the system. Rhyolitic magmas with very low Sr concentrations (???1 ppm) cannot be explained by any partial melting models involving typical crustal source compositions. The only plausible mechanism for the production of such rhyolites is Rayleigh fractional crystallization involving substantial volumes of cumulates. A variety of methods for modelling the differentiation of magmas with extremely high Rb/Sr is discussed. In each case it is concluded that the bulk partition coefficients for Sr have to be large. In the simplest models, the bulk DSr of the most evolved types is modelled as > 50. Evidence from phenocryst/glass/whole-rock concentrations supports high Sr partition coefficients in feldspars from high silica rhyolites. However, the low modal abundance of plagioclase commonly observed in such rocks is difficult to reconcile with such simple fractionation models of the observed trace-element trends. In certain cases, this may be because the apparent trace-element trend defined by the suite of cognetic rhyolites is the product of different batches of magma with separate differentiation histories accumulating in the magma chamber roof zone. ?? 1991.
NASA Astrophysics Data System (ADS)
Kiseeva, Ekaterina S.; Wood, Bernard J.
2015-08-01
We develop a comprehensive model to describe trace and minor element partitioning between sulphide liquids and anhydrous silicate liquids of approximately basaltic composition. We are able thereby to account completely for the effects of temperature and sulphide composition on the partitioning of Ag, Cd, Co, Cr, Cu, Ga, Ge, In, Mn, Ni, Pb, Sb, Ti, Tl, V and Zn. The model was developed from partitioning experiments performed in a piston-cylinder apparatus at 1.5 GPa and 1300 to 1700 °C with sulphide compositions covering the quaternary FeSsbnd NiSsbnd CuS0.5sbnd FeO. Partitioning of most elements is a strong function of the oxygen (or FeO) content of the sulphide. This increases linearly with the FeO content of the silicate melt and decreases with Ni content of the sulphide. As expected, lithophile elements partition more strongly into sulphide as its oxygen content increases, while chalcophile elements enter sulphide less readily with increasing oxygen. We parameterised the effects by using the ε-model of non-ideal interactions in metallic liquids. The resulting equation for partition coefficient of an element M between sulphide and silicate liquids can be expressed as We used our model to calculate the amount of sulphide liquid precipitated along the liquid line of descent of MORB melts and find that 70% of silicate crystallisation is accompanied by ∼0.23% of sulphide precipitation. The latter is sufficient to control the melt concentrations of chalcophile elements such as Cu, Ag and Pb. Our partition coefficients and observed chalcophile element concentrations in MORB glasses were used to estimate sulphur solubility in MORB liquids. We obtained between ∼800 ppm (for primitive MORB) and ∼2000 ppm (for evolved MORB), values in reasonable agreement with experimentally-derived models. The experimental data also enable us to reconsider Ce/Pb and Nd/Pb ratios in MORB. We find that constant Ce/Pb and Nd/Pb ratios of 25 and 20, respectively, can be achieved during fractional crystallisation of magmas generated by 10% melting of depleted mantle provided the latter contains >100 ppm S and about 650 ppm Ce, 550 ppm Nd and 27.5 ppb Pb. Finally, we investigated the hypothesis that the pattern of chalcophile element abundances in the mantle was established by segregation of a late sulphide matte. Taking the elements Cu, Ag, Pb and Zn as examples we find that the Pb/Zn and Cu/Ag ratios of the mantle can, in principle, be explained by segregation of ∼0.4% sulphide matte to the core.
Lunar Ferroan Anorthosite Petrogenesis: Clues from Trace Element Distributions in FAN Subgroups
NASA Astrophysics Data System (ADS)
Floss, Christine; James, Odette B.; McGee, James J.; Crozaz, Ghislaine
1998-04-01
The rare earth elements (REE) and selected other trace elements were measured in plagioclase and pyroxene from nine samples of the lunar ferroan anorthosite (FAN) suite of rocks. Samples were selected from each of four FAN subgroups previously defined by James et al. (1989). Plagioclase compositions are homogeneous within each sample, but high- and low-Ca pyroxenes from lithic clasts typically have different REE abundances from their counterparts in the surrounding granulated matrices. Measured plagioclase/low-Ca pyroxene concentration ratios for the REE have steeper patterns than experimentally determined plagioclase/low-Ca pyroxene partition coefficients in most samples. Textural and trace element evidence suggest that, although subsolidus equilibration may be responsible for some of the discrepancy, plagioclase compositions in most samples have been largely unaffected by intermineral redistribution of the REE. The REE systematics of plagioclase from the four subgroups are broadly consistent with their derivation through crystallization from a single evolving magma. However, samples from some of the subgroups exhibit a decoupling of plagioclase and pyroxene compositions that probably reflects the complexities inherent in crystallization from a large-scale magmatic system. For example, two anorthosites with very magnesian mafic minerals have highly evolved trace element compositions; major element compositions in plagioclase also do not reflect the evolutionary sequence recorded by their REE compositions. Finally, a noritic anorthosite breccia with relatively ferroan mafic minerals contains several clasts with high and variable REE and other trace element abundances. Although plagioclase REE compositions are consistent with their derivation from a magma with a KREEPy trace element signature, very shallow REE patterns in the pyroxenes suggest the addition of a component enriched in the light REE.
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Sensitivity of trace element pyritization to pyrite oxidation processes
NASA Astrophysics Data System (ADS)
Moreira, Manuel; Díaz, Rut; Mendoza, Ursula; Capilla, Ramses; Böttcher, Michael; Luiza Albuquerque, Ana; Machado, Wilson
2014-05-01
Total trace elements concentration variability in marine sediments has been widely used as a proxy for redox conditions and marine paleoprodutivity. However, partial extraction procedures reduce influences of detrital sedimentary fractions, and information on trace element geochemical partitioning can contribute to provide comprehensive evidences on elemental sensitivity to particular processes. The potential effect of sedimentary pyrite re-oxidative cycling on the degree of trace metal pyritization (DTMP) has not been previously evaluated. This study investigates this effect in 4 sediment cores from the continental shelf under the influence of a tropical upwelling system (Cabo Frio, Brazil). The relation of DTMP with stable isotope signals (δ34SCRS) of chromium reducible sulfur, which becomes lighter in response to intense pyrite re-oxidative cycling in the study area, suggests high (As, Cd and Mn), low (Cu and Zn) or negligible (Cr and Ni) re-oxidation influences. The oldest, pyrite-richer sediments provide an apparent threshold for intense pyrite re-oxidation, after which most trace elements (As, Cd, Zn and Mn) presented more accentuated pyritization. A middle shelf core presented negative correlations of reactive (HCl-soluble) Mn, Cu and Ni with pyrite iron, suggesting Mn oxide (and associated metals) depletion in reaction with pyrite. Results provided evidences for coupled influences from both aerobic and anaerobic oxidative processes on trace elements incorporation into pyrite. Pyrite δ34S signatures under the oxic bottom water from the study area were similar to those from euxinic sedimentary environments, suggesting that pyrite re-oxidative cycling can affect trace element susceptibility to be incorporated and preserved into pyrite in a wide range of sedimentary conditions. The evaluation of trace elements sensitivity to these processes can contribute to improve the use of multiple DTMP data (e.g., as paleoredox proxies). Considering that S re-oxidative cycling is ubiquitous in many sedimentary conditions, such coupled use of DTMP and δ34SCRS proxies can be possibly applied to a large variety of sedimentary environments.
NASA Astrophysics Data System (ADS)
Beard, Charles; van Hinsberg, Vincent; Stix, John; Wilke, Max
2017-04-01
Sodic clinopyroxene is a key fractionating phase in alkaline magmatic systems but its impact on metal enrichment processes, and the formation of REE + HFSE mineralizations in particular, is not fully understood. Sodic pyroxenes appear to more readily incorporate REE than their calcic equivalents1. Despite this, melts in evolved alkaline systems can attain high REE contents, even up to economic levels (e.g. the Nechalacho layered suite in Canada2). To constrain the control of pyroxene on REE + HFSE behaviour in alkaline magmas, a series of internally heated pressure vessel experiments was performed to determine pyroxene-melt element partitioning systematics. Synthetic trachy-andesite to phonolite compositions were run water saturated at 650-825°C with fO2 buffered by ca. 1 bar of H2 (QFM + 1) or by Hm-Mt (QFM +5). Fluorine was added to selected experiments (0.3 to 2.5 wt %) to ascertain its effect on element partitioning. Run products were analysed by EMP for major elements and LA-ICP-MS for trace elements. Mineral and glass compositions bracket the compositions of natural alkaline systems, allowing for direct application of our experimental results to nature. Our results indicate that REE partitioning systematics vary strongly with pyroxene composition: Diopside-rich pyroxenes (Aeg5-25) prefer the MREE, medium aegirine pyroxenes (Aeg25-50) preferentially incorporate the LREE, whereas high aegirine pyroxenes (Aeg55-95) strongly prefer HREE. REE partitioning coefficients are 0.3-40, typically 2-6, with minima for high aegirine pyroxenes. Melt composition (e.g. (Na+K)/Al) also impacts partitioning although to a lesser extent, except for the F-content, which shows no impact at all. The composition of fractionating pyroxene has a major impact on the REE pattern of the residual melt, and thus on the ability of a system to develop economic concentrations of the REE. Element partitioning systematics suggest that late-crystallising aegirine-rich cumulates would be HREE-rich, in accord with the composition of mineralised intrusions, such as Nechalacho2. 1 - Marks, M., Halama, R., Wenzel, T. & Markl, G., 2004. Chem. Geol. 211, 185-215. 2 - Möller, V. & Williams-Jones, A. E., 2016. J. Petrology 57, 229-276.
Micron-Scale Correlations Among Ti, P, Ce, and Y in Hadean Jack Hills Zircons
NASA Astrophysics Data System (ADS)
Hofmann, A. E.; Cavosie, A. J.; Valley, J. W.; Eiler, J. M.
2007-12-01
Detrital zircons and the inclusions found therein are our only mineralogical constraints on geologic events that occurred on the Hadean Earth. These zircons are commonly small (ca. <100 μm in the longest dimension) and preserve micron to sub-micron chemical zonations indicative of a dynamic petrological history. Trace elements within zircon are of particular interest because concentrations and ratios of these elements can provide information regarding chemical and physical conditions during zircon growth. In this study, we analyzed Hadean-age detrital zircons from Archean metasediment in the Jack Hills (Australia) using the Caltech Microanalysis Center Cameca NanoSIMS 50L. Trace elements analyzed included Ti, P, Ce, and Y. Ti- thermometry [1,2,3] can potentially constrain growth and/or re-equilibration temperatures of zircons; P, Ce, and Y are known to enter the zircon lattice by the coupled xenotime-type substitution mechanism: (Y, REE)3+ + P5+ = Zr4+ + Si4+ [5]. The 89Y/28Si ratio was observed to correlate with, and was used as a proxy for, cathodoluminescence (CL) banding. Growth features manifested in CL (e.g., sector, oscillatory zoning) were observed in all zircons analyzed. CL zones vary from <1 μm to several microns in width; therefore, the NanoSIMS---with a beam diameter resolved to ca. 250 nm on the sample surface when operating with an O- primary beam---is uniquely suited for this scale of analysis. Regions displaying CL banding were imaged as 20 x 20 μm areas. All elements were normalized to 28Si; 49Ti/28Si ratios were converted to [Ti] via calibration based on analyses of synthetic, high-Ti zircons (provided by B. Watson) that were independently analyzed on Caltech's JEOL JXA-8200 electron microprobe. We observe three types of relationships between trace element distribution and CL banding in the zircons imaged: 1) strong positive correlations between CL banding, P, Ce, and Ti; 2) subtle positive correlations between CL banding, P, Ce, and Ti; 3) no correlation between minor/trace elements and CL banding. Positive correlations between CL banding, 3+ cations, and [Ti] have previously been reported by Holden et al. [4]. In this study, gradients at least as sharp as a factor of ~3 in [Ti] are observed between adjacent CL bands in the strongly correlated images. These images also have the highest absolute concentrations of trace elements and display both sector and oscillatory zoning in CL. The correlations observed may be due to: temperature-dependent equilibrium partitioning of all trace elements during rapid cycles in growth temperature; episodic diffusion-limited enrichment of incompatible trace elements in the boundary layer melt adjacent to growing crystals; and/or kinetically controlled, non- equilibrium crystal-melt partitioning caused by trace element enrichments in the boundary layer melt surrounding fast-growing grains (e.g., [6]). We will discriminate between these alternatives based on quantitative relationships between relative enrichments of [Ti] and other trace elements. [1]Watson, E.B. & Harrison, T.M. (2005) Science 308, 841-844. [2]Watson, E.B., Wark, D.A., & Thomas, J.B. (2006) CMP 151, 413-433. [3]Ferry, J.M. & Watson, E.B. (2007) CMP 154, 429-437. [4] Holden, P. et al. (2005) Eos Trans. AGU 86 (52) Fall Meet. Suppl., Abstract V41F-1539. [5] Speer, J.A. (1982) Zircon. In Rev. Min. 5 (ed. P.H. Ribbe), 67-112. [6] Watson, E.B. (2004) GCA 68, 1473-1488.
NASA Astrophysics Data System (ADS)
Cartier, Camille; Hammouda, Tahar; Doucelance, Régis; Boyet, Maud; Devidal, Jean-Luc; Moine, Bertrand
2014-04-01
In order to investigate the influence of very reducing conditions, we report enstatite-melt trace element partition coefficients (D) obtained on enstatite chondrite material at 5 GPa and under oxygen fugacities (fO2) ranging between 0.8 and 8.2 log units below the iron-wustite (IW) buffer. Experiments were conducted in a multianvil apparatus between 1580 and 1850 °C, using doped (Sc, V, REE, HFSE, U, Th) starting materials. We used a two-site lattice strain model and a Monte-Carlo-type approach to model experimentally determined partition coefficient data. The model can fit our partitioning data, i.e. trace elements repartition in enstatite, which provides evidence for the attainment of equilibrium in our experiments. The precision on the lattice strain model parameters obtained from modelling does not enable determination of the influence of intensive parameters on crystal chemical partitioning, within our range of conditions (fO2, P, T, composition). We document the effect of variable oxygen fugacity on the partitioning of multivalent elements. Cr and V, which are trivalent in the pyroxene at around IW - 1 are reduced to 2+ state with increasingly reducing conditions, thus affecting their partition coefficients. In our range of redox conditions Ti is always present as a mixture between 4+ and 3+ states. However the Ti3+-Ti4+ ratio increases strongly with increasingly reducing conditions. Moreover in highly reducing conditions, Nb and Ta, that usually are pentavalent in magmatic systems, appear to be reduced to lower valence species, which may be Nb2+ and Ta3+. We propose a new proxy for fO2 based on D(Cr)/D(V). Our new data extend the redox range covered by previous studies and allows this proxy to be used in the whole range of redox conditions of the solar system objects. We selected trace-element literature data of six chondrules on the criterion of their equilibrium. Applying the proxy to opx-matrix systems, we estimated that three type I chondrules have equilibrated at IW - 7 ± 1, one type I chondrule at IW - 4 ± 1, and two type II chondrules at IW + 3 ± 1. This first accurate estimation of enstatite-melt fO2 for type I chondrules is very close to CAI values. Find the best-fit for trivalent elements. We set the r0M1 (3+) range to 0.55-0.75 Å, based on visual observations of the datapoints. For the other variables we have set boundary values beyond which the solutions would be unacceptable. For example, r0M2 (3+) has to be larger than r0M1 (3+). Finally we restricted the D0 range as follow: 0.2
Saqib, Naeem; Bäckström, Mattias
2015-10-01
Impact of waste fuels (virgin/waste wood, mixed biofuel (peat, bark, wood chips) industrial, household, mixed waste fuel) and incineration technologies on partitioning and leaching behavior of trace elements has been investigated. Study included 4 grate fired and 9 fluidized boilers. Results showed that mixed waste incineration mostly caused increased transfer of trace elements to fly ash; particularly Pb/Zn. Waste wood incineration showed higher transfer of Cr, As and Zn to fly ash as compared to virgin wood. The possible reasons could be high input of trace element in waste fuel/change in volatilization behavior due to addition of certain waste fractions. The concentration of Cd and Zn increased in fly ash with incineration temperature. Total concentration in ashes decreased in order of Zn>Cu>Pb>Cr>Sb>As>Mo. The concentration levels of trace elements were mostly higher in fluidized boilers fly ashes as compared to grate boilers (especially for biofuel incineration). It might be attributed to high combustion efficiency due to pre-treatment of waste in fluidized boilers. Leaching results indicated that water soluble forms of elements in ashes were low with few exceptions. Concentration levels in ash and ash matrix properties (association of elements on ash particles) are crucial parameters affecting leaching. Leached amounts of Pb, Zn and Cr in >50% of fly ashes exceeded regulatory limit for disposal. 87% of chlorine in fly ashes washed out with water at the liquid to solid ratio 10 indicating excessive presence of alkali metal chlorides/alkaline earths. Copyright © 2015. Published by Elsevier B.V.
USDA-ARS?s Scientific Manuscript database
In risk assessment models, the solid-solution partition coefficient (Kd), and plant uptake factor (PUF), are often employed to model the fate and transport of trace elements in soils. The trustworthiness of risk assessments depends on the reliability of the parameters used. In this study, we exami...
Marine chemistry of the permian phosphoria formation and basin, Southeast Idaho
Piper, D.Z.
2001-01-01
Major components in the Meade Peak Member of the Phosphoria Formation are apatite, dolomite, calcite, organic matter, and biogenic silica-a marine fraction; and aluminosilicate quartz debris-a terrigenous fraction. Samples from Enoch Valley, in southeast Idaho, have major element oxide abundances of Al2O3, Fe2O3, K2O, and TiO2 that closely approach the composition of the world shale average. Factor analysis further identifies the partitioning of several trace elements-Ba, Ga, Li, Sc, and Th and, at other sites in southeast Idaho and western Wyoming, B, Co, Cs, Hf, Rb, and Ta-totally into this fraction. Trace elements that fail to show such correlations or factor loadings include Ag, As, Cd, Cr, Cu, Mo, Ni, Se, the rare earth elements (REE), U, V, and Zn. Their terrigenous contribution is determined from minimum values of trace elements versus the terrigenous fraction. These minima too define trace element concentrations in the terrigenous fraction that approximately equal their concentrations in the world shale average. The marine fraction of trace elements represents the difference between the bulk trace element content of a sample and the terrigenous contribution. Of the trace elements enriched above a terrigenous contribution, Ag, Cr, Cu, Mo, and Se show strong loadings on the factor with an organic matter loading and U and the REE on the factor with a strong apatite loading. Cd, Ni, V, and Zn do not show a strong correlation with any of the marine components but are, nonetheless, strongly enriched above a terrigenous contribution. Interelement relationships between the trace elements identify two seawater sources-planktonic debris and basinal bottom water. Relationships between Cd, Cu, Mo, Zn, and possibly Ni and Se suggest a solely biogenic source. Their accumulation rates, and that of PO3-4, further identify the level of primary productivity as having been moderate and the residence time of water in the basin at 4.5 yr. Enrichments of Cr, U, V, and the REE, above both terrigenous and biogenic contributions, define bottom-water redox conditions as having been oxygen depleted, that is, denitrifying but not sulfate reducing.
NASA Astrophysics Data System (ADS)
Tomlinson, E. L.; Müller, W.; EIMF
2009-03-01
We have determined the trace element compositions of coexisting fluid (carbonate-K-chloride-H 2O) and single-phase mineral inclusions in peridotitic (Cr-diopside) and eclogitic (omphacite, garnet) inclusions in fibrous diamonds from the Panda kimberlite (Slave craton, Canada). These diamonds provide a unique insight into the nature of the metasomatic agent, the metasomatised minerals and the pre-metasomatic protolith. The fluid component is strongly enriched in light rare earth elements (LREE) and large ion lithophile elements (LILE). Co-existing peridotitic minerals record a melt extraction event (high Cr and Ni) in the protolith prior to the influx of the trapped metasomatic fluid. The silicate minerals are also strongly enriched in LREE. Calculated partition coefficients agree with experimentally determined values in the literature, despite the complex composition of the natural fluid. This indicates that the minerals have re-equilibrated with the metasomatic fluid. The trace element compositions of the mineral inclusions are comparable to many equivalent phases in monocrystalline diamonds. This suggests that the metasomatic fluid and the process recorded in these samples may also be responsible for the growth of some types of monocrystalline diamonds.
NASA Astrophysics Data System (ADS)
Wilmot, M. S.; Candela, P. A.; Piccoli, P. M.; Simon, A. C.; McDonough, W. F.
2006-05-01
The partitioning of ore metals between melt and crystals affects the concentrations of these metals in an evolving ore fluid, and therefore the efficiency of their removal from the magma by hydrothermal processes. Some porphyry-type W-Mo deposits contain recoverable amounts of Bi, whereas others contain only trace amounts. In order to determine the magmatic controls on the ratio of Bi to other commodities in these and other deposits, we examined the partitioning behavior of bismuth between melt, minerals and aqueous phases. Hydrothermal experiments were performed by using externally heated cold seal vessels and employing a double capsule technique. Experiments contained 40 mg of Bishop Tuff glass (SiO2 = 74% ) and 40 mg of either magnetite or pyrrhotite. Bi was added as elemental Bi (< 1 mg). Two different aqueous solutions were used. Initially, the added aqueous phase comprised the solutes HCl, KCl and NaCl in a molar1:1:1 ratio, with a bulk salinity of 10 wt % NaCl eq. The aqueous phase for later experiments contained only the solutes KCl and NaCl in a 1:1 molar ratio. Pre-fractured quartz was added to the experiments to trap fluid inclusions at run PTX conditions. Experiments were performed in Au or Pt capsules held inside Rene 41 cold-seal vessels at 800°C and 100 MPa for durations of up to 36 hours. Analytical data have been collected from the run product solids by using an electron probe microanalyzer (major and trace elements) and laser ablation inductively coupled plasma mass spectrometry (trace elements). Bi in Mt is found in concentrations up to 100 ppm, with higher concentrations in runs where Po decomposed to form magnetite. The Bi concentration in the glass ranges up to 100 ppm. In the Po-bearing runs, data were only collected from Po grains in the experiments containing the HCl-free aqueous solution (the Po grains in the other experiments were too small to analyze). Pyrrhotite contained 10-20 ppm Bi, whereas the glass contained 5-10 ppm. Preliminary Nernst- type partition coefficients for Bi between Mt and melt and Po and melt are approximately 5 and 2, respectively. These data reveal that Bi is only slightly compatible in Mt and Po, and that the Po/melt partition coefficient for Bi is much lower than for Cu, Ag and Au, and is comparable to Mn and Zn. Additional experiments are in progress to more compare the partitioning of Bi with that of W and Mo.
Tang, Jianwu; Whittecar, G Richard; Johannesson, Karen H; Daniels, W Lee
2004-01-01
Backfills of dredged sediments onto a former sand and gravel mine site in Charles City County, VA may have the potential to contaminate local groundwater. To evaluate the mobility of trace elements and to identify the potential contaminants from the dredged sediments, a sequential extraction scheme was used to partition trace elements associated with the sediments from the local aquifer and the dredged sediments into five fractions: exchangeable, acidic, reducible, oxidizable, and residual phases. Sequential extractions indicate that, for most of the trace elements examined, the residual phases account for the largest proportion of the total concentrations, and their total extractable fractions are mainly from reducible and oxidizable phases. Only Cd, Pb, and Zn have an appreciable extractable proportion from the acidic phase in the filled dredged sediments. Our groundwater monitoring data suggest that the dredged sediments are mainly subject to a decrease in pH and a series of oxidation reactions, when exposed to the atmosphere. Because the trace elements released by carbonate dissolution and the oxidation (e.g., organic matter degradation, iron sulfide and, ammonia oxidation) are subsequently immobilized by sorption to iron, manganese, and aluminum oxides, no potential contaminants to local groundwater are expected by addition of the dredged sediments to this site.
Analysis of Trace Siderophile Elements at High Spatial Resolution Using Laser Ablation ICP-MS
NASA Astrophysics Data System (ADS)
Campbell, A. J.; Humayun, M.
2006-05-01
Laser ablation inductively coupled plasma mass spectometry is an increasingly important method of performing spatially resolved trace element analyses. Over the last several years we have applied this technique to measure siderophile element distributions at the ppm level in a variety of natural and synthetic samples, especially metallic phases in meteorites and experimental run products intended for trace element partitioning studies. These samples frequently require trace element analyses to be made at a finer spatial resolution (25 microns or better) than is frequently attained using LA-ICP-MS. In this presentation we review analytical protocols that were developed to optimize the LA-ICP-MS measurements for high spatial resolution. Particular attention is paid to the trade-offs involving sensitivity, ablation pit depth and diameter, background levels, and number of elements measured. To maximize signal/background ratios and avoid difficulties associated with ablating to depths greater than the ablation pit diameter, measurement involved integration of rapidly varying, transient but well-behaved signals. The abundances of platinum group elements and other siderophile elements in ferrous metals were calibrated against well-characterized standards, including iron meteorites and NIST certified steels. The calibrations can be set against the known abundance of an independently determined element, but normalization to 100 percent can also be employed, and was more useful in many circumstances. Evaluation of uncertainties incorporated counting statistics as well as a measure of instrumental uncertainty, determined by replicate analyses of the standards. These methods have led to a number of insights into the formation and chemical processing of metal in the early solar system.
Oxygen Fugacity at High Pressure: Equations of State of Metal-Oxide Pairs
NASA Technical Reports Server (NTRS)
Campbell A. J.; Danielson, L.; Righter, K.; Wang, Y.; Davidson, G.; Wang, Y.
2006-01-01
Oxygen fugacity (fO2) varies by orders of magnitude in nature, and can induce profound changes in the chemical state of a substance, and also in the chemical equilibrium of multicomponent systems. One prominent area in high pressure geochemistry, in which fO2 is widely recognized as a principal controlling factor, is that of metal-silicate partitioning of siderophile trace elements (e.g., [1]). Numerous experiments have shown that high pressures and temperatures can significantly affect metal/silicate partitioning of siderophile and moderately siderophile elements. Parameterization of these experimental results over P, T, X, and fO2 can allow the observed siderophile element composition of the mantle to be associated with particular thermodynamic conditions [2]. However, this is best done only if quantitative control exists over each thermodynamic variable relevant to the experiments. The fO2 values for many of these partitioning experiments were determined relative to a particular metal-oxide buffer (e.g., Fe-FeO (IW), Ni-NiO (NNO), Co-CoO, Re-ReO2 (RRO)), but the parameterization of all experimental results is weakened by the fact that the pressure-induced relative changes between these buffer systems are imprecisely known.
Donohue, Patrick H; Hill, Eddy; Huss, Gary R
2018-02-01
Pallasite meteorites, which consist primarily of olivine and metal, may be remnants of disrupted core-mantle boundaries of differentiated asteroids or planetesimals. The early thermal histories of pallasites are potentially recorded by minor- and trace-element zonation in olivine. However, constraining this history requires knowledge of element behavior under the conditions of pallasite formation, which is lacking for many of the main elements of interest (e.g., Co, Cr, Mn). In this study, we experimentally determined metal/olivine partition coefficients for Fe, Ni, Co, Cr, and Mn in a pallasite analogue at subsolidus temperatures. Metal/olivine partition coefficients ( K M ) increase in the order K Mn < K Cr < 1 < K Fe < K Co < K Ni , with five orders of magnitude separating K Mn from K Ni . Transition metals also become more siderophile with increasing experimental temperature (900 to 1550°C). The experiments incidentally produced diffusion profiles in olivine for these elements; Our results suggest they diffuse through olivine at similar rates. Core compositions of pallasite olivines are consistent with high-temperature equilibration with FeNi-metal. Olivine zonation toward crystal rims varies significantly for the investigated transition metals. We suggest rim zonation results from partial re-equilibration during late stage crystallization of minor phases (e.g., chromite, phosphates). This re- equilibration occurred over short timescales relative to overall pallasite cooling, likely tied to initial cooling rates on the order of 100-300°C/Myr.
NASA Astrophysics Data System (ADS)
Donohue, Patrick H.; Hill, Eddy; Huss, Gary R.
2018-02-01
Pallasite meteorites, which consist primarily of olivine and metal, may be remnants of disrupted core-mantle boundaries of differentiated asteroids or planetesimals. The early thermal histories of pallasites are potentially recorded by minor- and trace-element zonation in olivine. However, constraining this history requires knowledge of element behavior under the conditions of pallasite formation, which is lacking for many of the main elements of interest (e.g., Co, Cr, Mn). In this study, we experimentally determined metal/olivine partition coefficients for Fe, Ni, Co, Cr, and Mn in a pallasite analogue at subsolidus temperatures. Metal/olivine partition coefficients (KM) increase in the order KMn < KCr < 1 < KFe < KCo < KNi, with five orders of magnitude separating KMn from KNi. Transition metals also become more siderophile with increasing experimental temperature (900-1550 °C). The experiments incidentally produced diffusion profiles in olivine for these elements; our results suggest they diffuse through olivine at similar rates. Core compositions of pallasite olivines are consistent with high-temperature equilibration with FeNi-metal. Olivine zonation toward crystal rims varies significantly for the investigated transition metals. We suggest rim zonation results from partial re-equilibration during late stage crystallization of minor phases (e.g., chromite, phosphates). This re-equilibration occurred over short timescales relative to overall pallasite cooling, likely tied to initial cooling rates on the order of 100-300 °C/Myr.
Highly Reducing Partitioning Experiments Relevant to the Planet Mercury
NASA Technical Reports Server (NTRS)
Rowland, Rick, II; Vander Kaaden, Kathleen E.; McCubbin, Francis M.; Danielson, Lisa R.
2017-01-01
With the data returned from the MErcury Surface Space ENvironment GEochemistry and Ranging (MESSENGER) mission, there are now numerous constraints on the physical and chemical properties of Mercury, including its surface composition. The high S and low FeO contents observed from MESSENGER on the planet's surface suggests a low oxygen fugacity of the present planetary materials. Estimates of the oxygen fugacity for Mercurian magmas are approximately 3-7 log units below the Iron-Wüstite (Fe-FeO) oxygen buffer, several orders of magnitude more reducing than other terrestrial bodies we have data from such as the Earth, Moon, or Mars. Most of our understanding of elemental partitioning behavior comes from observations made on terrestrial rocks, but Mercury's oxygen fugacity is far outside the conditions of those samples. With limited oxygen available, lithophile elements may instead exhibit chalcophile, halophile, or siderophile behaviors. Furthermore, very few natural samples of rocks that formed under reducing conditions are available in our collections (e.g., enstatite chondrites, achondrites, aubrites). With this limited amount of material, we must perform experiments to determine the elemental partitioning behavior of typically lithophile elements as a function of decreasing oxygen fugacity. Experiments are being conducted at 4 GPa in an 880-ton multi-anvil press, at temperatures up to 1850degC. The composition of starting materials for the experiments were selected for the final run products to contain metal, silicate melt, and sulfide melt phases. Oxygen fugacity is controlled in the experiments by adding silicon metal to the samples, using the Si-SiO2 oxygen buffer, which is approximately 5 log units more reducing than the Fe-FeO oxygen buffer at our temperatures of interest. The target silicate melt compositional is diopside (CaMgSi2O6) because measured surface compositions indicate partial melting of a pyroxene-rich mantle. Elements detected on Mercury's surface by MESSENGER (K, Na, Fe, Ti, Cl, Al, Cr, Mn, U, Th) and other geochemically relevant elements (P, F, H, N, C, Co, Ni, Mo, Ce, Nd, Sm, Eu, Gd, Dy, Yb) are added to the starting composition at trace abundances (approximately 500 ppm) so that they are close enough to infinite dilution to follow Henry's law of trace elements, and their partitioning behavior can be measured between the metal, silicate, and sulfide phases. The results of these experiments will allow us to assess the thermal and magmatic evolution of the planet Mercury from a geochemical standpoint.
Xu, Liqiang; Liu, Xiaodong; Nie, Yaguang
2016-05-01
Seabird subfossils were collected on three islands of the Xisha Archipelago, South China Sea. Via elemental analysis, we identified that bird guano was a significant source for heavy metals Cu, Zn, and Hg. Cu and Zn levels in these guano samples are comparable to their levels in wildbird feces, but guano Hg was lower than previously reported. Trophic positions significantly impacted transfer efficiency of heavy metals by seabirds. Despite of a common source, trace elements, as well as stable isotopes (i.e., guano δ(13)C and collagen δ(15)N), showed island-specific characteristics. Bird subfossils on larger island had relatively greater metal concentrations and revealed higher trophic positions. Partition of element and isotope levels among the islands suggested that transfer efficacy of seabirds on different islands was different, and bird species were probably unevenly distributed among the islets. Island area is possibly a driving factor for distributions of seabird species.
Gliding Box method applied to trace element distribution of a geochemical data set
NASA Astrophysics Data System (ADS)
Paz González, Antonio; Vidal Vázquez, Eva; Rosario García Moreno, M.; Paz Ferreiro, Jorge; Saa Requejo, Antonio; María Tarquis, Ana
2010-05-01
The application of fractal theory to process geochemical prospecting data can provide useful information for evaluating mineralization potential. A geochemical survey was carried out in the west area of Coruña province (NW Spain). Major elements and trace elements were determined by standard analytical techniques. It is well known that there are specific elements or arrays of elements, which are associated with specific types of mineralization. Arsenic has been used to evaluate the metallogenetic importance of the studied zone. Moreover, as can be considered as a pathfinder of Au, as these two elements are genetically associated. The main objective of this study was to use multifractal analysis to characterize the distribution of three trace elements, namely Au, As, and Sb. Concerning the local geology, the study area comprises predominantly acid rocks, mainly alkaline and calcalkaline granites, gneiss and migmatites. The most significant structural feature of this zone is the presence of a mylonitic band, with an approximate NE-SW orientation. The data set used in this study comprises 323 samples collected, with standard geochemical criteria, preferentially in the B horizon of the soil. Occasionally where this horizon was not present, samples were collected from the C horizon. Samples were taken in a rectilinear grid. The sampling lines were perpendicular to the NE-SW tectonic structures. Frequency distributions of the studied elements departed from normal. Coefficients of variation ranked as follows: Sb < As < Au. Significant correlation coefficients between Au, Sb, and As were found, even if these were low. The so-called ‘gliding box' algorithm (GB) proposed originally for lacunarity analysis has been extended to multifractal modelling and provides an alternative to the ‘box-counting' method for implementing multifractal analysis. The partitioning method applied in GB algorithm constructs samples by gliding a box of certain size (a) over the grid map in all possible directions. An "up-scaling" partitioning process will begin with a minimum size or area box (amin) up to a certain size less than the total area A. An advantage of the GB method is the large sample size that usually leads to better statistical results on Dq values, particularly for negative values of q. Because this partitioning overlaps, the measure defined on these boxes is not statistically independent and the definition of the measure in the gliding boxes is different. In order to show the advantages of the GB method, spatial distributions of As, Sb, and Au in the studied area were analyzed. We discussed the usefulness of this method to achieve the numerical characterization of anomalies and its differentiation from the background from the available data of the geochemistry survey.
NASA Astrophysics Data System (ADS)
Pokrovsky, O. S.; Schott, J.; Dupré, B.
2006-07-01
The chemical status of ˜40 major and trace elements (TE) and organic carbon (OC) in pristine boreal rivers draining the basaltic plateau of Central Siberia (Putorana) and interstitial solutions of permafrost soils was investigated. Water samples were filtered in the field through progressively decreasing pore size (5 μm → 0.22 μm → 0.025 μm → 10 kDa → 1 kDa) using cascade frontal filtration technique. Most rivers and soil porewaters exhibit 2-5 times higher than the world average concentration of dissolved (i.e., <0.22 μm) iron (0.03-0.4 mg/L), aluminum (0.03-0.4 mg/L), OC (10-20 mg/L) and various trace elements that are usually considered as immobile in weathering processes (Ti, Zr, Ga, Y, REEs). Ultrafiltration revealed strong relationships between concentration of TE and that of colloidal Fe and Al. According to their partition during filtration and association with colloids, two groups of elements can be distinguished: (i) those weakly dependent on ultrafiltration and that are likely to be present as truly dissolved inorganic species (Li, Na, K, Si, Mn, Mo, Rb, Cs, As, Sb) or, partially (20-30%) associated with small size Fe- and Al-colloids (Ca, Mg, Sr, Ba) and to small (<1-10 kDa) organic complexes (Co, Ni, Cu, Zn), and (ii) elements strongly associated with colloidal iron and aluminum in all ultrafiltrates largely present in 1-100 kDa fraction (Ga, Y, REEs, Pb, V, Cr, Ti, Ge, Zr, Th, U). TE concentrations and partition coefficients did not show any detectable variations between different colloidal fractions for soil porewaters, suprapermafrost flow and surface streams. TE concentration measurements in river suspended particles demonstrated significant contribution (i.e., ⩾30%) of conventionally dissolved (<0.22 μm) forms for usually "immobile" elements such as divalent transition metals, Cd, Pb, V, Sn, Y, REEs, Zr, Hf, Th. The Al-normalized accumulation coefficients of TE in vegetation litter compared to basalts achieve 10-100 for B, Mn, Zn, As, Sr, Sn, Sb, and the larch litter degradation is able to provide the major contribution to the annual dissolved flux of most trace elements. It is hypothesized that the decomposition of plant litter in the topsoil horizon leads to Fe(III)-, Al-organic colloids formation and serves as an important source of elements in downward percolating fluids.
Metal biogeochemistry in surface-water systems; a review of principles and concepts
Elder, John F.
1988-01-01
Metals are ubiquitous in natural surface-water systems, both as dissolved constituents and as particulate constituents. Although concentrations of many metals are generally very low (hence the common term 'trace metals'), their effects on the water quality and the biota of surfacewater systems are likely to be substantial. Biogeochemical partitioning of metals results in a diversity of forms, including hydrated or 'free' ions, colloids, precipitates, adsorbed phases, and various coordination complexes with dissolved organic and inorganic ligands. Much research has been dedicated to answering questions about the complexities of metal behavior and effects in aquatic systems. Voluminous literature on the subject has been produced. This paper synthesizes the findings of aquatic metal studies and describes some general concepts that emerge from such a synthesis. Emphasis is on sources, occurrence, partitioning, transport, and biological interactions of metals in freshwater systems of North America. Biological interactions, in this case, refer to bioavailability, effects of metals on ecological characteristics and functions of aquatic systems, and roles of biota in controlling metal partitioning. This discussion is devoted primarily to the elements aluminum, arsenic, cadmium, chromium, copper, iron, lead, manganese, mercury, nickel, and zinc and secondarily to cobalt, molybdenum, selenium, silver, and vanadium. Sources of these elements are both natural and anthropogenic. Significant anthropogenic sources are atmospheric deposition, discharges of municipal and industrial wastes, mine drainage, and urban and agricultural runoff. Biogeochemical partitioning of metals is controlled by various characteristics of the water and sediments in which the metals are found. Among the most important controlling factors are pH, oxidation-reduction potential, hydrologic features, sediment grain size, and the existence and nature of clay minerals, organic matter, and hydrous oxides of manganese and iron. Partitioning is also controlled by biological processes that provide mechanisms for detoxification of metals and for enhanced uptake of nutritive metals. Partitioning is important largely because availability to biota is highly variable among different phases. Hence, accumulation in biological tissues and toxicity of an element are dependent not only on total concentration of the element but also on the factors that control partitioning.
SilMush: A procedure for modeling of the geochemical evolution of silicic magmas and granitic rocks
NASA Astrophysics Data System (ADS)
Hertogen, Jan; Mareels, Joyce
2016-07-01
A boundary layer crystallization modeling program is presented that specifically addresses the chemical fractionation in silicic magma systems and the solidification of plutonic bodies. The model is a Langmuir (1989) type approach and does not invoke crystal settling in high-viscosity silicic melts. The primary aim is to model a granitic rock as a congealed crystal-liquid mush, and to integrate major element and trace element modeling. The procedure allows for some exploratory investigation of the exsolution of H2O-fluids and of the fluid/melt partitioning of trace elements. The procedure is implemented as a collection of subroutines for the MS Excel spreadsheet environment and is coded in the Visual Basic for Applications (VBA) language. To increase the flexibility of the modeling, the procedure is based on discrete numeric process simulation rather than on solution of continuous differential equations. The program is applied to a study of the geochemical variation within and among three granitic units (Senones, Natzwiller, Kagenfels) from the Variscan Northern Vosges Massif, France. The three units cover the compositional range from monzogranite, over syenogranite to alkali-feldspar granite. An extensive set of new major element and trace element data is presented. Special attention is paid to the essential role of accessory minerals in the fractionation of the Rare Earth Elements. The crystallization model is able to reproduce the essential major and trace element variation trends in the data sets of the three separate granitic plutons. The Kagenfels alkali-feldspar leucogranite couples very limited variation in major element composition to a considerable and complex variation of trace elements. The modeling results can serve as a guide for the reconstruction of the emplacement sequence of petrographically distinct units. Although the modeling procedure essentially deals with geochemical fractionation within a single pluton, the modeling results bring up a number of questions about the petrogenetic relationships among parental magmas of nearly coeval granitic units emplaced in close proximity.
NASA Astrophysics Data System (ADS)
Cauzid, J.; Philippot, P.; Bleuet, P.; Simionovici, A.; Somogyi, A.; Golosio, B.
2007-08-01
World class Cu resources are concentrated in porphyry and epithermal ore deposits. Their formation remains partially understood, however, due to a lack of constraints on the partitioning properties of trace elements in general, and Cu in particular, between vapour and liquid phases evolved from boiling fluids at depth in the Earth's crust. Immiscible liquid and vapour fluid inclusions coexisting in a single quartz grain have been imaged in three dimensions by X-ray Fluorescence Computed Tomography (XFCT). Elemental spatial distributions confirm that Cu, and to a lesser extent As, partition into the vapour phase, whereas Mn, Fe, Zn, Br, Rb, Sr and Pb concentrate in the liquid inclusion. High resolution mapping of the vapour inclusions revealed that Cu is heterogeneously distributed at the scale of a single inclusion and is mostly concentrated as tiny daughter crystals.
Bioturbating animals control the mobility of redox-sensitive trace elements in organic-rich mudstone
DOE Office of Scientific and Technical Information (OSTI.GOV)
Harazim, Dario; McIlroy, Duncan; Edwards, Nicholas P.
Bioturbating animals modify the original mineralogy, porosity, organic content, and fabric of mud, thus affecting the burial diagenetic pathways of potential hydrocarbon source, seal, and reservoir rocks. High-sensitivity, synchrotron rapid scanning X-ray fluorescence elemental mapping reveals that producers of phycosiphoniform burrows systematically partition redox-sensitive trace elements (i.e., Fe, V, Cr, Mn, Co, Ni, Cu, and As) in fine-grained siliciclastic rocks. Systematic differences in organic carbon content (total organic carbon >1.5 wt%) and quality (Δ 13C org~0.6‰) are measured between the burrow core and host sediment. The relative enrichment of redox-sensitive elements in the burrow core does not correlate with significantmore » neo-formation of early diagenetic pyrite (via trace metal pyritization), but is best explained by physical concentration of clay- and silt-sized components. A measured loss (~–15%) of the large-ionic-radius elements Sr and Ba from both burrow halo and core is most likely associated with the release of Sr and Ba to pore waters during biological ( in vivo) weathering of silt- to clay-sized lithic components and feldspar. In conclusion, this newly documented effect has significant potential to inform the interpretation of geochemical proxy and rock property data, particularly from shales, where elemental analyses are commonly employed to predict reservoir quality and support paleoenvironmental analysis.« less
Bioturbating animals control the mobility of redox-sensitive trace elements in organic-rich mudstone
Harazim, Dario; McIlroy, Duncan; Edwards, Nicholas P.; ...
2015-10-07
Bioturbating animals modify the original mineralogy, porosity, organic content, and fabric of mud, thus affecting the burial diagenetic pathways of potential hydrocarbon source, seal, and reservoir rocks. High-sensitivity, synchrotron rapid scanning X-ray fluorescence elemental mapping reveals that producers of phycosiphoniform burrows systematically partition redox-sensitive trace elements (i.e., Fe, V, Cr, Mn, Co, Ni, Cu, and As) in fine-grained siliciclastic rocks. Systematic differences in organic carbon content (total organic carbon >1.5 wt%) and quality (Δ 13C org~0.6‰) are measured between the burrow core and host sediment. The relative enrichment of redox-sensitive elements in the burrow core does not correlate with significantmore » neo-formation of early diagenetic pyrite (via trace metal pyritization), but is best explained by physical concentration of clay- and silt-sized components. A measured loss (~–15%) of the large-ionic-radius elements Sr and Ba from both burrow halo and core is most likely associated with the release of Sr and Ba to pore waters during biological ( in vivo) weathering of silt- to clay-sized lithic components and feldspar. In conclusion, this newly documented effect has significant potential to inform the interpretation of geochemical proxy and rock property data, particularly from shales, where elemental analyses are commonly employed to predict reservoir quality and support paleoenvironmental analysis.« less
NASA Astrophysics Data System (ADS)
Dailey, S. R.; Christiansen, E. H.; Dorais, M.; Fernandez, D. P.
2015-12-01
The Miocene topaz rhyolite at Spor Mountain in western Utah hosts one of the largest beryllium deposits in the world and was responsible for producing 85% of the beryllium mined worldwide in 2010 (Boland, 2012). The Spor Mountain rhyolite is composed primarily of Ca-poor plagioclase (An8), sodic sanidine (Or40), Fe-rich biotite (Fe/(Fe+Mg)>0.95; Al 1.2-1.4 apfu), and Ti-poor quartz, along with several trace-element rich accessory phases including zircon, monazite, thorite, columbite, and allanite. Cathodoluminescence (CL) studies of quartz show oscillatory zoning, with 80% of the examined crystals displaying euhedral edges and slightly darker rims. CL images were used to guide laser ablation (LA) ICP-MS analysis of quartz, along with analyses of plagioclase, sanidine, biotite, and glass. Ti concentrations in quartz are 20±6 ppm; there is no quantifiable variation of Ti from core to rim within the diameter of the laser spot (53 microns). Temperatures, calculated using Ti in quartz (at 2 kb, aTiO2=0.34), vary between 529±10 C (Thomas et al., 2011), 669±13 C (Huang and Audetat, 2012), and 691±13 C (Wark and Watson, 2006). Two feldspar thermometry yield temperatures of 686±33 C (Elkins and Grove, 1990) and 670±41 C (Benisek et al., 2010). Zr saturation temperatures (Watson and Harrison, 1983) average 711±28 C. Analysis of the glass reveal the Spor Mountain rhyolite is greatly enriched in rare elements (i.e. Li, Be, F, Ga, Rb, Nb, Mo, Sn, and Ta) compared to average continental crust (Rudnick and Gao, 2003). Be in the glass can have as much as 100 ppm, nearly 50 times the concentration in continental crust. REE partition coefficients for sanidine are 2 to 3 times higher in the Spor Mountain rhyolite when compared to other silicic magmas (Nash and Crecraft, 1985; Mahood and Hildreth, 1983), although plagioclase tends to have lower partition coefficients; biotite has lower partition coefficients for LREE and higher partition coefficients for HREE. The patterns of trace element enrichment and depletion are similar to those of the measured partition coefficients, consistent with a major role for extensive fractional crystallization in the origin of the Be enriched magma.
Kinetic determinations of trace element bioaccumulation in the mussel Mytilus edulis
Wang, W.-X.; Fisher, N.S.; Luoma, S.N.
1996-01-01
Laboratory experiments employing radiotracer methodology were conducted to determine the assimilation efficiencies from ingested natural seston, the influx rates from the dissolved phase and the efflux rates of 6 trace elements (Ag, Am, Cd, Co, Se and Zn) in the mussel Mytilus edulis. A kinetic model was then employed to predict trace element concentration in mussel tissues in 2 locations for which mussel and environmental data are well described: South San Francisco Bay (California, USA) and Long Island Sound (New York, USA). Assimilation efficiencies from natural seston ranged from 5 to 18% for Ag, 0.6 to 1% for Am, 8 to 20% for Cd, 12 to 16% for Co, 28 to 34% for Se, and 32 to 41% for Zn. Differences in chlorophyll a concentration in ingested natural seston did not have significant impact on the assimilation of Am, Co, Se and Zn. The influx rate of elements from the dissolved phase increased with the dissolved concentration, conforming to Freundlich adsorption isotherms. The calculated dissolved uptake rate constant was greatest for Ag, followed by Zn > Am = Cd > Co > Se. The estimated absorption efficiency from the dissolved phase was 1.53% for Ag, 0.34% for Am, 0.31% for Cd, 0.11% for Co, 0.03% for Se and 0.89% for Zn. Salinity had an inverse effect on the influx rate from the dissolved phase and dissolved organic carbon concentration had no significant effect on trace element uptake. The calculated efflux rate constants for all elements ranged from 1.0 to 3.0% d-1. The route of trace element uptake (food vs dissolved) and the duration of exposure to dissolved trace elements (12 h vs 6 d) did not significantly influence trace element efflux rates. A model which used the experimentally determined influx and efflux rates for each of the trace elements, following exposure from ingested food and from water, predicted concentrations of Ag, Cd, Se and Zn in mussels that were directly comparable to actual tissue concentrations independently measured in the 2 reference sites in national monitoring programs. Sensitivity analysis indicated that the total suspended solids load, which can affect mussel feeding activity, assimilation, and trace element concentration in the dissolved and particulate phases, can significantly influence metal bioaccumulation for particle-reactive elements such as Ag and Am. For all metals, concentrations in mussels are proportionately related to total metal load in the water column and their assimilation efficiency from ingested particles. Further, the model predicted that over 96% of Se in mussels is obtained from ingested food, under conditions typical of coastal waters. For Ag, Am, Cd, Co and Zn, the relative contribution from the dissolved phase decreases significantly with increasing trace element partition coefficients for suspended particles and the assimilation efficiency in mussels of ingested trace elements; values range between 33 and 67% for Ag, 5 and 17% for Am, 47 and 82% for Cd, 4 and 30% for Co, and 17 and 51% for Zn.
Prouty, Nancy G.; Swarzenski, Peter W.; Fackrell, Joseph; Johannesson, Karen H.; Palmore, C. Diane
2017-01-01
Study regionThe groundwater influenced coastal waters along the arid Kona coast of the Big Island, Hawai’i.Study focusA salinity-and phase partitioning-based mixing experiment was constructed using contrasting groundwater endmembers along the arid Konacoast of the Big Island, Hawai’i and local open seawater to better understand biogeochemical and physicochemical processes that influence the fate of submarine groundwater discharge (SGD)-derived nutrients and trace elements.New Hydrological Insights for the RegionTreated wastewater effluent was the main source for nutrient enrichment downstream at the Honokōhau Harbor site. Conservative mixing for some constituents, such as nitrate + nitrite, illustrate the effectiveness of physical mixing to maintain oceanic concentrations in the colloid (0.02–0.45 μm) and truly dissolved (
Horowitz, Arthur J.; Elrick, Kent A.; Cook, Robert B.
1993-01-01
During the summer of 1989 surface sediment samples were collected in Lake Coeur d'Alene, the Coeur d'Alene River and the St Joe River, Idaho, at a density of approximately one sample per square kilometre. Additional samples were collected from the banks of the South Fork of the Coeur d'Alene and the Coeur d'Alene Rivers in 1991. All the samples were collected to determine trace element concentrations, partitioning and distribution patterns, and to relate them to mining, mining related and discharge operations that have occurred in the Coeur d'Alene district since the 1880s, some of which are ongoing.Most of the surface sediments in Lake Coeur d'Alene north of Conkling Point and Carey Bay are substantially enriched in Ag, As, Cu, Cd, Hg, Pb, Sb and Zn relative to unaffected sediments in the southern portion of the lake near the St Joe River. All the trace element enriched sediments are extremely fine grained (mean grain sizes « 63 μm). Most of the enriched trace elements, based on both the chemical analyses of separated heavy and light mineral fractions and a two step sequential extraction procedure, are associated with an operationally defined Fe oxide phase; much smaller percentages are associated either with operationally defined organics/sulphides or refractory phases.The presence, concentration and distribution of the Fe oxides and heavy minerals indicates that a substantial portion of the enriched trace elements are probably coming from the Coeur d'Alene River, which is serving as a point source. Within the lake, this relatively simple point source pattern is complicated by a combination of (1) the formation of trace element rich authigenic Fe oxides that appear to have reprecipitated from material solubilized from anoxic bed sediments and (2) physical remobilization by currents and wind driven waves. The processes that have caused the trace element enrichment in the surface sediments of Lake Coeur d'Alene are likely to continue for the foreseeable future.
NASA Astrophysics Data System (ADS)
Morizet, Y.; Blundy, J.; McDade, P.
2003-04-01
During subduction, the slab undergoes several processes such as dehydration and partial melting at pressures of 2-3 GPa and temperatures of 600-900^oC. Under these conditions, there is little or no distinction between melt and fluid phases (Bureau &Keppler, 1999, EPSL 165, 187-196). To investigate the behaviour of trace elements under these conditions we have carried out partitioning experiments in the system CMASH at 2.2 GPa, 700-920^oC. CMAS starting compositions were doped with trace elements, and loaded together with quartz and water into a Pt capsule, which was in turn contained within a Ni-lined Ti capsule. Run durations were 3-7 days. A run at 810^oC produced euhedral calcic garnet, zoisite, quartz, hydrous melt and tiny clinopyroxene interpreted as quench crystals. LA-ICPMS and SIMS were used to quantify trace element concentrations of the phases. Garnet-melt D's for the HREE decrease from ˜300 for Lu to less than 0.2 for La. DSc and D_V are less than 5, consistent with the large X-site dimension in the garnet. DLi DSr and DBa are considerably less than the adjacent REE. There is a very slight negative partitioning anomaly for Zr and Hf relative to Nd and Sm; DHf is slightly greater than DZr. D_U < DTh, due largely to the oxidizing conditions of the experiment (NNO). The most striking result is very high D's for Nb and Ta: 18±10 and 5.4±1.9 (LA-ICPMS), 25.8±11.9 and 6.6±1.3 (SIMS) for Nb and Ta respectively. These are considerably larger than any previously measured (at much higher temperatures). The observed partitioning behaviour is consistent with the large temperature dependence for DREE proposed by Van Westrenen et al. (2001, Contrib Min Pet, 142, 219-234), and an even larger temperature dependence for DNb and DTa. These preliminary results suggest that garnet (rather than rutile) may play the key role in controlling the Nb and Ta budget of arc magmas and the Nb/Ta ratio of residual eclogites. For example, modelling of eclogite melting, using a N-MORB source and the new D's, shows that a residue with Nb > 2 ppm, 19 < Nb/Ta < 37 (as proposed by Rudnick et al., 2000, Science 287, 278-281), can be produced by ˜30% partial melting. Slightly lower melt fractions (˜15%) reproduce their proposed Nb/La (>1.2).
Trace element analyses of fluid-bearing diamonds from Jwaneng, Botswana
NASA Astrophysics Data System (ADS)
Schrauder, Marcus; Koeberl, Christian; Navon, Oded
1996-12-01
Fibrous diamonds from Botswana contain abundant micro-inclusions, which represent syngenetic mantle fluids under high pressure. The major element composition of the fluids within individual diamonds was found to be uniform, but a significant compositional variation exists between different diamond specimens. The composition of the fluids varies between a carbonatitic and a hydrous endmember. To constrain the composition of fluids in the mantle, the trace element contents of thirteen micro-inclusion-bearing fibrous diamonds from Botswana was studied using neutron activation analysis. The concentrations of incompatible elements (including K, Na, Br, Rb, Sr, Zr, Cs, Ba, Hf, Ta, Th, U, and the LREEs) in the fluids are higher than those of mantle-derived rocks and melt inclusions. The compatible elements (e.g., Cr, Co, Ni) have abundances that are similar to those of the primitive mantle. The concentrations of most trace elements decrease by a factor of two from the carbonate-rich fluids to the hydrous fluids. Several models may explain the observed elemental variations. Minerals in equilibrium with the fluid were most likely enriched in incompatible elements, which does not agree with derivation of the fluids by partial melting of common peridotites or eclogites. Fractional crystallization of a kimberlite-like magma at depth may yield carbonatitic fluids with low mg numbers (atomic ratio [Mg/(Mg+Fe)]) and high trace element contents. Fractionation of carbonates and additional phases (e.g., rutile, apatite, zircon) may, in general, explain the concentrations of incompatible elements in the fluids, which preferably partition into these phases. Alternatively, mixing of fluids with compositions similar to those of the two endmembers may explain the observed variation of the elemental contents. The fluids in fibrous diamonds might have equilibrated with mineral inclusions in eclogitic diamonds, while peridotitic diamonds do not show evidence of interaction with these fluids. The chemical composition of the fluids in fibrous diamonds indicates that, at p, T conditions that are characteristic for diamond formation, carbonatitic and hydrous fluids are efficient carriers of incompatible elements.
Senior, C.L.; Zeng, T.; Che, J.; Ames, M.R.; Sarofim, A.F.; Olmez, I.; Huggins, Frank E.; Shah, N.; Huffman, G.P.; Kolker, A.; Mroczkowski, S.; Palmer, C.; Finkelman, R.
2000-01-01
Trace elements in coal have diverse modes of occurrence that will greatly influence their behavior in many coal utilization processes. Mode of occurrence is important in determining the partitioning during coal cleaning by conventional processes, the susceptibility to oxidation upon exposure to air, as well as the changes in physical properties upon heating. In this study, three complementary methods were used to determine the concentrations and chemical states of trace elements in pulverized samples of four US coals: Pittsburgh, Illinois No. 6, Elkhorn and Hazard, and Wyodak coals. Neutron Activation Analysis (NAA) was used to measure the absolute concentration of elements in the parent coals and in the size- and density-fractionated samples. Chemical leaching and X-ray absorption fine structure (XAFS) spectroscopy were used to provide information on the form of occurrence of an element in the parent coals. The composition differences between size-segregated coal samples of different density mainly reflect the large density difference between minerals, especially pyrite, and the organic portion of the coal. The heavy density fractions are therefore enriched in pyrite and the elements associated with pyrite, as also shown by the leaching and XAFS methods. Nearly all the As is associated with pyrite in the three bituminous coals studied. The sub-bituminous coal has a very low content of pyrite and arsenic; in this coal arsenic appears to be primarily organically associated. Selenium is mainly associated with pyrite in the bituminous coal samples. In two bituminous coal samples, zinc is mostly in the form of ZnS or associated with pyrite, whereas it appears to be associated with other minerals in the other two coals. Zinc is also the only trace element studied that is significantly more concentrated in the smaller (45 to 63 ??m) coal particles.
NASA Astrophysics Data System (ADS)
Gregory, Daniel D.; Lyons, Timothy W.; Large, Ross R.; Jiang, Ganqing; Stepanov, Aleksandr S.; Diamond, Charles W.; Figueroa, Maria C.; Olin, Paul
2017-11-01
The trace element content of pyrite is a recently developed proxy for metal abundance in paleo-oceans. Previous studies have shown that the results broadly match those of whole rock studies through geologic time. However, no detailed study has evaluated the more traditional proxies for ocean chemistry for comparison to pyrite trace element data from the same samples. In this study we compare pyrite trace element data from 14 samples from the Wuhe section of the Ediacaran-age Doushantuo Formation, south China, measured by laser ablation inductively coupled plasma mass spectrometry with new and existing whole rock trace element concentrations; total organic carbon; Fe mineral speciation; S isotope ratios; and pyrite textural relationships. This approach allows for comparison of data for individual trace elements within the broader environmental context defined by the other chemical parameters. The results for discrete pyrite analyses show that several chalcophile and siderophile elements (Ag, Sb, Se, Pb, Cd, Te, Bi, Mo, Ni, and Au) vary among the samples with patterns that mirror those of the independent whole rock data. A comparison with existing databases for sedimentary and hydrothermal pyrite allows us to discriminate between signatures of changing ocean conditions and those of known hydrothermal sources. In the case of the Wuhe samples, the observed patterns for trace element variation point to primary marine controls rather than higher temperature processes. Specifically, our new data are consistent with previous arguments for pulses of redox sensitive trace elements interpreted to be due to marine oxygenation against a backdrop of mostly O2-poor conditions in the Ediacaran ocean-with important implications for the availability of bioessential elements. The agreement between the pyrite and whole rock data supports the use of trace element content of pyrite as a tracer of ocean chemistry in ways that complement existing approaches, while also opening additional windows of opportunity. For example, unlike the potential vulnerability of whole rock data to secondary alteration, the pyrite record may survive greenschist facies metamorphism. Furthermore, early-formed pyrite can be identified through textural relationships as a proxy of primary marine chemistry even in the presence of hydrothermal overprints on whole rock chemistry via secondary fluids. Finally, pyrite analyses may allow for the possibility of more quantitative interpretations of the ancient ocean once the elemental partitioning between the mineral and host fluids are better constrained. Collectively, these advances can greatly increase the number of basins that may be investigated for early ocean chemistry, especially those of Precambrian age.
Horsfall, M; Spiff, A I
2002-09-01
The distribution of trace metals in sediments of the lower reaches of the New Calabar River, Nigeria was evaluated together with the partitioning of their chemical species between five geochemical phases. Samplings were made in five zones at the lower reaches of the New Calaber River. All the trace metals were determined by AAS after selective chemical extractions and concentrations given in microg gm(-1) (dry weight basis). The average total concentrations found for trace metals in the sediment were ( mean +/- rsd.) Pb: 41.6 +/- 0.29, Zn: 31.60 +/- 0.42, Cd: 12.80 +/- 0.92, Co: 92 +/- 0.25, Cu: 25.5 +/- 0.65 and Ni: 3.2 +/- 0.25. Maxima and minima concentrations are inconsistent with previous studies in other rivers of this region. Spatial distribution revealed that the sources of trace metals into the river appeared to be of non-point. Five contamination indices were applied in studying the partitioning of the trace metals in the sediment. These indices provided bases for ascertaining the potential environmental risk of trace metals in the river system. The results denote high partition levels in the more mobile and more dangerous phases.
Composition of the earth's upper mantle. II - Volatile trace elements in ultramafic xenoliths
NASA Technical Reports Server (NTRS)
Morgan, J. W.; Wandless, G. A.; Petrie, R. K.; Irving, A. J.
1980-01-01
Radiochemical neutron activation analysis was used to determine the nine volatile elements Ag, Bi, Cd, In, Sb, Se, Te, Tl, and Zn in 19 ultramafic rocks, consisting mainly of spinel and garnet lherzolites. A sheared garnet lherzolite, PHN 1611, may approximate undepleted mantle material and tends to have a higher volatile element content than the depleted mantle material represented by spinel lherzolites. Comparisons of continental basalts with PHN 1611 and of oceanic ridge basalts with spinel lherzolites show similar basalt: source material partition factors for eight of the nine volatile elements, Sb being the exception. The strong depletion of Te and Se in the mantle, relative to lithophile elements of similar volatility, suggests that 97% of the earth's S, Se and Te may be in the outer core.
TRACES OF ORIGINAL PARTITIONS AT JUNCTURE OF FRONT ROOM, REAR ...
TRACES OF ORIGINAL PARTITIONS AT JUNCTURE OF FRONT ROOM, REAR ROOM AND HALL, SECOND FLOOR. ALSO SHOWS ORIGINAL STUCCO CORNICE OF FRONT AND REAR ROOMS (LEFT) AND HALL (RIGHT) - Kid-Chandler House, 323 Walnut Street, Philadelphia, Philadelphia County, PA
Mineralogy and the release of trace elements from slag from the Hegeler Zinc smelter, Illinois (USA)
Piatak, Nadine M.; Seal, Robert R.
2010-01-01
Slag from the former Hegeler Zn-smelting facility in Illinois (USA) is mainly composed of spinifex Ca-rich plagioclase, fine-grained dendritic or coarse-grained subhedral to anhedral clinopyroxenes, euhedral to subhedral spinels, spherical blebs of Fe sulfides, silicate glass, and less commonly fayalitic olivine. Mullite and quartz were also identified in one sample as representing remnants of the furnace lining. Secondary phases such as goethite, hematite and gypsum are significant in some samples and reflect surficial weathering of the dump piles or represent byproducts of roasting. A relatively rare Zn-rich material contains anhedral willemite, subhedral gahnite, massive zincite, hardystonite and a Zn sulfate (brianyoungite), among other phases, and likely represents the molten content of the smelting furnace before Zn extraction. The bulk major-element chemistry of most slag samples is dominated by SiO2, Al2O3, Fe2O3 and CaO. The bulk composition of the slag suggests a high viscosity of the melt and the mineralogy suggests a high silica content of the melt. Bulk slag trace-element chemistry shows that the dominant metal is Zn with >28.4 wt.% in the Zn-rich material and between 212 and 14,900 mg/kg in the other slags. The concentrations of other trace elements reach the following: 45 mg/kg As, 1170 mg/kg Ba, 191 mg/kg Cd, 242 mg/kg Co, 103 mg/kg Cr, 6360 mg/kg Cu, 107 mg/kg Ni, and 711 mg/kg Pb.Zinc, as the dominant metal in the slags, is likely the most environmentally significant metal in these samples; Cd, Cu, and Pb are also of concern and their concentrations exceed US Environmental Protection Agency preliminary remediation goals for residential soils. Spinel was found to be the dominant concentrator of Zn for samples containing significant Zn (>1 wt.%); the silicate glass also contained relatively high concentrations of Zn compared to other phases. Zinc partitioned into the silicates and oxides in these samples is generally more resistant to weathering and therefore less leached when compared to the slag samples with lower bulk Zn concentrations where Zn is likely partitioned into volumetrically minor sulfides. This is confirmed by leachate tests that resulted in low leachate Zn concentrations for samples with Zn partitioned into spinel. In contrast, the concentrations of Zn and SO4 are close to those expected from the dissolution of stoichiometric ZnS in leachates from samples in which the dominant host of Zn is suspected to be sulfides. The fact that Zn and other metals occur commonly as sulfides, which are more reactive than the silicates and oxides into which they dominantly partition according to other slag studies, indicates the Hegeler slag pile may be more of an environmental concern than other slag piles.
Kolker, Allan; Senior, Connie L.; van Alphen, Chris; Koenig, Alan E.; Geboy, Nicholas J.
2017-01-01
Eight density separates of Permian Highveld (#4) coal were investigated for partitioning of Hg and trace elements. The separates include float fractions obtained in heavy media having densities of 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0 g/cm3, and the sink fraction for 2.0 g/cm3. Bulk analysis of the separates shows strong (R2 ≥ 0.80) positive correlations between pyritic sulfur and mercury, and between ash yield and both pyritic sulfur and mercury. Laser ablation (LA) ICP-MS analysis of individual pyrite grains in the separates confirms association of Hg and As with pyrite as indicated by bulk analysis. Other elements detected in pyrite by LA-ICP-MS include Mn, Co, Ni, Tl, and Pb. Results for the separates allow prediction of Hg, trace elements, and ash yields expected in specific South African coal products. These range from 0.06 ppm Hg and an ash yield of 11.5% ash for the export fraction to 0.47 ppm Hg and an ash yield of 60.9% for the discard (stone) fraction (dry basis). Results show pronounced differences expected between coal used for domestic power generation and coal which is exported.
The effects of pressure, temperature and composition on olivine-liquid exchange coefficients
NASA Astrophysics Data System (ADS)
Matzen, A. K.; Wood, B. J.
2017-12-01
It has recently been observed that there is a correlation between trace element (Ni and Mn) concentrations in olivine (ol) phenocrysts and thickness of the lithosphere on which they were erupted [1]. There are a number of potential explanations for this observation: the mantle may have interacted with the Ni-rich core; the trace element concentrations reflect presence of recycled crust in the mantle; or it arises from melting of peridotite at different temperatures (T) and pressures (P). Discriminating between these hypotheses requires accurate models of olivine-silicate liquid (liq) partitioning. The three variables that control the observed variations in experimentally-derived ol-liq partition coefficients are T, P, and the composition of the silicate liquid (and to a lesser extent the olivine composition). However, experiments cannot unambiguously disentangle the effects of these variables. For olivine-saturated liquids at constant P, any change in T results in the crystallization or dissolution of olivine and thus a change in liquid composition, resulting in a correlation between T and silicate liquid composition (note that changing the bulk composition such that olivine saturation occurs at a different T also results in a correlation with composition and T). Alternatively, P and T can be varied in concert such that liquid and olivine compositions remain approximately constant [e.g., 2], resulting in a correlation between T and P. In an attempt to resolve the conflation of T, P and compositional effects we turned to metal (met)-liq partitioning studies. Experiments show that, unlike most other elements, P has a strong effect on the partitioning of Ni between Fe-rich metal and silicate melt. Assuming that the pressure dependence of K_{D, Ni-Fe}^{met-liq} (0-25 GPa) [3] is driven primarily by the changing activities in the silicate melt, we can approximate the effect that pressure will have on K_{D, Ni-Fe}^{ol-liq} as measured by [2], using Kress and Carmichael [4] to calculate Fe3+/Fe2+. We find that the pressure effect should be a significant contributor to the observed systematics of K_{D, Ni-Fe}^{ol-liq} between 1 atm and 3 GPa [2]. [1] Sobolev et al (2007) Science, 316, 412-417, [2] Matzen et al (2017) CMP 172:3, [3] Kegler et al (2008) EPSL 268, 28-40, [4] Kress & Carmichael (1991) CMP 108, 82-92.
Grotti, Marco; Soggia, Francesco; Ardini, Francisco; Magi, Emanuele; Becagli, Silvia; Traversi, Rita; Udisti, Roberto
2015-11-01
From January to December 2010, surface snow samples were collected with monthly resolution at the Concordia station (75°06'S, 123°20'E), on the Antarctic plateau, and analysed for major and trace elements in both dissolved and particulate (i.e. insoluble particles, >0.45 μm) phase. Additional surface snow samples were collected with daily resolution, for the determination of sea-salt sodium and not-sea-salt calcium, in order to support the discussion on the seasonal variations of trace elements. Concentrations of alkaline and alkaline-earth elements were higher in winter (April-October) than in summer (November-March) by a factor of 1.2-3.3, in agreement with the higher concentration of sea-salt atmospheric particles reaching the Antarctic plateau during the winter. Similarly, trace elements were generally higher in winter by a factor of 1.2-1.5, whereas Al and Fe did not show any significant seasonal trend. Partitioning between dissolved and particulate phases did not change with the sampling period, but it depended only on the element: alkaline and alkaline-earth elements, as well as Co, Cu, Mn, Pb and Zn were for the most part (>80%) in the dissolved phase, whereas Al and Fe were mainly associated with the particulate phase (>80%) and Cd, Cr, V were nearly equally distributed between the phases. Finally, the estimated marine and crustal enrichment factors indicated that Cd, Cr, Cu, Pb and Zn have a dominant anthropogenic origin, with a possible contribution from the Concordia station activities. Copyright © 2014 Elsevier Ltd. All rights reserved.
Rare Earth Element Partitioning in Lunar Minerals: An Experimental Study
NASA Technical Reports Server (NTRS)
McIntosh, E. C.; Rapp, J. F.; Draper, D. S.
2016-01-01
The partitioning behavior of rare earth elements (REE) between minerals and melts is widely used to interpret the petrogenesis and geologic context of terrestrial and extra-terrestrial samples. REE are important tools for modelling the evolution of the lunar interior. The ubiquitous negative Eu anomaly in lunar basalts is one of the main lines of evidence to support the lunar magma ocean (LMO) hypothesis, by which the plagioclase-rich lunar highlands were formed as a flotation crust during differentiation of a global-scale magma ocean. The separation of plagioclase from the mafic cumulates is thought to be the source of the Eu depletion, as Eu is very compatible in plagioclase. Lunar basalts and volcanic glasses are commonly depleted in light REEs (LREE), and more enriched in heavy REEs (HREE). However, there is very little experimental data available on REE partitioning between lunar minerals and melts. In order to interpret the source of these distinctive REE patterns, and to model lunar petrogenetic processes, REE partition coefficients (D) between lunar minerals and melts are needed at conditions relevant to lunar processes. New data on D(sub REE) for plagioclase, and pyroxenes are now available, but there is limited available data for olivine/melt D(sub REE), particularly at pressures higher than 1 bar, and in Fe-rich and reduced compositions - all conditions relevant to the lunar mantle. Based on terrestrial data, REE are highly incompatible in olivine (i.e. D much less than 1), however olivine is the predominant mineral in the lunar interior, so it is important to understand whether it is capable of storing even small amounts of REE, and how the REEs might be fractionatied, in order to understand the trace element budget of the lunar interior. This abstract presents results from high-pressure and temperature experiments investigating REE partitioning between olivine and melt in a composition relevant to lunar magmatism.
NASA Astrophysics Data System (ADS)
Gascoyne, Melvyn
1983-02-01
Speleothems (stalactites, stalagmites) formed in limestone caves have been found to contain much information on the timing and intensity of past climates, from analysis of their U, Th, 13C and 18O contents. Because the incorporation of certain trace elements (e.g., Mg, Mn and Zn) in calcite is known to be temperature-dependent, it may be possible to use variations in trace-metal content of fossil speleothems as an alternative paleotem-perature indicator. Using specially developed ion-exchange sampling techniques, analysis of trace-metal content of seepage water and associated fresh calcite deposits in caves in Vancouver Island and Jamaica shows that Mg is distributed between phases in a consistent manner within the temperature regimes of the caves (7° and 23°C, respectively). Average values of the distribution coefficient for Mg are respectively 0.017 and 0.045 at these temperatures. These results indicate that the Mg content of calcite varies directly with temperature and in a sufficiently pronounced manner that a 1°C rise in depositional temperature of a speleothem containing 500 ppm Mg, at ˜10°C, would be seen as an increase of ˜35ppm Mg — a readily determinable shift. Other factors affecting Mg content of a speleothem are considered.
NASA Astrophysics Data System (ADS)
Manoochehri, S.; Schmidt, M. W.; Guenther, D.
2013-12-01
Gravitational settling of immiscible, dense sulfide melt droplets together with other cumulate phases such as chromite, combined with downward percolation of these droplets through a cumulate pile, is thought to be one of the possible processes leading to the formation of PGE rich sulfide deposits in layered mafic intrusions. Furthermore some chromitite seams in the Merensky Reef (Bushveld Complex) are considered to be acting as a filter or barrier for further downward percolation of sulfide melts into footwall layers. To investigate the feasibility of such mechanical processes and to study the partitioning behavior of 50 elements including transition metals and REEs (but not PGEs) between a silicate and a sulfide melt, two separate series of high temperature (1250-1380 °C) centrifuge-assisted experiments at 1000 g, 0.4-0.6 GPa were conducted. A synthetic silicate glass with a composition representative of the parental magma of the Bushveld Complex (~ 55 wt% SiO2) was mixed with pure FeS powder. For the first series of experiments, 15 or 25 wt% natural chromite with average grain sizes of ~ 5 or 31 μm were added to a mixture of silicate glass and FeS (10 wt%) adding 1 wt% water. For the second series, a mixture of the same glass and FeS was doped with 50 trace elements. These mixtures were first statically equilibrated and then centrifuged. In the first experimental series, sulfide melt droplets settled together with, but did not segregate from chromite grains even after centrifugation at 1000 g for 12 hours. A change in initial chromite grain size and proportions didn't have any effect on segregation. Without chromite, the starting mixture resulted in the formation of large sulfide melt pools together with finer droplets still disseminated through the silicate glass and both at the bottom of the capsule. The incomplete segregation of sulfide melt is interpreted as being due to high interfacial energies between sulfide and silicate melts/crystals which hinder both, the nucleation of newly formed sulfide droplets and the interconnectivity of separate droplets. The interfacial energies between sulfide melt and silicate or oxide crystals is even higher than for silicate melt, consequently in experiments with chromite, sulfide segregation is even more hindered. Partition coefficients of 50 elements between a sulfide and a silicate melt are determined as a function of differing temperature between 1250 - 1380 °C. As a proxy to investigate the bond strength of network modifier cations, the relation between the partition coefficients and ionic potentials of different groups of elements has been determined.
Trace Metal-Humic Complexes in Natural Waters: Insights From Speciation Experiments
NASA Astrophysics Data System (ADS)
Stern, J. C.; Salters, V.; Sonke, J.
2006-12-01
The DOM cycle is intimately linked to the cycling and bioavailability of trace metals in aqueous environments. The presence or absence of DOM in the water column can determined whether trace elements will be present in limited quantities as a nutrient, or in surplus quantities as a toxicant. Humic substances (HS), which represent the refractory products of DOM degradation, strongly affect the speciation of trace metals in natural waters. To simulate metal-HS interactions in nature, experiments must be carried out using trace metal concentrations. Sensitive detection systems such as ICP-MS make working with small (nanomolar) concentrations possible. Capillary electrophoresis coupled with ICP-MS (CE-ICP-MS) has recently been identified as a rapid and accurate method to separate metal species and calculate conditional binding constants (log K_c) of metal-humic complexes. CE-ICP-MS was used to measure partitioning of metals between humic substances and a competing ligand (EDTA) and calculate binding constants of rare earth element (REE) and Th, Hf, and Zr-humic complexes at pH 3.5-8 and ionic strength of 0.1. Equilibrium dialysis ligand exchange (EDLE) experiments to validate the CE-ICP-MS method were performed to separate the metal-HS and metal-EDTA species by partitioning due to size exclusion via diffusion through a 1000 Da membrane. CE-ICP-MS experiments were also conducted to compare binding constants of REE with humic substances of various origin, including soil, peat, and aquatic DOM. Results of our experiments show an increase in log K_c with decrease in ionic radius for REE-humic complexes (the lanthanide contraction effect). Conditional binding constants of tetravalent metal-humic complexes were found to be several orders of magnitude higher than REE-humic complexes, indicating that tetravalent metals have a very strong affinity for humic substances. Because thorium is often used as a proxy for the tetravalent actinides, Th-HS binding constants can allow us to assess the importance of tetravalent actinide-humic complexes in groundwater transport from nuclear repositories. Our results suggest that tetravalent actinide-humic complexes couild be more important to account for in predictive speciation models than previously thought.
Microbial biofilms control economic metal mobility in an acid-sulfate hydrothermal system
NASA Astrophysics Data System (ADS)
Phillips-Lander, C. M.; Roberts, J. A.; Hernandez, W.; Mora, M.; Fowle, D. A.
2012-12-01
Trace metal cycling in hydrothermal systems has been the subject of a variety of geochemical and economical geology studies. Typically in these settings these elements are sequestered in sulfide and oxide mineral fractions, however in near-surface low-temperature environments organic matter and microorganisms (typically in mats) have been implicated in their mobility through sorption. Here we specifically examine the role of microbial biofilms on metal partitioning in an acid-sulfate hydrothermal system. We studied the influence of microorganisms and microbial biofilms on trace metal adsorption in Pailas de Aguas I, an acid-sulfate hot spring on the southwest flank of Rincon de la Vieja, a composite stratovolcano in the Guanacaste Province, Costa Rica. Spring waters contain high suspended loads, and are characterized by high T (79.6-89.3oC), low pH (2.6-4), and high ionic strengths (I= 0.5-0.8). Waters contain high concentrations of the biogeochemically active elements Fe (4-6 mmol/l) and SO42- (38 mmol/l), but PO43- are below detection limits (bdl). Silver, Ni, and Mo concentrations are bdl; however other trace metals are present in solution in concentrations of 0.1-0.2 mg/l Cd, 0.2-0.4 mg/l Cr and V, 0.04-1 mg/l Cu,. Preliminary 16S rRNA analyses of microorganisms in sediments reveal several species of algae, including Galderia sp., Cyanidium sp, γ-proteobacteria, Acidithiobacillus caldus, Euryarcheota, and methanogens. To evaluate microbial biofilms' impact on trace metal mobility we analyzed a combination of suspended, bulk and biofilm associated sediment samples via X-ray diffraction (XRD) and trace element sequential extractions (SE). XRD analysis indicated all samples were primarily composed of Fe/Al clay minerals (nontronite, kaolinite), 2- and 6-line ferrihydrite, goethite, and hematite, quartz, and opal-α. SE showed the highest concentrations of Cu, Mo, and V were found in the suspended load. Molybdenum was found primarily in the residual and organic fractions of suspended sediments. Copper is distributed in all but the carbonate fraction of suspended sediments. Vanadium was bound primarily to the oxide and residual fractions with Si, which is probably found as opal-α. In contrast, biofilm sediments had the highest concentrations of Fe, Si, Cd, Al, Zn, Ag, and Ni. Trace metals were sequestered mainly in the organic fraction in decreasing concentrations of: Cu
Minor and trace element concentrations in adjacent kamacite and taenite in the Krymka chondrite
NASA Astrophysics Data System (ADS)
Meftah, N.; Mostefaoui, S.; Jambon, A.; Guedda, E. H.; Pont, S.
2016-04-01
We report in situ NanoSIMS siderophile minor and trace element abundances in individual Fe-Ni metal grains in the unequilibrated chondrite Krymka (LL3.2). Associated kamacite and taenite of 10 metal grains in four chondrules and one matrix metal were analyzed for elemental concentrations of Fe, Ni, Co, Cu, Rh, Ir, and Pt. The results show large elemental variations among the metal grains. However, complementary and correlative variations exist between adjacent kamacite-taenite. This is consistent with the unequilibrated character of the chondrite and corroborates an attainment of chemical equilibrium between the metal phases. The calculated equilibrium temperature is 446 ± 9 °C. This is concordant with the range given by Kimura et al. (2008) for the Krymka postaccretion thermal metamorphism. Based on Ni diffusivity in taenite, a slow cooling rate is estimated of the Krymka parent body that does not exceed ~1K Myr-1, which is consistent with cooling rates inferred by other workers for unequilibrated ordinary chondrites. Elemental ionic radii might have played a role in controlling elemental partitioning between kamacite and taenite. The bulk compositions of the Krymka metal grains have nonsolar (mostly subsolar) element/Ni ratios suggesting the Fe-Ni grains could have formed from distinct precursors of nonsolar compositions or had their compositions modified subsequent to chondrule formation events.
NASA Astrophysics Data System (ADS)
Krause, J.; Brügmann, G. E.; Pushkarev, E. V.
2009-04-01
The partitioning of trace elements between rock forming minerals in igneous rocks is largely controlled by physical and chemical parameters e.g. temperature, pressure and chemical composition of the minerals and the coexisting melt. In the present study partition coefficients for REE between hornblende, orthopyroxene, feldspars, apatite and clinopyroxene in a suite of co-genetic alkaline and tholeiitic mafic rocks from the Ural Mountains (Russia) were calculated. The results give insights to the influence of the chemical composition of the parental melt on the partitioning behaviour of the REE. Nepheline-bearing, alkaline melanogabbros (tilaites) are assumed to represent the most fractionated products of the melt that formed the ultramafic cumulates in zoned mafic-ultramafic complexes in the Ural Mountains. Co-genetic with the latter is a suite of olivine gabbros, gabbronorites and hornblende gabbros formed from a tholeiitic parental melt. Negative anomalies for the HFSE along with low Nb and Ta contents and a positive Sr anomaly indicate a subduction related origin of all parental melts. The nepheline gabbros consist predominantly of coarse-grained clinopyroxene phenocrysts in a matrix of fine grained clinopyroxene, olivine, plagioclase, K-feldspar and nepheline with accessory apatite. The tholeiitic gabbros have equigranular to porphyric textures with phenocrysts of olivine, pyroxene and hornblende in a plagioclase rich matrix with olivine hornblende, pyroxene and accessory apatite. Element concentrations of adjacent matrix grains and rims of phenochrysts were measured with LA-ICPMS. The distribution of REE between hornblende and clinopyroxene in the tholeiitic rocks is similar for most of the elements (DHblCpx(La-Tm) = 2.7-2.8, decreasing to 2.6 and 2.4 for Yb and Lu, respectively). These values are about two times higher than published data (e.g. Ionov et al. 1997). Partition coefficients for orthopyroxene/clinopyroxene systematically decrease from the HREE (DOpxCpx(Lu) = 0.31) towards the LREE (DOpxCpx(Nd) = 0.01). The partition coefficients for plagioclase/clinopyroxene and K-feldspar/clinopyroxene in the alkaline melanogabbros decrease from the LREE (DPlgCpx(La) = 0.91, DK-fsCpx(La)=0.26) to the MREE (DPlgCpx(Sm) = 0.02, DK-fsCpx(Sm) = 0.006), but both mineral pairs have similar DEu (DPlgCpx(Eu) = 0.25, DK-fsCpx(Eu) = 0.23). Plagioclase/clinopyroxene partition coefficients for all REE in the tholeiitic gabbros are 3-5 times higher, if compared to those of the alkaline gabbros (DPlgCpx(La) = 1.7, DPlgCpx(Sm) = 0.034). Apatite/clinopyroxene partition coefficients for the REE decrease from the LREE (DApCpx(La) = 65 in alkaline and 120 in tholeiitic gabbro) to the HREE (DApCpx(Lu) = 4.5 in alkaline and 5.3 in tholeiitic gabbro). The lower partition coefficients for apatite/clinopyroxene and plagioclase/clinopyroxene in the alkaline melanogabbros can be explained by higher clinopyroxene/melt partition coefficients in this system. The higher Al2O3-content in clinopyroxene from the alkali gabbros (Al2O3 = 3.5-7 wt.%), if compared to clinopyroxene in the tholeiitic gabbros (Al2O3 = 2.0-4.5 wt.%) can account for a stronger partitioning of the REE into clinopyroxene in the alkaline rocks (e.g. Gaetani and Grove 1995). Experimental data by Gaetani (2004) also indicate a systematic increase of the Cpx/melt partition coefficients for the REE with increasing Al2O3 and Na2O contents of the parental melt in mafic systems. This is in agreement with the assumed compositional differences between the alkaline and the tholeiitic parental melts. Gaetani, G.A., 2004. Contributions to Mineralogy and Petrology, Vol. 147, 511-527. Gaetani, G.A., Grove, T.L, 1995. Geochimica et Cosmochimica Acta, Vol. 59, 1951-1962. Ionov, D.A., Griffin, W.L., O'Reily, S.Y., 1997. Chemical Geology, Vol. 141, 153-184.
NASA Technical Reports Server (NTRS)
Karner, J. M.; Jones, J. H.; Le, L.
2017-01-01
The partitioning of multivalent elements in basaltic systems can elucidate the oxygen fugacity (fO2) conditions under which basalts formed on planetary bodies (Earth, Moon, Mars, asteroids). Chromium and V are minor and trace elements in basaltic melts, partition into several minerals that crystallize from basaltic melts, exist in multiple valence states at differing fO2 conditions, and can therefore be used as oxybarometers for basaltic melts. Chromium is mostly 3+ in terrestrial basaltic melts at relatively high fO2 values (= IW+3.5), and mostly 2+ in melts at low fO2 values (= IW-1), such as those on the Moon and some asteroids. At intermediate fO2s, (i.e., IW-1 to IW+3.5), basaltic melts contain both Cr3+ and Cr2+. Vanadium in basaltic melts is mostly 4+ at high fO2, mostly 3+ at low fO2, and a mix of V3+ and V4+ at intermediate fO2 con-ditions. Understanding the partitioning of Cr and V into silicate phases with changing fO2 is therefore critical to the employment of Cr and V oxybarometers. In this abstract we examine the equilibrium partitioning of Cr and V between olivine/melt and pyroxene/melt in experimental charges of a eucritic composition produced at differing fO2 conditions. This study will add to the experimental data on DCr and DV (i.e., olivine/melt, pyroxene/melt) at differing fO2, and in turn these D values will be used to assess the fO2 of eucrite basalts and perhaps other compositionally similar planetary basalts.
Wang, W.-X.; Fisher, N.S.; Luoma, S.N.
1995-01-01
Pulse-chase feeding and multi-labeled radiotracer techniques were employed to measure the assimilation of 6 trace elements (110mAg, 241Am, 109Cd, 57Co, 75Se and 65Zn) from ingested diatoms in the mussel Mytilus edulis feeding at different rates (0.1, 0.49 and 1.5 mg dry wt h-1). Uniformly radiolabeled diatoms Thalassiosira pseudonana were fed to mussels for 0.5 h, and the behavior of the radiotracers in individual mussels was followed for 96 h in a depuration seawater system. Assimilation efficiency (AE) of each element declined with increasing ingestion rate and increased with gut passage time. The importance of extracellular digestion relative to intracellular digestion increased with ingestion activity, which, when coupled with a decline in AE, suggested that extracellular digestion is less efficient in metal absorption. Zn assimilation was most affected by ingestion rate, suggesting that AE may play a role in the physiological regulation of this metal in M. edulis. In an experiment to simulate the effects of an acidic gut, lowered pH (5.5) enhanced the release of elements from intact diatom cells, especially at low particle concentration. These results indicate that both feeding components of the mussel (i.e. gut passage time, digestive partitioning) and metal chemistry (i.e. metal release at lowered pH within the bivalve gut) are responsible for the difference in the assimilation of trace metals at different food quantities observed in mussels.
An Element-Based Concurrent Partitioner for Unstructured Finite Element Meshes
NASA Technical Reports Server (NTRS)
Ding, Hong Q.; Ferraro, Robert D.
1996-01-01
A concurrent partitioner for partitioning unstructured finite element meshes on distributed memory architectures is developed. The partitioner uses an element-based partitioning strategy. Its main advantage over the more conventional node-based partitioning strategy is its modular programming approach to the development of parallel applications. The partitioner first partitions element centroids using a recursive inertial bisection algorithm. Elements and nodes then migrate according to the partitioned centroids, using a data request communication template for unpredictable incoming messages. Our scalable implementation is contrasted to a non-scalable implementation which is a straightforward parallelization of a sequential partitioner.
Reduced sediment melting at 7.5-12 GPa: phase relations, geochemical signals and diamond nucleation
NASA Astrophysics Data System (ADS)
Brey, G. P.; Girnis, A. V.; Bulatov, V. K.; Höfer, H. E.; Gerdes, A.; Woodland, A. B.
2015-08-01
Melting of carbonated sediment in the presence of graphite or diamond was experimentally investigated at 7.5-12 GPa and 800-1600 °C in a multianvil apparatus. Two starting materials similar to GLOSS of Plank and Langmuir (Chem Geol 145:325-394, 1998) were prepared from oxides, carbonates, hydroxides and graphite. One mixture (Na-gloss) was identical in major element composition to GLOSS, and the other was poorer in Na and richer in K (K-gloss). Both starting mixtures contained ~6 wt% CO2 and 7 wt% H2O and were doped at a ~100 ppm level with a number of trace elements, including REE, LILE and HFSE. The near-solidus mineral assemblage contained a silica polymorph (coesite or stishovite), garnet, kyanite, clinopyroxene, carbonates (aragonite and magnesite-siderite solid solution), zircon, rutile, bearthite and hydrous phases (phengite and lawsonite at <9 GPa and the hydrous aluminosilicates topaz-OH and phase egg at >10 GPa). Hydrous phases disappear at ~900 °C, and carbonates persist up to 1000-1100 °C. At temperatures >1200 °C, the mineral assemblage consists of coesite or stishovite, kyanite and garnet. Clinopyroxene stability depends strongly on the Na content in the starting mixture; it remains in the Na-gloss composition up to 1600 °C at 12 GPa, but was not observed in K-gloss experiments above 1200 °C. The composition of melt or fluid changes gradually with increasing temperature from hydrous carbonate-rich (<10 wt% SiO2) at 800-1000 °C to volatile-rich silicate liquids (up to 40 wt% SiO2) at high temperatures. Trace elements were analyzed in melts and crystalline phases by LA ICP MS. The garnet-melt and clinopyroxene-melt partition coefficients are in general consistent with results from the literature for volatile-free systems and silicocarbonate melts derived by melting carbonated peridotites. Most trace elements are strongly incompatible in kyanite and silica polymorphs ( D < 0.01), except for V, Cr and Ni, which are slightly compatible in kyanite ( D > 1). Aragonite and Fe-Mg carbonate have very different REE partition coefficients ( D Mst-Sd/L ~ 0.01 and D Arg/L ~ 1). Nb, Ta, Zr and Hf are strongly incompatible in both carbonates. The bearthite/melt partition coefficients are very high for LREE (>10) and decrease to ~1 for HREE. All HFSE are strongly incompatible in bearthite. In contrast, Ta, Nb, Zr and Hf are moderately to strongly compatible in ZrSiO4 and TiO2 phases. Based on the obtained partition coefficients, the composition of a mobile phase derived by sediment melting in deep subduction zones was calculated. This phase is strongly enriched in incompatible elements and displays a pronounced negative Ta-Nb anomaly but no Zr-Hf anomaly. Although all experiments were conducted in the diamond stability field, only graphite was observed in low-temperature experiments. Spontaneous diamond nucleation and the complete transformation of graphite to diamond were observed at temperatures above 1200-1300 °C. We speculate that the observed character of graphite-diamond transformation is controlled by relationships between the kinetics of metastable graphite dissolution and diamond nucleation in a hydrous silicocarbonate melt that is oversaturated in C.
Terrestrial magma ocean and core segregation in the earth
NASA Technical Reports Server (NTRS)
Ohtani, Eiji; Yurimoto, Naoyoshi
1992-01-01
According to the recent theories of formation of the earth, the outer layer of the proto-earth was molten and the terrestrial magma ocean was formed when its radius exceeded 3000 km. Core formation should have started in this magma ocean stage, since segregation of metallic iron occurs effectively by melting of the proto-earth. Therefore, interactions between magma, mantle minerals, and metallic iron in the magma ocean stage controlled the geochemistry of the mantle and core. We have studied the partitioning behaviors of elements into the silicate melt, high pressure minerals, and metallic iron under the deep upper mantle and lower mantle conditions. We employed the multi-anvil apparatus for preparing the equilibrating samples in the ranges from 16 to 27 GPa and 1700-2400 C. Both the electron probe microanalyzer (EPMA) and the Secondary Ion Mass spectrometer (SIMS) were used for analyzing the run products. We obtained the partition coefficients of various trace elements between majorite, Mg-perovskite, and liquid, and magnesiowustite, Mg-perovskite, and metallic iron. The examples of the partition coefficients of some key elements are summarized in figures, together with the previous data. We may be able to assess the origin of the mantle abundances of the elements such as transition metals by using the partitioning data obtained above. The mantle abundances of some transition metals expected by the core-mantle equilibrium under the lower mantle conditions cannot explain the observed abundance of some elements such as Mn and Ge in the mantle. Estimations of the densities of the ultrabasic magma Mg-perovskite at high pressure suggest existence of a density crossover in the deep lower mantle; flotation of Mg-perovskite occurs in the deep magma ocean under the lower mantle conditions. The observed depletion of some transition metals such as V, Cr, Mn, Fe, Co, and Ni in the mantle may be explained by the two stage process, the core-mantle equilibrium under the lower mantle conditions in the first stage, and subsequent downwards separation of the ultrabasic liquid (and magnesiowustite) and flotation of Mg-perovskite in the lower mantle.
Environmental characteristics and utilization potential of metallurgical slag: Chapter 19
Piatak, Nadine; De Vivo, Benedetto; Belkin, Harvey E.; Lima, Annamaria
2018-01-01
Slag, an abundant byproduct from the pyrometallurgical processing of ores, can be an environmental liability or a valuable resource. The most common environmental impact of slag is from the leaching of potentially toxic elements, acidity, or alkalinity that may impact nearby soils and surface water and groundwater. Factors that influence its environmental behavior include physical characteristics, such as grain size and porosity, chemical composition with some slag being enriched in certain elements, the mineralogy and partitioning of elements in more or less reactive phases, water-slag interactions, and site conditions. Many of these same factors also influence its resource potential. For example, crystalline ferrous slag is most commonly used as construction aggregate, whereas glassy (i.e., granulated) slag is used in cement. Also, the calcium minerals found in ferrous slag result in useful applications in water treatment. In contrast, the high trace-element content of some base-metal slags makes the slags economically attractive for extraction of residual elements. An evaluation tool is used to help categorize a particular slag as an environmental hazard or valuable byproduct. Results for one type of slag, legacy steelmaking slag from the Chicago area in the USA, suggest the material has potential to be used for treating phosphate-rich or acidic waters; however, the pH and trace-element content of resulting solutions may warrant further examination.
The influence of fluorine on phase relations and REE enrichment in alkaline magmas
NASA Astrophysics Data System (ADS)
Beard, C. D.; van Hinsberg, V.; Stix, J.; Wilke, M.
2017-12-01
Fluorine is a minor element in most magmas, but higher concentrations to wt% levels have been reported in alkaline systems, including those which host economic deposits of REE + HFSE1. Despite low abundance in most natural melts, fluorine has received great attention from the experimental community because it has a strong influence on melt structure, lowering melting points and drastically reducing viscosity. The effect of fluorine on element speciation has important implications for phase relations and the partitioning of trace elements between minerals and melts, thus metal enrichment processes in alkaline magmas. We have experimentally investigated the impact of fluorine on phase relations and partitioning of rare metals, the REE in particular, in evolved alkaline melts. Synthetic glasses of tephriphonolite to phonolite composition were doped with a wide range of elements at trace levels, and fluorine contents were varied from fluorine-free to 2.5 wt%. Experiments were performed water-saturated in an internally heated pressure vessel at 200 MPa with log fO2 at ca. QFM+1, which represents the intrinsic redox conditions of the setup. Charges were heated to super-liquidus conditions for 16 hours, cooled slowly (1˚C/min) to run temperature and subsequently equilibrated for at least 40 hours. Run products were analysed by EPMA and LA-ICP-MS. The experiments produce an equilibrium assemblage of sodic pyroxene, biotite, Fe-oxide, melt, fluid, ±K-feldspar, ±titanite, ±fluorite. Addition of fluorine markedly increases the mode of biotite, which initially buffers melt F content at low levels (< 0.2 wt%). Only in experiments with more than 0.6 wt% F do we observe a significant increase in the melt F-content. Here, fluorine decreases pyroxene/melt partitioning coefficients equally for all REE where pyroxene composition and P-T conditions are equivalent (ca. 1/2 with 0.6% F). We suggest that the formation of REE-F complexes in the melt2 lowers the availability of metals for incorporation into solid phases. An increasing fluorine content of the melt will thus make the REE progressively more incompatible and available for residual enrichment. 1. Vasyukova, O. & Williams-Jones, A. E. Geochim. Cosmochim. Acta 139, 110-130 (2014). 2. Ponader, C. W. & Brown Jr., G. E. Geochim. Cosmochim. Acta 53, 2905-2914 (1989).
Siderophile Volatile Element Partitioning during Core Formation.
NASA Astrophysics Data System (ADS)
Loroch, D. C.; Hackler, S.; Rohrbach, A.; Klemme, S.
2017-12-01
Since the nineteen sixties it is known, that the Earth's mantle is depleted relative to CI chondrite in numerous elements as a result of accretion and core-mantle differentiation. Additionally, if we take the chondritic composition as the initial solar nebular element abundances, the Earth lacks 85 % of K and up to 98 % of other volatiles. However one potentially very important group of elements has received considerably less attention in this context and these elements are the siderophile but volatile elements (SVEs). SVEs perhaps provide important information regarding the timing of volatile delivery to Earth. Especially for the SVEs the partitioning between metal melt and silicate melt (Dmetal/silicate) at core formation conditions is poorly constrained, never the less they are very important for most of the core formation models. This study is producing new metal-silicate partitioning data for a wide range of SVEs (S, Se, Te, Tl, Ag, As, Au, Cd, Bi, Pb, Sn, Cu, Ge, Zn, In and Ga) with a focus on the P, T and fO2dependencies. The initial hypothesis that we are aiming to test uses the accretion of major portions of volatile elements while the core formation was still active. The key points of this study are: - What are the effects of P, T and fO2 on SVE metal-silicate partioning? - What is the effect of compositional complexity on SVE metal-silicate partioning? - How can SVE's D-values fit into current models of core formation? The partitioning experiments will be performed using a Walker type multi anvil apparatus in a pressure range between 10 and 20 GPa and temperatures of 1700 up to 2100 °C. To determine the Dmetal/silicate values we are using a field emission high-resolution JEOL JXA-8530F EPMA for major elements and a Photon Machines Analyte G2 Excimer laser (193 nm) ablation system coupled to a Thermo Fisher Element 2 single-collector ICP-MS (LA-ICP-MS) for the trace elements. We recently finished the first sets of experiments and can provide the corresponding datasets. Based on the general understanding of Dmetal/silicate values we expect to depend on the composition, in this particular case this means a variation in sulfur and carbon content of the core composition, and also a change of the redox conditions. The major goal however is to derive a model of core formation on Earth that includes and also explains the SVEs.
Distribution and availability of trace elements in municipal solid waste composts.
Paradelo, Remigio; Villada, Antía; Devesa-Rey, Rosa; Moldes, Ana Belén; Domínguez, Marta; Patiño, Jacobo; Barral, María Teresa
2011-01-01
Trace element contamination is one of the main problems linked to the quality of compost, especially when it is produced from urban wastes, which can lead to high levels of some potentially toxic elements such as Cu, Pb or Zn. In this work, the distribution and bioavailability of five elements (Cu, Zn, Pb, Cr and Ni) were studied in five Spanish composts obtained from different feedstocks (municipal solid waste, garden trimmings, sewage sludge and mixed manure). The five composts showed high total concentrations of these elements, which in some cases limited their commercialization due to legal imperatives. First, a physical fractionation of the composts was performed, and the five elements were determined in each size fraction. Their availability was assessed by several methods of extraction (water, CaCl(2)-DTPA, the PBET extract, the TCLP extract, and sodium pyrophosphate), and their chemical distribution was assessed using the BCR sequential extraction procedure. The results showed that the finer fractions were enriched with the elements studied, and that Cu, Pb and Zn were the most potentially problematic ones, due to both their high total concentrations and availability. The partition into the BCR fractions was different for each element, but the differences between composts were scarce. Pb was evenly distributed among the four fractions defined in the BCR (soluble, oxidizable, reducible and residual); Cu was mainly found in the oxidizable fraction, linked to organic matter, and Zn was mainly associated to the reducible fraction (iron oxides), while Ni and Cr were mainly present almost exclusively in the residual fraction. It was not possible to establish a univocal relation between trace elements availability and their BCR fractionation. Given the differences existing for the availability and distribution of these elements, which not always were related to their total concentrations, we think that legal limits should consider availability, in order to achieve a more realistic assessment of the risks linked to compost use.
Trace-element evidence for the origin of desert varnish by direct aqueous atmospheric deposition
NASA Astrophysics Data System (ADS)
Thiagarajan, Nivedita; Aeolus Lee, Cin-Ty
2004-07-01
Smooth rock surfaces in arid environments are often covered with a thin coating of Fe-Mn oxyhydroxides known as desert varnish. It is debated whether such varnish is formed (a) by slow diagenesis of dust particles deposited on rock surfaces, (b) by leaching from the underlying rock substrate, or (c) by direct deposition of dissolved constituents in the atmosphere. Varnishes collected from smooth rock surfaces in the Mojave Desert and Death Valley, California are shown here to have highly enriched and fractionated trace-element abundances relative to upper continental crust (UCC). They are highly enriched in Co, Ni, Pb and the rare-earth elements (REEs). In particular, they have anomalously high Ce/La and low Y/Ho ratios. These features can only be explained by preferential scavenging of Co, Ni, Pb and the REEs by Fe-Mn oxyhydroxides in an aqueous environment. High field strength elements (HFSEs: Zr, Hf, Ta, Nb, Th), however, show only small enrichments despite the fact that these elements should also be strongly scavenged by Fe-Mn oxyhydroxides. This suggests that their lack of enrichment is a feature inherited from a solution initially poor in HFSEs. The first two scenarios for varnish formation can be ruled out as follows. The high enrichment factors of Fe, Mn and many trace elements cannot be generated by mass loss associated with post-depositional diagenesis of dust particles because such a process predicts only a small increase in concentration. In addition, the highly fractionated abundance patterns of particle reactive element pairs (e.g., Ce/La and Y/Ho) rules out leaching of the rock substrate. This is because if leaching were to occur, varnishes would grow from the inside to the outside, and thus any particle-reactive trace element leached from the substrate would be quantitatively sequestered in the Fe-Mn oxyhydroxide layers, prohibiting any significant elemental fractionations. One remaining possibility is that the Fe, Mn and trace metals in varnish are derived from leaching of dust particles entrained in rain or fog droplets either in the atmosphere or during wet atmospheric deposition. The high trace metal enrichment factors require that most of the dust was physically removed before or during varnish formation. The remaining aqueous counterpart would be depleted in HFSEs and Th relative to the REEs, Co, Ni and Pb because the former are more insoluble and hence largely retained in the removed dust fraction. The high Ce/La ratios suggest that precipitation of trace metals may have been governed by equilibrium partitioning in an excess of wet atmospheric deposition. If varnishes are indeed derived from wet atmospheric deposition, they may provide a record of the aqueous component of atmospheric dust inputs to various environments.
NASA Astrophysics Data System (ADS)
Milani, Lorenzo; Bolhar, Robert; Frei, Dirk; Harlov, Daniel E.; Samuel, Vinod O.
2017-12-01
In-situ trace element analyses of fluorapatite, calcite, dolomite, olivine, and phlogopite have been undertaken on representative phoscorite and carbonatite rocks of the Palaeoproterozoic Phalaborwa Complex. Textural and compositional characterization reveals uniformity of fluorapatite and calcite among most of the intrusions, and seems to favor a common genetic origin for the phoscorite-carbonatite association. Representing major repositories for rare earth elements (REE), fluorapatite and calcite exhibit tightly correlated light REE (LREE) abundances, suggesting that partitioning of LREE into these rock forming minerals was principally controlled by simple igneous differentiation. However, light rare earth element distribution in apatite and calcite cannot be adequately explained by equilibrium and fractional crystallization and instead favors a complex crystallization history involving mixing of compositionally distinct magma batches, in agreement with previously reported mineral isotope variability that requires open-system behaviour.
NASA Astrophysics Data System (ADS)
Turetta, C.; Planchon, F.; Gabrielli, P.; Cozzi, G.; Cairns, W.; Barbaro, E.; Petit, J. R.; Bulat, S.; Boutron, C.; Barbante, C.
2016-12-01
We present in this study comprehensive data on the occurrence of 25 trace and ultra-trace elements in the deepest part of the Vostok ice core. The determination of Li, Na, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Cu, Zn, As, Se, Rb, Sr, Mo, Ag, Cd, Sb, Ba, Pb, Bi and U has been performed in the different types of ice encountered from 3271 m to 3609 m of depth, corresponding to atmospheric ice, glacial flour and to accreted ice originating from the freezing of Lake Vostok waters. From atmospheric ice and glacial flour, the relative contributions of primary aerosols were evaluated for each element using a chemical mass balance approach in order to provide a first order evaluation of their partition between soluble (sea-salt) and insoluble (wind-blown dust) fractions in the ice. Sea-salt spray aerosols are the main source of impurities to the ice for certain elements (Na, Mg and K levels, and in a lesser extent to Ca, Sr, Rb, Li and U) while for other elements (Al, V, Cr, Mn, Fe, Co, Cu, Zn, Mo, Sb, Ba and Pb as well as the non sea salt fractions of Mg, K, Ca, Sr, Rb, Li and U) dust inputs appear to primarily control their depositional variability. For the glacial flour, the comparable levels of elements with the overlying atmospheric ice suggest that incorporation of abrasion debris at the glacier is quite limited in the sections considered. For the accreted ice originating from the subglacial waters of Lake Vostok, we observed a major chemical shift in the composition of the ice showing two distinct trends that we assumed to be derived from the chemical speciation of elements. The study of the glacier ice and the glacial flour has allowed us to perform a detailed characterisation of elemental abundances related to the aerosol sources variability and also to illustrate the interaction between the ice-sheet and the bedrock.
Javed, Muhammad Babar; Shotyk, William
2018-05-10
Employing protocols developed for polar snow and ice, water samples were collected upstream, midstream and downstream of open pit bitumen mines and upgraders along the Lower Athabasca River (AR). The purpose was to: i) estimate the bioaccessibility of trace elements associated with particulate matter in the AR using sequential extraction, and ii) determine whether their forms have been measurably impacted by industrial activities. Of the trace metals known to be enriched in bitumen (V, Ni, Mo and Re), a substantial proportion of V (78-93%) and Ni (35-81%) was found in the residual fraction representing stable minerals. In contrast, Mo and Re were partitioned mainly into more reactive forms (water soluble, acid extractable, reducible and oxidisable). Comparing the non-residual fractions in upstream versus downstream sites, only water soluble Re was significantly (P = 0.005) greater downstream of industry. In respect to the potentially toxic chalcophile elements (Cu, Pb and Tl), no measurable change was observed in Cu and Pb distribution in upstream versus downstream sites. Only residual Tl was found at upstream and midstream sites, whereas a significant proportion of Tl was also present in the reducible fraction in downstream sites. Overall, a greater proportion of trace metals in the residual fraction at midstream sites appears to be due to inputs of atmospheric dust, clearly evident in microscopic images: energy dispersive spectroscopy and x-ray diffraction analyses showed that these particles were predominantly silicates, which are assumed to have limited bioaccessibility. Copyright © 2018 Elsevier Ltd. All rights reserved.
Regimes of association of arsenic and selenium during pulverized coal combustion
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wayne S. Seames; Jost O.L. Wendt
2007-07-01
A suite of six coals, of widely differing As, Se, Ca, Fe, and sulfur contents, was burned under self-sustaining conditions in a 17 kW downflow laboratory combustor. Size segregated ash-laden aerosol samples were isokinetically withdrawn and collected on a Berner low pressure impactor. Correlations between trace element concentration (As or Se) and that of major elements (as functions of particle size) were then used to infer chemical associations between trace metals and Ca and/or Fe, and how these depended on sulfur. These baseline data led to formation of the following hypotheses, namely: (1) dominant As and Se partitioning mechanisms dependmore » on the availability of Ca and/or Fe active sites for surface reaction; (2) increasing combustion temperature increases the availability of active cation sites, and increases partitioning of As and Se to fly ash by surface reaction; (3) sulfur competes with these surface reactions, decreasing As and Se partitioning to fly ash surfaces. These hypotheses were tested by manipulating the As, Se, Ca, Fe, and S contents for various coals by doping. Temperature was adjusted in order to achieve comparisons of different coals and different coal constituents at similar thermal conditions, through O{sub 2} and CO{sub 2} addition, as required. These results confirmed the hypotheses above, and allowed an association regime map to be constructed. This map shows that both As and Se associate with Fe and Ca, provided active sites are available. Se reacts preferentially with Fe over Ca when both are available while As reactions with both Fe and Ca are comparable. Sulfur can prevent association of both As and Se, by preferentially reacting with active sites, especially those on Fe. When sufficient sites are not available, the release of vapor-phase As and Se species is promoted. 23 refs., 4 figs., 4 tabs.« less
NASA Astrophysics Data System (ADS)
González-Garcia, Diego; Petrelli, Maurizio; Behrens, Harald; Vetere, Francesco; Fischer, Lennart A.; Morgavi, Daniele; Perugini, Diego
2018-07-01
The diffusive exchange of 30 trace elements (Cs, Rb, Ba, Sr, Co, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ta, V, Cr, Pb, Th, U, Zr, Hf, Sn and Nb) during the interaction of natural mafic and silicic alkaline melts was experimentally studied at conditions relevant to shallow magmatic systems. In detail, a set of 12 diffusion couple experiments have been performed between natural shoshonitic and rhyolitic melts from the Vulcano Island (Aeolian archipelago, Italy) at a temperature of 1200 °C, pressures from 50 to 500 MPa, and water contents ranging from nominally dry to ca. 2 wt.%. Concentration-distance profiles, measured by Laser Ablation ICP-MS, highlight different behaviours, and trace elements were divided into two groups: (1) elements with normal diffusion profiles (13 elements, mainly low field strength and transition elements), and (2) elements showing uphill diffusion (17 elements including Y, Zr, Nb, Pb and rare earth elements, except Eu). For the elements showing normal diffusion profiles, chemical diffusion coefficients were estimated using a concentration-dependent evaluation method, and values are given at four intermediate compositions (SiO2 equal to 58, 62, 66 and 70 wt.%, respectively). A general coupling of diffusion coefficients to silica diffusivity is observed, and variations in systematics are observed between mafic and silicic compositions. Results show that water plays a decisive role on diffusive rates in the studied conditions, producing an enhancement between 0.4 and 0.7 log units per 1 wt.% of added H2O. Particularly notable is the behaviour of the trivalent-only REEs (La to Nd and Gd to Lu), with strong uphill diffusion minima, diminishing from light to heavy REEs. Modelling of REE profiles by a modified effective binary diffusion model indicates that activity gradients induced by the SiO2 concentration contrast are responsible for their development, inducing a transient partitioning of REEs towards the shoshonitic melt. These results indicate that diffusive fractionation of trace elements is possible during magma mixing events, especially in the more silicic melts, and that the presence of water in such events can lead to enhanced chemical diffusive mixing efficiency, affecting also the estimation of mixing to eruption timescales.
Mechanisms for trace metal enrichment at the surface microlayer in an estuarine salt marsh
Lion, Leonard W.
1982-01-01
The relative contributions of adsorption to particulate surfaces, complexation with surface-active organic ligands and uptake by micro-organisms were evaluated with respect to their importance in the surface microlayer enrichment (‘partitioning’) of Cd, Pb and Cu. The contributions of each process were inferred from field data in which partitioning of the dissolved and particulate forms of Cd, Pb and Cu, total and dissolved organic carbon, particles and total bacteria were observed. In the South San Francisco Bay estuary, particle enrichment appears to control trace metal partitioning. Trace metal association with the particulate phase and the levels of partitioning observed were in the order Pb > Cu > Cd and reflect the calculated equilibrium chemical speciation of these metals in computer-simulated seawater matrices.
Piper, David Z.; Dean, Walter E.
2002-01-01
A sediment core from the Cariaco Basin on the Venezuelan continental shelf, which recovered sediment that has been dated back to 20 ka (thousand years ago), was examined for its major-element-oxide and trace-element composition. Cadmium (Cd), chromium (Cr), copper (Cu), molybdenum (Mo), nickel (Ni), vanadium (V), and zinc (Zn) can be partitioned between a siliciclastic, terrigenous-derived fraction and two seawater-derived fractions. The two marine fractions are (1) a biogenic fraction represented by nutrient trace elements taken up mostly in the photic zone by phytoplankton, and (2) a hydrogenous fraction that has been derived from bottom water via adsorption and precipitation reactions. This suite of trace elements contrasts with a second suite of trace elements—barium (Ba), cobalt (Co), gallium (Ga), lithium (Li), the rare-earth elements, thorium (Th), yttrium (Y), and several of the major-element oxides—that has had solely a terrigenous source. The partitioning scheme, coupled with bulk sediment accumulation rates measured by others, allows us to determine the accumulation rate of trace elements in each of the three sediment fractions and of the fractions themselves. The current export of organic matter from the photic zone, redox conditions and advection of bottom water, and flux of terrigenous debris into the basin can be used to calculate independently trace-element depositional rates. The calculated rates show excellent agreement with the measured rates of the surface sediment. This agreement supports a model of trace-element accumulation rates in the subsurface sediment that gives a 20-kyr history of upwelling into the photic zone (that is, primary productivity), bottom-water advection and redox, and provenance. Correspondence of extrema in the geochemical signals with global changes in sea level and climate demonstrates the high degree to which the basin hydrography and provenance have responded to the paleoceanographic and paleoclimatic regimes of the last 20 kyr. The accumulation rate of the marine fraction of Mo increased abruptly at about 14.8 ka (calendar years), from less than 0.5 µg cm-2 yr-1 to greater than 4 µg cm-2 yr-1. Its accumulation rate remained high but variable until 8.6 ka, when it decreased sharply to 1 µg cm-2 yr-1. It continued to decrease to 4.0 ka, to its lowest value for the past 15 kyr, before gradually increasing to the present. Between 14.8 ka and 8.6 ka, its accumulation rate exhibited strong maxima at 14.4, 13.0, and 9.9 ka. The oldest maximum corresponds to melt-water pulse IA into the Gulf of Mexico. A relative minimum, centered at about 11.1 ka, corresponds to melt-water pulse IB; a strong maximum occurs in the immediately overlying sediment. The maximum at 13.0 ka corresponds to onset of the Younger Dryas cold event. This pattern to the accumulation rate of Mo (and V) can be interpreted in terms of its deposition from bottom water of the basin, the hydrogenous fraction, under SO42- -reducing conditions, during times of intense bottom-water advection 14.8 ka to 11.1 ka and significantly less intense bottom-water advection 11 ka to the present. The accumulation rate of Cd shows a pattern that is only slightly different from that of Mo, although its deposition was determined largely by the rain rate of organic matter into the bottom water, a biogenic fraction whose deposition was driven by upwelling of nutrient-enriched water into the photic zone. Its accumulation exhibits only moderately high rates, on average, during both melt-water pulses. Its highest rate, and that of upwelling, occurred during the Younger Dryas, and again following melt-water pulse IB. The marine fractions of Cu, Ni, and Zn also have a strong biogenic signal. The siliciclastic terrigenous debris, however, represents the dominant source, and host, of Cu, Ni, and Zn. All four trace elements have a consid-erably weaker hydrogenous signal than biogenic signal. Accumulation rates of the terrigenous fraction, as reflected by accumulation rates of Th and Ga, show strong maxima at 16.2 and 12.7 ka and minima at 14.1 and 11.1 ka. Co, Li, REE, and Y have a similar distribution. The minima occurred during melt-water pulses IA and IB, the maxima during the Younger Dryas and the rise in sea level following the last glacial maximum.
Tabelin, Carlito Baltazar; Hashimoto, Ayaka; Igarashi, Toshifumi; Yoneda, Tetsuro
2014-03-01
Sedimentary rocks excavated in Japan from road- and railway-tunnel projects contain relatively low concentrations of hazardous trace elements like boron (B), arsenic (As) and selenium (Se). However, these seemingly harmless waste rocks often produced leachates with concentrations of hazardous trace elements that exceeded the environmental standards. In this study, the leaching behaviors and release mechanisms of B, As and Se were evaluated using batch leaching experiments, sequential extraction and geochemical modeling calculations. The results showed that B was mostly partitioned with the residual/crystalline phase that is relatively stable under normal environmental conditions. In contrast, the majority of As and Se were associated with the exchangeable and organics/sulfides phases that are unstable under oxidizing conditions. Dissolution of water-soluble phases controlled the leaching of B, As and Se from these rocks in the short term, but pyrite oxidation, calcite dissolution and adsorption/desorption reactions became more important in the long term. The mobilities of these trace elements were also strongly influenced by the pH of the rock-water system. Although the leaching of Se only increased in the acidic region, those of B and As were enhanced under both acidic and alkaline conditions. Under strongly acidic conditions, the primarily release mechanism of B, As and Se was the dissolution of mineral phases that incorporated and/or adsorbed these elements. Lower concentrations of these trace elements in the circumneutral pH range could be attributed to their strong adsorption onto minerals like Al-/Fe-oxyhydroxides and clays, which are inherently present and/or precipitated in the rock-water system. The leaching of As and B increased under strongly alkaline conditions because of enhanced desorption and pyrite oxidation while that of Se remained minimal due to its adsorption onto Fe-oxyhydroxides and co-precipitation with calcite. Copyright © 2013 Elsevier B.V. All rights reserved.
An examination of the role of particles in oceanic mercury cycling
NASA Astrophysics Data System (ADS)
Lamborg, Carl H.; Hammerschmidt, Chad R.; Bowman, Katlin L.
2016-11-01
Recent models of global mercury (Hg) cycling have identified the downward flux of sinking particles in the ocean as a prominent Hg removal process from the ocean. At least one of these models estimates the amount of anthropogenic Hg in the ocean to be about 400 Mmol, with deep water formation and sinking fluxes representing the largest vectors by which pollutant Hg is able to penetrate the ocean interior. Using data from recent cruises to the Atlantic, we examined the dissolved and particulate partitioning of Hg in the oceanic water column as a cross-check on the hypothesis that sinking particle fluxes are important. Interestingly, these new data suggest particle-dissolved partitioning (Kd) that is approximately 20× greater than previous estimates, which thereby challenges certain assumptions about the scavenging and active partitioning of Hg in the ocean used in earlier models. For example, the new particle data suggest that regenerative scavenging is the most likely mechanism by which the association of Hg and particles occurs. This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.
Horowitz, A.J.; Elrick, K.A.; Smith, J.J.
2001-01-01
Suspended sediment, sediment-associated, total trace element, phosphorus (P), and total organic carbon (TOC) fluxes were determined for the Mississippi, Columbia, Rio Grande, and Colorado Basins for the study period (the 1996, 1997, and 1998 water years) as part of the US Geological Survey's redesigned National Stream Quality Accounting Network (NASQAN) programme. The majority (??? 70%) of Cu, Zn, Cr, Ni, Ba, P, As, Fe, Mn, and Al are transported in association with suspended sediment; Sr transport seems dominated by the dissolved phase, whereas the transport of Li and TOC seems to be divided equally between both phases. Average dissolved trace element levels are markedly lower than reported during the original NASQAN programme; this seems due to the use of 'clean' sampling, processing, and analytical techniques rather than to improvements in water quality. Partitioning between sediment and water for Ag, Pb, Cd, Cr, Co, V, Be, As, Sb, Hg, and Ti could not be estimated due to a lack of detectable dissolved concentrations in most samples. Elevated suspended sediment-associated Zn levels were detected in the Ohio River Basin and elevated Hg levels were detected in the Tennessee River, the former may affect the mainstem Mississippi River, whereas the latter probably do not. Sediment-associated concentrations of Ag, Cu, Pb, Zn, Cd, Cr, Co, Ba, Mo, Sb, Hg, and Fe are markedly elevated in the upper Columbia Basin, and appear to be detectable (Zn, Cd) as far downstream as the middle of the basin. These elevated concentrations seem to result from mining and/or mining-related activities. Consistently detectable concentrations of dissolved Se were found only in the Colorado River Basin. Calculated average annual suspended sediment fluxes at the mouths of the Mississippi and Rio Grande Basins were below, whereas those for the Columbia and Colorado Basins were above previously published annual values. Downstream suspended sediment-associated and total trace element fluxes increase in the Mississippi and Columbia Basins, whereas fluxes markedly decrease in the Colorado Basin. No consistent pattern in trace element fluxes was detected in the Rio Grande Basin.
Davide, Vignati; Pardos, Michel; Diserens, Jérôme; Ugazio, Giancarlo; Thomas, Richard; Dominik, Janusz
2003-07-01
Grain-size distribution, major elements, nutrients and trace metals were determined in bed sediments and suspension collected at 10 representative sites along the river Po under normal and high flow conditions. Grain-size distribution and major element composition of suspension highlighted the presence of two distinct particle populations in the upper-middle Po (coarser particles, lower carbonate content) and in the lower Po (finer particles, higher carbonate content). This change partly reflects the geological differences between the two parts of the basin, and also the presence of a hydroelectric power plant at Isola Serafini (Piacenza). With respect to environmental quality issues, bed sediments and suspension provide similar results. A moderate nutrient pollution is found in all but the uppermost parts of the river basin, while the most significant inputs of trace metals appear to originate from the urban areas of Turin and Milan. Calculation of sediment enrichment factors identifies Cd, Cu, Hg and Zn as the most impacted elements by human activities. On the other hand, the high levels of Ni and Cr throughout the river seem to derive mainly from the presence of basic rocks in the upper and middle parts of the basin. Both nutrient and trace metal particulate concentrations substantially decrease under high flow conditions possibly due to "flushing" of contaminated bed sediments and resuspension of coarser material. Under normal flow conditions, water hydrochemistry and concentrations of some elements (As, Ca, Cr, Cu, K, Mg, Mn, Na, Ni, and Pb) in the dissolved phase (<0.45 microm) were also determined. Calculation of trace metals partition coefficients shows that the relative importance of the particulate and water phases varies in response to water hydrochemistry and suspended solid content, but that most elements achieve a conditional equilibrium in the lower stretches of the river Po. These results are the first of this kind reported for the whole river course and highlight the factors and mechanisms controlling the origin, mobility and fate of nutrients and trace metals in the river Po.
Partition Coefficients at High Pressure and Temperature
NASA Astrophysics Data System (ADS)
Righter, K.; Drake, M. J.
2003-12-01
Differentiation of terrestrial planets includes separation of a metallic core and possible later fractionation of mineral phases within either a solid or molten mantle (Figure 1). Lithophile and siderophile elements can be used to understand these two different physical processes, and ascertain whether they operated in the early Earth. The distribution of elements in planets can be understood by measuring the partition coefficient, D (ratio of concentrations of an element in different phases (minerals, metals, or melts)). (14K)Figure 1. Schematic cross-section through the Earth, showing: (a) an early magma ocean stage and (b) a later cool and differentiated stage. The siderophile elements (iron-loving) encompass over 30 elements and are defined as those elements for which D(metal/silicate)>1, and are useful for deciphering the details of core formation. This group of elements is commonly broken up into several subclasses, including the slightly siderophile elements (1
Wang, W.-X.; Fisher, N.S.; Luoma, S. N.
1995-01-01
Pulse-chase feeding and multi-labeled radiotracer techniques were employed to measure the assimilation of 6 trace elements (110mAg, 241Am, 109Cd, 57Co, 75Se and 65Zn) from ingested diatoms in the mussel Mytilus edulis feeding at different rates (0.1, 0.49 and 1.5 mg dry wt h-1). Uniformly radiolabeled diatoms Thalassiosira pseudonana were fed to mussels for 0.5 h, and the behavior of the radiotracers in individual mussels was followed for 96 h in a depuration seawater system. Assimilation efficiency (AE) of each element declined with increasing ingestion rate and increased with gut passage time. The importance of extracellular digestion relative to intracellular digestion increased with ingestion activity, which, when coupled with a decline in AE, suggested that extracellular digestion is less efficient in metal absorption. Zn assimilation was most affected by ingestion rate, suggesting that AE may play a role in the physiological regulation of this metal in M. edulis. In an experiment to simulate the effects of an acidic gut, lowered pH (5.5) enhanced the release of elements from intact diatom cells, especially at low particle concentration. These results indicate that both feeding components of the mussel (i.e. gut passage time, digestive partitioning) and metal chemistry (i.e. metal release at lowered pH within the bivalve gut) are responsible for the difference in the assimilation of trace metals at different food quantities observed in mussels.
Elder, John F.
2007-01-01
A study of concentrations and distribution of major and trace elements in surficial bottom sediments of Little Rock Lake in northern Wisconsin included examination of spatial variation and grain-size effects. No significant differences with respect to metal distribution in sediments were observed between the two basins of the lake, despite the experimental acidification of one of the basins from pH 6.1 to 4.6. The concentrations of most elements in the lake sediments were generally similar to soil concentrations in the area and were well below sediment quality criteria. Two exceptions were lead and zinc, whose concentrations in July 1990 exceeded the criteria of 50 μg/g and 100 μg/g, respectively, in both littoral and pelagic sediments. Concentrations of some elements, particularly Cu, Pb, and Zn, increased along transects from nearshore to midlake, following a similar gradient of sedimentary organic carbon. In contrast, Mn, Fe, and alkali/alkaline-earth elements were at maximum concentrations in nearshore sediments. These elements are less likely to partition to organic particles, and their distribution is more dependent on mineralogical composition, grain size, and other factors. Element concentrations varied among different sediment grain-size fractions, although a simple inverse relation to grain size was not observed. Fe, Mn, Pb, and Zn were more concentrated in a grain-size range 20–60 tm than in either the very fine or the coarse fractions, possibly because of the aggregation of smaller particles cemented together by organic and Fe/Mn hydrous-oxide coatings.
NASA Astrophysics Data System (ADS)
Fischer, R. A.; Campbell, A. J.; Frost, D. J.; Harries, D.; Langenhorst, F.; Miyajima, N.; Pollok, K.; Rubie, D. C.
2013-12-01
During core formation, metal and silicate of accreted bodies equilibrated with the proto-Earth in a series of partitioning reactions, characterized by average (or time-intregrated) partition coefficients that can be calculated assuming a bulk Earth that is chondritic in nonvolatile elements [e.g. 1]. Comparisons to experimentally-measured partition coefficients allow constraints on the time-integrated conditions of core-mantle equilibration [e.g. 2-7], providing valuable input into more complex chemical models of Earth's evolution [8]. Partitioning has been studied extensively in the multi-anvil press [e.g. 3, 7], but very few studies extend to pressures above ~25 GPa [e.g. 2, 5-6]. In this study, we measure the metal-silicate partitioning of Co, Ni, V, Cr, Si, and O at higher pressures and temperatures. Thin foils of Fe-rich alloy doped with trace elements were loaded in a diamond anvil cell between layers of (Mg,Fe)2SiO4. Samples were laser-heated to melt the metal and silicate. After decompression, samples were cut parallel to the compression axis into sections ~100 nm thick with a focused ion beam (FIB). Chemical analyses of all elements except oxygen in the coexisting metal, silicate, and oxide were performed using energy dispersive X-ray spectroscopy (EDXS) in a transmission electron microscope (TEM). Later, samples were further thinned by FIB to ~60 nm and analyzed by electron energy loss spectroscopy (EELS) in a TEM to determine the Fe/O ratio of the metal. Analysis was performed on a suite of six experiments from pressures of 25, 31, 43, 57, 58, and 100 GPa and temperatures above the silicate liquidus, up to 5500 K. Our results are generally consistent with the recent findings of [5-6], although our log(KD) values for cobalt are ~0.1-0.2 log units lower. Some of our experiments contain carbon in the metal which may affect the partitioning of some elements. The metal in the experiment from 100 GPa and 5500 K contains 9 wt% silicon and an estimated 11 wt% oxygen, which is a significantly higher percentage of light elements than the Earth's outer core is thought to contain [e.g. 1]. Using our results, we develop a model for metal/silicate exchange during core formation, the light element composition of the core, and possible chemical reactions at the core-mantle boundary. [1] McDonough, W.F. (2003) Treatise on Geochemistry, Vol. 2, pp 547-568. [2] Bouhifd, M.A. and A.P. Jephcoat (2011) Earth Planet. Sci. Lett. 307, 341-348. [3] Mann, U., D.J. Frost, and D.C. Rubie (2009) Geochim. Cosmochim. Acta 73, 7360-7386. [4] Righter, K. et al. (2010) Earth Planet. Sci. Lett. 291, 1-9. [5] Siebert, J. et al. (2012) Earth Planet. Sci. Lett. 321-322, 189-197. [6] Siebert, J. et al. (2013) Science 339, 1194-1197. [7] Wade, J., and B.J. Wood (2005) Earth Planet. Sci. Lett. 236, 78-95. [8] Rubie, D.C. et al. (2011) Earth Planet. Sci. Lett. 301, 31-42.
NASA Astrophysics Data System (ADS)
Rosenthal, A.; Hauri, E. H.; Hirschmann, M. M.; Davis, F. A.; Withers, A. C.; Fogel, M. L.
2012-12-01
Inventories of C in the mantle and magmatic fluxes of C between the mantle and the Earth's outer envelopes are poorly constrained in part owing to challenges in determining undegassed C concentrations of pristine basalts. Saal et al. [1] proposed that the behavior of Nb could be used as a proxy for C, owing to apparently similar behavior of the two elements in Siqueiros Transform MORB, but higher C/Nb ratios in popping rocks [2] call into question the applicability of the C/Nb proxy. Here, we present experimentally determined carbon partition coefficients (D's) between nominally volatile-free mantle minerals (olivine, OL; orthopyroxene, OPX; clinopyroxene, CPX; garnet, GA) and melts at 0.8-3 GPa, and 1250-1500°C. We conducted piston-cylinder experiments using an olivine-tholeiite + 4 wt% CO2, doped with Nb, Rb, U, Th, and 13C to enhance detection limits. To promote growth of crystals big enough for SIMS analyses, experiments were either long (<6 days), or at an initial higher temperature (T) before cooling slowly to a target T. We also produced SIMS calibration glass standards with varying amounts of C, and subject to ongoing analyses. We analyzed carbon (12C, 13C), H, F, and trace elements (Nb, Rb, Ba, U, Th, K) of both mineral phases and quenched liquids in subsets of experimental runs (21 in graphite-lined Pt-capsules, 6 in Fe-doped Pt-lined capsules) using both Cameca IMS 6F and NanoSIMS instruments. D's measured for 12C and 13C are close to 5x10-4, in most cases D13C>D12C, but a few have the opposite. Continuous exchange of the liquid (initially rich in 13C) with the graphite capsules (rich in 12C) may yield D's with 13C>12C. D's with 12C>13C are likely owing to either low count rates or comparatively high analytical contamination. Concentrations in minerals vary from 0.20-3.46 ppm for C, 25-176 ppm for H2O, and 0.05-1.21 ppm for F, whereas liquids tend to much higher values (C≤0.9 wt%; H2O≤1.5 wt%; F≤34 ppm; P≤0.25 wt%; S≤43 ppm; Cl≤77 ppm). Resulting D's indicate that C is highly incompatible in all major mantle mineral phases, with D's for OL, OPX and CPX of close to 5x10-4, and for GA ~2.2x10-4. D's for H2O (2x10-4 to ~3x10-2) and F (~2.3x10-3 to ~5.8x10-2) are comparable to those found in previous studies. Trace element partition determinations are in progress, but comparison to previous studies indicates that carbon is significantly more incompatible during mantle melting than Nb, U, or Th, and has behavior approximately similar to Ba. We therefore suggest that undegassed C/Ba ratios may be useful indicators of C fluxes and concentrations in basalt source regions where very low degrees of melting might fractionate C/Nb ratios. [1] Saal, A, Hauri, EH, Langmuir, CH, Perfit, M (2002) Nature 419, 451-455. [2] Cartigny, P, Pineau, F, Aubaud, C, Javoy, M (2008) Earth Planet Sci Lett 265, 672-685.
NASA Technical Reports Server (NTRS)
Mckay, G. A.; Weill, D. F.
1975-01-01
Solid/liquid distribution coefficients (weight basis) were experimentally determined for a number of trace elements for olivine, orthopyroxene, plagioclase and ilmenite. Values of distribution coefficients were measured at 1200 C and a f sub O2 of 10 to the -13.0 power for liquids similar in composition to the olivine-opx-plagioclase peritectic in the pseudoternary system (Fe,Mg)2SiO4-CaAl2Si2O8-SiO2. Values were also measured at 1140 C and a f sub O2 of 10 to the -12.8 power for liquids similar in composition to high-Ti mare basalts. Major and trace element partitioning and relevant phase equilibria were used to investigate possible parent-daughter relationships between a number of highland samples and highly evolved KREEP-rich materials. Out of about 80 highlands samples tested, 33 were found to be possible parents to the KREEP-rich materials. The average composition of these samples is very similar to that of the Low-K Fra Mauro basalt (LKFM). A model is proposed to explain the production of LKFM-type material and more evolved members of the KREEP suite.
NASA Astrophysics Data System (ADS)
Li, Yuan; Audétat, Andreas
2012-11-01
The partitioning of 15 major to trace metals between monosulfide solid solution (MSS), sulfide liquid (SL) and mafic silicate melt (SM) was determined in piston-cylinder experiments performed at 1175-1300 °C, 1.5-3.0 GPa and oxygen fugacities ranging from 3.1 log units below to 1.0 log units above the quartz-fayalite-magnetite fO2 buffer, which conditions are representative of partial melting in the upper mantle in different tectonic settings. The silicate melt was produced by partial melting of a natural, amphibole-rich mantle source rock, resulting in hydrous (˜5 wt% H2O) basanitic melts similar to low-degree partial melts of metasomatized mantle, whereas the major element composition of the starting sulfide (˜52 wt% Fe; 39 wt% S; 7 wt% Ni; 2 wt% Cu) was similar to the average composition of sulfides in this environment. SL/SM partition coefficients are high (≥100) for Au, Ni, Cu, Ag, Bi, intermediate (1-100) for Co, Pb, Sn, Sb (±As, Mo), and low (≤1) for the remaining elements. MSS/SM partition coefficients are generally lower than SL/SM partition coefficients and are high (≥100) for Ni, Cu, Au, intermediate (1-100) for Co, Ag (±Bi, Mo), and low (≤1) for the remaining elements. Most sulfide-silicate melt partition coefficients vary as a function of fO2, with Mo, Bi, As (±W) varying by a factor >10 over the investigated fO2 range, Sb, Ag, Sn (±V) varying by a factor of 3-10, and Pb, Cu, Ni, Co, Au, Zn, Mn varying by a factor of 3-10. The partitioning data were used to model the behavior of Cu, Au, Ag, and Bi during partial melting of upper mantle and during fractional crystallization of primitive MORB and arc magmas. Sulfide phase relationships and comparison of the modeling results with reported Cu, Au, Ag, and Bi concentrations from MORB and arc magmas suggest that: (i) MSS is the dominant sulfide in the source region of arc magmas, and thus that Au/Cu ratios in the silicate melt and residual sulfides may decrease with increasing degree of partial melting, (ii) both MSS and sulfide liquid are precipitated during fractional crystallization of MORB, and (iii) fractional crystallization of arc magmas is strongly dominated by MSS.
Size distribution of rare earth elements in coal ash
Scott, Clinton T.; Deonarine, Amrika; Kolker, Allan; Adams, Monique; Holland, James F.
2015-01-01
Rare earth elements (REEs) are utilized in various applications that are vital to the automotive, petrochemical, medical, and information technology industries. As world demand for REEs increases, critical shortages are expected. Due to the retention of REEs during coal combustion, coal fly ash is increasingly considered a potential resource. Previous studies have demonstrated that coal fly ash is variably enriched in REEs relative to feed coal (e.g, Seredin and Dai, 2012) and that enrichment increases with decreasing size fractions (Blissett et al., 2014). In order to further explore the REE resource potential of coal ash, and determine the partitioning behavior of REE as a function of grain size, we studied whole coal and fly ash size-fractions collected from three U.S commercial-scale coal-fired generating stations burning Appalachian or Powder River Basin coal. Whole fly ash was separated into , 5 um, to 5 to 10 um and 10 to 100 um particle size fractions by mechanical shaking using trace-metal clean procedures. In these samples REE enrichments in whole fly ash ranges 5.6 to 18.5 times that of feedcoals. Partitioning results for size separates relative to whole coal and whole fly ash will also be reported.
Volatility in the lunar crust: Trace element analyses of lunar minerals by PIXE proton microprobe
NASA Technical Reports Server (NTRS)
Norman, M. D.; Griffin, W. L.; Ryan, C. G.
1993-01-01
In situ determination of mineral compositions using microbeam techniques can characterize magma compositions through mineral-melt partitioning, and be used to investigate fine-grained or rare phases which cannot be extracted for analysis. Abundances of Fe, Mn, Sr, Ga, Zr, Y, Nb, Zn, Cu, Ni, Se, and Sb were determined for various mineral phases in a small number of lunar highlands rocks using the PIXE proton microprobe. Sr/Ga ratios of plagioclase and Mn/Zn ratios of mafic silicates show that the ferroan anorthosites and Mg-suite cumulates are depleted in volatile lithophile elements to about the same degree compared with chondrites and the Earth. This links the entire lunar crust to common processes or source compositions. In contrast, secondary sulfides in Descartes breccia clasts are enriched in chalcophile elements such as Cu, Zn, Ni, Se, and Sb, and represent a potential resource in the lunar highlands.
Chemical evolution of a pleistocene rhyolitic center: Sierra La Primavera, Jalisco, México
NASA Astrophysics Data System (ADS)
Mahood, Gail A.
1981-06-01
The late Pleistocene caldera complex of the Sierra La Primavera, Jalisco, México, contains well-exposed lava flows and domes, ash-flow tuff, air-fall pumice, and caldera-lake sediments. All eruptive units are high-silica rhyolites, but systematic chemical differences correlate with age and eruptive mode. The caldera-producing unit, the 45-km3 Tala Tuff, is zoned from a mildly peralkaline first-erupted portion enriched in Na, Rb, Cs, Cl, F, Zn, Y, Zr, Hf, Ta, Nb, Sb, HREE, Pb, Th, and U to a metaluminous last-erupted part enriched in K, LREE, Sc, and Ti; Al, Ca, Mg, Mn, Fe, and Eu are constant within analytical errors. The earliest post-caldera lava, the south-central dome, is nearly identical to the last-erupted portion of the Tala Tuff, whereas the slightly younger north-central dome is chemically transitional from the south-central dome to later, moremafic, ring domes. This sequence of ash-flow tuff and domes represents the tapping of progressively deeper levels of a zoned magma chamber 95,000 ± 5,000 years ago. Since that time, the lavas that erupted 75,000, 60,000, and 30,000 years ago have become decreasingly peralkaline and progressively enriched only in Si, Rb, Cs, and possibly U. They represent successive eruption of the uppermost magma in the post-95,000-year magma chamber. Eruptive units of La Primavera are either aphyric or contain up to 15% phenocrysts of sodic sanidine ≧quartz >ferrohedenbergite >fayalite>ilmenite±titanomagnetite. Whereas major-element compositions of sanidine, clinopyroxene, and fayalite phenocrysts changed only slightly between eruptive groups, concentrations of many trace elements changed by factors of 5 to 10, resulting in crystal/glass partition coefficients that differ by factors of up to 20 between successively erupted units. The extreme variations in partitioning behavior are attributed to small changes in bulk composition of the melt because major-element compositions of the phenocrysts and temperature, pressure, and oxygen fugacity of the magma all remained essentially constant. Crystal settling and incremental partial melting by themselves appear incapable of producing either the chemical gradients within the Tala Tuff magma chamber or the trends with time in the post-caldera lavas. Transport of trace metals as volatile complexes within the thermal and gravitational gradient in volatilerich but water-undersaturated magma is considered the dominant process responsible for compositional zonation in the Tala Tuff. The evolution of the post-caldera lavas with time is thought to involve the diffusive emigration of trace elements from a relatively dry magma as a decreasing proportion of network modifiers and/or a decreasing concentration of complexing ligands progressively reduced trace-metal-site availability in the silicate melt.
NASA Astrophysics Data System (ADS)
Mason, P. R.
2004-05-01
Our knowledge of how chalcophile and siderophile elements partition in minerals is limited, mainly due to the lack of suitable techniques for their accurate in situ determination. Host minerals (e.g. sulphides) are typically of small size (<30 μ m) and highly heterogeneous in composition, requiring analysis of high spatial resolution. Concentrations of chalcophile elements in silicates and oxides are low (sub μ gg-1) and thus challenging to measure. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), offering high sensitivity and good spatial resolution (10-100 μ m) is thus highly suited for this purpose. Unfortunately, the widespread use of this technique has been limited by enhanced problems specific to chalcophile and siderophile elements. These include inaccuracy due to the presence of spectral interferences, elemental fractionation during ablation/ionization and the lack of suitable calibration standards. Polyatomic spectral interferences, present either as a background component (e.g. O2+, ArAr+) or based around the recombination of matrix elements with argon (e.g. ArS+, ArNi+) hinder accurate analysis. These depend upon the relative concentrations of major matrix components and trace elements to be measured and are significant in many relevant minerals (e.g. sulphides). The use of a collision and reaction cells in ICP-MS is a new method for selective interference attenuation, significantly improving detection limits for elements such as Fe, S and Se by between 1 and 4 orders of magnitude. ArNi+ and ArCu+ interferences in sulphides can be attenuated by at least an order of magnitude leading to improved accuracy for the measurement of the Platinum Group elements Rh and Ru. Sulphur isotopes can be measured interference-free at m/z=32 and 34 by eliminating background O2+. These improvements open up new possibilities for the use of LA-ICP-MS in trace element and isotopic studies at the lowest concentration levels or where sample preparation creates additional problems (e.g. NiS fire assay beads). I will give examples of applications for this technique in the study of ore minerals, meteorites and precipitates from hydrothermal vents.
NASA Astrophysics Data System (ADS)
McKnight, D. M.; Rue, G.
2017-12-01
Recent research in Snake River Watershed, located near the historic boomtown of Montezuma and adjacent the Continental Divide in the Colorado Rocky Mountains, has revealed the distinctive occurrence of rare earth elements (REE) at high concentrations. Here the weathering of the mineralized lithology naturally generates acid rock drainage (ARD) in addition to drainage recieved from abandoned mine adits throughout the area, results in aqueous REE concentrations three orders of magnitude higher than in most major rivers. The dominant mechanism responsible for this enrichment; their dissolution from secondary and accessory mineral stocks, abundant in REEs, promoted by the low pH waters generated from geochemical weathering of disseminated sulfide minerals. While REEs behave conservatively in acidic conditions, as well as in the presence of stabilizing ligands such as sulfate, downstream circumneutral inputs from pristine streams and a rising pH are resulting in observed fractional losses of heavy rare earth elements as well as partitioning towards colloidal and solid phases. These finding in combination with the established role of dissolved organic matter (DOM) in binding with both trace metals and REEs, suggest that competitive interactions, complexation, and scavenging are likely contributing to these proportional losses. However, outstanding questions yet remain regarding the effects of an increasing flux of trace metals as well as REEs from the Snake River Watershed into Dillon Reservoir, a major drinking water supply for the City of Denver, in part due to hydroclimatological drivers that are enhancing geochemical weathering and reducing groundwater recharge in alpine areas across the Colorado Rockies. Based on these findings also we seek to broaden this body of work to further investigate the behavior of rare earth elements (REE) in other aquatic environment as well the influence of trace metals, DOM, and pH in altering their reactivity and subsequent watershed transport.
Metal speciation in Julia Creek oil shale
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hirner, A.V.
1989-03-01
The concentrations of 19 elements were determined in organic and inorganic phases of the Julia Creek Oil Shale (Queensland/Australia). The phases were obtained by solvent and alkaline extractions as well as by stepwise demineralization with strong acids. Together with the results of other groups, a consistent model concerning the partition of trace elements in the various sedimentary components could be achieved. Whereas V, Ni and Ag show distributions comparable to the abundances of the correspondent phases in the sample, Ca, Mn and Co are concentrated in the mineral components, and B, As and Pb are enriched in kerogen. Al, Cr,more » Fe, Cu, Zn, Mo, Cd and Sb range between these extremes, while Au and Hg are contained in the humic substances only.« less
NASA Astrophysics Data System (ADS)
Chakhmouradian, Anton R.; Reguir, Ekaterina P.; Zaitsev, Anatoly N.; Couëslan, Christopher; Xu, Cheng; Kynický, Jindřich; Mumin, A. Hamid; Yang, Panseok
2017-03-01
Apatite-group phosphates are nearly ubiquitous in carbonatites, but our understanding of these minerals is inadequate, particularly in the areas of element partitioning and petrogenetic interpretation of their compositional variation among spatially associated rocks and within individual crystals. In the present work, the mode of occurrence, and major- and trace-element chemistry of apatite (sensu lato) from calcite and dolomite carbonatites, their associated cumulate rocks (including phoscorites) and hydrothermal parageneses were studied using a set of 80 samples from 50 localities worldwide. The majority of this set represents material for which no analytical data are available in the literature. Electron-microprobe and laser-ablation mass-spectrometry data ( 600 and 400 analyses, respectively), accompanied by back-scattered-electron and cathodoluminescence images and Raman spectra, were used to identify the key compositional characteristics and zoning patterns of carbonatitic apatite. These data are placed in the context of phosphorus geochemistry in carbonatitic systems and carbonatite evolution, and compared to the models proposed by previous workers. The documented variations in apatite morphology and zoning represent a detailed record of a wide range of evolutionary processes, both magmatic and fluid-driven. The majority of igneous apatite from the examined rocks is Cl-poor fluorapatite or F-rich hydroxylapatite (≥ 0.3 apfu F) with 0.2-2.7 wt.% SrO, 0-4.5 wt.% LREE2O3, 0-0.8 wt.% Na2O, and low levels of other cations accommodated in the Ca site (up to 1000 ppm Mn, 2300 ppm Fe, 200 ppm Ba, 150 ppm Pb, 700 ppm Th and 150 ppm U), none of which show meaningful correlation with the host-rock type. Silicate, (SO4)2 - and (VO4)3 - anions, substituting for (PO4)3 -, tend to occur in greater abundance in crystals from calcite carbonatites (up to 4.2 wt.% SiO2, 1.5 wt.% SO3 and 660 ppm V). Although (CO3)2 - groups are very likely present in some samples, Raman micro-spectroscopy proved inconclusive for apatites with small P-site deficiencies and other substituent elements in this site. Indicator REE ratios sensitive to redox conditions (δCe, δEu) and hydrothermal overprint (δY) form a fairly tight cluster of values (0.8-1.3, 0.8-1.1 and 0.6-0.9, respectively) and may be used in combination with trace-element abundances for the development of geochemical exploration tools. Hydrothermal apatite forms in carbonatites as the product of replacement of primary apatite, or is deposited in fractures and interstices as euhedral crystals and aggregates associated with typical late-stage minerals (e.g., quartz and chlorite). Hydrothermal apatite is typically depleted in Sr, REE, Mn and Th, but enriched in F (up to 4.8 wt.%) relative to its igneous precursor, and also differs from the latter in at least some of key REE ratios [e.g., shows (La/Yb)cn ≤ 25, or a negative Ce anomaly]. The only significant exception is Sr(± REE,Na)-rich replacement zones and overgrowths on igneous apatite from some dolomite(-bearing) carbonatites. Their crystallization conditions and source fluid appear to be very different from the more common Sr-REE-depleted variety. Based on the new evidence presented in this work, trace-element partitioning between apatite and carbonatitic magmas, phosphate solubility in these magmas, and compositional variation of apatite-group minerals from spatially associated carbonatitic rocks are critically re-evaluated.
Ray tracing a three-dimensional scene using a hierarchical data structure
Wald, Ingo; Boulos, Solomon; Shirley, Peter
2012-09-04
Ray tracing a three-dimensional scene made up of geometric primitives that are spatially partitioned into a hierarchical data structure. One example embodiment is a method for ray tracing a three-dimensional scene made up of geometric primitives that are spatially partitioned into a hierarchical data structure. In this example embodiment, the hierarchical data structure includes at least a parent node and a corresponding plurality of child nodes. The method includes a first act of determining that a first active ray in the packet hits the parent node and a second act of descending to each of the plurality of child nodes.
Geochemical Evidence for a Terrestrial Magma Ocean
NASA Technical Reports Server (NTRS)
Agee, Carl B.
1999-01-01
The aftermath of phase separation and crystal-liquid fractionation in a magma ocean should leave a planet geochemically differentiated. Subsequent convective and other mixing processes may operate over time to obscure geochemical evidence of magma ocean differentiation. On the other hand, core formation is probably the most permanent, irreversible part of planetary differentiation. Hence the geochemical traces of core separation should be the most distinct remnants left behind in the mantle and crust, In the case of the Earth, core formation apparently coincided with a magma ocean that extended to a depth of approximately 1000 km. Evidence for this is found in high pressure element partitioning behavior of Ni and Co between liquid silicate and liquid iron alloy, and with the Ni-Co ratio and the abundance of Ni and Co in the Earth's upper mantle. A terrestrial magma ocean with a depth of 1000 km will solidify from the bottom up and first crystallize in the perovskite stability field. The largest effect of perovskite fractionation on major element distribution is to decrease the Si-Mg ratio in the silicate liquid and increase the Si-Mg ratio in the crystalline cumulate. Therefore, if a magma ocean with perovskite fractionation existed, then one could expect to observe an upper mantle with a lower than chondritic Si-Mg ratio. This is indeed observed in modern upper mantle peridotites. Although more experimental work is needed to fully understand the high-pressure behavior of trace element partitioning, it is likely that Hf is more compatible than Lu in perovskite-silicate liquid pairs. Thus, perovskite fractionation produces a molten mantle with a higher than chondritic Lu-Hf ratio. Arndt and Blichert-Toft measured Hf isotope compositions of Barberton komatiites that seem to require a source region with a long-lived, high Lu-Hf ratio. It is plausible that that these Barberton komatiites were generated within the majorite stability field by remelting a perovskite-depleted part of the upper mantle transition zone.
Swanson, Sharon M.; Engle, Mark A.; Ruppert, Leslie F.; Affolter, Ronald H.; Jones, Kevin B.
2013-01-01
Samples of feed coal (FC), bottom ash (BA), economizer fly ash (EFA), and fly ash (FA) were collected from power plants in the Central Appalachian basin and Colorado Plateau to determine the partitioning of As, Cr, Hg, Pb, and Se in coal combustion products (CCPs). The Appalachian plant burns a high-sulfur (about 3.9 wt.%) bituminous coal from the Upper Pennsylvanian Pittsburgh coal bed and operates with electrostatic precipitators (ESPs), with flue gas temperatures of about 163 °C in the ESPs. At this plant, As, Pb, Hg, and Se have the greatest median concentrations in FA samples, compared to BA and EFA. A mass balance (not including the FGD process) suggests that the following percentages of trace elements are captured in FA: As (48%), Cr (58%), Pb (54%), Se (20%), and Hg (2%). The relatively high temperatures of the flue gas in the ESPs and low amounts of unburned C in FA (0.5% loss-on-ignition for FA) may have led to the low amount of Hg captured in FA. The Colorado Plateau plant burns a blend of three low-S (about 0.74 wt.%) bituminous coals from the Upper Cretaceous Fruitland Formation and operates with fabric filters (FFs). Flue gas temperatures in the baghouses are about 104 °C. The elements As, Cr, Pb, Hg, and Se have the greatest median concentrations in the fine-grained fly ash product (FAP) produced by cyclone separators, compared to the other CCPs at this plant. The median concentration of Hg in FA (0.0983 ppm) at the Colorado Plateau plant is significantly higher than that for the Appalachian plant (0.0315 ppm); this higher concentration is related to the efficiency of FFs in Hg capture, the relatively low temperatures of flue gas in the baghouses (particularly in downstream compartments), and the amount of unburned C in FA (0.29% loss-on-ignition for FA).
An examination of the role of particles in oceanic mercury cycling.
Lamborg, Carl H; Hammerschmidt, Chad R; Bowman, Katlin L
2016-11-28
Recent models of global mercury (Hg) cycling have identified the downward flux of sinking particles in the ocean as a prominent Hg removal process from the ocean. At least one of these models estimates the amount of anthropogenic Hg in the ocean to be about 400 Mmol, with deep water formation and sinking fluxes representing the largest vectors by which pollutant Hg is able to penetrate the ocean interior. Using data from recent cruises to the Atlantic, we examined the dissolved and particulate partitioning of Hg in the oceanic water column as a cross-check on the hypothesis that sinking particle fluxes are important. Interestingly, these new data suggest particle-dissolved partitioning ( K d ) that is approximately 20× greater than previous estimates, which thereby challenges certain assumptions about the scavenging and active partitioning of Hg in the ocean used in earlier models. For example, the new particle data suggest that regenerative scavenging is the most likely mechanism by which the association of Hg and particles occurs.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'. © 2016 The Author(s).
Trace Uranium Partitioning in a Multiphase Nano-FeOOH System.
McBriarty, Martin E; Soltis, Jennifer A; Kerisit, Sebastien; Qafoku, Odeta; Bowden, Mark E; Bylaska, Eric J; De Yoreo, James J; Ilton, Eugene S
2017-05-02
The characterization of trace elements in minerals using extended X-ray absorption fine structure (EXAFS) spectroscopy constitutes a first step toward understanding how impurities and contaminants interact with the host phase and the environment. However, limitations to EXAFS interpretation complicate the analysis of trace concentrations of impurities that are distributed across multiple phases in a heterogeneous system. Ab initio molecular dynamics (AIMD)-informed EXAFS analysis was employed to investigate the immobilization of trace uranium associated with nanophase iron (oxyhydr)oxides, a model system for the geochemical sequestration of radiotoxic actinides. The reductive transformation of ferrihydrite [Fe(OH) 3 ] to nanoparticulate iron oxyhydroxide minerals in the presence of uranyl (UO 2 ) 2+ (aq) resulted in the preferential incorporation of U into goethite (α-FeOOH) over lepidocrocite (γ-FeOOH), even though reaction conditions favored the formation of excess lepidocrocite. This unexpected result is supported by atomically resolved transmission electron microscopy. We demonstrate how AIMD-informed EXAFS analysis lifts the strict statistical limitations and uncertainty of traditional shell-by-shell EXAFS fitting, enabling the detailed characterization of the local bonding environment, charge compensation mechanisms, and oxidation states of polyvalent impurities in complex multiphase mineral systems.
Trace Uranium Partitioning in a Multiphase Nano-FeOOH System
DOE Office of Scientific and Technical Information (OSTI.GOV)
McBriarty, Martin E.; Soltis, Jennifer A.; Kerisit, Sebastien
The characterization of trace elements in minerals using extended X-ray absorption fine structure (EXAFS) spectroscopy constitutes a first step toward understanding how impurities and contaminants interact with the host phase and the environment. However, limitations to EXAFS interpretation complicate the analysis of trace concentrations of impurities that are distributed across multiple phases in a heterogeneous system. Ab initio molecular dynamics (AIMD)-informed EXAFS analysis was employed to investigate the immobilization of trace uranium associated with nanophase iron (oxyhydr)oxides, a model system for the geochemical sequestration of radiotoxic actinides. The reductive transformation of ferrihydrite [Fe(OH)3] to nanoparticulate iron oxyhydroxide minerals in themore » presence of uranyl (UO 2) 2+(aq) resulted in the preferential incorporation of U into goethite (α-FeOOH) over lepidocrocite (γ-FeOOH), even though reaction conditions favored the formation of excess lepidocrocite. This unexpected result is supported by atomically resolved transmission electron microscopy. We demonstrate how AIMD-informed EXAFS analysis lifts the strict statistical limitations and uncertainty of traditional shell-by-shell EXAFS fitting, enabling the detailed characterization of the local bonding environment, charge compensation mechanisms, and oxidation states of polyvalent impurities in complex multiphase mineral systems.« less
Trace Uranium Partitioning in a Multiphase Nano-FeOOH System
DOE Office of Scientific and Technical Information (OSTI.GOV)
McBriarty, Martin E.; Soltis, Jennifer A.; Kerisit, Sebastien
The characterization of trace elements in nanomaterials using extended X-ray absorption fine structure (EXAFS) spectroscopy constitutes a first step toward understanding how impurities or dopants affect the properties of the host phase. However, limitations to EXAFS interpretation complicate the analysis of trace concentrations of impurities that are distributed across multiple phases in a heterogeneous system. Ab initio molecular dynamics (AIMD)-informed EXAFS analysis was employed to investigate the immobilization of trace uranium associated with nanophase iron (oxyhydr)oxides, a model system for the geochemical sequestration of radiotoxic contaminants. The reductive transformation of ferrihydrite (Fe(OH)3) to nano-particulate iron oxyhydroxide minerals in the presencemore » of uranyl (UO2)2+(aq) resulted in the preferential incorporation of U into goethite (a-FeOOH) over lepidocrocite (g-FeOOH), even though reaction conditions favored the formation of excess lepidocrocite. This unexpected result is supported by atomically resolved transmission electron microscopy. Using this model system, we demonstrate how AIMD-informed EXAFS analysis lifts the strict statistical limitations of traditional shell-by-shell EXAFS modeling, enabling the detailed analysis of the local bonding environment, charge compensation mechanisms, and oxidation states of polyvalent impurities in complex multi-phase nano-systems.« less
Hoggard, Timothy; Liachko, Ivan; Burt, Cassaundra; Meikle, Troy; Jiang, Katherine; Craciun, Gheorghe; Dunham, Maitreya J.; Fox, Catherine A.
2016-01-01
The ability of plasmids to propagate in Saccharomyces cerevisiae has been instrumental in defining eukaryotic chromosomal control elements. Stable propagation demands both plasmid replication, which requires a chromosomal replication origin (i.e., an ARS), and plasmid distribution to dividing cells, which requires either a chromosomal centromere for segregation or a plasmid-partitioning element. While our knowledge of yeast ARSs and centromeres is relatively advanced, we know less about chromosomal regions that can function as plasmid partitioning elements. The Rap1 protein-binding site (RAP1) present in transcriptional silencers and telomeres of budding yeast is a known plasmid-partitioning element that functions to anchor a plasmid to the inner nuclear membrane (INM), which in turn facilitates plasmid distribution to daughter cells. This Rap1-dependent INM-anchoring also has an important chromosomal role in higher-order chromosomal structures that enhance transcriptional silencing and telomere stability. Thus, plasmid partitioning can reflect fundamental features of chromosome structure and biology, yet a systematic screen for plasmid partitioning elements has not been reported. Here, we couple deep sequencing with competitive growth experiments of a plasmid library containing thousands of short ARS fragments to identify new plasmid partitioning elements. Competitive growth experiments were performed with libraries that differed only in terms of the presence or absence of a centromere. Comparisons of the behavior of ARS fragments in the two experiments allowed us to identify sequences that were likely to drive plasmid partitioning. In addition to the silencer RAP1 site, we identified 74 new putative plasmid-partitioning motifs predicted to act as binding sites for DNA binding proteins enriched for roles in negative regulation of gene expression and G2/M-phase associated biology. These data expand our knowledge of chromosomal elements that may function in plasmid partitioning and suggest underlying biological roles shared by such elements. PMID:26865697
Córdoba, Patricia; Castro, Iria; Maroto-Valer, Mercedes; Querol, Xavier
2015-06-01
Experimental and geochemical modelling studies were carried out to identify mineral and solid phases containing major, minor, and trace elements and the mechanism of the retention of these elements in Flue Gas Desulphurisation (FGD)-gypsum samples from a coal-fired power plant under filtered water recirculation to the scrubber and forced oxidation conditions. The role of the pH and related environmental factors on the mobility of Li, Ni, Zn, As, Se, Mo, and U from FGD-gypsums for a comprehensive assessment of element leaching behaviour were also carried out. Results show that the extraction rate of the studied elements generally increases with decreasing the pH value of the FGD-gypsum leachates. The increase of the mobility of elements such as U, Se, and As in the FGD-gypsum entails the modification of their aqueous speciation in the leachates; UO2SO4, H2Se, and HAsO2 are the aqueous complexes with the highest activities under acidic conditions. The speciation of Zn, Li, and Ni is not affected in spite of pH changes; these elements occur as free cations and associated to SO4(2) in the FGD-gypsum leachates. The mobility of Cu and Mo decreases by decreasing the pH of the FGD-gypsum leachates, which might be associated to the precipitation of CuSe2 and MoSe2, respectively. Time-of-Flight mass spectrometry of the solid phase combined with geochemical modelling of the aqueous phase has proved useful in understanding the mobility and geochemical behaviour of elements and their partitioning into FGD-gypsum samples. Copyright © 2015. Published by Elsevier B.V.
Influence of Silicate Melt Composition on Metal/Silicate Partitioning of W, Ge, Ga and Ni
NASA Technical Reports Server (NTRS)
Singletary, S. J.; Domanik, K.; Drake, M. J.
2005-01-01
The depletion of the siderophile elements in the Earth's upper mantle relative to the chondritic meteorites is a geochemical imprint of core segregation. Therefore, metal/silicate partition coefficients (Dm/s) for siderophile elements are essential to investigations of core formation when used in conjunction with the pattern of elemental abundances in the Earth's mantle. The partitioning of siderophile elements is controlled by temperature, pressure, oxygen fugacity, and by the compositions of the metal and silicate phases. Several recent studies have shown the importance of silicate melt composition on the partitioning of siderophile elements between silicate and metallic liquids. It has been demonstrated that many elements display increased solubility in less polymerized (mafic) melts. However, the importance of silicate melt composition was believed to be minor compared to the influence of oxygen fugacity until studies showed that melt composition is an important factor at high pressures and temperatures. It was found that melt composition is also important for partitioning of high valency siderophile elements. Atmospheric experiments were conducted, varying only silicate melt composition, to assess the importance of silicate melt composition for the partitioning of W, Co and Ga and found that the valence of the dissolving species plays an important role in determining the effect of composition on solubility. In this study, we extend the data set to higher pressures and investigate the role of silicate melt composition on the partitioning of the siderophile elements W, Ge, Ga and Ni between metallic and silicate liquid.
NASA Technical Reports Server (NTRS)
Schwandt, C. S.; McKay, G. A.
1996-01-01
Determining the petrogenesis of eucrites (basaltic achondrites) and diogenites (orthopyroxenites) and the possible links between the meteorite types was initiated 30 years ago by Mason. Since then, most investigators have worked on this question. A few contrasting theories have emerged, with the important distinction being whether or not there is a direct genetic link between eucrites and diogenites. One theory suggests that diogenites are cumulates resulting from the fractional crystallization of a parent magma with the eucrites crystallizing, from the residual magma after separation from the diogenite cumulates. Another model proposes that diogenites are cumulates formed from partial melts derived from a source region depleted by the prior generation of eucrite melts. It has also been proposed that the diogenites may not be directly linked to the eucrites and that they are cumulates derived from melts that are more orthopyroxene normative than the eucrites. This last theory has recently received more analytical and experimental support. One of the difficulties with petrogenetic modeling is that it requires appropriate partition coefficients for modeling because they are dependent on temperature, pressure, and composition. For this reason, we set out to determine minor- and trace-element partition coefficients for diogenite-like orthopyroxene. We have accomplished this task and now have enstatite/melt partition coefficients for Al, Cr, Ti, La, Ce, Nd, Sm, Eu, Dy, Er, Yb, and La.
NASA Astrophysics Data System (ADS)
Paquette, J.; Zangooi, A.; Thornton, K.
2004-05-01
The influence of surface structure on partitioning between mineral and melt (or solution) has been noted by other workers in a handful of minerals, including calcite, dolomite, apatite, topaz and diamond. Each one of these minerals displays at least one crystallographic face where steps present during crystal growth are not equivalent by symmetry. When this is the case, sectors grown at the edge of these steps commonly show differential incorporation of minor or trace elements. In the diopside investigated here, electron probe microanalyses performed on the as-grown (100) surface of several crystals show concentric and sectoral zoning defined by variations in Fe content. Atomic force microscopy (AFM) was used to study the surfaces of the three crystallographic forms present on the diopside crystals, with the goal of relating the compositional zoning to the surface structure of the faces. The dominant {100} faces are covered with growth hillocks consisting of four vicinal faces defined by steps parallel to [010] and [001]. The steps are often bunched into macrosteps and the resulting hillocks are visible optically. The steps along the two crystallographic directions show significant differences in straightness and smoothness that indicate non-equivalent kinetics. The wavier steps correspond to Fe-enriched areas within the {100} sectors. The {010} faces, next in morphological importance, are dominated by a single step orientation and show no differential incorporation. They display topography related to polysynthetic twinning. The {110} faces are much smaller and very few show resolvable steps. Sector zoning (i.e. diffential partitioning among non-equivalent crystallographic faces) has been described in the past from pyroxenes. Explanations have invoked either differences in surface structure among non-equivalent faces or their unequal growth rates. This particular occurrence indicates that trace element incorporation is, in fact, highly site-specific and that significant compositioinal zoning can be induced on a single face without invoking the effect of growth rate. The natural diopside crystals from the Orford nickel mine (Brompton, Quebec) show a unusual bladed habit flattened on {100} faces. Exceptional fluid chemistry during crystallization may therefore be required for the persistence of steps responsible for differential incorporation. Nevertheless, whenever this zoning is present, the trace element involved cannot be expected to reflect thermodynamic equilibrium between the solid and the fluid from which it crystallized.
Petrology of enstatite chondrites and anomalous enstatite achondrites
NASA Astrophysics Data System (ADS)
van Niekerk, Deon
2012-01-01
Chondrites are meteorites that represent unmelted portions of asteroids. The enstatite chondrites are one class of chondrites. They consist of reduced mineral assemblages that formed under low oxygen fugacity in the solar nebula, prior to accretion into asteroids. There are two groups of enstatite chondrites---EH and EL. I studied EL3 meteorites, which are understood to be unmetamorphosed and thus to only preserve primitive nebular products. I show in a petrographic study that the EL3s are in fact melt--breccias in which impact-melting produced new mineral assemblages and textures in portions of the host chondrites, after accretion. I document meta- land sulfide assemblages that are intergrown with silicate minerals (which are often euhedral), and occur outside chondrules; these assemblages probably represent impact-melting products, and are different from those in EH3 chondrites that probably represent nebular products. In situ siderophile trace element compositions of the metal in EL3s, obtained by laser ablation inductively coupled plasma mass spectrometry, are consistent with an impact-melting hypothesis. The trace element concentrations show no clear volatility trend, and are thus probably not the result of volatile-driven petrogenetic processes that operated in the solar nebula. Trace element modeling suggests that the character of the trace element patterns together with deviations from the mean bulk EL metal pattern is consistent with metal that crystallized in a coexisting liquid-solid metal system in which dissolved carbon influenced element partitioning. I also conducted a petrographic and mineral-chemistry study of several anomalous enstatite meteorites. These have igneous textures, but unfractionated mineralogy similar to unmelted chondrites. I show that with the exception of one, the meteorites are related to each other, and probably formed by crystallization from an impact melt instead of metamorphism through the decay of short lived radionuclides. The broad importance of these studies lies in documenting the petrology of extraterrestrial materials that reveal the geological history of the young solar system prior to the existence of planets. Furthermore, they serve to identify which mineral assemblages record nebular processes and which record processes on asteroids, so that future studies may select the correct material to address particular questions.
Chemical diffusion during isobaric degassing of magma
NASA Astrophysics Data System (ADS)
von Aulock, Felix W.; Kennedy, Ben M.; Lavallée, Yan; Henton-de Angelis, Sarah; Oze, Christopher; Morgan, Daniel J.; Clesham, Steve
2014-05-01
During ascent of magma, volatiles exsolve and bubbles form. Volatiles can either escape through a permeable network of bubbles in an open system or be trapped in non-connected pores during closed system degassing. Geochemical studies have shown that in most cases both- open system and closed system degassing take place at the same time. During cooling of the melt, diffusion slows down and eventually diffusional gradients get frozen in, preserving a history of degassing and rehydration during bubble growth, bubble collapse and crystal growth. We present data from experiments in which natural obsidian was degassed at atmospheric pressures at 950ºC over timescales of 3-24h. During bubble growth, a skin formed, at the outer edge of the sample, effectively prohibiting any degassing of its interior. Diffusion gradients were measured across the glass surrounding vesicles, and across this impermeable skin. Water contents were analyzed with synchrotron sourced Fourier transform infrared spectroscopy and several major, minor and trace elements were mapped using synchrotron sourced X-ray fluorescence spectroscopy. The samples show a dimpled surface, as well as signs of oxidation and growth of submicroscopic crystals. Water contents around bubbles decrease in simple heating experiments (from ~0.13 wt. % down to ~0.1 wt. %), whereas slight rehydration of the vesicle wall can be observed when a second, cooler step at 850ºC follows the initial 950ºC. Water gradients towards the outside of the sample decrease linearly to a minimum of ~0.045 wt. %, far below the solubility of water in melts at these temperatures. We mapped the distribution of K, Ca, Fe, Ti, Mn, Rb, Sr, Y and Zr. Especially the trace elements show a decrease towards the outside of the sample, whereas K, Fe, Ca and Ti generally do not show significant partitioning between melt and gas/crystal phase. Several effects could attribute to the distribution of these elements, such as the crystal growth and exchange with atmospheric oxygen, and detailed models of the diffusion of these elements will have to verify the mechanisms of elemental partitioning during degassing Our experiments show that even on a small scale, open system and closed system degassing inherently coexist. This manifests itself in different elemental distribution in the quenched glass. Water distribution gradients can be explained with diffusion during exsolution and rehydration during cooling, however, the surface of the sample is undersaturated in water. Some trace elements follow the same pattern, even though they might not be considered as volatile. Therefore we suggest that chemical gradients may be partially induced by the growth of sub-microscopic crystals and by exchange with the atmosphere. Crystal rich, volatile poor outer skins, as produced in the experiments of this study, have locally drastically increased viscosities and can therefore withstand higher pressures during foaming of the interior of the sample. This self sealing of magma could be an important process on different scales of magma degassing, from bread crust bombs to rising magma in conduits.
NASA Technical Reports Server (NTRS)
Turner, Amber; Vander Kaaden, Kathleen; McCubbin, Francis; Danielson, Lisa R.
2017-01-01
The mineral apatite (Ca5 (PO4)3(F, Cl, OH)) is known for its ability to constrain the petrogenesis of the rock in which it is hosted and for its ubiquity throughout the Solar System, as it is found in lunar, martian, and terrestrial rocks alike (McCubbin et. al, 2015). The abundance of volatile elements, and for this particular study, the elevated abundance of sulfur (S2-) in high-Al basalt samples bearing apatite, could provide more insight for inquiries posed about the behavior of volatiles in lunar and martian magmatic systems (Boyce et. al, 2010). Oxygen fugacity will be an important parameter for these experiments, as the Moon, Mars, and Earth have different redox states (Herd, 2008). The objective of this experimental endeavor is to determine apatite-melt partition coefficients for the volatile elements (F-, Cl-, OH-, S2-) that make up the X-site (i.e., the typically monovalent anion site) in the mineral apatite in a lunar melt composition under lunar oxygen fugacity conditions approx.1-2 log units below the iron-wüstite buffer). All experiments will be conducted at NASA, Johnson Space Center in the High Pressure Experimental Petrology Laboratory. In order to conduct apatite-melt partition experiments with oxygen fugacity as an additional parameter, we will create a synthetic mix of the lunar KREEP basalt 15386, a sample retrieved during Apollo 15 that is believed to represent an indigenous volcanic melt derived from the lunar interior (Rhodes, J.M et. al, 2006). Other geochemically significant elements including C, Co, Ni, Mo, and rare earth elements will be included in the mix at trace abundances in order to assess their partitioning behavior without effecting the overall behavior of the system. The synthetic mix will then be loaded into a piston cylinder, an apparatus used to simulate high-pressure/high-temperature conditions of planetary interiors, and exposed to 0.5 GPa of pressure, the pressure observed in the upper mantle of the Moon, and heated to the melting temperature of the materials. To make sure crystals grow large enough for the necessary analyses, the sample will be kept at the crystallization temperature for 8 hours. This extended run time should also allow the sample to achieve a steady state which is necessary to accurately assess the partitioning of these elements between apatite and melt. The results from this experimental study will allow us to determine the fate of F-, Cl-, OH-, and S2- during the magmatic evolution of the Moon.
Hierarchically partitioned nonlinear equation solvers
NASA Technical Reports Server (NTRS)
Padovan, Joseph
1987-01-01
By partitioning solution space into a number of subspaces, a new multiply constrained partitioned Newton-Raphson nonlinear equation solver is developed. Specifically, for a given iteration, each of the various separate partitions are individually and simultaneously controlled. Due to the generality of the scheme, a hierarchy of partition levels can be employed. For finite-element-type applications, this includes the possibility of degree-of-freedom, nodal, elemental, geometric substructural, material and kinematically nonlinear group controls. It is noted that such partitioning can be continuously updated, depending on solution conditioning. In this context, convergence is ascertained at the individual partition level.
NASA Astrophysics Data System (ADS)
Chapelle, F. H.
2003-12-01
Differentiation of terrestrial planets includes separation of a metallic core and possible later fractionation of mineral phases within either a solid or molten mantle (Figure 1). Lithophile and siderophile elements can be used to understand these two different physical processes, and ascertain whether they operated in the early Earth. The distribution of elements in planets can be understood by measuring the partition coefficient, D (ratio of concentrations of an element in different phases (minerals, metals, or melts)). (14K)Figure 1. Schematic cross-section through the Earth, showing: (a) an early magma ocean stage and (b) a later cool and differentiated stage. The siderophile elements (iron-loving) encompass over 30 elements and are defined as those elements for which D(metal/silicate)>1, and are useful for deciphering the details of core formation. This group of elements is commonly broken up into several subclasses, including the slightly siderophile elements (1
Botsou, Fotini; Sungur, Ali; Kelepertzis, Efstratios; Soylak, Mustafa
2016-10-01
We report in this study the magnetic properties and partitioning patterns of selected trace metals (Pb, Zn, Cu, Cd, Ni) in roadside and off-road (>200m distance from the road edge) agricultural soils collected along two major highways in Greece. Sequential extractions revealed that the examined trace metals for the entire data set were predominantly found in the residual fraction, averaging 37% for Cd up to 80% for Cu. Due to the strong influence of lithogenic factors, trace metal pseudototal contents of the roadside soils did not differ significantly to those of the off-road soils. Magnetic susceptibility and frequency dependent magnetic susceptibility determinations showed a magnetic enhancement of soils; however, it was primarily related to geogenic factors and not to traffic-derived magnetic particles. These results highlight that in areas characterized by strong geogenic backgrounds, neither pseudototal trace metal contents nor magnetic properties determinations effectively capture traffic-related contamination of topsoils. The vehicular emission signal was traced by the increased acid-soluble and reducible trace metal contents of the roadside soils compared to their off-road counterparts. In the case of Cu and Zn, changes in the partitioning patterns were also observed between the roadside and off-road soils. Environmental risks associated with agricultural lands extending at the margins of the studied highways may arise from the elevated Ni contents (both pseudototal and potentially mobile), and future studies should investigate Ni levels in the edible parts of plants grown on these agricultural soils. Copyright © 2016 Elsevier Inc. All rights reserved.
NASA Astrophysics Data System (ADS)
Park, Jung-Woo; Kamenetsky, Vadim; Campbell, Ian; Park, Gyuseung; Hanski, Eero; Pushkarev, Evgeny
2017-11-01
Recent experimental studies and in situ LA-ICP-MS analysis on natural Cr-spinel have shown that Rh and IPGEs (Ir-group platinum group elements: Ru, Ir, Os) are enriched in the lattice of Cr-spinel. However, the factors controlling the partitioning behaviour of these elements are not well constrained. In this study, we report the Rh, IPGE, and trace element contents in primitive Cr-spinel, measured by LA-ICP-MS, from nine volcanic suites covering various tectonic settings including island arc picrites, boninites, large igneous province picrites and mid-ocean ridge basalts. The aim is to understand the factors controlling the enrichment of Rh and IPGEs in Cr-spinels, to estimate empirical partition coefficients between Cr-spinel and silicate melts, and to investigate the role of Cr-spinel fractional crystallization on the PGE geochemistry of primitive magmas during the early stages of fractional crystallization. There are systematic differences in trace elements, Rh and IPGEs in Cr-spinels from arc-related magmas (Arc Group Cr-spinel), intraplate magmas (Intraplate Group Cr-spinel), and mid-ocean ridge magmas (MORB Group Cr-spinel). Arc Group Cr-spinels are systematically enriched in Sc, Co and Mn and depleted in Ni compared to the MORB Group Cr-spinels. Intraplate Group Cr-spinels are distinguished from the Arc Group Cr-spinels by their high Ni contents. Both the Arc and Intraplate Group Cr-spinels have total Rh and IPGE contents of 22-689 ppb whereas the MORB Group Cr-spinels are depleted in Rh and IPGE (total < 20 ppb). Palladium and Pt contents are below detection limit for all of the studied Cr-spinels (<1-5 ppb). The time-resolved spectra of LA-ICP-MS data for Cr-spinels mostly show constant count rates for trace element and Rh and IPGEs, suggesting homogeneous distribution of these elements in Cr-spinels. The PGE spikes observed in several Cr-spinels were interpreted to be PGE-bearing mineral inclusions and excluded from calculating the PGE contents of the Cr-spinels. On primitive mantle normalized diagrams the Arc Group Cr-spinels are characterized by a fractionated pattern with high Rh and low Os. The Intraplate Group Cr-spinels show flat patterns with positive Ru anomalies. Our results, together with the experimental and empirical data from previous studies, show that PGE patterns of Cr-spinel largely mimic that of the rock in which they are found, and that Rh, Ir and Os contents increase with increasing Fe3+ contents (i.e. magnetite component) in Cr-spinel, although Ru does not. These observations suggest that the enrichment of Rh and IPGEs in Cr-spinel is controlled by a combination of the Rh and IPGE contents in parental melts and the magnetite component of the spinel. Empirical partition coefficients (D) for Rh and IPGEs between Cr-spinels and silicate melts were calculated using the Rh and IPGE contents of the Cr-spinel and their host volcanic rocks after subtracting the accumulation effect of Cr-spinel. The D values for the Intraplate and MORB Group Cr-spinels increase with increasing magnetite component in Cr-spinel and range from 6 to 512, which is consistent with previously reported experimental and empirical values. In contrast, the Arc Group Cr-spinels have significantly higher D values (e.g. up to ∼3700 for Ru) than those of the Intraplate and MORB Group at the same magnetite concentration in the Cr-spinel, suggesting Rh and IPGEs dissolved in silicate melt have stronger affinity for Cr spinel under arc magma conditions than in intraplate magmas. This may be partly attributed to the low temperature of arc magmas relative to intraplate magmas, which leads to the Arc Group Cr-spinels having more octahedral sites at the same magnetite components than the Intraplate Group Cr-spinels. Because of significantly higher D values for the Arc Group Cr-spinels, compared with the Intraplate Group and MORB Group spinels, fractional crystallization of Cr-spinel will more efficiently fractionate Rh and IPGE from Pd and Pt in arc systems than in intraplate and MORB systems, which accounts for the highly fractionated PGE patterns in arc basalts.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Marcus, Matthew A.; Edwards, Katrina J.; Gueguen, Bleuenn
Deep-sea ferromanganese nodules accumulate trace elements from seawater and underlying sediment porewaters during the growth of concentric mineral layers over millions of years. These trace elements have the potential to record past ocean geochemical conditions. The goal of this study was to determine whether Fe mineral alteration occurs and how the speciation of trace elements responds to alteration over ~3.7Ma of marine ferromanganese nodule (MFN) formation, a timeline constrained by estimates from 9 Be/ 10 Be concentrations in the nodule material. We determined Fe-bearing phases and Fe isotope composition in a South Pacific Gyre (SPG) nodule. Specifically, the distribution patternsmore » and speciation of trace element uptake by these Fe phases were investigated. The time interval covered by the growth of our sample of the nodule was derived from 9 Be/ 10 Be accelerator mass spectrometry (AMS). The composition and distribution of major and trace elements were mapped at various spatial scales, using micro-X-ray fluorescence (μXRF), electron microprobe analysis (EMPA), and inductively coupled plasma mass spectrometry (ICP-MS). Fe phases were characterized by micro-extended X-ray absorption fine structure (μEXAFS) spectroscopy and micro-X-ray diffraction (μXRD). Speciation of Ti and V, associated with Fe, was measured using micro-X-ray absorption near edge structure (μXANES) spectroscopy. Iron isotope composition (δ 56/54 Fe) in subsamples of 1-3mm increments along the radius of the nodule was determined with multiple-collector ICP-MS (MC-ICP-MS). The SPG nodule formed through primarily hydrogeneous inputs at a rate of 4.0±0.4mm/Ma. The nodule exhibited a high diversity of Fe mineral phases: feroxyhite (δ-FeOOH), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and poorly ordered ferrihydrite-like phases. These findings provide evidence that Fe oxyhydroxides within the nodule undergo alteration to more stable phases over millions of years. Trace Ti and V were spatially correlated with Fe and found to be adsorbed to Fe-bearing minerals. Ti/Fe and V/Fe ratios, and Ti and V speciation, did not vary along the nodule radius. The δ 56/54 Fe values, when averaged over sample increments representing 0.25-0.75Ma, were homogeneous within uncertainty along the nodule radius, at -0.12±0.07‰ (2sd, n=10). Our results indicate that the Fe isotope composition of the nodule remained constant during nodule growth and that mineral alteration did not affect the primary Fe isotope composition of the nodule. Furthermore, the average δ 56/54 Fe value of -0.12‰ we find is consistent with Fe sourced from continental eolian particles (dust). Despite mineral alteration, the trace element partitioning of Ti and V, and Fe isotope composition, do not appear to change within the sensitivity of our measurements. These findings suggest that Fe oxyhydroxides within hydrogenetic ferromanganese nodules are out of geochemical contact with seawater once they are covered by subsequent concentric mineral layers. Even though Fe-bearing minerals are altered, trace element ratios, speciation and Fe isotope composition are preserved within the nodule.« less
Marcus, Matthew A.; Edwards, Katrina J.; Gueguen, Bleuenn; ...
2015-09-05
Deep-sea ferromanganese nodules accumulate trace elements from seawater and underlying sediment porewaters during the growth of concentric mineral layers over millions of years. These trace elements have the potential to record past ocean geochemical conditions. The goal of this study was to determine whether Fe mineral alteration occurs and how the speciation of trace elements responds to alteration over ~3.7Ma of marine ferromanganese nodule (MFN) formation, a timeline constrained by estimates from 9 Be/ 10 Be concentrations in the nodule material. We determined Fe-bearing phases and Fe isotope composition in a South Pacific Gyre (SPG) nodule. Specifically, the distribution patternsmore » and speciation of trace element uptake by these Fe phases were investigated. The time interval covered by the growth of our sample of the nodule was derived from 9 Be/ 10 Be accelerator mass spectrometry (AMS). The composition and distribution of major and trace elements were mapped at various spatial scales, using micro-X-ray fluorescence (μXRF), electron microprobe analysis (EMPA), and inductively coupled plasma mass spectrometry (ICP-MS). Fe phases were characterized by micro-extended X-ray absorption fine structure (μEXAFS) spectroscopy and micro-X-ray diffraction (μXRD). Speciation of Ti and V, associated with Fe, was measured using micro-X-ray absorption near edge structure (μXANES) spectroscopy. Iron isotope composition (δ 56/54 Fe) in subsamples of 1-3mm increments along the radius of the nodule was determined with multiple-collector ICP-MS (MC-ICP-MS). The SPG nodule formed through primarily hydrogeneous inputs at a rate of 4.0±0.4mm/Ma. The nodule exhibited a high diversity of Fe mineral phases: feroxyhite (δ-FeOOH), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and poorly ordered ferrihydrite-like phases. These findings provide evidence that Fe oxyhydroxides within the nodule undergo alteration to more stable phases over millions of years. Trace Ti and V were spatially correlated with Fe and found to be adsorbed to Fe-bearing minerals. Ti/Fe and V/Fe ratios, and Ti and V speciation, did not vary along the nodule radius. The δ 56/54 Fe values, when averaged over sample increments representing 0.25-0.75Ma, were homogeneous within uncertainty along the nodule radius, at -0.12±0.07‰ (2sd, n=10). Our results indicate that the Fe isotope composition of the nodule remained constant during nodule growth and that mineral alteration did not affect the primary Fe isotope composition of the nodule. Furthermore, the average δ 56/54 Fe value of -0.12‰ we find is consistent with Fe sourced from continental eolian particles (dust). Despite mineral alteration, the trace element partitioning of Ti and V, and Fe isotope composition, do not appear to change within the sensitivity of our measurements. These findings suggest that Fe oxyhydroxides within hydrogenetic ferromanganese nodules are out of geochemical contact with seawater once they are covered by subsequent concentric mineral layers. Even though Fe-bearing minerals are altered, trace element ratios, speciation and Fe isotope composition are preserved within the nodule.« less
Piper, D Z; Ludington, Steve; Duval, J S; Taylor, H E
2006-06-01
Stream-bed sediment for the size fraction less than 150 microm, examined in 14,000 samples collected mostly from minor tributaries to the major rivers throughout the Mississippi River drainage system, is composed of 5 mineral fractions identified by factor analysis-Al-silicate minerals, quartz, calcite and dolomite, heavy minerals, and an Fe-Mn fraction. The Al-silicate fraction parallels its distribution in the regolith, emphasizing the local sediment source as a primary control to its distribution. Quartz and the heavy-mineral fraction, and associated trace elements, exhibit a complementary distribution to that of the Al-silicate fraction, with a level of enrichment in the bed sediment that is achieved through winnowing and sorting. The carbonate fraction has a distribution suggesting its dissolution during transport. Trace elements partitioned onto the Fe-Mn, possibly amorphous oxyhydride, fraction are introduced to the streams, in part, through human activity. Except for the heavy-mineral fraction, these fractions are identified in suspended sediment from the Mississippi River itself. Although comparison of the tributary bed sediment with the riverine suspended sediment is problematic, the geochemistry of the suspended sediment seems to corroborate the interpretation of the geochemistry of the bed sediment.
Piper, D.Z.; Ludington, S.; Duval, J.S.; Taylor, Howard E.
2006-01-01
Stream-bed sediment for the size fraction less than 150 ??m, examined in 14,000 samples collected mostly from minor tributaries to the major rivers throughout the Mississippi River drainage system, is composed of 5 mineral fractions identified by factor analysis-Al-silicate minerals, quartz, calcite and dolomite, heavy minerals, and an Fe-Mn fraction. The Al-silicate fraction parallels its distribution in the regolith, emphasizing the local sediment source as a primary control to its distribution. Quartz and the heavy-mineral fraction, and associated trace elements, exhibit a complementary distribution to that of the Al-silicate fraction, with a level of enrichment in the bed sediment that is achieved through winnowing and sorting. The carbonate fraction has a distribution suggesting its dissolution during transport. Trace elements partitioned onto the Fe-Mn, possibly amorphous oxyhydride, fraction are introduced to the streams, in part, through human activity. Except for the heavy-mineral fraction, these fractions are identified in suspended sediment from the Mississippi River itself. Although comparison of the tributary bed sediment with the riverine suspended sediment is problematic, the geochemistry of the suspended sediment seems to corroborate the interpretation of the geochemistry of the bed sediment.
New Experimental Constraints on Crystallization Differentiation in a Deep Magma Ocean
NASA Astrophysics Data System (ADS)
Walter, M. J.; Ito, E.; Nakamura, E.; Tronnes, R.; Frost, D.
2001-12-01
Most of Earth's mass probably accreted as a consequence of numerous impacts between large bodies and proto-Earth, and a giant impact with a Mars-sized object is the most plausible explanation for a Moon forming event. 1 Physical models show that large impacts would have caused high-degrees of melting and a global magma ocean. 2 Crystallization differentiation in a deep magma ocean could impart stratification in the solidified mantle, forming large geochemical domains. To accurately model crystallization in a deep magma ocean the liquidus phase-relations of peridotite, as well as mineral/melt element partitioning, must be known at lower mantle conditions. Here, we report the results of liquidus experiments on fertile model peridotite compositions at 23 - 33 GPa. Experiments were performed in 6/8-type multi-anvil apparatus using carbide and sintered-diamond second-stage anvils with 4 and 2 mm truncations, respectively. Samples were encapsulated by either graphite or Re. High-temperatures were generated using LaCrO3 or Re furnaces, and temperatures were held from 2 to 50 minutes at 2300 - 2500 C. Run products were analyzed for major and trace elements using EPMA and SIMS. At 23 GPa the liquidus phase is majorite, followed closely down temperature by ferropericlase (Fp) and Mg-perovskite (Mg-Pv). At 24 GPa the liquidus phase has changed to Fp, followed closely by majorite and Mg-Pv. Ca-perovskite (Ca-Pv) is present only at much lower temperatures close to the solidus. At approximately 31 GPa Mg-Pv is the liquidus phase followed down-temperature by Fp then Ca-Pv. At ~ 33 GPa Ca-Pv crystallizes closer to the liquidus, within about 50 C, at a similar temperature to Fp. Thus, important phases crystallizing in a deep magma ocean are Mg-Pv, Ca-Pv and Fp. Crystallization models based on major element partitioning show that only very modest amounts of crystal separation of a Mg-Pv + Fp assemblage can be tolerated before Ca/Al, Al/Ti and Ca/Ti ratios become unrealistic for estimates of primitive upper mantle (PUM). 3 However, even small amounts of Ca-Pv in the crystal assemblage effectively buffer these ratios at values close to the starting composition (e.g. chondritic). Further, based on our new trace element partitioning data, models involving considerable Mg-Pv fractionation generally show poor matches with model PUM. For example, model PUM has sub-chondritic REE/Ti, whereas these ratios increase considerably during Mg-Pv crystallization. Notable exceptions are super-chondritic Zr/Ti, chondritic Sr/Ti, and sub-chondritic Zr/Nb and Sm/Yb ratios, all of which are well matched by considerable Mg-Pv crystallization. Although trace element D's for Ca-Pv are not yet measured quantitatively, the observed affinity of Ca-Pv for REE could conceivably account for the the sub-chondritic REE/Ti ratios in PUM. Ca-Pv also concentrates K, and could be an important source of heat from radioactive decay in the lower mantle. 1. Canup, R. and Agnor, C., Origin of the Earth and Moon, Righter and Canup, eds., U. Arizona Press, 113-144, 2000. 2. Melosh, H., Origin of the Earth, Newsom and Jones, eds., Oxford Press, 69-84, 1990. 3. McFarlane, E. et al., Geochimica et Cosmochimica Acta, 5161-5172, 1994.
NASA Astrophysics Data System (ADS)
Togashi, Shigeko; Kita, Noriko T.; Tomiya, Akihiko; Morishita, Yuichi
2017-08-01
The compositions of host magmas of ferroan anorthosites (FAN-host magmas) were estimated from secondary ion mass spectrometry analyses of plagioclase in lunar highland rocks. The evolution of the magmas was investigated by considering phase relations based on the MELTS algorithm and by re-examining partition coefficients for trace elements between plagioclase and melts. Data little affected by post-magmatic processes were selected by using plagioclase with relatively primitive Sc and Co contents. The FAN-host magma contained 90-174 ppm Sr, 40-119 ppm Ba and 0.5-1.3% TiO2, and had sub-chondritic Sr/Ba and Ti/Ba ratios. It is difficult to account for the formation of FAN-host magma on the basis of magma evolution processes of previously proposed bulk silicate Moon models with chondritic ratios for refractory elements at global scale. Therefore, the source of the FAN-host magma must have had primordial sub-chondritic Sr/Ba and Ti/Ba ratios. The FAN-host magmas were consistent in refractory elements with the estimated host mafic magma for feldspathic crust based on lunar meteorites, and some very-low-Ti mare rocks from lunar meteorites. Here, we propose an alternative bulk silicate Moon model (the cBSM model), which is enriched in crustal components of proto-bodies relative to the present whole Earth-Moon system.
Adams, David T.; Nielsen, Roger L.; Kent, Adam J.R.; Tepley, Frank J.
2011-01-01
Melt inclusions trapped in phenocryst phases are important primarily due to their potential of preserving a significant proportion of the diversity of magma composition prior to modification of the parent magma array during transport through the crust. The goal of this investigation was to evaluate the impact of formational and post-entrapment processes on the composition of melt inclusions hosted in high anorthite plagioclase in MORB. Our observations from three plagioclase ultra-phyric lavas from the Endeavor Segment of the Juan de Fuca Ridge document a narrow range of major elements and a dramatically greater range of minor and trace elements within most host plagioclase crystals. Observed host/inclusion partition coefficients for Ti are consistent with experimental determinations. In addition, observed values of DTi are independent of inclusion size and inclusion TiO2 content of the melt inclusion. These observations preclude significant effects from the re-homogenization process, entrapment of incompatible element boundary layers or dissolution/precipitation. The observed wide range of TiO2 contents in the host feldspar, and between bands of melt inclusions within individual crystals rule out modification of TiO contents by diffusion, either pre-eruption or due to re-homogenization. However, we do observe comparatively small ranges for values of K2O and Sr compared to P2O5 and TiO2 in both inclusions and crystals that can be attributed to diffusive processes that occurred prior to eruption.
Metal-silicate partitioning and the light element in the core (Invited)
NASA Astrophysics Data System (ADS)
Wood, B. J.; Wade, J.; Tuff, J.
2009-12-01
Most attempts to constrain the concentrations of “light” elements in the Earth’s core rely either on cosmochemical arguments or on arguments based on the densities and equations of state of Fe-alloys containing the element of concern. Despite its utility, the latter approach yields a wide range of permissible compositions and hence weak constraints. The major problem with the cosmochemical approach is that the abundances in the bulk Earth of all the candidate “light” elements- H, C, O, Si and S are highly uncertain because of their volatile behavior during planetary accretion. In contrast, refractory elements appear to be in approximately CI chondritic relative abundances in the Earth. This leads to the potential for using the partitioning of refractory siderophile elements between the mantle and core to constrain the concentrations of light elements in the core. Recent experimental metal-silicate partitioning data, coupled with mantle abundances of refractory siderophile elements (e.g. Wade and Wood, EPSL v.236, 78—95,2005; Kegler et. al. EPSL v.268, 28-40,2008) have shown that the core segregated from the mantle under high pressure conditions (~40 GPa). If a wide range of elements, from very siderophile, (e.g. Mo) through moderately (Ni, Co, W) to weakly siderophile (V, Cr, Nb, Si) are considered, the Earth also appears to have become more oxidized during accretion. Metal-silicate partitioning of some elements is also sensitive to the light element content of the metal. For example, Nb and W partitioning depend strongly on carbon, Mo on silicon and Cr on sulfur. Given the measured mantle abundances of the refractory elements, these observations enable the Si and C contents of the core to be constrained at ~5% and <2% respectively while partitioning is consistent with a cosmochemically-estimated S content of ~2%.
Mantle Mineral/Silicate Melt Partitioning
NASA Astrophysics Data System (ADS)
McFarlane, E. A.; Drake, M. J.
1992-07-01
Introduction: The partitioning of elements among mantle phases and silicate melts is of interest in unraveling the early thermal history of the Earth. It has been proposed that the elevated Mg/Si ratio of the upper mantle of the Earth is a consequence of the flotation of olivine into the upper mantle (Agee and Walker, 1988). Agee and Walker (1988) have generated a model via mass balance by assuming average mineral compositions to generate upper mantle peridotite. This model determines that upper mantle peridotite could result from the addition of 32.7% olivine and 0.9% majorite garnet into the upper mantle, and subtraction of 27.6% perovskite from the upper mantle (Agee and Walker, 1988). The present contribution uses experimental data to examine the consequences of such multiple phase fractionations enabling an independent evaluation of the above mentioned model. Here we use Mg-perovskite/melt partition coefficients from both a synthetic and a natural system (KLB-1) obtained from this laboratory. Also used are partition coefficient values for majorite garnet/melt, beta spinel/melt and olivine/melt partitioning (McFarlane et al., 1991b; McFarlane et al., 1992). Multiple phase fractionations are examined using the equilibrium crystallization equation and partition coefficient values. The mineral proportions determined by Agee and Walker (1988) are converted into weight fractions and used to compute a bulk partition coefficient value. Discussion: There has been a significant debate concerning whether measured values of trace element partition coefficients permit large-scale fractionation of liquidus phases from an early terrestrial magma ocean (Kato et al., 1988a,b; Walker and Agee, 1989; Drake, 1989; Drake et al., 1991; McFarlane et al., 1990, 1991). It should be noted that it is unclear which, if any, numerical values of partition coefficients are appropriate for examining this question, and certainly the assumptions for the current model must be more fully examined. However, our preliminary calculations do not appear to be consistent with large scale fractionation of phases in the proportions postulated from an early ocean, because approximately chondritic ratios and abundances of refractory lithophile elements inferred for the primitive upper mantle of the Earth would not be preserved. References: Agee, C.B. and Walker, D. (1988) Earth. Planet. Sci. Lett. 90, 144-156. Drake, M.J. (1989) Z. Naturforsch., 44a, 883-890. Drake, M.J. et al. (1991) Magma Oceans Workshop. Drake, M.J. et al. (1989) Geochim. Cosmochim. Acta, 53, 2101-2111. Kato, T. et al. (1988a) Earth. Planet. Sci. Lett. 89, 123-145. Kato, T. et al. (1988b) Earth. Planet. Sci. Lett. 90, 65-68. McFarlane, E.A. et al. (1990) Lunar and Planetary Science 21, 759-760. McFarlane, E.A. et al. (199la) Magma Oceans Workshop. McFarlane, E.A. et al. (199lb) Lunar and Planetary Science 22, 875-876. McFarlane, E.A. et al. (1992) Lunar and Planetary Science 23, 883-884. Walker, D. and Agee, C.B. (1989) Earth. Planet. Sci. Lett. 96, 49-60.
NASA Astrophysics Data System (ADS)
Aulbach, Sonja; Stachel, Thomas; Seitz, Hans-Michael; Brey, Gerhard P.
2012-09-01
In the central Slave craton, eclogitic diamonds are suggested to have formed during Paleoproterozoic subduction in a meta-gabbroic substrate representing former lower oceanic crust that interacted with serpentinite-derived fluids at high fluid-rock ratios. In order to assess the behaviour of chalcophile and siderophile elements (CSE) during this process, we measured trace-element concentrations of sulphide inclusions in diamonds from the Diavik mine by laser ablation ICPMS. The nitrogen systematics of the diamonds (average N concentration of ˜600 ppm and aggregation state 4% N as B-aggregates) indicate average mantle residence temperatures of ˜1050 °C for a 1.85 Ga formation age, corresponding ˜170 km depth. Based on the available evidence from natural samples and experiments, we suggest that the highly siderophile elements (HSE: Os, Ir, Ru, Rh, Pd, Pt, Re) except Au behaved largely conservatively during fluid-induced metamorphism, which may point to a reducing and Cl-poor nature of the fluid. The abundances of the moderately siderophile and chalcophile elements Cr, Co, Ni, Cu, Ag, Sn, Mo and W may also have changed little, whereas As, Sb, Tl, Pb and Bi may have been mobilised from the subducting lower oceanic crust. The partitioning of CSE in eclogite and geochemical behaviour during oceanic crust formation was assessed for inferred conservative elements. Assuming an average sulphide mode of 0.3 wt.% for the oceanic crust, its abundances of HSE, Cu, Mo, Se and Te can mostly be accounted for by sulphide minerals alone. Lithophile behaviour of W, Cd, In and Sn and enrichment in residual melts may explain their lower abundances in the gabbroic eclogitic sulphide inclusions compared to MORB sulphide. These elements, as well as Cr, Co, Ni, Zn and Ga require additional host phases both in eclogite, where rutile partitions significant amounts of Cr, Zn, W, Ga and Sn, and in the oceanic crust.
Geochemistry of Martian Meteorites and the Petrologic Evolution of Mars
NASA Technical Reports Server (NTRS)
Mittlefehldt, D. W.
2002-01-01
Mafic igneous rocks serve as probes of the interiors of their parent bodies - the compositions of the magmas contain an imprint of the source region composition and mineralogy, the melting and crystallization processes, and mixing and assimilation. Although complicated by their multifarious history, it is possible to constrain the petrologic evolution of an igneous province through compositional study of the rocks. Incompatible trace elements provide one means of doing this. I will use incompatible element ratios of martian meteorites to constrain the early petrologic evolution of Mars. Incompatible elements are strongly partitioned into the melt phase during igneous processes. The degree of incompatibility will differ depending on the mineral phases in equilibrium with the melt. Most martian meteorites contain some cumulus grains, but nevertheless, incompatible element ratios of bulk meteorites will be close to those of their parent magmas. ALH 84001 is an exception, and it will not be discussed. The martian meteorites will be considered in two groups; a 1.3 Ga group composed of the clinopyroxenites and dunite, and a younger group composed of all others.
NASA Astrophysics Data System (ADS)
Andersen, N. L.; Dufek, J.; Singer, B. S.
2017-12-01
Magma reservoirs in the middle to upper crust are though to accumulate incrementally over 104 -105 years. Coupled crystallization ages and compositions of zircon are a potentially powerful tracer of reservoir growth and magma evolution. However, complex age distributions and disequilibrium trace element partitioning complicate the interpretation of the zircon record in terms of magmatic processes. In order to make quantitative predictions of the effects of magmatic processes that contribute reservoir growth and evolution—such as cooling and crystallization, magma recharge and mixing, and rejuvenation and remelting of cumulate-rich reservoir margins—we develop a model of zircon saturation and growth within a numerical framework of coupled thermal transfer, phase equilibrium, and magma dynamics. We apply this model to the Laguna del Maule volcanic field (LdM), located in central Chile. LdM has erupted at least 40 km3 of rhyolite from 36 vents distributed within a 250 km2 lake basin. Ongoing unrest demonstrates the large, silicic magma system beneath LdM remains active to this day. Zircon from rhyolite erupted between c. 23 and 1.8 ka produce a continuous distribution of 230Th-238U ages ranging from eruption to 40 ka, as well as less common crystal domains up to 165 ka and rare xenocrysts. Zircon trace element compositions fingerprint compositionally distinct reservoirs that grew within the larger magma system. Despite the dominantly continuous distributions of ages, many crystals are characterized by volumetrically substantial, trace element enriched domains consistent with rapid crystal growth. We utilize numerical simulations to assess the magmatic conditions required to catalyze these "blooms" of crystallization and the magma dynamics that contributed to the assembly of the LdM magma system.
Sorensen, Sorena S.; Grossman, J.N.
1989-01-01
The abundance, P-T stability, solubility, and element-partitioning behavior of minerals such as rutile, garnet, sphene, apatite, zircon, zoisite, and allanite are critical variables in models for mass transfer from the slab to the mantle wedge in deep regions of subduction zones. The influence of these minerals on the composition of subduction-related magmas has been inferred (and disputed) from inverse modelling of the geochemistry of island-arc basalt, or by experiment. Although direct samples of the dehydration + partial-melting region of a mature subduction zone have not been reported from subduction complexes, garnet amphibolites from melanges of circumpacific and Caribbean blueschist terranes reflect high T (>600??C) conditions in shallower regions. Such rocks record geochemical processes that affected deep-seated, high-T portions of paleo-subduction zones. In the Catalina Schist, a subduction-zone metamorphic terrane of southern California, metasomatized and migmatitic garnet amphibolites occur as blocks in a matrix of meta-ultramafic rocks. This mafic and ultramafic complex may represent either slab-derived material accreted to the mantle wedge of a nascent subduction zone or a portion of a shear zone closely related to the slab-mantle wedge contact, or both. The trace-element geochemistry of the complex and the distribution of trace elements among the minerals of garnet amphibolites were studied by INAA, XRF, electron microprobe, and SEM. In order of increasing alteration from a probable metabasalt protolith, three common types of garnet amphibolite blocks in the Catalina Schist are: (1) non-migmatitic, clinopyroxene-bearing blocks, which are compositionally similar to MORB that has lost an albite component; (2) garnet-amphibolite blocks, which have rinds that reflect local interaction between metabasite, metaperidotite, and fluid; and (3) migmatites that are extremely enriched in Th, HFSE, LREE, and other trace elements. These trace-element enrichments are mineralogically controlled by rutile, garnet, sphene, apatite, zircon, zoisite, and allanite. Alkali and alkaline earth elements are much less enriched in the solid assemblage, and thus appear to be decoupled from the other elements in the inferred metasomatic process(es). The compositions of migmatitic garnet amphibolite blocks seem to complement that of "average" island-arc tholeiite. Trace-element metasomatism reflects fluid-solid, rather than melt-solid, interaction. The metasomatic effects indicate that H2O-rich fluid, perhaps with a significant component of Na-Al silicate and alkalis, carried Th, U, Sr, REE, and HFSE. Fractionations of LREE in migmatites resemble those of migmatitic metasedimentary rocks underlying the mafic and ultramafic complex. "Exotic" LREE deposited in allanite in migmatites could have been derived from fluids in equilibrium with subducted sediment. If the paleo-subduction zone represented by the mafic and ultramafic complex of the Catalina Schist had continued its thermal and fluid evolution, a selvage of similarly enriched rocks might have been generated along the slab-mantle wedge contact between ~30 and 85 km depth. Rocks affected by "subduction-zone metasomatism," although rarely recognized at the surface, could be volumetrically significant products of the initiation of subduction and may prove to be geochemical probes of convergent margins that approach the significance of xenoliths in the study of other magmatic environments. ?? 1989.
Effect of Sulfur on Siderophile Element Partitioning Between Olivine and Martian Primary Melt
NASA Technical Reports Server (NTRS)
Usui, T.; Shearer, C. K.; Righter, K.; Jones, J. H.
2011-01-01
Since olivine is a common early crystallizing phase in basaltic magmas that have produced planetary and asteroidal crusts, a number of experimental studies have investigated elemental partitioning between olivine and silicate melt [e.g., 1, 2, 3]. In particular, olivine/melt partition coefficients of Ni and Co (DNi and DCo) have been intensively studied because these elements are preferentially partitioned into olivine and thus provide a uniquely useful insight into the basalt petrogenesis [e.g., 4, 5]. However, none of these experimental studies are consistent with incompatible signatures of Co [e.g., 6, 7, 8] and Ni [7] in olivines from Martian meteorites. Chemical analyses of undegassed MORB samples suggest that S dissolved in silicate melts can reduce DNi up to 50 % compared to S-free experimental systems [9]. High S solubility (up to 4000 ppm) for primitive shergottite melts [10] implies that S might have significantly influenced the Ni and Co partitioning into shergottite olivines. This study conducts melting experiments on Martian magmatic conditions to investigate the effect of S on the partitioning of siderophile elements between olivine and Martian primary melt.
REE Incorporation into Calcite Individual Crystals as One Time Spike Addition
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gabitov, Rinat; Sadekov, Aleksey; Migdisov, Artas
Experiments on the incorporation of trace elements into calcite were performed, and rare earth elements (REE) were used to mark the growth zones of individual crystals. Experiments were conducted at different pH (7.7 to 8.8) and temperatures (2 °C to 24.6 °C) in NH 4Cl + CaCl 2 solutions, where REE were rapidly consumed by growing calcite. LA-ICP-MS line-scans yielded the distribution of (REE/Ca) calcite within individual crystals in a manner consistent with the addition of REE into fluid. A sharp decrease of (REE/Ca) calcite toward the crystal edge suggests the fast depletion of (REE/Ca) fluid due to strong REEmore » consumption by growing calcite. An attempt was made to estimate the lower limit of the partition coefficients between calcite and fluid using selected REE/Ca data within individual calcite crystals and the amount of REE added into fluid.« less
REE Incorporation into Calcite Individual Crystals as One Time Spike Addition
Gabitov, Rinat; Sadekov, Aleksey; Migdisov, Artas
2017-10-26
Experiments on the incorporation of trace elements into calcite were performed, and rare earth elements (REE) were used to mark the growth zones of individual crystals. Experiments were conducted at different pH (7.7 to 8.8) and temperatures (2 °C to 24.6 °C) in NH 4Cl + CaCl 2 solutions, where REE were rapidly consumed by growing calcite. LA-ICP-MS line-scans yielded the distribution of (REE/Ca) calcite within individual crystals in a manner consistent with the addition of REE into fluid. A sharp decrease of (REE/Ca) calcite toward the crystal edge suggests the fast depletion of (REE/Ca) fluid due to strong REEmore » consumption by growing calcite. An attempt was made to estimate the lower limit of the partition coefficients between calcite and fluid using selected REE/Ca data within individual calcite crystals and the amount of REE added into fluid.« less
THE INFLUENCE OF IRON AND SULFUR CYCLING ON ARSENIC PARTITIONING IN SOILS AND SEDIMENTS
Field evidence suggests that arsenic solid-solution partitioning in natural systems is often tied to iron and sulfur cycling. This is likely due to the coprecipitation of arsenic as a trace component in poorly crystalline iron oxides and monosulfides. However, there is limited ...
NASA Astrophysics Data System (ADS)
Bosze, Stephanie; Rakovan, John
2002-03-01
The concentration and distribution of rare earth elements (REE) in sectorally zoned fluorite crystals from Long Lake, New York, and the Hansonburg Mining District, Bingham, New Mexico, have been studied using cathodoluminescence and synchrotron X-ray fluorescence microanalysis (SXRFMA). In cubo-octahedral samples from Long Lake, New York, Ce, Nd, Gd, Dy, Ho, Er, and Tm are preferentially partitioned into the |111| sector relative to the |100| sector. Partition coefficients (K d = concentration in |111| sector/concentration in |100| sector) range between 3.5 for Ce, to 1.4 for Tm, with a general decrease in K d as elements deviated from the ionic radius of Ca 2+, for which REE substitute in fluorite. Diffusion of the REE has occurred, as evidenced by gradual changes in composition over distances of 0.2 to 0.3 mm at sector boundaries. In Bingham samples, three different partition coefficients were determined for Dy: K d|100|/|111| = 2.83, K d |100|/|110| = 1.77, and K d |110|/|111| = 1.60. These are mean K d values for a 95% confidence interval. In another sample from the same deposit, Dy, Er, and Gd were found to be preferentially incorporated into the |100| sector relative to the |210| sector with average K d |100|/|210| of 3.1, 2.4, and 2.9, respectively. In a third sample, Nd was found to be preferentially incorporated into the |110| sector relative to the |321| sector with an average K d |110|/|321| value of 2.3. Compositional heterogeneities in a given sector (concentric zoning) have been resolved using SXRFMA but are significantly less than the concentration difference across sector boundaries. Often fluorite exists in a wide variety of morphologies, as is the case in the Hansonburg Mining District of Bingham. We suggest caution when using the REE as petrogenetic indicators because fluorite trace element chemistry can vary greatly among crystals within a deposit depending on the internal morphology of a particular crystal.
NASA Astrophysics Data System (ADS)
Righter, K.; Pando, K.; Humayun, M.; Waeselmann, N.; Yang, S.; Boujibar, A.; Danielson, L. R.
2018-07-01
Earth's core contains ∼10% of a light element that may be a combination of Si, S, C, O or H, with Si potentially being the major light element. Metal-silicate partitioning of siderophile elements can place important constraints on the P-T-fO2 and composition of the early Earth, but the effect of Si alloyed in Fe liquids is unknown for many of these elements. In particular, the effect of Si on the partitioning of highly siderophile elements (Au, Re and PGE) is virtually unknown. To address this gap in understanding, we have undertaken a systematic study of the highly siderophile elements Au, Pd, and Pt, and the volatile siderophile elements P, Ga, Cu, Zn, and Pb at variable Si content of metal, and 1600 °C and 1 GPa. From our experiments we derive epsilon interaction parameters between these elements and Si in Fe metallic liquids. The new parameters are used to update an activity model for trace siderophile elements in Fe alloys; Si causes large variation in the magnitude of activity coefficients of these elements in FeSi liquids. Because the interaction parameters are all positive, Si causes a decrease in their metal/silicate partition coefficients. We combine these new activity results with experimental studies of Au, Pd, Pt, P, Ga, Cu, Zn and Pb, to derive predictive expressions for metal/silicate partition coefficients which can then be applied to Earth. The expressions are applied to two scenarios for continuous accretion of Earth; specifically for constant and increasing fO2 during accretion. The results indicate that mantle concentrations of P, Ga, Cu, Zn, and Pb can be explained by metal-silicate equilibrium during accretion of the Earth where Earth's early magma ocean deepens to pressures of 40-60 GPa. Au, Pd, and Pt, on the other hand become too high in the mantle in such a scenario, and require a later removal mechanism, rather than an addition as traditionally argued. A late reduction event that removes 0.5% metal from a shallow magma ocean can lower the Au, Pd, and Pt contents to values near the current day BSE. On the other hand, removal of 0.2-1.0% of a late sulfide-rich matte to the core would lower the Au, Pd, and Pt concentrations in the mantle, but not to chondritic relative concentrations observed in the BSE. If sulfide matte is called upon to remove HSEs, they must be later added via a late veneer to re-establish the high and chondritic relative PUM concentrations. These results suggest that although accretion and core formation (involving a Si, S, and C-bearing metallic liquid) were the primary processes establishing many of Earth's mantle volatile elements and HSE, a secondary removal process is required to establish HSEs at their current and near-chondritic relative BSE levels. Mn and P - two siderophile elements that are central to biochemical processes (photosynthesis and triphosphates, respectively) - have significant and opposite interactions with FeSi liquids, and their mantle concentrations would be notably different if Earth had a Si-free core.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Achariya Suriyawong; Rogan Magee; Ken Peebles
2009-05-15
This paper presents the results of an experimental study of particulate emission and the fate of 13 trace elements (arsenic (As), barium (Ba), cadmium (Cd), chromium (Cr), copper (Cu), cobalt (Co), manganese (Mn), molybdenum (Mo), nickel (Ni), lead (Pb), mercury (Hg), vanadium (V), and zinc (Zn)) during combustion tests of recovered paint solids (RPS) and coal. The emissions from combustions of coal or RPS alone were compared with those of co-combustion of RPS with subbituminous coal. The distribution/partitioning of these toxic elements between a coarse-mode ash (particle diameter (d{sub p}) > 0.5 {mu}m), a submicrometer-mode ash (d{sub p} < 0.5more » {mu}m), and flue gases was also evaluated. Submicrometer particles generated by combustion of RPS alone were lower in concentration and smaller in size than that from combustion of coal. However, co-combustion of RPS and coal increased the formation of submicrometer-sized particles because of the higher reducing environment in the vicinity of burning particles and the higher volatile chlorine species. Hg was completely volatilized in all cases; however, the fraction in the oxidized state increased with co-combustion. Most trace elements, except Zn, were retained in ash during combustion of RPS alone. Mo was mostly retained in all samples. The behavior of elements, except Mn and Mo, varied depending on the fuel samples. As, Ba, Cr, Co, Cu, and Pb were vaporized to a greater extent from cocombustion of RPS and coal than from combustion of either fuel. Evidence of the enrichment of certain toxic elements in submicrometer particles has also been observed for As, Cd, Cr, Cu, and Ni during co-combustion. 27 refs., 6 figs., 5 tabs.« less
Rutile solubility in NaF–NaCl–KCl-bearing aqueous fluids at 0.5–2.79GPa and 250–650°C
Tanis, Elizabeth A.; Simon, Adam; Zhang, Youxue; ...
2016-01-14
The complex nature of trace element mobility in subduction zone environments is thought to be primarily controlled by fluid-rock interactions, episodic behavior of fluids released, mineral assemblages, and element partitioning during phase transformations and mineral breakdown throughout the transition from hydrated basalt to blueschist to eclogite. Quantitative data that constrain the partitioning of trace elements between fluid(s) and mineral(s) are required in order to model trace element mobility during prograde and retrograde metamorphic fluid evolution in subduction environments. The stability of rutile has been proposed to control the mobility of HFSE during subduction, accounting for the observed depletion of Nbmore » and Ta in arc magmas. Recent experimental studies demonstrate that the solubility of rutile in aqueous fluids at temperatures >700 degrees C and pressures <2 GPa increases by several orders of magnitude relative to pure H2O as the concentrations of ligands (e.g., F and Cl) in the fluid increase. Considering that prograde devolatilization in arcs begins at similar to 300 degrees C, there is a need for quantitative constraints on rutile solubility and the partitioning of HFSE between rutile and aqueous fluid over a wider range of temperature and pressure than is currently available. In this study, new experimental data are presented that quantify the solubility of rutile in aqueous fluids from 0.5 to 2.79 GPa and 250 to 650 degrees C. Rutile solubility was determined by using synchrotron X-ray fluorescence to measure the concentration of Zr in an aqueous fluid saturated with a Zr-bearing rutile crystal within a hydrothermal diamond anvil cell. At the PT conditions of the experiments, published diffusion data indicate that Zr is effectively immobile (log D-Zr similar to 10(-25) m(2)/s at 650 degrees C and similar to 10(-30) m(2)/s at 250 degrees C) with diffusion length-scales of <0.2 mu m in rutile for our run durations (<10 h). Hence, the Zr/Ti ratio of the starting rutile, which was quantified, does not change during the experiment, and the measured concentration of Zr in the fluid was used to calculate the concentration of Ti (i.e., the solubility of rutile) in the fluid. The salts NaF, NaCl, and KCl were systematically added to the aqueous fluid, and the relative effects of fluid composition, pressure, and temperature on rutile solubility were quantified. The results indicate that fluid composition exerts the greatest control on rutile solubility in aqueous fluid, consistent with previous studies, and that increasing temperature has a positive, albeit less pronounced, effect. The solubility of Zr-rutile in aqueous fluid increases with the addition of halides in the following order: 2 wt% NaF < 30 wt% KCl < 30 wt% NaCl < 3 wt% NaF < (10 wt% NaCl + 2 wt% NaF) < 4 wt% NaF. The solubility of rutile in the fluid increases with the 2nd to 3rd power of the Cl- concentration, and the 3rd to 4th power of the F- concentration. These new data are consistent with observations from field studies of exhumed terranes that indicate that rutile is soluble in complex aqueous fluids, and that fluid composition is the primary control on rutile solubility and HFSE mobility« less
Rutile solubility in NaF-NaCl-KCl-bearing aqueous fluids at 0.5-2.79 GPa and 250-650 °C
NASA Astrophysics Data System (ADS)
Tanis, Elizabeth A.; Simon, Adam; Zhang, Youxue; Chow, Paul; Xiao, Yuming; Hanchar, John M.; Tschauner, Oliver; Shen, Guoyin
2016-03-01
The complex nature of trace element mobility in subduction zone environments is thought to be primarily controlled by fluid-rock interactions, episodic behavior of fluids released, mineral assemblages, and element partitioning during phase transformations and mineral breakdown throughout the transition from hydrated basalt to blueschist to eclogite. Quantitative data that constrain the partitioning of trace elements between fluid(s) and mineral(s) are required in order to model trace element mobility during prograde and retrograde metamorphic fluid evolution in subduction environments. The stability of rutile has been proposed to control the mobility of HFSE during subduction, accounting for the observed depletion of Nb and Ta in arc magmas. Recent experimental studies demonstrate that the solubility of rutile in aqueous fluids at temperatures >700 °C and pressures <2 GPa increases by several orders of magnitude relative to pure H2O as the concentrations of ligands (e.g., F and Cl) in the fluid increase. Considering that prograde devolatilization in arcs begins at ∼300 °C, there is a need for quantitative constraints on rutile solubility and the partitioning of HFSE between rutile and aqueous fluid over a wider range of temperature and pressure than is currently available. In this study, new experimental data are presented that quantify the solubility of rutile in aqueous fluids from 0.5 to 2.79 GPa and 250 to 650 °C. Rutile solubility was determined by using synchrotron X-ray fluorescence to measure the concentration of Zr in an aqueous fluid saturated with a Zr-bearing rutile crystal within a hydrothermal diamond anvil cell. At the PT conditions of the experiments, published diffusion data indicate that Zr is effectively immobile (log DZr ∼10-25 m2/s at 650 °C and ∼10-30 m2/s at 250 °C) with diffusion length-scales of <0.2 μm in rutile for our run durations (<10 h). Hence, the Zr/Ti ratio of the starting rutile, which was quantified, does not change during the experiment, and the measured concentration of Zr in the fluid was used to calculate the concentration of Ti (i.e., the solubility of rutile) in the fluid. The salts NaF, NaCl, and KCl were systematically added to the aqueous fluid, and the relative effects of fluid composition, pressure, and temperature on rutile solubility were quantified. The results indicate that fluid composition exerts the greatest control on rutile solubility in aqueous fluid, consistent with previous studies, and that increasing temperature has a positive, albeit less pronounced, effect. The solubility of Zr-rutile in aqueous fluid increases with the addition of halides in the following order: 2 wt% NaF < 30 wt% KCl < 30 wt% NaCl < 3 wt% NaF < (10 wt% NaCl + 2 wt% NaF) < 4 wt% NaF. The solubility of rutile in the fluid increases with the 2nd to 3rd power of the Cl- concentration, and the 3rd to 4th power of the F- concentration. These new data are consistent with observations from field studies of exhumed terranes that indicate that rutile is soluble in complex aqueous fluids, and that fluid composition is the primary control on rutile solubility and HFSE mobility.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tanis, Elizabeth A.; Simon, Adam; Zhang, Youxue
The complex nature of trace element mobility in subduction zone environments is thought to be primarily controlled by fluid-rock interactions, episodic behavior of fluids released, mineral assemblages, and element partitioning during phase transformations and mineral breakdown throughout the transition from hydrated basalt to blueschist to eclogite. Quantitative data that constrain the partitioning of trace elements between fluid(s) and mineral(s) are required in order to model trace element mobility during prograde and retrograde metamorphic fluid evolution in subduction environments. The stability of rutile has been proposed to control the mobility of HFSE during subduction, accounting for the observed depletion of Nbmore » and Ta in arc magmas. Recent experimental studies demonstrate that the solubility of rutile in aqueous fluids at temperatures >700 degrees C and pressures <2 GPa increases by several orders of magnitude relative to pure H2O as the concentrations of ligands (e.g., F and Cl) in the fluid increase. Considering that prograde devolatilization in arcs begins at similar to 300 degrees C, there is a need for quantitative constraints on rutile solubility and the partitioning of HFSE between rutile and aqueous fluid over a wider range of temperature and pressure than is currently available. In this study, new experimental data are presented that quantify the solubility of rutile in aqueous fluids from 0.5 to 2.79 GPa and 250 to 650 degrees C. Rutile solubility was determined by using synchrotron X-ray fluorescence to measure the concentration of Zr in an aqueous fluid saturated with a Zr-bearing rutile crystal within a hydrothermal diamond anvil cell. At the PT conditions of the experiments, published diffusion data indicate that Zr is effectively immobile (log D-Zr similar to 10(-25) m(2)/s at 650 degrees C and similar to 10(-30) m(2)/s at 250 degrees C) with diffusion length-scales of <0.2 mu m in rutile for our run durations (<10 h). Hence, the Zr/Ti ratio of the starting rutile, which was quantified, does not change during the experiment, and the measured concentration of Zr in the fluid was used to calculate the concentration of Ti (i.e., the solubility of rutile) in the fluid. The salts NaF, NaCl, and KCl were systematically added to the aqueous fluid, and the relative effects of fluid composition, pressure, and temperature on rutile solubility were quantified. The results indicate that fluid composition exerts the greatest control on rutile solubility in aqueous fluid, consistent with previous studies, and that increasing temperature has a positive, albeit less pronounced, effect. The solubility of Zr-rutile in aqueous fluid increases with the addition of halides in the following order: 2 wt% NaF < 30 wt% KCl < 30 wt% NaCl < 3 wt% NaF < (10 wt% NaCl + 2 wt% NaF) < 4 wt% NaF. The solubility of rutile in the fluid increases with the 2nd to 3rd power of the Cl- concentration, and the 3rd to 4th power of the F- concentration. These new data are consistent with observations from field studies of exhumed terranes that indicate that rutile is soluble in complex aqueous fluids, and that fluid composition is the primary control on rutile solubility and HFSE mobility« less
NASA Astrophysics Data System (ADS)
Tolu, Julie; Thiry, Yves; Potin-gautier, Martine; Le hécho, Isabelle; Bueno, Maïté
2013-04-01
Selenium is an element of environmental concern given its dual beneficial and toxic character to animal and human health. Its radioactive isotope 79Se, a fission product of 235U, is considered critical in safety assessment of nuclear waste repositories in case of leakage and hypothetical soil contamination. Therefore, Se species transformations and interactions with soil components have to be clearly understood to predict its dispersion in the biosphere (e.g., accumulation in soils, migration to waters, transfer to living organisms). While natural Se interactions with soils run over centuries to millennia time scales, transformations and partitioning are generally studied with short-term experiments (often inferior to 1 month) after Se addition. The influence of slower, long-term processes involved in Se speciation and mobility in soils is thus not properly accounted for. We tested if using ambient Se would be relevant for long-term risk assessment while added Se would be more representative of short-term contamination impact. For that purpose, we developed a new methodology to trace the differential reactivity of ambient and spiked Se at trace level (µg kg-1) in soils. It combined the use of a stable isotopically enriched tracer with our previous published analytical method based on specific extractions and HPLC-ICP-MS to determine trace Se species partition in different soil phases. Given that soil extracts contains very high concentrations of various elements interfering Se (e.g., Fe, Cl, Br), the ICP-MS parameters and mathematical corrections were optimized to cope with such interferences. Following optimization, three correct and accurate (<2%) isotope ratios were obtained with 77Se, 78Se, 80Se and 82Se. The optimized method was then applied to an arable and a forest soil submitted to an aging process (drying/wetting cycles) during three months, to which 77Se(IV) was previously added. The results showed that ambient Se was at steady state in terms of water leachability, partition between soil solid phases (exchangeable Se and Se associated to organic matter) and speciation. At the opposite, the retention strength, solid phase partition and speciation of 77Se(IV) were modified during the experiment time-course and presented different kinetics. 77Se(IV) behavior tended to be similar to the one of ambient Se but still remained less strongly retained and chemically transformed at three months. We concluded that kinetically limited processes are involved in Se retention and transformation in soils and that commonly used short-term experiments (<1 month) do not consider them properly. Otherwise, it seems more judicious to study ambient Se to infer the processes and parameters used in long-term risk assessment modeling. Since three correct and accurate Se isotope ratios were obtained, this new methodology can be further used to simultaneous monitor the reactivity of three different Se forms (e.g., added Se(IV), Se(VI) or Se(0), ambient Se), that will be useful for both soil Se contamination and supplementation contexts.
Trace element distributions in the water column near the Deepwater Horizon well blowout.
Joung, DongJoo; Shiller, Alan M
2013-03-05
To understand the impact of the Deepwater Horizon well blowout on dissolved trace element concentrations, samples were collected from areas around the oil rig explosion site during four cruises in early and late May 2010, October 2010, and October 2011. In surface waters, Ba, Fe, Cu, Ni, Mn, and Co were relatively well correlated with salinity during all cruises, suggesting mixing with river water was the main influence on metal distributions in these waters. However, in deep oil/gas plumes (1000-1400 m depth), modestly elevated concentrations of Co and Ba were observed in late May, compared with postblowout conditions. Analysis of the oil itself along with leaching experiments confirm the oil as the source of the Co, whereas increased Ba was likely due to drilling mud used in the top kill attempt. Deep plume dissolved Mn largely reflected natural benthic input, though some samples showed slight elevation probably associated with the top kill. Dissolved Fe concentrations were low and also appeared largely topographically controlled and reflective of benthic input. Estimates suggest that microbial Fe demand may have affected the Fe distribution but probably not to the extent of Fe becoming a growth-limiting factor. Experiments showed that the dispersant can have some limited impact on dissolved-particulate metal partitioning.
Shear Stress Partitioning in Large Patches of Roughness in the Atmospheric Inertial Sublayer
NASA Technical Reports Server (NTRS)
Gillies, John A.; Nickling, William G.; King, James
2007-01-01
Drag partition measurements were made in the atmospheric inertial sublayer for six roughness configurations made up of solid elements in staggered arrays of different roughness densities. The roughness was in the form of a patch within a large open area and in the shape of an equilateral triangle with 60 m long sides. Measurements were obtained of the total shear stress (tau) acting on the surfaces, the surface shear stress on the ground between the elements (tau(sub S)) and the drag force on the elements for each roughness array. The measurements indicated that tau(sub S) quickly reduced near the leading edge of the roughness compared with tau, and a tau(sub S) minimum occurs at a normalized distance (x/h, where h is element height) of approx. -42 (downwind of the roughness leading edge is negative), then recovers to a relatively stable value. The location of the minimum appears to scale with element height and not roughness density. The force on the elements decreases exponentially with normalized downwind distance and this rate of change scales with the roughness density, with the rate of change increasing as roughness density increases. Average tau(sub S): tau values for the six roughness surfaces scale predictably as a function of roughness density and in accordance with a shear stress partitioning model. The shear stress partitioning model performed very well in predicting the amount of surface shear stress, given knowledge of the stated input parameters for these patches of roughness. As the shear stress partitioning relationship within the roughness appears to come into equilibrium faster for smaller roughness element sizes it would also appear the shear stress partitioning model can be applied with confidence for smaller patches of smaller roughness elements than those used in this experiment.
Horta-Puga, Guillermo
2017-03-15
The fate of trace elements in reef depositional environments has not been extensively investigated. The aim of this study was to determine the partitioning of Pb in sediments of the Veracruz Reef System, and its relation to local environmental sources. Lead was determined in four geochemical fractions: exchangeable (3.8±0.4μgg -1 ), carbonate (57.0±13.6μgg -1 ), organic matter (2.0±0.9μgg -1 ), and mineral (17.5±5.4μgg -1 ). For the mineral fraction, lead concentrations were higher in those reefs influenced by river discharge or by long-distance transport of terrigenous sediments. The bioavailable concentration of lead (range: 21.9-85.6μgg -1 ) indicates that the Veracruz Reef System is a moderately polluted area. As expected, the carbonate fraction contained the highest proportion of Pb (70%), and because the reef framework is largely made up of by biogenic carbonate sediments, hence, it is therefore the most important repository of Pb in coral reef depositional environments. Copyright © 2016 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Churnet, Habte G.; Misra, Kula C.
1981-11-01
The Lower Ordovician, Upper Knox Group rocks (the Kingsport and Mascot formations) in the Copper Ridge district consist predominantly of fine-grained dolostones, medium and coarser grained dolostones, and limestones. Dolomite crystals of medium and coarser grained dolostones show up to eight cathodoluminescent zones of variable width and intensity. Electron microprobe analyses indicate that the zoning is related to variation in Fe/Mn ratios, the brighter luminescent zones corresponding to lower ratios. Superposed on this growth zoning is a compositional zoning characterized by a general increase in Fe from core to rim of individual dolomite crystals. Field and petrographic studies (Churnet, 1979; Churnet et al., 1981) indicate that the fine-grained dolostones formed in supratidal to upper intratidal environments, whereas the precursor lime muds of the limestones as well as of the medium and coarser grained dolostones formed in shallow subtidal to lower intertidal environments. The large areal extent of the dolostones must have required a regionally abundant source of Mg such as marine water. Yet, both limestones and dolostones have low Na and Sr contents suggestive of their formation in solutions more dilute than normal marine water. It is proposed that the fine-grained dolostones formed by aggradation of initially very fine-grained dolostones in presence of fresh water, and that the limestones stabilized and the medium and coarser grained dolostones formed in environments of mixed marine and fresh waters. Considered in the light of ordering of partition coefficients, such a mixing model can account for the observed correlation pattern of trace elements (especially, SMn and SrFe) as well as the Fe distribution in the zoned dolomite crystals. Variation of the partition coefficient of Mn due to fluctuations in the relative proportions of fresh and marine waters in the diagenetic solution may explain the different Fe/Mn ratios observed in the growth zones (luminescence bands) of zoned dolomite crystals.
Rosende, Maria; Savonina, Elena Yu; Fedotov, Petr S; Miró, Manuel; Cerdà, Víctor; Wennrich, Rainer
2009-09-15
Dynamic fractionation has been recognized as an appealing alternative to conventional equilibrium-based sequential extraction procedures (SEPs) for partitioning of trace elements (TE) in environmental solid samples. This paper reports the first attempt for harmonization of flow-through dynamic fractionation using two novel methods, the so-called sequential injection microcolumn (SIMC) extraction and rotating coiled column (RCC) extraction. In SIMC extraction, a column packed with the solid sample is clustered in a sequential injection system, while in RCC, the particulate matter is retained under the action of centrifugal forces. In both methods, the leachants are continuously pumped through the solid substrates by the use of either peristaltic or syringe pumps. A five-step SEP was selected for partitioning of Cu, Pb and Zn in water soluble/exchangeable, acid-soluble, easily reducible, easily oxidizable and moderately reducible fractions from 0.2 to 0.5 g samples at an extractant flow rate of 1.0 mL min(-1) prior to leachate analysis by inductively coupled plasma-atomic emission spectrometry. Similarities and discrepancies between both dynamic approaches were ascertained by fractionation of TE in certified reference materials, namely, SRM 2711 Montana Soil and GBW 07311 sediment, and two real soil samples as well. Notwithstanding the different extraction conditions set by both methods, similar trends of metal distribution were in generally found. The most critical parameters for reliable assessment of mobilizable pools of TE in worse-case scenarios are the size-distribution of sample particles, the density of particles, the content of organic matter and the concentration of major elements. For reference materials and a soil rich in organic matter, the extraction in RCC results in slightly higher recoveries of environmentally relevant fractions of TE, whereas SIMC leaching is more effective for calcareous soils.
A Dual Super-Element Domain Decomposition Approach for Parallel Nonlinear Finite Element Analysis
NASA Astrophysics Data System (ADS)
Jokhio, G. A.; Izzuddin, B. A.
2015-05-01
This article presents a new domain decomposition method for nonlinear finite element analysis introducing the concept of dual partition super-elements. The method extends ideas from the displacement frame method and is ideally suited for parallel nonlinear static/dynamic analysis of structural systems. In the new method, domain decomposition is realized by replacing one or more subdomains in a "parent system," each with a placeholder super-element, where the subdomains are processed separately as "child partitions," each wrapped by a dual super-element along the partition boundary. The analysis of the overall system, including the satisfaction of equilibrium and compatibility at all partition boundaries, is realized through direct communication between all pairs of placeholder and dual super-elements. The proposed method has particular advantages for matrix solution methods based on the frontal scheme, and can be readily implemented for existing finite element analysis programs to achieve parallelization on distributed memory systems with minimal intervention, thus overcoming memory bottlenecks typically faced in the analysis of large-scale problems. Several examples are presented in this article which demonstrate the computational benefits of the proposed parallel domain decomposition approach and its applicability to the nonlinear structural analysis of realistic structural systems.
NASA Astrophysics Data System (ADS)
Dare, Sarah A. S.; Barnes, Sarah-Jane; Beaudoin, Georges
2012-07-01
Laser ablation ICP-MS analysis has been applied to many accessory minerals in order to understand better the process by which the rock formed and for provenance discrimination. We have determined trace element concentrations of Fe-oxides in massive sulfides that form Ni-Cu-PGE deposits at the base of the Sudbury Igneous Complex in Canada. The samples represent the crystallization products of fractionating sulfide liquids and consist of early-forming Fe-rich monosulfide solution (MSS) cumulates and residual Cu-rich intermediate solid solution (ISS). This study shows that Fe-oxide geochemistry is a sensitive petrogenetic indicator for the degree of fractionation of the sulfide liquid and provides an insight into the partitioning of elements between sulfide and Fe-oxide phases. In addition, it is useful in determining the provenance of detrital Fe-oxide. In a sulfide melt, all lithophile elements (Cr, Ti, V, Al, Mn, Sc, Nb, Ga, Ge, Ta, Hf, W and Zr) are compatible into Fe-oxide. The concentrations of these elements are highest in the early-forming Fe-oxide (titanomagnetite) which crystallized with Fe-rich MSS. Upon the continual crystallization of Fe-oxide from the sulfide liquid, the lithophile elements gradually decrease so that late-forming Fe-oxide (magnetite), which crystallized from the residual Cu-rich liquid, is depleted in these elements. This behavior is in contrast with Fe-oxides that crystallized from a fractionating silicate melt, whereby the concentration of incompatible elements, such as Ti, increases rather than decreases. The behavior of the chalcophile elements in magnetite is largely controlled by the crystallization of the sulfide minerals with only Ni, Co, Zn, Mo, Sn and Pb present above detection limit in magnetite. Nickel, Mo and Co are compatible in Fe-rich MSS and thus the co-crystallizing Fe-oxide is depleted in these elements. In contrast, magnetite that crystallized later from the fractionated liquid with Cu-rich ISS is enriched in Ni, Mo and Co because Fe-rich MSS is absent. The concentrations of Sn and Pb, which are incompatible with Fe-rich MSS, are highest in magnetite that formed from the fractionated Cu-rich liquid. At subsolidus temperatures, ilmenite exsolved from titanomagnetite whereas Al-spinel exsolved from the cores of some magnetite, locally redistributing the trace elements. However, during laser ablation ICP-MS analysis of these Fe-oxides both the magnetite and its exsolution products are ablated so that the analysis represents the original magmatic composition of the Fe-oxide that crystallized from the sulfide melt.
NASA Astrophysics Data System (ADS)
Buono, A. S.; Dasgupta, R.; Walker, D.
2011-12-01
Secular cooling of terrestrial planets is known to cause crystallization of a solid inner core from metallic liquid core. Fractionation of light and siderophile elements is important during such crystallization for evolution of outer core and possible core-mantle interaction. Thus far studies focused on a pure Fe inner core in simple binary systems but the effects of possible formation of a carbide inner core component on siderophile element partitioning in a multi-component system has yet to be looked at in detail. We investigated the effects of pressure and S content on partition coefficients (D) between cohenite and liquid in the Fe-Ni-S-C system. Multi-anvil experiments were performed at 3 and 6 GPa at 1150 °C, in an Fe-rich mix containing a constant C and Ni to which S contents of 0, 5, and 14 wt.% were added. All the mixes were doped with W, Re, Os, Pt, and Co. Samples were imaged and analyzed for Fe, Ni, S, and C using an EPMA. Fe, Ni, and trace elements were analyzed using a LA-ICP-MS. All the experiments produced cohenite and Fe-Ni-C±S liquid. Compared to solid-Fe/melt Ds [1-2], cohenite/melt Ds are lower for all elements except W. The light element (S+C) content of the liquid is the dominant controlling factor in siderophile element partitioning between cohenite and liquid as it is between crystalline Fe and liquid. In the cohenite-metallic melt experiments, D Ni decreases as S+C increases. Ni is excluded from the crystallizing solid if the solid is cohenite. We also find that in the Fe-Ni-S-C system, cohenite is stabilized to higher P than in the Fe-S-C system [3-5]. Similar to the Fe-metallic liquid systems the non-metal avoidance model [6] is applicable to the Fe3C-metallic liquid system studied here. Our study has implications for both the cores of smaller planets and the mantles of larger planets. If inner core forms a cohenite layer we would predict that depletions in the outer core will be less than they might be for Fe metal crystallization. For the mantle of the earth, which is thought to become Fe-Ni metal-saturated as shallow as 250 km, the sub-system Fe-Ni + C + S becomes relevant and Fe-Ni carbide rather than metallic Fe-Ni alloy may become the crystalline phase of interest. Our study implies that because the partition coefficients between cohenite and Fe-C-S melts are significantly lower than those between Fe-metal and S-rich liquid, in the presence of cohenite and Fe-C-S melt in the mantle, the mantle budget of Ni, Co, and Pt may be dominated by Fe-C-S liquid. W, Re, and Os will also be slightly enriched in C-rich Fe-Ni liquid over cohenite if the metal sub-system of interest is S-free. [1] Chabot et al., GCA 70, 1322-1335, 2006 [2] Chabot et al., GCA 72, 4146-4158, 2008 [3] Chabot et al., Meteorit. Planet. Sci. 42, 1735-1750, 2007 [4] Stewart et al., EPSL 284, 302-309, 2009 [5] Van Orman et al., EPSL 274, 250-257, 2008 [6] Jones, J.H., Malvin, D.J., Metall Mater Trans B 21, 697-706, 1990
NASA Astrophysics Data System (ADS)
Rushmer, T.; Corgne, A.
2008-12-01
One important method in which to gain insight into metallic liquid compositions and their ability to control HSE (highly siderophile element) distribution is through experimentation. Deformation experiments can additionally provide information into mechanisms and chemical consequences of dynamic liquid metal segregation under a variety of conditions. We report results on metallic liquid HSE compositions and their distribution from a set of deformation experiments on a natural H6 ordinary chondrite, performed under very reducing conditions and a series of phase equilibria experiments focused on HSE partitioning between Si-rich and S-rich Fe molten alloys. The deformation experiments were conducted at temperatures between 925°C and 950°C, at 1.3 GPa confining pressure with a strain rate of 10-4/s. Major element analyses of both silicate and metal phases show that they are considerably reduced and the typically lithophile elements are behaving like siderophiles. Fe-Ni-Si compositions are found in the shear zones produced during the deformation experiment. Metallic compositions also include (Mg,Fe,Ca)S, Fe-Ni-Si, FeP, and Fe-Ni-S quench metal. Silicate phases include forsterite (Fo92-96) and enstatite (En98). Highly siderophile element (HSE) concentrations have been measured in the sulphide ((Fe,Mg,Ca)S) and metal (Fe- Ni-Si) phases by LA-ICPMS and compared with results from an earlier set of experiments on the same material but which were not performed under reducing conditions. The partitioning of the PGE is modified by the changing conditions with elements such as Ir and Os having higher DMetal/Sulphide values under reducing conditions. Partitioning experiments between molten FeS and Ni-, Si-bearing molten Fe were performed at 1.5-5.0 GPa and 1500-1750° to further investigate this observation. The starting material is synthetic, doped with a range of trace and HSE elements. The results confirm the preference of the HSE for the metallic phase with DMetal/Sulphide > 100 in most cases, in contrast to Cu and Ag, which have D values near or below 1, respectively. Our results also suggest the possibility of significant PGE fractionation since D values are larger for Ir and Os and smaller for Pd and Au, with Pt, Ru, Rh having intermediate values. It is not clear with the present data set whether T and P variations can affect significantly HSE partitioning. These results have been applied to the most naturally reduced material we know, the Enstatite chondrites. Several E chondrites have bulk HSE data available, but no HSE data available on sulphide and metallic phases themselves. We have now a set of HSE data for individual metallic phases in several enstatite chondrites, both EH and ELs. The bulk data show that for elements such as Os and Pd, the abundances are positively correlated and overall Pd is much higher in abundance. We find in the experiments that DPd ranges between 10-100, but do not fully explain the bulk trends. Additional phases, such as FeP have therefore been analyzed and we find that Pd is concentrated in FeP and the presence of schreibersite may help explain the high Pd ratios (e.g. Pd/Ir) observed in the Enstatite chondrites.
NASA Astrophysics Data System (ADS)
Gelabert, A.; Wang, Y.; Gescher, J.; Ha, J.; Cordova, C. D.; Singer, D. M.; Spormann, A. M.; Trainor, T. P.; Eng, P. J.; Brown, G. E.
2006-12-01
Fe- and Al-(oxyhydr)oxides are among the most reactive mineral surfaces contacted by surface and ground waters, and thus they constitute important sorbents for heavy metal and metalloid ions. As microbial biofilms may be present as coatings on these minerals, they are likely to induce major changes in surface charges and sorption capacities for metal(loid) ions compared to biofilm-free mineral surfaces. In addition, the micro- environments in biofilms can be quite different from those in bulk solutions, which can enhance (or inhibit) metal adsorption on mineral surfaces and produce biominerals that are not predicted by equilibrium thermodynamics based on the bulk solution values. In order to provide a more quantitative understanding of these effects, we have carried out a study of the interaction of Zn(II), Pb(II), and As(V) with Shewanella oneidensis (wild type, EPS-deficient mutant, and ppx- and ppk-deficient mutants) grown on highly polished and oriented single crystal surfaces of α-Al2O3 (1-102) and α-Fe2O3 (0001). This gram-negative bacterium commonly found in soil and sediments can use a wide range of electron donors and terminal electron acceptors including Fe(III) and Mn(IV) oxides under anaerobic conditions. In-situ ATR-FTIR analyses and potentiometric titrations of S. oneidensis biofilm collected from a glass bead-filled column inoculated with S. oneidensis were conducted in order to determine the nature of functional groups present on the bacterial surfaces, to quantify the site densities and protonation constants for these groups, and to determine the electrostatic parameters for S. oneidensis surfaces. GI-XAFS analyses performed on BL 11-2 at SSRL, together with macroscopic metal adsorption experiments as a function of pH (2 to 6.5), metal concentration (10-3 to 10-7 M), and ionic strength (10-1 to 10-3 M), were used to determine ion speciation and local coordination environments in the biofilm and to develop a surface complexation model describing the interactions among biofilm, metal(loid)s, and mineral surfaces. The long-period X-ray Standing Wave- fluorescent yield (XSW-FY) method, performed on BL ID-13-C at the APS, was used to obtain quantitative in situ information on the partitioning of Zn(II), Pb(II), and As(V) at these interfaces as a function of pH and ion concentration. XSW-FY results show that S. oneidensis biofilms do not block reactive sites on the hematite or alumina surfaces under our experimental conditions, which is consistent with the conclusion of our previous studies on trace element distributions at Burkholderia cepacia/mineral/water interfaces. Comparison of the observed trace element partitioning measured by XSW-FY with theoretical predictions of partitioning through thermodynamic models (using binding constants of metal(loid)s with the biofilm determined in this study and published binding constants of metal(loid)s with mineral substrates) allows us to describe biofilm local microenvironments and to understand how the biofilm coatings affect the reactivity of mineral surfaces.
High Pressure/Temperature Metal Silicate Partitioning of Tungsten
NASA Technical Reports Server (NTRS)
Shofner, G. A.; Danielson, L.; Righter, K.; Campbell, A. J.
2010-01-01
The behavior of chemical elements during metal/silicate segregation and their resulting distribution in Earth's mantle and core provide insight into core formation processes. Experimental determination of partition coefficients allows calculations of element distributions that can be compared to accepted values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Tungsten (W) is a moderately siderophile element and thus preferentially partitions into metal versus silicate under many planetary conditions. The partitioning behavior has been shown to vary with temperature, silicate composition, oxygen fugacity, and pressure. Most of the previous work on W partitioning has been conducted at 1-bar conditions or at relatively low pressures, i.e. <10 GPa, and in two cases at or near 20 GPa. According to those data, the stronger influences on the distribution coefficient of W are temperature, composition, and oxygen fugacity with a relatively slight influence in pressure. Predictions based on extrapolation of existing data and parameterizations suggest an increased pressured dependence on metal/ silicate partitioning of W at higher pressures 5. However, the dependence on pressure is not as well constrained as T, fO2, and silicate composition. This poses a problem because proposed equilibration pressures for core formation range from 27 to 50 GPa, falling well outside the experimental range, therefore requiring exptrapolation of a parametereized model. Higher pressure data are needed to improve our understanding of W partitioning at these more extreme conditions.
Rare Earth Element Partition Coefficients from Enstatite/Melt Synthesis Experiments
NASA Technical Reports Server (NTRS)
Schwandt, Craig S.; McKay, Gordon A.
1997-01-01
Enstatite (En(80)Fs(19)Wo(01)) was synthesized from a hypersthene normative basaltic melt doped at the same time with La, Ce, Nd, Sm, Eu, Dy, Er, Yb and Lu. The rare earth element concentrations were measured in both the basaltic glass and the enstatite. Rare earth element concentrations in the glass were determined by electron microprobe analysis with uncertainties less than two percent relative. Rare earth element concentrations in enstatite were determined by secondary ion mass spectrometry with uncertainties less than five percent relative. The resulting rare earth element partition signature for enstatite is similar to previous calculated and composite low-Ca pigeonite signatures, but is better defined and differs in several details. The partition coefficients are consistent with crystal structural constraints.
The Contribution of Recycled Crust to Mantle Inventories of Trace elements, Hydrogen, and Carbon
NASA Astrophysics Data System (ADS)
Hirschmann, M. M.
2008-12-01
It is clear that crustal recycling has had a profound impact on the non-volatile trace element budget of the mantle, but its impact on mantle carbon and hydrogen are less well-understood. If an active crust recycling mechanism such as plate tectonics has operated since early in Earth history, and if magmatic production has diminished through time according to the decay in heat production, then the mass of recycled crust may dominate the mantle inventory of many trace elements. For example, Earth evolution models suggest time- integrated crust production equal to 7-15% of the mantle, and this accounts for ~25 to >100% of the mantle inventory of LREE and HFSE elements, depending on the mean concentration of these elements in the average crust produced. A key question is the role of recycling in the budgets of H and C. Consideration of the near-surface reservoirs and fluxes of C and H indicates that these principal volatiles have residence times of billions of years, and so they may be grouped with continental crust as a single long-lived near-surface geochemical reservoir (NSGR) that results from extraction from the mantle by melting combined with selective return to the mantle by subduction. The primitive mantle-normalized mass concentrations of H and C and the NSGR are equal to 90-200 and 1.5-18, respectively, with the primitive mantle inventories of H and C as the chief uncertainty. When the NSGR is plotted on a compatibility diagram, H and C form extreme positive and negative anomalies relative to their mineral/melt partition coefficients, meaning that there is much more H and much less C in the NSGR than would be predicted based solely on their magmatic flux from the mantle. The most straightforward interpretation is that H subduction is highly inefficient, but that recycled C amounts to at least half and possibly dominates the mantle C budget. This interpretation is supported by H/C mass ratios of the mantle sources inferred from undegassed oceanic basalts (H/C=0.75±0.25), which are substantially lower than that for the NSGR (H/C=1.95±0.15).
NASA Technical Reports Server (NTRS)
Medard, E.; Martin, A. M.; Righter, K.; Malouta, A.; Lee, C.-T.
2017-01-01
Most siderophile element concentrations in planetary mantles can be explained by metal/ silicate equilibration at high temperature and pressure during core formation. Highly siderophile elements (HSE = Au, Re, and the Pt-group elements), however, usually have higher mantle abundances than predicted by partitioning models, suggesting that their concentrations have been set by late accretion of material that did not equilibrate with the core. The partitioning of HSE at the low oxygen fugacities relevant for core formation is however poorly constrained due to the lack of sufficient experimental constraints to describe the variations of partitioning with key variables like temperature, pressure, and oxygen fugacity. To better understand the relative roles of metal/silicate partitioning and late accretion, we performed a self-consistent set of experiments that parameterizes the influence of oxygen fugacity, temperature and melt composition on the partitioning of Pt, one of the HSE, between metal and silicate melts. The major outcome of this project is the fact that Pt dissolves in an anionic form in silicate melts, causing a dependence of partitioning on oxygen fugacity opposite to that reported in previous studies.
NASA Astrophysics Data System (ADS)
Sandler, A.; Brenner, I. B.; Halicz, L.
1988-02-01
Waters of the northern watershed of Lake Kineret, sampled during the period 1978 1983, were analyzed for their major and trace element contents. The trace element concentrations of the major water sources of the watershed (the Dan and Banias springs) represent background values. After emergence, the waters are subjected to human activity. In crossing the populated and cultivated Hula Basin in man-made canals, the major and trace element contents increase. In comparison to the trace element concentrations, those of the major elements have narrow ranges and small temporal fluctuations. Trace element concentrations varied by 3 orders of magnitude, and temporal variations were large but not neccessarily seasonal. Point sources of trace elements were urban effluents, fish pond wastes, and peat soil drainage. The trace element concentrations decrease in the waters of the last segment of the Jordan River. All measured trace elements were below the criteria levels established by regulatory agencies. Several, however, were of the same order of magnitude. Addition of wastes from enhanced recycling, and morphologic modification of the final course of the Jordan River could result in increase in the trace element concentrations in the water.
Development of fly ash boards with thermal, acoustic and fire insulation properties.
Leiva, C; Arenas, C; Vilches, L F; Alonso-Fariñas, B; Rodriguez-Galán, M
2015-12-01
This paper presents an experimental analysis on a new board composed of gypsum and fly ashes from coal combustion, which are mutually compatible. Physical and mechanical properties, sound absorption coefficient, thermal properties and leaching test have been obtained. The mechanical properties showed similar values to other commercial products. As far as the acoustic insulation characteristics are concerned, sound absorption coefficients of 0.3 and 0.8 were found. The board presents a low thermal conductivity and a fire resistance higher than 50 min (for 4 cm of thickness). The leaching of trace elements was below the leaching limit values. These boards can be considered as suitable to be used in building applications as partitions. Copyright © 2015 Elsevier Ltd. All rights reserved.
Improving Unstructured Mesh Partitions for Multiple Criteria Using Mesh Adjacencies
Smith, Cameron W.; Rasquin, Michel; Ibanez, Dan; ...
2018-02-13
The scalability of unstructured mesh based applications depends on partitioning methods that quickly balance the computational work while reducing communication costs. Zhou et al. [SIAM J. Sci. Comput., 32 (2010), pp. 3201{3227; J. Supercomput., 59 (2012), pp. 1218{1228] demonstrated the combination of (hyper)graph methods with vertex and element partition improvement for PHASTA CFD scaling to hundreds of thousands of processes. Our work generalizes partition improvement to support balancing combinations of all the mesh entity dimensions (vertices, edges, faces, regions) in partitions with imbalances exceeding 70%. Improvement results are then presented for multiple entity dimensions on up to one million processesmore » on meshes with over 12 billion tetrahedral elements.« less
Improving Unstructured Mesh Partitions for Multiple Criteria Using Mesh Adjacencies
DOE Office of Scientific and Technical Information (OSTI.GOV)
Smith, Cameron W.; Rasquin, Michel; Ibanez, Dan
The scalability of unstructured mesh based applications depends on partitioning methods that quickly balance the computational work while reducing communication costs. Zhou et al. [SIAM J. Sci. Comput., 32 (2010), pp. 3201{3227; J. Supercomput., 59 (2012), pp. 1218{1228] demonstrated the combination of (hyper)graph methods with vertex and element partition improvement for PHASTA CFD scaling to hundreds of thousands of processes. Our work generalizes partition improvement to support balancing combinations of all the mesh entity dimensions (vertices, edges, faces, regions) in partitions with imbalances exceeding 70%. Improvement results are then presented for multiple entity dimensions on up to one million processesmore » on meshes with over 12 billion tetrahedral elements.« less
Qiang, Xue; Bing, Liang; Hui-yun, Wang; Lei, Liu
2006-01-01
An understanding of the dynamic behavior of trace elements leaching from coal mine spoil is important in predicting the groundwater quality. The relationship between trace element concentrations and leaching times, pH values of the media is studied. Column leaching tests conducted in the laboratory showed that there was a close correlation between pH value and trace element concentrations. The longer the leaching time, the higher the trace element concentrations. Different trace elements are differently affected by pH values of leaching media. A numerical model for water flow and trace element transport has been developed based on analyzing the characteristics of migration and transformation of trace elements leached from coal mine spoil. Solutions to the coupled model are accomplished by Eulerian-Lagrangian localized adjoint method. Numerical simulation shows that rainfall intensity determined maximum leaching depth. As rainfall intensity is 3.6ml/s, the outflow concentrations indicate a breakthrough of trace elements beyond the column base, with peak concentration at 90cm depth. And the subsurface pollution range has a trend of increase with time. The model simulations are compared to experimental results of trace element concentrations, with reasonable agreement between them. The analysis and modeling of trace elements suggested that the infiltration of rainwater through the mine spoil might lead to potential groundwater pollution. It provides theoretical evidence for quantitative assessment soil-water quality of trace element transport on environment pollution.
Trace elements in fish from Taihu Lake, China: levels, associated risks, and trophic transfer.
Hao, Ying; Chen, Liang; Zhang, Xiaolan; Zhang, Dongping; Zhang, Xinyu; Yu, Yingxin; Fu, Jiamo
2013-04-01
Concentrations of eight trace elements [iron (Fe), manganese (Mn), zinc (Zn), chromium (Cr), mercury (Hg), cadmium (Cd), lead (Pb), and arsenic (As)] were measured in a total of 198 samples covering 24 fish species collected from Taihu Lake, China, in September 2009. The trace elements were detected in all samples, and the total mean concentrations ranged from 18.2 to 215.8 μg/g dw (dry weight). The concentrations of the trace elements followed the sequence of Zn>Fe>Mn>Cr>As>Hg>Pb>Cd. The measured trace element concentrations in fish from Taihu Lake were similar to or lower than the reported values in fish around the world. The metal pollution index was used to compare the total trace element accumulation levels among various species. Toxabramis swinhonis (1.606) accumulated the highest level of the total trace elements, and Saurogobio dabryi (0.315) contained the lowest. The concentrations of human non-essential trace elements (Hg, Cd, Pb, and As) were lower than the allowable maximum levels in fish in China and the European Union. The relationships between the trace element concentrations and the δ(15)N values of fish species were used to investigate the trophic transfer potential of the trace elements. Of the trace elements, Hg might be biomagnified through the food chain in Taihu Lake if the significant level of p-value was set at 0.1. No biomagnification and biodilution were observed for other trace elements. Copyright © 2012 Elsevier Inc. All rights reserved.
Lyons, P.C.; Morelli, J.J.; Hercules, D.M.; Lineman, D.; Thompson-Rizer, C. L.; Dulong, F.T.
1990-01-01
A study of the elemental composition of intimately associated coal macerals in the English Swallow Wood coal bed was conducted using a laser microprobe mass analyser, and indicated a similar trace and minor elemental chemistry in the vitrinite and cutinite and a different elemental signature in the fusinite. Three to six sites were analysed within each maceral during the study by laser micro mass spectrometry (LAMMS). Al, Ba, Ca, Cl, Cr, Dy, F, Fe, Ga, K, Li, Mg, Na, S, Si, Sr, Ti, V, and Y were detected by LAMMS in all three macerals but not necessarily at each site analysed. The signal intensities of major isotopic peaks were normalized to the signal intensity of the m z 85 peak (C7H) to determine the relative minor- and trace-element concentrations among the three dominant macerals. The vitrinite and the cutinite were depleted in Ba, Ca, Dy, Li, Mg, Sr, and Y relative to their concentrations observed in the fusinite. The cutinite was distinguished over vitrinite by less Ti, V, Cr and Ca, and K Ca $ ??1 (relative signal intensities). The fusinite, relative to the cutinite and vitrinite, was relatively depleted in Cr, Sc, Ti, and V. The fusinite, as compared with both the cutinite and vitrinite, was relatively enriched in Ba, Ca, Dy, Li, Mg, Sr, and Y, and also showed the most intense m z 64, 65, 66 signals (possibly S2+, HS2+, H2S2+, respectively). The LAMMS data indicate a common source for most elements and selective loss from the maceral precursors in the peat or entrapment of certain elements as mineral matter, most likely during the peat stage or during early diagenesis. The relatively high amounts of Ba, Ca, Dy, Li, Mg, Sr, and Y in the fusinite are consistent with micron and submicron mineral-matter inclusions such as carbonates and Ca-Al phosphates (probably crandallite group minerals). Mineralogical data on the whole coal, the LAMMS chemistry of the vitrinite and cutinite, and scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDAX) of the elements in the macerals are consistent with the presence of micron and submicron inclusions of clays such as kaolinite, illite, and Ca-rich or Ca-bearing minerals (e.g. calcite, Ca-Al phosphates, and illite) which are different in kind and proportions in the three macerals. The variance as measured by the F-statistic for all three macerals indicates generally a nonuniform distribution of minor and trace elements in all three macerals, thus supporting a mineral-matter (inorganic) origin of the elements analysed. Exceptions are Al, K, Fe, Ga, and Sr in the vitrinite and cutinite, which is consistent with organic complexing or a uniform distribution of micron or submicron mineral matter such as illite and phosphate(s). ?? 1990.
The Effect of fO2 on Partition Coefficients of U and Th between Garnet and Silicate Melt
NASA Astrophysics Data System (ADS)
Huang, F.; He, Z.; Schmidt, M. W.; Li, Q.
2014-12-01
Garnet is one of the most important minerals controlling partitioning of U and Th in the upper mantle. U is redox sensitive, while Th is tetra-valent at redox conditions of the silicate Earth. U-series disequilibria have provided a unique tool to constrain the time-scales and processes of magmatism at convergent margins. Variation of garnet/meltDU/Th with fO2 is critical to understand U-series disequilibria in arc lavas. However, there is still no systematic experimental study about the effect of fO2 on partitioning of U and Th between garnet and melt. Here we present experiments on partitioning of U, Th, Zr, Hf, Nb, Ta, and REE between garnet and silicate melts at various fO2. The starting material was hydrous haplo-basalt. The piston cylinder experiments were performed with Pt double capsules with C-CO, MnO-Mn3O4 (MM), and hematite-magnetite (HM) buffers at 3 GPa and 1185-1230 oC. The experiments produced garnets with diameters > 50μm and quenched melt. Major elements were measured by EMPA at ETH Zurich. Trace elements were determined using LA-ICP-MS at Northwestern University (Xi'an, China) and SIMS (Cameca1280 at the Institute of Geology and Geophysics, Beijing, China), producing consistent partition coefficient data for U and Th. With fO2 increasing from CCO to MM and HM, garnet/meltDU decreases from 0.041 to 0.005, while garnet/meltDTh ranges from 0.003 to 0.007 without correlation with fO2. Notably, garnet/meltDTh/U increases from 0.136 at CCO to 0.41 at HM. Our results indicate that U is still more compatible than Th in garnet even at the highest fO2 considered for the subarc mantle wedge (~NNO). Therefore, we predict that if garnet is the dominant phase controlling U-Th partitioning during melting of the mantle wedge, melts would still have 230Th excess over 238U. This explains why most young continental arc lavas have 230Th excess. If clinopyroxene is the dominant residual phase during mantle melting, U could be more incompatible than Th at high fO2 because increasing fO2 can increase clinopyroxene/meltDTh/U by more than two magnitudes (Lundstrom et al. 1994). In this case, in-growth melting of the mantle can produce 238U excess over 230Th observed in the oceanic arc lavas.
An Experimental Analog for Metal-Sulfide Partitioning in Acapulcoite-Lodranite Meteorites
NASA Astrophysics Data System (ADS)
Dhaliwal, J. K.; Chabot, N. L.; Ash, R. D.; McCoy, T. J.
2018-05-01
This study builds on prior analyses of highly siderophile element (HSE) abundances in primitive achondrites. We performed melting experiments of naturally occurring FeNi and FeS to examine the effect of sulfur on HSE inter-element partitioning.
Recycling of trace elements required for humans in CELSS.
Ashida, A
1994-11-01
Recycle of complete nourishment necessary for human should be constructed in CELSS (Controlled Ecological Life Support Systems). Essential elements necessary for human support are categorized as major elements, semi-major elements and trace elements. Recently, trace elements have been identified from considerations of local diseases, food additive problems, pollution problems and adult diseases, consisting of Fe, Zn, Cu, Se, Co, F, Si, Mn, Cr, I, As, Mo, Ni, V, Sn, Li, Br, Cd, Pb, B. A review of the biogeochemical history of the earth's biosphere and the physiological nature of humans and plants explains some of the requirements. A possible route for intake of trace elements is considered that trace elements are dissolved in some chemical form in water, absorbed by plants through their roots and then transfered to human as foods. There may be a possibility that living things absorb some trace elements from atmosphere. Management and recycling of trace elements in CELSS is discussed.
Recycling of trace elements required for humans in CELSS
NASA Astrophysics Data System (ADS)
Ashida, A.
1994-11-01
Recycle of complete nourishment necessary for human should be constructed in CELSS (Controlled Ecological Life Support Systems). Essential elements necessary for human support are categorized as major elements, semi-major elements and trace elements. Recently, trace elements have been identified from considerations of local diseases, food additive problems, pollution problems and adult diseases, consisting of Fe, Zn, Cu, Se, Co, F, Si, Mn, Cr, I, As, Mo, Ni, V, Sn, Li, Br, Cd, Pb, B. A review of the biogeochemical history of the earth's biosphere and the physiological nature of humans and plants explains some of the requirements. A possible route for intake of trace elements is considered that trace elements are dissolved in some chemical form in water, absorbed by plants through their roots and then transfered to human as foods. There may be a posibility that living things absorb some trace elements from atmosphere. Management and recycling of trace elements in CELSS is discussed.
Trace Elements in River Waters
NASA Astrophysics Data System (ADS)
Gaillardet, J.; Viers, J.; Dupré, B.
2003-12-01
Trace elements are characterized by concentrations lower than 1 mg L-1 in natural waters. This means that trace elements are not considered when "total dissolved solids" are calculated in rivers, lakes, or groundwaters, because their combined mass is not significant compared to the sum of Na+, K+, Ca2+, Mg2+, H4SiO4, HCO3-, CO32-, SO42-, Cl-, and NO3-. Therefore, most of the elements, except about ten of them, occur at trace levels in natural waters. Being trace elements in natural waters does not necessarily qualify them as trace elements in rocks. For example, aluminum, iron, and titanium are major elements in rocks, but they occur as trace elements in waters, due to their low mobility at the Earth's surface. Conversely, trace elements in rocks such as chlorine and carbon are major elements in waters.The geochemistry of trace elements in river waters, like that of groundwater and seawater, is receiving increasing attention. This growing interest is clearly triggered by the technical advances made in the determination of concentrations at lower levels in water. In particular, the development of inductively coupled plasma mass spectrometry (ICP-MS) has considerably improved our knowledge of trace-element levels in waters since the early 1990s. ICP-MS provides the capability of determining trace elements having isotopes of interest for geochemical dating or tracing, even where their dissolved concentrations are extremely low.The determination of trace elements in natural waters is motivated by a number of issues. Although rare, trace elements in natural systems can play a major role in hydrosystems. This is particularly evident for toxic elements such as aluminum, whose concentrations are related to the abundance of fish in rivers. Many trace elements have been exploited from natural accumulation sites and used over thousands of years by human activities. Trace elements are therefore highly sensitive indexes of human impact from local to global scale. Pollution impact studies require knowledge of the natural background concentrations and knowledge of pollutant behavior. For example, it is generally accepted that rare earth elements (REEs) in waters behave as good analogues for the actinides, whose natural levels are quite low and rarely measured. Water quality investigations have clearly been a stimulus for measurement of toxic heavy metals in order to understand their behavior in natural systems.From a more fundamental point of view, it is crucial to understand the behavior of trace elements in geological processes, in particular during chemical weathering and transport by waters. Trace elements are much more fractionated by weathering and transport processes than major elements, and these fractionations give clues for understanding the nature and intensity of the weathering+transport processes. This has not only applications for weathering studies or for the past mobilization and transport of elements to the ocean (potentially recorded in the sediments), but also for the possibility of better utilization of trace elements in the aqueous environment as an exploration tool.In this chapter, we have tried to review the recent literature on trace elements in rivers, in particular by incorporating the results derived from recent ICP-MS measurements. We have favored a "field approach" by focusing on studies of natural hydrosystems. The basic questions which we want to address are the following: What are the trace element levels in river waters? What controls their abundance in rivers and fractionation in the weathering+transport system? Are trace elements, like major elements in rivers, essentially controlled by source-rock abundances? What do we know about the chemical speciation of trace elements in water? To what extent do colloids and interaction with solids regulate processes of trace elements in river waters? Can we relate the geochemistry of trace elements in aquatic systems to the periodic table? And finally, are we able to satisfactorily model and predict the behavior of most of the trace elements in hydrosystems?An impressive literature has dealt with experimental works on aqueous complexation, uptake of trace elements by surface complexation (inorganic and organic), uptake by living organisms (bioaccumulation) that we have not reported here, except when the results of such studies directly explain natural data. As continental waters encompass a greater range of physical and chemical conditions, we focus on river waters and do not discuss trace elements in groundwaters, lakes, and the ocean. In lakes and in the ocean, the great importance of life processes in regulating trace elements is probably the major difference from rivers.Section 5.09.2 of this chapter reports data. We will review the present-day literature on trace elements in rivers to show that our knowledge is still poor. By comparing with the continental abundances, a global mobility index is calculated for each trace element. The spatial and temporal variability of trace-element concentrations in rivers will be shown to be important. In Section 5.09.3, sources of trace elements in river waters are indicated. We will point out the great diversity of sources and the importance of global anthropogenic contamination for a number of elements. The question of inorganic and organic speciation of trace elements in river water will then be addressed in Section 5.09.4, considering some general relationships between speciation and placement in the periodic table. In Section 5.09.5, we will show that studies on organic-rich rivers have led to an exploration of the "colloidal world" in rivers. Colloids are small particles, passing through the conventional filters used to separate dissolved and suspended loads in rivers. They appear as major carriers of trace elements in rivers and considerably complicate aqueous-speciation calculation. Finally, in Section 5.09.6, the significance of interactions between solutes and solid surfaces in river waters will be reviewed. Regulation by surfaces is of major importance for a great range of elements. Although for both colloids and surface interactions, some progress has been made, we are still far from a unified model that can accurately predict trace-element concentrations in natural water systems. This is mainly due to our poor physical description of natural colloids, surface site complexation, and their interaction with solutes.
Petrology of basalts from Loihi Seamount, Hawaii
NASA Astrophysics Data System (ADS)
Hawkins, James; Melchior, John
1983-12-01
Loihi Seamount is the southeasternmost active volcano of the Emperor-Hawaii linear volcanic chain. It comprises a spectrum of basalt compositional varieties including basanite, alkali basalt, transitional basalt and tholeiite. Samples from four dredge collections made on Scripps Institution of Oceanography Benthic Expedition in October 1982 are tholeiite. The samples include highly vesicular, olivine-rich basalt and dense glass-rich pillow fragments containing olivine and augite phenocrysts. Both quartz-normative and olivine-normative tholeiites are present. Minor and trace element data indicate relatively high abundances of low partition coefficient elements (e.g., Ti, K, P. Rb, Ba, Zr) and suggest that the samples were derived by relatively small to moderate extent of partial melting, of an undepleted mantle source. Olivine composition, MgO, Cr and Ni abundances, and Mg/(Mg+Fe), are typical of moderately fractionated to relatively unfractionated "primary" magmas. The variations in chemistry between samples cannot be adequately explained by low-pressure fractional crystallization but can be satisfied by minor variations in extent of melting if a homogeneous source is postulated. Alternatively, a heterogeneous source with variable abundances of certain trace elements, or mixing of liquids, may have been involved. Data for 3He/ 4He, presented in a separate paper, implies a mantle plume origin for the helium composition of the Loihi samples. There is little variation in the helium isotope ratio for samples having different compositions and textures. The helium data are not distinctive enough to unequivocally separate the magma sources for the tholeiitic rocks from the other rock types such as Loihi alkalic basalts and the whole source region for Loihi may have a nearly uniform helium compositions even though other element abundances may be variable. Complex petrologic processes including variable melting, fractional crystallization and magma mixing may have blurred original helium isotopic signatures.
The role of the seagrass Posidonia oceanica in the cycling of trace elements
NASA Astrophysics Data System (ADS)
Sanz-Lázaro, C.; Malea, P.; Apostolaki, E. T.; Kalantzi, I.; Marín, A.; Karakassis, I.
2012-03-01
The aim of this work was to study the role of the seagrass Posidonia oceanica on the cycling of a wide set of trace elements (Ag, As, Ba, Bi, Cd, Co, Cr, Cs, Cu, Fe, Ga, Li, Mn, Ni, Pb, Rb, Sr, Tl, V and Zn). We measured the concentration of these trace elements in the different compartments of P. oceanica (leaves, rhizomes, roots and epibiota) in a non-polluted seagrass meadow representative of the Mediterranean and calculated the annual budget from a mass balance. We provide novel data on accumulation dynamics of many trace elements in P. oceanica compartments and demonstrate that trace element accumulation patterns are mainly determined by plant compartment rather than by temporal variability. Epibiota was the compartment which showed the greatest concentrations for most trace elements. Thus, they constitute a key compartment when estimating trace element transfer to higher trophic levels by P. oceanica. For most trace elements, translocation seemed to be low and acropetal. Zn, Cd, Sr and Rb were the trace elements that showed the highest release rate through decomposition of plant detritus, while Cs, Tl and Bi the lowest. P. oceanica acts as a sink of potentially toxic trace elements (Ni, Cr, As and Ag), which can be sequestered, decreasing their bioavailability. P. oceanica may have a relevant role in the cycling of trace elements in the Mediterranean.
The role of the seagrass Posidonia oceanica in the cycling of trace elements
NASA Astrophysics Data System (ADS)
Sanz-Lázaro, C.; Malea, P.; Apostolaki, E. T.; Kalantzi, I.; Marín, A.; Karakassis, I.
2012-07-01
The aim of this study was to investigate the role of the seagrass Posidonia oceanica on the cycling of a wide set of trace elements (Ag, As, Ba, Bi, Cd, Co, Cr, Cs, Cu, Fe, Ga, Li, Mn, Ni, Pb, Rb, Sr, Tl, V and Zn). We measured the concentration of these trace elements in different compartments of P. oceanica (leaves, rhizomes, roots and epiphytes) in a non-polluted seagrass meadow representative of the Mediterranean and calculated the annual budget from a mass balance. We provide novel data on accumulation dynamics of many trace elements in P. oceanica compartments and demonstrate that trace element accumulation patterns are mainly determined by plant compartment rather than by temporal variability. Epiphytes were the compartment, which showed the greatest concentrations for most trace elements. Thus, they constitute a key compartment when estimating trace element transfer to higher trophic levels by P. oceanica. Trace element translocation in P. oceanica seemed to be low and acropetal in most cases. Zn, Cd, Sr and Rb were the trace elements that showed the highest release rate through decomposition of plant detritus, while Cs, Tl and Bi showed the lowest. P. oceanica acts as a sink of potentially toxic trace elements (Ni, Cr, As and Ag), which can be sequestered, decreasing their bioavailability. P. oceanica may have a relevant role in the cycling of trace elements in the Mediterranean.
Trace Elements and Healthcare: A Bioinformatics Perspective.
Zhang, Yan
2017-01-01
Biological trace elements are essential for human health. Imbalance in trace element metabolism and homeostasis may play an important role in a variety of diseases and disorders. While the majority of previous researches focused on experimental verification of genes involved in trace element metabolism and those encoding trace element-dependent proteins, bioinformatics study on trace elements is relatively rare and still at the starting stage. This chapter offers an overview of recent progress in bioinformatics analyses of trace element utilization, metabolism, and function, especially comparative genomics of several important metals. The relationship between individual elements and several diseases based on recent large-scale systematic studies such as genome-wide association studies and case-control studies is discussed. Lastly, developments of ionomics and its recent application in human health are also introduced.
Atmospheric transport of trace elements and nutrients to the oceans
Chance, R.
2016-01-01
This paper reviews atmospheric inputs of trace elements and nutrients to the oceans in the context of the GEOTRACES programme and provides new data from two Atlantic GEOTRACES cruises. We consider the deposition of nitrogen to the oceans, which is now dominated by anthropogenic emissions, the deposition of mineral dust and related trace elements, and the deposition of other trace elements which have a mixture of anthropogenic and dust sources. We then consider the solubility (as a surrogate for bioavailability) of the various elements. We consider briefly the sources, atmospheric transport and transformations of these elements and how this results in strong spatial deposition gradients. Solubility of the trace elements also varies systematically between elements, reflecting their sources and cycling, and for some trace elements there are also systematic gradients in solubility related to dust loading. Together, these effects create strong spatial gradients in the inputs of bioavailable trace elements to the oceans, and we are only just beginning to understand how these affect ocean biogeochemistry. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’. PMID:29035252
NASA Astrophysics Data System (ADS)
Mann, Ute; Frost, Daniel J.; Rubie, David C.; Becker, Harry; Audétat, Andreas
2012-05-01
The apparent overabundance of the highly siderophile elements (HSEs: Pt-group elements, Re and Au) in the mantles of Earth, Moon and Mars has not been satisfactorily explained. Although late accretion of a chondritic component seems to provide the most plausible explanation, metal-silicate equilibration in a magma ocean cannot be ruled out due to a lack of HSE partitioning data suitable for extrapolations to the relevant high pressure and high temperature conditions. We provide a new data set of partition coefficients simultaneously determined for Ru, Rh, Pd, Re, Ir and Pt over a range of 3.5-18 GPa and 2423-2773 K. In multianvil experiments, molten peridotite was equilibrated in MgO single crystal capsules with liquid Fe-alloy that contained bulk HSE concentrations of 53.2-98.9 wt% (XFe = 0.03-0.67) such that oxygen fugacities of IW - 1.5 to IW + 1.6 (i.e. logarithmic units relative to the iron-wüstite buffer) were established at run conditions. To analyse trace concentrations of the HSEs in the silicate melt with LA-ICP-MS, two silicate glass standards (1-119 ppm Ru, Rh, Pd, Re, Ir, Pt) were produced and evaluated for this study. Using an asymmetric regular solution model we have corrected experimental partition coefficients to account for the differences between HSE metal activities in the multicomponent Fe-alloys and infinite dilution. Based on the experimental data, the P and T dependence of the partition coefficients (D) was parameterized. The partition coefficients of all HSEs studied decrease with increasing pressure and to a greater extent with increasing temperature. Except for Pt, the decrease with pressure is stronger below ˜6 GPa and much weaker in the range 6-18 GPa. This change might result from pressure induced coordination changes in the silicate liquid. Extrapolating the D values over a large range of potential P-T conditions in a terrestrial magma ocean (peridotite liquidus at P ⩽ 60-80 GPa) we conclude that the P-T-induced decrease of D would not have been sufficient to explain HSE mantle abundances by metal-silicate equilibration at a common set of P-T-oxygen fugacity conditions. Therefore, the mantle concentrations of most HSEs cannot have been established during core formation. The comparatively less siderophile Pd might have been partly retained in the magma ocean if effective equilibration pressures reached 35-50 GPa. To a much smaller extent this could also apply to Pt and Rh providing that equilibration pressures reached ⩾60 GPa in the late stage of accretion. With most of the HSE partition coefficients at 60 GPa still differing by 0.5-3 orders of magnitude, metal-silicate equilibration alone cannot have produced the observed near-chondritic HSE abundances of the mantles of the Earth as well as of the Moon or Mars. Our results show that an additional process, such as the accretion of a late veneer composed of some type of chondritic material, was required. The results, therefore, support recent hybrid models, which propose that the observed HSE signatures are a combined result of both metal-silicate partitioning as well as an overprint by late accretion.
Sessitsch, Angela; Kuffner, Melanie; Kidd, Petra; Vangronsveld, Jaco; Wenzel, Walter W.; Fallmann, Katharina; Puschenreiter, Markus
2013-01-01
Phytoextraction makes use of trace element-accumulating plants that concentrate the pollutants in their tissues. Pollutants can be then removed by harvesting plants. The success of phytoextraction depends on trace element availability to the roots and the ability of the plant to intercept, take up, and accumulate trace elements in shoots. Current phytoextraction practises either employ hyperaccumulators or fast-growing high biomass plants; the phytoextraction process may be enhanced by soil amendments that increase trace element availability in the soil. This review will focus on the role of plant-associated bacteria to enhance trace element availability in the rhizosphere. We report on the kind of bacteria typically found in association with trace element – tolerating or – accumulating plants and discuss how they can contribute to improve trace element uptake by plants and thus the efficiency and rate of phytoextraction. This enhanced trace element uptake can be attributed to a microbial modification of the absorptive properties of the roots such as increasing the root length and surface area and numbers of root hairs, or by increasing the plant availability of trace elements in the rhizosphere and the subsequent translocation to shoots via beneficial effects on plant growth, trace element complexation and alleviation of phytotoxicity. An analysis of data from literature shows that effects of bacterial inoculation on phytoextraction efficiency are currently inconsistent. Some key processes in plant–bacteria interactions and colonization by inoculated strains still need to be unravelled more in detail to allow full-scale application of bacteria assisted phytoremediation of trace element contaminated soils. PMID:23645938
Sessitsch, Angela; Kuffner, Melanie; Kidd, Petra; Vangronsveld, Jaco; Wenzel, Walter W; Fallmann, Katharina; Puschenreiter, Markus
2013-05-01
Phytoextraction makes use of trace element-accumulating plants that concentrate the pollutants in their tissues. Pollutants can be then removed by harvesting plants. The success of phytoextraction depends on trace element availability to the roots and the ability of the plant to intercept, take up, and accumulate trace elements in shoots. Current phytoextraction practises either employ hyperaccumulators or fast-growing high biomass plants; the phytoextraction process may be enhanced by soil amendments that increase trace element availability in the soil. This review will focus on the role of plant-associated bacteria to enhance trace element availability in the rhizosphere. We report on the kind of bacteria typically found in association with trace element - tolerating or - accumulating plants and discuss how they can contribute to improve trace element uptake by plants and thus the efficiency and rate of phytoextraction. This enhanced trace element uptake can be attributed to a microbial modification of the absorptive properties of the roots such as increasing the root length and surface area and numbers of root hairs, or by increasing the plant availability of trace elements in the rhizosphere and the subsequent translocation to shoots via beneficial effects on plant growth, trace element complexation and alleviation of phytotoxicity. An analysis of data from literature shows that effects of bacterial inoculation on phytoextraction efficiency are currently inconsistent. Some key processes in plant-bacteria interactions and colonization by inoculated strains still need to be unravelled more in detail to allow full-scale application of bacteria assisted phytoremediation of trace element contaminated soils.
NASA Astrophysics Data System (ADS)
Mohamed, Abdel-Baset A.
2018-04-01
In this paper, some non-classical correlations are investigated for bipartite partitions of two qubits trapped in two spatially separated cavities connected by an optical fiber. The results show that the trace distance discord and Bell's non-locality introduce other quantum correlations beyond the entanglement. Moreover, the correlation functions of the trace distance discord and the Bell's non-locality are very sensitive to the initial correlations, the coupling strengths, and the dissipation rates of the cavities. The fluctuations of the correlation functions between their initial values and gained (loss) values appear due to the unitary evolution of the system. These fluctuations depend on the chosen initial correlations between the two subsystems. The maximal violations of Bell's inequality occur when the logarithmic negativity and the trace distance discord reach certain values. It is shown that the robustness of the non-classical correlations, against the dissipation rates of the cavities, depends on the bipartite partitions reduced density matrices of the system, and is also greatly enhanced by choosing appropriate coupling strengths.
NASA Technical Reports Server (NTRS)
Dungan, M. A.; Lindstrom, M. M.; Mcmillan, N. J.; Moorbath, S.; Hoefs, J.
1986-01-01
MULTIFIT, an embodiment of the conceptual structure needed in modeling multisource and multiprocess magmatic systems, is described. This program, which uses familiar materials balance methodology and the equilibrium form of the Rayleigh equations, links evolutionary arrays, which is turn collectively relate the starting and final compositions of a given magmatic system. Moreover, MULTIFIT incorporates variations within major element data arrays; the linkage between them can be tested using an extension of the least squares algorithm, which selects the best branch point according to the minimum-sum-of-squared-residuals criterion. Advantages and disadvantages of the materials balance approach used in this program are discussed, an example is provided, and equations utilized by MULTIFIT are summarized. While MULTIFIT may not be the best approach for poorly constrained models involving partial melting for complex mixing, it may ultimately prove useful for ascertaining trace element partition coefficients in magnetic systems.
Trace Elements and Carbon and Nitrogen Stable Isotopes in Organisms from a Tropical Coastal Lagoon
van Hattum, B.; de Boer, J.; van Bodegom, P. M.; Rezende, C. E.; Salomons, W.
2010-01-01
Trace elements (Fe, Mn, Al, Zn, Cr, Cu, Ni, Pb, Cd, Hg, and As) and stable isotope ratios (δ13C and δ15N) were analyzed in sediments, invertebrates, and fishes from a tropical coastal lagoon influenced by iron ore mining and processing activities to assess the differences in trace element accumulation patterns among species and to investigate relations with trophic levels of the organisms involved. Overall significant negative relations between trophic level (given by 15N) and trace element concentrations in gastropods and crustaceans showed differences in internal controls of trace element accumulation among the species of different trophic positions, leading to trace element dilution. Generally, no significant relation between δ15N and trace element concentrations was observed among fish species, probably due to omnivory in a number of species as well as fast growth. Trace element accumulation was observed in the fish tissues, with higher levels of most trace elements found in liver compared with muscle and gill. Levels of Fe, Mn, Al, and Hg in invertebrates, and Fe and Cu in fish livers, were comparable with levels in organisms and tissues from other contaminated areas. Trace element levels in fish muscle were below the international safety baseline standards for human consumption. PMID:20217062
Trace elements and carbon and nitrogen stable isotopes in organisms from a tropical coastal lagoon.
Pereira, A A; van Hattum, B; de Boer, J; van Bodegom, P M; Rezende, C E; Salomons, W
2010-10-01
Trace elements (Fe, Mn, Al, Zn, Cr, Cu, Ni, Pb, Cd, Hg, and As) and stable isotope ratios (delta(13)C and delta(15)N) were analyzed in sediments, invertebrates, and fishes from a tropical coastal lagoon influenced by iron ore mining and processing activities to assess the differences in trace element accumulation patterns among species and to investigate relations with trophic levels of the organisms involved. Overall significant negative relations between trophic level (given by (15)N) and trace element concentrations in gastropods and crustaceans showed differences in internal controls of trace element accumulation among the species of different trophic positions, leading to trace element dilution. Generally, no significant relation between delta(15)N and trace element concentrations was observed among fish species, probably due to omnivory in a number of species as well as fast growth. Trace element accumulation was observed in the fish tissues, with higher levels of most trace elements found in liver compared with muscle and gill. Levels of Fe, Mn, Al, and Hg in invertebrates, and Fe and Cu in fish livers, were comparable with levels in organisms and tissues from other contaminated areas. Trace element levels in fish muscle were below the international safety baseline standards for human consumption.
Hower, J.C.; Trimble, A.S.; Eble, C.F.; Palmer, C.A.; Kolker, A.
1999-01-01
Fly ash samples were collected in November and December of 1994, from generating units at a Kentucky power station using high- and low-sulfur feed coals. The samples are part of a two-year study of the coal and coal combustion byproducts from the power station. The ashes were wet screened at 100, 200, 325, and 500 mesh (150, 75, 42, and 25 ??m, respectively). The size fractions were then dried, weighed, split for petrographic and chemical analysis, and analyzed for ash yield and carbon content. The low-sulfur "heavy side" and "light side" ashes each have a similar size distribution in the November samples. In contrast, the December fly ashes showed the trend observed in later months, the light-side ash being finer (over 20 % more ash in the -500 mesh [-25 ??m] fraction) than the heavy-side ash. Carbon tended to be concentrated in the coarse fractions in the December samples. The dominance of the -325 mesh (-42 ??m) fractions in the overall size analysis implies, though, that carbon in the fine sizes may be an important consideration in the utilization of the fly ash. Element partitioning follows several patterns. Volatile elements, such as Zn and As, are enriched in the finer sizes, particularly in fly ashes collected at cooler, light-side electrostatic precipitator (ESP) temperatures. The latter trend is a function of precipitation at the cooler-ESP temperatures and of increasing concentration with the increased surface area of the finest fraction. Mercury concentrations are higher in high-carbon fly ashes, suggesting Hg adsorption on the fly ash carbon. Ni and Cr are associated, in part, with the spinel minerals in the fly ash. Copyright ?? 1999 Taylor & Francis.
NASA Astrophysics Data System (ADS)
Ritter, Simon M.; Isenbeck-Schröter, Margot; Schröder-Ritzrau, Andrea; Scholz, Christian; Rheinberger, Stefan; Höfle, Bernhard; Frank, Norbert
2018-03-01
The formation of tufa is essentially influenced by biological processes and, in order to infer environmental information from tufa deposits, it has to be determined how the geochemistry of biologically influenced tufa deviates from equilibrium conditions between water and calcite precipitate. We investigated the evolution of the water and tufa geochemistry of consecutive tufa barrages in a small tufa-depositing creek in Southern Germany. High incorporation of divalent cations into tufa is ubiquitous, which is probably promoted by an influence of biofilms in the tufa element partitioning. The distribution coefficients for the incorporation of Mg, Sr and Ba into tufa at the Kaisinger creek D(Mg), D(Sr) and D(Ba) are 0.020-0.031, 0.13-0.18 and 0.26-0.43, respectively. This agrees with previous research suggesting that biofilm influenced tufa will be enriched in divalent cations over equilibrium values in the order of Mg < Sr < Ba. Furthermore, the incorporation of Mg, Sr and Ba into tufa of the Kaisinger creek decreases downstream, which can be attributed to changes of the relative portions of bio-influenced tufa formation with likely higher distribution coefficients and inorganically-driven tufa formation with likely lower distribution coefficients. Additionally, the distribution coefficients of metals in tufa of the Kaisinger creek D(Cd), D(Zn), D(Co) and D(Mn) show values of 11-22, 2.2-12, 0.7-4.9 and 30-57, respectively. These metals are highly enriched in upstream tufa deposits and their contents in tufa strongly decrease downstream. Such highly compatible elements could therefore be used to distinguish easily between different lateral sections in fluvial barrage-dam tufa depositional systems and could serve as a useful geochemical tool in studying ancient barrage-dam tufa depositional systems.
Platinum Partitioning at Low Oxygen Fugacity: Implications for Core Formation Processes
NASA Technical Reports Server (NTRS)
Medard, E.; Martin, A. M.; Righter, K.; Lanziroti, A.; Newville, M.
2016-01-01
Highly siderophile elements (HSE = Au, Re, and the Pt-group elements) are tracers of silicate / metal interactions during planetary processes. Since most core-formation models involve some state of equilibrium between liquid silicate and liquid metal, understanding the partioning of highly siderophile elements (HSE) between silicate and metallic melts is a key issue for models of core / mantle equilibria and for core formation scenarios. However, partitioning models for HSE are still inaccurate due to the lack of sufficient experimental constraints to describe the variations of partitioning with key variable like temperature, pressure, and oxygen fugacity. In this abstract, we describe a self-consistent set of experiments aimed at determining the valence of platinum, one of the HSE, in silicate melts. This is a key information required to parameterize the evolution of platinum partitioning with oxygen fugacity.
Spectral Upscaling for Graph Laplacian Problems with Application to Reservoir Simulation
Barker, Andrew T.; Lee, Chak S.; Vassilevski, Panayot S.
2017-10-26
Here, we consider coarsening procedures for graph Laplacian problems written in a mixed saddle-point form. In that form, in addition to the original (vertex) degrees of freedom (dofs), we also have edge degrees of freedom. We extend previously developed aggregation-based coarsening procedures applied to both sets of dofs to now allow more than one coarse vertex dof per aggregate. Those dofs are selected as certain eigenvectors of local graph Laplacians associated with each aggregate. Additionally, we coarsen the edge dofs by using traces of the discrete gradients of the already constructed coarse vertex dofs. These traces are defined on themore » interface edges that connect any two adjacent aggregates. The overall procedure is a modification of the spectral upscaling procedure developed in for the mixed finite element discretization of diffusion type PDEs which has the important property of maintaining inf-sup stability on coarse levels and having provable approximation properties. We consider applications to partitioning a general graph and to a finite volume discretization interpreted as a graph Laplacian, developing consistent and accurate coarse-scale models of a fine-scale problem.« less
Fuhrer, Gregory J.; Cain, Daniel J.; McKenzie, Stuart W.; Rinella, Joseph F.; Crawford, J. Kent; Skach, Kenneth A.; Hornberger, Michelle I.; Gannett, Marshall W.
1999-01-01
The report describes the distribution of trace elements in sediment, water, and aquatic biota in the Yakima River basin, Washington. Trace elements were determined from streambed sediment, suspended sediment, filtered and unfiltered water samples, aquatic insects, clams, fish livers, and fish fillets between 1987 and 1991. The distribution of trace elements in these media was related to local geology and anthropogenic sources. Additionally, annual and instantaneous loads were estimated for trace elements associated with suspended sediment and trace elements in filtered water samples. Trace elements also were screened against U.S. Environmental Protection Agency guidelines established for the protection of human health and aquatic life.
Bau, M.; Koschinsky, A.; Dulski, P.; Hein, J.R.
1996-01-01
In order to evaluate details of the partitioning behaviours of Y, rare earth elements (REEs), and Ti between inorganic metal oxide surfaces and seawater, we studied the distribution of these elements in hydrogenetic marine ferromanganese (Fe-Mn) crusts from the Central Pacific Ocean. Nonphosphatized Fe-Mn crusts display shale-normalized rare earths and yttrium (REYSN) patterns (Y inserted between Dy and Ho) that are depleted in light REEs (LREEs) and which show negative anomalies for YSN, and positive anomalies for LaSN, EuSN, GdSN, and in most cases, CeSN. They show considerably smaller Y/ Ho ratios than seawater or common igneous and clastic rocks, indicating that Y and Ho are fractionated in the marine environment. Compared to P-poor crusts, REYSN patterns of phosphatized Fe-Mn crusts are similar, but yield pronounced positive YSN anomalies, stronger positive LaSN anomalies, and enrichment of the HREEs relative to the MREEs. The data suggest modification of REY during phosphatization and indicate that studies requiring primary REY distributions or isotopic ratios should be restricted to nonphosphatized (layers of) Fe-Mn crusts. Apparent bulk coefficients, KMD, describing trace metal partitioning between nonphosphatized hydrogenetic Fe-Mn crusts and seawater, are similar for Pr to Eu and decrease for Eu to Yb. Exceptionally high values of KCeD, which are similar to those of Ti, result from oxidative scavenging of Ce and support previous suggestions that Ce(IV) is a hydroxide-dominated element in seawater. Yttrium and Gd show lower KD values than their respective neighbours in the REY series. Results of modelling the exchange equilibrium between REY dissolved in seawater and REY sorbed on hydrous Fe-Mn oxides corroborate previous studies that suggested the surface complexation of REY can be approximated by their first hydroxide binding constant. Negative "anomalies" occur for stabilities of bulk surface complexes of Gd, La, and particularly Y. The differences in inorganic surface complex stability between Y and Ho and between Gd and its REE neighbours are similar to those shown by the stabilities of complexes with aminocarboxylic acids and are significantly larger than those shown by stabilities of complexes with carboxylic acids. Hence, sorption of Y and REEs onto hydrous Fe-Mn oxides may contribute significantly to the positive YSN and GdSN anomalies in seawater.
Speciations of trace metals in the Danube alluvial sediments within an oil refinery.
Relić, Dubravka; Dordević, Dragana; Popović, Aleksandar; Blagojević, Tamara
2005-07-01
A sequential extraction procedure was applied to identify forms of Ni, Zn, Pb and Cu with Fe- and Mn-oxides associated in alluvial sediments of the River Danube within Pancevo Oil Refinery (Serbia). The five steps of the sequential extraction procedure partitioned metals into: CH(3)COONH(4) extractable (S1); NH(2)OH.HCl carbonate extractable and easily reducible (S2); (NH(4))(2)C(2)O(2)/H(2)C(2)O(2) moderately reducible (S3); H(2)O(2)-HNO(3) organic extractable (S4); and HCl acid soluble residue (S5). Extracted concentrations of trace metals, analyzed after all five steps, were found to be (mg kg(-1)) for Mn: 656, Fe: 26734, Ni: 32.3, Zn: 72.8, Pb: 13.4 and Cu: 27.0. Most of the elements were found in acid soluble residue, characterizing stable compounds in sediments. Non-residual fractions of trace metals (sum of the first four fractions) were analyzed because they are more bioavailable than the residual amount. Correlation analysis and two multivariate analysis methods (principal component and cluster analysis) were used to understand and visualize the associations between the non-residual fractions of trace metals and certain forms, more or less crystalline of Fe- and Mn-oxides within the analyzed sediments, since Fe- and Mn-oxides play an important role in trace metal sorption within aquatic systems, especially within the Danube alluvium where the fluctuations of groundwater are very frequent and the level of groundwater could come close to surface.
Metal/Silicate Partitioning at High Pressures and Temperatures
NASA Technical Reports Server (NTRS)
Shofner, G.; Campbell, A.; Danielson, L.; Righter, K.; Rahman, Z.
2010-01-01
The behavior of siderophile elements during metal-silicate segregation, and their resulting distributions provide insight into core formation processes. Determination of partition coefficients allows the calculation of element distributions that can be compared to established values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Moderately siderophile elements, including W, are particularly useful in constraining core formation conditions because they are sensitive to variations in T, P, oxygen fugacity (fO2), and silicate composition. To constrain the effect of pressure on W metal/silicate partitioning, we performed experiments at high pressures and temperatures using a multi anvil press (MAP) at NASA Johnson Space Center and laser-heated diamond anvil cells (LHDAC) at the University of Maryland. Starting materials consisted of natural peridotite mixed with Fe and W metals. Pressure conditions in the MAP experiments ranged from 10 to 16 GPa at 2400 K. Pressures in the LHDAC experiments ranged from 26 to 58 GPa, and peak temperatures ranged up to 5000 K. LHDAC experimental run products were sectioned by focused ion beam (FIB) at NASA JSC. Run products were analyzed by electron microprobe using wavelength dispersive spectroscopy. Liquid metal/liquid silicate partition coefficients for W were calculated from element abundances determined by microprobe analyses, and corrected to a common fO2 condition of IW-2 assuming +4 valence for W. Within analytical uncertainties, W partitioning shows a flat trend with increasing pressure from 10 to 16 GPa. At higher pressures, W becomes more siderophile, with an increase in partition coefficient of approximately 0.5 log units.
NASA Astrophysics Data System (ADS)
Badro, J.; Blanchard, I.; Siebert, J.
2015-12-01
Core formation is the major chemical fractionation that occurred on Earth. This event is widely believed to have happened at pressures of at least 40 GPa and temperatures exceeding 3000 K. It has left a significant imprint on the chemistry of the mantle by removing most of the siderophile (iron-loving) elements from it. Abundances of most siderophile elements in the bulk silicate Earth are significantly different than those predicted from experiments at low P-T. Among them, vanadium, chromium, cobalt and gallium are four siderophile elements which abundances in the mantle have been marked by core formation processes. Thus, understand their respective abundance in the mantle can help bringing constraints on the conditions of Earth's differentiation. We performed high-pressure high-temperature experiments using laser heating diamond anvil cell to investigate the metal-silicate partitioning of those four elements. Homogeneous glasses doped in vanadium, chromium, cobalt and gallium were synthesized using a levitation furnace and load inside the diamond anvil cell along with metallic powder. Samples were recovered using a Focused Ion Beam and chemically analyzed using an electron microprobe. We investigate the effect of pressure, temperature and metal composition on the metal-silicate partitioning of V, Cr, Co and Ga. Three previous studies focused on V, Cr and Co partitioning at those conditions of pressure and temperature, but none explore gallium partitioning at the relevant extreme conditions of core formation. We will present the first measurements of gallium metal-silicate partitioning performed at the appropriate conditions of pressure and temperature of Earth's differentiation.
Cai, Yafan; Wang, Jungang; Zhao, Yubin; Zhao, Xiaoling; Zheng, Zehui; Wen, Boting; Cui, Zongjun; Wang, Xiaofen
2018-09-01
Trace elements were commonly used as additives to facilitate anaerobic digestion. However, their addition is often blind because of the complexity of reaction conditions, which has impeded their widespread application. Therefore, this study was conducted to evaluate deficiencies in trace elements during anaerobic digestion by establishing relationships between changes in trace element bioavailability (the degree to which elements are available for interaction with biological systems) and digestion performance. To accomplish this, two batch experiments were conducted. In the first, sequential extraction was used to detect changes in trace element fractions and then to evaluate trace element bioavailability in the whole digestion cycle. In the second batch experiment, trace elements (Co, Fe, Cu, Zn, Mn, Mo and Se) were added to the reaction system at three concentrations (low, medium and high) and their effects were monitored. The results showed that sequential extraction was a suitable method for assessment of the bioavailability of trace elements (appropriate coefficient of variation and recovery rate). The results revealed that Se had the highest (44.2%-70.9%) bioavailability, while Fe had the lowest (1.7%-3.0%). A lack of trace elements was not directly related to their absolute bioavailability, but was instead associated with changes in their bioavailability throughout the digestion cycle. Trace elements were insufficient when their bioavailability was steady or increased over the digestion cycle. These results indicate that changes in trace element bioavailability during the digestion cycle can be used to predict their deficiency. Copyright © 2018 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Carvalho, Bruna Borges; Janasi, Valdecir de Assis
2012-11-01
Major and trace-element microanalyses of the main minerals from the 610 Ma Pedra Branca Syenite, southeast Brazil, allow inferences on intensive parameters of magmatic crystallization and on the partition of trace-elements among these minerals, with important implications for the petrogenetic evolution of the pluton. Two main syenite types make up the pluton, a quartz-free syenite with tabular alkali feldspar (laminated silica-saturated syenite, LSS, with Na-rich augite + phlogopite + hematite + magnetite + titanite + apatite) and a quartz-bearing syenite (laminated silica-oversaturated syenite, LSO, with scarce corroded plagioclase plus diopside + biotite ± hornblende + ilmenite ± magnetite + titanite + apatite). Both types share a remarkable enrichment in incompatible elements as K, Ba, Sr, P and LREE. Apatite saturation temperatures of ~ 1060-1090 °C are the best estimates of liquidus, whereas the pressure of emplacement, based on Al-in-hornblende barometry, is estimated as 3.3 to 4.8 kbar. Although both units crystallized under oxidizing conditions, oxygen fugacity was probably higher in LSS, as shown by higher mg# of the mafic minerals and higher hematite contents in Hem-Ilmss. In contrast with the Ca-bearing alkali-feldspar from LSO, which hosts most of the whole-rock Sr and Pb, virtually Ca-free alkali-feldspar from LSS hosts ~ 50% of whole-rock Sr and ~ 80% of Pb, the remainder of these elements being shared by apatite, pyroxene and titanite. This contrast reflects a strong crystal-chemical control, whereby a higher proportion of an element with similar ratio and charge (Ca2 +) enhances the residence of Sr and Pb in the M-site of alkali feldspar. The more alkaline character of the LSS magma is inferred to have inhibited zircon saturation; Zr + Hf remained in solution until late in the crystallization, and were mostly accommodated in the structure of Ca-Na pyroxene and titanite, which are one order of magnitude richer in these elements compared to the same minerals in LSO, where most of Zr and Hf are inferred to reside in zircon. The REE, Th and U reside mostly in titanite and apatite; D(REE)Tit/Ap raises steadily from 1 to 6 from La to Tb then remains constant up to Lu in the LSO sample; these values are about half as much in the LSS sample, where lower contents of incompatible elements in titanite are attributed to its greater modal abundance and earlier crystallization.
NASA Astrophysics Data System (ADS)
Steenstra, E. S.; Sitabi, A. B.; Lin, Y. H.; Rai, N.; Knibbe, J. S.; Berndt, J.; Matveev, S.; van Westrenen, W.
2017-09-01
We present 275 new metal-silicate partition coefficients for P, S, V, Cr, Mn, Co, Ni, Ge, Mo, and W obtained at moderate P (1.5 GPa) and high T (1683-1883 K). We investigate the effect of silicate melt composition using four end member silicate melt compositions. We identify possible silicate melt dependencies of the metal-silicate partitioning of lower valence elements Ni, Ge and V, elements that are usually assumed to remain unaffected by changes in silicate melt composition. Results for the other elements are consistent with the dependence of their metal-silicate partition coefficients on the individual major oxide components of the silicate melt composition suggested by recently reported parameterizations and theoretical considerations. Using multiple linear regression, we parameterize compiled metal-silicate partitioning results including our new data and report revised expressions that predict their metal-silicate partitioning behavior as a function of P-T-X-fO2. We apply these results to constrain the conditions that prevailed during core formation in the angrite parent body (APB). Our results suggest the siderophile element depletions in angrite meteorites are consistent with a CV bulk composition and constrain APB core formation to have occurred at mildly reducing conditions of 1.4 ± 0.5 log units below the iron-wüstite buffer (ΔIW), corresponding to a APB core mass of 18 ± 11%. The core mass range is constrained to 21 ± 8 mass% if light elements (S and/or C) are assumed to reside in the APB core. Incorporation of light elements in the APB core does not yield significantly different redox states for APB core-mantle differentiation. The inferred redox state is in excellent agreement with independent fO2 estimates recorded by pyroxene and olivine in angrites.
Garnet lherzolites from Louwrensia, Namibia: Bulk composition and P/T relations
Boyd, F.R.; Pearson, D.G.; Hoal, Karin O.; Hoal, B.G.; Nixon, P.H.; Kingston, M.J.; Mertzman, S.A.
2004-01-01
Bulk, mineral and trace element analyses of garnet lherzolite xenoliths from the Louwrensia kimberlite pipe, south-central Namibia, together with previously published Re-Os isotopic data [Chem. Geol. (2004)], form the most extensive set of chemical data for off-craton suites from southern Africa. The Louwrensia suite is similar to those from the Kaapvaal craton in that it includes both predominantly coarse-grained, equant-textured peridotites characterised by equilibration temperatures 1200 ??C. Redepletion ages range back to 2.1 Gy, concordant with the age of the crustal basement and about 1 Gy younger than the older peridotites of the adjacent Kaapvaal craton root. The coarse, low-temperature Louwrensia peridotites have an average Mg number for olivine of 91.6 in comparison to 92.6 for low-temperature peridotites from the craton. Orthopyroxene content averages 24 wt.% with a range of 11-40 wt.% for Louwrensia low-temperature peridotites, in comparison to a mean of 31.5 wt.% and a range of 11-44 wt.% for low-temperature peridotites from the Kaapvaal craton. Other major, minor and trace element concentrations in minerals forming Louwrensia lherzolites are more similar to values in corresponding Kaapvaal peridotite minerals than to those in lithospheric peridotites of Phanerozoic age as represented by off-craton basalt-hosted xenoliths and orogenic peridotites. Proportions of clinopyroxene and garnet in both the Louwrensia and Kaapvaal lherzolites overlap in the range up to 10 wt.% forming a trend extending towards pyrolite composition. Disequilibrium element partitioning between clinopyroxene and garnet for some incompatible trace elements is evidence that some of the trend is caused by enrichment following depletion. The disequilibrium is interpreted to have been caused by relatively recent growth of diopside, as previously suggested for cratonic peridotites. Attempts to constrain the depth of melting required to produce the Louwrensia peridotites suggests formation at pressures 200 km). Temperature-depth plots for the high-temperature Louwrensia rocks, however, form pronounced, apparent higher-temperature thermal anomalies at depths of 140 km and above. These anomalies are believed to reflect regional igneous activity, perhaps associated with thermal erosion of an originally thicker lithosphere, a short time prior to eruption. ?? 2004 Elsevier B.V. All rights reserved.
Parenteral trace element provision: recent clinical research and practical conclusions
Stehle, P; Stoffel-Wagner, B; Kuhn, K S
2016-01-01
The aim of this systematic review (PubMed, www.ncbi.nlm.nih.gov/pubmed and Cochrane, www.cochrane.org; last entry 31 December 2014) was to present data from recent clinical studies investigating parenteral trace element provision in adult patients and to draw conclusions for clinical practice. Important physiological functions in human metabolism are known for nine trace elements: selenium, zinc, copper, manganese, chromium, iron, molybdenum, iodine and fluoride. Lack of, or an insufficient supply of, these trace elements in nutrition therapy over a prolonged period is associated with trace element deprivation, which may lead to a deterioration of existing clinical symptoms and/or the development of characteristic malnutrition syndromes. Therefore, all parenteral nutrition prescriptions should include a daily dose of trace elements. To avoid trace element deprivation or imbalances, physiological doses are recommended. PMID:27049031
Wang, Xinsheng; Wu, Yanfang; Wu, Chengying; Wu, Qinan; Niu, Qingshan
2018-04-01
The aim of the present work was to investigate the trace elements and the correlation with flavonoids from Sparganii rhizoma. The ICP-AES and ultraviolet-visible spectroscopy were employed to analyze trace elements and flavonoids. The concentrations of trace elements and flavonoids were calculated using standard curve. The content of flavonoids was expressed as rutin equivalents. The cluster analysis was applied to evaluate geographical features of S. rhizoma from different geographical regions. The correlation analysis was used to obtain the relationship between the trace elements and flavonoids. The results indicated that the 15 trace elements were measured and the K, Ca, Mg, Na, Mn, Al, Cu, and Zn are rich in Sparganii rhizome. The different producing regions samples were classified into four groups. There was a weak relationship between trace elements and flavonoids.
Trace Elements in Ovaries: Measurement and Physiology.
Ceko, Melanie J; O'Leary, Sean; Harris, Hugh H; Hummitzsch, Katja; Rodgers, Raymond J
2016-04-01
Traditionally, research in the field of trace element biology and human and animal health has largely depended on epidemiological methods to demonstrate involvement in biological processes. These studies were typically followed by trace element supplementation trials or attempts at identification of the biochemical pathways involved. With the discovery of biological molecules that contain the trace elements, such as matrix metalloproteinases containing zinc (Zn), cytochrome P450 enzymes containing iron (Fe), and selenoproteins containing selenium (Se), much of the current research focuses on these molecules, and, hence, only indirectly on trace elements themselves. This review focuses largely on two synchrotron-based x-ray techniques: X-ray absorption spectroscopy and x-ray fluorescence imaging that can be used to identify the in situ speciation and distribution of trace elements in tissues, using our recent studies of bovine ovaries, where the distribution of Fe, Se, Zn, and bromine were determined. It also discusses the value of other techniques, such as inductively coupled plasma mass spectrometry, used to garner information about the concentrations and elemental state of the trace elements. These applications to measure trace elemental distributions in bovine ovaries at high resolutions provide new insights into possible roles for trace elements in the ovary. © 2016 by the Society for the Study of Reproduction, Inc.
Warr, Oliver; Rochelle, Christopher A; Masters, Andrew J; Ballentine, Christopher J
2016-01-01
An experimental approach is presented which can be used to determine partitioning of trace gases within CO2-water systems. The key advantages of this system are (1) The system can be isolated with no external exchange, making it ideal for experiments with conservative tracers. (2) Both phases can be sampled concurrently to give an accurate composition at each phase at any given time. (3) Use of a lower temperature flow loop outside of the reactor removes contamination and facilitates sampling. (4) Rapid equilibration at given pressure/temperature conditions is significantly aided by stirring and circulating the water phase using a magnetic stirrer and high-pressure liquid chromatography pump, respectively.
Chen, Ting; Jin, Yiying; Qiu, Xiaopeng; Chen, Xin
2015-03-01
Using laboratory experiments, the authors investigated the impact of dry-heat and moist-heat treatment processes on hazardous trace elements (As, Hg, Cd, Cr, and Pb) in food waste and explored their distribution patterns for three waste components: oil, aqueous, and solid components. The results indicated that an insignificant reduction of hazardous trace elements in heat-treated waste-0.61-14.29% after moist-heat treatment and 4.53-12.25% after dry-heat treatment-and a significant reduction in hazardous trace elements (except for Hg without external addition) after centrifugal dehydration (P < 0.5). Moreover, after heat treatment, over 90% of the hazardous trace elements in the waste were detected in the aqueous and solid components, whereas only a trace amount of hazardous trace elements was detected in the oil component (<0.01%). In addition, results indicated that heat treatment process did not significantly reduce the concentration of hazardous trace elements in food waste, but the separation process for solid and aqueous components, such as centrifugal dehydration, could reduce the risk considerably. Finally, combined with the separation technology for solid and liquid components, dry-heat treatment is superior to moist-heat treatment on the removal of external water-soluble ionic hazardous trace elements. An insignificant reduction of hazardous trace elements in heat-treated waste showed that heat treatment does not reduce trace elements contamination in food waste considerably, whereas the separation process for solid and aqueous components, such as centrifugal dehydration, could reduce the risk significantly. Moreover, combined with the separation technology for solid and liquid components, dry-heat treatment is superior to moist-heat treatment for the removal of external water-soluble ionic hazardous trace elements, by exploring distribution patterns of trace elements in three waste components: oil, aqueous, and solid components.
Meillère, Alizée; Brischoux, François; Bustamante, Paco; Michaud, Bruno; Parenteau, Charline; Marciau, Coline; Angelier, Frédéric
2016-10-01
In a rapidly urbanizing world, trace element pollution may represent a threat to human health and wildlife, and it is therefore crucial to assess both exposition levels and associated effects of trace element contamination on urban vertebrates. In this study, we investigated the impact of urbanization on trace element contamination and stress physiology in a wild bird species, the common blackbird (Turdus merula), along an urbanization gradient (from rural to moderately urbanized areas). Specifically, we described the contamination levels of blackbirds by 4 non-essential (Ag, Cd, Hg, Pb) and 9 essential trace elements (As, Co, Cr, Cu, Fe, Mn, Ni, Se, Zn), and explored the putative disrupting effects of the non-essential element contamination on corticosterone levels (a hormonal proxy for environmental challenges). We found that non-essential trace element burden (Cd and Pb specifically) increased with increasing urbanization, indicating a significant trace element contamination even in medium sized cities and suburban areas. Interestingly, the increased feather non-essential trace element concentrations were also associated with elevated feather corticosterone levels, suggesting that urbanization probably constrains birds and that this effect may be mediated by trace element contamination. Future experimental studies are now required to disentangle the influence of multiple urban-related constraints on corticosterone levels and to specifically test the influence of each of these trace elements on corticosterone secretion. Copyright © 2016 Elsevier B.V. All rights reserved.
A Method for Assessing the Retention of Trace Elements in Human Body Using Neural Network Technology
Ragimov, Aligejdar; Faizullin, Rashat; Valiev, Vsevolod
2017-01-01
Models that describe the trace element status formation in the human organism are essential for a correction of micromineral (trace elements) deficiency. A direct trace element retention assessment in the body is difficult due to the many internal mechanisms. The trace element retention is determined by the amount and the ratio of incoming and excreted substance. So, the concentration of trace elements in drinking water characterizes the intake, whereas the element concentration in urine characterizes the excretion. This system can be interpreted as three interrelated elements that are in equilibrium. Since many relationships in the system are not known, the use of standard mathematical models is difficult. The artificial neural network use is suitable for constructing a model in the best way because it can take into account all dependencies in the system implicitly and process inaccurate and incomplete data. We created several neural network models to describe the retentions of trace elements in the human body. On the model basis, we can calculate the microelement levels in the body, knowing the trace element levels in drinking water and urine. These results can be used in health care to provide the population with safe drinking water. PMID:29065586
Hesterberg, Dean; Polizzotto, Matthew L; Crozier, Carl; Austin, Robert E
2016-04-01
Catastrophic events require rapid, scientifically sound decision making to mitigate impacts on human welfare and the environment. The objective of this study was to analyze potential impacts of coal ash-derived trace elements on agriculture following a 35,000-tonne release of coal ash into the Dan River at the Duke Energy Steam Station in Eden, North Carolina. We performed scenario calculations to assess the potential for excessive trace element loading to soils via irrigation and flooding with Dan River water, uptake of trace elements by crops, and livestock consumption of trace elements via drinking water. Concentrations of 13 trace elements measured in Dan River water samples within 4 km of the release site declined sharply after the release and were equivalent within 5 d to measurements taken upriver. Mass-balance calculations based on estimates of soil trace-element concentrations and the nominal river water concentrations indicated that irrigation or flooding with 25 cm of Dan River water would increase soil concentrations of all trace elements by less than 0.5%. Calculations of potential increases of trace elements in corn grain and silage, fescue, and tobacco leaves suggested that As, Cr, Se, Sr, and V were elements of most concern. Concentrations of trace elements measured in river water following the ash release never exceeded adopted standards for livestock drinking water. Based on our analyses, we present guidelines for safe usage of Dan River water to diminish negative impacts of trace elements on soils and crop production. In general, the approach we describe here may serve as a basis for rapid assessment of environmental and agricultural risks associated with any similar types of releases that arise in the future. © 2015 SETAC.
New Perspectives on the Essential Trace Elements.
ERIC Educational Resources Information Center
Frieden, Earl
1985-01-01
Provides a comprehensive overview of the 19 essential trace elements, examining: the concept of essentiality; evolution of these elements; possible future essential elements; the lanthanides and actinides; how essential trace elements work; the metalloenzymes; the nonmetals; iodine and the thyroid hormones; and antagonism among these elements. (JN)
High Pressure and Temperature Core Formation as an Alternative to the "Late Veneer" Hypothesis
NASA Technical Reports Server (NTRS)
Righter, Kevin; Pando, K.; Humayun, M.; Danielson, L.
2011-01-01
The highly siderophile elements (HSE; Re, Au and the Platinum Group Elements - Pd Pt, Rh, Ru, Ir, Os) are commonly utilized to constrain accretion processes in terrestrial differentiated bodies due to their affinity for FeNi metal [1]. These eight elements exhibit highly siderophile behavior, but nonetheless have highly diverse metal-silicate partition coefficients [2]. Therefore the near chondritic relative concentrations of HSEs in the terrestrial and lunar mantles, as well as some other bodies, are attributed to late accretion rather than core formation [1]. Evaluation of competing theories, such as high pressure metal-silicate partitioning or magma ocean hypotheses has been hindered by a lack of relevant partitioning data for this group of eight elements. In particular, systematic studies isolating the effect of one variable (e.g. temperature or melt compositions) are lacking. Here we undertake new experiments on all eight elements, using Fe metal and FeO-bearing silicate melts at fixed pressure, but variable temperatures. These experiments, as well as some additional planned experiments should allow partition coefficients to be more accurately calculated or estimated at the PT conditions and compositions at which core formation is thought to have occurred.
Trace element contaminants in mineral fertilizers used in Iran.
Latifi, Zahra; Jalali, Mohsen
2018-05-25
The application of mineral fertilizers which have contaminants of trace elements may impose concern regarding the entry and toxic accumulation of these elements in agro-ecosystems. In this study, 57 mineral fertilizers (nitrogen, potassium, phosphate, and compound fertilizers) distributed in Iran were analyzed for their contents of Cd, Co, Cr, Cu, Mn, Ni, Pb, Zn, and Fe. The results revealed that the contents of these trace elements varied considerably depending on the type of the element and the fertilizer. Among these elements, Fe displayed the highest average content, whereas Cd showed the lowest. Generally, the trace element contents in P-containing fertilizers were higher than those in nitrogen and potassium fertilizers. The mean values of trace elements (mg kg -1 ) in P-containing fertilizers were 4.0 (Cd), 5.5 (Co), 35.7 (Cr), 24.4 (Cu), 272 (Mn), 14.3 (Ni), 6.0 (Pb), 226 (Zn), and 2532 (Fe). Comparing trace element contents to limit values set by the German Fertilizer Ordinance showed that the mean contents of potentially toxic trace elements, such as Cd and Pb, were lower than their limit values in all groups of fertilizers. On the other hand, while a number of fertilizers contained a high content of some essential trace elements, particularly Fe, they were not labeled as such.
Smith, C.L.; Motooka, J.M.; Willson, W.R.
1984-01-01
Since concentrations of trace elements in most natural waters seldom exceed the ??g/L level, analysis of trace elements in natural waters by inductively coupled plasma emission spectrometry (ICP) requires a preconcentration procedure. The elements Ag, Bi, Cd, Co, Cu, Fe, Mo, Ni, Pb, Sn, V, W, and Zn were separated and concentrated from 500 mL of water by coprecipitating them with sodium dibenzyldithiocarbamate (NaDBDTC) using nickel or silver as a carrier. The precipitated trace elements were collected on a membrane filter, redissolved from the filter with hot nitric and hydrochloric acids, and analyzed using ICP. Recoveries for all the trace elements except tungsten exceeded 80%. Coprecipitation of trace elements with NaDBDTC eliminated the use of difficult-to-inject organic solvents, and NaDBDTC coprecipitated a wider array of trace elements than ammoniumpyrrolidinedithiocarbamate (APDC), another commonly used coprecipitate.
Akter, Fouzia; Saito, Shingo; Tasaki-Handa, Yuiko; Shibukawa, Masami
2018-01-01
A new analytical methodology for a simple and efficient on-line preconcentration of trace inorganic anions in water and salt samples prior to ion chromatographic determination is proposed. The preconcentration method is based on partition/ion-exclusion chromatographic ion stacking (PIEC ion stacking) with a hydrophilic polymer gel column containing a small amount of fixed anionic charges. The developed on-line PIEC ion stacking-ion chromatography method was validated by recovery experiments for the determination of nitrate in tap water in terms of both accuracy and precision, and the results showed the reliability of the method. The method proposed was also successfully applied to the determination of trace impurity nitrite and nitrate in reagent-grade salts of sodium sulfate. A low background level can be achieved since pure water is used as the eluant for the PIEC ion stacking. It is possible to reach sensitive detection at sub-μg L -1 levels by on-line PIEC ion stacking-ion chromatography.
NASA Technical Reports Server (NTRS)
Righter, K.; Pando, K.; Danielson, L. R.; Humayun, M.; Righter, M.; Lapen, T.; Boujibar, A.
2016-01-01
Earth's core contains approximately 10 percent light elements that are likely a combination of S, C, Si, and O, with Si possibly being the most abundant. Si dissolved into Fe liquids can have a large effect on the magnitude of the activity coefficient of siderophile elements (SE) in Fe liquids, and thus the partitioning behavior of those elements between core and mantle. The effect of Si can be small such as for Ni and Co, or large such as for Mo, Ge, Sb, As. The effect of Si on many siderophile elements is unknown yet could be an important, and as yet unquantified, influence on the core-mantle partitioning of SE. Here we report new experiments designed to quantify the effect of Si on the partitioning of P, Au, Pd, and many other SE between metal and silicate melt. The results will be applied to Earth, for which we have excellent constraints on the mantle siderophile element concentrations.
Liu, Fengjie; Wang, Wen-Xiong
2015-09-01
Marine mussels have long been used as biomonitors of contamination of trace elements, but little is known about whether variation in tissue trace elements is significantly associated with those of macronutrients and major cations. The authors examined the variability of macronutrients and major cations and their potential relationships with bioaccumulation of trace elements. The authors analyzed the concentrations of macronutrients (C, N, P, S), major cations (Na, Mg, K, Ca), and trace elements (Al, V, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Ba, Pb) in the whole soft tissues of marine mussels Mytilus edulis and Perna viridis collected globally from 21 sites. The results showed that 12% to 84% of the variances in the trace elements was associated with major cations, and the tissue concentration of major cations such as Na and Mg in mussels was a good proxy for ambient seawater concentrations of the major cations. Specifically, bioaccumulation of most of the trace elements was significantly associated with major cations, and the relationships of major cations with trace cations and trace oxyanions were totally opposite. Furthermore, 14% to 69% of the variances in the trace elements were significantly associated with macronutrients. Notably, more than half of the variance in the tissue concentrations of As, Cd, V, Ba, and Pb was explained by the variance in macronutrients in one or both species. Because the tissue macronutrient concentrations were strongly associated with animal growth and reproduction, the observed coupling relationships indicated that these biological processes strongly influenced the bioaccumulation of some trace elements. The present study indicated that simultaneous quantification of macronutrients and major cations with trace elements can improve the interpretation of biomonitoring data. © 2015 SETAC.
Recurrence relations in one-dimensional Ising models.
da Conceição, C M Silva; Maia, R N P
2017-09-01
The exact finite-size partition function for the nonhomogeneous one-dimensional (1D) Ising model is found through an approach using algebra operators. Specifically, in this paper we show that the partition function can be computed through a trace from a linear second-order recurrence relation with nonconstant coefficients in matrix form. A relation between the finite-size partition function and the generalized Lucas polynomials is found for the simple homogeneous model, thus establishing a recursive formula for the partition function. This is an important property and it might indicate the possible existence of recurrence relations in higher-dimensional Ising models. Moreover, assuming quenched disorder for the interactions within the model, the quenched averaged magnetic susceptibility displays a nontrivial behavior due to changes in the ferromagnetic concentration probability.
Ramírez Hernández, Javier; Bonete Pérez, María José; Martínez Espinosa, Rosa María
2014-12-17
1) to propose a new classification of the trace elements based on a study of the recently reported research; 2) to offer detailed and actualized information about trace elements. the analysis of the research results recently reported reveals that the advances of the molecular analysis techniques point out the importance of certain trace elements in human health. A detailed analysis of the catalytic function related to several elements not considered essential o probably essentials up to now is also offered. To perform the integral analysis of the enzymes containing trace elements informatics tools have been used. Actualized information about physiological role, kinetics, metabolism, dietetic sources and factors promoting trace elements scarcity or toxicity is also presented. Oligotherapy uses catalytic active trace elements with therapeutic proposals. The new trace element classification here presented will be of high interest for different professional sectors: doctors and other professions related to medicine; nutritionist, pharmaceutics, etc. Using this new classification and approaches, new therapeutic strategies could be designed to mitigate symptomatology related to several pathologies, particularly carential and metabolic diseases. Copyright AULA MEDICA EDICIONES 2014. Published by AULA MEDICA. All rights reserved.
Torres-Dowdall, J.; Farmer, A.H.; Abril, M.; Bucher, E.H.; Ridley, I.
2010-01-01
Trace-element analysis has been suggested as a tool for the study of migratory connectivity because (1) trace-element abundance varies spatially in the environment, (2) trace elements are assimilated into animals' tissues through the diet, and (3) current technology permits the analysis of multiple trace elements in a small tissue sample, allowing the simultaneous exploration of several elements. We explored the potential of trace elements (B, Na, Mg, Al, Si, P, S, K, Ca, Ti, Cr, Mn, Ni, Cu, Zn, As, Sr, Cs, Hg, Tl, Pb, Bi, Th, and U) to clarify the migratory connectivity of shorebirds that breed in North America and winter in southern South America. We collected 66 recently replaced secondary feathers from Red Knots (Calidris canutus) at three sites in Patagonia and 76 from White-rumped Sandpipers (C. fuscicollis) at nine sites across Argentina. There were significant differences in trace-element abundance in shorebird feathers grown at different nonbreeding sites, and annual variability within a site was small compared to variability among sites. Across Argentina, there was no large-scale gradient in trace elements. The lack of such a gradient restricts the application of this technique to questions concerning the origin of shorebirds to a small number of discrete sites. Furthermore, our results including three additional species, the Pectoral Sandpiper (C. melanotos), Wilson's Phalarope (Phalaropus tricolor), and Collared Plover (Charadrius collaris), suggest that trace-element profiles change as feathers age. Temporal instability of trace-element values could undermine their application to the study of migratory connectivity in shorebirds. ?? The Cooper Ornithological Society 2010.
Composition of the core from gallium metal–silicate partitioning experiments
Blanchard, I.; Badro, J.; Siebert, J.; ...
2015-07-24
We present gallium concentration (normalized to CI chondrites) in the mantle is at the same level as that of lithophile elements with similar volatility, implying that there must be little to no gallium in Earth's core. Metal-silicate partitioning experiments, however, have shown that gallium is a moderately siderophile element and should be therefore depleted in the mantle by core formation. Moreover, gallium concentrations in the mantle (4 ppm) are too high to be only brought by the late veneer; and neither pressure, nor temperature, nor silicate composition has a large enough effect on gallium partitioning to make it lithophile. Wemore » therefore systematically investigated the effect of core composition (light element content) on the partitioning of gallium by carrying out metal–silicate partitioning experiments in a piston–cylinder press at 2 GPa between 1673 K and 2073 K. Four light elements (Si, O, S, C) were considered, and their effect was found to be sufficiently strong to make gallium lithophile. The partitioning of gallium was then modeled and parameterized as a function of pressure, temperature, redox and core composition. A continuous core formation model was used to track the evolution of gallium partitioning during core formation, for various magma ocean depths, geotherms, core light element contents, and magma ocean composition (redox) during accretion. The only model for which the final gallium concentration in the silicate Earth matched the observed value is the one involving a light-element rich core equilibrating in a FeO-rich deep magma ocean (>1300 km) with a final pressure of at least 50 GPa. More specifically, the incorporation of S and C in the core provided successful models only for concentrations that lie far beyond their allowable cosmochemical or geophysical limits, whereas realistic O and Si amounts (less than 5 wt.%) in the core provided successful models for magma oceans deeper that 1300 km. In conclusion, these results offer a strong argument for an O- and Si-rich core, formed in a deep terrestrial magma ocean, along with oxidizing conditions.« less
Metalloids, soil chemistry and the environment.
Lombi, Enzo; Holm, Peter E
2010-01-01
This chapter reviews physical chemical properties, origin and use ofmetalloids and their relevance in the environment. The elements boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), polonium (Po) and astatine (At) are considered metalloids. Metalloids conduct heat and electricity intermediate between nonmetals and metals and they generally form oxides. The natural abundance ofmetalloids varies from Si being the second most common element in the Earth's crust to At as the rarest of natural elements on Earth. The metalloid elements Ge, Te, Po and At are normally present in trace or ultratrace levels in the environment and as such are not considered of relevance in terms of environmental health. The environmental geochemical processes, factors and parameters controlling the partitioning and the speciation of B, Si, As and Sb are reviewed in relation to the bioavailability of these metalloids. Approaches based on the hypothesis that metal toxicity is related to both the metal-ligand complexation processes and the metal interactions with competing cations at the cell surface (biotic ligand) have so far not been successful for assessing metalloid bioavailability. The chapter concludes that our understanding of metalloids toxicity will improve in the future if, in addition to the points discussed above, surface membrane potentials are considered. This should represent a robust approach to the prediction of metalloid toxicity.
Trace elements in agroecosystems and impacts on the environment.
He, Zhenli L; Yang, Xiaoe E; Stoffella, Peter J
2005-01-01
Trace elements mean elements present at low concentrations (mg kg-1 or less) in agroecosystems. Some trace elements, including copper (Cu), zinc (Zn), manganese (Mn), iron (Fe), molybdenum (Mo), and boron (B) are essential to plant growth and are called micronutrients. Except for B, these elements are also heavy metals, and are toxic to plants at high concentrations. Some trace elements, such as cobalt (Co) and selenium (Se), are not essential to plant growth but are required by animals and human beings. Other trace elements such as cadmium (Cd), lead (Pb), chromium (Cr), nickel (Ni), mercury (Hg), and arsenic (As) have toxic effects on living organisms and are often considered as contaminants. Trace elements in an agroecosystem are either inherited from soil parent materials or inputs through human activities. Soil contamination with heavy metals and toxic elements due to parent materials or point sources often occurs in a limited area and is easy to identify. Repeated use of metal-enriched chemicals, fertilizers, and organic amendments such as sewage sludge as well as wastewater may cause contamination at a large scale. A good example is the increased concentration of Cu and Zn in soils under long-term production of citrus and other fruit crops. Many chemical processes are involved in the transformation of trace elements in soils, but precipitation-dissolution, adsorption-desorption, and complexation are the most important processes controlling bioavailability and mobility of trace elements in soils. Both deficiency and toxicity of trace elements occur in agroecosystems. Application of trace elements in fertilizers is effective in correcting micronutrient deficiencies for crop production, whereas remediation of soils contaminated with metals is still costly and difficult although phytoremediation appears promising as a cost-effective approach. Soil microorganisms are the first living organisms subjected to the impacts of metal contamination. Being responsive and sensitive, changes in microbial biomass, activity, and community structure as a result of increased metal concentration in soil may be used as indicators of soil contamination or soil environmental quality. Future research needs to focus on the balance of trace elements in an agroecosystem, elaboration of soil chemical and biochemical parameters that can be used to diagnose soil contamination with or deficiency in trace elements, and quantification of trace metal transport from an agroecosystem to the environment.
Braun, Christopher L.; Wilson, Jennifer T.; Van Metre, Peter C.; Weakland, Rhonda J.; Fosness, Ryan L.; Williams, Marshall L.
2012-01-01
Fifty subsamples from 15 cores were analyzed for major and trace elements. Concentrations of trace elements were low, with respect to sediment quality guidelines, in most cores. Typically, major and trace element concentrations were lower in the subsamples collected from the Snake River compared to those collected from the Clearwater River, the confluence of the Snake and Clearwater Rivers, and Lower Granite Reservoir. Generally, lower concentrations of major and trace elements were associated with coarser sediments (larger than 0.0625 millimeter) and higher concentrations of major and trace elements were associated with finer sediments (smaller than 0.0625 millimeter).
DOE Office of Scientific and Technical Information (OSTI.GOV)
Blanchard, I.; Badro, J.; Siebert, J.
We present gallium concentration (normalized to CI chondrites) in the mantle is at the same level as that of lithophile elements with similar volatility, implying that there must be little to no gallium in Earth's core. Metal-silicate partitioning experiments, however, have shown that gallium is a moderately siderophile element and should be therefore depleted in the mantle by core formation. Moreover, gallium concentrations in the mantle (4 ppm) are too high to be only brought by the late veneer; and neither pressure, nor temperature, nor silicate composition has a large enough effect on gallium partitioning to make it lithophile. Wemore » therefore systematically investigated the effect of core composition (light element content) on the partitioning of gallium by carrying out metal–silicate partitioning experiments in a piston–cylinder press at 2 GPa between 1673 K and 2073 K. Four light elements (Si, O, S, C) were considered, and their effect was found to be sufficiently strong to make gallium lithophile. The partitioning of gallium was then modeled and parameterized as a function of pressure, temperature, redox and core composition. A continuous core formation model was used to track the evolution of gallium partitioning during core formation, for various magma ocean depths, geotherms, core light element contents, and magma ocean composition (redox) during accretion. The only model for which the final gallium concentration in the silicate Earth matched the observed value is the one involving a light-element rich core equilibrating in a FeO-rich deep magma ocean (>1300 km) with a final pressure of at least 50 GPa. More specifically, the incorporation of S and C in the core provided successful models only for concentrations that lie far beyond their allowable cosmochemical or geophysical limits, whereas realistic O and Si amounts (less than 5 wt.%) in the core provided successful models for magma oceans deeper that 1300 km. In conclusion, these results offer a strong argument for an O- and Si-rich core, formed in a deep terrestrial magma ocean, along with oxidizing conditions.« less
Nuclear microscopy in trace-element biology — from cellular studies to the clinic
NASA Astrophysics Data System (ADS)
Lindh, Ulf
1993-05-01
The concentration and distribution of trace and major elements in cells are of great interest in cell biology. PIXE can provide elemental concentrations in the bulk of cells or organelles as other bulk techniques such as atomic absorption spectrophotometry and nuclear activation analysis. Supplementary information, perhaps more exciting, on the intracellular distributions of trace elements can be provided using nuclear microscopy. Intracellular distributions of trace elements in normal and malignant cells are presented. The toxicity of mercury and cadmium can be prevented by supplementation of the essential trace element selenium. Some results from an experimental animal model are discussed. The intercellular distribution of major and trace elements in isolated blood cells, as revealed by nuclear microscopy, provides useful clinical information. Examples are given concerning inflammatory connective-tissue diseases and the chronic fatigue syndrome.
NASA Astrophysics Data System (ADS)
Konrad-Schmolke, M.; Halama, R.
2014-12-01
The subduction of hydrated slab mantle to beyond-arc depths is the most important and yet weakly constrained factor in the quantification of the Earth's deep geologic water cycle. During subduction of hydrated oceanic lithosphere, dehydration reactions in the downgoing plate lead to a partitioning of water between upper and lower plate. Water retained in the slab is recycled into the mantle where it controls its rheology and thus plate tectonic velocities. Hence, quantification of the water partitioning in subduction zones is crucial for the understanding of mass transfer between the Earth's surface and the mantle. Combined thermomechanical and thermodynamic models yield quantitative constraints on the water cycle in subduction zones, but unless model results can be linked to natural observations, the reliability of such models remains speculative. We present combined thermomechanical, thermodynamic and geochemical models of active and paleo-subduction zones, whose results can be tested with independent geochemical features in natural rocks. In active subduction zones, evidence for the validity of our model comes from the agreement between modeled and observed across-arc trends of boron concentrations and isotopic compositions in arc volcanic rocks. In the Kamchatkan subduction zone, for example, the model successfully predicts complex geochemical patterns and the spatial distribution of arc volcanoes. In paleo-subduction zones (e.g. Western Gneiss Region and Western Alps), constraints on the water budget and dehydration behavior of the subducting slab come from trace element zoning patterns in ultra-high pressure (UHP) garnets. Distinct enrichments of Cr, Ni and REE in the UHP zones of the garnets can be reconciled by our models that predict intense rehydration and trace element re-enrichment of the eclogites at UHP conditions by fluids released from the underlying slab mantle. Models of present-day subduction zones indicate the presence of 2.5-6 wt.% of water within the uppermost 15 km of the subducted slab mantle. Depending on hydration depth, between 25 and 90% of this water is recycled into the deeper mantle. The Lower Devonian example from the Western Gneiss Region indicates that subduction of water into the Earth's deeper mantle is an active process at least since the middle Paleozoic.
Zu, Yanqun; Bock, Laurent; Schvartz, Christian; Colinet, Gilles; Li, Yuan
2011-01-01
Field investigations were conducted to measure subsoil trace element content and factors influencing content in an intensive periurban market garden in Chenggong County, Yunnan Province, South-West China. The area was divided into three different geomorphological units: specifically, mountain (M), transition (T) and lacustrine (L). Mean trace element content in subsoil were determined for Pb (58.2 mg/kg), Cd (0.89 mg/kg), Cu (129.2 mg/kg), and Zn (97.0 mg/kg). Strong significant relationships between trace element content in topsoil and subsoil were observed. Both Pb and Zn were accumulated in topsoil (RTS (ratio of mean trace element in topsoil to subsoil) of Pb and Zn > or =1.0) and Cd and Cu in subsoil (RTS of Cd and Cu < or = 1.0). Subsoil trace element content was related to relief, stoniness, soil color, clay content, and cation exchange capacity. Except for 7.5 YR (yellow-red) color, trace element content increased with color intensity from brown to reddish brown. Significant positive relationships were observed between Fe content and that of Pb and Cu. Trace element content in mountain unit subsoil was higher than in transition and lacustrine units (M > T > L), except for Cu (T > M > L). Mean trace element content in calcareous subsoil was higher than in sandstone and shale. Mean trace element content in clay texture subsoil was higher than in sandy and sandy loam subsoil, and higher Cu and Zn content in subsoil with few mottles. It is possible to model Pb, Cd, Cu, and Zn distribution in subsoil physico-chemical characteristics to help improve agricultural practice.
Trace elements at the intersection of marine biological and geochemical evolution
Robbins, Leslie J.; Lalonde, Stefan V.; Planavsky, Noah J.; Partin, Camille A.; Reinhard, Christopher T.; Kendall, Brian; Scott, Clinton T.; Hardisty, Dalton S.; Gill, Benjamin C.; Alessi, Daniel S.; Dupont, Christopher L.; Saito, Mak A.; Crowe, Sean A.; Poulton, Simon W.; Bekker, Andrey; Lyons, Timothy W.; Konhauser, Kurt O.
2016-01-01
Life requires a wide variety of bioessential trace elements to act as structural components and reactive centers in metalloenzymes. These requirements differ between organisms and have evolved over geological time, likely guided in some part by environmental conditions. Until recently, most of what was understood regarding trace element concentrations in the Precambrian oceans was inferred by extrapolation, geochemical modeling, and/or genomic studies. However, in the past decade, the increasing availability of trace element and isotopic data for sedimentary rocks of all ages has yielded new, and potentially more direct, insights into secular changes in seawater composition – and ultimately the evolution of the marine biosphere. Compiled records of many bioessential trace elements (including Ni, Mo, P, Zn, Co, Cr, Se, and I) provide new insight into how trace element abundance in Earth's ancient oceans may have been linked to biological evolution. Several of these trace elements display redox-sensitive behavior, while others are redox-sensitive but not bioessential (e.g., Cr, U). Their temporal trends in sedimentary archives provide useful constraints on changes in atmosphere-ocean redox conditions that are linked to biological evolution, for example, the activity of oxygen-producing, photosynthetic cyanobacteria. In this review, we summarize available Precambrian trace element proxy data, and discuss how temporal trends in the seawater concentrations of specific trace elements may be linked to the evolution of both simple and complex life. We also examine several biologically relevant and/or redox-sensitive trace elements that have yet to be fully examined in the sedimentary rock record (e.g., Cu, Cd, W) and suggest several directions for future studies.
Wang, Feng; Xu, Shaochun; Zhou, Yi; Wang, Pengmei; Zhang, Xiaomei
2017-06-30
Trace element poisoning remains a great threat to various waterfowl and waterbirds throughout the world. In this study, we determined the trace element exposure of herbivorous whooper swans (Cygnus cygnus) wintering in Swan Lake (Rongcheng), an important swan protection area in northern China. A total of 70 samples including abiotic factors (seawater, sediments), food sources (seagrass, macroalgae), feathers and feces of whooper swans were collected from the marine lagoon during the winters of 2014/2015 and 2015/2016. Concentrations of Cu, Zn, Pb, Cr, Cd, Hg and As were determined to investigate the trace element exposure of whooper swans wintering in the area. Results showed that there was an increasing trend in sediment trace element concentrations, compared with historical data. The trace element concentrations in swan feces most closely resembled those of Zostera marina leaves, especially for Cd and Cr. The Zn and Hg concentrations in the swan feces (49.57 and 0.01mg/kg, respectively) were lower than the minimum values reported in the literature for other waterfowls, waterbirds and terrestrial birds. However, the concentrations of the other five trace elements fell within the lower and mediate range of values reported for birds across the world. These results suggest that the whooper swans wintering in Swan Lake, Rongcheng are not suffering severe trace element exposure; however, with the increasing input of trace elements to the lagoon, severe adverse impacts may occur in the future, and we therefore suggest that the input of trace elements to this area should be curbed. Copyright © 2017 Elsevier Ltd. All rights reserved.
Heavy Metals and Related Trace Elements.
ERIC Educational Resources Information Center
Leland, Harry V.; And Others
1978-01-01
Presents a literature review of heavy metals and related trace elements in the environment, covering publications of 1976-77. This review includes: (1) trace treatment in natural water and in sediments; and (2) bioaccumulation and toxicity of trace elements. A list of 466 references is presented. (HM)
DOE Office of Scientific and Technical Information (OSTI.GOV)
Warr, Oliver, E-mail: oliver.warr@earth.ox.ac.uk; Ballentine, Christopher J.; Rochelle, Christopher A.
An experimental approach is presented which can be used to determine partitioning of trace gases within CO{sub 2}-water systems. The key advantages of this system are (1) The system can be isolated with no external exchange, making it ideal for experiments with conservative tracers. (2) Both phases can be sampled concurrently to give an accurate composition at each phase at any given time. (3) Use of a lower temperature flow loop outside of the reactor removes contamination and facilitates sampling. (4) Rapid equilibration at given pressure/temperature conditions is significantly aided by stirring and circulating the water phase using a magneticmore » stirrer and high-pressure liquid chromatography pump, respectively.« less
NASA Astrophysics Data System (ADS)
Shang, J. S.; Andrienko, D. A.; Huang, P. G.; Surzhikov, S. T.
2014-06-01
An efficient computational capability for nonequilibrium radiation simulation via the ray tracing technique has been accomplished. The radiative rate equation is iteratively coupled with the aerodynamic conservation laws including nonequilibrium chemical and chemical-physical kinetic models. The spectral properties along tracing rays are determined by a space partition algorithm of the nearest neighbor search process, and the numerical accuracy is further enhanced by a local resolution refinement using the Gauss-Lobatto polynomial. The interdisciplinary governing equations are solved by an implicit delta formulation through the diminishing residual approach. The axisymmetric radiating flow fields over the reentry RAM-CII probe have been simulated and verified with flight data and previous solutions by traditional methods. A computational efficiency gain nearly forty times is realized over that of the existing simulation procedures.
Santos, A J G; Mazzilli, B P; Fávaro, D I T; Silva, P S C
2006-01-01
Phosphogypsum is a waste produced by the phosphate fertilizer industry. Although phosphogypsum is mainly calcium sulphate dihydrate, it contains elevated levels of impurities, which originate from the source phosphate rock used in the phosphoric acid production. Among these impurities, radionuclides from 238U and 232Th decay series are of most concern due to their radiotoxicity. Other elements, such as rare earth elements (REE) and Ba are also enriched in the phosphogypsum. The bioavailability of radionuclides (226Ra, 210Pb and 232Th), rare earth elements and Ba to the surrounding aquatic system was evaluated by the application of sequential leaching of the phosphogypsum samples from the Brazilian phosphoric acid producers. The sequential extraction results show that most of the radium and lead are located in the "iron oxide" (non-CaSO4) fraction, and that only 13-18% of these radionuclides are distributed in the most labile fraction. Th, REE and Ba were found predominantly in the residual phase, which corresponds to a small fraction of the phosphate rock or monazite that did not react and to insoluble compounds such as sulphates, phosphates and silicates. It can be concluded that although all these elements are enriched in the phosphogypsum samples they are not associated with CaSO4 itself and therefore do not represent a threat to the surrounding aquatic environment.
Meteoritic trace element toxification and the terminal Mesozoic mass extinction
DOE Office of Scientific and Technical Information (OSTI.GOV)
Dickson, S.M.; Erickson, D.J. III
1985-01-01
Calculations of trace element fluxes to the earth associated with 5 and 10 kilometer diameter Cl chondrites and iron meteorites are presented. The data indicate that the masses of certain trace elements contained in the bolide, such as Fe, Co, Ni, Cr, Pb, and Cu, are as large as or larger than the world ocean burden. The authors believe that this pulse of trace elements was of sufficient magnitude to perturb the biogeochemical cycles operative 65 million years ago, a probably time of meteorite impact. Geochemical anomalies in Cretaceous-Tertiary boundary sediments suggest that elevated concentrations of trace elements may havemore » persisted for thousands of years in the ocean. Through direct exposure and bioaccumulation, many trophic levels of the global food chain, including that of the dinosaurs, would have been adversely affected by these meteoritic trace elements. The trace element toxification hypothesis may account for the selective extinction of both marine and terrestrial species in the enigmatic terminal Mesozoic event.« less
Zhang, Jiahua; Ren, D.; Zheng, C.; Zeng, R.; Chou, C.-L.; Liu, J.
2002-01-01
Fourteen samples of minerals were separated by handpicking from Late Permian coals in southwestern Guizhou province, China. These 14 minerals were nodular pyrite, massive recrystallized pyrite, pyrite deposited from low-temperature hydrothermal fluid and from ground water; clay minerals; and calcite deposited from low-temperature hydrothermal fluid and from ground water. The mineralogy, elemental composition, and distribution of 33 elements in these samples were studied by optical microscopy, scanning electron microscope equipped with energy-dispersive X-ray spectrometer (SEM-EDX), X-ray diffraction (XRD), cold-vapor atomic absorption spectrometry (CV-AAS), atomic fluorescence spectrometry (AFS), inductively coupled-plasma mass spectrometry (ICP-MS), and ion-selective electrode (ISE). The results show that various minerals in coal contain variable amounts of trace elements. Clay minerals have high concentrations of Ba, Be, Cs, F, Ga, Nb, Rb, Th, U, and Zr. Quartz has little contribution to the concentration of trace elements in bulk coal. Arsenic, Mn, and Sr are in high concentrations in calcite. Pyrite has high concentrations of As, Cd, Hg, Mo, Sb, Se, Tl, and Zn. Different genetic types of calcite in coal can accumulate different trace elements; for example Ba, Co, Cr, Hg, Ni, Rb, Sn, Sr, and Zn are in higher concentrations in calcite deposited from low-temperature hydrothermal fluid than in that deposited from ground water. Furthermore, the concentrations of some trace elements are quite variable in pyrite; different genetic types of pyrites (Py-A, B, C, D) have different concentrations of trace elements, and the concentrations of trace elements are also different in pyrite of low-temperature hydrothermal origin collected from different locations. The study shows that elemental concentration is rather uniform in a pyrite vein. There are many micron and submicron mosaic pyrites in a pyrite vein, which is enriched in some trace elements, such as As and Mo. The content of trace element in pyrite vein depends upon the content of mosaic pyrite and of trace elements in it. Many environmentally sensitive trace elements are mainly contained in the minerals in coal, and hence the physical coal cleaning techniques can remove minerals from coal and decrease the emissions of potentially hazardous trace elements. ?? 2002 Elsevier Science B.V. All rights reserved.
Gandois, L; Nicolas, M; VanderHeijden, G; Probst, A
2010-11-01
The trace metal (TM: Cd, Cu, Ni, Pb and Zn) budget (stocks and annual fluxes) was evaluated in a forest stand (silver fir, Abies alba Miller) in north-eastern France. Trace metal concentrations were measured in different tree compartments in order to assess TM partitioning and dynamics in the trees. Inputs included bulk deposition, estimated dry deposition and weathering. Outputs were leaching and biomass exportation. Atmospheric deposition was the main input flux. The estimated dry deposition accounted for about 40% of the total trace metal deposition. The relative importance of leaching (estimated by a lumped parameter water balance model, BILJOU) and net biomass uptake (harvesting) for ecosystem exportation depended on the element. Trace metal distribution between tree compartments (stem wood and bark, branches and needles) indicated that Pb was mainly stored in the stem, whereas Zn and Ni, and to a lesser extent Cd and Cu, were translocated to aerial parts of the trees and cycled in the ecosystem. For Zn and Ni, leaching was the main output flux (>95% of the total output) and the plot budget (input-output) was negative, whereas for Pb the biomass net exportation represented 60% of the outputs and the budget was balanced. Cadmium and Cu had intermediate behaviours, with 18% and 30% of the total output relative to biomass exportation, respectively, and the budgets were negative. The net uptake by biomass was particularly important for Pb budgets, less so for Cd and Cu and not very important for Zn and Ni in such forest stands. Copyright © 2010 Elsevier B.V. All rights reserved.
Trace elemental analysis of human breast cancerous blood by advanced PC-WDXRF technique
NASA Astrophysics Data System (ADS)
Singh, Ranjit; Kainth, Harpreet Singh; Prasher, Puneet; Singh, Tejbir
2018-03-01
The objective of this work is to quantify the trace elements of healthy and non-healthy blood samples by using advanced polychromatic source based wavelength dispersive X-ray fluorescence (PC-WDXRF) technique. The imbalances in trace elements present in the human blood directly or indirectly lead to the carcinogenic process. The trace elements 11Na, 12Mg, 15P, 16S, 17Cl, 19K, 20Ca, 26Fe, 29Cu and 30Zn are identified and their concentrations are estimated. The experimental results clearly discuss the variation and role of various trace elements present in the non-healthy blood samples relative to the healthy blood samples. These results establish future guidelines to probe the possible roles of essential trace elements in the breast carcinogenic processes. The instrumental sensitivity and detection limits for measuring the elements in the atomic range 11 ≤ Z ≤ 30 have also been discussed in the present work.
INAA Application for Trace Element Determination in Biological Reference Material
NASA Astrophysics Data System (ADS)
Atmodjo, D. P. D.; Kurniawati, S.; Lestiani, D. D.; Adventini, N.
2017-06-01
Trace element determination in biological samples is often used in the study of health and toxicology. Determination change to its essentiality and toxicity of trace element require an accurate determination method, which implies that a good Quality Control (QC) procedure should be performed. In this study, QC for trace element determination in biological samples was applied by analyzing the Standard Reference Material (SRM) Bovine muscle 8414 NIST using Instrumental Neutron Activation Analysis (INAA). Three selected trace element such as Fe, Zn, and Se were determined. Accuracy of the elements showed as %recovery and precision as %coefficient of variance (%CV). The result showed that %recovery of Fe, Zn, and Se were in the range between 99.4-107%, 92.7-103%, and 91.9-112%, respectively, whereas %CV were 2.92, 3.70, and 5.37%, respectively. These results showed that INAA method is precise and accurate for trace element determination in biological matrices.
NASA Astrophysics Data System (ADS)
Bartels-Rausch, T.; Wren, S. N.; Schreiber, S.; Riche, F.; Schneebeli, M.; Ammann, M.
2013-07-01
Release of trace gases from surface snow on earth drives atmospheric chemistry, especially in the polar regions. The gas-phase diffusion of methanol and of acetone through the interstitial air of snow was investigated in a well-controlled laboratory study in the temperature range of 223 to 263 K. The aim of this study was to evaluate how the structure of the snowpack, the interaction of the trace gases with the snow surface, and the grain boundaries influence the diffusion on timescales up to 1 h. The diffusive loss of these two volatile organics into packed snow samples was measured using a chemical ionization mass spectrometer. The structure of the snow was analysed by means of X-ray-computed micro-tomography. The observed diffusion profiles could be well described based on gas-phase diffusion and the known structure of the snow sample at temperatures ≥ 253 K. At colder temperatures, surface interactions start to dominate the diffusive transport. Parameterizing these interactions in terms of adsorption to the solid ice surface, i.e. using temperature-dependent air-ice partitioning coefficients, better described the observed diffusion profiles than the use of air-liquid partitioning coefficients. No changes in the diffusive fluxes were observed by increasing the number of grain boundaries in the snow sample by a factor of 7, indicating that for these volatile organic trace gases, uptake into grain boundaries does not play a role on the timescale of diffusion through porous surface snow. For this, a snow sample with an artificially high amount of ice grains was produced and the grain boundary surface measured using thin sections. In conclusion, we have shown that the diffusivity can be predicted when the structure of the snowpack and the partitioning of the trace gas to solid ice is known.
NASA Astrophysics Data System (ADS)
Bartels-Rausch, T.; Wren, S. N.; Schreiber, S.; Riche, F.; Schneebeli, M.; Ammann, M.
2013-03-01
Release of trace gases from surface snow on Earth drives atmospheric chemistry, especially in the polar regions. The gas-phase diffusion of methanol and of acetone through the interstitial air of snow was investigated in a well-controlled laboratory study in the temperature range of 223 to 263 K. The aim of this study was to evaluate how the structure of the snowpack, the interaction of the trace gases with the snow surface, and the grain boundaries influence the diffusion on timescales up to 1 h. The diffusive loss of these two volatile organics into packed snow samples was measured using a chemical ionization mass spectrometer. The structure of the snow was analyzed by means of X-ray computed micro-tomography. The observed diffusion profiles could be well described based on gas-phase diffusion and the known structure of the snow sample at temperatures ≥ 253 K. At colder temperatures surface interactions start to dominate the diffusive transport. Parameterizing these interactions in terms of adsorption to the solid ice surface, i.e. using temperature dependent air-ice partitioning coefficients, better described the observed diffusion profiles than the use of air-liquid partitioning coefficients. No changes in the diffusive fluxes were observed by increasing the number of grain boundaries in the snow sample by a factor of 7, indicating that for these volatile organic trace gases, uptake into grain boundaries does not play a role on the timescale of diffusion through porous surface snow. In conclusion, we have shown that the diffusivity can be predicted when the structure of the snowpack and the partitioning of the trace gas to solid ice is known.
Cong, Zhiyuan; Kang, Shichang; Zhang, Yulan; Gao, Shaopeng; Wang, Zhongyan; Liu, Bin; Wan, Xin
2015-02-01
Our research provides the first complete year-long dataset of wet deposition of trace elements in the high Himalayas based on a total of 42 wet deposition events on the northern slope of Mt. Qomolangma (Everest). Except for typical crustal elements (Al, Fe, and Mn), the concentration level of most trace elements (Sc, V, Cr, Co, Ni, Cu, Zn, As, Mo, Cd, Sn, Cs, Pb, Bi, and U) are generally comparable to those preserved in snow pits and ice cores from the nearby East Rongbuk Glacier. Cadmium was the element most affected by anthropogenic emissions. No pronounced seasonal variations are observed for most trace elements despite different transport pathways. In our study, the composition of wet precipitation reflects a regional background condition and is not clearly related to specific source regions. For the trace element record from ice cores and snow pits in the Himalayas, it could be deduced that the pronounced seasonal patterns were caused by the dry deposition of trace elements (aerosols) during their long exposure to the atmosphere after precipitation events. Our findings are of value for the understanding of the trace element deposition mechanisms in the Himalayas.
NASA Technical Reports Server (NTRS)
Righter, K.; Pando, K.; Yang, S.; Humayun, M.
2018-01-01
Metallic cores contain light alloying elements that can be a combination of S, C, Si, and O, all of which have important chemical and physical influences. For Earth, Si may be the most abundant light element in the core. Si dissolved into Fe liquids can have a large effect on the magnitude of the activity coefficient of siderophile elements (SE), and thus the partitioning behavior of those elements between core and mantle. The effect of Si on the highly siderophile elements is only beginning to be studied and the effects on Au, Pd and Pt are significant. Here we report new experiments designed to quantify the effect of Si on the partitioning of Re between metal and silicate melt. A solid understanding of Re partitioning is required for a complete understanding of the Re-Os isotopic systems. The results will be applied to understanding the HSEs and Os isotopic data for planetary mantles, and especially Earth.
NASA Technical Reports Server (NTRS)
Righter, K.; Pando, K.; Danielson, L. R.; Humayun, M.
2017-01-01
Earth's core contains approximately 10% of a light element that is likely a combination of S, C, Si, and O, with Si possibly being the most abundant light element. Si dissolved into Fe liquids can have a large effect on the magnitude of the activity coefficient of siderophile elements (SE) in Fe liquids, and thus the partitioning behavior of those elements between core and mantle. The effect of Si can be small such as for Ni and Co, or large such as for Mo, Ge, Sb, As. The effect of Si on many siderophile elements is unknown yet could be an important, and as yet unquantified, influence on the core-mantle partitioning of SE. Here we report new experiments designed to quantify the effect of Si on the partitioning of Pt (with Re and Ru in progress or planned) between metal and silicate melt. The results will be applied to Earth, for which we have excellent constraints on the mantle Pt concentrations.
NASA Technical Reports Server (NTRS)
Bailey, Edward; Drake, Michael J.
2004-01-01
The distinctive pattern of element concentrations in the upper mantle provides essential evidence in our attempts to understand the accretion and differentiation of the Earth (e.g., Drake and Righter, 2002; Jones and Drake, 1986; Righter et al., 1997; Wanke 1981). Core formation is best investigated through use of metal/silicate partition coefficients for siderophile elements. The variables influencing partition coefficients are temperature, pressure, the major element compositions of the silicate and metal phases, and oxygen fugacity. Examples of studies investigating the effects of these variables on partitioning behavior are: composition of the metal phase by Capobianco et al. (1999) and Righter et al. (1997); silicate melt composition by Watson (1976), Walter and Thibault (1995), Hillgren et al. (1996), Jana and Walker (1997), and Jaeger and Drake (2000); and oxygen fugacity by Capobianco et al. (1999), and Walter and Thibault (1995). Here we address the relative influences of silicate melt composition, pressure and temperature.
NASA Astrophysics Data System (ADS)
Creech, J. B.; Moynier, F.; Bizzarro, M.
2017-11-01
Stable isotope studies of highly siderophile elements (HSE) have the potential to yield valuable insights into a range of geological processes. In particular, the strong partitioning of these elements into metal over silicates may lead to stable isotope fractionation during metal-silicate segregation, making them sensitive tracers of planetary differentiation processes. We present the first techniques for the precise determination of palladium stable isotopes by MC-ICPMS using a 106Pd-110Pd double-spike to correct for instrumental mass fractionation. Results are expressed as the per mil (‰) difference in the 106Pd/105Pd ratio (δ106Pd) relative to an in-house solution standard (Pd_IPGP) in the absence of a certified Pd isotopic standard. Repeated analyses of the Pd isotopic composition of the chondrite Allende demonstrate the external reproducibility of the technique of ±0.032‰ on δ106Pd. Using these techniques, we have analysed Pd stable isotopes from a range of terrestrial and extraterrestrial samples. We find that chondrites define a mean δ106Pdchondrite = -0.19 ± 0.05‰. Ureilites reveal a weak trend towards heavier δ106Pd with decreasing Pd content, similar to recent findings based on Pt stable isotopes (Creech et al., 2017), although fractionation of Pd isotopes is significantly less than for Pt, possibly related to its weaker metal-silicate partitioning behaviour and the limited field shift effect. Terrestrial mantle samples have a mean δ106Pdmantle = -0.182 ± 0.130‰, which is consistent with a late-veneer of chondritic material after core formation.
NASA Technical Reports Server (NTRS)
Farhat, Charbel; Lesoinne, Michel
1993-01-01
Most of the recently proposed computational methods for solving partial differential equations on multiprocessor architectures stem from the 'divide and conquer' paradigm and involve some form of domain decomposition. For those methods which also require grids of points or patches of elements, it is often necessary to explicitly partition the underlying mesh, especially when working with local memory parallel processors. In this paper, a family of cost-effective algorithms for the automatic partitioning of arbitrary two- and three-dimensional finite element and finite difference meshes is presented and discussed in view of a domain decomposed solution procedure and parallel processing. The influence of the algorithmic aspects of a solution method (implicit/explicit computations), and the architectural specifics of a multiprocessor (SIMD/MIMD, startup/transmission time), on the design of a mesh partitioning algorithm are discussed. The impact of the partitioning strategy on load balancing, operation count, operator conditioning, rate of convergence and processor mapping is also addressed. Finally, the proposed mesh decomposition algorithms are demonstrated with realistic examples of finite element, finite volume, and finite difference meshes associated with the parallel solution of solid and fluid mechanics problems on the iPSC/2 and iPSC/860 multiprocessors.
NASA Astrophysics Data System (ADS)
Lechtenfeld, O. J.; Koch, B. P.; Kattner, G.
2010-12-01
Recent developments in analytical instrumentation enable to describe biogeochemical processes in oceanic waters on a molecular level. This is the prerequisite to integrate biological and geochemical parameters and to develop chemical cycles on a global perspective. The state-of-the-art Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) applications for dissolved organic matter (DOM) focus mainly on carbon, hydrogen, oxygen and nitrogen isotopes. Implementation of sulfur and especially phosphorus in the molecular formula assignment has been questionable because of ambiguous calculated elemental formulas. On the other hand, many compounds bearing these elements are well known to occur in the dissolved state as part of the permanent recycling processes (e.g. phospholipids, phosphonates) but analytics of dissolved organic phosphorus (DOP) and sulfur (DOS) are often hampered by the large inorganic P and S pools. Even less is known about complexation characteristics of the DOM moieties. Although electrochemical methods provide some information about trace metal speciation, the high amount of organic molecules and its insufficient description as chemical functional classes prevent the assignment of trace metals to ligand classes. Nevertheless, it is undoubtful that a varying but extensive amount of transition metals is bond in form of organic complexes. Hyphenation of reversed phase high performance liquid chromatography (RP-HPLC) with high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) is a valuable tool to study these metal-organic interactions in a qualitative and quantitative approach. We established a desolvation method that allows direct transfer of high organic solvent loads into the plasma. Thus, in combination with internal standardization and external calibration, the investigation of a broad polarity scale was possible. This approach overcomes previous restrictions to non-organic solvent separation techniques like size exclusion chromatography (SEC). We used solid phase extracted DOM (SPE-DOM) from Atlantic and Southern Ocean water samples to show that organic sulfur and phosphorus species can be separated via RP-HPLC and that the partitioning can be correlated to trace metal binding capabilities in the different fractions. A molecular level investigation of these fractions via FT-ICR-MS revealed further details of the complexation features and connects the polarity-based separation on a C18 column to O/C and H/C elemental ratios. With our study, we showed that biologically relevant transition metals (e.g. Fe, Ni, Cu) and uranium are intrinsic constituents of the DOM fractions. Moreover, a comparison between samples from different ecological provinces and diagenetic conditions was performed to highlight the benefits of this approach for future marine biogeochemical research.
Crystallochemistry and origin of pyroxenes in komatiites
NASA Astrophysics Data System (ADS)
Bouquain, Sebastien; Arndt, N. T.; Hellebrand, E.; Faure, F.
2009-11-01
We present a detailed mineralogical and major- and trace-element study of pyroxenes in two Archean komatiitic flows in Alexo, Canada. The pyroxenes in spinifex-textured lavas commonly are zoned with cores of magnesian pigeonite and rims of augite. Concentrations of incompatible trace elements are low in pigeonite and jump to higher values in the augite mantles, a variation that can be modelled using accepted partition coefficients and assuming crystallization from komatiitic liquids. Crystallization sequences are very different in different parts of both flows. In the flow top, the sequence is olivine followed by augite: deeper in the spinifex sequence, pigeonite crystallizes after olivine, followed by augite; in lower cumulates, orthopyroxene or augite accompany olivine. In spinifex lavas, pigeonite crystallizes sooner than would be predicted on the basis of equilibrium phase relations. We propose that contrasting crystallization sequences depend on the position in the flow and on the conditions of crystal growth. In the flowtop, rapid cooling causes quench crystallization. Deeper in the spinifex layer, constrained growth in a thermal gradient, perhaps augmented by Soret differentiation, accounts for the early crystallization of pigeonite. The cumulus minerals represent a near-equilibrium assemblage. Augites in Al-undepleted Archean komatiites in various localities in Canada and Zimbabwe have high moderate to high Wo contents but their Mg# (Mg/(Mg + Fe) are lower than in augites in komatiites from Barberton, South Africa. We attribute the combination of high Wo and high Mg# in Barberton rocks to the unusually high CaO/Al2O3 of these Al-depleted komatiites.
A Global Overview of Exposure Levels and Biological Effects of Trace Elements in Penguins.
Espejo, Winfred; Celis, José E; GonzÃlez-Acuña, Daniel; Banegas, Andiranel; Barra, Ricardo; Chiang, Gustavo
2018-01-01
Trace elements are chemical contaminants that can be present almost anywhere on the planet. The study of trace elements in biotic matrices is a topic of great relevance for the implications that it can have on wildlife and human health. Penguins are very useful, since they live exclusively in the Southern Hemisphere and represent about 90% of the biomass of birds of the Southern Ocean. The levels of trace elements (dry weight) in different biotic matrices of penguins were reviewed here. Maps of trace element records in penguins were included. Data on exposure and effects of trace elements in penguins were collected from the literature. The most reported trace elements in penguins are aluminum, arsenic, cadmium, lead, mercury, copper, zinc, and manganese. Trace elements have been measured in 11 of the 18 species of penguins. The most studied biotic matrices are feathers and excreta. Most of the studies have been performed in Antarctica and subantarctic Islands. Little is known about the interaction among metals, which could provide better knowledge about certain mechanisms of detoxification in penguins. Future studies of trace elements in penguins must incorporate other metals such as vanadium, cobalt, nickel, and chromium. Data of metals in the species such as Eudyptes pachyrhynchus, Eudyptes moseleyi, Eudyptes sclateri, Eudyptes robustus, Eudyptes schlegeli, Spheniscus demersus, Spheniscus mendiculus, and Megadyptes antipodes are urged. It is important to correlate levels of metals in different biotic matrices with the effects on different species and in different geographic locations.
Schmidt, Thomas; Nelles, Michael; Scholwin, Frank; Pröter, Jürgen
2014-09-01
A trace element dosing strategy for the anaerobic digestion of wheat stillage was developed in this study. Mesophilic CSTR reactors were operated with the sulfuric substrate wheat stillage in some cases under trace element deficiency. After supplementing trace elements during the start-up, one of the elements of Fe, Ni, Co, Mo, and W were depleted in one digester while still augmenting the other elements to determine minimum requirements for each element. The depletion of Fe and Ni resulted in a rapid accumulation of volatile fatty acids while Co and W seem to have a long-term effect. Based on the results it was possible to reduce the dosing of trace elements, which is positive with reference to economic and environmental aspects. Copyright © 2014 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Mendes Godinho, R.; Raimundo, J.; Vale, C.; Anes, B.; Brito, P.; Alves, L. C.; Pinheiro, T.
2013-07-01
In the scope of a monitoring program to assess the environmental impact of automobile traffic over one main bridge in Lisbon, both water and duckweed (Lemna minor L.) were sampled from the road drainage tanks and analyzed for chemical elements. Plants uptake Cr, Mn, Cu, and Zn metals from rain water draining the bridge road. Nuclear microprobe elemental maps of cryosections of L. minor tissues showed that incorporated elements were internalized in fronds of the plant. This approach at micrometer level allows a better knowledge of the elemental tissue partitioning in this biomonitor organism.
Loess as an environmental archive of atmospheric trace element deposition
NASA Astrophysics Data System (ADS)
Blazina, T.; Winkel, L. H.
2013-12-01
Environmental archives such as ice cores, lake sediment cores, and peat cores have been used extensively to reconstruct past atmospheric deposition of trace elements. These records have provided information about how anthropogenic activities such as mining and fossil fuel combustion have disturbed the natural cycles of various atmospherically transported trace elements (e.g. Pb, Hg and Se). While these records are invaluable for tracing human impacts on such trace elements, they often provide limited information about the long term natural cycles of these elements. An assumption of these records is that the observed variations in trace element input, prior to any assumed anthropogenic perturbations, represent the full range of natural variations. However, records such as those mentioned above which extend back to a maximum of ~400kyr may not capture the potentially large variations of trace element input occurring over millions of years. Windblown loess sediments, often representing atmospheric deposition over time scales >1Ma, are the most widely distributed terrestrial sediments on Earth. These deposits have been used extensively to reconstruct continental climate variability throughout the Quaternary and late Neogene periods. In addition to being a valuable record of continental climate change, loess deposits may represent a long term environmental archive of atmospheric trace element deposition and may be combined with paleoclimate records to elucidate how fluctuations in climate have impacted the natural cycle of such elements. Our research uses the loess-paleosol deposits on the Chinese Loess Plateau (CLP) to quantify how atmospheric deposition of trace elements has fluctuated in central China over the past 6.8Ma. The CLP has been used extensively to reconstruct past changes of East Asian monsoon system (EAM). We present a suite of trace element concentration records (e.g. Pb, Hg, and Se) from the CLP which exemplifies how loess deposits can be used as an environmental archive to reconstruct long term natural variations in atmospheric trace element input. By comparing paleomonsoon proxy data with geochemical data we can directly correlate variations in atmospheric trace element input to fluctuations in the EAM. For example we are able to link Se input into the CLP to EAM derived precipitation. In interglacial climatic periods from 2.3-1.56Ma and 1.50-1.29Ma, we find very strong positive correlations between Se concentration and the summer monsoon index, a proxy for effective precipitation. In later interglacial periods from 1.26-0.83Ma and 0.78-0.16Ma, we find dust input plays a greater role. Our findings demonstrate that the CLP is a valuable environmental archive of atmospheric trace element deposition and suggest that other loess deposits worldwide may serve as useful records for investigating long term natural variations in atmospheric trace element cycling.
Choi, Rihwa; Kim, Hyoung-Tae; Lim, Yaeji; Kim, Min-Ji; Kwon, O Jung; Jeon, Kyeongman; Park, Hye Yun; Jeong, Byeong-Ho; Koh, Won-Jung; Lee, Soo-Youn
2015-01-01
Deficiencies in essential trace elements are associated with impaired immunity in tuberculosis infection. However, the trace element concentrations in the serum of Korean patients with tuberculosis have not yet been investigated. This study aimed to compare the serum trace element concentrations of Korean adult patients with tuberculosis with noninfected controls and to assess the impact of serum trace element concentration on clinical outcome after antituberculosis treatment. The serum concentrations of four trace elements in 141 consecutively recruited patients with tuberculosis and 79 controls were analyzed by inductively coupled plasma-mass spectrometry. Demographic characteristics were also analyzed. Serum cobalt and copper concentrations were significantly higher in patients with tuberculosis compared with controls, while zinc and selenium concentrations were significantly lower (p < 0.01). Moreover, serum selenium and zinc concentrations were positively correlated (ρ = 0.41, p < 0.05). A high serum copper concentration was associated with a worse clinical outcome, as assessed after one month of antituberculosis therapy. Specifically, culture-positive patients had higher serum copper concentrations than culture-negative patients (p < 0.05). Patients with tuberculosis had altered serum trace element concentrations. Further research is needed to elucidate the roles of individual trace elements and to determine their clinical impact on patients with tuberculosis. PMID:26197334
NASA Astrophysics Data System (ADS)
Liang, Yayun; Deng, Jun; Liu, Xuefei; Wang, Qingfei; Qin, Cheng; Li, Yan; Yang, Yi; Zhou, Mian; Jiang, Jieyan
2018-03-01
Early Cretaceous mafic dyke swarms are widely developed on Jiaodong Peninsula in the southeastern part of the North China Craton (NCC), but their petrogenesis remains enigmatic. We have examined the in-situ major element, trace element and Sr isotope compositions of the clinopyroxene phenocrysts in these dykes in order to evaluate the extent of magma mixing and source metasomatism. Depending on the type of mineral zoning, the clinopyroxene phenocrysts in our samples can be classified into two groups: Group I (reverse zoning) and Group II (no zoning). Based on core compositions, the Group I phenocrysts with obvious reverse zoning can be divided into two subgroups: Groups IA and IB. The cores of Group IA clinopyroxenes have low values of Mg#, low Al2O3 contents, high Na2O contents, and high 87Sr/86Sr ratios, and they were probably derived from newly accreted lower crust that formed through the underplating of basaltic magma. In contrast, the cores of Group IB clinopyroxenes have lower Mg# values and lower contents of Al2O3, ΣREE (total rare earth elements), and incompatible elements, but they have similar 87Sr/86Sr ratios; these cores crystallised from crust-derived andesitic-dacitic magma. Group IA and IB clinopyroxene phenocryst rims (Group I rims) all have similar compositions with higher values of Mg# and higher Al2O3, Cr and Ni contents than the cores. The rims have high 87Sr/86Sr ratios, are enriched in LREEs (light rare earth elements) and LILEs (large ion lithophile elements), and are depleted in HFSEs (high field strength elements); these characteristics indicate that all the high-Mg rims were derived from a similar magma, possibly a relatively primitive magma derived from lithospheric mantle. We suggest, therefore, that the reversely-zoned clinopyroxene phenocrysts (Group I) in the Jiaodong mafic dykes provide evidence of magma mixing between a magma derived from lithospheric mantle and crust-derived andesitic-dacitic melt alongside with the newly accreted lower crust. The Group II clinopyroxene phenocrysts, which lack zoning, display major and trace element compositions and 87Sr/86Sr ratios that are similar to those of the Group I rims, which indicates that all the high-Mg clinopyroxenes were derived from a common source in the lithospheric mantle. These high-Mg clinopyroxenes exhibit high 87Sr/86Sr ratios, high Sr contents and remarkable depletions in HFSEs, reflecting metasomatism of the mantle source by aqueous fluids derived by dehydration of the subducting slab and its marine sediments. The metasomatism of the source reveals that the lithospheric mantle beneath Jiaodong Peninsula was metasomatised by fluids from the subducting Paleo-Pacific slab. Progressive thinning of the lithosphere mantle under the NCC was induced by continuous thermo-mechanical erosion, promoting the partial melting of lithospheric mantle and generating the mafic dykes at Jiaodong. Table A2 Analytical results for the trace element standards used during LA-ICP-MS analyses of clinopyroxene phenocrysts. Table A3 Analytical results for the Sr isotope standards used during MC-ICP-MS analyses of clinopyroxene phenocrysts. Table A4 Major element contents (wt%) of clinopyroxene phenocrysts from the mafic dykes on Jiaodong Peninsula. Table A5 Representative Sr isotopic compositions of clinopyroxene phenocrysts from the mafic dykes on Jiaodong Peninsula. Table A6 Geochemistry of the mafic dykes on Jiaodong Peninsula. Table A7 Partition coefficients (KD) and end-member components used for REE modeling.
Chen, H L; Wang, J K; Ren, Y Q; Wu, Z Y
2001-03-01
Determine and compare the contents of ten trace elements in crude E. acuminatum and its three different processed products. Using flame atomic absorption spectrometry. The ten trace elements were found in both the crude drug and its three processed products, and in terms of contents some of the trace elements in all the three processed products are higher than those in the crude drug. According to the trace element contents, the three processed products of E. acuminatum have their own advantages. It is thus suggested that thoroughgoing clinical and experimental researches be performed anew for the long-shelved processing methods.
NASA Technical Reports Server (NTRS)
Treiman, Allan H.
1996-01-01
The chemical compositions of magmas can be derived from the compositions of their equilibrium minerals through mineral/magma partition coefficients. This method cannot be applied safely to basaltic rocks, either solidified lavas or cumulates, which have chemically equilibrated or partially equilibrated at subsolidus temperatures, i.e., in the absence of magma. Applying mineral/ melt partition coefficients to mineral compositions from such rocks will typically yield 'magma compositions' that are strongly fractionated and unreasonably enriched in incompatible elements (e.g., REE's). In the absence of magma, incompatible elements must go somewhere; they are forced into minerals (e.g., pyroxenes, plagioclase) at abundance levels far beyond those established during normal mineral/magma equilibria. Further, using mineral/magma partition coefficients with such rocks may suggest that different minerals equilibrated with different magmas, and the fractionation sequence of those melts (i.e., enrichment in incompatible elements) may not be consistent with independent constraints on the order of crystallization. Subsolidus equilibration is a reasonable cause for incompatible- element-enriched minerals in some eucrites, diogenites, and martian meteorites and offers a simple alternative to petrogenetic schemes involving highly fractionated magmas or magma infiltration metasomatism.
Kim, Min-Suk; Min, Hyun-Gi; Lee, Sang-Hwan; Kim, Jeong-Gyu
2016-01-01
Many studies have examined the application of soil amendments, including pH change-induced immobilizers, adsorbents, and organic materials, for soil remediation. This study evaluated the effects of various amendments on trace element stabilization and phytotoxicity, depending on the initial soil pH in acid, neutral, and alkali conditions. As in all types of soils, Fe and Ca were well stabilized on adsorption sites. There was an effect from pH control or adsorption mechanisms on the stabilization of cationic trace elements from inorganic amendments in acidic and neutral soil. Furthermore, acid mine drainage sludge has shown great potential for stabilizing most trace elements. In a phytotoxicity test, the ratio of the bioavailable fraction to the pseudo-total fraction significantly affected the uptake of trace elements by bok choy. While inorganic amendments efficiently decreased the bioavailability of trace elements, significant effects from organic amendments were not noticeable due to the short-term cultivation period. Therefore, the application of organic amendments for stabilizing trace elements in agricultural soil requires further study. PMID:27835687
Kanda, Artwell; Ncube, France; Hwende, Tamuka; Makumbe, Peter
2018-05-29
Trace elements released by human activity are ubiquitously detected in surface soil. The trace element contamination statuses of 20 sampling stations at two busy informal industrial sites of Harare city, Zimbabwe, were evaluated using geochemical indices. Spectrophotometric determinations of concentrations of trace elements in surface soil indicated generally higher values than the reference site and the average upper earth's crust. High contamination factors were observed for trace elements across sampling stations at Gazaland and Siyaso informal industrial sites. Concentrations exhibited heterogeneous distribution of trace elements in surface soil varying with the nature of activity at a sampling station. The pollution load index and degree of contamination suggested highly contaminated surface soil with Cd, Cu and Pb particularly where the following activities were done: (1) welding, (2) automobile maintenance and (3) waste dumping. These results may be very important to reduce soil contamination. Paving surfaces may help to reduce dispersal of trace elements deposited on surface soil to other stations and minimise human exposure via inhalation and contact.
Risk assessment of trace elements in cultured freshwater fishes from Jiangxi province, China.
Zhang, Li; Zhang, Dawen; Wei, Yihua; Luo, Linguan; Dai, Tingcan
2014-04-01
The levels of trace elements (As, Cd, Cr, Cu, Fe, Ni, Pb, Se, and Zn) in eight species of cultured freshwater fishes from Jiangxi province were determined by inductively coupled plasma-mass spectroscopy. All the studied trace element levels in fish muscles from Jiangxi province did not exceed Chinese national standard and European Union standard, and they were often lower than previous studies. The calculated target hazard quotient values for all the studied trace elements in fish samples were much less than 1, suggesting that the studied trace elements in fish muscles from Jiangxi province had not pose obvious health hazards to consumers. As and Cd concentrations in northern snakehead were much higher than that in other fishes, demonstrating that this fish species could be valuable as a bioindicator of As and Cd in environmental surveys. In addition, the highest concentrations of Fe, Zn, and moderate contents of other essential trace elements in crucian carp indicated that crucian carp could be a good nutrient source of essential trace elements for human health.
Kim, Min-Suk; Min, Hyun-Gi; Lee, Sang-Hwan; Kim, Jeong-Gyu
2016-01-01
Many studies have examined the application of soil amendments, including pH change-induced immobilizers, adsorbents, and organic materials, for soil remediation. This study evaluated the effects of various amendments on trace element stabilization and phytotoxicity, depending on the initial soil pH in acid, neutral, and alkali conditions. As in all types of soils, Fe and Ca were well stabilized on adsorption sites. There was an effect from pH control or adsorption mechanisms on the stabilization of cationic trace elements from inorganic amendments in acidic and neutral soil. Furthermore, acid mine drainage sludge has shown great potential for stabilizing most trace elements. In a phytotoxicity test, the ratio of the bioavailable fraction to the pseudo-total fraction significantly affected the uptake of trace elements by bok choy. While inorganic amendments efficiently decreased the bioavailability of trace elements, significant effects from organic amendments were not noticeable due to the short-term cultivation period. Therefore, the application of organic amendments for stabilizing trace elements in agricultural soil requires further study.
NASA Astrophysics Data System (ADS)
Brandt, Frederik Ejvang; Holm, Paul Martin; Søager, Nina
2017-01-01
New high-precision minor element analysis of the most magnesian olivine cores (Fo85-88) in fifteen high-MgO (Mg#66-74) alkali basalts or trachybasalts from the Quaternary backarc volcanic province, Payenia, of the Andean Southern Volcanic Zone in Argentina displays a clear north-to-south decrease in Mn/Feol. This is interpreted as the transition from mainly peridotite-derived melts in the north to mainly pyroxenite-derived melts in the south. The peridotite-pyroxenite source variation correlates with a transition of rock compositions from arc-type to OIB-type trace element signatures, where samples from the central part of the province are intermediate. The southernmost rocks have, e.g., relatively low La/Nb, Th/Nb and Th/La ratios as well as high Nb/U, Ce/Pb, Ba/Th and Eu/Eu* = 1.08. The northern samples are characterized by the opposite and have Eu/Eu* down to 0.86. Several incompatible trace element ratios in the rocks correlate with Mn/Feol and also reflect mixing of two geochemically distinct mantle sources. The peridotite melt end-member carries an arc signature that cannot solely be explained by fluid enrichment since these melts have relatively low Eu/Eu*, Ba/Th and high Th/La ratios, which suggest a component of upper continental crust (UCC) in the metasomatizing agent of the northern mantle. However, the addition to the mantle source of crustal materials or varying oxidation state cannot explain the variation in Mn and Mn/Fe of the melts and olivines along Payenia. Instead, the correlation between Mn/Feol and whole-rock (wr) trace element compositions is evidence of two-component mixing of melts derived from peridotite mantle source enriched by slab fluids and UCC melts and a pyroxenite mantle source with an EM1-type trace element signature. Very low Ca/Fe ratios ( 1.1) in the olivines of the peridotite melt component and lower calculated partition coefficients for Ca in olivine for these samples are suggested to be caused by higher H2O contents in the magmas derived from subduction zone enriched mantle. Well-correlated Mn/Fe ratios in the wr and primitive olivines demonstrate that the Mn/Fewr of these basalts that only fractionated olivine and chromite reflects the Mn/Fe of the primitive melts and can be used as a proxy for the amount of pyroxenite melt in the magmas. Using Mn/Fewr for a large dataset of primitive Payenia rocks, we show that decreasing Mn/Fewr is correlated with decreasing Mn and increasing Zn/Mn as expected for pyroxenite melts.
Methods for detecting the mobility of trace elements during medium-temperature pyrolysis
Shiley, R.H.; Konopka, K.L.; Cahill, R.A.; Hinckley, C.C.; Smith, Gerard V.; Twardowska, H.; Saporoschenko, Mykola
1983-01-01
The mobility (volatility) of trace elements in coal during pyrolysis has been studied for distances of up to 40 cm between the coal and the trace element collector, which was graphite or a baffled solvent trap. Nineteen elements not previously recorded as mobile were detected. ?? 1983.
The role of high-energy synchrotron radiation in biomedical trace element research
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pounds, J.G.; Long, G.J.; Kwiatek, W.M.
1987-01-01
This paper will present the results of an investigation of the distribution of essential elements in the normal hepatic lobule. the liver is the organ responsible for metabolism and storage of most trace elements. Although parenchymal hepatocytes are rather uniform histologically, morphometry, histochemistry, immunohistochemistry, and microdissection with microchemical investigations have revealed marked heterogeneity on a functional and biochemical level. Hepatocytes from the periportal and perivenous zones of the liver parrenchyma differ in oxidative energy metabolism, glucose uptake and output, unreagenesis, biotransformation, bile acid secretion, and palsma protein synthesis and secretion. Although trace elements are intimately involved in the regulation andmore » maintenance of these functions, little is known regarding the heterogeneity of trace element localization of the liver parenchyma. Histochemical techniques for trace elements generally give high spatial resolution, but lack specificity and stoichiometry. Microdissection has been of marginal usefulness for trace element analyses due to the very small size of the dissected parenchyma. The characteristics of the high-energy x-ray microscope provide an effective approach for elucidating the trace element content of these small biological structures or regions. 5 refs., 1 fig., 1 tab.« less
Maternal transfer of trace elements in the Atlantic horseshoe crab (Limulus polyphemus).
Bakker, Aaron K; Dutton, Jessica; Sclafani, Matthew; Santangelo, Nicholas
2017-01-01
The maternal transfer of trace elements is a process by which offspring may accumulate trace elements from their maternal parent. Although maternal transfer has been assessed in many vertebrates, there is little understanding of this process in invertebrate species. This study investigated the maternal transfer of 13 trace elements (Ag, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, and Zn) in Atlantic horseshoe crab (Limulus polyphemus) eggs and compared concentrations to those in adult leg and gill tissue. For the majority of individuals, all trace elements were transferred, with the exception of Cr, from the female to the eggs. The greatest concentrations on average transferred to egg tissue were Zn (140 µg/g), Cu (47.8 µg/g), and Fe (38.6 µg/g) for essential elements and As (10.9 µg/g) and Ag (1.23 µg/g) for nonessential elements. For elements that were maternally transferred, correlation analyses were run to assess if the concentration in the eggs were similar to that of adult tissue that is completely internalized (leg) or a boundary to the external environment (gill). Positive correlations between egg and leg tissue were found for As, Hg, Se, Mn, Pb, and Ni. Mercury, Mn, Ni, and Se were the only elements correlated between egg and gill tissue. Although, many trace elements were in low concentration in the eggs, we speculate that the higher transfer of essential elements is related to their potential benefit during early development versus nonessential trace elements, which are known to be toxic. We conclude that maternal transfer as a source of trace elements to horseshoe crabs should not be overlooked and warrants further investigation.
Remediation using trace element humate surfactant
Riddle, Catherine Lynn; Taylor, Steven Cheney; Bruhn, Debra Fox
2016-08-30
A method of remediation at a remediation site having one or more undesirable conditions in which one or more soil characteristics, preferably soil pH and/or elemental concentrations, are measured at a remediation site. A trace element humate surfactant composition is prepared comprising a humate solution, element solution and at least one surfactant. The prepared trace element humate surfactant composition is then dispensed onto the remediation site whereby the trace element humate surfactant composition will reduce the amount of undesirable compounds by promoting growth of native species activity. By promoting native species activity, remediation occurs quickly and environmental impact is minimal.
English, Matthew D; Robertson, Gregory J; Mallory, Mark L
2015-12-15
The Bay of Fundy, Canada, is a macrotidal bay with a highly productive intertidal zone, hosting a large abundance and diversity of marine invertebrates. We analysed trace element concentrations and stable isotopic values of δ(15)N and δ(13)C in 14 species of benthic marine invertebrates from the Bay of Fundy's intertidal zone to investigate bioaccumulation or biodilution of trace elements in the lower level of this marine food web. Barnacles (Balanus balanus) consistently had significantly greater concentrations of trace elements compared to the other species studied, but otherwise we found low concentrations of non-essential trace elements. In the range of trophic levels that we studied, we found limited evidence of bioaccumulation or biodilution of trace elements across species, likely due to the species examined occupying similar trophic levels in different food chains. Copyright © 2015 Elsevier Ltd. All rights reserved.
Ribeiro, C; Couto, C; Ribeiro, A R; Maia, A S; Santos, M; Tiritan, M E; Pinto, E; Almeida, A A
2018-10-15
The present study evaluated the content and distribution of several trace elements (Li, Be, Al, V, Cr, Co, Ni, Cu, Zn, Se, Mo, Ag, Cd, Sb, Ba, Tl, Pb, and U) in the Douro River estuary. For that, three matrices were collected (water, sediments and native local flora) to assess the extent of contamination by these elements in this estuarine ecosystem. Results showed their occurrence in estuarine water and sediments, but significant differences were recorded on the concentration levels and pattern of distribution among both matrices and sampling points. Generally, the levels of trace elements were higher in the sediments than in the respective estuarine water. Nonetheless, no correlation among trace elements was determined between water and sediments, except for Cd. Al was the trace element found at highest concentration at both sediments and water followed by Zn. Pollution indices such as geo-accumulation (I geo ), enrichment factor (EF) and contamination factor (CF) were determined to understand the levels and sources of trace elements pollution. I geo showed strong contamination by anthropogenic activities for Li, Al, V, Cr, Ni, Cu, Zn, Ba and Pb at all sampling points while EF and CF demonstrated severe enrichment and contamination by Se, Sb and Pb. Levels of trace elements were compared to acceptable values for aquatic organisms and Sediment Quality Guidelines. The concentration of some trace elements, namely Al, Pb and Cu, were higher than those considered acceptable, with potential negative impact on local living organisms. Nevertheless, permissible values for all trace elements are still not available, demonstrating that further studies are needed in order to have a complete assessment of environmental risk. Furthermore, the occurrence and possible accumulation of trace elements by local plant species and macroalgae were investigated as well as their potential use as bioindicators of local pollution and for phytoremediation purposes. Copyright © 2018 Elsevier B.V. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pastorok, R.; Schoof, R.; LaTier, A.
1995-12-31
At mining and smelting sites, the bioavailability of waste-related trace elements to terrestrial wildlife is limited by mineralogy of the waste material and the geochemistry of the waste-soil mixture. For example, encapsulation of trace elements in inert mineral matrices limits the assimilation of particle-associated trace elements that are ingested by wildlife. The bioavailability of arsenic, cadmium, copper, lead, silver, and zinc at mining and smelting sites in Oklahoma and Montana was evaluated based on analysis of waste material, soil chemistry, and concentrations of trace elements in whole-body samples of key food web species. Concentrations of trace elements were generally elevatedmore » relative to reference area values for selected species of vegetation, insects, spiders, and small mammals. Soil-to-tissue bioconcentration factors derived from field data at these sites were generally low (< 1), with the exception of cadmium in vegetation. For all of the trace elements evaluated, wildlife exposure models indicate that the potential for transfer of contaminants to wildlife species of public concern and high trophic-level predators is limited. Moreover, laboratory feeding experiments conducted with cadmium and lead indicate that the assimilation of waste-related trace elements by mammals is relatively low (24--47 percent for lead in blood and bone; 22--44 percent for cadmium in kidney). The relatively low bioavailability of trace elements at mining and smelting sites should be considered when estimating exposure of ecological receptors and when deriving soil cleanup criteria based on measured or modeled ecological risk.« less
Assessment of serum trace elements and electrolytes in children with childhood and atypical autism.
Skalny, Anatoly V; Simashkova, Natalia V; Klyushnik, Tatiana P; Grabeklis, Andrei R; Radysh, Ivan V; Skalnaya, Margarita G; Nikonorov, Alexandr A; Tinkov, Alexey A
2017-09-01
The existing data demonstrate a significant interrelation between ASD and essential and toxic trace elements status of the organism. However, data on trace element homeostasis in particular ASD forms are insufficient. Therefore, the objective of the present study was to assess the level of trace elements and electrolytes in serum of children with childhood and atypical autism. A total of 48 children with ASD (24 with childhood and 24 with atypical autism) and age- and sex-adjusted controls were examined. Serum trace elements and electrolytes were assessed using inductively-coupled plasma mass spectrometry. The obtained data demonstrate that children with ASD unspecified are characterized by significantly lower Ni, Cr, and Se levels as compared to the age- and sex-matched controls. At the same time, significantly decreased serum Ni and Se concentrations were detected in patients with childhood autism. In turn, children with atypical autism were characterized by more variable serum trace element spectrum. In particular, atypical autism is associated with lower serum Al, As, Ni, Cr, Mn, and Se levels in comparison to the control values. Moreover, Al and Mn concentration in this group was also lower than that in childhood autism patients. Generally, the obtained data demonstrate lower levels of both essential and toxic trace elements in atypical autism group, being indicative of profound alteration of trace elements metabolism. However, further detailed metabolic studies are required to reveal critical differences in metabolic pathways being responsible for difference in trace element status and clinical course of the disease. Copyright © 2016 Elsevier GmbH. All rights reserved.
A physics-motivated Centroidal Voronoi Particle domain decomposition method
DOE Office of Scientific and Technical Information (OSTI.GOV)
Fu, Lin, E-mail: lin.fu@tum.de; Hu, Xiangyu Y., E-mail: xiangyu.hu@tum.de; Adams, Nikolaus A., E-mail: nikolaus.adams@tum.de
2017-04-15
In this paper, we propose a novel domain decomposition method for large-scale simulations in continuum mechanics by merging the concepts of Centroidal Voronoi Tessellation (CVT) and Voronoi Particle dynamics (VP). The CVT is introduced to achieve a high-level compactness of the partitioning subdomains by the Lloyd algorithm which monotonically decreases the CVT energy. The number of computational elements between neighboring partitioning subdomains, which scales the communication effort for parallel simulations, is optimized implicitly as the generated partitioning subdomains are convex and simply connected with small aspect-ratios. Moreover, Voronoi Particle dynamics employing physical analogy with a tailored equation of state ismore » developed, which relaxes the particle system towards the target partition with good load balance. Since the equilibrium is computed by an iterative approach, the partitioning subdomains exhibit locality and the incremental property. Numerical experiments reveal that the proposed Centroidal Voronoi Particle (CVP) based algorithm produces high-quality partitioning with high efficiency, independently of computational-element types. Thus it can be used for a wide range of applications in computational science and engineering.« less
A physics-motivated Centroidal Voronoi Particle domain decomposition method
NASA Astrophysics Data System (ADS)
Fu, Lin; Hu, Xiangyu Y.; Adams, Nikolaus A.
2017-04-01
In this paper, we propose a novel domain decomposition method for large-scale simulations in continuum mechanics by merging the concepts of Centroidal Voronoi Tessellation (CVT) and Voronoi Particle dynamics (VP). The CVT is introduced to achieve a high-level compactness of the partitioning subdomains by the Lloyd algorithm which monotonically decreases the CVT energy. The number of computational elements between neighboring partitioning subdomains, which scales the communication effort for parallel simulations, is optimized implicitly as the generated partitioning subdomains are convex and simply connected with small aspect-ratios. Moreover, Voronoi Particle dynamics employing physical analogy with a tailored equation of state is developed, which relaxes the particle system towards the target partition with good load balance. Since the equilibrium is computed by an iterative approach, the partitioning subdomains exhibit locality and the incremental property. Numerical experiments reveal that the proposed Centroidal Voronoi Particle (CVP) based algorithm produces high-quality partitioning with high efficiency, independently of computational-element types. Thus it can be used for a wide range of applications in computational science and engineering.
[Determination of Trace Elements in Marine Cetaceans by ICP-MS and Health Risk Assessment].
Ding, Yu-long; Ning, Xi; Gui, Duan; Mo, Hui; Li, Yu-sen; Wu, Yu-ping
2015-09-01
The liver, kidney and muscle samples from seven cetaceans were digested by microwave digestion, and trace elements amounts of V, Cd, Cu, Zn, As, Cr, Ni, Mn, Se, Hg and Pb were determined by inductively coupled plasma mass spectrometry (ICP-MS), and the health risk assessment for Zn, Cu, Cd, Hg, Se in the liver was conducted. The results of international lobster hepatopancreas standard (TORT-2) showed acceptable agreement with the certified values, and the relative standard deviation (RSD) of eleven kinds of trace elements were less than 3.54%, showing that the method is suitable for the determination of trace elements in cetaceans. The experimental results indicated that different tissues and organs of the dolphins had different trace elements, presenting the tissue specificity. There is a certain inter-species difference among different dolphins about the bioaccumulation ability of the trace elements. The distribution of trace elements in whales presented a certain regularity: the contents of most elements in liver, kidney were much higher than the contents of muscle tissues, Cu, Mn, Hg, Se, and Zn exhibit the higher concentrations in liver, while Cd was mainly accumulated in kidney. And according to the health risk assessment in liver, the exceeding standardrate of selenium and copper in seven kinds of whales was 100%, suggesting that these whales were suffering the contamination of trace elements. The experimental results is instructive to the study of trace elements in cetaceans, while this is the first report for the concentrations in organs of Striped dolphin, Bottlenose dolphin, Fraser's Dolphin and Risso's dolphin in China, it may provide us valuable data for the conservation of cetaceans.
Incorporation of Metals into Calcite in a Deep Anoxic Granite Aquifer.
Drake, Henrik; Mathurin, Frédéric A; Zack, Thomas; Schäfer, Thorsten; Roberts, Nick Mw; Whitehouse, Martin; Karlsson, Andreas; Broman, Curt; Åström, Mats E
2018-01-16
Understanding metal scavenging by calcite in deep aquifers in granite is of importance for deciphering and modeling hydrochemical fluctuations and water-rock interaction in the upper crust and for retention mechanisms associated with underground repositories for toxic wastes. Metal scavenging into calcite has generally been established in the laboratory or in natural environments that cannot be unreservedly applied to conditions in deep crystalline rocks, an environment of broad interest for nuclear waste repositories. Here, we report a microanalytical study of calcite precipitated over a period of 17 years from anoxic, low-temperature (14 °C), neutral (pH: 7.4-7.7), and brackish (Cl: 1700-7100 mg/L) groundwater flowing in fractures at >400 m depth in granite rock. This enabled assessment of the trace metal uptake by calcite under these deep-seated conditions. Aquatic speciation modeling was carried out to assess influence of metal complexation on the partitioning into calcite. The resulting environment-specific partition coefficients were for several divalent ions in line with values obtained in controlled laboratory experiments, whereas for several other ions they differed substantially. High absolute uptake of rare earth elements and U(IV) suggests that coprecipitation into calcite can be an important sink for these metals and analogousactinides in the vicinity of geological repositories.
Palmer, C.A.; Lyons, P.C.
1996-01-01
The four most abundant minerals generally found in Euramerican bituminous coals are quartz, kaolinite, illite and pyrite. These four minerals were isolated by density separation and handpicking from bituminous coal samples collected in the Ruhr Basin, Germany and the Appalachian basin, U.S.A. Trace-element concentrations of relatively pure (??? 99+%) separates of major minerals from these coals were determined directly by using instrumental neutron activation analysis (INAA). As expected, quartz contributes little to the trace-element mass balance. Illite generally has higher trace-element concentrations than kaolinite, but, for the concentrates analyzed in this study, Hf, Ta, W, Th and U are in lower concentrations in illite than in kaolinite. Pyrite has higher concentrations of chalcophile elements (e.g., As and Se) and is considerably lower in lithophile elements as compared to kaolinite and illite. Our study provides a direct and sensitive method of determining trace-element relationships with minerals in coal. Mass-balance calculations suggest that the trace-element content of coal can be explained mainly by three major minerals: pyrite, kaolinite and illite. This conclusion indicates that the size and textural relationships of these major coal minerals may be a more important consideration as to whether coal cleaning can effectively remove the most environmentally sensitive trace elements in coal than what trace minerals are present.
Origin and distribution of trace elements in high-elevation precipitation in southern China.
Zhou, Jie; Wang, Yan; Yue, Taixing; Li, Yuhua; Wai, Ka-Ming; Wang, Wenxing
2012-09-01
During a 2009 investigation of the transport and deposition of trace elements in southern China, 37 event-based precipitation samples were collected at an observatory on Mount Heng, China (1,269 m asl). Concentrations of trace elements were analyzed using inductively coupled plasma-mass spectrometry and the wet deposition fluxes were established. A combination of techniques including enrichment factor analysis, principal component analysis, and back trajectory models were used to identify pollutant sources. Trace element concentrations at Mount Heng were among the highest with respect to measured values reported elsewhere. All elements were of non-marine origin. The elements Pb, As, Cu, Se, and Cd were anthropogenic, while Fe, Cr, V, Ba, Mn, and Ni were of mixed crustal/anthropogenic origin. The crustal and anthropogenic contributions of trace elements were 12.8 % (0.9 ~ 17.4 %) and 87.2 % (82.6 ~ 99.1 %), with the maximum crustal fraction being 17.4 % for Fe. Coal combustion, soil and road dust, metallurgical processes, and industrial activities contributed to the element composition. Summit precipitation events were primarily distant in origin. Medium- to long-range transport of trace elements from the Yangtze River Delta and northern China played an important role in wet deposition at Mount Heng, while air masses from south or southeast of the station were generally low in trace element concentrations.
NASA Technical Reports Server (NTRS)
King, C.; Righter, K.; Danielson, L.; Pando, K.; Lee, C.
2010-01-01
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.
Responses of trace elements to aerobic maximal exercise in elite sportsmen.
Otag, Aynur; Hazar, Muhsin; Otag, Ilhan; Gürkan, Alper Cenk; Okan, Ilyas
2014-02-21
Trace elements are chemical elements needed in minute quantities for the proper growth, development, and physiology of the organism. In biochemistry, a trace element is also referred to as a micronutrient. Trace elements, such as nickel, cadmium, aluminum, silver, chromium, molybdenum, germanium, tin, titanium, tungsten, scandium, are found naturally in the environment and human exposure derives from a variety of sources, including air, drinking water and food. The Purpose of this study was investigated the effect of aerobic maximal intensity endurance exercise on serum trace elements as well-trained individuals of 28 wrestlers (age (year) 19.64±1.13, weight (Kg) 70.07 ± 15.69, height (cm) 176.97 ± 6.69) during and after a 2000 meter Ergometer test protocol was used to perform aerobic (75 %) maximal endurance exercise. Trace element serum levels were analyzed from blood samples taken before, immediately after and one hour after the exercise. While an increase was detected in Chromium (Cr), Nickel (Ni), Molybdenum (Mo) and Titanium (Ti) serum levels immediately after the exercise, a decrease was detected in Aluminum (Al), Scandium (Sc) and Tungsten (W) serum levels. Except for aluminum, the trace elements we worked on showed statistically meaningful responses (P < 0.05 and P < 0.001). According to the responses of trace elements to the exercise showed us the selection and application of the convenient sport is important not only in terms of sportsman performance but also in terms of future healthy life plans and clinically.
Chen, Yong; Huang, Biao; Hu, Wenyou; Weindorf, David C; Liu, Xiaoxiao; Niedermann, Silvana
2014-02-01
The risk assessment of trace elements of different environmental media in conventional and organic greenhouse vegetable production systems (CGVPS and OGVPS) can reveal the influence of different farming philosophy on the trace element accumulations and their effects on human health. These provide important basic data for the environmental protection and human health. This paper presents trace element accumulation characteristics of different land uses; reveals the difference of soil trace element accumulation both with and without consideration of background levels; compares the trace element uptake by main vegetables; and assesses the trace element risks of soils, vegetables, waters and agricultural inputs, using two selected greenhouse vegetable systems in Nanjing, China as examples. Results showed that greenhouse vegetable fields contained significant accumulations of Zn in CGVPS relative to rice-wheat rotation fields, open vegetable fields, and geochemical background levels, and this was the case for organic matter in OGVPS. The comparative analysis of the soil medium in two systems with consideration of geochemical background levels and evaluation of the geo-accumulation pollution index achieved a more reasonable comparison and accurate assessment relative to the direct comparison analysis and the evaluation of the Nemerow pollution index, respectively. According to the Chinese food safety standards and the value of the target hazard quotient or hazard index, trace element contents of vegetables were safe for local residents in both systems. However, the spatial distribution of the estimated hazard index for producers still presented certain specific hotspots which may cause potential risk for human health in CGVPS. The water was mainly influenced by nitrogen, especially for CGVPS, while the potential risk of Cd and Cu pollution came from sediments in OGVPS. The main inputs for trace elements were fertilizers which were relatively safe based on relevant standards; but excess application caused trace element accumulations in the environmental media. Copyright © 2013 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Smieska, Louisa M.; Mullett, Ruth; Ferri, Laurent; Woll, Arthur R.
2017-07-01
We present trace-element and composition analysis of azurite pigments in six illuminated manuscript leaves, dating from the thirteenth to sixteenth century, using synchrotron-based, large-area x-ray fluorescence (SR-XRF) and diffraction (SR-XRD) mapping. SR-XRF mapping reveals several trace elements correlated with azurite, including arsenic, zirconium, antimony, barium, and bismuth, that appear in multiple manuscripts but were not always detected by point XRF. Within some manuscript leaves, variations in the concentration of trace elements associated with azurite coincide with distinct regions of the illuminations, suggesting systematic differences in azurite preparation or purification. Variations of the trace element concentrations in azurite are greater among different manuscript leaves than the variations within each individual leaf, suggesting the possibility that such impurities reflect distinct mineralogical/geologic sources. SR-XRD maps collected simultaneously with the SR-XRF maps confirm the identification of azurite regions and are consistent with impurities found in natural mineral sources of azurite. In general, our results suggest the feasibility of using azurite trace element analysis for provenance studies of illuminated manuscript fragments, and demonstrate the value of XRF mapping in non-destructive determination of trace element concentrations within a single pigment.
Co-digestion of manure and industrial waste--The effects of trace element addition.
Nordell, Erik; Nilsson, Britt; Nilsson Påledal, Sören; Karisalmi, Kaisa; Moestedt, Jan
2016-01-01
Manure is one of the most common substrates for biogas production. Manure from dairy- and swine animals are often considered to stabilize the biogas process by contributing nutrients and trace elements needed for the biogas process. In this study two lab-scale reactors were used to evaluate the effects of trace element addition during co-digestion of manure from swine- and dairy animals with industrial waste. The substrate used contained high background concentrations of both cobalt and nickel, which are considered to be the most important trace elements. In the reactor receiving additional trace elements, the volatile fatty acids (VFA) concentration was 89% lower than in the control reactor. The lower VFA concentration contributed to a more digested digestate, and thus lower methane emissions in the subsequent storage. Also, the biogas production rate increased with 24% and the biogas production yield with 10%, both as a result of the additional trace elements at high organic loading rates. All in all, even though 50% of the feedstock consisted of manure, trace element addition resulted in multiple positive effects and a more reliable process with stable and high yield. Copyright © 2015 Elsevier Ltd. All rights reserved.
Filler, Guido; Felder, Sarah
2014-08-01
In end-stage chronic kidney disease (CKD), pediatric nephrologists must consider the homeostasis of the multiple water-soluble ions that are influenced by renal replacement therapy (RRT). While certain ions such as potassium and calcium are closely monitored, little is known about the handling of trace elements in pediatric dialysis. RRT may lead to accumulation of toxic trace elements, either due to insufficient elimination or due to contamination, or to excessive removal of essential trace elements. However, trace elements are not routinely monitored in dialysis patients and no mechanism for these deficits or toxicities has been established. This review summarizes the handling of trace elements, with particular attention to pediatric data. The best data describe lead and indicate that there is a higher prevalence of elevated lead (Pb, atomic number 82) levels in children on RRT when compared to adults. Lead is particularly toxic in neurodevelopment and lead levels should therefore be monitored. Monitoring of zinc (Zn, atomic number 30) and selenium (Se, atomic number 34) may be indicated in the monitoring of all pediatric dialysis patients to reduce morbidity from deficiency. Prospective studies evaluating the impact of abnormal trace elements and the possible therapeutic value of intervention are required.
Arhin, Emmanuel; Zango, Musah S
2017-02-01
Ten samples of 100 g weight were subsampled from 1400 g of the clay balls from which the contained trace element levels were determined by X-ray fluorescence technique. The results of trace elements in the clay balls were calibrated using certified reference materials "MAJMON" and "BH-1." The results showed elevated concentrations but with different concentration levels in the regions, particularly with arsenic, chromium, cobalt, Cs, Zr and La. These trace elements contained in the clay balls are known to be hazardous to human health. Thence the relatively high concentrations of these listed trace elements in clay balls in the three regions, namely Ashanti, Upper East and Volta, which are widely sold in markets in Ghana, could present negative health impact on consumers if consumed at 70 g per day or more and on regular basis. On the basis of these, the study concludes an investigation to establish breakeven range for trace element concentrations in the clay balls as it has been able to demonstrate the uneven and elevated values in them. The standardized safe ranges of trace elements will make the practice safer for the people that ingest clay balls in Ghana.
Trace-element concentrations in streambed sediment across the conterminous United States
Rice, Karen C.
1999-01-01
Trace-element concentrations in 541 streambed-sediment samples collected from 20 study areas across the conterminous United States were examined as part of the National Water-Quality Assessment Program of the U.S. Geological Survey. Sediment samples were sieved and the <63-μm fraction was retained for determination of total concentrations of trace elements. Aluminum, iron, titanium, and organic carbon were weakly or not at all correlated with the nine trace elements examined: arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, and zinc. Four different methods of accounting for background/baseline concentrations were examined; however, normalization was not required because field sieving removed most of the background differences between samples. The sum of concentrations of trace elements characteristic of urban settings - copper, mercury, lead, and zinc - was well correlated with population density, nationwide. Median concentrations of seven trace elements (all nine examined except arsenic and selenium) were enriched in samples collected from urban settings relative to agricultural or forested settings. Forty-nine percent of the sites sampled in urban settings had concentrations of one or more trace elements that exceeded levels at which adverse biological effects could occur in aquatic biota.
Soluble trace elements and total mercury in Arctic Alaskan snow
Snyder-Conn, E.; Garbarino, J.R.; Hoffman, G.L.; Oelkers, A.
1997-01-01
Ultraclean field and laboratory procedures were used to examine trace element concentrations in northern Alaskan snow. Sixteen soluble trace elements and total mercury were determined in snow core samples representing the annual snowfall deposited during the 1993-94 season at two sites in the Prudhoe Bay oil field and nine sites in the Arctic National Wildlife Refuge (Arctic NWR). Results indicate there were two distinct point sources for trace elements in the Prudhoe Bay oil field - a source associated with oil and gas production and a source associated with municipal solid-waste incineration. Soluble trace element concentrations measured in snow from the Arctic NWR resembled concentrations of trace elements measured elsewhere in the Arctic using clean sample-collection and processing techniques and were consistent with deposition resulting from widespread arctic atmospheric contamination. With the exception of elements associated with sea salts, there were no orographic or east-west trends observed in the Arctic NWR data, nor were there any detectable influences from the Prudhoe Bay oil field, probably because of the predominant easterly and northeasterly winds on the North Slope of Alaska. However, regression analysis on latitude suggested significant south-to-north increases in selected trace element concentrations, many of which appear unrelated to the sea salt contribution.
The effects of trace element content on pyrite oxidation rates
NASA Astrophysics Data System (ADS)
Gregory, D. D.; Lyons, T.; Cliff, J. B.; Perea, D. E.; Johnson, A.; Romaniello, S. J.; Large, R. R.
2017-12-01
Pyrite acts as both an important source and sink for many different metals and metalloids in the environment, including many that are toxic. Oxidation of pyrite can release these elements while at the same time producing significant amounts of sulfuric acid. Such issues are common in the vicinity of abandoned mines and smelters, but, as pyrite is a common accessory mineral in many different lithologies, significant pyrite oxidation can occur whenever pyritic rocks are exposed to oxygenated water or the atmosphere. Accelerated exposure to oxygen can occur during deforestation, fracking for petroleum, and construction projects. Geochemical models for pyrite oxidation can help us develop strategies to mitigate these deleterious effects. An important component of these models is an accurate pyrite oxidation rate; however, current pyrite oxidation rates have been determined using relatively pure pyrite. Natural pyrite is rarely pure and has a wide range of trace element concentrations that may affect the oxidation rate. Furthermore, the position of trace elements within the mineral lattice can also affect the oxidation rate. For example, elements such as Ni and Co, which substitute into the pyrite lattice, are thought to stabilize the lattice and thus prevent pyrite oxidation. Alternatively, trace elements that are held within inclusions of other minerals could form a galvanic cell with the surrounding pyrite, thus enhancing pyrite oxidation rates. In this study, we present preliminary analyses from three different pyrite oxidation experiments each using natural pyrite with different trace element compositions. These results show that the pyrite with the highest trace element concentration has approximately an order of magnitude higher oxidation rate compared to the lowest trace element sample. To further elucidate the mechanisms, we employed microanalytical techniques to investigate how the trace elements are held within the pyrite. LA-ICPMS was used to determine the variability of trace element content from the pyrite samples. These data were then used to select areas of interest for NanoSIMS analyses, which in turn was used to select areas for TEM and APT. These analyses show that the trace element content of pyrite can be highly variable, which may significantly affect the rate of pyrite oxidation.
Maret, Terry R.; Skinner, K.D.
2000-01-01
Fish tissue and bed sediment samples were collected from 16 stream sites in the Northern Rockies Intermontane Basins study area in 1998 as part of the U.S. Geological Survey National Water-Quality Assessment Program. Bed sediment samples were analyzed for 45 trace elements, and fish livers and sportfish fillets were analyzed for 22 elements to characterize the occurrence and distribution of these elements in relation to stream characteristics and land use activities. Nine trace elements of environmental concern—arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, and zinc—were detected in bed sediment, but not all of these elements were detected in fish tissue. Trace-element concentrations were highest in bed sediment samples collected at sites downstream from significant natural mineral deposits and (or) mining activities. Arsenic, cadmium, copper, lead, mercury, and zinc in bed sediment at some sites were elevated relative to national median concentrations, and some concentrations were at levels that can adversely affect aquatic biota. Although trace-element concentrations in bed sediment exceeded various guidelines, no concentrations in sportfish fillets exceeded U.S. Environmental Protection Agency screening values for the protection of human health. Correlations between most trace-element concentrations in bed sediment and fish tissue (liver and fillet) were not significant (r0.05). Concentrations of arsenic, cadmium, copper, lead, mercury, nickel, selenium, and zinc in bed sediment were significantly correlated (r=0.53 to 0.88, p2=0.95 and 0.99, p<0.001) that corresponded to trace-element enrichment categories. These strong relations warrant further study using mine density as an explanatory variable to predict trace-element concentrations in bed sediment.
Trace Elements in Marine Sediment and Organisms in the Gulf of Thailand
Worakhunpiset, Suwalee
2018-01-01
This review summarizes the findings from studies of trace element levels in marine sediment and organisms in the Gulf of Thailand. Spatial and temporal variations in trace element concentrations were observed. Although trace element contamination levels were low, the increased urbanization and agricultural and industrial activities may adversely affect ecosystems and human health. The periodic monitoring of marine environments is recommended in order to minimize human health risks from the consumption of contaminated marine organisms. PMID:29677146
Model of Silicon Refining During Tapping: Removal of Ca, Al, and Other Selected Element Groups
NASA Astrophysics Data System (ADS)
Olsen, Jan Erik; Kero, Ida T.; Engh, Thorvald A.; Tranell, Gabriella
2017-04-01
A mathematical model for industrial refining of silicon alloys has been developed for the so-called oxidative ladle refining process. It is a lumped (zero-dimensional) model, based on the mass balances of metal, slag, and gas in the ladle, developed to operate with relatively short computational times for the sake of industrial relevance. The model accounts for a semi-continuous process which includes both the tapping and post-tapping refining stages. It predicts the concentrations of Ca, Al, and trace elements, most notably the alkaline metals, alkaline earth metal, and rare earth metals. The predictive power of the model depends on the quality of the model coefficients, the kinetic coefficient, τ, and the equilibrium partition coefficient, L for a given element. A sensitivity analysis indicates that the model results are most sensitive to L. The model has been compared to industrial measurement data and found to be able to qualitatively, and to some extent quantitatively, predict the data. The model is very well suited for alkaline and alkaline earth metals which respond relatively fast to the refining process. The model is less well suited for elements such as the lanthanides and Al, which are refined more slowly. A major challenge for the prediction of the behavior of the rare earth metals is that reliable thermodynamic data for true equilibrium conditions relevant to the industrial process is not typically available in literature.
NASA Astrophysics Data System (ADS)
George, Freya; Gaidies, Fred
2017-04-01
In comparison to our understanding of major element zoning, relatively little is known about the incorporation of trace elements into metamorphic garnet. Given their extremely slow diffusivities and sensitivity to changing mineral assemblages, the analysis of the distribution of trace elements in garnet has the potential to yield a wealth of information pertaining to interfacial attachment mechanisms during garnet crystallisation, the mobility of trace elements in both garnet and the matrix, and trace element geochronology. Due to advances in the spatial resolution and analytical precision of modern microbeam techniques, small-scale trace element variations can increasingly be documented and used to inform models of metamorphic crystallisation. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) in particular, can be used to rapidly quantify a wide range of elemental masses as a series of laser rasters, producing large volumes of spatially constrained trace element data. In this study, we present LA-ICP-MS maps of trace element concentrations from numerous centrally-sectioned garnets representative of the crystal size-distribution of a single sample's population. The study sample originates from the garnet-grade Barrovian zone of the Lesser Himalayan Sequence in Sikkim, northeast India, and has been shown to have crystallised garnet within a single assemblage between 515 ˚C and 565˚C, with no evidence for accessory phase reaction over the duration of garnet growth. Previous models have indicated that the duration of garnet crystallisation was extremely rapid (<1 Myr), with negligible diffusional homogenisation of major divalent cations. Consequently, the trace element record likely documents the primary zonation generated during garnet growth. In spite of straightforward (i.e. concentrically-zoned) major element garnet zonation, trace elements maps are characterised by significant complexity and variability. Y and the heavy rare earth elements are strongly enriched in crystal cores, where there is overprinting of the observed internal fabric, and exhibit numerous concentric annuli towards crystal rims. Conversely, the medium rare earth elements (e.g. Gd, Eu and Sm) exhibit bowl-shaped zoning from core to rim, with no annuli, and core and rim compositions of the medium rare earth elements are the same throughout the population within crystals of differing size. Cr exhibits pronounced spiral zoning, and the average Cr content increases towards garnet rims. In all cases, spirals are centered on the geometric core of the crystals. These LA-ICP-MS maps highlight the complexity of garnet growth over a single prograde event, and indicate that there is still much to be learnt from the analysis of garnet using ever-improving analytical methods. We explore the potential causes of the variations in the distribution of trace elements in garnet, and assess how these zoning patterns may be used to refine our understanding of the intricacies of garnet crystallisation and the spatial and temporal degree of trace element equilibration during metamorphism.
Trace elements in Mediterranean seagrasses and macroalgae. A review.
Bonanno, Giuseppe; Orlando-Bonaca, Martina
2018-03-15
This review investigates the current state of knowledge on the levels of the main essential and non-essential trace elements in Mediterranean vascular plants and macroalgae. The research focuses also on the so far known effects of high element concentrations on these marine organisms. The possible use of plants and algae as bioindicators of marine pollution is discussed as well. The presence of trace elements is overall well known in all five Mediterranean vascular plants, whereas current studies investigated element concentrations in only c. 5.0% of all native Mediterranean macroalgae. Although seagrasses and macroalgae can generally accumulate and tolerate high concentrations of trace elements, phytotoxic levels are still not clearly identified for both groups of organisms. Moreover, although the high accumulation of trace elements in seagrasses and macroalgae is considered as a significant risk for the associated food webs, the real magnitude of this risk has not been adequately investigated yet. The current research provides enough scientific evidence that seagrasses and macroalgae may act as effective bioindicators, especially the former for trace elements in sediments, and the latter in seawater. The combined use of seagrasses and macroalgae as bioindicators still lacks validated protocols, whose application should be strongly encouraged to biomonitor exhaustively the presence of trace elements in the abiotic and biotic components of coastal ecosystems. Copyright © 2017 Elsevier B.V. All rights reserved.
Rusk, Brian; Koenig, Alan; Lowers, Heather
2011-01-01
Cathodoluminescent (CL) textures in quartz reveal successive histories of the physical and chemical fluctuations that accompany crystal growth. Such CL textures reflect trace element concentration variations that can be mapped by electron microprobe or laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Trace element maps in hydrothermal quartz from four different ore deposit types (Carlin-type Au, epithermal Ag, porphyry-Cu, and MVT Pb-Zn) reveal correlations among trace elements and between trace element concentrations and CL textures. The distributions of trace elements reflect variations in the physical and chemical conditions of quartz precipitation. These maps show that Al is the most abundant trace element in hydrothermal quartz. In crystals grown at temperatures below 300 °C, Al concentrations may vary by up to two orders of magnitude between adjacent growth zones, with no evidence for diffusion. The monovalent cations Li, Na, and K, where detectable, always correlate with Al, with Li being the most abundant of the three. In most samples, Al is more abundant than the combined total of the monovalent cations; however, in the MVT sample, molar Al/Li ratios are ~0.8. Antimony is present in concentrations up to ~120 ppm in epithermal quartz (~200–300 °C), but is not detectable in MVT, Carlin, or porphyry-Cu quartz. Concentrations of Sb do not correlate consistently with those of other trace elements or with CL textures. Titanium is only abundant enough to be mapped in quartz from porphyry-type ore deposits that precipitate at temperatures above ~400 °C. In such quartz, Ti concentration correlates positively with CL intensity, suggesting a causative relationship. In contrast, in quartz from other deposit types, there is no consistent correlation between concentrations of any trace element and CL intensity fluctuations.
NASA Astrophysics Data System (ADS)
de Winter, Niels; Goderis, Steven; van Malderen, Stijn; Vanhaecke, Frank; Claeys, Philippe
2016-04-01
A combination of laboratory micro-X-ray Fluorescence (μXRF) and stable carbon and oxygen isotope analysis shows that trace element profiles from modern horse molars reveal a seasonal pattern that co-varies with seasonality in the oxygen isotope records of enamel carbonate from the same teeth. A combination of six cheek teeth (premolars and molars) from the same individual yields a seasonal isotope and trace element record of approximately three years recorded during the growth of the molars. This record shows that reproducible measurements of various trace element ratios (e.g., Sr/Ca, Zn/Ca, Fe/Ca, K/Ca and S/Ca) lag the seasonal pattern in oxygen isotope records by 2-3 months. Laser Ablation-ICP-Mass Spectrometry (LA-ICP-MS) analysis on a cross-section of the first molar of the same individual is compared to the bench-top tube-excitation μXRF results to test the robustness of the measurements and to compare both methods. Furthermore, trace element (e.g. Sr, Zn, Mg & Ba) profiles perpendicular to the growth direction of the same tooth, as well as profiles parallel to the growth direction are measured with LA-ICP-MS and μXRF to study the internal distribution of trace element ratios in two dimensions. Results of this extensive complementary line-scanning procedure shows the robustness of state of the art laboratory micro-XRF scanning for the measurement of trace elements in bioapatite. The comparison highlights the advantages and disadvantages of both methods for trace element analysis and illustrates their complementarity. Results of internal variation within the teeth shed light on the origins of trace elements in mammal teeth and their potential use for paleo-environmental reconstruction.
Wang, Guanxing; Zeng, Chen; Zhang, Fan; Zhang, Yili; Scott, Christopher A; Yan, Xuedong
2017-03-01
The accumulation of traffic-related trace elements in soil as the result of anthropogenic activities raises serious concerns about environmental pollution and public health. Traffic is the main source of trace elements in roadside soil on the Tibetan Plateau, an area otherwise devoid of industrial emissions. Indeed, the rapid development of tourism and transportation in this region means it is becoming increasingly important to identify the accumulation levels, influence distance, spatial distribution, and other relevant factors influencing trace elements. In this study, 229 soil samples along six segments of the major transportation routes on the Tibetan Plateau (highways G214, S308, and G109), were collected for analysis of eight trace elements (Cr, Co, Ni, As, Cu, Zn, Cd, and Pb). The results of statistical analyses showed that of the eight trace elements in soils, Cu, Zn, Cd, and Pb were primarily derived from traffic. The relationship between the trace element accumulation levels and the distance from the roadside followed an exponential decline, with the exception of Segment 3, the only unpaved gravel road studied. In addition, the distance of influence from the roadside varied by trace element and segment, ranging from 16m to 144m. Background values for each segment were different because of soil heterogeneity, while a number of other potential influencing factors (including traffic volume, road surface material, roadside distance, land cover, terrain, and altitude) all had significant effects on trace-element concentrations. Overall, however, concentrations along most of the road segments investigated were at, or below, levels defined as low on the Nemero Synthesis index. Copyright © 2017 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Li, Tao; Wang, Yan; Zhou, Jie; Wang, Tao; Ding, Aijun; Nie, Wei; Xue, Likun; Wang, Xinfeng; Wang, Wenxing
2017-03-01
Aerosols and cloud water were analyzed at a mountaintop in the planetary boundary layer in southern China during March-May 2009, when two Asian dust storms occurred, to investigate the effects of aerosol-cloud interactions (ACIs) on chemical evolution of atmospheric trace elements. Fe, Al, and Zn predominated in both coarse and fine aerosols, followed by high concentrations of toxic Pb, As, and Cd. Most of these aerosol trace elements, which were affected by dust storms, exhibited various increases in concentrations but consistent decreases in solubility. Zn, Fe, Al, and Pb were the most abundant trace elements in cloud water. The trace element concentrations exhibited logarithmic inverse relationships with the cloud liquid water content and were found highly pH dependent with minimum concentrations at the threshold of pH 5.0. The calculation of Visual MINTEQ model showed that 80.7-96.3% of Fe(II), Zn(II), Pb(II), and Cu(II) existed in divalent free ions, while 71.7% of Fe(III) and 71.5% of Al(III) were complexed by oxalate and fluoride, respectively. ACIs could markedly change the speciation distributions of trace elements in cloud water by pH modification. The in-cloud scavenging of aerosol trace elements likely reached a peak after the first 2-3 h of cloud processing, with scavenging ratios between 0.12 for Cr and 0.57 for Pb. The increases of the trace element solubility (4-33%) were determined in both in-cloud aerosols and postcloud aerosols. These results indicated the significant importance of aerosol-cloud interactions to the evolution of trace elements during the first several cloud condensation/evaporation cycles.
Hansen, Angela M. K.; Bryan, Colleen E.; West, Kristi; Jensen, Brenda A.
2016-01-01
The impacts of anthropogenic contaminants on marine ecosystems are a concern worldwide. Anthropogenic activities can enrich trace elements in marine biota to concentrations that may negatively impact organism health. Exposure to elevated concentrations of trace elements is considered a contributing factor in marine mammal population declines. Hawai'i is an increasingly important geographic location for global monitoring, yet trace element concentrations have not been quantified in Hawaiian cetaceans, and there is little trace element data for Pacific cetaceans. This study measured trace elements (Cr, Mn, Cu, Zn, As, Se, Sr, Cd, Sn, Hg, and Pb) in liver of 16 species of cetaceans that stranded on U.S. Pacific Islands from 1997–2013, using high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) (n = 31), and direct mercury analysis atomic absorption spectrometry (DMA-AAS) (n = 43). Concentration ranges (µg/g wet mass fraction) for non-essential trace elements such as Cd (0.0031–58.93) and Hg (0.0062–1571.75) were much greater than essential trace elements such as Mn (0.590–17.31) and Zn (14.72–245.38). Differences were found among age classes in Cu, Zn, Hg, and Se concentrations. The highest concentrations of Se, Cd, Sn, Hg, and Pb were found in one adult female false killer whale (Pseudorca crassidens) at concentrations that are known to affect health in marine mammals. The results of this study establish initial trace element concentration ranges for Pacific cetaceans in the Hawaiian Islands region, provide insights into contaminant exposure of these marine mammals, and contribute to a greater understanding of anthropogenic impacts in the Pacific Ocean. PMID:26283019
Hansen, Angela M K; Bryan, Colleen E; West, Kristi; Jensen, Brenda A
2016-01-01
The impacts of anthropogenic contaminants on marine ecosystems are a concern worldwide. Anthropogenic activities can enrich trace elements in marine biota to concentrations that may negatively impact organism health. Exposure to elevated concentrations of trace elements is considered a contributing factor in marine mammal population declines. Hawai'i is an increasingly important geographic location for global monitoring, yet trace element concentrations have not been quantified in Hawaiian cetaceans, and there is little trace element data for Pacific cetaceans. This study measured trace elements (Cr, Mn, Cu, Zn, As, Se, Sr, Cd, Sn, Hg, and Pb) in liver of 16 species of cetaceans that stranded on U.S. Pacific Islands from 1997 to 2013, using high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) (n = 31), and direct mercury analysis atomic absorption spectrometry (DMA-AAS) (n = 43). Concentration ranges (μg/g wet mass fraction) for non-essential trace elements, such as Cd (0.0031-58.93) and Hg (0.0062-1571.75) were much greater than essential trace elements, such as Mn (0.590-17.31) and Zn (14.72-245.38). Differences were found among age classes in Cu, Zn, Hg, and Se concentrations. The highest concentrations of Se, Cd, Sn, Hg, and Pb were found in one adult female false killer whale (Pseudorca crassidens) at concentrations that are known to affect health in marine mammals. The results of this study establish initial trace element concentration ranges for Pacific cetaceans in the Hawaiian Islands region, provide insights into contaminant exposure of these marine mammals, and contribute to a greater understanding of anthropogenic impacts in the Pacific Ocean.
Ünal, Burcu; Perry, Verlin Ryan; Sheth, Mili; Gomez-Alvarez, Vicente; Chin, Kuk-Jeong; Nüsslein, Klaus
2012-01-01
Microbial methane from coal beds accounts for a significant and growing percentage of natural gas worldwide. Our knowledge of physical and geochemical factors regulating methanogenesis is still in its infancy. We hypothesized that in these closed systems, trace elements (as micronutrients) are a limiting factor for methanogenic growth and activity. Trace elements are essential components of enzymes or cofactors of metabolic pathways associated with methanogenesis. This study examined the effects of eight trace elements (iron, nickel, cobalt, molybdenum, zinc, manganese, boron, and copper) on methane production, on mcrA transcript levels, and on methanogenic community structure in enrichment cultures obtained from coal bed methane (CBM) well produced water samples from the Powder River Basin, Wyoming. Methane production was shown to be limited both by a lack of additional trace elements as well as by the addition of an overly concentrated trace element mixture. Addition of trace elements at concentrations optimized for standard media enhanced methane production by 37%. After 7 days of incubation, the levels of mcrA transcripts in enrichment cultures with trace element amendment were much higher than in cultures without amendment. Transcript levels of mcrA correlated positively with elevated rates of methane production in supplemented enrichments (R2 = 0.95). Metabolically active methanogens, identified by clone sequences of mcrA mRNA retrieved from enrichment cultures, were closely related to Methanobacterium subterraneum and Methanobacterium formicicum. Enrichment cultures were dominated by M. subterraneum and had slightly higher predicted methanogenic richness, but less diversity than enrichment cultures without amendments. These results suggest that varying concentrations of trace elements in produced water from different subsurface coal wells may cause changing levels of CBM production and alter the composition of the active methanogenic community. PMID:22590465
Pongpiachan, Siwatt; Ho, Kin Fai; Cao, Junji
2013-01-01
To assess environmental contamination with carcinogens, carbonaceous compounds, water-soluble ionic species and trace gaseous species were identified and quantified every three hours for three days at three different atmospheric layers at the heart of Chiang-Mai, Bangkok and Hat-Yai from December 2006 to February 2007. A DRI Model 2001 Thermal/Optical Carbon Analyzer with the IMPROVE thermal/optical reflectance (TOR) protocol was used to quantify the organic carbon (OC) and elemental carbon (EC) contents in PM10. Diurnal and vertical variability was also carefully investigated. In general, OC and EC mass concentration showed the highest values at the monitoring period of 21.00-00.00 as consequences of human activities at night bazaar coupled with reduction of mixing layer, decreased wind speed and termination of photolysis at nighttime. Morning peaks of carbonaceous compounds were observed during the sampling period of 06:00-09:00, emphasizing the main contribution of traffic emission in the three cities. The estimation of incremental lifetime particulate matter exposure (ILPE) raises concern of high risk of carbonaceous accumulation over workers and residents living close to the observatory sites. The average values of incremental lifetime particulate matter exposure (ILPE) of total carbon at Baiyoke Suit Hotel and Baiyoke Sky Hotel are approximately ten times higher than those air samples collected at Prince of Songkla University Hat-Yai campus corpse incinerator and fish-can manufacturing factory but only slightly higher than those of rice straw burning in Songkla province. This indicates a high risk of developing lung cancer and other respiratory diseases across workers and residents living in high buildings located in Pratunam area. Using knowledge of carbonaceous fractions in PM10, one can estimate the gas-particle partitioning of polycyclic aromatic hydrocarbons (PAHs). Dachs-Eisenreich model highlights the crucial role of adsorption in gas-particle partitioning of low molecular weight PAHs, whereas both absorption and adsorption tend to account for gas-particle partitioning of high molecular weight PAHs in urban residential zones of Thailand. Interestingly, the absorption mode alone plays a minor role in gas-particle partitioning of PAHs in Chiang-Mai, Bangkok and Hat-Yai.
Trace Element Concentrations in Beef Cattle Related to the Breed Aptitude.
Pereira, Victor; Carbajales, Paloma; López-Alonso, Marta; Miranda, Marta
2018-02-24
Animal feed has traditionally been supplemented with trace elements at dietary concentrations well above physiological needs. However, environmental concerns have led to calls for better adjustment of mineral supplementation to actual physiological needs and, in this context, consideration of breed-related differences in trace element requirements. The aim of this study was to analyze trace element concentrations in the main breeds used for intensive beef production in northern Spain (Holstein-Friesian [HF], Galician Blonde [GB], and GB × HF cross). Samples of blood, internal organs, and muscle were obtained at slaughter from 10 HF, GB, and GB × HF cross calves in the same feedlot. Overall, trace element concentrations in serum and internal organs were within adequate ranges and did not differ between those of breeds, suggesting that trace mineral supplementation was adequate in all groups. The only exception to this was copper, and hepatic copper concentrations were above adequate levels in all calves. This was particularly evident in the HF calves, and the maximum recommended level for human consumption was exceeded in 90% of these animals. Copper, iron, manganese, selenium, and zinc concentrations in muscle were significantly higher in the HF than those in the GB calves, with intermediate values for the crosses. These breed-related differences in trace element concentrations in the muscle may be related to lower muscle mass and/or higher hepatic activity in the HF (dairy) calves than in GB (beef) calves. As meat is an essential source of highly available trace elements in human diets, breed-related differences in trace element concentrations in meat deserve further investigation.
Trace Elements in Parenteral Nutrition: Considerations for the Prescribing Clinician
Jin, Jennifer; Mulesa, Leanne; Carrilero Rouillet, Mariana
2017-01-01
Trace elements (TEs) are an essential component of parenteral nutrition (PN). Over the last few decades, there has been increased experience with PN, and with this knowledge more information about the management of trace elements has become available. There is increasing awareness of the effects of deficiencies and toxicities of certain trace elements. Despite this heightened awareness, much is still unknown in terms of trace element monitoring, the accuracy of different assays, and current TE contamination of solutions. The supplementation of TEs is a complex and important part of the PN prescription. Understanding the role of different disease states and the need for reduced or increased doses is essential. Given the heterogeneity of the PN patients, supplementation should be individualized. PMID:28452962
Fessler, Theresa A
2013-12-01
Parenteral nutrition (PN) is a life-sustaining therapy for hundreds of thousands of people who have severe impairment of gastrointestinal function. Trace elements are a small but very important part of PN that can be overlooked during busy practice. Serious complications can result from trace element deficiencies and toxicities, and this is especially problematic during times of product shortages. Practical information on parenteral trace element use can be gleaned from case reports, some retrospective studies, and very few randomized controlled trials. A general knowledge of trace element metabolism and excretion, deficiency and toxicity symptoms, products, optimal dosages, and strategies for supplementation, restriction, and monitoring will equip practitioners to provide optimal care for their patients who depend on PN.
Trace Elements in Parenteral Nutrition: Considerations for the Prescribing Clinician.
Jin, Jennifer; Mulesa, Leanne; Carrilero Rouillet, Mariana
2017-04-28
Trace elements (TEs) are an essential component of parenteral nutrition (PN). Over the last few decades, there has been increased experience with PN, and with this knowledge more information about the management of trace elements has become available. There is increasing awareness of the effects of deficiencies and toxicities of certain trace elements. Despite this heightened awareness, much is still unknown in terms of trace element monitoring, the accuracy of different assays, and current TE contamination of solutions. The supplementation of TEs is a complex and important part of the PN prescription. Understanding the role of different disease states and the need for reduced or increased doses is essential. Given the heterogeneity of the PN patients, supplementation should be individualized.
Approximation algorithm for the problem of partitioning a sequence into clusters
NASA Astrophysics Data System (ADS)
Kel'manov, A. V.; Mikhailova, L. V.; Khamidullin, S. A.; Khandeev, V. I.
2017-08-01
We consider the problem of partitioning a finite sequence of Euclidean points into a given number of clusters (subsequences) using the criterion of the minimal sum (over all clusters) of intercluster sums of squared distances from the elements of the clusters to their centers. It is assumed that the center of one of the desired clusters is at the origin, while the center of each of the other clusters is unknown and determined as the mean value over all elements in this cluster. Additionally, the partition obeys two structural constraints on the indices of sequence elements contained in the clusters with unknown centers: (1) the concatenation of the indices of elements in these clusters is an increasing sequence, and (2) the difference between an index and the preceding one is bounded above and below by prescribed constants. It is shown that this problem is strongly NP-hard. A 2-approximation algorithm is constructed that is polynomial-time for a fixed number of clusters.
NASA Astrophysics Data System (ADS)
Dungan, M. A.; Vance, J. A.; Blanchard, D. P.
1983-06-01
The Shuksan schist comprises a structurally coherent, metabasaltic member of the Easton Formation, the uppermost allochthon (Shuksan thrust plate) in the thrust system of the western North Cascades of Washington State. Late Jurassic metamorphism at moderately high P/T produced interlayering of actinolite-bearing greenschist assemblages with blue amphibole-bearing rocks. Major and trace element analyses of twelve greenschist and blueschist samples have been used to establish similarities between the basaltic protolith and moderately to strongly fractionated Type I MORB, to distinguish the effects of seafloor alteration superimposed on the primary igneous chemistry, and to evaluate the origin and nature of the chemical controls which produced the two mineral assemblages. The twelve analyzed samples exhibit moderate to strong LREE depletion, and characteristically low concentrations of other non-labile trace elements such as Nb, Th and Hf. The highly to moderately incompatible elements Ti, P, Nb, Zr, Hf, Y, Sc, and the REE vary by factors of 1.5 to 3.5 within the suite in a systematic pattern, increasing smoothly with increasing total iron. The relative enrichments of these elements are inversely proportional to bulk partition coefficients estimated for fractionation of basaltic magmas. The magnitude of the negative europium anomaly increases with overall incompatible element enrichment. These variations are consistent with the production of a wide spectrum of compositions by different degrees of low pressure fractionation of similar Type I MORB parent magmas. The concentrations of Sr, Rb, Na, and K vary irregularly and do not correlate with the non-labile trace elements. K and Rb are substantially elevated over typical MORB values in most samples and exhibit a consistently lower ratio (K/Rb=400 vs 1000) than fresh MORB. Concentrations of these four elements are believed to have been modified by low temperature seafloor alteration (pre-metamorphic) characterized by the formation of K-rich celadonitic clays, palagonite and minor potassium feldspar. The critical chemical variables that control the occurrence of actinolite and blue amphibole in the Shuksan schists are total iron, Fe2O3-content and Na/Ca (all high in blueschists). The chemical features were largely established by magmatic processes and inherited from the igneous parent rocks; the chemically more evolved samples are blueschists. The Fe2O3-content and Na/Ca, however, may be modified during alteration, rendering initial bulk compositions near the chemical boundary susceptible to changes which may shift rock compositions from one compatibility field to the other. Heterogeneous alteration of pillow lavas and other fragmental deposits, followed by intense flattening during metamorphism, provides a mechanism for generating blueschists and greenschists interlayered on the cm scale.
Sanal, Hasan; Güler, Zehra; Park, Young W
2011-01-01
The objectives of this study were to determine the profiles of non-essential trace elements in ewes' and goats' milk and manufactured products, such as yoghurt, torba yoghurt and whey, as well as changes in trace element content during Torba yoghurt-making processes. Concentrations of non-essential trace elements in ewe (Awassi) and goat (Damascus) milk and their yoghurt, torba yoghurt and whey were quantitatively determined by simultaneous inductively coupled plasma optical emission spectrometer (ICP-OES), after microwave digestion. Aluminium, antimony, arsenic, boron, beryllium, cadmium, nickel, lead, silver, titanium, thallium and vanadium were determined for both types of milk and their products. Barium was not detected in goats' milk or their products. Among all trace elements, boron was the most abundant and beryllium was least present in milk and the manufactured products. The results showed that goats' and ewes' milk and their manufactured products may be a source of 13 non-essential trace elements.
NASA Astrophysics Data System (ADS)
Xia, Xiaohong; Qin, Yong; Yang, Weifeng
2013-03-01
Coal liquefaction is an adoptable method to transfer the solid fossil energy into liquid oil in large scale, but the dirty material in which will migrate to different step of liquefaction. The migration rule of some trace elements is response to the react activity of macerals in coal and the geological occurrence of the element nature of itself. In this paper, from the SPSS data correlation analysis and hierarchical clustering dendrogram about the trace elements with macerals respond to coal liquefaction yield, it shows the trace elements in No.11 Antaibao coal seam originated from some of lithophile and sulphophle elements. Correlation coefficient between liquefaction yield of three organic macerals and migration of the elements in liquefaction residue indicated that the lithophile are easy to transfer to residue, while sulphophle are apt to in the liquid products. The activated macerals are response to sulphophle trace elements. The conclusion is useful to the coal blending and environmental effects on coal direct liquefaction.
Variation in Macro and Trace Elements in Progression of Type 2 Diabetes
2014-01-01
Macro elements are the minerals of which the body needs more amounts and are more important than any other elements. Trace elements constitute a minute part of the living tissues and have various metabolic characteristics and functions. Trace elements participate in tissue and cellular and subcellular functions; these include immune regulation by humoral and cellular mechanisms, nerve conduction, muscle contractions, membrane potential regulations, and mitochondrial activity and enzyme reactions. The status of micronutrients such as iron and vanadium is higher in type 2 diabetes. The calcium, magnesium, sodium, chromium, cobalt, iodine, iron, selenium, manganese, and zinc seem to be low in type 2 diabetes while elements such as potassium and copper have no effect. In this review, we emphasized the status of macro and trace elements in type 2 diabetes and its advantages or disadvantages; this helps to understand the mechanism, progression, and prevention of type 2 diabetes due to the lack and deficiency of different macro and trace elements. PMID:25162051
NASA Astrophysics Data System (ADS)
Fehrenbacher, J. S.; Russell, A. D.; Davis, C. V.; Spero, H. J.; Chu, E.
2015-12-01
The Ba/Ca ratio in several spinose planktic foraminifer species varies as a function of the Ba/Ca concentration of seawater and is not affected by other parameters such as the seawater salinity, temperature and pH (Honisch et al., 2011). Since seawater Ba concentration is linearly related to Ba in nearshore environments, Ba/Ca ratios in spinose species shows promise as an indicator of past changes in monsoon strength and river runoff (e. g. Weldeab et al. 2007). In contrast, the non-spinose foraminifers often have intrashell variability in Ba/Ca, with Ba/Ca ratios much higher than expected for the range of Ba concentrations observed in the ocean. Furthermore, the Ba/Ca ratio can vary by over a factor of 10 within a single specimen. This suggests either 1) the partition coefficient for Ba in non-spinose species differs from that determined for spinose species, or 2) non-spinose species calcify in a micro-environment that is enriched in Ba. We conducted experiments on live specimens to determine the partition coefficient for Ba in the non-spinose foraminifer N. dutertrei. Specimens were collected via plankton net from the Southern California Bight and cultured at the Wrigley Marine Science Center, Santa Catalina Island during the summer of 2013-2015. We use isotopically labeled seawater (87Sr) to identify discrete portions of calcite that grew in culture. We use laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for trace element analyses and to identify ocean grown vs. culture grown calcite. We show that the partition coefficient is similar to the spinose species: N. dutertrei incorporates Ba as a function of seawater chemistry. We conclude from these observations that N. dutertrei forms its calcite from fluids enriched in Ba, and hypothesize that this process occurs via attachment to organic-rich particles such as marine snow.
High-fluorine rhyolite: An eruptive pegmatite magma at the Honeycomb Hills, Utah
NASA Astrophysics Data System (ADS)
Congdon, Roger D.; Nash, W. P.
1988-11-01
The Honeycomb Hills rhyolite dome in western Utah displays chemical and mineralogical features characteristic of a rare-element pegmatite magma. The lavas show extreme enrichments in such trace elements as Rb (≤1960 ppm), Cs (≤78), Li (≤344), Sn (≤33), Be (≤270), and Y (≤156). Phenocrysts (10%-50% by volume) include sanidine (Or66-70), plagioclase (Ab83-92), quartz, biotite approaching fluorsiderophyllite, and fluortopaz, as well as accessory phases common to highly differentiated granites and pegmatites, including zircon, thorite, fluocerite, columbite, fergusonite, and samarskite. Low temperatures (600 to 640 °C), coupled with high phenocryst and silica content, might normally preclude eruption due to the extremely high viscosity of the melt. However, high concentrations of fluorine (2%-3%) could domal lavas significantly reduce viscosity and allow eruption of domal lavas even after dewatering of the mama during the initial pyroclastic phase of the eruptive cycle. Fractionation of phenocrysts and accessory phases, for which partition coefficients have been measured, is sufficient to account for most compositional gradients inferred in the preeruptive magma body, although transport by a fluid phase formed a may have caused upward enrichments in Li, Be, and Cs. If the Honeycomb Hills magma had crystallized at depth, it would have formed a rare-element pegmatite.
Pardo, Tania; Bes, Cleménce; Bernal, Maria Pilar; Clemente, Rafael
2016-11-01
Tailings are considered one of the most relevant sources of contamination associated with mining activities. Phytostabilization of mine spoils may need the application of the adequate combination of amendments to facilitate plant establishment and reduce their environmental impact. Two pot experiments were set up to assess the capability of 2 inorganic materials (calcium carbonate and a red mud derivate, ViroBind TM ), alone or in combination with organic amendments, for the stabilization of highly acidic trace element-contaminated mine tailings using Atriplex halimus. The effects of the treatments on tailings and porewater physico-chemical properties and trace-element accumulation by the plants, as well as the processes governing trace elements speciation and solubility in soil solution and their bioavailability were modeled. The application of the amendments increased tailings pH and decreased (>99%) trace elements solubility in porewater, but also changed the speciation of soluble Cd, Cu, and Pb. All the treatments made A. halimus growth in the tailings possible; organic amendments increased plant biomass and nutritional status, and reduced trace-element accumulation in the plants. Tailings amendments modified trace-element speciation in porewater (favoring the formation of chlorides and/or organo-metallic forms) and their solubility and plant uptake, which were found to be mainly governed by tailing/porewater pH, electrical conductivity, and organic carbon content, as well as soluble/available trace-element concentrations. Environ Toxicol Chem 2016;35:2874-2884. © 2016 SETAC. © 2016 SETAC.
The geographic distribution of trace elements in the environment: the REGARDS study.
Rembert, Nicole; He, Ka; Judd, Suzanne E; McClure, Leslie A
2017-02-01
Research on trace elements and the effects of their ingestion on human health is often seen in scientific literature. However, little research has been done on the distribution of trace elements in the environment and their impact on health. This paper examines what characteristics among participants in the Reasons for Geographic and Racial Differences in Stroke (REGARDS) study are associated with levels of environmental exposure to arsenic, magnesium, mercury, and selenium. Demographic information from REGARDS participants was combined with trace element concentration data from the US Geochemical Survey (USGS). Each trace element was characterized as either low (magnesium and selenium) or high (arsenic and mercury) exposure. Associations between demographic characteristics and trace element concentrations were analyzed with unadjusted and adjusted logistic regression models. Individuals who reside in the Stroke Belt have lower odds of high exposure (4th quartile) to arsenic (OR 0.33, CI 0.31, 0.35) and increased exposure to mercury (OR 0.65, CI 0.62, 0.70) than those living outside of these areas, while the odds of low exposure to trace element concentrations were increased for magnesium (OR 5.48, CI 5.05, 5.95) and selenium (OR 2.37, CI 2.22, 2.54). We found an association between levels of trace elements in the environment and geographic region of residence, among other factors. Future studies are needed to further examine this association and determine whether or not these differences may be related to geographic variation in disease.
Jablan, Jasna; Inić, Suzana; Stosnach, Hagen; Hadžiabdić, Maja Ortner; Vujić, Lovorka; Domijan, Ana-Marija
2017-05-01
The aim of the present study was to explore impact of endurance exercise on urinary level of minerals and trace elements as well as on some oxidative stress and biochemical parameters. Urine samples were collected from participants (n=21) of mountain ultra-marathon race (53km; Medvednica, Zagreb, Croatia), before (baseline value), immediately after, 12h and 24h after the race. In urine samples level of minerals (Ca, P, K and Na) and trace elements (Se, Zn, Mn, Cu, Fe and Co) were assessed using the bench top Total reflection X-ray Fluorescence (TXRF) spectrometer. Oxidative stress was determined as level of malondialdehyde (MDA). Immediately after the race level of minerals, trace elements, MDA, creatinine, ketones, erythrocytes and specific gravity increased compared to their baseline value. In 24h follow-up trace elements involved in antioxidant defence, MDA and biochemical parameters returned to their baseline values, Cu and Co remained increased as after the race, Fe and K tended to return to baseline values while Ca, P and Na continued to increase. Mountain ultra-marathon resulted in alteration of physiologically important minerals and trace elements that for some minerals and trace elements persist, indicating their involvement in recovery processes. However, due to their loss in urine, level of minerals and trace elements in athletes participating in endurance exercise should be monitored. Copyright © 2017 Elsevier GmbH. All rights reserved.
Iron Partitioning in Ferropericlase and Consequences for the Magma Ocean.
NASA Astrophysics Data System (ADS)
Braithwaite, J. W. H.; Stixrude, L. P.; Holmstrom, E.; Pinilla, C.
2016-12-01
The relative buoyancy of crystals and liquid is likely to exert a strong influence on the thermal and chemical evolution of the magma ocean. Theory indicates that liquids approach, but do not exceed the density of iso-chemical crystals in the deep mantle. The partitioning of heavy elements, such as Fe, is therefore likely to control whether crystals sink or float. While some experimental results exist, our knowledge of silicate liquid-crystal element partitioning is still limited in the deep mantle. We have developed a method for computing the Mg-Fe partitioning of Fe in such systems. We have focused initially on ferropericlase, as a relatively simple system where the buoyancy effects of Fe partitioning are likely to be large. The method is based on molecular dynamics driven by density functional theory (spin polarized, PBEsol+U). We compute the free energy of Mg for Fe substitution in simulations of liquid and B1 crystalline phases via adiabatic switching. We investigate the dependence of partitioning on pressure, temperature, and iron concentration. We find that the liquid is denser than the coexisting crystalline phase at all conditions studies. We also find that the high-spin to low-spin transition in the crystal and the liquid, have an important influence on partitioning behavior.
Bai, Junhong; Xiao, Rong; Zhao, Qingqing; Lu, Qiongqiong; Wang, Junjing; Reddy, K. Ramesh
2014-01-01
Soil profiles were collected in three salt marshes with different plant species (i.e. Phragmites australis, Tamarix chinensis and Suaeda salsa) in the Yellow River Delta (YRD) of China during three seasons (summer and fall of 2007 and the following spring of 2008) after the flow-sediment regulation regime. Total elemental contents of As, Cd, Cu, Pb and Zn were determined using inductively coupled plasma atomic absorption spectrometry to investigate temporal variations in trace elements in soil profiles of the three salt marshes, assess the enrichment levels and ecological risks of these trace elements in three sampling seasons and identify their influencing factors. Trace elements did not change significantly along soil profiles at each site in each sampling season. The highest value for each sampling site was observed in summer and the lowest one in fall. Soils in both P. australis and S. salsa wetlands tended to have higher trace element levels than those in T. chinensis wetland. Compared to other elements, both Cd and As had higher enrichment factors exceeding moderate enrichment levels. However, the toxic unit (TU) values of these trace elements did not exceed probable effect levels. Correlation analysis showed that these trace elements were closely linked to soil properties such as moisture, sulfur, salinity, soil organic matter, soil texture and pH values. Principal component analysis showed that the sampling season affected by the flow-sediment regulation regime was the dominant factor influencing the distribution patterns of these trace elements in soils, and plant community type was another important factor. The findings of this study could contribute to wetland conservation and management in coastal regions affected by the hydrological engineering. PMID:25216278
NASA Astrophysics Data System (ADS)
Rosenthal, A.; Hauri, E. H.; Hirschmann, M. M.
2015-02-01
To determine partitioning of C between upper mantle silicate minerals and basaltic melts, we executed 26 experiments between 0.8 and 3 GPa and 1250-1500 °C which yielded 37 mineral/glass pairs suitable for C analysis by secondary ion mass spectrometry (SIMS). To enhance detection limits, experiments were conducted with 13C-enriched bulk compositions. Independent measurements of 13C and 12C in coexisting phases produced two C partition coefficients for each mineral pair and allowed assessment of the approach to equilibrium during each experiment. Concentrations of C in olivine (ol), orthopyroxene (opx), clinopyroxene (cpx) and garnet (gt) range from 0.2 to 3.5 ppm, and resulting C partition coefficients for ol/melt, opx/melt, cpx/melt and gt/melt are, respectively, 0.0007 ± 0.0004 (n = 2), 0.0003 ± 0.0002 (n = 45), 0.0005 ± 0.0004 (n = 17) and 0.0001 ± 0.00007 (n = 5). The effective partition coefficient of C during partial melting of peridotite is 0.00055 ± 0.00025, and therefore C is significantly more incompatible than Nb, slightly more compatible than Ba, and, among refractory trace elements, most similar in behavior to U or Th. Experiments also yielded partition coefficients for F and H between minerals and melts. Combining new and previous values of DFmineral/melt yields bulk DFperidotite/melt = 0.011 ± 0.002, which suggests that F behaves similarly to La during partial melting of peridotite. Values of DHpyx/melt correlate with tetrahedral Al along a trend consistent with previously published determinations. Small-degree partial melting of the mantle results in considerable CO2/Nb fractionation, which is likely the cause of high CO2/Nb evident in some Nb-rich oceanic basalts. CO2/Ba is much less easily fractionated, with incompatible-element-enriched partial melts having lower CO2/Ba than less enriched basalts. Comparison of calculated behavior of CO2, Nb, and Ba to systematics of oceanic basalts suggests that depleted (DMM-like) sources have 75 ± 25 ppm CO2 (CO2/Nb = 505 ± 168, CO2/Ba = 133 ± 44), whereas enriched sources of intraplate basalts similar in concentrations to primitive mantle have 600 ± 200 ppm CO2. If all mantle reservoirs are expressed in the current inventory of oceanic basalts for which nearly undegassed CO2 concentrations are available, then we estimate the likely range of mantle C concentrations to be 1.4-4.8 × 1023 grams of C, or 1.5-5.2 times the mass of the current C surface reservoir. Depending on the assumed Ba and Nb contents of average oceanic crust, resulting ridge fluxes of C range from 7.2 × 1013 to 2.9 × 1014 g/yr.
NASA Astrophysics Data System (ADS)
Uno, M.; Nakamura, H.; Iwamori, H.
2011-12-01
Individual parcel of regional metamorphic rock records physico-chemical conditions such as P-T path, mass transfer and deformation with the Lagrangian specification. On the other hand, a metamorphic belt as an ensemble of such parcels may provide a large-scale flow field of energy (e.g., temperature, entropy) and mass (including both solid and fluid phases with elements and isotopes) with the Eulerian specification. However, there is so far few model that integrates all the variables stated above. Phase petrology provides mostly the intensive variables (e.g., P-T path), whereas geochemistry provides mostly the extensive variables (time-integrated mass transfer), and these two have been treated separately. Here we combine phase petrology and geochemistry from a scale of mineral grain, and solve them under a simultaneous and consistent set of thermodynamic and mass balance equation. For this sake, the Sanbagawa metamorphic belt in Japan has been surveyed. To understand the nature of fluid during rehydration, we analyzed both basic rocks and pelitic rocks that record retrograde reactions. Major and trace element compositions of each mineral, and bulk rock chemistry have been analyzed with EPMA, LA-ICP-MS, XRF and ICP-MS, respectively. Retrograde P-T path and the extent of rehydration of each rock have been obtained by applying the Gibbs' method (e.g. Spear, 1993; Okamoto&Toriumi, 2001) to amphiboles. Trace element budget along a specific P-T path were calculated by equating differential mass balance equation for major and trace elements as follows; XfluiddMfluid = ⊙MsolidXsolid + ⊙XsoliddMsolid Where the X and M denotes compositions and modes of minerals and dX and dM are their changes along a specific P-T change. The mineral compositions (Xsolid), mineral modes (Msolid), mineral growths (dMsolid) for zoned minerals (amphibole and/or garnet) and fluid compositions (Xfluid) were derived from the results of Gibbs' method, X-ray map and fluid/mineral partition coefficients, respectively. Thus, the unknowns are dMs, and the equations are solved for them. As a result, the mass transfer during the specific P-T change (Xfluid dMfluid) can be specified. It is revealed that fluid mobile elements such as LIL elements, Sr and Pb are mostly proportional to LOI (loss on ignition). LOI and extent of rehydration is proportional in the Sanbagawa belt (Okamoto&Toriumi, 2005), thus the observed enrichment of LILE, Sr and Pb are interpreted to be associated with rehydration. The Sr isotope ratios of the basic shists also increase with LOI, implying that the differences in bulk rock chemistry are not attributed to differences in mineral modes,but addition and/or reaction with external source of fluids with high 87Sr/86Sr. The estimated fluid composition is similar to calculated compositions of slab-derived fluids (Nakamura et al., 2008). From mass balance calculation, trace element budget associated with rehydration reactions and their spatial distribution will be presented, and the mechanisms of mass and fluid transfer will be discussed.
NASA Technical Reports Server (NTRS)
Jolliff, Bradley L.; Haskin, Larry A.; Colson, Russell O.; Wadhwa, Meenakshi
1993-01-01
Compositions, including REEs determined by ion microprobe, of apatite and whitlockite in lunar rock assemblages rich in incompatible trace elements, are presented. Concentrations of REEs in lunar whitlockites are high, ranging from about 1.2 to 2.1 REEs (lanthanides + Y) per 56 oxygens. This slightly exceeds the level of two REE atoms per 56 oxygens at which the dominant substitution theoretically becomes saturated. This saturation effect leads to whitlockite REE(3+) D values at typical lunar whitlockite REE concentrations which are 30-40 percent lower than the D values at low concentrations. The halogen-to-phosphorous ratio in lunar melts is a key factor determining the REE distribution with crystalline assemblages. As long as P and REE concentrations of melts are in KREEP-like proportions, one or both of the phosphates will saturate in melts at similar REE concentrations.
Cai, Yaomin; Guo, Zhixiong
2018-04-20
The Monte Carlo model was developed to simulate the collimated solar irradiation transfer and energy harvest in a hollow louver made of silica glass and filled with water. The full solar spectrum from the air mass 1.5 database was adopted and divided into various discrete bands for spectral calculations. The band-averaged spectral properties for the silica glass and water were obtained. Ray tracing was employed to find the solar energy harvested by the louver. Computational efficiency and accuracy were examined through intensive comparisons of different band partition approaches, various photon numbers, and element divisions. The influence of irradiation direction on the solar energy harvest efficiency was scrutinized. It was found that within a 15° polar angle of incidence, the harvested solar energy in the louver was high, and the total absorption efficiency reached 61.2% under normal incidence for the current louver geometry.
Chromium fractionation and speciation in natural waters.
Pereira, Catarinie Diniz; Techy, João Gabriel; Ganzarolli, Edgard Moreira; Quináia, Sueli Pércio
2012-05-01
It is common for leather industries to dump chromium-contaminated effluent into rivers and other bodies of water. Thus, it is crucial to know the impacts caused by this practice to the environment. A study on chromium partitioning and speciation, with determination at trace levels, was carried out in a potentially contaminated creek. Chromium fractionation and speciation was performed using a flow-injection preconcentration system and detection by flame atomic absorption spectrometry. High levels of this element were found in the particulate material (449-9320 mg kg(-1)), which indicates its compatibility with this fraction. The concentration of Cr(iii) in the water samples collected ranged from 5.2-105.2 μg L(-1). Cr(vi) was always below of the DL (0.3 μg L(-1)). Chromium accumulation observed in the sediment (873-1691 mg kg(-1)) may confirm contamination due to the long term release of contaminated effluents in the creek.
Progress of pharmacogenomic research related to minerals and trace elements.
Zeng, Mei-Zi; Tang, Jie; Liu, Zhao-Qian; Zhou, Hong-Hao; Zhang, Wei
2015-10-01
Pharmacogenomics explores the variations in both the benefits and the adverse effects of a drug among patients in a target population by analyzing genomic profiles of individual patients. Minerals and trace elements, which can be found in human tissues and maintain normal physiological functions, are also in the focus of pharmacogenomic research. Single-nucleotide polymorphisms (SNPs) affect the metabolism, disposition and efficacy of minerals and trace elements in humans, resulting in changes of body function. This review describes some of the recent progress in pharmacogenomic research related to minerals and trace elements.
Uccello-Barretta, Gloria; Balzano, Federica; Aiello, Federica; Falugiani, Niccolò; Desideri, Ielizza
2015-03-25
In total parenteral nutrition (TPN), especially in the case of preterm infants, simultaneous administration of vitamins and trace elements is still a problematic issue: guidelines put in evidence the lack of specific documentation. In this work NMR spectroscopy was applied to the study of vitamins (pyridoxine hydrochloride, thiamine nitrate, riboflavin-5'-phosphate and nicotinamide) stability in presence of salts and trace elements. Vitamins in D2O were first analyzed by (1)H NMR spectroscopy in absence of salts and trace elements; changes in chemical shifts or in diffusion coefficients, measured by NMR DOSY technique, were analyzed. The effects of salts and trace elements on single vitamins and on their admixtures were then investigated by performing quantitative analyses during 48h. Selected vitamins are subject to intermolecular interactions. No degradative effects were observed in presence of salts and trace elements. Only riboflavin-5'-phosphate is subject to precipitation in presence of divalent cations; however, at low concentration and in presence of other vitamins this effect was not observed. Solutions analyzed, in the condition of this study, are stable for at least 48h and vitamins and trace elements can be administered together in TPN. Copyright © 2014 Elsevier B.V. All rights reserved.
Toxic effects of trace elements on newborns and their birth outcomes.
Tang, Mengling; Xu, Chenye; Lin, Nan; Yin, Shanshan; Zhang, Yongli; Yu, Xinwei; Liu, Weiping
2016-04-15
Some trace elements are essential for newborns, their deficiency may cause abnormal biological functions, whereas excessive intakes due to environmental contamination may create adverse health effects. This study was conducted to measure the levels of selected trace elements in Chinese fish consumers by assessing their essentiality and toxicity via colostrum intake in newborns, and evaluated the effects of these trace elements on birth outcomes. Trace elements in umbilical cord serum and colostrum of the studied population were relatively high compared with other populations. The geometric means (GM) of estimated daily intake (EDI, mgday(-1)) of the trace elements were in the safe ranges for infant Dietary Reference Intakes (DRIs) recommended by the United States Food and Drug Administration (FDA). When using total dietary intake (TDI, mgkg(-1)bwday(-1)), zinc (Zn) (0.880mgkg(-1)bwday(-1)) and selenium (Se) (6.39×10(-3)mgkg(-1)bwday(-1)) were above the Reference Doses (RfD), set by the United States Environmental Protection Agency (EPA). Multivariable linear regression analyses showed that Se was negatively correlated with birth outcomes. Our findings suggested that overloading of trace elements due to environmental contamination may contribute to negative birth outcomes. Copyright © 2016 Elsevier B.V. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Best, F.M.; Ferrieri, R.; Best, F.M.
Validamycin A was used to inhibit in vivo trehalase activity in tobacco enabling the study of subsequent changes in new C partitioning into cellulosic biomass and lignin precursors. After 12-h exposure to treatment, plants were pulse labeled using radioactive {sup 11}CO{sub 2}, and the partitioning of isotope was traced into [{sup 11}C]cellulose and [{sup 11}C]hemicellulose, as well as into [{sup 11}C]phenylalanine, the precursor for lignin. Over this time course of treatment, new carbon partitioning into hemicellulose and cellulose was increased, while new carbon partitioning into phenylalanine was decreased. This trend was accompanied by a decrease in phenylalanine ammonia-lyase activity. Aftermore » 4 d of exposure to validamycin A, we also measured leaf protein content and key C and N metabolite pools. Extended treatment increased foliar cellulose and starch content, decreased sucrose, and total amino acid and nitrate content, and had no effect on total protein.« less
Foraminiferal Stable Isotope Geochemistry At The Micrometer Scale: Is It A Dream Or Reality?
NASA Astrophysics Data System (ADS)
Misra, S.; Shuttleworth, S.; Lloyd, N. S.; Sadekov, A.; Elderfield, H.
2012-12-01
Over last few decades trace metals and stable isotope compositions of foraminiferal shells became one of the major tools to study past oceans and associated climate change. Empirical calibrations of δ11B, δ18O, Mg/Ca, Cd/Ca, Ba/Ca shells compositions have linked them to various environmental parameters such as seawater pH, temperature, salinity and productivity. Despite their common use as proxies, little is known about mechanisms of trace metals incorporation into foraminiferal calcite. Trace metals partition coefficients for foraminiferal calcite is significantly different from inorganic calcite precipitates underlining strong biological control on metal transport to the calcification sites and their incorporation into the calcite. Microscale distribution of light elements isotopes (e.g. Li, B, Mg) could potentially provide unique inside into these biomineralization processes improving our understanding of foraminiferal geochemistry. In this work we explore potentials of using recent advances in analytical geochemistry by employing laser ablation and multi-collector ICP-MS to study microscale distribution of Mg isotopes across individual foraminiferal shells and δ11B, and δ7Li analyses of individual shell chambers. The analytical setup includes an Analyte.G2 193nm excimer laser ablation system with two volume ablation cell connected to a Thermo Scientific NEPTUNE Plus MC-ICP-MS with Jet Interface option. We will discuss method limitations and advantages for foraminiferal geochemistry as well as our data on Mg isotopes distribution within shells of planktonic foraminifera.
TRACE ELEMENT ANALYSES OF URANIUM MATERIALS
DOE Office of Scientific and Technical Information (OSTI.GOV)
Beals, D; Charles Shick, C
The Savannah River National Laboratory (SRNL) has developed an analytical method to measure many trace elements in a variety of uranium materials at the high part-per-billion (ppb) to low part-per-million (ppm) levels using matrix removal and analysis by quadrapole ICP-MS. Over 35 elements were measured in uranium oxides, acetate, ore and metal. Replicate analyses of samples did provide precise results however none of the materials was certified for trace element content thus no measure of the accuracy could be made. The DOE New Brunswick Laboratory (NBL) does provide a Certified Reference Material (CRM) that has provisional values for a seriesmore » of trace elements. The NBL CRM were purchased and analyzed to determine the accuracy of the method for the analysis of trace elements in uranium oxide. These results are presented and discussed in the following paper.« less
In situ experimental study of subduction zone fluids using diamond anvil cells
NASA Astrophysics Data System (ADS)
Bureau, H.; Foy, E.; Somogyi, A.; Munsch, P.; Simon, G.; Kubsky, S.
2008-12-01
Experiments carried out in diamond anvil cells combined with in situ synchrotron light source measurements represent the only one issue to observe and study fluid equilibria in real time, at the pressure and temperature conditions of the subduction zones. We will present new results recently obtained at the DIFFABS beam line (SOLEIL Synchrotron) aiming at studying equilibria between silica-rich hydrous melts and aqueous fluids in the presence of U, Th, Pb, Ba and Br. We used synchrotron X-Ray fluorescence analysis performed in situ in Bassett-modified hydrothermal diamond anvil cells in order to monitor the chemical transfers of the studied elements between the phases in equilibrium at different pressures (up to 1.6 GPa) and temperatures (up to 900°C). We have calculated the partition coefficients for each studied element (i): Difluid/melt = Cifluid/Cimelt. Results show that U and Th exhibit more affinities for the silica-rich hydrous fluids in the presence or absence of Br, considered here such as an analogue for Cl, (i.e. 0.4 < DUfluid/melt < 0.7 depending on P,T conditions). Br partitioning shows that whereas this halogen element has very strong affinity to the aqueous fluid during magma degassing (DBrfluid/melt >> 10 after decompression) this coefficient decreases with pressure suggesting that Br would not be immediately washed out from the subducted plate during dehydration but may be recycled deeper in the mantle. These new data combined with previous ones obtained for Pb, Ba (Bureau et al., 2007, HPR vol 27, p. 235) and Rb, Sr, Zr (Bureau et al., 2004, Eos Trans. AGU, 85(47), V11C-05), allow us to propose a general outline of the fluid phase transfers through the subduction factory: (1) at shallow level: their nature and composition, the impact of the presence of halogens and the fertilizing role of such fluids in the mantle wedge, where the generation of arc magmas takes place (2) deeper in the mantle: where hydrous silica-rich supercritical fluids may also favour a deep recycling of a fraction of volatiles and trace elements present in the subducted oceanic crust.
Reduced trace element concentrations in fast-growing juvenile Atlantic salmon in natural streams.
Ward, Darren M; Nislow, Keith H; Chen, Celia Y; Folt, Carol L
2010-05-01
To assess the effect of rapid individual growth on trace element concentrations in fish, we measured concentrations of seven trace elements (As, Cd, Cs, Hg, Pb, Se, Zn) in stream-dwelling Atlantic salmon (Salmo salar) from 15 sites encompassing a 10-fold range in salmon growth. All salmon were hatched under uniform conditions, released into streams, and sampled approximately 120 days later for trace element analysis. For most elements, element concentrations in salmon tracked those in their prey. Fast-growing salmon had lower concentrations of all elements than slow growers, after accounting for prey concentrations. This pattern held for essential and nonessential elements, as well as elements that accumulate from food and those that can accumulate from water. At the sites with the fastest salmon growth, trace element concentrations in salmon were 37% (Cs) to 86% (Pb) lower than at sites where growth was suppressed. Given that concentrations were generally below levels harmful to salmon and that the pattern was consistent across all elements, we suggest that dilution of elements in larger biomass led to lower concentrations in fast-growing fish. Streams that foster rapid, efficient fish growth may produce fish with lower concentrations of elements potentially toxic for human and wildlife consumers.
Badran, M; Morsy, R; Soliman, H; Elnimr, T
2016-01-01
The trace elements metabolism has been reported to possess specific roles in the pathogenesis and progress of diabetes mellitus. Due to the continuous increase in the population of patients with Type 2 diabetes (T2D), this study aims to assess the levels and inter-relationships of fast blood glucose (FBG) and serum trace elements in Type 2 diabetic patients. This study was conducted on 40 Egyptian Type 2 diabetic patients and 36 healthy volunteers (Hospital of Tanta University, Tanta, Egypt). The blood serum was digested and then used to determine the levels of 24 trace elements using an inductive coupled plasma mass spectroscopy (ICP-MS). Multivariate statistical analysis depended on correlation coefficient, cluster analysis (CA) and principal component analysis (PCA), were used to analysis the data. The results exhibited significant changes in FBG and eight of trace elements, Zn, Cu, Se, Fe, Mn, Cr, Mg, and As, levels in the blood serum of Type 2 diabetic patients relative to those of healthy controls. The statistical analyses using multivariate statistical techniques were obvious in the reduction of the experimental variables, and grouping the trace elements in patients into three clusters. The application of PCA revealed a distinct difference in associations of trace elements and their clustering patterns in control and patients group in particular for Mg, Fe, Cu, and Zn that appeared to be the most crucial factors which related with Type 2 diabetes. Therefore, on the basis of this study, the contributors of trace elements content in Type 2 diabetic patients can be determine and specify with correlation relationship and multivariate statistical analysis, which confirm that the alteration of some essential trace metals may play a role in the development of diabetes mellitus. Copyright © 2015 Elsevier GmbH. All rights reserved.
Chen, J.; Liu, Gaisheng; Jiang, M.; Chou, C.-L.; Li, H.; Wu, B.; Zheng, Lingyun; Jiang, D.
2011-01-01
To study the geochemical characteristics of 11 environmentally sensitive trace elements in the coals of the Permian Period from the Huainan coalfield, Anhui province, China, borehole samples of 336 coals, two partings, and four roof and floor mudstones were collected from mineable coal seams. Major elements and selected trace elements were determined by inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), and hydride generation atomic absorption spectrometry (HAAS). The depositional environment, abundances, distribution, and modes of occurrence of trace elements were investigated. Results show that clay and carbonate minerals are the principal inorganic constituents in the coals. A lower deltaic plain, where fluvial channel systems developed successively, was the likely depositional environment of the Permian coals in the Huainan coalfield. All major elements have wider variation ranges than those of Chinese coals except for Mg and Fe. The contents of Cr, Co, Ni, and Se are higher than their averages for Chinese coals and world coals. Vertical variations of trace elements in different formations are not significant except for B and Ba. Certain roof and partings are distinctly higher in trace elements than underlying coal bench samples. The modes of occurrence of trace elements vary in different coal seams as a result of different coal-forming environments. Vanadium, Cr, and Th are associated with aluminosilicate minerals, Ba with carbonate minerals, and Cu, Zn, As, Se, and Pb mainly with sulfide minerals. ?? 2011 Elsevier B.V.
Trace elements in ocean ridge basalts
NASA Technical Reports Server (NTRS)
Kay, R. W.; Hubbard, N. J.
1978-01-01
A study is made of the trace elements found in ocean ridge basalts. General assumptions regarding melting behavior, trace element fractionation, and alteration effects are presented. Data on the trace elements are grouped according to refractory lithophile elements, refractory siderophile elements, and volatile metals. Variations in ocean ridge basalt chemistry are noted both for regional and temporal characteristics. Ocean ridge basalts are compared to other terrestrial basalts, such as those having La/Yb ratios greater than those of chondrites, and those having La/Yb ratios less than those of chondrites. It is found that (1) as compared to solar or chondrite ratios, ocean ridge basalts have low ratios of large, highly-charged elements to smaller less highly-charged elements, (2) ocean ridge basalts exhibit low ratios of volatile to nonvolatile elements, and (3) the transition metals Cr through Zn in ocean ridge basalts are not fractionated more than a factor of 2 or 3 from the chondritic abundance ratios.
NASA Technical Reports Server (NTRS)
Thomas, K. L.; Clemett, S. J.; Flynn, G. J.; Keller, L. P.; Mckay, David S.; Messenger, S.; Nier, A. O.; Schlutter, D. J.; Sutton, S. R.; Walker, R. M.
1994-01-01
The topics discussed include the following: noble gas content and release temperatures; trace element abundances; heating summary of cluster fragments; isotopic measurements; and trace organic chemistry.
NASA Technical Reports Server (NTRS)
Righter, K.; Pando, K.; Ross, D. K.; Righter, M.; Lapen, T. J.
2018-01-01
Cores of differentiated bodies (Earth, Mars, Mercury, Moon, Vesta) contain light elements such as S, C, Si, and O. We have previously measured small effects of Si on Ni and Co, and larger effects on Mo, Ge, Sb, As metal/silicate partitioning. The effect of Si on metal-silicate partitioning has been quantified for many siderophile elements, but there are a few key elements for which the effects are not yet quantified. Here we report new experiments designed to quantify the effect of Si on the partitioning of Bi, Cd, Sn, Ag, and P between metal and silicate melt. The results will be applied to Earth, Mars, Moon, and Vesta, for which we have good constraints on the mantle Bi, Cd, Sn, Ag, and P concentrations from mantle and/or basalt samples.
A Synopsis of Technical Issues of Concern for Monitoring Trace Elements in Highway and Urban Runoff
Breault, Robert F.; Granato, Gregory E.
2000-01-01
Trace elements, which are regulated for aquatic life protection, are a primary concern in highway- and urban-runoff studies because stormwater runoff may transport these constituents from the land surface to receiving waters. Many of these trace elements are essential for biological activity and become detrimental only when geologic or anthropogenic sources exceed concentrations beyond ranges typical of the natural environment. The Federal Highway Administration and State Transportation Agencies are concerned about the potential effects of highway runoff on the watershed scale and for the management and protection of watersheds. Transportation agencies need information that is documented as valid, current, and scientifically defensible to support planning and management decisions. There are many technical issues of concern for monitoring trace elements; therefore, trace-element data commonly are considered suspect, and the responsibility to provide data-quality information to support the validity of reported results rests with the data-collection agency. Paved surfaces are fundamentally different physically, hydraulically, and chemically from the natural surfaces typical of most freshwater systems that have been the focus of many traceelement- monitoring studies. Existing scientific conceptions of the behavior of trace elements in the environment are based largely upon research on natural systems, rather than on systems typical of pavement runoff. Additionally, the logistics of stormwater sampling are difficult because of the great uncertainty in the occurrence and magnitude of storm events. Therefore, trace-element monitoring programs may be enhanced if monitoring and sampling programs are automated. Automation would standardize the process and provide a continuous record of the variations in flow and water-quality characteristics. Great care is required to collect and process samples in a manner that will minimize potential contamination or attenuation of trace elements and other sources of bias and variability in the sampling process. Trace elements have both natural and anthropogenic sources that may affect the sampling process, including the sample-collection and handling materials used in many trace-element monitoring studies. Trace elements also react with these materials within the timescales typical for collection, processing and analysis of runoff samples. To study the characteristics and potential effects of trace elements in highway and urban runoff, investigators typically sample one or more operationally defined matrixes including: whole water, dissolved (filtered water), suspended sediment, bottom sediment, biological tissue, and contaminant sources. The sampling and analysis of each of these sample matrixes can provide specific information about the occurrence and distribution of trace elements in runoff and receiving waters. There are, however, technical concerns specific to each matrix that must be understood and addressed through use of proper collection and processing protocols. Valid protocols are designed to minimize inherent problems and to maximize the accuracy, precision, comparability, and representativeness of data collected. Documentation, including information about monitoring protocols, quality assurance and quality control efforts, and ancillary data also is necessary to establish data quality. This documentation is especially important for evaluation of historical traceelement monitoring data, because trace-element monitoring protocols and analysis methods have been constantly changing over the past 30 years.
A relatively reduced Hadean continental crust
NASA Astrophysics Data System (ADS)
Yang, Xiaozhi; Gaillard, Fabrice; Scaillet, Bruno
2014-05-01
Among the physical and chemical parameters used to characterize the Earth, oxidation state, as reflected by its prevailing oxygen fugacity (fO2), is a particularly important one. It controls many physicochemical properties and geological processes of the Earth's different reservoirs, and affects the partitioning of elements between coexisting phases and the speciation of degassed volatiles in melts. In the past decades, numerous studies have been conducted to document the evolution of mantle and atmospheric oxidation state with time and in particular the possible transition from an early reduced state to the present oxidized conditions. So far, it has been established that the oxidation state of the uppermost mantle is within ±2 log units of the quartz-fayalite-magnetite (QFM) buffer, probably back to ~4.4 billion years ago (Ga) based on trace-elements studies of mantle-derived komatiites, kimberlites, basalts, volcanics and zircons, and that the O2 levels of atmosphere were initially low and rose markedly ~2.3 Ga known as the Great Oxidation Event (GOE), progressively reaching its present oxidation state of ~10 log units above QFM. In contrast, the secular evolution of oxidation state of the continental crust, an important boundary separating the underlying upper mantle from the surrounding atmosphere and buffering the exchanges and interactions between the Earth's interior and exterior, has rarely been addressed, although the presence of evolved crustal materials on the Earth can be traced back to ~4.4 Ga, e.g. by detrital zircons. Zircon is a common accessory mineral in nature, occurring in a wide variety of igneous, sedimentary and metamorphic rocks, and is almost ubiquitous in crustal rocks. The physical and chemical durability of zircons makes them widely used in geochemical studies in terms of trace-elements, isotopes, ages and melt/mineral inclusions; in particular, zircons are persistent under most crustal conditions and can survive many secondary processes such as metamorphism, weathering and erosion. Thus, zircons in granites of shallow crust may record the chemical/isotopic composition of the deep crust that is otherwise inaccessible, and offer robust records of the magmatic and crust-forming events preserved in the continental crust. In fact, due to the absence of suitable rock records (in particular for periods older than ~4.0 Ga), studies in recent years concerning the nature, composition, growth and evolution of the continental crust, and especially the Hadean crust, have heavily relied on inherited/detrital zircons. Natural igneous zircons incorporate rare-earth elements (REE) and other trace elements in their structure at concentrations controlled by the temperature, pressure, fO2 and composition of their crystallization environment. Petrological observations and recent experiments have shown that the concentration of Ce relative to other REE in igneous zircons can be used to constrain the fO2 during their growth. By combining available trace-elements data of igneous zircons of crustal origin, we show that the Hadean continental crust was significantly more reduced than its modern counterpart and experienced progressive oxidation till ~3.6 billions years ago. We suggest that the increase in the oxidation state of the Hadean continental crust is related to the progressive decline in the intensity of meteorite impacts during the late veneer. Impacts of carbon- and hydrogen-rich materials during the formation of Hadean granitic crust must have favoured strongly reduced magmatism. The conjunction of cold, wet and reduced granitic magmatism during the Hadean implies the degassing of methane and water. When impacts ended, magma produced by normal decompression melting of the mantle imparted more oxidizing conditions to erupted lavas and the related crust.
Diffusion, phase equilibria and partitioning experiments in the Ni-Fe-Ru system
NASA Technical Reports Server (NTRS)
Blum, Joel D.; Wasserburg, G. J.; Hutcheon, I. D.; Beckett, J. R.; Stolper, E. M.
1989-01-01
Results are presented on thin-film diffusion experiments designed to investigate phase equilibria in systems containing high concentrations of Pt-group elements, such as Ni-Fe-Ru-rich systems containing Pt, at temperatures of 1273, 1073, and 873 K. The rate of Ru diffusion in Ni was determined as a function of temperature, and, in addition, the degree of Pt and Ir partitioning between phases in a Ni-Fe-Ru-rich system and of V between phases in a Ni-Fe-O-rich system at 873 were determined. It was found that Pt preferentially partitions into the (gamma)Ni-Fe phase, whereas Ir prefers the (epsilon)Ru-Fe phase. V partitions strongly into Fe oxides relative to (gamma)Ni-Fe. These results have direct application to the origin and thermal history of the alloys rich in Pt-group elements in meteorites.
Trace element emissions from spontaneous combustion of gob piles in coal mines, Shanxi, China
Zhao, Y.; Zhang, Jiahua; Chou, C.-L.; Li, Y.; Wang, Z.; Ge, Y.; Zheng, C.
2008-01-01
The emissions of potentially hazardous trace elements from spontaneous combustion of gob piles from coal mining in Shanxi Province, China, have been studied. More than ninety samples of solid waste from gob piles in Shanxi were collected and the contents of twenty potentially hazardous trace elements (Be, F, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Sn, Sb, Hg, Tl, Pb, Th, and U) in these samples were determined. Trace element contents in solid waste samples showed wide ranges. As compared with the upper continental crust, the solid waste samples are significantly enriched in Se (20x) and Tl (12x) and are moderately enriched in F, As, Mo, Sn, Sb, Hg, Th, and U (2-5x). The solid waste samples are depleted in V, Cr, Mn, Co, Ni, Cu, and Zn. The solid waste samples are enriched in F, V, Mn, Cr, Co, Ni, Cu, Zn, Sb, Th, and U as compared with the Shanxi coals. Most trace elements are higher in the clinker than in the unburnt solid waste except F, Sn, and Hg. Trace element abundances are related to the ash content and composition of the samples. The content of F is negatively correlated with the ash content, while Pb is positively correlated with the ash. The concentrations of As, Mn, Zn, and Cd are highly positively correlated with Fe2O3 in the solid waste. The As content increases with increasing sulfur content in the solid waste. The trace element emissions are calculated for mass balance. The emission factors of trace elements during the spontaneous combustion of the gobs are determined and the trace element concentrations in the flue gas from the spontaneous combustion of solid waste are calculated. More than a half of F, Se, Hg and Pb are released to the atmosphere during spontaneous combustion. Some trace element concentrations in flue gas are higher than the national emission standards. Thus, gob piles from coal mining pose a serious environmental problem. ?? 2007 Elsevier B.V. All rights reserved.
Trace element contamination in feather and tissue samples from Anna’s hummingbirds
Mikoni, Nicole A.; Poppenga, Robert H.; Ackerman, Joshua T.; Foley, Janet E.; Hazlehurst, Jenny; Purdin, Güthrum; Aston, Linda; Hargrave, Sabine; Jelks, Karen; Tell, Lisa A.
2017-01-01
Trace element contamination (17 elements; Be, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Ba, Hg, Tl, and Pb) of live (feather samples only) and deceased (feather and tissue samples) Anna's hummingbirds (Calypte anna) was evaluated. Samples were analyzed using inductively coupled plasma-mass spectrometry (ICP-MS; 17 elements) and atomic absorption spectrophotometry (Hg only). Mean plus one standard deviation (SD) was considered the benchmark, and concentrations above the mean + 1 SD were considered elevated above normal. Contour feathers were sampled from live birds of varying age, sex, and California locations. In order to reduce thermal impacts, minimal feathers were taken from live birds, therefore a novel method was developed for preparation of low mass feather samples for ICP-MS analysis. The study found that the novel feather preparation method enabled small mass feather samples to be analyzed for trace elements using ICP-MS. For feather samples from live birds, all trace elements, with the exception of beryllium, had concentrations above the mean + 1 SD. Important risk factors for elevated trace element concentrations in feathers of live birds were age for iron, zinc, and arsenic, and location for iron, manganese, zinc, and selenium. For samples from deceased birds, ICP-MS results from body and tail feathers were correlated for Fe, Zn, and Pb, and feather concentrations were correlated with renal (Fe, Zn, Pb) or hepatic (Hg) tissue concentrations. Results for AA spectrophotometry analyzed samples from deceased birds further supported the ICP-MS findings where a strong correlation between mercury concentrations in feather and tissue (pectoral muscle) samples was found. These study results support that sampling feathers from live free-ranging hummingbirds might be a useful, non-lethal sampling method for evaluating trace element exposure and provides a sampling alternative since their small body size limits traditional sampling of blood and tissues. The results from this study provide a benchmark for the distribution of trace element concentrations in feather and tissue samples from hummingbirds and suggests a reference mark for exceeding normal. Lastly, pollinating avian species are minimally represented in the literature as bioindicators for environmental trace element contamination. Given that trace elements can move through food chains by a variety of routes, our study indicates that hummingbirds are possible bioindicators of environmental trace element contamination.
Evaluation of trace element status of organic dairy cattle.
Orjales, I; Herrero-Latorre, C; Miranda, M; Rey-Crespo, F; Rodríguez-Bermúdez, R; López-Alonso, M
2018-06-01
The present study aimed to evaluate trace mineral status of organic dairy herds in northern Spain and the sources of minerals in different types of feed. Blood samples from organic and conventional dairy cattle and feed samples from the respective farms were analysed by inductively coupled plasma mass spectrometry to determine the concentrations of the essential trace elements (cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), iodine (I), manganese (Mn), molybdenum (Mo), nickel (Ni), selenium (Se) and zinc (Zn)) and toxic trace elements (arsenic (As), cadmium (Cd), mercury (Hg) and lead (Pb)). Overall, no differences between organic and conventional farms were detected in serum concentrations of essential and toxic trace elements (except for higher concentrations of Cd on the organic farms), although a high level of inter-farm variation was detected in the organic systems, indicating that organic production greatly depends on the specific local conditions. The dietary concentrations of the essential trace elements I, Cu, Se and Zn were significantly higher in the conventional than in the organic systems, which can be attributed to the high concentration of these minerals in the concentrate feed. No differences in the concentrations of trace minerals were found in the other types of feed. Multivariate chemometric analysis was conducted to determine the contribution of different feed sources to the trace element status of the cattle. Concentrate samples were mainly associated with Co, Cu, I, Se and Zn (i.e. with the elements supplemented in this type of feed). However, pasture and grass silage were associated with soil-derived elements (As, Cr, Fe and Pb) which cattle may thus ingest during grazing.
Turconi, Giovanna; Minoia, Claudio; Ronchi, Anna; Roggi, Carla
2009-04-01
The significant role of trace elements in human health is well documented. Trace elements are those compounds that need to be present in the human diet to maintain normal physiological functions. However, some microelements may become harmful at high levels of exposure, or, on the other hand, may give rise to malnutrition, when their exposure is too low. The aim of the present study was to provide a reliable estimate of the dietary exposure of twenty-one trace elements in a Northern Italian area. For this purpose, trace element analyses were undertaken on total diet samples collected from a university cafeteria in Pavia, Northern Italy. The average daily exposure for the adult people was calculated on the basis of food consumption frequency, portion size and trace element levels in foodstuffs. The mean exposure values satisfy the Italian RDA for all the essential trace elements, except for Fe exposure in females, and are well below the Provisional Tolerable Daily Intake for all the toxic compounds, showing that the probability of dietary exposure to health risks is overall small. As far as Fe exposure is concerned, a potential risk of anaemia in the female adult population should be considered, then studies aimed at evaluating the Fe nutritional status of adult Italian women should be addressed. In conclusion, while not excluding the possibility that the daily exposure determined in the present study may not be representative of the population as a whole, this study provides a good estimate of the Italian adult consumer exposure to twenty-one trace elements.
The effect of pasteurization on trace elements in donor breast milk.
Mohd-Taufek, N; Cartwright, D; Davies, M; Hewavitharana, A K; Koorts, P; McConachy, H; Shaw, P N; Sumner, R; Whitfield, K
2016-10-01
Premature infants often receive pasteurized donor human milk when mothers are unable to provide their own milk. This study aims to establish the effect of the pasteurization process on a range of trace elements in donor milk. Breast milk was collected from 16 mothers donating to the milk bank at the Royal Brisbane and Women's Hospital. Samples were divided into pre- and post-pasteurization aliquots and were Holder pasteurized. Inductively coupled plasma mass spectrometry was used to analyze the trace elements zinc (Zn), copper (Cu), selenium (Se), manganese (Mn), iodine (I), iron (Fe), molybdenum (Mo) and bromine (Br). Differences in trace elements pre- and post-pasteurization were analyzed. No significant differences were found between the trace elements tested pre- and post-pasteurization, except for Fe (P<0.05). The median (interquartile range, 25 to 75%; μg l(-1)) of trace elements for pre- and post- pasteurization aliquots were-Zn: 1639 (888-4508), 1743 (878-4143), Cu: 360 (258-571), 367 (253-531), Se: 12.34 (11.73-17.60), 12.62 (11.94-16.64), Mn: (1.48 (1.01-1.75), 1.49 (1.11-1.75), I (153 (94-189), 158 (93-183), Fe (211 (171-277), 194 (153-253), Mo (1.46 (0.37-2.99), 1.42 (0.29-3.73) and Br (1066 (834-1443), 989 (902-1396). Pasteurization had minimal effect on several trace elements in donor breast milk but high levels of inter-donor variability of trace elements were observed. The observed decrease in the iron content of pasteurized donor milk is, however, unlikely to be clinically relevant.
Leventhal, Joel S.
1979-01-01
Core samples from Devonian shales from five localities in the Appalachian Basin have been analyzed for major, minor, and trace constituents. The contents of major elements are rather similar; however, the minor constituents, organic C, S, PO4, and CO3, show variations by a factor of 10. Trace elements Mo, Ni, Cu, V, Co, U, Zn, Hg, As, and Mn show variations that can be related graphically and statistically to the minor constituents. Down-hole plots show the relationships most clearly. Mn is associated with CO3 content, the other trace elements are strongly Controlled by organic C. Amounts of organic C are generally in the range of 3-6 percent, and S is in the range of 2-5 percent. Trace-element amounts show the following general ranges (ppm, parts per million)- Co, 20-40; Cu,40-70; U, 10-40; As, 20-40, V, 150-300; Ni, 80-150; high values are as much as twice these values. The organic C was probably the concentrating agent, whereas the organic C and sulfide S created an environment for preservation or immobilization of trace elements. Closely spaced samples showing an abrupt transition in color from black to gray and gray to black shale show similar effects of trace-element changes, that is, black shale contains enhanced amounts of organic C and trace elements. Ratios of trace elements to organic C or sulfide S were relatively constant even though deposition rates varied from 10 to 300 meters in 5 million years.
Minor element partitioning and mineralogy in limpets from the Ischia CO2 vent site
NASA Astrophysics Data System (ADS)
Langer, Gerald; Sadekov, Aleksey; Nehrke, Gernot; Baggini, Cecilia; Rodolfo-Metalpa, Riccardo; Hall-Spencer, Jason; Bijma, Jelle; Elderfield, Henry
2015-04-01
Specimens of the patellogastropod limpet Patella caerulea were collected within and outside a CO2 vent site at Ischia, Italy. The shells were sectioned transversally and scanned for polymorph distribution by means of confocal Raman microscopy. Minor element to calcium ratios were measured using laser-ablation-inductively-coupled-plasma-mass-spectroscopy (LA-ICPMS). Mg/Ca, Sr/Ca, and Li/Ca ratios were determined in calcitic as well as aragonitic parts of the shells. This approach allows for investigating the effects of the polymorph and the seawater carbonate chemistry on minor element partitioning separately.
NASA Astrophysics Data System (ADS)
Zheng, Yongjun; Zheng, Kang; Li, Yantuan
2012-09-01
In order to investigate the relationship between the trace elements and the characteristics of the oysters, we analyzed the trace elements present in the germplasm of oysters from different producing areas in the Jiaozhou Bay. The element fingerprints were established to reflect the elemental characteristics of the oysters. Concentration patterns of the elements were deciphered by principle component analysis (PCA) and hierarchical cluster analysis (HCA). The six regions were discriminated with accuracy using HCA and PCA based on the concentration of 16 trace elements. The elements were viewed as characteristic elements of the oysters and the fingerprints of these elements could be used to distinguish the quality of the oysters.
Mercury and trace metal partitioning and fluxes in suburban Southwest Ohio watersheds.
Naik, Avani P; Hammerschmidt, Chad R
2011-10-15
Many natural watersheds are increasingly affected by changes in land use associated with suburban sprawl and such alterations may influence concentrations, partitioning, and fluxes of toxic trace metals in fluvial ecosystems. We investigated the cycling of mercury (Hg), monomethylmercury, cadmium, copper, lead, nickel, and zinc in three watersheds at the urban fringe of Dayton, Ohio, over a 13-month period. Metal concentrations were related positively to discharge in each stream, with each metal having a high affinity for suspended particles and Hg also having a noticeable association with dissolved organic carbon. Although not observed for the other metals, levels of Hg in river water varied seasonally and among streams. Yields of Hg from two of the catchments were comparable to that predicted for runoff of atmospherically deposited Hg (∼25% of wet atmospheric flux), whereas the third watershed had a significantly greater annual flux associated with greater particle-specific and filtered water Hg concentrations, presumably from a point source. Fluxes of metals other than Hg were similar among each watershed and suggestive of a ubiquitous source, which could be either atmospheric deposition or weathering. Results of this study indicate that, with the exception of Hg being increased in one watershed, processes affecting metal partitioning and loadings are similar among southwest Ohio streams and comparable to other North American rivers that are equally or less impacted by urban development. Relative differences in land use, catchment area, and presence or absence of waste water treatment facilities had little or no detectable effect on most trace metal concentrations and fluxes. This suggests that suburban encroachment on agricultural and undeveloped lands has either similarly or not substantially impacted trace metal cycling in streams at the urban fringe of Dayton and, by extension, other comparable metropolitan areas. Copyright © 2011 Elsevier Ltd. All rights reserved.
Previous studies have revealed that hair trace element concentrations can reflect exposure in cases of frank poisoning and deficiency. Correlations have been found also in some populations living in regions where metallurgic processes are conducted. This study reports significant...
Seventeen trace elements - arsenic (As), barium (Ba), boron (B), cadmium (Cd), chromium (Cr), copper (Cu), Iron (Fe), lead (Pb), lithium (Li), manganese (Mn), mercury (Hg), nickle (Ni), selenium (Se), silver (Ag), tin (Sn), vanadium (V), and zinc (Zn) - were measured in human sca...
USDA-ARS?s Scientific Manuscript database
While many studies have examined the effect of microbial infections on the status of trace elements in mammalian tissues, similar studies have not been performed in insects. We used inductively coupled plasma-mass spectrometry (ICP-MS) to quantify changes in trace elements of Mg, Mn, Fe, Cu, Zn and ...
USDA-ARS?s Scientific Manuscript database
The application of poultry (Gallus gallus domesticus) litter to agricultural soils may exacerbate losses of trace elements in runoff water, an emerging concern to water quality. We evaluated trace elements (arsenic, cadmium, copper, lead, manganese, mercury, selenium and zinc) in surface runoff and ...
Schmidt, Thomas; McCabe, Bernadette K; Harris, Peter W; Lee, Seonmi
2018-05-18
In this study, anaerobic digestion of slaughterhouse wastewater with the addition of trace elements was monitored for biogas quantity, quality and process stability using CSTR digesters operated at mesophilic temperature. The determination of trace element concentrations was shown to be deficient in Fe, Ni, Co, Mn and Mo compared to recommendations given in the literature. Addition of these trace elements resulted in enhanced degradation efficiency, higher biogas production and improved process stability. Higher organic loading rates and lower hydraulic retention times were achieved in comparison to the control digesters. A critical accumulation of volatile fatty acids was observed at an organic loading rate of 1.82 g L -1 d -1 in the control compared to 2.36 g L -1 d -1 in the digesters with trace element addition. The improved process stability was evident in the final weeks of experimentation, in which control reactors produced 84% less biogas per day compared to the reactors containing trace elements. Copyright © 2018 Elsevier Ltd. All rights reserved.
Discrimination of trait-based characteristics by trace element bioaccumulation in riverine fishes
Short, T.M.; DeWeese, L.R.; Dubrovsky, N.M.
2008-01-01
Relations between tissue trace element concentrations and species traits were examined for 45 fish species to determine the extent to which trait-based characteristics accounted for relative differences among species in trace element bioaccumulation. Percentages of fish species correctly classified by discriminant analysis according to traits predicted by tissue trace element concentrations ranged from 72% to 87%. Tissue concentrations of copper, mercury, selenium, and zinc appeared to have the greatest overall influence on differentiating species according to trait characteristics. Discrimination of trait characteristics did not appear to be strongly influenced by local sources of trace elements in the streambed sediment. Bioaccumulation was greatest for those species classified as primarily detritivores, having relatively large adult body size, considered nonmigratory with respect to reproductive strategy, occurring mostly in large or variable size streams and rivers, preferring depositional areas within the stream channel, and preferring benthic rather than open-water habitats. Our findings provide evidence of the strong relationship between bioaccumulation of environmental trace elements and trait-based factors that influence contaminant exposure. ?? 2008 NRC.
[Measurement of the status of trace elements in cattle using liver biopsy samples].
Ouweltjes, W; de Zeeuw, A C; Moen, A; Counotte, G H M
2007-02-01
Serum, plasma, or urine samples are usually used for the measurement of the trace elements copper; zinc, iron, selenium, because these samples are easy to obtain; however; these samples are not always appropriate. For example, it is not possible to measure molybdenum, the major antagonist of copper; in blood or urine. Therefore measurement of trace elements in liver tissue is considered the gold standard. For the assessment of selenium the method of choice remains determination of glutathion peroxidase in erythrocytes and for the assessment of magnesium determination of magnesium in urine. We determined the accuracy and repeatability of measuring trace elements in liver biopsies and whole liver homogenates. The levels of trace elements measured were similar in both preparations (92% agreement). Liver biopsy in live animals is a relatively simple procedure but not common in The Netherlands. Reference levels of trace elements, classified as too low, low, adequate, high, and too high, were established on the basis of our research and information in the literature. In a second study we investigated the practical aspects of obtaining liver tissue samples and their use. Samples were collected from cattle on a commercial dairy farm. Liver biopsy provided additional information to that obtained from serum and urine samples. We prepared a biopsy protocol and a test package, which we tested on 14 farms where an imbalance of trace minerals was suspected. Biopsy samples taken from 4 to 6 animals revealed extreme levels of trace elements.
Lu, Shaoyou; Ren, Lu; Fang, Jianzhang; Ji, Jiajia; Liu, Guihua; Zhang, Jianqing; Zhang, Huimin; Luo, Ruorong; Lin, Kai; Fan, Ruifang
2016-05-01
Many trace heavy elements are carcinogenic and increase the incidence of cancer. However, a comprehensive study of the correlation between multiple trace elements and DNA oxidative damage is still lacking. The aim of this study is to investigate the relationships between the body burden of multiple trace elements and DNA oxidative stress in college students in Guangzhou, China. Seventeen trace elements in urine samples were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Urinary 8-hydroxy-2'-deoxyguanosine (8-OHdG), a biomarker of DNA oxidative stress, was also measured using liquid chromatography tandem mass spectrometer (LC-MS/MS). The concentrations of six essential elements including manganese (Mn), copper (Cu), nickel (Ni), selenium (Se), strontium (Sr), and molybdenum (Mo), and five non-essential elements including arsenic (As), cadmium (Cd), aluminum (Al), stibium (Sb), and thallium (Tl), were found to be significantly correlated with urinary 8-OHdG levels. Moreover, urinary levels of Ni, Se, Mo, As, Sr, and Tl were strongly significantly correlated with 8-OHdG (P < 0.01) concentration. Environmental exposure and dietary intake of these trace elements may play important roles in DNA oxidative damage in the population of Guangzhou, China.
Diel cycling of trace elements in streams draining mineralized areas: a review
Gammons, Christopher H.; Nimick, David A.; Parker, Stephen R.
2015-01-01
Many trace elements exhibit persistent diel, or 24-h, concentration cycles in streams draining mineralized areas. These cycles can be caused by various physical and biogeochemical mechanisms including streamflow variation, photosynthesis and respiration, as well as reactions involving photochemistry, adsorption and desorption, mineral precipitation and dissolution, and plant assimilation. Iron is the primary trace element that exhibits diel cycling in acidic streams. In contrast, many cationic and anionic trace elements exhibit diel cycling in near-neutral and alkaline streams. Maximum reported changes in concentration for these diel cycles have been as much as a factor of 10 (988% change in Zn concentration over a 24-h period). Thus, monitoring and scientific studies must account for diel trace-element cycling to ensure that water-quality data collected in streams appropriately represent the conditions intended to be studied.
Total-reflection X-ray fluorescence studies of trace elements in biomedical samples
NASA Astrophysics Data System (ADS)
Kubala-Kukuś, A.; Braziewicz, J.; Pajek, M.
2004-08-01
Application of the total-reflection X-ray fluorescence (TXRF) analysis in the studies of trace element contents in biomedical samples is discussed in the following aspects: (i) a nature of trace element concentration distributions, (ii) censoring approach to the detection limits, and (iii) a comparison of two sets of censored data. The paper summarizes the recent results achieved in this topics, in particular, the lognormal, or more general logstable, nature of concentration distribution of trace elements, the random left-censoring and the Kaplan-Meier approach accounting for detection limits and, finally, the application of the logrank test to compare the censored concentrations measured for two groups. These new aspects, which are of importance for applications of the TXRF in different fields, are discussed here in the context of TXRF studies of trace element in various samples of medical interest.
Atmospheric Deposition of Trace Elements in Ombrotrophic Peat as a Result of Anthropic Activities
NASA Astrophysics Data System (ADS)
Fabio Lourençato, Lucio; Cabral Teixeira, Daniel; Vieira Silva-Filho, Emmanoel
2014-05-01
Ombrotrophic peat can be defined as a soil rich in organic matter, formed from the partial decomposition of vegetable organic material in a humid and anoxic environment, where the accumulation of material is necessarily faster than the decomposition. From the physical-chemical point of view, it is a porous and highly polar material with high adsorption capacity and cation exchange. The high ability of trace elements to undergo complexation by humic substances happens due to the presence of large amounts of oxygenated functional groups in these substances. Since the beginning of industrialization human activities have scattered a large amount of trace elements in the environment. Soil contamination by atmospheric deposition can be expressed as a sum of site contamination by past/present human activities and atmospheric long-range transport of trace elements. Ombrotrophic peat records can provide valuable information about the entries of trace metals into the atmosphere and that are subsequently deposited on the soil. These trace elements are toxic, non-biodegradable and accumulate in the food chain, even in relatively low quantities. Thus studies on the increase of trace elements in the environment due to human activities are necessary, particularly in the southern hemisphere, where these data are scarce. The aims of this study is to evaluate the concentrations of mercury in ombrotrophic peat altomontanas coming from atmospheric deposition. The study is conducted in the Itatiaia National Park, Brazilian conservation unit, situated between the southeastern state of Rio de Janeiro, São Paulo and Minas Gerais. An ombrotrophic peat core is being sampled in altitude (1980m), to measure the trace elements concentrations of this material. As it is conservation area, the trace elements found in the samples is mainly from atmospheric deposition, since in Brazil don't exist significant lithology of trace elements. The samples are characterized by organic matter content which is determined by calcination and pH. For the determination of mercury, an aliquot of 10 mL of sample with 5 mL of the reducing agent 2 % SnCl2, purged with air by atomic absorption spectrophotometry by cold vapor, EAAVF is being used. The determination of other trace elements (Zn, Cd and Pb) is analyzed by flame atomic absorption spectroscopy (FAAS).
Integrating end-to-end threads of control into object-oriented analysis and design
NASA Technical Reports Server (NTRS)
Mccandlish, Janet E.; Macdonald, James R.; Graves, Sara J.
1993-01-01
Current object-oriented analysis and design methodologies fall short in their use of mechanisms for identifying threads of control for the system being developed. The scenarios which typically describe a system are more global than looking at the individual objects and representing their behavior. Unlike conventional methodologies that use data flow and process-dependency diagrams, object-oriented methodologies do not provide a model for representing these global threads end-to-end. Tracing through threads of control is key to ensuring that a system is complete and timing constraints are addressed. The existence of multiple threads of control in a system necessitates a partitioning of the system into processes. This paper describes the application and representation of end-to-end threads of control to the object-oriented analysis and design process using object-oriented constructs. The issue of representation is viewed as a grouping problem, that is, how to group classes/objects at a higher level of abstraction so that the system may be viewed as a whole with both classes/objects and their associated dynamic behavior. Existing object-oriented development methodology techniques are extended by adding design-level constructs termed logical composite classes and process composite classes. Logical composite classes are design-level classes which group classes/objects both logically and by thread of control information. Process composite classes further refine the logical composite class groupings by using process partitioning criteria to produce optimum concurrent execution results. The goal of these design-level constructs is to ultimately provide the basis for a mechanism that can support the creation of process composite classes in an automated way. Using an automated mechanism makes it easier to partition a system into concurrently executing elements that can be run in parallel on multiple processors.
Zhu, LiuCun; Chen, XiJia; Kong, Xiangyin; Cai, Yu-Dong
2016-11-01
Hepatitis is a type of infectious disease that induces inflammation of the liver without pinpointing a particular pathogen or pathogenesis. Type C hepatitis, as a type of hepatitis, has been reported to induce cirrhosis and hepatocellular carcinoma within a very short amount of time. It is a great threat to human health. Some studies have revealed that trace elements are associated with infection with and immune rejection against hepatitis C virus (HCV). However, the mechanism underlying this phenomenon is still unclear. In this study, we aimed to expand our knowledge of this phenomenon by designing a computational method to identify genes that may be related to both HCV and trace element metabolic processes. The searching procedure included three stages. First, a shortest path algorithm was applied to a large network, constructed by protein-protein interactions, to identify potential genes of interest. Second, a permutation test was executed to exclude false discoveries. Finally, some rules based on the betweenness and associations between candidate genes and HCV and trace elements were built to select core genes among the remaining genes. 12 lists of genes, corresponding to 12 types of trace elements, were obtained. These genes are deemed to be associated with HCV infection and trace elements metabolism. The analyses indicate that some genes may be related to both HCV and trace element metabolic processes, further confirming the associations between HCV and trace elements. The method was further tested on another set of HCV genes, the results indicate that this method is quite robustness. The newly found genes may partially reveal unknown mechanisms between HCV infection and trace element metabolism. This article is part of a Special Issue entitled "System Genetics" Guest Editor: Dr. Yudong Cai and Dr. Tao Huang. Copyright © 2016 Elsevier B.V. All rights reserved.
Doig, Lorne E; Carr, Meghan K; Meissner, Anna G N; Jardine, Tim D; Jones, Paul D; Bharadwaj, Lalita; Lindenschmidt, Karl-Erich
2017-11-01
Across the circumpolar world, intensive anthropogenic activities in the southern reaches of many large, northward-flowing rivers can cause sediment contamination in the downstream depositional environment. The influence of ice cover on concentrations of inorganic contaminants in bed sediment (i.e., sediment quality) is unknown in these rivers, where winter is the dominant season. A geomorphic response unit approach was used to select hydraulically diverse sampling sites across a northern test-case system, the Slave River and delta (Northwest Territories, Canada). Surface sediment samples (top 1 cm) were collected from 6 predefined geomorphic response units (12 sites) to assess the relationships between bed sediment physicochemistry (particle size distribution and total organic carbon content) and trace element content (mercury and 18 other trace elements) during open-water conditions. A subset of sites was resampled under-ice to assess the influence of season on these relationships and on total trace element content. Concentrations of the majority of trace elements were strongly correlated with percent fines and proxies for grain size (aluminum and iron), with similar trace element grain size/grain size proxy relationships between seasons. However, finer materials were deposited under ice with associated increases in sediment total organic carbon content and the concentrations of most trace elements investigated. The geomorphic response unit approach was effective at identifying diverse hydrological environments for sampling prior to field operations. Our data demonstrate the need for under-ice sampling to confirm year-round consistency in trace element-geochemical relationships in fluvial systems and to define the upper extremes of these relationships. Whether contaminated or not, under-ice bed sediment can represent a "worst-case" scenario in terms of trace element concentrations and exposure for sediment-associated organisms in northern fluvial systems. Environ Toxicol Chem 2017;36:2916-2924. © 2017 SETAC. © 2017 SETAC.
Mashburn, Shana L.; Smith, S. Jerrod
2007-01-01
The U.S. Geological Survey, in cooperation with the Absentee Shawnee Tribe of Oklahoma, began a reconnaissance study of a site in Pottawatomie County, Oklahoma, in 2005 by testing soil, shallow ground water, and plant material for the presence of trace elements and semivolatile organic compounds. Chemical analysis of plant material at the site was investigated as a preliminary tool to determine the extent of contamination at the site. Thirty soil samples were collected from 15 soil cores during October 2005 and analyzed for trace elements and semivolatile organic compounds. Five small-diameter, polyvinyl-chloride-cased wells were installed and ground-water samples were collected during December 2005 and May 2006 and analyzed for trace elements and semivolatile organic compounds. Thirty Johnsongrass samples and 16 Coralberry samples were collected during September 2005 and analyzed for 53 constituents, including trace elements. Results of the soil, ground-water, and plant data indicate that the areas of trace element and semivolatile organic compound contamination are located in the shallow (A-horizon) soils near the threading barn. Most of the trace-element concentrations in the soils on the study site were either similar to or less than trace-element concentrations in background soils. Several trace elements and semivolatile organic compounds exceeded the U.S. Environmental Protection Agency, Region 6, Human Health Medium-Specific Screening Levels 2007 for Tap Water, Residential Soils, Industrial Indoor Soils, and Industrial Outdoor Soils. There was little or no correlation between the plant and soil sample concentrations and the plant and ground-water concentrations based on the current sample size and study design. The lack of correlation between trace-element concentrations in plants and soils, and plants and ground water indicate that plant sampling was not useful as a preliminary tool to assess contamination at the study site.
Marine Bioinorganic Chemistry: The Role of Trace Metals in the Oceanic Cycles of Major Nutrients
NASA Astrophysics Data System (ADS)
Morel, F. M. M.; Milligan, A. J.; Saito, M. A.
2003-12-01
The bulk of living biomass is chiefly made up of only a dozen "major" elements - carbon, hydrogen, oxygen, nitrogen, phosphorus, sodium, potassium, chlorine, calcium, magnesium, sulfur (and silicon in diatoms) - whose proportions vary within a relatively narrow range in most organisms. A number of trace elements, particularly first row transition metals - manganese, iron, nickel, cobalt, copper, and zinc - are also "essential" for the growth of organisms. At the molecular level, the chemical mechanisms by which such elements function as active centers or structural factors in enzymes and by which they are accumulated and stored by organisms is the central topic of bioinorganic chemistry. At the scale of ocean basins, the interplay of physical, chemical, and biological processes that govern the cycling of biologically essential elements in seawater is the subject of marine biogeochemistry. For those interested in the growth of marine organisms, particularly in the one-half of the Earth's primary production contributed by marine phytoplankton, bioinorganic chemistry and marine biogeochemistry are critically linked by the extraordinary paucity of essential trace elements in surface seawater, which results from their biological utilization and incorporation in sinking organic matter. How marine organisms acquire elements that are present at nano- or picomolar concentrations in surface seawater; how they perform critical enzymatic functions when necessary metal cofactors are almost unavailable are the central topics of "marine bioinorganic chemistry." The central aim of this field is to elucidate at the molecular level the metal-dependent biological processes involved in the major biogeochemical cycles.By examining the solutions that emerged from the problems posed by the scarcity of essential trace elements, marine bioinorganic chemists bring to light hitherto unknown ways to take up or utilize trace elements, new molecules, and newer "essential" elements. Focusing on molecular mechanisms involved in such processes as inorganic carbon fixation, organic carbon respiration, or nitrogen transformation, they explain how the cycles of trace elements are critically linked to those of major nutrients such as carbon or nitrogen. But we have relatively little understanding of the binding molecules and the enzymes that mediate the biochemical role of trace metals in the marine environment. In this sense, this chapter is more a "preview" than a review of the field of marine bioinorganic chemistry. To exemplify the concepts and methods of this field, we have chosen to focus on one of its most important topics: the potentially limiting role of trace elements in primary marine production. As a result we center our discussion on particular subsets of organisms, biogeochemical cycles, and trace elements. Our chief actors are marine phytoplankton, particularly eukaryotes, while heterotrophic bacteria make only cameo appearances. The biogeochemical cycles that will serve as our plot are those of the elements involved in phytoplankton growth, the major algal nutrients - carbon, nitrogen, phosphorus, and silicon - leaving aside, e.g., the interesting topic of the marine sulfur cycle. Seven trace metals provide the intrigue: manganese, iron, nickel, cobalt, copper, zinc, and cadmium. But several other trace elements such as selenium, vanadium, molybdenum, and tungsten (and, probably, others not yet identified) will assuredly add further twists in future episodes.We begin this chapter by discussing what we know of the concentrations of trace elements in marine microorganisms and of the relevant mechanisms and kinetics of trace-metal uptake. We then review the biochemical role of trace elements in the marine cycles of carbon, nitrogen, phosphorus, and silicon. Using this information, we examine the evidence, emanating from both laboratory cultures and field measurements, relevant to the mechanisms and the extent of control by trace metals of marine biogeochemical cycles. Before concluding with a wistful glimpse of the future of marine bioinorganic chemistry we discuss briefly some paleoceanographic aspects of this new field: how the chemistry of the planet "Earth" - particularly the concentrations of trace elements in the oceans - has evolved since its origin, chiefly as a result of biological processes and how the evolution of life has, in turn, been affected by the availability of essential trace elements.
Research on Crack Formation in Gypsum Partitions with Doorway by Means of FEM and Fracture Mechanics
NASA Astrophysics Data System (ADS)
Kania, Tomasz; Stawiski, Bohdan
2017-10-01
Cracking damage in non-loadbearing internal partition walls is a serious problem that frequently occurs in new buildings within the short term after putting them into service or even before completion of construction. Damage in partition walls is sometimes so great that they cannot be accepted by their occupiers. This problem was illustrated by the example of damage in a gypsum partition wall with doorway attributed to deflection of the slabs beneath and above it. In searching for the deflection which causes damage in masonry walls, fracture mechanics applied to the Finite Element Method (FEM) have been used. For a description of gypsum behaviour, the smeared cracking material model has been selected, where stresses are transferred across the narrowly opened crack until its width reaches the ultimate value. Cracks in the Finite Element models overlapped the real damage observed in the buildings. In order to avoid cracks under the deflection of large floor slabs, the model of a wall with reinforcement in the doorstep zone and a 40 mm thick elastic junction between the partition and ceiling has been analysed.
PIXE analysis of ancient Chinese Qing dynasty porcelain
NASA Astrophysics Data System (ADS)
Cheng, Huansheng; He, Wenquan; Tang, Jiayong; Yang, Fujia; Wang, Jianhua
1996-09-01
The major and minor chemical compositions and trace element content of white glaze made in Qing dynasty at kuan kiln have been determined by PIXE. Experimental results show that trace element contents RbSrZr are useful to distinguish the place of production of ancient porcelain. In the porcelain from different kilns situated in a same province, the trace element contents can be different from each other. Determining and comparing the major and minor compositions and trace elemental concentrations in white glaze by PIXE technique, we can distinguish a precious Qing dynasty porcelain made at kuan kiln from a fake.
Kroening, Sharon E.; Fallon, James D.; Lee, Kathy E.
2000-01-01
In fish livers, all of the trace elements analyzed were detected except antimony, beryllium, cobalt, and uranium. Trace element concentrations in fish livers generally did not show any pronounced patterns. Ranges for concentrations of arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, and zinc were similar to those measured in 20 other NAWQA studies across the United States. Cadmium concentrations in fish livers were moderately correlated to fish length and weight. There were no relations between trace element concentrations in fish livers and streambed sediment.
NASA Astrophysics Data System (ADS)
Hartland, Adam; Fairchild, Ian J.; Müller, Wolfgang; Dominguez-Villar, David
2014-03-01
We report the first quantitative study of the capture of colloidal natural organic matter (NOM) and NOM-complexed trace metals (V, Co, Cu, Ni) in speleothems. This study combines published NOM-metal dripwater speciation measurements with high-resolution laser ablation ICPMS (LA-ICPMS) and sub-annual stable isotope ratio (δ18O and δ13C), fluorescence and total organic carbon (TOC) analyses of a fast-growing hyperalkaline stalagmite (pH ˜11) from Poole’s Cavern, Derbyshire UK, which formed between 1997 and 2008 AD. We suggest that the findings reported here elucidate trace element variations arising from colloidal transport and calcite precipitation rate changes observed in multiple, natural speleothems deposited at ca. pH 7-8. We find that NOM-metal(aq) complexes on the boundary between colloidal and dissolved (˜1 nm diameter) show an annual cyclicity which is inversely correlated with the alkaline earth metals and is explained by calcite precipitation rate changes (as recorded by kinetically-fractionated stable isotopes). This relates to the strength of the NOM-metal complexation reaction, resulting in very strongly bound metals (Co in this system) essentially recording NOM co-precipitation (ternary complexation). More specifically, empirical partition coefficient (Kd) values between surface-reactive metals (V, Co, Cu, Ni) [expressed as ratio of trace element to Ca ratios in calcite and in solution] arise from variations in the ‘free’ fraction of total metal in aqueous solution (fm). Hence, differences in the preservation of each metal in calcite can be explained quantitatively by their complexation behaviour with aqueous NOM. Differences between inorganic Kd values and field measurements for metal partitioning into calcite occur where [free metal] ≪ [total metal] due to complexation reactions between metals and organic ligands (and potentially inorganic colloids). It follows that where fm ≈ 0, apparent inorganic Kd app values are also ≈0, but the true partition coefficient (Kd actual) is significantly higher. Importantly, the Kd of NOM-metal complexes [organic carbon-metal ratio) approaches 1 for the most stable aqueous complexes, as is shown here for Co, but has values of 24-150 for V, Ni and Cu. This implies that ternary surface complexation (metal-ligand co-adsorption) can occur (as for NOM-Co), but is the exception rather than the rule. We also demonstrate the potential for trace metals to record information on NOM composition as expressed through changing NOM-metal complexation patterns in dripwaters. Therefore, a suite of trace metals in stalagmites show variations clearly attributable to changes in organic ligand concentration and composition, and which potentially reflect the state of overlying surface ecosystems. The heterogeneous speciation and size distribution of aqueous NOM and metals (Lead and Wilkinson, 2006; Aiken et al., 2011). The variability in NOM-metal transport in caves that arises from the interaction between infiltration, flow routing, and the hydrodynamic properties of the fine colloids and particulates (Hartland et al., 2012). Variable dissociation kinetics through time as a function of (a) (Hartland et al., 2011). The surface charge of calcite and the availability of CaCO3 lattice sites as well as increased incidence of crystallographic defects with implications for incorporation of a range of trace species (Fairchild and Treble, 2009; Fairchild and Hartland, 2010). Thus, incorporation in speleothem calcite with consistent surface site properties will be determined by: The size and composition (i.e. hydrophilicity/hydrophobicity) of the NOM ligand, affecting adsorption and stability at the calcite surface. The lability (i.e. exchangeability) of the complexed metal and its binding affinity for the calcite surface. The concentration of aqueous complexes. Given the complexities, a partitioning approach to the problem is appropriate as a first approximation rather than a precise description. This study seeks to make the first quantitative connection between the organic and inorganic compositions of speleothems and thus determine the potential for speleothems to encode fluctuations in colloid-facilitated trace metal transport in karst aquifers. Recent findings of direct relevance to the present studyThe conjugate dripwater (PE1) to the stalagmite studied here (PC-08-1) was characterised in June 2009 using an array of complementary techniques, in which the size, speciation and lability of NOM-metal complexes was characterised (Hartland et al., 2011), where lability is defined as the capacity for complexes to dissociate in the context of the on-going interfacial process at the stalagmite surface. In PE1 dripwater, the most stable aqueous complexes were formed between Co and the finest, low molecular weight component of the NOM spectrum (Hartland et al., 2011). Speciation experiments demonstrated that Co was essentially non-exchangeable (free metal (fm) = <0.05), being retained in aqueous complexes, whilst Cu, Ni and V were all predominantly bound by NOM (fm = 0.2-0.3).In contrast, Sr and Ba were freely exchangeable between the solution and solid phase (Hartland et al., 2011) and Mg was absent, presumably due to the poor solubility of Mg(OH)2 at hyperalkaline pH (Ksp = 1.5 × 10-11): Mg2+(aq)+2OH-(aq)↔Mg( On the other hand, the transition metals were not lost as insoluble hydroxides (Hartland et al., 2012), despite having lower solubility than Mg (e.g. Cu(OH)2Ksp = 2.2 × 10-20); and this is consistent with the dominant role of NOM in solubilising and transporting the transition metals in this system (Hartland et al., 2011).The transport of metals by complexes with NOM in PE1 dripwater through the hydrological year was studied by Hartland et al. (2012). This study had two findings of direct relevance to the study of trace metal variations in the conjugate PC-08-1 stalagmite: Complexes between metals and the smallest, low-molecular weight fraction of NOM showed an attenuated delivery in dripwaters consistent with the non-conservative behaviour of analogous tracers in fractured-rock studies due to diffusion into micro-fractures. This mode of transport was termed ‘low-flux’ and was the dominant mode of transport for Co and V. Complexes between metals and coarse colloids (>100 nm) and particulates (>1000 nm) showed a rapid responsiveness to infiltration events. This was termed the ‘high-flux’ mode of NOM-metal transport and was interpreted as being dominantly fracture-fed. This mode of transport was dominated by Cu, Zn and Ni. The ‘high-flux’ vs ‘low-flux’ interplay of trace metal transport is summarised in Fig. 1.The PC-08-1 stalagmite studied here was deposited following the removal of stalagmite PC-97-1 studied by Baker et al. (1999b) and which grew under the PE1 drip point between 1927 and 1997. Both the PC-97-1 stalagmite and its regrowth (PC-08-1) are characterised by annual lamina couplets consisting of a porous pale layer and a dense fluorescent layer. Fluorescence in the PC-97-1 stalagmite displayed a marked sinusoidal pattern with 10% of laminae exhibiting a double band structure (Baker et al., 1999b).
NASA Astrophysics Data System (ADS)
Uglietti, C.; Gabrielli, P.; Lutton, A.; Olesik, J.; Thompson, L. G.
2012-12-01
Trace elements in micro-particles entrapped in ice cores are a valuable proxy of past climate and environmental variations. Inductively coupled plasma sector field mass spectrometry (ICP-SFMS) is generally recognized as a sensitive and accurate technique for the quantification of ultra-trace element concentrations in ice cores. Usually, ICP-SFMS analyses of ice core samples are performed by melting and acidifying aliquots. Acidification is important to transfer trace elements from particles into solution by partial and/or complete dissolution. Only elements in solution and in sufficiently small particles will be vaporized and converted to elemental ions in the plasma for detection by ICP-SFMS. However, experimental results indicate that differences in acidified sample storage time at room temperature may lead to the recovery of different trace element fractions. Moreover, different lithologies of the relatively abundant crustal material entrapped in the ice matrix could also influence the fraction of trace elements that are converted into elemental ions in the plasma. These factors might affect the determination of trace elements concentrations in ice core samples and hamper the comparison of results obtained from ice cores from different locations and/or epochs. In order to monitor the transfer of elements from particles into solution in acidified melted ice core samples during storage, a test was performed on sections from nine ice cores retrieved from low latitude drilling sites around the world. When compared to ice cores from polar regions, these samples are characterized by a relative high content of micro-particles that may leach trace elements into solution differently. Of the nine ice cores, five are from the Tibetan Plateau (Dasuopu, Guliya, Naimonanyi, Puruogangri and Dunde), two from the Andes (Quelccaya and Huascaran), one from Africa (Kilimanjaro) and one from the Eastern Alps (Ortles). These samples were decontaminated by triple rinsing, melted and stored in pre-cleaned low-density polyethylene bottles, and kept frozen until acidification (2% v/v ultra-pure HNO3). Determination of twenty trace elements (Ag, Al, As, Bi, Cd, Co, Cr, Cu, Fe, Mn, Mo, Pb, Rb, Sb, Sn, Ti, Tl, U, V, and Zn) was repeated at different times after acidification using the same aliquot. Analyses show a mean increase of 40-50% in trace element concentration in all the samples during the first 15 days of storage after acidification, except Al, Fe, V and Cr, which show a larger increase (90-100%). After 15 days the trace element concentrations reach generally stable values (with small increases within measurement uncertainty), except for the Naimonanyi and Kilimanjaro samples which continue to increase. In contrast, Ag concentration decreases after one week, likely due to its low stability in the acidified solution that may depend on the Cl- concentration. We froze the samples 43 days after the acidification. After two weeks the samples were melted and re-analyzed by ICP-SFMS in two different laboratories as an inter-calibration exercise. The results show a good correspondence between the measured concentrations determined by the two instruments and a consistent additional increase of 20-30% of measured trace element concentrations in almost all samples.
Di Leonardo, Rossella; Mazzola, Antonio; Cundy, Andrew B; Tramati, Cecilia Doriana; Vizzini, Salvatrice
2017-01-01
Posidonia oceanica mat is considered a long-term bioindicator of contamination. Storage and sequestration of trace elements and organic carbon (C org ) were assessed in dead P. oceanica mat and bare sediments from a highly polluted coastal marine area (Augusta Bay, central Mediterranean). Sediment elemental composition and sources of organic matter have been altered since the 1950s. Dead P. oceanica mat displayed a greater ability to bury and store trace elements and C org than nearby bare sediments, acting as a long-term contaminant sink over the past 120 yr. Trace elements, probably associated with the mineral fraction, were stabilized and trapped despite die-off of the overlying P. oceanica meadow. Mat deposits registered historic contamination phases well, confirming their role as natural archives for recording trace element trends in marine coastal environments. This sediment typology is enriched with seagrass-derived refractory organic matter, which acts mainly as a diluent of trace elements. Bare sediments showed evidence of inwash of contaminated sediments via reworking; more rapid and irregular sediment accumulation; and, because of the high proportions of labile organic matter, a greater capacity to store trace elements. Through different processes, both sediment typologies represent a repository for chemicals and may pose a risk to the marine ecosystem as a secondary source of contaminants in the case of sediment dredging or erosion. Environ Toxicol Chem 2017;36:49-58. © 2016 SETAC. © 2016 SETAC.
D'Haese, P C; Couttenye, M M; Lamberts, L V; Elseviers, M M; Goodman, W G; Schrooten, I; Cabrera, W E; De Broe, M E
1999-09-01
Little is known about trace metal alterations in the bones of dialysis patients or whether particular types of renal osteodystrophy are associated with either increased or decreased skeletal concentrations of trace elements. Because these patients are at risk for alterations of trace elements as well as for morbidity from skeletal disorders, we measured trace elements in bone of patients with end-stage renal disease. We analyzed bone biopsies of 100 end-stage renal failure patients enrolled in a hemodialysis program. The trace metal contents of bone biopsies with histological features of either osteomalacia, adynamic bone disease, mixed lesion, normal histology, or hyperparathyroidism were compared with each other and with the trace metal contents of bone of subjects with normal renal function. Trace metals were measured by atomic absorption spectrometry. The concentrations of aluminum, chromium, and cadmium were increased in bone of end-stage renal failure patients. Comparing the trace metal/calcium ratio, significantly higher values were found for the bone chromium/calcium, aluminum/calcium, zinc/calcium, magnesium/calcium, and strontium/calcium ratios. Among types of renal osteodystrophy, increased bone aluminum, lead, and strontium concentrations and strontium/calcium and aluminum/calcium ratios were found in dialysis patients with osteomalacia vs the other types of renal osteodystrophy considered as one group. Moreover, the concentrations of several trace elements in bone were significantly correlated with each other. Bone aluminum was correlated with the time on dialysis, whereas bone iron, aluminum, magnesium, and strontium tended to be associated with patient age. Bone trace metal concentrations did not depend on vitamin D intake nor on the patients' gender. The concentration of several trace elements in bone of end-stage renal failure patients is disturbed, and some of the trace metals under study might share pathways of absorption, distribution, and accumulation. The clinical significance of the increased/decreased concentrations of several trace elements other than aluminum in bone of dialysis patients deserves further investigation.
Trace element levels and cognitive function in rural elderly Chinese.
Gao, Sujuan; Jin, Yinlong; Unverzagt, Frederick W; Ma, Feng; Hall, Kathleen S; Murrell, Jill R; Cheng, Yibin; Shen, Jianzhao; Ying, Bo; Ji, Rongdi; Matesan, Janetta; Liang, Chaoke; Hendrie, Hugh C
2008-06-01
Trace elements are involved in metabolic processes and oxidation-reduction reactions in the central nervous system and could have a possible effect on cognitive function. The relationship between trace elements measured in individual biological samples and cognitive function in an elderly population had not been investigated extensively. The participant population is part of a large cohort study of 2000 rural elderly Chinese persons. Six cognitive assessment tests were used to evaluate cognitive function in this population, and a composite score was created to represent global cognitive function. Trace element levels of aluminum, calcium, cadmium, copper, iron, lead, and zinc were analyzed in plasma samples of 188 individuals who were randomly selected and consented to donating fasting blood. Analysis of covariance models were used to assess the association between each trace element and the composite cognitive score adjusting for demographics, medical history of chronic diseases, and the apolipoprotein E (APOE) genotype. Three trace elements-calcium, cadmium, and copper-were found to be significantly related to the composite cognitive score. Increasing plasma calcium level was associated with higher cognitive score (p <.0001). Increasing cadmium and copper, in contrast, were significantly associated with lower composite score (p =.0044 and p =.0121, respectively). Other trace elements did not show significant association with the composite cognitive score. Our results suggest that calcium, cadmium, and copper may be associated with cognitive function in the elderly population.
Epidemiology of trace elements deficiencies in Belgian beef and dairy cattle herds.
Guyot, Hugues; Saegerman, Claude; Lebreton, Pascal; Sandersen, Charlotte; Rollin, Frédéric
2009-01-01
Selenium (Se), iodine (I), zinc (Zn) and copper (Cu) deficiencies in cattle have been reported in Europe. These deficiencies are often associated with diseases. The aim of the study was to assess trace element status in Belgian cattle herds showing pathologies and to compare them to healthy cattle herds. Eighty-two beef herds with pathologies, 11 healthy beef herds, 65 dairy herds with pathologies and 20 healthy dairy herds were studied during barn period. Blood and/or milk samples were taken in healthy animals. Plasma Zn, Cu, inorganic I (PII) and activity of glutathione peroxidase in erythrocytes (GPX) were assayed. In milk, I concentration was measured. Data about pathologies and nutrition in the herds were collected. According to defined thresholds, it appeared that a large proportion of deficient herds belonged to "sick" group of herds. This conclusion was supported by the mean value of trace elements and by the fact that a majority of individual values of trace elements was below the threshold. Dairy herds had mean values of trace elements higher than beef herds. More concentrates and minerals were used in healthy herds versus "sick" herds. These feed supplements were also used more often in dairy herds, compared to beef herds. Trace elements deficiencies are present in cattle herds in Belgium and are linked to diseases. Nutrition plays a major role in the trace elements status.
Long-term anaerobic digestion of food waste stabilized by trace elements
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhang Lei, E-mail: wxzyfx@yahoo.com; Jahng, Deokjin, E-mail: djahng@mju.ac.kr
Highlights: Black-Right-Pointing-Pointer Korean food waste was found to contain low level of trace elements. Black-Right-Pointing-Pointer Stable anaerobic digestion of food waste was achieved by adding trace elements. Black-Right-Pointing-Pointer Iron played an important role in anaerobic digestion of food waste. Black-Right-Pointing-Pointer Cobalt addition further enhanced the process performance in the presence of iron. - Abstract: The purpose of this study was to examine if long-term anaerobic digestion of food waste in a semi-continuous single-stage reactor could be stabilized by supplementing trace elements. Contrary to the failure of anaerobic digestion of food waste alone, stable anaerobic digestion of food waste was achievedmore » for 368 days by supplementing trace elements. Under the conditions of OLR (organic loading rates) of 2.19-6.64 g VS (volatile solid)/L day and 20-30 days of HRT (hydraulic retention time), a high methane yield (352-450 mL CH{sub 4}/g VS{sub added}) was obtained, and no significant accumulation of volatile fatty acids was observed. The subsequent investigation on effects of individual trace elements (Co, Fe, Mo and Ni) showed that iron was essential for maintaining stable methane production. These results proved that the food waste used in this study was deficient in trace elements.« less
Migaszewski, Z.M.; Lamothe, P.J.; Crock, J.G.; Galuszka, A.; Dolegowska, S.
2011-01-01
Trace element concentrations in plant bioindicators are often determined to assess the quality of the environment. Instrumental methods used for trace element determination require digestion of samples. There are different methods of sample preparation for trace element analysis, and the selection of the best method should be fitted for the purpose of a study. Our hypothesis is that the method of sample preparation is important for interpretation of the results. Here we compare the results of 36 element determinations performed by ICP-MS on ashed and on acid-digested (HNO3, H2O2) samples of two moss species (Hylocomium splendens and Pleurozium schreberi) collected in Alaska and in south-central Poland. We found that dry ashing of the moss samples prior to analysis resulted in considerably lower detection limits of all the elements examined. We also show that this sample preparation technique facilitated the determination of interregional and interspecies differences in the chemistry of trace elements. Compared to the Polish mosses, the Alaskan mosses displayed more positive correlations of the major rock-forming elements with ash content, reflecting those elements' geogenic origin. Of the two moss species, P. schreberi from both Alaska and Poland was also highlighted by a larger number of positive element pair correlations. The cluster analysis suggests that the more uniform element distribution pattern of the Polish mosses primarily reflects regional air pollution sources. Our study has shown that the method of sample preparation is an important factor in statistical interpretation of the results of trace element determinations. ?? 2010 Springer-Verlag.
Oyewumi, Oluyinka; Schreiber, Madeline E
2017-08-01
Trace elements are added to poultry feed to control infection and improve weight gain. However, the fate of these trace elements in poultry litter is poorly understood. Because poultry litter is applied as fertilizer in many agricultural regions, evaluation of the environmental processes that influence the mobility of litter-derived trace elements is critical for predicting if trace elements are retained in soil or released to water. This study examined the effect of dissolved organic carbon (DOC) in poultry litter leachate on the fate and transport of litter-derived elements (As, Cu, P and Zn) using laboratory column experiments with soil collected from the Delmarva Peninsula (Mid-Atlantic, USA), a region of intense poultry production. Results of the experiments showed that DOC enhanced the mobility of all of the studied elements. However, despite the increased mobility, 60-70% of Zn, As and P mass was retained within the soil. In contrast, almost all of the Cu was mobilized in the litter leachate experiments, with very little retention in soil. Overall, our results demonstrate that the mobility of As, Cu, Zn and P in soils which receive poultry litter application is strongly influenced by both litter leachate composition, specifically organic acids, and adsorption to soil. Results have implications for understanding fate and transport of trace elements released from litter application to soil water and groundwater, which can affect both human health and the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.
Thanh-Nho, Nguyen; Strady, Emilie; Nhu-Trang, Tran-Thi; David, Frank; Marchand, Cyril
2018-04-01
Mangroves can be considered as biogeochemical reactors along (sub)tropical coastlines, acting both as sinks or sources for trace metals depending on environmental factors. In this study, we characterized the role of a mangrove estuary, developing downstream a densely populated megacity (Ho Chi Minh City, Vietnam), on the fate and partitioning of trace metals. Surface water and suspended particulate matter were collected at four sites along the estuarine salinity gradient during 24 h cycling in dry and rainy seasons. Salinity, pH, DO, TSS, POC, DOC, dissolved and particulate Fe, Mn, Cr, As, Cu, Ni, Co and Pb were measured. TSS was the main trace metals carrier during their transit in the estuary. However, TSS variations did not explain the whole variability of metals distribution. Mn, Cr and As were highly reactive metals while the other metals (Fe, Ni, Cu, Co and Pb) presented stable log K D values along the estuary. Organic matter dynamic appeared to play a key role in metals fractioning. Its decomposition during water transit in the estuary induced metal desorption, especially for Cr and As. Conversely, dissolved Mn concentrations decreased along the estuary, which was suggested to result from Mn oxidative precipitation onto solid phase due to oxidation and pH changes. Extra sources as pore-water release, runoff from adjacent soils, or aquaculture effluents were suggested to be involved in trace metal dynamic in this estuary. In addition, the monsoon increased metal loads, notably dissolved and particulate Fe, Cr, Ni and Pb. Copyright © 2018 Elsevier Ltd. All rights reserved.
Seventeen trace elements - arsenic (As), barium (Ba), boron, (B), cadmium, (Cd), chromium (Cr), copper (Cu), Iron (Fe), lead (Pb), lithium (Li), manganese (Mn), mercury (Hg), nickel (Ni), selenium (Se), silver (Ag), tin (Sn), vanadium (V), and Zinc (Zn) - were measured in human s...
Li, Peimiao; Gao, Xuelu
2014-11-01
One hundred and fifty nine samples of nine edible bivalve species (Argopecten irradians, Chlamys farreri, Crassostrea virginica, Lasaea nipponica, Meretrix meretrix, Mytilus edulis, Ruditapes philippinarum, Scapharca subcrenata and Sinonovacula constricta) were randomly collected from eight local seafood markets in six big cities (Dalian, Qingdao, Rizhao, Weifang, Weihai and Yantai) in the northern coastal areas of China for the investigation of trace element contamination. As, Cd, Cr, Cu, Hg, Pb and Zn were quantified. The risk of these trace elements to humans through bivalve consumption was then assessed. Results indicated that the concentrations of most of the studied trace element varied significantly with species: the average concentration of Cu in C. virginica was an order of magnitude higher than that in the remaining species; the average concentration of Zn was also highest in C. virginica; the average concentration of As, Cd and Pb was highest in R. philippinarum, C. farreri and A. irradians, respectively. Spatial differences in the concentrations of elements were generally less than those of interspecies, yet some elements such as Cr and Hg in the samples from different cities showed a significant difference in concentrations for some bivalve species. Trace element concentrations in edible tissues followed the order of Zn>Cu>As>Cd>Cr>Pb>Hg generally. Statistical analysis (one-way ANOVA) indicated that different species examined showed different bioaccumulation of trace elements. There were significant correlations between the concentrations of some elements. The calculated hazard quotients indicated in general that there was no obvious health risk from the intake of trace elements through bivalve consumption. But care must be taken considering the increasing amount of seafood consumption. Copyright © 2014 Elsevier Inc. All rights reserved.
Choosing the best partition of the output from a large-scale simulation
DOE Office of Scientific and Technical Information (OSTI.GOV)
Challacombe, Chelsea Jordan; Casleton, Emily Michele
Data partitioning becomes necessary when a large-scale simulation produces more data than can be feasibly stored. The goal is to partition the data, typically so that every element belongs to one and only one partition, and store summary information about the partition, either a representative value plus an estimate of the error or a distribution. Once the partitions are determined and the summary information stored, the raw data is discarded. This process can be performed in-situ; meaning while the simulation is running. When creating the partitions there are many decisions that researchers must make. For instance, how to determine oncemore » an adequate number of partitions have been created, how are the partitions created with respect to dividing the data, or how many variables should be considered simultaneously. In addition, decisions must be made for how to summarize the information within each partition. Because of the combinatorial number of possible ways to partition and summarize the data, a method of comparing the different possibilities will help guide researchers into choosing a good partitioning and summarization scheme for their application.« less
Taylor, Howard E.; Antweiler, Ronald C.; Roth, D.A.; Brinton, T.I.; Peart, D.B.; Healy, D.F.
2001-01-01
Two sampling trips were undertaken in 1994 to determine the distribution of trace elements in the Upper Rio Grande and several of its tributaries. Water discharges decreased in the main stem of the Rio Grande from June to September, whereas dissolved concentrations of trace elements generally increased. This is attributed to dilution of base flow from snowmelt runoff in the June samples. Of the three major mining districts (Creede, Summitville, and Red River) in the Upper Rio Grande drainage basin, only the Creede District appears to impact the Rio Grande in a significant manner, with both waters and sediments having elevated concentrations of some trace elements considerably downriver. For example, dissolved zinc concentrations upriver of Willow Creek, which primarily drains the Creede District, were about 2-3 μg/L; immediately downstream of the Willow Creek confluence, concentrations were above 20 μg/L; and elevated concentrations occurred in the Rio Grande for the next 100 km. The Red River District does not significantly impact the Upper Rio Grande for most trace elements. Because of current water management practices, it is difficult to assess the impact of the Summitville District on the Upper Rio Grande. There are, however, large increases in many dissolved trace element concentrations as the Rio Grande passes through the San Luis Valley, coincident with elevated concentrations of those same trace elements in tributaries. Among these elements are As, B, Cr, Li, Mn, Mo, Ni, Sr, U, and V. None of the trace elements exceeded U.S. EPA primary drinking water standards in either survey, with the exception of cadmium in Willow Creek. Secondary drinking water standards were frequently violated, especially in tributaries draining areas where mining has occurred. Dissolved zinc (in Willow Creek in both June and September) was the only element that exceeded the EPA Water Quality Criteria for aquatic life of 120 μg/L.
Lu, Shao-You; Zhang, Hui-Min; Sojinu, Samuel O; Liu, Gui-Hua; Zhang, Jian-Qing; Ni, Hong-Gang
2015-01-01
The levels of seven essential trace elements (Mn, Co, Ni, Cu, Zn, Se, and Mo) and six non-essential trace elements (Cr, As, Cd, Sb, Hg, and Pb) in a total of 89 drinking water samples collected in Shenzhen, China were determined using inductively coupled plasma mass spectrometry (ICP-MS) in the present study. Both the essential and non-essential trace elements were frequently detectable in the different kinds of drinking waters assessed. Remarkable temporal and spatial variations were observed among most of the trace elements in the tap water collected from two tap water treatment plants. Meanwhile, potential human health risk from these non-essential trace elements in the drinking water for local residents was also assessed. The median values of cancer risks associated with exposure to carcinogenic metals via drinking water consumption were estimated to be 6.1 × 10(-7), 2.1 × 10(-8), and 2.5 × 10(-7) for As, Cd, and Cr, respectively; the median values of incremental lifetime for non-cancer risks were estimated to be 6.1 × 10(-6), 4.4 × 10(-5), and 2.2 × 10(-5) for Hg, Pb, and Sb, respectively. The median value of total incremental lifetime health risk induced by the six non-essential trace elements for the population was 3.5 × 10(-5), indicating that the potential health risks from non-carcinogenic trace elements in drinking water also require some attention. Sensitivity analysis indicates that the most important factor for health risk assessment should be the levels of heavy metal in drinking water.
Biomineralization in foraminifera
NASA Astrophysics Data System (ADS)
Nooijer, L. D.; Toyofuku, T.; Bijma, J.; Reichart, G. J.
2015-12-01
Foraminifera are popular tools in paleoceanography since incorporation of minor/ major elements and fractionation of stable isotopes into their carbonate shells depend on environmental conditions (e.g. temperature, salinity, pH). Their shell chemistry is markedly different from that of inorganically precipitated CaCO3, reflecting that calcification is a process under strong biological control. The cellular components responsible for calcification are only partly identified in foraminifera and include the involvement of organic templates, trans-membrane ion transporters and selective ion removal. Recent results suggest that transmembrane exchange of H+ for Ca2+ is directly responsible for calcification. The resulting high pH inside and lowered pH outside the foraminifer results in an efficient CO2 'trap' after which carbon dioxide is converted to carbonate prior to calcification. Amongst others, this explains how some foraminifera are able to calcify in undersaturated seawater and may explain their moderate response to ocean acidification. Minor and trace metals incorporated into test carbonate reflect the processes involved in biomineralization and can thus be used to unravel the different factors and processes involved. Still, a more detailed understanding of the processes involved in foraminiferal calcification is needed to explain observed (inter-species) differences in partition coefficients for the incorporation of minor and trace metals and isotopic fractionation.
Distribution of trace elements in the coastal sea sediments of Maslinica Bay, Croatia
NASA Astrophysics Data System (ADS)
Mikulic, Nenad; Orescanin, Visnja; Elez, Loris; Pavicic, Ljiljana; Pezelj, Durdica; Lovrencic, Ivanka; Lulic, Stipe
2008-02-01
Spatial distributions of trace elements in the coastal sea sediments and water of Maslinica Bay (Southern Adriatic), Croatia and possible changes in marine flora and foraminifera communities due to pollution were investigated. Macro, micro and trace elements’ distributions in five granulometric fractions were determined for each sediment sample. Bulk sediment samples were also subjected to leaching tests. Elemental concentrations in sediments, sediment extracts and seawater were measured by source excited energy dispersive X-ray fluorescence (EDXRF). Concentrations of the elements Cr, Cu, Zn, and Pb in bulk sediment samples taken in the Maslinica Bay were from 2.1 to over six times enriched when compared with the background level determined for coarse grained carbonate sediments. A low degree of trace elements leaching determined for bulk sediments pointed to strong bonding of trace elements to sediment mineral phases. The analyses of marine flora pointed to higher eutrophication, which disturbs the balance between communities and natural habitats.
Ju, Yun-Ru; Yang, Ying-Fei; Tsai, Jeng-Wei; Cheng, Yi-Hsien; Chen, Wei-Yu; Liao, Chung-Min
2017-07-01
Fluctuation exposure of trace metal copper (Cu) is ubiquitous in aquatic environments. The purpose of this study was to investigate the impacts of chronically pulsed exposure on biodynamics and subcellular partitioning of Cu in freshwater tilapia (Oreochromis mossambicus). Long-term 28-day pulsed Cu exposure experiments were performed to explore subcellular partitioning and toxicokinetics/toxicodynamics of Cu in tilapia. Subcellular partitioning linking with a metal influx scheme was used to estimate detoxification and elimination rates. A biotic ligand model-based damage assessment model was used to take into account environmental effects and biological mechanisms of Cu toxicity. We demonstrated that the probability causing 50% of susceptibility risk in response to pulse Cu exposure in generic Taiwan aquaculture ponds was ~33% of Cu in adverse physiologically associated, metabolically active pool, implicating no significant susceptibility risk for tilapia. We suggest that our integrated ecotoxicological models linking chronic exposure measurements with subcellular partitioning can facilitate a risk assessment framework that provides a predictive tool for preventive susceptibility reduction strategies for freshwater fish exposed to pulse metal stressors.
Long-term anaerobic digestion of food waste stabilized by trace elements.
Zhang, Lei; Jahng, Deokjin
2012-08-01
The purpose of this study was to examine if long-term anaerobic digestion of food waste in a semi-continuous single-stage reactor could be stabilized by supplementing trace elements. Contrary to the failure of anaerobic digestion of food waste alone, stable anaerobic digestion of food waste was achieved for 368 days by supplementing trace elements. Under the conditions of OLR (organic loading rates) of 2.19-6.64 g VS (volatile solid)/L day and 20-30 days of HRT (hydraulic retention time), a high methane yield (352-450 mL CH(4)/g VS(added)) was obtained, and no significant accumulation of volatile fatty acids was observed. The subsequent investigation on effects of individual trace elements (Co, Fe, Mo and Ni) showed that iron was essential for maintaining stable methane production. These results proved that the food waste used in this study was deficient in trace elements. Copyright © 2012. Published by Elsevier Ltd.
Munn, M.D.; Cox, S.E.; Dean, C.J.
1995-01-01
Three species of sportfish--walleye, smallmouth bass, and rainbow trout--were collected from Franklin D. Roosevelt Lake and the upstream reach of the Columbia River within the state of Washington, to determine the concentrations of mercury and other selected trace elements in fish tissue. Concentrations of total mercury in walleye fillets ranged from 0.11 to 0.44 milligram per kilogram, with the higher concentrations in the larger fish. Fillets of smallmouth bass and rainbow trout also contained mercury, but generally at lower concentrations. Other selected trace elements were found in fillet samples, but the concentrations were generally low depending on species and the specific trace element. The trace elements cadmium, copper, lead, and zinc were found in liver tissue of these same species with zinc consistently present in the highest concentration.
Cabral, Lucélia; Soares, Claúdio Roberto Fonsêca Sousa; Giachini, Admir José; Siqueira, José Oswaldo
2015-11-01
In recent decades, the concentration of trace elements has increased in soil and water, mainly by industrialization and urbanization. Recovery of contaminated areas is generally complex. In that respect, microorganisms can be of vital importance by making significant contributions towards the establishment of plants and the stabilization of impacted areas. Among the available strategies for environmental recovery, bioremediation and phytoremediation outstand. Arbuscular mycorrhizal fungi (AMF) are considered the most important type of mycorrhizae for phytoremediation. AMF have broad occurrence in contaminated soils, and evidences suggest they improve plant tolerance to excess of certain trace elements. In this review, the use of AMF in phytoremediation and mechanisms involved in their trace element tolerance are discussed. Additionally, we present some techniques used to study the retention of trace elements by AMF, as well as a summary of studies showing major benefits of AMF for phytoremediation.
Frontalini, Fabrizio; Buosi, Carla; Da Pelo, Stefania; Coccioni, Rodolfo; Cherchi, Antonietta; Bucci, Carla
2009-06-01
In order to assess the response of benthic foraminifera to trace element pollution, a study of benthic foraminiferal assemblages was carried out into sediment samples collected from the Santa Gilla lagoon (Sardinia, Italy). The lagoon has been contaminated by industrial waste, mainly trace elements, as well as by agricultural and domestic effluent. The analysis of surficial sediment shows enrichment in trace elements, including Cr, Cu, Hg, Ni, Pb and Zn. Biotic and abiotic data, analyzed with multivariate techniques of statistical analysis, reveal a distinct separation of both the highly polluted and less polluted sampling sites. The innermost part of the lagoon, comprising the industrial complex at Macchiareddu, is exposed to a high load of trace elements which are probably enhanced by their accumulation in the finer sediment fraction. This area reveals lower diversity and higher percentages of abnormalities when compared to the outermost part of the lagoon.
Temperature and Gravity Dependence of Trace Element Abundances in Hot DA White Dwarfs (94-EUVE-094)
NASA Technical Reports Server (NTRS)
Finley, David S.
1998-01-01
EUV spectroscopy has shown that DA white dwarfs hotter than about 45,000 K may contain trace heavy elements, while those hotter than about 50,000 K almost always have significant abundances of trace heavy elements. One of our continuing challenges is to identify and determine the abundances of these trace constituents, and then to relate the observed abundance patterns to the present conditions and previous evolutionary histories of the hot DA white dwarfs.
NASA Technical Reports Server (NTRS)
Neal, C. R.; Taylor, L. A.
1989-01-01
Elemental partitioning between immiscible melts has been studied using experimental liquid-liquid Kds and those determined by analysis of immiscible glasses in basalt mesostases in order to investigate lunar granite petrogenesis. Experimental data show that Ba is partitioned into the basic immiscible melt, while probe analysis results show that Ba is partitioned into the granitic immiscible melt. It is concluded that lunar granite of significant size can only occur in a plutonic or deep hypabyssal environment.
Trace elements in urban and suburban rainfall, Mersin, Northeastern Mediterranean
NASA Astrophysics Data System (ADS)
Özsoy, Türkan; Örnektekin, Sermin
2009-10-01
Spatial/temporal variabilities of rainwater constituents are examined based on soluble/insoluble trace elements, pH and electrical conductivity measurements in rainfall sampled during December 2003-May 2005 at two urban and two suburban sites in Mersin, an industrialized city of 850,000 inhabitants on the southern coast of Turkey. In the analyses, backward air mass trajectories for rainy days were used in addition to factor analyses, enrichment factors, phase distributions and correlations between trace elements. The pH varied from 4.8 to 8.5 with an average value of 6.2, reflecting a mainly alkaline regime. Mean concentrations of trace elements collected from urban and suburban sites are spatially variable. Based on the overall data, total concentrations of trace elements were ordered as Ca > Na > Fe > Al > Mg > K > Zn > Mn > Sr > Pb > Ni > Cr > Ba > Cu > Co > Cd. Mainly terrigeneous (Ca, Fe, Al) and, to a lesser extent, sea salt particles (Na, Mg) were shown to be the major source of trace elements. Excluding major cations, the solubilities of trace elements were found to be ordered as Sr > Zn > Ba > Mn > Cu > Ni > Cr > Fe > Al, confirming the lower solubility of crustal elements. Cd, Co and Pb were excluded from the above evaluation because of the low numbers of soluble samples allowing quantitative measurements. The solubilities of Al, Fe, Mn and particularly of Ni were found to be considerably lower than those reported for various sites around the world, most likely due to the effect of pH. During the entire sampling period, a total of 28 dust transport episodes associated with 31 red rain events were identified. Extremely high mean concentration ratios of Al (8.2), Fe (14.4) and Mn (13.1) were observed in red rain, compared to normal rain. The degree of this enhancement displayed a decrease from crustal to anthropogenic origin elements and the lowest enhancements were found for anthropogenic origin elements of Zn and Cd (both having a ratio of 1.1). Aerosol dust was found to be the main source of almost all analyzed elements in Mersin precipitation, regardless that they are crustal or anthropic derived elements. The magnitude of crustal source contribution to trace element budget of precipitation was at its highest levels for crustal originated elements, most probably due to much higher scavenging ratios of crustal elements compared to anthropogenic ones.
Ultrastructurally-smooth thick partitioning and volume stitching for larger-scale connectomics
Hayworth, Kenneth J.; Xu, C. Shan; Lu, Zhiyuan; Knott, Graham W.; Fetter, Richard D.; Tapia, Juan Carlos; Lichtman, Jeff W.; Hess, Harald F.
2015-01-01
FIB-SEM has become an essential tool for studying neural tissue at resolutions below 10×10×10 nm, producing datasets superior for automatic connectome tracing. We present a technical advance, ultrathick sectioning, which reliably subdivides embedded tissue samples into chunks (20 µm thick) optimally sized and mounted for efficient, parallel FIB-SEM imaging. These chunks are imaged separately and then ‘volume stitched’ back together, producing a final 3D dataset suitable for connectome tracing. PMID:25686390
Tracing the atomic nitrogen abundance in star-forming regions with ammonia deuteration
NASA Astrophysics Data System (ADS)
Furuya, Kenji; Persson, Magnus V.
2018-06-01
Partitioning of elemental nitrogen in star-forming regions is not well constrained. Most nitrogen is expected to be partitioned among atomic nitrogen (N I), molecular nitrogen (N_2), and icy N-bearing molecules, such as NH_3 and N_2. N I is not directly observable in the cold gas. In this paper, we propose an indirect way to constrain the amount of N I in the cold gas of star-forming clouds, via deuteration in ammonia ice, the [ND2H/NH2D]/[NH2D/NH3] ratio. Using gas-ice astrochemical simulations, we show that if atomic nitrogen remains as the primary reservoir of nitrogen during cold ice formation stages, the [ND2H/NH2D]/[NH2D/NH3] ratio is close to the statistical value of 1/3 and lower than unity, whereas if atomic nitrogen is largely converted into N-bearing molecules, the ratio should be larger than unity. Observability of ammonia isotopologues in the inner hot regions around low-mass protostars, where ammonia ice has sublimated, is also discussed. We conclude that the [ND2H/NH2D]/[NH2D/NH3] ratio can be quantified using a combination of Very Large Array and Atacama Large Millimeter/submillimeter Array observations with reasonable integration times, at least towards IRAS 16293-2422, where high molecular column densities are expected.
Lei, Bingli; Chen, Liang; Hao, Ying; Cao, Tiehua; Zhang, Xinyu; Yu, Yingxin; Fu, Jiamo
2013-10-01
The concentrations of four human essential trace elements [iron (Fe), manganese (Mn), zinc (Zn), chromium (Cr)] and non-essential elements [cadmium (Cd), lead (Pb), arsenic (As), and mercury (Hg)] in eighteen animal-based foods including meat, fish, and shellfish collected from markets in Shanghai, China, were analyzed, and the associated human daily intake and uptake considering bioaccessibility were estimated. The mean concentration ranges for eight trace elements measured in the foods were 3.98-131µgg(-1) for Fe, 0.437-18.5µgg(-1) for Mn, 5.47-53.8µgg(-1) for Zn, none detected-0.101µgg(-1) for Cr, 2.88×10(-4)-2.48×10(-2)µgg(-1) for Cd, 1.18×10(-3)-0.747µgg(-1) for Pb, none detected-0.498µgg(-1) for As, and 8.98×10(-4)-6.52×10(-2)µgg(-1) for Hg. The highest mean concentrations of four human essential elements were all found in shellfish. For all the trace elements, the observed mean concentrations are mostly in agreement with the reported values around the world. The total daily intake of trace elements via ingestion of animal-based food via an average Shanghai resident was estimated as 7371µgd(-1) for the human essential elements and 13.0µgd(-1) for the human non-essential elements, but the uptake decreased to 4826µgd(-1) and 6.90µgd(-1), respectively, after trace element bioaccessibility was considered. Livestock and fish for human essential and non-essential elements, respectively, were the main contributor, no matter whether the bioaccessibility was considered or not. Risk estimations showed that the intake and uptake of a signal trace element for an average Shanghai resident via ingestion animal-based foods from Shanghai markets do not exceed the recommended dietary allowance values; consequently, a health risk situation is not indicated. Copyright © 2013. Published by Elsevier Inc.
Olafisoye, O B; Oguntibeju, O O; Osibote, O A
2017-05-03
Oil palm (Elaeisguineensis) is one of the most productive oil producing plant in the world. Crude palm oil is composed of triglycerides supplying the world's need of edible oils and fats. Palm oil also provides essential elements and antioxidants that are potential mediators of cellular functions. Experimental studies have demonstrated the toxicity of the accumulation of significant amounts of nonessential trace elements and radionuclides in palm oil that affects the health of consumers. It has been reported that uptake of trace elements and radionuclides from the oil palm tree may be from water and soil on the palm plantations. In the present review, an attempt was made to revise and access knowledge on the presence of some selected trace elements and radionuclides in palm oil, soil, water, and leaves from oil palm plantations based on the available facts and data. Existing reports show that the presence of nonessential trace elements and radionuclides in palm oil may be from natural or anthropogenic sources in the environment. However, the available literature is limited and further research need to be channeled to the investigation of trace elements and radionuclides in soil, water, leaves, and palm oil from oil palm plantations around the globe.
Nutritional Aspects of Essential Trace Elements in Oral Health and Disease: An Extensive Review
Hussain, Mohsina
2016-01-01
Human body requires certain essential elements in small quantities and their absence or excess may result in severe malfunctioning of the body and even death in extreme cases because these essential trace elements directly influence the metabolic and physiologic processes of the organism. Rapid urbanization and economic development have resulted in drastic changes in diets with developing preference towards refined diet and nutritionally deprived junk food. Poor nutrition can lead to reduced immunity, augmented vulnerability to various oral and systemic diseases, impaired physical and mental growth, and reduced efficiency. Diet and nutrition affect oral health in a variety of ways with influence on craniofacial development and growth and maintenance of dental and oral soft tissues. Oral potentially malignant disorders (OPMD) are treated with antioxidants containing essential trace elements like selenium but even increased dietary intake of trace elements like copper could lead to oral submucous fibrosis. The deficiency or excess of other trace elements like iodine, iron, zinc, and so forth has a profound effect on the body and such conditions are often diagnosed through their early oral manifestations. This review appraises the biological functions of significant trace elements and their role in preservation of oral health and progression of various oral diseases. PMID:27433374
Phytoaccumulation of trace elements by wetland plants. 2: Water hyacinth
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhu, Y.L.; Zayed, A.M.; Qian, J.H.
Wetland plants are being used successfully for the phytoremediation of trace elements in natural and constructed wetlands. This study demonstrates the potential of water hyacinth (Eichhornia crassipes), an aquatic floating plant, for the phytoremediation of six trace elements. The ability of water hyacinth to take up and translocate six trace elements--As(V), Cd(II), Cr(VI), Cu(II), Ni(II), and Se(VI)--was studied under controlled conditions. Water hyacinth accumulated Cd and Cr best, Se and Cu at moderate levels, and was a poor accumulator of As and Ni. The highest levels of Cd found in shoots and roots were 371 and 6103 mg kg[sup [minus]1]more » dry wt., respectively, and those of Cr were 119 and 32951 mg kg[sup [minus]1] dry wt, respectively. Cadmium, Cr, Cu, Ni, and As were more highly accumulated in roots than in shoots. In contrast, Se was accumulated more in shoots than in roots at most external concentrations. Water hyacinth had high trace element bioconcentration factors when supplied with low external concentrations of all six elements, particularly Cd, Cr, and Cu. Therefore, water hyacinth will be very efficient at phytoextracting trace elements from wastewater containing low concentrations of these elements. The authors conclude that water hyacinth is a promising candidate for phytoremediation of wastewater polluted with Cd, Cr, Cu, and Se.« less
Trace element analysis of soil type collected from the Manjung and central Perak
NASA Astrophysics Data System (ADS)
Azman, Muhammad Azfar; Hamzah, Suhaimi; Rahman, Shamsiah Abdul; Elias, Md Suhaimi; Abdullah, Nazaratul Ashifa; Hashim, Azian; Shukor, Shakirah Abd; Kamaruddin, Ahmad Hasnulhadi Che
2015-04-01
Trace elements in soils primarily originated from their parent materials. Parents' material is the underlying geological material that has been undergone different types of chemical weathering and leaching processes. Soil trace elements concentrations may be increases as a result of continuous input from various human activities, including power generation, agriculture, mining and manufacturing. This paper describes the Neutron Activation Analysis (NAA) method used for the determination of trace elements concentrations in part per million (ppm) present in the terrestrial environment soil in Perak. The data may indicate any contamination of trace elements contributed from human activities in the area. The enrichment factors were used to check if there any contamination due to the human activities (power plants, agricultural, mining, etc.) otherwise the values would serve as a baseline data for future study. The samples were collected from 27 locations of different soil series in the area at two different depths: the top soil (0-15cm) and the sub soil (15-30cm). The collected soil samples were air dried at 60°C and passed through 2 µm sieve. Instrumental Neutron Activation Analysis (NAA) has been used for the determination of trace elements. Samples were activated in the Nuclear Malaysia TRIGA Mark II reactor followed by gamma spectrometric analysis. By activating the stable elements in the samples, the elements can be determined from the intensities of gamma energies emitted by the respected radionuclides.
Seasonal variations of trace elements in precipitation at the largest city in Tibet, Lhasa
NASA Astrophysics Data System (ADS)
Guo, Junming; Kang, Shichang; Huang, Jie; Zhang, Qianggong; Tripathee, Lekhendra; Sillanpää, Mika
2015-02-01
Precipitation samples were collected from March 2010 to August 2012 at an urban site in Lhasa, the capital and largest city of Tibet. The volume weighted mean (VWM) concentrations of 17 trace elements in precipitation were higher during the non-monsoon season than in the monsoon season, but inverse seasonal variations occurred for wet deposition fluxes of most of the trace elements. Concentrations for most of trace elements were negatively correlated with precipitation amount, indicating that below-cloud scavenging of trace elements was an important mechanism contributing to wet deposition of these elements. The elements Al, Sc, V, Cr, Mn, Fe, Mn, Ni, and U displayed low crustal enrichment factors (EFs), whereas Co, Cu, Zn, As, Cd Sn, Pb, and Bi showed high EF values in precipitation, suggesting that anthropogenic activities might be important contributors of these elements at Lhasa. However, this present work indicates a much lower anthropogenic emission at Lhasa than in seriously polluted regions. Our study will not only provide insights for assessing the current status of the atmospheric environment in Lhasa but also enhance our understanding for updating the baseline for environmental protection over the Tibetan Plateau.
NASA Technical Reports Server (NTRS)
Kornacki, Alan S.; Fegley, Bruce, Jr.
1986-01-01
The relative volatilities of lithophile refractory trace elements (LRTE) were determined using calculated 50-percent condensation temperatures. Then, the refractory trace-element abundances were measured in about 100 Allende inclusions. The abundance patterns found in Allende Ca,Al-rich inclusions (CAIs) and ultrarefractory inclusions were used to empirically modify the calculated LRTE volatility sequence. In addition, the importance of crystal-chemical effects, diffusion constraints, and grain transport for the origin of the trace-element chemistry of Allende CAIs (which have important implications for chemical and physical processes in the solar nebula) is discussed.
Nanometer-sized materials for solid-phase extraction of trace elements.
Hu, Bin; He, Man; Chen, Beibei
2015-04-01
This review presents a comprehensive update on the state-of-the-art of nanometer-sized materials in solid-phase extraction (SPE) of trace elements followed by atomic-spectrometry detection. Zero-dimensional nanomaterials (fullerene), one-dimensional nanomaterials (carbon nanotubes, inorganic nanotubes, and nanowires), two-dimensional nanomaterials (nanofibers), and three-dimensional nanomaterials (nanoparticles, mesoporous nanoparticles, magnetic nanoparticles, and dendrimers) for SPE are discussed, with their application for trace-element analysis and their speciation in different matrices. A variety of other novel SPE sorbents, including restricted-access sorbents, ion-imprinted polymers, and metal-organic frameworks, are also discussed, although their applications in trace-element analysis are relatively scarce so far.
NASA Astrophysics Data System (ADS)
Mapoma, Harold Wilson Tumwitike; Xie, Xianjun; Nyirenda, Mathews Tananga; Zhang, Liping; Kaonga, Chikumbusko Chiziwa; Mbewe, Rex
2017-07-01
In this study, twenty one (21) trace elements in the basement complex groundwater of Blantyre district, Malawi were analyzed. The majority of the analyzed trace elements in the water were within the standards set by World Health Organization (WHO) and Malawi Standards Board (MSB). But, iron (Fe) (BH16 and 21), manganese (Mn) (BH01) and selenium (Se) (BH02, 13, 18, 19 and 20) were higher than the WHO and MSB standards. Factor analysis (FA) revealed up to five significant factors which accounted for 87.4% of the variance. Factor 1, 2 and 3 suggest evaporite dissolution and silicate weathering processes while the fourth factor may explain carbonate dissolution and pH influence on trace element geochemistry of the studied groundwater samples. According to PHREEQC computed saturation indices, dissolution, precipitation and rock-water-interaction control the levels of trace elements in this aquifer. Elevated concentrations of Fe, Mn and Se in certain boreholes are due to the geology of the aquifer and probable redox status of groundwater. From PHREEQC speciation results, variations in trace element species were observed. Based on this study, boreholes need constant monitoring and assessment for human consumption to avoid health related issues.
MACROMOLECULES FACILITATE THE TRANSPORT OF TRACE ORGANICS
Macromolecules in the pore fluid of a soil may influence the mobility of hydrophobic compounds by their partitioning to the macromolecule, which moves with, or even faster than, the water. The mobility is described mathematically by a chemical transport model. The significance of...
Co-occurrence profiles of trace elements in potable water systems: a case study.
Andra, Syam S; Makris, Konstantinos C; Charisiadis, Pantelis; Costa, Costas N
2014-11-01
Potable water samples (N = 74) from 19 zip code locations in a region of Greece were profiled for 13 trace elements composition using inductively coupled plasma mass spectrometry. The primary objective was to monitor the drinking water quality, while the primary focus was to find novel associations in trace elements occurrence that may further shed light on common links in their occurrence and fate in the pipe scales and corrosion products observed in urban drinking water distribution systems. Except for arsenic at two locations and in six samples, rest of the analyzed elements was below maximum contaminant levels, for which regulatory values are available. Further, we attempted to hierarchically cluster trace elements based on their covariances resulting in two groups; one with arsenic, antimony, zinc, cadmium, and copper and the second with the rest of the elements. The grouping trends were partially explained by elements' similar chemical activities in water, underscoring their potential for co-accumulation and co-mobilization phenomena from pipe scales into finished water. Profiling patterns of trace elements in finished water could be indicative of their load on pipe scales and corrosion products, with a corresponding risk of episodic contaminant release. Speculation was made on the role of disinfectants and disinfection byproducts in mobilizing chemically similar trace elements of human health interest from pipe scales to tap water. It is warranted that further studies may eventually prove useful to water regulators from incorporating the acquired knowledge in the drinking water safety plans.
Trace elements in hazardous mineral fibres.
Bloise, Andrea; Barca, Donatella; Gualtieri, Alessandro Francesco; Pollastri, Simone; Belluso, Elena
2016-09-01
Both occupational and environmental exposure to asbestos-mineral fibres can be associated with lung diseases. The pathogenic effects are related to the dimension, biopersistence and chemical composition of the fibres. In addition to the major mineral elements, mineral fibres contain trace elements and their content may play a role in fibre toxicity. To shed light on the role of trace elements in asbestos carcinogenesis, knowledge on their concentration in asbestos-mineral fibres is mandatory. It is possible that trace elements play a synergetic factor in the pathogenesis of diseases caused by the inhalation of mineral fibres. In this paper, the concentration levels of trace elements from three chrysotile samples, four amphibole asbestos samples (UICC amosite, UICC anthophyllite, UICC crocidolite and tremolite) and fibrous erionite from Jersey, Nevada (USA) were determined using inductively coupled plasma mass spectrometry (ICP-MS). For all samples, the following trace elements were measured: Li, Be, Sc, V, Cr, Mn, Co, Ni, Cu, Zn, As, Rb, Sr, Y, Sb, Cs, Ba, La, Pb, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, U. Their distribution in the various mineral species is thoroughly discussed. The obtained results indicate that the amount of trace metals such as Mn, Cr, Co, Ni, Cu and Zn is higher in anthophyllite and chrysotile samples, whereas the amount of rare earth elements (REE) is higher in erionite and tremolite samples. The results of this work can be useful to the pathologists and biochemists who use asbestos minerals and fibrous erionite in-vitro studies as positive cyto- and geno-toxic standard references. Copyright © 2016 Elsevier Ltd. All rights reserved.
NASA Technical Reports Server (NTRS)
Capobianco, Christopher J.; Jones, John H.; Drake, Michael J.
1993-01-01
Low-temperature metal-silicate partition coefficients are extrapolated to magma ocean temperatures. If the low-temperature chemistry data is found to be applicable at high temperatures, an important assumption, then the results indicate that high temperature alone cannot account for the excess siderophile element problem of the upper mantle. For most elements, a rise in temperature will result in a modest increase in siderophile behavior if an iron-wuestite redox buffer is paralleled. However, long-range extrapolation of experimental data is hazardous when the data contains even modest experimental errors. For a given element, extrapolated high-temperature partition coefficients can differ by orders of magnitude, even when data from independent studies is consistent within quoted errors. In order to accurately assess siderophile element behavior in a magma ocean, it will be necessary to obtain direct experimental measurements for at least some of the siderophile elements.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Qian, J.H.; Zayed, A.; Zhu, Y.L.
1999-10-01
Interest is increasing in using wetland plants in constructed wetlands to remove toxic elements from polluted wastewater. To identify those wetland plants that hyperaccumulate trace elements, 12 plant species were tested for their efficiency to bioconcentrate 10 potentially toxic trace elements including As, b, Cd, Cr, Cu, Pb, Mn, Hg, Ni, and Se. Individual plants were grown under carefully controlled conditions and supplied with 1 mg L{sup {minus}1} of each trace element individually for 10 d. Except B, all elements accumulated to much higher concentrations in roots than in shoots. Highest shoot tissue concentrations (mg kg{sup {minus}1} DW) of themore » various trace elements were attained by the following species: umbrella plant (Cyperus alternifolius L.) for Mn (198) and Cr (44); water zinnia (Wedelia trilobata Hitchc.) for Cd (148) and Ni (80); smartweed (Polygonum hydropiperoides Michx.) for Cu (95) and Pb (64); water lettuce (Pistia stratiotes L.) for Hg (92), As (34), and Se (39); and mare's tail (hippuris vulgaris L.) for B (1132). Whereas, the following species attained the highest root tissue concentrations (mg kg{sup {minus}1} DW); stripped rush (Baumia rubiginosa) for Mn (1683); parrot's feather (Myriophyllum brasiliense Camb.) for Cd (1426) and Ni (1077); water lettuce for Cu (1038), Hg (1217), and As (177); smartweed for Cr (2980) and Pb (1882); mare's tail for B (1277); and monkey flower (Mimulus guttatus Fisch.) for Se (384). From a phytoremediation perspective, smartweed was probably the best plant species for trace element removal from wastewater due to its faster growth and higher plant density.« less
NASA Astrophysics Data System (ADS)
Izzati, Munifatul; Haryanti, Sri; Parman, Sarjana
2018-05-01
Gracilaria widely known as a source of essential trace elements. However this red seaweeds also has great potential for being developed into commercial products. This study examined the sequential pattern of essential trace elements composition in fresh Gracilaria verrucosa and a selection of its generated products, nemely extracted agar, Gracilaria salt and Gracilaria residue. The sample was collected from a brackish water pond, located in north part Semarang, Central Java. The collected sample was then dried under the sun, and subsequently processed into aformentioned generated products. The Gracilaria salt was obtain by soaking the sun dried Gracilaria overnight in fresh water overnight. The resulted salt solution was then boiled leaving crystal salt. Extracted agar was obtained with alkali agar extraction method. The rest of remaining material was considered as Gracilaria residue. The entire process was repeated 3 times. The compositin of trace elements was examined using ICP-MS Spectrometry. Collected data was then analyzed by ANOVA single factor. Resulting sequential pattern of its essential trace elements composition was compared. A regular table salt was used as controls. Resuts from this study revealed that Gracilaria verrucosa and its all generated products all have similarly patterned the composition of essential trace elements, where Mn>Zn>Cu>Mo. Additionally this pattern is similar to different subspecies of Gracilaria from different location and and different season. However, Gracilaria salt has distinctly different pattern of sequential essential trace elements composition compared to table salt.
Early Diagenesis of Trace Elements in Modern Fjord Sediments of the High Arctic
NASA Astrophysics Data System (ADS)
Herbert, L.; Riedinger, N.; Aller, R. C.; Jørgensen, B. B.; Wehrmann, L.
2017-12-01
Marine sediments are critical repositories for elements that are only available at trace concentrations in seawater, such as Fe, Mn, Co, Ni, As, Mo, and U. The behavior of these trace elements in the sediment is governed by a dynamic interplay of diagenetic reactions involving organic carbon, Fe and Mn oxides, and sulfur phases. In the Arctic fjords of Svalbard, glacial meltwater delivers large amounts of reactive Fe and Mn oxides to the sediment, while organic carbon is deposited episodically and diluted by lithogenic material. These conditions result in pronounced Fe and Mn cycling, which in turn drives other diagenetic processes such as rapid sulfide oxidation. These conditions make the Svalbard fjords ideal sites for investigating trace element diagenesis because they allow resolution of the interconnections between Fe and Mn dynamics and trace element cycling. In August 2016, we collected sediment cores from three Svalbard fjords and analyzed trace elements in the pore water and solid sediment over the top meter. Initial results reveal the dynamic nature of these fjords, which are dominated by non-steady state processes and episodic events such as meltwater pulses and phytoplankton blooms. Within this system, the distribution of As appears to be strongly linked to the Fe cycle, while Co and Ni follow Mn; thus, these three elements may be released from the sediment through diffusion and bioturbation along with Fe and Mn. The pore water profiles of U and Mo indicate removal processes that are independent from Fe or Mn, and which are rather unexpected given the apparent diagenetic conditions. Our results will help elucidate the processes controlling trace element cycling in a dynamic, glacially impacted environment and will ultimately contribute to our understanding of the role of fjords in the biogeochemical cycling of trace elements in a rapidly changing Arctic Ocean.
Trace elements: implications for nursing.
Hayter, J
1980-01-01
Although most were unknown a few years ago, present evidence indicates that at least 25 trace elements have some pertinence to health. Unlike vitamins, they cannot be synthesized. Some trace elements are now considered important only because of their harmful effects but traces of them may be essential. Zinc is especially important during puberty, pregnancy and menopause and is related to protein metabolism. Both fluoride and cadmium accumulate in the body year after year. Cadmium is positively correlated with several chronic diseases, especially hypertension. It is obtained from smoking and drinking soft water. Silicon, generally associated with silicosis, may be necessary for healthy bone and connective tissue. Chromium, believed to be the glucose tolerance factor, is obtained from brewer's yeast, spices, and whole wheat products. Copper deficiency may be implicated in a wide range of cardiovascular and blood related disorders. Either marginal deficiencies or slight excesses of most trace elements are harmful. Nurses should instruct patients to avoid highly refined foods, fad diets, or synthetic and fabricated foods. A well balanced and varied diet is the best safeguard against trace element excesses or deficiencies.
Trace element diffusion and kinetic fractionation in wet rhyolitic melt
NASA Astrophysics Data System (ADS)
Holycross, Megan E.; Watson, E. Bruce
2018-07-01
Piston-cylinder experiments were run to determine the chemical diffusivities of 21 trace elements (Sc, V, Y, Zr, Nb, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Hf, Th and U) in hydrous rhyolitic melts at 1 GPa pressure and temperatures from 850 to 1250 °C. Diffusion couple glasses were doped with trace elements in low concentrations to characterize the diffusivities of all cations in a single experiment. Laser ablation ICP-MS was used to evaluate the trace element concentration gradients that developed in the silicate glasses. All calculated diffusion coefficients correspond to the temperature dependence D = D0exp(-Ea/RT). Rhyolite liquids contained either ∼4.1 wt% or ∼6.2 wt% dissolved H2O; separate Arrhenius relationships are produced for each melt composition. Trace element diffusivities in the melt with 6.2 wt% H2O are roughly two times higher than those in the less hydrous melt. Calculated trace element diffusion coefficients cover nearly two orders of magnitude at a given temperature. The high field strength elements are the slowest diffusers, followed by the transition metals and heavy rare earth elements. The light rare earth elements have the fastest diffusion rates in hydrous rhyolitic melt. The measured diffusion coefficients range down to values sufficiently low to preclude diffusive homogenization over geochemically realistic time scales in some cases. The substantial differences in the diffusivities of individual cations may result in fractionated trace element signatures in rhyolite melt pockets. A simple model is used to explore the potential for kinetic fractionation of REE during growth of an apatite crystal in a diffusive boundary layer locally saturated in P2O5. The faster-diffusing light REE are more efficiently transported away from the crystal interface than the slower-moving heavy REE. Diffusion effects will enrich the melt boundary layer in slow-moving HREE relative to the faster LREE. The kinetic fractionation of REE in the melt growth medium will result in a precipitated apatite crystal with a disequilibrium trace element composition.
Dynamics of trace elements in shallow groundwater of an agricultural land in the northeast of Mexico
NASA Astrophysics Data System (ADS)
Mora, Abrahan; Mahlknecht, Jürgen; Hernández-Antonio, Arturo
2017-04-01
The citrus zone located in northeastern Mexico covers an area of 8000 km2 and produces 10% of the Mexican citrus production. The aquifer system of this zone constitutes the major source of water for drinking and irrigation purposes for local population and provides base flows to surface water supplied to the city of Monterrey ( 4.5 million inhabitants). Although the study area is near the recharge zones, several works have reported nitrate pollution in shallow groundwater of this agricultural area, mainly due to animal manure and human waste produced by infiltration of urban sewers and septic tanks. Thus, the goals of this work were to assess the dynamics of selected trace elements in this aquifer system and determine if the trace element content in groundwater poses a threat to the population living in the area. Thirty-nine shallow water wells were sampled in 2010. These water samples were filtered through 0,45 µm pore size membranes and preserved with nitric acid for storage. The concentrations of Cd, Cs, Cu, Mo, Pb, Rb, Si, Ti, U, Y, and Zn were measured by ICP-MS. Also, sulfate concentrations were measured by ion chromatography in unacidified samples. Principal Component Analysis (PCA) performed in the data set show five principal components (PC). PC1 includes elements derived from silicate weathering, such as Si and Ti. The relationship found between Mo and U with sulfates in PC2 indicates that both elements show a high mobility in groundwater. Indeed, the concentrations of sulfate, Mo and U are increased as groundwater moves eastward. PC3 includes the alkali trace elements (Rb and Cs), indicating that both elements could be derived from the same source of origin. PC4 represents the heavy trace elements (Cd and Pb) whereas PC5 includes divalent trace elements such as Zn and Cu. None of the water samples showed trace element concentrations higher than the guideline values for drinking water proposed by the World Health Organization, which indicates that the analyzed trace elements in groundwater do not pose any significant threat to the population living in this area.
NASA Technical Reports Server (NTRS)
Jurewicz, Stephen R.; Jones, John H.
1993-01-01
El Goresy et al.'s observation of Nb, Zr, and Ta in refractory platinum metal nuggets (RPMN's) from Ca-Al-rich inclusions (CAI's) in the Allende meteorite led them to propose that these lithophile elements alloyed in the metallic state with noble metals in the early solar nebula. However, Grossman pointed out that the thermodynamic stability of Zr in the oxide phase is vastly greater than metallic Zr at estimated solar nebula conditions. Jones and Burnett suggested this discrepancy may be explained by the very non-ideal behavior of some lithophile transition elements in noble metal solutions and/or intermetallic compounds. Subsequently, Fegley and Kornacki used thermodynamic data taken from the literature to predict the stability of several of these intermetallic compounds at estimated solar nebula conditions. Palme and Schmitt and Treiman et al. conducted experiments to quantify the partitioning behavior of certain lithophile elements between silicate liquid and Pt-metal. Although their results were somewhat variable, they did suggest that Zr partition coefficients were too small to explain the observed 'percent' levels in some RPMN's. Palme and Schmitt also observed large partition coefficients for Nb and Ta. No intermetallic phases were identified. Following the work of Treiman et al., Jurewicz and Jones performed experiments to examine Zr, Nb, and Ti partitioning near solar nebula conditions. Their results showed that Zr, Nb, and Ti all have an affinity for the platinum metal, with Nb and Ti having a very strong preference for the metal. The intermetallic phases (Zr,Fe)Pt3, (Nb,Fe)Pt3, and (Ti,Fe)Pt3 were identified. Curiously, although both experiments and calculations indicate that Ti should partition strongly into Pt-metal (possibly as TiPt3), no Ti has ever been observed in any RPMN's. Fegley and Kornacki also noticed this discrepancy and hypothesized that the Ti was stabilized in perovskite which is a common phase in Allende CAI's.
NASA Astrophysics Data System (ADS)
Norling, B.; Rowe, M. C.; Chambefort, I.; Tepley, F. J.; Morrow, S.
2016-05-01
The present-day hydrothermal system beneath the Kawerau Geothermal Field, in the Taupo Volcanic Zone, New Zealand, is likely heated from the Pūtauaki (Mt. Edgecumbe) magma system. The aim of this work, as an analog for present day processes, is to identify whether or not earlier erupted Pūtauaki magmas show evidence for volatile exsolution. This may have led to the transfer of volatile components from the magmatic to hydrothermal systems. To accomplish this, minerals and melt inclusions from volcanic products were analyzed for abundances of volatile and ore-forming elements (S, Cl, Li, Cu, Sn, Mo, W, Sb, As, and Tl). The variations in abundance of these elements were used to assess magma evolution and volatile exsolution or fluxing in the magma system. Melt inclusions suggest the evolution of Pūtauaki andesite-dacite magmas is predominantly driven by crystallization processes resulting in rhyodacite-rhyolite glass compositions (although textural and geochemical evidence still indicate a role for magma mixing). Measured mineral-melt partition coefficients for trace metals of interest indicates that, with the exception of Tl in biotite, analyzed metals are all incompatible in Pūtauaki crystallization products. Excluding Li and Cu, other volatile and ore metals recorded in melt inclusions behave incompatibly, with concentrations increasing during evolution from rhyodacitic to rhyolitic melt compositions. Li and Cu appear to have increased mobility likely resulting from diffusive exchange post-crystallization, and may be related to late volatile fluxing. Although S and Cl concentrations decrease with melt evolution, no mineralogical evidence exists to indicate the exsolution and mobility of ore-forming metals from the magma at the time of crystallization. This observation cannot rule out the potential for post-crystallization volatile exsolution and ore-forming metal mobilization, which may only be recorded as diffusive re-equilibration of more rapidly diffusing elements (e.g., Li and Cu).
ERIC Educational Resources Information Center
Pettyjohn, Wayne A.
1972-01-01
Summarizes the effects of arsenic, lead, zinc, mercury, and cadmium on human health, indicates the sources of the elements in water, and considers the possibility of students in high schools analyzing water for trace amounts of the elements. (AL)
NASA Technical Reports Server (NTRS)
Wignarajah, K.; Fisher, John W.; Pisharody, Suresh A.
2003-01-01
The nutritional requirements of humans and astronauts are well defined and show consistency, but the same cannot be said of human wastes. Nutrients taken up by humans can be considered to fall into two major categories - organic and inorganic fractions. Carbon, hydrogen, oxygen, nitrogen and sulfur are elements that are associated with the organic fraction. These elements are taken up in large amounts by humans and when metabolized released in wastes often in gaseous forms or as water. On the other hand, a large number of the elements are simply exchanged and can be accounted for in the liquid and solid wastes of humans. These elements fall into three major categories - cationic macroelements (e.g. Ca, K, Na, Mg and Si), anionic macroelements (e.g P, S and Cl), 17 essential microelements, (e.g. Fe, Mn, Cr, Co, Cu, Zn, Se and Sr). When provided in the recommended concentrations to an adult human, these elements should not normally accumulate in humans, but will be excreted in the different human wastes. Knowledge of the partitioning of these elements between the different human waste fractions is fundamental to understanding (a) how these elements can be recovered for reuse in space habitats, and (b) to developing the processors for waste management. The current literature is exhaustive but sometimes also conflicting. We have used the existing knowledge of nutrition and waste from medical literature and NASA documentation to develop a consensus to typify and chemically characterize the various human wastes. The partitioning of these elements has been developed into a functional model.
Dynamic Load Balancing Based on Constrained K-D Tree Decomposition for Parallel Particle Tracing
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhang, Jiang; Guo, Hanqi; Yuan, Xiaoru
Particle tracing is a fundamental technique in flow field data visualization. In this work, we present a novel dynamic load balancing method for parallel particle tracing. Specifically, we employ a constrained k-d tree decomposition approach to dynamically redistribute tasks among processes. Each process is initially assigned a regularly partitioned block along with duplicated ghost layer under the memory limit. During particle tracing, the k-d tree decomposition is dynamically performed by constraining the cutting planes in the overlap range of duplicated data. This ensures that each process is reassigned particles as even as possible, and on the other hand the newmore » assigned particles for a process always locate in its block. Result shows good load balance and high efficiency of our method.« less
Trace Element Levels and Cognitive Function in Rural Elderly Chinese
Gao, Sujuan; Jin, Yinlong; Unverzagt, Frederick W.; Ma, Feng; Hall, Kathleen S.; Murrell, Jill R.; Cheng, Yibin; Shen, Jianzhao; Ying, Bo; Ji, Rongdi; Matesan, Janetta; Liang, Chaoke; Hendrie, Hugh C.
2009-01-01
Background Trace elements are involved in metabolic processes and oxidation-reduction reactions in the central nervous system and could have a possible effect on cognitive function. The relationship between trace elements measured in individual biological samples and cognitive function in an elderly population had not been investigated extensively. Methods The participant population is part of a large cohort study of 2000 rural elderly Chinese persons. Six cognitive assessment tests were used to evaluate cognitive function in this population, and a composite score was created to represent global cognitive function. Trace element levels of aluminum, calcium, cadmium, copper, iron, lead, and zinc were analyzed in plasma samples of 188 individuals who were randomly selected and consented to donating fasting blood. Analysis of covariance models were used to assess the association between each trace element and the composite cognitive score adjusting for demographics, medical history of chronic diseases, and the apolipoprotein E (APOE) genotype. Results Three trace elements—calcium, cadmium, and copper—were found to be significantly related to the composite cognitive score. Increasing plasma calcium level was associated with higher cognitive score (p < .0001). Increasing cadmium and copper, in contrast, were significantly associated with lower composite score (p = .0044 and p = .0121, respectively). Other trace elements did not show significant association with the composite cognitive score. Conclusions Our results suggest that calcium, cadmium, and copper may be associated with cognitive function in the elderly population. PMID:18559640
Transport of trace metals in runoff from soil and pond ash feedlot surfaces
Vogel, J.R.; Gilley, J.E.; Cottrell, G.L.; Woodbury, B.L.; Berry, E.D.; Eigenbert, R.A.
2011-01-01
The use of pond ash (fly ash that has been placed in evaporative ponds for storage and subsequently dewatered) for feedlot surfaces provides a drier environment for livestock and furnishes economic benefits. However, pond ash is known to have high concentrations of trace elements, and the runoff water-quality effects of feedlot surfaces amended with pond ash are not well defined. For this study, two experimental units (plots) were established in eight feedlot pens. Four of the pens contained unamended soil surfaces, and the remaining four pens had pond-ash amended surfaces. Before each test, unconsolidated surface material was removed from four of the plots for each of the amendment treatments, resulting in eight unamended plots and eight pond-ash amended plots. Concentrations for 23 trace elements were measured in cattle feedlot surface material and in the runoff water from three simulated rainfall events. Trace element concentrations in surface material and runoff did not differ between surface consolidation treatments. Amending the feedlot surface material with pond ash resulted in a significant increase in concentration for 14 of the 17 trace elements. Runoff concentrations for 21 trace elements were affected by pond-ash amendment. Sixteen of 21 trace element concentrations that differed significantly were greater in runoff from unamended soil surfaces. Concentrations in runoff were significantly correlated with concentrations in feedlot surface material for boron, manganese, molybdenum, selenium, and uranium.
Bennett, Neil R; Brenan, James M; Fei, Yingwei
2015-06-13
Estimates of the primitive upper mantle (PUM) composition reveal a depletion in many of the siderophile (iron-loving) elements, thought to result from their extraction to the core during terrestrial accretion. Experiments to investigate the partitioning of these elements between metal and silicate melts suggest that the PUM composition is best matched if metal-silicate equilibrium occurred at high pressures and temperatures, in a deep magma ocean environment. The behavior of the most highly siderophile elements (HSEs) during this process however, has remained enigmatic. Silicate run-products from HSE solubility experiments are commonly contaminated by dispersed metal inclusions that hinder the measurement of element concentrations in the melt. The resulting uncertainty over the true solubility and metal-silicate partitioning of these elements has made it difficult to predict their expected depletion in PUM. Recently, several studies have employed changes to the experimental design used for high pressure and temperature solubility experiments in order to suppress the formation of metal inclusions. The addition of Au (Re, Os, Ir, Ru experiments) or elemental Si (Pt experiments) to the sample acts to alter either the geometry or rate of sample reduction respectively, in order to avoid transient metal oversaturation of the silicate melt. This contribution outlines procedures for using the piston-cylinder and multi-anvil apparatus to conduct solubility and metal-silicate partitioning experiments respectively. A protocol is also described for the synthesis of uncontaminated run-products from HSE solubility experiments in which the oxygen fugacity is similar to that during terrestrial core-formation. Time-resolved LA-ICP-MS spectra are presented as evidence for the absence of metal-inclusions in run-products from earlier studies, and also confirm that the technique may be extended to investigate Ru. Examples are also given of how these data may be applied.
Bennett, Neil R.; Brenan, James M.; Fei, Yingwei
2015-01-01
Estimates of the primitive upper mantle (PUM) composition reveal a depletion in many of the siderophile (iron-loving) elements, thought to result from their extraction to the core during terrestrial accretion. Experiments to investigate the partitioning of these elements between metal and silicate melts suggest that the PUM composition is best matched if metal-silicate equilibrium occurred at high pressures and temperatures, in a deep magma ocean environment. The behavior of the most highly siderophile elements (HSEs) during this process however, has remained enigmatic. Silicate run-products from HSE solubility experiments are commonly contaminated by dispersed metal inclusions that hinder the measurement of element concentrations in the melt. The resulting uncertainty over the true solubility and metal-silicate partitioning of these elements has made it difficult to predict their expected depletion in PUM. Recently, several studies have employed changes to the experimental design used for high pressure and temperature solubility experiments in order to suppress the formation of metal inclusions. The addition of Au (Re, Os, Ir, Ru experiments) or elemental Si (Pt experiments) to the sample acts to alter either the geometry or rate of sample reduction respectively, in order to avoid transient metal oversaturation of the silicate melt. This contribution outlines procedures for using the piston-cylinder and multi-anvil apparatus to conduct solubility and metal-silicate partitioning experiments respectively. A protocol is also described for the synthesis of uncontaminated run-products from HSE solubility experiments in which the oxygen fugacity is similar to that during terrestrial core-formation. Time-resolved LA-ICP-MS spectra are presented as evidence for the absence of metal-inclusions in run-products from earlier studies, and also confirm that the technique may be extended to investigate Ru. Examples are also given of how these data may be applied. PMID:26132380
Brabets, Timothy P.
2004-01-01
Cape Krusenstern National Monument is located in Northwest Alaska. In 1985, an exchange of lands and interests in lands between the Northwest Alaska Native Association and the United States resulted in a 100-year transportation system easement for 19,747 acres in the monument. A road was then constructed along the easement from the Red Dog Mine, a large zinc concentrate producer and located northeast of the monument, through the monument to the coast and a port facility. Each year approximately 1.3 million tonnes of zinc and lead concentrate are transported from the Red Dog Mine via this access road. Concern about the possible deposition of cadmium, lead, zinc and other trace elements in the monument was the basis of a cooperative project with the National Park Service. Concentrations of dissolved cadmium, dissolved lead, and dissolved zinc from 28 snow samples from a 28 mile by 16 mile grid were below drinking water standards. In the particulate phase, approximately 25 percent of the samples analyzed for these trace elements were higher than the typical range found in Alaska soils. Boxplots of concentrations of these trace elements, both in the dissolved and particulate phase, indicate higher concentrations north of the access road, most likely due to the prevailing southeast wind. The waters of four streams sampled in Cape Krusenstern National Monument are classified as calcium bicarbonate. Trace-element concentrations from these streams were below drinking water standards. Median concentrations of 39 trace elements from streambed sediments collected from 29 sites are similar to the median concentrations of trace elements from the U.S. Geological Survey?s National Water-Quality Assessment database. Statistical differences were noted between trace-element concentrations of cadmium, lead, and zinc at sites along the access road and sites north and south of the access road; concentrations along the access road being higher than north or south of the road. When normalized to 1 percent organic carbon, the concentrations of these trace elements are not expected to be toxic to aquatic life when compared to criteria established by the Canadian government and other recent research.
NASA Technical Reports Server (NTRS)
Douglas, S.
2001-01-01
ESEM-EDS studies of an endolithic evaporite community from Death Valley revealed its ability to sequester water and affect the partitioning of trace metals in this environment. Additional information is contained in the original extended abstract.
A DYNAMIC SIMULATOR OF ENVIRONMENTAL CHEMICAL PARTITIONING
A version of the Community Multiscale Air Quality (CMAQ) model has been developed by the U.S. EPA that is capable of addressing the atmospheric fate, transport and deposition of some common trace toxics. An initial, 36-km rectangular grid-cell application for atrazine has been...
[Analysis of primary elemental speciation distribution in mungbean during enzymatic hydrolization].
Li, Ji-Hua; Huang, Mao-Fang; Zhu, De-Ming; Zheng, Wei-Wan; Zhong, Ye-Jun
2009-03-01
In the present paper, trace elements contents of cuprum, zincum, manganese and ferrum in mungbean and their primary speciation distribution during enzymatic hydrolization were investigated with ICP-AES OPTIMA 5300DV plasma emission spectroscopy. The trace elements were separated into two forms, i.e. dissolvable form and particulate form, by cellulose membrane with 0.45 microm of pore diameter. All the samples were digested by strong acid (perchloric acid and nitric acid with 1 : 4 ratio ). The parameters of primary speciations of the four elements were calculated and discussed. The results showed: (1) Contents of cuprum, zincum, manganese and ferrum in mungbean were 12.77, 31.26, 18.14 and 69.38 microg x g(-1) (of dry matter), respectively. Different treatment resulted in different elemental formulation in product, indicating that more attention should be paid to the trace elements pattern when producing mungbean beverage with different processes. (2) Extraction rates of cuprum, zincum, manganese and ferrum in extract were 68.84%, 51.84%, 63.97% and 30.40% with enzymatic treatments and 36.22%, 17.58%, 7.85% and 22.99% with boil treatment, respectively. Both boil and enzymatic treatments led to poor elemental extraction rates, which proved that it was necessary to take deep enzymatic hydrolysis treatment in mungbean beverage process as the trace element utilization rate was concerned. (3) Amylase, protease and cellulose showed different extraction effectiveness of the four trace elements. Generally, protease exhibited highest efficiency for the four elements extraction. All of the four trace elements were mostly in dissolvable form in all hydrolysates and soup. (4) Relative standard deviations and recovery yields are within 0.12%-0.90% (n = 11) and 98.6%-101.4%, respectively. The analysis method in this paper proved to be accurate.
Igneous fractionation and subsolidus equilibration of diogenite meteorites
NASA Technical Reports Server (NTRS)
Mittlefehldt, David W.
1993-01-01
Diogenites are coarse-grained orthopyroxenite breccias of remarkably uniform major element composition. Most diogenites contain homogeneous pyroxene fragments up to 5 cm across of Wo2En74Fs24 composition. Common minor constituents are chromite, olivine, trolite and metal, while silica, plagioclase, merrillite and diopside are trace phases. Diogenites are generally believed to be cumulates from the eucrite parent body, although their relationship with eucrites remains obscure. It has been suggested that some diogenites are residues after partial melting. I have performed EMPA and INAA for major, minor and trace elements on most diogenites, concentrating on coarse-grained mineral and lithic clasts in order to elucidate their igneous formation and subsequent metamorphic history. Major element compositions of diogenites are decoupled from minor and trace element compositions; the latter record an igneous fractionation sequence that is not preserved in the former. Low equilibration temperatures indicate that major element diffusion continued long after crystallization. Diffusion coefficients for trivalent and tetravalent elements in pyroxene are lower than those of divalent elements. Therefore, major element compositions of diogenites may represent means of unknown portions of a cumulate homogenized by diffusion, while minor and trace elements still yield information on their igneous history. The scale of major element equilibration is unknown, but is likely to be on the order of a few cm. Therefore, the diogenite precursors may have consisted largely of cm-sized, igneously zoned orthopyroxene grains, which were subsequently annealed during slow cooling, obliterating major element zoning but preserving minor and trace incompatible element zoning.
Plate tectonics and continental basaltic geochemistry throughout Earth history
NASA Astrophysics Data System (ADS)
Keller, Brenhin; Schoene, Blair
2018-01-01
Basaltic magmas constitute the primary mass flux from Earth's mantle to its crust, carrying information about the conditions of mantle melting through which they were generated. As such, changes in the average basaltic geochemistry through time reflect changes in underlying parameters such as mantle potential temperature and the geodynamic setting of mantle melting. However, sampling bias, preservation bias, and geological heterogeneity complicate the calculation of representative average compositions. Here we use weighted bootstrap resampling to minimize sampling bias over the heterogeneous rock record and obtain maximally representative average basaltic compositions through time. Over the approximately 4 Ga of the continental rock record, the average composition of preserved continental basalts has evolved along a generally continuous trajectory, with decreasing compatible element concentrations and increasing incompatible element concentrations, punctuated by a comparatively rapid transition in some variables such as La/Yb ratios and Zr, Nb, and Ti abundances approximately 2.5 Ga ago. Geochemical modeling of mantle melting systematics and trace element partitioning suggests that these observations can be explained by discontinuous changes in the mineralogy of mantle partial melting driven by a gradual decrease in mantle potential temperature, without appealing to any change in tectonic process. This interpretation is supported by the geochemical record of slab fluid input to continental basalts, which indicates no long-term change in the global proportion of arc versus non-arc basaltic magmatism at any time in the preserved rock record.
Gauge field entanglement in Kitaev's honeycomb model
NASA Astrophysics Data System (ADS)
Dóra, Balázs; Moessner, Roderich
2018-01-01
A spin fractionalizes into matter and gauge fermions in Kitaev's spin liquid on the honeycomb lattice. This follows from a Jordan-Wigner mapping to fermions, allowing for the construction of a minimal entropy ground-state wave function on the cylinder. We use this to calculate the entanglement entropy by choosing several distinct partitionings. First, by partitioning an infinite cylinder into two, the -ln2 topological entanglement entropy is reconfirmed. Second, the reduced density matrix of the gauge sector on the full cylinder is obtained after tracing out the matter degrees of freedom. This allows for evaluating the gauge entanglement Hamiltonian, which contains infinitely long-range correlations along the symmetry axis of the cylinder. The matter-gauge entanglement entropy is (Ny-1 )ln2 , with Ny the circumference of the cylinder. Third, the rules for calculating the gauge sector entanglement of any partition are determined. Rather small correctly chosen gauge partitions can still account for the topological entanglement entropy in spite of long-range correlations in the gauge entanglement Hamiltonian.
Van Hook, R I
1979-01-01
This report addresses the effects of coal-derived trace and radioactive elements. A summary of our current understanding of health and environmental effects of trace and radioactive elements released during coal mining, cleaning, combustion, and ash disposal is presented. Physical and biological transport phenomena which are important in determining organism exposure are also discussed. Biological concentration and transformation as well as synergistic and antagonistic actions among trace contaminants are discussed in terms of their importance in mobility, persistence, availability, and ultimate toxicity. The consequences of implementing the President's National Energy Plan are considered in terms of the impact of the NEP in 1985 and 2000 on the potential effects of trace and radioactive elements from the coal fuel cycle. Areas of needed research are identified in specific recommendations. PMID:540619
The novel approach to the biomonitor survey using one- and two-dimensional Kohonen networks.
Deljanin, Isidora; Antanasijević, Davor; Urošević, Mira Aničić; Tomašević, Milica; Perić-Grujić, Aleksandra; Ristić, Mirjana
2015-10-01
To compare the applicability of the leaves of horse chestnut (Aesculus hippocastanum) and linden (Tilia spp.) as biomonitors of trace element concentrations, a coupled approach of one- and two-dimensional Kohonen networks was applied for the first time. The self-organizing networks (SONs) and the self-organizing maps (SOMs) were applied on the database obtained for the element accumulation (Cr, Fe, Ni, Cu, Zn, Pb, V, As, Cd) and the SOM for the Pb isotopes in the leaves for a multiyear period (2002-2006). A. hippocastanum seems to be a more appropriate biomonitor since it showed more consistent results in the analysis of trace elements and Pb isotopes. The SOM proved to be a suitable and sensitive tool for assessing differences in trace element concentrations and for the Pb isotopic composition in leaves of different species. In addition, the SON provided more clear data on seasonal and temporal accumulation of trace elements in the leaves and could be recommended complementary to the SOM analysis of trace elements in biomonitoring studies.
Multielement extraction system for the determination of 18 trace elements in geochemical samples
Clark, J.R.; Viets, J.G.
1981-01-01
A Methyl isobutyl ketone-Amine synerGistic Iodide Complex (MAGIC) extraction system has been developed for use in geochemical exploration which separates a maximum number of trace elements from interfering matrices. Extraction curves for 18 of these trace elements are presented: Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Ga, In, Tl, Sa, Pb, As, Sb, Bi, Se, and Te. The acid normality of the aqueous phase controls the extraction into the organic phase, and each of these 18 elements has a broad range of HCl normality over which H is quantitatively extracted, making H possible to determine all 18 trace elements from a single sample digestion or leach solution. The extract can be analyzed directly by flame atomic absorption or inductively coupled plasma emission spectroscopy. Most of these 18 elements can be determined by Nameless atomic absorption after special treatment of the organic extract.
Mantle End-Members: The Trace Element Perspective
NASA Astrophysics Data System (ADS)
Willbold, M.; Stracke, A.; Hofmann, A. W.
2004-12-01
On the basis of their isotopic composition, ocean island basalts (OIB) have been classified into three to four end-members; HIMU with the most radiogenic Pb isotope ratios of OIB and Enriched Mantle 1 and 2 (EM1, EM2) with less radiogenic but variable Pb isotope and highly radiogenic Sr isotope signatures. It has also been argued that each of these isotopic families has common trace element characteristics that distinguish them from one another and so substantiated this classification. Here, we present new high-precision trace element data for samples from St. Helena, Tristan da Cunha and Gough in the Atlantic Ocean. The overall data-set is augmented by OIB data from the GEOROC database and includes data from all major isotopic families (HIMU: St. Helena, Mangaia, Tubuai, and Rururtu; EM1: Tristan da Cunha, Gough, Pitcairn; and EM2: Samoa, Marquesas, and Society). For each locality we use only islands defining the most extreme isotopic compositions. The entire data-set has been screened to exclude altered and highly differentiated samples. HIMU basalts have a very uniform trace element composition. Compared to HIMU-type basalts, EM-type basalts are enriched in Rb, Ba, and K, and depleted in U, Nb, and Ta, relative to La. Different EM-type OIBs from the same isotopic family (EM1 or EM2), have distinct trace element characteristics that can ultimately only be caused by different source compositions. For example, Ba/Th ratios in samples from both Tristan da Cunha (EM1) and Samoa (EM2) are similarly high (ca. 110) whereas Ba/Th ratios in samples from Pitcairn (EM1) and Society (EM2) samples are consistently lower (ca. 70). Thus on the basis of their trace element composition, EM-type OIB cannot be classified into EM1 and EM2 type basalts, nor can any other grouping be identified. The remarkably uniform isotopic and trace element composition of HIMU-type basalts suggests derivation from a single common source reservoir, most likely subduction-modified oceanic crust. Although there are some trace element characteristics common to all EM-type basalts, which distinguish them from HIMU-type basalts (e.g. uniformly high Th/U ratios of 4.7 ± 0.3, and enrichment in Cs-U), each suite of EM-type basalts has unique trace element signatures that distinguish them from any other suite of EM-type basalts. This is especially obvious when comparing the trace element composition of EM basalts from one isotopic family, for example EM1-type basalts from Tristan, Gough and Pitcairn. Consequently, the trace element systematics of EM-type basalts suggest that there are many different EM-type sources, whereas the isotopic composition of EM-type basalts suggest derivation from two broadly similar sources, i.e. EM1 and EM2. The large variability in subducting sediments with respect to both parent-daughter (e.g. Rb/Sr, Sm/Nd, U/Pb, Th/Pb,...) and other trace element ratios makes it unlikely that there are reproducible mixtures of sediments leading to two different isotopic evolution paths (EM1 and EM2) while preserving a range of incompatible element contents for each isotopic family, as would be required to reconcile the isotopic and trace element characteristics of EM-type basalts. Although this does not a priori argue against sediments as possible source components for OIB, it does argue against two distinct groups of sediments as EM1 and EM2 sources. Further characterization of sources with the same general origin (e.g. a certain type of crust or lithosphere) or identification of processes leading to reservoirs with similar parent-daughter ratio characteristics but different incompatible trace element contents could resolve the apparent conundrum.
Factors to consider for trace element deposition biomonitoring surveys with lichen transplants
Ayrault, S.; Clochiatti, R.; Carrot, F.; Daudin, L.; Bennett, J.P.
2007-01-01
A trace element deposition biomonitoring experiment with transplants of the fruticose lichen Evernia prunastri was developed, aimed at monitoring the effects of different exposure parameters (exposure orientation and direct rain) and to the elements Ti, V, Cr, Co, Cu, Zn, Rb, Cd, Sb and Pb. Accumulations were observed for most of the elements, confirming the ability of Evernia transplants for atmospheric metal deposition monitoring. The accumulation trends were mainly affected by the exposure orientation and slightly less so by the protection from rain. The zonation of the trace elements inside the thallus was also studied. It was concluded that trace element concentrations were not homogeneous in Evernia, thus imposing some cautions on the sampling approach. A nuclear microprobe analysis of an E. prunastri transplanted thallus in thin cross-sections concluded that the trace elements were mainly concentrated on the cortex of the thallus, except Zn, Ca and K which were also present in the internal layers. The size of the particles deposited or entrapped on the cortex surface averaged 7????m. A list of key parameters to ensure the comparability of surveys aiming at observing temporal or spatial deposition variation is presented. ?? 2006 Elsevier B.V. All rights reserved.
Investigation of the seismic resistance of interior building partitions, phase 1
NASA Astrophysics Data System (ADS)
Anderson, R. W.; Yee, Y. C.; Savulian, G.; Barclay, B.; Lee, G.
1981-02-01
The effective participation of wood-framed interior shear wall partitions when determining the ultimate resistance capacity of two- and three-story masonry apartment buildings to seismic loading was investigated. Load vs. deflection tests were performed on 8 ft by 8 ft wall panel specimens constructed of four different facing materials, including wood lath and plaster, gypsum lath and plaster, and gypsum wallboard with joints placed either horizontally or vertically. The wood lath and plaster construction is found to be significantly stronger and stiffer than the other three specimens. Analyses of the test panels using finite element methods to predict their static resistance characteristics indicates that the facing material acts as the primary shear-resisting structural element. Resistance of shear wall partitions to lateral loads was assessed.
Ngole-Jeme, Veronica M; Ekosse, Georges-Ive E; Songca, Sandile P
2018-01-01
Fifty-seven samples of soils commonly ingested in South Africa, Swaziland, Democratic Republic of Congo (DRC), and Togo were analyzed for the concentrations of arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), lead (Pb), manganese (Mn), nickel (Ni), and zinc (Zn) and their bioaccessibility in the human gastrointestinal tract. Bioaccessibility values were used to calculate daily intake, and hazard quotient of each trace element, and chronic hazard index (CHI) of each sample. Carcinogenic risk associated with As and Ni exposure were also calculated. Mean pseudo-total concentrations of trace elements in all samples were 7.2, 83.3, 77.1, 15.4, 28.6, 24.9, 56.1, 2.8, and 26.5 mg/kg for As, Cr, Mn, Co, Ni, Cu, Zn, Cd, and Pb, respectively. Percent bioaccessibility of Pb (13-49%) and Zn (38-56%) were highest among trace elements studied. Average daily intake values were lower than their respective reference doses for ell elements except for Pb in selected samples. Samples from DRC presented the highest health risks associated with trace element exposure with most of the samples having CHI values between 0.5 and 1.0. Some samples had higher than unacceptable values of carcinogenic risk associated with As and Ni exposure. Results indicate low trace element exposure risk from ingesting most of the soil samples.
Liu, ChunMei; Yuan, HaiRong; Zou, DeXun; Liu, YanPing; Zhu, BaoNing; Li, XiuJin
2015-01-01
This research applied sodium hydroxide (NaOH) pretreatment and trace elements to improve biomethane production when using corn stover for anaerobic digestion. Full-factor experimental tests identified the best combination of trace elements with the NaOH pretreatment, indicating that the best combination was with 1.0, 0.4, and 0.4 mg·L−1·d−1 of elements Fe, Co, and Ni, respectively. The cumulative biomethane production adding NaOH pretreatment and trace elements was 11,367 mL; total solid bioconversion rate was 55.7%, which was 41.8%–62.2% higher than with NaOH-pretreatment alone and 22.2%–56.3% higher than with untreated corn stover. The best combination was obtained 5–9 days shorter than T90 and maintained good system operation stability. Only a fraction of the trace elements in the best combination was present in the resulting solution; more than 85% of the total amounts added were transferred into the solid fraction. Adding 0.897 g of Fe, 0.389 g of Co, and 0.349 g of Ni satisfied anaerobic digestion needs and enhanced biological activity at the beginning of the operation. The results showed that NaOH pretreatment and adding trace elements improve corn stover biodegradability and enhance biomethane production. PMID:26137469
Trace element analysis of soil type collected from the Manjung and central Perak
DOE Office of Scientific and Technical Information (OSTI.GOV)
Azman, Muhammad Azfar, E-mail: m-azfar@nuclearmalaysia.gov.my; Hamzah, Suhaimi; Rahman, Shamsiah Abdul
2015-04-29
Trace elements in soils primarily originated from their parent materials. Parents’ material is the underlying geological material that has been undergone different types of chemical weathering and leaching processes. Soil trace elements concentrations may be increases as a result of continuous input from various human activities, including power generation, agriculture, mining and manufacturing. This paper describes the Neutron Activation Analysis (NAA) method used for the determination of trace elements concentrations in part per million (ppm) present in the terrestrial environment soil in Perak. The data may indicate any contamination of trace elements contributed from human activities in the area. Themore » enrichment factors were used to check if there any contamination due to the human activities (power plants, agricultural, mining, etc.) otherwise the values would serve as a baseline data for future study. The samples were collected from 27 locations of different soil series in the area at two different depths: the top soil (0-15cm) and the sub soil (15-30cm). The collected soil samples were air dried at 60°C and passed through 2 µm sieve. Instrumental Neutron Activation Analysis (NAA) has been used for the determination of trace elements. Samples were activated in the Nuclear Malaysia TRIGA Mark II reactor followed by gamma spectrometric analysis. By activating the stable elements in the samples, the elements can be determined from the intensities of gamma energies emitted by the respected radionuclides.« less
Capson-Tojo, Gabriel; Moscoviz, Roman; Ruiz, Diane; Santa-Catalina, Gaëlle; Trably, Eric; Rouez, Maxime; Crest, Marion; Steyer, Jean-Philippe; Bernet, Nicolas; Delgenès, Jean-Philippe; Escudié, Renaud
2018-07-01
The effect of supplementing granular activated carbon and trace elements on the anaerobic digestion performance of consecutive batch reactors treating food waste was investigated. The results from the first batch suggest that addition of activated carbon favored biomass acclimation, improving acetic acid consumption and enhancing methane production. Adding trace elements allowed a faster consumption of propionic acid. A second batch proved that a synergy existed when activated carbon and trace elements were supplemented simultaneously. The degradation kinetics of propionate oxidation were particularly improved, reducing significantly the batch duration and improving the average methane productivities. Addition of activated carbon favored the growth of archaea and syntrophic bacteria, suggesting that interactions between these microorganisms were enhanced. Interestingly, microbial analyses showed that hydrogenotrophic methanogens were predominant. This study shows for the first time that addition of granular activated carbon and trace elements may be a feasible solution to stabilize food waste anaerobic digestion. Copyright © 2018 Elsevier Ltd. All rights reserved.